LIBRARY OF THE UNIVERSITY OF CALIFORNIA. Gl FT OF i fiLJk Class 1 . s. DEPARTMENT OF AGRICULTURE BUREAU OF CHEMISTRY BKI.LETIN NO. I I ! ', [NSECTICIBE STI DIKS. I. I'YIMTIIIMM POWDERS CONTAINING I'olsoNoFS MFTALS. II. A COMPILATION OF ANALYSFS ol-' I NSK( Tl< 'I I )KS AND Fr\<;i<'ii>i<:s. III. STATK LAWS ( JOY Kl!\ I N( i THF COMPOSITION AND SALM OK I NSI X'TICl I >FS. HV J. K. ii A ^'^v< )< WASHINGTON: aoyER'NMENT PRINTING OFFICE ' U. S. DEPARTMENT OF AGRICULTURE, BUREAU OF CHEMISTRY- BULLETIN NO. H. XV. WILEY. Chief of Bn [NSECTICIDK STl DIES. I. I'VUKTHKCM POWDERS CONTAINING r< • !-« >N< U'S METALS. II. A COMPILATION OF ANALYSES <>K i.\si-: AND FUNGICIDES. 111. STATK LAW- GOVERNING TIM. COMPOSITION AND SALT, or [NSECTICIDES. BY J. K. 3IAV\VOOD, ,i,,VKKNM KN'T PRINTINti < ' F F I « B, 1 903. LI-TTKR OF TRANSMITTAL U. S. DEPAKTMKM OF A<;KI< i I.TI i;i . HW///,r//"//. />. r.. JA//V-// /.;. 1903. Sin: I have the honor to transmit for your approval three papers on insecticide- prepared in the Insecticide and Agricultural Watei- Labo- ratory of thi- lUireaii. and to recommend their publication a< liullctin No. T'» of the r>uroau of Chemistry. Respectfully. H. W. WILEY, Chi ]Ion. JA.MK> \ T I-! X T S . I. Py roth run i powders containing poison on.- metal- ................. 7 Introduction ......................................... 7 Cast'- ..f p..iniates ...................... 7 Loa«l poisoning caused l>y tin- manufacture <-\ fu-e- .;inir pill-poses .................................................... .S Fatal poisoning !>y oatini: e«.!iiWtionery .•,,!,, ivd with leal . hr inato ....................................................... Fatal poix.nini: \t from yarn '-oii.ivd \\ith lead « ' mat;' ........................................................ 9 Moinoirs oojicorniivj dan-jors to which workmon in chrom: rios a ro o\j)oo> of pyrothnim jpowdrrs ..................................... |:i Colloctioii of is ................................. }'.'> Correspondence with manufacturers ............................. i'1 II. A compilation of analyses of insecticides and fungicides ........ ........ 23 Introduction ...................................................... Source- . .f analyse^ and description • f saint !os ........................ Paris -reeii- .................................................... Mot h< id.- ................................................... ::L' < 'oimiieni on analy-es ...................................... :;'.« London. Miiirli-h, and Pari- jiurjile- ............................. H* Inoth a- active cun-tittieiii-. 11 White ar-eiioids ........................................... 4'J Paris ( Jrecii and P>or«'eaux Mixture .......................... 4l' shi.ir sh..ts ................................................. IL' Pero.xid of silicates ......................................... 1- P.laok I 'oath .............................................. 43 Lnirlish Bug Compound .................................... !•"• < iriental Fi-rtili/.or and P.r.'j I ' ....................... Lead Ai>onato and Pink Ar.-enoid ........................... XX. Purple Poison, and Insecticide ......................... H Copper carl x.nate ........................................... Fo>tite ........................................... ':> Sulphatine and Death t .................. »•"> Lyes Hollol-ores Mixtures containing l««iax Hooker's Cockroach an,l \Vator P.UL: Lxtenninator Tohacco extracts Formalin- . . <) CONTENTS. II. A compilation of analyst'.*! of insecticides and fungicides — Continued. Page. Sources of analyses and description of samples— Continued. IVtn .leiims 49 .Miscellaneous solid insecticides and fungicides 50 Sulphurs 50 Pine-tar insecticides 50 Hii- I >eaths 50 Potassium cyanid ~^o NonpOlSOnoua Potato p.ug I)estroyer 51 Xoiipoisoiions Insect Kxterminator 51 X. <). Dust 51 Klectric Vermin Exterminator 52 - Par'( )idium 52 A ntinonnin 52 Miscellaneous liquid insecticides and fungicides 52 Bollene Insecticide ~)'2 Kxcelsior Insecticide and Wood Preserver, Red Cedar brand.. 54 Fly Preventative 55 Karbo-Kresolate 55 Professor De Graff's Carpet Bug Destroyer 56 III. State laws governing the composition and sale of insecticides 57 California 57 Louisiana 58 New York 59 < )i egon 61 Texas 61 Washington 63 INSECTICIDE STUDIES. I. PYRETHRUM POWDERS roXTAIMNi; I'nlSoNors MKTALS. INTRODUCTION. In the course of a recent examination of a large number of miscel- laneous insecticides it was observed that a number of pyrethrum powders contained lead chromate. Those powders arc .sold under such names as Persian Insect Powder, Dalmatian Insect Powder, Buhach, and Pyrethrum, and are colored yellow because there seems to be a popular demand for this grade of goods, the public apparently believing that the preparation must he bright yellow in order to kill insecN. As a matter of fact pure pyrethrum, which is composed of the ground flower heads of Pyrrflu'mn rosewm and J'yrethrum cinerariasfolium^ usually possesses a light yellow color, but never the brio-ht. intense yellow color given to it by lead chromato. As lead chromato is known to be poisonous, it would appear that it i* a very reprehensible practice to add it to pyrethrum powders, since they are often blown about living rooms with a bellows to kill insects, and are consequently inhaled by human beings. Besides this, pvro- thrum is always advertised to be harmless to human beings, which it is when pure, but ceases to be so when it has been mixed with lead chromato or other yellow colored chromates. In view of the above facts it was deemed advisable to examine the py roth rum powders sold upon the American market to discover which of them contain yellow chromates and at the same time to cite eases of poisoning by chromates to substantiate the claim that any of the yellow chromates that might be used for this purpose, and especially lead chromato. are poisonous to human beings. The facts which have been collected on these points are embodied in the following report: CASES OF POISONING BY LEAD AND OTHER CHROMATES. Since it is not generally known that many pyrethrum powders con- tain lead chroma te, it doubtless often happens that physicians are much puzzled as to the cause of the illness of persons who have been exposed to the action of such powders. In order, therefore, that physicians and others may recognize the symptoms of chromate 7 8 INSECTICIDE STUDIES. poisoning caused by this class of goods, the following account is given of cases of eliminate poisoning found in medical records: LEAD POISON! N<1 < A I'M-: I) BY THE MANUFACTURE OF FUSES FOR LICHTIV; ' On February L'L'. 1*7"). a woman of about 4»i years of age came under my rare at the hospital. Sh«> complained of pains in the stomach and a general indisposition or breaking down. For a number of days she had suffered with severe gripes. Her stomach was not swollen, but her skin was very sensitive and palpation caused a contraction of the abdominal muscles. There was, however, no tumor in the abdom- inal cavity. She had suffered fur about lifteen days with obstinate constipation that could be relieved only by an injection; her liver was .small and not painful; her tongue white, appetite nearly entirely lacking and breath foul. There was nausea and a distaste for food. a:.«l one could observe the existence of a grayish-black slate- colored border on the edges of her teeth next to the gums, which had all the char- acteristics of lead bands. That symptom, added to the gripes and to cramps in the calves of the legs during the night, caused me to diagnose the case as lead poisoning. This woman was under mv care until _the 16th of March, at which time she began to convalesce, although at that time she was still an;emie and feeble: but there was unquestionable improvement. Being well convinced that my patient was suffering with lead poisoning. I thought I oiiL'ht to find the cause. I found that she had worked for live years in a well-aired factory employing about :!<» people, where they were engaged in the manufacture of fusi-> which were to be used by smokers to light their pipes and cigars. Her work differed from that of her fellow-workers in that she was employed in winding the cotton that was to be used for the manufacture of fuses, while they wove the threads of cotton. She was thus more exposed than her companions to the emanating dust, .ally as the cold weather had obliged them to close the windows of the shop. These fuses were about as large around as a pencil or the little linger and of a yel- lowish oranire color, indicating that they were colored with lead eliminate. A chemical analysis showed the presence of this compound. At tin- shop where these fuses were manufactured I found that those who were engaged in weaving them did not show any appreciable symptoms of lead poisoning. \\hile those who were employed to shake out and wind the cotton all had fairly well developed ,-;!-,-. Tin- merchant at Paris who manufactured these fuses said that they wen- originated in Germany, but were now exported largely, especially to America. FATAL POISONING i'.v BATING CI>NFF.NF.IIY <<>L<>RKI> WITH i HAD i IllloMATK. '' On March 14, 1*7-, between !« and 11 a. m., the two sons of Mr. II.. aged respec- tively :ii Mini 1 ; yean, ate -everal small ornaments representing bees that had been placed .MI a cake. In the afternoon .,f the same day they became very ill and were attacked with severe vomiting and great prostration. The vomited mass was at first yell. >\v, and was tliro\\n up with irn-at pain. Vomiting continued until 11 p.m., after \\ liieh it became infrequent. When the physician arrived, at t> p. m.. they were in bed and suffering extremely. They had reddened faces, complained of irreat thirst, were languid, had no dysentery, allli-m-h they complained of .-light pains. " Annales d'h\ L'iene. I'd - 1 I. L875, '> Vierteljahres.-chrift lur L'erichtl. Medi/.in. Is7l. 'JO: 90, 1'YRKTHIMM POWDEB8 CONTAINING POISONOUS tfKTALS, It was easy to see that they had been poisoned, and since in the in. irning they had catni the -aim- food as tin- rot of the household, \\li«» remained in perfect health, probably the poi.-oning was due t > t!ie above-mentioned bees, -even df which had been -jivel! to the children t<> play WJtll, while only <'Iie could lie found. They finally confessed that they had eaten the remaining six. and the nurse had Been tlu-ni d<> it. The nur-e thinking it might In- harmful, had taken a softened ' fnun tlie younger child and wiped out his mouth. ( >ne .if the "bee-." of which inoiv were found at the coiifect i. HUT'S \\ ho had tin- cake, uas examined by a chemist and found to consist of Lr,lm ;m,l l,.a,l rhromate. On the following day both patients ha, evidently because their sense- weiv lieinnniie.l. The younger had some diarrhea and toward noon convulsions, from which his face was livid. The convulsions became more freijiie.it toward evei:in-_r. and at '.» o'clock on the morning of the following day, March M, tin- younger boy died. The older child still had a red, heated face and displayed no interest, beim; almost unconscious. The skin upon his In-east and alidomen was strikingly red. The even- ing temperature was :'•° in the armpits. On the 17th the pulse was irregular and the temperature in the eveiiin-j M. «>°. Drinking \yas extremely painful, in spite. ,f ureat thii'st. ' >n the ISth a foul smell came from the mouth, i-edness was still pi'es- ent. acemn]»anif«l l»y stupidity and painful swallowing; temperature in the eveniir: was 39.2°. < »n tlie lUth a c<»llapse took place, a very foul smell came from the mouth, and swallowing was almost impossible. The senses were very much benumbed. anH death followed at 11 a. in. The result of the post-mortem may be summed up in tl e words of tlie physician as follows: "The death of the children is the direct result of the lU-st ruction which ha< befallen the digestive, canal from the throat to the duode- num. Coiu-erninir the cause of this destruction and concerning some further con- ditions \ve will not express an explicit opinion." The liver, gtomach and contents, and urine were then subjected to a chemical examination. This gave negative results, except that in the liver of both corpses traces of copper were found, a dis- covery of no toxological interest. The absence of all poisonous metals in all other parts ,,f the corpses was shown. The "bees" were also examined, and o.L'7 -ram of gum and 0.0(141* uram of neutral lead chromate were found in one that was 1:5 mm long and "> mm thick. The pow- der used by the conk-ction«-r was also analyzed and found to contain lead chromate. The illness of both children, occurring at the .-ante time and showing it-elf by E vomiting, must be traced back to their eating some poisonous food; and since it was known that they both ate the "bees" which contained lead chromate and that they vomited up yellow vomit, the eatinir of the metallic salt must be considered as the cause of the deaths. It is not remarkable that no lead chromate was f.itind in the alimentary tract, since the children vomited a great deal and thus threw up all of the poison. FATA I. 1'MlMiMMi 11 Y IMIAUV; Dl>T FIIO.M YAKN CoLoliKD WITH I. MAD On December 21.), lS7(i, a weaver. I'... at E., received a package of yellow threads, colored with lead chromate, which were to be used for the manufacture of curtains. P.. and his mate. < ... worked at one spool and Mrs. I',, and a girl, L., at the other. They worked from 7 a. m. to 10 and 11 p. m. While they were working the threads shed powder, according to P.. '»tatement, >o that their faces and hair became entirely a VierteljahresBchrift fur gerichtl Medi/in. Is77. 27: 2n < No, 1 ). 10 INSECTICIDE STUDIES. « yellow. Their spittle appeared yellow, and the powder had a hitter taste. Accord- ing to Mrs. B. the powder had a sweeti>h-bitter taste. The male helper sickened alter working upon the threads about eight days; he had a headache, with a ringing in the ears, pains in his hreast and stomach, and lost his appetite. lie had a desire to vomit and was constipated. This continued for six weeks, until he ceased working and went to the doctor. Mr.-. P.. during' the meantime hecame ill : she complained of loss of appetite and pains in the chest. P>. on the last day of the third week of the work was attacked with pains in the stomach. Then appeared nausea, languor, and sleeplessness KL'ht <>r ten days later he was ohliged to stop work and send for the doctor (.n account of pains in the bowels and costiveness. The girl helper was also ill. having diarrhea, loss of appetite, and pains in the breast. Dr. ,T. stated the symptoms of B. and the helpers in the following terms: Yellow- coated tongue and yellow expectoration, entire loss of appetite, nausea, temporary vomiting, and pains in the region of the navel, accompanied by obstinate constipation. The excrement was also colored yellow, and all the patients were very weak. The doctor stated that these symptoms were all caused by breathing yellow dust from the yarn and indicated plainly lead-chromate poisoning. Although all of the above-mentioned persons finally recovered, B. lost a ^-weeks- old baby, whose death could be ascribed only to the breathing or swallowing of the yarn dust. When the l».'s noticed how much dust was (lying about they sought to protect their baby by spreading a white woolen cloth of medium thickness over his fact-. Thn doth was said to have been yellow with the dust all the time, as well as the bed on which the child was lying. The child's crib stood midway between the two B.'s stools and at night the mother took the child to bed with her. It was healthy and lively, so that continued poor feeding could not have caused the bad condition of the stomach (jelly-like softening and perforation) observed at the post- mortem. Suddenly, six or eight days before its death, which occurred on February L'4. the child was taken sick. Its face became pale and its body hot. It had a couple of loose, yellow actions each day, which were accompanied by restlessness and freijuent screaming. The skin upon the breast and stomach became red. In the bfjmnini: the baby drank, but refused to eat; later it drank with trouble, and on the day it died it swallowed with difficulty. The lips were dry, the breathing short, and death followed slowly. It is to be remarked that the child, after remain- ing healthy for -ix weeks in spite of the surrounding yarn dust, was suddenly taken sick six or eight days before death and grew worse at a time when the yellow yarn was not beini: worked upon. Since the child remained covered with the cloth up to the time of its death, it appears likely that the dust gradually worked its way throii-jh the cloth and sifted down so that the child always had to breathe this impure air until its death. A chemical examination \va> made of the following organs of the child and the articles that were used at the the time of his death: Contents of the nose, contents of the -tomach. urine and gall taken from the urine and irall bladders, organs of the stomach and breast, the hair of the head, shirt slip, the child's nipple, and a portion of the yellow yarn. The brain would have been examined, but the vessel contain- ing it was ln>t. The yarn «•• .ntained ll.s:; percent lead chromate. Lead chrmnate wa- found in the hair of the head, and the little slip contained >;."> mi: lightly strewn t. The organs of the neck, chest, and gullet contained 36 mg of lead chromate. The ..ther tluids of the body and organs, the shirt, and nipple did not show the presence "f any lead chromate. It will thus l>e >een that mimt>rr> of authentic ra^vs of poisoning, by either luvathino- or ^wallowmo- Ira<4 found sc-voral typical cax>s of poisoning by alkaline PYRKTHKl'M 1'<>\V 1>KKS ( '< »NT A I M N(i POISONOUS MKTALS. 11 eliminate^ and l>irhn>male- -circled from the larov number (hat havo been oldened l,v Messrs, Dt'lperh and Hillahv:" MKMMII:> CONCERNING DANGERS T« » WINCH \V<>I;KMI.\ i\ M\n: KA \ 1:1: < >i:>r.i:v \TIOX I. — Workmen tmptoyed for a /<>n beginnim: at the grinder and sifter, and is thus constantly enveloped in an atmosphere charired with line elin>me-iron powder. He says that he feels no indisposition. He wipes his nose ami s[)its Itlaekish matter, luit neither roiurhs nor has any smotlieresi'j«- wnv .•\amined. and a per- foration of tlu> cartilage was observed. He says that since entcrin-_r tin- facti'iy In- has sometimes worked at the kettles. At the commencement of this labor he was attacked with headache and swelling of the nose accompanied l.y an abundant dis- charge from the nostrils. His eyes did not smart. These symptoms lasted about fifteen days, after which he regained the most perfect health without even experi- encing again the symptoms enumerated, although employed at the same work. This workman has since (October, 1804) died after a few days' illness of inflamma- tion of the chest, without having previously shown any prolonged symptoms of suf- fering with the respiratory organs. MK>I-:UVATION III. — \\'<>rL-//ioul four //w/-.« — Injln i tlon of fjif' in neon* iiicintii-iiin' of tin' nnsc -- V,,,r /'/;'/// ffie rlf/lit tJnn/lh — A nnxd/ JH rfOTCL- fion — rirci-dtioii of hot 1 1 of t)n' t'.i-fi'i-ttn/ nitxiil n-allx. \'... aged 2S, who had a good constitution, had been employed for five weeks in a potassium bichromate manufacturing plant when he was examined by us. He was employed about eight days inside the works carrying the bichromate and for three weeks at the kettles. From the first day he was attack* d by prolonged ami intense sneezing. After four days he suffered greatly with intense prickling, abundant run- ning of the nose, an incessant desire to blow his nose, and the passage of red mem- braneous shreds. He had no watering of the eyes, or at most it was slight. The most severe sym i >toms lasted from ten to twelve days. He had nearly recovered when he stopped working at the kettle, and has since completely recovered. This workman still has his sense of smell. He was afflicted by a sore on his right hand, caused by penetration of particles of bichromate in a slight excoriation, and a slight ulceration still remains. One can also note brown spots, caused by sores of the same nature, upon the side of his face and on the ring finger. E. has never suffered with his feet. He has no eruption either on the skin of his body or genital organs. His eyelids are not excoriated, and he has neither vomited, suffered with diarrhea, nor a cough. The nasal partition is perforated at the usual place. " Annales d' Hygiene Publique et de Medicine Legale, 1869, and 1876, 2d series. 12 1. \SK(Tiri I >K STUDIES. < >I',M:I:VA HON VI. — Workman, a coppersmith -in«l t, tin- iit«iiujf tin1 L-itf/<« — of tin' iittK-'iiix nn,iinr«ii: <>f tin nOSe "//'/ F., a coppersmith ami a strainer to the chromate factory, came into the factory for a short time TO repair the kettles. This repairing required a readjusting of the sides by hitting with a hammer, and these Mows caused the crust of bichromate that a«lheres in the slightest irregularities to fly about in tin- form of a dust. He was attacked quickly l»y inflammation of the mucous membrane of the nose and lost his .nasal partition in eight days. ( >i:>i-:i:vATioN XI. — Superintendent^ not employed «t i'<-in} n-oi-k — <']ir<>nir irrita- tion, x/r, //;,/,/ <>J ill i' tin nioi'iiin' d( tin' usual filar, , /,/// )i<> /„ ,-f<, ration . 0., aged 20 (December, lsi;:5i, has been employed for four years in tlie eliminate works. He ha< never worked at the kettles or the culciner. Charged with general surveillance, he merely walks through the works; in exceptional cases, however, he helps solder the lead crystalli/ini: vats that are in need of repairs. He has conse- quently to a certain extent been subjected to the action of bichromate. At the time we examined him he had felt a tingling of the nose and had frequent (its of snee/- inir. but his nasal membrane had not been badly inflamed. His na-al partition is not perforated, but at the usual point he has a slight swelling and reddening of the membrane. His general health is good. ( M-.>KKVATlo\ XVII 1. — /•*.",-, ;//'/!/ <, has Itt-eii employed at the works for two years, ami for the last ten months at the manufacture of potassium eliminate. He is employed as a fireman, but often helps his fellow-workmen, and so •luring much of the time spent in the factory he is expo-ed to chnnnate dust. He had always enjoyed the best of health. He had never had syphilitic symptoms, but during his infancy the glands at the side of his neck were swollen fora longtime. His general condition is good. He had worked at the manufacture of potassium chromate for scarcely iifteen days when he was taken witli nose bleeding, snee/inir. pain in the nose, and watering of the eyes. He .-oiiii'tiinrs experienced a little uneasiness in breathing. It was fifteen or twenty days after he had ceased to work at the preparation of potassium chromate that he examined his nose and found a small perforation. The nose preserves its normal form. There is an ulcer on the nasal cartilage in the right nostril, and at the edges of this the mucous membrane is very much inflamed. In the left nostril is an open- ing corresponding to this ulceration. Hi- sense of smell is pre.-erved: neither the throat, palate, m,r roof ,,f the mouth have been attacked, and he has no cough. Thi- workman has hard, cartilaginous, livid scars upon his thumb and his right hand. On the left index linger there exists a sore which is much swollen and exudes a sen .-purulent liquid. This workman has never had any swelling or ulcera- tion of his feet. Tin-re are many other observations cited in the ahove article, hut eiKuio-l, l)aVe |MM.n o-ivcn to ^how that pei-Noii* who are ohlio-ed to hreathe air charged with the du>t from chromate^ or bichromate- are nearly ahvav- atleeh-d more or lr-s >rriou-dv. PYRKTHRl'M I'oWhKliS CONTAINING POISONOUS MKTALS. 13 ANALYSES OF PYRETHRUM POWDERS. COI.LKCTION « >! -\M1M.I 9. In order that -ample- of pyrethrum. repiv-rntat i\ e of all grades, might be obtained. :i circular letter wa- forwarded to the chemist of each of the experiment station-, with the request that they puivha-e for us. upon the open market, three or four samples of those product- sold under the name of either Pyrethrum. Huhach. Persian Insect Powder, or I)almatian In-ect Powder. They were also asked to give data, a- to the price per two-ounce -ample, the name and addiv-- of the retail dealer, and the name and address of the pel-son who originally prepared the sample. In answer to these letters In;. Cample- were received, all of which were subjected to chemical examination. It is helieved that these samples represent fairly well the present state of the American market. Credit is due to the assistants in the laboratory. IVrnard II. Smith and Harry AY. Houghton. who aided in performing the analytical work. MKTIlons AND IJKsn/rs OF ANALYSIS. Since lead, potassium, and harium chromate have all a bright yellow color, and any of them might he used to color the pyrethrum powders, tests for all of these substances were made in the samples under exam- ination according to the following methods: (hnil'tinl'it; f.str'ur I, <-/u' x • ^ : ~ T ~ -^ E ^ Z -~ ' "T > -— - ** - " = r JSEJE--.^^-:^ jl: : ^z -: . 51 ^l^f K 5Z*rfJ ^7 ^.= -~^" = -X. rx. ~ X ^ t ^ >* • z. ''• - '- & 2 w o = -^cr:- ^ - _- i -'. = - 2i^.3r.:T- jj^Ul^^l -£.L'--i giS^ •^ - - /; - & ~ it ^'c :t:::t «*:«:«>'::: :::::::t:: : : : : = -:::- - r|: . |||||I| I i: ll l I .•Z^£L:i; n ri7.7i7iti7.Vit. : :: :: :: :: :: PYRETHRUM PoWDKKs CONTAINING! I'ols<>N. .; : : -j . . ^ ^'C-- : : ; : :T; £ H : r^ . I 7 = s ~ -- _£_£ = - I I' r : = = ' r ;^ = z = = m - f^ji IJ!1 = 7;7'/ ::: 16 INSECTICIDE STUDIES, TAMI.K [.—D&cription of samp . an • 1 _-x- : . Parks. Davis A Co.. Detroit, Mich rln .. Bnimdi Manufacturing Co., Stoc .. I'arke. Davis A: Co., Detroit, Midi . . Hrowncll A^ Field, I'rovideiiee, K < )|j\ er ,|i,|in-uii A Co., l'fo\ idellei \ii-lin. Nieho Is A CO., N.-w York, /.. D. (,'iiinan. Washington, D. c . : : : : a, < iaraon, Ka-i r.radi'i.ni, Vu . \V. Lyle, r.radlord.Va 1. Mei 'arlor, Moscow. Idaho . II 1'iif-ell. Mo-ri.W. Idaho ... ;d ;fl I 1 IN - .- _ - - j ; : Ca-tillian In-eei l',,w«ler .. I'er-lall Ill-eel \;>\\,\, 1 Ill-eel p..wdiT •i Ili-iet l'n\\ di r Mnhadi II Ill-eel I'M \\del . di, •- .- } <— r 1'YRKTllRl.M I'oWDKRS CONTAINING POISONOUS ICETALS, 17 dr\ lie--. Treat ULi'ain with concentrated hydrochloric acid and evaporate (,, dryne-^. Take up the re-idue with ahout <>.> <•<• of concentrated hydrochloric acid with the aid of heat. Filter and pass hydrogen >ulphid through the solution until all lead i> precipitated. Filter and evaporate the tiltrate to dryne--. Take up the re-idue with a little water and 1 cc of hydrochloric acid with the aid of heat. Precipitate out the chromium (with iron, aluminum, and some phosphoric acid) by means of ammonia, taking care not to add any excess of ammonia. Filter and wash with hot water. Dissolve the precipitate on the tiller by means of hot dilute hydrochloric acid and evaporate to dryno-. Take up with a little hot water and »'• to s drop- of concentrated hydro- chloric acid, heating for a short time if necessary. Transfer to a 50 cc 01- Inn (•(• Hash and make up to the mark. Now prepare an alkaline permanganate solution in the following manner: Make an approxi- mately X 1<> solution of potassium permanganate and standardize it against ammonium ferrous sulphate. Measure out exactly a liter of this solution and add a few grams of sodium carbonate and 1 gram of sodium hydroxid and make the entire volume up to 2 liters. This is the standard solution required. A convenient number of cubic centimeters of this standard is measured into a beaker and about 50 cc of distilled water, accompanied by a little sodium carbonate, is added. The solution of chromium previously prepared is then run in from a burette, while the contents of the beaker are boiling, until the pink color is dissipated and a pure yellow color results. Knowing the strength of the permanganate and the number of cubic centimeters of the chromium solution used, one can calculate the percentage of chromium in the original powder accord- ing to the following equation: CrCl3 + KMn04 + 4 KOH = K2CrO4 -h MnO2 + 3 KC1 + 2H2O In Table II are found the results obtained upon the samples of pyrethrum powder examined: TABLE II. — nf />;/i-;'.i 270 'J / 1 272 Persian Inject Powder . . Absent Ab<,-nt ... Present... do ;»• /• •-, „(. .071 I'' r cent. ""6." 32 .23 Dalmatian Insect I' do « Examination for barium grave negative results for all samples. 26958— No. 7&— 03- 18 INSECTICIDE STUDIES. TAHI.K II. — Ebcamination <>f ],;//•< thrum j>mnl, r*j<>r ru/f/riin/ mail* i- — Continued. Serial No. Name. Chromium. Lead. Chromium trioxid (Cr03). Lead chro- ma te (PbCrCV). a 273 Dalmatian Insect Powder Present Present l'ir c> nt. 068 /'M- <•< at. >•) 274 Spa la t<> Insect Powder Absent Absent •'!••> Dalmatian Inject Powder Present Present L80 4-> 27 •J7>> do Absent Absent .. 279 lllsect PoWU'diT .... .... . ...do .... do 315 Pyre thrum Present Present I'M 40 316 .' do do.... do... .102 .33 317 1 >aimatian Insect Powder Absent \bsent 318 do do.... do.... a3l9 Persian Insect Powder Present Present 1st; .60 393 Buliach Vbselit Mi^ent 324 I'vri-t liruin ...do... do 325 do do do 3'>6 do Present. Present .'Jol .M 327 Persian Insect Powder do do 365 1.18 do Vli^-ent Absent 3'>9 do Present Present 421 1.36 330 Insect Powder \hselit V ' psi-nt 331 ....do do do 332 do do do 333 do do do 334 do do 335 do do do 336 Pvivt hnim do do 337 do do do 338 do do.... .. .do Persian Insect Powder do do « 340 Pvrethrum Present Present .090 . 'J'.t 341 do Lbsenl Absent Dalmatian Insect Powder . . do. do do do do IVr-ian Insect Powder Present Present .043 .14 387 Inject Po\vdcr Absent Vlisellt 388 'i Inject PI, wtK-r do 389 do do 390 . do 391 ...do do do 392 Inject Powder do do 393 d.. do.... . . .do . . . 394 do do do Biihach do do 3% I'i-r^iaii In-eet Pouder do do 397 do do do 401 I>aliiiatinii Inject I'nwder do do 402 I'vrethruin do . .do. 403 l'er>-iaii Iiioi'i't 1'owder do do 404 Pilack Fla" I ll^eet I'owder do do •ll'i Pvtet liruin Present Present 087 12 420 do do do 056 .18 •rji Insect 1'owder \hseiit Vlisrllt 422 IVr-ian I n^cct IN i\\ dcr do do (.'.; In^t-cl piiuder.. Present Present . IM; .<\o I 'i do Absent Absent 425 ...do. . do do do do do Iiiilinatian Insect Powder 1'n-M'iit Prevent. . 1.17 08 Ilix-cl Powder. Absent \l)-rllt ,; do 430 do do . .do do ...do ... ...do ... ill) do do ... do do do r.i do do d.> do do.. . 492 1 IK hunt liin In»'-«-t l'ii\\di-r do do Hnhac:. do do. 494 Pyrethrain do do Ill-i.-ct J '..•..'. do... do!.. agee eorretpondenoe with manafaoturers, p. J". 1'YRKTHKIM l'<>wi>KK- OOJTTAINING POISONOUS METALS, 1(.> Tvr.iK II. — Kniiiiiniitioii »f f,i/ntli mm powdcrsfor coloring until, >• ( '< nit inin-i 1. Serial No. Nairn-. cliroiiiiiiin. Chromium Irioxid (Cr08). I.i': id I'll To mate 1 ' '•<>«). I iiM'i't ]>o\vdrr Ibeenl Pei- <•• nt. M'M'lIt . /•< /• ,-i nt. Mil I'vivthnmi lVr!" I'yrt'thruin Oalmat iilll Ill^cct I'oudrr <\« . . . . do do do 513 Buhach . do. . do... :."i do do do .1(1 . do . .. do lVr»ian Inject 1'oxvdrr do do Huhach ...do. . ...do... 642 I'vri't hrum do do 847 In^'i't I'mvtlrr do do 648 do do.... do 649 IVrMan IiiM'i'i I'owdiT do do Huhacli . . .. do. ...do... 604 IllM'i'I I'oNVdtT do do do do • I' > do do t'>''7 IllMTt I'oU'dcr do do n I'l/SSt) Persian IiiMM't l'o\vd«'r ... I'lVM'Ilt . I'M -rill . 1 IT oQeneral index number. A glance Jit this tiihlo shows that wherever the powder^ arc colored by a foreign siil)stan(.-e lead chroinate is the compound used. Nine- teen of the 10.") samples, or 18 percent, were colored by lead rhromate. the amount of which varied from 0.1*2 to 1.47 per cent. Of the adulterated samples, 5 were sold under the name of Dalmatian Insect Powder. ."> under the name of Persian Insect Powder. T under the name of pyivthrum, and :> simply as insect powder. It is also evident from Tallies I and II that some linns are sending out two grades of pyrethrum, one containing lead chromate and the other not containing that substance. It is unfortunate that the names of all those who originally prepared the above -ample* could not be obtained since the powders containing the largest amount of lead chromate lack the name of the manufacturer with surprising regularity. It seems hardly necessary to call attention to the widespread harm that is undoubtedly caused by powders thus colored. They are sold in all parts of the country and are especially advocated to kill or drive away flies, fleas, cockroaches, and other household pests, and thus they are used principally in the home. Consequently they are breathed by many people for days and weeks at a time. Such powders not only possess the poisonous characteristic.* of nearly all lead salts, but in addition have the toxic properties of chromic acid. It would appear, therefore, that the influence of lead chromate day by day no doubt occasions many of the mysterious ca-es of lead poisoning in which it seems impossible for the physician to tind the -oiirce of the lead taken into the system. CORRKSI'ONDKVK WITH MAN t - 1 \< I I K Kl>. In order that the manufacturers might have an opportunity to com- ment upon the analyses before they were published, a circular letter INSECTICIDE STUDIES. M-nt to ouch 0110 whose goods had been examined. giving him the ivsults of our analysis and asking for any comments that he might desire to make. Such parts of the an-wer> as throw any light upon the subject are given, as follows: SferioZ X<>. 340. * * * You say that tin- Yaroter-Bo--- I>rnir Company. of Lafayette, Ind., fur- nished you with a sample of our insect powder containing O.L".» i»ercent of lead chro- matf. If such is the case, they added the lead eliminate themselves, as we do not use it. We do not color our insect powder, hut leave that for the customers to do if their trade demands a highly colored powder. ALLAIRE. WOODWARD A: Co. Comment: Et appears that the above sample was probably colored after it left the hand* of the manufacturer, since seven other samples of Allaire. Woodward oc Co.'s goods (N OS, i'«5i». i>71. L>SO. L>,sl. 'V.4. 4'.»»;, and .V.U ) contained no lead chromate. Serial No. * * * From the mana-vr of <>ur importing department we also receive the posi- tive assurance that the powder entering into your sample No. 27.'5 could net possibly have contained lead chromate as it left the hands of his department. It goes without saying that wt- never add lead chromate or any other foreign substance to our insect powder and that the adulteration which you report must have been deliberately put into it by s .me interested person after it passed out of our possession. I'AKKK, DAVIS ^ Co. Comment: It appear- from investigations which have been made that the above sample received the lead chromate after it left the hands of the manufacturer named, if indeed it were manufactured by the linn originally. Fourteen other samples of Parke. Davis c£ Co. 'a good- (Nos. 272, 313, 331, 334. 885, :-JiH. 4<>i>. 403, 510, Ml, r,47. 648, »'>4!». »;i>4) contained no lead chromate. N- I'ifll \n. 386. * * * M.-H--. K. I >. Stearns ^ Co.. r.urlin^ton. Vt.. are in error as to the source oi the per.-ian insect powder which they furnislu-d your representative, stating that it c;ime from mir firm, and we have written them to that effect and asked for an expla- nation. We have examined their entire account for the year I'.iOl*. and positively -tale that they did in>t purchase any insect powder of u>. and if they had it would have been found to b<- perfectly pure, as we d« not allow any adulteration of lVr>ian powder Mild by us. >i 1111:1 l'i:i IN A : It i< probable that the retailer made a mistake in giving the -oiii-ce nf hi- inject powder, since another >ample furnished by SchiellVlin ^ ('<>. (No. iv.') contaiin'd no lead chromate. "' \". .;/;>. We presume that this analysis is approximately correct, and that then-litre there i> foici-n matter in the ins.-ct powder amountim: t" a little over one-half ol 1 per rent. This additional matter i< undoul)tedly added, not for the purpose of adnl- I'YRKTHRIM l'( )\V 1 > K K- CONTAINING POISONOUS MKTALS. 1>1 teration. I'm for the purpose of brightening tin- color of the -roods. * I'ntil recent years it \\as the custom to sell only rly the colored only, we Jselieve, to one customer, who ineista on getting the same. * * * The part it-ii la r lot ot' \\ hich you sent us the te-t, ho \\c\er. i- not of our o\\ n po\\ . and \\etherefore lioiiLilit in thiscounti-y the insect powder of a hrand that ha- l»eeii held to l>e one «>f the most reliable and has had an established reputation tor OVCf fifty year-. Tin- exceedingly small am<.unt <.f finviirn mattei- ad p.'i- cent, proves conclusively that the oliject \vas not to adulterate the powtler. SMITH. KI.INK ^ Ki:r:.\rn Co. II. A COMPILATION or ANALYSES or INSECTICIDES AND FUNGICIDES/ INTRODUCTION. In a recent publication8 of the Bureau of Chemistry analyses <>t' all the insecticides and fungicides that could he obtained on the American market were o-iven. together with such remark- concerning their etlWt- iveness as the re-nlt- -ecmed to justify. It was originally intended that all of the analyses which had previously heen made by the various experiment stations should he included iii that bulletin. By rea><>n. however, of unavoidable delays, two years passed between the time of collecting the samples and the time of completing the analyses. Since results of this kind, to he of the most value, should be published at once, it was thought desirable to reserve the compilation of results obtained in the various States for a future publication. This article- therefore includes a compilation of analyses of insecticides and fungi- cides made bv the various experiment stations, together with a few analyses made by the Bureau of Chemistry since the publication of Bulletin «i.s. The insecticides are arranged in oT<>ups. as in the previous bulletin, with the addition of two or three <-las not taken up in that publica- tion, and the omission of a few classes not examined by the experi- ment stations. They will be considered in the following order: (1) Paris o-reens: ('2) London purples; (•">) insecticides and fungicides, other than Paiis greens and London purples, that contain arsenic, copper, or both: (4) soaps: (.'•) lyes: (»'.) hellebores: (7) mixtures containing borax: (N tobacco extract.-: (!») formalins: (in) petroleums: (11) mis- cellaneous solid insecticides and fungicides, and 111') miscellaneous liquid insecticides and fungicides. SOURCES OF ANALYSES AND DESCRIPTION OF SAMPLES. Table I. on the following pao-<^. is introduced to show the publica- tions from which the analyses were taken anjd, when possible, the names of the manufacturers of the various compounds. " Xo responsibility is assumed l>y tin- Drpartment for the correctness of compiled analyses, not made within the Department itself. ''U. S. Dept. Agr., Him an of Chemistry I'.ul. US. The Chemical Composition of Insecticides and Funiricides. 23 24 INSECTICIDE STUDIES. ancashire s. •<>, Cal. ali Works Co. y A- Maels, San Fra w York City. A i n.t. nirle Ne Hal.l.i rican '. — — — — — — •— ~ — — — - — = - in N tal io in n pe cn ;£-5-5-f-r-f;£-r-f-5-r-r-f~-f-f-^^y^ =:1.^Z:-i!_-1r - : ANALYSES OF [N8E< CICIDE8 AND FUNGICIDES, i if 'r x B« d £8 «| « '.' t -rcf -:_ 1 Jl lt= sh • • < • ; : i ; i i i ; : :i i i i 1 1 •§ 1 i i i ;| 1 i ::::::::::::- --\ •-. ----- ••;• ;;•;;''• x X X X x x. x x. ••?•»••.= = = = = = = = - r :::::::::: ;| • £ £ • • - "— ~ "- "- *- ~ *— ~ • — — • i^ ; ;l .! 1 i I I I I .! :::::::::: itTimlly unit Slat • ::••- S . jS 3> jj - - . ~ - - ; -^ ~ ; ; V. / >.' /. — 'L • / /- p '/. '/. V- | g • • r • S S •••—••——•—— i. —Z - — - - tl .•:-•-..:=:—=:— r— :r— r r~ r z ; jlfl • X ~ X ~ X ~ X .T X ~ X - X -7 X ~ X _ . i. i, . ...,-... L- -.- •_• '.- =: '.- lr -.- lr •.- L %• ^- -.- = : x x ; ; ~ -/ ~ y ~ ? ~ ?_ ~ 7. ~ y. ~ ',[ ~ 7 ~ - J •C o-c _£-£.£_£_£_£_£.£,£,£.;: ;~ ^ •c f -^ « ::::::::: i i ; : : : : o : - - j-'-j j j :^:§:§^^^ j i: : ! : I I i ! 3 |i Jj :u :^ I "* *« "S s -cccc: • =• y • r .-•-.- - • \i --. i \ = = i = H HI £ ; 1 1 f. 1 * i 1 1 ill | c -r-5-f-T-5-r-r-r-5-f-5-f-5 /. LJ ^ -f Doooloeo* - : - - - ~ — — — = —71 y. / / . / — ' ' / ilP -. -. -. -. r : - -.-r; -jj fl f - f •_ I ::::::::- = = ~ •= .- ~ ~ = 26 [N8EOTICIDE STUDIES. Manufacturer of sample. etin No. James Blanchard, New York Cily. Do. Do. Do. etin No. Adlcr Color and Chemical Works, New York City. Do. Do. Nichols Chemical Co., S\ raeii-e, N. Y. Dan forth Chemical Co., Lcomi lister. Mav-. I. I'feitTcr. New York Citv. A. B.Anshachcr. New York citv. Alsbertf A: I'fcilVer. New York Cily. llampden I'aint and Chemical Co., Springfield. Ma-s Caw lev Clark A: Co., Newark, N. J. 1. A. Blanchard, New York citv. Do. A.B. Anshacher. New York Citj Let^elt A: Bro., New York Citv. !•:. & P. King Company, Boston, Mass. C.T. Reynolds & Co., New York citv. J. A. Blanchard. New York Citv. ir 2 — V C.T. Rev -nolds A Co., New York Citv. I. I'feilVer, New York Citv. .1. A. Blanchard, New York Citv. C. N.Childs A- Co., New York citv. Letfirett A- Br >., New York City. \. B. Ansl.acher A: Co., New \urk Citv. Do. 1 > IV.MI,. ;j| M £ X . Hutch Kxperimeiit Station. Miissucliiisells, Bull ilion, Massachusetts. Bull X, f; i | c ~ c • •/. :::::: : 2, : : : xpcriment Station Repot do do.... do Hatch Kxperiiiient si 71 i I'.HH). 4444444 4444 444 4444 llaleh K.xpcriment St •::::: : jt; :::::: 7 : : -•f-f-r-f-5-r-r 7 --r-r-f-f-f- 7---?-r 7. '.:::• :?§: : : : : : jid :' : c — I —~ • • • • l.ion hraiid) l.ion l.rand, ne\v ]>r< [| j ii -: • - ^ : : ;•- . . z : \i •f -c-r^: : if Hi jd • • • _ c • : : - - aii i :-^ '•.- jjig i i Illi -• op- - 4 ^ SaS! li:.^ 44 sssa '- L Z • = - -J i = 'if'£ i g C — ~\:- — •'. -~ i-rr. =-i\z~ 3$ b o§ A.NALY8E8 0! [MBECT1CIDES AND iiiijMiii ( IV'I i. p. :;f. LeWet( »V Co., New York Citv. A. ,1. Peek, Meridian. M Mansfield Dnm Co., Memphis. Teim. L L. Lvon-. Neu < irleai No. L'.") (1 '.»(« H lohn LUCEB & CO., N.-u York Citv. . Acme Color Work-. New York Citv. . A. H. Ansbachet A Co., New York cit\ K \\ D &CO '-' 1 ITOI c. T. Reynold* A Co., New York City. Do - 3 /^ ~ QQ IlemiiiLru a\ '- London I'urple ( o 1 W W.-i A .i.n mj Boston L.'-L'.'il A Mm- N.-u York Citv. Hulk-tin No. 43.. . pp. o'.tT- Wet here] 1 A John Li K -a- A Co., N.-u York Citv caui.-v. clark A Co., Newark, N. .1. .... C. T. Revnold- A CO., We* York Citv. Cawley, Clark A CO., Newark. N. .1. Robert Slioeinak' lohn 1 \. u York Citv. .1. A. Hlanelinnl, New York Citv. Do. . .. l.elTL'ett iV Hlo- . N. U York CitV. (; s z z z — — ~ ; ; ; = P 1^:||| : : .y.y. - - - ; - - : : z - - - -^ i i : i I i I i ; i'S S ! i 1 1-' ::::::::: :^ Bf | j-j >o « • . . . . . and In-eet De-tr. <•( l-.M.Tiniiiator : : : :::::- .[•Bill t i|j.p!Ul!l- ! .•!;!] y- -r-~^c--— - '5 ~ "9 ^ o o o o o o o o p o c -~^.J;i~3J:~;f £-.i ------ ~ ~ ~ -r ~ ( uiental Kertili/er Nollpoi-olloUs Iu-( I'uris (ireen • ;i \ en London I'urjili-. . . Hellebore do 4441- : : £ 44 ~- 1 l|n 4 4 4 4 1 1 1 ~L 4 4 4 : i£££$ 5 2 28 INSECTICIDE STUDIES. j iCsSsllag ^ :^i -5 •f -E 4, -r-r-r-5 -f -T -f ^: Y !: ^.'^T^ I 71 Tl ri TJ Tl ANAIAH— OF IN-K( TK'IDES AM) 1. 444-4-444:14444444444444 — ———— — — i ; g£ 30 INSECTICIDE STUDIES. i I £J ;< .11? Iljlf I<1!=4 *fsSJ C ^ £ ^'s- = — > ,=:J ? - ii II ; I ^f : Tlf 51 E« :-~ = = * :• iiifSi i^i£ 1-jjjjJI ::::;: x : * i i!i|*jj*j| jijiji n 'I "/- : x. ; iniiniii in 111*1 ; ; :=A If -\\ :• ;?--| ! Mil! Ml if M IS l| H| 1 r!!i:iu: ::::::: 1 - ' i 7 riiiu-nt Station, l'i §1 1 1 1 111 i 11 ill PI if i! §1 Pi : : :|« : :a :--.= : : : : j.;.= • -~ -••=•- ^ = - - 'iT ;! : : :i~ : :.= :;;x- : : : '.i-c ::::::: '— - -• • i : x ; . . v - . . . . ^ 2 • '• \-Z \ : = :•= i- ; j : \u^; ;;;;;; ;;;;;; llf x : •i"^ "5 : : : --. <§•§•§ is-§<@s-sMi-§-8-§-si;3 FUNGICIDES, 31 1 '- •?'5~5"5 c'S : : : : p : : : : cc crc - --- E • ; ; ; \ £ ! : : : : 1 j^. - : = . ^ 1 n ! ! : ?; ' 1 i J •! 5 •eldor in>cctii'i(lf {(•(I Cedar brand ). ite A rscllic "T _£ .- = ^ •bo K reaolate Mssiuin c\Miiid C.t'.i | -~ i - s* :££ 2l ^ ^ - •• -^ i~ 32 INSECTICIDE STUDIES. I'AIIIS The analyses of a large number of samples of Paris (ireen arc given in Table II. together with notes that aid in explaining the methods of analysis used. Whenever the method of analysis was given in the <•rigin-.il publication it i> quoted in full, not only in this table, but throughout the bulletin, in order that the reader may judge for him- self of its accuracy. In a number of cases in which only one or two constituents were determined in samples of Paris greens the average of all the result* is given, mentioning, however, the number that fall below the generally accepted standard for such goods. METHODS. The method of determining arsenious oxid in samples Xos. 1 to U, inclusive, was a< follows: \\Viirli 1 Lirani of the matt-rial into a beaker, add .'-JO cc of strong hydrochloric acid and digest at a temperature below the boiling point, adding small quantitiesof KC103 at moment intervals. Continue lieatin.tr until the odor of chlorin lias disappeared, dilute with water, add ammonia in slight exce.-s. cool, add magnesia mixture drop by drop. stirring vigorously, and let stand twelve hours. Filter, wash with ammonia water, and dry. Ih-tach precipitate from lilter and iirnite lilter, usin^ ammonium nitrate. Transfer tlie ]>i>ecij)itate to a porcelain crucible and heat for a while on an iron plate and linally in the direct flame. Add lilter ash and wei.irh as ina.iriH'siuni pyr< -arsenate. In. simples No-. :•;? to .">.">. inclusive (19 samples), the following method was uM-d for determining soluble arsenious oxid: Allow 0..") if ram of the ^reen to stand in suspension in 50 cc of distilled water in a stoppered cylinder for one week, with occasional shaking, and titrate an aliquot littered portion of this solution for arsenious oxid. The method for determining total arsenious oxid in samples No>. r!» to M». inclusive, wa- practically the same as that used for samples Nos. 1 to »',. inclusive. In determining total arsenious oxid in .simple- No*. ll».s to l>b4, indu-ivc (n-j samples), the method given in Bulletin <>'s. Hureau of Chemistry. I'. S. I)e])artment of Agriculture, for the total arsenious oxid in Pari> (ireen wa- u-ed. In determining copper the electro- lytic method wa^ used. In determining soluble arsenious oxid 1 gram wa- -u-])ende(l in iJMin <•<• of water and allowed to >tand over twenty- four hours in a >toppered llask. with occasional shaking. The arseniou- oxid going into solution was titrated with iodin solution. The soluble arsenious o\id in .simple No. •_'<• \va- determined by extracting 1 gram of Paris (Jreen with 4<><> <•<• of water for nine day-, with occasional >haking. and titrating the arsenious oxid in an ali<|ii«'t portion of the resulting solution with iodin. ANALYSES OF INSECTICIDES AND 1-TM.UCIDKS. 33 = = = . i! = Si I! c-s r- =- 1* m . i « I § = s r *: fe» 1*1*1 Pijr * zl-=2 | : : : • i r I : : : : i : :§ °%. °2.2. 1 ^^T |.^ t ::;::;: :;:::: :~ :.WA _• -~-2 ^ = ? =' fe : I : : : ! I :::::: ;e 1 ||' •MMi.M !!!!!!!- i 1 *jjjjjjj !!!iJH I H i 1 1 N "'8 Mr M I i f j ^r_^ ^ i : : i : is SiH2£ : :S 8S §§5 Ifl! |:|||j|d '^ |:d ^ 88S892 S'SBSa - r :< £ ' ::::::: §5$S : : is : : 8 5 • • • • • • • - '-; ' : ! :- • • 5 ^ :::.::! : : : : : ... ^^ .. ..,. ...\%z~ ^^-^--. 26958— No. 76—03 3 INSECTICIDE STUDIES. ^ !. •^ i-5 •- — ^c **« ^ ^ ^ c >- o -t2 ~ — «vd n 11 ;; ! , •I ;- --• '- *Z* ^ » -i cj ? e - 5 ^ » c B J| ]| 11 'I Remarks. P:1 !i Hfl E1-^ > 0 ~ = ^ / <*g;J ^4 llfl 11 jjj! ^ • ;| 11 fl | - : = - E . rf '. . S ? - =£.= 'i u i ? i i :, t o 1 t -k=fs32 5c = ISS^S&l^&Sg,!)^ ,. .= = ^ £ | i; ., r r -if c '= •£ £ c c c c x ^ — '- -•• 5. r- < §::::!:!::::::::: : i 5? < FUNGICIDES. 35 -o contained u..V, per cent of magnesium oxid. so contained 1.1"> per cent of mai-'iiesium oxid ami of potassium o.xid. -o contained 1 ,:;7 per cent of mauMie-inm oxid and of potassium oxid. H H /. 1 M "c i I 1 Gl •/: - a composite of j -ample- manufactured hy the m pie- NO-. ]:',s-l n. inclusive, the chemist r. a- copper hydrate, added the copper hydrate, d ar-e;;ii .us acid together and -u lit rac ted from In i. c remainder as impurities. The acetic acid \va- ount. 1 o ~ s ' This sample n I'his sample a n. "1 per cen 'I'his .simple a 0.013 per cell S "B. \ 1 same per-oi This sample i -ame firm. / - U - .- ._ Hill I - 1 ~ - •M: ' 09 29 14 84 09 Tlii- liuure i- i £'c ', :?? * '• co ri :::::::: g : ~ '"- f- iC r-" >rt I j i 1 1 |.j j i j j ! j jii ' ww^iij | ^r. >, •~ s i - --^^RfifiSf^s-^ -:;-:; £2 ,= SK8«S88 Sle S8SS -7.7 in- ^^- i ^'- ^ 8$ §5 S EgSgSgSSSSgSSSSSS ~ ~ :~. — — — — r"i '-" L: ::::::: ~ r-'''" INSECTICIDE STUDLES, '= gc '- ill r-~f <— s- . c ~ ^ -"= .S •r 71 S T ~ - I I | C X V. c § a 5-a|f * ^ : : : i i : i : : i : i : ! i : : I : ! i i i :. i : i : : : i j : i 1 p|ft !!!Miii!iM!MMiMMMM:M^M^i 00 --= ^ — :~ _: ^ ::::::::::: :g SSS-Sssssffsffogggoggps.??, 1 1 I a g ^ 7- X -y1 T'x ^ 3°~ 13 s iinuniiNHinnNHiMinninH 1 ;:;;;;;;;;;;;;;;;:;;;;;i;i;MM;;ih | ii iiiiiiiiliii!! ii.iiiijij::: iiiMiii 'y. "£^ fc.^ •_ I? < • \\\\\'\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\ I i i i ; 1 j i ! ; i i i I'' i i ! i ! ! I ! I ! i ! ! i i ! i i ! i i i i [jjijjjjjjjj •---;;;-!;;--:;;; jj i ::::::::::: :8SaSfiSS8$8Sa8SS8S8!$fSS;3Sg?5 ~ ^ — _^ |8 S^SS^JS^^^ff^^^S^Silx^fi^i'^^-c1^ r!^ JgM -L JJ j j !': jlli: : ! 1 I III: 1 1 I I j : 1:1 I Ill'll 1 1 E^ : HI j |o» " •' •' •' •' •' •' •' •' •' •' •' •' •' •' •' •' •' •' •' •' ANAI.YSKS K CNSEOTIOIDES AND FUNGICIDES. 89 I (>MM i \ 1 . N \ \ \ I A glance at Table II at once makes it apparent that onlv 1 sample out of more than 650 examined contains neither copper, acetic acid, nor arsenious oxid this is sample No. 7. One other sample, No. !.'.!», consists of about equal parts Paris (Ireen and some insoluble material that appear* to be clay or infusorial earth. ( )ut of the total number examined -".1 contained le-*s than .">o per cent ar-eiiiotis oxid. It will be noted, however, that a number of these samples said to contain [ess than :»M per cent ar>enious oxid were analy/ed by a method (the magnesium pyro-arsenate method) that has since been shown to jj'ive results about 1 pel1 cent low. I f a more accurate met hod of analvsis had been used, the number falling below ;><> per cent arsenious oxid would very likely be materially diminished. It aUo appear-* that the Western States receive more of those samples that contain small per- centages of arsenious oxid than do the Northern States. The State of Louisiana, which previous to IS'.W occasionally received samples containing small percentages of arsenious oxid, does not seem to have had any upon the market during 1S9D and llfuo. Out of !>»; Dimples of Paris (Jreen examined in New York State during the years ls(,»!> to 1901, inclusive, none was found that contained less than 50 per cent arsenious oxid. In both California and Oregon, until a very recent date, quite a large amount of the Paris Green on the market contained small percentages of arsenious oxid, although it is said that this condition has been very much improved during the last two years. Concerning soluble arsenious oxid in Paris greens, it appears that those upon the market in California until recently contained very large quantities, those in Idaho were very fair, only 2 out of li> con- taining more than 4 per cent, those in Illinois. Montana, and Texas contained very small percentages, and those in New York the same, only 1 out of iK) containing more than 4 per cent. This one was sample No. 204, containing l/UW per cent of free arsenious oxid. It must be borne in mind, however, in looking over the ligures for free arsenious oxid that the results in one State can not be compared with those in another, since the methods of analysis were very likely different in every case and would lead to entirely different results. It may be of interest to those who have not read the previous bulle- tin of the Bureau of Chemistry on this subject to mention that out of the 45 samples of Paris Green, from all parts of the I'nited State-. which were examined 71 per cent contained more than 4 per cent of soluble arsenious oxid and 16 per cent contained more than r, per cent of arsenious oxid when a ten-day extraction of 1 gram with LOUD cc of water was made. In view of the facts brought out in that bulletin, a 6 per cent, rather than a 4 per cent, limit for soluble arsenious oxid was advocated when the above method of nnaly.-i> was employed. 40 INSECTICIDE STUDIES. From the figures given above, together with information received from the various States, it appears that upon the whole the purity of the Paris greens upon the American market is steadily and rapidly upon the increase. LONDON, ENGLISH, AND PARIS PURPLES. The analyses of lo samples of London Purple. 1 sample of English Purple, and 8 samples of Paris Purple are given in the following table (III). All of these are products obtained by boiling a waste product from the analine-dye industry with lime. Since it was not known at the time these analyses were made that the arsenic was present, both as arsenious and arsenic acids, the total arsenic was determined and reported as arsenious oxid, only the soluble arsenious oxid being deter- mined, instead of both soluble arsenic and arsenious oxids. TABLE III. — Omijtoxition of L< union purples and closely allied mixtures. Sam- e Name. Moisture. Arseni- ous oxid (As,0,). Calcium oxid (CaO). Ferric oxid and alumina arid A1.,O3). Sulphur trioxid Dye. Soluble arsenious oxid (AsoO-j). 148 Per cent. Per cent. 51 43 Per cent. Per rent. Per cent. Per cent. Per cent. 0 54 1 11' 37 18 2.58 153 do 37.56 176 .do... 3. 27 41.44 24.32 3.37 0.31 27.29 (") 196 do 32. £8 268 do 32 32 12.21 284 do 3 99 49 60 do 3 37 46.73 24.35 1.31 & 46 802 303 do do 31.90 31 50 C25.78 rf25 00 178 36 75 5. 06 179 47 05 11 >6 ISO 34 10 1:; v,s 288 do 6 05 33 72 4 55 4 70 e 91 "A portion digested 40 hours with water at room temperature gave 8.11 per cent arsenious <>xid and •J.s:> pi-r r, Tit soluble calcium oxid. A portion digested with hot water until all the soluble arsenious oxid had dissolved gave 16.45 per cent soluble arsenious oxid and :\.->i'> per cent soluble calcium oxid. '< A No contains \A\^ per cent nitrogen. ••This analysis was made in accordance with the Texas law regulating the sale of Paris (Ireen and other Insecticide* and is good only until May 1, 1903. '/.Mud.- in accordance with Texas law, butgood only until May 1. I'.iu-j. « Also contained 2.8 per cent nitrogen and <>.">7 percent potassium oxid. It will at once be noted that the variation in the amount of arsenic in different Camples of London Purple and Paris Purple is very large. In the ease of 11 samples examined more recently in thU Bureau (pub- lished in Bulletin US) this variation in the arsenic content is not nearly 90 great. It would, therefore, appeal1 that the amount of this constituent in Mich goods is becoming more constant in the more recently manufactured Dimple-. The ligures for soluble arsenious oxid can not he compared with those obtained more recently in this laboratory, since the soluble ar-enic oxid was not determined in the earlier analyso, and it i> only w'.ien both tigure> are at hand that any conclusion-; of a po>itive nature can be drawn. ANALYSIS OF EN8ECTICIDE8 AND FUNGIC] 11 K.s \\i> FUNGICIDES, OTHER THAN PARIS GREEN &KD LONDON 1TIM-I.K. TIIVI ri.vr\i\ IE8ENIC, cniM-Ki:. <»i: Horn. \> ini.ii: A given a compilation of aiialx >e-> of (irecn Arsenoid. (liven Aisenite. 1'aragivne. Laurel ( i iv< MI. and White Arsenic. t«»get her with two analyses of White Ar>enic made in this laborator. TAMI.K IN'. — ( of Green .l/>irturv. Total itrsciiiou^ oxld °sg^r (CuO). Ca'ciuin oxM Sulphur trioxid Soluble iirsi-uioiH oxid (Aii.Ou). 29« • ircrn \r$ 29 P.HI do. fNo.Wl .. 53.71 •_".>. i:? :; 7u 220 do 1 1U W 82 30 76 •> >\\ IM; (irct'ii Arst-nitf 54. in 31. 59 :}. 7o •2 :;»; 30 /' . 1'nrayri'iK' li •>() III Ml •_':; if, 23 08 68 do 1^ 31 19 92 l;{ :>l l.VJ do .").") .".7 •>7 us i ".i 3 21 T.t:> do i:; :;i 18 08 . ' ' 194 ...do 52. 30 21.64 2-_>l do S ,5 36 11 17 s7 1 1 "ii 1 »7 92 Laurel (Jivi'ii 7 til 7 34 13 50 26 31 182 do 7 75 ].. -,., 191 Laurel (iroon ( ^pecial) 1" c,1) 4 50 35 39 1 15 !%<• Laurel (Jreen 3.83 11.50 2C>6 do 4 85 V1 (\x 00 2157 do ;. i:> I'J (!-"> .00 ;;<«;<' White Arsenic 98 00 l-4'Ji I.iV \\ . • . ...do .. 99.86 148(1 ,v W. \t do 99 99 oTlu- followin?,' coustituents were also i»resi-ut: Silica. (I. id per rent: organic matter, r,.C.7 IHT cmt. ''In sample No. 30 the following constituents wen- also present: Acetic acid. (1.7'J per cent: calcium sulphate. 19.31 per eeiit: sodium sulphate. 'J.'Jti i>er cent: sodium ehlorid, 0.'J5 percent: ferric oxid, 0.20 per cent '•Large amounts of caloium carhonaieand liydrate were also present. , '/This analysis was made in accordance with'the Texas law regulating the sale of Paris (Jreen and other insecticides and is good only until May 1. 1902. eThe method of analysis used is that described for total arseuious oxid in I'ari- (Jreen in Bulletin 68 of this Bureau. The figures obtained by different analysts for (Jivon Arscnoid. 1'ara- grene, and Laurel Green show that the composition of these substances is very variable, especially as to the content of arscnious oxid. which varies in the first case from 50.77 per cent to 61.43 per cent, in the second from 19.31 per cent to 55.57 per cent, and in the third from 3.83 per cent to 42.69 per cent. The figures obtained for soluble arsenious oxid, here as elsewhere in this compilation, can not be com- pared, since the methods of extraction were very likely different. The two samples of White Arsenic analyzed in this laboratory were' received from Boise City, Idaho, by the Division of Entomology. They are both evidently of exceptional purity and will give good results when used for preparing Calcium Arsenite. the purpose for which they were purchased. 42 INSECTICIDE STUDIES. \VIIITK ARSENOIDS. T.M5I.K V. t'nlii/iitxititiii nf U'liitf Constituents. Sample Sumple No. 27. No. 91. l'i r ri nf. I'l /• fi nt. Barium oxid 42. 39 \\.\\\ Hariuin to join with chlorin 8.60 c>. Iti 1. 1 -id oxid 1. 55 .96 Carbon dioxid in. 1 5 ( 'hlorin 1. 15 3. 19 Silica .20 A rsenii >ns ox id 27. f, 1 31. 90 M « risture 4. 00 2. 35 Sol i:l.].- arsenious oxid 27.64 PARIS (iREKN AND HoRDKAt \ MIV1TRK. The composition of this sample. No. _?7<». was us follows: IV r cent. Total arsenious oxid 15. 49 Copper oxid 16. 02 Soluble arsenious oxid 1. 7'2 SLU<; SHOTS. TABLE VI. — Composition of Slny Mint*. f. „, Sample Sample Sample Constituents. No. 181. No. L-W. No. W7. Percent. I'IT cent. l'i r r< nt. Arsenious oxid I). 60 1 . 5S Copper oxid 1.44 .60 Lime ' 30.25 28.82 Sulphur triozid 43.02 . 41.18 Ferric oxid and alumina . "'.» Si id i urn chlorid 2. 83 Insoluble 1. 38 Volatile organic matter (by difference) ' 4.79 The sodium chlorid in sample No. 2!io was calculated from a content of 1.72 per cent of chlorin. The volatile organic matter in this sample consist «-d principally of dead oil. In sample No. 307 small amounts of sulphur, copper sulphate, oxid of iron, carbolic acid, and tobacco, with less than 1 per cent of arsenic, were also present. Slu^- Shot is evidently a mixture of fairly constant composition con- taining in all cases small amounts of arsenious oxid and copper oxid as active poisonous constituents. PKi:o\ ID OK si 1. 1C \TI->. T MM K VI I. — «/ i>< rOXid "f siHnifi.t. Moi>tun- Ar-niious oxid Copper oxid Sulphur trioxid Calcium oxid Insoluble Ferric oxid and alumina organic and volatile matter iby ditTi-rem-e > Sample Sample No. 289. /'<;• cuit. .:.7 49.66 41.18 2. :u I'tr c, nt. 1. 11 1.47 .28 52.29 W. \:\ 1.93 1.40 4.76 ANALYSES OF I N-I.< TICI m.s AND I-T x<;in DKS. 43 This mixture evident!} contain-* ar>eniou> oxid and copper a^ t he active constituents, diluted with a large amount of gypsupi. In so far as the arsenious oxid and copper content are concerned, this mixture is of value as an insecticide: luit the gypsum is inert in its act ion upon insects, except that when thespiraclo are not well protected they may he closed up with this or any other line dust. [No. 222.] 1'iT edit. Moist lire ..................................................... '.'• 7S Sulphate nf lime (^vpsum) .................................... l'». ."»4 Magnesium oxid ......................... .................... : Ferric oxid ami alumina ...................................... 3. 02 Arsenious oxid ................................................ 7'.' Copper oxid ....... . ........................................... 41 silica ........................................................ 5. 42 I.o-s on iirnition .............................................. L'S. <»1 KX<;LLSH Bl'CJ COMI-ofM). The coni})osition of this compound, No. 265, is as follows: Percent. Arsenions oxid ............................................... 1. 4t> C'oj>}»er oxid ................................................... till ORIENTAL FERTILIZER AND HI'*, PKsTKoYEK. [X,,. 13(5.] ( 'v/HjHifitioii of Oriented Fertilizer and l><"j ueftroyer, I'.T cent. Water ....................................................... 37. 1 4 Total solids .................................................. 12. Sf> Arsenic oxid ............................................. 2. 38 Potassium oxid ........................................... 3. 50 Sodium oxid ............................................. 6. 08 Nitrogen .................................................. <>7 Chlorin .................................................. :5. < M i Sulphur trioxid ........................................... <>4 This mixture is evident!}' sodium and potassium arsenates dissolved in water. In so far as its content of arsenic is concerned, it would be of value in killing insects. It might, however, if sprayed upon trees, cause some damage by scorching, as the arsenic is in a soluble condi- tion. Its fertilizing value is shown by its content of potash and nitrogen. Another sample of Oriental Fertilizer and Bug Destroyer. No. 150, gave, in 1,000 cc of liquid, 13.1:2 grams of arsenic and In.^.s grams of potassium oxid. INSECTICIDE STUDIES. I.KAD AKSK.VATK AM) I'INK AKSKNOII). The analyses of samples of Lead -Arsenate and Pink Arsenoid, or Lead Arsenite. arc given in- the following table: TAUI.K VIII. — i'nnii,nx'itinit of /,,<>i-pa''elle r> r nut. nO 4U /'r/' n Percent. ]:; "v A /• o ///. l'< r n nt. l> -111 Lead Arse i ate 06. 61 39 14 1 J >3 f>9> do 29 00 40 60 \ ->o j •••".':; ...f'O... (';;:, :;u 32. 31 <13Q 00 . --it do f.\\ :>o 44 40 '/Is 00 ...<:o... f37.40 44.98 '' 14 70 dp 34 83 '/:-u» r." '/ ->S I'ink Arsenoid 31 4'i r,s 43 26 3 ''4 do .83 53 83 40 16 188 do 49 09 4'» 1't 1 93 •i All tin- k-iid oxid calculated to JM...,. AsO4)2 leaves an excess of 0.05 per cent arsenic oxid. probably combined as sodium arsenate. i> All the lead oxid calculated to Pb:{(AsO4)2 leaver an excess of 1.38 percent arsenic oxid, ]>rol)al)ly eomV)ined as sodium arsenate. -•This analysis \vas made in accordance with the Texas law retfulatintf the sale of Paris Green and other insecticides and is good only until May 1, 1903. In addition to constituents named, 2.7 per cen organic matter was found. '/The chemist reported arsenic in the following ways on these :> samples: (1) White arsenic. (2) total arsenic, (3) white arsenic, (4) white arsenic, (5) arsenious oxid. These terms are usually applied to arsenic when in the "ous" condition and mean s:> much As,O:<. If these compounds are ar-enates, as claimed, the arsenic should be reported as As.,0,. In several of the above analyses, however, it" the figures as given were calculated to As.,0,-,, the sum total of the constituents would be markedly above 100 per cent. •J Analysis made according to Texas law, but good only until May 1, 1902. /Includes organic; matter also. >j In addition to constituents named 6.85 per cent of organic matter, lead sulphate, etc., was found It is at once evident that the variation in the composition of samples of Lead Arsenate is considerable, depending* to a large extent on the variation in the moisture content and somewhat on the variation in method of manufacture. These differences in composition should be borne in mind in using such compounds for spraying purposes, since some of them would not have the same insect-killing powers as others at the same dilution. Pink Arsenoid, although somewhat variable in composition, is much more constant than is Lead Arsenatc. \\. ITKPI.K 1'MlSoN, \M> I\SK( TICIDK. Tvi'.I.K IX. — t'nmiKixilinii nl' XX, /'tirii/f I'nifnin. tal a r^enious oxid I'ir <-nit I', r n nl /'< i ( 'aleimii o\id 1 • :i' 1 o\ld ( ci illlbllicd • 15 W i >riranic ma Her i v< >la t i le > -. >1 ul >li- a i -en ii ins o\ jil h 00 "The I'urple poison, sample No :.o|, n\-» eontaiiiM'olonni: matter. The two analy-es, N..S. :>oi ami :'.!'«>, KTere made in accordance with the Texa- law rei:iilatiim tlie sale of 1'an- i.iei-u (see i'aure«'.l) and other m-eetieidev and In. Ids ^,,,,,1 ,,iily until May 1 ANAI.YSKS OF I NSKCTICI I ) KS A M > FUNGICIDES, 45 None of tin- three anah -••- i- Millieiently eomplete lo sho\\ -defini- tively tlif chemical composition of the compound examined, although from the data a> v;iven the Purple Poison appears to be at least par- tially composed of London Purple or some do-dy allied product. [No. 2* I an. I \V.| The analysis of this .simple in the Bureau of Chemistry >ho\ved that it contained ."i.s.-j-l per cent of total copper oxid. It is hasie in cha,'- ueter and of somewhat variable eomposition. so that the purity can not he calculated from the copper-oxid content. It contain--, however, a >omewhat smaller amount of copper oxid than other samples examined iu this lahoratorv. The method of analysis used \\a- that de>eribed in Bulletin 68. FOSTITE. < n/il/xixilioii of fo*titf. [No. 2SO.] Percent. Loss at dull-red heat .......................................... 2. 92 Soluble in aqua regia: Copper oxid ........................ ..................... 2. 98 Ferric oxid and alumina .................................. 1 . 36 Calcium oxid ............................................ 2. 31 Magnesium oxid ......................................... 1.51 Sulphur trioxid ... ....................................... 3. 28 Silica ..................................................... ::."> Insoluble in aqua regia ...... .................................. 83. 77 Soluble in hot water .......................................... 7. 4'.' This material is said by the analyst to be composed of copper sul- phate and finely powdered soapstone in the ratio of approximately 1:9. Sn.l'HATINK AND DKATH To K< )SK lU'tiS. TABLE X. — <'oxitiim of Sulphqtine f. 120). Death to (No. 121)! Moisture ' "/'-in /'/;• ,-mt ( 'alcium oxid IS f,(l 17 7rt Copper oxid 2.61 ' 1.06 Sulphur trioxid 1 7:; Sulphur |S "v Insoluble 1/08 .49 Ash . :. i 11 Neither of the above .substances has ever been examined in this laboratory, but from the analyses it would appear that sulphur and copper, probably as copper sulphate, are the active constituents. These are diluted with inert materials, probably to mitigate their action upon the foliage. 46 INSECTICIDE STUDIES. SOAPS. TABLE XI. — Gniijn>xitiun <> Sample No. Moisture. Potash lye. Soda lye. 171. Perce&t. •11. 30 Per cent. 10.55 ]>> r out. ~ 51 17'' 71 5S 6 86 1 x() 17:^ ti •>'» l:1, »,; 9 QO 171... t\. -Jo 10.66 7.61 The above analyses do not indicate that both soda and potash are present, but show how much of either would be present calculated from the number of cubic centimeters of normal acid necessary to neutralize a known weight of soap. LYES. The compiled analyst's of a number of samples of lyes and the results on one sample (No. 24 I & W) examined in this laboratory are given in Table XII. TABLE XII. — Composition o Sample number. Name. Mois- ture. Sodium hvdrate (NaOH). Potas- sium car- bonate Sodium ehlorid iNaCli. Sodium carbo- nate (NasCOs). Sodium sulphate Potas- sium hy- drate. Potas- sium sul- phate. 16 Solid Lve Perct. 6 4 I'd- n nf. •>•> - Per cent. /'//• <•< nt. tit; t; Pi r n nt. I'ir nut. I 'i r rt. 16 ( '< mcent rated I ve 5 80 4 5 9 13 2 17 Double Concen- trated Caustic Soda 99.3 18 Refined Pearl Ashes ':; * (V.l 1 PJ" Commercial Pot- 1.5 16.8 4.9 14.8 52. 3 7.5 20'' Canadian Crude Potash 4 5 71 4 " X 14 4 32 Com-en t ra t ed Potash Lve 86 90 7 5f, 1 *5 33** 1 sy 7" nl It', 7n 33 1 'U 2, fl, , .V Royal Concen- t rated I ve 70 96 "The following constituents were also determined: L'.l )ier cent insoluble, and tl.l per cent silica. '•The following constituent* were aNo determined: :',.f. per cent potassium clilorid, and 'J.7 per cent insoluble. '•The following constituent* were al-o found: o.oi', JUT cent of alumina and trace* of ferric oxid, magnesium oxid, and insoluble. The mcthof the Koval Concentrated Lye (No. '24 I cv \V) is as follows:" The ly<- is \vci'_Mic«| in a wriuhini: Imttlt-,
  • iinn aciiv. of Soils lUil. 18. ANAIASKS OF iN>i-:rnrim-:s AND I-TN(;ICIDKS. 47 sodium hydroxid and one-hall the sodium rarlx.nate, sinee the .-odium rarl>. mate is rlumvri'd to sodium liirarl>oiiau> (Nall('()s). A drop nf methyl orange is added and the titraiion rontinued until the appearance of a pink rolt.r. Let this niiinlit-r ••!' ee IK- represented l>y "in." Sinee this last titration represents the sodium bicarbonate present (.r one-half the sodium carbonate. "I'm" rep resents all the sodium carbon- ate, and "n-m" tin- sodium hydn.xid. Theiigmvs in most ea explain themselves, although a f,.\v remarks emphasi/ing certain points might not he out of place. Sample No. i:> is evidently a very pool" example of a soda lye. as two-thirds of it is composed of sodium chlorid. No. !»'• i> a vei-y fair sample of can-tie soda, while No. IT is a most excellent sample of the same o-oocU. No. 3'J is not a j)ota-h lye. as it claims to be, but a soda lye. Nos. 32, 33, and L'4- I cSc \Y are all fair samples of commercial soda lye. HELLEBORES. TABLE XIII. — ( 'oni/inxltinit of ht-fl, -I,,,,;-*. Ash insol- uble in hy- ' acid. Tula! ash. Sample No. Ash Insol- uble in hy- drochloric acid. Total ash. 133 Per c< at. •> 34 l'i r c< nt. " 166 l'i /• cent. l'< ;' ,; nt. 12,00 134 3S l'> 157 111 Ml 154 33 13 84. qp 16.00 Samples Nos. 134:, 154, and 158 are evidently l>adly contaminated with dirt, probably because the roots of the plant were not properly cleaned. Sample No. 155 also appears to have a slightly higher ash content than should be allowed in preparations of this kind. MIXTURKS COXTAIXIM; P.OKAX. A single example of this class of compounds, the analysis of which was made in this laboratory, is given below: HOOKER'S COCKROACH AND \VATKR BH; KXTKRMINATOR. (tii'l \\'t gi\ •«>•* a])])roximate results when a large portion of the material is used. The borax was determined by the same method as given in Bulletin r>s for similar compounds, except that the ammonia was all driven off from the solution by boiling before the boric acid was determined. This mixture would very likely be efficacious in driving away cock- roaches and water bugs, but probably it would not kill them. TOBACCO EXTRACTS. % The analyses of five samples of tobacco extracts are given in Table XI\r. In two of these only the most important constituent, nicotin, was determined, while in one of them the determination of this con- stituent was not made. TABLE XIV. — ('<>mjt. 5.">0 Trace. .530 .017 1.466 1.121 .057 .525 16.340 4.55 4. S'_> Ferric oxid and alumina Calcium oxid 1. 4.') Maync-inm oxid IJh< )S]>horus pentoxid Sodium oxid I'i ita^ium oxid y. ir> 2. 12 Insoluble a Specific gravity, 1.3858. Specific gravity, 1.37 Iii the first four of these samples the nicotin figure is much too low for a good tobacco extract; especially is this true of the first two. FORMALINS, The analysis of three samples of formalin, and the average of the results obtained on five samples, together with one anal made in this laboratory, are given in the following table: T \ lil.i: XV. — ( 'i>in/Hi*ifinn of Inn/I'll ins. Formaldehyde. sample ->o. By volume. I'ir i; nt. 86.9 /'/ r<; nt. 10. s 87.0 4(1.0 :;s •! 41.9 ,v \V i 87. l> f "> -ample*. . ANAI.Y-i:- i'K IN-] VJNIV£' "" fNGICI DI->. The method used for determining formaldehyde in samples*;;, to 68, inclusive, is a> follow-: Fifteen eul»ie eetiliiiu'trrs .«!' N 1" kgNO MIV treatr.l \\ it li .") . I n .| ..- . .|' ,"iU JUT rent nitrir ariil in a '^ OC flask. Tni OC «•!' :i solution of potassium ryuiiiil I ront:iiniiiur .'!. 1 grains of W per rrnt potassium ryuuM in -r>()() rr of water) an- then added, tin- flask filled to the mark with .listille.l water, well shaken, and MM aliquot portion of the tiltratr. say 25 OC, titrate.1 aeeonlini: to tin- method ,,f Volhart with a N lo solution of ammonium sul]>horyaiiatr for thr excess of silver. Another \'t re portion of N lo .\L:N<>, is treated with r> drops of .~>u p.-r ceni nitric acid and 10 CC «»f the ].otassinm rvanid solution, to whicli has lieeii added a known amount of the formalin solution. The whole is made up to :>(> cc. ;md a I'-') OC liltrate from it titrated with N 10 ammonium sulphoryanate, the same as he fore for the exoeee of silver. The difference between these two results -.rives tin- amount of potassium cyanid that has l.eeu used l>y the formaldehyde in terms of X 111 ammo- nium sulphoryanate, and since each cuhic <-entimetei- of this is equal to .'! milligrams of formaldehyde, we can ohtain the amount «»f fonnal. I'M. <;<;, 07, and 1J6 I & W all contain less than 40 per rent formaldehyde by weight they contain 4o per cent or over by volume, so that the manufacturers are perfectly correct in claim- ing that their goods contain as much as 4<> per cent of formaldehyde. PETBOLEUMS. The results obtained by fractionally distilling four samples of crude petroleum rre given in the following table: TAU:.K XVI. — ( '<>/iij»>xifi(in of rriuli //< trofeum. Trinprraturv. Cluirncti-r of ilistillaU- ol)t;iiiuMl. Sample No. L'T.V' SampK- NM. •-•:»;.•• Sami)U- No. 277.-' Sample No. Z7M Bi-low50°C... /'> r ri)tt. Percent. cent. Per c< i/t. 0.85 50°-70° C I't'troleuni c'tlK'T 2 06 70°-90°C (iasoliiic . . . . ... 1.00 Bflm\.80°C Liy tit naphtha 1 49 0 14 \ ^'i 80°-1'20° C Heavv naphtha 4 35 1 f>3 9 26 90°-120°C Naphtha ">. 12 120°-150°C Benzine 5 03 9 04 5 35 150°-200°C... Light burning oils 7.64 I:1,. 1^ 10.73 W.7D 200° ''/WC 1". ~>1 1" n-; 15 80 ]•' l'» 250°-300°C... Illuminating oils 1 / 17! 7(5 300°-315°C. . ... .do • r.s 711 f> »;•' 1 45. 60 1 23. 93 315° C-^ residue | I 7 70 16 98 nZeit fiir anal, clu-inic. lx<7. p. 19. i> Specific gravity, 35° BaumC'. 20958— No. 70—03 4 o Specific gravity, 34° Haiiin.'. rfSpec-itk- gravity, 4r>° BaiuiiO. 50 INSECTICIDE STUDIES. MIsCKLI.ANKors SOLID INSECTICIDES AND Fl'Nl ilCIDKS. i The analyses of a number of solid insecticides and fungicides that do not come under any of the previous headino-s are given in the following tables: SULPHURS, TABLK XVII. — <.'itxif!<>n <> ConstitUt'iits. Sample No. 85. Sample No. 96. Solul)le sulphur 1'rr cent. 99 960 Percent, Insoluble sulphur 144 576 Lime. 000 Trace Foreign matter 196 764 Total 100 300 100 000 The total for sample No. 35 is given by the chemist who made the analysis as 100 per cent, but all the constituents added together amount to 100.3 per cent, as above. PINE TAR INSECTICIDES. This is an insecticide obtained from the destructive distillation of pine knots. It readily mixes with water and is slightly sticky and greasy. Mf(i DEATHS. TABLE XVIII. — Composition <>//>" Ferric < ixi'l ami alumina 3 80 2 % I. ' >»* i in ignition . •j j;{ I'hi i^phoric acid 03 04 l',,ta-h to I'oTASSIl'M CYAXID. [Ni»s. L'Saiid 117(1 I & W.] Sample No. -2''\ contained 53.1^ ]>er <-eni of potassium cyanid calcu- lated from the cyanogen. The remainder of the sample appeared to consist principally of moisture and ><>me potassium carbonate and chlorid. The method of analy^i< u^ed was that described in Bulletin 68, Bureau of Cheini-trv. ANALYSKS MK I N>K< ' TI < "I I >KS AND I-T N< i I ( I I ) !•:>. 51 Composition of potassium fi/milif. [NO. lITii. I A- \V.] IVr edit. Id. jj» Potassium •_>!. |s Sodium •_•:;. 74 Chlorin s. Carl'onic aci.l ra.lical I. '.is Moisture . S'J 100.00 The al)o\ -e analyses show that both samples of potassium cyanid an- very impure, although the second sample contains just about the amount of cyanogen demanded by theory. NoM'OlSONors I'OTATO-Urci DKSTKOYKK. Composition <>f nonpoisonout potato-bug . sr> Potassium oxid 00 Calcium oxid 68. 20 Magnesium oxid 7. L'i» Ferric oxid and alumina 1 . 38 Phosphorus pentoxid Trace. Insoluble before calcination 7. L". • Insoluble after calcination 1 . r>( ) As this analysis is not complete, no opinion as to the substance^ of which the mixture is composed can be expressed. XOXPOlSONors INSECT EXTERMINATOR. [No. 151.] This sample contained 78.12 per cent of lime and 3.61 per cent crude carbolic acid, determined as ether extract. It had an odor of carbolic acid and appeared to be partly composed of carbolate of lime. X. O. DUST. [No. 176.] Composition of A*. 0. Dust. Per cent. Moisture 6. 98 Organic and volatile matter 53. 69 Carbon dioxid 3. 40 Carbolic acid.. Trace. 52 INSECTICIDE STl'DIKS. iVr cent. Mineral matter ............................................... 39. 33 Sand .................................................... 14. H<> Ferric oxid and alumina .................................. 2. 47 ( 'alcin in ox ill ........................................... 17. 10 Majrm'siuni oxid ........................................ 2.09 Phosphorus pentoxid ...................................... 40 Potassium oxid ........................................... "2. ">s This mixture appears to be partly composed of carbonate of calcium with an excess of lime. No opinion as to the character of the organic and volatile matter can he based upon the data given. exclusive of the carbolic acid alreadv mentioned. 4 KI.KCTKH1 VKK.MIX KXTEKM I XATOR. [No. 197.] This insecticide is chiefly a mixture of calcium carbonate and cal- cium hydroxid with a very small amount of organic matter. Upon examination in this laboratory the organic matter present was found to consist of carbolic acid. TAK' oimr.M. [No. 281.] From the analyst's report this product would appear to consist of silicate of iron mixed with calcium sulphate. The analysis does not show the presence of sulphur and tobacco, both of which were found on examining a sample of the product in this laboratory. AXTIXOXXIX. [No. 2S2.] A qualitative test of this substance showed that it contains dinitro- . together with soap and glycerin. MISCKLLANKors U^l U> INSKCTH'IDKS AM) FIN< \ K 'I I >!•>. KOU.KXK IXSK:>, /;;.;, r,'t~>. [No. :{o:.. ] I'tT crtit. Carbon liisiilphi*! ............................................. 47. S Mineral and «-s«-ntial oils ..................................... ll*. L' Watt-rand i-t-sidur ............................................ 40.0 This analy>i> was made in accordance with the Tr\a> law (>cc p. 61) regulating the sile <>t' Paris Green and other insecticides and U good only until May 1 ANALYSES OF [N8EOTICIDB8 AM> FUNGICIDES, f>.S • ••I i ami i;i:, I .v \Vi.] Of tin1 two sample^ <>!' this product received at the Bureau <>!' Chein- isiry one consisted of a black oil (»J1I), while the other (»;|.".) -epa ratctl into two layer-. <>ne a hlaek oil and the other a white milky emulsion. The lirM sample was fractionally distilled a- it stood, and the second sample wa- separated into its two parts and cadi part subjected to fractional distillation. A". '/./'./' ( 1 1(~ II i, rixii/t* <>/' diftittdtion /••-/. per cent, Q?CO r^ f/ " i / v / yo ^ u 01* ui 95°-108° C '' . 41 108°-130° C 190°-220° C • 260°-3000 C «13.46 300°-350° C eft. 16 350° C. + el. 02 and residue.. 14. 2ti " I'riu-tU'Jilly sill carbon bisuljihid. '• rt-uotrating odor of some essential oil. c'Odor of iH'troU'iim j.roducts with ]»nniHin which crystallizes out in the higher fraction \n. f I/,.! ( I A- IT), rfsii/t* of (li.xtill,ttinn t.-xt. WHITK K.Mfl.SION, SI. 28 PER CENT. I'cr cent. Below 95° C " 1 . 24 95°-108° C /' 76. 10 108°-130° C '• 13. 47 Loss and residue i>. 1 '. * BLACK OIL, IS. 72 I'KK CENT. 1'i-r cent. Below 40° C '/ 4:;. 4s 40°-650 C 'i 22. 00 65°-95° C (/ 5. :,:; 95°-108° C « ..50 108°-130° C ' 4. S4 130°-160° C rg.21 160° C. + f 6. 53 i:> sidue and loss.. « Odor of carbon bisulphid. '' Mostly water with solid particles of j>a ratlin. ••Nearly all paraflin mixed with water. ''Nearly all carbon bisiilphid. ^Some hitrli-snu'llinjr essential oil present. /Mineral oils with odor of petroleum product-. 54 INSECTICIDE STUDIES. It is evident from the analyses of the two samples of boilene insecti- eide made in the laboratory that the first one (04-4- I iSc W) consists of about 50 per cent carbon bisulphid and 50 per cent crude petroleum with a very small (jiiantity of some essential oil having a strong odor, while the second (04-5 1 & W) consists of about (r2 per cent water. 14- per cent carbon bisulphid, and *1'.\ per cent petroleum, with a little essential oil and a small quantity of soap. Whether or not a compound of this composition, which is evidently very variable, would kill the bollworm is a matter for experimentation. The results of the analy>e> of these two samples were forwarded to the manufacturer, who in reply said: "This analysis is not at all correct, and since the analysis was made I have perfected my prepara- tion/' Another letter was then sent, asking in what particular the analysis was unsatisfactory, but to this no reply was received. The analyses of these samples was repeated, but the same results were obtained. Besides this it is found that the analyses made in this laboratory gave very much the same results as those made by the Texas authorities from a qualitative standpoint. Unless the results obtained by the Texas authorities and by this laboratory are approx- imately correct the manufacturer is selling all of his goods under a false label, since the Texas law requires that all insecticides sold in the State shall comply with the official analysis on every package. KXCKI.Sloi; IVSKCTICIDK AND WOOD PRESERVER, RED CEDAR BRAND. [No. <-•:;, I A:\V.] AY.SV//V.S- <>f distillation test. iVr cent. (1) 80°-110° C .............................................. « 1. 01 (2) 110°-180° C ............................................. ".31 (3) 180°-230° C ............................................. '' 7. 42 (4) 230°-270° C ............................................. '' 21 . W (5) 270°-300° C ............................................ 16. 50 (6) 300°-330° C ............................................. 15). 1 1 ( 7 ) :v.\o°-:tt°C ............................................. 1 5. 84 (8) R<->i«lii<- ami IOSH ........................................ 17. W " Li.irlit nils with odor of IHMI/CIH-, tolia-iu-, etc. /M.ivc u--t< for phenol Fractions 4. 5. «J. and Tare heavier than water. At about :)4" C1. the distillate hco-in- to -olidify in the condenser, and at 355° C. the condenser i> >o >topped up with naphthalene that it is necessary to rea>e di>t illin^1. Thi^ ap]>ear< to be a simple of coal-tar creo>ote. and when properly n-ed i^ of value both a- an in>ecticide and a wood preserver. ANALYSES OF [N8ECTIOIDE8 AND FUNGIOID] 55 FLY \-\i\-:\ I:\T\TI\ i-:. [ No. •-'(>•_', I ,v \\ I'rr relit. BO°-160°C ................................................. L60 215 C ................................................ ''7 2 1 r>°-L>:o° r ................................................ •• H> (4) L'70°-:j:>o° ( ' ................................................ -• l'.» 150 C .................................................... '' :;:'• IJrsidui' and loss...- ........................................ ' 17 .it <>il LjiviiiL: test I'or phenol ;m arc all lighter than water. From the above analysis this sample appears to be a mixture of coal-tar creosote and petroleum. These substances are often used as fly preventatives. KAKHO KKKSOLATK. [No. S.l (3) 180°-220° C ^7.6 4 220°-270°C '/5.7 (5) 270°-285° C < s. s (6) 285°-312°C M4. 7 (7) Residue and loss % 2s. 7 "Light oil and water mixed: smell of carbon bisulphul and heii/ine. bLightoil, test for phenol and enrols. <"Oil, heavier than water, tt-st for phenol and cresols. d Oil heavier than water. c Thick oil; pungent odor. Fractions 3 and 4 contain solid naphthalene. A small amount of alkali is also present. From the distillation test it would appear that this sample consists of .coal-tar creosote which ha- bc«'n boiled with resin and an alkali, or with resin, fatty matter, and alkali, to cause it to form an emulsion with water. From the si/e. appearance, and smell of the first fraction it also appears that some carbon bisulphid has been added. It is well known that creosote emulsions have o-j\ -en good roults both as disinfectants and sheep dips. This preparation, therefore, would very likely be of value for the purposes intended. 56 INSECTICIDE STUDIES. DE <, RAFF'S CAKPKT un; DKSTUOYKH itinii of 1'i-ofixxor I >< f//v/7/''x <''tr/t'". Ml Mt/rctirv 782 78 ( 'hinriii - - .... 266 27 Sulphur trioxid 484 48 Muinina . . '.« > i ..90 ]'i ita-*ium o\id 267 26 These two analyses aiv o-iven in two different reports of the Muni- ch usetts State Experiment Station, but were very likely made upon the same samples, since they are identical. The active poisonous principle of this solution is evidently mercuric chlorid, which is often used for the destruction of various insects which infest houses. III. STATK LAWS (inVKIIMM; Till'. dlMI'nslTlON AM> SAL I- INSECTICIDES. A circular letter was scut to the various experiment station* that they forward copies of the laws in their respective States relative to the composition and sale of Paris (irecn and other insecticide*. In 08868 where the experiment stations could not furnish the information a similar request was made of the secretary of state. It is believed that the following compilation of State laws is a complete resume of all such laws passed in the United States. CALIFORNIA. AN ACT to prevent fraud in the sale of Paris (Jrrrn used us an inf < '<(liforiti/<> > intrt e final as regards the quality. SK< . r>. Any person or persons, linn, association, company, or corporation violating any of the provisions of this act. and any person who shall sell any package of Paris Green. or any part thereof, which lias not heen laheled as herein provided, shall he guilty of a misdemeanor, and shall he lined not less than S5() nor more than SL'uO, together with cost of the suit, in an action caused to he brought hy the State hoard of horticulture, through its secretary, in the name of the people of the State of California. Si-:< . »;. The attorney-general of the State of California is charged with the prosecu- tion of all such suits. SKC. 7. This act will take effect immediately. — Jifrmin- n Inn- h,, cnnxfitntiniml Innifti- 1901. LOUISIANA. Act N<>. i:H of tin- general assembly of the State of Louisiana. Hi it iinirind hi/ tJn' <> percent or m»re of ai>enic shall be classed as "strictly pure." and, second, all falling below this peiventaire shall be classed as "impure." That it shall be the duty of the commissioner of agriculture to cause to be prepared labels of suitable material, fitted to be attached t« > packages of Paris (iieen and ti • have printed t liereon " iruaranteed." with a blank space into which there may STATK LAWS ( '< t.N( ' KM M N < ; 1 NS K< T1C1 1 >KS. 59 be Stamped by the commissioner of agriculture the \vi.raid commissioner of lifty cents for a snllicient miml.er to label one hundred pounds of Paris ( ireen. SKC. (i. That it shall he the duty of every person. before offering for sale any Paris ( ireen as an in>ect icide in this State, to attach or cause to U- attached to each pack- age one of the Iain-Is hereinl>efo:v described. deHgnating tin- <|iiantity of Paris < ireen in the package to which it is attached. Any per.-on who shall sell any packages of Paris (ireen, or any part thereof, which has not been labeled as herein provided for shall be guilty of a misdemeanor, ami on conviction thereof shall !><• fined in the sum of one hundred dollars for each omission, which penalty may be sued for either by tin- Commissioner of Agriculture orany person for the uses hereinafter declared. Any person \\ ho shall counterfeit or use a counterfeit label prescribed by this act, or who shall use them a second time, shall be guilty of a misdemeanor, and on conviction thereof shall be lined in a sum not exceeding two hundred and lifty dollars, one-half of which shall be paid to the informer, which may be doubled or trebled at each second or third conviction, and so on progress! vely for subsequent c m\ -ictimis. BBC. 7. That it shall be the duty of every person who sells a package of Paris (ireen, upon the request of the purchaser, to draw from the same and in the presence of the pirn-baser or his agent a fair or correct wimple and to have the same securely enclosed and sealed and sent to the Commissioner of Agriculture for analysis by the oliicial chemist of the State, and if upon analysis the said Paris (ireen shall be found below the guarantee given to the Commissioner of Agriculture and printed on the package, then the said seller shall be liable to the said purchaser for all damage accruing from said difference, recoverable in any court of competent jurisdiction in the State. SKC. s. That the copy of the oliicial chemist's analysis of any Paris Green certified to by him shall be admissible as evidence in any court of the State on trial of any issue involving the merits of said Paris Green. SEC. 9. That the Bureau of Agriculture shall adopt needful rules and regulations providing for the collecting of money arising from the sale of labels, or for any fines imposed under this act, and shall deposit the same with the Treasurer of the State. NEW YORK. AN ACT to amend the agricultural law. to prevent fraud in tin- sale of Paris (Jreeii. The People' of Hhe State of New York, /vy»y.-' n>«ct as f»ll/i/i xtftli' iit'tn nfdrfii ri'i' anil ili'uli ,• in original packages, livery purchaser of Paris green in original packages which is manufactured outside of this state, who intends to sell or expose the same for sale, and every manufacturer of Paris green within this State, shall, after filing the statement above provided for with the commissioner of agriculture, receive from the said commissioner of agriculture a certificate stating that he has complied with the foregoing statement, which certificate shall he furnished without any charge therefor; said certificate when furnished shall authorize the party receiving the same to deal in tins state in Paris green. Any person who fails to tile the statement aforesaid shall not be entitled to such certificate and shall not be entitled to deal in Paris green within this State; nothing in this section shall be construed as applying to retail dealers. SKC. 111'. Composition <>f 1'iiri* (/recn or (iiKt/o'/onx prof AV/'- York, <-h. us.} AMKNDMKNT TO l'AKIS-< JRKKN LAW. Iii accordance with the sujrovstion made by the New York State Kxperiment Station in 1M>0, that portion of the Paris (liven law which 'related to the definition of Paris ( liven was changed. The essential portion of the amended law embodying this change is as follows: . 112. Coiitjxixifion of I'tirix '/''"'" '"' nd. It shall nut contain arsenic in water-soluMe forms equivalent to more than three and one-half per centum of arseiiioiis oxide. STATE LAWS roNVKKMNt; INSKC'I lcil>l->. 01 OREGON. Only those sections of the act named below which deal direct ly with the subject of insecticide^ arc o'Jven. \ \ ACT t.< protect the fruit mul li<>(, industry of OP-HOII. SKC. .",. It shall !»»• unlawful lor any person, linn ..r corporation d-Miiir l-n-inc— in the State < it' Oregon to sell paris green, arsenic, london purple, sulphur or any spray material or coni|)onnil for spraying purposes, in (|tiantitics exceeding one pound, without providing with cadi package sold a certificate duly signed l»y the seller thereof guaranteeing the quality ami per cent of purity of said materials. SEC. 4. Any person, linn or corporation selling any of the al>o\e materials \\ hicli do not conform with the certificate furniflhed therewith shall U- deemed guilty of a misdemeanor, and upon conviction thereof shall l»e subject to a line of not less than twenty-live (*L'.V) dollars nor more than one hundred (*1(K)) dollars. SKC. s. It shall be the duty of the Commissioner of the State Board of Horticulture of the district in which a violation of this act occurs to present the evidence of the case to the district attorney, whose duty it shall be to prosecute any person guilty of a violation of this act. which prosecution may be brought in any of the justice courts of this state. SKC. 9. Inasmuch as the horticultural interests of the state demand immediate attention, this act shall be in full force and effect from and after its approval by the Governor. Approved % tin' Governor, February 17, 1899. TEXAS. AN ACT for the better protection of the farmer in the purchase <>f ronmuTcial fcrtili/crs and com- mercial poisons used for destroying bollworms and other posts. Hi' it enacted l>i/ tin1 I;('e in force from and after its passage, and said rule is so suspended and it is so enacted. Passed by the '/'"•< /////-.•>•'. |,n>viilc :ii;.-iiiivi tin- H'lultrrnlioii of Paris ( Jn-rii mnl Other compounds tued fur >|mi\ inu' tivi-* ninl |>]antx Be U enacted by the Legi^oture of the State of MW// //_'//<>//, That it shall hen-after in- unlawful for any persun. linn, .n- corporation doing l>iiHiir.-s in tin- Stateof \Vashing- t«'ii to sell or ol'lVr for sale adulterated or lo\v grade Paris green, aix-nic, London purple, sulphur, or any spray material or compound for >pra\ \i\-j; purposes. SKC. L'. For tin- pnrposrs of this act Paris «rivrii shall contain not less than fifty per cent of arsenic trioxide in combination, and not more than four per cent of \\ater- BOlllble arsenic tlioxide, and connnercial arsenic shall contain not less than ninety- six (1MD percent of arsenic trio\i,le. S !•:<-. .",. Any person, tirm, or corporation violating any of the provisions of this act shall l>e y a tine of not less than twenty-live dollars nor more than one hundred dollars. All tines imposed fur violation of the provisions of this act shall l>e paid to the treasurer of the county wherein the violation was committed and placed to tin- general fund of such county. SKC. 4. That the State Commissioner of Horticulture and the county fruit inspectors under his supervision be charged with the enforcement of thiH act, with the assistance of the prosecuting attorney. SEC. 5. It shall be the duty of the chemist of the State Agricultural Kxperiment Station to correctly analyze, without extra compensation and without extra charge to the state other than the necessary expenses, all substances and compounds used or offered for sale for spraying trees and plants, that the State Commissioner of Horti- culture may send for analysis, and report to him without unnecessary delay the result of any analysis so made; any such chemist shall assist him in prosecuting violations of the law, by giving testimony, expert or otherwise. Approved ly flu' (lorernor February ,.'