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Dinitroaniline herbicides (Issue No. 1)
Chemosphere Vol. 9, PP 67 - 69
0045-65~5/80/0101-0067~02.00/0
~)Perg'amonPress Ltd. 1980. Printed in Great Britain
DINITROANILINE HERBICIDES(IssueNo.I) Comparative Summary. See Chemosphere, 1973, ~ (2), pp. 37 e%se~. by Ladonin, V.F., H~ssan, A., and Winterin~nam, F.P.W. Joint FAO/IAEA Division~ Vienna International Centre, Austria 1 - Usage. trends:
Important ~Toup of the numerous aniline-substituted and
r e l a t e d p h e n y l c a r b a m a t e h e r b i c i d e s ( 1 ) c h a r a c t e r i z e d by b a s i c s t r u c t u r e ( I ) b e l o w f o r s e l e c t i v e c o n t r o l o f a wide v a r i e t y o f g r a s s and b r o a d l e a f weeds. Wide u s e f o r c o t t o n and i n c r e a s i n g u s e f o r v e g e t a b l e and t r e e f r u i t s ( 2 ) .
Limited statistics on N-herbicide usage generally suggest sharp growth 43). -
Chemic%l structure: B~sic structure of group:
R2-N-R3
02N~
NO2
Rl (I) E.g., trifluralin (R1 = CF~t P~t R~ = C3Hv), isopropalin (RI = iso- C 3~,
~,
3 - Net&boliteso (~u&!itatlive composition of residuesz
o,5.o,o,.5,, R1
R1
R1
(II)
(III)
(IV)
Rl
R1
(VI)
(VII)
(V)
~"3 %
oN2~.o 2
NH2~
COOH CO2
(VIII)
(IX)
I~I + (iii)+ (iv)+ (v) fo~d in ~i~l tissue,(4, p.
(x)
274) + ( i i ~ + ( i v ) + ( i x ) f o ~ d in p l ~ t tis,uee 42, p. 228) / ~ / + ~II~ + ~IV~ + ~ + ( V I I ) + ( V I I I ) ~o~d in soil (5) .~nly
+ (II~ + (IV; + (Iz)
fo~d
in food (2, p. 228)
67
No. ]
68
Degraded only slowly by most higher plants,~9.g. , only trifluralin found in cotton, corn and soybean plants treated with ~*C-trifluralin by foliar aPplication or in nutrient solutions (6). Trifluralin metabolites If, IV, and IX d~tected in carrot (2,1P.228). Erbensive degradation of 14C-trifluralin or 14C-benefin in soil. *C-activity of harvested plants mainly recovered in lipids t glycosides, protein, cellular fractions and as hydrolysis products of the herbicides (2, p.232). 28 degradation products of trifluralin found in soil by oxidative N dealkylation, reduction of the nitro groups, cyclisation in the form of benzimidazoles, dimeric condensation in the form of amox~ and azo compounds, and by various oxidation/hydroxylation and reduction reactions (5). There is some evidence that aniline derivatives may be slowly degraded by opening of the Benzene ring (7) with formation of CO2 (X). 4 - Persistenceaetc."
Moderately persistent, e. 6. i0-15% of trifluralin was found in soils 6-12 months following application (8, p.370), effective half-life of nitralin in soil: 35 days (8, P.374), in air (daylight): 21-193 rain. (9)t near complete degradation in peanut and sweet potato after 72 hours (i0), near complete elimination in goats after 5 days (urine I0.8~ and feces 89.1%) (ii), and near complete destruction of benefin in aritficial tureen fluid after 12 hour incubation (ii). 5 - Typical residues found f ollowi~g aEricultuFal usage: Residues of benefin in peanut meat ~ 0 . 0 0 1 ppm, in alfalfa 0.008 ppm at harvest (4, p.268). Residues of trifluralin in vegetables following supervised trials and allowing specified periods between application, harvest and assay: 0.005 - 0.01 ppm in cabbage, cauliflower, asparagus after 7-14 weeks~ no detectable residues in leaves and seeds of cotton and soybean (8, P.373). Following ingestion by cows of feed mixed with trifluralin at I and 1000 ppm for 39 and 13 days respectively, no detectable residues found in milk (12), Similar results obtained in goat (12). USA-recommended maximum residue limit (MRL) for trifluralin in cottonseed t peas t ground nut t potato t cabbage t beet t soybean, sunflower t tomato 0.05 ppm; in hay of lucerne 0.2 ppm, in carrot 1.0 ppm (8, P.395). MRL recommended for nitralin in cottonseed, peas, cabbage, soybean, tomato and watermelon 0.I ppm (8, P.395). 6 - Mode of action: Dinitroaniline herbicides inhibit root growth of many species; common symptom is inhibition of lateral root formation. The most relevant effect as related to phytotoxicity is the change in nucleic acids. Uncoupling of oxidative phosphorylation and the inhibition of the develo~memt of several hormone-induced enzymes have also been observed (2, pp.230-232). 7 - Biological response data: Extensive toxicological data on trifluralin. indicated no hazard to man or animals. Acute oral L D ~ for rat > I0 g kg-A I body weight; for mouse 5 g kg -I body weight; for rabb~, dog, and hen 2 g kgbody weight. No adverse effects in rats exposed to 2.8 mg of trifluralin per litre; no skin irritation in rabbits treated dermally with 2.5 g of $rifluralin per kg body weight. No effect level in rat in 2 y feeding trial 2000 ppm in diet - i00 mg k_g~1 body weight, d-1, in dog in 2 y feeding trial I000 ppm in diet = 35 mg kg- body weight, d-1, these d a t a (d, pp.257-258). Dinitroanilines are toxic to fish. e.g. LCso of formulated trifluralin in sunfish bluegill and goldfish 0.6 pDm (13), and lethal concentration for rainbow trout and b]ueg~ll 0.i and 1.0 ppm respectively (14). 96-hour LC=n for nitralin in rainbow trout and bluegill 27 and 31 ppm, respectively (8, P.~75), and bioaccumulation ratios for mosquito fish after 3 days 235-755 in dark an~ 32-~3 in sunlight (15). Acute oral LDso of trifluralin for birds ~ 2 0 0 0 mg k g - body weight (16). 8 - Isotopic sTntheses. analytical methodolo~,~v: Preparation of 14C-side chain or ring labelled compounds reported (17). Thin layer (18) and gas (19) chromatogTaphic methods available for residue analysis.
No.
69
I
9 - References: (I) Martin, H. and Worthing, C.R. (Editors) Pesticide manual. British Crop Protection Council, 1977. (2) Ash,on, F.M. and Crafts, A.S. Mode of action of herbicides. J~hn Wiley and Sons, New York, 1973, p. 221. l~I FAO Production Yearbook, Rome, 1974, p. 267. Kearney, P.C. and Kaufmann, D.D. (Editors) Degradation of herbicides. Marcell Dekker, Inc., New York, 1969. (5) Colab. T., Althaus, W.&., and Wooten, H.L. J. Agric. Food Chem., ]979
2_I (]), (6) (7) (8) (9) (]0) ()II (12) 13) I14) (15) (16) (17) (18) ()19
p. ]63.
Funderburk, H.H. t Jr., Sehultz, D.P., Negi, N.S., Rodri~uez-Kabana, R., and C~,rl, E.A., Proc. 20%h Southern Weed Conf., 1967, p. 389. S~sS, A. and Eben, C. IAFA Panel Proceedings Series, Vienna, 1975, ST[/PUB/399, p. 19. Maier-Bode, H. Herbizide ,md ih~e R%{ck-stKnde, Ver]~ Eh~n Ulmer, Stuttgart, 1971. Woodrow, J.E., Crosby, D.G., Mast 8 R., Mailanen, K.W., and Seiber, J.M. J. Agric. Food Chem., 1978, 26 (6), p. 1312. Biswas, P.K., and Hamilton, W. Weed Sci. 1969, 17, pp. 206-211. Golab, T., Herberg, R.J., Gramlich, J.V., Raun, A.P. and Prober, G.W. J. Agric. Food Chem., 1970, 18 (5), P- 838. Herberg, R.J., Golab, T., Raun, A.P., and Holzer, F.J. American Chemical Society, 153rd meeting, Miami Beach, 1967, Abstract No. 45. Eli Lilly and Company, U.S.A. Treflan, Technical Report, January 1968. Eli Lilly and Company, U.S.A. The Toxicology of Trifluralin, Progress report, June 1961 -March 1964. Kearney, P.C., Isensee, A.R. and Kontson, A. Pest. Biochem. Physiol. 1977, 7, p.242. Pimental, D. Ecological effects of pesticides on non-target species. U.S. Gov't. Printing Office, Washington, D.C., 1971, p. 128. Marshall, F.J., McMahan, R.E., and Jones, R.G. J. Agric. Food Chem. 1966, 14, p. 498. Colab, T. J. Chromatog. 1965, 18, p.406. Tepe, J.B. and Scroggs, R.E. Analytical methods for pesticides, plant growth regulators and food additives, Vol. 5 (supplemental volume), (G. Zweig, Editor), Academic Press, New York, 1967, P. 527.
(Received in Austria 5 December 1979)
0045-65~5/80/0101-0067~02.00/0
~)Perg'amonPress Ltd. 1980. Printed in Great Britain
DINITROANILINE HERBICIDES(IssueNo.I) Comparative Summary. See Chemosphere, 1973, ~ (2), pp. 37 e%se~. by Ladonin, V.F., H~ssan, A., and Winterin~nam, F.P.W. Joint FAO/IAEA Division~ Vienna International Centre, Austria 1 - Usage. trends:
Important ~Toup of the numerous aniline-substituted and
r e l a t e d p h e n y l c a r b a m a t e h e r b i c i d e s ( 1 ) c h a r a c t e r i z e d by b a s i c s t r u c t u r e ( I ) b e l o w f o r s e l e c t i v e c o n t r o l o f a wide v a r i e t y o f g r a s s and b r o a d l e a f weeds. Wide u s e f o r c o t t o n and i n c r e a s i n g u s e f o r v e g e t a b l e and t r e e f r u i t s ( 2 ) .
Limited statistics on N-herbicide usage generally suggest sharp growth 43). -
Chemic%l structure: B~sic structure of group:
R2-N-R3
02N~
NO2
Rl (I) E.g., trifluralin (R1 = CF~t P~t R~ = C3Hv), isopropalin (RI = iso- C 3~,
~,
3 - Net&boliteso (~u&!itatlive composition of residuesz
o,5.o,o,.5,, R1
R1
R1
(II)
(III)
(IV)
Rl
R1
(VI)
(VII)
(V)
~"3 %
oN2~.o 2
NH2~
COOH CO2
(VIII)
(IX)
I~I + (iii)+ (iv)+ (v) fo~d in ~i~l tissue,(4, p.
(x)
274) + ( i i ~ + ( i v ) + ( i x ) f o ~ d in p l ~ t tis,uee 42, p. 228) / ~ / + ~II~ + ~IV~ + ~ + ( V I I ) + ( V I I I ) ~o~d in soil (5) .~nly
+ (II~ + (IV; + (Iz)
fo~d
in food (2, p. 228)
67
No. ]
68
Degraded only slowly by most higher plants,~9.g. , only trifluralin found in cotton, corn and soybean plants treated with ~*C-trifluralin by foliar aPplication or in nutrient solutions (6). Trifluralin metabolites If, IV, and IX d~tected in carrot (2,1P.228). Erbensive degradation of 14C-trifluralin or 14C-benefin in soil. *C-activity of harvested plants mainly recovered in lipids t glycosides, protein, cellular fractions and as hydrolysis products of the herbicides (2, p.232). 28 degradation products of trifluralin found in soil by oxidative N dealkylation, reduction of the nitro groups, cyclisation in the form of benzimidazoles, dimeric condensation in the form of amox~ and azo compounds, and by various oxidation/hydroxylation and reduction reactions (5). There is some evidence that aniline derivatives may be slowly degraded by opening of the Benzene ring (7) with formation of CO2 (X). 4 - Persistenceaetc."
Moderately persistent, e. 6. i0-15% of trifluralin was found in soils 6-12 months following application (8, p.370), effective half-life of nitralin in soil: 35 days (8, P.374), in air (daylight): 21-193 rain. (9)t near complete degradation in peanut and sweet potato after 72 hours (i0), near complete elimination in goats after 5 days (urine I0.8~ and feces 89.1%) (ii), and near complete destruction of benefin in aritficial tureen fluid after 12 hour incubation (ii). 5 - Typical residues found f ollowi~g aEricultuFal usage: Residues of benefin in peanut meat ~ 0 . 0 0 1 ppm, in alfalfa 0.008 ppm at harvest (4, p.268). Residues of trifluralin in vegetables following supervised trials and allowing specified periods between application, harvest and assay: 0.005 - 0.01 ppm in cabbage, cauliflower, asparagus after 7-14 weeks~ no detectable residues in leaves and seeds of cotton and soybean (8, P.373). Following ingestion by cows of feed mixed with trifluralin at I and 1000 ppm for 39 and 13 days respectively, no detectable residues found in milk (12), Similar results obtained in goat (12). USA-recommended maximum residue limit (MRL) for trifluralin in cottonseed t peas t ground nut t potato t cabbage t beet t soybean, sunflower t tomato 0.05 ppm; in hay of lucerne 0.2 ppm, in carrot 1.0 ppm (8, P.395). MRL recommended for nitralin in cottonseed, peas, cabbage, soybean, tomato and watermelon 0.I ppm (8, P.395). 6 - Mode of action: Dinitroaniline herbicides inhibit root growth of many species; common symptom is inhibition of lateral root formation. The most relevant effect as related to phytotoxicity is the change in nucleic acids. Uncoupling of oxidative phosphorylation and the inhibition of the develo~memt of several hormone-induced enzymes have also been observed (2, pp.230-232). 7 - Biological response data: Extensive toxicological data on trifluralin. indicated no hazard to man or animals. Acute oral L D ~ for rat > I0 g kg-A I body weight; for mouse 5 g kg -I body weight; for rabb~, dog, and hen 2 g kgbody weight. No adverse effects in rats exposed to 2.8 mg of trifluralin per litre; no skin irritation in rabbits treated dermally with 2.5 g of $rifluralin per kg body weight. No effect level in rat in 2 y feeding trial 2000 ppm in diet - i00 mg k_g~1 body weight, d-1, in dog in 2 y feeding trial I000 ppm in diet = 35 mg kg- body weight, d-1, these d a t a (d, pp.257-258). Dinitroanilines are toxic to fish. e.g. LCso of formulated trifluralin in sunfish bluegill and goldfish 0.6 pDm (13), and lethal concentration for rainbow trout and b]ueg~ll 0.i and 1.0 ppm respectively (14). 96-hour LC=n for nitralin in rainbow trout and bluegill 27 and 31 ppm, respectively (8, P.~75), and bioaccumulation ratios for mosquito fish after 3 days 235-755 in dark an~ 32-~3 in sunlight (15). Acute oral LDso of trifluralin for birds ~ 2 0 0 0 mg k g - body weight (16). 8 - Isotopic sTntheses. analytical methodolo~,~v: Preparation of 14C-side chain or ring labelled compounds reported (17). Thin layer (18) and gas (19) chromatogTaphic methods available for residue analysis.
No.
69
I
9 - References: (I) Martin, H. and Worthing, C.R. (Editors) Pesticide manual. British Crop Protection Council, 1977. (2) Ash,on, F.M. and Crafts, A.S. Mode of action of herbicides. J~hn Wiley and Sons, New York, 1973, p. 221. l~I FAO Production Yearbook, Rome, 1974, p. 267. Kearney, P.C. and Kaufmann, D.D. (Editors) Degradation of herbicides. Marcell Dekker, Inc., New York, 1969. (5) Colab. T., Althaus, W.&., and Wooten, H.L. J. Agric. Food Chem., ]979
2_I (]), (6) (7) (8) (9) (]0) ()II (12) 13) I14) (15) (16) (17) (18) ()19
p. ]63.
Funderburk, H.H. t Jr., Sehultz, D.P., Negi, N.S., Rodri~uez-Kabana, R., and C~,rl, E.A., Proc. 20%h Southern Weed Conf., 1967, p. 389. S~sS, A. and Eben, C. IAFA Panel Proceedings Series, Vienna, 1975, ST[/PUB/399, p. 19. Maier-Bode, H. Herbizide ,md ih~e R%{ck-stKnde, Ver]~ Eh~n Ulmer, Stuttgart, 1971. Woodrow, J.E., Crosby, D.G., Mast 8 R., Mailanen, K.W., and Seiber, J.M. J. Agric. Food Chem., 1978, 26 (6), p. 1312. Biswas, P.K., and Hamilton, W. Weed Sci. 1969, 17, pp. 206-211. Golab, T., Herberg, R.J., Gramlich, J.V., Raun, A.P. and Prober, G.W. J. Agric. Food Chem., 1970, 18 (5), P- 838. Herberg, R.J., Golab, T., Raun, A.P., and Holzer, F.J. American Chemical Society, 153rd meeting, Miami Beach, 1967, Abstract No. 45. Eli Lilly and Company, U.S.A. Treflan, Technical Report, January 1968. Eli Lilly and Company, U.S.A. The Toxicology of Trifluralin, Progress report, June 1961 -March 1964. Kearney, P.C., Isensee, A.R. and Kontson, A. Pest. Biochem. Physiol. 1977, 7, p.242. Pimental, D. Ecological effects of pesticides on non-target species. U.S. Gov't. Printing Office, Washington, D.C., 1971, p. 128. Marshall, F.J., McMahan, R.E., and Jones, R.G. J. Agric. Food Chem. 1966, 14, p. 498. Colab, T. J. Chromatog. 1965, 18, p.406. Tepe, J.B. and Scroggs, R.E. Analytical methods for pesticides, plant growth regulators and food additives, Vol. 5 (supplemental volume), (G. Zweig, Editor), Academic Press, New York, 1967, P. 527.
(Received in Austria 5 December 1979)