p^^'ip^J^ THE CALDWELL COLLECTION THE GIFT OF THE FAMILY OF GEORGE CHAPMAN CAILDWELL TO THE DEPARTMENT OF CHEMISTRY whose senior Professor he was from 1868 to 1903 Cornell University Library TX 531.F68 ""'■ Foods and food adulterants . 3 1924 003 566 795 The original of tiiis book is in tine Cornell University Library. There are no known copyright restrictions in the United States on the use of the text. http://www.archive.org/details/cu31924003566795 r=r U. S. DEPARTMENT OF AGRICULTURE. DIVISION OF CHEMISTEY. BULLETIN No. 13. FOODS FOOD ADULTEEANTS. BY DIBi:CTION OF THE COMMISSIONER OP AGRICULTURE. 1 ^ " It 06 PART FT^^ST: DAIRY PR'oDU-CTS. WASHINGTON: GOVEENMENT PBINTINO OFF.ICE. 1887. U. S. DEPARTMENT OF AGRICULTURE. PlVISIOi^ OF CHEMISTRY. BULLETIN No. 13. FOODS FOOD ADULTERANTS. HY DIRECTION OF THE COMMISSIONER OF AGRICULTURE. PART FIRST: DAIRY PRODUCTS. WASHINGTON: GOVERNMENT PRINTING OFFICE. 18S7. 19330— Ni). 13 LETTER OF SUBMITTAL. Sir : I have the honor to submit herewith for your inspection and ap- proval Bulletin Ko. 13, devoted chiefly to a discussion of the best meth- ods of detecting the adulteration of foods! The first part, which is now placed in your hands, treats of dairy products. Much interest has lately been manifested among those en- gaged in agriculture in respect of the adulteration of butter, and this part of the subject has been treated with greater detail than any other. It has been my object iu this work to determine the best methods of analysis of the various products in question, and all the recent improve- ments in analytical methods have been thoroughly tried, and those which have given good results have been adopted iu the analytical work which has been done. Within the last year my division has been supplied with apparatus for photo-micrography, and the illustrations in the following pages are entirely the work of the division unless otherwise stated. Great benefit has been derived from this method of fixing photo- graphic appearances, as the illustration of the crystalline characters of butters and butter substitutes sufficiently show. The examination of condiments, &c., the report of which will soon follow, was made al- most entirely with the microscope, and the illustrations will show how satisfactory this kind of work proves to be. In the matter of photo- graphic illustration no attempt has been made to confine the exhibition to phenomenally fine specimens, but the ordinary appearance of the field of vision has been reproduced. This, I think, is of greater advan- tage to the general investigation than would be the publication only of the strikingly good negatives. It is believed that by following the methods of analysis recommended in the report it will be possible to detect without fail any adulteration of butter that could possibly prove a commercial success. All other forms of adulteration will be sup- pressed by the laws of trade. In addition to the report herewith sub- mitted the following parts of the bulletin are almost ready for the press, viz, condiments, sugar, sirup and honey, drinks and canned goods, flour and meal, tea and coffee, and baking powders. Other parts will follow as soon as time is afforded to submit all the process involved to a thorough examination in the laboratory. Respectfully, ^ H. W. WILEY, Chemist. Hon. l!fOEMAN J. OOLMAN, Commissioner of AgrioV/Uure, 3 CONTENTS. Page. An act defining butter, &c " Artificial butter VV-l'I"" -.tI List of patents granted in United States for manufacture of butter substitutes. 10 Wholesomeness of artificial butter -- 17 Nutritive values of butter and oleomargarine 23 The manufacture of artificial butter in the United States 25 Coloring matters in butter - - 26 Examination of butters 29 Forms of fat crystals - 34 Description of plates ■ 37 Specific gravity of fats 40 Specific gravity of fats; method employed in Division of Chemistry 43 Temperature at ■which specific gravity is stated 43 The melting point, of fats - - 43 Effect of time on melting point of fat disks - -. 50 Effect of the preliminary heating of the fat to diff'erent temperatures 51 Effect of sudden rise of temperature 51 Viscosity 52 Kefractive index of oils - 53 Estimation of soluble acids in butter fats 53 Estimation of insoluble acids in butter fats .-- 59 Other methods 62 Eesults of Hanssen's investigation 62 Absorption of bromine and iodine by butter fats 63 Determination of soluble and insoluble fats in acids 66 Behavior of coooanut oil with some of the methods used in analysis of butter fats 71 Use of cotton-seed oil as a butter adulterant 72 Estimation of salt 73 Estimation of curd 74 Qualitative tests 74 Kesultsof analyses of genuine and suspected butters and butter adulterants.. 77 Analytical results 78 Examination of milk 80 Specific gravity 8-2 Quantity of -water or dry solids in milk S3 Estimation of fat S.Ti Adams's method 8.5 Soxhlet's areometrio method $7 Liebermann's method Fleischmann and Morgen's method 100 by volume of cream lOO by the lactocrite 101 lactobutyrometric method 103 Optical methods of estimating fat in milk 104 Estimation of lactose IO5 Specific rotatory power of milk sugar 105 Specific rotatory power of albumen remaining in filtrate from Pb. Acet. and H6I sol Ill Estimation of the albuminoids .1'.. ".! 114 Analyses of milk ....".". ..." 115 Koumiss '.'.'.'.....'.'.'.. 117 Koumiss, method of analysis .[ .!...] Hfi Analyses of koumiss ' " 1.. . 120 Cheese .".."" !J]1 122 Tyrotoxicon '.. _]" jgg Estimation of fat iu milk, Morse and Piggot's method .' " 107 Estimation of water in milk [_"" 127 Substances sometimes added to milk to mask the removal of tlie cream audad- difcionof water _ ,,,. Milk adulterant Ill" 128 Occurrence of ultramarine as an adulterant iu milk nou Filled cheese H" "" ,52 4 BUTTER AND ITS ADULTERATIONS. The adulteration of butter with other fats has of late years attracted the attention not only of the analyst but also of the political economist and health officer. This matter has been deemed of sufficient importance to demand reg- ulation by law of Congress. This law provides for the inspection atid analysis of commercial butters and their substitutes. Following is the text of the act : An Act tleflning batter, also imposing a tax upon and rogalating the raanufaotaro, sale, importation, and exportation of oleomargarine. Be it enacted Jiy the Senate and Souse of Representatives of the United States of America in Congress assembled, That for the purposes of this act the word "butter" shall he nuderstood to mean the food product usually known as hutter, and which is made exclusively from milk or cream, or hoth, with or without common salt, and with or without additional coloring matter. Sec. 2. That for the purposes of this act certain manufactured substances, certain extracts, and certain mixtures and compounds, including such mixtures and com- pounds with butter, shall be known and designated as "oleomargarine," namely: All substances heretofore known as oleomargarine, oleo, oleomargarine-oil, hutteriue, lardine, suine, and neutral ; all mixtures and compounds of oleomargarine, oleo, oleo- margarine-oil, butteriue, lardine, suine; and neutral ; all lard extracts and tiillow extracts ; and all mixtures and compounds of tallow, beef-fat, suet, lard, lard-oil, vegetable-oil, annotto, and other coloring matter, intestinal fat, and offal fat made in imitation or semblance of bntter, or when so made, calculated, or intended to be sold as butter or for butter. Sec. 3. That special taxes are imposed as follows : Manufacturers of oleomargarine shall pay six hundred dollars. Every person who manufactures oleomargarine for sale shall be deemed a manufacturer of oleomarga- rine. Wholesale dealers in oleomargarine shall pay four hundred and eighty dollars. Every person who sells or ofifers for sale oleomargarine in the original manufacturer's packages shall be deemed a wJiolesale dealer in oleomargarine. But any manufacturer of oleomargarine who has given the required bond and paid the required special tax, and who sells only oleomargarine of his own production, at the place of manufacture, in the original packages to which the tax-paid stamps are affixecl, shall not be required to pay the special tax of a wholesale dealer in oleomargarine on account of such sales. Retail dealers in oleomargarine shall pay forty-eight dollars. Every person who sells oleomargarine in less quantities than ten pounds at one time shall be regarded as a retail dealer in oleomargarine ; and sections thirty-two hundred and thirty-two, thirty-two hundred and thirty- three,' thirty-two hundred and thirty-four, thirty-two hundred and thirty-five, thirty-two hundred and thirty-six, thirty-two hundred and thirty-seven, thirfcy-two hundred and thirty-eight, thirty-two hundred and th'rty- 5 6 Pooi)S Ai^b FOOD ADtfL'rfiitAiJ'rS. nine, thirty-two liundred and forty, thirty-two hundred and forty-one, and thirty -tWd hundred and forty-three of the Revised Statutes of the United States are, so far aa applicable, made to extend to and include and apply to the special taxes imposed by this section, and to the persons upon whom they are imposed : Provided, That in case any manufacturer otf oleomargarine commences business subsequent to the thirtieth day of June in any year, the special tax shall be reckoned from the first day of July in that year, and shall be five hundred dollars. Sec. 4. That every person ■who carries on the business of a manufacturer of oleo- margarine without having paid the special tax therefor, as required by law, shall, besides beiug liable to the payment of the tax, be fined not less than one thousand and not more than five thousand dollars ; and every person who carries on the busi- ness of a wholesale dealer in oleomargarine without having paid the special tax there- for, as required by law, shall, besides being liable to the payment of the tax, be fined not less than five hundred nor more than two thousand dollars ; and every person who carries on the business of a retail dealer in oleomargarine without having paid the special tax therefor, as required by law, shall, besides being liable to the payment of the tax, be fined not less than fifty nor more than five hundred dollars for each and every ofiense. Sec. 5. That every manufacturer of oleomargarine shall file with the collector of internal revenue of the district in which his manufactory is located such notices, in. ventories, and bonds, shall keep such books and render such returns of material and products, shall put up such signs and affix such number to his factory, and conduct his business ujider snch surveillance of officers and agents as the Commissioner of In- ternal Eevenne, with the approval of the Secretary of the Treasury, may, by regula- tion, require. But the bond required of such manufacturer shall be with sureties satisfactory to the collector of internal revenue, and in a penal sum of not less than five thousand dollars; and the sum of said bond may be increased from time to time, aud additional sureties required at the discretion of the collector, or under iustmc- tions of the Commissioner of Internal Revenue. Skc. C. That all oleomargarine shall be packed by the manufacturer thereof in fir- kins, tubs, or other wooden packages not before used for that purpose, each contaiu- ing not less than ten pounds, and marked, stamped, and branded as the Commissioner of Internal Revenue, with the approval of the Secretary of the Treasury, shall pre- scribe ; and all sales made by the manufacturers of oleomargarine, aud wholcs.ile dealers in oleomargarine, shall be in original stamped packages. Retail dealers in oleomargarine must sell only from original stamped packages, in quantities not ex- ceeding ton pounds, and shall pack the oleomargarine sold by them in suitable wooden or paper packages, which shall be marked aud branded as the Commissioner of la- ternal Revenue, with the approval of the Secretary of the Treasury, shall prescribe. Every person who knowingly sells or offers for sale, or delivers or offers to deliver, any oleomargarine in any other form than in new wooden or paper packages as above described, or who packs in any package any oleomargarine in any manner contrary to law, or who falsely brands any package or affixes a stamp on any package denot- ing a loss amount of tax than that required by law, shall be fined for each oflfense not more than one thousand dollars, and be imprisoned not more than two years. Sec, 7. That every manufacturer of oleomargarine shall securely affix, by nastin"- on each package containing oleomargarine manufactured by him, a label on whidi shall bo printed, besides the number of the manufactory aud the district and State in which it is situated, these words: "Notice— The manufacturer of the oleomart'arino herein contained has complied with all the requirements of law. Every peraou is cautioned not to use cither this package or the stamp thereon again, nor to remove the contents of this package without destroying said stamp, under the penalty pro- vided by law in such cases." Every manufacturer of oleomargarine who neglects to affix such label to any package containhig oleomargarine made by him, or sold or of- fered for sale by or for him, ami every person who removes any such label .so affixed DAIRY PRODUCTS. 7 from any such package, shall bo fined fifty dollars for oach package in respect to which such offense is committed. Sec. 8. That upon oleomargarine which shall bo manufactured and sold, or re- moved for consumption or use, there shall ho assessed and collected a tax of two cents per pound, to be paid by the manufacturer thereof ; and any fractional part of a pound m a package shall bo taxed as a pound. The tax levied by this section shall be repre- sented by coupon stamps ; and the provisions of existing laws governing the engrav- ing, issue, salo, accountahility, effacement, and dostrnctiou of stamps relating to to- bacco and suuft-, as far as applicable, are hereby made to apply to stamps provided for by this section, Sec. 9. That whenever any manufacturer of oleomargarine sells, or removes for sale or consumption, any oleomargarine upon which the tax is reciuired to bo paid by stamps, without the use of the proper stamps, it shall be the duty of the Commissioner of Internal Revenue, within a period of not more than two years after such sale or removal, upon satisfactory proof, to estimate the amount of tax which has been i>mitted.to be paid, and to make an assessment therefor and certify the same to the collector. The tax so assessed shall bo in addition to the penalties imposed by law for such sale or removal. Skc. 10. That all oleomargarine imported from foreign countries shall, in addition to any import dnty imposed on the same, pay an internal- revenue tax of fifteen cents" per pound, such tax to be represented by coupon stamps as in the case of oleomarga- rine manufactured in the United States. The stamps shall be affixed and canceled by the owner or importer of tho oleomargarine while it is in the custody of the proper custom-house officers ; and the oleomargarine shall not pass out of the custody of said officers until the stamps have been so affixed and canceled, but shall he put up in wooden packages, each containing not less than ten pounds, as prescribed in this act for oleomargarine manufactured in the United States, before tho stamps are affixed; and the owner or importer of such oleomargarine shall be liable to all the penal provisions of this act prescribed for manufacturers of oleomargarine manufactured in the United States. Whenever it is necessary to take any oleomargarine so im- ported to any place other than the public stores of tho United States for the purpose of affixing and canceling such stamps, the collector of customs of tho port where such oleomargarine is entered shall designate a bonded warehouse to which it shail be taken, under the control of such customs officer as sncli collector may direct ; and every officer of customs who permits any such oleomargarine to pass out of his cus- tody or control without compliance by tlie owner or importer thereof with tho provis- ions of this section relating thereto, shall he guilty of a misdemeanor, and shall bo fined not less than one thousand dollars nor more than five thousand dollars, and im- prisoned not loss than six months ndr more than three years. Every person who sells or offers for sale any imported oleomargarine, or oleomargarine purporting or claimed to have been imported, not put up in packages and stamped as provided by this act, shall be fined not less than five hundred dollars nor more than five thousand dollars, and be imprisoned not less than six months nor more than two years. Skc. 11. That every person who knowingly purchases or receives for sale any oleo- margarine which has not been branded or stamped according to law shall be liable to a penalty of fifty dollars for each such offense. / Sec. 12. That every person who knowingly purchases or receives forsale any oleo- margarine from any manufacturer who has not paid the special tax shall be liable for each offense to a penalty of- one hundred dollars, and to a forfeiture of all articles so purchased or received, or of the full value thereof Sbc. 13. That whenever any atamp'ed package containing oleomargarine is emptied, it shall be tho duty of tho person iu Avhoso hands the same is to destroy utterly the stamps thereon ; and any person who willfully neglects or refuses so to do shall for each such offense be fined not exceeding fifty dollars, and imprisoned not less than ten days nor more than six months. And any person who fraudulently gives away or accepts 8 FOODS AND FOOD ADULTERANTS. from another, or who sells, buys, or uses for packing oleomargarine, any such stamped package, shall for each such offense he fined not exceeding one hundred dollars, and he imprisoned not more than one year. Any revenue oificer may destroy any emptied oleomargarine package upon which the tax-paid stamp is found. Sec. 14. That there shall he in the offlce of the Commissioner of Internal Eevenue an analytical chemist and a microscopist, who shall each he appointed by the Secretary of the Treasury, and shall each receive a salary of two thousand five hundred dollars per annum ; and the Commissioner of Internal Eevenue may, whenever iu his judg- ment the necessities of the service so require, employ chemists and microscopists, to be paid such compensation as he may deem proper, not exceeding in the aggregate any appropriation made for that purpose. And such Commissioner is authorized to decide what substances, extracts, mixtures, or compounds which may be submitted for his inspection in. contested cases are to be taxed under this act; and his decision in matters of taxation under this act shall be final. The Commissioner may also de- cide whether any substance made in imitation or semblance of butter, and intended for human consumption, contains ingredients deleterious to the public health ; but in case of doubt or contest his decisions in this class of cases may be appealed from to a board hereby constituted for the purpose, and composed of the Surgeon-Greneral of the Army, the Surgeon-General of the Navy, and the Commissioner of Agriculture . and the decisions of this hoard shall be final in the premises. Sec. 15. That all packages of oleomargarine subject to tax under this act that shall be found without stamps or marks as herein provided, and all oleomargarine intended for human consumption which contains ingredients adjudged, as herein beforeprovided, to be deleterious to the public health, shall be forfeited to the United States. Any person who shall willfully remove or deface the stamps, marks, or brands on package containing oleomargarine taxed as provided herein shall be guilty of a misdemeanor, and shall be punished by a fine of not less than one hundred dollars nor more than two thousand dollars, and by imprisonment for not less than thirty days nor more than six months. ^ Sec. l(i. That oleomargarine may be removed from the place of manufacture for export to a foreign country without payment of tax or afi6xing stamps thereto, under such regulations and the filing of such bonds and other security as the Commissioner of Internal Revenue, with the approval of the Secretary of the Treasury, may iirescribe. Every person who shall export oleomargarine shall brand upon every tub, firkin, or other package containing such article the word "oleomargarine," in plain Roman letters not less than one half inch square. Sec. 17. That whenever any person engaged in carrying on the business of manu- facturing oleomargarine defrauds, or attempts to defraud, the United States of the tax on the oleomargarine produced by him, or any part thereof, ho shall forfeit the factory and manufacturing apparatus used by him, and all oleomargarine and all raw material for the production of oleomargarine found in the factory and on the factoiy premises, and shall be fined not less than five hundi-ed dollars nor more than five thousand dollars, and be imprisoned not less than six months nor more than three years. Sec. 18. That if any manufacturer of oleomargarine, any dealer therein or any im- porter or exporter thereof shall knowingly or willfully omit, neglect, or refuse to do, or cause to he done, any of the things required bylaw in the carryiug.ou or conduct- ing of his business, or shall do anything by this act prohibited, if there be no specific penalty or punishment imposed by any other section of this act for the neglect- ing, omitting, or refusing to do, or for the doing oi- causing to bo done, the thing re- quired or prohibited, he shall pay a penalty of one thousand dollars ; and if the person so offending be the manufacturer of or a wholesale dealer in oloomaigarino all the oleomargarine owned by him, or in which ho has any interest as owner, shall bo forfeited to the United States. Sec. id. That all flues, penalties, and forfeitures imposed by this act may be re- covered in any court of competent jurisdiction, DAIRY PEODUCTS. 9 Sec. 20. That the Comraissiouor of Interaal Revenue, with the approval of the Sec- retary of the Treasury, may make all needful regulations for the carryiug into effect of this act. Sec. 21. That this act shall go into effect on the ninetieth day after its passage; and all wooden packages containing ten or more pounds of oleomargarine found.,on the premises of any dealer on or after the ninetieth day succeeding the date of the passage of this act shall bo deemed to be taxable under section eight of this act, and shall be taxed, and shall have afSxod thereto the stamps, marks, and brands required by this act or by regulations made pursuant to this act ; and for the purposes of secur- ing the afSxing of the stamps, marks, and brands required by this act, the oleomar- garine shall be regarded as having been manufactured and sold, or removed from the manufactory for consumption or use, on or after the day this act takes effect ; and such stock on hand at the time of the taking effect of this act may be stamped, marked, and branded under special regulations of the Commissioner of Internal Eev- enue, approved by the Secretary of the Treasury ; and the Commissioner of Internal Revenue may authorize the holder of such packages to mark and brand the same and to afSx tbereto the proper tax-paid stamps. Approved, August 2, 1886. ARTIFICIAL BUTTER. The French chemist, M6ge-Mouries, in 1870 first described a method of making artificial butter on a large scale. M6ge, who was employed on the Imperial farm at Vincennes, was led to undertake this study through a desire to furnish to the poorer classes and to sailors an article which should bo cheaper and more stable in its composition than ordinary butter. He endeavored to imitate the physiological process which he sup- posed took place when cows were insufficiently fed, and when, there- fore, the butter which they furnished was derived from their own fat. Prom beef be obtained a fat " which melted at almost the exact temper- ature of butter, possessed a sweet and agreeable taste, and which for most purposes could replace ordinary butter, not, of course, the finest kinds, but which was superior to it in possessing the advantageous pe- culiarity of keeping for a long time without becoming rancid." Before the breaking out of the Franco-Prussian war M6ge had estab- lished a factory at Poissy. The war suspended the operations of this factory, but at the cessation of hostilities they were again commenced. Following is the method employed in the year 1873, in the manufact- ure of artificial butters : The fat of best quality from recently killed bullocks is finely cut in a kind of sausage grinder in order to break up the membranes. The frag- ments fall into a tank heated with steam, which for every 1,000 parts of fat contains 300 parts of water and 1 part of carbonate of potash and 2 stomachs of sheep or pigs. The temperature of the mixture is raised to 45° 0. After two hours, under the influence of the pepsin in the stomachs, the membranes are dissolv-ed and the fat melted and risen to the top of the mixture. The fat is next drawn off into a second tank, kept at a somewhat higher temperature, and J [)er cent, of common salt added. After two 10 rOObS AND FOOD ADtTLTERANTS. hours more the fat becomes clear and takes on a yellow color aad ac- quires somewhat the taste and odor of fresh batter. The fat is now drawn off into vessels and allowed to cool. It is then cut into pieces, wrapped in linen, and i^ut in a hydraulic press and kept at a temperature of about 25° G. By pressure the fat is separated into two portions, viz : stearine 40 to 50 per cent., and fluid oleo 50 to 60 per cent. The stearine remain- ing iu the presses is used in candle-making. Mege's patent, possessing as it does historical interest, is given in full. A full citation of the various patents taken out in foreign countries is found in •' Sell's Kuustbutter." i The patents taken out in this country for the manufacture of artificial butter are given below : LIST OP PATENTS GRANTED IN THE UNITED STATES FOlT THE MANUFACTURE OF BUTTER SUBSTITUTES. Bippolyte Mege, No. 146012, dated December 30, 1873. To all whom it may concein u Be it known that I, Hippolytc Moge, of Paris, Franco, have discovered a new and improved process of transforming animal fats into butter, of which the fol- lowing is a full, clear, and exact description : The butter which is obtained from milli is produced by the cow elaborating her own fat throngh her celhilar mammary tissues at the low rate of tempera- ture of the body. The animal fat from which the batter-cells in milk are produced is composed chlelly of oleine, margarine, and stearine, and small quantities of other sub- stances. The natural process performed by the cow consists, mainly, first, in separating the oleomargarine from the stearine without developing disagreeable odois or flavors in thu oleomargarine ; and, secondly, iu producing a slight change in the oleomargarine, by which it assumes the character of butter. My invention, hereinafter described, is based upon a discovery made by me, that when the fat is rendered at a low temperature, considerably below that here- tofore employed in the ordinary rendering of fat, it has the taste of molten butter, and docs not acquire that peculiarly disagreeable flavor heretofore supposed to be necessarily attached to melted fat or t.illow, and which is desig- nated as "tallowy flavor." I have succeeded in obtaining excoUent results by rendering the crude fat at a temperature of 103° Fahrenheit, which^is below the temperature at which the tallowy flavor is created. The temperature may be raised above this point iu order to facilit.ate the operation, provided care be t.iken to avoid attaining the temperature at which the tallowy flavor is created. The precise limit to which it is safe to increase the rendering-temperature can be ascertained by trial under various circumstances with tho different kinds of fac. The temperature must, however, be far below that heretofore ordinarily used in rendering fats when no such object as I propose- to wit, the making of a hnttLTliko product— was had in view. I do not think it would bo safe to vary many doKrocs above that specifically indicated. I have also tliscoverod tliat, in order to neutralize any fermentation of the fat bo- (ore or dni-ing its treatment, the raw fat should, as soon as possible .after tho death of tlio animal, ho plunged iu a solution of liftoen (15) per cent, of com- mon salt and one per cent, of sulphate of soda, tho effect of which would be to prevent such fermentation. "'Arbeiten a. d. ICaiserlichen Gosundhoitsamte, jjp. 481-493. bAmV PRODUCTS. 11 In carryiug out my process I first crush, grind, or disintegrate tlie fat by any suitable machinery, such as rollers ormillstones, in order to break up the cel- lular tissues in which the fat is containod in the auimal, and.thus cause it to be more easily melted or rendered by the application 'of low temperatures. This fat thiis disintegrated is to be slowly raised to a temperature of 103° Fahrenheit in a vessel in which the temperature can be raised at will until the rendering shall bo complete. Tho temperature, as before stated, must be so regulated that the rendered fat will have the taste of molten butter, and care should be taken not to heat it so as to induce the change which pro- duces tho usual disagreeable taste of melted fat or tallow, Instead of the taste of molten butter, which temperature is considerably below that heretofore ordinarily used in rendering fat, and will be found to vary not many degrees above the point already stated. I also add to tho fat while being rendered, for the purpose of aiding in this proc- ess, two liters of gastric juice to a hundred (100) kilograms of fat. This gastric juice is made by macerating, for three hours, half of the stomach of a pig -or sheep, well washed, and three litres of water containing thirty grams of bi-phosphateof lime. After maceration this macerated substance is passed through a sieve, and then added to the fat under treatment in the proportion of two litres to one hundred (100) kilograms. The separation of the organized tissues from the fat is aided by the introduction of salt during the rendering ; and as soon as there are no lumps of fat visible in the kettle I add about one per cent, of common salt. I stir it for some time. The rendered fat is then allowed to stand until it attains perfect lim- pidity, when it can be drawn off. By this meansthe separation is well made, and tho organized tissues which do deposit are not altered. I then allow the melted fat to stand in a vessel, maintained at a temperature of about 86° to 98°, until the stearine is crystallized. The mixture of stearine and oleomar- garine may then bo put in a centrifugal machine ; and by the operation of this machine the oleomargarine will pass through the cloth and the stearine remain within ; or the mixture may be subjected to pressure in a press. The effect produced in either case is that the oleomargarine practically separates from the stearine and flows out. The oleomargarine thus separated from the stearine, wLen cooled, constitutes a fatty matter of very good taste, which may replace the butter used in the kitchen. If it is desired, however, to trans- form it into more perfect butter, I employ the following means : I mix the oleomargarine, as it comes from the press or centrifugal machine, with milk and cream, equal to ten per cent, of the weight of tho oleomargarine, the' temperature of the milk and cream being about seventy-one (71) degrees, and thoroughly agitate them together. I then let the mixture become completely ^oM and solid, and then cause it to be worked between rollers, which give it the homogeneonsness and the consistency which are the qualities of the nat- ural butter. Tho above process of agitating the oleomargarine with milk is intended to bo adopted when thebutter is to be immediately used. If the butter is intended to be preserved, it will be better to mis the oleomargarine at animal beat with ten per cent, of its weight of water instead of milk or cream, and then agitate the two together, as above described. I have also found it expedient to mix with the cream or milk, in the iirst case above described, before agitating, or with the water in tho other case above described, before agitating, a fiftieth part of maunnary tissue, which is the udder of the cow, minced fine, a one-hundredth part of bicarbonate of soda, and some coloring matter. It may be desirable to add ordinary butter, and this I do by mixing the oleomar- garine and the ordinary butter together at a tempernt.ure of about 70° Fahr- enheit. 12 FOODS AND POOD ADULTERANTS. What I claim as my invention, and desire to secure by Letters Patent, is — (1) The rendering of animal fat at a low temperature, substantially as above set forth, for the production of a fatty matter devoid of disagreeable taste. (2) As a new product of manufacture, fat rendered at the low temperature, sub- stantially as above described, devoid of disagreeable taste. (3) The combined process of rendering animal fat at a low temperature and then separating the oleomargarine for the purpose of producing a material adapted to be used as ordinary butter for culinary purposes, or to be further treated for making more perfect butter, substantially as above described. (4) As anew product of manufacture, oleomargarine obtained from fat rendered at a low temperature and separated from the stearine, substantially as above described. (5) The agitating of oleomargarine with water or milk for the purpose of mak- ing a more perfect imitation of butter, substantially as above described. (6) The butter-like product produced by the agitation of oleomargarine with water or milk, substantially as above described. (7) The treatment with artificial gastric juice for facilitating the process of ren- dering the fat at a low temperature, substantially as above described. (8) The treatment of the oleomargarine with the mammary tissue of the cow, or mammary pepsin, substantially as above described. (9) The addition of ordinary butter to oleomargarine, substantially aa above de- scribed. H. MfiGE. Witnesses : EOBT. M. Hooper, M. D. Desiiler. William, E. Andrew, No. 153,999, dated August 11, 1874. The process, herein described, for rendering fats, consisting in the application of dry heat or dry hot air to liquefy, and pressure to separate, the oily jwr- tion from the membrane, and removing the liquid portions from contact with the membranous portions aa fast as separated. William E. Andrew, No. 106,955, dated August 24, 1875. Complete process of manufacturing artificial butter, herein described, consisting first in rupturing and destroying the globular condition of animal oil by aa\. tation and then refrigerating the same, then combining the product thus obtained with butter, cream, or milk and churning until a thorough amalga- mation takes place. William E. Andrew, No. 172,942, daied February 1, 1876. The process of clarifying liquid tallow or oil by injecting into the oil, under force, in the form of mist or fine spray, water prepared with chloride of sodium or nitrate of potash, and heated to a higher degree of temperature than the oil. Garret Cosine, No. 173,591, dated Febriiarij 15, 187r). The process of making artificial butter by mixing together oleine and margarine from animal fats, and from fruit and vegetable nuts, and lactic acid and lop- pered cream or milk. William E. Andrexo, No. 179,883, daied July 18, 187(>. (Mechanical.) Alfred Springer, No. 187,327, dated February 13, 1877. The process of producing ediblo fat or tallow by heating the crude fat at a tem- perature of 140*^ to 1J.5J Fahronlieit, in contact with common salt, saltpeter, borax, and boracic and salicylic acids, withdrawing the separated fat and incorporating therewith a second and smaller charge of the above chemicals, with the addition of benzoic acid. DAIEY PKODUCTS. 13 Amor Smith, No. 188,428, dated March 13, 1877. Method of separating oleomargarine from the fat of kino, that is to nay, by sepa- rating it directly from the stearino and membrane at a low heat, without having first heated the mass to a higher point, for the purpose of removing the membrane from the stearino and oleine. Royal W. Barnard, No. 198,334, dated December 18, 1877. , Method of reclaiming sour "tubby," or rancid butter, which consists in treating the same with a solution of brine containing an alkaline carbonate mixed with a solution of tartaric acid, or its equivalent. Thomas F. WilUns, No. 226,467, dated April 13, 1880. Butter containing motaphosphoric acid intimately incorporated therewith, where- by the butter is preserved. Otto Boysen, No. 236,483, dated January 11, 1881. Process of making a substitute for butter, consisting in adding to oleomargarine an alkaline solution, and agitating the mixture until partial saponification ensues, and then adding a minute quantity of butyric acid. Thomas F. WilMns, No. 9,892, reissued, dated Octoler 11, 1881. The method herein described of preserving fats and other organic matter by mechanically mingling phosphoric acid therewith. Samuel M. Cochran, No. 258,992, dated June 6, 1882. The combination ol beef-suet oil, cotton-seed oil and its equivalents, purified and flavored as described, with beef-steariue and slippery-elm bark. Sippolyte Mege, No. 10,137, reissued, dated June 13, 1882. Treating animal fats so as to remove the tissues and other portions named, with or without the addition of substances to change the flavor. Samuel S. Cochran, No. 10,171, reissued, dated August 1, 1882. A comhination of beef-suet oil, cotton-seed oil and its equivalents, with beef- stearine. Samuel M. Cochran, No. 262,207, dated August 8, 1882. Compound composed of the oil obtained from swine fat, cotton-seed oil and its equivalents, deodorized and purified by slippery-elm bark and beef-stearine. John HoUs, No. 263,042, dated August 22, 1882. The vegetable stearine to be used can he obtained from any pure vegetable, seed, or nut oils by pressing them at a temperature as above set forth, or it may be obtained in the market at times as vegetable stearine. Mixing "vegetable stearine" or " margarine " obtained substantially as described, with what is called "animal oleomargarine" and emulsionizing the said mixt- ure with milk, cream or other watery fluid. Nathan I. Nathan, No. 263,199, dated August 22, 1882. Process of manufacturing artificial butter by uniting oleomargarine with leaf lard, the latter having been previously cleaned, fused, strained, and sub- jected to a washing action in a solution of water, borax, and nitric acid, then rewashed and the united mass heated and subjected to the ordinary churning operation. George S. Marshall, No. 264,545, dated Septemter 19, 1SS2. Process of deodorizing, purifying and flavoring stearine obtained from animal fats, or vegetable oils, by hoiling the same with water and mixing therewith powdered orris-root. William Cooley, No. 264, 516, dated Septemler 19, 1882. An artificial cream composed of an oleaginous substance mechanically blended, or otherwise incorporated with milk, buttermilk, or cream, the oleaginous material being in a state of minute and even division, and each particle en- cased in a oo3.ting of caseine. 14 FOODS AND FOOD ADULTERANTS. Henry Lau/erly, M. 265,833, dated Octoher 10, 1883. Improvement in the manufacture of artificial butter, or oleomargarine, which consists in treating in the manner desorihed hoth the milk and the oleomar- garine oil separately with sal-soda, prepared and taken in the proportions as specified, then mixing or churning the creamy suhstaucc produced from the treated milk with the prepared oleomargarine oil, and coloring, salting, and working the mixture. Hugo Bcriliold, No. 260,417, dated OcioVer 24, 1882. A coloring compound for admixture with oleomargarine oil after the usual churn- ing operation, consisting of saccharine matti;r, glyceriuc, annotto, and oil of ben, mixed togther. Georcje U. llchster, No. 266,.'5G8, dated OcloUr 24, 1882. Process of making artiiicial butter, which consists in minutely dividing leaf-lard, rendering and straiuing it, mixing a butter-coloring matter with it, immers- ing it for thirty-six hours in cold brine, transferring it from the brine to dry tables or shelves and keeping it there covered with salt for thirtj'-six houis ; then hcatiug it to about 130° Fahrenheit and mixing it with lukewarm but- termilk, a small quantity of clarified tallow, and a minute (jnantity of pep- siu, aud allowing the mixture to settle ; theu tiausferrinrr the liquid lard and tallow to a vessel containingcomminutedbutterof about half the weight of the lard, thoroughly mixing the contents of the vessel by stirring, pour- ing the mixture into cold water, and thoroughly working it in the usual manner. William H. Burnett, No. 266,r)8(), dated Ocioier 24, 1882. The butter-liko product described, consisting of the ingredients specified, to wit, lard, beef-KUut, butter, glycerine, salt water, aud coloring material. Oscar II. Comnbe, No. '^GGjI'f^, dated Octoher 31, 1882. A new article of manufacture, oleard, consistingof vegetable oil, in combination with cooked farinaceous Hour. Oscar II. Conmlie,No. 2GG,777, dated October 'il, 1882. An improved article of commerce known as bntteroid, aud consisting of cotton- seed or other vegetable oil treated with a solution of caustic soda, in combi- nation with farinaceous flour first thoroughly cooked in salt water. Henry B. Wright, No. 267,637, dated No ccmier 14, 1882. Process of making artificial butter or creamine, which consists in mixing to"-ether the oils derived from animal fat at low temperatures with sweet cream the oil of butter, vegetable oil, and coloring matter; then allowing these incre- dients to become sour while together; then removing the whey, and finally churning the mass. Joseph H. McDonald, iVb. 270,4.54, dated January 9, 1883. (Mechanical.) Joh7i Hohbs, No. 271,239, dated January 30, 1883. (Mechanical.) John Hobbs, No. 271,240, dated January 30, 1883. (Mechanical.) John Hobbs, No. 271,244, dated January 30, 1883. (Mechanical.) John Hobbs, No. 271,241, dated January 30, 1883. (Mechanical.) John Hobbs, No. 271,243, dated January 30, 1883. (Mechanical.) John Hobbs, No. 271,242, dated January 30, 1883. (Mechanical.) DAIRY PKODUCTS. 15 John BoUs, No. 280,823, dated July 10, 1883. Process of refining fats, which consists in first finely grinding tlie fat of the leaf of the hog, mixing it thoroughly with salt, placing it in tanks of cold water for two or three days, when it is worked over, as described, then rendering • it at a low temperature, and as quickly as possible, with or without adding the solution mentioned, then drawing it off from the tissue, clarifying it and again drawing it oif and cooling it. Samud M. Cocltran, No. 285,878, dated Octolier 2, 1883. The mode above described of giving a butter-flavor to animal fats or oils, which consists in mixing therewith in the manner above described a quantity of dairy or creamery butter in its normal or hard condition. Samuel II. Cochran, No. 285,973, dated Oetoher 2, 1883. (Mechanical. ; Samuel H. Cochran, No. 285,974, dated October 2, 1883. (Mechanical.) Andreio J. Chase, No. 280,778, dated October IG, 1883. The method herein described of manufacturing butter fuom animal oils, said method consisting in subjecting tlie oils to a low temperature, and at the same time agitating them, both during the process of solidifying and after- wards. John Hobbs, No. 289,100, daUd November 97, 1883. The manufacture of deodorized fats or oxyline, the use or employment of the substance herein mentioned— vegetable stearine — in combination with the other ingredients named--oleomargarine-stearine and oleomargarine-stock. George Lawrence, No. 295,180, dated March 18, 1884. Process of treating milk with fatty and other matters by passing it and them, mingled with gases, through one or more steam-ejectors, for separating and mixing the particles. Samuel Sehwarzacldld, No. 299,685, dated June 3, lti84. (Mechanical.) Mmma J. Woodruff, No. 327,636, dated October 6, 1885. Adding to the milk white- wine' rennet, sugar, salt, bicarbonate of soda, bicar- bonate potassium, alum, and butter. Lyman Guinnip, No. 334,430, dated January 19, 1886. Consisting in mingling two bodies of cream of different age, then churning the same, then removing a portion thereof from the churn and mingling with the removed part a quantity of butter, then churning the residue until but- ter begins to separate, then adding butter thereto, as specified, and churning the mixture, and finally adding thereto the portion first abstracted, and churning the whole until the butter is made. William A. Murray, No. 335,084, dated January 26, 1886. Mixing 1 gallon of sweet milk with 1 ounce of liquid rennet, 25 grains (Troy) of nitrate of potash, 1 ounce granulated sugar, half-teaspoonful of butter-col- oring, and 8 pounds of butter, churned together and worked. Carl August Johansson, No. 336,324, dated February 16, 1886. (Mechanical. ) George Wm. Sample, No. 336,438, dated February 16, 1886. (Mechanical.) ^ Charles Marchand, No. 338,638, daUd March 23, 1886. (Mechanical.) Edward J. Oatman, No. 346,062, dated July 20, 1886. Producing an emulsion from milk or its derivates and a suitable oleaginous ma- terial, which consists in thoroughly dividing and commingling the ingredi- ents by injecting a steam jet into the mixture, 16 FOODS AND FOOD ADULTERANTS. The common motbod of manufacture employed in this couutiy is set forth by Armsby: ' Although numerous iiatciits have beeu taken out for the maunfacturc almitin have crystallized out, and the l^asty mass is then subjected to hydraulic pressure. The still fluid (abont two-thirds of the whole) flows out into a tank of cold water, where it solidifies into a granular mass which is known in the trade as " oleo " oil or simply " oleo " . The name '' oil" is somewhat misleading, as the product is a granular solid of a slightly yellow color. Fresh leaf-lard treated iu substantially the same way as the beef-tallow, yields the "neutral lard" or "neutral" of the trade, also a granular solid of a white color. The objects of this treatment are twofold : first, to produce fats as free as possible from taste or odor; second, to remove some of the diflicultly fusible stearine and palmitin, in order that the finished product may melt readily in the mouth. Having tlius secured the fats in proper condition, the manufacturer proceeds to mix the "oleo" and "neutral", the proportions varying according to the destination of product ; a warm climate calling for more " oleo," a cold one for more " neutral," and to flavor tho mixture with butter. This flavoring is conducted iu large, steam- jacketed vessels provided with revolving paddles, by which their contents can bo thoroughly agitated. Here the " oleo " and " neutral " are melted and thoroughly agitated with u, certain proportion of milk, or sometimes of cream, and a proper amount of butter-color. Forty -eight gallons of milk per 2,000 pounds of product are stated to be a common proportion. After sufficient agitation, the melted mass is run into cold water, and as it cools is broken up by paddles so as to granulate the mass. After thorough washing, it is salted and worked exactly like butter. The product is known as oleomargarine. Although it contains hardly more than a trace of butter fat, the latter flavors tho whole mass so strongly that, when well salted as it usually is, it might readily pass with an inexpert or careless consumer for a rather flavorless butter. Oleomargarine is the cheapest product made. Hy adding to tho material in tho agitator or " churn " more or less pure butter, what is known as butterine is pro- duced, two grades of which are commonly sold, viz, " creamery butterine" contain- ing more, and "dairy butterine" containing less butter. The method of manufacture used by the firm of Armour & Co., of Chi- cago, is thus described by Mr. Philip D. Armour i^ The fat is taken from the cattle in the process ol slaughtering, and after thorough washing is placed iu a bath of clean, cold water, and surrounded with ice, where it is allowed to remain until all animal heat has been removed. It is then cut into small pieces by machinery and cooked at a temperature of about ir>0° until the fat, in liquid form, has separated from the fibrine or tissue, then settled until it is perfectly clear. Then it is drawn into graining vats and allowed to stand a div when It 18 ready for the presses. The pressing extiaots tho stcarino, leaviunr the re- maining product, which is conmiercially known as oleo oil, which, whon°churned with cream or milk or both and with usually n proportion of creamery butter the whole being properly ealtoil, gives the now Ibod-prodact, oleomargarine.' ' 'Science, vol. 7, pp. 471-47:2. 'Senate Mis. Doc. No. 131, Forty-nintb Congress, first session, p. 2-H. DAIRY PEODUCTS. 17 In maUing butterine we use neutral lard, which is made from selected leaf lard in a very similar manner to oleo oil, eioepting that no steariue is extracted. This neu- tral lard is cured in salt brine for forty-eight to seventy hours at an ice-water tem- l^erature. It is then talien, and, with the desired proportion of oleo oil and flue but- ter, is churned with cream and milk, producing an article which, when properly salted and packed, is ready for market. In both cases colonng matter is used, which is the same as that used by dairymen to color their butter. A1; certain seasons of the year, viz, in cold weather, a small quantity of salad oil made from cotton seed is used to soften the texture of the prod- uct, but this is not generally used by us. Gnstavas F. Swift, of the firm of Swift & Co., of tlia town of Lake (near Otiicago), describes as follows the motJOil in use in the mauufactaro of artificial butter by his company : ' The fat is taken from the cattle in the process of slaughtering, and after thorough washing is place'd in a bath of clean, cold water and surrounded with ice, where it is allowed to remain until all animal heat has been removed. It is then cut into small pieces by machinery and cooked at a temperature of about 150° until the fat in liquid form has separated from the fibrine or tissue; then settled until it is perfectly clear. Then it is drawn into draining vats and allowed to stand a day, when it is ready for the presses. The pressing extracts fhe steariue, leaving the remaining product, which is commercially known as oleo oil, which, when churned with cream or milk, or both, and with usually a proportion of creamery butter, the whole being properly salted, gives the new food product, oleomargarine. In making butterine we use neutral lard, which is made from selected leaf-lard in a very similar manner to oleo oil, excepting that no steariue is extracted. Tbis neu- tral lard is cured in salt brine for forty-eight to seventy hours at an ice-water tem- perature. It is then taken, and with the desired proportion of oleo oil and fine but- ter, is churned with cream and milk, producing an article which, when properly salted and packed, is ready for market. In both cases coloring matter is used, which is the same as that used by dairymen to color their butter. At certain seasons of the year, viz, in cold weather, a small quantity of sesame oil, or salad oil made from cotton seed, is used to soften the texture of the product. WHOLESOMENESS OF ARTIFICIAL BUTTER. On this subject there is a wide difference of opinion. It is undoubt- edly true that a great deal of artificial butter has been thrown upon the market that has been carelessly made, and therefore harmful to the health. On the other hand a butter substitute, made carefully out of the fat of a perfectly liealthy bullock or swine, is not prejudicial to health. Prof. Henry Morton, of the Stevens Institute, Hobokeu, N. J., made the following statements before the Senate Committee on Agriculture, pending the consideration of the "Oleomargarine" bill:^ The subject is oue which has been of great interest to all scientific men from the time ofthe original discovery by M6ge, which was made, as yon are aware, during the siege of Paris. Many persons have been interested in it and have followed it up. I have been freqiiently called upon to examine processes and superintend operations where modifications in the manufacture have been suggested, and so on, and speci- mens have been brought to me as a chemist, to examine from time to time miorosoopio- ' Op. at, p. 225. • ^ Op. Bit., p. 47. 19330— No. 13 2 18 FOODS AND FOOD ADULTERANTS. ally and cUouiically. Wlion the substance was first iiitroduood, tlio queslion was raised as to whotlior it could bo disfcinguisbed from butter by any test, aud I was led in tbat way to investigate the subject, aud to examine as to all the properties which it (sxhibited, as well as to cprnparo different samples of it, and I have in my experi- muuts in this line examined great uunibers of spocimeus of oleomargarine prepared us butter aud of oleomargarine oil for the preparation of butter, from all parts of the country, aud also have visited factories very frequently and spent long periods there. I have remained as long as a week in one of these factories coutiuuonsly — sometimes sDendiug the uight as well as the day there, in order to watch the process completely aud see the operation from beginning to end, to see what was put in and what was not, and to observe what was doue and what was not done. In the course of these examinations I have reached the conclu.sion , fouuded on these observations, that the material is of necessity, a pare one, and caunot iiossibly beuu- wholeaome, aud is, in fact, in that sense a thoroughly desirable and safe article of food. 1 will express as brieHy as I can my reasons for this opinion, and state the facts on which they are founded. lu tlie first place I have found, as a matter of observation, that fat ^vhich is to he used in the manufacture of oleomargarine, if it is in the slightest degree tainted be- fore the uianufaeture begins, if it is not strictly ficsli, if it is not taken almost directly from the slaughtered animal, if it is allowed to stand in a barrel for a few honrs in ordinary weather or in cold weather, if put in a barrel with any uuiuial heat initfor ii, few hours, thou an incipient change begins whuih, in the succee ding process, is ex- aggerated so that an utterly offensive material is produced, which could not be used for any such purpose. Prof. C. P. Chandler says : ^ In all of those reports I have taken the ground that this is a new process for making an old article, aud that article is butter. This is a new process for making butter. It is made of materials which aroin every respect wholesome aud proper articles of food, whether it be made solely from the oleomargarine extracted from beef fat, or whether it has added to it more or less leaf lard properly prepared, or more or less sesame oil or cottou-seed oil, and whether it be or not colored with aunatto or the other coloring matters used. I take the ground that there is nothing in any one of these materials in any sense unwholesome, aud nothing in any one of them which makes it inferior as an article of food to dairy butter. I regard the discovery of Mege-Mouries, of a process by which beef fat aud hog fat can be extracted from adipoee tissue aud con- verted into a wholesouic article of food free from any disagreeable taste or odor, as one of tlic most important discoveries made in this century, a discovery by which it is iJossiblo to make a parfectly pure and satisfactory, as well as wholesome, article of food at a reasouahle price. I have visited various factories where this article is man- ufactured, from the time the industry began dowu to date. I am perfectly familiar with the materials employed aud the different processes, an d know there is nothing whatever used either in material or process which is unwholesome or in any way dele- terious to the public health. Professor Chandler further lias reported as follows to the Board of Ucalth of New York Clty:'= New Vouk, Maj 2, lt*>l. lu the ISoavd of Beallh of the lleaUh Vcparlmcnl : Having been directed by this board to investigate the subject of oleomargarine, in response to the resolutions of the Board of Aldormou, 1 would bc>g leave to submit the following rei)ort: The resolutions directing the inquiry are as follows: Whereds there is existing at the presont time in the minds of the public great alarm and distrust in relation to the adulteration of food products ; aud Oj). cit. , p. 07. 2 Op. ci,_^ p 70. DAIRY PEODUCTIS. 19 Wlicroas tlie coiniuiUou oii pulilic lioaltli of tlio asscmljly ol' tliis State has boon for some time iuvestigatiug tho adulteration of food products, and especially oleomar- garine; and Whereas tliis committee have conducted sucli iuvestigation by calling as witncssea principally dealers in butter and have not examined as witnesses medical or chemical experts to deterinine the value of oleomargarine as food ; therefore Scsolvcd, That the board of health of this city be, and they are hereby letiuostod and directed to take immediate measures to investigate in the most thorough manner, by medical and chemical aid, the iiurity, healthfulness, and value of said product as an article of food, and to report to this body the results of their investigation, with such recommendations, if any be necessary, as may relate to the manufacture and dis- tribution of the same as an article of food. This subject has been before the board on former occasions, and I have little to add to what has been previously stated. Oleomargarine, invented by the distinguished French cliemist, M6ge-Mouries, is manufactured in NcwYork City in a few large establishments. Tlio material is fresh beef suet, brought directly from the slaughter-houses. It is thoroughly washed, ren- dered very carefully, strained to remove a portion of the hard stearine, and then churned with milk to convert it into artificial butter, which contains the same con- stituents as dairy butter. The process is extremely ingenious and simple and exe- cuted by machinery. Nothing objectionable exists in tlie original material, nor is anything objectionable added during the process, and the operations are conducted with the utmost cleanliness, /fhe product is palatable and wholesome, can be made of uniform quality the year round, is in every respect superior as an article of food to a large proportion of dairy, butter sold in this city, and can be man ufaotured at a much lower price. I regard it as a most valuable article of food and consider it entirely un- exceptional in every respect. In this opinion I am supported by the best scientilic authorities in the country. The foUowingdistinguished chemists, after carefully study- ing the manufacture, have made the most decided statements in favor of this new article of food : Prof. George F. Barker, University of Pennsylvania. Dr. Henry A. Mott, jr., New York. Prof. G. C. Caldwell, Cornell University, Ithaca, N. Y. Prof. S. W. Johnson, Yale College, New Haven, Conn. Prof. C. A. Goessmanu, Massachusetts Agricultural College, Amherst, Mass. Prof. Henry Morton, Stevens Institute, I-Iobokcn, N. J. Prof. Charles P. Williams, Philadelphia, Pa. , Prof. W. 0. Atwater, Wosleyan University, Middletown, Conn. Prof. J. W. S. Arnold, University of New York. I would further say that this question is one on which there is no dilferouce of opinion among scientific investigators familiar with the chemistry of dairy products and fats. I have never seen a statement emanating from any person having any , standin"- among scientific men in which a contrary opinion is advaucedj, ' Tiiere lias recently been a very strong confirmation of my opinion published in England. A bill came before the House of Commons in England, directed against this kind of butter from America, and, after considerable discussion, was defeated by a vote of 75 to 59. In the discussion the strongest opponent to legislation against it was Dr. Lyon Playfair, one of the most distinguished chemists and sanitary authori- ties in England. A pnpil of Graham and Leihig, ho has filled the chairs of chemistry in the Eoyal Institution of Manchester and at the University of Edinburgh, was ap- pointed chemist to the Museum of Practical Geology by Sir Robert Peel, represented the universities of Edinburgh and Aberdeen in Parliament, was postmaster-general in the fiirst Gladstone cabinet, has been member of several sanitary commissions, and is now a leading member of Parliament. In his remarks he stated that " bad butter was a fraud upon the poor, and oleomargarine would sooner or later drive it out of the 20 FOODS AND FOOD ADULTEKANTS. market;" lie " tlioughb tliut good oleomargariue at quo sliilllug a i)ouiid was a great deal better aud cheaper than bad butter at oao shillin;^ four puuce a pouad," and he said that "as a general rule the former (oleomargariue) did uofc become so readily raucid as the latter (butter)." I would further state tliat, as there is uotbing unwholesome in oleomargarine, no legislation ia regard to this article is necessary to protect the public health. C. F. CHANDLEE, Premdent. Prof. Cr. 1<\ Barker suys:' Univeksity oi' Pknnsvlvania, I'Mladelphia, March 22, lci80. To the United Stales Dairy Comx>any : Gentlemen : lu reply to your inquiry, 1 would say that I have been acquainted for several years with the discovery of Mdge-Mouries for producing butteriuo from oleo- margarine fat. Ju theory the process should yield a product resembling butter iu all essential respects, having identically the same fatty constituents. The butterine pre- pared under the iuveutor's pateuts is, therefore, in my opiniou, quite as valuable a nutritive agent as Imtter itself. Ia practice the iirocess of manufacture, as I have witnessed it, is conducted with care and great cleanliness. The butterine iiroduced is pure and of excellent quality, is perfectly wholesome, aud is desirable as an article of food. I can see no reason why butterine should not be an entirely satisfactory equii-aleut for ordinary butter, whether considered from the i)hysiologlcal or com- mercial standpoint. Prof. Gr. 0. Caldwell, of Ooruell University, gives tlie following tes- timony : '' Chemical Labraioey, Cornell Univeesity', Jihacti, X. y., March 20, 1680. I have witnessed, iu all its stages, the manufacture of '■ oleomargarine" and of oleo- margarine butter or " butterine." The process for oleomargariac, when properly conducted, as in the works of the Commercial Manufacturing Company, is cleanly throughout, aud includes every reasonable precaution necessary to secure a product entirely free from animal tissue, or any other impurity, aud which shall ooasist of pure fat made up of the fats com- monly known as oleiue and margarine. It is, when thus prejiared, a tasteless and in- odoroussubstance, possessing no qualities whatever that can make it in the least degree unwholesome when used iu reasonable quantities as an article of food. In the manufacture of butterine, since uothiug but milk, annotto, and salt, together with, perhaps, a little water fropj clean icu, are added to this oleomargarine, to bo intimately mi.-ced with it by cliuniiag and other operations, I have no he-sitatiou iu affirming that this also, when properly made according to the Mego patent, aud other patents held by the United States Dairy Com pany, . and when used in reasonable quantities, is a perfectly wholesome article of food ; aud that, while uotequal to fine butter in respect to flavor, it nevertheless contains all the csseu tial ingredients of butter, and since it contains a smaller proportion of volatile fats than is found iu genuine butter it is, iu my opiniou, loss liable to become rancid. It canuot enter iuto competition with lino butter ; but in so far as it may serve to drive poor butter out of the market, its manufacture will be a public benefit. Prof. S. W. Johnson, of Yale College, makes the following statement:' S.iEFFiELD SciExnric School of Yale College, ,„, ^, ., , yew Haveu, Conn., 2Iarch-M, 18:^0. 1 he United itulcs Dairy Company : Gentle.mex ; I am acquainted with the process discovered by il. M6ge for produc- ing the article known in eonimereo as oleomargarine or butterine. ' Op. cit., p. 73. ^ Op. ciL, p. 7U. ^p. at., p. li. DAIRY PRODUCTS. 21 I have witnessed the manufacture in all its sta gas, as carried out on the largo scale, and I can assert that when it is conducted according to the specifications of M. M^ge it cannot fail to yield a product that is entirely attractive and wholesome as food, and one that is for all ordinary culinary and nutritive purposes the full equivalent of good butter made from cream. Oleomargarine butter has the closest resemblance to butter made from cream in the external qualities — color, flavor, and texture. It has the same appearance under the microscope, and in chemical oompoaition differs not in 'the nature, but only in the proportions of its components. It is, therefore, fair to pronounce them esseutially identical. While oleomargarine contains less of those flavoring principles which characterize the choicest butter, it is, perhaps for that very reason, comparatively free from the tendency to change and taint, which speedily renders a large proportion of butter unfit for human food. I regard the manufacture of oleomargarine or butteriue as a legitimate aud benefi- cent industry. S. W. JOHNSON, Professor of Theoretical and Ac/rieultural Chemislrrj, \ Director of the Connecticut Agricultural Experiment Station. Dr. 0. A, Groessinann, of Amherst, indorses ia general the above statements : ^ Amherst, Mass., March 20, 1880. United States Dairy Company, New TorJc : Gentlemen : I have visited on the 17th and 18th of the present month your factory, on West Forty-eighth street, for the purpose of studying your mode of applying Mage's discovery for the maunfacture of oleomargarine butter or bntterine. A care- ful examination into the character of the material turned to account, as well as into the details of the entire management of the manufacturing operation, has convinced me that yonr product is made with care, and furnishes thus i. wholesome article of food. Your oleomargarine butter or butterine compares in general appearance and in taste very favorably with the average quality of the better kinds of the dairy butter in our markets. In its composition it resembles that of the ordinary dairy butter; and in its keeping quality, under corresponding circumstances, I believe it will surpass the former, for it conliains a, smaller" percentage of those constituents (glycerides of volatile acids) which, in the main, cause tho well-known rancid taste and odor of a stored butter. I am, very respectfully, yours, C. A. GOESSMANN, Pii. D., Professor of Chemistry. To these I may add the names of Prof. Charles P. Williams, of the State University of Missouri, Dr. Henry Mott, jr.. Prof. W. O. Atwater, and Prof. J. W. S. Arnold.^ Armsby ^ says in respect of the healthfulness of oleomargarine: Very exaggerated and' absurd statements have been made regarding the unhcalth- fnlness of butterine and oleomargarine. The charges have in general been that the fat used is practically uncooked, and that raw animal fiit is unwholesome; that filthy fat and fat from diseased animals are nsed, aud thiit thB product contains, or is liable to contain, the germs of disease; aud that in cleansing tlioso diseased aud filthy fats dangerous chemicals are used, which are not snbseqiiently completely removed. That the fats used are of themselves nnwholesome tliero is no proof whatever. They 'contain nothing that butter-fat does not also contain, aud dilfor from it only by the •absence of about 6 per eent. of the glyceride of certain sidiible fatty acids, viz, caprinic. 1 Op. cit, p. 7"). "^ Op. ait., pp. 73, 74, 75. ' Science, vol. 7, No. 172. 22 FOODS ANiD roob adulterants. caprylic, capronic, and butyric acUls. Tho only experiments upon the diftestibilily of imitation butter are two, by A. A. Mayer, upon oleomargarine. These showed a diifereuce of only about 2 per cent, in favor of butter. That the higher flavor ol butter acting upon the nervous system would give it a greater nutritive value than the flavorless " neutral " or " oleo " may be cone edod ; but that an article which even exports fail to distinguish from genuine butter is at any serious disadvantage in this respect may well bo doubted. The manufacturers claim that imitation butter can only be made from the best quality of fat from freshly-killed animals, and I know of no evidence •which disproves their assertions. The sensational article recently published in a prominent agricult- ural paper in the Northwest, accompanied by cuts of the num erous organisms found in butterino, is of no siguificauce in this connection, both because the species de- scribed arc all harmless, and because no comparative examinations of genuine butter were made. It is highly probable that many samples of t he latter would show as miscellaneous an assortment of formidable looking, harmless organisms as did the butterino. On tho other hand, however, there is at present no guaranty, except the statement of the uianufaoturcrs, that diseased fat is not or cannot be used, the maunfactiire be- ing couductcd euDirely without any official inspection, aud visitors being in most (not all) cases e.-ccluded. I believe that the chances of disease being conveyed in this way arc small, but they are not yet proved to bo non-cxistont. As regards lilthy processes of manufacture, it may safely be asserted that butterino could not snccossfally imitate butter were it not as clean as most things are which pass for clean iu this dirty world. Tho charge that dangerous chemicals arc used iu the mauufacture may bo disposed of in a few words. If a dangerous" amount of any chemical which is claimed to be used were le.t in the finished product the latter would be inedible. Should trace of these cheiaicals be found their significance would not lie in themselves, but in the in- dication they would furnish that the original fats were impure and required chemical treatment. Sell ' lias made au examination of the evidence for and against the un- vvholesomeness of artifleial batter and has reached the following con- clusions : The artificial butter prepared from the fat of healthy animals, apart from possibly a somewhat loss digestibility, iu comparison with milk-butter furnishes in general no reason for tho sup])ositiou that it can affect injuriously human health. There is ground for the suspicion that a part of tho iirtificial butter occurring iu commerce is manufactured out of such material or by such processes as do not with certainty exclude the danger of cojveying to man disease whether produced by vege- table spores or animal par;isitos. There is ground for suspicion that a part of the artificial butter is made from naus- eating substances. The possibility of injury to health from a carelessly-prepared artificial butter must not be neglected. Dr. Thomas Taylor presented this aspect of the case to the Senate Committee.^ It has already been, mentioned that in the earlier processes employed in the manufacture of artificial butter the stomachs of sheep and pigs were digested with the fats employed. ' Arbeilcn n. d. Kaiserlielicn Gi'sundheitsanile, pp. HH, fiOO. - Op. ril. pp. IJ-IC, and '27:1-1. DAIRY PRODUCTS. 23 Tidy aud Wiguer ' have investigated the action of mammary tissue on fats used as butter substitutes. By digesting a pure animal fat witli the chopped-up tissues of tluj udders of cows the authors found a marlied chemical change produced. Cleomargai'iue or tallow when treated in this way give rise to both soluble and volatile fatty acids. Since both milk aud butter contain a certain amount of mammary tissue, in the form of casts from the mam- mary glands, it is believed that they also would exert an influence on animal fats. Cutter appears to act more vigorously than milk in this way, probably because it contains a larger percentage -of mammary tissue. NUTRITIVE VALUES OF BUTTER AND OLEOMARGARINES. On this subject Atwater ^ has collected valuable information, he says : The value of butter, as of any other food material for nourishment, depends npou the amounts of its nutritive ingredients, their digestibility, and their nses in the nu- trition of the body. CHEMICAL COMPOSITION. The food values of real and imitation butter, as compared with each other and with other food materials, can bo best shown by first comparing their composition. It appears that the nutrients of the leaner kinds of meat aud fish consist mostly of protein, that the fatter meats and fish contain eonsiderahle fat with the pro- tein, that the vegetable foods have for the most part very little fat, and abound especially in carbohydrates, while the nutriments of butter and oleomargarine con- sist almost exclusively of fats. Indeed, the protein and carbohydrates in both must be regarded as impurities.- - The quantities of fat are shown by analysis to be very nearly the same in both. DIGESTIBILITY. Regarding the relative digestibility of butter aud oleomargarine the experimental facts at hand are meager. They imply, as would be expected from the composition, that there is very little difference between the two. The study of the question is rendered difficult by the fact that what is ordinarily called the digestibility of a food includes several different things, the ease with which it is digested, the time required for di- gesting it, and the proportions of its several constituents that are digested. As to the comparative ease and time of digestion of hutter and oleomargarine nothing is definitely known, thongh there is little ground for assuming that, in the alimentary canal of a healthy person, at any rate, one would be digested aud taken into the circulation much more readily than the other. The actual amounts digested are capable of more nearly accurate experimental estimate. During the past few years very many experiments have been made, in Germany especially, to test the quantities of the more important constituents of diflerent foods digested by domestic animals, and a considerable number have heen carried ont with men and children. The only comparative experiments on the digestibility of butter and oleomargarine that have been reported are two series conducted by Professor Mayer, u, Gorman chemist. One series was with a full-grown man and the other with a boy of nine years of .age, both strong, healthy persons. The outcome was that both the man and the boy digested from 97.7 to 98.4 per cent, of the fat of the butter, and from 96.1 to 96.3 per cent, of the fat of the oleomargarine. The average difference was about l.G per cent, in favor of the butter. There are, however, certain unavoidable sources of 1 Analyst, 1883, pp. 113 el seq. ^ Bradstreet's, Saturday, June 19, 1886. 24 FOODS AND rOOD ADULTERANTS. error in such experiments, and it is very probable that Ibe proportioDS actually di- gested were somewhat larger than these figures imply. Very likely each of the two persons may have digested practically all of the fat of the butter, and all but 1 or 2 per cent, or oven less of that of the oleomargarine. In these experiments the butter and oleomargarine were eaten with bread, cheese, white of eggs, potatoes, peas, and sugar. The digestibility of butter has been tested in two or three other series of experi- ments. Thus Dr. Rubner, in Munich, found that a healthy man, on a diet of but- ter, bread, and meat, digested 97.3 per cent, of the total fat of the food, of which the bulk came from the butter. In some experiments by myself, in which a man received a diet of fish (haddock) and butter, 91 per cent, of the total fat, nearly all of which came from the butter, was found to bo digested. The experiments of Rubner and myself were conducted in the same manner as those of Mayer, and exposed to the same slight sources of error. The results of all of them are just what would naturally be expected, namely, that very nearly all of the fat of butter and of oleomargarine is tligested in a healthy organism. It might seem that the relative digestibility ofthe two materials could be tested by experiments In artificial digestion ; that is to say, by treating both substances with digestive fluid;, or with materials similar to them, and observing the results. Such cxpcriuKuts are not accurate tests of the actual digestibility of tho substances in the body, since the conditions which obtain in ihc alimentary canal cannot be ex- actly imitated by any artificial means which physiological chemistry has yet sug- gested. Professor Mayer, taking into account that the fats are more or less split up in the process of natural digestion, has made some experiments to test the compara- tive readiness with which butter and oleomargarine are split up, and finds a very slight diflerence in favor of butter. As the result of all his experiments ho concludes that, while the butter .appears to bo a little more digestible than oleomargarine, the difference is too small to be of practical consequence for healthy persons. At the same time there may bo cases, especially those of invalids and children just past the nursing period, when butter would bo preferable ; but, considering simply tho nntri- tivo values for ordinary use. Professor Mayer considers the choice between the two to bo essentially one of comparative cost, au opinion from which there is, so far as I am aware, scarcely any dissent among those who have devoted the most study to this class of subjects. It is a common and perhaps correct theory, though it lacks experimental confirma- tion, that tho flavor of the fats peculiar to butter may in some way increase its value for nutriment. But, granting this to bo true, it would be hardly reasonable to as- sume that a difference in flavor which even exports may fail to detect could make any considerable difference in tho nutritive effect of two substances otherwise so similar as real and imitation butter. To recapitulate briefly, butter and oleomargarine have very nearly the same chemi- cal composition ; in digestibility there may bo a .slight bilance in favor of butter, though for the nourishment of healthy persons this difference can hardly be of any considerable consequence ; for supplying the body with heat and muscular energy, which is their chief use in nutrition, they are of practically equal value, excelling in this respect all other common food materials. Such, at auy rate, is the practically unanimous testimony of the latest and best experimental research. While it is true that chemical analysis and certaiu digestive experi- ments have uot hitherto shown that pure butter possesses any marked superiority over butter surrogates as a food, yet it must not be forgot- ten that butter has a much more complex composition than lard or tal- low or cotton-seed oil ; that it is a natural food, and doubtless possesses many digestive advantages which science has not yet been able to demonstrate. DAIRY PRODUCTS. 25 THE MANUFACTURE OF ARTIFICIAL BUTTER IN THE UNITED STATES. The following information bus been Idndly furnished by the Hon. Joseph S. Miller, Commissioner of Internal Revenue: TiiEASURY Department, Office of Intern-af, Revenue, WasMngtou, March 4, 18S7. Sir: Iiiroply to your letter of lat instant, I havo the hoiioi- tostato that there are thirty-sevou factories ongagod iu the mannfacturo of artificial butter now in opera- tion in the Unitetl States, located as follows : Location. No. of factories. t-ocation. No. of factories. Denver, Col 2 n Bnffiilo N Y 1 1 Chicago, 111 ICokoiuo, Ind Kansas City, Kans Philadelpbia Ta 3 Armoiirdale, Kaus ^ PittaburgL Pa Brooklyn, N.T 3 New York, N.Y Pawtucket, R. I 2 There are two liundred and fifty-nine wholesale dealers in the United States, lo- cated as follows : Location. Birmingham, Ala Fort Smith, Ark Hot Sprinj^s, Ark Little Kook, Ark Pino Bluff, Ark Denver, Col Jaokaonvillo, Fla Atlanta, Ga En^lewood, 111 Sprinjjflelcl, IU Cairo, 111 Council Bluffs, Iowa Elwood,Kan3 Louiaville, Ky New Orleans, La Boston, Mass Fall Kivcr, Mass Lowell, Mass Aspen, Col Pueblo, Col Durango, Col Buena Vista, Col Hartford, Conn New Haven, Conn Leadville, Col Chicago, 111 Peoria, 111 Danville, 111 Indianapolis, Ind Kansas City, Kans To leka, Kans Covington, Ky Baltimore, Md Salem, Mass New Bedford, Mass G-loucester, Mass Lawrence, Mass Springflela, Mass Iron wood Mich Bay City, Mich East Saginaw, Mich MuskO"on, Mich Grand liapids, Micb . - r. East Saint Louis, III Butte, Mont Missoula. Mont Omaha, Nebr No. of wholesale dealers. Location. Salt Lake, Utah Hoboken, N. J Jersey City, N. J Doming, N. Mox Eairbanks, Ariz Saratoga Springs, N. Y . Eochester, N. Y Youngstown, Ohio PJiiladelphia, Pa Allegheny City, Pa Woonsocket, K. I ..:... Memphis, Tenn ElPaso, Tex Dallas, Tex Dennison, Tex Milwaukee, "Wis Ashland, Wis Eau Claire,Wis ■Worcester, Mass Houghton, Mick Detroit, Mich Grayling, Mich Saginaw, Mich Luddington, Mich Saint Paul, Minn Helena, Mont Jefferson City, Mont . - . South Butte, Mont Ogden, trtah Dover, N. H Newark, N.J Saute Ed, N. Mex Albuquerque, N. Mex - - New York, N.Y Bu£f^lo,N.Y Cincinnati, Ohio , Cleveland, Ohio Pittsburgli, Pa Providence, K. I Pawtucket, E. I Nashville, Tenn San Antonio, Tex ForfWoith, Tex Itichraond, Va Oshkosh, Wis Hurley, "Wis Chippewa Falls, Wis — No. of who'eea'e dealers. 1 1 1 1 1 1 1 2 12 1 1 8 2 1 1 3 1 1 3 1 6 1 1 1 2 2 1 1 1 1 1 1 1 IS 1 6 3 14 16 1 1 1 2 1 1 2 1 26 POODS AND FOOD ADULTERANTS. Tlio quantity manufactured anil romoveil foi- cousumptiou or sale at 2 cents per pound during the months of Novomher and December, 1886, and January, 1887, is as follows : Founds. November 4,742,569 December 2,786,278 January 2,501, 114 Total 10,029,961 The quantity exported from the UnitedStates during Un; i>oiiod above, all cxporta- tions being from the port of New York, is as follows : Ponndaw November 3,247 December ,. 58, 689 .January 52,761 Total - 114,697 Respectfully, JOS. S. MILLER, Commismoncr. Hon. N. J. OoLMAN, CommiKKinncr of Jgricnlture, JVanlihgton, 7). C. COLORING MATTERS IN BUTTER. Tbe pure animal fats, prepared in the manner described, are almost colorless. Tbe tint of genuine butter is imparted to these bodies by various coloring matters. The principal artificial colors which have been employed are : Annotto [Bixa orellana). Turmeric {Curcuma longa and viridiflora). Saffron (dried stigmas Crocus sativus). Marigold leaves (Calendula officinalis). Yellow wood {Morns tinctoria). Carrot juice (Daucus caroia). Chrome yellow (PbCr04) Dinitrocressol — kal i um . ANNOTTO. This substance is used more than any other in imparting to artificial butter a yellow tint. Indeed it is used to color genuine butter, which often in winter is almost white in its natural state. The coloring substance called annotto, antalta, or roiieou is the reddish pulp snr. rounding the seeds in the fruit of liixa orellana, a middliug-sizod tree growiu" in Guiana and other parts of Sontb America. The pulp is separated by b'raising''the fruit, mixing it with water, then straining through a sieve, and allowing the irqnid to stand till the undissolved portion subsides. The water is then poured" off and the mass which remains, having been sufficiently dried, is forincd into flat cakes or cylin- drical rolls and sent iulo tlio market. Another mode is to bruise the seeds, mix tlicni with water, and allow the mixture to ferment. The coloring matter is deposited during the fermentation, after which it is removed .and dried. In commerce there are two kinds of annotto the Spanish or Brazilian and French, the former cominn- in DAIRY PRODUCTS. 27 baskets from Brazil, the latter in casks from rrcnoh Guiana. The FroncL, which is also called flag annotto, has a disagreeable smell, probably from having been prepared by the fermenting process, but Is superior as a dye-stuff to the Spanish, which is with- out any disagreeable odor. Annotto is of a brownish red color, usually rather soft but hard and brittle whou dry, of a dull fracture, of a sweetish peculiar odor, and a rough, saline, bitterish taste. It is inflammable, but docs not melt with heat. It softens in water, to which it imparts a yellow color, but does not dissolve. Alcohol, ether, the oils, and alkaline solutions dissolve the greater part of it. It contains a l^eculiar crystallizable coloring principle, to which M. Preisser, its discoverer, gave the name of bixin. It is frequently adulterated with red ooher, powdered bricks, eol- cothar, farinaceous substances, chalk, sulphate of calcium, turmeric, &c. The miu. eral substances, if present, will be left behind when the annotto is burned.' Saffron has a peculiar, sweetish, aromatic odor, a warm, pungent, bitter taste, and a rich deep orange color, which it imparts to the saliva when chewed. The stigmas of which it consists are an inch or more in length, expanded and notched at the up- per extremity, and narrowing towards the lower, where they terminate in a slender, capillary, yellowish portion, forming a part of the style. When chewed it tinges the saliva deep orange-yellow. Saffron should not be mixed .with the yellow styles. When pressed between filtering paper it should not leave an oily stain. When soaked in water it colors the liquid orange-yellow, and should not deposit any pulverulent mineral matter nor show the presence of organic substances differing in shape from that described.^ Adulteration of saffron. — Saffron is often adulterated with cheaper yellow Vogeta' bio coloring matter, turmeric, annotto, the flowers of the marigold (Calerldilta offici- nalis), Carthamus flowers, the flowers of Arnica montana, Soolymus hisiianiOitS, PiUi- caria (lysenterica, Puniea granatum, Foionia, Croons vermis, &c.' Of these the marigold flowers are perhaps the most commonly used. They have a natural yellow color, and when they are saturated with carmine or aniline red, and dried, they possess a striking similarity to the genuine saffron. If they are pnt for a few minutes in water, however, they assume their original form, and are then easily distinguished from the stigmas of the saffron flower. If a mixture of saffron stigmas and the substitutes just mentioned be put into a vessel of water where the individual pieces are widely sepa- rated, the saffron stigmas soon become surrounded with a yellow ex- tract, while the others suffer no change or impart only a weak carmine tint to the water. The use of mineral coloring matters like the chromate of lead is highly reprehensible from a sanitary point of view. Annotto and saffron in butter 'may be detected by the following method, proposed by Cornwall : * About 5 grams of the warm filtered fat are dissolved in about 50oc. of ordinary ether in a wide tube, and the solution is vigorously shaken for ten to fifteen seconds with 12 to 15cc. of a very dilute solution of caustic potash or soda in water, only alkaline Enough to give a distinct reaction with turmeric paper, and to remain alkaline after separating from the ethereal fat solution. The corked tube is set aside and in a few ' U. S. Dispensatory, p. 1572. 2 U. S. Dispensatory, p. 501. ^Schimpfer, Anleit. z. Mikroskopischen Untcrsuchung d. Nahrnngs- und Gennss- mittel, p. 101. ^Chem. News, vol. 53, p. 49. 28 FOODS AND FOOD ADULTERANTS, Lours, at most, the greater part of tho afiuoous solution, now colored luoro or loss yellow by the aunotto, can be drawa from benoatb the ether with a pipette or by a stopcock below, in a sufficiently clear state to be evaporated to dryness and tested in the usual way with a drop of concentrated sulphuric acid. Sometimes it is well to further purify the aqueous solution by shaking it with some fresh ether before evaporating it, and any fat globules that raay float on its surface duriug evaporation should bo removed by touching them with a slip of filter-paper ; but the solution should not be filtered, because the filter-paper may retain much of the coloring matter. The dry-yellow or slightly orange residue turns blue or violot blue with sulphuric acid, then quickly green, and finally brownish or somewhat violet (this final change being variable, according to the purity of the extract). Saffron can be extracted in tho same way ; it differs from annotto very decidedly the most important difference being in the absence of the green coloration. Genuine butter, free from foreign coloring matter, imparts at most a very pale yel- low color to the alkaline solution ; but it is important to note that a mere green col- oration of the dry residue on addition of sulphuric acid is not a certain indication of annotto (as some books state) because the writer has thus obtained from gennino butter, free from foreign coloring matter, a dirty green coloration, but not preceded by any blue or violet blue tint. Blank tests should be made with the ether ; it is easy to obtain ether that leaves nothing to be desired as to purity. Turmeric is easily identified by the brownish to reddish stratum that forms between the ethereal fat solution and the alkaline solution before they are intimately mixed. It may bo even better recognized by carefully bringing a feebly alkaline solution of ammonia in alcohol beneath the ethereal fat solution with a pipette, and gently agitat- ing the two, so as to mix them partially. Martini gives a, method of separating and determining artificial color- ing matters in butter. To 5 grams of fat, dry, are added 25cc. GS^ and the mixture well shaken with water made slightly alkaline with JfaOH or KOH and the mixture gently shaken. The alkaline water will dis- solve all the coloring matter. This is now determined qualitatively by the spectroscope or quantitatively by making up a comparative mixture with the coloring matter found. Butters act better when treated as above than oleomargarine. The relative amount of color in butters is thus estimated by Babcock -.^ The relative amount of color in butters maybe determined with accuracy as follows : One gram of the fresh butter is digested with 15cc. of refined kerosene till tbe fats are completely dissolved and the solutions filtered. The filtrate will be colori-d in proportion to the coloring matter of the butter, and raay bo conipnred to that i'rom another butter or preferably to a standard solution by means of a Diibesqno colorimeter. A standard color for comparison may be prepared by adding a small quantity of any of the commercial butter colors to kerosene oil. This standard will keep for a long time without changing, if kept from tho light. Tho scale of the colorimeter on the side which the butter solution occupies is always set at the same degree, while the scale for the other standard is made variable Tho reading of this side will, therefore, vary with tho amount of color in tho saraplo. If some of the kerosene oil in which the butters are dissolved bo substituted for the sol ution of butter, a small reading will bo obtained which should bo deducted ' Analyst, 1885, p. 163. '^'"ifth An. Rcp't B'd Control, N. Y. Exp. Sta., p. n;!-.-:i:!0. DAIRY PRODUCTS. 29 from tbat for each of tlie Ijuttors. The numbers remaining are directly proijortioual to the colors of the butters. In tho butters thus far uxamiued a fair colored Jersey butter was takcu lor a standard and called 100. The others were calculated to this standard from the scale reading. The use of a small amouut of vegetable coloring matters mentioned above does not seem to be prejudicial to health. EXAMINATION OF BUTTERS. The examination of butters to detect adulterations may be divided iuto two parts : (1) Determination of physical properties ; (2) deter- mination of chemical properties. Physical properties.— The physical properties of fats which are useful in butter analysis are their crystalline state, specific gravity, and melt- ing point. Pure fresh butter prepared in the ordinary manner is not crystalline. The microscope shows the absence of all forms of crystalline structure, and thin films of the butter fat have no influence whatever on polarized light. On the contrary, old butters, or butters which have been melted and allowed to crystallize, and oils and fats which have been once in a fluid state, show, as solids, quite a distinct crystalline structure readily re- \'ealed by the microscope and affecting, in a marked manner, the po- larized ray. liecently much attention has been excited by a discussion of the ap- plication of polarized light to the qualitative examination of suspected butters, and since many analysts have not the time to fully investigate this matter I have thought it useful to enter upou the discussion of it in considerable detail. Polarization is a term applied to a phenomenon of light, in which the vibrations of the ether are supposed to be restricted to a particular form of an ellipse whose axes remain fixed in direction. If the ellipse becomes a straight line it is called " plane polarization." This well- known phenomenon is most easily produced by a Mcol prism, consist- ing of a crystal of carbonate of calcium (Iceland spar). This rhombo- hedral crystal, the natural ends of which form angles of 71° and 109°, respectively, with the opposite edges of its principal section, is prepared as follows : The ends of the crystal are ground until the angles just mentioned become 68° and 112°. The crystal is then divided diagonally at right angles with the planes of the ends and with the principal section, and after the new surfaces are polished they are joined again by Canada balsam. The principal section of this prism i)asses through the shorter diagonal of the two rhombic ends. If now a ray of light fall on one of the ends of this prism, parallel with the edge of its longer side, it suffers double refraction, and each ray is plane polarized, the one at right angles with the other. That part of the entering ray of light 30 FOODS AND FOOD ADULTERANTS. wliich is most refracted is called the ordinary and the otber tLc extraor- dinary ray. Tbe refractive index of the film of balsam being inter- mediate between those of the rays, permits the total reflection of the ordinary ray, which, passing to the blackened sides of the prism, is ab- sorbed. The extraordinary ray passes the film of balsam without de- viation and emerges from the prism in a direction parallel with the incident ray, having, however, only half of its luminous intensity. Two such prisms, properly mounted, furnish the essential parts of a polarizing apparatus. They are called the "polarizer" and the "ana- lyzer," respectively. If now the plane of vibration in each prism be regarded as coincident with its i)rincipal section, the following phenomena are observed: If the prisms are so placed that the principal sections lie in the prolonga- tion of the same plane, then the extraordinary polarized ray from the polarizer passes into the analyzer, which practically may be regarded in this position as a continuation of the same prism. It happens, there- fore, that the extraordinary polarized ray iiasses through the analyzer exactly as it did through the polarizer, and is not reflected by the film of balsam, but emerges from the analyzer in seemingly the same con- dition as from the polarizer. If now the analyzer be rotated 180°, bringing the principal section again in the same plane, the same phe- nomenon is observed. But if the rotation be in either direction only 90°, then the polarized ray from the first prism, incident on the second, de- ports itself exactly as the ordinary ray, and on meeting the film of bal- sam is totally reflected. The field of vision, therefore, is perfectly dark. In all other inclinations of the planes of the principal sections of the two prisms the ray incident in the analyzer is separated into two, an ordi- nary and extraordinary, varying in luminous intensity in i>roportion to the square of the cosine of the angle of the two planes. Thus by gradually turning the analyzer, the field of vision passes slowly from maximum luminosity to complete obscurity. The expression ".crossed Mcols" refers to the latter condition of the field of vision. Selenite plate.— In the practical application of polarized light to the ex- amination of facts, an important use is made of a selenite plate (crystal- lized sulphate of calcium). A disk of selenite, interposed between the polarizer and analyzer imparts a coloration to the field of vision which varies with the relative position of the principal sections of the two prisms. This phenomenon depends on the fact that a plane ])olarized .ray of light can be decomposed, in passing a section of a bi-refracting crystal like selenite or mica, into two rays, polarized at right angles and dif- fering in phase. This fact is illnstrated by passing a polarized ray (from a Nicol prism) through a very thin crystallized plate of mica or gypsum (selenite) obtained by cleavage. By the double refraction of the thin plate the po- DAIRY PRODUCTS. 31 larizetl ray is separated into two, ordinary and extraordinary. Tlie ex- traordinary, having to pass over a greater distance, joints tlio ordinary ray, after emergence, with a phase slightly different, the degree of dif- ference depending on the nature of the lamina, the inclination of the in- cident ray, &c., but in every case this difference of phase can be easily calculated, and the resultant beam of light is said to be elliptically po- larized. Each of the components of this ray enters Ihc analyzer and is again resolved. One of its elements is suppressed in the Nicol and the other, consisting of vibrations in the principal plane, passes througli. The result is two sets of vibrations in the same plane slightly different in phase, which are, therefore, in a condition to interfere and produce color. If the source of light be monochromatic, when the analyzer is rotated, only certain variations in luminous intensity will be observed ; but if, on the other hand, white light be employed these variations in phase will give rise to a display of colors. In order that the field of vision be of a uniform tint it is necessary that the lamina of crystal be of uniform thickness. For ordinary use the selenite plate n ground to a thickness which will give green and red tints. For crossed Mcols the colors of the selenite plate appear brightest when it is so placed that the plane of vibration in the crystal forms an angle of 45° with the plane of vibrations of the polarized incident ray. If the selenite plate is rotated in its own plane, the color appears in the four quadrants at its maximum and disappears at intervals of 90°. If the planes of the two Nicols are parallel, the same order of phe- nomena appear as before, except that the positions of maximum and minimum are reversed. If the analyzer be rotated and the selenite plate and polarizer re- main stationary there is no effect produced, when the principal section of the selenite is parallel or perpendicular to the polarizing plane of the under Nicol. But if this plane is inclined less than 45° to that of the polarizer, then the selenite plate in a complete revolution of the analyzer will appear four times brightly colored and four times color- less. In adjoining quadrants the colors will be complementary. When the Nicols are so placed as to produce the maximum intensity of color, if small bi-refracting crystals be introduced at random into the field of vision, they will, in general, have the same effect on the plane polar- ized ray as the selenite plate. Since the. axes of these crystals may have any accidental position with reference to the planes of the Ificols, it follows that the field of vision, which before appeared of a uniform tint, will now become variegated, the color disappearing in some cases md becoming more intense in others. When a bi-refracting crystal is cnt into laminae normal to its axis, Df appropriate thickness, it gives some peculiar phenomena when ex- amined with polarized light. When the analyzer is perpendicular to the polarizer, there is seen in the ordinary image a black cross, the ex- istence of which can be explained by the mathematical theory of polar- 32 FOODS AND FOOD ADULTERANTS. izatiou. The arms of this cross are parallel aud perpendicular to the primitive plane of polarization. Between the anus are generally to be ibund rings which present the successive tints of tlie fringes of inter- ference. In the extraordinary image the order of the phenomenon is entirely reversed. Having now briefly described the more important oi)tical phenome- non which forms the basis of the examination of butters with j)olarized light, I will next say something of the nature of the substances to be examined. The expressions "fats " and "oils " designate those natural products of animals and vegetables known as glycerides. Chemically consid- ered they are the normal propenyl ethers of the fatty acids, or, in other words, compounds of the triad alcohol, glycerine, with the fatty acids. The term "fat" is applied to such bodies when they are solid at ordi- nary temperatures, and " oil" when they are semi-solid or liquid. Those which are most important are: Tri-stearin, 03115(010113502)3, occurs in natural fats. It may be ob- tained in a considerable degree of purity by repeated crystallizations from ether. It crystallizes in plates of a pearly luster. Its melting point is 55° 0. Tri-palmitiu, 03H5(0i6H3iO2)3, is found in animal fats and palm oil. It crystallizes with a pearly luster from ether. The crystals have a melting point of from 50° to C6° 0. Tri-butyriri, 03115(0411702)3, occurs chiefly in butter. At ordinary temperature it is liquid, and has a distinct and peculiar odor and taste. Tri-olein, C3H5(0ibH33O2)3, occurs in animal fats and in almond and olive oil. At ordinary temperatures it is liquid, is neutral to test pa- pers, and has neither taste nor smell. Minute quantities of tri-myristin, caprin, capryliu, and caproin are also found in butter. Pure butter fat is supposed to contain — Per ccDt_ Tri-olein, about 4-j. 5 Tii-stcariij^ about .',1.0 Tri-butyrin, aboat C. 3 Other glycerides, about 2 100. 00 Olive oil is composed chiefly of tri-palmitin and olein. Tri-stearin/is the chief constituent of mutton fat, it having only small quautines of olein and palmitin. Beef fat has somewhat more palmitin and stearin than mutton tallow. Lard has more olein. It is thus seen that in dealing with butter fats and their substitutes wo have to consider chiefly tri olein and stearin, and, in smaller quantities, tri-palmitiu, butyrin, &c. It follows, therefore, that the chief dififer- ences in the several substances will be due to the different proportionfi DAIRY PRODUCTS. 33 iu wliicli these glycerides are mixed and to such other physical difi'er- dices as the various sources of the substances under examination would produce. These differences, however, prove greater when subjected to l)hysical and chemical analysis thau the foregoing r6sum6 of their chemical constitution would indicate. Advantage has been taken of these differences of physical structure to discriminate between fats and oils of different origins. The specific gravity and the melting point furnish two valuable points of discrimination, but both of these are perhaps inferior in vaUie to the evidence afforded by the crystalline structnre of the fats. Tiie observation with the microscope of the crystals obtained in various ways furnishes valuable data for discrim- ination, and if the light employed be plane polarized or elliptically polarized by a selenite plate, these data become still more valuable. The first account of the use of the selenite plate in such examinations was given by Dr. J. Campbell Brown in the Chemical News, vol. 28, pages 1, et seq. lie gives the following directions for the polaro-micro- scopic work : lixiMuiue several portions of the original samplo by means of a good microscope, usinT a one-fourtli or ono-flfth. inoli oliject-glass. In butter made from milli or cream nolLiug is seen except the cliaracteristic globules, and the granular masses of curd and the cubical crystals of salt. The bard fats of butter are present in the globules in a state of solution, and are not recognizable in a separate form. If stearic acid, stearin, or i)alraitiu bo present in separate form, they will bo recog- nizable by simple fasiform crystals, or starlike aggregations of acicular crystals. They indicate the presence of melted fats. Otlier substances, snob as staroli flour, palm oil, corpuscles, Irish mesa, coloring matter, &c., may also be distinguished by the microscope as distinct from butter or fats. Examine the same portions with tho same object-glass, together with a polariscopo, consisting of two Nicol's jwisms and a selenite plate. The crystals referred to polarize lio-lit, and when viewed by tho polariscopo are distinctly defined. Particles of suet and other fats which have not been melted may also be distinguished by their action on iwlarized light, by their amorphous form, and by their membranes. The value of this deportment of fresh butter fat with elliptically po- larized light did uot meet with tho appreciation its merits deserved un- til attention was again called to it by Prof. Thomas Taylor, of the De- partment of Agriculture. Any fat or oil which is homogeneous and uon crystalline will present the same phenomena when viewed with polarized light and selenite plate; in other words will have no effect on the appearance of the field of vision. It is only, therefore, fats which are in a crystalline or semi- crystalline state that can thus be distinguished from fresh, amorphous butter. TSTaturally it follows that a butter which has been melted antl cooled, or butter which has stood a long time, would impart a mottled iippearancc to the field of vision. For a simple preliminaiy test, how- ever the procedure is worthy of more attention than its discoverer, Dr. J. Campbell Brown, accorded to it. 19330— No. 13 3 34 FOODS AND FOOD ADULTERANTS. FOEMS OF FAT CRYSTALS. Tlic lorras of (at crystals differ greatly with tbe kinds of fat and the proportions in ^vllich they arc mixed. It would be idle to attempt a description of all these modifications. Hussoa' has published an illustrated descriptiou of some of the more i-mportaut fat crystals. Suet crystals, according to Husson, are very characteristic of stearin. They arc small, rounded, or elliptical masses formed by stiff, needle-like crystals, and resemble a sea urchin or hedge hog. In lard are seen polyhedral cells arising from the compression of the fatty globules. In impure lard are also seen the remains of cells and adipose tissue. Fresh butter shows some long and delicate needles of margarine (?) united in bundles and grouped in various ways. When the butter is melted these needles diminish in length and become grouped round a central point. I have mentioned these descriptions especially lor the purpose of calling attention to the fact, that, in the illustratioDS of the microscopic appearance of butter and other fats, emphasis is often given to one particular phenomenon, and the real appearance as seen in the microscope is not reproduced. The only reliable representation is found in the actual photo-micro- graph or its exact graphic reproduction. When the crystals of certain fats are prepared in a special way they show, with polarized light, a distinct cross, the existence of which is explained by the laws of elliptical polarization already mentioned. This cross was first described by Messrs. Hehner and Angell in 1874 in the following words : If sonic of a fat containing crystals be placeil on a slide and a drop of castor or olive oil Ijo applied and pressed out with a thin glass cover, the depolarization of light is much enhanced ; a revolving blade cross, not unlike that on some starch grains, issceu in great perfection. These crosses are most clearly defined in tho crystals obtained from butter, and these thus mounted form a brilliant polariscopic object. They add further : Thus far and no farther, as it seems to us, can the microscope assist us in this mat- ter ; but even such indications are valuable, especially whou subsequent analysis proves tho sample to bo au adulterated article. Tlie microscopic evidence in such case frequently serves to clinch together tho whole superstructure, and thus certainty is made doubly sure. Dr. Thomas Taylor has further called attention to this phenomenon in a i)aper read before the American Society of Microscopists at its Cleveland meeting, August, 1885. On page 3 of the reprint of this paper he says : Since the publicatiou of that ])aper 1 havo oxperinieuted largely with butter, and have made tho discovery that when it is boiled and cooled slowly for a period of from twelve to twenty-four hours at a temperature of from 50° to 70^ Fahr. it notonly bo- comes crystallized, but, with proper mounting and tho use of polarized light, it ex- 'Auu- d. Chem. et d. Pharni. DAIRY PRODUCTS. 35 liibitJ on <;iioh ci'.ystal a weU-doflaod figure rosembllng wliat is knowu as the crosa of Saint Auiliow. In coui'so of time, tho period ranging from afew days to a few weoUa according to tho quality of tho butter used and the temperature to which it is ex- posed, tho crystals, which at first are globular, degenerate, giving way to numerous roscttoliko forms peculiar to butter. Ou page 5 be says : About ten years ago, while making some experiments with boiled butter, I first ob- served it exliibitod small crystals somewhat stellar in form, but gave no further at- tention lo tho faot'uutil May last. For the purpose of determining tho real form of the ci'ysial of boiled butter I procured a sample of pure dairy butter from Ohio. I boiled it, and when cold oxamiued it under a power of 75 diameters. To my surprise 1 found globular bodies. When I subjected them to polarized light a cross consist- ing of arms of equal length was observed on each crystal. Ou rotating the polarizer thecrossof cachcrystalrotated. Onrotatingthe glass ou which the specimen of butter was mounted tho crosses remained stationary, thus showing that tho appearauco of tho cross depends, probably, ou tho fact that the crystals are (1) globular, (2) polarizing bodies, (!) tr.anslucent, and (4) comparatively smooth. Were they opaque or non- polarized or did they consist of long spiues, causing great divergence of the rays of light, no image of the cross would be visible; showing that the appearance of the cross under polarized light and the conditions stated is not duo to any physical struc- ture of iho fatty crystals themselves. But from whatever catiso tho appearance of the cross on the butter crystals arises, it4 constant appearance on new butter under the conditions above described is a fact beyond any question ; and, as far as my ex- perience goes, I ho bettor the quality of tho butter the more clearly defined is tho cross; it is black, large, and well defined. When these crystals are under polarized light and a seleuite plate combined thoy exhibit tho prismatic colors, but tho cross proper is not visible in this case, although tho crystals are still divided into four equal parts aud .are exceedingly interesting objects. Dr. Taylor having tliiis directed tho atteutiou of scientists to these important ])heuomena, it has not taken long to show' that there is little reason for the rather mean opinion of European chemists of the value of the microscope in detecting adulterations of butter. In several cases of pi osecution before the District authorities the offenders have been convicted solely on tho microscopical evidence and have admitted the justice of the sentence. If only fresh butters were exposed for sale, and all adulterants were certainly once melted and slowly cooled, but little more than this qualitative exaraination would be necessary. Prof. H. A. Weber, of Columbus, Ohio, has made some interesting ex- periments with the microscope on fats, which in the main bear out the conclusions of Messrs. Brown, Hehner and Augell, and Taylor. As was to bo expected, however, ho has shown that the appearance of the cross on a crystal of natural fat does not show that it is derived from pure but- ter. He says, in Bulletin Ko. 13 of the Ohio Experimental Station, Ex- periments 7, 8, 9, and 10 : Expcrimmt ".- -Tho ditferenco between the behavior of the tallow fats in Experi- ment 3 and the asc three experiments could only bo ascribed to a difference of condi- tions. It is well known that table butter normally contains 4 to G per cent, of salt and 5 to 20 per cent, of water. Ttiose ingredients coustituto tho most marked dift'er- euce between butter and the rendered animal fats as tallow aud lard. lu order to test the effect of this mixlcre upon the tallow fats, about half an ounce of the oleo oil used in Experiment 3 was mixed in a porcelain mortar with a small quantity of 36 FOODS AND FOOD ADUl^TERANTS. salt and eigliL or ten drojjs of water. Aflcr (be water was tlioiouglily incorporated, tliii mass was transferred to a test tube and boiled for 1 iriinuLr as in the case of bnt- ler. It was tlieu ponred into a wooden pill-box and allowed to cool as before. Tbe cooled mass j)rosented qu i te a marked difference in appearance from that obtained from the same substance in Experuneut 3. It retained to a great extent tbe yellow color of tlie oleo oil, was of a more granular nature, and in fact resembled boiled butter in every respect. When a small particle was stirred np witb olivo oil on a glass slide it separated readily. Wbon covered and viewed witb a pocket lens it revealed a mass of globules resembling insect eggs. Under tbe microscope these globules exhibited essentially the same characteristics as those obtained from butter in Experiment 1. The crystalline mass of tho oleo globule seemed somewhat coarser, and to this condi- tion was ascribed the fact that the cross, as vfell as the colors produced by tho selen- ilo plate, were less sharply defined than in the globules obtaiucd from butter. Tbe slides i)repared from this material were remarkably free from the small detached crys- tals of fat observed in Experiment 3. Experiment 8.— Having thus discovered that these globular masses may be obtained from pure tallow fat by simply observing tho conditions which obtain in butter mak- ing, tho following test was made : Nine grams of oleo oil and 1 gram of lard were placed in ,1 small beaker glass and eight or ten drops of a saturated solution of salt in water adilod. The mixture was then gently heated to melt the fats. After shaking violently for a few moments to uux tho salt solution with tho fats, the mixture was boiled gently for 1 minute and then allowed to cool as before in a wooden pill-box. Tho microscopic examination of this preparation revealed globular masses which could in no wise bo distinguished from those obtained from puro bntter. The crystalline tex- ture was dense, tho cross of St. Andrew's plainly marked, and the colors produced by tho selenite sharply defined. Experiment 9. — A mixture of one part of lard to five parts of oleo oil was treated as i u the last oxiieriment with like results. Eixjeriment 10. — In this test a mixture cuusisting of 20 per cent, of lard and SOpor cent, of oleo oil was employed. Whether the consistency of thiij mixture was peculi" arly adapted to the formation of tho globules, or whether possible variations of condi- tions in manipulation were more favorable, the writer is unable to judge from a sin- gle ex]ierimont, bnt the fact is that in this case the. individual "butter crystals"' wore exceedingly large and characteristic. Tho use of polarized light in photomicrography is also valuable in eiiiibliug the photographer to print the light-colored crystals on a dark background. To illustrate some of the forms of crystals of butter and its substitutes as they appear uuder polarized light a largo number of microscopic samples were prepared and photographed by Messrs. Eich- ards and Kichardson. Eesults of some of the more interesting of these photographs are herewith transmitted. lu all cases the figures arc inagnilied 40 diameters, unless otherwise stated. bAiRY PRODUCTS. 3? DESCRIPTION OP PLATES. Plate I. Pig. I.— Fre.sh butter boiled. Pig. 2. — Fresh butter matlo ia tlie laboratory without the use of salt, molted, ClLorcd, .and boiled. A small sample of the butter was taken and boiled for one minute in a test tube over the naked flame, then set aside and allowed to coolslowly for twenty-four hours. A suitable quantity was then taken, sufQciout to make a slide for the microscope, thinned with olive oil, and liressed out on the cover. Plate II. Fig. 3. — Fresh Virginia butter boiled and let stand for seven days. Specimen jire- parod by Dr. T. Taylor, March 11, 1886. i^'lG. 4. — Fresh Virginia butter boiled. Specimen prepared by Dr. T. Taylor March 11, 188G. Plate III. Fig. 5. — Fresh Kentucky butter boiled. Specimen prepared by Dr. T. Taylor March 11, 1886. Fig. 6. — Fresh butter boiled. Specimen prepared by Dr. T. Taylor March 15, 1886. Plate IV. Fig. 7. — Filtered butter fat dissolved lu boiling alcohol and allowed to cool slowly. Pig. 8. — Filtered butter fat dissolved in boiling ether and allowed to cool slowly. The fresh butter was molted and filtered through a jacketed filter, llins getting rid of the water, curd, and salt ; al lowed to cool and jireparcd as above. Plate V. Fig. 9. — Beef suet fat. Not boiled. The suet fat was cut up into fine pieces and melted in the water bath at a low heat and filtered; allowed to cool slowly. Specimen was taken several days after the sample was prepared. Fig. 10. — Beef suet fat boiled with the addition of salt and cooled slowly. Plate VI. Fig. 11. — Beef suet fat, "oleo oil," dissolved in boiling ether '.and allowed to cool slowly. Fig. 12. — Beef suet fat, " oico oil," dissolved in boiling alcohol and allowed to cool slowly. Plate VII. Fig. 13. — Leaf lard. Not boiled. Specimen takeu direct from can as purchased in the open market. Magnified 160 diameters. Fig. 14. — Lard dissolved in boiling ether and allowed to cool slowly. Plate VIII. Fig. 15. — Beef fat, '' oleo oil," and lard, "neutral," boiled with salt and water and allowed to cool slowly. Fig. 16. — Butterine, from Armour & Co., Chicago. Boiled and allowed to cool slowly. 38 FOODS AND FOOD ADULTERANTS. Plate IX. Fig. 17. — Biilteiine, from Armour & Co., Chicago. Not boiled. Specimen (akeu di- rect from tub as received July, 188G. Magnified 160 diameters. Fig. 18.— Butterine, from Armour &. Co., Chicago. Melted, filtered, and boiled. Pl.vte X. Fig. 19. — Butterine, from Armour & Co., Chicago. Dissolved in boiling otlicr and allowed to cool slowly. Fig. 20.— Oleo oil, from Armour & Co., Chicago. Melted, filtered, and bnilod. Al- lowed to stand four days under cover glass. Plate XI. Fig. 21. — Oleomargarine, from Armour & Co., Chicago. Not boiled. Specimen taken direct from tub as received July, 1886. Magnified 160 diameters. Fig. 22. — Oleomargarine, from Armour & Co., Chicago. Boiled with salt and watei and allowed to cool slowly. Plate XII. Fig. 23.— Same as Fig. 22. Fig. 24.— Same as Fig. 22. BULL N?I3 DIV OF CHEMISTRY. PLATE I BUTTKR x40 Fi^i '1 BUTTER x40 Phoio.'by Clifford Tti<3iaJ-dion . A.HoBn &i;^LHiIlocuiiUe JaltiiT BULL.N9I3 OIV.OF CHEMISTRY. HI^ATE XL HUTTKR x40 Piii 4. HUTTKR x4() plioto.ljy CJif ford Richai^lson . A.HDen(Ca HellDcaiuUe Baltimnrf). BULL.N9I3 OIV.OF CHEMISTRY. PI-u^XE m n r «p i^' ^^ V ; *^i,- ■:f#. BUTTER x40 Fi_^6 BUTTER x40 PJiolo.ljy Clifford Ri cliarda on , A Haen SfCo.HEl'DcausLic BaliimQre BUUL,N9I3 DIV.OF CHEMISTRY. T'LA.TE nr Fi6 7 BUTTER X4.0 BUTTER x40 PJiolo.'by CJifford Richardson. A.HaenJ^Ca.NBligoEttistic BsltimDre BULL.N9I3 DIV.OF CHEMISTRY, PJ^^AXE Y BEET- FAT x40 Firt 10 BEEF FAT x40 PJiot€^.l>y Clifford lUcllax-daon . A.HoEn IrCa. HflllaBausticBEltiniDre BULL.N^IS DIV.OF CHEMISTRY. PLATE YI Fip II BEEF FAT x40 •%...*^%: ,5- BEEF FAT x40 PJiolo.'by Clifford HicliaJ-dson . A.HDEii£Ca HellDcausUcBHltimarB. BULL.N?I3 D IV. OF CHEMISTRY. Pl-JVXE YH Fi>i 13 LARD x\6<) Fi<^ 14 LARD x4.0 PJiolo.by Clifford Richaj-daon . A.Hoen &Cd HeliacakisbcBoltimDre. BULL.N?I3 DIV.OF CHEMISTRY. PI-ATE vm BEEF FAT Kr LARD .x4(» BLTTTEKfXE x40 PJioto.by Clifford Richardson. A.Hdbti ICg HeligcausLic, Baltimore BULL.N^ia DIV.OF CHEMISTRY. PI^u^TK IX Fi.'. 17 BUTTERISE xl60 F±^ 10 ,^ *-^^ BLTTTERfNE x40 FJtolo.by Clifford Richru-dson. A.HDenlCD HaliDcnusLic BaltiinoT-e. BULL.N"?i3 DIV OF CHEMISTRY PI.JVTK X FiO 19 BITTTERI^STE x40 Fi$ 20 BEEF FAT x-i-O PJ,olo.T>y Clifford Hichoi-d-on. A.Haen&CD HBllDcauHtic .BBltiinnre. BULL.N9I3 OIV.OF CHEMISTRY. yi^-ATK XL Fi^> 21 OLEOMARGARINE .xl60 Fig 22 OLEOMARGARINE x40 i^lo.l.V rJlftonl tti.;ll.'.v.l»**>n. AHoenlCa Htl-nMusLicBallirr BULL.N9I3 DIV.OF CHEMISTRY. PIRATE xn OLEDALARCJARINE x-J-0 Fig 24 OLEOiMARG-ARII^E x4() Pitoto-ty CJiffortl Ricliaj-dson . A.naEn&Ca HBllaDsusLic.Baltimm-c. DAIRY PRODUCTS. 39 A careful study of these illustrations will show that the microscope and polarized light are most valuable aud reasonably certain means whereby a qualitative examination of butters can be made. The ap- proximate amount of added fat can only be determined by a chemical analysis of the suspected sample, taken in connection with some of its further physical characteristics. T have given above all the really valuable points heretofore estab- lished in respect of the use of polarized light in butter and fat analyses.' The use of the microscope in butter examinations has not commanded as much attention among analysts as its merits deserve. Sell says : ^ Thougli investigations Lave shown that the differences in structure under the mi- croscope are not in all cases snfflciently oharaotoristio to determine a sharp distinc- tion between twodifferent fats, yetit must he admitted that the microscopic exami- nation is able to prove the presence of foreign fats at the moment it succeeds in es- tablishing the presence of molecular tissues iu animal or vegetable parasites. JLaadtner and Hilger say : ^ The use of the microscoiio in the examination of fats requires a still further devel- opment before it can become generally applicable. Having written to the editor of the Analyst for some information on the subject of the use of the microscopic methods in England, he re- plied: "The whole subject has been studied over and there is nothing in it." Dr. S. M. Babcock, chemist of the New York Experimental Station, says : '' At the time these butters were received there was considerable controversy regard- ing the efficiency of Dr. Taylor's method for the detection of adulterations in butter by means of the microscope. An excellent opportunity was oiiored iu these samples for testing this method in an impartial manner, aud u, microscopical examination of them was made before the nature of the butters was revealed by other tests. The butters were examined directly with polarized light and a selenito plate, and afterwards the crystals from the melted butters were examined in the same way for the " Saint Andrew's cross." - Tlie direct examination with iiolarized light and a soleuito plate showed prismatic colors in all of the adulterated bntters, and a uniform tint in all of the genniuo but- ters, except No. 2, which appeared very much like the adulterated samples. The crystals from.iill of the butters, adulterated as well as genuine, gave a well-defined Saint Andrew's cross with jjolarized light. This was also the case with neutral lard (No. 14), in which the cross was sharply defined, though quite small. No. 16 consisted of stcarine from the oleo-oil factories, and showed no cross when examined by itself, but when combined with a small quantity of butter fat the crystals formed had the same appearance as those from pure butter. The method has also been quite unsatisfactory in trials made at the station with butters .whoso character was known. Whether these results were due to a lack of skill or to imperfect knowledge in the details of the work I do not know. The ' Notices of minor importance on the same subject can bo fonnd iu Chem. News, vol. 4. pp. 230, 283, 309, 322 ; Zeit. Anal. Chem., 1872, p. 334 ; Jonrn. Royal Microscop- ical Society, 1878, p. 378; American Quarterly Microscopical Journal, 1878, p. 294; American Journal of Microscopy, October, 1878; Bied. CentrUlblatt, 1879, pp. 861-865; 1882, p. 345; 1832, p. 4D; Amor. Chemist, vol. 2, p. 428. ^Op. cit, p. 503. 3 Ver. Bay. Vertroter d. Angowand. Chem., p. 222. •< Fifth Ann. Kept. Bd. Control N". Y. Exp. Sta., pp. 330, 331. 40 FOODS AND FOOD ADULTERANTS. uncertain rosulta of some skilled microscopists, however, would indicate tliat tlic iifficulty is inherent in the motliod. It certainly is not simple, and is not calcnlatcd supersede the chemical methods now in nse. Caldwell,' after references to the notices of the use of the microscope n the exaraiuatioii of butter published up to that time (1882), says, (). 519 : 't is plain, therefore, that little dependence can be placed ou any microscopic (est ) Ibe genuineness of hnttcr, at least so far as the observation of the crystalline forms of foreign fats is concerned, for neither does the absence of such forms prove that the butter does not contain oleomargarine, nor does their presence prove the adulteration. 'Jn the other hand, Mylius^ has shown that the polarization micro- scoi'c may bo used for the detection of minute quantities of foreign fat.s in b itter. Pure butter gives with crossed Nicols a dark field, whereas crystals of foreign fat will appear bright. Skalweit" recommends this methcil highly, and affirms that even the kind of foreign fat present may be defc^.rmined. In spite of the generally unfavorable opinions I feel sure that the chemist who neglects to make a simple microscopic examination of a suspectt 1 butter with polarized light and a selenite plate loses a valua- ble qualitative indication of the character of the samples with which be lias to work. The melting of the sample of butter and its slow cooling to secure good bi-refracting crystals I consider a much less valuable indication tlian the simple observations above described. SPECIFIC GRAVITY. The determ.jation of the specific gravity of a butter fat gives a most valuable indication of its purity. The density of pure butter glycerides is distinctly greater than that of the common adulterants, with the ex- ception of cottonseed oil. Wiiile this difference is not great, it is nevertheless large enough to be easily detected by careful manipulation. Manipulation. — The relative weight of the filtered and dried fat is to be determined in a picnometer. This flask should be carefully cali- brated by weighing the pure distilled water it will contain at the tem- l)eraturo at which the subsequent determinations arc to be made. The Hash should be provided with a delicate thermometer, but this is not essential, since the temperature can be determined by an external ther- mometer. The temperature at which the determinations should be made is evi- dently that at which all the common butter adulterants -will be in a perfectly fluid state. Generally the temiierature of 100° F. has been employed. Since, however, "neutral lard" may have a melting point as high as 40° 0. or even a little above that I have uniformly taken the specific gravity at that degree. In case the fat should have a melting point a little above this the temperature can bo raised until tho fat is ' Second Ann. Rept. N. Y. S. Ikl. of Health. = Correspoudensblatt des Vereins Anal. Chem., 1373, No. 3. » Hid., 1879, Nos. 5 aud 13. DAIRY PRODUCTS. 41 fluid and can then be reduced to 40° 0., without danger of solidifica- tion. Tlio difference between the specific gravities expressed at 37° C. and 40° 0. is not of very great magnitude. Ely til' recommends tlie use of a picnometer of 50 to 100 grams ca- pacity, with a thermometer stopper. This is filled with water at 35° 0. and placed in a beaker of water at 43° 0. W hen the water has reached a temperature of 37o.7 0. the flask is removed and weighed. The fat whose density is to be determ ined is treated in the same manner and weighed at the same temperature. Wigner- places the butter-fat in a wide tube where a bubble of the specific gravity of .890 is kept below the surface by the bnlb of the thermometer. xVt a certain temperature the babbles will slowly sink to the bottom. lu butters of .911 density, above which a sample may be passed as pure, these beads will sink as follows : Specific gravity of beads 889 .8896 Temperature 62°. 7 C. 55°. 5 C. If the beads sink at any temperature lower than these the butter will need further examination. Bstcourt^ describes a method of taking specific gravity of fats as follows : The bulb of a Westphal balauco is suspended in a test-tu.be contain- ing the fat, the test-tube being immersed in paraffin, in a water bath. The adjustment of the weights takes place at a temperature of 92o.2 C. This process has been modified by Konig.'' In Konig's process there are several water baths which are closed with the exception of a tube for carrying off the steam. In the cover of each bath are four openings for the reception of four test-tubes 1^ inches in diameter and 8 to 9 inches long. These are fastened air-tight into the openings mentioned. Each tube stands one-half inch above the cover of the water bath. Each piece of apparatus wlien in use contains in one of the tubes a sample of pure butter and in the others the samples under examination. The specific gravity is determined by small areometers C inches long and with a scale marked from .845 to .870. The numbers obtained at 100° 0. were as follows : Pure butter, .807 ; artificial butter, .859; beef fat, .860; mutton fat, .860 ; lard, .861; horse far, .801. Mixture of pure butter with other fats gave numbers between .859 and .805. The process of Konig has been tested by the Board of Health at Eerlin and found relatively useful.' The method has also been approved by Eisner;" by Ambuhl and Dietzsch;'^ and Meyer." ' Foods, p. 295. ^Blytli, op. ciL, p. 295. ^Clieni. News, vol. 34, p. 254. ■i Industriebliitter, 1879, p. 455. "Sell, 0]}. cit., p. 505. "Die Praxis des Naliruiigsmittelcliemikers, 2d ed., p. 50. 'Rep. d. Ver. Anal. Chem., 1884, p. 359. sZeit. Anal. Chem,, 1881, p. 376. 42 POODS AND POOD ADULTERANTS. Jones ' calls attention to the fact that the specific gravity of butter increases with age. The specific gravities of several samples are compared in the following table, the numbers in second column being obtained after eightec-u months : Speoijic gravity at 37,7 C Sample. 1. 2. 1 .9123 .9105 .9119 .9112 .9125 .9133 .9083 .9114 .9185 .9165 .9155 .9132 2 3 4 .... 5 In other samples there was a decrease in specific gravity. In five samples out of nine there was an increase and the percentage of soluble acids had also increased. Since butters in general are obtained for analysis without having been long kept the observation of Jones does not have much practicii! importance. Sendtncr' and Hilger^ find that a filtered pure butter fat does not show a specific gravity less than .860 at 100° O. In the Erlangeu Uui versity numerous exijeriments with twenty difterent samples of butter i>liowed variations from .866 to .8685. Allen ^ recommends Sprengel's tube for the determination of specific gravity of oils at the temperature of boiling water. Tho weight of the Sprengel tube and that of water contained iu it at 15°.5 C.biins known, tho tube should bo completely filled with tho oil by immersing one of lliu orifices in tho lic[uid and gently sucking tho air from tho other orifice oflholubu. The tube is then jilaoed in the mouth of a conical flask containing water kept iu a rapid ebullition, and the cover of a porcelain crucible placed over it. As the oil gets hot it expands and is expelled in drops from the horizontal capillai-y orifice of tlic tubes. When tho expansion ceases any oil adhering to tho orifice is removed by cautious application of filter paper, the tube removed from the bath, wiped dry, al- lowed to cool, and weighed. Tho weight of tho contents divided by the weight ol water at 15°.5 C. previously known to be contained by tho tube will give the density of tho oil at the temperature of the boiling water ; water at 15°. 5 C. being taken .^s unity. Bendikf prefers tho Sprengel tube to all the other methods of esti- mating the specific gravity of oils. He also recommends the Westphal balance as used by Bell and Walkenhaar. I Analyst, 1879, p. 39. = Veroinbarungen botreffs d. Untersnch. u. Beurteilnug v. Nahrung.s-Gennssmitteln, pp. 221-2. " Com. Organic Analysis, Vol. 2, 2d ed.. p. 15. ■•Analyse der Fette, &.c., p. 53. DAIRY PRODUCTS. 43 Dr. Muter^ gives the following table of tlie specific gravity of various oils at 370.7 0. Kind of oil. Specific gravity. Kind of oil. SpeoiBo gravity. Olivooil 907.0 905.0 908.5 900.7 908.4 917.0 913. 915.4 919.3 'Jl'5. 2 Linseed oil (boiled) 938.0 955.8 872.4 Kapo oil W halo oil , 900,0 Nut oil 915. Cotton-seed oil (brown) .. Codliver oil 917.9 Cotton-seed oil (roflned) Poppy-aoed oil 907. 8 Xoat's-foot oil 907.0 903 to 908. 13uttor-fat 012 to 914. METHOD EMPLOYED IN CHEMICAL DIVISION. Wlien convenient the determination of specific gravity is not made nntil a number of samples is on hand. Bach determination is made in duplicate. The picnometers, holding about 25 grams, are filled with the filtered fat, at as low a temperature as possible, and ijlaced in a flat dish filled with water as nearly to the tops of the flasks as possible. The picnometers used should all be of the same height. The stopper has a capillary perforation for the escape of the oil as the temperature rises, if the picnometers are not furnished with thermometers of their own, a delicate thermometer is suspended in the water surrounding them. The water-bath is slowly warmed and geutly but constantly stirred uiitil the temperature reaches 40° 0. It is kept at this temperature for fifteen or twenty minutes, until the fat has taken on the same temperature as the water. The picnometers are then carefully cleaned and dried, and, after cooling to the temperature of the balance-room, are weighed. This method is somewhat tedious when only one determination is to be made, but where jnany samples are to bo examined it is sufficiently speedy. In respect of accuracy it leaves nothing to be desired. TEMPERATURE AT WHICH SPECIFIC GRAVITY IS STATED. Different analysts select different temperatures for determining spe- cific gravity. It would bo well to have some agreement on this point to avoid confusion. Since the specific gravity determined at any temperature can be easily calculated for any other given temperature, I suggest that it might be well to express all specific gravities in terms of water at 4° G. THE MELTING POINT OF FATS. The fats pass rather slowly from the semi-solid state, which is their natural condition at ordinary temperatures, to complete fluidity. It is, therefore, difficult to determine accurately the exact temperature at which they melt. ' AUcD, op. cit., p. 15, foot-noto. 44 POODS AND FOOD ADULTEEANTS. The value of the melting point ia the examination of fats is at once apparent, provided it is jtossible to be assured that it represents a definite temperature which can be easily and accurately determined. At a temperature of 40° G. pure butter fat has a specific gravity of .912, while the substitutes therefor, viz, lard, tallow, oleo-oil, neutral lard, &c., have specific gravities varying from .900 to .905. Yet even these small differences are extremely valuable in distinguishing the fats from each other. The differences in melting points, when they can be accurately deter- mined, will also prove helpful to the analyst. The usual methods em- ployed to determine melting points have been based on the assumption that a fat becomes transparent at the moment it assumes the liquid state. Usually the fat is melted and placed in glass capillary tubes, and, after cooling, put into water near the bulb of a thermometer. The water is slowly warmed, and the moment the fat in the tube becomes transpar- ent the reading of the thermometer is taken. A careful observer is able in this way to make multiple determinations which agree well together, but the readings of different persons are apt to varj^ greatly. Moreover, it is not the melting but the transparent point that is determined. In 1883, at the Minneapolis meeting of the Association for the Ad- vancement of Science, I described a method of determining the flowing point of a fat. The melted fat having been put into a small bent me- tallic tube, was, after cooling, placed in a bath of mercury. One arm of this U-tube was slightly longer than the other. The bent tube was imiiieraed in the mercury until the longer arm was just below the sur. face. The fat in the tube was, therefore, subjected to a certain definite pressure from the mercury, due to the difference in length of the two arms. When the melted fat first appeared on the surface of the mer- cury, the therraoaietric reading was made. It is scarcely necessary to add that the bulb of the thermometer was wholly immersed in the mer- cury. Fairly good results were obtained by this method. Another method, which gave rather good results, I tried at the same time. A thin film of fat was spread over the surface of the mercury and the temperature noted at which a platinum wire drawn through it left no trace. The solidifying point was determined in the same op- eration by observing where the wire left a mark. Various methods for determining the melting point of fats are given by Ueichert.' The method preferred by him is a modification of Guichard's process,* in which the fat is forced out of the tube by a water pressure of n constant magnitude. Dr. 11. Kriiss= describes an apparatus for estimating the melting point by the completion of an electric circuit dependent on the melting of the fat used as an insulating material. A platinum wire, bent into the ' Zeit. Anal. Chem., 1835, pp. H etseq. 'Ihid., 1883, p. 70. "Zeit. f. Instrumoiitenkiinde, vol. 4, pp. 32, 33. DAIRY PKODUCTS. ' 45 form of ii small hook, is dipped iuto the melted fat, ii portion of which adheres to it. This process is repeated until a sufficient insulatiou is pro duced. The fat-covered end of the wire is theu dipped into a mercury cup, which coutains also the bulb of the thermometer. The cup is placed iu the electric circuit and the moment of contact is determined by the ringing of an electric bell. Thorough trial of this method convinced me that it was loss accurate than any of those which have already been mentioned. Realizing the importance of determining some definite point at which fats would assume a constant condition under the influence of tempera- ture, I was led to select another libysical aspect of fats, easily and cer- tainly visible, which could be regarded as the melting point. This con- dition may be defined as the point at which the molecular attraction of the fat becomes greater than the molecular cohesion. If a thin film of any fat be suspended in a liquid of equal specific gravity with it and this liquid be slowly warmed, a point will be reached at which the film will roll up and finally assume tl(e form of a sphere. By imparting to the globule a gentle motion of rotation the observer is easily able to distinguish the moment when it becomes sensibly sym- metrical. I use the following method and apparatus for applying this principle to the determination of the melting points of fats.' The aj) paratus consists of (1) an accurate thermometer for reading easily tenths of a degree ; (2) a less accurate thermometer for measuring the tem- perature of water in the large beaker glass ; (3) a tall beaker glass, 35cm. high and 10cm. in diameter ; (4) a test tube 30om. high and 3.5cm. in diameter; (5) a stand for supporting the apparatus; (6) some method of stirring the water in the beaker. I use a blowing bulb of rubber and a bent glass tube extending to near the bottom of the beaker ; (7) a mixture of alcohol and water of the same specific gravity as the fat to be examined. Manipulation. — The disks of the fat are prepared .as follows : The melted and filtered fat is allowed to fall from a dropping tube from a height of 15 to 20cm. onto a smooth piece of ice floating in water. The disks thus formed are from 1 to IJcm. iu diameter and weigh about 200 milligrams. By pressing the ice under the water the disks are made to float on the surface, whence they are easily removed with a steel spatula. The mixture of alcohol and water is prepared by boiling distilled water and 95 per cent, alcohol for ten minutes to remove the gases which they may hold iu solution. While still hot the water is poured into the test-tube already described until it is nearly half full. The test tube is then filled with the hot alcohol. It should be poured in gently down the side of the inclined tube to avoid too much mixing. If the tube is not filled until the water has cooled the mixture will contain so many air bubbles as to be unfit for use. These bubbles will gather on ijonrnal Anal. Chemistry, vol. 1, No. 1, pp. 39 et seq. 46 FOODS AND I'OOD ADULTERANTS. tlie disk of fat as the teinperature rises and finally force it to tbe top of the mixture. TIio test tube containing tlio alcohol and water is placed in a vessel containing cold water, and tbe whole cooled to below 10° C. The disk of fat is dropped into the tube from the spatula, and at once sinks until it reaches a i^art of the tu be where the density of the alcohol-water is exactly equivalent to its own. Here it remains at rest and free from the action of any force save that inherent in its own molecules. The delicate thermometer is pi aced in the test tube and lowered until the bulb is just above the disk. In order to secure an even tempera- ture in all parts of the alcohol mixture in the vicinity of the disk the thermometer is moved from time to time in a circularlj-, jjendulous manner. A tube prepared in this way wilKbe suitable for use for sev- eral days, in fact, until the air bubbles begin to attach themselves to the disk of fat. In no case did the two liquids become so thoroughly mixed as to lose the property of holding the disk at a fixed point, even when • they were kept for several weeks. In practice, owing to the absorption of air, I have found it necessary to prepare new solutions every third or fourth day. The disk having been placed iu position, the water in the beaker glass is slowly heated and kept constantly stirred by means of the blowing apparatus already described. When the temperature of the alcohol- water mixture rises to about 6 degrees below the melting point, the disk of fat begins to shrivel, and gradually rolls up into an irregular mass. The thermometer is now lowered until the fat particle is even with the center of the bulb. The bulb of the thermometer should be small, so as to indicate only the temperature of the mixture near the fat. A gentle rotary movement should be given to the thermometer bulb, and I have thought it would bo convenient to do this with a kind of clock- work, although I have not carried this idea into execution. The rise of temperature should be so regulated that the last 2 degrees of increment require about ten minutes. The mass of fat gradually approaches the form of a sphere, and when it is sensibly so the reading of the ther- mometer is to be made. As soon as the temperature is taken, the test tube is removed from the bath and placed again in the cooler. A sec- ond tube, containing alcohol and water, is at once placed in the bath. It is not necessary to cool the water in the batli. The test tube (I use ice water as a cooler) is of low enough temperature to cool the bath sufficiently. After the first determination, which should be only a trial, the temperature of the bath should bo so regulated as to reach a maximum about lo.5 above the melting point of the fat under exam- ination. Working thus with two tubes about three determinations can be made in an hour, DAIRY PEOUUCTS, 47 After the test Lube has been cooled the globule of fat is removed with a small spoon attached to a wire before another disk of fat is put iu. Agreement of mullqiU determinations. FILTERED BUTTEK I'AT. Bogives C. No. 1, by ouo observer 33. r, No. 2, by auotlior 33. j No. 3, by a tbiril 33. ij No. 4, by a third 33.4 No. .'), by a third 34.4 A second set of observations made with the same butter gave — Degrees C. No. 1 33.7 No. 2 33.8 No. 3 33.5 N0.4 33.5 A different butter gave the following numbers : Degrees C. No. 1 34.0 No. 2 33.7 No. 3 33.8 No. 4 34.0 Another batter, "Creamery Tub," gave the numbers below : Degrees 0. No. 1 33.7 No. 2 33.7 No. 3 33.6 No. 4 „. 33.0 A neutral lard, from Armour & Co., Chicago, gave the following results : Degrees C. N0.I '. 42.8 No. 2 42.4 No. 3 .^ , 42.3 No. 4 r. 42.6 No. 5 4i.2 No. 6 42.0 An oleo oil, from Armour & Co., gave — Degrees C. No. 1 29.4 N0.2 21). 5 No. 3 ..: - 29.5 N0.4 29.7 No. 5 30.0 No. 6 ...30.3 N0.7 29.7 No. 8 39.8 48 I'OODS AND FOOD ADULTERANTS. Aiiotlier butter, shown by the microscope to bo adulterated, gave — Degreoa C. No.l 33.?; No, 2 „ 33.7 No. 3 33.5 No. 1777, a doubtful bnllei gave— Degrees C. No. 1 , 34.3 No. 2 34.5 No. 3 33.6 No. 4 34.0 No. 1779, also a doubtful butter, gave — Degrees C. No.l 34.2 No. 2 ' 33.5 No. 3 33.0 These results show that the method is capable of geueral application. Collecting together the mean results obtained with butter-fats the following table is obtained : Table No. 1.— Melting points, etc., of genuine butter. Serial number. 1745 1760 1768 1709 1772 , 1785 1786 Mean MolrincT Per cent. Specific point. soluble - acid. gravitv at40°C. i °C. ' 34.5 6.48 .911 34.3 4.52 .910 34.2 5. 21 .910 1 33.7 5.05 .912 31.0 5.20 .911 32.0 4.48 .012 [ 34^7 4.32 .912 33.8 4.86 .911 i Table No. 2. — Melting points, if-c, of halters of doaUfal piiriti/. Serial number. Melting point. Per cent. Soluble acid. Specifle 1777 ' I °C. 34.1 33.0 34.4 34.5 3.92 3. IC 3.02 3.97 .910 .909 .910 .910 1770 1780 1781 Mean 34.1 3.51 .900 The above were all boupht as pure butters. They are condemned on account of the low percentage of soluble acid, while by their specific gravity they appear to fall near the limit of purity The soluble acid in the above was determined by washing out and not by Reichert's method. DAIliY PRODUCTS. 49 Table No. 3. — Melting point of siibstances sold as iuttc'r, but proved liy analysis to he adulterated. Serial number. Melting point. Per cent. fl-.iluble acid. Speciflo gravity at 40° 0. 1755 1778 °C. 39.0 33.0 34.0 33. a 37.8 1.53 0.21 0.09 0.09 0.90 .900 .004 .900 .904 .905 1787 4694 4595 Table No. i.— Melting point, 6, 35.2 32.8 34.5 °0. +0.5 +0.4 +0.4 +0.7 -0.1 +1.4 2 . . 3 4 5 6 In every case except No. 5 in the above table it is seen that the melt- ing point of the disks of butter was raised by standing on water at or- dinary temi)eratures for twenty-four hours. In one instance, a butter whose melting point was 'S4P.5 C. stood in the form of disks from May 27 until August 3. An attempt was made on this latter date to determine its melting point. At a temperature of 75° C. the disk had not assumed a spherical shape, and the temperature could be carried no higher on account of approaching the boiling point of the alcohol. ADULTERATED BUTTERS. Number. Melting point directly disk was inado. Melting point after— Increase. 1 2 3 4 5 °C. 34.0 32.9 38.1 35.3 37.8 "C. Sdays CI. 4 18 hours . . 37. 24 hours . . 42. 46 hours ...35.3 44 hours ...40.3 °C. 20.8 4.1 5.0 0.0 2.5 Again iu every case but one a marked rise in the melting x^oiut. "OLEO OIL.' Melting' ' points i i °C- 'Qleo," at onco 29.C 'Olco," after 42 Jiours i 42.5 Increase 1 2.9 It would appear from the above results that adulterated buttera and butter adulterants show a g^Qator vis^ in melting points when the disks DAIRY PRODUCTS. 51 arc a day or more old than pure butter. The analytical data, however, are too meager to permit a definite statement of this kind. Should it prove to be true, it would be a valuable indication in the discrimation between pure and adulterated butters. An examination of the old disks with the microscope did not reveal a crystalline structure, and this change, therefore, must bo attributed to a molecular modification or superficial oxidation. KFFECT OF THE PRELIMINARY HEATING OF THE FAT TO DIFFERENT TEMPERATURES. A butter fat was melted at a low temperature and allowed to stand until the temperature had fallen to 30° O.; it was still perfectly fluid. The disks were formed by dropping on ice as usual. The melting point obtained was 33° C. The fat was now heated to 50° C. and treated as above; melting point, 33o.4 0. The temperature was then raised to 80° C. ; melting point, 32o.8 C. The above results, falling within the possible error of observation show that the temperature to which the fat is subjected before the for- mation of the disks has no appreciable efiFect on the point at which the fat particle becomes a sphere. EFFECT OF SUDDEN KISE OP TEMPEEATUBE. A sudden rise of temperature toads to greatly lower the melting point, A fat which showed a melting point of 35°.3 0. when determined in the usual way, melted at once into a perfect sphere when dropped into the water-alcohol mixture having a temperature of 29° C. At 28o.5 C. the globule was irregular. A disk of neutral lard, having by the usual method a melting ]Doint of 420.4 0., became at once a sphere when dropped into the water-alcohol at 360.2 0. Below that temperature the spheroidal shape was not sym- metrical. In all cases this phenomenon will appear. It may be suggested, therefore, with strict propriety, whether this may not be regarded as the proper melting point. Since the temperature at which the sphe- roidal state is assumed can bo determined within one or two degrees by a preliminary trial, it would not bo difficult to have a series of mixtures of water and alcohol arranged so as to show differences of temperature of 0O.5 C. By dropping the disks successively into these mixtures the instantaneous fusing point could be determined with accuracy. The method Set forth in the preceding pages has been proved by 165 determinations to be capable of giving agreeing results. Not only will llie numbers obtained by the same observer be concordant, but also those of different analysts. This arises from the fact that the moment of the assumption of the spheroidal state is easily determined even by an unpracticed eye. I have also noticed that in this condition pure butter and oleo are quite transparent, while on the other hand neutral 52 FOODS AND FOOD ADULTERANTS. yd aud adulterated butters are still somewbat opalescent. From tbis ■it is seen tbat tbo data obtained by the old method of determining the temperature of traus))areucy would differ somewbat from those obtained by the proposed procedure. Since the ago of the disk has a great deal to do with its melting point, I suggest that all determinations be made within fifteen minutes to two hours from the making of the disks. The method can also be extended to such bodies as parafBue and bees-wax. The melting point of a parafflne was found to be — Melting point. No.l <=C. 55 No.2 55.1 No.3 55 2 ISV4 53 3 An interesting phenomenon was observed in determining the melting point of the parafHne, which may be made to show, in a lecture experi- ment, the change of volume which bodies sometimes undergo in passing from a solid to a liquid state. The same mixture of water and alcohol used in the examination of fats, allowed the disk of parafflne to sink to about the same point as the disk of ftit. When the temperature rose, however, to within one or two degrees of the melting point, there was a sudden increase in volume. The pellet of parafflne rapidly rose to the top of the tube. To avoid this and keep the globule within the liquid 1 made a mixture of water-alcohol aud absolute alcohol. With this arrangement the rise of the parafflne was arrested in the upper third of the tube occupied by the absolute alcohol, where its assumption of the spheroidal state could bo readily observed. On placing the tube in a cooling bath the globule of parafflne rapidly sinks as it solidifies- The disks of parafflne and bees-wax are quite irregular, but nevertheless suitable for the process. The melting point of the one ^ami>le of bees- wax examined was found to be G4o.2 G. VISCOSITY. The speed with which at identical temperatures aud pressures dif- ferent oils flow through an orifice may bo used to dintinguish them from each other. For a description of the methods used in viscosime- try 1 refer to Allen's Com. Organic Analysis.' An ingenious and useful apparatus for viscosiiuetry has been invented by Babcock.- Babcock has applied his apparatus to the investigation of the ^-iscos ity of butter soaps with prouiisiug results.' ' Vol. 2, 2cl ed., pp. 104 cl scq. = Fifth Ann. Eopt. Bd. Control N. Y. Exp. Sta., pp. 316 et sen. "Ibid., x>p. 'i'iSetseq. DAIRY PRODUCTS. 55 REFRACTIVE INDEX OE OILS. Tlio (ISO of tlio I'ofriictoaiofcer ol:' Abb6 iu tlio examination oi butters liat) been proposed by MuUer.' Tlia priuciple of the use of this iustni nieiit iri, tliat the fats of pure butter possess a les5 refractive i)ower tliati the glycerides of a higher molecular weight. Tliif. subject lias also been treated by Skalweit.^ ESTIMATION OF SOLUBLE ACIDS IN BUTTER EATS. Method of Hehner and AngelU — Hehner and Augell, in Juno, 1874, pub- lished a pamphlet on butter analysis in which the details of their method were given. The followiug is au abstract of this method i"" A weighed quantitj^, usually 3 grams, of the fat was saponified iu a porcelain dish with caustic potash, with frequent stirrings with a glass rod. The clear butter soap was transferred to a flask or retort and decomposed by means of dilute sulphuric acid. This mixture, which contained sulphate of potash, glycerine, and the volatile acids in solu- tion and the insoluble fatty acids floating on the top, was distilled, and the acidity of the distillate estimated by means of a soda solution of known strength. The practical difficulties of (his method, such as the violent bumping of the boiling liquid and the impossibility of obtain- ing a distillate perfectly free from acid, led the authors to adopt a somewhat different method. This modification is based upon the different percentages of the insoluble fatty acids in butter and other animal fats. The insoluble acids, after saponification, were collected on a moistened filter paper, washed with hot water, and when the soluble acid was washed out, dried and weighed. They found the percentage of insoluble fats iu butter to vary from 85.40 to 8G.20, while in other animal fats the percentage of insoluble fatty acids was about 95.5. As will be shown further along, a small error is introduced into this method by washing the insoluble fatty acids on the filter. When this error is avoided, it is found ttiat the per- centage of the insoluble fatty acids in butter fat is considerably higher than the flgnre which has just been given. A detailed description of this part of the process will be given farther on. Turner^ suggested the employment of alcohol, with the view to hasten the saponification of (he fat; a modification of the process which has been almost uni- \er.sally adopted by analysts. About 30 or 40c:'. of spirits of whie are added tO' the butter in the por- celain dish and heated over the water bath to near the boiling-point. i~Arcliiv (1. Phanu., 18d6, p. 210. 2 Rep. d. Ver. Aiuil., Clicm., 1S8S, p. 181. ^Aualyst, 1877, p. 147. ■'Hassall, Eootl and its adiiUeratious, p. 446. , ^ Ihifl., p. 447. 54 FOODS AND POOD ADULTEEANTS. About 5 grams of solid caustic potash arc tlien added, and from time ta time a few drops of water, to facilitate its solution, the liquid being stirred all the time. lu this manner the butter becomes rapidly sapon- ified. The clear yellowish solution is then freed frnn all alcoliol over the water bath and the soap decomposed as already described. (Jarc should be taken to remove all the tilcohol, as a small quantity of the fatty acids might bo held dissolved should any alcohol remain, and so lead to an erroneous result. HeUner's method modified by BeicUcrt? — Weigh out 2^ grams of dried and filtered butter fat in an Erlenmeyfir flask of 150cc. capacity ; add 1 gram of solid potassium hydrate and 20cc. of 80 per cent, alcohol. This mixture is kept upon the water bath with constant shaking untiljthc soap obtained no longer forms a foamy, greasy mass.A Afterwards 50cc. of water are added to the flask, and the soap, after it has dissolved in water, is decomposed with 20cc. of dilute sulphuric acid (lee. of pure sulphuric acid to lOcc. of water). The contents of the flask arc now subjected to distillation, with the precaution of conducting through it a slow stream of air, in order to avoid bumping. It is also recommended to use a bulb tube with a wide opening, in order to avoid carrying over the sulphuric acid. The distillate, which, especially with fats poor in bntte:- and by rapid distillation, always deposits a little of the solid fat acids, is filtered through a moistened filter paper and collected in a 50cc. flask. After 10 to 20cc. are passed over it is poured back into the flask and the distilla- tion is novi continued until the distillate amounts to exactly 50cc The distillate, which, wheu the distillation ]ias gone on evenly, forms a water clear liquid, is immediately titrated with deciuormal soda lyfe after the addition of l drops of litmus tincture. The titration is finished if the blue color of the litmus remains constant for some time. Six analyses of an artificial butter fat required lO.Scc. of decinormal soda lye to ueu- tralizp the acid in the distillate. The genuine butter gave on three trials 14 50, 14.45, and 14.G0cc., re- spectively, of the decinormal soda. Two samples of cocoanut fat required 5.70 and 3.70cc. of soda lyo. ThirtecH samples of pure butter requii^d a mean of 13.97cc. of the decinormal soda. All the other fats which are used iu the adulteration of butter re- quired a much smaller amount of the decinormal soda for the saturation of the distilled acid. In artificial butters the proportion of pure butter and added fat may be calculated from the following formula: B=a (n—b). iu which n represents the most probable value of the number represent- ing the quantity of decinormal soda solution required either for pure butter or for the fat with which it may bo adulterated. Wheu B equals 'Zeit. Anal. Clicra., 1879, j)p. 68, cl seq. DAIRY PRODUCTS. 55 O, that is, when the substance coataius no pnre batter, the value of n may be taken at .30. We Lave, therefore, 0=a (0.30 -&) from which 6=.30. When B is equal to 100, that is, when the butter is pure, as has already been said, the most probable valne of «, according to the thirteen anal- yses given, is 13.97, or in round numbers 14±4:5, then we have the equation 100=a (14.00± 0.45-0.30) and from this the value of a=7.30zl=.24. The above equations may therefore be condensed into B = (7.30± 0.24) (n — 30), that is, in order to find the probable butter content of a fat mixture subtract from the number of the cubic centimeters of deci- normal soda lye used for titration .30 and multiply the remainder by 7.30. The probable «rror which will be met with by this estimation amounts to ±0.24(11-0.30). Medicus and Scherer^ examined the method of Eeichert and found it to be quite exact. For pure butter they found the quantity of decinormal soda lye required should be 13cc. ; a mixture of equal pnrts of butter fat and tallow required 7cc. Two parts of butter fat and one of tallow required O.lcc; three parts of butter fat and one of tallow required lO.lcc. The authors call attention to the fact that melted butter fat slowly cooled may separate into portions requiring different quantities of the decinormal soda for the saturation of the distilled acid which they afford. Two and one-half to 3 iwuuds of pure butter fat were used. This was melted and allowed to cool with continued stirring in order to secure a i)erfectly homogeneous mass. 2J grams of this mixture, by Eeichert's method, required 14cc. of decinormal soda. The fat was now again melted, poured into a large beaker glass, and uncovered allowed to cool without stirring. The solidiflcatiou took place slowly. After solidification 2| grams from the upper layer required 13.3cc..of soda. Allen ^ also highly recommends Ecichert's method. He uses it as ibl- lows : Weigh out^ grams ol the clarified butter fat and saponify in a closed llask (a closed flask has been used in the work of the Chemical N Division with butter since 1883) with 2occ. of approximately — KOH. Transfer the product to a porcelain basin and evaporate the alcohol at a steam heat. Dissolve the residue in waler, add some fragments of pomace coiled round with platinum wire, and distil gently until 50cc. N have passed over. Titrate the distillate with — caustic alkali using pheeol-phthaloin as an indicator. iZeifc. Aual. Chom., 1880, pp. 159 ct»cs; the ebullition continued from beginning to end as quietly as could bo desired. MeisseP has described a modification of Eeichcrt's process as follows: Five grams of the melted and filtered butter fat are treated iu a 200cc. flask with 2 grams of stick alkali and 50cc. 70 per cent, alcohol. After complete saponification the alcohol is evapoi'ated. The soap is dissolved in lOOcc. water and decomposed with 40cc. one-tenth UaSOj. The flask is supplied with some pieces of pumice-stono and connected by means of a bulb with a condenser.- The distillation is continued until llOcc. are drawn over. After fil- tration lOOcc. arc titrated in presence of litmus with onotenth 1*J" potash and the number of cubic centimeters required increased by one-tenth. If less than 2Gcc. of the alkali solution are required in the titration the butter may be suspected of falsification. Mode of procedure in Reicherfs method {used by Dr. G. A. Crampton, Department of Agriculture). — About 2. ,5 grams of the melted butter fat are weighed out by means of a small piiietto and beaker, which are weighed again after the sample has been taken out, and run into a bot tie provided with a patent India rubber stopper; 25cc. of a solution of (approximately) semi-normal alcholic potash is added, the bottle dosetl and placed in the steam bath until the contents are entirely saponified, facilitating the operation by occasional agitation. The bottle is then removed from the bath, allowed to stand a few moments until partially cooled off", when its contents arc transferred to a porcelain evapoi'ating dish, the bottle being rinsed with a little alcohol. The alcohol is then driven off' as rapidly as possible, and when the mass of soap and alkali is nearly dry, it is dissolved up in 25cc. of water, and transferred to a suitable flask of about 200cc. capacity, which is fitted with a delivery tube and condenser; the delivery tube '.s carried up about 8 inches be fore it is bent to enter the condenser and a bulb is blown in it just below ' Second Ann. Ropt. N. Y. S. Bd. of Health, p. 52G, != Ding. Poly. ,T., vol. 2.33, p. 229. 58 FOODS AND FOOD ADULTERANTS. the elbow aud filled with broken glass or glass wool. After the soap solution has been transferred to this Msk, the evaporating dish is rinsed out with 25cc. more water, which is added to the contents of the flask, and the fatty acids are then set free by the addition of 20cc. of a solution of phosphoric acid,' making the liquidracasure in all about 70cc. Heat is applied gently at first, and gradually increased until the distillate comes over regularly. When 60cc. have distilled off the operation is finished and the distillate is titrated with one-tenth alkali, using phenol- phthalein as an indicator. I have adopted phosphoric acid in preference to sulphuric for setting free the fatty acids, because it is not so liable to carry over as the lat- ter; much greater care is necessary when sulphuric acid is used. Be- fore the modification of the delivery tube was adopted, I frequently found Hj SO4 iu the distillate. Thus, before using the bulb, two blank experiments required 1.8 to 2.0cc., one-tenth alkali, for neutralization and gave a perceptible precipitate of BaS04. After adding the bulb I found blanks occasionally to require as much as .8cc. when the distillatiou had not been carefully watched. The following comparative results show that there is practically no difference which acid is used, when the operation is carried on with care. The processes used were identical, except that in the second, 20cc. of 10 per cent, sulphuric acid was substi- tuted for the phosphoric acid. The results are for 2.5 grams of fat. No.l No. 2 C With pbospboric acid . \r [ With snlpliuric .acid . ! With phosphoric acid. 12.7 12.7 15 No. 4 ] With suiptinric acid j 15. 3 i With phosphoric acid ( With snlphuric acid I Willi phosphoric acid I With sulphuric acid 13.1 13.2 15.3 14.8 12.0 12.7 14.1 14.0 12.7 12.0 14.5 14.9 Blanks should always bo run, and will be generally found to require .1 to .See. of the deci-normal soda before they will show the color with tlie phenol indicator. Koettstorferh process'' {as used in this laboraiory). — About 2.5 grams butter fat (filtered and free from water) are weighed into a patent rubber- stoppered bottle ancllfcc. (approximately) semi normal alcoholic potash added. The exact amount taken is determined by weighing a small pipette with the beaker of fat, running the fat into the bottle from the pipette aud weighing beaker and pipette again. The alcoholic potash is measured always in the same pipette and uniformity further insured by always allowing it to drain the same length of time (thirty seconds). Tbe bottle is then placed in the steam bath together with a blank, con- raining no fat. After saponification is complete, and the bottles cooled down, the contents are titrated with accurately semi-normal hydro- ' Made by dissolviug 200 grams of commercial glacial phosphoric acid in a litre of ivater; its specilio gravity is 1.140. 2 Zcit. Anal. Chem. 1879, p. 199 ; Analyst, 1879, p. 103. DAIRY PRODUCTS. 59 chloric acid, using pUeuolpbthaleiu as an iucllcator. Tbc number of cubic ceutiineters of tbe acid used for tb'o sample deducted irnm the number required for tlie blank gives the number of cubic centimeters which combines with the fat, and the saturation equivalent is calculated by the following formula, in which W equals the weight of fat taken iu milligrams and N the number of cubic centimeters which lias com- bined with the fat. 2 W Sat. Equiv. =^r-' For pure butters the mean value of N is about ^ when 2.5 grams of butter fat are taken, and the saturation equivalent may vary from 230 to 255. On the other hand for lards, tallows, and otlier fats commonly used for adulterants the equivalent rises to 270 and 290. Tliesc num- _ bars, therefore, give a fair idea of the iinrity of a butter, or if an adul- teration has been practiced, of its extent. ESTIMATION OF INSOLUBLE ACIDS IN BUTTER FAT. Method of Hehner.^ — This method consists in saponifying the fat with alcoholic caustic potash, subsequent evaporation of the alcohol, decom- position of the soap witli sulphuric or hydrochloric acid, and the deter- mination of the insoluble acid gravimetrically. The process as originally described by Hehner is carried on as fol- lows : The filtered butter fat is weighed in a beaker glass with a glass rod ; 3 or 4 grams are taken out by means of the glass rod and put in an evaporating dish about o inclies in diameter; the glass rod witli the fat which remains on it is left in the evaporating dish. The beaker glass is again weighed and the amount of butter fat determined from the difference in weight; To the weighed fat arc added 50cc. alcohol and 1 to 2 grams of pure caustic potash. Tlie alcohol is warmed gradually upon the water bath, by wliich the butter fat, especially when stirred witli the glass rod, easily dissolves to a clear yellow liquid, giving off a dis tinct odor of butyric ether. The heating is continued for about five minutes and distilled water is then added drop by drop to the mass. If this produces a cloudiness in the liquid, duo to the separation of uu- decomposed fiit, the heating is continued somewhat longer until finally the further addition of water does not produce the least cloudiness. Should, however, through the careless addition of water, some fat sepa- rate ill the form of oily drops which do not again easily pass into tbc solution in the diluted alcohol, the whole mass must be evaporated to dryness and treated anew with alcohol, or the experiment be done over again with some fresh fat. ■ The clear soap solution is now evaporated on the water bath to the consistency of sirup in order to. remove the alcohol, and the residue ' Zcit. Anal. Chem. 1877, pp. 145 ct seq. 60 POODS AND FOOD ADULTERANTS. dissolved in 100 to I50cc. of water. To the clear liquid hydrochloric or sulphuric acid is added to a strongly acid reaction, in order to de- compose the soap. The inS'duble fat acids are uow separated out iis a cheesy mass, which for the most part quickly rise to the surface. The heating is continued for a half hour until the fat acids are melted to a clear oil and the acid aqueous liquid is almost completely clear. Mean- while a thick Swedish filter paper of 4 or 5 inches in diameter has been dried in a water bath. The filter paper must be of tlie best quality and so thick that even Lot water will only pass through it drop by drop. A small beaker glass is now weighed, afterwards a filter tube, and then the filter tube and the filter ; in this way is obtained the weight of the filter and the beaker glass. The weighed filter is now fitted to a funnel moistened and half filled with water. The aqueous liquid and the melted fat are then poured out of the cvaporatiug-disli into the filter, and the dish and glass rod arc washed with boiling water. There is no difficulty in bringing all of the fat on the filter, so that the evaporating dish does not a2>])ear in (he least greasy. To make sure, however, the dish can be washed with ether and the liquid obtained added to the fatty acids. The fatty acids are washed upon the filter with boiling water. The filter should be never more than two-thirds full. If the liltrate tested with sensitive litmus tincture does not appear acid, the rest of the water is allowed to run through,. and the funnel is dipiied iuto a beaker- glass filled with cold water, so that the surface of the liquids within and without the funnel a,re at the same level. As soon as the fatty acids have solidified the filter is taken out of the funnel, placed in the weighed beaker-glass, and dried in a water-bath to constant weight. The dry- ing is continued for two hours and the filter paper is then weighed. It is again dried for two and a half hours aud weighed a secon7T, pp. 10,11. DAIRY PEODUCTS. 61 placed ill a basin with Iiot water, and kept boiling for a considerable time, until oil adding water uot the faintest turbidity occurs. Teu ounces of water are added, the os'aporatiou continued (just short of boiling) until all traces of alcohol are dissipated. The contents of Iho flask are then made up to 7 ounces with nearly boiling water, and a good fitting- cork having been introduced througli which just passes a tube 2 feet long and ending in a small funnel, 5 grams of full strength sulphuric acid arepourcd in down the tube followed by some water. The whole is then agitated with a circular motion until tjie soap, which rises suddenly, is changed into a perfectly clear and transparent stratum of fatty acids. The flask and contents are then cooled down to 40° F., till a perfectly solid cake of fatty acid forms. A few drops of cold water are run in to wash the tube, and, the cork having been removed, a small jiiece of fine cambric is placed over the mouth of the flask, held in situ by an ordinary Ihdia- rubber ring. The fat cake is caused to detach itself from the sides of the flask by a gentle movement, and then tlie filtrate is decanted, with- out breaking the cake, into a litre test mixer with a good stopper. About an ounce of cold water is poured into the flask through the cam- bric, and the whole cake and flask rinsed out by gently turning round, and the washings added to the filtrate. Six ounces of water at 120° F. are now added through the muslin, which is then quickly detached, and the cork and tube inserted; the whole agaiu heated, this time to 200° F., and kept constantly agitated Avith a circular but uot a jerky mo- tion for five minutes. This agitation so divides the fat that it almost forms an emulsion with the water, and is the only means of thoroughly and rapidly washing fatty acids without loss. lu practice no butyric acid comes off at 200° F., but any trace that might do so is caught in the long tube. The cooling and filtering are then again proceeded with as above described (the filtrate being added to the contents of the test mixer), and the washings are repeated alternately, cold with 1 ounce, and hot with G ounces of water, until they do uot give the slightest change to neutral litmus. After thoroughly draining the residual cake by letting the flasks stand upside down for some time, the cambric is re- moved and the flask is laid on its side in the drying oveu, with a sup- port under the neck, until the acids are thoroughly fused, wheu they are poured while hot into a tarred platinum capsule, dried and weighed. The film of fatty acid still remaining on the flask is rinsed out with ether and dried in a small weighed beaker, and the weight added to the whole. If any drops of water be observed under the fatty acids in the capsule after an hour's drying the addition of a few drops of abso- lute alcohol will quickly cause them to dry off. If any trace of fat is on the cambric it should be also dried and extracted with ether, but with, care not to break the cake at the last pouring off this does not occur. The process is absolutely accurate, and the merest tyro cannot make any loss so long as he does not deliberately shake the melted acids 62 FOODS^ AND FOOD ADULTERANTS. against the cork, which he could not do if be practiced a circular agita- tion while wiishinp. The filtrate iu the test mixer is now made to a definite bulk of 1 litre, aud iu 200cc. the total acidity is taken with a weak solution of sodium hydrate. The solution I generally use represents .01 of NH3 in each cubic centimeter, as it serves also for nitrogen combustions ; but a use- ful strength would bo deciuormal soda, containing .004= NaOH in each cubic centimeter. The acidity found is multiplied by 5, calculated to H2 SO4 and noted as " total acidity as H2SO4" ; lOOcc. are next taken, and precipitated with barium chloride in the presence of a strong acid- ulation, Avith hydrochloric acid, well boiled and washed by three de- cantatious, boiling each time ; and lastly on a filter, till every trace of soluble barium is removed. The precipitate is dried, ignited, and weighed as usual, multiplied by 10, and calculated to H2SO4 and noted as '• total sulphuric acid." Lastly, lOOcc. are evaporated to dryness over the water bath in a tarred platinum dish holding 120cc. and furnished witli a cover of platinum foil, also tarred. When dry the dish is covered and heated over a Bunseu till all fumes cease, and, a fragment of pure ammonium carbonate having been added, the whole is again ignited and weighed. The amount of potassium sulphate found is multiplied by 10 and calculated to H2SO4 and noted as "combined sulphuric acid." OTHER METHODS. Liebschlitz' has described a method for the examination of butter and oleomargarine, being a modification of David's process.^ The fatty acids are saponified by baryta in alcoholic solution. The alcohol is evaporated aud the glycerine washed out. The excess of baryta is removed by exactly neutralizing with suliihuric acid and fil- tering. The residue, however, is not merely a mixture of glyceiine and water. The addition of alcohol in excess throws down a considerable quantity of salts which have remained in solution. The alcohol is again evaporated and the glycerine obtained, dried, aiid weighed. Pure but- ter yields about 1.3.7 percent, of glycerine iu ihis way, while oleomar- garine yields only 7 per cent. The glycerine from butter when ignited left about 5 per cent, ash (barium) whila that from oleo left only .?< to .0 per cent. RESULTS OF UANSSEN'S INVESTIGATIONS. Dr. August Hanssen^ has made a cogiparative study of the more important methods of analysis mentioned in the foregoing pages and has reached the following conclusions : (1) Tho dctcrmiuation of tlio moltiug-points of tlio difforou t fats is to bostrongly roc- onmiendecl. ' Analyst, If 85, p. Ill, ct seq. "Compt. Reud., 188C, vol. XCIV, i). 1427. ' Studien iiber deu chomischen Naoliwcis frouidcr Fette iiu Butterfette, p. 34. DAIEY PRODUCTS. 63 (2) The olementary analysis of the fats gives uo indicatiou whether adulteration has been practiced or uot. (3) Buttor fat is not easily decomposed by beat. With a rise of temperature the de- composition is at first, for the greater part, conflnod to the glycerides of the uon-volatilo acids. (4) In the sapouilication of batter fat by Hehner's method there is no appreciable loss of ethers. There is also no loss of volatile acids in direct saponilioation in alcohol. (5) For the detection of foreign fats in butter, the best method is that of Eeichert- Meissel, and next that of Koettstorfer. (6) For a comparative test of the various methods the mean for insoluble acid (Heh- ner) is taken at 87.50 per cent. ; for Koettstorfer's equivalent 227, and for Eeich- ert-Meissol 28.8. (7) The washing out of the soluble acids must not bo carried too far ; for 2 to 2.5 grams of fat three litres of water seem best. ABSORPTION OF BROMINE AND IODINE BY BUTTER FATS. Oleic acid is capable of absorbing for each formula molecule one mole- cule of bromine or iodine. Stearic acid does not possess this property. Therefore it is easj' to approximately determine the relative quantities of these two acids when present in the same fat by the quantity of the halogen absorbed. Thus (stearic acid) OjoHsaOj does not absorb bromine and iodine, while (oleic acid) does. OinHsiOz-l- gp-=Cj8H34g^02. The glycerides of the above acids, i. e., the natural fats, have the same absorptive power as the acids themselves. Mills, Snodgrass & Akitt* have determined the quantities of bromine absorbed by various fixed oils. The method employed is as follows : The weight of dry oil taken is about .1 gram ; this is dissolved in a stoppered bottle of lOOcc. volume by GOcc. dry COI4. To this is now added a solution of about 8 grams per litre of bromine dissolved in OOI4. The addition of this reagent is continued until apermanent coloration is produced at the end of fifteen minutes. If greater accuracy is required an excess of bromine may be added, afterwards treated with a solution of KI and some starch, and titrated with a standard solution of sodium thiosulphate. The excess of bromine may also bo determined by titration with a standard solution of yS-naphthol in COI4 HiibP has described the reactions of fats with iodine. The reagents employed are an.alcoholic solution of iodine and HgCl2, in the proportion I2: HgOIz. The iodine is dissolved (25 grams) in absolute alcohol (500cc.) The mercuric chloride is also dissolved (30 grams) in nearly absolute alcohol I Journ. Soc. Cliem. Industry, vol. 2, p. 435, and vol. 3, p. 366, ?Ping. Poly. J., vol. 2/3, p. 281. G4 FOODS AND FOOD ADULTERANTS. (OOOcc). After fllteriug it ifi added to the solution of iodine. After stand- ing twelve bours its iodine strengtli is determined by titration with deci- normal solutions of sodium thiosulphate. From .8 to 1 gram of the fat is dissolved in lOcc. cbloroform. To tliis,in a stoppered bottle, is added the sohuion of iodo mercuric chloride (20 to 30cc.) After standing for two hours the solution must still be brown. Add now 10 to 15cc. 10 per cent, water solution of KI and dilute with water to lOOcc. The free iodine is then determined by standard thio- sulphate of sodium. The compound formed when pure oleic acid is treated as above is chloroiodo-oleic acid (GjoHjjIClOi). Moore^ has tried Hiibl's method and finds it valuable. The fat of butter containing less oleic-glycerides than the fats ordi- narily used as adulterants for butter shows, consequently, less bromine or iodine absorption : Kind of fat. Butter fat Lard Tallow CottoD-seed oil. Cocoanut oil . . . Absorption of Absorption of bromine. iodino. Per cent 24. 5 to 27. 9 37.3 60. 5.7 Per cent. 26. to 35. 50. 61.0 40. 109. 8.9 105, The method is therefore of value in determining the nature of the fat under examination. If there be a mixture of two fats the methods will also give a fairly good approximation of the percentages of each. Thus, let X be the percentage of one fat and y of the other. Then— X -f i/=100 Let m be the representative of the iodine absorption of x and n ofy, and let A be the number found for the mixture. Then— 100 (A — n) m — n Jones^ points out the changes which butter fats undergo when kept for a long while at a high temperature. He notices in a few hours that the specific gravity of such a fat kept at 100° F. increased from 912.1 to 912.G. He uses the following method of estimating the insoluble fatty acids : REAGENTS. (a) Tn'onty-eigbt grams roughly woigliett of the best potassimu hydrate dissolved to a litre with alcohol, specific gravity .840, (b) Twouty-fivo grams of strong sulphuric iieid made up to a litre of distilled water. (c) Decinormal soda solution of exact strength. Saponification is carried on in liasks about 250cc. capacity. About 6 grams of butter fat are used i'or Ciicli Rnpniiilication. The alcoholic 'Am. Chcm. Jonr., vol. (i, p. OUi. ^ Analyst, 1878, pp. 19 ct scq. DAIRY PRODUCTS. G5 potasti is measured by 50cc. pipette, wliicli is allowed to drain into eacli flasli for exactly the same length of time. The flasks are closed with glass marbles, placed upon the water bath and saponified at a temijera. tare of about 50° C. After perfect solution has taken place they are allowed to remain for an hour or two and then diluted with slightly warmed distilled water. Into each flask and likewise into two beakers containing 50cc. of the alcoholic potash are now run about Ice. of the approximately semi-normal acid more than is necessary to neutralize the 50cc. of alcoholic potash. The excess of the acid over the potash is afterwards determined by the decinormal soda. The flasks after the addition of the acid are nearly filled with water and gently agitated, then placed on the water bath until the fatty acids form a clear stratum. They are then allowed to cool and stand over night. On the following morning the solutions from the cakes of fat are poured into a filter. When the whole solution is ou the filter the flasks are rinsed with 15 to 20cc. of cold distilled water, and when this is poured oft" about 150cc. of hot water are added and the flasks briskly shaken for a minute or two. Two good washings with hot water are believed to be enough. The filtrates are now treated with the decinormal soda, the amount for the excess of sulphuric acid deducted, the remainder being the index of the soluble acids of the butter, which are calculated as butyric acid. The insoluble fatty acids in the flasks and the small amount that may have passed on to the filter paper are allowed to remain until the fol- lowing day, by which time the latter become air-dried and in a fit state to rinse with ether. The fat in the flasks is then melted and poured, together with the rinsings of the ether, into counterpoised dishes with perpendicular sides, about 3 inches across and IJ inches deep, and the filter papers are also thoroughly washed with ether, the funnels being covered during the process. After the evaporation of the ether a little absolute alcohol is added, the dishes dried in the water-bath for half an hour, cooled, and weighed. Afterwards they are again dried for twenty minutes and reweighed. For a more convenient method of manipulating fatty acids, Blyth,' has recommended the following: The flask in which the saponification is made should be of 300 to 400cc. capacity, with a rather long and narrow neck, furnished with an accu- rately fitting stopper, through which two tubes pass, one provided with a stop-cock to let out the liquid, and therefore terminating on a level with the interior surface of the stopper, the other to let in the air, pro- longed to nearly the bottom of the flask and externally bent siphon- like. The fat is saponified in the flask and the soap decomposed in the usual way ; when this is eft'ected, the stopper is inserted, and the flask is turned upside down and kept in that position during the entire wash- ing process. Directly the whole of the fat has risen to the surface the lower liquid is run off', whilst hot or cold water is introduced by opening 'Analyst, 1878, p. 112. 19330— No. 13 5 66 FOODS AND POOD ADULTERANTS. the stopper under the water aaJ simultaneously sucking at the syphotl. Thus all waiting for tVie fat to cool is discarded, and reasonable quan- tity of water can be rapidly used to thoroughly wash the fatty acids, and a filter is not required. DETERMINATION OF SOLUBLE AND INSOLUBLE FAT ACIDS. METHOD ADOPTED BY ALLEN.' (a). Dissolve 14 grams of good stick-potash in 500cc. of rectified spirit, or methylated spirit which has heen redistilled with caustic alliali, and allow the liquid to stand till clear. This solutioa will be approximately seminormal. (6). A standard hydrochloric or sulphuric acid of approximately seminormal strength. (o). Accurately prepared decinormal caustic soda. Each l.Occ. contains .0040 grams of NaOH and neutralizes, .0088 grams of butyric acid, 041180.2. A quantity of the butter fat (separated from water, curd, and salt, as described on page 15'2) is melted in a small beaker, a small glass rod introduced, and the whole allowed to cool, and then weighed. It is remelted, stirred thoroughly, and about 5 grams poured into a strong 6-ounce bottle. The exact weight of fat taken is ascer- tained by reweighing the beaker containing the residual fat. By means of a fast-delivering pipette 50cc. measure of the alcoholic potash (solution a), is run into the bottle, aud the pipette drained exactly thirty seconds. At the same time another quantity of 50cc. is measured off in an exactly similar manner into an empty flask. The bottle is fitted with an india-rubber stopper, which is tightly wired down, and is placed in the water-oven, and from to time removed and agitated, avoiding contact between the liquid aud the stopper. In about half an hour the liquid will appear perfectly homogeneous, aud when this is the case the saponification is complete, and the bottle may be removed. When sufficiently cool, the stopper is re moved, aud the contents of the bottle rinsed with boiliug water into a flask of about 250cc. capacity, which is placed over a steam bath, together with the flask containing merely alco- holic potash, nntil the alcohol has evaporated. Into each of the two flasks is now ruu about Ice. more seminormal acid (solution b) than is required to neutralize the potash, and the quantity used accurately noted. The flask containing the decomposed butter fat is nearly filled with boiling water, a cork with a long upright tube fitted to it, and the whole allowed to stand ou the water-bath until the separated fatty acids form a clear stratum on the surface of the liquid. When this occurs the flask and contents are allowed to become porfeolly cold. Meanwhile the blank experiment is completed by carefully titrating the contents of the flask with the decinormal soda, a few drops of an alcoholic solution of phenol- phthalein being added to indicate the point of neutrality. The fatty acids having quite solidified, the resultant cake is detached by gently agitating the flask, so as to allow the liquid to be poured out, but avoiding fracture of the cake. The liquid is passed through a filter to catch any flakes of fatty acids, and is collected in a capacious flask. If any genuine butter bo contained in the sam- ple, the filtrate will have a marked odor of butyric acid, especially on warming. Boiling water is next poured into the flask containing the fatty acids, a cork and long glass tube attached, and the liquid cautiously ]\oated till it begins to boil, when the flask is removed and strongly agitated till the melted fatty acids form a sort of emulsion with the water. When the fatty acids have again separated as an oily layer, the contents of the flask should be thoroughly cooled, the cake of fatty acids detached, ' Commercial Organic Analysis, vol. 2, 2d ed., pp. 156 et acq. DAIRY PEODtCTS, 67 and the liquid filtered as before. This process of alternitte Wastliugs Iti the flask by agitatioa with boiling water, followed by cooling, and filtration of the wash-water, is repeated three times, the washings being added to the first filtrate. It is often difficult or impossible to obtain the wash-water wholly free from acid reaction, but when the operation is judged to be complete the washings may be collected separately and titrated with deoinormal soda. If the measure of this solution required for neu- tralization does not exceed 0.2co. further washing of the fatty acids is uunecessary. The mixed washings and filtrate are next made up to l,0O0cc., or some other definite measure, and an aliquot part carefully titrated with decinormal soda (solution c). The volume required is calculated to the whole liquid. The number so obtained repre- sents the measure of deoinormal soda neutralized by the soluble fatty acids of the but- ter fat taken, plus that corresponding to the excess of standard acid used. This last will have been previously ascertained by the blank experiment. The amount of soda employed in this is deducted from the total amount required by the butter fat quan- tity, when the difference is the number of cubic centimeters of standard soda corre- sponding to the soluble fatty acids. This volume multiplied by the factor 0.0088 gives the butyric acid in the weight of butter fat employed.' The flask containing the cake of insoluble fatty acids is thoroughly drained and then placed on the water-bath to melt the contents, which are poured as completely as possible into the (wet) filter, through which the aqueous liquid was previously passed. The fatty acids are then washed on the filter with boiling water, to remove the last traces of sparingly soluble acids. The filter is then placed in a small dry beaker and treated in the manner described on page 38, the main quantity of fatty acids and the supplementary portion siibsequently dissolved out of the flask and filter being weighed separately.^ When it is only required to determine the insoluble acids of butter fat the foregoing tedious mode of operating may be avoided by diluting the soap solution obtained by saponifying 5 grams of the fat till it measures about 300co. The large excess of alkali is then neutralized by cautious addition of hydrochloric acid, and the hot solution treated with a slight excess of barium chloride or magnesium sulphate. The precip- itated barium or magnesium soap is well washed with hot water, and then rinsed off the filter into a separator, where it is decomposed by dilute hydrochloric acid. The resultant layer of insoluble fatty acids is washed by agitation several times wi th warm water, and is then treated as directed on page 38. In the analysis of butter fat, the sum of the insoluble fatty acids by weight and of the soluble fatty acids, calculated as butyric acid, should always amount to fully 94 per cent, of the fat taken. In the author's own experience the sum more frequently approaches or even exceeds 95 per cent., especially if the butter be adulterated. The soluble fatty acids, calculated as butyric acid, should amount to at least 5 per cent., any notably smaller proportion being due to adulteration.' The insoluble fatty 'Thus, suppose an experiment to have given the following figures: Weight of butter fat taken, 5.120 grams; deoinormal soda required in the blank experiment, 3.90cc. ; decinormal soda required to neutralize one-fifth of the solution of the soluble fatty acids, 6.25C0. ; then .008 (31.25—3.9) X 100 5T20 ^^ I*®''' ''^'^^• 2 Instead of weighing the insoluble fatty acids, W. F. Perkins has proposed to dis- solve them in alcohol, and titrate with standard alkali in the manner described on page 76. The objection to this plan is the somewhat variable character of the fatty acids themselves. Calculating their neutralizing power on the assumption that they are wholly stearic acid, Perkins found 92.0 and 91.7 per cent, of insoluble acids in pure butter fat. Calculated to oleic acJid these figures would not be materially mod- . ified, but their equivalents in palmitic acid are 83.3 and 83.0 percent, respectively. 'According to J. Bell, the proportion of soluble acids calculated as butyric acid not nnfrequently falls as low as 4.5, and the percentage of insoluble acids sometimes slightly exceeds 89,0. 68 FOODS AND FOOD ADULTERANTS. acids from genuine butter fat rarely exceed 83J per cent , occasionally reaching 89 per cent., but a sample ought scarcely to be regarded as certainly adulterated unless the insoluble acids exceed 89i per cent. As a standard for calculation 88 per cent, of insoluble acids' may be regarded as a fair average, the soluble acids being taken at 5i per cent. Allen, iu a later coatributioa to the literature of Keicliert's method, says:^ A farther experience in the employment of Eeichert's process for examining fats has led me to abandon the expression of the results in terms of butyric acid, in favor of a statement of the weight of caustic potash neutralized by the distillation from 100 grams of the oil. This is obtainable by multiplying the volume of decinormal al- kali neutralized by the distillate from 2.5 grams by the factor 0.2244.' The following table contains a number of results expressed in both ways : Butter or milk fat j Cow's Ewe's Goat's Poipoise's ■ Cocoanat oil Palm-nut oil Palm oil ■ Cacao butter Butteriue and oloomarg.irino Whale oil Do Porpoiao oil - Sperm oil Bottle-noae oil Menhaden oil Cod-liver oil Sesame oil Cottou-sced oil Castor oil i alkali re- quired by2.5 grams. ,2. S to 1.-). 2 13.7 13.0 li.3 3. 5 to 3. 7 2.4 0.8 1.0 1.0 3.7 13.5 12.0 1.3 1.4 1.2 1. 1 to 2. 1 2.2 0.3 1.4 0.2 to 11. to KOH re- quired by 100 parts of oil. 2.80 to 3.41 3.07 3.0.5 2. 51 0. 78 to 0. 83 0.54 0.18 0.30 0. 04 to 0. 30 83 2.80 2. 47 to 2. CO 0.29 0.31 0,27 0. 24 to 0. 47 0.48 0.07 0.31 Observer. Eeicbert, Caldwell, Moore, Allen, &c. Schmitt. Do. Allen. P-oicbort, Moore, Allen. Allen. Mooro. Do. Caldwell, Moore, Allen. Allen. Do. Do. Do. Do. Do. Do. Do. Mooro. Alien. From these results it is evident that the fats of different kinds of luillc (butter fats) are sharply distinguished from nearly all other fats by the large proportion, of soluble vola- tile fatty acids they yield by Eeichert's proce33. The most remarkable exception is presented by porpoise oil and some samiilea of whale oil. In porpoise oil I have found 5 per cent, of valeric acid, and Chevreul obtained as much as 9.63 iier cent. In a re. cent paper I jjointed out that in porpoise butccr the glyoeride of valeric acid appeared to replace the butyrin characteristic of the butter of terrestrial mammals. Some of the chemists who have employed Keichert's process take the precaution to filter the distillate before titrating it, so as to get rid of auy volatile acids which may be insoluble or very sparingly soluble in water. This plan may sometimes be adopted with great advantage. Thus when the solution of the soap obtained by saponifying cocoanut or palm-nut oil is acidulated and distilled, a notable proportion of lauric acid passes over and solidifies in the condenser or on the surface of the distillato; and ' The percentage of adulterant in a butter fat may be calculated from the following formula, in which F. is the percentage of foreign fat and 1 that of the insoluble fatty . acids: F= (1-88)X13.3. Or each 0.1 per cent, of soluble acids above 0.5 may be re- garded as showing the presence of 2 per cent, of butler fat. ^Analyst, 1887, pp. 11 et seq. n cc. of 1^ alkali contains 0.005GI gram of KOH; and -0^561 X 100 _ 2-244 DAIEY PRODUCTS. 69 I by adding water to the coateiits of the retort, again distilling, and repeating this process several times, a very considerable proportion of volatile fatty acids can be obtained from cocoauut oil. In assaying butter, the appearance of insoluble acids in the distillate -would furnish a valuable indication of the presence of coooanut oil, and they should bo removed by filtration, or the distillate will be found to neutralize so large a volume of alkali as considerably to diminish the practical value of the process as a means of distinguishing butter from butter substitutes, as has been pointed out by Moore and others. Latterly, I have adopted the plan of filtering t)ie distillate in all oases, washing the filter with cold water, and then immersing the filter, with-any adhering insoluble acids, in alcohol, which is then titrated with decinorraal alkali and phenol-phthalein. In the case of ordinary butters and butter substitutes the in- soluble volatile acids only neutralize about 0.2cc. of decinormal alkali. The question having recently been raised, the following experiments were made at my request by Mr. William Barraolough on a sample of butter fat, in order to ascer- tain the variation in the results of Eeichert's process produced by modifications in the methods of conducting the saponification and distillation: (1) Two and ahalf cubic centimeters of butter fat was saponified by alcoholic potash in an open basin, the alcohol evaporated off completely at a steam heat, the residual soap dissolved in water, the solution acidulated with sulphuric acid in slight excess, di- luted to 75oo. and distilled gently in a globular flask with side tubulure adapted to a condenser until 50cc. had passed over. The flask held 460cc. up to the side tube, and some fragments of pumice-stone coiled round with platiuum wire were added to the contents to promote evolution of vapor. (2) An exact repetition of No. 1 experiment. (3) Saponification was effected in a flask furnished with a long tube and heated by steam. The subsequent manipulations were the same as in experiment 1. (4) Saponification was effected in a well-closed bottle placed in the water oven. Other manipulations unchanged. (5) Manipulation exactly as in experiment 3, except that the distillation was con- ducted in a flask fitted to the condenser by a cork and bent tube. (6) Conducted as in experiment 3, except that the distillation was conducted in a retort. (7) Blank experiment with th« alcoholic potash employed in the previous experi- ments, the manipulation being that in experiment 3. The alcoholic potash was brown and not very recently prepared. JUxperiments. Decinormal alkaU for 2.5 grams. No 1 CO. 11 80 No. 2 : No. 3 No. 4 12 50 No. 5 No. 6 12.45 No. 7 These results show that a sensible loss occurs if the saponification bo-conducted in an open basin, doubtless owing to the formation of butyric ether. On the other hand, the exact nature of the distilling apparatus appears to be of little importance. This latter conclusion is not in accordance with the experience of some other chemists. Zalkowsky and Grroger' have studied and modified Haussman's method^ of volumetric fat analysis. This method is based on the fact iBer. Chem. Gesel., vol. 16, p. 1140. =Ding. Poly., J., vol. 244, p. 303, and vol. 246, p. 286. 70 FOODS AND FOOD ADULTERANTS. that an alcoholic solution of a fat acid is immediately saponified by the addition of alcoholic potash, while a neutral fat requires timt) and heat to secure complete saponilication. When, therefore, an alcoholic solution of fat acids and neutral fats to which phenol-phthalein has been added is titrated with caustic potash? the red color only appears when the fat acids are saponified, and only comes ])ermanently when all the fats are saponified. When the red color appears an excess of caustic potash is added and the whole boiled for half an hour to saponify all the neutral fats and retitrated, whereby the amount of caustic potash required to effect the saponification of all the fats is ascertained, and the quantity of potash required for each titra- tion represents the relativ^e proportion of fat acids and neutral fats in the mixture operated on. When a neutral fat is saponified the follow- ing reaction takes place : C3H, (C„H,„_,0,),+ 3 KOH=03H, (OH)3+3 K (0„H,„_,O,) and therefore every litre of normal potash splits up one-third equivalent of glycerine, i. e., 30.667 grams. One cubic centimeter normal potash is therefore equivalent to 0.030667 gram glycerine. The theoretical yield of fat acids could also be calculated by the following formula : O3H5 (c„H,„_^o,)3=- 03n,o„n,„_.o,. Then one litre normal potash represents one-third equivalent of gly- cerine residue, or 12.667 grams. If 5cc. normal potash have been em- ployed the weight of the glycerine residue would be .012667x5. F. W. A. WolP gives the results of his studies with butter and artifi- cial butter. Mixtures of pure butter with "oleo oil" were made and examined by the methods of Koettstorfer and Eeichert, and the results compared with theory. The following numbers were obtained : Por ceDt. but- ter. Koettstorfer. Eeichert. Calculated. Found. Difference. Calculated. Pound. Difference. 20 40 mg. 200.8 206.2 208.5 211.5 217.7 mg. 201. 4 207.3 209.0 212.7 215.0 mg. +0.6 +1.1 +0.5 +1.2 -2.1 cc. 2.98 5.81 6.55 8.65 10.37 3.11 0.39 7.08 9.00 n.56 cc. +0.13 +0.58 +0.53 +0.41 +1.19 50 60 80 1.1 0.57 Note. — It Is very oaay to get exact results by the above metbod of mixture. But- ter and an oil are used whose behavior with the reagents employed was determiued by preliminary experiment. The case is very different when the analyst is called on to examine an unknown sample. The butter in an unknown sample may have quite a different per cent, of volatile acid from that used in the samples given. The value of this method, therefore, is seriously impaired for determining the extent of adul- terations iu case where the separate examination of the constituents is impossible. 'Zeit. Anal. Chem., 1884, p. 28, and Am. Chem. Jour., vol. 9, p. 62. DAIRY PRODUCTS. 71 The author gives a table of the analyses of 37 samples of batter and butter substitutes giving the percentage of water, the specific gravity at 370.7 C, the melting point determinetl by the method of Blyth, the milligrams of KOH required in Koettstorfer's method and of cubic centi- meters by lleichert's method.^ The author concludes that the melting point is of no value in discrim- inating between pure and false butters, but the specific gravity, the, sa- ponification process, and the distillation of the volatile acid are sufftcient to distinguish at once between the true and the false. The oleo oil employed had a mean specific gravity at 37°.7 C. of 0.90369 and its melting point was 27o.6 G. The "neutral" had a specific gravity of 0.9053 and a melting point of 38°.! 0. BEHAVIOR OF COCOANUT OIL WITH SOME OF THE METHODS USED IN ANALYSIS OF BUTTER FATS. R. W. Moore, in a paper read before the American Chemical Society, September 18, 1885,^ calls attention to cocoanut oil as a substitute for butter. He gives its fusing point at 24°. 2 C. to 24°.3 C, and calls at- tention to the fact that its specific gravity is higher than that of butter fat. It is also noticed that the insoluble acids in butter fats may sometimes amount to as much as 90 per cent.' The author has found that cocoanut oil yielded 86.43 per cent, insol- uble acids,'' and thus infers that it could be mixed with other fats and escape detection by this method, calling attention to the facit, however, that if the soluble acids be estimated according to the method of Dapr6^ the sophistications might at once appear. The low figures obtained are ascribed to the volatility of lauric acid which escapes on drying the insoluble fats. By Koettstorfer's pro- cess the number of milligrams potash necessary to saponify one gram cocoanut oil was found to be 257.3 to 258.3" the large quantity required being due to the presence of lauric, caproic, capryllic, and caprio acids. It is, therefore, possible to mix oleomargarine ami cocoanut oil in such a manner as to produce results similar to those given by pure butter. This is shown by the following figures : Cocoanut oil. Oleomargarine. Per cent. 49.3 + 70.2+ 53.1+ 75.9+ Per cent. MiUigramt. 60. 7 required of KOH 220. 29. 8 required of KOH 234. 9 46. 9 required of KOH 223. C 24. 1 required of KOH 234. 9 1 Op. Bit., pp. 31, 62, 63. ''Analyst, 1885, p. 224 et aeq, 'Fleischmann and Veith, Zeit. Anal. Chem., 1878, p. 287; Kretsohmar, Ber. Chem. Gesel., vol. 10, p. 2091 ; Kuleschoef, Wag. Jahresberioht, 1878, p. 999; Jehn, Axchiy der Pharm., vol. 9, p. 335 ; De la Source, Ibid., vol. 12, p. 929. .er cent, required 35.5 of iodine per 100 grams, and lard 40 per cent. + cocoanut oil CO per cent, required 32.2 of iodine. In samples of butter the iodine numbers found by Hiibl varied from 20.8 to 35.1. By Eeichort's method, liowever,^ the presence of cocoanut oil mixed with butter and oleo is at once detected. Thus a mixture of 50 per cent, butter, 27.5 per cent, oleomargarine, and 33.5 cocoanut oil gave by Hehner's method 89.50 x^er cent, insoluble acids ; by Koettstorfer's metliod, 227.5 mg. KOH; by Hiibl's method, 35.4 per cent, iodine fac- IST torj by Iteichcrt's method, 8.7cc. -— soda solution. Pure butter requires by Eeichert's method about 13cc., — alkali to neutralize the volatile acids distilled over, while cocoanut oil in similar circumstances requires only 3.7cc. Little evidence is forthcoming in respect of the use of cocoanut oil as an adulterant of butter. It has been mentioned as an adulterant of lard"" and Dietszch^ mentions it as a compound of " Schmalzbutter." In attempts to use it as an adulterant of butter no great success was secured, since the oil not having been properly purified made the butter unpalatable. The smell and taste of the oil can be removed by a patent process of Jeserich and Meinert* which consists in treating the od with superheated steam and saponify- ing any free fatty acids by calcined magnesia. The author closes his paper by recommending Eeichert's process as superior to all others in examining for the purity of butters. USE OF COTTON-SEED OIL AS A BUTTER ADULTERANT. Cotton-seed oil is used largely as an adulterant for lard and butter. It has saponification equivalent of 285 to 29C and specific gravity at 99° O. .872, pure butter fat at the same temperature being .808. Its further properties are thus described by Allen:' The oil as expressed from the seeds contains iu solution, often to the extent of 1 per cent., a peculiar coloring matter, which is characteristic of this oil and its seed, and ■which gives the oil a ruby-red color, sometimes so intense as to canse the oil to appear nearly black. Crude cotton-seed oil gives a very bright rod coloration with stron"- sulphuric acid (pajje 59). When hoilod with an alU.aliue solution, alcoholic potash heing preferable for laboratory experiments, crude cotton-sopd oil is saiionified, and the resultant soap rapidly oxidizes on exposure to air, with production of a tine pur- 1 Moore, Am. Cliom. J., vol. 0, p. 41G. '■•NahrUngsmittel nnd Getriinke, p. SIS. «Diug, Poly. J., vol. 2:>:i, p. 281. "Wag. Jahresbericht, 1882, p. 932. 3 Zeit. Anal. Chcm. 1880, p. 68. ' Op. clt., M cd., p. 112. "Analyst, 1882, p. 11);!. DAIRY PRODUCTS. 73 pie or violot blue coloration.' This reaction is oliaraoteristio of crude cotton -seed oil . The coloring matter cauaes crude cotton-seed oil to produce stains, and hence is re- moved by a process of relinlug. This is usually effected by agitating the crude oil at the ordinary temperature with 10 to 15 per cent, of solution of caustic soda of 1.060 specific gravity, when the alkali combines with the coloring matter and saponifies a portion of the oil. The niixtui'e becomes filled with black flocks which deposit on standing- and leave the oil but slightly colored. Tlie loss in refiniug'is usually from 4 to 7i per cent., but occasionally amounts to 12 or !.'>. Hence it is desirable, before purchasing crude cotton-seed oil for refining, to ascertain, by a laboratory experiment, what the percentage of loss is likely to be. Frequently the treatment with alkali is only carrietl far enough to remove the major part of the coloring matter, the oil being then boiled with a solution of bleacliiag powder, and aubseiiuently treated with di- lute sulphuric acid.^ Refined cotton-seed oil is of a ctraw or golden-yellow color, or, occasionaly, nearly colorless. The density ranges from .922 to .926, and the solidifying point from 1° to 10° C. By subjection to cold and pressure a certain proportion of stearine is separated, the melting point of the residual oil being correspondingly lowered. Refined cotton- seed oil is usually very free from acid, and when ^Jroperly prepared is of pleasant taste and admirably adapted for .edible and culinary i)urposes, for whicb it is now extensively employed, botb with and without its nature being acknowledged. It is now substituted for olive oil in some of the liniments of the United States Pharma- coiiceia, but its principal applications are in soap making and the manufacture of fac- titious butter. ESTIMATION OF SALT. The method employed in this laboratory since 1883 has continued to give satisfaction, and can be recommended as the best in use. From 10 to 20 grams of the well-mixed butter or butter substitute are placed in a separatory bulb provided with a closely fitting glass stopper. Add 25 to 50cc. hot distilled water, and after shaking well al- low to stand for a few minutes. The water, which has dissolved most of the salt, is now drawn off through the stoppered tube of the appa- ratus. Fresh hot water is added and this operation repeated. until the ' " Cotton-seed blue " is stated by Kublmann to have the composition of C17HMO4. It is amorphous, readily destroyed by oxidizing agents, insoluble in water, -diluted acids, and alkalies, sparingly soluble in carbon disulphide and chloroform, but more readily in alcohol and etber, and dissolves with purple color in strong sulphuric acid. The unoxidized coloring matter of cotton-seed oil has been Recently examined by J. Longmore, who, in a communication to the autho^r, states that it is a pungent golden- yellow product, insoluble in water, but soluble in alcohol and altaline solutions, and precipitated from the latter on addition of acids. It dyes well and perfectly fast on both wool and silk. 'The deposit thus formed, consisting of coloring and albuminous matters, alkali, and partially saponified oil, is technically called "mucilage." It is decomposed with a s'ight excess of acid, and the resulting dark-colored grease is heated to a tempera- ture of 120° C. (=250°F.) with concentrated sulphuric acid, which renders insoluble the coloring matters, &c., while the impure fatty acids rise to the surface. On distil- ling these with superheated steam, a mixture of fatty acids is obtained, which is sep- arated into stearic and oleic acids by pressure. The " cotton-seed stearine" thus ob- tained is employed for making soap and composite candles, as also for adulterating tallow, &c. 3 This method of treatment is economical, but causes the oil to acquire an unpleas- ant taste and smell, which cannot be removed. 74 FOODS AND FOOD ADULTERANTS. volume of the wash water amounts to 250 to SOOcc. By this time all the salt has been dissolved and separated from the butter. Ohromate of potassium is now added to the salt solution, and the titra- tion is accomplished by a standard silver nitrate solution. The amount of NaOl in butter is also determined by dissolving the fat with ether or light petroleum, and after incineration of the curd, weighing the residual ash, which is taken as the amount of salt present. This method is not to be recommended since it includes the salt found in the other mineral constituents. Sell'- gives the following method: Ten grams of butter are weighed into a porcelain crucible and dried at 100° C. for six hours. The melted fat, &c., is now filtered, and crucible and filter are washed with ether. The filter with its contents is then incinerated. The ash is extracted with water, filtered, and the NaGl estimated volumetricaily in the fil- trate. ESTIMATION OF CURD. The methods of estimating curd depend on the principle of first dry- ing a weighed portion of the butter, and afterwards extracting the fat with ether or petroleum. The residual mass is then weighed and the curd determined by loss on ignition. This process is carried on in this laboratory as follows : Five to teu grams of butter are dried at 100° C. for a few hours in a porcelain dish. The dried fat, &c., are filtered through a Gooch ernci- cle, the contents of the dish all brought into the crucible and well washed with ether or light petroleum. The filter crucible is dried for two hours aud weighed. The curd is then determined by loss of weight on ignition. A number of experiments have also been made to convert the curd directly into an ammonium compound by Kjel- dahl's process. This method has not met with sufficient success to merit a recommendation to general use. This method was first tried in the laboratory in 1884. Babcock finds this method more satisfactory.^ Teu grams of the fat are treated with light petroleum, and after the fat solution has been de- canted the treatment is repeated. The purified curd is then treated by Kjeldahl's process. QUALITATIVE TESTS. The qualitative tests employed in the detection of artificial butter are the following : (1) Microscopic examination. This method has already been suflS- ciently described. (2) Solubility in a mixture* of amyl-alcohol and ether. 1 Op (At., p. 5a7. 'Fifth Ann. Kept. Bd. Control N. Y. Exp. Sta., p. 335. DAIEY PEODUCTS. 75 The quantity of stearin in butter fat is small compared with that in lard, tallow, &c. On this difference of constitution Professor Schefifepi has based a method of analysis. A mixture is made containing^ 40 volumes of rectified amyl-alcohol and CO volumes ether of .725 specific gravity at 15° 0. One gram of butter fat is dissolved in 3co. of tliia mixture at 26° to 28° 0. On the other hand, 1 gram lard requires 16cc. of the solvent, 1 gram tallow SOcc, and 1 gram stearin 360cc. For the experiment take a test tabe of 12cc. capacity and place in it 1 gram fat, add 3cc. of the amyl-alcohol ether mixture. After tightly corking the tube pu c it in a water bath of 18° 0. and with frequent shaking bringing the temperature to 28° 0. If the butter is pure the solation be- comes lierfectly clear at this temperature. If not clear more of the solution can be run iu but of a burette and the additional quantity re- quired will be some indication of the quantity or quality of the adul- terant which has been used. According to Scheffer, mixtures of pure butter and lard gave the following data: Butter: Lard. Quantity of mixture' required. Gram. .1 .9 .8 .7 .0 .1 Grain. CC. 3.0 3.9 4.8 6.7 6.5 14.4 .1 .2 .3 .4 .9 A trial of this method has shown that it is capable of giving valuable qualitative indications in respect of the purity of the sample under examination. I believe it is the best simple test aside from the micro- scopic examination capable of general application which has been pro- posed. The easiest method to secure a certain weight of fats is to melt them and measure out from a pipette 1 cubic centimeter of each. The fats which do not melt easily should' be stirred up thoroughly with a wire, while the temperature is raised from 18° to 28° 0. (3) Odor of the burning grease.^ (4) The insolubility of the stearate of potash in alkaline solutions.' (5) Insolubility of tallow, lard, &c., in petroleum ether of .69 specific gravity.* (6) The relative solubility of butter fats and substitutes therefor in a mixture of 50 per cent, alcohol and 66 per cent, ether.^ 1 Pharm. Eundsoh., 1886, p. 248. 2 Kunstmann. Pharm. Ceutralh., 1875, No. 9. 3 Gatehouse, Chem. News, vol. 32, p. 297. ■iZeit. Anal. Chem., 1872, p. 334. "Hiisson Zeit. Anal. Chem., 1880, p. 236; Filsinger, Pharm. Centralh., 1878, p. 860. 76 FOODS AND FOOD ADULTERANTS. (7) Crooki vrarms half a gram of bhe filtered fat in a test tube to 66° C, aud adds 1.5cc. pbenol, shakes and warms in water bath until the liquid is clear. On standing pure butter gives a homogeneous solution- Tallow and lard appear, however, in distinct laj-ers. A method somewhat similar to this was proposed in 1877 by Bach.^ The apparatus required consists of a test tube and a thermometer. The reagent is a mixture of 3 volumes ether and 1 volume alcohol of 95 per cent, aud 1 gram of the butter or tallow and put in the test tube with 20cc. of the above mixture, and this is placed in water at 20° 0. At this temperature pure butter is completely dissolved. Butter, however, containing lard, beef, or mutton tallow remains undissolved. (8) Horsely ' calls attention to the perfect solubility of pure butter in ether, aud that it is not precipitated from this solution by methyl- alcohol, while other common fats are thus separated at 20° C. Leuz" confirms the general results of the foregoing process. (9) BelfiekP allows the fats dissolved in ether to crystallize, and distinguishes between them by their crystalline form. (10) Pailliit" has found that pure butter when mixed with copper oxide in ammonia gives a turquoisblue color, while a butter adulterated with n)argariue (?) gives a greenish tint. (11 ) Dubois and Pad6'' point out that the addition of any considerable quantity of foreign fats to butter not only changes the melting point of the fatty acids obtained, but also diminishes their solubility in alcohol. (12) Wolkenhaar " distinguishes between the dilferent fats by means of nitric acid, which gives to cotton seed oil, palm oil, lard, sesame oil, and several others a red brown color. For a fuller discussion of most of these qualitative tests, consult either the original articles or Sell." (13) Method of Mayer." This test is made as follows : About O.C gram of butter fat is placed in a test tube with 12cc. water made slightly alkaline by a few drops of a solution of 2 per cent, soda, or two drops of G per cent, ammonia-water. The tube closed by the thumb is then well shaken, afterwards carried to a temperature of 37° O. to 40° 0., with frequent shaking. The emulsion thus formed is poured into a separatory funnel. The fat is now washed several times with water at 37° C. to 40° 0.,the wash- water being drawn ofi by the stop-cock so as to maintain a constant level in the funnel. The fatty matter having thus been placed in contact with about 400cc. water, the stop-cock is so ' Analyst, Ib/'J, p. 111. 'Pharm. Centralb., 1877, p. 166. sCliem. News, vol. 30, p. 135 aud 154. iZeit. Aual. Cbem., 1880, p. :i70. ■'Eep. d. Ver. Aual. Cljem., vol. 3, p. ^.^^<^^. "L' Allude Scieutiliiiue par Louis Figuier, 29th year, 1885. ' Bui. Soc. Cliim., vol. 4-1, p. 6(3. 8 Rep. d. Vcr. Aual. Cheui., vol. 3, p. 103. "Op. cil., pp. 505-.'")09. '"Jour, de Pharm. et de Chim., vol. 15, p. 97. DAIRY PEODTJCTS. 77 adjusted as to allow the removal of the wash-water as completely as possible. After cooling, the fatty matter remaining on the sides of the funnel is examineu. If the butter be pure, there will be seen only a finely-divided mass, but the addition of a small portion of other fats will be revealed by greasy drops, which can be seen even during the progress of the washing. Natural butters made iu summer require a lower temperature for the washing, viz, 35° C. to 37° 0. In most cases the micxoscopic test with polarized light and selenite plate combined with the solubility of the fat in the ether amyl-alcohol solutions will be found sufficient for the qualitative examination of a suspected butter. RESULTS OF ANALYSES OF GENUINE AND SUSPECTED BUTTERS AND BUTTER ADULTERANTS. Table No. G.— Analyses of butter. Serial number. k CD 1 1 a M 1» II 'A "0 a 5 i a m "t. ■ II % i . 91046 .91110 .91032 . 910O7 . 910J9 .91244 .91165 .91004 . 91013 .910u:j . 91067 . 91089 . 91078 .91155 . 90938 . 91042 .90995 .91183 . 91069 . 91079 . 91093 . 91064 .91034 . 91239 . 91031 .910)0 .91112 .91082 . 91180 . 91061 .91080 .91106 .91136 Fr. ct. 13.33 8.53 8.57 8.14 16.82 4.59 11. 4'i 17.38 13.95 23. 12 23.46 21.02 11.89 21.90 31.55 11.17 7.68 9.68- 7.35 12.28 8.89 18.75 9.87 10.84 12.28 7.26 12.32 6.03 8.29 8.44 4.44 13.67 8.22 Pr.ct. 88.04 87.85 88.65 88.08 88.91 86.00 87.60 88.07 87.47 87.81 87.47 87.38 87.71 83.63 88.09 "si'Ai' 87.30 88.14 87.ro 87.21 80.08 87.58 80.01 88.48 "87." 23' 87.60 87.10 87.73 87.85 88.25 87.75 Fr. ct. 4.01 4.14 3.53 3.08 3.00 5.02 5.49 3.70 4.73 4.98 5.27 5.15 4.09 6.34 4.45 5.31 5.08 5.94 5.05 5.37 6.47 4.75 5.17 5.42. 4.06 3.07 4.24 3.92 4.48 3.91 4.41 3.47 4.18 Fr.ct. 4.50 4.57 4.78 6.48 4.56 -5.51 4.61 4.54 4.80 4.70 4.99 4.93 4.98 4.74 5.03 4.52 5.21 5.05 4.47 4.93 5.20 4.03 4.50 4.45 3.93 Pr. ct. 2.84 3.09 2.81 2.04 3.79 8.41 1.48 0.00 0.00 0.00 0.00 0.00 2.61 0.00 0.57 2.56 5.62 4.09 5.28 3.69 3.18 0.00 4.83 3.12 5.79 6.42 6.53 3.92 5.11 3.15 1.81 7.10 4.37 Fr.ct. .7875 .8312 . 87.J0 .5038 .7438. .5350 .■8:112 .4375 .4375 .1750 .1750 .2188 .2625 .4375 .6125 .4375 .2025 . 6230 .4375 .4813 .3003 .7000 .4375 .4375 .7438 .4375 . .5350 .5350 .4375 .7000 .7000 .4375 .5126 Pr. ct. 1.46 1.31 1.30 1.25 1.50 , .83 ' 1.14 0.68 81 0.40 0.59 l.Ol 1.30 1.21 1.83 1. U 0.71 -1.37 0.91 1.08 1.03 1.41 1.12 0.9; 1.43 1.43 2.03 1.33 1.10 1.42 1.03 3.10 1.34 254.20 250. 60 268. 50 264. 90 252. 70 244. 30 230. 10 238. 60 249. 70 248. 70 243. 00 248. 80 244.90 244. 00 . 253 00 247. 00 247. 00 244.10 252. 10 240. 40 245. 10 260. 70 251.80 250. 90 236. 50 247. 10 246. 40 248.40 247. 50 246.60 251.50 240.20 2(0.70 12.50 1743 13.10 13. 50 16.30 1746 17i7 12.00 15. 60 1749 13. JO J752 12.80 1759 13. CO 1760 - i:i.40 1761 14.10 14.10 1763 14.10 13.20 1765 14.30 1766 12.80 1768 14.80 1769 14.30 1770 12.70 1771 14.00 1772 14.90 1773 11.40 1775 12.90 1776 12.70 1777 11.10 1781 .. : 13.20 1782 13.00 1783 1785 12.50 14.50 1789 12.60 1790 13. 90 1792 12.30 1795 14.60 Table No. 7.- -Analyses of douhlful huHcrs.^ 1748 . 00968 .90904 . 90987 . 90974 . 90972 . 90947 . 90004 . 90938 . 90965 7.45 11.30 12.12 10.90 29. 84 11.59 10.00 8.50 9.00 89.46 89.44 87.00 88.08 87.82 88.01 88. 43 88.00 88.50 3.61 8.54 4.71 4.73 4.84 3.16 3.02 3.31 3.44 4.60 4.25 4.64 rf.46 4.27 2.64 5.28 0.00 2.16 0.00 5.00 5.40 13.00 2.84 .7443 . 6088 .4375 .4813 .9635 .8750 .8750 ' '.'4375' 1.41 ].03 0.93 1.33 1.86 1.56 1.68 1.12 0.98 252. 80 253. 60 251. 50 249. 70 260. 10 250. 00 250.70 253. 50 252. 00 13.10 1757 12.10 12.90 J767 12.60 3774 12.10 1779 13.50 1780 11.60 1793 12.30 1794 11.70 ' Thes9 samples were bongUt for pure butter, but, on analysis, p«esed.to contain adulterants. 78 POOCS AM) Foot) ADULTESANTS. Table No. 8. — Anali/ses of biittei' subsliiatei. >> (>j c& u ^ r:S .a^ .a . , ©^ r Pr. ct. Pr. ct. Pr. ct. Pr. ct. Pr. ct. Pr. ct. Pr. ct. 1750 Lard . 90538 0.00 92.59 0.41 0.08 0.00 .0875 Trace. 294. 30 0.20 1751 Beet 9aet . 9C158 . 90490 0.00 9.34 92. 59 93.59 0.23 0.12 0.04 0.25 0.00 3. 04 '".3000' 0.01 0.C3 290. 90 274. 00 0.10 1753 Oleomatgaiino - . - 0.70 1754 Neutral lard . 90369 7.42 90. CO O.20 0.10 0.40 0.02 270. 50 0.30 1755 Creamery butter- . 90569 . 9C237 11.00 14.23 92.90 93. 35 1.16 0.10 1.53 0.08 2.39 0.97 .3063 0.74 O.CO 274.80 286. 10 4.30 1756 Oleofat^ 0.20 1787 Country priut . 9CS61 14 45 93.72 0.09 2.42 .8750 1.82 281. 10 l.flO ' 40 butter fat, 15 oleo fat, 30 neutral lard. '^ Average 40 pounds per fat steer. ANALYTICAL RESULTS. The butters iu table No. 6 were bought iu open market and accepted as genuine on the results of the analysis. Some of these, however, ought justly to be classed la Table No. 7, as of doubtful purity. In quite a uumber of cases the number of cubic centimeters of decinormal alkali required to neutralize the distillate from -!.5 grams of the fat was less than 13. Nos. 1742, 174C, 1752, 17C6, 1770, 1773, 177i5, 177G, 1777, 1783, 1789, and 1792 come under this category. In all these cases, however, except 1735 and 17G8, the specific gravity is above .910 at 40° C, and it would not be safe to condemn a butter as adulter- ated which had that specific gravity, unless the microscope should re- veal crystals of foreign fat. In these samples such was not the case. In the two cases mentioned, where the specific gravity fell below .910, there are other reasons for thinking the samples pure. Iu 1765 the percentage of soluble acid, by Eeichert's method, is high, viz, 5.02. In 1768 it is still higher, viz, 5.21. With such proportions of soluble acid it would not be possible to condemn the samples as adulterated on the evidence of the specific gravity alone, On the other hand, when the percentage of soluble acid is low, as iu 1777, the specific gravity and saponification equivalent prevent the classification of the sample among the doubtful butters. Neverthe- less, should such a sample show with polarized light and a selenite plate bi-refractive crystals, it would be a strong presumptive evidence of adulteration. In any case, such a sample as 1777 would present nu- merous diflflculties to the analyst, especially if he were called to testify in respect to its purity. In Table No. 7 similar difficulties are encountered. The specific gravi- ties are uniformly low. On the other hand, the percentage of insoluble acids are only suspiciously high in two instances, viz, 1748 and 1757. In the first of these instances, however, the soluble acid is above the limit of suspicion. The saturation equivalent is uniformly rather high, DAIRY PEODUCTS. 79 bilt uofc above tlie range of pure butters. While the butters are classed for convenience as " doubtful," tbey could not be so proved before a court on the chemical evidence alone. In Table No. 8 we have plain sailing. A.11 analytical data show the fats of the samples examined are not butter. Since the adulteration of butters with less than 30 per cent, of a cheaper fat could scarcely prove profitable, the chemist should be careful not to condemn a suspicious sample, if its purity be attested by any one of the processes employed in the examinittion, unless some one test shows it to be undoubtedly adulterated. In the foregoing study of methods of analysis t have not attempted to give a complete citation of all the papers which have been written on this subject. A very complete bibliography of the subject up to 1882 is given by Caldwell,' and in the work of Sell.^ The probability of the detection of an adulterated butter by the phys- ical and chemical processes described in the foregoing pages is very great. In the order of value the quantitative processes employed may be ar- ranged as follows: (1) Determination of volatile acids by distillation. (2) Determination of specific gravity. (3) Determination of the sapon- ification equivalent. (4) Determination of the insoluble acids. (5) De- termination of the melting point. » Second Ann. Eept. N. Y. S. Bd. of Health, pp. 544-7. 'Arbeit a. d. Kaiserlichen Gesundheitsamte. EXAMINATION OF MILK. The adulteration of milk in this country consists usually either in the removal of cream or the addition of water. Without making any attempt whatever to notice the prolific litera- ture of this subject, which has accumulated during the past few years, such portions thereof as seem to be most helpful in the work of analy- sis will be cited. Those who care to study the subject in greater detail are referred to the periodical literature, especially to the "Analyst" and " Milch Zeitung." The constituents of milk which are to bo determined by analysis are (!) water; (2) sugar; (3) nitrogenous constituents; (4) ash, and (5) fat. Water. — The simplest method for estimating water in milk consists iu evaporating one or two grams in aflat platinum dish. The larger the diameter of the dish the quicker and more accurate will be the re- sult s. If larger quantities of milk be used or the dish have not a flat bot- tom, the film which forms over the surface of the milk during evapora- tion will prevent complete desiccation. To avoid this many plans have been proposed. The milk may be mixed with gypsum, and then a larger surface be exposed and more rapid and complete drying secured. Instead of gypsum, sulphate of barium, pure quartz sand, sulphate of strontium, and powdered glass have been used. All of these methods are capable of giving fairly accurate results when properly conducted. The addition of acetic acid or alcohol to coagulate the albuminous matter before desiccation has been largely practiced, but Gerber and Eadenhausen have shown' this treatment is without influence on the re- sults. Jenks has also shown ^ that simple evaporation without any treat- ment whatever gives results which agree well with those obtained by using sand. In fifty determinations the maximum and minimum diflerence between the two methods was only .14 per cent, and the mean difterence .003 per cent. Babcock^ has proposed an ingenious and accurate method of determ- ining the water in milk : About two grams of rather coarse asbestos are placed in a platinum evaporator of 30cc. capacity, ignited and weiglied. Five cubic centimeters of niilk from the pipette, ' Bied. Ceutralblatt, 187G, p. t>-2. = Chem. Centralblatt, 1882, p. 13. » Second Ann. Eept. Bd. Control N. Y. Exp. Sta., pp. 167-8. 80 DAIEY PRODUCTS. ^1 previously weighed, is rtin into the evaporator and the pipette weighed again. The milk in the evaporator is then dried at 100° C, until the weights taken one-half hour apart do not vary more than a milligram from each other. The asbestos serves as an absorbent of the milk and presents a large surface which greatly facilitates the drying. For this purpose asbestos is much to be preferred to sand or any fine powder which requires frequent stirring for complete desiccation When a number of analyses are to be made in suooession^a second portion of milk may be dried in the same asbestos with advantage. In the series of analyses made during the feeding experiments the morning's and evening's milk were dried together in this way. The dried residue may be ignited for ash. The figures given for solids in all analyses made during the year have been deter- mined in the above manner. The solids may, however, be found with equal accuracy and in much less time by the method given below. In the bottom of a perforated test-tube, such as is 'used in the estimation of the fat in fodders, is placed a tuft of clean cotton. The tube is then filled three-quarters full of ignited asbestos and a plug of cotton inserted to prevent the escape of loose fibers of asbestos. The asbestos must be slightly pressed together so as to leave nj large spaces. The tube and contents are weighed, the plug of cotton carefully removed and five grams of milk, from the weighed pipette, described before, run into it and the plug of cotton replaced. The tube, connected at its lower end by a rubber tube and adapter with a filter pnmp, is placed in a drying oven at 100° C. and a slow cur- rent of dry air drawn through it till the water is completely expelled, which in no case requires more than two hours. * Since the publication of the method of Adams for the estimation of fat, which will be given further on, I have made some attempts to esti- mate the water by drying the milk on long strips of asbestos paper, which are rolled up while still hot and weighed after cooling in a dessic- cator. I have not yet secured an asbestos paper sufdciently bibulous to make this method completely successful. But it has the advantage of being very speedy, since on so large a surface exposed for two or three minutes to a temperature of 100° to 105° C. over a sand bath the water is completely evaporated. An indirect method of estimating the water from the specific gravity has been prepared by Behrend and Morgen ' by the formula — S(Y-A) ^ - V ' — 8 '- in which S = specific gravity of the milk, S^ = specific gravity of the milk free of fat, S' = specific gravity of the milk fat = .94, and V = vol- ume taken = lOOcc,) Numerous tables are given by the authors to show the agreement between the calculated percentage of fat and total solids obtained by the above formula and the gravimetric determinations. Another indirect method of determining the quantity of water in milk consists in measuring the quantity of finely-pulverized common salt a given volume of it will dissolve. This procedure was proposed by Eeichelt. ^ The apparatus consists of a glass vessel 24cm. high. The upper part has a diameter of 2.5cm. and the lower of 8mm. On the under side is a I Jour. Landw., 1879, p. 249. "Bayerish Kunst und Gewerbeblatt, 1860, p. 706. 19330—2^0. 13 6 82 FOODS AND FOOD ADULTERANTS. scale marked to 45° 0. The principle of the apx)aratus is based on the fact that at 30° to 35° C, 100 parts of water will dissolve 36 parts of salt. The operation is carried on as follows : Mix C2.5 grams of milk with 20.25 grams of salt and add 15 grams of litmus tincture, saturated with salt, to color the milk. Eaise the temperature to 30° to 35° C, shake thoroughly, and then place the apparatus so that all the undissolved salt will fall into the under-graduated stem of the apparatus. Each degree of the scale corresponds to 62.5u)gr. of the salt. The part undissolved subtracted from the total quantity will give the quantity dissolved, from which the quantity of water is easily calculated. The lactometer of Geissler' is too complicated for ordinary use, and the method of estimating the water content of milk by measuring the volume of whey filtered from the coagulated albumens proposed by Zenneck^ does not aftbrd sufficiently exact results to merit further description. SPECIFIC GEAVITY. The specific gravity of a milk diminishus as its content of fat increases, and hence within certain limits it may be a valuable index of the char- acter of the samiile under examination. When the cream has been removed, however, the specific gravity may be reduced to that of normal milk by the addition of water, and then the determination of the specific gravity alone is not a certain method of detecting adulteration, yet it is a valuable indication and should al- ways be determined. This determination may be made by any of the methods already de- noted for fats and oils or by a hydrometer. Since the use of this latter instrument (lactometer, lactodensimeter) is easy and speedy, it is gen- erally employed instead of the slower but more exact procedure with a picnometer. Martin^ found the average specific gravity of the milk from fifty cows from E. B. Brady's farm, Westchester, N. Y., to be 1.03101. From another lot of thirty one cows, farm of Peter Knox, it was 1.03149; from sixteen cows, farm of George Kelson, 1.03175. Jenkins'' makes the following observations respecting the values of the specific gravity determination: A coDsideratioii of the observations uoticcd above brings us to the foUowiu"- con- clusious with regard to the value of total solids, aud of sptcific graiiti/, as criteria for judging of the quality of milk. We have seen that pure herd-mills shows very wide variations in its content of solids aud fat, and varaitions lessbtrikins; in its specific gravity. No instance appears to be on record where a competent observer has found for the mixed milk of a num- ber of healthy cows a specific gravity less than 1.029, and we may conclude with cer- tainty that milk which falls below that density has been watered. >Ber. Cheui. Gesel., Vol. 10, p. 1272. ''Vieth, Milchpriifungsmethoden, p. 87. ■> Fourth Ann. Kept., N. Y. State Bd. of Health, pp. 429 etseq. , p. 86. 'Ibid., 188C, p. 71. ''Ibid., 1886, p. 73. DAIRY PKODUCTS. 91 ing is accomplished. I have been able to put 5cc. of milk on a strip of paper, hang it over a sand bath and have it rolled and in the extractor within five minutes. I mention this to show that even in the matter of gravimetric deter- ming,tions by which the areometric method is finally judged, there is still a certain limit of variability. I will return now to the subject more immediately under discussion. Schmoeger further says' that with skimmed milk, buttermilk, and such milks as have stood twenty-four hours on ice the ether-fat solution sep- arates diflicultly or not at all. To avoid this he recommends, after the addition of the potash, fully five minutes shaking, in order to form but- ter of the fat. Then the ether is added and the process continued as usual. In this case the percentage obtained by the areometric method must be increased .1 per cent, in order to agree with the gravimetric de- terminations. Schmoeger further recommends that skimmed milk or sweet buttermilk after treatment with potash be shaken with 10 grams potassium sulphate until the latter is dissolved. But this method also influences the specific gravity of the ether-fat solution, and the correc- tions to be made are found in the table given.^ Soxhlet himself^ has called attention to the fact that with skimmed milk the ether-fat solution does not readily separate. A special scale has been constructed for such fat-poor milks giving areometric readings from 21.1 to 43, with the corresponding percentages of fat. For such milks Soxhlet proposes the following treatment, viz : A soap solution is made by taking 15 grams of a stearine candle, adding to it 2occ. alco- hol, and lOcc. of the potash solution of the strength before given. The stearine is saponified by heating the mixture, and after the solution has become clear it is made up to lOOcc. with water. Prom .4 to .5cc. of this solution is added to the milk under examination, and after a good shaking the rest of the process is carried on in the usual way. After the first thorough shaking on the addition of the ether the light jolting must be continued for fifteen minutes at intervals of half a minute in order to have the ether solution collect at the top. At longest, the so- lution separated after three or four hours. Halenke and Moslinger* call attention to the fact that if samples of milk are kept for some time, even on ice, the ether-fat solution will no longer separate. They prefer in such cases a modification of Lieber- mann's method, which they describe. In general I may say the areo- metric method has met with the approval of all analysts who have used it with exception of Preusse", but Soxhlet^ has shown that Preusse did not understand how to use the apparatus. 1 Op. cit. ^Ibid., p. 132. 'Zelt. landw. Vcr. Bayern, 1882, p. 18. " Ver. Bay. Vertreter d Angewand. Cliem., p. 110. ''Mittheil. Eeiohsgesundlieitsamt, vol. I, p. 378, li^eit. l3,ndw. Ver. Bayern, 1881, p. 700, 92 FOODS AND FOOD ADULTEEANTS. The following chemists, in addition to those already mentioned, have given the method their entire approval : Egger, Kellner, Schrodt, Fried- lander, Meissel, Fleischman, Hofmeister, Deitzell, Moser, Schreiner, Janke, Gerner, and Angstrom. I will give now some of my own experiences with the areometric method : The milk examined by me was mostly obtained from a neighboring dairy and was a mixture from forty cows. Samples were also bought from dealers in the city. The milk from the dairy mentioned was drawn at 5 p. m., and the examination made the following morning. This may partially account for the small success I had in securing a good separa- tion of the ether-fat. The work extended from March 23 to May 7, 1886. With the first series of samples in which the method of separation recommended by Soxhlet was followed ninety-three trials were made. In only four cases was the separation sufBciently good to get a reading within thirty minutes. A larger number of readings was obtained within an hour, and about half the number could be read at the end of three or four hours. Of the remainder about one-half could be read after twenty-four hours, and the rest did not separate at all. The results of reading the areometer at different times, however, showed that the density of the either-fat solution underwent quite a change. The fol- lowing data will show the nature and extent of this change: No. Per cent. fat. Krst re- sults. Eesnlts alter 24 hours. f Differcuce. 1 2 3 4 5 6 7 4.16 3.52 3.20 3. 03 6.28 4.81 4. SI 4.08 3.83 3.52 3.68 5.28 5.13 4.71 -0.08 0.31 0.30 0.05 0.00 0.32 -0.10 From the above it is seen that there is no uniformity in the character of this change, but in the greater number of cases the areometer shows an increase in the percentage of fat on standing. Attempts also to obtain a more perfect separation by varying the quantity of potash employed gave only conflicting results. I was, therefore, forced to the conclusion that for general work Soxhlet's method would prove useless unless some method could be de- vised to secure a prompt and uniform separation of the ether-fat solu- tion. Various theories have been proposed to account for this peculiarity of milk in refusing to allow the ether solution to separate. Caldwell and Parr have supposed itto be due to the bran in the cow's food ; Lieber- mann ascribes it to failure of manipulation ; Scbmoeger that it is caused DAIRY PKODUCTS. 93 jTiG. a. 94 POODS AND FOOD ADULTERANTS. by the milk standing on ice ; Soxhlet tbinks it is the result of deficiency of fat; and others attribute it to diflerences in age and breed of the cows. The r(5sum6 which precedes shows that not onlj"^ the actual vol- ume of the ethereal solution, but also the time of the separation required, has a serious disturbing influence on the specific gravity of the ether-fat solution. Therefore, the method, in order to be of general application, must be subjected to some radical modification. In this direction were the attempts to secure a more prompt separa- tion by varying the amounts of caustic-potash solution employed. These attempts, as the record has shown, were entirely unsuccessful. Even if the different kinds of milk would permit a prompt separation by vary- ing the quantities of alkali employed, the amount for each sample could only be determined by numerous and tedious experiments. I, therefore, turned my attention in another direction. It seemed to me that a centrifugal machine might be used to secure this separation, and accordingly I had a castaway drug-mill, formerly used in the labo- ratory, modified so as to serve for this purpose. The machine was so arranged as to hold four separatory flasks and impart to them a high speed of rotation. The form of the machine, with modifications made, is shown in figure 2. At this point of my investigations this apparatus was finished and I immediately subjected it to a trial.' Four samples which had not separated at all at the end of three hours were placed in the apparatus and whirled for ten minutes. At the end of this time three of them had completely separated, and the fourth nearly so. The apparatus was set in motion again for five miuutes, at the end of which time the separation of the fourth sample was accom- plished. The number of revolutions per minute of the machiue was about 350. It will be seen from the above that the very first trial of the machine was completely successful, securing a perfect separation of the ether-fat solution in a few moments in samples which x)revions trial, by the usual method, had failed to separate in several hours. The next determinations were made on a sample of milk purchased at the Department resteurant. Duplicate flasks were treated in the usual way to secure the separa- tion, and only at the end of two and a half hours was enough clear solu- tion obtained to get a reading: No. 1 gavje 2.40 per cent, fat; No. 2, 2.30 per cent. fat. The first set of samples of the same milk separated by the centrifugal gave the percentages following : No. 1, 5.52 per cent, fat ; No. 2, 2.32 per cent. fat. • This apparatus was first described before the Chemical Society of Washington, May, 1886, and next at the Buffalo meeting of the A. A. A. S,, August, 188G. DAIRY PRODUCTS. 95 The separattou took place perfectly in ten minutes, with a rate of rev- olution of about 300 per minute. The second set of four samples was treated in the same way and sep- arated completely in eight minutes. The following readings were ob- tained: No. 1 gave 2.36 per cent, fat; No. 2, 2.34 per cent, fat; No. 3, 2,31 per cent, fat; No. i, 2.30 per cent. fat. The third set of samples separated by the centrifugal showed the following percentages: No. 1 gave 2.23 per cent, fat; No. 2, 2.30 per cent. fat. The volume of the clear ether-fat solution in each case was about 40cc. The next trial was with milk also purchased in the Department res- taurant. It proved to be one of the rare cases in which a reasonably prompt separation was securei by the old method. After thirty min- utes about 25cc. of the ether solution had separated, which was enough to get a reading. Duplicate determinations were made : No. 1 gave 2.0S per cent, fat ; No. 2, 2.04 per cent. fat. Four separations of the same milk were also made with the centrif- ugal. Separation took place promptly in eight minutes at a speed of about 200 revolutions per minute, and the volume of ether-fat in each case was .about 40cc. : No. 1 gave 2.01 per cent, fat; No. 2, 2.01. per cent, fat; No. 3, 2.00 per cent, fat; No. 4, 2.04 per cent, fat; which is an agreement as close as any one could expect. Having thus shown that the centrifugal method was capable of making the areometric method applicable to almost every sample of milk, I un- dertook a new series of experiments. In all, 155 samples were subjected to treatment. Of the 155 samples examined only 57 gave a good separation by the Soxhlet method in thirty minutes. Of the remaining 98, about half did not separate at all so as to permit a reading, and the other half only after several hours. Compare this with the centrifugal method, in which only 6 samples out of the whole lot required over fifteen minutes for separation and only one was abandoned as entirely inseparable, and the more general application of the process is at once apparent. Of the 6 samples mentioned above, 3 were from the same cow, a grade Shorthorn, four years old, weight about 800 pounds, in milk since July 1, 1885. She gave 6 quarts of milk a day, was milked at 5 a. m. and 5 p. m. The samples of milk sent were taken at 5 p. m., on April 13, 17, and 22, respectively. The food received by this cow was the same as for all the others (36) from which samples were taken for analysis. They received at 5 a. m. 3 pounds of wheat bran, and the same of hom- iny chops, and then as much corn (maize) fodder as they could eat. The bran and chops were fed dry. In pleasant weather the cows were out until 3 p."m. They were then fed 10 pounds each of unthrashed oats. At 5 p. m. they got a half peck of chopped turnips and a repetition of the morning's feed of bran and chops. 96 FOODS AND POOD ADULTEEANTS. The hominy chops used showed, on analysis, the following compo- sition : Per cent. Water 7.13 2.53 9.03 69.32 2.30 9.63 Ash Two of the other samples were received April 27 and 30 from a thor- oughbred Jersey, four years old, weight about 600 pounds, in milk since July 1, 1885, giving at the time about 5 quarts daily. On the 29th of April samples of milk were also treated from the same cow, but after dilution the centrifugal separation, although more than usually diffi- cult, did not require so long a time as on the occasion mentioned. There is nothing shown by the analysis, by the breed of cow, nor by the food which gives any definite idea of the cause of the peculiarity in these milks which does not permit a speedy separation. It certainly is not the quantity of fat present, for other milks having the same, more or less, amounts of fat separated without difiScuIty. Inr the ab" sence of any further evidence on this point we can only attribute the phenomenon to bovine idiosyncrasy. In all 90 samples were compared by the usual method of separation and by the centrifugal. By the former method the mean percentage of fat obtained was 4.01 and by the latter 3.88. It thus appears that the numbers obtained by the centrifugal method must be increased by .13 in order to correspond to those of the old method. This discrepancy is readily explained when it is remembered that by the centrifugal motion the percentage of ether left in emulsion would naturally be less than with the former process of separation. The ether-fat solution thus be- comes more dilute and consequently has a lower specific gravity. When, therefore, the percentage of fat in a milk determined arcometrically, is calculated by the tables given for the old method of separation, it should be increased by .13 in order to represent the actual quantity present. I think it safe to conclude from the data which have been obtained : First, that the method of Soxhlet cannot be applied to the determi- nation of fat in American milks, especially if they be from individual animals. It works somewhat better on mixed milks from a large dairy but even in this case it is a rare thing to secure a p rompt separation and in most cases the method would be very difficult of application. Second, that by the use of the centrifugal machine described a prompt separation of the other-fat solution can bo obtained in all cases even in those in which after forty-eight hours no separation whatever takes place by the usual method. Third, that the estimation of the fat in milk by'Soxhlet's areometer can only be accurately secured when standard volumes of aqueons ether DAIRY PRODUCTS. 97' aud caustic potash are employed, wheu the voluuie of the other-fat so- lution separated is sousibly coustant and the time employed iu separa- tion sensibly the same. These conditions can only be secured by the use of the centrifugal machine described. I propose to use a centrifugal apparatus also for assisting iu the sepa- ration of the ether-fat solution in the lactobutyrometer ; and it has al- ready proved its usefulness in separating precipitates which subside very slowly. I am of the opinion that such a machine would prove of great value in every chemical laboratory aside from its utility in determining the fats iu milk. Cronanderi has proposed the following method of estimating the fat in milk : A glass flask of 200 to 250cc. capacity, and two glass tubes constitute the chief parts of the apparatus. One of the tubes is furnished with a scale dividing it into ten equal parts. Below the last division the scale is expanded into a bulb, below which the tube extends for about 5cm. The other tube is bent to an obtuse angle and serves for the in- troduction of hot water into the flask to drive the fat into the measur- ing tube at the end of the operation. Both tubes are fastened to a cork stopper iu such a manner as to have the measuring-tube end even with the under surface of the stopper, while the other extends almost to the bottom of the flask. Of the milk to be analyzed lOOco. are taken at 17.5° 0., lOcc. potash lye (200 grams to the litre) added and 30cc. aqueous ether. The flask is corked and thoroughly shaken. The ether-fat solution collects at the top (after one hour), and after evaporating the ether the residual fat is forced into the measuring tube by pouriug water at 70° C. to 80° 0. into the flask. The volume of the fat is thus determined and its per cent, can be calculated. liebermann's method. 3 This' method, like that of Soxhlet's, depends on the separation of a fat from a mixture of milk and caustic potash by shaking it with ether. Apparatus. — (1) A glass cylinder with ground glass-stopper, 26cm. high and 3.5cm. diameter. (2) Burettes of the form shown in Figs. 3, 4. (3) A glass flask holding from 45 to 47cc., according to size of burette employed ; neck 1cm. diameter, with edge ground accurately in a hori- zontal plane. (4) Four pipettes, two of 50cc. and one each of 20cc. and Sec. Before beginning the operation the flask is graduated as follows: The burette. Fig. 3, is filled to the zero-point with pure water at the temperature of the working room. The water is now run out of the >Milohzeitung, vol. 11, pp. 161-164. 2Zeit. Anal. Cliem,, 1883, p. 383; 1884, p. 476; 1884, p. 87, 19330— No. 13 7 •* i)8 FOOJJS AND FOOD ADULTEKANTS. taii\ .as good rosnlta as the ap- paratus is al)lo to yield. In order to illnstrate this, I give below tho rcsnlta obtjiiued by two persons at their lirst attempts; the tirst person is a dairyman used to heavy work. By way of a check I myself made some testa of the same milks: By myself. Dairyman 3.1 3.1 .3.2 3.2 Failed 3.2 3.2 3.1 3.3 2. 65 2.05 2.0 2.65 '.'.. 05 2.0 3.2 I 3. 2 ' ;i. 2 2.6 2.65 1 These very favorable resnlts are of imiiortiiiicci as showing thai, in the lactocrite is at last found tho long wished-for apparatiLs, po,s,soai=ring tll(^ two qualities not hither- ' Analyst, 1SS7, p. :!4. -'.Vnaly.sl , Irts?, p]). i\ ,.( nrq. DAIRY PEODUCTS. 103 lo conibiucd — simplicity of construction and worldug and sufficient coireotuess for all practical purposes. Tlie lactocrite will, no doubt, be found invaluable for butter dairies, or dairy fac- tories buying milk from different farmers, by enabling them to carry out the syslem of paying for the milk according to the amount of butter-fat which is the only fair system. At present, both in England aud in other countries, the farmer whoso milk will make butter at a rate of 3 pounds per 100 jjounds of milk gets the same price as the farmers whose milk is so rich as to give 5 pounds of butter per 100 pounds of millc, which of course is most unfair. When milk is paid for according to the fat con- tained in it, the temptation to skim it is done away with, and, besides, a great cucour- agemeut is given to the iiroduction of rich milk. The lactocrite will also prove of use for analysts who have access to a separator stand, as it will give in short time a more exact determination of the amount of I'at than any other apparatus. In this counection it will be of interest to know that a special construction of it has been adapted to fit Dr. De Laval's small hand separator, worked by hand and requiring no foundation. Sebelien has published a comparisoa of the results obtained with the lactocrite and Oronander's method with the gravimetric methods.' Cronander's method gave in general results slightly below those fur- nished by the gravimetric and Soxhlet's processes. Dr. Cronander, to avoid this error, has introduced a slight modiflca- tion into his process by adding a little alcohol to the mixture of potash, ether and milk. The principle of the separation of the fat thus becomes the same as in the lacobutyrometer of M. Chevreul. By using this modified process it was found possible to bring the results up near to those of the gravimetric method. The results furnished by the lactocrite showed an almost perfect agreement with the gravimetric numbers, the differences being usually within 0.05 per cent. Attention must be paid to keeping the test tube holding the milk and acids well shaken, especially before pouring its contents into the metal box, artd that the rest of the apparatus be pressed in the box at once when the milk has been found. In proceeding in this way uo separa- tion of the different parts of the test liquid is possible, and thus a fair average sample is recovered in the test glass. Concerning the question of the advantages of the lactocrite as com- pared with other forms of apparatus for estimating the fat in milk Se- belien is somewhat conservative, but seems to think that the matter will soon be determined by comparative trials. LACTOBUTyROMBTRIC METHOD.^ This volumetric method depends on the separation of the fat from the milk by a mixture of ether and alcohol. The method has been carefully studied by Caldwell and Parr.' A mixture of T.'i parts of pure ether, 100 of absolute alcohol, and 135 of water are em- ployed. The instrument employed is made of moderately thick-walled tubing (about 1 Landw. Versuchs-Stationen, vol. 3.% pp. 393 et seq. ^Marchand, Instruction sui- I'emploi du lactobutyrometer, Paris,. 185G and 1878. ■'Am. Chem. Jour., vol 7, pp. 238 et seq. 104 FOODS AND POOD ADtJLTEEANTS. 1mm.); the stem is about 23cm., and IhuLulli about 8cm. long. It is important that the shoulder between the stem and the bulb should not be too abrupt. The bore of the stem is about 6mm., and it is graduated in-^ucc. Themder part ofthe tube has such a capac- ity that in passing from the lowest graduation on the stem to the inner end of the stopper in the lower mouth one passes from li to 33cc. ; then the ether-fat solution will al ways come within the range of the graduation on the stem. This instrument differs from that originally given by Marchand only in being open at the bottom as well as at the top ; this is a matter of some importance with reference to cleaning and drying it. The narrow stem in which the ether-fat solution collects makes more accurate readings possible than is the case with the wider tube with the same width of bore throughout, such as is now commonl.y used. The manipulation is carried on as follows : Closing the lower mouth with a good cork, lOcc. of the well-mixed sample of milk are delivered into the well-dried tube from a pipette, Mxen 8cc. of ether (Squibbs's stronger) and 2cc. of 80 per cent, alcohol. Close the smaller month of the tube with a cork, and mix the liquids by thorough shaking, which, however, need not bo either violent or prolonged. Both corks should be held in place by the fingers during this operation, and the upper one should be once or twice carefully removed to relieve the pressure within, otherwise it is liable to be forced out suddenly unless carefully watched, with consequent danger of loss of material. Lay the tube on its side for a few minutes and then shake it again, add Ice. of ordinary ammonia diluted with about its volume of water, and mix as before by shaking ; then add lOcc. of 80 per cent, alcohol, and mix again thoroughly by moderate shaking, and holding the tube from time to time in an inverted position while the lighter portion of the liquid rises to the surface. Now put the tube in water kept at 40° to 45° C. till the ether-fat solution separates- this separation may be hastened by transferring the tube to cold water after it has stood in the warm water for a few minutes and then returning it to the warm water. Finally transfer the tube to water kept at about 20° C, and as the level of the liquid falls iu the stem by the contraction of the main body of it in the bnlb, gently tap the side of the tube below the ether-fat solution, to dislodge any flakes of solid matter that may adhere to the walls ; then as this solution finally takes its permanent posi- tion in the tube, its volume will not be increased by the presence of such foreign matters. The readings are to' be taken from the lowest part of the surface meniscus to the line of separation between the other-fat solution and the liquid below it. In this laboratory the use of the lactobutyrometer has been attended with the same difficulties, though to a less extent, which led to the modifi- cation of Soxhlet's method already noticed. The late improvements in both the volumetric and gravimetric determinations of fat in milk ren- der a further discussion of the merits of the lactobutyrometer unnec- essary. OPTICAI., METHODS OF ESTIMATING FAT IN MILK. Since the white color of milk is due to the suspension of the fat glob- ules, many devices have been contrived to determine the quantity of fat present by the opacity of the milk. The most convenient of these ap- paratus is the one designed by Fcser. It consists of a glass cylinder, in the lower part of which a smaller cylinder made of wliite glass is flxed. On this white glass aroli few black lines. Tlie outer cylinder carries a double scale, one set of num- bers representing cubic centimeters and the other the percentage of fat. DAtEY PllODtJCTS. l06 Pour cubic ceutimoters of milk are put in tlie cyliudiT and then water added until the black lines on tbe inner white cylinder become visible. The percentage of fat is then read from the top of the column of water in the large cylinder. For a full description of the different Jbrms of lactoscope the mon- ograph of von der Becke may be consulted.^ For sorting milks, the lactoscope in the hands of an experienced operator will give valuable indications in respect of the quantity of fat. A delicate lactometer, a good lactoscope, and an experienced operator will generally be able to determine whether a given sample of milk be wliole or skimmed. The lactoscope, however, is of no value in determining with accuracy the percentage of fat present in a sample of milk. ESTIMATION OF LACTOSE. Chemical. — The chemical methods employed in estimating the sugar in milk will be fully discussed in another part of this" bulletin devoted to the study of sugars and their adulterations. Optical. — The optical method of determining the quantity of lactose in milk is both speedy and accurate when properly carried out. The principles which underlie this investigation and the proper method of carrying it out are given below.^ The usual method of determining milk sugar by evaporating the sam- ple to dryness and extracting the sugar with alcohol after exhausting with ether requires a great deal of time and labor. If some reliable optical method could bo devised the determination of the lactose in milk would be the work of only a few minutes. The difiSculties which are encountered in seeking for such a method are numerous and serious, so much so that little credit has heretofore been given to any of the processes of optical analysis in use. SPECIFIC ROTATORY POWER OP MILK SUGAR. Crystallized milk sugar when iirst dissolved possesses a higher rotatory power than it has in the milk from which it was derived. This increased optical activity may be compared with the original by the ratio 8 : 5, nearly. After the solution has stood for twelve to twenty hours, or im- mediately on boiling it, this extra rotatory power is lost. . In estimating the specific rotatory power of milk sugar the numbers given always refer to the constant and not the transient gyratory property. Among the earliest numbers assigned to the rotation of lactose are those of Poggiale (a)„ = 542 and Erdmann (a)„ = 51.5 [Sucrose (a)„ = 66.5]. Biot^ places this number for lactose at 60.23, and Berthelof at o9.3 for the transition tint {a)j. Hoppe-Seyler, in his "Handbuch der physiolo- gisch-chemischen Analyse," gives this number at (a)j=58.2. Since the ' Op. Bit., pp. 4.5 et seq. ''Am. Cbom. Jour., vol. 6, pp. 289 ct seq. aCompt. Rencl., vol. 42, p. 349. "WurtzDiot. deChim., vol. 2, lstpart,p.l88. 106 FOODS AND FOOD ADULTERANTS. ratio of («)„ to (a)j is 1 : 1.1306, the abov6 numbers become for Biot («)„= 53.27, for Berthelot (a)„=52.47, and Hoppe-Seyler (a)„=51.48. Hessei observed the rotation number to be (a)„=52.6( when the solution con- tained 12 grams per lOOcc. and the temperature was 15° C On the other hand, when the concentration is only 2 grams per lOOcc. the number assigned is (a)„=53.63. It appears from this that the specific rotation power of a solution of milii sugar diminishes with the increase of its concentration, and this view is adopted by Landolt, Tollens, and Schmidt. The following general formula^ is used to correct the reading of the polariscope for concentration of solution : (a)„=54.54 — .5575c + .05475e' — .001774c-'', in which c = number grams sugar in lOOcc. solution. These observa- tions are contradicted by the work of Schmoeger,^ who, in an elaborate series of experiments, using instruments of different construction and observing all necessary precautions, found the rotation number of lac- tose sensibly constant for all degrees of concentration up to the satura- tion point. In thirty-two series of investigations, in which the degree of concentration gradually increases from c=2.35.j4 to c=36.077G, and in which a constant temperature of 20° C. was maintained, the variations ii: the numbers obtained were always within the limits of error of ob- servation. The mean of all these numbers fixes the value of («)„ at 52..')3. According to Schmoeger variations in temperature have far more to do with changes in rotatory power than differences of concentration. Tbe value of («)„ falls as the temperature rises. Under 20° G. the dis- turbing influence of temperature is greater than above 20° C. At the latter degree {a)„ varies inversely about .075 for each 1° C. change of tem- perature. Pellet and Biard,* as a result of their observations, fix the rotatory power of milk sugar at 58.91 for (a)j [S. (a)„=52.12)]. After a careful review of the methods used in the above rdsumd and the numbers determined by them, I am inclined to accept the mean ob- tained by Schmoeger as the one entitled to the greatest credit. It also has the advantage of being almost the mean of all the various num- bers which have been assigned as (he specific rotating power of lactose, viz : Poggiale 54.20 Erdmann ' 51.50 Biot .• 53.27 Berthelot Ti-i. 'tT Hoppe-Seyler 51.48 Hesse 52.67 Hesse 53.63 Schmoeger ; 52.5.3 Pellet and Biard 52.12 Mean 52.65 'Anal. Chem. n. Pharm., vol. 176, p. 98. ' Bnll. do I'Assoc. dcs Cliimist«8 vol. 1, ■^Taelcer, Sngar Analysis, p. 91. p. ITl ct seq. ^ Bor. choin. Gessell., vol. 12, p. 1922 et seq. DAIRY PEOmiCTS. 107 In the present state of our knowledge, therefore, the specific rotatory power of milk sugar should be taken at (a)„ = 52.5. 1 propose, at an early date, to make a careful study of this subject, in order to fix, if possible, an exact uumber for the exjiression of the rotating power, and to examine the conflicting evidence respecting the influence of the degree of concentration on the same. The estiinaLioii of lactose in milk by the polariscope is rendered difficult also by the presence in milk of various albumens — all of which turn the plane of polarization to the left. As will be seen by the data given further along, the ordi- nary method of removing these albumens, viz, by a solution of basic lead acetate, is far from being perfect. If, therefore, a portion of the albumen be left in the liquid submitted to polarization, the rotation to the right will be diminished by its presence. Hoppe-Seyler^ assigns as the rotation power of egg albumen (a),, = — 35.5, and for serum albumen {a)j) = — 66. Uoth acids and alka- lies seem to increase the rotating power, which may with acetic acid reach («), - - 71. JTredericq* gives the rotation number for blood serum for the rabbit, cow, and horse at (»)„=— 57.3, and for the dog at —44. Paraglobulin, according to the same author, has a rotation number («)„=— 47.8. Milk albumen^ has the following numbers assigned to it : Dissolved in Mg.SO^ sol. ((i)d=— 80 Dissolved in dil. HCl. (a)n=-87 Dissolved in dil. NaOH sol. («')d=— 7C Dissolved in strong KOH sol. (01)1,=:— 91 The hydrates of albumen^ have rotation powers which vary from (a)„=— 71.40 to (a)„=— 79.05. From the chaotic state of knowledge concerning the specific rotating power of the various albumens, it is im- possible to assign any number which will bear the test of criticism. For the purposes of this report, however, this number may be fixed at (a)„=— 70 for the albumens which remain in solution in the liquids po- larized for milk sugar. The phenomenon of "birotation" in milk sugar has already been noticed. The problem of analysis of this sugar is, however, still fur- ther complicated by the facts pointed out by Schmoeger'' and Erdmann," that when milk is rapidly evaporated in a plain dish the sugar is left in the anhydrous state, and that this sugar in fresh solutions exhibits the phenomenon of " half rotation." When such sugar is extracted with alcohol and re-evaporated, it, doubtless, is still anhydrous. But in the calculation of results this sugar is generally estimated as con- taining water of crystallization, and thus an error, which Schmoeger reckons at as much as .2 \)ev cent., is introduced into the results. This ' Wiirtz, Diet, de Cliimie, vol. 1, 1st part, p. 91. ^Compt. Eend., vol. 93, p. 46,5. 3 Hpppc-Scylcr in Handbook of the Polariscopo, Landolt, p. 948. ■• Killino and Chittenden, Am. Clicni. .loiir. vol. 6, p. 45. "Ber. chem. Gesoll, vol. 12, 1915 et seq.; vol. 13, p. '212 et scq. "Ber. chem. Gesell., vol. 12, p. 2180 et scq. 108 POODS A:t^D F00t> ADtJLTEEANTS. fact, not well recognized, combined with the knowledge that in the proc- ess of evaporation many particles of sugar must be occluded by the hardening caseine, teads to throw doubt upon the accuracy of estimat- ing the sugar by the extraction method. The work which I undertook had for its object the determination of the best method of preparing the milk-sugar solution for -the polari- scope, and a comparison of the numbers obtained by this instrument with those given by the ordinary process of extraction. The reagents used for removing the albumens were : (1) Saturated solution basic lead acetate, specific gravity 1.97. (2) Nitric acid solution of mercuric nitrate diluted with an equal vol- ume of water. (3) Acetic acid, specific gravity 1.040, containing 29 per cent. HC2H3 O,. (4) Nitric acid, specific gravity 1.197, containing 30 per cent. HNOj. (5) Sulphuric acid, specific gravity 1.255, containing 31 per cent. IIjS (6) Saturated solution sodium chloride. (7) Saturated solution magnesium sulphate. (8) Solution of mercuric iodide in acetic acid; formula' Kl, 33.2 grams Hg CU, 13.5 grams. Strong IIO2H3O2, 20.0cc. Water, 64.0cc. Alcohol, ether, and many solutions of mineral salts, hydrochloric, and other acids were also tried as precipitants for albumen, but none of them presented any advantages which would make a detailed account of the experiments of any interest. Table No. 9 contains a record of the experiments which led to the adop- tion of Ice. acetate of lead solution, or Ice. acid mercuric nitrate, as the best amount of each for 50cc. of milk. Nearly all the polarisations were made in a 400mm. tube. From two to four observations were made with each sample. An average of these readings was taken for each determination. In the calculations the value of (a)„ was taken at 53 instead of 52.5, the number which subse. quent investigations have led me to believe more exact. The instni- raent employed was a "Laurent Large Model" polariscope. In all cases the volume of the solution was corrected for the volume of the precipitated caseine. The volume was assumed to occupy 2cc. for each 60cc. milk. Since in the Laurent instrument the weight of sucrose in lOOcc. to read even degrees on the scale is 10.19 grams [(a)„=66.67], it follows that the weight of lactose in lOOcc. to read one degree on the scale for each percent, lactose present would be 16.19 : a;=53: 66.07; a;=20.37. If 52.5 be taken as the value of (a)„ for lactose, then a; = 20.56. In table No. 9, A indicates acetic acid, Pb basic acetate of lead, MR acid mercuric nitrate, &c. The letters O and H indicate the tempera- ture ; denoting the ordinary temperature of the room, and H that the sample was heated to 100° C and cooled before filtering. '.)oiir. do Phnriri. ol. do. Oliiin., vol. 10, p. 108. UAIKY PRODUCTS. 109 The numbers obtuiued by extraction witb iilcoliol are taken as the basis of coiU'ptirisou, not because I believe tlieni to be more reliable, but because that metboil is the one geuertilly employed in the estimation of milk sugar. In the alcohol extraction the milk was evaporated to dryness in a thin glass capsule, the dish and dried residue pulverized in a mortar, washed with ether into a continuous extraction apparatus, exhausted with ether, and then with 80 per cent, alcohol for ten hours. Duplicate analyses are indicated in the table by the small brackets. Table No. 9. — Percentage of milk sugar. 11. Eeagents employed in precipitating albumens. ill i PI) loo. Pb2co. Pb3oo. Pb4oc. Pb 5gc. A5oc. Other reagentB. r-^ ^ Per cent, lactose. 4.57 1 (10-.) 3.67 4.23 2 4.52 2.45 3.57 4.14 3 4.46 4.48 3.57 4 3.92 4.19 3.35 5 4.35 3.55 4.32 6 3.71 4.01 3.00 7 4.10 (4.63 i4.96H (4.44 54.68 H 8 4.16 f4.29 14.33 (3.80 5 3.67 H 9 4.48 C4.59 i4. 56 H (4.04 J 4. 12 H HsSOi 10 4.10 4.12 H 3.47 H H 4.80 4.87 H (4".) 4.44H 4". 5". 6". 8"". 12 4.77 5.02H 482H 4. BOH 4.31H 4.70 H 4.76 H 3" 3.89 4.76H 4.78H 13 4.25 4.25 3.75 3.38 3.38 3.97 HNOa 14 4.22 3.14 4.90 H (4.40 5 4.32 H 4.58H m 4.68H 4.66H 4.50H 16 3.30 4.43H 3.98 17 4.72 4.45 4.18 3.87 3.65 3.26 3.96 (3.98 53. 88 H 3.88 18 4.88 (4.87 > 4. 87 H (4.37 5 4.25 (5". ) 4.27 4.43H2SO4 19 4.31 (4.71 i 4. 86 H (4.43 5 4.43 H (•4.51 i4.79H 54.59 54. 59 H 20 4.89 4.11 21 4.70 4.17 23 4.96 (4.93 i 4. 97 H (4.45 54.43 H (4.69 J4. 67 H 23 4.60 (4.41 5 4.45 (3.86 5 3.86 (3.90 5 3.90 53.94 54.10 24 4.74 (4.41 i 4. 45 H (4.21 5 4. 35 H (4.32 5 4.44H 54.32 H55H 25 4.59 (4.33 { 4. 37 H (NaCl H29H 1".MR (3.84 5 3.93 H (4.03 5 4.10 H (3.98 54. 10 H 26 4.39 4.29H 27 4.00 4.18 H 4.66 28 4.26 3.67 H 4.09 Eema/rTcs on Table No. 9. — The results obtained by using various other reagents for the precipitation of the caseine, viz, MgSOi, CUSO4, HOI, &c., have not been entered in the table. In none of these cases was there sufficient encoui'agement to warrant an extended trial. In most cases the precipitation was slow or imperfect, and the filtration difiScult. One important fact should not be overlooked, viz, that any excess of basic plumbic acetate causes a rapid decrease in the rotatory power of the solution ; whether this decrease is due to precipitation of the sugar 110 FOODS AND FOOD ADULTEKANTS. or solution of the albumeus does not clearly appear. Illustrations of this decrease are seen in analyses 2, 12, 13, and 17. It seems to make little difterence whether the precipatition is made hot or cold. The question of temperature is set forth in greater detail iu the next table. From all the experiments made it clearly appeared that the best optical results are obtained by the use of a minimum quan- tity of basic lead acetate, or of either the acid mercuric nitrate or iodide. For oOcc. to GOcc. of milk. Ice. of the lead acetate or mercuric nitrate solu- tion of the strength noted, and 25cc. of the mercuric iodide solution are the proper quantities. It makes no difference, however, if a large excess of the two latter reagents is employed. Of the. three the last is to be preferred. In Table No. 10 will be found the results of the comparative determina- tions of milk sugar by extraction with alcohol, by precipitation with Ice. basic lead acetate, and the same with Ice. acid mercuric nitrate, hot and cold, to each GOcc. of milk. Iu many of the analyses the large differences in results by the three methods show a fault of manipulation, but all the results have been given without selection. Table No. 10. — rercentage of milk sugar. No. Reagents employed. No. Keagents employed. Extract ed by al- cboUol. C. Pb loo. H. Pb loo. C. MKlco. H. MRloc. Extract- ed by al- cbobol. 0. Pb Ice. H. Pb Ice. C. MR Ice. H. ME Ice. Perct. Per ct. Pcrct. Perct. Perct. PercU Perct. Perct. Perct. PereL 1 4.65 4.74 4.92 34 - 4.37 4.65 4.93 4.93 •2 4.10 4.22 4.60 35 4.62 4.27 4.41 4.66 3 4.51 4.54 4.2J 4.08 4.02 36 4.88 4.83 493 5.17 4 4.30 4.55 4.53 4.89 4.90 37 4.61 4.30 4.43 4.57 5 4.05 4.14 4.09 4.48 4.39 38 4.79 4.59 4.67 4.91 fi 3.84 3.84 3.98 3.98 39 4.67 4.20 4.41 4.51 7 4.52 4.07 4.73 5.01 5.00 40 4.79 4 64 4.74 4.94 8 4.25 4.21 4.20 4.51 41 3.95 4.10 4.26 4.38 9 4.46 4.61 4.54 4 87 4.87 42 4.00 4.61 4.61 4.77 10 4.92 5.20 5.22 5.43 5.47 43 4.03 4.24 4.37 4.57 11 3.84 3.72 4.00 3.90 44 4.77 4.64 4.70 4.94 12 4.53 4.61 4.64 4.87 4.85 45 4.85 4.63 4.73 lit 4.57 4.64 4.55 4.91 4.84 40 4.71 467 4.93 U 4.G6 4.29 4.45 4.63 47 4.34 4 06 4.12 4.40 15 4.17 3.05 3.75 3.95 3.87 48 4.05 4.67 4.77 4.83 1« 5.oa 4.66 4.61 4. SO 4.86 49 3.67 4.12 4.18 4.36 17 4. 08 4.03 3.94 4.39 4.37 60 3.78 4.68 4.62 4.82 IK 4.23 3.82 3.89 4.08 4.02 51 4.19 4.27 4.57 4.53 19 4.00 4.70 4.84 5.04 5.04 62 3.83 4.68 4.78 4.97 20 4.85 4.39 4.41 4.53 4.05 53 3.86 3.97 4.07 4.21 ai 4.03 4.47 4.47 4.09 4.67 54 4.69 4.59 4.61 4.83 aa 4 47 4.39 4.43 4.67 4.71 55 4.02 4.26 4.36 4.40 a;i 4.4C 4.23 4.31 4.65 4.63 56 4.36 4.62 4.76' 4.94 'ii 4.47 4.50 4.67 5.01 4.05 .57 4.20 4.18 4.28 4.48 as 4.40 4.41 4. 55 4.45 .58 4.09 4.52 4.56 4.74 aii 4.85 4.67 4.73 4.97 59 4.09 4.28 4.46 a7 4.45 4.21 4.33 - 4.57 00 4.12 4.49 4.81 aH 4.44 3.98 4.10 4.28 61 4.20 4.33 4.41 ao 4.10 4.21 4.65 63 4.46 4.25 4.77 30 4.38 6.57 4.00 4.89 03 4.33 4.00 4.37 ai 4.20 4.21 4.37 4.67 64 4.02 4.33 4.99 32 4 GO 4 59 4 67 4 89 38 4.52 4.27 4.41 4.41 Iav 4.33 4.34 4.38 4.58 4.63 Iu the following table will be found the percentage of milk sugar ob- tained by using varying quantities of the mercuric iodide reagent, and a comparison of the results obtained with those given by the use of acid mercuric nitrate and basic plumbic acetate: DAIKY PKODUCTS. Table No. 11. — I'lsrcvnlaije of milk sugar. Ill ti Heagouts-omployod. Mercuric iudido. Pb. ME. 1 20uc. 25oc. 30oc. 3500. Per c.t. I'ar ct. I'cr at. Per ct. I'er ct. Per el. 1 2 it 4.28 4.40 4.37 4.48 4.57 4.05 4.00 4.02 4.03 4.50 4 00 4.03 4.00 4.65 4 4.37 4.53 4.0U 4.03 4.03 4.60 .•i 4.38 4.03 4. 50 4.53 4.53 4.59 fi 4.3.1 4.07 4.43 4.63 4.00 4.66 7 4.30 4.07 4.07 4.07 4.59 4.57 K 4.33 4.50 4.50 4.53 4.50 4.59 9 4.27 4. GO 4.03 4.00 4.00 4.06 Av. 4.34 4.00 4.57 4.58 4.01 4.62 ALBUMEN UEMAINING IN I'lLTKATE FltOM LEAD ACJiTATE AND MERCUlilC IODIDE SOLUTIONS. From the fact that the polariscojnc readings show that solutions of milk prepared with lead acetate have a lower rotating- power than those prepared with mercury salts, it is to be iuferred that Ihe lead Vi agent either leaves certain soluble and transparent kinds of albumen in solu- tion, or else dissolves a portion of those which are at lirst precipitated. To test the accuracy of this supposition a few analyses were made to determine the amount of albumen left in the filtrate from the lead and mercury reagents. At the f?ame time different quantities of the mer- curic iodide solution were used, in order to determine the amount which would give the best results. For COcc. milk the quantity of mercuric iodide to be used should be 25cc. to 30cc. In the following table will be found the percentages of albumen iu the whey after precipitating with the reagents noted and filtering. Ten cubic centimeters of the filtrate were evaporated to dryness in a thin glass dish, and the dried residue (with the glass) burned with soda lime. The calculated nitrogen was then multiplied by 0.25 and the pro- duct taken as the percentage of albumen : Table No. 12. — Per cent, albumen infiltrate. From Pb. From Ugh. 15co. From Hgla. 20cc. From Hsr-. 25cc. From Hgl2. 30cc. From Hgla. 35oc. .0805 .1130 .1130 .0865 . 1130 .1130 .1130 .1950 .1130 .1412 .U30 .1950. .0074 .0074 .0674 .0674 .0090 .0805 .0805 .0502 .0502 .0562 .0805 .1412 .1412 .1412 .1130 .1302 .1250 .0090 .0090 .0805 .0805 .1130 .1130 .0312 .0300 .1130 .1130 .0805 .1412 .0090 .0502 .0805 .0502 .0502 .0805 .0805 .1412 .1412 .1412 .1130 .0805 .0805 .0312 .0502 ' . 0502 .1412 .0562 .1412 .0805 .0805 AV...U82 .0789 .0888 .0839 .0904 .0828 112 FOODS AND FOOD ADULTERANTS. In Table No. 13 will be found percentages of albumen remaining in fil- trate from lead acetate precipitation of forty -two samples taken from those represented in Table No. 10. From these two tables it is at once seen that the quantity of laevo-rotatory matter remaining in milk after treatment with basic lead acetate is much greater than in those samples treated with the two mercuric salts. This explains at once the higher percent, of milk sugar obtained by using the last-named reagents, and ' shows that the use of lead acetate as a clarifying agent must be aban- doned : , ' Table No. 13 — Per cent, albumen aftet- precipitation ly lead acetate. So. Percent. So. Pel- cent. No. Per cent. 1 .250 10 .237 31 .329 2 .306 17 .237 32 .305 8 .136 18 .169 33 .305 4 .272 !9 .103 34 .237* 6 .134 20 .271 35 ■ .305 6 .239 21 .237 30 .339 7 .301 22 .271 37 .237 8 ..305 23 .235 38 .374 9 .237 24 .271 30 .203 10 .339 26 .2^7 40 .373 11 .271 26 .237 41 .305 12 .305 27 .271 42 .339 13 .207 28 .339 11 .237 29 .360 Av.. .278 15 .271 30 .374 COMPAniSON OP RESULTS OBTAINED BY EXTRACTION WITH ALCOHOL AND POLARIZA. TION. ■ By consulting Table No. 10, it will be seen that the percentage of sugar obtained by extraction with alcohol is practically the same as that got by polarization of the lead acetate filtrate. Thus, the mean percentage of sugar by alcohol (65 analyses) is 4.32 ; by lead acetate, cold (53 analyses) is 4.34 ; by lead acetate, hot (64 anal- yses) is 4.38 J by mercuric nitrate, cold (61 analyses) is 4.58; by mer- curic nitrate, hot (24 analyses) is 4.63. If now the milk sugar, as has already been intimated, exists in an anhydrous state after extraction with alcohol, the percentage of it after the addition of the molecule of water would be increased. Thus molec. ular weight of anhydrous milk sugar, 342 : molecular weight of the hydrous 360=4.38 : x, whence the value of a;=4.61. This agrees very nearly with the number obtained by acid mercuric nitrate. By a study of Table No. 13 it is found that the mercuric iodide gives nearly the same rotatory power as mercuric nitrate, and also by com- bustion the filtrates from the milks clarified by lead acetate contain more albumen than those prepared with mercuric iodide. There is, therefore, every reasou for believing that the numbers given by the mercury salts are nearer the truth than those from the lead. It may be urged that the increased rotatory pow er observed by the mercury salts is due to the conversion by the dilute acids of a part of the lactose into galactose, which has a rotatory power greater than that of milk sugar. But when it is remembered that the quantity of acid introduced is extremely minute, tU^lit the samples nee4 Mt be warmed^ DAIRY PRODUCTS. 1 1 3 that they cau be filtered and polarized within a few minutes of the time of the introduction of the reagents, the suggestion is seen to be of no force. For example, in the acid mercuric nitrate it was found that the per- centage of sugar was the same whether one, five, or teu cubic centime- ters of the reagent were employed, and whether it was polarized imme- diately or after heating and cooling. It is evident that Ice. of the re- agent, containing less than a half cubic centimeter of nitric acid and diluted in lOOcc. of liquid, could not exert any notable effect on the rotatory power of the solution. In the mercuric iodide solution 20cc. of acetic acid are used for every 660cc. of the reagent. Thirty cubic centimeters of this reagent contain, therefore, about Ice. of acid. This in lOOcc. of liquid, immediately filtered and polarized, could not affect in any marked degree the rotatory power. Since combustion with soda-lime shows that the filtrate from the mer- curic iodide sample is practically free from albumen, it is evident that the numbers obtained in this way must be a near approximation to the truth. THE PROCESS OF ANALYSIS. The reagents, apparatus, and manipulation necessary to give the most reliable results in milk sugar estimation are as follows: Reagents. — (I) Basic plumbic acetate, specific gravity 1.97. Boil a sat- urated solution of sugar of lead with an excess of litharge, and make it of the strength indicated above. One cubic centimeter of this will pre cipitate the albumens in 50cc. to 60cc. of milk. (2) Acid mercuric nitrate, dissolve mercury in double its weight of nitric acid, specific gravity 1.42. Add to the solution an equal volume of water. One cubic centimeter of this reagent is sufficient for the quantity of milk mentioned above. Larger quantities can be used without affecting the results of polarization. (3) Mercuric iodide with asetic acid (composition already given). Apparatus. — (1) Pipettes marked at 59.5cc., GOcc, and 60.5cc. (2) Sugar flasks marked at 102.4cc. (3) Filters, observation tubes, and polariscope. (4) Specific gravity spindle and cylinder. (5) Thermom- eters. MANIPULATION. (1) The room and milk -should be kept at a constant temperature. It is not important that the temperature should be any given degree. The work can be carried on equally well at 15° C, 20° 0., or 25° 0. The slight variations in rotatory power within the above limits will not affect the result for analytical purposes. The temperature selected should be the one which is mOst easily kept constant. (2) The specific gravity of milk is determined. For general work this is done by-a delicate specific gravity spindle. Where greater ac- curacy is required use specific gravity flask. 19330— No. 13 8 114 FOODS AND FOOD ADULTERANTS. (3) If the specific gravity be 1.036 or nearly so, measure out 60.5cc. into the sugar flask. Add Ice. of mercuric nitrate solution or 30cc. mercuric iodide solution and fill to 102.4cc. mark. The precipitated albumen occu- pies a volume of about 2.4cc. Hence the milk solution is really lOOcc. If the specific gravity is 1.030 use 60cc. of milk. If specific gravity is 1.034 use 59.5CC. of milk. / (4) Fill up to mark in lu2.4cc. flask, shake well, filt«r, and polarire. KOTES. In the above method of analysis the specific rotatory power of milk sugar is taken at 52.5, and the weight of it in lOOcc. solution to read 100 degrees in the cane sugar scale at 20.56 grams. This is for instruments requiring 16.19 grams sucrose to produce a rotation of 100 sugar de- grees. It will be easy to calculate the number for milk sugar whatever instrument is employed. Since the quality of milk taken is three times 20.56 grams, the polar- iscopic readings divided by 3 give at once the percentage of milk sugar when a 200mm. tube is used. If a 400mm. tube is employed, divide reading by 6; if a 500mm tube is used, divide by 7.5. Since it requires but little more time, it is advisable to make the analysis in duplicate, aud take four readings for each tube. By follow- ing this method gross errors of observation are detected and avoided. By using a flask graduated at 102.4 for OOcc. no correction for volume of precipitated caseino need be made. In no case is it necessary to heat the sample before polarizing. ESTIMATION OF THE ALBUMINOIDS. The albuminoids in milk are most easily estimated by combustion with soda-lime or by previous conversion into ammouic sulphate and subsequent distillation from an alkaline liquid. (1) Combustion with soda-lime— From 4 to 5 grams of milk measured from a weighing flask are evaporated to dryness in a scbalchen either alone or with saud, gypsum, pumice-stone or asbestos. When dry the whole is rubbed up in a mortar, transferred to a combustion tube, and burned in the usual way. The nitrogen calculated from the ammonia formed multiplied by 6.25 gives the total albuminoids. (2) The estimation of the albuminoids by Kjeldahl's method is so well understood that it will not be necessary to describe it here. Following are the results of the analyses of milks made in this labo- ratory. > In table No. 14 are the results of the daily analyses of milk from the Maythorpe Dairy. In table No. 15 are the numbers obtained with milks from various sources. In these analyses the fat was estimated by the modified Soxhlet method, the sugar by the optical method, aud the albuminoids by com- bustion with soda-lime. DAIRY PEODUCTS. 115 Tablk No. 14. — Analyses of milk froiti May thorpe Dairy. [All tliese eamplos woi'o bouu,lit from D. M, Nusbit, CoUoy;© Station, Md.l ^Number. Speoifio gravity at 15° to. Wiiter. Tut areomo- trio. Albu- mi- noids. Sugar. Asb, Total soliUa. 1 1.0348 1. 0340 1. 0333 1. 0339 1. 0326 1.0316 1.0337 1.0362 1. 0341 1.0333 1.0316 1.0367 1.0334 1. 0368 1.0328 1.0358 1. 0335 1.0325 1. 0323 1. 0353 1.-0328 1. 0368 1. 0328 1. 0326 1. 0329 1. 0349 1. 0323 1. 0369 1. 0330 1. 0344 1. 0339 1. 0363 1. 03:i4 1. 0369 1.0339 1. 0346 1. 0350 1. 0340 1.0340 1. 0355 1. 0325 1.0333 1.0338 1. 0318 1.0343 1. 0343 1.0328 1. 0334 1.0342 1.0327 1.0338 1. 0319 1. 0319 1. 0318 J. 0343 1. 0323 ]. 0338 1.0332 1.0317 1. 0325 1.0354 1. 0339 1. 0340 1. 0340 1. 0306 1.0331 1.0305 1.0328 1.0314 1.0320 1. 0320 1. 0334 1. 0317 1. 0345 1.0310 1.0340 Per ct. 87.31 86.96 87.62 "87." 69 - 87.08 87.27 87.98 86.07 87.62 87.89 87.04 86. 09 85.44 86,73 84.58 87.84 87.33 86.60 86.24 88.56 84.03 84.64 88.10 86.17 85.46 86.69 84.93 85.73 86.00 86.85 85.67 86.65 83.7.1 86.66 "85.67' "87." is' 88.98 87.71 87.04 85.49 86.92 86.10 87.18 87.44 86.79 85.85 87.87 86.56 86.10 87.63 87.60 85.37 86.86 86.14 86.23 87.82 86.61 84.64 86.89 86.98 87.74 87.96 ■ 87.57 89.20 89.01 86.32 87.22 86.89 86.55 88.35 87.12 88.01 87.62 Per ct. '3." 64 4.12 4.00 3.92 "'3.'2i' 3.66 3.98 3.51 4.25 4.62 ""473 4.98 '"i'OT" ""5.' 22" 4.24 '""4." 74' "4." 92' ""5." 08' 4.87 4.75 4.47 4.78 - 4-00 4.11 6.25 4.26 4,66 3.75 3.57 4.03 4.81 4.18 4.03 4.96 3.38 3.51 ■ 4.72 3.76 4.08 4.50 3,16 4,21 '"I'.'OQ 3,94 3.72 3.13 3.88 3.57 3.26 3.02 4,65 4.63 4,11 3.55 3.69 3.06 3.67 Per et. 2.57 2.81 2.61 2.84 2.72 3.63 2.80 3,77 2,75 3,78 2,80 2.80 2.98 3,92 3,04 4,06 3.16 2.03 2.03 4.13 2,98 4.51 2.84 2.73 2.76 3.64 2.87 3.61 2,98 2,59 3.18 3.92 2.80 4.73 3 29 3.11 2.94 3.22 2.76 2.76 2,69 3.04 2,84 2.87 2.69 2.59 2.66 2.80 3.15 2.80 2.87 2.63 2.76 2.60 3.16 2.87 3.87 2.66 2.56 2.66 3.43 2,84 2,80 2,59 2,66 2,63 2.76 2.87 2.73 2.39 2.98 2.87 2.73 2.91 2.69 2.45 Per ct. 4.60 5.00 4.80 4.85 5.05 5.14 6.19 6.10 6,19 5,27 4.99 4.99 5.02 4.65 5.00 4.67 4.92 5.04 4.05 4.70 4.76 4.65 4,90 6.04 4.99 4.85 4.82 4,38 6,14 6.17 6.00 4.70 4.84 3.69 5.13 6.02 5.67 5.02 5.30 5.57 6.0S 4.75 4.90 4.80 4 89 6.03 5.01 4.80 4,97 4.80 5,19 6,20 4.95 4.49 4.86 4.77 5.07 6.15 4.86 4.85 5.16 6,02 6.33 5.37 4,87 4.95 4.33 4.99 '4.67 5.27 4.97 5.15 4.57 6.10 4.49 5,40 Perct. .73 .74 .73 .72 .72 .72 .72 .74 .72 .71 .66 .78 .77 .85 .72 .94 .73 .71 .71 1.21 .65 1.15 .61 .72 .74 .86 .64 .81 .58 .68 .62 .85 .70 .84 .68 .64 .74 .68 .70 .03 .66 .64 .80 .70 .70 .66 .73 .65 .75 .72 .61 .63 .70 .81 .80 .71 .73 .77 .08 .69 .84. .78 .69 .69 .68 .73 .73 .73 .69 .69 .76 .65 .55 .64 .66 .70 Per ct. 12.69 13.04 12,38 'i2.92' 12.73 12.02 13.03 12.38 12,11 12.46 13.91 14.56 13.27 15.42 12.16 12.67 13.40 13.76 11.44 15.97 15.36 11.90 13.83 14.54 13.41 15.07 14.27 13.40 13.15 14.33 13.45 16.25 14.34 "u'-ii' "12." 85" 11.02 12.29 12.98 14.51 13.08 14.90 12.83 12.56 13.21 14.16 12.13 13.44 13.90 12.37 12.50 14.63 1.3. 15 13.86 13.77 12,18 13.49 15.36 13.11 13.02 13.26 13.04 12.43 10.80 10.99 13.68 12.78 13.11 13.45 11.65 12.88 11.99 12.38 2 a 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25.- 26 27 28 29 30 31 32 33 34 36 dG 37 38 39 40 41 42 43 44 45 48 47 48 49 50 51 52 53 64 65 66 67 58 .. 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 116 FOODS AND FOOD ADULTEEANTS. Table No. 14. — Analyses of milk from Maytlu>rjie Dairy — Continued. Number. 77.. 78.. 79.. 80.. 81.. 82.. 83.. 84.. 85., 8G.. 87., 88., 89., 90. 91., 92., 93. 94. 95. 90. 97. 98.. 99., 100 101 102 103 104 106 lOS 107 108 109 110, 111. 112, 113 114, 115. 116. 117, 118, 119, 120, 121. 122, 123. 124, 125 126. 127. 128. 129. 130. 131. 132. 133, 134. 136. 137. 138. 139. 140, 141. 142. 143, 144, 145. 146. 147. 148. 149. 150. 151. 152. 153. 154, 155. Specific gravity at 15° C. 1. 0330 1. 0320 1,0320 1. 0328 1.0318 1. 0334 1. 0325 1. 0330 1. 0311 1. 0332 1. 0321 1. 0322 1. 0333 1.0312 1. 0328 1.0341 1. 0322 1.0322 1. 0312 1. 0322 1. 0332 1.0332 1.0313 1. 0328 1. 0325 1.0345 1. 0,145 1. 0355 1. 0330 1. 0345 1. 0335 1. 0317 1. 0325 1. 0320 1. 0320 1. 0315 1. 0315 1. 0367 1. 0350 1.0354 1. 0i36 1. 0340 1. 0326 1. 0338 1. 0352 1. 0342 1- 0352 1. 0338 1. 0348 1. 0343 1. 0352 1. 0357 1. 0330 1. 0330 1. 0341 1. 0351 1. 0354 1. 0353 1. 0340 1. 0338 1. 0345 1. 0315 1. 0320 1. 0330 1. 0340 1. 0330 1.0341 1. 0320 1. 0333 1. 0336 1. 0360 1.0332 1.0344 1. 0333 1. 0333 1. 0342 1. 0338 1. 0345 Water. Fer ct. 86.10 86.80 84.73 86.34 88.71 86.94 86.01 80.41 87.73 87.09 86.54 80.73 85.75 88.06 87.87 80.94 87.03 86.59 88.30 87.42 87.05 87.22 88.93 87.29 88.31 87.40 87.78 88.38 88.24 88.00 88.58 88.80 87.89 88.47 88.97 87.a'J 87.29 86.10 86.61 87.59 86.37 86.17 86.09 85.88 80.91 87.17 85.99 86.64 87.55 85.41 80.47 87.81 87.66 86.32 86.88 80.57 85.81 87.33 80.34 86.48 86.60 85.60 86.85 87.18 86.18 87.54 86. 98 87.66 80.06 80. 24 88.02 89.38 86.72 85.34 86.41 87.35 86.66 87.08 Fat areorae trie. Per ct. 4.76 4.36 4.25 3.50 3.71 3.97 4.58 4.23 3.61 3.79 4.11 4.41 3.85 4.64 3.61 4.06 3.75 3.78 2.73 4.30 3.08 4.35 4.79 4.07 3.05 3.65 3.60 3.97 3.14 3.73 3.06 3.67 2.01 4.02 4.08 4.67 4.19 4.74 4.28 3.13 4.41 4.45 5.12 5.09 4.16 3.80 4.57 4.47 3.78 4.91 3.99 3.15 4.74 4 50 5.02 4.05 4.51 3.06 4.68 6.05 3.74 5.63 4.09 3.49 4.30 3.51 3.82 6.03 3.33 3^21 3.54 5.35 4.18 3.50 3.83 2.01 AlLu- mi- Doids. Per ct. 2.84 2.45 2.66 2.91 2.59 2.31 2.91 2.63 2.73 2.09 2.63 2.24 3.01 2.34 2.48 2.38 2.56 2.28 2.46 2.45 2.41 2.66 2.59 2.38 2.45 2.41 2.38 2.63 2.63 2.45 2.63 2.24 2.45 2.34 2.52 2.34 2.45 2.84 3.08 2.63 a 52 2.73 2.80 2.69 2.94 2.69 2.80 2.31 2.76 3.01 2.91 2.76 2.91 2.66 2.69 2.69 2.98 2.45 2.03 2.80 2.87 2.48 2.63 3.94 2.98 3.04 2.45 2.34 2.87 2. 91 3.08 2.87 3.15 2.45 2.80 8.04 2.60 2.76 Sugar. Percl. 6.13 5.15 4.90 4.89 4.80 5.49 5.13 5.22 4.60 4.99 4.90 5.30 6.25 6.23 5.25 5.49 6.02 5.29 4.93 5.26 6.27 5.37 4.95 5.37 5.50 5.45 5.33 5.75 5.22 5.67 5.30 5.06 5.07 6.23 5.27 6.07 4.93 5.49 5.36 5.52 5.23 5.25 5.29 5.43 5.30 5.33 5.42 5.24 5.50 5.47 5.32 5.62 5.20 5.27 5.49 6.55 5.58 .5.07 5.39 5.39 Ash. Per ct. .79 .62 .54 .60 .54 .57 .74 .76 .70 .64 .64 .66 .71 .68 .68 .07 .69 .58 .05 .66 .69 .66 .70 .72 .63 .70 .72 .59 .72 .72 .55 .65 .60 .66 .70 68 .66 .60 .76 .73 .73 .74 .69 .72 .74 .70 .71 .72 .79 .71 .72 .77 .72 .71 .69 .75 .76 .89 .75 .79 .77 .71 .73 .73 .74 .60 .67 .74 .66 .58 .73 .59 .78 .70 .60 .75 .64 .69 Total solids. Perct. 13.84 13.20 14.27 13.66 11.29 13.06 13.99 13.59 12.27 12.91 13.46 13.27 14.25 11.34 12.13 13.06 12.37 13.41 11.70 12.58 12.35 12.78 12.07 12.71 11.69 12.60 12.22 11.62 11.78 11.40 11.42 11.14 12.11 11.43 12.03 13.15 12.71 13.90 13.39 12.41 13.63 13.83 13.91 14.12 13. 09 12.83 14.01 13.36 12.45 14.59 13.43 12.19 12.34 13.68 14.12 13.43 14.19 12.67 13. «G 14.52 13.40 14.40 13.15 12.82 13.82 12.46 13.02 12.34 13.35 13.76 11.98 13.28 14.66 13.59 12.65 13.34 12. 32 DAlEV PRODUCTS. 117 Table No. 14. — Anahjses of milk from Maijtliorjpe Dairy — Continued. Number. Specific gravity at 15° C. Water. Fat aroome- tvio. Albn. mi- noida. Sugar. Ash. Total solids. 156 1. 0353 1. 0320 1. 0335 1.0340 1. 0339 1. 0333 Per ci. 86.43 86.40 86.99 80.89 80.73 87.59 87.03 87.73 87.09 Per et. 3.87 5.29 3.91 3.73 ,3.97 3. .30 3.0t 3.43 3.76 4.04 5.41 3.70 Peret. 2.37 2.52 2.63 3.19 2.91 2. GO 3.15 2.06 2.91 2.73 2.27 3.11 3.85 3.92 Per ct. Per ct. .70 .54 .53 .58 .70 .71 .00 .60 .64 Per et. 13.57 13.54 13.01 13.11 13.27 12.41 12.97 12.27 12.91 157 158 159 100 161 102 103 lot 105 166 167 168 169 3.94 Means . .. 1.0334 86.95 4.08 2.78 6.05 .70 13.09 Table 15. — Analyses ofmilTcfrom, various sources. 1* 1. 0315 1.0320 1. 0316 1. 0265 1. 02!;4 1.0245 1.0285 1. 0335 88.14 "87.' 48" 90.91 91.59 88.76 89.84 86.97 4.73 5.86 5.05 2.35 2.01 4.51 2.68 4.07 2.88 2.81 2.84 2.10 .L96 2.06 2.17 2.91 4.67 5.00 4.75 3.77 3.63 2.02 4.23 4.92 .69 .71 .73 .62 .52 .56 .69 .68 11.86 "ii'ra' 9.09 8.41 11.24 10.16 13.03 2* 3* -4t 5t Ct 7t 8J Means . . . L0292 89 09 3.91 2.47 4.12 .65 9.54 " Piom C. J. Loomis, 1413 Stonghton Hill, t Department lunch room. X Thompson's Dairy. KOUMISS. The use of koumiss, both as a beverage and in the sick-room, is rap- idly increasing in this country, and for this reason I have thought it would be of interest to add here the results of the investigations on some home-made koumiss.^ Fermented mare's milk has long been a favorite beverage in the East, where it is known as "koumiss." Although the Tartars and other Asiatic tribes use mare's milk for the manufacture of koumiss, yet it is not the only kind that can be employed. Since the consumption of milk-wine has extended westward cow's milk is chiefly employed for making it both in Europe and America. Mare's milk is considered most suitable for fermentation because of the large percentage of milk-sugar which it contains. Konig'' gives as the average percentage of milk-sugar in mare's milk 5.31. The same author^ gives as a mean of 377 analyses of cow's milk 4.81 per cent, of lactose. Dr. Stahlberg,* who brought forty mares from the steppes of Eussia to Vienna for the purpose of using their milk for 'Am. Chem. Jour., vol. 8, p. 200. » Nahruagsraittel, p. 46. ^ Op. eit., p. 40. ■•Tymowskis' Bodeiitnngdeskumy.B, p. 12, 118 POODS AND FOOD ADULTERANTS. koumisa, fouud its percentage of lactose to be 7.26. On the other hand, ordinary mares that were kept at work gave a milk containing only 5.95 Ijer cent, sugar. The quantity of milk-sugar in mare's milk is great, but there is a deficiency of fat and other solids. It appears to contain fully 89 per cent, water, while cow's milk does not have more than 87 per cent. The process of manufacture is not uniform. In the East the mare's milk is placed in leathern vessels ; to it is added a portion of a previ- ous brewing, and also a little yeast. In thirty to forty-eight hours the process is complete. During this time the vessels are frequently shaken. In the samples analyzed by me the milk was treated with a lactic ferment and yeast. After twenty-four to forty-eight h ours' fermenta- tion the koumiss was bottled. The bottles were kept in a cool place, not above 50° F., and in a horizontal position. When shipped to me they were packed in ice. After they were received in the laboratory they were kept on ice until analyzed. MKTHOD OF ANALYSIS. Carbonic dioxide. — The estiination of the carbonic dioxide was a prob- lem of considerable difficulty. It was evidently impracticable to at- tempt opening the bottle and determining the gas in a portion of the contents. Fortunately I had access to a large balance which would turn with a milligram. On this I weighed the whole bottle, into the cork of which I had inserted a stop-cock such as is sometimes used with a champagne bottle. With the bottle of koumiss were also weighed two drying flasks containing concentrated sulphuric acid with their connec- tions. Having obtained the weight of 1»he whole, the gas was allowed to escape slowly from the stop-cock and to bubble through the sulphuric acid in the washing flasks. These flasks, previously to being weighed, were filled with the gas from an ordinary carbonic dioxide generator. After the gas had almost ceased to flow the bottle of koumiss was frequently shaken. It was also placed in a pail of water having a temperature of 30° C. After half an hour the gas ceased to come over. The whole apparatus was again weighed. The loss of weight gave the quantity of free carbonic dioxide ip the sample. After the analysis was completed the volume of the bottle was measured. It is fair to assume that at 30° C. the koumiss still contained an equal volume of dis- solved OO2. In determining the total CO2 this volume, or its equivalent weight, was added to that obtained by direct determination. By this method the CO2 dissolved under pressure in the bottles is esti- mated separately from that which the koumiss contains in solution under the weight of one atmosphere. Since it is of no importance to separate the gas into these two portions, I have given it altogether in the tables in volume, by weight; and in percentage by weight. DAIRY PRODUCTS. 119 Acidity. — The samples examined showed under the microscope the acetic ferment, and a portion of the acidity was therefore due to acetic acid. It is the custom ia giviag the results of analyses of koumiss to represent the whole of the acidity as due to lactic acid. If ordinary yeast is used, and it generally is, it is possible that acetic acid may be formed. This appeared to be the case with the samples in question, since in distilling them a larger percentage of acid was found in the distillate than could have been expected had lactic acid only been present. I made no attempt to separate these two acids, but estimated the total acidity, and then represented it in terms of both acids. The direct titration of the lactic acid in the koumiss was attended with such diffidulty that the attempt was abandoaed. Whatever indicator was employed, the change in color was so obscured that no sharp reac- tion could be obtained. To obviate this trouble the koumiss was mixed with an equal volume of saturated solution of magnesium sulphate. After shaking the mixture it was poured through a linen filter. The first portions running through were tnrbid. After reflltering these the filtrate was quite clear. Better results were obtained by using with the koumiss equal volumes of alcohol. The filtrate from this mixture was uniformly bright. In this filtrate the acid was estimated by titration with standard sodic- hydrate solution, making the proper corrections for dilnrion and using phenol-phthalein as an indicator. I would recommend this alcoholic method of clarification to all who may have occasion to determine acid in milk. Aleoliol. — The alcohol was estimated by distilling 500ce. koumiss with lOOcc. water uhtil the distillate amounted to 500cc. This, being still tur- bid, was redistilled with a small quantity of water. The flual distillate of 500cc. was used for the estimation of the alcohol in the usual way, viz, by taking its specific gravity and calculating the alcohol from tables. Milk-sugar. — The milk-sugar was estimated by the method I recom- mended in a paper read at the Philadelphia meeting of the A. A. A. S.' Fat. — Twenty grams of the koumiss were evaporated -to dryness in a schalchen, the whole rubbed to a flue powder, and extracted with ether in a continuous extractor. The process of extraction lasted six hours. Albuminoids. — The albuminoids were estimated by evaporating 5 grams of the material in a schalchen, rubbing to a fine powder with soda-lime, and burning with the same in the usual way. ' Am. Chem. Jour., vol. 6, p. 289 etseq. 120 FOODS AND FOOD ADULT-ilRANTS. Water. — In a flat platinum diah partly filled vvit,li washed and dried sand 2 grams of material were weighed and dried to a constant weight at 100° C. Following are the results of the analyses : Table No. 16. — Analyses of Icoumiee. 13 M s .a ■2 1 .5 «S . Ho. of analysis. °.2 ■s o ^ S5 bO s 1 1 r § & rs ■3 i a ID ^ > ^ o < <1 «l ^ ■< fH ^ '^ Grams. Litreg. drams. Pr. ct. Pr. ct. Pr. ct. Pr. ct. Pr. ct. Pr. ct. Pr. ct. Pr. ct. Pr. ct. .67 .87 .431 2.69 2.21 4.33 4.3] 2 729. n7fi 3.140 6.186 .85 .31 .47 .60 .412 2.58 2.15 89.53 3 768. 575 730. 035 746. 187 750. 247 738.840 752. 550 3.170 3.281 3. 67D 2.073 3.204 3.203 0.260 6. 463 6. 850 5.767 6.313 6.428 .82 .88 .91 .77 .85 .86 .34 .30 .32 .27 .33 .51 .45 .48 .43 .40 69 .81 .86 .70 .73 .77 .483 .482 .423 .450 .462 .450 3.02 3.01 2.64 2.81 2.89 2.81 2.07 1.99 1.67 1.75 2.44 2.34 89.15 89. 3i 89.97 89.87 89.01 88.87 4.33 4 5 4 43 6 7 4 48 g .83 .31 .47 .70 .449 2.56 2.08 89.32 4 .IS It will be of interest to compare these results with those obtained by other analysts, both with koumiss from mare's milk and from other sources. As a mean of fourteen analyses of mare's milk koumiss, Konig' gives the following figures, viz: Per cent. 1.84 0.91 1.24 1.97 1.20 0.30 0.952 Lactic acid Fat Ash Carbonic dioxide The mean of two samples of koumiss made of cow's milk is given by the same author, as follows : Per cent. 2.G4 0.80 3.10 2.02 0.45 1.03 Lactic acid Albuminoids Ash Carbonic dioxide In nine analyses of koumiss* probably made of cow's milk the means are as follows : Per cent. 1.38 0.82 3.95 2.89 0.88 • 0.53 0.77 Lactic acid Milt-sugar. Fat Ash Carbonic dioxide ' Kouig, Nahrungsmittel, vol, 1, p. 68. Qp. oU., vol, 1, p. 68. DAIRY PRODUCTS. 121 Interesting analyses of koumiss prepared from mare's milk have also been made by Dr. P. Vieth.* The mares from which the milk was taken were on exhibition at the London International Exposition for 1884. These animals were obtained from the steppes of Southeastern Eussia. The mares were from five to six years old, and were cared for and milked by natives of the country from which they were taken. When milked five times daily the best of these mares gave from four to live litres of milk. It is to be regretted that the milk-sugar, the most important ingredient of milk in respect of koumiss manufacture, was estimated by difference. Eleven analyses of the mixed milk gave the following numbers : TaMe of analyses. Specific gravity. Water. Fat. Albuminoids. MUlt angar. Asli. 1.0335 1.0360 Per cent. 89.74 90.41 Per cent. 0.87 1.25 Per cent. 1.71 2.11 Per cent. 6.30 6.82 Per cent. 0.20 0.36 Mean - . 1.0349 90.06 1.09 1.89 6.65 0.31 The koumiss from the above milk had the following composition: Sample Ko. Water. Alcohol. Fat. Albumi- noids. Lactic acid. M'ilk- sugar. Ash. 1 Per cent. 90.99 91.95 91.79 91.87 92.38 92.43 91.42 92.04 91.99 Per cent. 2.47 2.70 2.84 3.29 3.26 3.29 2.25 2.84 2.81 Per cent. 1.08 1.13 1.27 1.17 1.14 1.20 1.22 1.10 1.44 Per cent. 2.25 2'. 00 1.97 1.90 1.76 1.87 1.75 1.89 1.69 Per cent. 0.64 1.16 1.26 0.96 1.03 1.00 0.70 1.06 1.54 Per cent. 2.21 0.69 0.51 0.39 0.09 0.00 2.30 0.73 0.19 Per cent. 0.36 0.37 0.36 0.33 0.34 0.35 0.36 0.34 0.34 2 3 4 5 6 ... , 7 8 9 Mean 91.87 2.86 1.10 1.91 1.04 0.79 0.35 Collecting the above means together, we have the following compara. tive table : Sample M'o. Alcohol. Lactic acid. Sugar. Albumi- noids. Fat. CO2. Water. 1 Per cent. 1.84 2.64 1.38 2.86 0.76 Per cent. 0.91 0.80 0.82 1.04 0.47 Per cent. 1.24 3.10 3.95 0.79 4.38 Per cent. 1.97 2.02 2.89 1.91 2.56 Per cent. 1.26 0.85 0.88 1.19 2.08 Percent. 0.95 1.03 0.77 Per emt. 292. 47 88.72 289. 55 91.87 89.32 2 3 5 0.83 NOTHS.^No. 1, mean of 14 analyses of lioumiss from mare's milk ; No. 2, mean of 2 analyses of koumiss from cow's milk ; No. 3, mean of 9 analyses of koumiss, origin unknown, probably from skimmed ow's milk ■ No. 4, mean of 9 analyses of koumiss made from mare's milk, London Exposition of 1884 ; No. 5, mean of 8 analyses of koumiss from cow's milk, made by Division of Chemistry, United States Department of Agriculture. ' Landw. Versnohs-Stationen, vol. 31, pp. 353 et seq. > By difference. 122 POODS AND FOOD ADULTEEANTS. The comparison of the above results shows that the American koumiss differs from that of other countries in the following points, viz : (a) The percentage of alcohol is quite low and as a consequence the percentage of sugar is high. (&) American koumiss contains more fat; showing that it has been made from milk from which the cream had not been so carefully re- moved as in those milks from which the European koumiss was made. Mare's milk, as will be seen by the above analyses, contains much less fat and more sugar than that of the cow, thus making it more suitable for the production of koumiss. Good cow's milk, however, is suitable for the manufacture of koumiss after most of the cream has been removed. Should it be desired to make a koumiss richer in alcohol, some milk- sugar could be added. The samples analyzed were kindly furnished me by Mr. Julius Haag, of Indianapolis. This koumiss makes a delightfully refreshing drink. When drawn from the bottle and poured a few times from glass to glass it becomes thick like whipped cream, and is then most palatable. It is much relished as a beverage, and is highly recommended by physicians in cases of imperfect nutrition. Those desiring to study the therapeutic action of koumiss should consult the monographs of Biel,' Stahlberg,' Landowski,^ and Tymowski.* CHEESE. No studies of cheese have been made in this laboratory. OaldwelF has given a r6sum6 of the subject up to 1882, as follows: Literature. — Tho subject, of tht adulteration of cheese receives only brief meutioD either in the journals or iu mouograpli works on adulteration of food. The Analyst" quotes from the Chicago Journal of Commerce tho statement that soapstoue, soda, and potaali aro added to cheese. Hassell' states that cheese is adulterated with potatoes in Thuringia and in Sax- ony, and that bean meal is sometimes added in the place of potatoes ; that Vene- tian red has been detected in several cases iu tho coloring of tho rind, and as this color sometimes contains lead, aud the riud is sometimes eaten, tho frand may be dangerous. He also says it is stated that blue vitriol and arsenic (green ? ) are some- times added, perhaps to give the appearance of age to the cheese, but he has never found them. Ellsner'* says that adulterations of cheese are not known. He mentions oleo- margarine cheese as an article recently introduced in Germany. Griessmayer ' also says that cheese is not adulterated ; but he mentions in appropriate terms a prac- tice of soaking certain kinds of cheese, such as Limbnrger, in urine in order to give ' Untersuchungen iiber den Kumys und den Stoffwechsel wiihrand der Kumyscur. i'Kumys, seine physiologischo und therapeutische Wirkung. St. Petersburg. "Du kumys et de son rrtle th<5rapeuti9,Bt&vch,m/ustard hulls, turmeric, minerals, cracker dust, burnt shells or charcoal. Spent cloves, clove stems, minerals, allspice, roasted shells, wheat flour, peas. Cereals, tv/rmeric, mustard hulls, cayenne, peas. Cereals or starch, buckwheat, wild mace. Cereals or starch, wild nutmeg. Refuse of all sorts, pepper dust, around crackers, or ship stuff; rice, nmstard hulls, charcoal, cocoanat ahelU, cayenne, beans, bran, yellow corn. Cereals amd starch, turmeric, peas, yeUow corn meal, ginger, gypsum. The materials in italics have been identified in spices examined in the laboratory of this division, but some of the commoner adulterants have not been found. Considering the spices individually, there are certain peculiarities, as they are met with pure and in the trade, which should not be overlooked. MUSTARD. Mustard, as sold in the ground state, should be the farina or flour of the black or white mustard seed — that is to say, the flour from the in- terior of the seed bolted or separated from the hulls. The two kinds of 140 POODS AND FOOD ADULTERANTS. seed, although derived from plants of the same genus, are somewhat different in their chemical composition. The black seed is much the most pungent, and develops, on mixing with water, a volatile oil, which gives this condiment its penetrating character. There is also present in the seed a complicated organic substance of a bitter nature, to which is due some of the peculiar flavor, and while the white seed forms no volatile oil with water, it contains more of the bitter substance. It is, therefore, very common to mix the two in grinding. The sources of the seed are various. In our markets at present there are quoted Califor- nia black and while, Dutch, Trieste black, and English — the last being the most valuable. In the manufacture of the seed into flour for the market, two customs have arisen which change the nature of the original substance, and there- fore would commonly come under the head of adulteration. One is ex- tremely old, the addition of wheat flour for the purpose of making the condiment keep better. This necessitates the restoration of the yellow color by turmeric, or other dye-stuff. These diluents are harmless as a rule, but there seems to be no reasons for their use, and it is gradually becoming commoner to find mustard free from them in English brands. The other custom is the abstraction of the fixed oil by pressure before grinding the seed. The percentage of this oil is over 30. It adds nothing to the flavor of the mustard, probably injures its keeping qualities, makes the seed more difficult to mill, and its removal is therefore a benefit. It is a nearly universal custom at the present day in this country, and is not considered as fraudulent by the Canadian analysts. Falsifications of mustard other than those mentioned are not common, although gypsum has been found in low-grade mustard and several other adulterants, among them ginger of low grade. The hulls bolted from the flour in the process of manufacture are preserved and form the basis of the adulteration of many other spices. PEPPEE, BLACK AND WHITE. Pepper is more in demand than any other spice, and in consequence is more adulterated. Its appearance in the ground form, especially of the black, is such as to make it possible to use all sorts of refuse for this purpose, and almost everything that has been used as an adulterant has been found in pepper. White pepper, which is simply the black deprived of its outer black coats, is, of course, less easily falsified; but in France is diluted to an immense extent with ground olive stones, which bear a striking resemblance. A?nong the samples from Washington grocers, pepper sweepings — that is, husks and dirt — rice or corn, and mustard-hulls were the commonest admixtures. Sand is said to be very commouly added abroad, but has not been met with here. In Can- ada and New York ground cocoanut-shells are a cheap source of adul- teration, but they have not extended so far south. SPICES AND CONDIMENTS. 141 Specimens from Baltimore mills of very low-quality goods were found to contain but little pepper, and that of the worst quality, being made upi of cracker dust, yellow corn, cayenne, and charcoal in so disgraceful a way as to be visible to the unassisted eye on close examination. The quality of a ground pepper can be told by an expert from its weight and color, and on examination with a lens of low magnifying power. The particles are not coarsely ground, and it is not difficult to l)ick oat pieces of husk, yellow corn, and rice, and, if necessary, a more careful investigation under a microscope of higher power will serve for confirmation. Black pepper, in our experience, is much more liable to adulteration than white, although it is perfectly easy to dilute the latter with broken rice or cracker dust, which are inexpensive. All these materials, fortunately, owing to the grossuess of the adulteration, are readily recognized, and there is hardly the necessity for recourse to chemical analysis. There has been, however, considerable investiga- tion in this direction, so that there are means of confirming the optical examination which are of great value. Determination of the amount of starch is one of the methods upon which some reliance can be placed ; for, if under the microscope foreign starch is not detected, then the ad- dition of " P. D." or other starch free adulterants, will diminish the per- centage found, and the reverse. In this way, too, one is able to arrive at an approximate conclusion as to the proportion of adulterants added, which can only be estimated within wide limits under the microscope. In spite of the immense amount of adulteration, it is possible, from the best shops, to obtain pure ground peppers, but it is at the same time safer with a family spice-mill to grind the whole berries as they are needed. The sources of our pepper supply are Tellicherry on the west coast of Hjndostan, which is graded high, and Penang and Sing- apore for the east, Sumatra, Java, &c. The importations are princi- pally through London, and not direct. The supply of ground pepper from England will usually be found more pure than our own brands, and at the same time is naturally more expensive. CAYENNE OE RED PEPPBK. This condiment should consist of the ground pods of any of several species of Capsicum, known as chilies or peppers. It is said to have been adulterated with many substances, brick dust, red lead, and coloring matters; but this has only been found to be the case in two cheap Balti- more cayennes, while in Washington only rice has been detected, but that quite frequently. Inferior material is no doubt often ground, but the small value of the pods and the small quantity consumed does not tend to increase adulteration. GINGER. Ginger is the root, or, technically, rhizome, of a plant somewhat similar in appearance to our iris and flag. Ic is grown in various parts of the world and prepared with great C£^re fmd great carelessness, being at 142 FOODS AND POOD ADULTERANTS. times scraped and bleached, at others simply dried in any condition, so that there is an immense number of varieties and qualities to be found in the market. They all, however, retain sufficiently the marked pecu- liarities of the starchy fibrous root to make the detection of adulterants easy. The common ones are the addition of wheat flour or some starch as a diluent, the coloring with turmeric to suit a popular fancy for gingerbread or of spent material which has been used in making tincture. Mustard hulls and cayenne are also found in some cases, but have seldom been detected here. They are added to give pungency and make up for the addition of flour. Their detection is easy. The sources of our supply are Jamaica and the West Indies, Cochin China, Africa and India. Jamaica is the best and most carefully prepared. CLOVES. The flower buds of the clove tree carefully picked and dried consti- tute the spice known by that name. Their valuable properties are due to the volatile oil which they contain, the best having as much as 16 per cent. The removal of this oil is so very easy that it is the commonest method of deception to do so before grinding the spice and to then dispose of it as pure. We have ready means of determining the loss chemically, but the microscope gives no indications. The addition of the cheaper clove stems is also practiced, as they cost but 6 cents when the buds cost 27. The microscope reveals their presence by certain cells which they contain which are absent in the buds. Pimento is sometimes substituted in part or entirely, as it has a clove- like flavor but only 4 or 5 per cent, of volatile oil. It is worth less than one-fifth the price of cloves. Its chemical composition and its struct- ure, that of a berry, reveals its presence. The addition of the coarser adulterants, mineral matter, cocoanut shells, flour, peas, and the like, have only been observed in two instances, but no doubt frequently occur, as has been found in Canada. The sources of our supply are the East Indies (Amboyna), African (Zanzibar), and American, ranking in value in the order named. Cloves should, if possible, be always purchased whole, as they deteriorate less readily in that form. CINNAMON AND CASSIA. These spices are the barks of several species of the genus Ginna- monum, the true cinnamon being a native of Ceylon, where it is largely cultivated, and the cassias being derived from several other species growing in China, India, and the East Indies. Cinnamon as it reaches the market is very thin, the outer and inner coats of the bark having been removed. Cassia on the other hand is thick, as it consists of the entire bark and can be distinguished by its retaining its natural outer surface. Cinnamon is by far more valuable than the cassia, as there is a smaller supply and iutriusicall y it contains a much greater proper- SPICES AND CONDIMENTS. 143 tioii of volatile oil and that of higher and more delicate aroma. In con- sequence cassia is largely substituted for cinnamon, and in fact not a particle of ground cinnamon can be found in the market. It can be found in the whole condition in good quality only in drug stores. Cas- sia exists in many forms and qualities, and sells at wholesale at from 7 to 40 cents a pound. That known as Saigon is the best, and that ex- ported from Batavia the poorest. Cassia buds also hold a small place in the market. The detection of the substitution of cassia for cinnamon, since the barks are of trees of the same species, is more difflcult than is usually the case and may prove troublesome to a novice. The presence of more woody fiber in the latter with the aid of chemical analysis serves, how- ever, as a reliable distinction. In the samples which have come into our hands not a particle of material labeled ground cinnamon proved to be anything other than cassia. The spice millers appeared, however, to be satisfied to stop at this point and in only one case was there ad- dition of cheap stuff to the cassia. When added there is no difficulty in detecting it as has been done here and in Canada, where peas, starch, ground shells, and crackers have been found in powder labeled both cassia and cinnamon. The barks can, in most cases, and especially the cinnamon, be used nearly as well in the whole condition and should at least be so pur- chased and then ground. A slight acquaintance with the appearance of the different qualities will teach one the proper selection to make. NUTMEG AND MACE. These spices are different portions of the fruit of a tree known as the nutmeg tree, Myristicafragrans, the nutmeg being the inner kernel and the mace one of the outer coats or arillus. The tree grows principally on the Banda Islands and the spices reach us through London. They can always be obtained in their original condition and should be so purchased. When ground they are mixed with diluents of various de- scriptions, principally cereals and their refuse, wh.ch are easUy detected. Owing to the infrequency of the sale of the powdered nutmeg and mace, their adulteration has attracted but little attention. SOURCES OP OUR SPICE SUPPLY. Although the countries where the spices are grown have been al- ready given in a general way and in a later chapter will be given more in detail, these countries, in many instances, are not the direct sources of our supplies. For instance, of the pepper imported in the fiscal year ending June 30, 1886, amounting to nearly 12,000,000 pounds, over 8,000,000 came to us from England, and about 3,000,000 from the British East Indies, including the ports of Singapore and Penang. In regard to the other spices data are found in the annual statement of the Bureau 144 FOODS AND FOOD ADULTERANTS. of Statistics of the Treasury Department and in some additional tables furnished to this office by the Bureau, which are here given: Imports of unground apices, free of duty, for the year ending June 30, 1886. Cotmtries from which imported. Nutmegs. Pepper. All other. Quantity. Value. Quantity. Valne. Quantity. | Value. Argeotiue Kepablic ................ Pmmdt. Founds. Pounds. 2,128 $225 Brazil - 194 $32 Central American States : 12 1 Nicaragua Chili 5,905 344,552 498 45,808 11,825 $3,982 257,402 21,737 Denmark - Danish West Indies Grreenland, Iceland, and the Faroe French "West Indies 300 120 Miquelon, Langley, and Saint Pierre adjacent islands 4,740 247,889 2,293 98,412 16,831 2,003,255 1,832 176,535 8,214,037 1, 167, 264 Gibraltar Nova Scotia, New Brunswick, and Prince Edward Island Quebec, Ontario, Manitoba, and the Northwest Territory 1,465 338 740 35 British Columbia 3,344 889 480 9 3, 017, 943 146,880 British Honduras 464, 862 179, 169 2,927,472 403, 090 1, 006, 938 1, 089, 089 1, 563. 073 66,536 91,650 59, 101 Kong-Kong British Possessions in Africa and 11,984 1,042 British Possessions in Australasia. . 840 66 Greece Hawaiian Islands Hayti Italy Japan Liberia 4,233 907 31, 038 296 100 7,292 50 210, 635 37 83,412 48, 255 7,528 Dutch West Indies ' Dutch Guiana Dutch Bast Indies 245, 912 90, 065 3,261 360 817, 756 35, 618 Peru Portugal Azore, Madeira, and Cape Yerde Islands Portngnese Possessions in Africa and adjacent islands KoUmania Spain 151 856 101,338 36 241 4,302 Cuba Porto Eico Sweden and Norway Switzerland Turkey in Asia 1,160 89 All other countries and porta in All other ooontries and ports in 283, 062 28,154 851,307 68,624 Total 1, 189, 507 458, 379 11,843,453 Missing Page 146 Statement FOODS AND FOOD ADULTERANTS. by customs districts and ports, the quantities and values of spices im- ported and entered for consumption, ^c. — Continued. FKEE OF DTJTr. CnetomB districts and ports. Cloves. Clove stem. Ginger root. Quantity. Value. Quantity. Value. Quantity. Talue. Pounds. PouTids. Pounds. 11,098 20,708 $1, 500. 00 2, 632. 00 88, 214 954, 716 $4, 961. 00 38 664 00 30, 000 $675. 00 Chicago 111 6,606 3,931 1, Oil. 00 601.00 95 1.00 Cinrinnati Ohio Corpus Cbristi, Tex 742 35.00 Kev West Fla 30 8.20 New York N T 1, 234, 576 14.5.. 634. 00 266, 127 5, 057. 00 3, 192, 245 420 174 178. OC 4.0C Oswegatch e N. X Philadelphia, Pa 13, 091 1, 732. 00 34,534 2,392.00 San Francisco, Cal Saint Tionifi Mo 8,101 1, 232 00 986 5,900 51 OC 194.00 Total 1,298,883 154,383.20 296, 127 5,732.00 4, 277, 110 220,415.00 FREE OF DUTY. Customs districts and ports. Mace. Nutmegs. Pepper, white and black. Quantity. Value. Quantity. Value. Quantity. Value. Pounds. Pounds. Pounds. 22, 314 66, 465 $8,634 27,462 429,849 476, 990 460 23, 746 139,726 $57,07* 54, 9.51 102 6,733 $1, 907. 00 Srazos de Santiago, Tex 3 575 20,424 Corpus Christi, Tex Detroit, Mich Dnlutb, Minn Galveston, Tex Key West, Fla 115 11.50 New York, N. Y 115,022 38, 617. 00 1,008,282 395,583 9, 119, 301 1,309,084 Oregon, Greg OswegatchierN. Y 1,465 338 Paso del Norte, Tex 139 118. 00 177 162 195, 455 25 509,882 98,887 25,702 Saluria, Tex 3an Francisco, Cal 86, 014 6,204 23,643 2,858 71,296 15,255 Saint Louis, Mo Willamette, Oreg Total 122,009 30, 653. 50 1,189,450 458,342 10,995,786 1,557,810 SPICES AND CONDIMENTS. 147 Statement showing, hi/ customs districts and ports, the quantities and values of spices im- ported and entered for consumption, ^c. — Continufed. FEBE OF DUTY. Customs districts and ports. Pepper, cayenne. Pimento. All other, n. h. e., or p. f. Quantity. Value. Quantity. Value. Quantity. Valiie. ■ Pounds. Poun,ds. Pounda. Baltimore, Md 130 $4 11, 585 920. 00 9,552 $1, 296 37, 446 6, 111. 00 KevWest Fla 54 5 20 2,400.00 Now Tork NT 723, 459 73, 789 2, 500, 523 109, 605 33, 600 Oa wegatchio IS.'Y 1,081 79, 118 47 5,503 Philadelnhift Pa 130 6 Saluria, Tex 151,313 16, 329 21 511 00 1, 265. 00 "Willamc-tto Oreg Total 813, 210 80, 635 2, 500, 783 109, 615 250, 327 32, 212. 20 DUTIABLE. Customs districts and ports. Aroostook, Me Baltimore, Md Boston, Mass Brazos de Santiago, Tex. Chicago, HI Cincinnati, Ohio Corpus Christi, Tex Detroit, Mich Duluth, Minn Galveston, Tex Key West, Fla Middletown, Conn Minnesota^ Minn New Orleans, La NewTork.N.T Oregon, Oreg Oswegatchie, N. Y Paso del Norte, Tex Philadelphia, Pa Saluria, -Tex San Francisco, Cal Saint Louis, Mo AVillamette, Orog Total . Mustard, ground or pre- serTed, in bottles, or o. Quantity. Pounds. 10, 660 24, 670 5 1,800 45, 207 404, 099 106, 735 4,490 637, 555i Value. $1.35 2, 839. 00 7, 074. 00 278. 00 1.00 317. 00 .42 8, 810.00 100, 609. 00 11, 195. 00 1,111.00 162, 936. 77 All other, ground or produced, n. 8. e. or p. f. Quantity. Pounds, 894' 20 2,762 3,312 90 36, 982 2,295 442 420 94 i 47, 317t Value. $392. 00 1.00 5.00 349. 41 246. 00 9.00 I, 704. 00 498. 00 70.62 167. 00 5.26 5, 431. 29 148 FOODS AND FOOD ADULTERANTS. Uafortuaately, with the exception of pepper and nutmeg, the tables giving the countries from which the imports were made do not distin- guish between the spices. We are, however, able to see that a large portion of our supply comes through England, and the effect of this upon its quality is certainly not to improve it. The amount of each spice entered for consumption is visible in the last table and the port of arrival as well. Ifew York of course receives the largest portion, followed by Boston and Baltimore, which are both milling centers. As the spices are offered by the wholesale merchant they have a va- riable value, the quotations in New York for the week ending Decem- ber 27, 1886, being as follows: Kind of spices. Price per pound. Kind of spices. Price per pound. Cassia : Cents. 7 to 74 51 36 40 30 9 10 lOJ 104 27 27 6 5 3i 4 10 13 50 50 50 Cents. 48 to 50 18 154 10 15 25 26 284 29 84 9 5 31 41 3i 4# 5J 6 61 64 54 5= Pepper : China Saigon : Eolls Acheen, prime Penang, -white SiDgapore, -white ... Zanzibar Bombay Pimento, prime Mnstard : California: Brown Yellow Dutch English Trieste, brown Chips Cloves: Ginger : African Mace: Banda It is of interest to examine these figures and compare them with the prices of wholesalers and retailers of ground spices. The following figures show that; prices alone are often a good indica- tion of adulteration, the ground article being sold at wholesale or even retail for less than the cost of the pure unground spice. Pare whole spices Price per pound. Wholesale. Small lots. Ginger root : Bleached : Cents. Genu. 16 11 14 12 8 10 30 32 32 IS 18 12 12 8 8 10 42 10 9 American Unbleached : 7i to H 35 4 6 26J 27 ■J 7 244 104 16 15} 64 5} 01 04 31 44 3J 41 7 74 36 40 9 ]0 174'"l7J' 04 Clove : Singapore Pepper: White Singapore Best west coast Acheen Mustnrd seed: Bfowii Tiieste Yellow English Califoruia Brown California Cassia bark: Saigon stick Saigou chip LJgna sticks Singapore black pepper- . . Zauzibar red ijeupci* 10 SPICES AND CONDIMENTS. Prices as supplied by spies mills. 149 Name. Price per pound. Wholesale, barrels. Small lots in tin. Cents. 12 16 18 12 10 12 10 7 6 12 10 6 5 20 17 50 25 Cents. 16 20 22 16 14 16 14 11 10 16 14 'I 24 21 54 29 Extra strong mustard Extra American mustard... Beat cloves Pure white pepper CHARACTER OF THE SPICES IN THE DISTRICT OP COLIMBIA. The spices found in Washington are from various markets. The first class grocers carry the best English and rarely good American brands. Adulteration, however, is frequent, especially among the mustards, pep- pers, and cinnamon, the first having lost its oil and added flour, and the last having cassia substituted for it. Amongthe cheaper class of dealers adulterated spices are nearly universal, the supply being obtained largely from Baltimore and to a small extent ground in Washington, both places in which yellow corn and charcoal are much used as adul- terants. Of a series of samples collected impartially from all classes of shops the ratio of adulterated to non-adulterated was as follows : Variety of spice. Pure. Adulter- ated. Substi- tuted. Inferior or sus- picious. Cassia 3 1 10 2" 4 2 ■ 10* 9 Ginger 4 3 1 Nutmeg Pepper : Black White Bed Pimento 3 1 2 1 5 •9 2 5 3 1 *0il expressed in one case and tumeric added and oil expressed in all American brands. The preceding samples, which have proved to be so largely adulter- ated, have been used in connection with a collection of authenticated whole spices obtained directly from the importers as a means ot inves- tigating the methods which have been recommended for the detection 150 FOODS AND FOOD ADULTERANTS. of adulterants, and the results of our examination of published methods and our own work are presented in the following pages, giving to the analyst a large amount of technical and scientific information which is of less interest to the general reader. PART II. THE DETECTION OF ADULTBEATION OF SPICES AND CONDIMENTS. In attempting to detect the adulteration of spices and condiments the methods which can be employed are of three kinds and depend upon the differences in structure between the adulterants and the sub- stances to which they are added, and upon their proximate composi- tion. The former differences are recognized by mechanical separation and the use of the microscope and the latter by chemical analysis. In the use of the microscope a knowledge of and ability to recognize the principal tissues which constitute the particular plant parts which are used as spices and also of those used as adulterants is necessary, while in the chemical examination the principles of proximate analysis must be understood and applied. It is as necessary that the analyst should be thoroughly acquainted with the application of the microscope to the determination of cellular structure as to be able to make determinations of proximate prin- ciples in the substances under examination. In fact, a mechanical sep- aration and microscopical examination is much more expeditious and more at the command of the majority of persons searching for adultera- tion. Chemical analysis requires a systematic and extensive investigation of large numbers of samples, both pure and adulterated, to fix a stand- ard of comparison, and this has hitherto been seldom done, owing to the elaborate nature of the work and the expense involved. It should not be neglected, however, since it serves as a most certain confirmation of the microscopic results, besides furnishing information in regard to the quality of the specimen examined and as to the quantity of any adulterant, which cannot be obtained in any other way. While, there- fore, the microscopic method will always retain its value for preliminary and qualitative examinations, it must, with the development of the means of chemical investigation, become more and more a mere adjunct of the latter, as in fact the microscope has become in all branches of science. The application of the microscope to the detection of adulter- ants will, therefore, be considered first. MECHANICAIi SEPARATION AND MICROSCOPIC! EXAMINATION OF SPICES AND CONDIMENTS. As a preliminary to the microscopic examination a mechanical sep- aration by means of sieves of diff'ereut mesh furnishes a means of de- tecting adulterants and selecting particles for further investigation, SPICES AND CONDIMENTS. 151 which is of the greatest value and often reveals without additional means the presence of foreign materials. Many adulterants are not ground as fine as the spice to which they are added, and by passing the substance through a sieve of from 40 to 60 meshes to the inch the coarser particles remaining will either be recognized at once by the un- aided eye or with a pocket lens or the microscope. In this way turmeric is readily separated from mustard, and yellow corn, mustard hulls and cayenne from low-grade peppers ; in no case was the aid of more than an ordinary pocket lens necessary for subsequent recognition, although higher powers of the microscope were confirmatory. Without entering here into the practical manipulation of the inicro- scope, it may be said that for the purposes of the food analyst it is only necessary to have a stand of good workmanship, not necessarily, though preferably, furnished with substage condenser, but supplied with Nicol prisms for the use of polarized light. Objectives of inch, half-inch, or, for some of the starches, one-fifth inch equivalent focus are sufftcient. One eye-piece of medium depth is also enough. It is also desirable to be provided with a dissecting microscope for selecting particles for ex- amination from large masses of ground spice. For those who can afford it, the large stand of Zeiss made for this purpose proves most useful, but simpler forms or even a hand lens will serve perfectly well. For smaller apparatus it is unnecessary to provide anything aside from what is found in ordinary laboratories. A few beakers, watch glasses, stirring rods, and specimen tubes, with bottles for reagents will be sufficient in addition to the ordinary glass slides and cover glasses. The reagents which are required include, in case no permanent mounts are required : Alcohol, strong. Ammonia. CHoralhydrat, solution 8 parts to 5 of water. Glycerine. Iodine solution : water IS parts, iodide of potash 20 parts, iodine 5 parts. Water, distilled. Schulze's reagent, a mixture of chlorate of potash and dilute nitric acid pre- pared as wanted. Balsam in benzol and glycerine jelly are desirable for mounting media and some sheet wax for making cells. In addition the analyst should supply himself with specimens of whole spices, starches, and known adulterants which can be used to become ac- quainted with the forms and appearances to be expected. It is easier to begin one's study in this way on sections prepared with the knife than upon the powdered substance, and it is often necessary to refer to them for comparison in the examination of trade samples. PHYSIOLOGICAL STEUOTTJBE IN THE SPICES AND THEIR ADULTERANTS. The vegetable tissues which made up the structure of the spices, and the material of a vegetable origin which are added as adulterants, con- sist of cells of different forms and thickness. Those which are most 152 FOODS AND FOOD ADULTERANTS. prominent and common are the parenchyma, the sclerenchyma, fibrous tissue, and the flbro-vascular bundles. Spiral and dotted vessels are also common in several of the adulterants, and in the epidermis other forms of tissue which it is necessary to be well acquainted with though not physiologically. The parenchyma is the most abundant tissue in all material of vegetable origin, making up the largest proportion of the main part of the plant. It is composed of thin-walled cells, which may be recognized in the potato and in the interior of the stems of maize. In the latter plant, also, the fibro-vascular system is well exemplified, running as scattered bundles between the nodes or joints, and easily made out. Fibrous tissue consists of elongated thick- walled cells or fibers which are ^'e^y common in the vegetable kingdom and are well illustrated in flax. They are not as common in spices as in the adulterants. They are optically active, and in the shorter forms somewhat resemble the cells next described. They are seen in one of the coats of buckwheat hulls and in the outer husk of the cocoanut. The sclerenchyma is found in the shells of many nuts and in one or two of the spices. The cells are known as stone cells, from the great thickening of their walls, and to them is due the hardness of the shell of the cocoanut, the pits of the olive, &c. Their structure is illustrated iu Fig. 5 from Strasburger. Fig. 5. Sclerenchyma or stone cells. X 240. (After Strasburger.) Spiral and dotted vessels are common in woody tissue and are readily recognized. With all these forms the analyst should familiarize him- self, and as an aid may consult Bessey's Botany iu the American Science Series. SPICES AND CONDIMENTS. 153 In pepper and in mustard the parenchyma-cells are prominent in the interior portion of the berry, while those constituting the outer coats are indistinct from their deep color in the pepper, but in the mustard characteristic of the particular species. In fact, in many of the spices, especially those which are seeds, the forms of the epidermal cells are very striking, and even if no attempt is made to classify them their peculiari- ties must be carefully noted, as the recognition of the presence of for- eign husky matter depends upon a knowledge of the normal appearance in any spice. The fibro- vascular bundles are most prominent in ginger and in the barks, where in the powdered spices they are found as stringy particles. The sclerenchyma or stone cells, are commoner in the adulterants, es- pecially in cocoanut shells, where may also be seen numerous spiral cells and in the exterior coats fibrous tissue. As aids to distinguishing these structures, the following peculiarities may be cited. The stone cells and fibrous tissue are optically active and are there- fore readily detected with polarized light, shining out in the dark field of the microscope as silver white or yellowish bodies. The flbro-vascular bundles are stained deep orange brown with iodine, owing to the nitrogenous matter which they contain, while parenchyma is not affected by this reagent aside from the cell contents, nor has it any action on polarized light, remaining quite invisible in the field with crossed prisms. STAKCH. Aside from the cellular tissue, starch is the most important element in the plant for the analyst, and its peculiarities will be considered quite fully. It possesses an organized structure and is distinguished by its reac- tion with iodine solution, with which it strikes a deep blue or blackish blue color, varying somewhat with different kinds of starch and with the strength of the reagent. Conversely its absence is marked by no blue color under the same circumstances. Heat, however, as in the process of baking, so alters starches, converting them into dextrine and related bodies, that they give a brown color with iodine instead of a blue black. They are then in fact no longer starch, although their form, often not being essentially changed, permits of their identification. Although a practical experience in recognizing the starches by these characteristics is essential for their rapid detection when occurring as adulterants, a valuable guide may be supplied to a certain extent by artificial classifications, such as Vogel, Muter, and Blyth, after Tripe's work, have arranged. VogePs and Muter's are based on the form and size ot the granules, of the hilum or central depression or nucleus and the prominence and position of the rings. Tripe showed that with polarized light and 154 FOODS AND FOOD ADULTERANTS. selenite the starches of tubers showed a more varied play of colors than the cereal and leguminous starches which are produced above ground. On this fact Blyth has made another classificatiou. Both are of value and interest. Vogel'e table of the different starches and arrowroots of commerce. A. — Granules simple, bounded by rounded surfaces. I. Nucleus central, layers concentric. a. Mostly round or from the side lens-shaped. 1. Large granules .0396 - .0528™™, ri/e starch. 2. Large granules .0352 - .0396""", wheat starch. 3. Large granules .0264, barley starch. b. Egg-shaped, oval, kiduey-shaped. Hilum often long and ragged. 1. Large granules .032 - .079™"", leguminous starches. II. Nucleus eccentric, layers plainly eccentric or meniscus shaped. a. Granules not at all or only slightly flattened. 1. Nucleus mostly at the sm.aller end .06 - .10™™, potato starch. 2. Nucleus mostly at the broader end or towards the middle in simple gran- ules .022 - .060™™, maranta starch, h. Granules more or less strongly flattened. 1. Many drawn out to a short point at one end. u. At most .060™™ long, curcuma starch, b. As much as .132™™ long, cauna starch. 2. Many lengthened to beau-shaped, disk-shaped, or flattened ; nnclens near the broader end .044 - .075™™, banana starch. 3. Many strongly kidney-shaped ; nucleus near the edge .048 - .056™™, sis- yrinchium starch. 4. Egg-shaped; at one end reduced to a wedge, at the other enlarged; nu- cleus at smaller end .05 - .07™™, yam starch. B. — Granules simple or compound, single granules or parts of grannies, either bound- ed entirely by plane surfaces, many angled, or by partly round surfaces. I. Grannies entirely angular. 1. Many with prominent nucleus. At most .0066™™, rice starch. 2. Without a nucleus. The largest .OOdS™™, millet starch. II. Among the many angled also rounded forms. a. No partly rounded forms present, angular form predominating. 1. Without nucleus or depression very small, .0044™™, oat starch. 2. With nucleus or depression .0132 - .0220™™. a. Nucleus or its depression considerably rounded ; here and there the granules united into differently formed groups, buckwiieat starch. b. Nucleus mostly radiatory or star-shaped; all the granules free, maize (corn) starch. b. More or less numerous kettle-drum and sugar-loaf like forms. 1. Very numerous eccentric layers ; the largest granules .022 - .0352™'", batata starch. 2. Without layers or rings .08 - .022™™. a. In the kettle drum-shaped granules the nucleal depression mostly widened on the flattened side, .008 - .0y2"'™, cassava starch. b. Depression wanting or not eul.arged. aa. Nucleus small, eccentric, .008 - .016™™, pachyrhizus starch, bb. Nucleus small, central, or wanting. aaa. Many irregular angular forms. 008 - .0176™™, sechium stai-ch. bbb. But few angular forms; some with radiatory nucleal fis- sure, .008 - .0176, castanos2>ermnm starch. SPICES AND CONDIMENTS. 155 C— Granules simple and compounds, predominant forms, egg form and oval, with eccentric nucleus and numerous layers, the compound granule made up of a large granule and one or more relatively small kettledrum-shaped ones, .025 - .066"'"', sago starch. Muter^s table for the detection of starclies xohen magnified ahout 230 diameters.* [All measurements are given in decimals of an inch.] Group I: All more or less oval in shape and liaving both hilum and rings visible. Name. Tons les mois Potato Bermuda arrowroot. - . St. Vincent arrowroot Natal arrowroot Galangal Calumba Orris root Turmeric Ginger Shape. Oval, with flat ends. . Oval Sack shaped Oval-oblong Broadly ovate Skittle- shaped Broadly pear-shaped. Elongated- oblong Oval-oblong, conical . Shortly conical, with rounded angles. Normal meas- urements. .00370 to. 00185 . 00270 . 00148 . 00148 . . 00129 . 00148 . 00129 . 00148 . 00129 t. 00135 t. 0018.5 t. 00092 t. 00148 t. 00148 Ke marks. Hilum annular, near one ond and incomplete i-ings. Hilum annular, rings incom- plete, shape and size very variable. Hilum distinct annular, shape variable, rings faint, Hilum semilunar, rings faint, shape not very vari- able. Hilumannuldr, incenterand well marked complete I'ings. Hilum elongated, very faint incomplete rings. Hilum semilunar, faint but complete rings, shape var- iable. Hilum faint, shape charac- tei'istic. Very strongly-marked in- complete rings. Hilum and rings scarcely visible, shape variable but cbaract eristic. Group II: "With strongly-developed hilum, more or less stellate. Bean ... Pea Lentil .. Nutmeg Dari Maize . . Oval-oblong Like bean Like bean Rounded Elongated hexagon Bound and polygonal... 00111 t. 00135 — .00074 t. 00111 t. 00055 t. 00074 t. 00074 Fairly uniform. Very variable in size, with granules under . 00111 pre- ponderating. Hilum, a loug depression seldom radiate. The small size and xounded form distinctive. Irregular appearance and great convexity distinct- ive. The rounded angles of the polygonal granules dis- tinctive. Group III : Hilum and rings practically invisible. "Wheat Circular and flat Slightly angular circles . Like barley .00185 to. 00009 *. 00073 . 00148 . 00009 Very variable in size and vety dull polarization in water. The majority measurinj; Rye about .00073 distinctive. Small granules, quite round, Like wheat and here and tliero cracked. Polarizes brightly in water. do .00065 ^.00033 . 00148 — . 00009) .00074— .00011 J .00074 — .00009) do wheat, and runs smaller and more convex. Measurements the only guide. do Sumbal do * Analyst 1, 172-174, November 15, 1876. fAbout. t And a few four times this size. § For small granules, 166 rOODS AND FOOD ADULTERANTS. Muter's table for the detection of starches, ^c. — Continued. Group III: Hjlum anfl rings practically invisible — Continued. Name. Shape. Normal meas- urement. Kemarks. .00090 — ,00009 *, 00074 . 00296 . 00180 regular size, distinctive. tinctive.. Large size and shape cbar- acteristic. Small size and shape dis- tinctive. Small, regular size and ro- tQudity, distinctive. Irregular shape and faint central depression, distinc- tive. Liquorice Helleljore (green or 'black) . . *. 00018 . 00037 . 00009 . 00055 . 00009 Perfectly rotand Irregular Group IV: More or less truncated at one end. Cassia . Cinnamon . Sago (raw) . Sago (prepared) Tapioca . Arum ; Belladonna . Colchicum . . Scammony., Canella Podophyiluin . Aconite . Round . Like cassia . Oval-ovate. - .do. Koundish. Like tapioca . , do do , .do- Very variable . Like tapioca... .do. OOIU to. 00018 00074 . C0009 00260 . 00111 00260 .00111 00074 . 00055 *. 00056 *. 00074 *. 00045 00033- -.00022 -. 00040 *. 00037 Kound or muller grannies and faint circular hilnm. More frequently truncated than cassia, aud smaller. Has circular hilnm at con- vex end and lings faintly visible. Has a la-ge oval or circular depression, covering one- third nearly of each gran- ule. A little over 50 per cent, truncated by one facet, and a pearly hUutn, Smaller than tapioca and truncated by two facets. Kot distinguishable from tapioca. Larger than tapioca, and contains many more trun- cated granules. Smaller than tapioca, more irregular, and hUum not visible. Very variable, form and small size thuouly points. Like scammony, but has visible hUum in most of the granules. Like tapioca, but half the Group Y: All granules more or loss polygonal. Tacca . Oat.... Kice . . . Pepper Ipecacuanha.. Poly or hexagonal. Polygonal do .do. .do. .00075 to. O0037 *. 00037 . 00030 — . O002O .00020 — .00002 *, 00018 Distinguished from maize by its sharp angles. Larger than rice and hilum visible iu some granules. Measurement using one- eighth or one-tweltth inch- power, and then hilum vis- ible. Do. Some round and truncated granules, adhering in groups of three. *Abotit. SPICES AND CONDIMENTS. 157 Blyth's classification. Division 1. — Starches showing a play of colors with polarized light and seleuite plate. Class I. The hilum and concentric rings clearly visible, all the starches oval or ovate, including tous les mois, potato, arrowroot, calumba, orris root, ginger, galangal, and turmeric. Division II. — Starches showing no iridescence, or scarcely any, when examined hy polarized light and selenite. Class II. The concentric rings all hut invisible, hilum stellate, including bean, pea, maize, lentil, dari, and nutmeg. Class III. Starches having both the concentric rings and hilum invisible in the majority of granules. This important class includes wheat, bar- ley, rye, chestnut, acorn, and many starches in medicinal plants. Class IV. All the granules truncated at one end. This class includes sago, tap- ioca and arum, several drugs, and cinnamon and cassia. Class V. In this class all the granules are angular in form and it includes oats, tacca, rice, pepper, as well as ipecacuanha starch. • Of the starches which are included in the preceding classiflcation bat a limited number will be met with in spices and their adulterants or in the commoner foods. One must, however, be able to readily recognize the following : Starches riaturRl to spices aad condimentB. Starches of admixture. Ginger. Wheat and other Pepper. cereals. Nutmeg. Corn. Cassia. Oats. Pimento. Barley. Cinnamon. Potato. Cayenne. Maranta and other arrowroots.- Rice. Bean. Pea. Sago. Buckwheat. The remainder may be found in other foods and in drugs and cannot well be omitted therefore from our classifications. No one of these is complete in itself, but from the characters given and with the aid of our illustrations the starches which commonly occur in the substances which are here considered may usually be identified with- out difi&culty. In practice the manipulation of the microscope and the preparation of the object requires some little experience, biit not more than analysts usually have had. For the benefit of those who have had none, it may be said that a small portion of the sta/rch or spice is taken up upon a clean camel's hair brush and dusted upon a common slide. The excess is blown away and what remains moistened with a drop of a mixture of equal parts of glycerine and water or glycerine and camphor- water and covered with a cover glass. It is well to have a small supply of the common starches in a series of tubes, which can be mounted at any moment and used for comparison. They can be permanently mounted by making with cork borers of two sizes a wax oell-ring equal to the diam- eter of the cover glass, aind after cementing the cell to the slide with 158 FOODS AND POOD ADULTERANTS. copal varnish thinned with turpentine and introducing the starch and glycerine mixture, fixing the cover glass on after running some of the cement over the top of the ring. A little experience will enable one to put the right amount of liquid in the cell and to make a preparation which will keep for some time. After several months, however, it is difficult to distinguish the rings which mark the development of the granule, and although for reference as to size and form the preparation is satisfactory, it is always advisable in doubtful cases to examine some fresh material. For other purposes the starches should be mounted in prepared Can- ada balsam or dammar by well-known methods. In this medium they can be preserved indefinitely, but are scarcely visible with ordinary illumination, and must be viewed by polarized light, which brings out distinctive characters, not seen as well or at all iu other mounts. Appearance in glycerine and water. — When mounted in the manner already described, or in water alone if for only temporary use, and ex- amined under a microscope with an objective of equivalent focus of one-half to oue-flfth inch, and with means for oblique illumination, the starches will display the characteristics which have been mentioned, and which are illustrated on Plates 26, 27, and 28. These illustrations have been drawn from nature by Dr. George Marx, and represent the starches as nearly as possible, as they are seen, and not as in many of the absurd illustrations of the handbooks of microsoopists of the past and present day, which are entirely ideal, representing the granules not as extremely translucent bodies, but with the rings or layers as strongly-marked lines. Examined in this manner the size, shape, pres- ence or absence of a nucleus or hilum, and of the rings and their ar- rangement, can be made out, and the starch referred to its proper posi- tion. Appearance in balsam icitli polarized light. — Mounted in balsam the starches are scarcely visible under any form of illumination with ordi- nary light, the index of refraction of the granules and the balsam being so nearly alike. When, however, polarized light is used the effect is a striking one, and is illustrated in Plates 19 to 21. It is very easy to distinguish all the characteiistics, except the rings, the center of the cross being at the nucleus of the granule. With the selenite plate a play of colors is produced, which is peculiar to some of the starches and forms the basis of Blyth's classification. The principal starches which are met with may be described as fol- lows, in connection with our illustrations, beginning with those of the arrowroot class, including the potato, ginger, and turmeric. Potato starch. — The starch grains of the potato are very variable in size, being found from ,05 to .10""" in length, and iu shape from oval and allied forms to irregular and even round in the smallest. These varia- tions are illustrated in Fig. 57, but the frequency of the smaller granules is not as evident as iu Figs. 30 and 31. The layers are visible in some granules with great distinctness and in others hardly at all, being rather SPICES AND CONDIMENTS. 159 more prominent in the starch as obtained from a freshly cut surface. The rings are more distinct, too, near the hilum or nucleus, which in this, as in all tuberous starches, is eccentric, shading off toward the broader or more expanded portion of the granule. The hilum appears as a shadowy depression (Fig. 57) and with polarized light its position iswell marked by the junction of the arms of the cross, and it will be found by comparison of Figs. 31 and 32, on Plate XYI, that in the potato it is oftener at the smaller end of the granule and in the arrowroot at the larger. With polarized light and a selenite plate the beautiful play of colors is obtained which is the basis of Blyth's classification. The smaller granules, which are nearly round, may readily be confused with other starches, but their presence serves at once to distinguish this from Maranta or Bermuda arrowroot starch. Earely compound granules are found composed of two or three sin- gle ones each with its own nuclus. Of the same type as the potato starch are the various arrowroots, the only one of which commonly met with in this country being the Bermuda, the starch of the rhizome of Maranta arundinacea, and the starch of Turmeric. Maranta starch. — The granules are usually not so varied in size or shape as those of the potato, as may be seen in Figs. 30, 31, and 32, averaging about .07""" in length. They are about the same size as the average of the latter, but are never found as large or as small, which, together with the fact that the end at which the nucleus appears is broader in the Maranta and more pointed in the potato, enables one to distinguish the starches without difficulty. With polarized light the results are similar to those seen with potato starch, and this is a ready means of distinguishing the two varieties, by displaying in a striking way the form of the granule and position of the hilum, as is illustrated in Figs. 31 and 32. Curcuma or turmeric starch. — Tumeric contains a starch (Fig. 63, Plate XXVIII), which, although of the arrowroot class, is quite distinct in appearance from those which we have described. It is most irregular in outline, so that it is impossible lo define its shape or to do more than refer to the illustration. Many of the granules are long and narrow and drawn out to quite a point. The rings are distinct iu the larger ones. The size is about that of the Maranta. Ginger starch (Figs. 41 and 42, Plate XXI, and Fig. 58, Plate XXVII).— This starch is of the same class as those from the potato and Maranta and several others which are of under- ground origin. In outline it is not oval like those named, but more rectangular, having more obtuse angles in the larger granules and being cylindrical or circular in outline in the smaller. It averages nearly the same size as Maranta starch, but is much more variable both in size and form. The riugs are scarcely visible even with the most favorable illumination. 160 FOODS AND POOD ADULTERANTS. Sago starch. — This exists in two modifications in the market ; as ra'V and as prepared sago. In the prepared condition it is characterized by a larger circular depression in the center of most of the granules. The rings are not visible. They are mostly circular in form or approaching it, and vary from .025 to .065°"° in diameter. Leguminous starches, pea and bean (Figs. 39 aud 40, Plate XX, and rigs. 60 and 01, Plate XXVII). — These starches produce but a slight effect with polarized light. The rings are scarcely visible, and the hilum is stellate or much cracked along a median line; the bean more so than the pea, the latter resembling fresh dough kneaded again into the cen- ter as in making rolls, and the former the shape assumed by the same after baking. They arc both somewhat variable in size, ranging from .025 to .10'°"' in length. Nutmeg starch (Fig. 64, Plate XXVIII).— This starch, which in some respects resembles the preceding — the rings being scarcely visible and not iridescent with polarized light — is much smaller in size and quite variable. The larger granules are at times as long at .05™'" and the smallest smaller than .005""°- They are of extremely irregular foriri, with angular depressions and angular outlines, and are distinguished by a budded appearance, caused by the adherence of small granules to the larger. Capsicum starch (Fig. 67, Plate XXYIII) is nearly circular or rounded, polyhedral in form, with scarcely visible rings, and in most cases a de- pressed hilum resembling in size and shape corn starch, but having peculiar irregularities, which distinguish it, such as a rosette-like forma- tion on a flattened granule or a round depression at one end. It does not polarize as actively as maize starch, and can be distinguished from rice by the greater angularity of the latter. Pepper starch (Fig. 65, Plate XXVIII) is the most minute starch that is usually met with, not averaging over .001™™, nor exceeding .005. It is irregularly polyhedral, polarizes well, but requires a high power to discover any detail when a hilum is found. It cannot be confused with other starches. Cinnamon starch (Fig. 46, Plate XXIV, and Fig. 66, Plate XXVIII) has an extremely irregular, polyhedral or distorted granule, often united in groups with smaller granules adherent to the larger one?. In size it varies from .001 to .025, averaging nearly the latter size. In some granules a hilum can be distinguished, but no rings. It is read- ily detected with polarized light. Buckwheat starch (Fig. 62, Plate XXVIII) is very characteristic. It consists of chains or groups of angular granules, with a not very evi- dent circular nucleus and without rings. The outline is strikingly angular and the size not .very variable, being about .01 to .015. Maize or corn starch (Fig. 33, Plate XVII, and Pig. 54, Plate XXVI). — The granules of corn-starch are largely of the same size, from .02 to .03™™ in diameter, with now and then a few which are much smaller. They are mostly circular in shape or rather polyhedral, with rounded SPICES AND CONDIMENTS. 161 angles. They form very brilliant objects with polarized light, but with ordinary illumination show but the faintest sign of rings, and a well-de- veloped hilum, at times star-shaped, and at others more like a circular depression. Bice starch (Pigs. 35 and 36, Plate XVIII, and Fig. 55, Plate XXVI) is very similar to corn starch, and easily confused with it, being about the same size. It is, however, distinguished from it by its polygonal form, and its well-defined angles. The hilum is more prominent and more often stellate or linear. Several granules are at times united. Wheat starch (Fig. 34, Plate XVII, and Fig. 50, Plate XXVI) is quite variable in size, varying from .05 to .012'""' in diameter. It belongs to the same class as barley and rye, the hilum being invisible and the rings not prominent. The granules are circular disks in form, and there are now and then contorted depressions resembling those in pea starch. It Is the least regular of the three starches named and does not polarize actively. Barley starch (Fig. 37, Plate XIX, and Fig. 51, Plate XXVI) is quite similar to that of wheat, but does not vary so much in size, averaging _05mm . ijas rings which are much more distinct, and very small granules adhering to the largest in bud-like forms. Bye starch (Fig. 52, Plate XXVI) is more variable in size, many of the granules not exceeding .02""'", while the largest reach .06 to .OT"""". It lacks distinctive characteristics entirely, and is the most simple in form of all the starches we have described. Oat starch (Fig. 38, Plate XIX, and Fig. 53, Plate XXVI) is unique, being composed of large compound masses of polyhedral granules from .12 to .02"""" in length, the single granules averaging .02 to .015 mm. It does not polarize actively as may be seen in figure and plate, and dis- plays neither rings nor hilum. The illustration shows its nature with accuracy. Our descriptions, it will be seen, do not agree entirely with those of other authors, which in the same way do not agree among themselves. This shows a variation in the peculiarities of size, shape, &c., which must be carefully allowed for, and the necessity for every investigator to compare a starch which he is desirous of identifying with authentic specimens. STB.XJOTTJEE AND PBCULIAKITIES OP THE COMMONER ADULTERANTS. Before proceeding to the consideration of the normal structure and composition of the spices and condiments and the adulterations detected in commercial specimens, it is well to become familiar with the charac- teristics of the common adulterants and materials which are liable to be used for this purpose. The starches have been already described and their value as a means of identifying different vegetable materials noted. By this means we are able to detect the different cereals which are often added as diluents. 22823— Bull. 13, pt. 2 3 162 FOODS AND POOD ADULTERANTS. Maize, or corn as it is commonl5' known, is a common adulterant. By selecting particles from, the ground material and crushing them the character of the starch may be recognized, but in a cursory examiua- tion the first sign of the presence of this cereal is the discovery of one of the thin outer coats of the grain which becomes detached in milling and, being tough, is not readily reduced. In yellow corn it has a pecul- iar pinkish color and simple structure of longitudinal cells. One should learn to recognize it from a specimen ground for the purpose. Rice, which in its broken unmarketable form is sometimes used as a diluent, may be recognized by the brilliant appearance of the hard white particles which must be picked out of the spice under a hand lens, crushed, and examined as usual. Eice bran has not been met with. The two cereals named are the only ones which are commonly met with which introduce starch. Earely clean wheat bran is added, which can be recognized by its distinctive structural character, illustrated in many hand-books, but which can be learned much better from an authen- tic specimen, which should be soaked in chloral hydrate. As modified cereals, we find refuse bread, cracker-dust, and ship-bread in which the wheat starch is much changed from its original form by ■the heat and moisture of the cooking process so that at times it might be confused with a leguminous starch. The softness of the particles and the ease with which they fall to pieces in water reveals the nature of the material. It is a common diluent. Oil-seed, oil-cake, and husks are very commonly used in many parts of the country for purposes of sophistication. They are most readily recog- nized by the peculiar structure of the outer coats of the seed. The particles which can usually be found and selected with a dissecting mi- croscope should be examined in alcohol or glycerine, or a mixture of the two, as the outer coats of some seeds, such as mustard, are swollen by water and become indistinct. The appearance of mustard hulls is given on page 172, and the many varieties of the cruciferous seeds re- semble it much, so that it is difificult to distinguish them, which is, how ever, not important. They are generally distinguished by the outei layer of hexagonal cells, and a middle and an inner coating which con- sist of peculiar angular cells, the latter much larger than the former, which are the most characteristic, and should be compared with speci. mens of seed of known origin. The structure of some of them is dia- gramatically presented in fig. 6, from Schimper. After soaking in chlo. ral hydrate the remaining interior layers are perhaps more easily made out, and in some cases after moderate bleaching with nitric acid and chlorate. The interior of these seeds is not blued by iodine. Peanut or groundnut cake is recognized by the characteristic struct- ure of the red-brown coat which surrounds the seed, which consists of polygonal cells with peculiar saw-toothed thickening of the walls. The seed itself consists of polygonal cells, full of oil and starch granules, which are globular in form and not easily confused with pepper starch. SPICES AND CONDIMENTS. 163 The structure of the brown membrane is best made out in chloral hj - drate, which removes the red color and leaves the fragments of a bright yellow. Linseed cake distinguished by the fact that its husk is made up of one or two characteristic elements. The outer coat or epiderimis is colorless and swells up in water, forming a mucilage like the mustard seed. Beneath this is a layer of thin round yellow cells, while the third is very characteristic, and consists of narrow, very thick- walled dotted vessels. Next to these is an inner layer of compact polygonal cells, with fairly thin but still thickly dotted white walls and dark-brown con- tents, containing tannin. The endosperm and embryo are free from starch ; nor are they colored yellow by potash, as is the case with mus- tard and rape cake. Fig. 6. Fig. 7. Fig. 8. Fig. 9. Fig. 6. Eape-seed husk (exterior surface). Fig. 7. Linaeed kusk. A more, J? less magnified. Fig. 8. Almond shell fragment, ft hairs, g spiral vessels. X 70. Fig. 9. Palm-seed. Interior. X 240. (After Schimper.) Palm-cake is probably not common enough in this country to be used as an adulterant ; nor are olive stones, which as they consist, after bleaching with Schulze's reagent, almost entirely of very thick stone cells, are easily made out under polarized light. Cocoanut shells are often used, it seems from the evidence of the Can- adian analysts. They are similar to the olive stones in structure but more complicated, as in addition to the numerous short stone cells there are many long ones with thinner walls, and here and there spiral ves- sels, from the fibrous tissue, all of which are only readily seen after 164 FOODS AND FOOD ADULTERANTS. bleaching. When the shells are roasted or charred they refuse to bleach, and it is then only possible to class the particles on which the reagents do not act as roasted shells or charcoal. They are frequently used in peppers to give color to material rendered too light by white adult- erants. The composition of these substances is shown in the foUowing deter- mination which reveal the effect of their addition upon the normal composition of the spices : OliTe stones. Cocoannt shells. Water S.63 4.28 41.33 1.56 .25 6.15 •2.13 37.15 1.25 .20 Ash Tiber Albnminoids More in regard to olive stones will be learned when the discussion of the adulteration of pepper is considered. Buckwheat hulls after bleaching with Schulze's reagent show a pre- ponderance of tissue made up of long, slender, and pointed scleren- chyma cells and a smaller amount of reticulated tissue resembling the cereals somewhat and cayenne pepper. Portions of the endosperm or interior of the seed are also visible, and consist of an agglomeration of small hexagonal cells which originally contained starch. The starch is readily recognized by its peculiar characteristics. The sclerenchyma is, of course, optically active and forms a beautiful and distinctive ob- ject with polarized light. Sawdust of various woods may be recognized by the fragments of various spiral and dotted vessels and fibrous material which are not found in the spices or other adulterants. Bark, in some parts of the world a common addition to pepper, is de- tected by its stone cells, which are larger than those of pepper, and of different form and more numerous, and by its fibrous vessels which are made out readily after bleaching. The source of a particular bark can- not, however,'be made out. Bice brail. — This, as several other similar products, is made up promi- nently of two series of cells at right angles to each other, which make up the outer coats of the grain. The structure is best made out after soaking in chloral-hydrate. The cells of one series are long, small, and thin-walled, and are arranged in parallel bundles. The others have very much thickened walls, and are only two or three times as long as broad. They are at times distinguished, for convenience, as the longi- tudinal and transverse cells. The remaining layers of the bran are not prominent. Glove stems, used frequently as a diluent, can be distinguished by their peculiar yellow-dotted vessels and their large and quite numerous stone- SPICES AND CONDIMENTS. 165 cells, neither of which are seen prominently in the substances which are adulterated. These suggestions of the peculiarites of the different adulterants should, of course, be confirmed and supplemented, and the eye accus- tomed to recognize their structure by means of a study of the actual substances, which should always be at hand in the dry and ground con- dition for reference. Quickness and certainty will be much advanced by such facilities. Reference may also be fittingly made here to chemical operations of a general nature, which are applicable .to all the spices. CHEMICAL EXAMINATION. Determinations of a quantitative nature should include — Water. — A. portion of the powdered spice which should pass a 60- mesh sieve, one gram, is to be dried at 105° to 110° 0. in an air bath, provided with a regulator, until on successive weighings a gain is found showing that oxidation has begun. Twelve hours, or overnight, usually sufflces. The loss is water, together with the largest part of the volatile oil. Deduction of the volatile oil, as determined in the ether extract, will give a close approximation to the water. Ash. — In the same portion the ash is determined by incineration at a very low temperature, such as may be best obtained in a gas mufle, which is a most convenient arrangement for work of this description, and far superior to any kind of lamp or burner. The proportion of ash insoluble in acid may also be determined where there is reason to be- lieve that sand is present. Volatile oil and ether extract, — Two grams of the substance are ex- tracted for twenty hours in a siphoning extraction apparatus on the Soxhlet principle, with Squibbs's best ether. The apparatus we use in this laboratory, arranged by Mr. A. E. Knorr, he describes as follows: The substance under examination is placed in a test tube, which is then inserted into a continuous extraction apparatus of the intermittent si- phon class. The tubes used for this purpose are ordinary test tubes, the bottom of which has been blown out. A wad of washed cotton of sufScient thickness is put into the lower end of the tubes to prevent any solid particles of the sample from finding their way into the receiv- ing flask ; another wad of cotton is packed on top of the sample, and the apparatus is then so adjusted that the condensed ether drops into the tube, and, percolating through the sample, siphons into the receiving flask, when the operation is continued ad infinitum. It is al^solutely necessary to use the best Squibbs's ether in order to avoid extracting substances other than oil and soluble in alcohol, and to continue the extraction for at least the time named, as piperine and several other proximate principles are not extremely soluble in ether. If these precautions are followed we have found no diflSculty in extract- ing all the piperine, for example, and obtaining duplicate results of 166 FOODS AND POOD ADULTEEANTS. great accuracy. On stopping the extraction the extract is washed into a light weighed glass dish, and the ether allowed to evaporate sponta- neously and not too rapidly, as in the latter case water is condensed in the dish, which it is difficult to remove. When the ether has disap- peared — which ought not to take too long, as in that case some oil is vol- atilized — the dish is placed in a large dessicator, with pumice and sul- phuric acid — chloride of calcium having been shown to be useless* — and allowed to remain overnight, to remove any moisture. The loss of oil by this process is hardly appreciable. The dish is then weighed, and afterwards heated to 110° O. for some hours, to drive off the volatile oil, beginning at a rather low temperature, as the oil is easily oxidized, and then is not volatile. The residue is weighed, the difference being calculated to volatile oil, and then examined as to its composition of purity. The results are fairly satisfactory, as appears from the follow- ing duplicates: Duplicate fat and volatile oil determinations in apices. No. Percent. Per cent. No. Per cent. Per cent. 4629 5.49 8.38 4632 4.11 3.66 4629 6.23 8.51 4632 3.93 4.22 4630 5.15 6.54 4633 5.00 6.94 4630 4.72 6.50 4633.... 5.33 7.68 46S1 6.64 13. 19 4634 5.15 3.50 4631 6.84 12.14 4634 2.26 3.59 Alcohol extract. — This may be made in the same manner as the ether extract, using, of course, the substance already extracted. The solvent may be either absolute alcohol, that of 95 per cent, by volume, or 80 per cent, by weight. The latter is preferable in most cases, as there is no definite point with the stronger spirit at which the extraction is complete. In the investigation of spices merely for adulteration this extraction is of little value. Starch, &c., reducing sugars. — The amount of reducing material pro- duced by boiling the spices with dilute acid serves with several as an index of purity. In the case of pepper, which contains naturally a large amount of starch, the addition of the common fibrous adulterants re- duces the equivalent of reducing sugars which are indicated by Fehl- ing's solution after boiling with acid. Leiiz and several others have examined the value of this determination. The conclusions which are deducible from their experience and our own are that with attention to proper condition to insure complete conversion to dextrose the results are of value, though apt to fall out too low. It has been found desirable in our laboratory to run as a check a parallel determination on a sub- stance of known reduction equivalent. In this way any variation may be detected. •Fleischer, E., 1884, Zeit. Anal. CUem., 23, 33. ' SPICES AND CONDIMENTS. 167 The method of Lenz is described under pepper and its composition. The conditions which wo have found most desirable are as follows : The '2 to 5 grams of the material, usually 4, which should pass an 80- mesh sieve, must be extracted with strong alcohol and with cold water for some time to remove substances not starch which might be acted on by the acid or reduce Pehling's solution. Then, without drying, it is washed off the filter into an Erlenmeyer flask with about 175 c. c. of water and enough strong C. P. hydrochloric acid added, about 25 c. c, to make the liquid 4 to 5 per cent, of acid gas. The flask is then supplied with a condenser and boiled for four hours, or the liquid may be put in a patent rubber-stoppered beer bottle and digested in a steam bath ; but the latter method is not as certain. After the boiling and cooling, the residue is filtered out, the liquid accurately neutralized with sodic hydrate and made up to 500 c. c. It is then titrated as usually, and can be calculated to glucose or starch on any basis desired. Thorough previous extraction and uninterrupted boiling are the two most important conditions. Without extraction the results are most uncertain and unreliable. Determination of tannin. — The amount of tannin in certain spices, such as filoves and allspice, is quite constant when they are of good quality. Dr. Ellis of Toronto has therefore recommended this as a good means of detecting adulteration in these spices. He has published as yet noth- ing in regard to his methods of application. In oui experiments it has been found to be of some value, but that it is hardly worth while as a mere aid to the detection of adulteration to go so far as the actual de- termination of tannin, it being quite sufficient to determine the amount of material oxidizable with permanganate which is extracted by water after the careful removal of the oil, &c., by ether. This avoids the tedious use of hide powder, or glue, and furnishes results which are rel- atively of the same value. The analyst should therefore prepare himself for carrying out the first part of the modified Loweuthal process, as it is described in Sutton,* and more elaborately in the Berichte iiber die Verhandlungen der Com- mission zur Bestellung eiuer einheitliche Methode der Gerbstoffbe- stimmung, and in Annales de la Science agronomique, Tome 1, 18S6. Particular paius should be taken to secure a good article of indigo carmine, as without this the results are unreliable. That recommended by Schroder is manufactured by Gehe & Co., of Dresden, and is known as Garminum oceruleum. It should be imported for use. Without going into particulars as to the reagents employed in the process, which are probably familiar to all, a few words of caution as to detail of manipulation will be of value. As has been said, preliminary extraction ofthe material with Squibbs lest ether is necessary to remove oil and o*^her substances not tannin, on which the permanganate may act. Ordinary ether will not answer, * Sutton, Volumetric Analysis, 3d edition, pp. 276. 168 FOODS AND FOOD ADULTERANTS. as it contains so much alcohol and water as to dissolve some of the tan- nin. The substance freed from ether should be extracted with boiling water, and the extract made up to such dilution that 10 c. c. is equal to about 10 c. c. of the thirtieth normal permanganate solution used. The titration must be performed slowly to insure accuracy, the permanganate being run in at a rate of not more than a drop in a second or three in two seconds. The eye must become accustomed to the bleaching of the indigo and select some one tint of yellow as the end of reaction. It iS then possible to obtain duplicates agreeing within .1 c. c. even on en- tirely diiiereut tests, as the following figures show : Serial No. 0. 0. of Perm. Per ot. of tannin. 4904 4.33 4.3 4.35 4.15 22.46 22.36 22.62 21.58 The results may be calculated to oxygen consumed or to percentage of quercitannic acid, which would not be strictly correct, 1 c. c. of ^ permanganate being equivalent to. 0052 grams of quercitannic acid. The results obtained with cloves and allspice will be found under those spices. Crude fiber. — This is a merely relative determination, as the term crude fiber designates nothing absolute beyond the fact that a cer- tain amount of substance is insoluble in acid and alkali of certain strength after treatment for a definite length of time at a definite tem- perature. The conditions selected by us are, 2 grams of substance, 200 c. c. of 5 per cent, hydrochloric acid, steam bath two hours, raising the liquid to a temperature of 90° to 95"^' C, flilration on linen cloth, washing back into beaker with 200 c. c. 5 per cent, sodic hydrate, steam bath two hours, filtration on asbestos, washing with hot water, alcohol, and ether, drying at 120° weighing, ignition and crude fiber from loss in weight. This method agrees practically with that known as the Weende method, and while furnishing results which are of some comparative value, leaves much to be desired. The subject will probably be reviewed soon by the Association of OfScial Agricultural Chemists of the United States- Nitrogen and albuminoids. — The methods of determining nitrogen and albuminoids have been discussed and described at length in Bulletin No. 12 of this division. The details of the method of Kjeldahl, as given by Dr. Jenkins, which is the most convenient, are as follows : Deter inination of nitrogen iy the method of Kjeldahl. KBAGBN'TS AND APPARATUS. (1) Hydrochloric acid whose absolute strength has beeu determined, (a) by precipi- tating with silver nitrate and weighing the silver chloride, (b) by sodium carbonate, as described iu Fresenius's Quautitative Analysis, second American edition, page 6d0. SPICES AND CONDIMENTS. 169 and (c) by determining the amount neutralized by the distillate from a weighed quan- tity of pure ammonium chloride boiled with an excess of sodium hydrate. (2) Standard ammonia whose strength, relative to the acid, has been accurately determined. (3) "C. P." sulphuric acid, Sp. Gr. 1.83, free from nitrates and also from ammo- nium sulphate, which is sometimes added in the process of manufacture to destroy oxides of nitrogen. (4) Mercuric ox'de, HgO, prepared in the wet way. That prepared from mercury nitrate cannot safely be used. (5) Potassium permanganate tolerably finely pulverized. (6) Granulated ziuc. (7) A solution of 40 grams of commercial potassium sulphide in one liter of water- (8) A saturated solution of sodium hydrate free from nitrates, which are sometimes added in the process of manufacture to destroy organic matter and improve the color of the product. (9) Solution of cochineal prepared according to Fresenius's Quantitative Analysis, second American edition, page 679. (10) Burettes should be calibrated in all cases by the user. (11) Digestion flasks of hard, moderately thick, weU-annealed glass. These flasks are about 9 inches long, with a round, pear-shaped bottom, having a maximum di- ameter of 2i inches, and tapering out gradually in a long neck, which is three-fourth- of an inch in diameter at the narrowest part, and flared a little at the edge. The total capacity Is 225 to 250 cubic centimeters. (12) Distillation flasks of ordinary shape, 550 cubic centimeters' capacity, and fitted with a rubber stopper and a bulb tube above to prevent the possibility of sodium hydrate being carried over mechanically during distillation. This is adjusted to the tube of the condenser by a rubber tube. (13) A condenser. Several forms have been described, no one of which is equally convenient for all laboratories. The essential thing is that the tube which carries the steam to be condensed shall be of block tin,^ All kinds of glass are decomposed by steam and ammonia vapor, and will give up alkali enough to impair accuracy. (See Kreussler and Henzold, Ber. Berichte, XVII, 34.) The condenser in use in the labora- tory of the Conn. Exp. Station, devised by Professor Johnson, consists of a copper tank supported by a wooden frame, so that its bottom is II inches above the work-bench on which it stands. This tank is 16 inches high, 32 inches long, and 3 inches wide from front to back, widening above to 6 inches. It is provided with a water-supply tube which goes to the bottom and a larger overflow pipe above. The block-tin condensing tubes, whose external diameter is f of an inch, 7 in number, enter the tank through holes in the front side of it near the top, above the level of the overflow, and pass down perpendicularly through the tank and out through rubber stoppers tightly fitted into holes in the bottom. They project about Ij inches below the bottom of the tank, and are connected by short rubber tubes with glass bulb tubes of the usual shape, which dip into glass precipitating beakers. These beakers are 6J inches high, 3 inches in diameter below, somewhat narrower above, and of about 500 cubic centi- meters capacity. The titration can be made directly in them. The seven distillation flasks are supported on a sheet-iron shelf attached to the wooden frame that supports the tank in front of the latter. Where each flask is to stand a circular hole is cut, with three projecting lips, which support the wire gauze under the flask, and three other lips which hold the flask in place and prevent its moving laterally out of place while distillation is going on. Below this sheet-iron shelf is a 'metal tube carrying seven Bnnsen burners, each with a stop-cock like those of a gas combustion furnace. These burners are of larger diameter at the top, which prevents smoking when cov- ered with fine gauze to prevent the flame from striking back. (14) The stand for holding the digestion flasks consists of a pan of sheet-iron 29 inches long by 8 inches wide, on the front of which is fastened a shelf of sheet-iron 170 FOODS AND FOOD ADULTERANTS. as long as the pan, 5 inches wide aud 4 inches high. In this are cat six holes If inches in diameter. At the back of the pan is a stout wire running lengthwise of the stand, 8 inches high, with a hend or depression opposite each hole in the shelf. The digestion ilask rests with its lower part over a hole in the shelf and its neck in one of the depressions in the wire frame, which holds it securely in position. Heat is supplied by low Bunsen burners below the shelf. Dr. Jenkins has used asbestns paper under the flasks, hut finds that with a little care the naked flame can be applied directly to the flask without danger. THE DETERMINATION. One gram of the substance to be analyzed is brought into a digestion flask with ap- proximately 0.7 gram of mercuric oxide and 20 cubic centimeters of sulphuric acid. The flask is placed ou the frame above described in an inclined position and heated be- low tho boiling point of the acid for from five to fifteen minutes, or uutilfrothing has ceased. The heat is then raised till the acid boils briskly. No further attention is required till the contents of the flask has become a clear liquid, which is colorless or at least has only a very pale straw color. The flask is then removed from the frame, held upright, and while still hot, potassium permanganate is dropped in carefully and in small quantity at a time till after shaking the liquid remains of a green or purple color. After cooling, the contents of the flask are transferred to the distilling flask with water, aud to this 2^ cubic centimeters of potassium sulphide solution are added, 50 cubic centimeters of the soda solution, or sufficient to make the reaction strongly alkaline, and a few pieces of granulated zinc. The flask is at once con- nected with the condenser and the contents of the flask are distilled till all ammonia has passed over into the standard acid contained in the precipiiatiug flask previously described and the concentrated solution can no longer he safely boiled. This opera- tion usually requires from twenty to forty minutes. The distillate is then titrated with standard ammonia. The use of mercuric oxide in this operation greatly shortens the time necessary for digestion, which is rarely over an houi'andahalf in the case of substances most diffi- cult to oxidize and is more commonly less than an hour. In most cases the use of potassium permanganate is quite unnecessary, but it is believed that in exceptional cases it is required for complete oxidation, and in view of the uncertainty it is always used. Potassium sulphide removes all mercury from solution and so prevents the formation of mercuro-animonium compojinds which are not completely decomposed by soda solution. The addition of zinc gives rise to an evolutiou of hydrogen aud prevents violent bumping. Previous to use the reagents should be tested by a blank experiment with sugar, which will partially reduce any nitrates that are present which might otherwise escape notice. This method cannot be used for the determination of nitrogen in substances which "yontaiu nitrates or certain albuminoids. In case non-albuminoid nitrogen is to be determined reference can be made to Stutzer and Ladd.* These methods of analysis are suitable to all the spices and have been used with them. They are nothing but general processes, aud are dependent for their value on uniformity in the way they are carried out aud tlie manner in which peculiarities of proximate composition in different spices are considered in drawing conclusious. Determinations of ])articnlar substances, such as piperine, require, however, modifica- tions, which must be described when discussing the analyses of each spice. 'Kept. anal. Chem., 5, Uf2, 163; Abs. Bfer., 19, 1885; and Ladd Kept, of New York Agric. Exp. Sta., 188G. SPICES AND CONDIMENTS. 171 MUSTARD. Mustard of commerce is the seed, whole or ground, of several species of the genus Brassica, cruciferous plants which grow wild and are cul- tivated under very various conditions. The two common varieties are the black or brown mustard, which has a very small seed and furnishes the most t.roma, and the white, which is two or three times as large, often used in the whole condition in pickles and ground, either by itself or oftener in mixture with the brown seed, for the purpose of obtaining the desirable qualities of both. In the ground mustard is found only the interior of the seed and small portions of the husks which have escaped the operation of bolt- ing, which is always employed to remove the coarse fragments. The presence of these particles from their characteristic structure enable us to recognize the source from which the flour is derived and to detect the use of the mustard hulls as adulterants of other food materials. The husk of white mustard is represented, after a drawing by Schimper, in Fig. 10. The outer colorless epidermis consists of angular plates or hexago- nal tabul.ar cells with a center of different brilliancy. They swell up and becpme slimy in water and must therefore, be observed in glycer- ine. At the best it requires some manipulation to see it well, and it is far less prominent in the brown seed. The next coat, denominated the subepidermal, is not prominent and can only be seen at all easily in the white seed. The third layer is an important one. In it is found the coloring mat- ter of the brown seed, and its absence is the cause of the lack of color in the white variety. Fragments of this layer are common in ground mustard. It is distinguished by the thick or colorless brown cell walls and their irregular dotted appearance. Once examined it will be readily recognized under other circumstances, as, for example, when the hull is used as an adulterant of pepper. Between this layer and the next are some unimportant and difficultly discernible cells carrying in the brown seed some color. Withiu these comes the important layer denominated the inner tunic by Hassall and the plasma layer by Schimper. It separates readily from the other parts of the husk and is often found by itself in the ground mustard. As its contents are broken up by water or chloral hydrate, glycerine or oil must be used as a mounting medium. The -oells of which the layer consists are 'large, and with their contents are similar to thie embryous envelope or false gluten cells of wheat, to which they correspond. They are much alike in both white and brown mustard. These structures are diagramatically represented in Fig. 7. From the character of the exterior layer and the lack of color in the third layer, as well as minor differences which are not describable, but will appear to the patient investigator, it is always possible to tell 172 FOODS AND FOOD ADULTERANTS. whether the flour of mustard is a mixture of the two varieties or from one alone. Mounts in chloral hydrate, to a certain degree, are use- ful for adding to the transparency of the substance. The interior of the seed is made up of small soft parenchyma cells containing the oil and other constituents of the mustard, but without any trace of starch. For this reason the presence of starch is a certain indication of the ad- dition of some diluent of a farinaceous nature. Simple treatment with iodine will therefore reveal the presence of wheat flour, which is a com- mon adulterant of this condiment. The white color of the flour of course reduces the yellow color of the mustard, and it is usual, there- fore, to restore the tint by either turmeric or Martin's yellow. c Pig. 10. Hnsk of Trhite mustard, o, 6, plasma layer ; c, sab-epldermal ; d, epidermis. The former can be detected by a mechanical separation or a brown coloration with ammonia or by the peculiar color cells which it contains and the starch granules of the arrowroot class. The latter is not suffi- cient in amount to be confused with potato starch or that of flour. It has been already described. Martin's yellow can be identified by extraction with cold 95 per cent, alcohol and examination, after evaporation of the solvent, as suggested by Waller and Martin, and this coloring matter seems to be often used, and cannot be pronounced as harmless as turmeric. The substances mentioned are the common adulterants of mustard, in fact, so common that they have been accepted as necessary dilu- SPICES AND CONDIMENTS. 173 ents, being considered desirable for toning down the pungency and adding to the keeping qualities of the ground material. Of late years, however, a reaction has taken place, and it is now possible to find brands of pure ground mustard. In most of the samples which have come into our hands for examina- tion flour and coloring matter are the only foreign substances which have been met with. From the investigations of foods chemists abroad, it would appear on the authority of Hassall and others that other species of mustard seed, rape seed, cayenne pepper, ginger, potato flour, rice pea flour, seed meals, and several mineral substances are frequently found in the mustards of commerce, a conclusion which we have found justified by the presence in some of the lower-grade mustards which have come into our hands of yellow corn, ginger, mustard hulls, gypsum, and sand. The presence of these adulterants, which is only too common in the cheaper article when sold in bulk and under no brand, can be deter- mined by mechanical means and by their structure, which is quite dif- ferent from that of the mustard, and by the starches, which character- ize some of them, as already explained. While the adulterants of mustard, therefore, are, owing to the char- acteristic structure of the seed, easily detected with the microscope, in cases where there is doubt, or where further information is desired as to the probable proportion of diluent, recourse must be had to deter- minations of the chemical constituents of the sample. CHEMISTRY OF MUSTARD, Several investigators have made proximate analyses of mustard. Hassall has collected the following in regard to its composition, and has also made several analyses of pure and adulterated samples : Of these seeds no very complete quantatitive analyses have as yet been made, al- thougli many highly important particulars have been ascertained respecting their composition ; thus black or brown mustard, as it is now generally named, consists for the most part of fixed oil, myronic acid C10H19NS3O10, which is combined with pot- ash, forming a myronate of potash, and which acid is converted into the volatile oil CN ) of mustard or aulphocyanide of allyl CiS^ NS or ^ „ > S through the agency of the myroain, another constituent of brown mustard, when the two are brought into con- tact through the medium of water, vegetable albuvun, a hitler principle, a little gum and sugar, apeouliar green suistance, cellulose and mineral matter. White mustard differs essentially in its composition from brown; it also contains _/KKe(Joii!, but in lieu of myronic acid, convertible as described into the volatile oil of mustard, it contains a non -volatile, bitter and acrid salt, termed sulpliocnanide ofsyna- pine (C17HS4N3SO6 or CieHasNOeCNHS), myrosim, gum, cellulose, and mineral matter. Now it is on the volatile oil and the acrid and somewhat bitter salt that the pungency and acridity of mustard depends, and hence we see a strong reason why in the mus- tards of commerce the farina of the two species should be blended together ; of the two active principles the volatile oil is by far the more important, and hence the seed of the brown mustard possesses the greatest commercial value. It should be stated that Henrie and Garot aflSrms that brown mustard contains the acrid principle as well as the white ; this statement we have been able to verify as shown specially by the action of nitric acid, caustic potash, and ferric chloride on the alcoholic extract. 174 FOODS AND FOOD ADULTERANTS. The acrid principle of white mustard appears to possess but little stability, and although it is stated by V. Baboto bear a tempei-ature of 130°C., we find that it is readily affected by heat, and that it is not safe to evaporate the alcoholic solution containing it at a higher temperature than about 30°C. If subjected to a much higher temperature it quicklyloses its acridity and acquires a bitter caramel-like taste. Of neither brown nor white mustard had any percentage analysis been given until those made aud published by ourselves in an article on mustard and its adnlterations, iu " Food, Water, aud Air," for February, 1874; and in the few cases in which the quan- tities of any of the constituents arestated, they vary greatly according to different ob- servers. Thus, according to Pereira, the fixed oil forms about 28 per cent, of the seeds of black mustard, while Watts puts the yield at 18 per cent, only, but white mustard seed, he says, furnishes 36 per cent. The volatile oil amounts to 0.20 per cent., accord- ing to Boutron an d Eobiquet ; 0.55 per cent., according to Aschoff, and 0.50 per cent, according to Wittstock ; all of which quantities are much below the mark, as will be seen hereafter. Now, as will be shown presently, there is little or no difference in the amount of fixed oil furnished by the two descriptions of mustard, that obtained by me from the farina of brown mustard reaching 35.701 per cent., and that from the white mustard 35.768 per cent. Again it is shown by the analyses given below that the volatile oil occurs iu much larger quantities than those enumerated above, the amount which we have obtained from one sample being no less than 1.271 per cent. Of both brown and white mustard we append the following original percentage analyses, first published in the article referred to : BEOWN MPSTAED FARINA. ■Water Fixed oil Myronic acid Myrosin and albamen Acrid salt Cellulose Ash Volatile oil Nitrogen Snlphnr 4.845 35. 701 4.840 29. 536 3.588 16.765 4.725 100. 000 1.271 5.068 L413 The oil extracted by ether from the brown seed is of a bright and beautiful emerald green color, owing to the presence of the peculiar green principle described as one of ita constituents. So deep and remarkable is the color of the oil that it would be easy, by means of a graduated scale of tints, to determine with very tolerable certainty the percentage of brown mustard contained in any samples of mixed mustard. WHITE MUSTAEB FAEINA. Per cent Water Fixed oil Acrid salt Myrosin and albnmen CellQlose Ash Nitrogen Sulphu" 5.360 35.788 10. 983 27.484 16. 295 4.110 100. 000 5.285 1.224 SPICES AND CONDIMENTS. 175 These analyses, \yhether regarded from a scientific or practical point of view, are possessed of much interest. The small quantity of sugar found in mustard would, from the method of analysis pursued, be included under the bitter principle and the gum with cellulose. Of the methods of analysis, Hassall writes: Estimation of mjjrome acid. — Myronate of potash decomposes, under the influence of the nitrogenous matter contained in brown mustard, into volatile oil, glucose, and acid sulphate of potash. The quantity of each of these products of decomposition gives, therefore, by simple calculation, the quantity of myronic acid. One hundred parts of this acid yield 23.85 parts of volatile oil. From 40 to 50 grams of the mus- tard farina are placed in a flask of about one-half liter capacity;- 250 c. c. of tepid water are poured over it, the flask closed with a cork, aud the whole is well shaken. After twenty-four hours' standing the flask is connected with a Liebig's condenser, and its contents are heated to boiling. Into the receiver 30 c. c. of strong ammonia are poured, and the end of the condenser is dipped below the surface of the liquid. Water and the volatile oil pass over, the latter at first fioating in the shape of oily drops on the surface of the liquid, which soon sink to the bottom, especially when the liquid is gently agitated. When the distillation is finished, which is the case when no more oil globules pass over, the receiver is closed with a cork aud allowed to stand twenty-four hours. At the end of that time all the oil is dissolved and is now con- tained in the liquid in the form of thiosiunarain. This solution is evaporated on the water bath in a weighed platinum basin, the residue dried aud weighed. The quan- tity of thioslnnamine obtained, minus one molecule of ammonia, represents the amount of volatile oil. Estimation of the myrosin or albumen and of the sulphocyanide of sinapin. — The total amouuts of nitrogen and sulphur contained in the mustard are next ascertained. The former by combustion with soda-lime in the well-known manner, the latter by deflagration of the mustard and oxidation of its sulphur in a mixture of nitrate of soda and carbonate of potash. The fused mass is dissolved in water or dilute acid, and the sulphuric acid contained in the solution is estimated by means of chloride of barium. From these data the amounts of the myrosin and of the sulphocyanide of sinapin, the acrid principle, are thus calculated ; as much sulphur and nitrogen are first deducted from the totals of these substances obtained as is contained in the quantity of myrouio acid previously determined. Next, the whole of the remaining sulphur and as much of the nitrogen as is required are then calculated into the acrid principle ; lastly, the surplus nitrogen is calculated into myrosin, which has the same formula as vegetable albumen. But now, having got approximately the amounts of the acrid principle and of the myrosin, a further calculation has to be made, since myrosin contains about 1 per cent, of sulphur. This has to be deducted from the total acrid principle, a corresponding quantity of nitrogen being in its turn calculated into myrosin. By those acquainted with algebra it will readily be perceived that a more precise calculation may be made, but the results would not, even then, differ to any practical extent. Acting on this method, Hassall made several analyses of genuine mustards of the trade and also of adulterated articles, which are here presented, merely dropping the third place in decimals, which is of no value. 176 FOODS AND FOOD ADULTEEANTS. Avalyses of genuine mustard. [Hassall, pp. 514-516.] Water Fixed oil Myronic acid Myroain and albumen Acrid salt and bitter principle Cellulose Ash , Oil of mustard Nitrogen Snlphur Genuine mustard. 5.70 36.49 2.70 31.69 5.72 13.37 4.33 100. 00 .71 5.34 1.31 Genuine double superfine. 5.16 35.94 2.21 27.30 9.09 15.58 4.66 Genuine superfine. 5.59 34.71 1.97 31.02 7.10 15.29 4.32 100. 00 .58 5.05 1.42 Genuine Pine. 35.24 .92 27.90 10.06 15 55 4.65 100. 00 .52 5.46 1.25 Pure. 27.02 11.26 16.81 4.29 100. 00 100. 00 .24 .25 5. 16 5. 21 1. 30 1. 40 House- hold. 5.29 36.75 1.72 8.75 27.48 3.69 16.32 100.00 .45 5.03 1.31 Analyses of mixed and bullc must^ird. "Water Fixed oil Hyronic acid Acrid principle Myrosin Wheat fiour and turmeric Cellulose Ash Volatile oil Nitrogen Sulphur Double super- fine. 4.94 27.52 3.14 1.85 23.16 22.99 13.05 3.35 .85 4.24 .95 Fine. 6.51 23.16 1.36 5.81 19.50 27 20 12.84 3.62 .36 3.85 .96 Supe- rior. 4.07 25.17 1.20 4.31 23.24 25. 83 11.50 3.79 .32 4.07 1.06 Saerls. Alexan- der. 8.94 2:i. 88 1.57 6.45 14.48 33.81 7.08 3.79 .41 3.34 1.00 8.34 29.60 1.92 3.15 13.89 30.52 8.99 3.59 .50 3.16 .90 Lind. sey. Gilbert. 8.87 21.54 .98 6.21 21.70 25.21 11.69 3.74 .26 4.30 .94 6.28 22. 06 1.13 4.25 15.30 38.82 8.41 3.75 .30 3.46 .82 Good- man. 8.95 26.90 1.82 5.18 15.58 30.56 7.27 3.74 .48 3.37 .94 Clark. 9.58 18.31 .39 7.03 20.82 32.81 ao5 2.41 .10 3.33 .91 "Of the first six analyses of genuine mustards" Hassall says that they " prove two things ; first, that all the samples are genuine ; this is shown by the quantities of fixed oil, nitrogen, and sulphur obtained; and that they consist of mixtures of the two mustards in diflferent pro- portions, the higher qualities containing larger proportions of the brown mustard ; that this is so is demonstrated by the different quan- tities of volatile oil obtained." In the analyses of the adulterated mustards allowance in the calcu- lation was made for the nitrogen of the wheat flour. Hassall says: From an examination of the foregoing analyses it is apparent that gonnine iroicn mustard should contain about 36 per cent, of fixed oil, at least 1 per cent, of volatile oil of mustard, about 4 per cent, of acrid principle.and that it should furnish about 1.5 per cent, of sulphur and 5 per cent, of nitrogen ; that genuine white mustard should yield about the same amount of fixed oil, over 10 per cent, of acrid principle and nearly the same amount of nitrogen and sulphur as the black ; that the composition of genuine mustards, which are lAade up in various proportions of brown and white mustard seed, differs according to the quantities of each liiud present, the relative proportions being determinable by analysis with considerable pre",ision ; that in the mixed or adulterated mustards the proportions of fixed and volatile oil, of nitrocen and sulphur are all much reduced, according to the extent of the admixtures these consisting in the mustards now reported upon in all cases of wheat llour »n4 tur- SPICES AND CONDIMENTS. 177 Thus the fixed oil was reduced in one of the sanrples from 36 per cent., the normal amount, to about one-half or 18 per cent., the volatile oil to 0.1 per cent., and the nitrogen to 3.33 per cent., while iu another sample the sulphur was as low as 0.81 per cent. The amount of wheat flour and turmeric varied from 22.91 per cent, to 38.82 per cent., that is to say, from one-fourth to one-third of the article. These' results furnish an excellent basis for the exaininatiou of the mustards met with in our country. In addition, however, we have the work of several other investigators. 0. H. Piesse and Lionel Stansell* have given their results of the analyses of several samples of pure farinas and their ashes, largely after the method of Hassall. Blyth copies thein.t and adds several pages on the chemistry of mustard and its adulterations, adding nothing new to what has been quoted from Hassall, with the exception of a formula for calculating the percentage of added flour in mixtures from the amount of fixed oil found. He says: Estimation of fat or oil. — This is particularly useful when wheat starch is the adulterating agent. Wheat flour does not contain more than 1.2 to 2.1 per cent, of oil; mustard, on the other hand, from 33.9 to 36.7 per cent. A weighed portion of the previously dried samples may be placed in an extraction apparatus, and from the oil found the following formuluB will serve as a guide to the amount of flour prese nt : X = amount of mustard, y = amount of oil found. 33.9 a! 1.2(100-a!) _ 36.7 x 2 (lOO-a;) _ 100 "^ 100 ^ 100 ^" 100 ^ according as the greater or less amount of oil is taken as being present in the pure farina and the flour. Accepting the mean for mustard and 2.0 per cent, as the proper figure for flour, the formula would read more conveniently, it would seem, 1.333 where 07=100 when the mustard is pure. Of the amount of ash Blyth says : " The total ash of dried mustard averages 5 per cent. The highest number the writer has obtained is 5.3 per cent.; the lowest 5.088 per cent. Of this ash 1.2 at least is soluble in water ; in other words, the ash of mustard consists of 30 parts per cent, soluble, 70 parts per cent, insoluble in water. It hence follows that if found above 5.5 per cent, mineral matters of foreign origin are present ; if below 4 per cent, it is an Indication of some organic adulterant." Albert E. Leeds and Edgar Bverhart| have taken up Hassall's and Blyth's work and shown that thelatter's formula for calculating added flour from the percentage of oil found will not serve in all cases, as it is not uncommon to express sorneof the oil from the seed before grinding, to adulterate with oil cake or seeds, or to add cheap oils to the flour used as a diluent to cover any deficiency. They also analyzed a sample of pure farina of brown mustard according to a meth od devised by themselves as a modification of Hassall, in which the determinations should be direct instead of calculated. Briefly, it is as follows : '~~~~~ » Analyst, 5, 161-165, 1880. t Foods and their adulterations, 485-486. t Zeit. anal. Chem. 81, 389-394, 1882. 22823— Bull. 13, pt. 2 4 178 FOODS AND FOOD ADULTERANTS. METHOD OF LEEDS AND EVEEHAKT. Moisture and ash are determined as usual ; oil, in a portion of mus- tard dried at 105°, by ether in an extraction apparatus, with subse- quent drying at 100°. From the dried residue the sulphocyanide of sin- apin and the myronate of potassium are extracted in a similar way by 50 per cent, alcohol. The extract is dried, weighed, and ignited, and from the sulphate of potash in the ash the myronate is reckoned and the sulphocyanide obtained by diflferenoe. The residue, containing myrosin and cellulose and a little coloring matter, is freed from alcohol and treated with one-half per cent, sodic hydrate solution. The washed residue it", weighed and ignited for cellulose. The filtrate containing all the myrosin is nearly neutralized with dilute hydrochloric acid, 50 c. c. of Ritthaasen's copper sulphate solution added, and then dilute sodic hy- drate to near neutrality. The heavy green myrosin copper compound is filtered off, dried at 110° C, weighed, and ignited. The difference is the myrosin. Analyses carried out after this method in triplicate are as follows : Per cent. Percent. Per cent. 6.78 .61 10.97 28.45 29.22 20.24 3.73 6.90 .61 11.19 28.70 29.21 19.55 3.84 6.82 .72 11.21 28.30 29.19 20.06 3.70 Siilpho-cyanide of sinapine. . . . Oil Cellnlose (by difference) Asli The amounts of nitrogen and sulphur in this mustard were : Nitrogen 5.337 Sulphur 1.489 Calculated from these figures according to the method of Hassall would be found the following : Myronate of potassium 61 Sulphocyanide of sinapine 10.71 Myrosin 28.52 Showing a close agreement with the direct determinations. Direct methods are, however, usually preferable and this would, no doubt, be a good one were it not that dilute alcohol in the case of ad- mixture of flour would dissolve so much of the albuminoid matter and ash of the latter as to invalidate the determination of myronate. It is therefore open to criticism. B. Waller and E. W. Martin* in 1882 made an examination of mus- tards manufactured and sold in New York City, attention being paid to moisture, oil, and soluble and insoluble ash. They also examined mustard pastes, and compared their results with some pure mustards from the English market. Their analyses are as follows : ' Analyst 9, 166-170. SPICES AND CONDIMENTS. Dry mustard manufactured and sold in New Jork City. 179 Ko. Muist uve. Fixed oil. Soluble ash. Insolu- ble ash. Total. Coloring. ^Remarks. 197 201 206 207 208 209 213 214 216 216 217 218 219 294 6.15 8.03 T.,'i5 8.23 8.50 7.24 7.65 7.60 7.15 5.45 6.50 8.45 6.62 9.86 21.17 12.79 12.54 8.43 10.92 6.81 13.32 7.74 9.02 20.57 8.59 14.59 22.56 6.21 .30 1.39 .23 .15 2.90 .10 .64 1.53 .20 .15 1.52 2.15 1.62 1.16 5.54 5.39 4.60 1.90 13.15 3.55 5.17 1.69 2.91 5.12 5.65 6.65 4.86 3.54 5.84 6.78 4.92 2.05 16.05 3.65 5.81 3.22 3.11 5.27 8.17 8.80 6.48 4.70 Martin's yellow.. Turmeric Contains starch. Contains starch and Ca SO4. Ash fixed starch. Contains starch. Contains starch, Ca SO4. Contains starch Contains starch, ash-fused. Contains starch. Contains starch. Contains starch. Contains starch, Ca SO4. Contains starch, Ca 5O4. No starch. do .... Martin's yellow... do Martin's yellow... do do do do Martin's yellow... Mustard paste, German mustard manufactured in New York City. No. Moist- ure. Acetic acid. Oil. Other organic sub- stance. Soluble ash. Insolu- ble ash. Total. Common salt. Oil on dry sub- stance. Metallic copper. 221 222 237 242 244 77.02 SI. 52 79.63 76.54 81.45 2.76 1.98 2.43 .^69 2.94 2.55 3.50 3.90 4.57 3.73 14.18 10.67 14. 60 11.53 9.09 2.51 1.77 2.52 2.69 2.14 0.93 .56 .97 .98 .65 3.49 2.33 3.49 3.67 2.79 2.11 1.63 24.98 21.24 19.51 23.14 22.44 .001 Trace. .009 .003 Trace. 1.86 1.77 Mustard fiour (fiolted^ purporting to be pure. No. Moist- ure. Oil. Soluble ash. insolu- ble ash. Total. Eemarks. 201 220 273 274 6.10 5.50 4.85 4.75 26.42 25.70 36.67 ■ 41.70 .2) .86 .175 .125 5.93 4.80 3.725 4.425 6.21 5.66 3.900 4.550 New York manufacture. New Tnrk manufacture, Trieste and Bombay seed, mixed. English samples, whole seed. En^ish samples, brown seed, ash -fused. Ctround mustard seeds. No. Hind of seed. Moist- ure. Oil. Soluble ash. Insolu- ble ash. Total. 231 232 233 234 271 272 American market : 7.52 6.35 4.95 6.10 7.10 7.30 36.96 36.45 34.00 35.46 34.45 34.71 1.25 .70 .50 .25 .70 .85 4.37 3.70 4.40 4.55 3.90 3.90 5.62 4.40 4.90 4.80 4.60 4.75 California yellow JBnglish market : ■White As comment they say : The results obtained for oil on Nos. 201 and 220 led to inquiry, the result of which was the discovery that it is the regular practice of the mustard manufacturers here to express a portion of the oil from the ground mustard seed before working it up into the condiment sold as mustard. In these samples, as well as in No. 219, which was sold under guarantee of being pure mustard without admixture, no starch, col- oring material, or other material known to be foreign to the mustard seed was found. 180 FOODS AND FOOD ADULTERANTS. If we calculate, then, that these mustards have been made up from mustard flour similar to 201 and 220, and containing 25 per cent, of oil, by multiplying the per- centages of oil given in the table by four, we shall get approximately the proportions of mustard flour present, in percentages. These investigators also examined a specimen of English mustard which was mixed with starch, and yet contained a normal amount of oil which, on extraction, was decidedly more fluid than mustard oil. This points to the truth of the assertion that the extraction of the mustard oil is often covered by the addition of oil of inferior character. The common use of Martin's yellow (Dinitrouapthol) as a coloring matter is startling, as it can hardly be anything but injurious. They detected it by extracting the flour with cold, strong alcohol, evaporating, taking up with water and dyeing wo j1 with it. Crystals, however, could not be obtained, but the authors came into i)osses8ion of a sample of the coloring matter which was analyzed. In Canada, large numbers of samples of mustard have been examined with results which have already been quoted, showing that the manu- facture of mustard from mustard cake and the addition of farinaceous matter is as common there as elsewhere. In the report for 1885, out of flfty-one specimens, only 10 contained over 25 per cent, of fixed oil and no starch, and but three contained over 30 per cent, oil, as they should, if of best quality. The chief analyst, however, is of the opinion that the removal of the oil is an advantage, as the flour will keep better and be as pungent without it. With the information of the nature which has been given a number of samples of mustard purchased in the open market in Washington, some of low grade obtained direct from Baltimore spice mills, and others in the whole seed from the importers and dealers, have been examined microscopically and chemically. They may be described as follows : Serial No. Price i pound (retail). Remarks. 4510 11 22 27 32 36 42 60 51 4241 71 72 4971 4835 86 i)D 4900 1 CenU. White aeed. Guaranteed pure. Ground in District of Columbia. Ground in Baltimore. Englisli brand. Ground in Baltimore. Englisli brand. Ground in Ne^v York. Mobawk, N. T. Extr.a American, Baltimore, Md. London, strong, extra, Baltimore, Md. Gi'ouudiii Balttnioru ; exteu^ively advertised as pure. AVbite-aced lioui'. ground in laboratory. Wbite-sci'd husk. ;iv.iund in laboratory. Califoinia yellow mustard sted. Califiiinia brown mustard .seed. English ,>ollow mustard send. Trieste brown mustard seed. 30 20 20 30 36 30 20 20 30 2 SPICES AND CONDIMENTS. 181 The analytical determinatious gave the followiug results : Analyses of mustard [Whole-seed flour.] h OD i .9 ^; Source. ■^=1 Quality. o <0 d 5 o ^, s 4 1 ID 1 4) 1 01 (5 1 1 4sin White aoed .635 5.57 4.29 .97 33.56 .00 5.40 28.88 21.33 100 4.62 4Sfi5 White flour a. 83 5.23 1.84 34.83 .00 9.05 25. 56 20. 16 100 4. 09 4S86 Seed huak .480 6.17 4.99 .,55 28. 12 .00 9.50 23.4427.23 100 3. 75 4899 California yellow. .460 4.83 5.96 1.27 31.96 .00 8.50 31. 13 16. 35 100 4.98 4900 California brown . l.fS 4.11 4.88 1.35 36.68 .00 10.18 24.69,12.16 lOU 3.95 4901 English yellow.. .419 3.11 4.07 2. OS 31.51 .00 0.90 30.2522.10 lOU 4.84 4902 Trieste brown . . . .435 4.62 5.61 .63 39.55 .00 10,84 25.8818.87 100 4.14 rCommercial mustard flour.] 4511 (?) Colored 5.97 6. -55 .43 18.16 .00 7.35 37.44 24,10 100 ,5, 95 4522 District of Colum- bia <» 38 7 24 11.20 21.15 2.95 20.63 «7. 04 100 3. 30 4527 Baltimore ..-.do 9,73 4.40 .80 9.85 29.14 2.40 13.31 30.37 100 2.13 4532 Enolish ...do 5 S+ 4.90 2 11 30.84 7.26 4.63 25.88 IH. ,'.4 100 4.14 4536 Baltimore ....do 6.60 ».70 .50 14.72 9.00 3.75 14.50 41.23 100 3.92 4542 English ....do 3 25 3.65 2.01 32.26 8.50 14.98 25.19 10.16 100 4.03 4550 (!) ....do .5.80 StMi .37 7.8i» 4(».50 2.43 14.38 25.46 100 2.30 4551 New York --..do fi.70 l.»0 1.31 6.50 45.00 2.97 13.63 21.99 100 2.18 4871 Baltimore .---do 4. ,57 3.24 2. 02 6.77 31.5() 2.90 20.31 28. 60 100 3.2b 4872 Baltimore .--.do 7.25 3.35 2.32 5.54 34.63 1.23 19.63 26. Ob 100 3.14 4971 ....do 6.08 5.98 .65 19.46 5.70 3.48 33.06 2b. 64 100 5.29 Abnormal figures in full-faced type. DISCUSSION OF THE ANALYSES. The results obtained with pure seed, ground in the laboratory, show that flour of mustard is fairly constant in its composition. Water is present in small amount, as is generally the case in oil seeds, varying between 3 and 7 per cent. Hassall found from 5.16 to 5.70, and Waller and Martin 7.52 to 4.95. Ash is quite constant between 4 and 6 per cent., so that the presence of foreign mineral matter is readily detected. Blyth places the varia- tion between 5.1 and 5.3, Waller and Martin between 4.40 and 5.62, while in ground samples it falls as low as 2.05, Waller and Martin, or 1.90, our own results, owing to the addition of organic adulterants, such as wheat flour, or rises to 16 per cent, from the addition of gypsum. The determination is therefore an extremely valuable one. Volatile oil is present naturally in the seed in but small amount. The percentage we have found to be rather variable, as much as 2.06 having been found in an English yellow seed and as little as .55 in another. Hassall found from .71 to 24 per cent. Its presence is not of importance. Fixed oil is one of the most prominent constituents of the seed, vary- ing in amount from 31 to 37 per cent. Waller and Martin give results 182 FOODS AND FOOD ADULTERANTS. varying from 34 to 37, and Hassall 34.71 to 36.49. It has become an almost universal practice, however, to express a portion of the oil, so that in good flour as little as 18 per cent, has been found. Starch is entirely absent, a contrast to the cereal grains and many other seeds. Its addition is of course common. Crude fiber varies in a way dependent on the method of milling and of determining its amount. Our samples were found to contain much more than the best flour of commerce, as our means of separating the husk are imperfect. With careful milling not more than 6 to 7 per cent, should be present, according to modern chemical methods. Hassall, on the other hand, found from 13 to 17 per cent. Albuminoids ui?tke up a large part of the seed, varying from 25 to 32 per cent. Anything below 20 per cent, points to dilution with material poor in nitrogen. The undetermined matter consists of gum and some unidentified sub- stances soluble in alcohol, whose estimation is of no particular value as a means of detecting adulteration. Our results, as a whole, agree closely with those of other investiga- tors, so that for general reference the following standard may be used : Per. cent. 3to7 4 6 4 2 31 37 16 18 None. 5 18 25 32 Ash Volatile oil Pixedoil: When from entire seed. When from cake When, however, the flour is ground from cake all the percentages may be somewhat increased. As compared with the pure mustards the flours of commerce give re- sults which show at once the universal extent of the adulteration which takes place, aside from any microscopic examination. 4511, purchased in Washington but ground elsewhere, has been de- prived of nearly half of its fixed oil, that is to say, is ground from mus- tard cake. It is the only specimen which contains no farinaceous ma- terial, and is higher in albuminoids than any of the pure seeds or flours. This is due to the fact that abstraction of the oil raises the relative per- centage of albuminoids, and this is not reduced at all by the addition of any diluent. The amount of fiber is relatively high for the same reason. It contains also a very small amount of mineral adulteration. The mi- croscope shows the presence of turmeric as coloring matter. This brand is perhaps the purest met with, as its only defects are lack of, oil which has been considered not a loss, the small amount mineral matter, and the presence of a little coloring matter. SPICES AND CONDIMENTS. 183 4522, repr( sented by two different specimens, has, in one case, that analyzed, been deprived of more oil than the preceding, has a consid- erable amount of gypsum in its ash, and 21 per cent, of starch in the shape of wheat flour. The relative percentages of fiber and albumin- oids are thereby reduced somewhat, since 21 per cent, of starch would correspond to about 30 per cent, of flour. Color is given by turmeric. In the other case the changes were similar, except that no turmeric was added, but large amounts of white mustard hulls. 4527, ground in Baltimore, consists to a large estent of flour, be- tween 40 and 50 per cent., and is made from mustard cake, the oil hav- ing been removed. The color has been restored by turmeric. The sam- ple leaves on sieving quite a large amount of husky and fibrous matter contaminated with wheat flour and turmeric. The husks are not those of the original mustard, and have not been identified, but seem to re- semble the exterior coats of ginger, and may represent an addition of spent ginger or ginger tailing. 4522, sieving leaves white mustard hulls and yellow corn meal, but no color; wheat flour is also present. 4551. This sample contains turmeric, wheat flour, and salt. 4532. An English brand, is made from whole seed and is diluted with but little flour and color, about 10 per cent, of the former. 4536 is made from mustard cake, contains a large amount of gypsum and some starch, and is colored (with turmeric). The large amount of undetermined matter would point also to the presence of other adulter- ants not identified. 4542 resembles the other English brand examined, 4532 being only altered by the addition of a little flour and color. 4550 and 4551 are perhaps the worst samples we have examined. They are made from cake, contain no mineral adulterants, but are more than half flour, and are of course much colored with turmeric. They were purchased from the same grocery. One also contained salt, de- tected by sifting. 4871 and 4872 are similar and but little superior. They were obtained directly from a Baltimore mill in a lot of spices, which were all adulter- ated. 4971 has been much advertised as quite pure, bu.t was found to con- tain sand and flour, but no color. It is made, as usual, from seed cake. Prom these samples we learn the quality of the ordinary flour mustard of the groceries. It is not good, and certainly demands reform. PEPPEE. The ordinary black and white peppers of commerce are the fruit of the true pepper plant. Piper nigrum, which grows in the East and West Indies. Eed pepper ,;or cayenne, is not a pepper, but the fruit of several species of Capsicum. Under the title of "pepper," therefore, attention 184 FOODS AND FOOD ADULTERANTS. will be confined to the genus Piper, reserving for a separate chapter the remaining substances which are commonly miscalled peppers. The pepper plant is a perennial climbing shrub, with a small, round, sessile, fleshy fruit, which grows spontaneously on the Malabar coast, and whose culture has been extended to Siam, Hindostan, Indo-China, Malacca, Singapore, Penang, Ceylon, Sumatra, Java, Borneo, and the neighboring islands, and to a small extent in Guiana and Cayenne. The greatest production is in Sumatra, and the ports of export are principally Singapore and Penang, the Malabar pepper coming from Tellicherry. Our imports are principally through England, and not direct, and it seems that, in England at least, it is customary to mix peppers of different origin in grinding, taking Malabar for weight, Pe- nang for strength, and Sumatra for color. Of the other characteristics and history of pepper a most complete account may be found in " Fliickiger and Hanbury's Pharmaco- graphia."* Of its preparation for the market these authors say : When one or two berries at the base of the spike begin to turn red the whole spike is pinched off. Next day the berries are rubbed off with the hands and picked clean, then dried for three days on mats or on smooth, hard ground or on bamboo baskets near a gentle fire. As thus prepared it is the black pepper of the trade. Wlieu the berries are allowed to ripen, and the black outer pericarp is removed on drying, they are known as white pepper. The grains of white pepper are of rather larger size than those of black, and of a warm, grayish tint. They are nearly spherical or a little flattened. At the base the skin of the fruit is thickened into a blunt prominence, whence about twelve light stripes run meridian-like toward the de pressed summit. If the skin is scraped off the dark-brown testa is seen inclosing the hard, translucent albumen. In anatomical structure, as well as in taste and smell, white pepper agrees with black, which, in fact, it represents in a rather more fully-grown state. A study of the structure of black pepper will, therefore, furnish every information in regard to the white. There are also two species of Piper which furnish a berry used in a similar way to that of Piper nigrum. They are known as long pepper. Piper longum and Piper officinarum. Their structure is similar to that of the common pepper, with some characteristic differences. It is diflficult to say how far they are an ar- ticle of commerce in this country. They come principally from Penang and Singapore, being brought from Java and other places. The structure of black pepper is described as foUows in the work last quoted : The small, round berry-like fruits grow somewhat loosely to the number of twenty to thirty ou a common pendulous fruit stalk. They are at first green, then become red, and, if allowed to ripen, yellow, but they are gathered before complete maturity, and by drying in that state turn blackish gray or brown. If left until quite ripe they lose some of their pungency and gradually fall off. The berries after drying are spherical, about one-fifth inch in diameter, wrinkled on the surface, indistinctly pointed below by the remains of a very s hort pedicel, and * Loudon, McMillan & Co., 1879. "~ SPICES AND CONDIMENTS. 185 crowned still more indistinctly by tho three or four lobed stigma. The thin pericarp tightly encloses a single seed, the embryo of which, in conseciuence of premature gath- ering, is undeveloped and merely replaced by a cavity situated below the apex. The seed itself contains within the thin red-brown testa a shining albumen, gray and horny without and mealy within. The pungent taste and peculiar smell of pepper are familiar to all. The transverse section of the grain of black pepper exhibits a soft yellowish epider- mis, covering the outer pericarp. This is formed of a closely-packed yellow layer of large, mostly radially arranged, thick-walled cells, each containing in its small cav- ity a mass of dark brown resin. The middle layer of the pericarp consists of soft tan- gentially extended parenchyrae, containing an abundance of extremely small starch granules and drops of oil. The shrinking of this loose middle layer isthe chief cause of the deep wrinkles on the surface of the berry. The next inner layer of the pericarp ex- hibits towards its circumference tangentially arranged, soft parenchyme, the cells of which possess either spiral striation or spiral fibers, but towards the interior loose parenchyme free from starch and containing very largo oil cells. The testa is formed in the first place of a row of small yellow thick-walled cells. Next to them follows the true testa, as a dense, dark brown layer of lignified cells, the individual outlines of which are indistinguishable. Tho albumen of the seeds consists of angu- lar, radially arranged, large-celled parenchyme. Most of its cells are colorless and loaded with starch, others contain a soft yellow amorphous mass. If thin slices are kept under glycerine for some time, these masses are slo wly transformed into needle- shaped crystals of piperin. Fig. 11. Pepper Imsk, cross-section. «», epidermis; a, stone cells; 6, parenchyme with oil cells; spiral vessels ; d!, inner parenchyme; e, inner layer of stone cells. (After Schimper.) Of the structure described so well in the preceding lines, of a portion of which a diagramatic illustration is given in Fig. 11, after Schimper, only parts are readily found in the powdered pepper of the shops. The angular cells of the interior of the seed are of course the most prominent, and when once seen their characteristic form and contents are easily rec- ognized again. The structure of the outer coats is made out with more difficulty. It is well, before attempting to do so ou a ground pepper, to soften some whele black and white pepper-corns in glycerine and cut sections from various parts of the exterior of the berry. Taking the white pepper first it will not be found difficult in such sections mounted in glycerine to pick out three layers of different cells compos- 186 FOODS AND FOOD ADULTERANTS. ing the outer coat of the corn, beside the angular large cells of the in- terior, which are filled with starch and piperine, the latter being yellow- in color. Tlie first of these layers and outer one is made up of colorless large loosel J -arranged cells, with some fibers, more compact toward the exterior than the interior of the layer and carrying globules of oil. This layer makes up tbe principal part of the husk of white pepper. The second layer is a part of what Pliickiger calls the testa, and consists of small yellow cells, thick walled and closely appressed. Next the third layer and second portion of the testa consists of liginitted brown cells, which in their transverse appearance resemble some of the cells of mus- tard hulls, the individuality not being made out easily owing to the thickness iff the walls. Having become thoroughly familiar with these appearances the white ground pepper should be examined and will be found to differ in the way in which these coats are presented. They can be recognized, however, and must be studied until thoroughly under- stood. The presence of the least portion of adulterant is then readily detected. The black pepper is not as simple in its arrangement as the white. The maturity of the latter gives its structure more distinctness, while in the black the more or less shrunken character of the berry ren- ders the recognition of the various tissues difficult. In a section from the exterior of a softened black pepper the interior coats, after what has been learned with the white, will be quickly recognized, but will be found to not be as plainly developed. The coats of the outer pericarp, which in the white pepper were wanting, will be found t o be dark-col- ored, shrunken, and confused, so that it will require much study to dis- cover the forms of cell which Fliickiger describes. It will be found easier, perhaps, in the ground black pepper. There the structures al- ready recognized in the ground white pepper will be seen and in addi- tion dark-brown particles, portions of the outer coats. Careful exam- ination of different particles will detect some which consist of the elon- gated vertical exterior cells, containing resin, while others are the shrunken parenchyma cells of the second layer, whose structure is in- distinct. Fliickiger calls the first layer yellow, which hardly seems correct, as the appearance is nearly black. It is unnecessary, however, to at- tempt a minute study of these cells, as one is only required to be able to recognize their appearance and in addition to know something of the relative proportion of ground pepper which they should form as they are added in excess as pepper dust, the waste hulls of pepper be- ing often used as an adulterant. The colored portion of a ground black pepper it will be found divides itself into two classes, the dark par- ticles which have just been mentioned and the deep reddish ones, which are made up of the testa of the seed and its adherent parenchyma. The two will be readily recognized and distinguished from adulterants by the investigator. SPICES AND CONDIMENTS. 187 The differences in the appearance of the peppers from various sources is sufficiently markeil to be reailily noticed when samp les of each are placed side by side, b it othersvise it is almost impossible to ideutily them. The best method ot' judging their quality and the one in use in the trade is by weight. Malabar is considered the heaviest. Blyth gives the following figures : 100 peppercorns of— Grams- Penang 6.2496 Malabar 6.0536 Sumatra 5.1476 Trevy 4.5736 Tellicherry 4.5076 Tellicherry is the Malabar or West Coast port, so that variations must occur, as would be natural, in different samples. We have found some samples to weigh — Serial !N"o. 4514 4840 4894 4895 4896 4516. Source. Black. Unknown Uiikno"wu Acheen West Coast Singapore White. Unknown Singapore Weight per 100 grama. 5. 9000 5. 4600 4.525 5.085 4.870 5. 1300 4. 9600 Percentage of dust and dirt. 2.6 4.3 The white pepper is of course the cleaner. ADULTERANTS. The common adulterants to be found in peppers are said to be flours or starches of cereals and potatoes, sago, mustard husk, linseed and capsicum, pepper dust, sawdust, gypsum, and other odds and ends. Of the adulterations of pepper Blyth enumerates many, among them the celebrated pepper dusts designated as " P. D.", " H. P. D.," and " W. P. D.," and known as pepper dust, composed of linseed cake ; hot- pepper dust, composed of mustard husks chiefly, and white-pepper dust, composed of ground rice. In this country the use of ground corn or rice, mustard hulls, cocoanut shells, and other similar refuse is very com- mon, but whether they have been derived from goods sold as H. P. D. and W. P. D." we were unable to ascertain. Other refuse is also frequently found in cheap peppers, but sand does not seem to be as often added here as abroad. We have found the white peppers much freer from adul- teration than the black. It is learned from Dr. Ellis, of Toronto, that roasted cocoanut shells are in common use now as an adulterant of all spices, and are of course easily intr oduced into peppers. They have not been found in the specimens which we have examined. Pepper husks, 188 FOODS AND FOOD ADULTERANTS. mustard bulls, yellow corn, cracker dust, charcoal, and mineral matter have been detected by their characteristic appearances. The presence of pepper husks and charcoal is generally known by the immensely in- creased proportion of black par'-icles in the field, as appears in Fig. 43, PlateXVII. Acarefulsortingof the coarser particles under a low power of the dissecting microscope and selection, for example, of the shining white grains of rice or yellow particles of corn from the more oily pepper cells, enables us to examine the starches separately with plain and polar- ized light. The appearance of the true pepper powder and one in which rice starch is present is given in Plate XXII, Figs. 43 and 44. Pepper starch is so much smaller than any other which we meet with, that it is not easily confused with it. Fig. 65, Plate XXVIII, gives an idea of its size as compared with others. With the dissecting micro- scope it is also convenient to go over the pepper powder and pick out any other classof suspicious particles for examination with higher power. With a little practice it soon becomes easy to tell an adulterated speci- men even with a cursory examination with a lower power or a hand lens. In this way, in our experience, one or two foreign substances have been found which have not been identified, but which were evidently parts of the husks or coverings of some seed or fruit. The shell of the cocoa- nut, as has been said, has not been met with as an adulterant, but it is not at all difficult to identify,- as its structure, with its innumerable stone cells and fibrous tissue, is very characteristic after treatment with Schulze's reagent. The microscopic examination thus gives very certain indications of the quality of peppers, although frequently the eye with out aid will detect a fictitious appearance. The chemical examination, on the other hand, as will be shown, serves as a reliable means of confirmation in many instances, and gives evidence of the quantity as well as kind of the adulteration. A considerable amount of information has been ac- cumulated in regard to the proximate composition of peppers. Fliick- iger quotes authorities for the statement that black pepper contains from 1.6 to 2.2 per cent, of volatile oil, of the character of a terpene and optically active; also a nitrogenous substance known as piperine to the extent of 2 to 8 per cent. Husemann and Hilger* give reference to papers by several investigators (seebiobligraphy), and describes piperine as soluble in alcohol, and less so in ether. This substance, which is characteristic, will be found, therefore, in the ether extract of the spice, together with the volatile oil. Blyth has made an examination of several peppers, and gives results which are useful for reference. * Die Pflanzeustoffe, B. 2, S. 486. SPICES AND CONDIMENTS. Analysis of ask of Tellicherry pepper. 189 Per cent. Potash Soda Magnesia Lime Iron Fbosphorio acid Sulphuric acid . Chlorine Carbonic acid . . Sand 24.38 3.23 13.00 11.60 .30 8.47 9.61 7.57 14.00 6.53 The sand, he finds, the most variable constituent, but never above 9 per cent, of the ash except in cases of willful adulteration. Phosphoric acid averages 8.5 per cent, of the ash, which is considered characteristic. He has also identified nitrates in peppers, finding in — Per cent. Penang Malabar . . . Tellicherry Sumatra . . - Trang . . 04470 . 03858 . 088G0 . 06560 . 11870 The average proximate composition he finds to be — Volatile oil Acrid resin — Piperine -' SuDstanoes soluble in water, gnm, starch, and other matters substractiug ash Substances insoluble in alcohol and water Water Per cent. 1.04 1.77 5.17 14.74 67.75 9.53 Following are some analyses made by Blyth in 1876 : £ i % & Ash in pepper. 1 •o ■So dried at 100°. 1 O49 fi a g;^ a^ % .s t •" « rt» §"= Sft ® ^ S-ft s w Ph' Pi <1 A H 9.53 12 90 5.57 4 68 2.08 1.70 18.33 16. 50 2.21 3.38 4.18 5.77 Sumatra 10.10 4.70 1.74 17.69 2.62 4.31 10.54 4.63 1.74 20.37 3.45 .'5.19 Trang 11.66 4.60 1.70 18.17 2.53 4.77 "White pepper (com ) . . 10.30 5.60 2.05 .56 1.12 1.80 .80 16.82 4.47 8.30 190 FOODS AND POOD ADULTERANTS. The process for the estimatioa of piperine approved by Blyth is ex- traction with petroleum ether and treatment of the extract with sodic hydrate to remove the resin. Subsequent investigations by Lenz con- demn this method, however. More recently Eottger* has investigated the pepper-corn with especial consideration of the question of detection of adulteration, and decided that the examination of commercial peppers should be directed to de- terminations of the inorganic constituents, the percentage of water, and the microscope, with determinations of the soluble and insoluble ash and piperine in certain instances. He decides that the alcohol and ether extracts are of no value, quoting great variations in his results and those of others. He found — For ether ex- tract, indirectly determined. For alcohol extract of 90 per cent. Per cent. 8. to 10. 7 7. 9 12. 1 Per cent. 10.0 to 11.8 12.3 16.7 Borgman, Wolff, and Biechelet likewise have determined the amount of alcohol extract, but have neglected the ether extract. It seems diffi- cult to understand why the alcohol extract should be selected, as the ether is much simpler, and refers almost directly to the amount of vola- tile oil and piperine which the spice contains, without so much of the indefinite resin and sugar which the alcohol extracts. The determina- tion of water was made as follows by Eottger : The powdered pepper was placed for three hours over sulphuric acid, and a portion then weighed out and dried at 100° O. for one and a half hours, then for a quar- ter of an hour at a time uutil it begins to gaiu weight. He found the variations to be between 12.6 and 14.7 for black pepper, and 12.9 and and 14.5 for white pepper. This striking agreement, he considers, makes this determination of value. It is open to serious criticism and is of little value, in our view, for the following reason: By consulting our investigations on the hy groscopic character of organic matter in a state of fine division,^ it will be seen that allowing peppers to remain over sulphuric acid for three hours would not accomplish the end desired, at least in our climate, viz, reducing the moisture in all to a constant figure, and in addition Eottger takes no accountofthe volatile oil lost at 100°. In our analyses we find, in fact, much less water than he does, as is usual in all organic material in our drier climate, and no greater variation among the peppers than the adulterated specimens. Practical tests of the method also proved unsatisfactory. " Bor. nber d. 4 Ver. Bayrisob. Vortreter der augew Cheraie, 97-102. t Vide Bibliography. tBull. No. 4, Div. of Choiu., Department of Agriculture, SPICES AND CONDIMENTS. 191 The per cent, of ash Eottger finds for black pepper to be between 3.4 and 5.1 per ceat., white pepper between .8 and 2.9 per cent., with an exception iu the case of Lainpoug pepper, whicli has 6.4 per cent. He concludes, with other investigators, that 6 is the highest allowable flguro for ash in black pepper, with anything above 5 as suspicious. Three per cent, is, in the same way, the highest allowable figure for white pepper.. Of the composition of the ash he says : Tho I'acts point to the concluaiou that an exhaustive investigation of the mineral constituents in many cases may he of benefit in formiag an opinion of the quality and purity of peppers. * He found the following extremes: Black. White. jJesOii 2 2 MnzOs...- .ffl KiO 27. 4 to 34. 7 5. 8. 7 1. 5 6. 3 .11 .91 8. 2 13. 5 5. 1 to 7. 1 .5 .9 1. 2. 6 CI SiOz PaOs, insol 10. 8 30. 7 He gives the following detailed analyses : Percentage composition of the pepper aali. Black pepper. White pepper. TJnkiiowii ori- gin. Malabar, 1883. Unknown origin. Singapore. SiOa nci SO3 CO2 P2O6 KaO JS^azO .... CaO MgO F2O3 MmOs ... 0. 30 to 1, 61 5. 59 6. 83 4. 03 4. 05 17. 28 . 20. 10 11.10 9.46 32. 49 34. 72 1. 55 4. 77 16. 07 13. 55 3.31 4.46 2. 16 . 99 .81 1.54 8.71 4.00 19.17 11.06 27.39 5.50 15.02 7.56 .85 .18 2.62 .58 3.24 11.90 , 29. 34 5.10 .74 35.12 9.54 2.22 .89 1.46 .90 .8.75 10.01 30.75 7.15 .84 31.05 11.64 1.80 .21 Eottger then discusses the determination of the piperine, and allows that for simplicity and accuracy drying the powder with milk of lime and extraction with ether is to be preferred. When the ether is pure, dry, and free from alcohol we find lime is of little use, or rather a com- plication, and that for purposes of detecting adulteration the ether ex- tract alone furnishes all the information desired. Jienzt has determined the amount of sugar produced by inverting the starch in fourteen peppers, and in the cnmmou adulterants, with acid. He found all the samples gave an equivalent of more than 50 per cent. * Halenke has more recently discussed this subject; vide bibliography, Appendix A. \ Zeit.Anal.Chem., 1884, 23, 501. 192 FOODS AND POOD ADULTERANTS. of sugar on the ash free organic matter of the pepper, while all the adulterants gave less than 30 per cent., with the exception of those which are starchy, as flours and meals. Eottger repeated this determination, showing that some other sub- stances besides starch were inverted by the acid, and obtained the fol- lowing results : Black pepper sugar equivalent 57.2 to 60.3 White pepper sugar equivalent 59.6 to 74.4 The Lampoug pepper gave only 41.70. Such great variations he con- siders fatal to the method as a means of detecting adulterations. His conclusions seem not entirely justified, as a review of Lena's figures will show. Lenz in his paper afiftrms that any extract determination is useless, as with various adulterants the results' may be very close to actual pepper. Petroleum ether he shows to be unreliable, the amount of ex- tract depending on the kind of extraction apparatus used. There cer- tainly should be no diflQculty of purely manipulative detail of this de- scription, for if sufficient time is given the solvent will work tlie same under all conditions, but not less than twenty hoars' continuous extrac- tion should be allowed, and it is not fair to generalize on an analysis where the extraction was continued less than that time, the poor re- sults being due only to a probable faultily manner of manipulation, as we have met with no such trouble. Ijenz's conclusions seem hardly just, and while there may be cases where adulterants would not be detected by an extract determination, in the majority it is a great assistance. Lenz also refers to the method of separation of the powdered particles of pepper adulterants by means of liquids of certain specific gravities, and pronounces it usuitable. He prefers the treatment with iodine solution and the selection of the par- ticles not blued for examination under the microscope as adulterants. We have found it perfectly simple and desirable to use the method of separation with sieves, and to examine the coarse powder, with or with- out treatment, under the microscope, when, with a little experience, it is easy to distinguish and recognize the source of particles not pepper after a careful examination with high powers. He also casts doubt upon the value of an ash determination, and owing to the great variations which he finds quoted as possible, recom- mends calculating all results on an ash free basis. He, however, admits that a carefully and properly cleaned pepper-corn will not usually con- tain more than 6 per cent., and his strictures, therefore, do not seem to be consistent. He places reliance only on the process of his own inven- tion, determinations of sugar corresponding to the starch and other in- vertible substances, with supplementary determinations of water and ash and microscopic examination. His results were as follows : SPICES AND CONDIMENTS. 193 List of equivalent percentage of reducing svgars in ash free organic substance of peppers and adulterants. No. Kame. Ash. Dry residue. A all free dry resi- due. Sugar equivalent in sample. Sugar equivalent in ash free dry sample. Kemarks. Black Batavia pepper Long pepper (2) . . . Black Singapore - Do ' Do White pepper Palm-cake meal (1) Do. Do. Palm-cake meal (2) . . Do Palm-cake meal (3) . Palm-cake, pure popper Pepper husks Pepper husks picked out o f commercial pepper. Commercial liusks. Commercial pepper powder containing - palm-cake meal. Pepper (3), with 28 per cent, of palm- cake meal (3). Same with 42.4 per cent. "Walnut shells Buckwheat meal Dried and roasted bread. Do 3.85 8.68 3.62 3.62 3.62 .99 3.71 3.71 3.71 3.05 3.66 3.54 1.89 15.61 9.21 20.29 5.15 3.58 1.04 2.10 1.15 87.68 88.77 86.88 86.88 86.88 87.59 89.76 89.76 89.76 89.35 89.35 89.88 93.44 89.60 88.64 88.42 88. 7C 89.34 86.68 100. 00 83.83 80.12 83.26 83.26 83.26 86.60 86.05 86.05 86.05 85.70 85.70 86.34 91.55 73.89 79.43 68.13 83.55 88.30 84.48 98.85 98.85 43.8 44.2 43.9 45.0 44.1 51.8 22.7 19.1 22.7 S 22.4 ( 22.5 19.7 19.4 11.1 11.5 13.0 11.5 35.9 17.7 56.1 52.3 56.2 52.8 54.1 63.0 59.9 26.4 23.2 26,4 26.1 26.2 23.0 22.5 12.1 15.6 16.4 16.9 43.0 42.7 20.0 06.4 86.3 62.6 Inverted directly. Inverted after ox- traction with wa- ter. Inverted directly. Inverted after ex- traction with alco- hol. After water. Do. Alter water and al- cohol. Af te r water. Direct. I Do. After water. Do. After ether and al- cohol. After water. Do. Do. Do. Do, Do. Do. Direct. Do. After water. Lenz's method of iavertiug was this : 3 to 4 grams of the substauce to be examiaed was treated for three to four hours in a flask with 250 c.c. of water, being repeatedly shaken. Ifc was then filtered off, washed with water, and the moist powder washed back into the flask, and to 200 CO. of water 25 c.c. of 25 per cent, hydrochloric acid added. The flask was provided with a cork and tube one meter long and placed in a bath of boiling water and kept there three hours, with shaking. It is then made up on cooling to 500 c.c, after careful neutralization with soda. This liquid was then titrated with Fehling solution. When palm-cake was present it was found necessary to add a little zinc chlo- ride to clear the solution. Most of the surrogates for pepper used in Germany Lenz found to be free from starch, so that this method would seem to be of wide applicability. He remarks, however, that other sub- stances besides starch may be inverted, and for this reason it is neces- sary to adhere closely to one method of working. We shall from our own experience and that of others lean; more io regard to tb© cap^i- tilitiea and usefulness of this method, 194 FOODS AND FOOD ADULTERANTS. Haslinger anil Moslinger* have also published some observations on pepper and its adulteration which are of interest. They show that in Germany the addition of grains of paradise, the seed of Amomum Melegueta, is a common practice whose detection can be accomplished most readily with the microscope, after a study of the structure of the grains of paradise, which is very characteristic. The starch cells are larger than in pepper, 3 to 6 times as long as hard, but the starch itself is scarcely distinguishable. The cells are arranged in parallel lines forming bundles pointed at the end. The cells remain white when treated with hydrochloric acid, while those of pepper are yellower. These writers also looked into the ash of commercial samples of pep- per and found from 4.1 to 27.0 per cent, of inorganic substance insoluble in hydrochloric acid where in peppers ground by themselves only .3 and .8 per cent, occurred. They also found pepper siftings, pepper husks, and other refuse in use as adulterants and followed up Lenz's suggestions as to determination of reducing sugar produced from the samples by acid, by examining pure pepper corns ground by themselves, and also pepper husks, and extending the determinations to cellulose also. The " dextrose," as they denominate it, was determined accord- ing to Allihn, the "cellulose" according to Henberger. The results were as follows : Dextrose. Cellalose. 56.0 16.4 46.4 40.8 44.9 41.3 21.6 15.6 45.0 23.4 28.1 23.3 26.8 ^7 4 Four samples for inTestigation : n . ". ^ '. ". " '. ...v. '. .'.V. .'.".'.'.'.'.. in IV Pepper siftings 3,. 4 1 From these figures they give the following formulae for calculating adulterations where : a;=per cent, of pure pepper. y—per cent, of hulls. s=per cent, of dextrose or cellulose in sample. a=per cent, of dextrose in pure pepper. 6=per cent, of dextrose in husks. For the dextrose figures : ,1! = lOOs -1640 For the cellulose figures : x= 4500 -100s 29.3S^~ • Ber. 4. Ver. Bay. Verterter ang. Chemie, 104-110. SPICES AND CONDIMENTS. 195 Calculated ou tliis basis the four samples were found to couslst of: Pure pepper husks and pepper. Ou the ground of dextrose det. On ground of cellulose det. I II . 75. 8 and 24. 2' 61.6 38.4 72. 1 27. 9 63. 3 36. 7 73.5 and 20.5 37. 5 42. 5 74. 26. 65. 4 34. 6 Ill IV These figures show a fair agreement, and, in the opinion of the au thors, entitle the method to consideration. They condemn, however, severely placing any reliance ou determinations of the alcohol extract. VVeigmann* has also examined a number of pure peppers, and obtained results which do not harmonize with those of Leuz. He finds : Ash starch (Lenz method) . . Fiber Water White. 1. to 3. 55. 63. U 6. U 6. Black. .10 to 7.0 32. U 44. 12.0 15.0 Our experience with the inversion of starch by acids is such as to make it seem very probable that, without the necessary attention to de- tails, it would be very possible to obtain such results as those last given from lack of complete conversion of starch to reducing sugar or the inversion of other substances, and in the discussion of our analyses this will be referred to. In the second report! of the Laboratoire Municipal de Paris the sub- ject of pepper and Its adulteration as practiced in France is discussed. There whole peppers are made artificially from plaster, gum, and a little pepper, and the ground article with the most diverse substances, such as hemp-seed cake, colza, rape and beechnut cakes, starches, residues from the manufacture of potato starch, mineral matter, sweeping of spice warehouses sold as pepper dust, and so forth. The residue from the manufacture of potato starch has, after fermentation, a pungent taste which makes it a desirable adulterant, but the most common one is the powdered kernel of the olive, which is yellowish white in color and possesses all the outward characteristics of white pepper and gives practically the same amount of ash. To give this powder the proper taste and pungency there was added Cayenne, powdered bay leaves, and dried and powdered orange skins. The mixture is recognized with- out dififlculty by chemical and microscopic examination, the latter of which gives an absolute proof of the character of the substance. It is recommended to separate the olive kernels from pepper by the. use of a mixture of glycerine and water of a Sp. Gr. of 1.173 at 10° C, in which the former sink. After decautation they can be examined ~^Rop. anal. Cliem. 6, 399-40. tDociimeats sur les falsifications desMatieres alimeataires, Paris, 1885, p. 688-695. 196 FOODS AND FOOD ADULTERANTS. microscopically. The structure is that characteristic of the hard thick- ened schlereuchyma or stone cells, polyhedral and elongated in shape with thickened walls and little filiform canals. They are most readily made out with polarized light, toward which they are optically active, while the remaining particles of pepper or pepper husks are not seen in the dark field, being inactive. Of this adulterant H. Babourdin has made some investigations, pub- lishing his results in an interesting paper,* giving a general account of the various peppers of commerce and the use of olive stones as an adulterant, as well as other materials already mentioned. He finds no difficulty in recognizing the falsification owing to the presence of the numerous sclerenchyma or stone cells, which are distinguished readily with polarized light, but the quantitative determination is more diflftcult. This, however, he afiftrms, can be accomplished by determining the resi- due left on boiling the suspected sample for one hour with 1 per cent, sulphuric acid after thorough washing with water. In the course of the operation the presence of the olive stones is apparent from their clinging in the form of a reddish powder to the walls of the flask or beaker in which the digestion has taken place, and separating more or less from the pepper hulls on account of their different specific gravity. For pure peppers the following percentage of residue was found: Per cent. Meau. TeJlicherry 30. 3 to 27. 8 31.6 31.8 28. 7 29. 2 33. 2 34. 33. 8 34. 2 33.0 37. 5 37. 7 17.5 29. 2 29. 30. 5 35. 5 29.4 31.7 29.0 33.7 34.0 37.6 17.5 Snraalra White, pure Powdered, pure Do On the other hand olive stones were found to contain: Per cent. Mean. Coarse gray Mne gray 74. 2 to 75. 74. 2 74. 6 74.5 74.5 65.5 74.5 74.4 Coarse white KUB white Pepper dust ... ... From these figures the following factors are derived : Percent "White peDBer 17.5 30.0 32.0 35.0 74.5 75.5 Malabar, TeUioUerry, and Saigon Others known as light peppers Olive stones , , . .. . Pepper refuse ,....- "J. d9 Pbarm. et 49 Oblmie, [6], 9, m-W, SPICES AND CONDIMENTS. 197 And if y is the per cent, of residue, a the per cent, in pure pepper, b the per cent, iu olive stones, the amount of addition can be calculated from the following equations : fl!+2/=100 ax+J)y=p p—a y= — where h can be replaced by 74.5 or 65.5 as the case may be. Working in this way 10 ground peppers, guaranteed pure, were found to contain from 40 to 60 per cent, of olive stones, and these contained "P.D," to the extent of 14 to 20 per cent. Control experiments with known mixtures seem to have been satis- factory. The same author also extended his experiments to a comparisor of the properties and separation of the cellulose derived from a mixture of pepper and olive stones, depending upon the difference in specific gravity, with results which can be found in his original paper. The residues of starch factories always contain enough starch grains. to make their identification easy. Very recently Chas. Heisch* has given in the Analyst his experience in the examination of peppers, to see if there were any reliable mode of judging of the amount of adulterants in adulterated samples except by determinations of ash which give no indication of added organic matter. He also endeavored to find if it were possible to cleanse pep- per corns so that the ash should be free from sand. Assisted by a large buyer and grinders of pepper he found that as the result of the grinder's experience no ground pepper should be sent to market which contains over 6 per cent, of total ash. In this respect they agree with the Bavarian chemists. He also placed some faith in the determina- tion of starch and calculated, as did Lenz, his results on dry ash free organic matter. The starch was estimated " by boiling tho finely ground pepper for three hours with 10 per cent, hydrochloric acid, and taking the rotation in the resulting liquid." He endeavored to check his results by deter, mining that there was insufQcient " gum or other matters to affect the rotatory power" but neglects to see how much of the substances allied to cellulose are converted into optically active substances which would probalily be important. Stating the results, however, as reducing sugar equivalent to pepper with Lenz, the error becomes of slight importance. The determination of piperine was rough, and the results seemed of little service. "Analyst, 2, 1S6-1U0, October, 1886. 198 FOODS AND FOOD ADULTERANTS. The lesultH were as follows : No. Name of sample. Black Pepper: Aclieen Penang Trang Singapore Tellicherry PenaDg Tellicherry (brushed) Gray light dusty Singapore Good B, Singapore White Pepper: Penang Singapore Siam As ground for market: Fine white Finest lauper Long pepper: No.l.H No.2,T Black pepper husks T)o., With same whole Sifting before grinding Black pepper, for sale of which fine was inflicted Poivrette used to mix with pL*ppor 10 per cent, poivrette, 90 pi-r cent. No. 4 30 per cent, rice, 70 per cent. No. 4 9.46 9.22 14.36 13.76 12. 98 13. 01 13.94 14.10 15.86 17.32 13.67 13.90 14.13 14.40 12.15 14.93 12.37 12.60 7.96 11.12 8.32 13.34 12.76 ! A.sh of dry pepper. 8.99 8.85 5.41 5.28 6.45 6.41 5.39 4.35 3.78 1.28 1.81 1.58 2.18 1.41 13.48 11.98 11.90 9.04 51.39 14.70 3.85 5.04 3.10 a a .iH ..H 5ta m 1.54 3.07 l.CO 3.83 2.07 2.52 3.34 1.90 3.10 2.44 2.38 2.84 2.48 2.18 2.48 1.51 0.62 2.80 .22 0.85 .25 .93 .16 .90 ..50 1.50 .37 1.03 4.38 3.42 .82 .04 .91 1.20 .73 .36 .r2 I .17 '' .00 2 37 2.12 3.00 1.02 5.83 6.37 4.12 6.47 3.69 3.41 1.92 43.90 2.02 .96 4.07 1.03 8.61 1.64 2.88 1.68 1.78 1.39 .38 ; .03 .72 .81 .91 1.41 1.19 1.57 1.09 1.14 .22 .00 .11 .00 .11 :::' .83 .48 .02 .80 1.14 .89 On ash and water free pepper. 48.53 54.06 56.24 .56. 67 51.06 65.87 54 93 54.54 77. 68 ' 76. 3.T 76.27 7.5. 31 84.69 83.20 . 58.98 ' 46:16 41.71 47.36 I 30.60 o.uo 49.98 1 8f. 21 , 12.26 [ 6.04 12.28 ! 4.05 12.41 12.67 16.20 13.62 11.62 10.47 9.73 0.49 I 9.23 10.60 9.53 9.63 8.29 8.52 13.81 13.07 11.. ^7 2.31 7.14 0.88 9.38 7.86 (i. 30 6.06 5. 54 6.14 5.13 4.31 4.70 4.50 1.71 1.70 4.84 4.10 1.15 2.02 Of the above samples Nos. 1 to 5 and 7 to 8 were black pepper corns ground just as imported. The uniformity in the starch in all these lead Heisch to believe that any result under 50 per cent, should be regarded as suspicious, it being very easy to detect the addition of foreign starch such as rice. Of the white peppers the first three are white pepper corns ground as imported, the next three black corns decorticated in England and then ground. Of the long pepper Heisch says the starch is double the size of the ordinary and much more angular and like rice. Care must be taken therefore not to confound them. The poivrette is made from oli\e stones. The figures are of interest and would seem to confirm the work of Lenz. Prof. J. Campbell Brown has devoted much time to the subject of pepper and has very recently called attention in England to an adul- terant which first made its appearance in Liverpool last summer and since then has been often met with. It is known a.s pepperette or poivrette, and proves to be the same adulterant so often mentioned in France, olive stones. It resembled walnut shells and almond shells somewhat, but olive stones more so. SPICES AND CONDIMENTS. Browa gives the following aiiiil.y.s(!s and says:* 199 White pepperette Black pepperette G-round almond shells Ground olive stones. - Ash. 1.33 2.47 2.05 1.61 Matters .soluble by boiling ill ■ diluted acid. 38.32 34. 55 23.63 39.08 Albumi- nous and other mat- ters soluble in alkili. 14.03 17.66 24.70 15.04 "Woody fiber, in.sol- uhlein acid and alkali. 43.48 47.09 51.68 45.38 Starch. None. None. None. None. The stones of olives, imported in pickle for table use, gave 3.68 per cent, of ash, but well-washed olive-stones, thoroughly burnt to a white ash, gave under 2 per cent, of ash-like poivrette. "White poivrette" is therefore cleaned very pale, and perhaps partly bleached olive-stones or precisely similar tissue ; black poivrette is the same, mixed with a little black husk. It is to be noted that although it contains no starch, yet it yields some sugar to Fehling's solution, after being boiled for some time with dilute hydrochloric acid. The quantity depends on the length of time and strength of acid, but may be stated approximately about 10 per .cent. It is importaut to bear this fact in mind when making a full chemical analysis of pepper containing poivrette. After removing from such a mixture the matters soluble by boiling in dilute caustic alkali, the woody fiber which remains has a yellow color. It consists of the poivrette and some of the cells of pepper h usk and one of the subcortical layers of the pep- per berry. The pepper cells are made lighter and the poivrette cells darker by the alkali, so that the two are more nearly of a similar yellow color after treatment with alkali. This renders it more difficult to distinguish such of the cells as have some- what similar markings, but it enables us to distinguish more clearly as poivrette the many torn particles which have no definite form or markings. The final examination of the complete cells is better made with good daylight rather than with artificial light, and in a portion which has been treated with water only. The pepper cells are mostly dilferent in shape and are colored, and have generally a dark substance in the interior. They are not numerous, but the quantity varies in commercial samples, owing to the modern practice of decorticating the pepper berry to every different extent possible, and mixing the various portions so obtained, in- cluding husks, in every variety of proportion with each other or with ordinary pep- per. Each individual analyst must make himself familiar with both kinds of cells, as no description can convey an adequate idea of either. In order to form a judgment regarding the proportions of the different chemical constituents of commercial sam- ples, we require to know the chemical composition of the different layers of the pep- per-corn, and I hope soon to communicate to the society some figures bearing on.this point, as well as to notice some other substances used in the sophistication of pepper. It is interesting to note that the exemption, mentioned in section 8 of the sale of food and drugs act, in the case of .a label being affixed to the article sold intimating that the same is a mixture, does not apply in the case of poivrette, the admixture be- ing made manifestly for the purpose of fraudulently increasing the weight and bulk. In a subsequent note Brown t warns analysts not to confuse an exces- sive amount of cortical cells of the pepper husk for poivrette, as they are somewhat similar. This, however, would certainly not occur if authentic samples of pepper and olive-stones were used for comparison. Brown also contributes a paper to the Analyst § on the use of "long pepper," Ghavica Boxburghii, as an admixture to the ordinary ground * Analyst, 12, 23-25. t Analyst, 12, 47-48. 5 Analyst, 12, 67-70. 200 FOODS AND POOD ADULTERANTS. article, showing that it sbould be discouraged, from the fact that . brings with it a large amount of dirt and mineral matter, and has a dis- agreeable offensive odor developed by warmth. Brown saj s : It is now time that all sbould take up a decided position in regard to this form of adulteration. Long pepper is the fruit of Chavica Moxburghii,* and does not consist merely of the berries analogous to the pepper-corns of the true pepper-plant; it bears much the same relation to them that wild grass-seed would bear to oatmeal. It consists of the small berries with the husks and indurated coverings hardened together and ' to the central woody stem, much iu the same way that in pines the seed and cover- ings are all hardened into one cone. Long pepper is for the most part derived from wild plants of Chcwica Eoxburghii, which grow by the sides of the water-courses in India. Consequently it always brings with it a mass of dirt, picked up from the soil of the banks whereon it grows, embedded iu the crevices and irregularitieii of the fruit, which dirt the native collector takes care not to lessen, but rather to increase, seeing that he is paid by weight for what he brings down to the merchants. In commerce we find accordingly that it has always from 3 to 7 per cent, of insoluble sand and clay, in addition to the proper ash of the fruit. And it is difficult, if not im- possible, to clean long pepper before grinding in the way that true pepper can easily be cleaned; it can with difficulty be cleaued by hand. The ash contains a very large proportion of salts insoluble iu hydrochloric acid. When ground, the hard husk and woody center, as well as the dirt, are necessarily ground along with the minute berries. The ground long pepper contains not only sand, but more woody fibre than ground genuine pepper of the corresponding shade, although not so much total cellulose as the most husky black pepper. It has the composition shown by Mr. Heisch in his paper. I can confirm his results by the fol- lowing : Analyses of long pepper carefully cleaued hy hand. ■9-i •Sa « .a flm af s.g >, a ea o «0 Is |°5 g S M ffl o s u a) .if 11:3 '3 .2^ !•§ V r3 . 1 1 H CD H & ■< w H H 1 8.91 1.2 67.83 44.04 15.47 15.70 7.7 5.5 2.1 2 8.98 1.1 68.31 49. .■!4 17.42 10. 50 7.6 4.9 2.0 3 9.61 1.5 65.91 44.61 15.51 10.73 10.5 8.6 2.3 Although the cost of long pepper is at present nearly as high as some very inferior varieties of black pepper, yet the price is generally decidedly lower ; even now long pepper is much cheaper than the pepper with which it has been sometimes mixed of late, and its use aifords a handsome illegitimate profit, to the detriment both of the grocer and his customer. Long pepper has been, and is, legitimately used for pickles, but it is not known, nor has it been recognized by the trade, as ground long pepper ; and all the respectable grocers, and others of whom I have inquired, say decidedly that they would not buy, nor retain, if received, any ground pepper which they knew or suspected to contain an admixture of long pepper. In fact, it is no more right to give pepper containing long pepper iu response to a request for simply "pepper" than it would be to give horse-chestnuts instead of Spanish chestnuts in response to a request for simply "chestnuts." It may, of course, be sold as ground long pepper without offense, but no one would buy it. Not only is long pepper a fraudulent ad- mixture in ground pepper, but it is objectionable ou the score of quality and flavor. Its disagreeable, offensive odor is developed by warmth. Any candid person can convince himself of the real cause of the objections which housekeepers and grocers * Known also as I'ipir officivmm and Phur Longwiti, SPICES AND CONDIMENTS. 201 alike have to ground long pepper if he will heat up a piece of cold meat between two plates and sprinkle some fresh long pepper on it ; the smell and flavor are so offensive that he will feel obliged to reject the meat. Much of that which one gets whole in shops is very old, and has lost much of its flavor and strength, so small a sale does it command. The presence of long pepper in ground pepper may be determined by the follow- ing characters : 1. Colot: — If any serious quantity of long pepper is ground in with the ordinary pepper it imparts some of its peculiar slaty color ; but this is made much lighter by the now very common practice of sifting out much of the darker or husky portions of the long pepper before mixing it with the genuine pepper. Bleaching is also resorted to, but not hitherto very effectively. 2. The odor of the mixture when warmed is unmistakable by an educated olfactory sense, even if the quantity is comparatively moderate. Attempts are made to disguise the odor by bleaching, but this has not been successful. The ethereal extract also, and even the alcohol extract from which the solvent has been evaporated at a low temperature, yields, when warmed, the characteristic odor very plainly. 3. Long pepper introduces sand into the pepper with which it is mixed, often to a considerable amount. If the pepper is white, this has more importance than has hitherto been accorded to it ; for white pepper does not contain, even as imported, 2^ per cent, of sand, and any white pepper containing so much sand must have had the sand improperly introduced, either by direct mixing of Calais sand or in some other way. Long pepper from which the husk particles have been sifted out when added to white pepper invariably introduces its sand along. with it, as well as some spent bleach, if attempts have been made to bleach it. 4. The woody matter in ground long pepper is always considerable, arising both from the smallness of the berries, compared with the hardened setting, and from the central woody tube. This may be detected either by chemical analysis or by the microscope, and some of it by the naked eye or a large hand lens. If the sample is spread out in a smooth thin layer on strong paper, by means of an ivory paper-knife, pieces of fluify woody fiber will be detected, especially if the smooth thin layer be tapped lightly from below. Those pieces come from the central part of the indurated catkin which caunot be completely ground fine as genuine pepper stalks are, and are very characteristic if carefully examined. Much of these are of course removed by the grinders' sieves, but enough finds its way through the meshes of the silk to be useful as a corroborative indication. 5. Particles of husks, if present, can be distinguished from' genuine pepper husks. 6. A proportion of the starch granules of long pepper are of larger size, above .0002 inch, and of angular shape, very slightly smaller than rice granules, and more loosely aggregated in clusters or isolated. Brown also calls attention to the statement of authorities that genuine pepper starch is round in form, and shows that this is not always the case. By reference to our illustration, Fig. 65, Plate XXVIII, it will be seen that he is correct. He has lately found* thatDhoura corn, a variety of sorghum,is being largely used in England as a diluent of pep- per. The grain is well known in this country as Egyptian corn, and is a common crop in the South and Southwest, but has not been used here as an adulterant. Brown says : I have met with it only about four times in pepper, but it probably occurs more frequently in olher districts. It is known in England as great millet or Turkish " 'Analyst, 12, 89-90. " ' 202 FOODS AND POOD ADULTERANTS. millet, and is tlio grain (witli an integument, bnt without the husk) of one of tlio cereal grasses, Sorghum vulgare. It is a roundisli or oval somewhat flattened grain, size from one-eighth to one-fifth of an inch in diameter, white in color and brittle, with a thin, smooth integument or testa, showing under a high microscopic power, on the inner surface, an aggregation of very small granules, which become blue by iodine. The body of the seed is very white, and consists mainly of roundish or irregular starch granules, varying in size from .0001 up to .0006 of an inch iu diameter, and showing under polarized light a nearly right-angled cross ; and of larger irregularly rounded granules of starch from .0005 up to .0013 of an inch in diameter, showing no cross, or only a very faint one, under polarized light. Some of the first-named granules have a hilum and star in the centre, somewhat like bean starch. By boiling with caustic alkali the cellular membrane which binds the starch granules together is disclosed. The Influence of an admixture of sorghum with pepper upon analysis of the latter will be seen from the following analysis of sorghum grains : Moisture 11 per cent. Composition of the dried sample. Ash Soluble in 10 per cent, hydrochloric acid Starch 1 AlbuminoQS matters aolnble in caustic alkali Cellnlose Alcoholic extract .' Ethereal extract Nitrogen I. n. 1.31 1.69 90.70 87.80 75.20 73.00 6.71 7.96 2. .56 4.19 10.36 7.96 10. iO 7.30 1.82 1.79 There would be no difficulty in detecting it. Although as yet these substances do not seem to have reached us as far as the samples which we have examined show they must be care- fully watched for. In this country considerable has been published as to the adulterations of pepper, but little in regard to the manner of detecting them. We have already spoken of the large numbers of samples which have been examined in different years by the public analysts of Canada and smaller numbers by those of Massachusetts and New York. Eeference to the reports of the department of inland revenue of the Dominion (supple- ments on adulteration of food) shows th at wheat flour, husks, cayenne, coacoanut shells, and pepper dust, milling refuse, pea meal, and sand and clay are in very common use. In the United States the samples examined have apparently proved no better, for while in Canada in 1S85 twenty-nine out of sixty samples were adulterated mostly from 10 to 20 percent., but reaching 75 per cent.; in New York in 1882, out of forty- seven, thirty- three were adulterated, and in Massachusetts in 1884 Wood found -one hundred and four In one hundred and ninety -nine impure, and in 1883 69 to 70 per cent, were bad. We are thus supplied with considerable experience in the examina- tion of peppers, the results of which furnish the basis of a scheme for general use. Thus in examining a sample 1 should propose to proceed as follows : SPICES AND CONDIMENTS. 203 METHOD OF EXAMINING PEPPERS MICKOSCOPICALLY. As a preliminary tlie sieve examination, already mentioned, is of value, the coarser particles left upon a 40 or 60 mesh sieve frequently revealing the nature of the adulterant or the too large proportion of pepper husk. Afterwards it is well, with a good dissecting microscope and a power of 15 to 30, to sort over the ground pepper, and judge of the frequency of the occurrence of the coarse particles, which after a little experience there will be no difficulty in doing. The presence of sand or a notable excess of P. D. can also be detected and estimated in this simple way. Backgrounds of white and black, with reflected light and afterwards transmitted light," may be used in the manner so con- veniently afforded by Zeiss's stand, made for tbis purpose. A portion of the powdered pepper or the separated coarse particles should also be treated with chloral-hydrate solution for twenty-four hours, ^o render it more transparent for examination with higher pow- ers, and in the mean time the coarse* particles sieved from the powder may be examined under a one and a one-half inch objective, and then crushed and re-examined, using both plain and polarized light. In this way husky matter may be distinguished and foreign starches detected. Polarized light is then the means of bringing out more plainly the starches, the proportion of which iodine will reveal, mak- ing due allowance for the small granules of pepper starch and all op- tically active tissue, such as the bast fibers and sclerenchyma or stone cells, which are found in olive-stones and cocoa-nut shells. The structure of the pepper itself, as has been explained, is so char- acteristic as not to be readily confused with foreign matter. In the chloral hydrate preparation, which should now be examined^ much of this disappears as the starch is much swollen by this reagent. The husky matter present is rendered thereby so much clearer on the other hand that its identification and differentiation is made much easier, and it is here that the possibility of fixing the source of the adulterant will often lie. Experience with a half dozen samples from a cheap grocery in com- parison with a laboratory sample of pure pepper will soon teach oni« the best means of making out what has been briefly described. It has also been found most valuable to digest about a gram of pep- per with nitric acid, sp. gr. 1. 1, and chlorate of potash for several hours, or until the color is bleached. It is then possible to distinguish the denser cellular structure more easily than in any other way, particu- larly the stone cells which make up the larger part of the cocoanut shells and ground olive stones, especially with polarized light, being careful not to confuse the stone cells of the pepper husk with those of olive stones or other adulterants. Charcoal at the same time remains unbleached. To determine the merits and correctness of the various chemical pro- cesses and statements in regard to them previously referred to, a series 204 FOODS AND FOOD ADULTERANTS. of i)ure whole peppers, direct froin importers, aud of the commercial ground article, have been collected. The results also reveal the extent and nature of the adulteration practiced in this part of the country. The specimens were of the origin described below. Sources of specimens of pepper. WHOLE PEPPERS. No. Kind. Remarks. 45U 4fi40 4894 4893 4896 4516 4898 Whole black... .. do First quality, probabl.v west coast. West coast, direct from importer. Aaclieu, direct from importer. West coast, direct from importer. Singapore, direct from importer. Eirst qualit.v, source doubtful. Singapore, direct from importers. ...do do do Whole white... ...Do GROUND PEPPERS. 4515 4523 28 33 37 43 52 53 48S3 4884 4324 4544 4555 4882 Black • First quality, grocers' guaranteed pure, (rronnd in Washington. Ground in Baltimore. Do. Do. Ground in London, 'guaranteed Ground in Washington. Do. Ground in Baltimore, low grade ' ' Best." Ground in Baltimore, low grade "Pure." Ground in Washington. Ground in London, ''Pure." (i round in Washington. Ground in Baltimore. ...do ....do ....do ...do ....do do ...do ...do ....do White ....do ...do do MECHANICAL AND MICROSCOPICAL EXAMINATION. The weight of the whole peppers and the amount of dirt present, as they are imported, have been given already. In the ground condition they of course displayed the normal structure of the berry, as has been already described. No further reference is necessary, therefore, under this head. In the ground specimens the following peculiarities were noted. 4515. Sifting reveals the presence of pepper stems which should not be present, showing that the pepper was ground without cleaning and an undue proportion of husky matter, unbleached by nitric acid and chlorate. 4523. This specimen is very coarsely ground, a large proportion of husk remaining on the 40-iuesh sieve, among which evidence of the presence of maize could be distinguished, and that P. D. in some form must be present. 4528. Sifting separated light chaffy and fibrous matter. The micro- scope detected yellow corn and its hulls. 4533. This proved of very bad quality, the sittings consisting of bran, roasted shells or charcoal, and corn. The microscope was confirmatory and the presence of the roasted shells prevented bleaching with Schulze's reagent. This is evidently a P. D. pepper of the worst sort. SPICES AND CONDIMENTS. 205 4537. Sifting and examination showed the presence of P. D. in some form and corn. It contains no roasted matter or charcoal. 4543. Proved to be quite pure and well ground, all the material pass- ing a 40-mesh and nearly all a 60-mesh sieve. This is the only pure ground sample met with. 4552. Sifting shows the presence of a complicated collection of adul- terants, husks of various origin, &o. Microscopic examination detected mustard hulls, corn, roasted shells, or charcoal not bleachable, and other foreign material not identified. 4553. Contains mustard hulls and branny matter, but no charcoal. Bad. 4883 and 4884. From the same mill in Baltimore were the worst speci- mens met with. They contained but little pepper and were made up of P. D,. yellow corn, cracker dust, cayenne, charcoal, and other foreign matter. 4882. A white pepper from the same source was of the same origin, leaving out the black elements. 4524 and 4544. These white peppers were found to be pure, but the former not carefully decorticated. 4555. Contained foreign starchy matter and probably cayenne. Sift- ing revealed nothing abnormal. These examples serve to show the variations which are met with and what the analyist may expect. It is always well, also, to be on one's guard for something new. As a confirmation of the physical examination and a means of deter- mining the amount of adulteration in the several cases determinations were made of the proximate composition: 206 FOODS AND FOOD ADULTEKANES. •jaddad 99JJ q«B ^.ip no '(jnsnTAlnbQ (O SBS2 1 ^c^^tb^i ■K moz l.,'i7 2.18 2.02 2.10 1.93 •9S'9X-KIE>ox ^ eD (O i-(0 Ol COIN cool •lE»ox mil ■spioniinnqiv SSSsSS . t-i-iO oo ■joqg opnJQ ssgss o CO o c5 o •psaitnaojopnji CJ ?1 ^ o> !0 <0 OO TS to ^^ w CO CO Ir- •qojms IM 71 O CO O looinr-ico CO CO CO CO CO •»ora^x9 lonooif 5.08 6.06 5.71 5.74 •msai p n t; 9 a T i&di^ 7.29 7.20 7.72 7.90 7.15 ■\\o aiB^loA .70 1.48 1.69 1.63 1.60 •qsv 4.04 2.91 4.70 4.52 3.70 in-BM. 8.91 8.15 8.29 9.36 9.83 5 Retail do do •Bnni.iS OOT JO '^qarajtt. 5.900 6.460 4.525 5. 085 4.870 'lenp JO -CfUOO 10 tl f Clean 2.6 4.3 CO i do West Coart •loquinn T^uog i 4840 4894 4895 4896 a-g SS 1^ o SS 2£ O "^ " S: © CO 5^ ^5 « =*= ■* *s *• ** ■* H<0 fflu |COi-ii-ii-'iH5S«We4r-i H^i— 1 — eO(ONN ci^cJoJClOJN^'- 5 lO Sji^O X w «3 — i^ L-i O MS© SS-* '^ « 22 W '-' ■»- d ■-. .PN " ■^ ^ "^ in o — ^ CO 0OU3 (O S ic o =» 3^'* ® =1 ■^ 5* ■* -* r in CO ! I ! I ! I ! I CO lA Oa4S3SAc430:£S CDOCOOOO'^SS'-'©® •^ • • • •e5,-;g^r^ Tf ■* «o -* b- m t^ as CD lo 33 jj» ^ ot>oomo6 : i ■ • ; i ; : : i OS. © O O O O . 10 o o o o : ; : ;"§ o ; ; ; rs . . . . o'a ■ ' • <1 ; i ; :oa)Aiii-it~oioo>09t*>ocOQOi- ■OJI JBU9g 3 o o o J o op S \eS OOOfflOOOOOOO 'C'CJ'S a -3 -a '3 "^ '3 13 13 ■"■a ioiAinmincOA^090i>ninmtomioaooo 02 222 FOODS AND FOOD ADULTERANTS. The preceding figures show that there is nothing particularly distinct- ive between the cinnamoas and cassias, and that the determination of volatile oil points more to the character and value of the bark than any other, though, at the same time, there is nothing distinctive there- in, as the variation in amount is so large iu thecinnamons as to attimes furnish samples containing far less volatile oil than even a fair cassia. The percentage of ash is extremely variable, depending on the age and quality of the bark. Saigon chips werefouad to have 8.23 per cent., while aspecimenof unidentified cassia bark had only 1.75 per cent. Cin- namon bark will probably average less than cassia. Fiber, like ash, is extremely variable, and forthesame reasons; 26.29percent. were found in Saigon chips and 33.08 per cent, in a cinnamon and from 14 to 20 in ordinary cassias. This determination, therefore, reveals nothing, and is of no assistance iu detecting adulterants. Albuminoids are variable, but within narrow limits, the extremes being 4.55 percent, in Saigon bark and 2.45 iu an unidentified cassia. The Ba- taviaand Saigon barks appear to contain the most, over four percent., and this percentage would seem 1o be an indication of inferior quality. Tbe amount of tannin in these barks is extremely small, not reaching iu our specimens an equivalent of quercitannic acid by the Lowenthal process of two per cent. The addition, therefore, of material contain- ing tannin can be readily detected, bat in no case under our observation did such an addition occur. Aside from the determination of volatile oil, chemical analysis seems to be of little value. Tbe principal dependence must, with our present knowledge, be placed on the mechanical and microscopic examination, since the worst mixtures, 4868 and 4869, scarcely revealed in their com- position the fact of their inferiority. CLOVES. Cloves are the flower-buds of an evergreen tree, Eugenia caryophyllata, growing wild in the Malaccas and introduced into Amboyna, the neigh- boring Zanzibar islands, Cayenne, and a few other places in the tropics. They are picked by hand when their development has reached a red color, and are dried in tbe sun, becoming dark brown. They are classed as East Indian, African, and American, and are ^•alued in that order. Fluckiger and Hanbury's description of them is as follows : Cloves are about six-tenths of aa inch iu length, aud consist of a long cylindrical calyx dividing above into four pointed spreading sepals which surround four petals, closely imbricated as a globular bud about two-tenths of au inch iu diameter. The petals, which are of a lighter color than the rest of the drug and somewhat trans- lucent froui numerous oil cells, spring from the base of a four-sided epigynous disc, the angles of which are directed toward the lobes the calyx. The stamens, which are very numerous, are inserted at the base of the petals aud are arched over the style. The latter, which is short and subulate, rises froui a depression in the center of the disc. Immediately below it, and unitedwith the upper portion of the calyx, is the SPICES AND CONDIMENTS. 223, ovary, which is two-celled and coutaius many ovules. The lower end of the calyx (hypautium) has a compressed form; it is solid, but has its internal tissue far more porous than the walls. The whole calyx is of a deep rich brown, has a dull wrinkled surface, a dense fleshy texture, and abounds in essential oil, which exudes on simple pressure with the nail. The varieties of cloves occurring in commerce do not exhibit any structural diUfer- ences. Inferior kinds are distinguished by being less plump, less bright in tint, and less rich in essential oil'. In London price-currents cloves are enumerated in the order of value thus: Penang, Bencoolen (Sumatra), Amboyua, Zanzibar. A transverse section of the lower part of a clove shows a dark rhomboid zone, the tissue on either side of which is of a lighter hue. The outer layer beneath the epi- dermis exhibits a large number of oil cells, frequently as ranch as 300 miornmillir,, meters iu diameter. About 200 oil cells may be counted in one transverse section, so that the large amount of essential oil in the drug is well shown by its microscopic characters. The above-mentioned zone is chiefly made up of about 30 flbro-vascular bundles, another stronger bundle traversing the center of the clove. The fibro- vas- cular bundles, as well as the tissue bordering the oil cells, assume a greenish-black hue by alcoholic perchloride of iron. Oil cells are also largely distributed iu the leaves, petals, and even stamens of Fugenia. No starch is found in it, however. Preparations from whole cloves enable one to familiarize himself with the structure, which in the ground cloves is recognized with greater difficulty. In both cases the use of chloral hydrate solution is desirable, as the sections and fragments are otherwise not transparent. Pre- liminary examination of the powder in water for starch should, how- ever, be made, ns the starch granules swell iu the chloral hydrate solu- tion. Among the fragments will be seen a large amount of debris of no apparent structure, but the larger pieces are chiefly the cells of the epidermis interspersed with the large oil cavities or cells, which are not as readily detected as in carefully prepared sections, being concealed- by a layer of the epidermal cells. Next in prominence are the flbro- vascular bundles with their spiral vessels and with shreds of deep brown cellular matter attached. Pollen grains and, at times, whole anthers are present, and concretions of oxalate of lime. All these characteristic appearances are made out much more easily under polar- ized light, the long cells of the flbro-vascular bundles being optically active, as are also the pollen grains, oxalate of lime to a less degree, and the contents of the oil cells which are thus easily distinguished. After a study of standard powder of cloves, the presence of adulter- ants is not difficult to recognize. Pimento is often added, and may be identified by the starch which it contains and the characters described under that spice. Clove stems are said to be the commonest adulterant, and the pres- ence in them of tiiick-walled stone cells and long yellow fibrous tissue serves as a means of recognition, since similar structures are not found in the clove, at least in the same abundance. The fruit of the clove is also added, and since it contains starch and a large embryo they are de- tected readily. We have not met either of these adultei:ants. 224 FOODS AND FOOD ADULTEEANTS. In the cheaper forms of ground cloves, where from the price it is evident that adulteration has been practiced, the common substitutes, which are added as diluents to all the spices, must be sought for and require no further experience beyond what has been obtained in the examination of pepper. In most of the samples which were examined during the preparation of this report the microscope revealed nothing foreign, and for a de- cision as to their quality it was necessary to have recourse to chemical analysis. Two specimens from Baltimore of the same low grade as several of the spices previously mentioned were found, however, to be Aiixtures of all sorts of cheap material, containing mineral coloring matter, roasted shells or charcoal, corn, and hulls of seeds. The sources of the cloves examined were as follows, being largely the ordinary article for sale at grocers : SOUKCKS OF CLOVES. 4504. Whole cloves, guaranteed, Washington. 4903. Amboyna cloves, whole, direct from importers. 4904. Singapore cloves, whole, direct from importers. 4905. Clove stems, whole, direct from importers. 4641. Whole cloves, druggists', 10 cents per ounce. 4642. Whole cloves, druggists', 10 cents per ounce. 4643. Whole cloves, druggists', 10 cents per ounce. 4505. Ground cloves, guaranteed, Washington. 4520. Ground gloves, ground in Washington. 4540. Ground cloves, genuine Amboyna, 30 cents per i ponnd ; English brand. 4548. Ground cloves, Washington grocers, second class, 26 cents per i iiound. 4629. Ground cloves, Washington grocers, second class, 20 cents per i pound. 4630. Ground cloees, Washington grocers, 30 cents per pound. 4631. Ground cloves, " strictly pure," 40 cents per pound. 4632. Ground cloves, Washington grocers, second class, 30 cents per pound. 4633. Ground cloVes, Washington grocers, second class, 30 cents per pound. 4873. Ground cloves, Baltimore Spice Mills ; "pure." 4874. Ground cloves, Baltimore Spice Mills ; " best." The results of the analyses are as follows : SPICES AND CONDIMENTS. 225 «> « a •panod i J3(1 80U J •ppB '(Hia^AinbQ noSXxQ •aeSom^ ■^■^lOpsw^Mam •sptoainrnq^y ■Mqj aptuQ 'ins9J pHB i!0 p9X!^ •IJO BIHEIOA •qsT ■J[9}B^ t G? OOT JO t^qSiQjii^ Trcecct-miniom aiwoooot-conm t-ososooioos-ch ooeo-j< LOffit-oat>iotoc0 «DCOint- eDOCDt-to-^eo-^iOTHTti COO^iMOCOVC^COO'^CTS tfSiOlOCOOOOt-t-COffiO irsoooooo<»«it-coi><-(oo & o inOOOOOJOiHNMM"^ 226 POODS AND FOOD ADULTERANTS. In comparison with these results it is of interest to refer to what has been already published. Fluckiger states that from 16 to 20 per cent, of volatile oil is present, and gives details in regard to its composition and reactions ; but be- yond this nothing. Dietsch gives the following figures as the percentages of oil to be expected in cloves from different sources : Per cent. Amboyna 16 to 21 Zanzibar 12 to 17 Cayenne 9 to 12- There are one or two very old analyses in detail which are hardly re- liable, and Dr. Ellis, of Toronto, has made investigations, still unpub- lished, in regard to the amount of tannin present, with a view to using the determination as a check on adulterants ; but with these exceptions we are not aware of any other work upon the composition of this spice. The authentic whole samples show that the percentage of water may be very variable, being at times as low as 2.90 per cent., and again as much as 10.67, which is high for so oily a substance. The ash, too, has rather wide extremes, varying from 5 to 13 per cent. The usual amount would not, however, be far from 5.50 to 6.50 per cent. Volatile oil falls in uo case below the amount given by Dietsch, and serves as, perhaps, the best means of judging of the quality of the specimens. The extremes found in the pure specimens were 1 0.23 and 18.89 per cent., while but five out of the eleven ground specimens reached 10 per cent. Other determinations do not seem especially characteristic. The ex- tremes, which cannot be exceeded without casting suspicion, are : Per cent. Water 11. 00 to 2. 75 13. 00 to 5. 00 21. 00 to 9. 00 11. 00 to 4. 00 10. 00 to B. 00 8. 00 to 4. 00 Ash Volatile oil Fixed oil and resin . . . Grade fiber Albaminoids The determination of tannin, following the suggestions of Dr. Ellis, of Toronto, has been examined with results showing it to be of some value, but not as great as that of volatile oil. Our experience showed that it was as well to determine the matter oxidizable by permanganate after removal of oil, &c., by Squibb's ether, as to make a more elaborate determination of tannin itself. In the best whole cloves from the Im- porters the quercitanuic acid equivalent of the oxidizable matter varied from 18.72 to -22.13 per cent., aud in the stem reached 23.24 per cent. The determination will not, therefore, show the presence of stems in ground cloves. The amount fell also in one unidentified specimen of whole clovei to 11.70 per cent., but the quality of these buds was un- known. It is fair to assume, then, that good cloves should contain ex- SPICES AND CONDIMENTS. 227 tractive oxidizable matter equivalent to 18 per cent, of quercitannic acid, or require an oxygen equivalent of about 4.50 per cent, for its re- duction; Of the 11 specimens of ground cloves examined, although none of them were of first quality, this tannin equivalent exceeded 18 in all but 3. The addition of stems and allspice would not be discovered, as both contain tannin in considerable amount. This determination is, then, in no way conclusive, but merely furnishes an indication which must be corroborated by other means. For the method of carrying it out refer- ence must be made to our pages on analyses. As has been said, none of the ground specimens of cloves were first class, analyses showing that in only one case did the essential oil reach as high as 13.93 per cent., and although but 2 from Baltimore contained cheap foreign adulterants and none were sophisticated with allspice, all the specimens must have been made from a low grade of . buds and many with the addition of large quantities of stems and spent cloves. The two cheapest specimens, 4873 and 4874, were, as has been said, terrible comi)ounds of mineral coloring matter, leaving a dark ferruginous ash, corn meal, and hulls, evidence of which appears in the analyses from the low oil, 3.59 and 4.06 per cent., and the high crude fiber. The addition of so much organic matter low inash conceals the presence of mineral coloring matter which is detected by its ferruginous appearance. In the ash of the whole buds, while there are at times some of a light reddish tinge, the color is dis- tinctly or often dark green from the presence of manganese. Our results show the universal and alarmingly poor quality of the commercial supply of ground cloves. PIMENTO OR ALLSPICE. Pimento is the fruit of Pimenta officinalis, an evergreen tree common in the West Indies. It is the only one of the common spices which had its origin in the New World. It is a small, dry, globular berry from two to three tenths of an inch in diameter, having a short style and sur- rounded by four short thick sepals which often, however, have become rubbed off, leaving a scar-lil.e ring. The berry has a woody shell, or pericarp, easily cut, and of dark, ferruginous brown, rugose by means of minute tubercles fi.lled with essential oil. It is two-celled, each cell containing a single seed. The seed is less aromatic than the pericarp. Under the microscope the outer layer of the pericarp, just beneath the epidermis, appears as a collection of very large brown parenchy- matous cells filled with oil. The more interior layers consist of thick walled or stone cells loaded with resin, the most characteristic struc- ture of the pimento, parenchyma cells, and smaller crystals of calcic ox- alate which are not easily seen. The whole tissue is traversed, but not plentifully, by fibro-vascular bundles. The seeds contain much starch in minute grains and have a few oil cells. The embryo is large and spi- rally curved. The hulls of the seeds consist of a delicate epidermis 228 FOODS AND FOOD ADULTERANTS. and of large thin- walled cells with light or dark red contents, which are very characteristic and are called by Hassall the port-wine cells, which should be examined in water, and after treatment with chloral hydrate, the starch grains being made oat in the water preparation and the re- maining structure among the particles rendered transparent by the chloral hydrate. Most prominent among the latter under polarized light, which is here a great assistance, are the stone cells or thick walled cells partly grouped and partly separate, and often, with plain light, showing shreds of parenchyma adherent to them. The brown cells which con- tain the oil are made out with less distinctness, but most striking are the red or port- wine cells of the seed hull, which are seen scattered ev- erywhere, and in color and form are very characteristic. Shreds of the embryo are also now and then seen. Fig. 13. Allspice powder, a, starch; 6, port- wine cells ; A, hairs; «, stone cells ; p, parenchyma. X 240. Schimper's diagramatic illustrations of this spice are here copied in Fig. 13, and serve as a slight aid to the recognition of the structures mentioned, but merely as suggestions, as nothing exactly correspond, ing to the drawings will be found in the ground powder. Polarized light is a most important aid in examining this spice. It brings out strongly the stone-cells and ligneous tissue and differentiates therefrom the great mass of other matter. It also makes the oil cavi. ties more distinct. The adulteration of this spice does not often occur, owing to it.s cheap- ness. We have only found three cases, and those from Baltimore. In No. 4530 a substitution had been made for allspice, of which not a par- ticle could be detected, of inferior cloves from which much of the volatile oil had been extracted, ami Xos. 4877 aud 4S7 ', where yellow corn and mineral coloring matter were plentiful. In these instances chemical analysis con Armed the microscopic examiuatiou. Abroad clove stems are said to be largely used as an adulterant. They differ from cloves, as has beea already explained, in the presence of SPICES AND CONDIMENTS. 229 numerous stone-cells and flbro-vascular bundles, and in Canada peas and roasted corn have been found. The presence of these cheap dilu- ents should be sought for, as in peppers, but they are less common in this spice. CHEMICAL COMPOSITION OP ALLSPICE. But little has been published in regard to the proximate principles of the pimento. The amount of volatile oil is said by Fliickiger to be from 3 to 4J per cent., while starch and much tannin are present in the berry. Dragendorff has also found a minute quantity of an alkaloid of the odor of coumarine. Hassall gives analyses, which are too old to be of any value, and quotes Pereira as an authority for the fact that the essential oil of pimento is made up of two distinct oils, which, of course, may be true in one sense but is hardly of value as a definite distinction, both for this spice and cloves, as has been already remarked. As a matter of fact but little is known of this spice. We have ex- amined seven samples with the results here given : 4500. Whole allspice. 4501. Ground allspice, guaranteed pure, Washington. 4518. Ground allspice, ground in Washington. 4525. Ground allspice, ground in Baltimore. 4530. Ground allspice, ground in Baltimore. 4534. Ground allspice, ground in Baltimore. 4538. Ground allspice, English brand. 4877. Ground allspice, best, cheap grade, Baltimore. 4878. Ground allspice, pure, cheap grade, Baltimore. All the samples were ground by different firms except the last two. Analyses of pimento, allspice. TS « «• ■^ 9 Serial No. Description. 1 4 < ■s 'o 'o t5 (0 'a g o o 1 1 '3 1 O 4S00 Whole 6.19 5.51 4.01 3.93 5.15 2.93 6.15 6.10 59.28 58.24 14.83 17.95 4.38 5.34 .70 .86 10.97 13.10 2 81 4501 3.36 4518 do 8.03 4.83 2.07 5. .50 57.20 18.00 4 38 .70 9.31 a. 39 4525 do 8.82 4.91 3.32 6.18 67.90 13.45 5.42 .87 9.39 2.40 4530 do 11.59 6.02 8.17 7.64 59. 57 11.93 5.08 .81 18.72 4.80 4534 do 7.31 3.45 3.16 6.92 58.58 16.65 4.03 .61 12.74 3.27 4538 do 8.71 4.60 1.29 5.35 55.90 18.83 5.42 .87 10.92 2.80 4877 do 7.98 5.53 2.80 3.77 56.86 18.98 4.38 .70 8.27 2.12 4878 -i" .• 7.31 5.19 1.82 1.60 56.45 23.60 4.03 .67 4.32 1.11 In our analyses there is considerable variation among the samples. Taking the whole berry as the standard the others fall off very much in quality, as judged by the volatile oil, with the exception of number 4530, which, too, from its low fiber, high ash, and high volatile and fixed oil is suspicious, and proves to be a substitution of cloves and clove stems. The microscope has shown that this sample is inferior cloves, and it must therefore be rejected. 230 POODS AND POOD ADULTERANTS. The amount of essential oil in our best sample exceeds Pliicklger's highest, but on the ground specimens falls off sadly, 4538 and 4878 being almost worthless as far as this valuable ingredient goes, perhaps in the first case having been exhausted for the preparation of the oil, although the ash is but little reduced in amount, and in the latter being nothing but mixtures, as shown under the microscope. The other determinations show no important variation in the constit- uents, and estimation of the volatile oil would perhaps be the only thing necessary in a chemical way in examining it, without it is desired to go into the determination of tannin, which is as serviceable a means of discriminating among allsj)ices as was found to be the case with cloves. In the same way our results show that good allspice contains oxid- izable matter extracted by water after removal of oil, etc., by ether equivalent to from 9-11.0 per cent, of quercetannic acid, the amount being considerably smaller than is found in cloves. This determination points out at once that specimens 4530 and 4878 are abnormal, and that 4534 is suspicions. It may be made of value and must be carried out in the same way as with cloves. Of the eight ground specimens ex- amined three were adulterated and one was suspicious, so that even of this cheap spice we can hardly expect a pure supply without some pro- tection. NUTMEG. Nutmegs are the interior lieruel of the fruit of Myrisiica fragrans, a tree growing in various parts of the East, but principally in the Banda Islands. Fliickiger and Hanbury describe in a most excellent way their char- acteristics as follows : The fruit is a pendulous, globose drupe, about 2 inches in diameter, and not unlike a small round pear. It is marked by a furrow which passes around it, and by which at maturity its thick fleshy pericarp splits into two pieces, exhibiting iu its interior a single seed, enveloped in a fleshy foliaceous mantle or arillns, of fine crimson hue, which is muee. The dark brown shining ovate seed is markethouusl BUL. 13, Part 2, Div. Chemistry, U. 8. Dept. Agriculture. PLATE XV. Fig. 29. POTATO Starch x 43 Fig. 30. potato Starch PHOTO BY CLIFFORB BICHARD80N. A.Hcttn &Ca..Lirl,ocausl BUL 13, Part 2, Div. Chemistry, U. 8. Dept. Agriculture. PLATE XVI. Pig. 31, Potato Starch x 144 Pig. 32. 'vi. '^' *s ' 9' qat Marunta Starch x i44 PHOTO BY CLIFFORD RICHARDSON. A Hoen ftCo,,LithocBlistic BUL. 13, Part 2, Div. Chemistry, U. 8. Dept. Aqrioulture. PLATE XVII. Pig. 33. Maize Starch x 145 Fig, 34. Wheat Starch x 145 PHOTO BY CLIFFORD RICHARDSON. A Hoen&Co.,Litho( BUL. 13, Part 2, Div. Chemistry, U. S. Dept. Agriculture. PLATE XVIII. Fig 35. Rice Starch x 150 Fig. 36. Rice Starch x 450 rilOTO BY CLIFFORD RICHARDSON. A Koen ecCo.,Lithocauslic BuL. 13, Part 2, Div. Chemistry. U. 8. Dept. Agriculture. PLATE XIX. Pig. 37. Barley Starch x iso Pig. 38. Oat Starch x i60 PHOTO BY CLIFFORD RICHARDSON. A Moen &Co..Lithocaustic But. 13, Part 2, Div. Chemistry, u. 8. Dept. Aqrioulture. PLATE XX. Fig. .39. Bean Starch x Fig. 40. PHOTO BY CLIPFOHD RICHAKI>S0:N. A HoBnaCo.,LiihoM,uslic, BUL. 13, PART 2, DIV. CHEMISTRY, U. S. DEPT. AQRIOULTURE. PLATE XXI. Fig. 41. QlNQER STAROH X 145 Fig. 43. QlNQER Adulterated x 145 PHOTO BY CLIFFORD RICHARDSON. A Hoen &Co..LJthocauslic- But 13, Part 2, Div. Chemistry, U. 8. Dept. Agriculture. PLATE XXII. Fig. 43. Black Pepper p. o. x 45 Fig. 44. Pepper Adulterated x is PHOTO BY CLIFFORD EICHARDSON. A HoenaCo.,Lrti BUL. 13, Part 2, Div. Chemistry, U. S. Dept. Agriculture, PLATE XXIII. Fig. 45. Cinnamon Adulterated PHOTO BY CLIFFORD RICHARDSON. A Moen 8, Co.. Lit! BUL. 13, PART 2, DlV. CHEMISTRY. U. 8. DEPT. AQRIOULTUR PLATE XXIV. Pig. 46. Cinnamon x 45 Fig. 47. Cassia x 45 PHOTO BY CLIFFORD RICHARDSON. AHoen aCo.^Lilhocaiistic. BUL. 13, PART 2, DIV. CHEMISTRY. U. S. DEPT. AQRIOULTURE. PLATE XXV. Fig. 48. Fig, 49. Cayenne Adulterated PHOTO BY CLIFFORD RICHARDSON. AHoen ftCo.,Llthocausllc BUL 13, Part 2, Div. Chemistry, U. 8. Oept. Aqrioulture. PLATE XXVI. WHEAT <«, . J %il,^- "^fe,.^^ BARLEY /■# i m OATS CORN _:i ?i i^_ ^/^ w^' RICE DRAWN Bl GEO. MARX. A Hoen &Co..L,tho« BuL 13, Part 2, Div. Chemistry, U. 8 Dept. Aqriouuture. PLATE XXVII. f'.V MARUNTA. POTATO ^^^ ■-«Jtr fr^ QINGER SAGO if ?§■■ '^■. ■'" "Y-h W PEAS .i- BEANS DRAWN 11^ GEO. MARX. A Hoen &Co.,l-ithocausiic BUL 13, Part 2, Div. Chemistry, U. S Dept. Aorioulture. PLATE XXVm. BUCKWHEAT TURMERIC b^ • ,,, • « /■■• * o c V . « a. ^ -^/^ ^ v>0 CINNAMON ^^' y ^ CAPSICUM URAWN la DRO. MARX. A Hoan ScCcLithacauslic