LIBRARY STATE PLANT BOARft May 1944 URITED STATES DEPARTMENT OF AGPJCuLTURE Agricultural Research Administration Eureau of Entomology and Plant Quarantine METHYL BROMIDE A REVIEW OR LS AR IRSECT RUMIGRRT-- LITEPATURE THROUGH 1940 E-618 By R. L. Busbey, Division of Insecticide Investigations Properties of Methyl Bromide Methyl bromide (CHjBr) as used in fumigation is a colorless gas with a slight sweetish odor similar to that of ether low-molecular- v/eight alRyl halides. It has the following physical constants: Molecular weight — — — — — 94.95 Boiling point — — i& .---. ,-- 3 56° C. Melting point -—-08 93.66° C, Specific gravity oV, iquid 1.732 °/0 ° C. Specific grivity oi as -- 3.28 at 20° C. and 760 mm. compared with air under the same conditions It is very slight^ soluble in -water and with cold water forms a white crystalline hydrate of the approximate formula CR3Br.20 HoO, It is soluble in the common organic solvents. It is noninflammable and in mixture with air can be exploded by a spark only within the narrow range of 13.5 to 14.5 percent by volume of methyl bromide. This compound has been used for years by the chemical industry as a methylating agent in the preparation of dyes and antipyrine. It has been employed to some extent as a fire-extinguishing a^ent, either alone or mixed with other materials such as carbon tetrachloride. It has found limited use also as a refrigerati -.;nt in mechanical re- fri gerators. The insecticidal possibilities of methyl bromide were first report- er 1 \)\r Le Goupil (63) in 1952. Since that time it has been tested ex- tensively and is now widely used in the fumigation of nursery sto< , fruits, seeds, bulbs, stored grain, arid vegetables to destroy certain insects against which quarantines have been estal , I has a] so been used tc some extent a? nhouse . Durin - 1! probably 400,000 pounds of 1 bromide were used as an insecticidal fumigant in the united States. An important use also is as a rodonti- cide. Methyl bromide possesses a nv i ' nt. It is highly toxic to many kinds of all stares of • ~t. It is stable chemically and in the con- ions use' has no deleter- ious effect on most plant tissues. It ' s no objectionable taste or odor to foodstuffs fumigated vdth it and 1< -ous residue. It is convenient to handle, since it is readily liquefied and yet vapor- izes at temperatures encountered in fVunigat: . It is the onl; on -2- fumigant which is a gas at room temperature and normal a tano spheric 'pres- sure, It presents no fire or explosion hazard. Because of the great density of the gas, it is necessary to provide .means for mixing it adequately with the air. Like other fumigants highly toxic tc insects, methyl bromide is also toxic to nan, and adequate precautions must be taken in its use. Irish and coworkers ( 53 ) stated in 1940 that the literature records 4-2 definite cases of methyl bromide poisoning, of which 12 proved fatal. It v/as earlier believed that the toxic action ras due to splitting of the methyl bromide in the body to form methanol and inorganic bromide, and that the methanol caused the poisoning,, It now appears, however, that methyl bromide exerts a toxic action of its own. It is more toxic than any of the closely related halides, such as methyl chloride and ethyl bromide. It has a delayed effect, the symptoms often not appear- ing until hours, or even a day or more, after exposure „ In mild ca.scs the usual symptoms are disturbance of equilibrium, double- vision, head- ache, and vertigo. In acute cases delirium, loss of consciousness, epi- leptiform convulsions and sometimes death occur. After recovery from severe poisoning there may be persistent neurasthenia for years. Biblioj The. references on methyl bromiVe -presented in this publication have been collected for the benefit of entomologists and others inter- ested in the control of pests by chemical means. Only references to the insecticide], use of the compound and to its toxicity to man and animals have been included, except for a few patents or articles giv- ing directions for the preparation of methyl bromide or for its deter- mination in air or fumigated materials. They have been obtained mainly from the following abstract journals through 1940: Chemical Abstracts, Review of Applied Entomology (A), Biological Abstracts, Chemisches Zcntralblatt, and Quarterly Cumulative Index Medicus. ArTOMMOUS. (1) Organic halogen compounds. [Gt, Brit.] Dcpt. Sci, and Indus. Res., •Methods for the Detection of Toxic Gases in Industry, Leaflet 12, 6 pp. 1940. Injuries from breathing industrial vapors containing a number of organic halogen compounds, including methyl bromide, arc discus- sod, and the procedure for detecting them is described. The only simple method is the use of a 'halide detector lamp which burns pure ethyl alcohol and causes the decomposition of the various compounds. The halogen reacts with a small copper screw in the nozzle of the lamp to form copper halide, which imparts a green' coloration to the flame j the degree of coloration depends upon the nature of the or- ganic halide and upon its concentration in the air. Directions for handling the lamp, carrying out the tests, and interpreting the results arc given. An experienced operator is needed, and he mil have to get accustomed to the surroundings before he is certain of getting accurate results. The lamp cannot be used whon inflammable 'a present. -3- ASLER, Hi J. (2) Einc todlichc Brommcthylvcrgiftung. Zcntbl. f. Oewerbc Hyg, u. Unfallvcrhutung (n.f". ) 4: 161. 1927. A fatal case cf poisoning by methyl bromide is reported, -bout 16 hours intervened after the exposure before the onset of symptoms with convulsions. BACHHI, C. (3) Bcitrag zur Toxikologio dor Halogenalfeyle . Arch. f. Expt. Path, u. Pharmakol. 122: 69-76. 1927. Several reports of cases of methyl bromide poisoning are re- viewed. Experiments arc described in which mice wore exposed to the vapors. A concentration of 0.001 mole per liter caused death in 75 minutes, and 0.000017 to 0.000136 mole per liter killed the mice within a few hours. In the narcosis the mice often reacted to strong tactile irritation (pinching); sporadically increased reflex excitability and indications of convulsions also occurred. A concentration of 0.000008 mole per liter in the course of many hours caused deep narcosis, which, however, was followed by rapid and lasting recovery. BEERY, C. E. (4) Methyl bromide as a rodenticide. Calif. Dcpt. Agr., Monthly 3ul. 27: 172-130. 1938. Methyl bromide is effective in the control of rodents as well as the insects harbored by them. It can be used in wet or dry soils and at various temperatures. Although the cost is high, it can be used where follow-up or eradication methods arc being carried on and around buildings where there is danger in using treated grain baits. It should be used only under proper supervision even by official agencies having a trained personnel, and should not be made available for general use until further safeguards have been developed. BEYNE and G-OETT. (5) Toxicitc" dc certains cxtinctcurs d'incendic ct pro'oautions qu'ils comportont. Arch, de Med. ct dc Pharm. IJav. 124: 409-427. 1934. The toxicity of methyl bromide is briefly reviewed. Experi- ments with rabbits and dogs are described. A concentration o^ 36 mg. per liter for 25 minutes was fatal to a rabbit. Dogs died after exposure to 10 to 21 mg. per liter for 30 to 33 minutes. BIMG, D. (6) [Methyl bromide poisoning.] Schwciz. Rundschau f. Med. 1910: 1167. [in German.] Two nonfatal cases are reported in which residual symptoms con- tinued for 3 and 7 mont] 5. -he symptoms include trcr.icr, dizzi- ness, vomiting, and muscular debility, with some transitory psychic changes. -4— BOULIN, C, and SUION, L. J. (7) Preparation of methyl chloride and methyl bromide from dimethyl sulfate. [Paris] Acad, des Sci. Compt, Rend. 170: 595-597. 1920. [In French,] In the presence of hydrochloric acid, water hydrolyzcs dimethyl sulfate to give, in part, methyl sulfuric acid and methyl chloride. With 3 parts of hydrochloric acid (22° Be'.) and 1 part of water 90 percent or more of practically pure methyl chloride results. A saturated solution of sodium chloride works nearly as well, but the solution should be warmed to 60°-65° C. to start the reaction. Hy- drobromic acid gives a similar reaction, but aqueous sodium bromide, slightly acidified with sulfuric acid, is preferred, giving (at 30°- 35° C.) methyl bromide in 90 percent yield. Methyl bromide is very soluble in glacial acetic acid (42 gm. per 100 gm, of acetic acid at 24° C.). These methods are recommended for laboratory prepara- tions, BUSBEY, R. L., and DRAKE*, N. L. (8) Determination of small quantities of methyl bromide in air. Indus. and Sngin. Chcm. , Analyt. Ed. 10: 390-392. 1938. The method proposed is for determining the methyl bromide con- tent of fumigated air. The sample of air is subjected to the sapon- ifying effect of potassium hydroxide in alcohol, for which purpose a special apparatus has been devised. The alcohol is finally re- moved by distillation, the bromide oxidized to bromatc hy sodium hypochlorite, and the bromatc determined iodomctrically, BYGDEN, A. (9) Preparation of methyl bromide. Jour, f . Prakt. Chcm. 83: 421-424. 1911, [in German,] Methyl bromide is obtained in 83-84 percent yield (as against 44,5 percent by the bromine and phosphorus method) by adding 450 gm. of methyl alcohol to GOO gm. of sulfuric acid, adding gradually 230 gm. of water and 300 gm. of powdered potassium bromide to the cold mixture, and heating until gas ceases to be evolved. (10) Preparation of methyl bromide. Jour. f. Prakt. Chcm. 104: 285- 288. 1922. [in Gorman.] Sulfuric acid (95 percent) is first diluted with water, the methyl alcohol is slowly added with cooling, followed by pulver- ized potassium bromide, and the flask with reflux condenser is slightly warmed. The evolved gases arc passed through water or sodium hydroxide to remove hydrobromic acid and then through two bottles of concentrated sulfuric acid. Methyl bromide is then con- densed in an ioc-sali bath. The yield varied between 93,5 and 97.3 percent, depending on the proportion of methyl alcohol to the other reactants. — ■ — " ■— -5- CADE, A., and IIaZEL, P* ^ (11) Intoxication par In bromurc do mcthyle. Soc. Med. des Hop. Paris, Bui. ct Mom, 47 (3): 722-727. '1923^ A rather sovcrc nonfatal case of poisoning by methyl brcmido is reported, in which symptoms persisted for 2 months. Another patient suffered from methyl bromide poisoning on four occasions in 27 years. CAIN, C. A. (12) A methyl bromide dispenser for use in the fumigation of quarantined products. U. S. Bur. Ent. and Plant Quar. ET-156, 4 pp. 1940. [Processed. ] A device is described for dispensing accurately measured small quantities of methyl bromide from a pressure cylinder. CAMERON, G. P., KaPITNAPATNE, W. A. E. , and TEOMAS, Jo C. (13) Massive necrosis (toxic infarction) of the liver following intra- portal administration of poisons. Jour. Path, and Bact. 44: 297-303. 1937. Many organic poisons, including methyl bromide, when intro- duced directly into the portal circulation, produce strong local necrosis. The result is due, not to embolism or ischemia, but to the direct action of the poison on the liver cells. The condition may be designated as "toxic infarction." CRAO-LUN TSENG, and CHIA-SHU HOIT. (14) Preparation of alkyl bromides by the phosphorus bromide method. I. Chinese Chem. Soc. Jour. 2: 57-72. * 1934. Parallel experiments with methyl and several other alcohols show that with theoretical amounts of ohosphorus tribromide the yield of alkyl bromide is 10 percent higher than with theoretical amounts of red phosphorus plus bromine. CHAPMAN, P. J. ' (15) Effect of methyl bromide on apple maggots in apples. (Scientific Note) Jour. Econ. Ent. 33: 817. 1940. Picked and windfall Wealthy apples were fumigated with 1, 2, and- 4 pounds of methyl bromide per 1,000 cubic feet for 1, 2, and 4 hours. The picked apples contained first and second in stars and the dropped fruit contained mainly second and third instars of Rhagoletis pononella (Walsh). All treatments gave complete kills except 1 pound of methyl bromide for 1 hour, which gave 91,2 percent control for picked fruit and 91,9 percent for dropped fruit. Injury to fruit occurred with the 2-pound dosage for 4 hours and with the 4— pound dosage for 2 and 4 hours. ■ -6- CERISTIE, F. R., and COBB, G. S. (16) The inefficacy of methyl bromide fumigation against the chrysan- themum foliar nematode [Aphelenchoides ritzemabosi (Schwartz 1911)]. Eelminthol. Soc* "iVaslT. Prac. 7: 62 ^ 1940. Fumigation with methyl "bromide did not eliminate this nema- tode even r.hen the chrysanthemum plants were treated under the most severe conditions- that they were likely to tolerate, namely, fumigation with 5 pounds of methyl bromide per 1,000 cubic feet for 1,5 hours at 70° F. under 15 inches of sustained vacuum. It is likely that such treatment will also be ineffective against the strawherry bud nematode ( Aph e 1 en c h o i d e_s fragariae Ritzema Bos, 1891). DER0BERT, L. (17) L T intoxication prof essionelle par le bromure de methyls. Gaz. He'd, de Strasbourg 99: 179-184. 1939. A review giving sources of intoxication and literature on toxicity of methyl bromide. DEUTSCHE GESELLSCRAFT FUR SCIAJXINGSBEKAHPFUNG m. b . ' E. (18) Insecticides. French Patent 835,883, Jan, 5, 1939, f An insecticide is described consisting of a liquid of rela- tively high boiling point (e.g., alcohols, aromatic and aliphatic hydrocarbons, esters, and ketones) and an insecticidal substance of low boiling point (e.g., methyl bromide, chloroc^anide, ethylene oxide, dimethyl amino, methyl mercaptan, and phosgene). The liquids may be absorbed in diatomite. D0N0H0E, H. C, JOHNSON, A. C, and BULGER, J. W, (19) Methyl bromide fumigation for Japanese beetle control. Jour. Econ. Ent. 33: 296-302. 1940. Complete mortality of the adult beetles is obtained by doses of 2 pounds of methyl bromide per 1,000 cubic feet for 2 hours at 18,3°-32.2° C. One pound per 1,000 cubic feet suffices at 24,4°- 32°, and 0.75 pound at 25°-30°. A method for treating refrigerator cars is described. and JOHNSON, V. ... (20) The effect on plants of methyl bromide fumigation in Japanese beetle treatment tests; preliminary report. U. S. Bur. Ent. and Plant Quar. E-482, 14 pp. 1939. [Processed.] Complete control of immature stages of the beetle in green- house and nursery stock was obtained by fumigating the plants with methyl bromide (2.5 pounds per 1,000 cubic feet, including the load) for 2„5 hours at a minimum 'soil and air temperature of 63° F. In tests of 187 genora of plants representing 503 horticultural varieties and unnamed entries, 6,6 percent showed injury or sus- pected injury sufficient to render the plants unsalable. Injury was most coivmon (12 percent) among growing greenhouse plants. Among the dormant and semidomant plants only 3,2 percent were injured. DOTY C HEKICAL C 01 IPA NY. ( 2 1 ) Dor: and Boar brand nethyl bromide. . .Ed. 3, 23 po. Midland, llich. 1939. This trade booklet sets forth the advantages of nethyl bro- mide as a fumigant and discusses methods of application under var- ious conditions. DOZISR, K. L. (22) Studios of control measures for sweetpotato weevil in Louisiana. Jour. Econ. Bit. 32: 315-318. 1939. Methyl bromide was the quickest acting and most effective fumigant tested for the control of Cylas formicarius elogantulus (Summers) in seed sveetpotatoes. A dosage of 5 cc. to 50 cubic feot gave complete kill of all stages in 12 hours at C8° F. DUDLEY, E. C. (23) Bromide content of fruits and vegetables following fumigation with methyl bromide. Indus, and Engin. Chen., Analyt. Ed. 11: 259-261. 1939. In samples of 50 to 100 gm. the methyl bromide is converted to potassium bromide by 1 percent alcoholic potassium hydroxide. This is ignited three times at 500° C„ and extracted with hot water* A chromic acid solution is added, and the bromine liberated is aspirated into 10 percent potassium iodide. The liberated iodine is then titrated worth standard 0.01 H sodium thio sulfate. KILLER, J. W., HEAL, P. A., and SHYERS, P. P.. (24) Studies on foodstuffs fumigated with methyl bromide. U. S. Pub. Health Serv. Rpts. 55: 2251-2282. 1940. The amount of methyl bromide (determined as brcnine) absorbed by fruits and vegetables during fumigation was found to bo several times the normal bromide content. In most cases the fumigated ma- terial showed a drop in bromides after aeration. Dried fruits, fresh fruits, and vegetables absorbed minor quantities of the fumi- gant. The foodstuffs which absorb greater amounts of the fumigant include milled grains, cheese, .nuts, and nut meats. The adsorptivo capacity of milled grains is due primarily to their greater surface area, -while the oily and fatty food absorb large quantities of methyl bromide because of its solubility in fats. Rats and rabbits were fed on diets consisting entirely of fumigated foodstuffs, all of which contained more methyl bromide than is found in similar foodstuffs fumigated by methods approximating commercial procedures. The results indicate that it is unlikely that tl. all amount of methyl bromide or bromide residues on commercially ;'; tf 3d fresh vegetables and fruits, or 'ied fruits, is harmful be the con- sumer. A bibliography lists 87 references to methyl bromide, a large part of them on its toxicoloi dustai, g. g. STATE PLANTcS9ARl> ■ The effects of temperature and ci als on choose mites. Ent. Soc. Ontario, Ann. Ppt. 63: 60-67. 1938. In experimental fumigation of chocs':- In an airtight room in which an electric fan was kept running, a complete kill of Tyroglyph'us farinae Deg., including the eggs, wa/s obtained with a mixture of 6.3 percent of methyl bromide and 93.2 percent of carbon dioxide at rentes from 8 to 20 pounds per 1,000 cubic feet and at temperatures from 58° to 63° F. An unpleasant taste, which extended to about 1/4 inch below unwaxed and exposed parts of the surface of the cheese, completely disappeared after expo- sure to the air for 38 to 48 hours. Animals were apparently not affected by feeding on cheese 24 hours after fumigation. DbTOIR, M., FABRE, R. , and LiiXilll, F. (26) Poisoning Vith methyl bromide. Soc Med, des H6p. Paris, Bui. et Mem. 53: 1540-1554. 1937. [in French.] (Also in Bui. Sci. Pharmacol. 46: 15-26. 1939.) Dogs kept in an atmosphere containing 35 to 43 mg. of methyl bromide per liter went into narcosis and died shortly after. The bromine could be detected in the organs, especially in those rich in lipoids. The pathologic picture points to a vasomotor crisis. Efforts to counteract this effect with vasoconstrictor substances, especially adrenaline, were not successful. Glutathione is sug- gested as a stabilizer of the vasomotor system, EASTER, S. S. (27) Fumigation of sweetpotatoos with methyl bromide for control of the sweetpotato weevil-. Jour. Econ. Ent. 33: 921-926. 1940. Methyl bromide is extremely toxic to Cylas formicarius e lega ntulus (Summers), killing the insects even when they are deeply imbedded in the sweetpotatoos. It produces a deleterious effect on the sweetpotatoos, which may result in considerable loss. Careful handling, partial curing, and postfumigation heating of the sweetpotatoos will partially avoid this loss. FEIL, A. / (28) L' intoxication prof cssionello par 1c bromurc dc methyl c. Scmaine d' Hop. Paris 6: 599-601. 1930. The symptoms, diagnosis, and treatment of methyl bromide poisoning arc discussed. FISK, : F, % , and SEEPARD, ' H." H. ( 29 ) Laboratory studies of -methyl bromide as an insect fumigant. Jour, Econ. Ent. 31: ' 79-84. ' 1938. Methyl bromide is a promising new fumigant with boiling point (4,5° C.) lower than that of other fumigants. Its toxicity to in- sects compares favorably with that of hydrocyanic acid gas, chloro- picrin, and ethylene oxido. The granary weevil (Sitophilus granaria (1.)), the rice weevil (S. oryza (L.)), and the bean weevil (Acanthosc elides cbteotus (Say) j are about equally susceptible to methyl bromide, the concentration for 50 percent mortality after 5 hours ranging from 4.0 to 6.1 mg, per liter. The adult confused flour beetle (Tribolium coxifusum Duv. ) requires 10.2 mg, per liter for 50 percent mortality; its eggs arc less resistant. Degree of absorption of the gases was determined by suspending a cage of test insects (Tribolium) above a 2-inch layer of vholc-whcat flour in I —9- the fumigation chamber. The ratio of the median lethal concentra- tion (M.L.C.) with flour to that without flour equals the absorp- tion ratio, which is 2. The M.L.C. of methyl bromide for Tribolium after GO minutes' exposure at 25° ir. the presence of various food- stuffs and at various pressures follows: (l) Atmospheric pressure: empty flask 32.5, raisins 28.1, wheat 30.4, flour 50.0; (2) 240-mm. pressure: Empty flask 16.8, •wheat 17.2, flour 34.0; (3) 30-mm. pressure: Empty flask 11.4, raisins 12.6, wheat 14.2, flour 26,0. The toxicity of methyl bromide is affected by temperature about as much an is that of carbon disulfide and less than that of chloro- picrin. Methyl bromide is more effective on insects in the pres- ence of moisture. The germination of corn, wheat, oats, barley, beans, and field pea seeds is not affected by fumigation with methyl bromide. FLORET. (30) TQinischer Beitrag zur gewerblichen Brcmmethylvergiftung. Zentbl. f. Gewerbe Hyg. und Unfallverhutung. 3: 146-1497 1915. Three nonfatal cases cf poisoning by methyl bromide are re- ported. A period of 4 to 6 weeks was required for recovery. Clinically, three stages were observed in the course of the ill- ness: (l) Prodromal stage with dizziness, visual disturbances, disturbance of equilibrium, reeling gait; (2) stage of psychic ex- citement with delirium, delusions, convulsions, unconsciousness, coma; (3) appearance of nervous weakness (hypochondria, melan- cholia, hystero-neurasthenia), which may last for years. FLURY, F., and ZANGGSR, K. (31) Lehrbuch der Toxikologie fur Studium und Praxis, 500 pp. Berlin. 1928. Symptoms of methyl bromide poisoning are briefly reviewed. There is o. typical interval of several hours or days before the onset of severe symptoms (p. 206), and ZERBHC, P. (32) Schadliche Case, Dampfe, Ilebel, Pauch-und Staubarten. 637 pp. Berlin. 1931. The action of methyl bromide as a nerve poiscn is probably duo tc decomposition to form methyl alcohol or formaldehyde (pp. 309-310) MC0LINI, J. DE. (33) L'emploi du bromure de methyle pour le traitoment des graines do semenoe. Rev. de Path. Veg. et d'Ent. ;.gr. de France 22: 1-8. 1935. In experiments in Lorocco in February 1934, 100 percent mor- tality of all stages of Si tophilus cryz a (L.) and of a small num- ber of S. granarir (L.) infesi g obtained by exposure to methyl bromide at the rate of 2 ounces per 100 cubic feet at 19.5° C. At first the weevil .ctivc, but activi' gradually diminished until after about 6 hours all movement ceased. In further tests 100 percent mortality of th Lts of S. oryza was obtained with the same amount of fumigant by exposin i 2 hours in glass tubes closed with muslin under bell jars at 22° C, -10- though some of the weevils did not die until the next day. All larvae within the grains were killed "by 24 hours' exposure to 1 ounce per 100 cubic feet at 21° C. Even at the rate of 5 l/2 ounces to 100 cubic feet for 24 hours, methyl bromide only slight- ly reduced the germinating power of wheat and other cereals. (34) Action sur les produits vege'taux du bromure de methyl e en fumiga- tion sous vide partiel. Rev. de Path. Veg et d'Ent. Agr. de France 22: 9-12. 1935. Tests were carried out in Morocco to determine the action of methyl bromide on various fruits, vegetables, and plants exposed to 6-7 ounces per 100 cubic feet for an hour at 22°-26° C. A par- tial vacuum wa's maintained for 20 minutes, after which the pres- sure was brought back to normal, and the products were ventilated for 10 minutes after fumigation. Bananas became soft and black- ened, pears became soft without showing outward change, and pota- toes became brown and slightly soft, but none of the other fruits or vegetables were affected. Of 25 plants the only ones injured were Fuchsia , Ire sine, and Zant cd e s c hia , the leaves of which withered and dropped 48 hours after exposure. Susceptibility to methyl bromide appears to be related to the water content of the plant or fruit, A series of tests showed that the hydrobromic acid given off by methyl bromide in a saturated atmosphere does not exceed 2 parts per 1,000 if the fumigation is of normal duration. FRIEMANN, W. (35) Beruflichc, tddlichc Brommethyl-Vorgif tung, Samml . Vcrgiftungs- fallcn 8: 31-32, 1937. A further report is made on a case of methyl bromide poison- ing first reported by Opperman ('see reference 95), in which there were repeated epileptiform attacks for 2 years, and even after 4 years there was some nystagmus and feeling of discomfort. Two new cases are reported, of which one was fatal. Both men were exposed at the same .time, but the one who died had been exposed repeatedly previously. GERBALDI, C. (36) Methyl bromide as an insecticide. Rev, Fruttic, 3: 281-283. 1939, [In Italian.] All the larvae of (Cydia) Grap holitha mojh^sta (Busck) and Carpocapsa pomon clla (L.") in pears exposed to 15 gm. of methyl bromide per cubic meter for 18 hours were killed. No injury to the fruit from methyl bromide was observed. In French crab apples, however, the type of injury described by Phillips and coworkers (100) was found. GL..SER, E. (37) Zur Kcnntnis dor gewcrblichen Bronmicthylvergiftungon. Dout, Ztschr. f. die Gcsam. Gerichtl. Mod. 12: 470-474. 1928. A fatal case of methyl bromide poisoning is reported. There was an interval after exposure before the onset of any symptoms. -11- The patient then soon lost consciousness and died within a few hours. The concentration of methyl bromide in the air to which workers are exposed should not exceed 1.9 mg. in 100 liters. and FRISCH, S. (38) The effect of technically and hygienically important gases and vapors upon the organism. Brominated hydrocarbons of the ali- phatic scries. Aroh. f. Hyg. 101: 48-64. 1929. [in German.] Subcutaneous injection showed that tctrabromocthane is six times, dibromcthane four times, and methyl bromide seven times as toxic as ethyl bromide. The toxic action of the vapors of dibromo- cthanc and methyl bromide is eight times greater than that of ethyl hromide vapor. The inhalation of tctrabromocthane vapor is without toxic result. Because of its greater volatility, the danger attend- ing the use of ethyl bromide is more than twice as great as that ettending the use of the more toxic dibromo ethane. Methyl bromide is still mere dangerous, and great caution should be observed in its use. The inhalation of subnarcotic doecs of dibromocthanc and methyl bromide may eventually result in death. The animals appear to tolerate large concentrations of the compounds for a short time better than ] or/or concentrations for longer periods. GOLDS CHMID, E. , and KUHN, E. (39) Brommethylvergif tung mit tddlichem Ausgang. Zentbl. f. Gev/erbe Hyg. u. Unfallverhutung 8: 28-36. 1920. Nine cases of poisoning occurred in a dye factory following the bursting of a large vessel containing methyl bromide. There were three deaths, and these cases all follov/ed the same general course a short period of feeling unwell followed by sudden epi- leptiform convulsions, loss of consciousness, disturbances of breathing and, in a few hours, death. The six other cases com- plained consistently of vertigo, headache, general weakness, and disturbance of equilibrium. GRONOW, W. E. (40) Die i-nvrcndung chemischer Sonder-Nassfeuerldscher in den gewerblichen Betrieben unter dem Gesichtspunkte ihrer Einwirkung auf die Benutzer. Zentbl. f. C-eiYerbc Kyg. u. Unfallverhutung (n.f.) 4: 161-166. 1927. en used as a fire-extinguisher liquid, methyl bromide sho^s less tendency than carbon tetrachloride to for;. ' ful decomposi- tion products. As yet, robromic acid has been observed, which irritates the respiratory organs but possesses no toxic prop- erties. GUEFFROY, W. , and EHRHARDT, . ( :1 ) The halogenated hydrocarbons of the fatty series as solvents and their significance to the medic c. . Zentbl. „ v rbe Hyg. u. Unfallverhutung 25: 224-230. 1938. [in German.] These solvents as a class arc capable of producing acute poisoning and occasionally blood <• e. The lungs are the chief -12- portal of entry into the body. Absorption through the skin is pos- sible. Frequently, on long exposures the chloride and neutral sul- fur content cf the urine increases, as does the acidity. Danger from fire and explosions frequently exists. The specific proper- ties and actions of a number of these compounds, including methyl bromide, are discussed in detail. No specific medical prophylaxis for chronic poisoning by this class of compounds is known, HAMILTON, C. C. (42) Methyl bromide used successfully to fumigate plants in soil beds. Eort. Topics 3 (6): 11. 19 39. Experiments have shewn that emulsions made by adding 50 cc. of methyl bromide to 250 cc. of wood alcohol and diluting in 3 gal- lons of water will kill grubs of An or.-ala o riental i s Waterh. in azalea beds both in the greenhouse and outdoors. Examination made 7 days after treatment revealed that all the larvae were either dead or disabled, but the azalea plants were not injured. (43) Methyl bromide fumigation for control of asiatic beetle grubs attacking azalea plants. Jour. Icon. Ent. 33: 486-490. 1940. Fumigation of soil and azalea plants in raised benches and floor benches by confining methyl bromide under a fumigating box at the rate cf 1 cc. per square foot caused no injury to plants in spring tests and only slight leaf burn to one variety in fall tests Soil temperature ranged from 54° to 81° F„ A complete kill of grubs of Anomala crientalis 7/aterh. was obtained in all tests ex- cept those conducted when the soil temperature was 54° at a depth of 8 inches and 58° at 4 inches. Fumigation of soil by injecting at 6-inch intervals methyl bro- mide and methyl or ethyl alcohol (1:15) at a rate of 0.5 cc. of methyl bromide killed most of the grubs and caused little or no injur},' - to plants. 3y diluting this solution with water and sprink- ling ever the area to be treated, a nearly complete kill of the grubs could be obtained without injury to plants, when 1 cc. of methyl bromide per square foot was used; 0.5 or 0.75 cc. gave less than 50 percent kill. HAWINS, L. A. (44) Fumigation of dormant deciduous nursery stock for the oriental fruit moth rath methyl bromide. U. S, Bur. Ent. and Plant Quar. E-458, 3 pp. 1938. [Processed.] Control of the immature stages of C-raph olitha molesta (Busck) on bare-root stock was obtained by fumigation at the rate of 3.5 pounds per 1,000 cubic feet for 4 hours at 70° F. . (45) The use of methyl bromide for the treatment of quarantined plant products. U. S. Bur. Ent. end Plant Quar. E-484, 6 pp. 1939. [Processed. ] Results are 'given of experiments for the control of various insects in green vegetables, sweotpotatoes, bulbs, potted plants, greenhouse stock, nursery stock, and other plant products. — ■— -13- (46) Fumigation cf vetch seed to control the vetch bruchid. U. S. Bur. Eat. and Plant Quar. 2-492, 2 pp. 1939. [Processed.] Bruchus "brachial is Fahr. in infested seed can be killed by fumigation at a dosage of 3 pounds per 1,000 cubic feet for 4 hours, at 70° F. There v.cs no appreciable lowering of the viability of the seed by this treatment. IIELLHOFF, E. (4?) [Cases of methyl bromide toxication.] Jnaug.-Diss. Berlin. 1924. Reference in article by L. LIcrzbach, Ztschr. f. die Gcsam. Expt. Med. 63: 363-592. 1928. HENDERSON, Y., and HaGGARD, H. W. (48) Kbxious gases and the principles of respiration influencing their action. 220 pp. New York, 1927. (Amor. Cher... Sec. Monograph Ho. 35.). The monohalogen compounds of methane methyl bromide, methyl iodide, and methyl chloride— — are reactive gases, for after absorp- tion by the body they are decomposed into methanol, :/hich is nearly nonreactive, and the halogen acid. The acid then combines v.dth the sodium of the blood to form the sodium halide. The marked cumu- lative effect of methanol and its destructive action upon the ner- vous system render these three methyl halides particularly poison- ous. They do not themselves accumulate in the body and reach an equilibrium preventing further absorption, as in the case of non- reactive gases, but they arc decomposed with the production of methanol. Consequently, methanol continues to accumulate in the body as long as the exposure persists. Thus severe poisoning by methanol results after prolonged exposure to concentrations of a methyl monohalide too small to exhibit the anesthetic action of the undecomposed substance. The symptoms are those of methanol poisoning. Their development may be slo-a and recovery delayed; there is usually intense excitement and even epileptiform con- vulsions. Gastric and intestinal disturbances, vomiting diarrhea, and pain may also occur (pp. 159-160). HOWARD, F. L. (49) Chloropicrin, steam, carbon disulfide and other treatments for injurious soil microorganisms. Veg. Grov/ers' Assoc. Amer. Ann, Rpt. 1939: 115-130. Methyl bromide is a powerful insecticide which it appears can be developed into an efficient soil ant for growing plants. I. G. FARBENINDUSTRIE A.-G. (50) Alkyl halides. German Patent 478,126, June 20, 1929. [in German.] Alkyl halides arc prepared by pi n aliphatic alcohol vapor with a hydrogen halide at an elevated 'ature over a catalyst comprising aotiv carbon and phosphoric acid. The examples describe the preparation of methyl chlor yl bromide, and propyl chloride. -14- — ~ (51) Alkyl halidcs. British Patent 375,199, June 23, 1932. Alkyl chlorides and bromides are obtained by action, in the liq- uid phase at temperatures exceeding 100° C c , of concentrated hydro- chloric or hydrobronic acid on the corresponding alcohol. The preparation of methyl bromide from methanol and 40 percent hydro- bromic acid is given as an example. INTERNATIONAL LABOUR OFFICE. (52) Occupation and health, v. 2, Geneve.. 1934. The chemistry, toxic action, pathology, and prophylaxis of methyl bromide are briefly reviewed (pp. 238-240). IRISH, D. D., ADAMS, S, M., SPENCER, H. C., and ROTiE, V, K. (53) The response attending exposure of laboratory animals to vapors of methyl bromide. Jour. Indus. Nyg. and Toxicol. 22: 218-250. 1940. Animals tolerate large doses for short oeriods of time. After long exposures severe lung irritation is observed. Animals succumb e ^bo single exposures of 12 to 24 hours at a concentration of 0.85 mg. per liter. Rats survived for a variable period (l to 3 weeks to 5 months or more) repeated exposures cf 7 l/2 to 8 hours daily to 0.42 mg. per liter, but they showed definite intox- ication and poor growth. Guinea pigs were more resistant, a majority surviving a full 6 months with nearly normal growth. Rabbits were more susceptible. When the concentration was lowered to 0.25 mg., it was tolerated by both rats and guinea pigs in re- peated exposures for 6 months. Monkeys tolerated 0,25 mg. for '5 weeks or more. Yftien the concentration was 0.13 mg. , rats, guinea pigs, and monkeys survived repeated exposures for 6 months without gross symptoms of histopathological changes. Rabbits survived re- peated exposures to 0.065 mg. for 6 months. Animals tolerated for a long period a daily 8-hour exposure to a concentration not far below the maximum tolerated for a single ex- posure of 8 hours. Rats and guinea pigs tolerated for 6 mouths approximately one quarter the maximum concentration when exposed for a single 8-hour period daily. This indicates the ability to destroy rapidly or excrete methyl bromide and recover quickly from each exposure. Animals exposed to concentrations and for periods sufficient to cause a definite paralysis were able to recover completely if removed from the chamber. Recovered animals showed no functional cr physiological abnormality. JAQUET, A. (54) Ueber Brommethylvergif tung. Dcut, Arch. f. Klin. Med. 71: 379-386. 1901. Two cases, neither fatal, of poisoning by methyl bromide are reported. The first symptoms were weakness and vertigo, visual disturbances, and dyspnea. In slight poisoning those seem to be the only symptoms . In more severe poisoning or in especially pre- disposed persons there may follow psychic disturbances, even reaching delirium. It is notable that the sovorc symptoms may -15- appear only after several days. Some residual neurasthenia was observed. A few experiments with animals are described. J0ACHH10GLU, G. (55) 'Toxikologischc Botrachtungcn ubcr einige moderne Fcucrloschmittcl. Dcut. Med. Wchnschr. 56: 785-787. 1930. Methyl bromide is much mere toxic than carbon tetrachloride. Concentrations as low as 0,00009 mole per liter were fatal to dogs upon prolonged exposure. The- animals displayed lung edema and finally died after severe dyspnea. JOHNSON, A, C. (56) A low-cost water seal fumigatcr. TJ. S„ Bur. Ent. and Plant Quar. ET-154, 2 pp., illus. '1940. [Processed.] Directions are given for the construction of a water-sealed fumigator from a 50-gallon oil drum. Carbon disulfide and methyl bromide have- been used in this fumi gator. JOHNSON, V, A. (57) Fumigating with hydrocyanic acid and methyl bromide. U. S. Patent 2,147,947, Feb. 21, 1939. For destroying living organisms such as Japanese beetles, 1 ounce of hydrogen cyanide and G ounces of methyl bromide are used per 1,000 cubic feet of space. Such a mixture has a mutual syner- gistic action. JONES, R. M. (58) Toxicity of methyl formate, ethylene oxide and methyl bromide, in admixture with carbon dioxide, to the rust-red flour beetle. Iowa State Col. Jour. Sci. 13: 73-74. 1938. The maximum insecticidal effects of methyl formate, ethylene oxide, and methyl bromide against Triboliu m castaneum (Hbst.) wore obtained with concentrations of 40, 60, and 20 percent, res- pectively, of carbon dioxide. Increase of carbon dioxide may de- crease the effectiveness. (59) the red flour beetle. Jour. Econ, Ent. 31: 298-309. 1938. Toxicity of funigant-carb n dioxide mixtures to the red flour The toxicity of methyl formate, methyl bromide, and ethylene oxide, alone and in mixture with various concentrations of carbon dioxide, was studied with Tribolium cas taneum (Hbst.) as test in- sect. The toxicity of these fumi gants may be markedly increased by the addition of ccrtaiii percentages of oarbon dioxide. The stimulative effect of carbon dioxide is considerably more pronounced with methyl formate and ethylene oxide than with methyl bromide. Maximum efficiency cf methyl formate, cthylonc oxide, and mothyl bromide is obtained with approximately 40, 20 and 10 percent cT car- bon dioxide, respectively. -16- KOHN-ABREST, E. (60) Precis dc toxicologic, 388 pp., illus. Paris. 1934. Methyl bromide is four times as toxic as carbon tetrachloride (p. 83). ' LANGE, W. H. , jr. (61) Tests with methyl bromide as a fumigant for larvae of the arti- - choke plume moth. Jour. Econ. Ent. 32: 66-69. 1940. Plat yptilia carduidactyla (Riley) is controlled with minimum plant injury by a dosage in vacuo of 1 pound per 1,000 cubic feet. The temperature should be 22.2° to 24.4° C. and the exposure 2 to 2.5 hours. Treatment at atmospheric pressure increases plant injury. LATTA, R. (62) Methyl bromide fumigation for destruction of pod-borer larvae. Jour. Eccn, Ent. 33: 176-179. 1940. Doses as lev.' as 0.5 pound per 1,000 cubic foot produced com- plete mortality of Maruca tcstulalis Gcycr, in 2 hours at tempera- tures above 21 ° C . at ~a!5mc spheric pressure, or in 90 minutes at a 15-inch vacuum. Low temperatures required higher doses. For com- mercial atmospheric fumigation 1.5 pounds per 1,000 cubic feet for 2 hours is advised (temperature 21°). Green lima beans, string beans, and pigeon peas arc not injured by doses necessary to kill the larvae of this insect. LE G0UPIL, (63) Les proprictc's insecticides du brcmure dc methyle. Rev. de Path. Vc'g. et d'Ent. Agr. dc France. 19: 169-172. 1932. In studies of vacuum fumigation with various substances, methyl bromide, which was originally used in combination with in- flammable liquid fumigant s to reduce the danger of fire, was fourld to possess a much higher specific toxicity than the fumigants with which it was mixed. Further tests were carried cut with methyl bromide alone and diluted in a liquid possessing slight insoctici- dal properties, such as carbon tetrachloride. Sitophilus granaria (L.) was chosen as the test insect on account of its resistance to insecticides. A few other species, notably Triboli um, wcro also used. The time cf exposure was 1 l/2 hours in every case, but tho dose ranged from 2 tc 13.5 ounces per 100 cubic foot. The insects were treated both isolated in vitro and buried in various types of commodities, in dry atmospheres as well as in varying degrees of moisture, in the presence of rags soaked in oil, and at tempera- tures from 15° to 26° C. With doses below 3.5 ounces some insects wore still alive when they wore withdrawn from the autoclave, but all succumbed within a few hours. Larvae, pupae, and adults still inside unsplit grains wore reached just as effectively as those developing between the grains, and it is probable that the eggs were also destroyed. lUcthyl bromide is toxic to man only in very largo doses, and since it is very volatile and soluble in v\ratcr, it is easily eliminated from fumigated commodities. It is uninflam- mable under all conditions and can be used to reduce the danger of -17- fire with such substances as ethylene :xide. Although its price is high, the snail quantities required render the cost of using it reasonable. It does not appear to affect the germinating power of cereals, but tests have not been carried far enough in this direc- tion to be conclusive. LEFESME, P. (64) The efficacy of methyl bromide in the disinfection of vegetables under partial vacuum. Acad. d'Agr. do France Compt. Rend. 24: 783-787. 1938. [in French.] ITinety-minute exposure to 40 gri. per cubic meter of methyl bromide under a partial vacuum of 50 mm. of mercury will completely destroy Sitophilus granaria (L.), _S. cryza (L.), P hizoperth a domin ica (?.), Tribolium castaneum (Ebst. ), C-nathccerus cornutus \V. ), Try z a e p h i Tus slfFina men s i s~~~HL"» ), Laemophl oeus spp . , 5ruchus~ signaticcrnis Oyll., and EpTiestia kuehniella Zell. This dose car- be lowered to 30 gm. in some cases. LEPIGRE, A. (65) The disinfection of grains with mixtures of ethylene oxide and carbon dioxide. Soc. d' Encouragement. pour Indus. Nat. Bui. 135: 385-462. 1936. [in French.] The use of methyl bromide as a fumigar.t for grain is discussed, It properties arc given end its action on man and higher animals is discussed, chiefly from the literature. The danger of its decompo- sition into hydrobromic acid in treated goeds is thought to bo con- siderable. Little is known cf its effect en wheat for milling, but its effect on the germination cf the grain is considered serious if a dosage of 6 ounces per 100 cubic feet of air is used. LINDGREN D. L. (66) Methyl bromide fumigation of ccdling-moth larvae. Jour. Scon. Ent. 29: 1174-1175. 1936. (Correction in Jour.. Econ. Ent. 30: 381. 1937.) Five pounds of a mixture containing 3.4 percent by volume of methyl bromide and 96.6 percent of carbon dioxide per 100 cubic feet killed all the larvf.e buried in sacks. Methyl bromide is much more toxic to these larvae than hydrogen cyanide or carbon disulfide. (67) Methyl iodide as a fumigant, Jour. Econ. Ent. 31: 320. 1938. Tests with methyl iodide rn scale insects (Cocoldac), lody beetles (Coccincllidac ), crnfused flcur booties (Tried? um con- fusurn Dirv.), codling moth larvae (Carp* '] 1 ^ (L, ) ) , and some other insects indicate that tT r '~ " ~~~ ailiti as a fumigant. In tests on citrus scedlir .bovc the sc lethal to the insects won n< t toxic to the plants. -18- LIVINGSTOKE, E. M. (68) Fumigation of bulk sell with methyl bromide for the white-fringed beetle in New Orleans. U. S. Bur. Ent. and Plant Quar. E-512, 4 pp. 1940. [processed.] Experimental work with methyl bromide as a fumigant for potting soil and five additional types of soil showed that larval infesta- tions of Pa ntom orus leucoloma (Boh.) in bulk quantities of these soils were destroyed by treatment with 38.3 cc. per cubic yard for 48 hours, at 42°-88° F. . Ho harmful effect on plants from the use of soil fumigated with methyl bromide has been noted by commercial users. — - — (69) Methyl bromide fumigation of the white-fringed beetle larva in small flowerpots in New Orleans. U. S Bur. Ent. and Plant Quar. E-513, 4 pp. 1940. [Processed.] Fumigation of the larva of Pantomo rus leu coloma (Boh. ) in New Orleans with methyl bromide at the rate of 1 pound to each 1,000 cubic feet of chamber space for 4 hours at about 85° F„ destroyed infestations in the soil about the roots of plants growing in 3- inch or smaller flowerpots, but not in 4-inch pots. The volume of the 4-inch pot is 2.3 times that of the 3-inch pot. The treatment has been used successfully in quarantine work in Now Orleans and is tolerated by approximately 90 percent of the plant species and varieties . „_ 5 EASTER, S. S., and SW1NK, G. R. (70) Methyl bromide in aqueous solution to control Pantomor oua leu col oma [Boh.] and P. persgrinus [Buch.]. Jour. Econ. Ent. ■3TTT3T^533. 1940. " ~~ An aqueous solution containing 0.3 percent of methyl bromide and 0.6 percent of ethyl alcohol destroyed larvae of both species about the roots of balled nursery stock. The application of 40 gallons per 100 square feet of soil surface gave complete mortal- ity of the larvae in 18 hours or less. LOFFLER, W., and RDTIHEYER, W. (71) TJcbcr Vcrgiftung mit Brommethyl und Nachweis dor Subctanz in Blut und Organcn vcrgiftetcr tiers. Vrtljschr. Gcrichtl. Med. 60: 60-67, 1920. A fatal case of methyl bromide poisoning is described. This acute seizure had been preceded by subacute intoxication during periods when the patient had worked in an enclosed space where there was some exposure to methyl bromide, with apparent remission of all symptoms during periods when he worked in the open. -19- LOS ANGELES COUNTY AGRICULTURAL COIJILI SSI ONER. (72) Codling moth. .Los Angeles Co., Calif., Agr. Comm. , Ann, Rpt. 1940: 7. Packers of pears and apples equipped themselves with fumiga- tion apparatus to take advantage of a change in the standardiza- tion lav/, which allowed 5 percent of visible worms and 5 percent of invisible worms in the packed fruit provided methyl bromide fumigation was used. LOUNSKY, J. (73) Note sur la resistance des azalees "&, la fumigation au bromure de methyle. Inst. Agron. et des Stas. de Rech. de Gembloux Bui. 8: 126-131. 1939. [Summaries in Dutch, German, and English.] In continued investigations 34 varieties of azalea plants were treated in winter, without being removed from their packing (wicker baskets or wooden packing cases), by vacuum fumigation with methyl bromide at the rate of 40 or 80 gm. per cubic meter for 2 hours. On the whole, the treatments had no injurious effects on the plants. ___„ and VANDEL-WALLS, R. (74) Observations sur le comportement de plantes d'azale'es dans divers essais de traitement de desiriscctisation. Inst. Agron. et des Stas. do Rech. de Gembloux Bui. 8: 52-58. 1939. Fumigation with methyl bromide c- used no injury to azalea plants when used at 40 gm. per cubic meter for 1, 2, or 3 hours at reduced or atmospheric pressure, but gave irregular results at higher dosages, sometimes causing injury that was found to be due chiefly to impurities and which was always more severe at the bottom of the fumigating chamber. MACK1E, D. B. (75) Entomological service. Calif. Dcpt. Agr. (Ann. Rpt. 1936) Bui. 25: 455-481, illus . 1937. Methyl bromide was used extensively as a fumigant during 1936, (76) Entomological si rvice. Calif. Dcpt. Agr. (Ann. Rpt. 1937) Bui. 26: 418-438. 1938. Fumigation with methyl bromide gas proved very satisfactory for destroying Kcifcria lycopcr cicclla (^usck) in harvested toma- toes, and was also used against Listrodoros o bliquus Klug in celery. In cold weather, however, this fumigant was loss effec- tive than hydrocyanic acre gas except at much higher dosagos, which sometimes caused injury to plants, especially those with a noticeable oil content. -20- (77) Methyl bromide— —its expectancy as a fumigant. Jour. Scon. Ent. 31: 70-79. 1938. Methyl bromide is toxic to a large group of insects and other animals. 1/iany plants in the active or dormant stage can accommodate themselves to its vapors at concentrations and exposure periods which are lethal to animals. The vapors are noninflammable and stable at temperatures, pressures, and moisture conditions met in practice. Lack of a distinctive odor at toxic vapor concentrations pre sents a hazard tc humans whic h will necessitate t he use of a warning compound (lachryna ting g asy. The equipment necessary in using this fumigant presents no great mechanical difficulty. (78) Entomological service, Calif. Dept. Agr. (Ann.. Rpt. 1938) Bui. 27: 645-668. 1939. As the second generation of C arpocapsa pomonella (L.) hatched at the time of the first picking of pears, newly hatched larvae, which were difficult to detect at the time of picking, were numerous in the fruit. .Fumigation of the packed and wrapped fruit in the trucks ready for shipment with 2 pounds of methyl bromide per 1,000 cubic feet was found to destroy all larvae in 2 to 5 hours. (79) Modern fumigation for pest control. Pests 7 (4): 6-8. 1939. The amount and type of material fumigated' greatly affect the concentration of gas in the air. Hydrocyanic acid gas and ethyl- ene oxide, being water-soluble, are greatly affected by moisture, whereas carbon disulfide, methyl bromide, carbon tetrachloride, and ethylene dichloride, being fat-soluble, are. less affected. In vacuum fumigation holding the vacuum throughout the exposure is more effective than dissipating the vacuum as soon as the fumigant is introduced. The control of termites by fumigant s is worth fur- ther investigation. The author is testing tri- and tctra-chloro- ethylcnc and methyl bromide. — and CARTER, W. B. (80) Methyl bromide as a fumigant. A preliminary report. Calif. Dept. Agr., Bui. 26: 153-162.' 1937. This fumigant possosscs certain properties which permit its use against a number of forms of insect' life not possible hitherto because of injury to the host. Data relative to its toxicity to human subjects are inconclusive. The gas has about the same insec- ticidal value as ethylene oxide. Methyl bromide was used at the rate of 2.5 pounds per 1,000 cubic feet for 90 minutes in the fumi- gation of potatoes for Gno r i mo s bhema ope rculella (Zell.) with 100 percent kill. In one season 220 cars of potatoes were fumigated without injury to vegetables or to personnel. The tomato pinworm is easily destroyed by the same dosage. Preliminary tests on citrus trees showed complete control, without injury to the tree, ..^.i—^.....-.-^- --... .-■■ . . ■ ^-~~~*~***~- -21- of resistant California red scale. The gas may be used in vacuum fumigatore and mixed with carbon dioxide. Insects which apparently survive the fumigation become comatose and die after several days. This fumigant is less injurious than hydrogen cyanide to certain plants and tissues, including colcus, begonias, ferns, and other succulent plants. — and CAFTER, W. B. (81) Observations on Hypera brunneipennis and its destruction in baled hay by fumigation. Calif. Dept. Agr. , Bui. 28: 387-392. 1939. Adults of K. brunneipennis in cages of perforated copper tub- ing were buried in" bales of tightly compressed alfalfa hay in or- dinary freight and refrigerator cars loaded to full capacity. Ordinary freight cars were found to be unsuitable for fumigation, but complete mortality in refrigerator cars was obtained with a dosage of 1,1 pounds of methyl bromide per 1,000 cubic feet in the baled hay and also in bags of flax seed, the periods of exposure ranging from 6 to 24 hours for the hay and 12 to 24 for the seed. Complete mortality was also obtained In 12 hours when bales of alfalfa hay were fumigated at 1 pound per 1,000 cubic feet under a gas-proof tarpaulin. — and CARTER, W. B. (82) Destruction of alfalfa weevil Hypera variabilis by fumigation and other means. Calif. Dopt. A"g~rT,~Bul . 28: 466-470. 1939, Penetration by methyl bromide was slower in timothy than in alfalfa hay. Yflicn 26 adults were placed in the center of a bale of each in a refrigerator car filled with timothy hay end furiig - ted for 10 hours at a dosage of 1.2 pounds of methyl bromide per 1,000 cubic feet, all these in the alfalfa wore dead 3 hours after treatment, whereas 5 of those in tiieothy were active 5 days after- ward. Complotc mortality was obtained in baled timothy hay in refrigerator cars by fumigation at dosages of 1.2 and 2.4 po\mds per 1,000 cubic feet for 24 and 6 hours, respectively. The bromine residue 72 hours after treatment for 24 hours at these dosages were 19*8 and 34.9 p.p.!?. compared with 5.8 p.p.m, for untreated hay. When tales of alfalfa hay were fumi o ated at 2 pounds per 1,000 cubic feet under a gas-proof tarpaulin, all the adults were dead immediately after treatment for 12 hours, and 4 hours after treatment for 6 hours, but heavy concentrations of bromide re- mained. Waen the dosage was halved, all the adults were dead 3 hours after fumigation for 6 or 12 hours. — and CARTER, W. 3. (83) Fumigation of fresh fruit with :iethyl bromide under industrial conditions. Calif. Dept. Agr., Bui. 29: 78-86. 1940. Packers during the 1939 reason fumigated 1956 carloads of California Bartlett pears to destroy codling moth larvae. The work was done in ref ri-erator cars, refrigerator trucks, or un- der gastight tarpaulins. Fumigation should not be done below 65° or above 95° F. in the car. The dosare is not less than 4 or -22- more than 5 pounds per car, with an exposure of 2 hours. Twenty c:.rs of mixed fruit (pears, plums, and peaches) were also treated without injury, as were 5,000 boxes of apples consigned to Hawaii. The same method was used in treating 5,310 boxes of winter pears to destroy the mealybug Pseu dococcus marit imus (Ehrh, ). MALLET, M. . (84) Insecticides for agricultural products. French Patent 747,798, June 25, 1933. Agricultural fumigants contain a considerable amount of methyl bromide, which is not only toxic to insects but has fireproofing properties, permitting the addition of inflammable products to the liquid -with safety. Carbon tetrachloride may be added to lower the vapor pressure. McLAINE, L. Si, and MUHRO, H. A. U. (85) Developments in vacuum fumigation at the port of Montreal. Ent. Soc. Ontario, Ann, Rpt. 67: 15-17. 1936. A proprietary fumigant containing approximately 7 percent of methyl bromide and 9 3 percent of carbon dioxide killed European corn borer larvae when used at the rate of 40 pounds per 1,000 cubic feet for 90 minutes. A 2-hour exposure at the same rate gave complete mortality of apple maggots and codling moth larvae in the centers of infested apples. Analysis of vegetables and fruits fumigated with the mixture under experimental conditions showed that to a very limited extent the methyl bromide reacted with the plant material to give a ■water- soluble bromine compound. MEIXEER, K. (86) Vergiftung durch Dampfe des Fcuerloschmittcls Polein (Kcthyl- bromid). Bcitr, z. G-crichtl. Med. 8: 10-17. 1928. A workman employed in filling fire extinguishers with this liquid was fatally poisoned by the fumes. Convulsions and marked cyanosis preceded death. Autopsy showed lung edema and an early stage of brain edema. MERZBACH, L. (87) Zur Pharmakologic des Brornmcthyls und einiger seiner Verwandtcn. Ztschr. f. die Gesam. Expt. Mod. 63: 383-392. 1928. Dogs wore killed by exposure to 0.00009-0.00054 mole of methyl bromide per liter. Marked edema of the lungs was produced. A con- centration of 0.000036 mole per liter was not fatal. Exposure of carp [Moorkarpfen] to 2.139 gm. of methyl bromide in 1,000 cc. of water caused narcosis in 1G minutes, .but 1.8373 gm. caused no nar- cosis after 20 minutes. Exposure of isolated frog hearts to 6.5115 gm. in 1,000 cc. of Ringer solution produced a diastolic stoppage, although the heart recovered spontaneously; with 5,7975 gm. in 1,000 cc. there was no stoppage, but the amplitude was less and the .frequency reduced. ^^^^^^t^^^^tJjiikmmma^timm^tM^iimm^t^im^^m^^mmi^m^Hmaa^ n» I ' ih -23- METCALF, C. L., and FLINT, W. P. ("8) Destructive and useful insects. 981 pp. New York and London. 1939.' The physical properties of methyl bromide are described, "It is about as toxic to many insects as chlo ropier In and is'' used at dosages from 1 to 2 l/2 lbs, per 1,000 cubic feet for 12 to 16 hours in buildings. It is not narcotic to tho insects and kills very slowly. It is recommended for use in ordinary atmospheric fumigation., as in mills and greenhouses, and in vacuum chambers, and also for such stored products as fresh fruits and green vege- tables, dried fruits and other stored food products, household goods, nursery stock and ornamental flowers, and for rodent con- trol. It does not injure the germination of seeds if they are dry. High temperature and humidity increase the effectiveness of this gas," It appears to be a very premising fumigant, but much is still to be learned about it (pp. 288-289). For the control of bedbugs in congested places, individual rooms or apartments can safely be fumigated with commercial gases containing methyl bromide (p. 888). MINISTERSTWO SPEAW VJ0JSK0V7YCH. (89) Preparation of methyl bromide. Polish Patent 24,777, May 25, 1937. Sulfur dioxide and bromine react in the presence of water to form hydrobromic acic! and sulfuric acid. To this are added, drop- wise, methyl alcohol and excess sulfuric acid, and the methyl bro- mide obtained is distilled off. MUNF.O, II. A. U. (90) Some observations on the use of methyl bromide as a fumigant, Ent. Soc. Ontario, Ann. Hpt. 68: 72. 1938. This is a brief summary of studies in Quebec on the use of methyl bromide as a fumigant for apples. It was highly toxic to apple insects when applied at the rate of 2 pounds per 1,000 cubic feet at 80° F. In each test an initial vacuum of 3 inches absolute pressure was dropped to 27 inches after introduction of the fumi- gant, the vault temperatures being maintained at 80° by fan circu- lation. In several varieties of apples exposures of 90 and 60 minutes killed larvae of Carpocapsa pomonolla (L.) and Rhagoletis pom onella (lYalsh), respectively. Eggs of Rhagoletis in the fruits •e killed in 30 minutes, but 60 minutes were necessary for eggs of Carpoc apsa . In same experiments, however, it appeared that methyl bromide caused injury to apples. (91) Some fumigation methods employed in the United States to prevent the spread of the Japanese beetle ( Pop il 1.1a japoni ca Hewn,). Rat. Soc. Ontario, Ann. Rpt. 70: 80-83. 1939, Methods of fumigating fruits, vegetable s, potted plants, and nursery stock with methyl bromide are described. -24- HATIOFAL INSTITUTE OF HEALTH. (92) Preliminary recommendations to fumi gators using methyl bromide or mixtures containing methyl bromide as a fumigant. U. S. Pub. Health Serv. , Natl. Inst". Health, Hay 16, 1938, 1 p. [processed.] (1) Avoid bre athing ai r containing methyl bromide. (2) On come lotion of fumigation, provide thorough ventila- tion for cars, rooms, or buildings before entering. T^T "When necessary to enter spaces containing methyl bro- mide, use a gas mash provided with a canister giving protection agains t organic vapors, or a positive pressure hose mask. (4) Avoid spilli ng methyl bro mide. Get to fresh a ir im med- iately in case of spillage. Remove any clothing in conta ct v jith skin which has become impregnated with the liquid. (~5) Post war ning si g ns notifyin g that methyl bromide is be- ing used and that the gas is toxic. (6) Store containers of methyl bromide in a cool, we ll- venti- lated place, outside inhabited buildings. Avoid leakage b y seeing that valves on cylinders are tightly closed. HUCKOLLS, A. H. (93) Comparative life, fire and explosion hazards of common refriger- ants. Underwriters Laboratories, Misc. Hazards Ho. 2375, 118 pp, 1933. Methyl bromide was among the materials investigated. Toxic- ity was determined with concentrations of 0.5-1.0 percent and 2-2.5 percent by volume (with higher concentration in some cases) by exposing guinea pigs for periods of 5 minutes to 2 hours. The effect of decomposition of the gas mixtures by heat from gas and oil flames and electric heating units was also determined, and analyses were made of the decomposition products. Investigation of fire and explosion hazards included determination of ignition temperature, limits of flammability or explosibility, explosion pressure, as well as time tests and speed-of-flame-propagation tests. The apparatus used and results of tests applied are de- scribed in detail. OETTIHGEH, W. F. von (94) The ho.logenatcd hydrocarbons: Their toxicity and potential dan- gers. Jour. Indus. Hyg. and Toxicol. 19: 349-448. 1937. The literature on the toxicity of methyl bromide is reviewed. OPPEFHANH, K. (95) Mcthylbromid-Vcrgiftungon, berufliche. Sarainl . Vorgiftungsfallen 4 (AM;. A): 157-160. 1933. Two nonfatal cases of methyl bromide poisoning are described in which there wore long symptom-free intervals. Brain irritation persisted for a long poriod in one case, and psychic debility in the other. ifiiBSp^i -25- PEPELIS," W. J. (96) Bromine tion of saturated aliphatic hydrocarbon gases. Indus, and Engin. Chem. , Indus. Ed. 25: 1160-1161. 1933. The .method described uses a low bromine concentration in the presence of iron powder at 290°-370° C. Methyl bromide was ob- tained by this means from methane. PETERS., G. (97) The biological-chemical evaluation of gaseous insecticides. Anz. f. Schadlingsk. 14: 116-122. 1938. [in German.] Data on the boiling point, specific heat, heat of vaporization, and saturation limit at 20° C. are given for a number of gaseous in- secticides, including methyl bromide. The vapor density, molecular weight, and explosion limits are also given. The most important factors in fumigation are gas concentration and time. PETRI, E. • (98) Pathologische Anatomic und Histologic dor Vcrgif tungen. In Henke, F. , and Lubarsch, 0. Handbuch der Speziellen pathologischen Anatomic und Histologie. v. 10, pp. 272-273. Berlin. 1930. The symptoms and pathology of methyl bromide poisoning are re- viewed from various literature sources. PHILLIPS, W. R., and MUNRO, K. A. U. (9 9) Methyl bromide injury to apples. Jour. Econ. Ent. 32: 344. 1939. Although fumigation with methyl bromide was previously repor- ted as injuring apples, later investigations gave different results , With a dose of 2.5 pounds per 1,000 cubic feet for 90 minutes 'in a vacuum vault and 80° F., only two of seven apple varieties were in- jured. MUNR0, H. A. U. , and ALLEN, C. E. (100) Some observations on the fumigation of apples with methyl bromide. 'Sci. Agr. 19: 7-20. 1938. The standard treatment was found to be lethal to insects feed- ing internally in apples. The residue of bromide was so slight as to be harmless to human beings. Under certain conditions, however, methyl bromide caused both internal and external injury to the apples. No injury resulted, however, when the apples were picked at tho proper stage of maturity and stored for 6 weeks at 32° or 39° i'. , and standard treatment was used. The damage, thercforo, appears to bo physiological rathor than mechanical. PIPER, W. R., Jr., and DAVIDSON, R. H. (101) Mothyl bromide vapor against five species of stored product in- sects. Jour. Econ. 'nt. 31: 460-461. 1938. Fumigation tests at atmospheric pressure and various room tem- peratures, concentrations and exposure periods were made on adults of Sitophilus granaria (L.) and Acan chosccl ides o >Uc t~us (Say), larvae of Trogo derma versicolor Crcutz., ] ts -26- of Catha rtus quadricollis (*Guer.) (Silvanus gemellatus Duv. ), and larvae- of Tencbrio ob sou r us F, , both exposed and covered to., a depth of 6 inches by wheat. It was estimated that 1. pound of methyl bromide per 1,000 cubic feet should kill all these insects in 12 hours at 58°-70°~F. Lower dosages may be sufficient or higher ones required in practical fumigation according to the species concerned and the quantity and nature of the infested material . Sitop hilus was the most susceptible, the species being increasingly resistant in the order named. Under conditions in which all the insects were killed, the germinating powers of wheat, oats, corn, and beans were not affected. Immersion in liquid methyl bromide and exposure to its vapor did not affect any of nine common metals or change the color of seven wallpapers or nine samples of dyed cotton goods,. ¥.o ill affects were exper- ienced by the operators, and the fumigant was found to be nonin- flammable and easy to handle. QUAYLE, H. J. ('102) The development of resistance to hydrocyanic acid in certain scale insects. Hilgardia 11: 183-210. 1938, Preliminary experiments indicated that forms of Aonidiella aurantii (Mask.) which are resistant and nonresistant to hydro- cyanic acid gas differ in their reaction to methyl bromide, RICHARDSON, B. W. (103) Some further additions to therapeutics, I. Organic bromides. Practitioner 6: 337-345. 1871. Methyl bromide is mentioned as a general anesthetic, (104) Methyl-bromide. Asclepiad 8: 239-240. 1891, Several deaths have occurred from the use of methyl bromide as a general anesthetic, RICHERT, P. H. ('105) Apparatus for dispensing methyl bromide. U. S „ Patent 2,156,869. May 2, 1939, to Dow Chemical Co. Various details of valve construction, etc. are given, ROHRER, F. Ueber Brcmmethylvergiftung. ■ Ein Beitrag zur Frage der Sp'atwirk- ungen von Gifts toff en. Vrtljrschr. f. Gerichtl, Med, 60: 61-59. 1920. A fatal case of poisoning by methyl bromide is reported. The patient was exposed while making repairs on a pipe carrying the material in a plant for the manufacture of antipyrine. There was a synptom-free interval of about 24 hours between exposure and the onset of epileptiform seizures, coma, and death. -27- " SAYERS, R. P.., YAUT, W. P., THOMAS, B. G, H.-, and BERGER ? -L. B. (107) Physiological response attending exposure to vapors of methyl bro- mide, methyl chloride, ethyl bromide, and ethyl chloride. U. S. Pub. Health Serv. 3ul. 185: 1-56. 1929. The purpose was to determine the effects cf these vapors es- caping in refrigeration plants. Guinea pigs were used. Short exposure to high concentration of the vapors produced similar symp- toms, anesthetic in character, excitement, rapid loss of equilibrium, struggling and running motion of the legs, followed by rapid recov- ery of those animals which had not died in the chamber. With low concentration of vapor and long exposure, the symptoms were similar— weakness, rapid pulse; convulsive, rapid respiration, with rales; and in some cases a frothy, bloody exudate from the nostrils; fol- lowed usually by death in 1 to 4 days. Ethyl chloride was the least toxic and methyl bromide the most. Addition of chemical agents to these refrigerants to serve as a v.-arning of their escape is suggested. SCHROTER, G. (108) Methyl bromide. German Patent 330,642, Nov. 25, 1917. Methane or methane-containing gas mixtures are passed with bromine over catalysts, particularly iron, at temperatures above 200° C. SCFAJLER. _ (109) Vergiftung durch Brommethyl? Deut. Vrtljrschr. f. Offentl, Gsndhtspflege. 31: 696-704. 1899. Three cases of poisoning by methyl bromide are reported, one of which was fatal. These men worked with apparatus in which methyl bromide was made from methyl sulfate and sodium bromide. Experiments on rabbits, guinea pigs, and mice are described. All the animals were killed by the concentrations of methyl bromide ranging from 1 to 8 percent by volume. Symptoms observed in the animals were somnolence, running of nose, slowness of pulse, and cyanosis. SCE7APTZ, F. (110) Brommethyl in der Schadlingsbckampfung. Arztl. Sachverstandigcnztg. 42: 258-259. 1936. The insccticidal use end the toxicology of methyl bromide are briefly discussed. SHEPARD, H. H. , and BUZICKY, A. W. (Ill) Further studies of methyl bromide as an insect fumigant. Jour. Econ. Ent. 32: 354-859. 1939. Laboratory tests wore continued in 1938 (see Fisk and Shepard 29) with common insects that occur in houses or infest storod pro- ducts. Their susceptibility to methyl bromide and its effective- ness in comparison with that of other fuiaigants are shorn in a table. With 5 hours' exposure at 25° C. the median lethal concen- trations cf methyl bromide, chloropicrin, ethylene oxido, carbon -28- . disulfide, and ethylene dichloride to the larvae of Atta genus piceus (Oliv. ), and of the first two compounds to the adults, were 17.5, 5, 17, 88, 195, 9.5^ and 1.3, mg. per liter, respec- tively, and those of methyl "bromide were 5 and 3.1 mg. to larvae and adults of Flodia i nterpunctella (Hbn. ), 13 and 7 to larvae of Tenebrio obscurus F. and Tineola "bissel l iella (Hum. ), 4.2 and 4,7 to male and female adults of Zabrot es su bfasciatus Boh., and 6.5 and 5.4 to adults of Stegobium paniceu m (L.) and Rhizopertha dominica (F. ). The insect material used was as nearly uniform as possible, most of the larvae being almost full-grown and most of the adults fairly young.. ' Differences in the speed of action of various fumigants against adults of Tri b olium confusum Duv. are shewn on graphs. Those exposed to methyl bromide at higher concentrations than that necessary for complete mortality seemed normally active immediately after the exposure but died within 48 hours. An added lethal effect of the low temperature appeared to depend on the cold resistance of the particular species concerned. The dose required to kill adult Tribolium increased down to about 8 °-9 ° C. and then decreased, whereas that necessary to kill adults of Sj tophil us granaria (L») increased down to nearly 0° C. The temperature appeared to have no effect on the flour- absorption ratio. Baking tests showed no detectable injury to flour fumigated for 5 hours at 2 pounds per 1,000 cubic feet. STAHL. (112) Die Anwendung chemischer Sonder-nassfeuerloscher in den gewerb- lichen Betrieben unter dem Gesichtspunkte ihrer Einwirkung auf die Benutzer. Zentbl . f. Gewerbe Hyg„ u. Unfallverhutung (n.f.) ' 5: 78-80, 1928, The author takes issue with the recommendation of methyl bro- mide as a fire extinguisher liquid by Von Gronorf (40) and quotes several authorities to show that its use is dangerous, STEIGER, 0. (113) Ueber Brommethylvergiftung. Munchen, Med, Wchnschr, 65: 753-755. 1918. A nonfatal caso of methyl bromide poisoning is reported. The usual symptoms of dizziness, vertigo, paralysis of the extremities, disturbances of vision, etc,, appeared, followed after several days by hallucinations and strong motor unrest. The blood contained methemoglobin, and blood was excreted through the kidneys. After 2 months there was a decrease in skin sensitivity in the region of the radial nerve in the right hand, with a feeling of "fuzziness," and a similar sensation in the right leg. -29- STEINKOPF, W., and FROMMEL, W. (114) Ueber die Darstellung von Brommethyl. Deut. Chen. Gesell. Ber. 38: 1865-1868. 1905. Methyl bromide is prepared by adding bromine slowly to a mix- ture of methyl alcohol and red phosphorus. and SCHWEN, G. (115) Preparation of methyl bromide. Jour. f. Prakt, Chem. 102: 363-364. 1921. [in German.] The authors increased the yield from 44.5 percent to 77 percent of the theory (calculated from the bromine) by using methyl alcohol (110 gm. ), bromine (110 gm.), and phosphorus (22 gm. ). To avoid the formation of an explosive mixture, they kept the methyl alcohol- phosphorus mixture slowly boiling before and during the addition of bromine, STENGER, V. A., SFRaDER, S. A., and BESKGETOOR, A. W. (115) Analytical methods for methyl bromide, Indus, and Engin, Chem e , Analyt. Ed. 11: 121-124. 1939. Since the vapors of methyl bromide are toxic, it is important to have a simple procedure for the rapid detection of the gas in air. The literature is reviewed and the results of 2 years' ex- perience at the plant of the Dow Chemical Company in Michigan are summarized. The well-known Beilstein test, which can be made quickly xvith the Frigidaire halide leak detector, can serve for the approximate determination of 50 to 500 p.p.m. The procedure of Kolthoff-Yutzy (Indus, and .Engin. Chem., Analyt. Ed. 9: 75-76. 1937) is, however, more accurate for these concentrations. For the analysis of fumigated products, this procedure can be applied after ashing with potassium hydroxide in alcohol and in the pres- ence of sodium chloride. Recoveries of 96 percent were obtained with 1 mg, of methyl bromide in 10 gm, of flour, nuts, dried fruits, or tobacco. For larger quantities the Volhard titration is recom- mended, STEWART, M. A. and iiACKIE, D. B. (117) The control of syl vatic plague vectors. Amer. Jour. Hyg. 28: 469-480. 1938. The control of fleas in rodent burrows, as veil as the rodents themselves, necessary in the suppression of sylvatic plague, may be accomplished by fumigation with methyl bromide. All stagos of fleas arc susceptible to this fumigant, but the adults are the most eas- ily killed. It appears from field tests that the dosage of liquid mothyl bromide, approximately 10 cc. per burrow opening, ordinarily used to kill ground squirrels is also sufficient to kill all stages of the fleas. It is believed that the spread of bubonic plague- occurring through the transportation of plaguc-flea-inf osted grains, cereals, etc., may be chocked by fumigating these cargoes with methyl bromide, and that the materials so treated will not in any way bo rendered unfit for human consumption. -30- STORER, T. I. (118) Control of injurious rodents in California, Calif. Agr. Col. Ext. Cir. 79, toy,, 62 pp. 1938. In 193S methyl bromide was tested experimentally as a means of ground squirrel control. The results were encouraging, and further studies are planned, especially as to practical means for handling the gas. If suitable methods are developed, its use will be limited, for a time, to follow-up operations, since the cost of methyl bro- mide is as yet too high to permit its use in regular control work. TAYLOR, A. J.,., and Ho BETH, CV W. (119) Preliminary tests of methyl bromide as a nematocide, Helminthol, Soc. Wash. Proc. 7: 94-96. 1940. Methyl bromide appears to be an effective soil nematocide for use against the root-knot and free-living nematodes. Satisfactory results were obtained in preliminary trials with 80 cc, to treat a layer of soil 15 cm. thick in a fumigation box of 1 cu. m. capacity. Fair results were obtained with 1.5 pounds to treat 225 square feet of soil, when the chemical was applied through hollow-tile lines buried 18 inches under the soil and 18 inches apart. There was some evidence that methyl bromide also controls fungi and bacteria, in the soil, but an attempt to elimate root-knot nematodes ^from tomato plants was unsuccessful. Nematodes in the larger galls were not killed, and most of the plants were killed or severely injured. TIETZE, A. (120) Clinical observations on intoxication by methyl bromide and carbon tetrachloride. Arch. f. Gewerbepath, u. Gewerbehyg. 4: 733-739, 1933. [In German.] These chemicals are very soluble in lipoids, and thus consti- tute poisons for the organism and particularly for the nervous system. The disturbances which they cause in the organism are de- scribed. UNITED STATES ^BUREAU OF ENTOMOLOGY AND PLANT QUARANTINE. (121) Dried-fruit insects. IT. S. Bur. Ent. and Plant Quar. Ann. Rpt. 1936: 6-7 . Fumigation of packed raisins with methyl bromide at the rate of 4 cc. per 25-pound box gave complete control of Ephestia figulllella Greg, and Plodia intorpun ctella (Hbn. ) ,~ (122) Methyl bromide as a fumigant. U. S. Bur. Ent. and Plant Quar. Ann. Rpt. 1937: 79. Fumigation with methyl bromide was effective in killing Japan- ese beetles in green beans packed in hampers and in killing larvae of the beetle infesting strawberry plants packed, with soil on their roots,- in cratos. It also gave promise of being a good green- house fumigant, giving nearly complete kills of three varieties of frn— i • ntm m m rr manmm -31- aphids, the common red spider, one species of thrips, two species of mealybugs, and immature stages of the southern armyworm. Con- centrations sufficient to kill Japanese beetles v:ere tested on a variety cf plants without injury. Special apparatus has been de- vised for introducing this and other fumlgants into refrigerator cars. (123) Fumigation of potatoes by methyl bromide as a condition of certifi- . cation of potatoes moving by refrigerator car from the area listed in regulation 5 of quarantine No, 48. U. S, Dept. Agr., B.E.P.Q. 473, 1 p. 1938. The following treatment was authorized as a basis for certifi- cation, of potatoes moving to points outside the ^Japanese beetle quarantine areas between June 15 and October 15: "Fumigation of potatoes in dry refrigerator cars with methyl bromide at a dosage of 2 pounds per 1,000 cubic feet of space, including the space occupied by the potatoes and bunkers of the cars, for a period of 2 hours during which time the car shall remain tightly closed with the plugs in place in the ventilator hatches. The temperature within the car when fumigated shall not be less than 70° F. Pro- vision shall be made for circulating the mixture of air and fumi- gant in the car for as long a time as is deemed necessary by the inspector. At the end of the fumigation. period the hatches shall be opened, the plugs removed, screens placed in the hatch openings, and the car shipped under standard ventilation." (124) Fumigation of onions by methyl bromide as a condition of certifi- cation of onions moving by refrigerator car from the area listed in regulation 5 of quarantine No. 48 „ U. So Dept. Agr., B.E.P.Q. 475, 1 p. 1938. The same treatment for Oiiions as that described for potatoes in the previous reference (B.E.P.Q. 473) is authorized. (125) Fumigation of tomatoes by methyl bromide as a condition of certi- fication of tomatoes moving by refrigerator car from the area listed in regulation 5 of quarantine No. 48. U. S. Dept. Agr«, B.E.P.Q. 480, 1 p. 1938. - . . The same treatment for tomatoes as that described for pota- toes in B.E.P.Q. 473 is authorized. (126) Administrative instructions to inspectors on the treatment of nursery -products, fruits, vegetables, and soil, for the Japan- ese beetle (Sec. 301.48a). U. S. Dept. Agr., B.E.P.Q. 499, 20 pp. 1939. The use of methyl bromide is ruthorized for treatment in a fumigation chamber of plants with or without soil, using 2 l/2 pounds of gas per 1,000 cubic feet (including space occupied by the load) at a temperature of not less than 63° F. for 2 l/2 hours. -32-' For fumigation of strawberry plants in shipping crates of field- packed "baskets, 3 pounds should be used per 1,000 cubic feet for 4 hours at a temperature of at least 60° F. For the treatment of fruits and vegetables in refrigerator cars, 2 pounds per 1,000 cubic feet (5 pounds per car) should be used for 2 hours at a temperature of at least 70° F, B.E.P.Q. 499, Sup. 1, 1 p. 1939. (127) The instructions in B.E.P.Q, 499 are modified to state that the method is to be applied only to plants with bare roots or in 12-inch pots or smaller, or in soil balls not larger than 12 inches in diameter or thicker than 12 inches when not spherical. The soil should not be puddled or saturated, and the balls should not be jammed tightly together. (128) B.E.P.Q. 499, Sup. 1, rev., 2 pp. 1940. The minimum temperatures ' in the dosage schedule provided in B.E.P.Q. 499 for fumigation of plants with or without soil are changed to the following: 63° F„ for an exposure of 2 l/2 hours - , 54° F. for 4 hours, and 50° for 4 l/2 hours. (129) B.E.P.Q. 499, Sup. 1, rev. 2, 2 pp. 1940. An approved fumigation chamber equipped with vaporizing, air- circulating, and ventilating systems must be provided. The air within the chamber must be kept in circulation during the fumiga- tion. At the completion of the treatment, the chamber must be well ventilated before it is entered and the plants are removed. The temperature of soil and air for each type of treatment must remain throughout the period of treatment at least that specified as follows: For dosage of 2 pounds per 1,000 cubic feet, 70° F. for 2 1/2 hours; for 2 l/2 pounds per 1,000 cubic feet, 63° for 2 l/2 hours, 54° for 4 hours, and 50° for 4 l/2 hours. (130) B.E.P.Q. 499, Sup. 2, 2 pp. 1940. The following dosages are specified for fumigation of refrig- erator cars: 1.6 pounds per 1,000 cubic feet (4 pounds per car) at a temperature of at least 80° F. , or 2 pounds per 1,000 cubic feet (5 pounds por car) at a temperature of at least 70° F. (131) Administrative instructions modifying the restrictions of tho white-fringed beetle quarantine by .authorizing treatment by methyl bromide solution of balled nursery stock not larger than six (6) inches in thickness (or of spocifiod thickness) (Sec. 301.72-5c). U. S. Dept. Agr.T.E.P.Q. 503, 2 pp. 1939. Tho soil balls must be buried in sand and plunged in boxes or trays approximately 1 foot deep, which are watertight. A 2-inch. MM -33- space filled with sand shall he provided between the balls. The balls shall be treated with a solution of 0.3 percent of methyl bromide and 0.6 percent of denatured alcohol by volume in water, applied evenly over the surface of the sand at the rate of 40 gallons per 100 square feet. The soil balls shall remain embedded thereafter for 24 hours. The temperature of the balls during treatment shall be not lower than 70° F. (132) B.E.P.Q. 503, rev., 1 p. 1940. As a result of more recent investigations, the instructions are revised to provide that soil balls 7 inches in diameter may be so exposed for 8 hours at a minimum temperature of 65° F. The modification is/restricted, however, to treatment for larvae of Panto morus leucoloma Boh. The former specifications remain in effect for treatment of larvae of P. peregrinus Buch. (133) Administrative instructions; conditions governing the entry of cipollini from Morocco (Sec, 319.56-2f). U. S. Dept. Agr. B.E.P.Q. 504, 1 p. 1939. Fumigation with methyl bromide is made a condition of entry for all sriipments of cipollini from Morocco in order to eliminate any infestation of Ex o soma lusitanica (L.) which might be present. (134) Administrative instructions amending authorization of the shipment of fruits and vegetables from Hawaii to the mainland subject to fumigation with methyl bromide under supervision. U. S. Dept. Agr. B.E.P.Q. 510, 2 pp. 1940. Provision is made for the certification of guavas, papayas, bell peppers, bitter melons, cucumbers, summer squash, string beans, and tomatoes for movement into the United States, when prescribed fumigation with methyl bromide is applied in Hawaii. The commodity must be fumigated in a gastight chamber for 3 l/2 hours with 2 pounds of methyl bromide per 1,000 cubic feet at a temperature of not less than 80° F. — — - (135) Methyl bromide fumigation. Construction details for an i red fumigation chamber. U. S. Bur Ent. and Plant Quar. 32 pp. 1940. [Processed.] Construction details arc given for a box-type fumigation c] ber, suitable for chambers of 50 and 100 cubic feet. VAYSSIERE, P. ■ (135) Les stations de dboinfection des ve'gdtaux sous vide partiel. Soc. d T Encouragement pour Indus. Nat. Bu. 1934: 295-308. Methyl bromide kills all stages of insects at doeos of 30 to 50 gm. per cubic meter (3 to 5 oz. per 100 cubic feet), and its action is comparable to that of ethylene oxide. Its vapors arc -34- rrot readily soluble, and it breaks up slowly in the presence of humidity, forming hydrogen "bromide. Its use in the fumigation of vegetable substances with an appreciable humidity content but not a continuous cuticle is therefore inadvisable. Excellent results, however, have been secured in the treatment of pears, the color and consistency of which remain unaffected, and for which ethylene oxide is unsuitable. — (137) La de'sinfection des chataignes. Rev, de Path. Veg. et d'Ent. Agr. de France 25; 277-29'3. *1938, ' ("Balaninus) Curculio elephas Gyll, and (Laspeyresia) Cydia splendana Hbn. are serious pests of chestnuts in France. Fumiga- tion with methyl bromide at the rate of 2 to 3 ounces per. 50 cubic feet for 3 hours at an initial vacuum of 700 mm. and subsequent vacuum of 20 man. gave a complete kill, VOSS. (138) New syntheses in the solvent industry. Kunststoffe 17: 79-80, 132-134, 205-207, 1927. Recent patents are reviewed on processes dealing-with the veneration of methyl alcohol from water e'as, direct oxidation of methane to methyl alcohol, manufacture of methyl chloride and bromide from methane, and the oxidation of these to methyl alco- hol and the manufacture of methyl alcohol from carbon monoxide. YffiBSTER, R, W. (139) Legal medicine and toxicology. 862 pp. Philadelphia. 1930, Early symptoms of methyl bromide poisoning are headache, weakness, vertigo, vomiting, and some disturbances • of vision. The gait may be staggering, and slight pain in the extremities and neuritic symptoms may be noted. After several hours or even days, severe symptoms may appear in the form of strong contractions of different groups of muscles, clonic spasms of the entire body, double vision, pareses of the extremities, sleepiness, and poly- neuritis. Convulsive type of' respiration may be noted, and in the fatal cases reported epileptiform attacks are merged into a terminal coma. Physical signs of pneumonia may be noted. Con- valescence is slow. WIESMANN, R. (140) Untersuchungen liber die Biologic und Bekampfung der Erdbeermilbe, Tarsoncmus fragariae, H. Zimmormann. Landw. Jahrb. dor Schweiz. 51 s 335-348. 1937, Tests we're made on the control of Tarsoncmus pal lidus Banks (T. fragariae Zimm, ) with a number of fumigants, including a Swiss preparation called S-gas, This is supplied in a liquid form in ampules, its active constituent being methyl bromide. Methyl bro- mide is a rather violent respiratory poison, but is easy to apply with safety to strawberry runners, which can bo fumigated in any tightly closed metal box in which the ampule is broken. A strength of 2 percent by volume killed all the mites and eggs in 6 hours at 15° C. Fumigation would not be effective at lower tem- peratures. At 13° the time could be reduced to 4 hours, but no harm was done to the plants by fumigating for 6 hours. All stages except the eggs were killed in 6 hours with. 0.75 percent at 18°. Atmospheric humidity did not affect S-gas, which acted perfectly in fully saturated air. No injury to the plants occurred, even with a strength of 2.4 percent. "HLMOT, R. J. (141) Fumigation of horticultural products. Fla. Agr. Expt. Sta, Ann. Rpt. 1938: 106, 1939. It was found that the green pods of cowpea could be fumigated safely with methyl bromide, and that fumigation with half the basal dosage [.2.5 lbs. per 1,000 cu. ft. for 90 minutes] gave com- plete control of larvae and adults of the cowpea pod borer. It also controlled larvae of the tomato pinworm without injury to the plants. -36- rKDEX TO INSECTS AGAIFST MUCH METHYL BROMIDE HAS BEEN TESTED Reference No. Acanthoscelides obtectus (Say) (bean weevil) - — -- r-~~ 29, 101 Anomala orientalis Waterh. (oriental beetle) --_-. _ 42, 43 Aonid iella au rantii (Mask.) (California red scale) — 80, 102 Aphids"-~~~--- --»■--- ~ — — — — — — — ——— — — — — — 122 Apple insects ------ ——-..-——._--. — — _ —„„„„..„_„_ 100 Apple maggot. See Rhagoletis pomonella ("Walsh). Artichoke plume moth. See Platyptilia carduidactyla (Riley). Asiatic beetle. See Anomala orientalis Waterh. Atta genu s piceus (Oliv. ) ("bTack carpet beetle) --------- 111 Balaninus elophas Gyll. See Curculio elephas Gyll. Bean weeyil^ See Acanthoscelides b t e c tu s ( Say ) * Bedbug. See Cimex lectularius L. Black carpet beetle. See Atta genus piceus (Oliv.), Bruchus brachial is Fahr. (vetch bruchid)' --—-----. -- — 46 Bruchus signaticornis Gyll. — .=———-. — ~ 64 Calandra granaria L. See Sitophilus granaria (L. ). Calandra or yza L. See Sitophilus oryza (LT) , California red scale. See Aonidiella aurantii (Mask.). Carioocapsa pomonell a (L.) (codling moth.) ------ — — — .._ 36, 66, 67, 72, 78, 83, 85, 90 Cathartus quadricollis (Gue'r.) (square-necked grain beetle) 101 Chalcodermus aeneus Boh. (Cowpea pod borer) — — — -__-— 141 Cheese mite. See Tyrogly phus f_ari_nae_ Deg. Cimex lect u lariu s TT. (bedbug J — — ._— — — — — . — -— -— 88 Coccidae (scale insects) — — - — 67 Coccinellidae (ladybeetles ) ■ — —- — -— ~ T — ._— — — 67 Codling moth. See Carpocapsa pomon ella (L.). Common red spider. See Tetranychus telarius L. Confused flour beetle. See Tribolium confusum Duv.. Cowpea pod borer. See Chalcodermus aeneus Boh. Curculi o elephas Gyll. ■- — — ._—.«—---— 137 Cydia molest a. See G raphe litha molesta (Busck). Cydi a pomon ella (L,)„ See Carpocapsa pomor^ejJ.ja (^*)« Cydia splondana Kbn, — — — — —----— — ------- — „_—„„„ — 137 Cylas formicarius elegantulus (Summers) (Cylas fo mi pari us F. ) 22, 27 (sweetpotato weevil) Dark mealworm. See Tenebrio obscurus F. Drug store weevil. See St e^ob ium pani c eum (L,)„ Ephcstia fig ulilel la Greg^ ("raisin moth) • •— — -- 121 Ephestia kuehrdella Zell. (Mediterranean flour moth) 64 European corn borer. See Pyrausta nubila lis (Hbn. )„. Ex c oma 1 u s i tan . 1 c a (L.) • ■-— -— --• - 133 Fleas --'— — 117 Gnathoc erus co rnutus ( F. ) - — 64 Gnorimo schema, lye op e r s io ell a Busck. See Keif aria t lycoporsicella (Busck) Gnorlmo schema operculolla (Zoll.) (potato tuber worm) - — • 80 Granary weevil. See Sitophilus gr anaria (L, ). Grape mealybug. Sen Psoudococcus mariti mus (Ehrh. ), Grapho litha mol esta (Busck) (oriental fruit moth) 36, 44 Hypera b runnc ipc nni s 81 -37- Reference No, Hypera variabilis 82 Indian-meal moth. See Flodia int erpunc t ella (Hbn.). Japanese beetle. See Fcpill ia .^aponic a Newm. Keiferia lycopersicella (Busck) (tomato pinworm) 76, 80, 141 Ladybeetles. See Coccinellidae. Laemophloeus spp, ; 64 Laspeyresia splendana Kbn. See Cydia splendana Hbn. Lesser grain borer. See Rhizopertha dominica "~("F. ). Listroderes obliauus Klug (vegetable weevil) ---- 76 Ma rue a testulalis Geyer . ■ 62 Mealybugs 122 Mediterranean flour moth. See Ephestia kuehniel la Zell. Oriental beetle. See Ano mala oriental is ITaterh. Oriental fruit moth. See C-rapholitha molesta (Busck). Oryzaephilu s su riramensis (L.) ( saw-toothed grain beetle) - 64 Fantcmorus leucolo ma (Boh,) (white-fringed beetle) 68, 69, 70, 131, 132 Fantomorus peregrinus Buch. (white-f ringed beetle) 70, 131, 132 Phthorimaea lycopersicella Busck. See Keiferia lycopersicella (Busck), Flatyptilia carduidactyla (Riley) (artichoke plume moth) — 61 interpunctella (Hbn. ) (Indian-meal moth) 111, 121 Fopillia japonica Newm. (Japanese beetle) — 19, 20, 57, 91, 122, 123, 124, 125, 126, 127, 128, 129, 130 Potato tuber worm. See Gnorimo schema operculella (Zell.). Frodenia eridania (Cram.) 122 Fseudococcus maritimus (Ehrh.) (grape mealybug) 83 Pyrausta nubilalis (Kbn.) (European corn borer) 85, 92 Raisin moth. See Ephestia figulilella Greg. Red flour beetle. See Triboliui: castaneum (Kbst.). Rhagoletis pomonella ("hlsh) (apple maggot) 15, 85, 90 Rhizopertha dominie a (F.) (lesser grain borer) 64, 111 Rice weevil . See Sitoohilus oryza (L.). Rust red flour beetle. See Tribolium castaneum (Hbst.). Saw-toothed grain beetle. See Oryzaephilus surinamensis (L.). Scale insects. See Coccidae. Silvanus gemellatus Duv. See Cathartus quadricollis ( Gue'r. ) , Sitophilus granaria (L.) (granary weevil; 29, 33, 63, 64, 101, 111 Sitophilus oryza (L.) (rice weevil) 29, 33, 64 Southern armyworm. See Frodenia eridania (Cram.). Spermophar;us subfasciatus Boh. See Zabrotes subfasciatus (Boh. ). Square-necked grain beetle. See Cathartus qnadricollis (GueV.). Ste^obium paniceum (L.) (drug store weevil) 111 Stored-grain insects 101, 111 Strawberry mite. See Tarsonemus pallidus Banks . Sweetpotato weevil. See Cylas formicarius olegantulus ( Summers) . Tarsonemus f ragariae Zimm. See Tarsonemus pall idus Banks , Tarsonenus pallidus Banks 140 lenebrio obscurus F. (dark mealworm) 101, 111 Termites 79 Tetranychus telarius L. (common red spider) 122 L -38- 3 1262 09227 9891 Reference No. Thrips 122 Tineola "bisselliella (Hum.) (webbing clothes moth) 111 Tomato pinvrorm. See Keif eri a l ye ope rs ic el la (Busck). Tribolium castaneum (Hbst. ) ("red flour beetle) 58, 59, 64 Tribolium confusu m Duv. (confused flour beetle) .... 29, 67, 111 Tribolium sp. — — 63 Tro ^oderma versicolor Creutz. 101 Tyroglyphus farinae Deg. (cheese mite) ■ 25 Vegetable Treev.il. See Listrodere s obliquus Klug. Vetch bruchid. See Bruchus brachialis Fahr, Webbing clothes moth. See Tineola bis-selliell a (Hum.). Tvhite-f ringed beetle. See Pan tomorus leucoloma (Boh.) and Po peregrinus Buch. Zabrotes subfasciatus (Boh.) — 111 I