Document VokwOnaxmBZkjdYVngNMrZOw

^CfV .-.< -. . Decsober, 1955 Mb. FINAL REPORT ON INSECTICIDE SPECIAL PROBLEMS COMPARATIVE LABORATORY EVALUATION OF NIRAN, NIRAN AND BENZIL, AND NIRAN AND AROCLOR 5^60 FORMULATIONS (JULY 14 TO OCTOBER 12, 1955) Job No. 2-02-750.01-2760 Monsanto Chemical Company Organic Chemicals Division St. Louis Research Department Work done by: 0. De Garmo W. o. Dempsey G. F. Ludvik VJ. E. Spring Written by. G . F . Ludvik DSW 620555 STLCOPCB4094582 ' ; A-- <- ,y,, ;,|MiBraQB;;? t-- OP REPORT HO.:1382 ; 1. Pile 2. 0. P hudvlk 3. ' H. a. Nason 4. Duplicate Pile 5. Clrc. Aasoc. and Safe Deposit 6. 0. DeGarmo 7. L V. Sherwood 8. J. M. Magner 9. M. W. Kosmin 10. Dayton, Library 11. G. W. Steahly 12. Nitro - Library 13. F. B. Zienty 14 . F. M. Murdock Ip Extra lb. Extra J-/'. Extra *r This report contains i property of the Monsanto Chemical Company and which shall be disclosed only to duly authorized persons. The recipient is held accountable for the filing and safe custody of the report, which must be returned or. demand. DSW 620556 * fa 17^ STLCOPCB4094583 ..... .... | ..... ...... .. ._ ^ f-- i3ABLB OP CONTENTS ' ' ' -V" ffe .. . I^eJio. INTRODUCTION .... .............................................................. SUMMARY................................. ............................. CONCLUSIONS ......................................... RECOMMENDATIONS............................................................................. REFERENCES............................................................................... EXPERIMENTAL WORK..... DISCUSSION ............................................................................. APPENDICES No. 1 - Mortality Data No. 2 - Statistical Appraisal 1 ' 2 2 , DSW 620557 STLCOPCB4094584 v' ---'f' Wrr fi'fm m mwm1 XHTRODOCTIOIf a ' 1 --'9iX^-:Vrr^: i ' tsjSi?. - --->? w- r- liran, Monsanto's.par&thlon,? is~ & potent lnaeotlclde with a broad spectrum ef activity, However, it is also very toxic to man and animals (aoute oral LD90 averages 3.5 mg./leg., chronic m.l.d. is 25 p.p.m., dangerous level fer inunction is 50 mg./leg. ). Our research, development and sales personnel would like to de velop a formulated product of lower texic hazard, and are ever watchful for premising leads in this direction, frarbenfabrlken Bayer, A.G. markets a "softened" parathion emulsion concentrate, "Polidol", Which contains an emulsifying agent that is claimed to reduce its toxicity via dermal absorption. . .. 4- Monsanto has been offered a license to a patent claiming a marked reduction in dermal toxicity by the addition of benzll (diphenyl glyoxal) to parathion emulsion concentrates. The inventor also claims that the addition of benzil Increases the effectual life of parathion residues by a factor of three times, and that it reduces the phytotoxicity produced by parathion formulations. ... * This report concerns only the evaluation of the la3t tw* claims. Since we were also Interested in evaluating the effectiveness of Arcelor 5460 as an additive to promote the longevity of para thion residues, formulations containing it were compared directly with parathion and parathion and benzil formulations. SUMMARY Spccifically, answers were required for the following questions: (GFL/LVS, 8/11/55) "1. Whether formulated combinations of parathion and benzyl maintain their insecticidal potency, compared to parathion formulated alone. 2. 'Whether the addition of benzil modifies longevity of effectual treatment. 3. Whether the addlt_or. of benzil decreases phytotoxicity .?l To obtain the answers and to compare with any action produced by Aroclor 5^60 several lots of potted, randomly selected Black Valentine bean plants were sprayed with three formulations twenty five per cent Miran, fifteen per cent Niran and fifteen per cent benzil and fifteen per cent N'iran and fifteen per cent Aroclor 5^6c. The concentration of Niran in the finished spray was one to two thousand on 0.4 pounds per one hundred gallons in each case. DSW 620558 STLCOPCB4094585 ^llj 5"'*? yji'T:' "' '-',>4- : m. ilT of the plants treated :wlt3Leach formulatloo^were * held ......... greenhouse and hair were,held under outdoor conditions. ^Evaluations were Bade' at varying^lntervals after'spraying by 'Infesting, plants with either Mexican bean beetle "or with : , : Southern armyworm larvae.^: All testing was done in the greenhouse. . -*-i. S - . ? f i -- -- - * . '/'Photographs of a series of-sprayed plants were taken to ob tain a pictorial record-of certain observed manifestations of toxicity. ' COnCUT/IONS 1. The incorporation of benzil in a parathion emulsion concentrate did not affect its insecticidal potency as compared to parathion formulated alone. This may be said for Aroclor 5^60 also. . 2. The addition of benzil neither shortened the longevity of effectual treatment; nor did it prolong effectual treatment as claimed by the inventor. Aroclor 5^60 likewise was feund to have hardly better than a neutral effect on the dur ation of effectual treatment. 3. The addition of benzil, contrary to the inventor's claim, appeared to increase rather than decrease the manifestation of phytotoxic symptons induced by paratnion on Black Valentine beans. Plants sprayed with a formulation containing Aroclor 5^60 showed less evidence of injury than did those sprayed only with parathion. RECOMMENDATION Unless a favorable report is returned on the pharmacological phase of thi3 evaluation, the attempt to obtain a license under this patent should be abandoned. REFERENCES Kimball, C. S. Toxicity tests on parathion and parathion-benzil. Memo to E. I. Sudy, July 25, 1955 Kimball, C. S. Toxicity tests. Letter to F. B. Zienty, July 26, 1955- Zier.ty, F. B. Parathion-benzil: toxicity tests. Memo to E. P. Wheeler, July 25, 1955- Magner, J. M. Parathion safer.er. Memo to F. B. Zier.ty, August 1, 1555. Sherwood, L. V. ithion safer.er. Memo to File, August 3, 195: DSW 620559 STLCOPCB4094586 Mjaeler/B.TT. -Toxloity'bf'ITIran'-beniiil formulatioaVr Kimball, C. S. Toxicity test program on parathlon-vs-parathion plus benzil7 Letter to Monsanto Chemical Company, August 8. 1955- Morrill, H. L. Parathion formulations. Letter to C. S. Kimball August 9, 1955. ` Morrill, H. L. Parathion-benrll formulations. Memo to E. P. Wheeler, August 9, I955. Sherwood, L. V. Benzil (diphenyl glyoxal) - Biologic tests needed. Memo to G. F. Ludvlk, August 11, 1955. Sherwood, L. V. Benzil (diphenyl glyoxal). Memo to file. August 11, 1955. Ludvlk, G. F. Plan for laboratory evaluation of Niran-benzil formulation. Memo to 0. DeGarmo. September 2, 1955- Ludvlk, G. F. Niran formulations. Memo to H. L. Morrill. September 6, 1955. Magner, J. M. Fara till on f ormulatlons-phytotoxiclty. Memo to G. P. Ludvik. September 8, 1955- Meaner, J. M. Dermal toxicity of benzil. Memo to L. V. Sherwood. September 9, 1955- Ludvlk, G. F. Evaluation of Niran-benzil formulations. Memo to F 3 Zienty. September 19, 1955- Ludvik, G. F. Comparative evaluation 01 Niran and Niran-benzil Formulations. Frogress Report 2-02-750.01-1760, No. 2. November 30, 1955. Hill, A. B., 1937- Principles of medical statistics, Laucet Limited, London vii &. 171. (Ref. pp I65-6.) EXPERIMENTAL WORK Potted, greenhouse grown. Black Valentine bean plants were used for this project. It was not possible to gr*w, spray, or hold sufficient plants at one time to satisfy the requirements of this evaluation so it was necessary to make several treat ments. All spraying was done outside of the laboratory under as nearly the same conditions as possible. A three gallon Hudson garden sprayer was used to make the applications. Similar volumes of spray were applied to similar numbers of plants on eacn occasion. Plants were selected randomly for each formulation, and the lot's of treated plants were held, infested, and observed DSW 620560 STLCOPCB4094587 %m\ ... ->h '"1- *V'' -5 /' - '.-~--,33> ,- i, <'-! V ' - -*- ' "- - under identical conditions. Three plants wore used for-each formulation, speoies and age of residue tested. Forty-hour mortality observations*were recorded. v The following three formulations were evaluated: 1 - Niran parathion - 25Jb Alrodyne 6104 - 5$b xylene - 70 II - -liran & benzil parathion - 15St> benzil - 1556 Alrodyne 6104 - 5$ xylene - 65# III - Niran A Aroclor 5460 parathion - 15/= Aroclor 5460 -15> Alrodyne 61C4 - 7.55b xylene - 62.5$ For the final analysis, calculations of per cent kill were based on the numbers of live larvae recovered from ten applied per plant. The residue ages reported are the means of the ages at the beginning and end of infestation e_.i. 3 a one day old residue was freshly dried when infested and was two days old when mortality observations were completed. Similarly, a five day old residue was infested four days and observed six days after spraying, respectively. Experimental data are recorded on notebook pages A-40394 40400 and A-71102-04. The following statistical procedures were utilized to test for significance. Standard Deviation: where = standard deviation, -j = deviation from the arithmetic mean. and = number of replicates. standard Error of the Difference Between Two (Arithmetic) Mean s : .) L DSW 620561 STLCOPCB4094588 4 2^1 SiJtTC r"': .:-' *g . ' Ip...' \V- -y _ MSf, 5* " V ' ~ "3igaificanca^.- results will occur by chance - . .' - ''': >' ; . * - a) about,:once In twenty observations whan ` ; ' '-t'rfe!' . ,`n *i ; * -i > *ia> - a/ ` 2 (SvBi), b) about once In eighty observations whan i - Ba / 2.5 (3.E.), where m arithmetic mean and S.E. standard error. Color and black and wh'te photographs were taken to preserve a record of one experiment made to evaluate phytotoxic effects of the active Ingredient, the additives, and the solvent as related to emulsifier content of the formulation. Figures 1,2,5, and 4 show the duration of effectiveness of the residues from the three formulations under interior and exterior conditions against larvae of the Mexican bean beetle and Southern armyworm. The data on which these figures are based are given in the Appendix, Tables 1,2, &. 5. Summaries of the statistical analyses are given in the Appendix, also. The arrows on the figures indicate the standard deviations from the means obtained for the various tests. DISCUSSION Since the inventor claimed that the addition of benzil would prolong the effectual life of Niran residues by a factor of three, it was necessary to plan for activity determinations at weekly intervals for a minimum of four weeks. A determination of the effectiveness of freshly applied sprays was also required. For some time we had been interested in similar reported effects for Aroclor 5^60 so we had an opportunity to kill two birds with one stone. Reference to Figures 1,2,5, and 4 shows that neither of the additives, benzil and Aroclor 5^60, depressed the activity of Niran formulations against either the Mexican bean beetle or the Southern armyworm. Aroclor 5^60 may have been of some benefit In prolonging the effectual residual life of Niran outdoors against the acutherr. armyworm as shown by Figure ^. Against both species, effectual residues of all formulations disappeared from plants held outdoors for seven days after spraying. Thi3 was observed ir. two separate series of tests. The inventor's claim that the incorporation of 1 n id prolong the effectual life of iilrar. residues ro-uld not be substantiated as shown by the data given in Figures 5 DSW 620562 STLCOPCB4094589 ^EffectualiMSiduess-off'.*ll*forinula.tidns-6rt plants bold in ^ the greenhouse dafinitaly^disappeared between seven d eleven "days after treatment ;es shown by the re&ctlods5of the test species. In one set of tests held in the greenhouse for seven days, the benzll formulation appeared to'be superior against Mexican bean beetle larvae, but no difference was shown among the three formulations in a second series of similar tests. The same situation occurred with Southern armyworm larvae, but in this case the second series of tests appeared to favor benzll. If such results had occurred for both species in the same test series, it might have been necessary to acknowledge that benzll does add a small plus valve under greenhouse conditions. Even if this actually were the case, the inventor's claim would still be much too extravagant. , _ Early in this work, evidences of phytotoxicity were observed. There appeared to be little difference between the Niran and Niran and benzll formulations in this respect, but was noticeably less apparent from the Niran and Aroclor 5^60 formulation. The injury was initially attributed principally to solvent toxicity resulting from poor wetting properties of the formulations; This thesis was supported by the fact that the Niran and Aroclor 5^60 formulation contained 2.5 per cent more emulsifier than did the other two. Subseo.uently, twelve formulations containing differing amounts of emulsifier were prepared and sprays were applied to Black Valentine bean plants. The formulations were: W 1. .Niran - 15^ Alrodyne 61Q4 - 10, 7.5 &. 5`^ Xylene - to make 100^ 2. Niran - 155b Ber.zil - 155b Alrodyne 6l4 - 10, 7.5 & 5S> Xylene - to midce 1005j 3. Niran - 155^ .Aroclor 5^60 155b Alrodyne 6104 - 10 , 7.5 4 554 Xylene - to make 1005- Three plants were sprayed at one part formulation to three hundred parts of water (Niran: 1/2000; with each formulation and were held in the (plastic) greenhouse six days. Color and black and white photograpas were taken to record the results . Injury decreased in all cases as the amount of emulsifier was increased from five to ten per cent. The least amount of injury was observed in the series containing Aroclor 5^60 and the most was observed on the plants treated with the Niran and fcenci' formulation ?hi3 observation negates another of the inventor's claims. y7 ds 1/9/-50 Ludvik DSW 620563 STLCOPCB4094590 ^ssssaH 'f'f/'-i ; ' 2b"K&fe. ' "-' x' . ^ Mortality &*/o -for- itfsstcan 3mmbft Baaff* J.orv+9 n %.6`S!</&** Moirrfotn &/ // Y~Aa CpraonA(Afc tt+MJu* Fomv/a it on AS** 0mJ* Nor Coni JC/l / M,'r*n too tOO /oO Miron y Q+njlt too too too Miron -b Aroc/or SVtO too too 90 J" Nirtrn 100 too too Miron b8*ftJit 100 too too Mira ft b AJro cjor S*tCO too too too <5 Miron 70 CO NO Mlran + 3 on ill 80 too 100 Mirer r> bAraetorSMCO 0 0 0 8 M/ran too too too Miron + Bo ft xil too too /OO Niran bArodor SiO too 10 too (2. Mira n Niran + Qonj.il HO 80 70 SO 7.0 o Miron b Aroe/or S60 20 20 0 /S Niran to to 0 Mir an * So n x i t 0 0 to MMon * Aroclor Si/6O 0 0 0 IS Niran o0 0 Niran * Bonjil V0 0 o Mimn rAroclor SNiO o NO 20 Ay*. S' too too - U.7 - (J-O 0.0 S.7 too r too - too t o-o o.o 0.0 Si. 7 9*3 - o- too Z too - fi.7 - IS. 3 tt.s 0.0 o.O 0.0 S.7 i 3.J it. 7 /J.J t zo. a /S.3 tt.S 10-0 t J. 3 r oz too s.7 0-0 0 U-b 20 t 0.0 r xs.i - 20.0 DSW 620564 STLCOPCB4094591 . - . T*v ' .: if:& Y* * . ^v' - ta b/e. / Morfafi/y Oa/a Par -SouT^crn Armywarm /Larvae , - "' ' # - ; . I . - ^W* ' V" ,. Afatnroin Cc/ in Jhe <$raenAouac RaoUja* Formulation a3*> ~J* / Niran Miran + Senzil Mir</n J Aroc./or SV iO Par Can/- Kit! /OO too /OO /OO /OO too 7 0 /oo /oo. sT A/iron /OO HO VO Miran VBrnxil too too 8o Miron + Aroc/or SViQ /OO 10 80 8 Miron 60 70 80 Miran J-Bonxll IO 8o too Niran * Aroc/or SV60 4 o 80 70 8 Niran SO so ?o A/iroh + Bonzi/ too 90 90 f/iran A Aroc/or SVIO SO 70 VO JZ Niran 20 o /O Miran xBonzi/ 0 20 VO Miran V-Aroc/or S'V^O JO O O IS Niran Niran Adonzi/ So Vo o So to to Miran i- Aroc/or SViO Ho VO 90 is Miran to to 20 Miran / 8nzi/ Jo JO 30 Miran 4- Aroc/or SV iO to -J o JO A9*. <r too 0.0 /OO 0.0 90 / 7.3 9X3 * 13.3 * 90 S. 7 t/.s l*,o 70 73.3 70 4 3.3 + 93.3 SJ.3 /O r 20 /O r to.o Jo. 6 /o.o 2X1 s. 7 ti.9 /O.O 20.0 173 30 23.3 S6.7 ZiS 20.V 28.9 /6.7 S.7 Jo r- o.a 20 + to.o DSW 620565 STLCOPCB4094592 pr f7Si5P as# -sa^se [A:*#/< , . _ . - ,%,'&,*! w"` _ f&ic<ft> 3*a*?BmmnV^XiorVac F*`~.'.' ws*' ^w^#f6afn?r IRrttdu* Forme/tanNo/Sf Arfo+fj y;`s*-- - w\-., :V>i~ f ' ' Par CanA /C/// ` ' : "v ' SnM A>ra. <r S Niro* too too too too * 0.0 Niran t Bantit too too too too t 0.0 A/iron /Araator S4f(0 too too too too - o.o |-S" 8 Niran 90 0 0 30 s Ht.o A/ifah r Sant if so so to Hi.7i JS.Z //iron / Aroc/or S460 0 70 60 HJ.JT 37.S 8 A/Iran to 10 to t3.it. S.8 //iron /Bantit 0 to 0 j.ji S.8 f/iran /Aroolor SNiO HO JO 60 9J.it /S.J tZ Niran Hiran * Ban xit Niran + Aroc/or SN60 _____ :_______ 0 0 to 000 000 jst ot o- S.3 0.0 0.0 7aAte it. Southern Army worm Z ar Va c Raaic/ua Formulation Aj&, &ys Par Cant Kit! S Niran 70 SO ZO Niran / Bant li So so ZO Niran * Aroc/or S'//0 too too too S Niron Niran / Bonzi/ NO SO 30 SO 60 JO Niran + Aroc/or St60 SO 70 60 <3 Niran to 0 to Niran / Bonzi/ 0 to o Niran +Aroc/or S96Q 10 to ZO /z Niran 30 Ho o Niran + Bonzii 0 o to Niran /Arocter SN60 20 to 0 Ar&. cr H6.7t 60 - too t 2S.Z 3i.6 0.0 0 - 967- 60 r to.o /S.3 to.o 6.7 Z 3.3 t U.7Z s.s S.8 S.8 Z13Z 3.3 Z to T 20.8 ss / 0.0 DSW 620566 STLCOPCB4094593 STLCOPCB4094594 STLCOPCB4094595 STLCOPCB4094596 STLCOPCB4094597 STLCOPCB4094598 STLCOPCB4094599