iB 953 L85 :opy 1 fNITED STATES DEPARTMENT OF AGRICULTURE BULLETIN No. 1027 < Contribntion from the Bureau of Chemistry W. G. CAMPBELL, AcUng Chief Washington, D. C. April 17, 1922 POISONOUS METALS ON SPRAYED FRUITS AND VEGETABLES BY W. D. LYNCH, Assistant Chemist, C. C. McDONNELL, Chief, Insecticide and Fungicide Laboratory, and J. K. HAYWOOD, Chief, Miscellaneous Division, Bureau of Chemistry; A. L. QUAINTANCE, Entomologist in Charge, Fruit Investigations, Bureau of Entomology; and M. B. WAITE, Pathologist in Charge, Fruit-Disease Investigations, Bureau of Plant Industry > CONTENTS Page Purpoas of InTestlgatlon 1 Results of Previous Investigations ..1 Experimental Worit 16 Results of Experimental Work "..... 18 Summary ........68 Uteratore Cited ^ , S8 WASHINGTON GOVERNMENT PRINTING OFFICE 1922 ^ X f LiBRyvwr OF congress" UNITED STATES DEPARTMENT OF AGRICULTURE J BULLETIN No. 1027 | J^^-^LTi. Cuntribution from the Bureau of Chemistry W. G. CAMPBKLL, Acting Chief Washington, D. C. April 17, 1922 POISONOUS METALS ON SPRAYED FRUITS AND VEGETABLES. By W. D. Lynch, Assistant Chemist, C. C. McDonnell, Chief, Insecticide and Fungicide Laboratory, and J. K. Haywood, Chief, Miscellaneous Division, Bureau of Chemistry: A. L. Quaintance, Entomologist in Charge, Fruit Investigations, Bureau of Entomology; and M. B. Waite, Pathologist in Charge, Fruit-Disease Investigatio7is, Bureau of Plant Industry.^ CONTENTS. Page. Purpose of investigation 1 Results o( previous investigations 1 Experimental work 16 Results of experimental work 18 Summary 58 Literature cited 58 PURPOSE OF INVESTIGATION. In the spring of 1915 a cooperative study was undertaken in the United States Department of Agriculture to ascertain the amounts of arsenic, lead, and copper remaining on fruits and vegetables treated with poisonous sprays. The spraying was done under the direction of the Bureau of Entomology and the Bureau of Plant Industry, and the chemical work by the Bureau of Chemistry. The plan was to spray various fruit trees and vegetables according to accepted schedules, and also with excessive amounts of material to determine how much of the metals may be present under adverse conditions. In case the investigation showed that poisonous metals remained on the fruit in amounts which might prove injurious to the consumer, the results would constitute a basis for so changing or regulating the spraying schedules as to eliminate this danger. RESULTS OF PREVIOUS INVESTIGATIONS. Arsenical compounds first appeared as insecticides in the United States (63)* about 18G0, when Paris green was used to check the > Credit is due to John O. Fairehild and Wilbur A. Gersdorfl for assistance in the analj-tical work re- ported in this paper. ' Figures in parentheses refer to Literature Cited, pp. 58 to C6. 7M3S— 22— Bull. 1027 1 2 BULLETIN 1027, V. S. DEPARTMENT OF AGRICULTURE. ravages of the Colorado potato beetle. In 1872 Le Baron (70) sug- gested the application of Paris green to fruit trees to combat the spring cankerworm, but Lodeman (75) states that only a few of the most progressive orchardists adopted arsenical spraying against the codling moth until after the establishment of the State agri- cultural experiment stations resulting from the passage of the Hatch Act in 1887. The question soon arose as to the possible danger to the consumer from the use of potatoes the vines of which had been treated with a poisonous compound, such as Paris green. One of the first in- vestigators of this subject, Kedzie, in 1872 (64) and 1875 (65), con- cluded "that there is but very little danger of the potato tuber being poisoned so as to endanger the health of the consumer. Ar- senic is equalh' deleterious to the vegetable as well as the animal system. If added in dangerous quantity to the plant, the plant dies, no potatoes are formed." McMurtrie (78) detected no arsenic in potatoes which had been subjected to applications of Paris green. Lodeman (75) states that London purple was recommended as an insecticide in 1877. Cook (26), who sprayed apple trees on May 25 and June 20, 1880,. at the rate of 1 pound of London purple to 100 gallons of water, reported that 100 blossom ends cut from the sprayed trees on August 19 showed no trace of arsenic. He proved also (27) that it took but a very small amount of the arsenites to kill potato beetles, currant slugs,, and cabbage caterpillars, and discovered that the poison was retained on plants sheltered from rain for 10 to 20 days. He concluded that it was safe to use Paris green or London purple on trees the fruit from which would not be eaten for four or five weeks after the application. Wheeler (132), in 1888, reported that it was safe in California, where rainless summers prevail, to spray vines with Paris green. When the vines were sprayed with 1 pound of Paris green to 16 gallons of water, "ten times as strong as the solution recommended for general use," Rising (114), the State analyst, found only traces of arsenic on the grapes and none in the wine made therefrom. Objection was offered to the use of arsenicals, on the ground that they frequently caused more or less injury to the foliage. Gillette (58), however, found that "lime added to London purple or Paris green in water greatly lessens the injury that these poisons would otherwise do to foliage." W^eed (129) recommended applying insecticides and fungicides together, and Gillette (58) showed that London purple can be used at least eight or ten 'times as strong without injury to foliage if applied in common Bordeaux mixture instead of in water. Gillette (59) stated, in 1891, that a mixture of 1 ounce of Paris green to 100 ounces of flour was the most eflFectual POISONOUS METALS ON SPnAYKD FIU'lTS AND Vi:( IKTAi'-I.KS. 3 roniotly ajijaiiisl llu^ cal)!)!!!;*" worm, applying ''just onuugh to make a slight show of (hist upon the leaves. " These discoveries were quickly adopted in j)ractice, and arsenicals were generally aivcpted as the best destroyers of external chewing insects. The most important insecticides recommended, other than I^iris green and London purple, were Scheele's green (113) in 1875, white arsenic plus lime t,()7) in 1S91, and lead arsenate (40) in 1893. L'ntil recently Paris green and lead arsenate have been the most extensively used, but calcium arsenate, now on the market, promises to become one of the leading arsenical insecticides. The use of Bordeaux mixture originated in France near the city of Medoc. Viticulturists noticed that the vines near the highways, which had been sprinkled with a paste of milk of lime and copper sulphate to prevent thieving, did not suffer from mildew. Prof. Millai-det, in 1882, attributed the benelicial action to copj)cr, and later proposed a mixture of copjjcr sulphate, lime, and water, since known as Bordeaux mixture (88) (89). The mixture was immediately accepted not only in France but in the Ignited States, where F. Lamson Scribner (116) was probably the first to publish a formula for it as a result of the work in France. Its use has been extended to the preven- tion of so many plant diseases that to-day it is perhaps the most important fungicide. When copper compounds were recommended as fungicides, the fpiestion arose as to whether or not spraying with them would leave a dangerous amount of copper on the grapes or in the wine. Perrett (107) stated, in 1885, that there would be no danger of introducing copper into wine made from grapes sprayed with copper salts, because the hydrogen sulphid formed during fermentation would precipitate the copper as the insoluble sulphid. Quantin (HI), in 1886, concluded that the reduction of the sulphate of copper by the ferments was sufhcient to effect the total elimination of the copper in wine, but that aeration of the lees which inclosed the precipitated sulphid of copper should be avoided. Chuard (23) announced in 1887 that the copper was present in the must as copper malate, but that it was precipitated during fermentation as the sulphid and tartrate. In October, 1885, Millardet and Gayon (90) obtained the following amounts of copper from vines that had been sprayed with Bordeaux mixture in July: Fro^li leaves (mg. per kgm.) 19. 1-95. 5 \ine brandies (nig. per kgm.) 5. 8 (irape stalks (ing. per kgm.) 15. 0-18. 6 Marcs (ing. i)or kgm.) 11- 1-21. 9 Musts (mg. per liter) 10- 2. 2 Wines (mg. per lit,( r), fr jiii doubtful traces lu less than 0-1 4 BULLETIN 1027, U. S. DEPARTMENT OF AGRICULTURE. The same authors, in 1886, report (56) the following amounts of copper at vintage from vines treated with various copper mixtures: Grapes (mg. per kgm.) 0. 2-12. 6 Must ( mg. per liter) 0-11. 8 Wine (mg. per liter) Fraction. Examination of wines from different places in the southwest of France showed the presence of copper in the following amounts : First wines: White (mg. per liter), less than 0. 01-1. Red (mg. per liter), less than 01-2. 8 Second Avines (sweet wines) (mg. per liter) 01- . 3 Press wine (mg. per liter) 05-1. 7 Piquettes: Normal (mg. per liter) 0-0. 75 Sour (mg. per liter), less than 01- 1. 6 They attributed the absence of copper in wine to the action of the fermentation, the tannin and sulphur added to the wines before fermentation favoring the purification of the wine. Crolas and Raulin (28) determined the amount of copper in the products of vines that had been treated six weeks to two months before vintage with different preparations containing copper, and found copper in the following amounts: Grapes (mg. per kgm. ) 1. 5- 3. 5 Marcs (mg. per kgm.) 9- 12. 8 Lees (mg. per kgm.) 49. 0-130. Piquettes (mg. per liter) 0- .14 Wines (mg. per liter) 0- .36 Other investigators who have determined the amount of copper in wine (8) (16) (25) (29) (36) (41) (42) (45) (79) (104) (108) (118) (134) agree that the amount found in every instance was too small to be harmful. C. L. Penny (105) reported, in 1889, 2.4 and 6.2 parts of copper per million for grapes that had been sprayed with Bordeaux mixture and 1 to 1.3 parts of copper per million for unsprayed grapes. These amounts were less than those found in some common articles of food. In 1890 (106) grapes so heavily sprayed that '' either the appearance or the taste of the fruit would have condemned it on the market" were shown by Penny to contain about 47 parts of copper per million, "less than has been found in some articles of food admitted to be healthful, as beef liver." In order to determine "whether there is any danger to be appre- hended from eating grapes which have been sprayed with the Bor- deaux mixture and other copper solutions," Galloway and Fairchild (47) gathered grapes from a plat which had been sprayed eight times with Bordeaux mixture. "The last spraying was made on these POISONOUS METALS ON SPRAYKU FRUITS AND VKtiKTABLES. 5 vines July 30, aiul l)otween that date and August 28, the date of harvest, only a few slight rains had fallen. The fruit showed the mixture plainly, more pronouncedly in fact than any treated grapes seen in the market. One kilogram of tlie clusters (2^ pounds), includ- ing the stems, which appeared to have the greater part of the copi)er, * * * yielded 0.005 gram (0.077 grain) of metallic copper," on analysis, about 0.035 grain of copper per pound of grapes. In September, 1891, the Board of Health of New York City seized a (juantity of grapes some of which had been heavily oversprayed with Bordeaux mixture (46). The following results of analysis of the most lieavily sprayed bunches of grapes obtainable from the vineyards from which the grapes seized had come were reported (128) : (1) The amount of copper, estimated as metallic copper, found on the berries was very constant in the different samples, averaging 1/120 grain for each pound of fruit (berries and stems). (2) The amount of copper, estimated as metallic copper, found on the stems varied from 1/90 to 1/14 grain for each pound of fruit (berries and sterns^ and averaged 1/30 grain. (3) If the copper were on the berries in the form of sulphate of copper, each pound of berries would contain about 1/30 grain of copper sulphate. (4) As a matter of fact, copper, when found upon sprayed grapes in New York State, exists, not in the form of a sulphate, but in the form of a carbonate or hydroxid, both of which are not readily soluble and would, therefore, be even less dangerous than if present in the form of sulphate of copper. Most of the copper found was on the sterna, and the rest of the copper was on the outside of the skin of the berries, which most people do not eat. (5) The results obtained from estimating by chemical analysis the amount of copper on grapes, which were selected as being the worst sprayed that could be found, there- fore, seem to justify the assertion that it is simply an absolute impossi))ility for a person to get enough copper from eating grapes to exert upon the health any injurious effect whatever. According to Popenoe and Mason (109), "as much of the fruit (grapes) at the time of ripening showed a greenish-blue discoloration from the deposit of lime and copper, which had been applied twice since a rain had fallen, some persons feared that it might be poison- ous." Analysis of those grapes showing the heaviest deposit gave for combined stems and berries 0.00188 per cent copper, or 0.52 grain of copper sulphate per pound of grapes. "A short time after this sample was taken a heavy shower washed off so much of the deposit that little of the remaining fruit was injured in appearance." Wheeler (131) found only slight traces of copper on grapes that had been sprayed with Bordeaux mixture. Alwood (6) reported no copper, or only traces, on grapes that had been sprayed with copper mixtures, and concluded "that these fungicides are perfectly harmless to con- sumers of the treated fruit." Maynard (84) reported that only 0.002 per cent of copper oxid was found on grapes which had been so heavily sprayed with Bordeaux as to be badly disfigured and that no 6 BULLETIN 1027, U. S. DEPARTMENT OF AGRICULTURE. trace of copper could he found on grapes which had been properly sprayed with copper mixtures. From this it would seem " that even under the most careless use of the copper solutions, no injurious effects need be feared, and that when properly applied there will not be a trace of copper left upon the fruit at harvesting." In 1S92 the United States Department of Agriculture (9) published the following: We take the ground that fruit sprayed with the copper compouuds in accordance ■with the directions of the department is harmless. * * * For five years the copper compounds have been used by hundreds and thousands of fruit growers in e^ery part of the United States, yet in all that time not a single authenticated case of poisoning, so far as we are aware, has lieen brought to light. * * * Accepting, then, 0.5 gram as the maximum amount of copper in any of the forms discussed that may with safety be daily absorbed, * * * that grapes sprayed intelligently rarely contain more than 5 milligrams (0.005 gram) of copper per kilogram, the average be- ing from 2h to 3 milligrams per kilogram, * * * an adult may eat from 300 to 500 pounds of sprayed grapes per day without fear of ill effects from the copper. This shows how ridiculously absurd are the statements that fruits properly sprayed with -the Bordeaux mixture or any other copper compound are poisonous. * * * According to numerous analyses, wheat may contain from 4 to 10 milligrams of cop- per per kilogram. * * * "We do not see how any foreign country can logically object to American fruits on the ground that they co.itain copper without also ob- jecting to wheat. Wheat, however, does not contain anything like as much copper as some other foods and drinks. Beef liver and sheep liver, according to reliable and repeated analyses, contain, respectively, from 56 to 58 and 35 to 41 milligrams of metallic copper per kilo- gram of fresh substance, while in chocolate the enormous amount of 125 milligrams to the kilogram has been found. In conclusion, it is o Iv necessary to call attention to one other matter to show how unjust and discriminating it would be to condemn American fruits on the ground that they contain copper in unwholesome quantities. Analyses of vegetables that have been regreened by the copper process show that they may contain from two to sixty times as much of the metal as sprayed grapes. In this connection the presence of copper reported in various foodstuffs in the following amounts is of interest: From 4 to 10 milligrams per kilogram in wheat (43); 56 to 58 milligrams per kilo- gram in beef liver (105); about 40 milligrams per kilogram in sheep liver (35) (100); from 5.6 to 20.8 (44) and from 5 to 125 (31) milligrams per kilogram in chocolate; from 11.2 to 29.2 (44) and from 9 to 40 (31) milligrams per kilogram in cocoa; from 35 to 250 milligrams per kilogram in cocoa shells (31). Instances are cited (77) where as much as 270 milligrams of copper per kilo was found in French peas that had been sub- jected to the regreening process. Tschirch stated (127) that copper is widely distrib- uted in plant and animal bodies, always, however, in small amounts; that it enters the animal bodies through food and dust; but that the presence of copper in the bodies of man and other higher animals is not to be considered as "normal." He stated further that plants absorb only small amounts of copper from the ground; that no danger to health need he expected from the consumption of wine from sprayed grapes or of potatoes from sprayed fields, and that even the must of coppered grapes may be eaten and the skins (containing 0.006 gram of copper per kilo) used as fodder; that spraying with copper against fungous diseases might be continued without fear of harm; that only very small (juantities of the copper compounds entering the mouth i POISOXOUS METALS ON SPRAYED FPvUITS AND VEGETABLES. 7 are taken up by the blood, and poisoning can occur only if the necessary quantity enters the circulation; and that to forbid copper in foods and drinks is to forbid those plants which take it up from the ground, and also to designate the use of bread and chocolate as dangerous to the health. Lehmann reported the following amounts of copper per kilogram in various plant and animal substances: In wheat, 7.5 milligrams; in cherries, 1.5 milligrams; in pears, 0.5 milligram; and in beef liver, from 6.4 to 59 milligrams (71) (73). He stated (72) that the species of the plant had far less influence than the quantity of the copper in the soil on the amount taken up by the plant. In 1891 objections to the use of American apples because of the presence on them of arsenic were made in certain British journals. However, Maynard (85), Munson (97), and Fletcher (38) proved that the objection had no basis in fact, and later (10) (103) (126) it became apparent that such objections to sprayed fruit in England were neither very general nor very deep-seated. Table 1 shows the amount of arsenic and copper found by R. C. Kedzie (66) on fruit sprayed with Bordeaux mixture and London purple in 1892 and 1893. Table 1. — Arsenic and copper on fruit sprayed in 1892 and 1893 with Bordeaux mixture and London purple (Kedzie). Fruit. Date sprayed. Date picked. Spray used. AS2O3. CuSOi.SHjO. Strawberries. Do Red cherries. Do White cherries Red currants . Raspberries... G ooseberries . Do. Pears... Do Russian cherries. Plums 1892. June 18,23. -do. June IS, 30. do June 30. Mav 25, June 7; 18, 30. June 6, 28, July 8. June IS, 29, July 8, 22. do June 15, July 7, 21, Aug. 7. 1893. Mav 15, June 12, July 10. May 14, June 16, IS, July 15. do ". 1892. June 24 .do. July 6 ...do July 1 July 8 July 20 Aug. 2 ...do.. Sept. 6-4-32 Bordeaux, 1 pound Lon- don purple, 200 gallons water. 2-1J-32 Bordeaux, 1 pound London purple, 200 gallons water. 6-4-32 Bordeaux, 1 pound Lon- don purple, 200 gallons water. 2-1^-32 Bordeaux, 1 pound London purj'le, 200 gallons water. 6-4-32 Bordeaux, 1 pound Lon- don purple, 200 gallons water. London purple 2-li-32 Bordeaux, 1 pound London purple, 200 gallons water. 6-4-32 Bordeaux, 1 pound Lon- don purple, 200 gallons water. do do No London purple, 2-2-32 Bor- deaux. First 3 dates, 2-2-32 Bordeaux; last date, "eauceleste." .do. Grains per pound 0.0440 .0882 .0250 .1210 .0503 .0098 .0233 .0372 .0088 4.870 1.821 .390 .252 .028 .362 .0738 .100 .147 .200 The skins from 1 pound of the sprayed pears gave 0.106 grain and the flesh gave 0.071 grain of copper sulphate, '^showing that while most of the copper salt adheres to the surface, a portion finds its way into the body of the fruits." 8 BULLETIN 1027, U. S. DEPARTMENT OF AGRICULTURE. In 1893 Davis (30) reported the determinations of arsenic on celery that had been sprayed with Paris green at the rate of 1 pound to 175 gallons of water. The results, obtained on the celery washed without separating the stalks and prepared as for market, were as follows: Sprayed once, 0.0244 grain of arsenious oxid per pound of celery; sprayed twice, 0.0368 grain of arsenious oxid per pound of celery. In 1893 Beach reported (12) the presence of from 0.00042 to 0.001 per cent of copper in celery that had been sprayed with Bordeaux or ammoniacal copper carbonate solution, and 0.00081 per cent in unsprayed celery, concluding that "these investigations show that when this sprayed celery was stripped and ready for market the sprayed plants were no more poisonous than the unsprayed." In 1894 Kinney (68) stated that the skins and stems of pears which had been sprayed five times with Bordeaux mixture (6 pounds of copper sulphate, 4 pounds of lime, and 22 gallons of water), and upon which the spray was still visible at harvest contained only 0.016 grain of copper oxid per pear, for which reason no serious objection to this treatment could be raised from a hygienic stand- point. In 1894 Garman reported (49) that the skins and ends of six apples from a tree that had' been sprayed once with London purple and five times with Paris green at the rate of 1 pound to 160 gallons of water showed on analysis no arsenic and only an unweighable amount of copper. The flesh and cores of these apples gave no reaction for arsenic or copper. He reported also (50) that cured tobacco which had been sprayed with arsenites. at the rate of 1 pound to 160 gallons of water, gave on analysis 0.077 grain of arsenious oxid and 0.042 grain of copper oxid per pound with one spraying with Paris green; 0.133, 0.259, and 0.329 grain of arsenious oxid and 0.126, 0.210, and 0.322 grain of copper oxid per pound with two sprayings with Paris green; and 0.245 grain of arsenious oxid per pound with two spray- ings with London purple. Later (1904) this author stated (51) that arsenites such as Paris green can be used on cabbage without leaving a trace sufficient for recognition by the chemist. In 1901, cabbages which had been sprayed with Paris green or lead arsenate showed on analysis 'traces of poison present." In 1902, and again in 1903, spraj^ed cabbages were analyzed, but the chemist "was unable to find a trace of poison present." In 1897 Teyxeira (123) found from 20 to 50 milligrams of copper in 1 kilogram of juice from tomatoes that had been sprayed with copper sulphate, and none after treatment with Bordeaux, unless the skin was cracked. He stated that the copper sulphate penetrates the skin into the flesh, but that the copper-lime mixture does not. POISONOUS METALS ON SPRAYED FRUITS AND VEGETABLES. 9 In 1898 Hoffmann reported (62) the presence of from 0.0046 to 0.0128 gram of copper per liter in wines, but failed to give the history of the samples. Later he reported 0.00096 and 0.0058 gram of copper per liter in wine. 0.0028 and 0.0056 gram of copper per liter in must, 0.0027 and 0.0045 gram of copper per liter in grape-skin wine, and 0.053 gram of copper per 100 grams in the grape skins. Selby found (117) 0.0004 gram of copper per 100 grams of grapes to be the maximum amount on the samples he examined. To show that sprayed grapes can be safely used for making wine he cites Kriiger (69), " that in the different musts different amounts of copper, at the beginning of fermentation, or just before the beginning, enter into an insoluble and consequently an inert (copper) compound, in consequence of the presence of greater or less amounts of organic acids. From this condition it is likely that the copper of the must, arising from the spraying of the grapes, is without any importance for the wine." Gibbs and James (57) reported that 292 of 352 samples of wine examined contained no arsenic, 58 contained from a trace to 1 part in 8,000,000, 1 contained 1 part in 5,000,000, and another 1 part in 2,500,000. They stated also that of 200 samples of wine examined by C. S. Ash the three highest in arsenic contained 1 part in 6,000,000, 1 part in 8,000,000, and 1 part in 14,000,000. ''The most probable sources of the major part of that found are arsenical sprays when used upon the vines, sulphur burned for the purpose of sulphuring the wines and receptacles, and perhaps to some extent the lead shot used in cleaning the bottles." A sample of sulphur from a California winery was found to contain arsenic in the proportion of 1 part in 5,000. It is not stated whether these wines were the product of sprayed vines. In 1906 Roger Mares (82) reported that he found no trace of arsenic in wine from a vine treated a month before grape gathering with a copper-arsenical mixture, and he accordingly continued to recommend this combined mixture as a spray for the vines in Algiers; The same year Von der Heide (61) reported the results shown in Table 2 on products of vines that had been sprayed with lead arse- nate. Table 2. — Metals on j^roducts of vines sprayed ivith lead arsenate {Von der Heide). Arsenic. Lead. Copper Grapes (bunches) (milligrams per 100 grams). . . Grapes (individual) (milligrams per 100 grams) . Stems (milligrams per 100 grams) Leaves (milligrams per 100 grams) Grape skins (milligrams per 100 grams) Must ( milligrams per 100 grams) Fall wine (milligrams per 100 grams) Spring wine (milligrams per 100 grams) Wet lees (milligrams per 100 grams) Dry lees (milligrams per 100 grams) 0.7 .3 10.6 48.0 27 ':!-}• .2 4.8 20.7 72638— 22— Bull. 1027 2 10 BULLETIN 1027, U. S. DEPARTMENT OF AGRICULTURE. The German Imperial Health Commission was opposed to the use of lead arsenate in the spra5^ing of grapes because arsenic and lead were found in the wine. In 1907 Szameitat (121) (122) .reported the following results of analyses of musts, wines, and grapes from vines sprayed with arsenic compounds: From a trace to 0.9 milligram of arsenic in 300 grams of grapes; none to 0.14 milligram of arsenic in 300 cubic centimeters of must; none, or only a trace in 300 cubic centimeters of wine. Of 38 samples of German wine examined, 24 showed small amounts of arse- nic, the largest amount being 0.05 milligram in 100 cubic centimeters of wine. The source of arsenic was not identified. The use of arsenic compounds for the destruction of insects that devastated vines having become more or less general in central France, in spite of the fact that the French ordinance of 1846 pro- hibited the use of arsenic for the destruction of insects, the question arose as to the danger of such use. In 1907 Bertin-Sans and Ros (14), who were among the first in France to publish an answer to this question, found less than 0.001 milligram of arsenic in 145 grams of unripe grapes gathered one month after spraying with sodium arsenate, and 0.002, 0.001, 0.030, and 0.040 milligram of arsenic per liter in wine from arsenical treated vines. These investigators stated that ag sheep and cows were not admitted to the sprayed vines and were not fed the sprayed foliage until after harvest there was no danger to these animals, but that rabbits and snails might be poisoned by eating sprayed foliage, and, since snails can tolerate a fairly large amount of arsenic, persons should refrain from eating them during the spraying season. As lead is a cumulative poison, it was considered more prudent to use arsen- icals other than lead arsenate, although no data existed to show that there was danger in the use of lead arsenate as an insecticide. Bertin- Sans and Ros believed that the chief danger in the use of arsenicals arose from mistakes due to carelessness and that if suitable regula- tions were enforced no danger was to be feared. Since the ordinance of 1846 was a dead letter, it seemed to them much better to have the arsenicals handled under definite regulations. In 1908 (15) they stated that as they had found only traces of arsenic in wine from vines sprayed with arsenicals, there was no ground for the fear that the arsenic would pass into the wine if the vines had been sprayed before the grapes were in bloom. In 1909 Truelle (125) (126) concluded that the advantages of arsenical spraying were so great that its use under regulation should be authorized in France. Cazeneuve (21), thinking that the use of arsenical insecticides was a serious menace to the public health, asked (1908) for the strict en- forcement of the ordinance of 1846. Riche (112) and Gautier (52), POISONOUS METALS ON SPRAYED FRUITS AND VEGETABLES. 11 on the other hand, beUeved that the use of arsenicals, with the ex- ception of lead arsenate, should be permitted in agriculture, but only under proper regulation. In 1909, a committee appointed by the Academy of Medicine (1) (21) (112) to study this question recommended (96) the strict en- forcement of the ordinance, thus causing a very lively discussion. Weiss (130), believing that the committee did not have sufficient evidence to substantiate its recommendation, proposed a medical investigation, this proposal being adopted (2) and sent to the min- ister of the interior as the advice of the academy. A year later the academy asked (32) that a new investigation, essentially medical, be carried on for two years, and, to avoid accidents, recommended strict regulations in the use of arsenicals and the complete exclusion of lead arsenate. The direction of the investigation was to be in- trusted to the councils of hygiene and the sanitary commissions of each department, after consultation with the professors of agricul- ture (33). In 1911, dissatisfied with the lack of enforcement of its suggestions, the academy decided (34) to recall to the public powers the conditions the}^ had recommended as to tKe use of arsenicals in agriculture. Malvy, undersecretary of state, stated (80) that since the investigation conducted by the minister of the interior had dis- closed no accident, either among the workers who handled the ar- senicals or among the consumers, to prohibit the use of lead arsenate would be to impose useless annoyances on merchants and viticul- turists. In 1913 the minister of the interior submitted to the Acade- my of Medicine a draft of a decree carrying modifications of the ordi- nance of 1846, permitting the use of insoluble arsenicals in agri- culture (3). After much discussion (.5) (22) (53) (54) (76), articles 9 and 10 of the draft, authorizing the use of arsenicals in agriculture under speci- fied regulations, were adopted by the academy (4) (5), with the recom- mendation" that the order of the minister of agriculture dealing with the precautions to be taken in their use should apply to all arsenicals and not merely to lead arsenate, *and article 11, which prohibited the sale and use of soluble arsenic salts, was amended to permit their sale when ''denatured" (5). The academy also voted (5) that the public powers be requested to take every means to inform the public of these regulations and to impose penalties for their infraction, and that the Government be requested to encourage researches to find substitutes for arsenicals. The French decree authorizing the use of insoluble arsenicals in agriculture, under regulation (81), and the minister of agriculture's instructions for the sale and use of these arsenical compounds were published in 1916 (86). The sale and use of soluble arsenicals as insecticides were prohibited. Breteau (17) analyzed 15 samples of wine from vines sprayed with arsenicals, finding from none to 0.04 milligram of arsenic per liter in 12 BULLETIN 1027, U. S. DEPARTMENT OF AGRICULTURE, 12 of the samples and 0.1, 0.1, and 0.2 milligram of arsenic per liter in the other three. He attributed the higher content of arsenic in the last three samples to the fact that the wines had been sulphured. If, as held by Gautier and Clausmann (55), a normal wine contains about 0.01 milligram of arsenic, he felt that the arsenical treatment of vines will introduce into the wine less than 0.03 milligram of arsenic per liter. Mestrezat (87) considered that the only danger from the use in viticulture of arsenical insecticides occurs when they are placed near other substances which resemble them so closely as to be easily mistaken for them. In 1906 Forbes (39) reported 36.6 and 32.9 parts of arsenious oxid per million in peelings of apples sprayed the preceding day with lead arsenate and 40.1 parts of arsenious oxid per million in peelings of apples gathered two months after being sprayed heavily with lead arsenate. He considered that lead arsenate could be substituted for the more common insecticide sprays if discretion were exercised in its use. In 1910 Giinther (60) reported the results given in Table 3 on fruits that had been sprayed once with a mixture containing 300 grams of sodium arsenite and 425 grams of lead acetate per 100 liters. Table 3. — Residue on. fruits sprayed once v>ith mixture containing oOO grams of sodium arsenite and 4-^,5 grams of lead acetate per 100 liters {Giinther). Days elapsed after spray- ing. Lead. Gooseberries Currants. . . Pears Apples Do 39 39 80-106 80-106 80-106 MiUigrams per 100 grams. 1.000 7. 140 . 129 .074 .057 2. 16 16.70 Trace. con He reported the results given in Table 4 on fruits dusted once with a mixture consisting of 2 parts of freshly slaked lime, 4 parts of sulphur, and 1 part of Paris green. Table 4. — Residue on fruits dusted once with'a mixture consisting of 2 parts of freshly slaked lime, 4 parts of sulphur, and 1 part of Paris green (Giinther). Days elapsed after dust- ing. Arsenic. Copper. Gooseberries.... . . 39 39 39 39 80-106 80-106 80-106 80-106 24 24 24 Milligrar qra 0. 8300 2. 1200 1.6100 1.5300 .0720 .0420 .0084 .0420 .2000 .3200 .5000 ns per 100 VIS. 0.560 Do .930 Currants Do .870 Pears .240 Apples .067 Do .095 Do .011 Sweet cherries .160 Sour cherries .250 Plums Trace. POISONOUS METAI.S ON SPKAYED FRUITS AND VE(jIETABLES. 13 In 1910 Bedini (13) reported from 0.2 to 0.4 milligram of arsenious oxid per kilogram in the skins of pears that had been sprayed with arsenate of iron, and only a trace of arsenic in the pulp. The same year Porchet (110) reported that pears sprayed with lead arsenate contained as much as 0.3 milligram of arsenious oxid per kilogram in both the pulp and the skin; that the skins of unspra3^ed pears contained 0.035 milligram of arsenious oxid per kilogram of fruit; that sprayed grapes contained traces of arsenic, apparently the same in the interior as on the exterior of the fruit, the highest amount obtained being 0.2 milligram per kilogram of grapes; and that the traces of arsenic passed from the grapes into the must, but that the arsenic was precipitated as sulphid during the fermentation. Chuard (24) also found that the arsenic in the must was precipitated as sulphid during the fermentation. Fetel (37), in 1910, reported that 10 samples of grapes bought on the market in Algeria on August 8 and 25, September 1 and 19, and October 3 contained an average of 0.038 milligram of arsenic per kilogram, while unsprayed grapes, collected on August 8 and September 1 and 8, contained no arsenic. Grapes sprayed twice before blossoming, with a Bordeaux-sodium-arsenate mixture, and gathered on August 10 and 25 and September 5 and 22, contained, respectively, 0.185, 0.083, 0.074, and 0.074 milligram of arsenic per kilogram. Grapes sprayed twice before fiow^ering with arsenious acid and on July 24 with Bordeaux-arsenious-acid mixtures, and gathered on July 24 before and after this last spraying, on August 22, and on September 15, contained, respectively, 0.05(3, 0.467, 0.149, and 0.112 milligram of arsenic per kilogram. In 1909 and 1910 Brioux and Griffon (18) found 0.001, 0.001, and 0.004 milligram of arsenic per kilogram in three lots of pears that had been sprayed with a Bordeaux-lead-arsenate mixture. They also reported that, although apples which had been sprayed with lead arsenate on June 8 and June 22, 1910, contained when ex- amined in July 1.3 milligrams of arsenic and 14.2 milligrams of lead per kilogram, yet in September, at harvest time, the apples and the cider contained no lead and only traces of arsenic. Moreau and Vinet (92), in 1910, reported that grapes sprayed with lead arsenate on May 27 and June 6 contained, respectively, on June 22 and September 14, about 2 and 0.28 milligrams of lead arse- nate per bunch, and that 1G5 grams of moist lees contained 1.38 milli- grams of lead arsenate, but that the wines contained no lead or arsenic. They found (93) that only 1 per cent of the lead arsenate w^hich they had applied on May 31 was retained })y the grapes, 0.58 milligram per bunch, and that with the development of the grapes a sect)nd spraying was necessary on June 14 to control the first generation of the cochylis larva. They also found that a spraying on August 6 to control the 14 BULLETIlsr 1027, U. S. DEPARTMENT OF AGRICULTURE. second generation of this insect adhered mostly to the stems. They concluded from other experiments (94) that, since grapes sprayed twice with lead arsenate before flowering, on May 31 and June 14, showed no lead or arsenic at harvest time, October 15, there would be no danger in consuming grapes sprayed so early, but that, since grapes sprayed after the flowering period, on August 6, showed 0.40 milligram of lead arsenate per 100 grams of grapes at harvest time, October 27, there might be danger in consuming grapes sprayed so late in the season. They reported further (95) that wines from vines treated before the flowering period with lead arsenate could be con- sumed without danger, since only faint traces of lead and arsenic were found in wines from such vines and that the lead and arsenic were eliminated during the process of the making of the wine, being found principally in the marc and in small amounts in the lees. In 1911 Ampola and Tommasi (7) stated that foodstuffs derived from plants treated with arsenical compounds always contain arsenic, usually in traces, but sometimes as much as 2 milligrams or even more per kilogram in fruits and 1.5 milligrams per liter in wine, amounts greater than that allowed by the Royal Commission on Arsenical Poisoning in England (11) (115). In 1912 Muttelet and Touplain (99) reported that the grapes, marcs, wines, picjuettes, and lees which came from vines treated with lead arsenate contained about the same amount of arsenic as was found in the products from vines not treated, that the wines and piquettes contained no lead, but that the lees in certain cases contained an appreciable quantity of lead, in which cases there w'as danger in the consumption of wine or piquette before the deposition of the lees, and that grapes sometimes retained on their surface a quantity of lead which rendered dangerous their consumption in a natural state. The same year Carles and Barthe (20) reported that the wines from vines sprayed before the formation of the fruit with excess of load arsenate contained only negligible traces of arsenic and lead and that those from vines normally treated with lead arsenate contained neither arsenic nor lead, but that the lees contained 0.0028 and 0.0001 gram of arsenic per liter and traces of lead. According to Mathieu (83), unsprayed grapes and wines made from them contain only traces of arsenic, grapes from vines sprayed with arsenicals before flowering contain not more than 0.05 milligram of arsenic per kilogram, even in a dry year, red wine made from grapes treated with arsenicals in a year of abundant rain contains only a little more arsenic than wine made from unsprayed grapes, the amount being less than 0.06 milligram per liter, and part of the arsenic in the grapes remains in the marc in making red wines, which wines, however, should not contain more than 0.05 milligram per liter. In 1914 Garino (48) stated that the amounts of arsenic met in analyses of POISOXOUS METALS OiST SPRAYED FRUITS AND VEGETABLES. 15 wines from grapes subjected to cupro-arsenical treatment are very small, being less than the minimum therapeutic dose of 5 milligrams, and therefore need cause no alarm. In 1913 Spallino (120) found in three samples of snuff 0.16, 0.40, and 0.34 milligram of arsenic per 100 grams of dried snuff, and in four samples of smoking tobacco 0.08, 1.02, 0.30, and 0.64 milligrams of arsenic per 100 grams of dry tobacco. Sonntag (119), in 1914, concluded from the results he obtained on ripe fruits and leaves treated in 1907 and 1908 with arsenical mix- tures that the arsenical sprays or dusts applied to fruit trees and bushes adhere to the fruits and are retained by them for a long time, in many cases even until the ripening of the fruit. O'Gara (101) stated that the skin of apples sprayed with lead arsenate may occasionally absorb some arsenic. In such cases the skin is likely to develop red or black spots. Analysis of such spotted apple skins showed the presence of fractions of a milligram of arsenic. Woods (133) reported that apples sprayed with lead arsenate during the first week in August, 1913, carried upon their surface, about two months after spraying, from one-eighth to one-third milligram of lead arsenate per apple. He concludes that "midsummer spraj^- ing with lead arsenate is an effective way of combating the brown- tail moth," and '' the amount of. arsenic or of lead that will remain at harvest upon the apples that are sprayed in midsummer with arsenate of lead is so slight as to have no practical bearing." In 1916 Trofimenko and Obiedoff (124) reported that grapes treated with wet arsenical mixtures under conditions most favorable for the continuance of the arsenical salts, both on the grapes ajid in the must, yielded unobjectionable wines. No arsenic was found in white wine and only 0.0002 gram of arsenious oxid per liter in red wine. The lees might be used for extracting the tartar, washing being enough to remove the arsenates. Muttelet (98) stated that the wine and piquette from vines treated with copper sulphate and lead arsenate, even after the formation of the grapes, contained no lead or copper, and no more than traces of arsenic. The pomace wine con- tained no lead, traces of copper, and 5 milligrams of arsenic per hectoliter. The lees contained 500 milligrams of lead. 10 milligrams of arsenic, and traces of copper per liter. The air-dried marc con- tained 200 milligrams of lead, 0.1 milligram of arsenic, and traces of copper per kilogram. Liberi, Cusmano, Marsiglia, and Zay (74) found copper in the fruit of tomatoes in amounts varying from 0.14 to 2.10 milligrams per kilogram of juice and pulp, and from 3.8 to 19.5 milligrams per kilogram of dry matter. The soils upon which the tomatoes were grown contained copper up to 110 milligrams per kilogram. These investigators stated that the spraying with copper mixtures had no 16 bullp:tin io27, u. s, department of agetcultuee. effect upon the copper content of the tomatoes. It appeared that the copper found in the tomatoes came from the soil, whence the plants assimilated it in different proportions, according to the nature of the soil or under the influence of other factors. In 1917 Carles (19) stated that copper occurs in small amounts in agricultural products and in larger amounts in calf liver and heef liver. O'Kane, Hadley, and Osgood (102) reported the following amounts of arsenic (calculated as AsjOj) on fruits and vegetables that had been sprayed with dry lead arsenate equivalent to 3 pounds of lead arsenate paste to 50 gallons of water: Apples picked at intervals ranging from 3 to 91, days after spraying, 0.08 to 0.77 milligram per apple when picked carefully, 0.02 to 0.50 milligram when picked in the ordinary way, 0.10 to 0.21 milligram when picked with cotton gloves, and O.OS to 0.18 milligram when picked with cotton gloves and wiped; strawberries picked 2 and 6 days after spraying, from 8.6 to 34.2 milligrams per quart; currants picked 3, 6, and 8 days after spraying, from 6.8 to 10.2 milligrams per quart; blackberries picked on the day they were sprayed, from 3.8 to 11.2 milligrams per quart; cabbage gathered 2 and 8 days after spraying, from 43.5 to 51.4 milligrams per head; and lettuce gathered 1 and 6 days after spraying, from 1.6 to 10.6 milligrams per head. The maximum amount of lead arsenate spray that would adhere to an apple, when sprayed directly, was found to be an amount ec;[uivalent to 4 milligrams of arsenious oxid. Such fruit gave evidence of spray material on its surface. EXPERIMENTAL WORK. The investigation conducted by the United States Department of Agriculture included experiments on peaches, cherries, plums, apples, pears, grapes, cranberries, tomatoes, celery, and cucumbers. The spraying schedules are shown in Tables 5 to 14. METHODS OF ANALYSIS. The following methods of analysis were employed: Of the whole fruit and pulp, dry 200 to 300 grams of sample on the steam 1 ath in glass dishes, and report loss as "loss on drying." (For the determinations on the skins, use parings from 4 ap])les; for the calyx and stem end determinations, rise 12 apples and corresponding amounts in the case of other fruits.) Transfer the dried residues to casseroles and add 100 to 200 cc. nitric acid. Heat the mixture, if neces- sary, to start action, and when violent action is over cautiously add 20 cc. sulphuric acid. Heat on hot plate, removing at intervals to add small amounts (3 to 5 cc.) of nitric acid (do not allow the solution to become 1 lack), and when the oxidation is complete evaporate until sulphuric acid fumes are given off. Cool, dilute with water, and again evaporate to sulphuric acid fumes. Cool, dilute with al out 100 cc. of 50 per cent alcohol, and let stand over night. Filter and wash with 80 per cent alcohol. Save sulphate precipitate for lead determination. The copper and arsenic are deter- mined in the filtrate. Evaporate the filtrate to email volume on steam 1 ath to remove alcohol. Make to volume. POISONOUS METALS ON SPKAYED FRUITS AND VEGETABLES. 17 Arsenic. — Determine arsenic in an aliquot by the Gutzeit method (Bur. Chem. (ire. 102), modified as follows: The aliquot should contain less than 0.08 mg. arsenic. Dilute to 50 CO. Add strong sulphuric acid so as to have 10 cc. present Add 1 gram sodium chlorid to the aliquot in a small Erlenmeyer flask, heat on steam bath to about 90° C, then add 1 cc. of a stannous chlorid solution containing 0.5 gram dissolved in hydro- chloric acid, and leave on steam liath for aliout 5 minutes (temperature near 90° ('.). Remove from steam bath, transfer to the 4-ounce generating bottle, dilute to 100 cc, and cool to room temperature. This generating bottle is connected by a rubl:er stopper with an upright tube 8 cm. long, 1 cm. diameter, containing lead acetate paper. This tube is connected by a rubber stopper with a similar tube containing cotton moistened with 5 per cent lead acetate solution. Connected by a rubber stopper with this tube is a capillary tube 3 mm. in diameter, 12 cm. in length, carrying the strip of mercuric bromid paper. Prepare these strips as follows: Cut heavy, close- textured drafting paper into strips 2 mm. by 12 cm.; then soak them for an hour in 5 per cent alcoholic mercuric bromid solution, take out, rapidly squeeze off excess of solution, separate on glass rods, and allow to dry. Place three pieces of stick zinc (about 10 grams) in the generating bottle and join it immediately to the apparatus tubes. Allow the determination to run for IJ hours, keeping the temperature down to room temperature by placing the bottle in cool water. From standards plot a curve showing milligrams of arsenic to millimeters in length. As high as 0.08 milli- gram of arsenic can be read on a paper. Determine the larger quantities of arsenic by passing the arsine into a mercuric chlorid solution and either weigh the mercurous chlorid or titrate the arsenious oxid. (Bur. Chem. Circ. 102, p. 5.) Copper. — Introduce an aliquot into a 100 cc. Erlenmeyer flask. Neutralize the acid with ammonia, add 2 to 3 cc. hydrochloric acid for every 50 cc. of solution, and saturate the solution with hydrogen sulphid. Stopper flask and let stand over night. Filter off the copper sulphid and wash with hydrogen sulphid water. Place the filter paper containing the copper sulphid in a 50 cc. casserole, burn off the paper, dissolve residue in 5 cc. (1: 1) nitric acid, evaporate to dryness, add water and 1 drop ammonia, make faintly acid with acetic acid, and add a few drops of a 2 per cent potassium ferrocyanide solution. Compare with standards. Lead. — Dissolve the sulphate precipitate, pre\iously referred to, in hot 10 per cent ammonium acetate solution, add 2 cc. (0.1 per cent solution) gum arabic, and make to volume with hydrogen sulphid water in 50 cc. (or 100 cc.) Nessler tubes. Com- pare the tubes thus prepared with standards made up similarly with gum arabic, ammonium acetate, known amounts of lead, and hydrogen sulphid water. Where copper alone is to be determined, heat the dried sample cautiously over a Bunsen Inirner and finally ash at the mouth of the electric-muffle furnace. Add 5 cc. (1:1) nitric acid to the ash, evaporate almost to dryness on steam lath, dilute, and make alkaline with ammonia. Filter off precipitate and wash. Dissolve precipitate, reprecipitate with ammonia, and wash. Evaporate the united filtrates to dryness, add water and one drop ammonia, make slightly acid with acetic acid, and add a few drops 2 per cent potassium ferrocyanide solution. Compare with standards. The presence of between 0.02 and 0.24 milligram of copper can be determined by this method. Larger amounts may be determined by taking an aliquot, by comparing in ammoniacal solutions, or by electrolysis. The presence of from 0.02 to 0.24 milligram of lead can be read in the 50 cubic centimeter Nessler tubes, larger amounts by using 100 cubic centimeter Nessler tubes or by taking a smaller aliquot. 72638— 22— Bull. 1027 3 18 BULLETIN 1027, U. S. DEPARTMENT OF AGRICULTURE. The whole and pulp of apples were fumed in 7-inch casseroles and the skins were fumed in 5-inch casseroles, all being transferred to 4-inch casseroles before final fuming. Casseroles were covered until final fuming. RESULTS OF EXPERIMENTAL WORK. The results of the chemical analyses appear in Tables 5 to 15, inclusive. Table 5. — Arsenic and lead remaining on sprayed peaches at picking time. .\.rsenic(As). Lead (Pb). M J3 Sam- ple No. Spray material used.' Date sprayed. Determi- nations made on. 01 ■6 C3 o "pJS 'm'3 ■nil -1 •Is t5 o ft o q"" < ►J hJ > 1915. Parts per million. Mg. per peach. p. CI. Gr. 23196 2 48 lbs . hydrated lime, 2 May 93 Wholes 0.13 0.90 0.40 2.7 0.014 0.042 85.3 105.3 lbs. lead arsenate Pulp.... .06 .40 .20 1.4 .005 .016 85.8 (powder). Skin .42 2.60 1.20 7.3 .009 .026 83.6 •J lbs. lead arsenate(pow- May 26 der), 32 lbs. hydrated lime, 16 lbs. sulphur. 16 lbs. sulphur, 34 lbs. July 10 hydrated lime. 23197 2 40 lbs. hydrated lime, May 93 Whole < . .18 1.30 .40 2.8 .018 .040 85.7 100.5 4 lbs. lead arsenate Pulp.... .08 .60 .10 . 7 .006 .008 86.0 fpowder). Skin.... .61 4.00 1.60 10.4 .012 .032 84.6 32 lbs. sulphur, 4 lbs. May 26 lead arsenate (powder). 14 lbs. hydrated lime. 32 lbs. sulphur, 18 lbs. July 10 hydrated lime. 23198 s 44 ibs. hydrated lime, May 93 Wholes ,25 1.80 .80 5.7 .024 .076 85.9 9,5.2 6 lbs. lead arsenate Pulp.... .08 .60 .20 1.4 .006 .015 86.1 (powder). Skin .90 6.10 3.00 20.4 .018 .061 85.3 44 lbs. sulphur, 6 lbs. May 26 lead arsenate (powder). Sulphur alone July 10 23199 2 1 lb. lead arsenate (pow- May 93 Whole*. .20 1.50 .30 2.2 .020 .029 86.2 9S.0 der), 50 galls, water. Pulp.... .08 .60 .10 .8 .007 .008 86.7 oOgalls. self-boiled lime- May 26 Skin .66 4.20 1.10 7.0 .m'S .021 84.2 sulphur, 1 lb. lead ar- senate (powder). Self-boiled lime-sulphur. July 10 23200 2 Check (un.sprayed) Whole <. .12 .90 .0 .0 .010 .0 86.7 83.6 Pulp.... .07 .50 .0 .0 .0ft5 .0 87.0 Skin .... .29 2.00 .0 .0 .005 .0 85.3 23201 2 78 lbs. terra alba, 32 lbs. May 93 Whole <. .13 1.00 .0 .0 .012 .0 86.5 92.2 sulphur. Pulp.... .02 .20 .0 .0 .001 .0 87.0 Do May 26 Skin .63 4.00 .0 .0 .011 .0 84.3 Do July May 10 93 Whole * . .10 .80 .0 .0 .009 .0 86.7 232022 78 Ihs. hydrated lime. SS.4 32 lbs. sulphur. Pulp.... .09 .70 .0 .0 .006 .0 87.1 Do May 26 Skin. . 14 .90 .0 .0 .003 .0 85.0 Do July May 10 232032 10 lbs. lead arsenate 93 Whole * . .13 .90 .30 2.1 .013 .030 85.4 101.8 (powder), 90 lbs. hy- Pulp.... .08 .60 .20 1.4 .007 .017 85.8 drated lime. Skin.... .35 2.10 .70 4.4 .006 .013 84.2 Do May May 26 93 Whole*. .10 .70 .30 2.0 .009 .02.5 85.1 2320 ■» 2 8 lbs. suIphur,3ozs. glue 86.0 (used in water to wet Pulp.... .04 .30 .10 .7 .003 .007 85.4 sulphur), 8 lbs. hy- Skin.... .34 2.10 1.00 6.3 .006 .018 84.1 drated lime, 1 lb. lead arsenate (powder), 50 galls, water. Do May July 26 10 8 lbs.sulphur,3ozs glue - (used in water to wet sulphur), 8 lbs. hy- drated 1 ime, 50 galls. water. 1 Where no mention is made of water in the formula the material was applied as di • Delaware yariety, harvested .\u?. 12-18, Berlin, Md • As shucks fell. < Without stones. J POISONOUS METALS ON SPRAYED FRUITS AND VEGETABLES. 19 Table 5. — Arsenic and lead remaining on sprayed peaches at picking time — Continued. Spray material used. Date sprayed. Determi- nations made on , Arsen ic(As). Lead (Pb). 6 ■ja •d ■« -o . ■Qi3 '5i"3 — 3 a O Q O Q < Sprayed lightly with 1 lb. lead arsenate (powder), 50 galls, water. 8 lbs. sulphur, 8 lbs. stonelime, 50galls.wa- ter (self-boiled lime- sulphur), 1 lb. lead arsenate (powder). Self-boiled lime-sulphur. Sprayed heavily witlTl lb. lead arsenate (powder), 50 galls, water. 8 lbs. sulphur, 8 lbs. stone 1 ime,50galls.wa- ter (self-boiled lime- sulphur), 1 lb. lead arsenate (powder). Self-boiled lime-sulphur. Commercially sprayed with 1 lb. "lead arse- nate (powder), 50 galls, water. 8 lbs. sulphur, 8 lbs. stone lime, 50galls. wa- ter (self-boiled lime- sulphur), 1 lb. lead arsenate (powder). Self-boiled lime-sulphur. 48 lbs. hydrated lime, 2 lbs. lead arsenate (powder). 2 lbs. lead arsenate (powder), 32 lbs. hy- drated lime, 16 lbs. sulphur. 16 lbs. sulphur, 34 lbs. hydrated lime. 46 lbs. hydrated lime, 4 lbs. lead arsenate (powder). 32 lbs. sulphur, i lbs. lead arsenate (pow- der), 14 lbs. hydrated lime. 32 lbs. sulphur, 18 lbs. hydrated lime. 44 lbs. hydrated lime, 6 lbs. lead arsenate (powder). 44 lbs. sulphur, 6 lbs. lead arsenate (pow- der). Sulphur, with 5 per cent hydrated lime added. 1 lb. lead arsenate (pow- der), 50 galls, water. 50 galls, self-boiled lime- sulphur, 1 lb. lead ar- senate (powder). Self-boiled lime-sulphur. Check (unsprayed) 78 lbs. terra alba, 32 lbs. sulphur. Do Do 1915, May 93 May 26 .Tuly 10 May 9' May 26 July 10 Mav 93 May 26 July 10 May 93 May 26 July 10 May 93 May 26 July 10 May 9 » May 26 July 10 May 93 May 26 July 10 May 9: May 26 July 10 Whole ' Pulp... Skin... Whole * Pulp... Skin.. . Whole*. Pulp... Skin.... Whole*. Pulp.... Skin.... Whole * . Pulp.... Skin.... Whole*. Pulp.... Skin.... Whole*. Pulp... Skin ... Whole * Pulp... Skin . . . Whole * Pulp... Skin . . . 0.16 .04 .60 Parts per million. .67 .09 2.50 .30 .10 1.00 1.20 .30 4.10 .30 1.90 .06 .40 1.30 7.80 1.50 .30 6.30 .60 .20 2.30 .21 1.40 .08 .50 . 70 4. 60 4.40 .60 15.40 2.00 .70 6.10 .30 .40 .14 .90 .70 .30 2.50 .60 .20 2.10 .40 .20 1.40 .70 .40 1.70 1.40 .20 5.10 1.20 .20 4.30 JV/ff . per peach. 2.2 0.013 .7 .003 .010 4.4 .021 1.9 .003 15.1 .018 4.0 1.3 13.7 2.6 1.3 4.8 2.7 11.2 9.1 1.3 31.5 7.9 1.4 26.1 .008 .002 .006 .014 .004 .010 .040 .004 .036 .018 .004 .014 .001 .000 .001 .0tt3 .001 .002 .083 .009 .074 .070 .007 .063 85.3 85.4 84.8 84.6 84.8 83.8 84.8 85.2 83.5 84.4 84.8 82.9 85.1 85.6 83.4 83.4 81.2 59.3 58.7 55.8 * Delaware variety, harvested .\ug. 12-18, Berlin, Md. » As shucks fell. * Without stones. 6 Delaware variety, harvested Aug. 12-18, Springfield, W. Va. 20 BULLETIN 1027, U. S. DEPARTMENT OF AGRICULTURE. Table 5. — Arsenic and lead remaming on sprayed peaches at picking time — Continued. 23215 s 23216 s 234408 23442 6 23443 » 78 lbs. hydrated lime, 32 lbs. sulphur. Do Do 10 lbs. lead arsenate (powder). 90 lbs. hy- drated lime. Do 8 lbs. sulphur, 3 ozs. ghie (used in water to wet sulphur), 8 lbs. hydrated lime, 1 lb. lead arsenate (pow- der), 50 galls, water. Do 8 lbs. sulphur, 3 ozs. glue (used in water to wet sulphur), 8 lbs. hydrated lime, 50 galls, water. Sprayed lightly with 2 lbs. lead arsenate (com. paste), 2 lbs. stone lime, 50 galls, water. 2 lbs. lead arsenate (com. paste), 50 galls, self-boiled lime-sul- phur (8-S-50). Self-boiled lime-sulphur (8-8-50). Same as No. 23440, but heavier applications. 4 lbs. lead arsenate (com. paste), 4 lbs. stone lime, 50 galls. water. 4 lbs. lead arsenate (com. paste), self- boiled lime-sulphur (8-8-50). Self-boiled lime-sulphur (8-8-50). 4 lbs. lead arsenate (powder), 96 lbs. hy- drated lime. 4 lbs. lead arsenate (powder), 32 lbs. sul- phur (200-mesh fine), 64 lbs. hvdrated lime. 32 lbs. sulphur (200- Mav Jrly May May 26 May 93 mesh fine), 68 lbs. hy- drated lime. 1.3444 « 8 lbs. lead arsenate, May 30 1 Whole*. (powder), 92 lbs. hy- j Pulp drated lime. Skin 8 lbs. load arsenate June 19 (powder t, 32 lbs. sul- phur (200-nuwh fine), 60 lbs. hydrated lime. 64 lbs. sulphur (200- July 29 mesh fine), 36 lbs. hydrated lime. ■• As shucks fell. ■• Without stones. 5 Delaware variety, harvested Aug. 12-18, Springfield, 8 Elberta variety, harvested Sept. 13, Benton Harbor, May July July 29 Same as No. 23440 July 29 May 30 July 29 Whole < Pulp... Skin . . . Whole <. Pulp.... Skin . . . . Whole * . Pulp.... Skin Parts per viillion. Whole < Pulp . . . Skin. . . Whole Pulp.. Skin.. Whole Pulp.. Skin . . Whole < Pulp.. Skin . . 03 0.20 0-0 03 .20 .0 06 .36 .0 12 .70 .40 06 .40 .20 40 2.40 1.40 17 1.10 .40 05 .30 .20 58 3. .50 1.20 IS 1.80 .70 04 .40 .20 72 5.80 2.50 36 3.70 .90 07 .80 .20 37 11.80 3.20 .30 2.90 .80 06 .60 .20 20 10.30 3.10 36 3.10 1.40 08 .70 .20 50 11.90 6.30 67 5.60 2.00 10 .90 .20 90 20.00 9.00 ^fl)■ per peach . 0.002 .001 .001 .007 .003 .004 .009 .002 .007 0.0 .024 .009 .015 .024 .011 .013 . 017 . 062 . 003 . 012 . 014 . 050 . 032 .005 .027 .028 .004 .024 .040 .007 .033 .070 .008 .062 .077 .014 .063 .076 .013 .063 .155 .017 .138 .209 .017 .192 P.ct. 85.0 85.5 83.2 83.4 83.5 83.0 84.9 85.3 83.5 89.8 90.4 87.5 90.3 90.8 88.4 89 7 90.1 88.3 88.3 88.5 87.4 88. 1 104. 5 88.8 85.5 W. Va. Mich. POISONOUS METALS ON SPRAYED FRUITS AND VEGETABLES. 21 Table 5. — -Arsenic and lead remaining on sprayed peaches al picking time — Continued. Sam- ple No. Spray material used. Date sprayed. Determi- nations made on. Arsenic(As). Lead "rt ■V « . 0^^ 04^ 'ScD T 3 O Q O (Pb). .9 23445' 12 lbs. lead arsenate (powder), 88 lbs. hy- drated lime. 12 lbs. lead arsenate (powder), 88 lbs. sul- phur (200-mesh fine). 100 lbs. sulphur (200- mesh fine). 2 lbs. lead arsenate (com. paste), 2 lbs. stone lime, 50 galls, water. 2 lbs. lead arsenate (com. paste), self- boiled lime-sulphur (8-8-50). Self-boiled lime-sulphur (8-8-50). 68 lbs. terra alba, 32 lbs. sulphur (200- mesh fine). Do Do 23448* t 68 lbs. hydrated lime, t 32 lbs. sulphur (200- I mesh fine). 23449" ! 10 lbs. lead arsenate ': (powder), 90 lbs. hy- drated lime. Do 23450« Check plat (unsprayed). I 23447 • 25637' : Check plat (unsprayed). 256387 ' Self-boiled lime-sulphur ! (8-8-50), 2 lbs. lead arsenate. 25639' 2 lbs. lead arsenate, 50 galls, water. 5 lbs. "soluble sulphur compd.," 3 lbs. lime, 50 galls, water, 2 lbs. lead arsenate. 4 lbs. "soluble sulphur compd.," 4 lbs. lime, 50 galls, water. Check plat (unsprayed) . 25709' : 1 lb. lead arsenate (powder), 2 lbs. stone lime, 50 galls, water. I 1 lb. lead arsenate : (powder), self-boiled lime-sulphur (8-8-50). Self-boiled lime-sulphur I (8-8-50). 1915. May 30 June 19 July 29 May 30 June 19 July 29 May 30 June 19 July 29 May 30 June 19 July 29 May 30 June 19 A b ou t Mav 1' .do. 3 weeks later About July 15 May 29- May 30 June 20- June 21 Aug. 1- Aug. 2 Whole * Pulp... Skin . . . Whole < Pulp... Skin . . . Whole < Pulp... Skin . . . Whole < Pulp... Skin... Whole * Pulp... Skin . . . Whole < Pulp... Skin... Whole ■ Pulp.. Skin.. Whole ■ Pulp.. Skin.. Whole ■ Pulp.. Skin.. Whole < Pulp... Skin... Whole * Pulp . . . Skin. . - Parts per million. 0.80 7.10 2.60 .07 .60 .20 3.50 27.80 11.60 .42 4.00 1.10 .10 1.00 .20 1.50 12.50 4.10 .20 1.80 .34 .10 .90 .10 .60 4.90 1.20 .24 2.30 .60 .07 .70 .20 1.10 8.70 2.50 .94 8.00 2.40 .14 1.20 .20 4.50 35.40 12.20 .23 2.00 .40 .10 .90 .14 _.77 6.10 1.50 .04 .30 .40 .01 .10 .30 .20 1.20 .90 .05 .30 .50 .01 .10 .40 .20 1.10 .90 .05 .30 .50 .01 .10 .30 .20 1.20 1.30 .06 .40 .40 .03 .20 .30 .20 1.20 .90 .08 .70 .40 .03 .30 .30 .30 2.20 .90 23.0 1.8 92.1 10.4 2.0 34.2 3.0 .9 9.8 1.9 19.7 20.5 1.7 96.1 3.4 1.2 11.9 2.7 2.2 5.3 3.4 2.9 5.2 3.5 2.1 2.7 2.2 5.6 3.7 2.9 6.6 ifg. per peach. 0.091 .006 .085 .044 .008 . 036 .020 .008 .012 .026 .006 .020 .115 .014 .101 .026 .009 .017 .005 .001 .004 .005 .001 .004 .005 .001 .004 .005 .002 .003 .008 .002 .006 0.297 .013 .284 .115 .016 .039 .034 .010 .024 .065 .020 .045 .295 .020 .275 .046 .013 .033 .0.52 . 031 .021 .045 .028 .017 .051 .025 . 026 .034 .021 .013 .042 .025 .017 P.ct. 88.7 89.0 87.4 89.4 89.8 88.0 88.8 89.1 87.8 89.4 89.8 87.3 88.3 88.5 87.3 88.3 88.5 87.4 85.1 86.4 83.0 8.5.4 86.2 82.6 85.7 85.9 83.1 85.3 86.4 83.9 89.1 89.5 86.3 Or. 114.3 104.7 107.5 90.9 102.3 85.5 3 As shucks fell. < Without stones. 1 Elberta variety, harvested Sept. 13, Benton Harbor, Mich. ' Elberta variety, harvested Aug. 21, Springfield, W. Va. • Elberta variety, harve,sted Sept. 16, Benton Harbor, Mich. 22 BULLETIN 1027, U. S. DEPARTMENT OF AGRICULTURE. Table 5. — Arsenic and lead remaining on sprayed peaches at picking time^Continued . Sam- ple No. Spray material used. Date sprayed. Determi- nations made on. iVrsemc(As) o Lead(Pb). O 27936 9 279389 1 lb. lead arsenate (powder), 2i lbs. lime, 50 galls, water. 8 lbs. sulphur, 8 lbs. hydrated lime, 3 ozs. glue, 1 lb. lead arse- nate (powder), 5Q galls, water. ' 8 lbs. sulphur, 8 lbs. hydrated lime, 3 ozs. glue, .50 galls, water. Check (unsprayed) . ... 1917. Apr. 4 Apr. 19 Whole < Pulp... Parts per million. 10 lbs. lead arsenate (powderi, 90 lbs. hy- drated lime. ' ure sulphur Conmiercial preparation containing .50 per cent sulphur and .50 per cent lead arsenate. Apr. 4 Apr. 19 June 7 Apr. 4 Apr. 19 June 7 Whole Pulp. Skin. Whole Pulp Skin Whole Pulp Skin 0.0.5 0.30 1.00 .01 .10 .40 .20 1.20 4.20 .0 .0 .60 .0 .0 .40 .0 .0 1.70 .02 .10 .90 .01 .10 .60 .04 .20 2.40 .07 .50 1.20 .0 .0 .80 .40 2.30 3.30 6.9 3.0 25.8 4.0 2.8 9.8 6.3 4.3 14.0 8.0 5.6 19.2 Mg. per piach. 0.004 .001 .003 .0 .0 .0 .002 .001 .001 .006 .0 .006 0.095 .032 .063 .0.57 .032 .025 .086 .048 .038 .110 .062 .048 P.ct. 85.5 86.6 83.7 85. 85.7 82.6 85.6 86.0 82.8 85.0 8.5.6 82.6 Gr. 95.0 95.4 96.2 91.5 < Without stones. ' Harvested July 9, Fort Valley, Ca. Table 6. — -Arsenic, lead, and copper remainijig on sprayed cherries at picking time. Sam- ple No. Spray material used. Date sprayed. Condition of fruit analyzed. Arsenic (As). Orig- inal fruit. Dried fruit Lead(Pb). Orig- inal fruit. Dried fruit Copper (Cu). Orig- inal fruit. Dried fruit. Loss on dry- 25452 1 254.53 1 25454 ' 25482 3 25483 3 25484 * 25485 < Check (unsprayed) Home-made Bordeaux. Commercial fungicide containing 12 per cent copper, 3 per cent arsenic. .3-4-50 Bordeaux, 2 lbs. lead arsenate (paste). 3-4-50 Bordeaux Check (unsprayed) U galls, lime-sulphur solution, 2 lbs. lead arsenate (paste), 50 galls, water. li galls, lime-sulphur solution, 50 galls, water. Check (unsprayed) U galls, lime-sulphur, 2 lbs. lead arsenate (paste), 50 galls, wa- ter. 3-4-50 Bordeaux, 2 lbs. lead arsenate (paste). May 30, June 2i. July 3. Unwashed Washed * . Unwashed Washed'.. Unwashed Washed'.. May 30, June 21. July 3. Unwashed Washed'.. May 29-30, June 20. May 29-30, June 20. Unwashed Washed'.. Unwashed . Washed' 0.02 .04 .02 .09 .07 .35 .17 Part's per million 0.16 .2 .1 .7 .5 1.0 1.0 2.3 1.1 1.2 .7 .7 1.3 1.3 5.4 3.2 2.8 2.8 1.9 5.3 8.1 8.1 4.6 3.3 0.5 2.1 1.4 2.0 1.2 3.2 1.8 2.3 1.6 4.0 11.9 7.9 15.0 9.0 14.4 8.1 15.2 10.6 P.ct. 87.5 82.3 77.8 78.8 78.9 86.7 83.0 84.9 1 Picked July 12, 1916, Wenatchee, Wash. ' Washed by holding under running tap water for a fe^ • Sweet cherries, picked July 20, 1916, Hart, Mich. * Sour cherries, picked July 20, 1916, Hart, Mich. minutes. POISONOUS METALS ON SPRAYED FRUITS AND VEGETABLES. 23 Table 7. — Arsenic, lead, mid copper remaining on sprayed plums at picking time. Sam- ple No. 25643 1 25646 1 25807 3 25808 J Spray material used. 2 lbs. lead arsenate , (paste), SOgalls. water 1 lb. Pom. spray con- taining 1.7 per cent copper, 5 per cent lead arsenate, 7 per centcalcium arsenate. 2 per cent sulphur, 50 galls, water. 2 lbs. lead arsenate (paste) ,50 galls, water. 5 lbs. sulphur, 50 galls. water. 2 lbs. lead arsenate (paste),. ')0 galls. water. 4 lbs. barium polysul- phid, 50 galls, water. 2 lbs. lead arsenate ( paste) , 50 galls, water. 1 lb. sodium polysul- phid, 50 galls, water. 2 lbs. lead arsenate (paste), 50 galls, water. Self-boiled lime-sul- phur (8-8-.50). 2 lbs. lead arsenate (paste), 50 galls, water. Self-boiled lime-sulphur (8-8-50), 2 lbs. soap... Check (unsprayed) 2 lbs. lead arsenate (paste), plus lime, 50 galls, water. U galls, lime-sulphur 'solution, 50 galls, wa- ter, 2 lbs. lead arse- nate (paste). U galls, lime-sulphur "solution, 50 galls, water. 2 lbs. lead arsenate (paste), 50 galls, water, plus lime. Self-boiled lime-sulphur (8-8-50), 2 lbs. lead arsenate (paste), 50 galls, water. Self-boiled lime-sulphur (8-8-50). 2 lbs. lead arsenate (paste), plus lime, .50 galls, water. Bordeaux 3-4-50, 2 lbs. lead arsenate (paste). Bordeaux 3-4-50 Che:"k (unsprayed) Date sprayed. 1916. Mav 26. June22,.\ug. 1,2. May 26. June 22, 1, 2. May 26. June 22 1,2. May 26 June 22 1,2. May 26 June 22, 1, 2. May 26, June 22, 1,2. Aug, Aug. Aug Aug. Aug May 27. June 21,22,23 Aug. 12. May 27. June 21, 22, 23 Aug. 12. May 27. .Tune 21, 22, 23 Aug. 12.'« Condition of fruit analysed. Unwashed Washed '. . l^nwashed Washed'.. Unwashed . Washed ^ Unwashed Washed s.. Unwashed . Washed > Unwashed Washed 2.. Unwashed Washed «.. Unwashed Washed!".. ITnwashed Washed 2. . Unwashed Washed a.. Unwashed Washed 2. . Arsenic (As). Orig- inal fruit. Dried fruit. Lead (Pb). Orig- inal fruit. Dried fruit. Copper (Cu). Orig- inal fruit. Dried fruit. 0.06 .06 P( 0.5 .5 .04 .03 .3 .2 .03 .03 .2 .2 .04 .04 .3 .3 .03 .02 .2 .2 .03 .03 .3 .3 .03 .02 .13 .07 .2 .1 .8 .4 .07 .07 .4 .4 .13 .10 .7 .6 .10 .07 .6 .4 Parts per mill ion. 0.2 1.6 0.3 .2 1.6 .3 3.1 1.5 2.4 1.6 1.7 1.7 2.2 1.4 2.9 2.9 1.7 1.7 2.3 2.3 2.3 1.7 2.4 2.4 0.5 .4 3.7 3.0 6.8 5.1 3.4 3.4 Loss on dry- ing. P.ct. 87.4 82.3 1 Burban'.-; pi-^Ved last of August, Hart, Mich. 'Washed by holding under running tap water for a few minutes. 1 Golden Domestica; pieVed last of September, Hart, Mich. 24 BULLETIN 1027, U. S. DEPARTMENT OF AGEICULTTJRE. Table 8. — Arsenic, lead, and copper remmning on sprayed tomatoes nt picking time. Sam- ple No. Spray malerial used. Date sprayed. Determina- tions made on. Arsenic (As). Origi- nal fruit. Dried fruit. Lead (Pb). «„^'f- Dried Copper (Cuj. Ori pi- ll ried fruit. Loss dry- ing. 23304 1 23305 1 23306 1 25664 s 25665 2 25825 3 25826 3 25706 < 25707 < 25710 < 25711 < Check (unsprayed) 8-9-50 Bordeaux mix- ture! 5-6-50 Bordeaux. Check (unsprayed) 5-5-50 Bordeaux, IJ lbs. lead arsenate (pow- der). Check (unsprayed) 5-5-50 Bordeaux, U lbs. lead arsenate (pow- der). 5-5-50 Bordeaux 4-4-50 Bordeaux Julv 8, 19, 21,31, Aug. 5, 11, 18, Sept. 11. .lulv 8, 19, 20;31,Aug. 5, 10, IS, Sept. 4, 11. 1916. Whole fruit. Pulp Whole fruit, Pulp Whole fruit Pulp Juh. 7, i 8. 13. Aug 5, Sept. Whole fruit Pulp Whole fruit. Pulp.... July 13, Aug. 7, 25, Sept. s. Sept. 18. Whole fruit. Pulp.... Whole fruit. Pulp.... 0.02 .02 .3 .05 .07 .02 .07 .02 Check (unsprayed). Check (unsprayed). 4-4-50 Bordeaux. . . Whole fruit Pulp Whole fruit Pulp Whole fruit Pulp Whole fruit Pulp Parts per milliov. 0.4 .4 5.2 .9 1.4 .4 1.1 .3 0.9 .6 1.7 1.2 16.1 10.7 29.8 21.1 .3 6. .2 4.0 .5 .2 3.3 1.8 1.2 5.7 2.2 5.7 1.6 .6 .5 1.0 .6 30.0 20.0 91.9 35. 5 91.9 25.8 10.7 8.9 17.5 10.5 14.0 14.0 60.6 13.6 17.0 9.4 10.5 8.8 13.2 13.2 14.3 12.5 P.ct. 94.0 94.0 93.8 93.8 93.8 93.8 94.4 94.4 94.3 94.3 95.0 95.0 94 94 7 7 3 94.3 94.7 94.7 94.4 94.4 1 Fruit picked Sept. 15, 1915, Camden, N. J. 2 Fruit picked Sept. 14, 1916. Arlington, Va. 3 Fruit picked Oct. 2, 1916, Arlington, Va. < Fruit picked Sept. 15, 1916, Salem, N. J.; samples represent commercial fruit ready for markel. Table 9. — Copper remaining on sprayed celery at gathering time.^ Coppe r (Cu). Sam- Spray material used. Date Determinations lyoss on ple No. ■ sprayed. made on. Original Dried drying. celery. celery. 1915. Parts pr ' million. Per cent. 23585 2 Check plat (unsprayed) . Unwashed (cheek) . . 2.3 24.2 90.5 235S6 2 Overspraved with 5-5-50 Aug. 14, 24, Unwashed leaves s. . 258. 1 2, 150. 8 88.0 Bordeaux mixture, 2 lbs. Sept. 2, 14. Unwashed stalks'.. . 16.6 207. 5 92.0 resin fish-oil soap. Washed leaves < 65.7 547.5 88. Washed stalks < 8.2 102. 5 92.0 23587 2 5-5-50 Bordeaux mixture, Aug. 14, 24, Unwashed leaves ' . . 213.0 1,775.0 88.0 2 lbs. resin fish-oil soap. Sept. 2, 14. Unwashed stalks '. . . 3.6 45.0 92.0 Washed leaves < 85.5 712.5 88.0 Washed stalks < 2.9 36.3 92.0 1917. 28783 5 Commerciallj' spraved with Sept. 11, 22, Unwashed leaves 4.7 33.6 86.0 5-5-50 B ordeaux plus soap. Oct. 1. Unwashed stalks W ash ed leaves ^ .9 2.9 11.5 20.7 92. 2 Washed stalks « .9 11.5 28784 ^ Overspraved with 5-5-50 Sept. 11, 22, Unwashed leaves 12.8 91.4 86.0 Bordeaux plus soap. Oct. 1. LTnwashed stalks 1.6 2 1 20.0 15.0 92.0 Washed stalks* .7 8.7 ' The samples sprayed in 1915 were coated with copper spray when received and represent extremely heavv applications; the 1917 samples represent celery as it usuallv appears on the market. 2 flarvested Oct. 29, 1915, North Liberty, Ind. ' These sprayed samples were heavily coated with the spra.v material when received. * Washing done by holding sample under faucet water for few minutes. 5 Harvested about Nov. 1, 1917, North Liberty, Ind. ' Washed by soaking celery in water for a short time and then rubbing with a small brush. POISONOUS METALS ON SPRAYED FRUITS AND VEGETABLES. 25 Table 10. — Copper remaining on sprayed cucumbers at picking time. Sam- Spray material used. Date sprayed. Determinations made on. Copper (Cu). Loss on drying. ple No. Original fruit. Dried fruit. 25660 1 1916 ' 1916 1916 1916 Parts pe 0.6 .3 . 5 1.2 .3 2.8 1.2 .3 2.5 1.4 .3 2.5 million. 11.3 7.1 7.7 25.5 7.3 44.4 25. 5 7.3 39.1 28.6 6.8 38.5 Per cent. 94.7 2-4-50 Bordeaux Pulp 95.8 Skin 93.5 2.5661 ' Whole fruit . . . 95.3 2^-50 Bordeau-x plus 2 lbs. resin fish-oil soap. 5-5-50 Bordeaux Pulp 95.9 Skin 93.7 25662' Whole fruit 95.3 Pulp 95.9 Skin 93.6 25663 ' Whole fruit 95.1 Pulp 95.6 Skin 93.5 1 Cucumbers picked Sept. 9, 1916, Plymouth, Ind. Table ll.^Aisenic, lead, and copper remaining on sprayed cranberries at picking time. Sam- Spray material used. Date sprayed. Condition of fruit analyzed. Arsenic (As). Lead (Pb). Copper (Cu). Loss ple No. Orig- inal fruit. Drted fruit. Orig- inal fruit. Dried fruit. Orig- inal fruit. Dried fruit. dry- ing. 23453 1 Sprayed lightly with 4^4-50 Bordeaux, 2 lbs. resin flsh-oil soap .2 Sprayed medium with 4-^50 Bordeaux, 2 lbs. resin fish-oil soap (normal spray for re- gion). 2 Sprayed heavily with 4-^50 Bordeaux, 2 lbs. resin fish-oil soap. 2 Overspraved with 4-4- 50 Bordeaux, 2 lbs. resin fish-oil soap. 2 Sprayed heavily with 4-4-50 Bordeaux, 2 lbs. resin flsh-oil soap." Sprayed medium with 4-4-50 Bordeaux, 2 lbs. resin fish-oil soap (normal spray for re- gion), s Sprayed lightly with 4-4-50 Bordeaux, 2 lbs. resin fish-oil soap. ^ 1915. June 24, July 26, Aug. 11, 28. do do June 10, July 10, 31, Aug. 16. June 19, July 27, Aug. 12. do do Pa rts per millioi 7.4 7.1 3.9 2.3 7.6 4.8 33.3 16.2 2.0 1.7 2.0 1.8 2.6 2.4 .9 7.2 3.0 62.7 60.2 33.9 20.0 66.1 41.7 268.5 130.6 15.0 12.8 14.4 12.9 17.9 16.5 7.1 62.1 25.9 P.ct. 88.2 Washed ' 88.2 23454 1 Unwashed 88.5 Washed '. . . 88.5 23455 » 88.5 88.5 234561 87.6 Washed'... 87.6 23684 < 86.7 Washed '... 86.7 23685 * 86.1 86.1 23686* Unwashed . Washed ' . 85.5 85.5 23687* 257271 87.4 Commercially sprayed with 3-3-50 Bordeaux, 2 lbs. resin flsh-oil soap. 6 1916. June 26, July 27, Aug. 5, 25. Unwashed . Washed' 88.4 j 88.4 1 Early Black. « Harvested Sept. 18, 1915, Brown Mills, N. J. • Washed by holding the berries in running tap water. * Howe. 5 Harvested Oct. 16, 1915, Brown Mills, N. J. •Serby'soSSSrwa'fer%?'Vlh time, pouring off the water, adding more water, and repeating operation three times. 726.38—22 4 26 BULLETIN 1027, U. S. DEPARTMENT OF AGRICULTUEE. Table 11. — Arsenic, lead, and copper remaining on sprayed cranberries at picking time- Continued. Sam- Spray material used. Date sprayed. Condition of fruit analyzed. Arsenic (As). Lead (Pb). Copper (Cu). Loss ple No. Orig- inal fruit. Dried fruit. Orig- inal fruit. Dried fruit. Orig- inal fruit. Dried fruit. dry- ing. 26166 26167 26168 26169 26170 Sprayed lightly with 4-4-50 Bordeaux, 2 lbs. resin fish-oil soap, 2 lbs. lead arsenate (powder). » Sprayed normally with 4-4-50 Bordeaux, 2 Jbs. resin fish-oil soap, 2 lbs. lead arsenate (powder). 8 Sprayed heavily with 4-4^50 Bordeaux, 2 lbs. resin fish-oil soap, 2 lbs. lead arsenate (powder). 8 Oversprayed with 4-4- 50 Bordeaux, 2 lbs. arsenate (powder), 2 lbs. resin fish-oil soap.s Check (unsprayed).8. . . 1916. Aug. 1, 24. do do Aug. 2, 24. Unwashed . Washed'... Unwashed . Washed'.-. Unwashed . Washed'... Unwashed . Washed'... Unwashed . 1.2 .8 1.3 1.0 1.7 1.0 2.5 1.0 .1 Part 8.7 5.8 9.4 7.2 12.8 7.5 19.1 7.6 .7 .7 s per n 4.8 2.5 5.7 2.5 7.4 3.8 9.2 4.4 .6 .6 lillion. 34.8 18.1 41.3 18.1 55.6 28.6 70.2 33.6 4.4 4.4 5.5 2.3 6.7 3.1 10.0 4.6 11.4 3.7 1.0 1.0 2.2 1.0 39.8 16.7 48.6 22.5 75.2 34.6 87.0 28.2 7.4 7.4 17.2 7.8 P.ct. 86.2 86.2 86.2 86.2 86.7 86.7 89.9 86.6 86.5 27337 1 4-5-50 Bordeaux, 2 lbs. resin fish-oil soap. ' 10 lbs. lead arsenate (paste), .50 galls. water, n 10 lbs. lead arsenate (paste), 21bs. laundry soap, 50 galls, water." 5 lbs. lead arsenate (powder), 50 galls. water. 11 3 lbs. lead arsenate (powder), 50 galls. water. 12 4-5-50 Bordeaux, 2 lbs. resin fish-oil soap. ^ 10 lbs. lead arsenate (past e), .50 galls. water. " 10 lbs. lead arsenate (paste), 2 lbs. laundry soap, 50 galls, water. » 5 lbs. lead arsenate (powder), 50 galls. water. 3 lbs. lead arsenate (powder), 50 galls. water. 12 Check (unsprayed)'i. . . June 24, Aug. 3. July 22. July 22, 24. June 28, Aug. Aug. 19. June 24, Aug. 3. July 222 July 22, 24. June 28, Aug. Aug. 19. Washed'... Unwashed . Washed'... .1 86.5 87.2 2733810 Unwashed . Washed'... Unwashed . Washed'... Unwashed . Washed'... .14 .14 .16 .16 3.9 1.5 1.1 1.1 1.2 1.2 30.7 11.8 1.5 .9 1.1 1.1 19.1 11.5 11.6 7.0 8.1 8.1 150.4 90.6 87.1 27339'" 86.5 27340 1 87.3 27346 • 3.0 1.6 23.4 12.5 87.2 Washed '. . . i 2734710 Unwashed . ' .14 Washed '...| .14 Unwashed . : .15 Washed'...' .09 Unwashed . 3. 9 Washed'... 1.4 Unwashed . . 02 Washed'... .02 Unwashed .1.1 AVashed'...{ .6 Unwashed . . 01 1.1 1.1 1.2 .7 30.7 11.0 .14 .14 9.6 5.3 .08 .08 .8 .8 10.0 2.5 1.4 1.1 1.5 1.0 18.9 12.4 .4 .4 4.5 2.9 .7 .7 .6 .6 4.8 1.9 10.5 8.3 11.7 7.8 148.8 97.7 2.9 2.9 39.5 25.4 5.6 5.6 4.9 4.9 40.0 15.8 86.7 2734810 87.2 27349 1 87.3 27181 0.9 .7 6.4 5.0 86.0 28686 4 lbs. lead arsenate (powder), 50 galls, water, 2 lbs. caustic potash fish-oil soap. " Check (unsprayed) i' 1917. June 26, July 26,30. 88.6 28685 0.6 .6 1.3 1.2 4.8 4.8 10.6 9.8 87.6 28556 28830 3 lbs. Ume,41bs. copper ■ sulphate, 2 lbs. resin fish-oil soap, .50 galls, water, i' 4 lbs. lead arsenate (powder), 2 lbs. caus- tic potash fish-oil soap, 50 galls, water." June 28, Aug. 4,20. June 26, July 26,30. Washed'... Unwashed . Washed'... Unwashed . Washed'... .01 .1 .1 1.2 .3 ' '87.' 8 88.6 1 Early Black. 7 Washed by soaking berries in water for a short lime, pouring off the water, adding more water, and repeating operation three times. 8 Harvested Oct. 9, 1916, Brown Mills, N. J. » Harvested Sept. 23, 1916, East Wareham, Mass. 10 Late Home. 11 Harvested Oct. 2, 1916, East Wareham, Mass. " Harvested Sept. 25, 1916, East Wareham, Mass. I' Harvested Oct., 1917, East Wareham, Mass. POISONOUS METALS ON SPRAYED FRUITS AND VEGETABLES. 27 Some of the samples from New Jersey reported in Table 1 1 represent plots which were purposely oversprayed and contain relatively large amounts of spray residues. The lots sprayed according to recom- mended schedule contain much less spray residue. Samples 27340 and 27349 show a comparatively large amount of spray residue, but these samples are from experimental plots which were sprayed late. The other Massachusetts samples show very little spray residue. The results indicate that when sprayed with the regulation spray and washed before using the berries contain but little spray material. Table 12. — Copper, lead, and arsenic remaining on sprayed grapes at picking time. Sam- Spray material used. Date sprayed. Condition of samples analyzed. Arsenic (As). Lead (Pb). Copper (Cu). Loss ple No. Orig- inal fruit. Dried fruit. 'Orig- inal fruit. Dried fruit. Orig- inal fruit. Dried fruit. on dry- ing.. 1915. Part" per milliov. P.ct. 23565' 2J lbs. lead arsenate June 4, July Unwashed . 0.25 1.50 2.6 15.1 0.8 4.7 82.8 (powder), 4-4-50 Bor- 16. Washed ^ . . .14 .80 2.4 14.0 .6 3.4 deaux.' 23566 » 1 lb. lead arsenate do Unwashed . .13 .80 2.1 13.1 .7 4.4 84.0 (powder), 4-4-50 Bor- Washed s . . .13 .80 1.3 8.1 .6 3.8 deaux.2 23567 ' Check plat (unsprayed)^ Cheek plat (unsprayed)* 3 lbs. lead arsenate .07 .40 1.1 6.8 .4 2.5 83.9 23571 1 .07 .40 .6 3.2 .4 2.1 81.0 23572 1 July 6.' Unwashed . .44 2.70 1.4 8.4 1.3 7.8 83.4 (paste), 2 lbs. fish-oil Washed s . . .30 1.80 1.2 7.2 1.1 6.6 soap, 3-3-50 Bor- deaux (sprayed with coarse nozzle). 3 lbs. lead arsenate July 19. (paste), 1 lb. laundry soap, 3-3-50 Bor- deaux (sprayed with coarse nozzle).* 23573' 5 lbs. lead arsenate July 6. Unwashed . .80 4.80 2.4 14.4 1.5 9.0 83.3 (paste), 2 lbs. fish-oil Washed ^ . . .35 2.10 1.3 7.8 1.1 6.6 soap, 3-3-50 Bor- deaux (sprayed with coarse nozzle). 5 lbs. lead arsenate July 19. (paste), 1 lb. laundry soap, 3-3-50 Bor- deaux (sprayed with coarse nozzle). < 23574 ' 5 lbs. lead arsenate July 6. Unwashed . .80 4.70 8.2 48.5 1.8 10.7 83.1 (paste), 2 lbs. fish-oil Washed 3.. .35 2.10 2.4 14.2 1.4 8.3 soap, 3-3-50 Bor- deaux (oversprayed, coarse nozzle). 5 lbs. lead arsenate July 19. (paste), 1 lb. laundry soap, 3-3-.50 Bor- deaux (oversprayed, coarse nozzle). < 23688 1 3 lbs. lead arsenate July 5, 17. Unwashed . .40 1.90 1.5 7.1 1.2 5.7 79.0 (paste), 3-3-50 Bor- Washed 3 . . .40 1.90 1.2 5.7 .7 3.3 deaux (sprayed with trailers, using fine 236S9 1 nozzles).'' 3 lbs. lead arsenate do Unwashed . .82 3.90 2.4 11.5 1.8 8.7 79.2 (paste), 1 lb. laundry Washed ' . . .50 2.40 1.4 6.7 1.2 5.8 soap, 3-3-50 Bor- deaux (sprayed with trailers, using fine nozzles) (normal schedule for this re- gion).5 ' Concord. ' Harvested Oct. 9, 1915, Benton Harbor, Mich. " Samples washed in running tap water. * Harvested Oct. 9, 1915, North East, Pa. » Harvested Oct. 27, 1915, North East, Pa. 28 BULLETIN 1027, U. S. DEPARTMENT OF AGRICULTURE. Table 12. — Copper, lead, and arsenic remaining on sprayed grapes at picking time- Continued. Sam- ple No. 258361 25837' 258381 25903 1 259041 Spray material used. 3 lbs. lead arsenate (paste), 1 lb. laundry soap, 3-3-50 Bor- deaux (spray applied with fine nozzles set at rear of sprayer).^ Cheek plat (unsprayed)^ 1 gall. lime-sulphur, 33' B.),7 galls, water. 4-4-50 Bordeaux e 8 lbs. Bordeaux (com. paste), I lb. lead arse- nate (powder), 50 galls, water. 8 lbs. Bordeaux (com. paste ) , 50 galls . water.e Check plat (unsprayed)' July 6, 21. .do 1 lb. soap, 11 lbs. lead arsenate ( powder) , 3-3-50 Bordeaux (used trailers with medium nozzles).' 25905 1 1 lb. soap, 2^ lbs. lead arsenate (powder), 3-3-50 Bordeaux (used trailers with medium nozzles).' 259061 I lb. soap, 2i lbs. lead arsenate (powder), 3-3-50 Bordeaux (used trailers with medium nozzles). 1 lb. lime, 1 lb. soap, 2-^ lbs. lead arsenate (powder), 50 galls. water (double appli- cation).' 25907 1 1 lb. soap, li lbs. lead arsenate (powder), 3-3-50 Bordeaux (used trailers with fine nozzle).' 26016 8 4-3-50 Bordeaux (me- dium set nozzle). s 26017 8 4-3-50 Bordeaux (me- dium set nozzle). 2h lbs. lead arsenate (powder), 2 lbs. laun- dry soap, 3-3-50 Bor- deaux (sprayed with trailer, fine nozzle). 2i lbs. lead arsenate (powder), 1 lb. resin soap, 3-3-50 Bor- deaux (sprayed with trailer, fine nozzle).'' 26018 8 4-3-50 Bordeaux (me- dium set nozzle). 2i lbs. lead arsenate (powder), 2 lbs. laun- dry soap, 3-3-50 Bor- deaux (sprayed with trailer, coarse nozzle). 2J lbs. lead arsenate (powder), 1 lb. resin • soap, 3-3-50 Bor- deaux (sprayed with trailer, coarse nozzle)', 1 Concord. 3 Samples washed in running tap water. 5 n.irvested Oct. 27, 1915. North East, Pa. « Harvested Sept. 30, 1916, Benton Harbor, Mich. Date sprayed. 1915. July 5, 17. 1916. Dormant spray. June 16. June 1, 12. Aug. 2. Condition of samples analyzed. Unwashed Washed 3 . Unwashed Washed ' . Unwashed Washed 3 . Unwashed Washed s . Unwashed Washed ' . Unwashed Washed ' . Unwashed Washed s . .do ! Unwashed Washed 3 . Aug. 12. July 6. 21. June 15. ....do.... June 28. Aug. 4. June 15. June 28. Aug. 4. Unwashed Washed 3.. Unwashed Washed 3.. Unwashed Washed 3.. Unwashed Washed 3. . Arsenic (As). ( )rig- inal fruit. Dried fruit. Lead (Pb). Orig- inal fruit. Dried fruit. Copper (Cu). Orig- inal fruit. Dried fruit. Parts per millinn. ' ' 2.9 1.4 4.7 3.2 0.29 1.40 0.9 4.3 0.6 .22 1.00 .4 1.9 .3 • .0 .0 .5 2.6 .9 .0 .0 .5 2.6 .6 .05 .26 .7 3.6 1.1 .02 .10 .6 3.1 1.1 .12 .63 .8 4.2 1.4 .07 .37 .6 3.2 1.1 .04 .17 .6 2.6 .8 .04 .17 .6 2.6 .4 3.00 12.60 7.5 31.6 4.1 1.00 4.20 3.5 14.8 1.4 .70 3.20 3.9 17.7 2.1 .60 2.70 2.8 12.7 1.3 3.80 16.10 12.0 50.8 3.2 2.60 11.00 7.6 32.2 1.7 .30 1.30 2.4 10.3 2.3 .30 1.30 1.3 5.6 1.5 .15 .60 .7 2.9 2.0 .15 .60 .7 2.9 1.3 1.80 7.30 5.1 20.7 2.7 .70 2.80 2.1 8.5 1.5 3.70 16.30 10.4 45.8 3.4 .90 4.00 3.1 1.3.7 1.4 5.6 5.6 7.4 5.8 3.4 1.7 17.3 5.9 9.5 5.5 13.6 7.2 8.3 5.4 11.0 6.1 1.5.0 6.2 Loss P.ct. 79.0 ' Harvested Oct. 6, 1916, North East, Pa. 8 Catawba. a Harvested Oct. 13, 1916, Sandusky, Ohio. POISONOUS METALS ON SPRAYED FRUITS AND VEGETABLES. 29 Table 12. — Copper, lead, and arsenic remaining on sprayed grapes at picking time — Continued. Sam- ple 26019 » 26021 8 2S881 8 Spray material used. Date sprayed. 1916. June 15. June 28. Aug. 4. June 15. June 28, July 12. June 15. June 28, July 12. Aug. 2. 1917. June 18. Julv2-4,24- 25. June 18-20. July 2-4, 24- 25, Aug. 14, June 18-20. July 2-4. July 24-25. Condition of samples analyied. Unwashed Washed'... Unwashed Washed 3... Unwashed . Washed'... 2.80 1.00 4.60 2.70 Unwashed . Washed m. . Unwashed Washed 'o Unwashed Washed lo. 3.20 1.30 7.10 3.60 6.20 3.30 12.70 4.50 21.10 12.40 16.00 6.50 35.50 18.00 30.10 16.00 6.2 3.2 13.3 6.4 8.1 3.7 17.6 11.3 15.5 8.6 28.2 14.6 61.0 29.4 10.5 18.5 88.0 56.5 75.2 41.7 3.1 1.7 4.6 1.8 2.7 2.0 4.2 2.6 3.7 2.8 18.0 8.1 14.1 7.7 21.1 8.3 78. (^ 4-3-50 Bordeaux (sprayed with me- dium set nozzle). 2\ lbs. lead arsenate (powder), 2 lbs. laun- dry soap, 3-3-50 Bor- deaux (oversprayed with trailer, coarse nozzle). 2 J lbs. lead arsenate (powder), 1 lb. resin soap, 3-3-50 Bor- deaux (oversprayed with trailer, coarse nozzle). s 4-3-50 Bordeaux (sprayed with me- dium' set nozzle). 2i lbs. lead arsenate (powder), 2 lbs. laun- dry soap, 3-3-50 Bor- deaux (sprayed with trailer, medium noz- zle ).9 4-3-50 Bordeaux (sprayed with me- dium set nozzle). 2J lbs. lead arsenate (powder), 2 lbs. laun- dry soap, 3-3-50 Bor- deaux (sprayed with trailer, medium noz- zle). 2i lbs. lead arsenate (powder), 1 lb. resin soap, 2-3-50 Bor- deaux.9 3-3-50 Bordeaux (set nozzle). \\ lbs. lead arsenate (powder), 1 lb. resin fish-oil soap, 2-3-50 Bordeaux (trailer, raedi um nozzle) (schedule recommend- ed for this region)." 3-3-50 Bordeaux (set nozzle). U lbs. lead arsenate "(powder), 1 lb. resin tish-oil soap, 2-3-50 Bordeaux (trailer, medium nozzle)." 3-3-50 Bordeaux (set nozzle). IJ lbs. lead arsenate (powder), 1 lb. resin fish-oil soap, 2-3-50 Bordeaux (sprayed with trailer, medium nozzle). 2 J lbs. lead arsenate (powder), 1 lb. resin fish-oil soap, 2-3-.50 Bordeaux (sprayed with trailer, medium nozzle)." 3 Samples washed in running tap water. 8 Catawba. 9 Harvested Oct. 13, 1916, Sandu^kv, Ohio. 10 Samples washed by soaking the grapes in water for 5 minutes, pouring off the water, and then washing in running tap water. » Harvested Oct. 27, 1917, Sandusky, Ohio. Arsenic (As). Lead(I'b). Copper (Cu). Orig- inal fruit. Dried fruit. Orig- inal fruit. Dried fruit. Orig- inal fruit. Dried fruit. Loss on dry- ing. Parts per million. 4.00 16.30 12.6 I 51.3 4.4 1.00 4.10 4.9 19.9 2.0 13.5 10.0 21.0 13.0 18.0 13.6 P.ct. 75.4 79.4 30 BULLETIN 1027, U. S. DEPARTMENT OF AGRIC;iTLTlIIlE. Table 12.— Copper, lend, and arsenic remaining on sprayed grapes at picking time — Continued. Sam- Spray material used. Date sprayed. Condition of samples analyzed. Arsenic (As). Lead ( ' b). Copper (Cu). Loss ple No. Orig- inal fruit. Dried fruit. Orig- inal fruit. Dried fruit. Orig- inal fruit. Dried fruit. on dry- ing. 1917. Parts per TniUio7i. P. cf. 2888412 3-3-60 Bordeaux June 1S'20. Unwashed . 5.70 31.10 13.0 71.0 4.3 23.5 81.7 (sprayed with set Washed '». . 4.40 24.00 12.0 65.6 3.3 18.0 nozzle). 2i lbs. lead arsenate July 2-4. 24- '(powder), 1 lb. resin 25. fish-oil soap, 2-3-50 Bordeaux, (sprayed with trailer, medium nozzle)." 288868 3-3-50 Bordeaux June lS-20. Unwashed . 5.90 30.30 14.8 75. 9 2.3 11. S 80.5 (sprayed with set Washed ifi.. 1. 30 6.70 3.9 20.0 1.7 8.7 nozzle). IJ lbs. lead arsenate J u 1 V 2-4, (powder), 1 lb. resin Aug. 14. fish-oil soap, 2-3-50 Bordeaux (sprayed with trailer, medium nozzle)." 28887" 3-3-50 Bordeaux June 18. Unwashed . 4.60 24.30 6.4 33.8 81.1 (sprayed with set nozzle). Washed i". . 1.80 9-.^0 4.2 22.2 1 lb. calcium arsenate July 2-4, 24- (powder), 1 lb. resin . 25. fish-oil soap, 2-3-50 Bordeaux (sprayed with trailer, medium nozzle).!' 28888» 3-3-50 Bordeaux June 18-20. Unwashed . .08 .40 .9 4.5 1.5 7.6 80.2 (sprayed with set Washed '" . . .08 .40 .9 4.5 1.3 6.6 nozzle)." 2888912 3-3-50 Bordeaux June 18-20. Unwashed . .08 .40 .5 2.5 1.5 7.6 80.2 (sprayed with set Washed w .08 .40 .3 1.5 1.5 7.6 nozzle)." 8 Cata\\ba. w Samples washed by soaking the grapes in water for 5 minutes, pouring off the water, and then wash- ing in running tap water. " Harvested Oct. 27, 1917, Sandusky, Ohio. "Ives. " Harvested Oct. 18, 1917, Sandusky, Ohio. WEATHER CONDITIO.VS. Nos. 23565-67: Ideal for spraynig during both applications; all foliage and fruit were covered. Nos. 23571-74 and 23688-90: Heavy ram on July 8, which seemed to wash off a large amount of the spray material. Nos. 25836-38 and 25903-07: No abnormal weather conditions reported. Nos. 26016-21: Dry, hot, clear: season unusually dry. Nos. 28881-89: Rainfall normal; in no case did rain interfere with the spraying, nor did rain fall before material was well dried. The Michigan samples and the Pennsylvania samples mentioned in Table 12 that were sprayed according to normal schedule showed very little spray residue at harvest. Grapes sprayed in Sandusky, Ohio, according to the schedule formerly used in that region showed a decided spray residue on their surface at harvest. As this spray residue was no doubt due mainly to late spraying, the Bureau of Entomology has recommended a new schedule which is given under Sample. 28881. Table 12 shows the composition of grapes sprayed according to the recommended schedule as compared with that of those sprayed under the schedule formerly used, as well as the com- position of grapes sprayed under various experimental schedules. 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DEPARTMENT OF AGRICULTURE. 9-S'> M . a: to a: -H c^ TO o i-< .— .ooooooo pI C^ CO -»t* -- •* ■* ^H CO CO rO 2^ rt c oo o oc O-Hooocooo-H ooooooo ^.g- • ^ OOOOOOOCC'-i--<0'-'^00"*'-'O^^OO^rOOO>-H--HOOO ?o ooooooooooooooooooooooooooooooo a. 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I ! I OOOiCOOQ'^OGCOQOtOQQCCOOOcOQOQCCN i-HCO^OO'COfOOC^^OO^OOOOOOO -aot^coo6jo 'loddiO'^d * 'cO'-hcoc^^oc ■assess =2-323 «s5 33-3 ss-as OS •-'^ c^ ^ ..v 0) 1 3 r^ Jc' ^ 3 .— 1 CO ^^ -^ > » -r 13 S T3 »'. •« ' C-Q Q.tn J (^^ ■5 0) 0; c £1 ■^p. — aj"" a; . o w ^ fO ■- S ^ « ce 3 c8 3 E S S S .2 ci-2 ». C OJ C Q; 03 03 C3 M E & E is ■S os,« £ >^ 0) So J-.-. 5) ;i;(N=i ^^fi 000 ooc a) 'I'lLS O 03 d S 2 > c t. t< >- - !3 S 03 05 03 MpqWWK 2 O tuD - 5 E £ H,' J.o'S-^ £ 32§5£ , oj K X^a^ ft _t ~ ■ P CD ' -O ^-'^ '-I c^ j2 eft - OJ o ^^ S „ 3 5 >- o ffi tjO M X o o ^ _ '^ " .S "^ S U (u I S £ ^3 9^ O O "^ - .77 .00- .00- .9 6.1 .0- .4 .0- 1.7 .0- .0- 2.8 11. e Cherries: Sprayed Whole . 04- . 35 .20- 2.3 . 6- 1. 3 2.8- 8.1 2.0- 3.2 11.9- 15.2 Whole 1 . 02- . 17 .10- 1.1 .4- 1.3 1.9- 8.1 1.2- 1.8 7.9- 10.6 Unspraved . . Whole . 02- . 08 .10- .ti .6- .7 2.8- 5.3 .5- 1.4 4.0- 8.3 Plums: Spraved Whole . 03- . 13 .20- . 8 .2- .5 1.6- 3.1 .3- 1.2 2.4- 6.8 Who'e 1 . 02- . 10 .20- .(■■ .2- .5 1.5- 2.9 .3- .9 2.4- 5.1 Unspraved . . Whole . 03- . l(t .20- .(■. .3- .4 2.2- 2.3 . 5- . 6 3.4- 3.7 Whole 1 . 02- . 07 .10- .4 .2- .3 1.4- 1.7 .4- .6 3.0- 3.4 Tomatoes: Spraved Whole . 07- . 30 1.10- 5.2 .5- 1.7 7. 6- 29.8 .8- 5.7 14.3- 91.9 Pulp .02- .05 .30- .9 .2- 1.2 3.3- 21.1 ..5- 2.2 9.4- .35.5 Unspraved . . Who'e . 02- . 07 .40- 1.4 .3- .9 6.0- 16. 1 .(i- 1.8 10.5- W.O Pulp . 02- . 02 .40- .4 .2- .6 •4.0- 10.7 .5- 1.2 8.8- 20.0 Celerv: Sprayed 4. 7-258. 1 .9- 16.6 2. 1- 85. 5 .7- 8.2 2.3- .... 33. 6-2 11.5- 15.0- 8.7- 24.2- , 150. 8 Stalks 207.5 712.5 Stalks I 102:5 Unspraved . . Whole Cucumbers: Spraved Whole 1.2- 1.4 25.5- 28. 6 Pulp .3- .3 2.5- 2.8 .6- 6.8- 38.5- 11.. 3- 7.3 Skin 44.4 Unspraved . . Whole Pnlp .3- 7.1- Skin .5- 7.7- Cranberries: Sprayed Who'e 0.10- 3.90 0.80- 30.7 0.6- 19.1 4.9- 150.4 1.3- 33.3 10. 6- 2i;8. 5 Whole 1 . 09- 1. 50 .70- 11.8 .61- 12.4 4.9- 97.7 1.0- 16.2 7.8- 130.6 Unspraved . . Whole .01- .10 .08- . 7 .4- .7 2.9- 5.6 .6- 1.0 4.8- 7.4 Grapes: Spraved Whole .05- 7.10 .20- :55.5 .5- 17.0 2..5- 88.0 .6- 6.4 2.9- 33.8 Whole ' .02- 4.40 .10- 24.0 .3- 12.0 1.5- 65.6 .3- 4.2 1.4- 22.2 Unsprayed . . Pears: Spraved Whole .00- .07 .00- .4 .5- 1.1 2.6- 6.8 .4- .9 2.1- 4.7 Whole . 10- . 32 .50- 2.1 .13- 1.0 1.6- 6.7 I..5- .3.0 10. 0- 14.5 Pulp . 02- . 10 .10- .8 .2- .2 1.0- 1.7 .7- 1.0 4.9- 5.1 Skin .30- 1.00 1.20- 4.3 .8- 3.2 3.1- 13.7 4.5- 16.2 19.3- 54.5 Calyx 1.20- 6.40 4. 80- 27.7 4. 2- 21. 3 16. 7- 92.2 12.1- 21.9 52.4- 68.9 Skin 2 .30- .90 1.20- 4.0 .8- 3.0 3.1- 13.4 2. 1- 12. 4 9.0- 41.8 Calyx 2 1.20- 0.40 4.80- 27.7 4.2- 21.3 16. 7- 92.2 7.8- 8.2 25. 8- .33. 8 Unspraved . . Whole .05- .10 . :bo- .(; .2- .3 1.0- 1.5 .3- .9 1.7- 4.5 Apples: Spraved Whole .03- 5.50 .20- 40.0 .3- 17.0 2.2- 130.0 .4- 5.2 2.4- 24.2 Pulp . 02- . 40 .10- 2.5 .2- 1.8 1.3- 15.0 .3- .8 1.8- 4.2 Skin . 10- 25. 70 .50- 1.30. . 7- 80. 3.3- 480. .(W 28.5 2.8- 111.3 Calyx . 70-127. 00 3. 50- 700. 2. 2-328. 11. C-2, 000.0 2.5- 29.5 12.4- 149.0 Stem ends. . . . 40-328. 00 2.70-2,000.0 2. 8-550. 17. 7-4 400.0 2. 7- 29. 4 15. :3- 136.1 Skin 2 . 10- 22. 70 .50- 92.3 . 5- 63. 2.4- 256. 1 . 6- 28. 5 2.8- 111.3 Calyx 2 .70- 83.00 3.50- 470.0 2.2-297.0 11. 6-1 700.0 2.5- 14.7 12.4- 74.2 Stem ends 2 . . 40- 70. 00 2.70- 600. 2. 8-252. 17. 7-1 500.0 2.7- 21.2 15.3- 98.1 Unsprayed. . Whole . 04- . 44 .2 - 2.2 .2- 1.5 1.3- 9.3 .3- .7 2..3- 4.3 POISONOUS METALS ON SPRAYED FRUITS AND VEGETABLES. 49 Table 15. — Arsenic, lead, and copper remaining on fruits and vegetables sprayed with poisonous sprays (summary) — Continued. Detenni- nation made on. Arsenic in eacli fruit. Lead in each fruit. Copper in each fruit. Peaches: Sprayed . . Unsp rayed. Pears: Sprayed . . Unsorayed Apples: Sprayed . . Who:e. Pulp... Skin... Whole. Pulp... Skin.... Whole... Pulp.... Skin . . . . Calyx... Skin 2... Calv-x 2 . Whole... Whole... Pulp.... Skin . . . . Calyx... Stem ends . . Skin 2... Calyx 2.. Stem ends 2. Unsprayed . Whole Afg. 0.002-0.115 . 000- . 014 .001- .101 . 000- . 02(i .000- .009 . 000- . 017 . 013- . 049 .003- .010 .005- .023 .002- .010 .005- .014 .002- .016 . 006- . 013 . 004- . 900 .002- .042 .002- .442 .001- .154 .001- .310 .002- .345 . 001- . 127 Grains. i Mg. 0. 000031-0. 00180 0. 024-0. 297 .000000- .00022' .007- .062 .000015- .00160 .013- .284 .000000- .00040 . 000000- . 00014 . 000000- . 00026 .000200- .00075 . 000046- . 00015 .000077- .00035 . 000031- . 00025 .000077- .00022 .000031- .00025 .000092- .00020 . 000062- . 000031- .000031- .000015- . 000015- .000031- .000015- .000- .05' .000- .032 . 000- . 033 .039- .015- .012- .005- .012- .005- .022- .151 .029 .073 .053 .054 .0.53 .037 .01400j .0.36-2.800 .000)51 .015- .230 .00680! .010-1.600 .00240 .00.3- .400 .00480 . 00530 . 00200 .000015- .00260 .Oa3- .768 . 007- . 958 . 003- . 332 . 005- . 051 . 000077- . 00079 . 019- . 178 Grains. 0. 00037-0. 00460 .00011- .00095 .00020- .00440 .00000- .00088 .00000- .00049 . 00000- . 00051 Mg. . OOO.'OO- .000230- .030180- .000077- .000180- . 000077- . 000340- .00230 .00045 .00110 .00082 .00083 .00082 .00057 . 000550- . 04300 . 000230- . 00350 .000150- .02500 . 000046- . 00620 .000046- .01200 .000110- .01500 .000046-. 00510 .000046- .00810 0.227-0.411 . 095- . 120 . 102- . 261 .030- .030 . 049- . 200 .011- .020 .033- .113 .054- .380 .035- .072 .010- .273 .003- .032 .00.3- .0.35 . 010- . 273 .003- .016 .003- .025 . 000290- . 00270 . 024- . 093 Grains. 0. oo:i.')i)a-o. 00630 ■ OOl.'iOl^- .ooiso .OOHiOO- .000160 . 000750- . 000170- . 000510- .00400 .111)046 .011310 .011031 . 00170 .0008:30- .00590 .00().')40- .00110 .0001.50 .0(l!20 .000046- .00049 .000046- .00054 .000150- .00420 .000046- .00025 .000046- .00039 .000370- .00140 1 Washed. 2 wiped. Table 16. — Precipitation reports for sections ivhere samples analyzed were harvested. BERLIN, MD., SECTION. Date. Precipita- tion. Date. Precipita- tion. Date. Precipita- tion. Date. Precipita- tion. 1915. Inches. 1915. Inches. 1915. Inches. 1915. Inches. May 3.... Trace June 1 0.02 July 2.... 0.58 Aug. 6.... .35 4.... 0.08 2.... 1.75 4.... .72 8.... .20 5.... .33 3.... 1.20 5.... .80 9.... .25 12.... .63 5.... .01 8.... .07 10.... .20 13.... Trace. 6.... .08 ]].... .57 12.... .28 15.... Trace. 12.... .07 13.... .58 14.... .04 16.... .44 13.... .13 17.... .48 21.... .01 17.... Trace. 14.... .05 20.... 2.20 22.... .01 20.... .02 16.... .02 21 ... . .10 27.... Trace. 21.... 24.... .20 .67 17.... 18.... .70 Trace. 28.... 29.... .53 .01 6.10 26.... 29.... 30.... .22 .47 .32 !9.... 22.... 27.... .58 .01 .22 '3.17 30.... .11 Aug. 1 Trace. 3.94 30.... Trace. 15 1 5 12 3.38 13.26 3.... 4 .60 1.20 4.84 13.84 5.... Trace. 50 BULLETIN 1027, U. S. DEPARTMENT OF AGRICULTURE. Table 16. — Precipitation reports for sections where samples analyzed were harvested — Continued. SPRINGFIELD, W. VA., SECTION. Date. Precipita- tion. Date. Precipita- tion. Date. Precipita- tion. Date. Precipita- tion. 1915. Inches. 1915. Inches. 1916. Inches. 1916. Inchis. May 3.... 0.21 June 1 Trace. May 2.... 0.06 June 3 0.3S 7.... .15 2.... 1.46 3.... .13 7.... .30 12.... .75 ^ 3.... .05 4.... .07 8.... .31 16.... 1.05 * ■?.... .21 7.... .38 9.... .20 17.... .20 11.... Trace. 8.... Trace. 10.... .27 20.... .21 13.... .37 13.... Trace. 15.... .32 21.... .03 14.... .34 16.... 1.02 16.... 1.36 22.... .57 16.... .06 23.... .42 19.... .12 24.... Trace. 22.... .06 26.... .13 21.... .31 29.... .42 26. . . . .06 29.... .30 25.... .30 30.... 31.... .67 .05 30.... .35 30. . . . .50 3.87 13.86 2.96 1 3 gg 3.01 1 3 gg 4 31 1 3 69 Aug. 3.... 6.... 7.... .32 1.05 Trace. Aug. 1.... 2.... .10 1.05 July 2. . . . 10.... .31 .23 July 4.... .35 5.... .13 3.... 1.10 12.... .05 8.... .10 8.... .17 8.... .30 13.... .15 11.... .11 11.... .79 9.... .18 14.... .20 13.... .34 12.... .14 11.... .15 16.... .32 15.... .14 15.... .07 12.... .13 17.... .21 21.... Trace. 16.... .05 17.... .40 18.... .23 22.... Trace. 19.... Trace. 21 ... . .42 21.... .40 28.... .60 20.... 21.... 22. . . . 25.... .15 .08 Trace. .75 27. . . . 28.... Trace. 1.75 25.... .60 ■ 2.66 13.88 2.70 13.57 5.58 29.... .64 13.88 3.32 13.57 FORT VALLEY, GA., SECTION. 1917. Apr. 2 4 5 8 13 14 22 26 0.62 Trace. 2.23 .33 Trace. .23 Trace. Trace. 1917. May 12 23 25 28 June 4 10.... 14.... 15.... 22.... 23.... 24.... Trace. .8.> Trace. .63 1917. June 25. . . . 26.... 27.... 29.... 30.... .July 4 5 6 H. ..'.'.'. 12 Trace. Trace. Trace. .20 .10 1917. July 14 16 17 18 19 20..... 21 22 23 24 25 26 27 Trace. .18 Trace. .53 .23 1.03 .10 Trace. Trace. 1.56 Trace. .10 Trace. 2.91 13.11 1.34 14.21 Trace . Trace. 0.10 .50 Trace. 0.44 Trace. May 4 5. .... . 7 8 11 3.41 14.28 0.30 .61 .45 0.10 Trace. 0.96 .10 Trace. Trace. Trace. Trace. 4.79 '5.87 WENATCHEE, WASH., SECTION. 1916 Mav5.. " 6.. 7.. 8.. 9.. 16.. 20.. 24.. 29.. 30.. 1 Normal. 0.09 .02 Trace. .10 Trace. .01 Trace. Trace. .01 .05 1916. May 31. June 3 18 20 22 23 0.04 Trace. Trace. .17 Trace. .32 1916. June 24. 25. 26. 27. 28. 29. 30. 0.06 Trace. .17 .22 .06 Trace. .01 1.04 1.96 1916. July 2.. 8.. 15.. 16.. 27.. 0.99 Trace. Trace. .52 Trace. 1.51 1.38 POISONOUS METALS ON SPRAYED FRUITS AND VEGETABLES. 51 Table 16. — Precipitation reports foi sections where samples analyzed were harvested- Continued. HART, MICH., SECTION. Precipita- tion. Inches. 0.75 Trace. .15 .27 1.27 .30 .18 .06 .28 .05 .07 .45 3.83 13.76 .70 .58 Date. 1916. Junes. 9. 14. 17. 18. 23. 26. 30. July 8 "13 16 20 22 25 Precipita- tion. Inches. 0.72 .28 .95 .45 .04 .25 Trace. .97 4.94 ■2.39 Trace. .15 2.27 .53 .04 .27 Date. 1916. July 31.. Aug. 3 4 5 6 10 13 26 30 Sept. 5. Precipita- tion. Inches. Trace. 3.26 2.92 .85 .13 .53 .10 .16 .10 .38 .25 2.50 1 2.42 .97 Date. 1916 Sept. 7. 12. 13. 14. 15. 16. 17. 21. 22. 26. 27. 28. Precipita- tion. Inches. 0.65 .05 .14 Trace. .04 .18 .14 .17 .07 .16 .40 .14 3.11 13.00 CAMDEN, N. J., SECTION. 1915. 1915. 1915. 1915. July 1 0.19 July 21 0.20 Aug. 7.... Trace. Sept. 7.... Trace. 2 .53 23 Trace. 8.,.. 1.05 12.... 0.08 3 Trace. 26 Trace. 9.... .20 17.... .29 4 .08 27 .28 12.... .53 18.... Trace - 5 Trace. 29 1.00 13.... .01 19.... .09 7 Trace. 30 .01 15.... .05 .21.... .40 8 11 12 14 .67 Trace. .64 .35 Trace. Trace. .07 .03 26.... Trace. 4.62 '4.30 21 ... . 25.... 28.... .86 13.74 15 Trace. Aug. 1.... .13 , 29.... 1.05 16 .27 2.... .02 1 .30.... .74 17 .15 3.... .32 18 Trace. 4.... 2.10 6.61 19 .25 5.... Trace. 14.59 20 Trace. 6.... .31 ARLINGTON, VA., SECTION. 1916. 1916. 1916. 1916. July 2 0.01 Aug. 4 0.13 Sept. 6.... 0.06 Oct. 6 Trace. 3 Trace. 6.... 1.46 / Trace. 9 0.03 9 .34 8.... .17 8.... .31 10 .01 10 .73 9.... Trace. 9.... Trace. 13 .09 15 .04 13.... .19 14.... Trace. 15 .02 16 Trace. 16.... .30 15.... 1.17 16 .04 17 .03 23.... .05 18.... .18 17 Trace. 19 .09 27 .45 22.... .46 18 .05 20 Trace. 28.... .08 23.... Trace. 19 1.24 22 1.67 30.... Trace. 29.... .38 20 .02 24 25 .15 1.85 31 .26 2.83 2.57 26 28 .02 .04 14.40 13.59 1.76 13.09 Sept. 2.... .01 Oct. 5 Trace. 4.97 • 14.65 SALEM, N. J., SECTION. 1.60 .34 .48 .02 1.80 .05 .90 .05 5.24 1 4.43 1916. Aug. 1.. 8.. 11.. 13.. 14.. 27.. 28.. 0.05 .30 .18 Trace. .08 .42 .20 1.23 14.74 1910. Sept. 2. 6. 7. Trace. 0.20 .22 .37 .32 1916. Sept. 19. 29., 0.20 .52 1.83 13. 81 » Normal. 52 BULLETIN 1027^ U, S. DEPARTMENT OF AGRICULTLTRe. Table 16. — Precipitat'on reports for sections where samples analyzed were hnrvested- Oontinued . NORTH LIBERT"i ', IND., SECTION. Date. Precipita- tion. Date. r Precipita- tion. Date. Precipita- tion. Date. Precipita- tion. 1915. Aug. 2...... 3 Inches. 0.70 .23 .05 .01 .02 .40 1.49 .04 .08 Trace. .09 1.31 .12 1915. Sept. 7.... 10.... 11.... 12.... 16.... 17.... 18.... 20.... 26.... 27.... Oct. 1 4 8 9 13 Inches. 0.01 .22 .02 Trace. .74 .35 .32 ..54 1.12 .09 1915. Oct. 17 18 1917. Sept. 2.... 5 6.... 7.... 8.... 14.... 20.... 27.... Oct. 3 Inches. 0.03 .10 1917. Oct. 4 5 10 11 12 13 14 17 18 19 21 23 26 27 29 30 31..... Inches. Trace. 0.13 5 6. . . 1.86 12.42 .11 .06 11 12 13 16 17 .04 Trace. .69 . 55 Trace. .05 .10 .04 Trace. .03 1.23 1.20 .29 20 21 24 4.21 13.03 .07 .38 .63 4.54 13.26 .10 .56 .13 .40 .54 .14 1.47 13.03 .06 Sept. 4 Trace. .25 .55 Trace. o 6.... .15 5.31 12.42 PLYMOUTH, IND., SECTION. 1916. July 2 12 13 14 19 Trace. 0.05 .51 .02 .41 1916. Aug. 7 10.... U.... 15.... 16.... 18.... 27.... 0.15 .04 1.55 Trace. .02 .27 .32 1916. Sept. 1.... 4 5.... 6.... 13.... 17.... Trace. 0.19 2.01 1.09 Trace. Trace. 1916. Sept. 26 27.... 28.... 0.02 1.73 .18 5.22 1 3. 27 .99 13.38 2.73 13.49 Aug. 4.... .38 EAST WAREHAM, MASS., SECTION. Date. 1916. June 4. July 3 4. 5, 10. 14. 17. 18. 21. 23. 24. 26. 27. 31. Precipita- tion. 0.40 .18 .96 .27 .19 .67 .18 .68 .27 Trace. .35 .65 .37 5.17 12.68 .78 .08 .12 1.33 .52 .15 .10 .78 4.13 .15 .49 .16 .21 9.00 "3.10 1916. Aug. 8.. 9.. 10.. 12.. 13.. 24.. 26.. 27.. Precipita- tion. 0.47 .24 .60 .17 .29 Trace. Trace. .20 .22 1916. Oct. 21.. 26.. 2.19 1 3. 25 Sept. 6.. 7.. 9.. 15.. 16.. 19.. 23.. 25.. 30.. Oct. 9. 13 17 18 20 .12 .71 Trace. .12 .50 .07 .10 .13 .05 .67 2.47 13.56 .09 .27 .11 Trace. 1.72 1917. June 2. 6. 11. 12. 13. 16. 17. 24. 27. 29. July 1 4 12 13 15 19 27 Precipita- tion. 0.39 .27 2.85 1 4.18 Date. 1917. Aug. 3. 5. .28 2.00 1.42 .05 .62 1.69 .23 .15 .13 6.65 12.68 Trace. .52 .22 Trace. .08 .18 1.23 2.23 13.10 10... 16... 17... 21... 23... 24... 25... 29... 30... Sept. 8... 18... 20... 24..., 28... 30.... Precipita- tion. 0.06 .03 .07 .43 .38 .95 .10 .07 .03 .44 .04 .70 3.30 13.26 .18 1.87 .24 .02 .44 .10 2.85 '3.56 25.02 14. 18 ' Normal. » Total; daily data not reported. POISONOUS METALS ON SPRAYED FEUITS AND VEGETABLES. 53 Table IQ.—Precipitntion reports for sections where samples analyzed were harvested — Continued . NORTH EAST, PA., SECTION. Date. Precipita- tion. Date. Precipita- tion. Date. Precipita- tion. Date. Precipita- tion. 1915. Inches. 1915. Inches. 1915. Inches. 1916. Inches. Julvl Trace. Aug. 22.... 0.33 Oct. 18 0.15 Sept. 1.... 0. 16 2 0.03 24.... .81 19 .02 4 .11 3 .65 28 .21 21 Trace. 5.... .16 4 .12 29.... .03 28 Trace. 7. . . . 1.61 5 .19 30.... Trace. 29 Trace. 8.... .81 .19 14.... .32 8 1.24 9.28 1 2.21 1 15.... .01 11 12 15 .81 .Mi .13 1 3. 26 j 13. 80 16.... ; 17.... 18.... .01 .06 .01 Sept. 4 Trace. 1916. 16 .18 5.... .05 July 2 .32 21.... .13 17 .04 6.... .36 3 Trace. 22.... .18 19 .08 8.... .07 4 Trace. 23.... .16 21 .09 10.... .01 13 .02 26.... Trace . 25 .19 12.... .31 16 .01 2S.... .59 26 .02 13-... .50 IS Trace. 29.... .15 28 .32 15.... 1.49 19 Trace. 30 Trace. 17 .15 20 Trace. 4.47 31 Trace. 18.... .55 25 Trace. 13.49 19.... 21.... Trace. .11 31 04 5.14 Oct. 9 .17 13.21 24.... .01 .39 13 1.00 26.... .58 13.21 16 .23 Aiii;. 2.... Trace. 17 .05 3.... 5.40 4.19 Aug. 3.... Trace . 19 .67 4 .38 13.49 4.... .03 20 .26 5.... .19 5.... .54 21 .07 7. .02 Oct. 1 .38 ■S .71 22 .08 8 .01 2 .04 11.... Trace. 25 .08 9.... .04 4 Trace. 13.. .. .49 28 .06 11 Trace. 5 .10 16.... Trace. 27 .01 12.... .66 6 Trace. 22.... .17 31 .20 .29 7 Trace . 23.... Trace. i 14.... .07 8 .20 26.... Trace. 2.88 15.... .24 9 .28 27.... .75 '3.80 .04 13 Trace. 20.... .02 14 1.04 2.69 21.... ..M 15 Trace. 13.26 1 SANDUSKY, OHIO, SECTION. 1916. 1916. 1916. 1917 June 2.... 0.43 .A.ug. 3... Trace. Oct. 8 0.07 June 19 ■ n.ii 3.... .12 4... 0.03 9.... .11 21 Trace. 4 . . .29 5... .02 12.... Trace. 22 .12 6 ... .28 8... .48 13.... .28 23 .22 7.... .72 11... .81 16.... .07 26 Trace. 8.... .01 16... .15 18.... .11 28 .18 9.... .34 .28 19... 22... Trace. .67 19.... 20.... .42 29 • 01 16.... .81 27... .liJ 21.... Trace. 4.21 Trace. 24.... 25.... Trace. .01 1 3. 82 2.28 19.... .01 Trace. .57 .17 27.... 31.... Trace. .02 July 7 9 10 11 ... 1 .08 20.... 21.... 24 Sept. 2... Trace. ...1 .01 4... Trace. 1.24 ! .03 26.... Trace. .08 5... Trace. .63 1 2. 43 ! 12 13 14 16 17 21 26 • OS 09 8 14... 17... 21... 22... 23... 26... 27... 28... .12 . 05 Trace. .01 .03 Trace. .20 .09 .90 1917. June 2 5 6 9.... 10.... 2.33 .66 .08 Trace. : Trace. 4.36 ■3.82 ...J -12 ...i Trace. 1 .05 July 2.... .03 Trace. Trace. 13.... 20.... .11 .12 12.... 13.... 14.... 15.... Trace. .14 Trace. .28 Aug. 2 .46 13.79 .26 2.03 .01 13.79 i I 2. 68 16.... .01 5 .20 17.... Trace. 7 .12 1 Normal. 54 BULLETIISr 1027, U. S. DEPARTMENT OF AGRICULTUKE, Table 16. — Precipitation reports for sections ivhere samples analyzed were harvested.- Continued. SANDUSKY, OHIO, SECTION^Continued. Date. Precipita- tion. Date. Precipita- tion. Date. Precipita- tion. Date. Precipita- tion. 1917. .\ug. 8.... 9.... 13.... 16.... 20.... Inches. 0.07 Trace. .54 .38 Trace. .01 .03 1.79 Trace. Trace. .50 .30 .04 1917. Sept. 2.... 5.... 6.... 7.... 20.... 27.... 29.... 30.... Inches. 0.02 .03 .73 .23 Trace. 1.31 .02 Trace. 1917 Oct. 2 3 4 5 7 8 11 12 14 17 18 19 22 23 24 26 Inches. 0.03 .67 .08 .05 Trace. Trace. .02 .72 Trace. Trace. .63 .85 .04 .54 Trace. .18 1917. Oct. 27.... 28.... 29.... 30.... 31.... Inches. .24 0.44 1.19 .06 .03 22.... 23.... 25.... 27.... 28.... 29.... 30.... 6.22 12.43 2.34 12.68 3.99 13.37 MOORESTOWN AND BROWN MILLS, N. J., SECTIONS. 1915 Apr. 3. 4. 6. 11. 21. 23. 27. 28. 29. 30. May 4 5 9 12 13 16 17 21 22 23 24 25 26 30 June 2 3 4 12 13 15 16 17 22 23 26 28 0.69 .17 .03 .73 Trace. Trace. .07 .10 .55 .50 2.84 1 3.19 .39 .69 .64 .36 .42 .07 .26 .70 1.50 .15 .17 .02 .06 .34 5.77 14.03 .63 .14 .04 .14 1.55 .44 .43 .03 .45 .17 .09 Trnce. 4.11 1 3.80 1915 luly 1 2 5 8 12 14 16 17 19 21 27 29 31 Aug. 1 3 4 6 8 9 12 15 25 28 29 30 Sept. 12. 18. 19. 21. 26. Oct. 1 5 7 8 14 0.03 .37 .40 1.04 .73 ..53 .97 .33 .35 .10 .33 .64 .06 5. SS 1 4.58 .19 .27 2.11 .21 .20 .37 .47 04 .04 Trace. 1.05 5.75 1 4.74 .06 .12 .13 .38 Trace. 1 3.76 .44 .26 .28 Trace. .65 Tnce. 191. '. Oct. 15 16 27 1916 May 4. 5. 7. 9. 14. 16. 17. 18. 23. 24. 25. 29. June 4 5 8 13 16 17 19 20 21 25 0.14 .20 .40 2.37 '3.64 .03 .39 .21 .43 Trace. .35 .19 .03 ..59 .02 1.05 .03 3. 32 14.03 .10 .17 1.40 .15 .42 .14 .06 .23 .40 .26 .45 3.' i3.i 1916 July 10. 14. 15. 17. 20. 21. 22. 23' 25. 26. Aug. 8 12 16 24 28 Sept. 6 7 8 15 19 29 30 Oct. 13. 19. 1 Normal. POISONOUS METALS ON SPRAYED FFtUITS AND VEGETABLES. 55 Table 16. — Precipitation reports for sections where samples analyzed tvere harvested — Continued. ROSEWELL, N. MEX., SECTION. Date. 1915. Apr. 1. 6. 7. 8. 9. 10. 13. U. 15. 16. 17. 18. 19. 21. 22. 23. 24. 25. 29. May June 9. 10. 15. 23. 25. 26. 27. Precipita- tion. Inches. Trace. 0.01 .06 Trace. Trace. .17 .27 .01 1.44 3.48 .23 .01 .02 Trace. Trace. Trace. .09 .02 .23 6.04 I .49 .04 .93 Trace. .01 .02 .18 1.18 I 1. 17 .06 .01 Trace. .06 .01 Trace. Trace. .14 12.08 Date. 1915. July 3. Aug. 7. Sept. 2. 4. 14. 16. 18. 21. 22. 23. 24. Precipita- tion. Inches. Trace. Trace. Trace. 0.04 .12 .13 .01 .01 .02 .01 Trace. .10 .01 .45 Trace. .28 .03 .23 .01 .48 .01 .08 .01 Trace. Trace. .52 .09 .03 1.77 1 1.46 .09 .01 .01 .08 .01 .03 .22 .01 .73 Date. 1915. Sept. 25. 29. Oct. 1916. Apr. 12. 13. 14. 25. 26. 30. Mav 1 June 8. 12. 19. 24. July 4. 6. Precipita- tion. Inches. 0.39 .71 2.29 12.29 .09 .01 Trace. .02 .12 11.52 1.11 1 .49 .17 11.17 Trace. .44 Trace. Trace. .44 12.08 Trace. .68 .05 Trace. .04 Trace. .01 .15 Date. 1916. July 20. 27. 28. 29. Aug. 7. 8. 16. 17. 18. 19. 20. 21. 22. 23. 27. 30. Sept. 2. 4. 10. 12. 19. 30. Oct. 10. 11. 12. 13. 14. 16. 27. Precipita- tion. Inches. Trace. 0.01 .02 .08 1.04 13.46 1.00 4.57 .27 .32 .06 1.07 .30 .01 .52 1.39 .05 Trace. 9.. 56 11.46 .01 Trace. Trace. .30 .06 Trace. .37 1 2. 29 .01 .05 2.31 1 1. 52 BENTON HARBOK, MICH., SECTION. 1915. Mav 2. 3. 4. Trace. O.fiO Trace. Trace. .15 .45 ..50 Trace. .22 .32 Trace. Trace. .30 .50 .10 Trace. .90 .60 .20 4.84 1 3.89 191' June ■; July 4. 0.09 Trace. Trace. .24 .12 Trace. .47 .08 .07 Trace. .04 .08 .25 .02 1.46 12.95 .63 1.20 .90 ..20 1.17 1915. Aug. 16. 21. 24. Sept. Trace. 0.61 .21 5.21 1 2. 23 .20 1.12 .06 .19 .70 Trace. .40 .40 .60 1.15 Trace. 1.23 Trace. fi705 1 3. Oil 'Normal. 56 BULLETIN 1027, LT. s. DEPARTMENT OF AGEICULTURE. Table 16. — Precipitation reports for sections ivhcrc sdinples analyzed were harvested- Continued. BENTON HARBOR, MICH., SECTION— Continued. Date. Precipita- tion. Date. Precipita- tion. Date. Precipita- tion. Date. Precipita- tion. 1915. Oct. 4...- X.... 9 13.... Inches. 0.3o Trace. .70 Trace. .25 . 30- .22 .20 1916. May 29.... 30. . . . June 2.... 3.... 6 S 9 14.... 16 IS.... 20. . . . 21 23.... 24.... 26.... 30.... Inches. 1.06 . .30 1916. July 16 28.... Aug. 3.... 5 Indies. 0.12 .39 1916. Sept. 13.... 22.... 26.... 27.... 28.... 29.... Oct. 9.... 13.... 15 20.... 21.... 26'.;;; 29 Inches. 0.30 .40 .04 . 68 .15 .38 7.01 1 3. 89 .51 .2. .52 18 19.... .23 .03 .10 1.05 .49 .04 .61 1 .06 . 05 .02 .37 .12 .27 ..52 .05 .80 3. 57 ' 3. 06 1.97 1 2. 76 10..-.' .69 11...., .50 24 Trono .15 .10 Trace. 1.25 .45 .12 Trace. Trace. 1911). May ti X 10.... 13.... 14.... 15.... 19.... 21.... 22.... 26.... 2S .10 . IX . 50 .40 , ■ ^^ \ .70 .70 j .30 .70 1 .70 ' .SO 26.... 28.... .26 .20 Sept. 4.... 5 . . . . 12;;;; 2.92 1 2. 28 .20 1.20 .20 .02 2.07 I 2. 76 4.01 ' 2. 95 (;R.\Xr) JUNCTION, COI>0., SECTION. 1915. 19!5. 1916. 1916. May 2 1.23 Sei)t. 2 Trace. July 16 Trace. Oct. 1 O.OS 2 .92 3 0.05 17 Trace. 3 .10 4 .04 Trace. 20 23 4 .27 .06. June 1 .20 Trace. 3 .03 8 .02 24 Trace. 6 .05 4 .08 13 Trace. 25 . .■!3 7 .51 5 .40 24 .03 26 .07 9 Trace. 6 .19 2.5 .81 I 27 .11 10 .51 9 IS Trace. .02 2M 29 01 11 14 .03 .37 .95 I .02 28 Trace. ' . 95 30 Trace. 15 IS .06. .08 .92 Oct. 14 Trace, i .76 ' .40 15 .01 i ' ..50 2.12 1 .91 July 5 .02 .01 Aug. 3 .73 12 Trace. ' .91 4 Trace. 26 27 .01 Trace. .10 .13 1917. May 1 1916. 6 Trace. 28 Tra"e. May 2 Trace. 8 Trace. 2 .02- 29 .13 13 Trace. 9 Trace. 4 .01 18 Trace. 12 .60 5 AS. . 16 lu .26 13 .25 7 .01 ' . 50 20 .78 15 Trace. 8 Trace. 21 22 .01 i Trace. 16 26 9 .\ug. 5 Trace. 20 Trace. 12 .12 6 Tra-e. 2'> .08 15 04 7 .25 1.05 30 .01 20 .07 11 Trace. ' .92 21 .11 Trace. 1 2.16 22 .24 15 16 22 . 05 Tra"e. .01 i Jiuie 5 IX Tra-e. Trace. .' 1. 04 23 25 .01 04 Sept. 2 Trace. 26 OS- 23 .0,t Trace. ;) .21 27 .01 24 .Ot 1 .40 8 .01 28 .01 2.5 26 .01 .01 0- 29 .08 July 5 Trace. 17 Trace. 30 .15 29 Trace. 6 Trace. 20 22 23 .01 Tra"e 31 .32 .51 9 Trace. 1 45 1 1.04 14 15 .01 .01 ..50 ' . 95 1.92 ' Normal. roiso:xoiTs metals ox sprayed fruits and vegetables. 57 Taisle 16. — -Prccipiiatinn reports for sections v'here savijiles analyzed were harvested — Continued. (iRAND JUNCTION, COLO., SECTKJN— Continued. Date. Precipita- tion. 1917. ! Inches. Juno 1 ; Trace. 4 0.01 10 Trace. 21 , Trace. July 5. 6. 10. 20. 24. 25. 26. .01 > .40 Trace. Trace. Trace. Trace. Trace. Trace. Trace. Date. 1917. July 28.. ■ 29.. 30.. Aug. 4. 9. 10. 12. 13. 14. 17. 18. Precipita- tion. Inches. Trace. 0.07 .21 Trace. Trace. .09 .02 .22 Trace. Trace. .01 Date. I Precipita- tion. 1917. Aug. 26. 27. 28. 31. Sept. Inches. 0.01 Trace. .03 Trace. I 1.04 Trace. .01 Trace. .04 .01 .01 .64 Date. I Precipita- tion. 1917. Sept. 12. 22. 23. 25. 30. Inches. 0.15 .10 .02 .02 Trace. 1.00 1 .95 Trace. Trace. Trace. Trace. 1.91 GREENWOOD, VA., SECTION. 1917. Apr. 5.... 8.... 13 IS 21.... 24.... 25.... 27 28.... 2.33 ..30 .44 Trace. .08 .05 .12 .06 .43 1917. June 1 5.".".! 9 10 11 12.... 14.... 15.... 20.... 23.... 25.... 26 27.... 28 Julv 2 3 s'.'.'.'.'. 10 11 14 15 0.43 .27 .03 1.40 .22 .03 .01 .38 .01 .12 .64 .18 .02 .38 1.37 1917. July 16.. 17.. 18.. 21.. 22.. 24.. 25.. 26.. 0.16 .14 .01 .05 .07 .35 .48 .10 1917. Sept. 2.... 6.... 7 8.... 9.... 15.... 16.... 21.... 27.... O.Oo .23 .58 .36 .04 .19 .05 .01 3.78 14.89 . 1 i 3.81 13.22 2.28 14. 18 .46 .01 1.08 2.21 .01 Trace. .13 2.80 .73 .60 .08 May 1 4 7 8 11 .03 .78 .38 .13 Trace. .02 Trace. .65 .68 9.. 14.. 15.. 16.. 23.. 24.. 30.. 31 5.49 15.48 26 27 28 .36 .07 .28 .81 .75 .13 .02 Trace. 2.67 14.62 8.11 15.00 YAKIMA, WASH., SECTION. 1919 Mav 4. 5. 11. 15. 16. 25. June 9. 10. 11. 13. 0.04 .18 Trace. .03 Trace. .33 .58 1 .83 Trace. Trace. Trace. .04 .04 1919 July 5. 6. 10. 11. 23. 31. Aug. 3. 30. 31. Trace. Trace. .03 Trace. Trace. Trace. .03 1 .25 Trace. Trace. .08 1.12 1919. Sept. 4. 5. 6. 8. 10. 11. 12. 27. 28. 30. Trace. 0.05 .01 .09 Trace. .44 .01 .02 .01 .06 .69 1 .48 1919 Ocl. 1. 17. 21. 22. 23. 26. 31. 0.12 Trace. Trace. Trace. Trace. Trace. Trace. .12 .51 1 Normal. 58 BULLETIN 1027, U. S. DEPARTMENT OF AGRICULTURE. SUMMARY. The amounts of arsenic, lead, and copper remaining on mature fruits and vegetables which have been sprayed according to various schedules were determined in the Bureau of Chemistry. Table 15 gives the maximum and minimum results. Because of overspraying or late spraying, comparatively large quantities of spray residues were found in some cases. This em- phasizes the importance of spraying according to the schedules rec- ommended by the Bureaus of Entomology and Plant Industry. The extent of the reduction of spray residues on the mature fruit and vegetables by washing and wiping them was determined by a series of analyses before and after such treatment . When peeled, sprayed fruits and vegetables contain essentially the same amounts of arsenic, lead, and copper as the unsprayed products, indicating that practically all of the spray residues can be removed b}^ peeling. From the results reported in this bulletin it is evident that when fruits and vegetables are sprayed in accordance with the schedules recommended by the Bureaus of Entomology and Plant Industry, but little of the material used remains on the fruit or vegetable at har- vest time. LITERATURE CITED. (1) Academy op Medicine (France). Proc. Acad. Med., Feb. 18, 1908. Bull. acad. med., 3 ser., 59 (1908): 246. (2) Proc. Acad. Med., Feb. 2, 1909. Bull. acad. med., 3 ser.. 61 (1909): 194. (3) Sur un projet de decret portant modification de I'ordonnance de 1846 relative a la vente des substances veneneuses. Bull. acad. med., 3 ser., 70 (1913): 152. (4) ' Proc. Acad. Med., Nov. 11, 1913. Bull. acad. med., 3 ser., 70 (1913): 368, 369. (5) . . Proc. Acad. Med., Mar. 3, 1914. Bull. acad. med.. 3 ser., 71 (1914): 324. 325, 326. (6) Alwood, W. B. Treatment of diseases of the grape. Va. Agr. Exp. Sta. Bull. 15 (1892): 41. (7) Ampola, G., and Tommasi, G. I composti di arsenico in agricoltura. Ann. staz. chim. agrar. sper. Roma, 2 ser., 5 (1911): 241; J. See. Chem. Ind., 31 (1912): 891; Chem. Abst., 7 (1913): 1255; Exp. Sta. Rec, 30 (1914): 130. (8) Andouard, a. Le cuivre dans les vins provenant de \dgnes traitees par le sulfate de cuivre. Compt. rend., 104 (1887): 195; Bull. soc. nat. agr. (France), 47 (1887): 40; J. pharm. chim., 5 ser., 15 (1887): 290. POISONOUS METALS ON SPEAYED FRUITS AND VEGETABLES. 59 (9) Anonymous. Spraying fruitsjfor insect pests and fungous diseases. TJ. S. Dept. Agr., Farmers' Bull. 7 (1892): 17-20. (10) Fruit spraying. J. Roy. Hort. Soc, 18 (1895): 185. (11) Baker, J. L. A resume of the report minutes of evidence and appendices of the Royal Commission on Arsenical Poisoning. J. Soc. Chem. Ind., 23 (1904): 168. (12) Beach, S. A. Some celery diseases. N. Y. Agr. Exp. Sta. Bull. 51, n. ser. (1893): 146; Exp. Sta. Rec, 4 (1892-93): 926. (13) Bedini, R. I sali arsenicali in frutticultura. L'istria agricola, 3 at. (1910): 538. (14) Bertin-Sans, H., and Ros, V. L'emploi de I'arsenic en agiiculture ses dangers. Rev. hyg. pol. sanit., 29 yr. (1907): 193. (15) A propos de 1' utilisation des composes arsenicaux en agriculture. Rev. hyg. pol. sanit., 30 >t. (1908): 281; Exp. Sta. Rec, 20 (1908-09): 459. (16) BOUFFARD, M. La presence du cuivre metallique dans les vins provenant des \dgnes traitees au sulfate de cuivre. Bull, ministere agr. 8 (1887): 832. (17) Breteau, p. Sur la teneur en arsenic des vins provenant de vignes traitees par les com- poses de I'arsenic. J. pharm. chim., 6 ser., 28 (1908): 154; Chem. Abst., 2 (1908): 3257. (18) Brioux and Griffon. Les traitements arsenicaux en arboriculture fruitiere. Bull. soc. nat. agr. (France), 70(1910): 864. (19) Carles, P. A propos du cuivre dans les tomates. Repert. pharm., 3 ser., 28 (1917): 193; Rev. sci., 55 yr. (1917): 183; Chem. Abst., 12 (1918): 192; Exp. Sta. Rec, 37(1917): 263. (20) and Barthe, L. Recherche de I'arsenic de plomb dans des vins, des lies et des p^pins provenant de vignes traitees a I'arseniate de plomb. Bull, soc chim., 4 ser., 11 (1912): 413; Chem. Abst., 6 (1912): 1805; Exp. Sta. Rec, 27 (1912): 243. (21)^Cazeneuve, p. Sur les dangers^de l'emploi des insecticides a base arsenicale en agriculture au point de vue de I'hygiene publique. Bull acad. med., 3 ser., 69 (1908): 133, 234. (22) Proc Acad. Med., Nov. 18, 1913. Bull. acad. med., 3 ser., 70 (1913): 415. (23) Chuard, E.^ Observations concernant le mecanisme de 1' introduction et de I'^limina- tion du cuivre dans les vins provenant de vignes traitees par les com- binaisons cuivriques. Compt. rend., 105 (1887): 1196. (24) Pr&ence et I'^limination de I'arsenic des \ans. Trav. chim. alim. hyg. bur. sanit. fed., 1, (1910): 82. 60 BULLETIN- 1027, U. S. DEPARTMENT OF AGRICULTURE. (25) COMBONI, E. Chemische Untersuchiingen iiber die Weine aus Trauben, die mit kupfer- haltigen Schutzmitteln gegen die Peronospora behandelt worden waren. Nuova Rassegna Vitic, 2: 209; through Chem. Centr., 3 ser., 19 yr. (1888): 875. (26) Cook. A. J. Two new uses of important insecticides. Proc. 29 Meeting Am. Assoc. Adv. Sci. (1880) : 669. (27) — Experiments with insecticides. Proc. 2 Ann. Meeting Soc. Prom. Agr. Sci. (1881) : 112. (28) Crola.s and Raulin. Traitement de la vigne par les sels de cuivre contre le mildew. Compt. rend., 103 (1886) : 1068; J. pharm. chim., 5 ser., 15 (1887) :156. (29) CuGiNi, G. Ueber die Bekampfung der Peronospora Viticula und den Einfluss der Mittel auf die Zusammensetzung des Mostes und Weines. Nat. Bot. Kongr. Parma, 1 (1887): 5', through Chem. Centr., 3 ser., 19 yr. (1888) : 532, (30) Davis. G. C. Celery insects. Mich. Agr. Exp. Sta. Bull. 102 (1893) :44. (31) DucLAUx, E. Sur le dosage de tres petites quantites de cuivre et la presence de ce metal dans les cacaos et chocolats. Bull. soc. chim. 16 (1871) : 33. (32) DUOUET ET AL. Proc. Acad. Med., June 28, 1910. Bull. acad. med., 3 ser., 63 (1910) :657. (33) Proc. Acad. Med.. Mar. 7, 1911. Bull. acad. med., 3 ser., 65 (1911) :346. (34) : Proc. Acad. Med., July 11, 1911. Bull. acad. med., 3 ser., 66 (1911) : 59. (35) DupRE, A. On copper in food. Analyst, 2 (1878) : 1. (36) Fallot, B. Le cuivre dans les vins. Prog. agr. vit., June 16, 1889; through U. S. Dept. Agr., Div. Bot. Bull. 11 (1890) :96. (37) Fetel, p. De la teneur en arsenic des raisins d'Algerie et en particulier des raisins provenant des vignes ayant subi des traitements aux sels arsenicaux. Bull. agr. Algerie et Tunisie, 16 (1910) : 430; Exp. Sta. Rec, 25 (1911) :40. (38) Fletcher, J. The results of an experiment to prove that apples are not poisoned by spraying with Paris green for codling moth. Can. Exp. Farms Rpt. for 1891, p. 189; Exp. Sta. Rec, 4 (1892-93) :437. (39) Forbes, S. A. Spraying apples for the plum curculio. 111. Agr. Exp. Sta. Bull. 108 (1906) :279; Exp. Sta. Rec. 18 (1906-7) : 160. (40) FoRBusH, E. H. On the work of extermination of the gypsy moth. Mass. Bd. Agr. 41, Ann. Rpt. (1893): 282. (41) Frechou. Le black-rot et les vins des vignes traitees. J. agr. (Barral), 24 yr. (1889): 649. POISONOUS METALS ON SPRAYED FRUITS AND VEGETABLES. 61 (42) Fruhauf, T., aud Ursic, G. Die Bestimmung sehr geringer Mengen Kupfer. Bol. soc. Adriatica sc. nat. Trieste, 10:103; through Chem. Centr., 3 ser., 19 yr. (1888): 198; Staz. sper. agrar. ital. (1888): 704; through J. Soc. Chem. Ind., 8 (1889) : 206. (43) Galippe. Sur la presence du cuivre dans les cereales, la farina, le pain et diverees autre substances alimentaires. Compt. rend. soc. biol., 7 ser., 4 (1882): 726; Rev. hyg. pol. sanit., 5 yr. (1883) : 23. (44) Sur la presence du cuivre dans le cacao et dans le chocolat. J. pharm. chim., 5 ser., 7 (1883) :505; Rupert, pharm., n. ser., 11 (1883) :267. (45)-, Le sulfate de cuivre et le mildew. J. pharm. chim., 5 ser., 16 (1887) :430. (46) Galloway, B. T. The grape scare in New York. U. S. Dept. Agr. Ann. Rpt. for 1891, p. 375. (47) and Fairchild, D. G. Copper on the fruit at the time of harvest. U. S. Dept. Agr., Div. Veg. Path. Jour. Mycol., 6 (1891) : 94. (48) Garino, E. Determination of arsenic in wine made from grapes that had been sub- jected to cuproarsenical treatment. Ann. accad. agr. Torino, 56 (1914): 78; Ann. chim. applicata, 3 : 148; through Chem. Abst., 9 (1915) : 1526. (49) Garman, H. Spraving for codling moth. Ky. Agr. Exp. Sta. Bull. 53 (1894) : 125. (50) ^ The use of arsenites on tobacco. Ky. Agr. Exp. Sta. Bull. 53 (1894) : 142. (51) Insects injurious to cabbage. Ky. Agr. Exp. Sta. Bull. 114 (1904). (52) Gautier, a. Sur I'emploi des arsenicaux en agriculture. Bull. acad. med., 3 ser., 69 (1908) : 229. (53) Proc. Acad. Med., Nov. 11, 1913. Bull. acad. med., 3 ser., 70 (1913) : 370. (54) Proc. Acad. Med., Mar. 3, 1914. Bull. acad. med., 3 ser., 71 (1914) :300. (55) and Clausmann, P. Origines alimentaires de I'arsenic normal chez I'homme. Compt. rend., 139 (1904) : 101; Exp. Sta. Rec, 16 (1904-05) : 489. (56) Gayon, U., and Millardet, A. Le cuivre dans la recolte des vignes soumises a divers procedes de traite- ment du mildew par les composes cuivreux. Compt. rend., 103 (1886): 1240; J. pharm. chim., 5 ser., 16 (1SS7) : 153. (57) GiBBS, H. D., and James, C. C. On the occurrence of arsenic in wine. J. Am. Chem. Soc, 27 (1905) : 1484. (58) Gillette, C. P. Experiments with arsenites. Iowa Agr. Exp. Sta. Bull. 10 (1890) :410. (59) _ Notes and experiments upon injurious insects and insecticides. Iowa Agr. Exp. Sta. Bull. 12 (1891) : 536. (60) GtJNTHER, A. Ergebnisse der amtlichen Weinstatistik, Berichtsjahr 1908-1909. Arb. Kais. Gesundh., 35 (1910) :1; Exp. Sta. Rec. 24 (1911) : 267. 62 BULLETIN 102':, U. S. DEPARTMENT OF AGRICULTURE. (61) Heide. C. Von der. Analytische Befunde von Mosten iind Weinen aus Trauben der mit Blei- arseniat bespritzten Reben. Ber. Kgl. Lehranst. Wein-, Obst- u. Gar- tenbaii, Geisenheim (1906): 228; Chem. Abst., 3 (1909) :2338. (62) Hoffmann, M. Ein Beitrag zur Translokation des Kupfers beim Keltern gekupferter Trauben. Centr. Bakt. Parasitenk, part 2, 4 (1898) : 369, 422. (63) Howard, L. O. Progress in economic entomology. U. S.Dept. Agr. 1899 Yearbook, p. 146. (64) Kedzte, R. C. Influence of Paris green on the potato. Michigan Farmer, .June G. 1872. (65)— The use of poisons in agriculture. Mich. Bd. Health. 3 Ann. Rpt. (^1875):11. (66) — Mineral residues in sprayed fruits. Mich. Agr. Exp. Sta. Bull. 101 (1893): 19; Exp. Sta. Rec, 5 (1893-94) : 793. (67) Kilgore, B. W. On the cause and prevention of the injury to foliage by arsenites, together with a new and cheap arsenite, and experiments on combining arsenites with some fungicides. N. C. Agr. Exp. Sta. Bull. 77-b (1891) : 7. (68) Kinney, L. F. Leaf blight of the pear. R. I. Agr. Exp. Sta. Bull. 27 (1894); Exp. Sta. Rec, 5 (1893-94) : 986. (69) KRtJGER, F. Ueber den Einfluss von Kupfervitriol auf die Vergiirung von Traubenmost durch Saccharomyces ellipsoideus. Centr. Bakt. Parasitenk, part 2, 1 (1895): 64. (70) Le Baron, W. Second annual report on the noxious insects of the State of Illinois (1872), p. 116. (71) Lehmann, K. B. Hvgienische Studien iiber Kupfer. Arch. Hyg., 24 (1895) : 18. (72) ' Hygienische Studien iiber Kupfer. Arch. Hyg., 27 (1896): 1; Analyst, 21 (1896): 290. (73) Hygienische Studien uber Kupfer. Arch. Hyg., 30 (1897): 250. (74) LiBERi, G., Cusmano, A., Marsiglia, T., and Zay, C. The presence of copper in tomatoes and tomato preserves. Ann. staz. chim. agrar. sper. Roma, ser. 2, 8 (1916): 163; through Bull. Agr. Intelli- gence, 7 yr. (1916): 662, and Chem. Abst., 11 (1917): 1701. (75) Lodeman, E. G. The spraying of plants (1896), p. 64, 65. 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(131) Wheeler, H. J. Grapes sprayed with Bordeaux. R. I. Agr. Exp. Sta. 4 Ann. Rjit. (1892): 84; Exp. Sta. Rec, 4 (1892-93): 242. (132) Wheeler, .1. H. Some pests and diseases of the vine, with remedies. Ri)t. 6 Ann. Calif. State Vit. Conven. (1888): 63. (133) Woods, C. D. Analyses for poison of apples sprayed with arsenate of lead in mid-summer. Maine Agr. Exp. Sta. Bull. 224 (1914): 46; Exp. Sta. Re<'., 31 (19Hi: 141; Chem. Ahst.. 9 (1915): 503. (134) Zecchini and R.wizza. Copper in wine. Staz. sper. agrar. ital. 16 (1889): 73; throv(j]i J. Soc. Chem. Ind., 8 (1889): 910. ADDITIONAL COPIES OF THIS PUBLICATION MAY BE PROCURED FROM THE SUPERINTENDENT OF DOCUMENTS GOVERNMENT PRINTING OFFICE WASHINGTON, D. C. AT 10 CENTS PER COPY k » LIBRARY OF CONGRESS m llllir'jiHiiij "I Ml I 'I li'iHiii I ;; CI PICIC^ ftPCTl ts,C)'? 9