Radiolabeled (14C) 2-[4-(3-chloro-5-trifluoromethyl-2-pyridinyloxy)phenoxy] propionic acid (Compound C); its methyl-,n-butyl-, and ethoxyethyl-esters; and fluazifop-butyl {(±)-butyl 2-[4-[(5-(trifluoromethyl)-2-pyridinyl)oxy] phenoxy] propionate} were applied to the primary shoots of young rhizomatous quackgrass [Agropyron repens (L.) Beauv. # AGRRE]. Plants were sampled from 0.5 to 24 days after treatment (DAT) and analyzed for radiochemical. All treatments caused phytotoxic symptoms in primary shoots, rhizomes, and tillers and significantly reduced growth of primary shoots and rhizomes. Treatment with compound C or its methyl and butyl esters eliminated regrowth from all rhizomes excised from treated plants. The ethoxyethyl-ester and fluazifop-butyl controlled regrowth from rhizomes from 50% of the plants and substantially reduced shoot regrowth from the remainder. Rhizomes that did produce shoots contained significantly less radiochemical than those from which no regrowth occurred. At 24 DAT, a maximum of only 1% of each radiochemical applied was translocated to the first tiller and rhizomes and had been sufficient to cause marked phytotoxic symptoms. Soon after application (1 DAT), the major metabolites in the treated leaves and remainder of the plant for all compounds were the free acid and substantial amounts of polar conjugates that were hydrolyzable to the free acids. Radiochromatography of extracts from rhizomes and first tillers from all treatments gave similar chemical profiles, with the free acids and their conjugates as the predominant components present. These results provide evidence that esters of the pyridinyloxyphenoxypropionic acids are rapidly hydrolyzed after absorption by quackgrass; the free acids are then translocated and are the active form of these herbicides.

Among the numerous research reports on the fate of herbicides in soils, the literature dealing with the degradation of herbicides under field conditions is probably most difficult to interpret. Few have attempted to evaluate critically the purposes of these studies. This review will not be a comprehensive recitation of previous studies on herbicide degradation under field conditions, but is aimed at pointing out certain problem areas in the approach to research on this subject. The problems relate both to a lack of clear understanding of the degradation process and a lack of appropriate methodology for studying degradation under field conditions.

The fate of 14C-sethoxydim {2-[1-(ethoxyimino) butyl]-5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-one} in an aqueous solution and on glass exposed to light was evaluated. Within 1 h, more than 80% of the 14C-sethoxydim was transformed to six major products. Qualitatively the transformations were similar for both systems, and a single end product constituted the majority of 14C after 72 h. Two transitory compounds were found to be phytotoxic to barnyardgrass [Echinochloa crus-galli (L.) Beauv. ♯ ECHCG] and were more stable than sethoxydim. A nonphytotoxic compound isolated and identified by mass spectroscopy was desethoxy-sethoxydim.

Investigations were made under controlled environmental conditions of isoproturon [N-(4-isopropylphenyl)-N’,N′-dimethylurea] absorption and translocation in wheat (Triticum aestivum L.) (tolerant) and slender foxtail (Alopecurus myosuroides Huds. ♯ ALOMY) (sensitive). Effects of isoproturon on 14CO2 fixation and 14C-assimilate translocation were also examined in the test species. The amount of 14C-isoproturon translocated by slender foxtail was about four times greater than by wheat. Foliar application of isoproturon resulted in greater inhibition of photosynthetic 14CO2 fixation in slender foxtail than in wheat. The reduction in 14C-assimilate translocation was also significantly greater in slender foxtail than in wheat.

Most herbicides are applied preemergence onto bare soil or during the early stage of plant development. Therefore, the major part of the active ingredient either reaches the soil surface immediately or later with decaying plant material. The further fate of the herbicide depends largely on the physicochemical behavior of the respective compound, the amount and method of application, and a number of soil, plant, and climatic factors influencing the persistence and bio availability of organic compounds in a given soil (5, 7). Especially in the upper 2-cm soil layer, drastic changes in temperature and moisture content during a growing season have a great influence on the degradation and adsorption of herbicides in soil (10, 31).

Absorption and translocation of 14C-glyphosate [N-(phosphonomethyl)glycine] by moisture-stressed common milkweed (Asclepias syriaca L. ♯ ASCSY) was studied in greenhouse and growth chamber experiments. Water-stressed [13% (w/w) soil moisture] common milkweed plants treated with glyphosate at 1.1 kg ae/ha produced shoot regrowth equal to untreated plants, whereas shoot regrowth of nonstressed [25% (w/w) soil moisture] glyphosate-treated plants was only 6% of untreated plants. All shoot regrowth originated from buds on the proximal half of roots. Common milkweed plants, maintained at 25% soil moisture, absorbed 44% of the 14C-glyphosate applied and translocated 20% from the treated leaf, whereas plants at 13% soil moisture absorbed 29% and translocated 7%. Wiping the leaf with tissue paper wetted with distilled water or chloroform prior to 14C-glyphosate application increased absorption from 35 (unwiped leaves) to 62 and 77%, respectively, for plants at 25% soil moisture, and increased absorption from 14 to 42 and 46%, respectively, for plants at 13% soil moisture. Wiping failed to increase translocation out of the treated leaf for plants at either soil moisture regime. Latex samples taken from the abaxial leaf surface opposite 14C-glyphosate-treated leaves and from petioles of treated leaves did not contain 14C, indicating that glyphosate did not enter laticifers. Proximal root buds accumulated less 14C-radioactivity than distal root buds and had lower respiratory rates, suggesting that proximal root buds are more dormant than distal root buds and thus accumulate less glyphosate.

Protein damage, as a primary phytotoxic consequence of in vivo lipid peroxidation, induced by the diphenyl ether herbicide oxyfluorfen [2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene] at a concentration of 10 μM, was measured with the green alga Scenedesmus acutus. In the light, water-soluble proteins are destroyed by a herbicide-induced peroxidation process that can be detected by production of fluorescent products and loss of specific amino acid residues of proteins. The water-soluble cytochrome c-553 and the membrane-bound cytochrome f-553, components of the photosynthetic electron transport, were specifically used as sensitive markers for protein damage, measured as decrease of redox reactions of the cytochromes. Under peroxidizing conditions, destruction of the algal cytochrome c is significantly higher than destruction of membrane-bound components, such as cytochrome f and chlorophyll. Protection against protein loss is achieved by the nonbiological antioxidant ethoxyquin (1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline) or the photosynthesis inhibitor diuron [N′-(3,4-dichlorophenyl)-N,N-dimethylurea].

The effects of hexazinone [3-cyclohexyl-6-(dimethylamino)-1-methyl-1,3,5-triazine-2,4 (1H, 3H)-dione] and its metabolites, A [3-(4-hydroxycyclohexyl)-6-(dimethylamino)-1-methyl-1,3,5-triazine-2,4 (1H,3H)-dione], B [3-cyclohexyl-6-(methylamino)-1-methyl-1,3,5-triazine-2,4 (1H,3H)-dione], C [3-(4-hydroxycyclohexyl)-6-(methylamino)-1-methyl-1,3,5-triazine-2,4 (1H,3H)-dione], D [3-cyclohexyl-1-methyl-1,3,5-triazine-2,4,6 (1H, 3H,5H)-trione], and E [3-(4-hydroxycy clohexyl)-1-methyl-1,3,5-triazine-2,4,6 (1H,3H,5H)-trione], on photosynthesis of loblolly pine primary needle segments were studied using a bioassay technique. Hexazinone, at concentrations equal to or greater than 1.0 × 10-6 M, inhibited photosynthesis, while 1.0 × 10-8 M and 1.0 × 10-7 M concentrations increased photosynthesis. Metabolite B at 1.0 × 10-4 M also inhibited photosynthesis. Metabolites A, C, D, and E did not affect photosynthesis at 1.0 × 10-4 in pine needle segments. The bioassay proved simple and useful for determining effects of certain herbicides and metabolites on photosynthesis.

Lipid metabolism and other biochemical responses to alachlor [2-chloro-2’,6’-dimethyl-N-(methoxymethyl) acetanilide] and the protectant flurazole [2-chloro-4-(trifluoromethyl)-5-thiazolecarboxylic acid, (phenylmethyl ester)] in germinated grain sorghum [Sorghum bicolor (L.) Moench. ‘MFA GS 301’] were studied. Treatments included flurazole, applied to grain sorghum seed at 2.5 g ai/kg, alachlor at 8.2 × 10−6 M, and alachlor plus flurazole at these rates. Treatments did not alter total lipid synthesis or fatty acid composition. Seeds that germinated for 48 h in media containing alachlor or alachlor plus flurazole had a greater triglyceride:phospholipid ratio than those treated with flurazole or the control seeds, indicating that alachlor plus flurazole retarded catabolism of storage lipid. Oxygen consumption of seeds was reduced after the herbicide plus protectant treatment. Oxidation of 14C-pyruvate to CO2 was inhibited by alachlor and alachlor plus flurazole treatments, but not by flurazole alone.

Dark germination of light-requiring lettuce seeds (Lactuca sativa L. ‘Grand Rapids’) was stimulated by SAN 9789 [4-chloro-5-(methylamino-2-(α,α,α-trifluoro-m-tolyl)-3(2H)-pyridazinone] and to a minor degree by BASF 13761 [4-chloro-5-methoxy-2-phenyl-3(2H)-pyridazinone] and BASF 44521 [4-chloro-5-methoxy-2-(α,α,α-trifluoro-m-tolyl)-3(2H)-pyridazinone], but not by’ pyrazon [5-amino-4-chloro-2-phenyl-3(2H)-pyridazinone], SAN 9785 [4-chloro-5-(dimethylamino)-2-phenyl-3 (2H)-pyridazinone], SAN 9774 [5-amino-4-chloro-2-(α,α,α-trifluoro-m-tolyl)-3(2H)-pyridazinone], or SAN 6706 [4-chloro-5-(dimethylamino)-2-(α,α,α-trifluoro-m-tolyl)-3(2H)-pyridazinone]. SAN 9789 stimulation was inhibited by cis-4-cyclohexene-1,2-dicarboximide (CHDC), and abscisic acid (ABA) at 1 × 10-4 M. Red light nullified the inhibitory effect of CHDC (1 × 10-4 M) but not the inhibitory effect of ABA (1 × 10-4 M) on SAN 9789 stimulated germination. Gibberellic acid (GA3) and kinetin (6-furfurylaminopurine) increased the germination stimulatory effect of SAN 9789 in darkness. Temperatures above 25 C decreased the effect of SAN 9789, with a temperature of 35 C completely inhibiting germination. The inhibitory effect of CHDC was strongly decreased at temperatures below 20 C. SAN 9789-induced germination in darkness was always the same (25 to 26% units increase in germination) even though the red light-stimulated germination differed with the seed batch.

Field experiments established that tetraploid soybean [Glycine max (L.) Merr.] plants were relatively tolerant while diploid plants were highly susceptible to metribuzin [4-amino-6-tert-butyl-3-(methylthio)-as-triazin-5(4H)-one] applied both preemergence and postemergence. Sensitivity of diploids and tolerance of tetraploids was also found in growth chamber experiments. Autoradiographs prepared 4 days after 14C-metribuzin application showed a high level of 14C-translocation to all parts of diploid plants including meristems. In contrast, only low levels of 14C were translocated in tetraploid plants, with no 14C-movement into meristems. Tetraploid plants rapidly transformed absorbed metribuzin to nontoxic products. Diploids were incapable of inactivating absorbed metribuzin at a rate sufficient to prevent injury. Differences in absorption, translocation, and metabolism of metribuzin appeared to be the main factors in the diploid and tetraploid differential response in field and growth chamber experiments. Differences in the rate of metribuzin metabolism appeared to be the factor responsible for the differential response in diploid and tetraploid cell suspension cultures. The primary polar metabolites were conjugates of metribuzin and deaminated metribuzin [6-tert-butyl-3-(methylthio)-1,2,4-triazin-5(4H)-one] with a ratio of 8:1, respectively.

Under greenhouse conditions, vaporization of oxyfluorfen [2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene] formulations (2 EC, 25 WP, 1G) was studied on cabbage (Brassica oleracea L. var. capitata L. F. alba DC. ‘Market Prize’), tomato (Lycopersicon esculentum Mill. ‘Campbell 37’), cucumber (Cucumis sativus L. ‘Straight 8’), and lettuce (Lactuca sativa L. ‘Salad Bowl’). The emulsifiable concentrate and granular formulations caused vapor injury to plants exposed under glass bell jars. Vapor injury to all species increased when exposure times were increased from 8 to 72 h. Lettuce was the most susceptible test species. Exposure temperatures of 18 and 29 C did not alter the amount of vapor injury apparent on tomato foliage. Oxyfluorfen vapor injury did not reduce dry weight of any test species.

Root absorption of 14C-5 (ring)-metribuzin [4-amino-6-tert-butyl-3-(methylthio)-as-triazin-5(4H)-one] from hydroponic culture and its subsequent translocation in tolerant (‘Russet Burbank’) and susceptible (‘Chipbelle’) potato (Solanum tuberosum L.) cultivars were measured. Differences in root absorption did not appear to be as important to differential tolerance as did translocation differences. Total available metribuzin absorbed was 6 and 7%, 18 and 29%, and 31 and 45% after 1, 4, and 8 days for Russet Burbank and Chipbelle, respectively. Radioactivity was concentrated in stems, petioles, and leaf veins in the tolerant cultivar, whereas interveinal leaf tissue was the major accumulation site for 14C in the susceptible cultivar. Of the total radioactivity in the plants after 8 days, 82 and 87% were in the foliage for the tolerant and the susceptible cultivar, respectively. Translocation was apoplastic. Metribuzin tolerance by Russet Burbank is due in part to restricted translocation to the leaf blades. A model for differential transport between cultivars is proposed.

The spatial variation of measured pesticide concentrations is often a complicating factor in interpreting the results from field studies. This is particularly true when the study objective is quantitative evaluation of pathways of pesticide loss (leaching, degradation) or efficacy. The variation can result from a lack of uniformity in pesticide or water application (an extrinsic factor) or from spatial differences in various physical, chemical, and biological processes (intrinsic factors) that act to transport and transform pesticides in the field. Most research attention to date has not focused on the spatial variation of these basic processes, but rather on the total spatial variation (extrinsic plus intrinsic) in the measured concentrations of residual pesticide.

14C-Sethoxydim {2-[1-(ethoxyimino)butyl]-5-[2-ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-one} was rapidly metabolized by quackgrass [Agropyron repens (L.) Beauv. ♯ AGRRE], barnyardgrass [Echinochloa crus-galli (L.) Beauv. ♯ ECHCG], alfalfa (Medicago sativa L. ‘Saranac’), and navy bean (Phaseolus vulgaris L. ‘Seafarer’). One hour after application, 46, 27, 38, and 46% of the total 14C in the ethyl acetate-soluble fraction from treated leaves was sethoxydim, respectively. After 24 h, less than 2% was sethoxydim in any species. Nine metabolites were found, seven of which cochromatographed with photo- and thermal-transformation products of sethoxydim. Two metabolites, previously shown to be phytotoxic to barnyardgrass, contained the majority of 14C up to 24 h after application. Quantitative or qualitative differences in the metabolites of treated leaves could not account for the observed differences in selectivity.

The sensitivities of chlorophyll fluorescence and fresh weight as bioassay techniques for the determination of metribuzin [4-amino-6-tert-butyl-3-(methylthio)-as-triazin-5 (4H)-one], diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea], and atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine] concentrations in soil were compared. The ratio of the initial inflection point (I) to the variable fluorescence maximum (P) of intact oat (Avena sativa L. ‘Chilocco’) leaves was determined for plants seeded directly into herbicide-treated soil and for those transplanted into treated soil after 14 days of growth in nutrient solution. Using the chlorophyll fluorescence of transplanted oats bioassay, 0-, 0.13-, 0.25-, and 0.50-ppm concentrations could be distinguished from one another within 8 h for metribuzin, within 24 h for diuron, and within 48 h for atrazine. These distinctions between rates could not be made 17 days after seeding into treated soil when using fresh weight as the bioassay indicator. Chlorophyll fluorescence of oats seeded directly into treated soil was also a reliable technique, but required much more time to attain sufficient plant size for convenient chlorophyll fluorescence determinations.

Effects of fluazifop-butyl {(±)-butyl 2-[4-[(5-(trifluoromethyl)-2-pyridinyl)oxy] phenoxy] propanoate} on cellular uptake and incorporation of 14C-leucine, 14C-uridine, and 14C-thymidine into protein, RNA, and DNA, respectively, were evaluated in corn (Zea mays L.) coleoptiles and soybean [Glycine max (L.) Merr.] hypocotyls. Uptake of 14C-leucine in corn coleoptiles was inhibited by fluazifop-butyl at 10-4 to 10-7 M, which was related to reductions in incorporation of 14C-leucine into protein at 10-4 to 10-6 M. The effect of fluazifop-butyl on 14C-leucine uptake and incorporation was reduced by 2 × 10-6 M 2,4-D [(2,4-dichlorophenoxy)acetic acid], indicating antagonism between these herbicides. RNA and DNA synthesis were inhibited at 10-5 and 10-4 M. Protein synthesis in soybean hypocotyls was stimulated by 10-7 and 10-6 M fluazifop-butyl 33 and 27%, respectively, and inhibited by 10-4 M 50%. RNA and DNA synthesis were also inhibited by 10-4 M in soybean.

From 1976 to 1981, emergence date, height, and dry weight per plant were taken for eight weed species grown at Bushland, TX, at two stand densities. Height and dry weight per plant were related to precipitation and degree-days for air and soil temperatures using base temperatures of 10, 15.5, or 21 C. Kochia [Kochia scoparia (L.) Schrad. ♯ KCHSC] emerged early in March and was followed by poison suckleya [Suckleya suckleyana (Torr.) Rydb. ♯ SUKSU], sunflower (Helianthus annuus L. ♯ HELAN), and common cocklebur (Xanthium pensylvanicum Wallr. ♯ XANPE) in early April. Buffalobu(Solanum rostratum Dunal. ♯ SOLCU), puncturevine (Tribulus terrestris L. ♯ TRBTE), lanceleaf sage (Salvia reflexa Hornem. ♯SALRE), and barnyardgrass (Echinochloa crus-galli L. Beauv. ♯ECHCG) emerged in late April. The weeds began to increase in height during May but plants did not start increasing in weight until June. Kochia, common cocklebur, and sunflower grew tallest, produced most dry matter, made most efficient use of water, and weighed most per plant. Heat unit accumulations were strongly correlated with plant height.