Trifluralin was evaluated at 1.1, 2.2, and 4.5 kg/ha in 1983 and 1984 at two locations in Iowa for residue carryover injury to corn the following seasons. Three methods of seedbed preparation (no-till, moldboard, and chisel plowing) for corn planting were also examined. There was no effect on corn growth at the 1.1 kg/ha rate of trifluralin. Averaged over the four experiments, reductions in corn height of 8 and 24% were observed 5 weeks after planting at 2.2 and 4.5 kg/ha, respectively. The relative degree of stunting due to trifluralin decreased as the growing season progressed. Early-season carryover injury was more severe in reduced tillage than in moldboard plow treatments in the 1983-84 Nashua experiment. Moldboard and chisel plowing reduced the concentration of trifluralin in the 0- to 7.5-cm zone of the soil profile by 62 and 31%, respectively, when compared to no-till. No yield reductions were observed at the 1.1 or 2.2 kg/ha rate of trifluralin. In 1984, grain yields were reduced by 8 and 16% at Ames and Nashua, respectively, by the 4.5 kg/ha trifluralin rate.

A leaching test conducted in field lysimeters for the purpose of pesticide registration is evaluated, particularly in terms of factors such as the effects of soil type, variability in leaching between replicate lysimeters, and simulation of worst-case scenarios. Two herbicides, dichlorprop and bentazon, were chosen as test compounds due to their documented high mobility in laboratory tests. Four different soil types (sand, loam, clay, peat) and two irrigation treatments were included. Both herbicides were applied at rates representing normal doses (1.6 and 0.6 kg ai ha−1 of dichlorprop and bentazon, respectively). 36Cl was also applied to sand and clay lysimeters to follow the pattern of water movement. Leaching of dichlorprop for the varying soil type/treatment combinations ranged from 0.02 to 1.8% of the amount applied. Leaching losses of bentazon reached up to 0.07% of that applied. Leaching of both herbicides was greater mostly in clay monoliths than in sand monoliths, which was explained in terms of macropore flow. A more effective macropore flow was also suggested to be the main reason why more dichlorprop leached in clay and peat monoliths treated with a small water input. Detectable, and in some cases large, concentrations of dichlorprop were found in the first drainage water in early autumn in all soil/treatment combinations, indicating the occurrence of preferential flow in all soils tested, including sand. A rapid breakthrough of 36Cl was also found in clay and low-irrigation input sand, providing additional confirmation of the role of preferential flow processes in these soils. It is concluded that field mobility tests for pesticide registration are a necessary complement to measurements of physical/chemical properties of a compound and that these should be performed in a range of soil types, including at least one structured soil. Other factors identified to be of importance when evaluating lysimeter studies such as this were the analytical detection limits of the pesticides and the need for replication.

Experiments were conducted in 1985 and 1986 to determine and compare the efficacy, phytotoxicity, and soil persistence of imazquin, imazethapyr, and clomazone in no-till double-crop soybeans. All herbicides controlled 93% or greater jimsonweed, velvetleaf, and giant foxtail. Imazaquin and imazethapyr controlled more common cocklebur and ivyleaf morningglory than clomazone. Soybeans were injured from imazaquin and imazethapyr applications in 1986 but yields were not reduced. First-order kinetics described the dissipation of each herbicide. Imazaquin and imazethapyr were more persistent in the soil than clomazone. Averaged over both years, half-lives of 10, 43, and 60 days were calculated for clomazone, imazaquin, and imazethapyr, respectively. Clomazone was not detected 10 to 20 cm in the soil profile. More imazethapyr was detected 10 to 20 cm in the soil profile than imazaquin in 1985. Slight corn injury (≤10%) was observed in 1987 following previous year applications of imazaquin to no-till double-crop soybeans but corn yields were not reduced.

Experiments were conducted in 1993 and 1994 to determine persistence of pyrithiobac as determined by bioavailability following different application times in a silty clay. Pyrithiobac was applied at PPI, PRE, pinhead square (PHS), and first bloom (FB) application timings. Greenhouse studies were also conducted in 1993 and 1994 to determine pyrithiobac persistence under controlled conditions on a sandy loam soil. Slope comparison indicated no difference in degradation patterns in the field for any application timing of pyrithiobac within years; thus, application timings were combined for 1993 and 1994. Slope comparison also indicated no difference in slope between 1993 and 1994; thus, years were combined to determine pyrithiobac persistence. The initial concentration was 30 ηg g−1. The half-life of pyrithiobac was 62 d in the field. Analysis of covariance indicated no difference in slope for the 1993 and 1994 greenhouse studies, and years were combined to determine the half-life. The initial concentration was 43 η g−1. The half-life was 43 d in the greenhouse study.

Experiments were conducted to monitor the dissipation of imazaquin and imazethapyr applied to the soil surface under conventional and no-tillage conditions. Imazaquin or imazethapyr dissipation rate was similar in no-tillage in 1985 and 1986. Dissipation of the herbicides under conventional tillage conditions varied. Imazaquin dissipation occurred 2.4 times faster in 1986 than in 1985. Imazethapyr dissipation was 3.5 times faster in 1986 than in 1985. Corn planted without tillage (no-till) was injured in 1986 where 210 or 280 g ha-1 of imazaquin or 105 g ha-1 of imazethapyr had been applied the previous year to conventionally tilled soybeans, but injury was not evident where these herbicides had been applied to no-tillage soybeans. Corn injury was evident 2 wk after planting in 1987 but yields were not reduced.

Concentrations of atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine] in contaminated groundwater recovered from 41 monitoring wells in Hall and Buffalo counties, Nebraska range from 0.01 to 8.29 μg/L. Over a 1-year period concentrations fluctuated sufficiently in a seasonal pattern to indicate that atrazine dissipation occurs. This reduction in concentration can be attributed to adsorption, dispersion, and degradation. A limited amount of atrazine degraded chemically to hydroxyatrazine [2-hydroxy-4-(ethylamino)-6-(isopropylamino)-s-triazine] under simulated aquifer conditions; microbial degradation could not be detected. A geometrical progression model for predicting long term residue accumulation indicates that current contamination levels probably reflect a steady-state situation between the amount that yearly enters into, and the partial degradation that occurs within, the aquifer. Oat (Avena sativa L. ‘Neal’) bioassays indicate that present levels of groundwater contamination remain well below the threshold necessary for phytotoxicity.

Applications of ethofumesate [(±)-2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl methanesulfonate] at rates from 0.3 to 1.4 kg/ha were made in the field to soils of 2 and 30% (w/w) soil moisture. After 2 to 4 days, all soils were irrigated to establish stands of either sweet corn (Zea mays L. ‘Jubilee’) or winter wheat (Triticum aestivum L. ‘Stephens’) used as bioassay species for ethofumesate activity. Ethofumesate, at most rates, was significantly less effective on both corn and wheat when applied to dry soil than to wet soil. In greenhouse studies, ethofumesate activity was significantly greater when incorporated into soil of 12% than 2% (w/w) moisture 2 or 4 days prior to irrigation. An increase in herbicide activity was apparent as the length of time between herbicide application and wetting increased from 2 to 4 days. Analysis of wet (20%, w/w) and dry (2%, w/w) soils treated with equal levels of ethofumesate revealed no loss of herbicide applied to wet soil over a 12-day period, but in the dry soil, the amount extracted after 12 days was 10% of the amount extracted at 0 days. These data and other considerations suggest that chemical degradation of ethofumesate is the most likely mechanism for the activity loss in dry soil.

Laboratory experiments were conducted to determine the effect of three phenolic acids, acetone, and riboflavin on aqueous photolysis of chlorimuron and imazaquin. The phenolic acids investigated were caffeic acid (CA), ferulic acid (FA), and p-coumaric acid (PCA). Treatment solutions were contained in quartz vessels and irradiated with 300 to 400 nm UV light in a photoreactor. The extrapolated photolysis half-life of chlorimuron in pure solution was 107 h, compared to a half-life of 0.42 h for pure aqueous imazaquin. Chlorimuron in solutions containing 10 ppmw riboflavin, acetone, CA, FA, or PCA exhibited half-lives of 9, 57, 58, 67, and 146 h, respectively. Imazaquin in solutions containing 10 ppmw riboflavin, acetone, CA, FA, or PCA had half-lives of 0.70, 0.55, 0.55, 0.48, and 0.55 h, respectively. The presence of PCA in aqueous media delayed chlorimuron photolysis, whereas all other compounds, especially riboflavin, sensitized chlorimuron photolysis. In contrast, imazaquin photolysis was delayed in the presence of the test compounds, with riboflavin having the greatest effect and causing in a 68% increase in imazaquin half-life over that of imazaquin alone. Quantum yields for sensitized photolysis of chlorimuron by riboflavin and for riboflavin by imazaquin were 0.1134 and 0.0477, respectively. These results suggest that some soluble and naturally occurring organic compounds may enhance chlorimuron photolysis yet delay imazaquin photolysis in surface waters.

Evidence has shown that fluometuron {N,N-dimethyl-N′-[3-(trifluoromethyl)phenyl]urea} persists beyond the end of the growing season when used in continuous cotton (Gossypium hirsutum L.) production. Samples were taken from three soils following cotton production in 1980, 1981, and 1982. All three soils had been in production under the same herbicide use regime, fluometuron preemergence followed by fluometuron plus MSMA (monosodium methanearsonate), since either 1976 or 1977. The fluometuron remaining in each soil was quantified using a greenhouse bioassay and a chemical extraction technique followed by high-performance liquid chromatography determinations. The fluometuron concentrations determined by bioassay and chemical extraction methods had partial correlation coefficients of 0.62, 0.91, and 0.72 for a Sharkey silty clay, a Dundee silt loam, and a Loring silt loam, respectively. Predictive equations were determined for each soil to relate chemical extraction findings to plant response. Bioassay analysis indicated nearly 2 ppmw of fluometuron in the Sharkey silty clay in October 1980, with 1 ppmw in the Dundee silt loam, and approximately 0.27 ppmw in the Loring silt loam with annual application rates of 4.0, 2.9, and 3.5 kg/ha, respectively. Fluometuron concentrations as determined by chemical analysis were 0.83, 0.34, and 0.14 ppmw, respectively. Fluometuron concentrations declined over the winter in all three soils. Samples taken in March of 1981, 1982, and 1983 showed little difference in carryover levels in the Sharkey silty clay but more yearly variation in the other two soils. Fluometuron was found in all three soils to depths of 60 cm, but more than 55% of the fluometuron was found in the upper 15 cm of each soil. A controlled laboratory study conducted with the three soils showed that both cold and dry conditions reduced fluometuron dissipation rates. In the laboratory under conditions favorable for dissipation, fluometuron had a half-life of 26 days in the Dundee silt loam, 43 days in the Loring silt loam, and 73 days in the Sharkey silty clay. In the field, dissipation was very rapid in the Loring silt loam compared to the Dundee silt loam and the Sharkey silty clay.

The effects of twelve soil metabolites of trifluralin [2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)benzenamine] on soybean [Glycine max (L.) Merr.] growth, yield, and seed oil and protein content were determined. The metabolites included oxidative dealkylated, reduced nitro group, benzimidazole, azoxy, azo, oxidized, and hydroxylated derivatives of trifluralin. When applied at 0.22 kg ai/ha and incorporated 7.5 cm deep, no individual metabolite had a significant adverse effect on growth or yield. Three of the metabolites significantly decreased seed oil content and two of the metabolites significantly increased seed protein content. These effects are not considered important in that the differences, while statistically significant, are very small. Also, the amounts of metabolites applied greatly exceeded those expected to be found after many years of continuous use of trifluralin. Potential accumulation of individual metabolites from long-term use of trifluralin does not appear to adversely affect soybean growth, yield, or quality.

Laboratory photolysis rates of 2,4-D [(2,4-dichlorophenoxy)acetic acid], bentazon [3-(1-methylethyl)-(1H)-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide], and haloxyfop {2-[4-[[3-chloro-5-(trifluoromethyl)-2-pyridinyl] oxy] phenoxy] propanoic acid} in dilute aqueous solution were enhanced by the presence of adjuvants. Addition of 1.0% (v/v) petroleum oil concentrate (POC), 1.0% (v/v) soybean oil concentrate (SBOC), and 0.15% (v/v) emulsifier package (EP) enhanced herbicide photolysis rates more than addition of 0.15% (v/v) oxysorbic (20 POE) (polyoxyethylene sorbitan monolaurate). Bioassays showed that phytotoxicity of photolyzed herbicide solutions was negatively correlated with time of exposure to ultraviolet light. Addition of 0.85% (v/v) acetophenone to aqueous herbicide solutions containing 0.15% (v/v) oxysorbic strongly sensitized photodegradation of 2,4-D, and to a lesser extent, haloxyfop. Acetophenone had no effect on bentazon photolysis in the presence of oxysorbic. In another study, herbicides were dissolved in white mineral oil or once-refined soybean oil and exposed to ultraviolet light. After a 6-h exposure, there was 92% loss of haloxyfop in mineral oil and 36% loss in soybean oil. There was no difference between oils in affecting the photolysis rate of 2,4-D or bentazon.

Experiments were conducted in 1985 to 1987 to evaluate the effects of conventional and no-tillage systems on the weed control provided by clomazone applied preemergence in soybeans. The persistence of clomazone in soil of the two tillage systems was also determined. Increasing the clomazone rate from 0.8 to 1.4 kg/ha did not increase weed control. Clomazone controlled 80% or more of jimsonweed, velvetleaf, and giant foxtail. Common cocklebur control ranged from about 50 to 70% in no-till and from 80 to 90% in conventional tillage. Generally, soybean pods/plant and yields were lower from clomazone treatments than from handweeded treatments due to inadequate common cocklebur control. Over 40% of the clomazone applied did not reach the soil surface; it was either intercepted by wheat straw, volatilized, or both. Clomazone persisted longer in conventional tillage than in no-tillage in. However, in 1986, clomazone was equally persistent in the two tillage systems. The half-life of clomazone was 34 and 6 days in 1985 in conventional and no-tillage, respectively, and in 1986, 18 and 16 days in conventional and no-tillage, respectively. Significant clomazone concentrations were not found below 10 cm in the soil profile. Corn planted without tillage (no-till) approximately 1 yr after clomazone application was not injured and yields were not reduced due to prior clomazone use.

The influence of wheat straw cover, tillage, and irrigation on metribuzin and alachlor movement and dissipation in an Appling coarse sandy loam (Typic Hapludult) and the influence of soil depth on their rate of dissipation were measured in field and laboratory experiments conducted in 1987 and 1988. Overall, metribuzin moved more than alachlor in both years. Alachlor movement was greater in tilled plots compared to no-till plots in 1988. Metribuzin movement was greater in no-till plots in 1987. Straw cover had little effect on the movement of alachlor, but the presence of 2800 kg ha−1 of straw on the soil surface increased the downward movement of metribuzin in both years compared to soil with no straw cover. The rate of alachlor dissipation in the soil was faster in straw-covered and no-till plots in both years and in the high irrigation level in 1988. Metribuzin dissipation was not affected by any of these factors. Alachlor rate of dissipation did not differ among depths in the field; however, dissipation differed in the laboratory in the order 0 to 20 cm > 20 to 45 cm = 45 to 68 cm. Metribuzin dissipated faster at the 8-cm depth in the field compared to the 58-cm depth. In the laboratory, metribuzin dissipation rates followed the order 0 to 20 cm > 20 to 45 cm > 45 to 68 cm. At the greatest depth, the dissipation of metribuzin was faster in the field than in the laboratory.

A column leaching study was conducted in a greenhouse to determine the movement of atrazine and alachlor through soil as affected by alfalfa roots in three stages of decay. Alfalfa was grown in soil columns for 6 months and then killed with glyphosate. The 14C-atrazine and 14C-alachlor were applied to soil columns with bromide following 2, 13, or 26 weeks of root decomposition. Most of the herbicide remained in the top 9 cm of soil. However, atrazine and alachlor soil distribution profiles indicated greater preferential movement in columns with roots than in columns without roots. Higher levels of atrazine and alachlor were bound to soil at lower depths in the presence of roots than without roots. Adsorption of atrazine and alachlor on soil with and without alfalfa roots was not significantly different as determined by Freundlich adsorption isotherms. Degradation rates for atrazine and alachlor were not substantially different between soil with and without roots. Although only small amounts of the applied herbicide leached through the columns, preferential flow of herbicides through root-mediated soil macropores and cracks could be a mechanism of herbicide transport through soil under appropriate conditions.

Translocation and metabolism of 14C-2,4-D [(2,4-dichlorophenoxy)acetic acid] and effects of 2,4-D on protein synthesis were compared in ‘T–68’ (2,4-D tolerant) and ‘Viking’ (susceptible) birdsfoot trefoil (Lotus corniculatus L.) in an attempt to elucidate some tolerance mechanisms. After 14C-2,4-D was applied to upper trifoliate leaves, significantly less 2,4-D was found in stems, in leaves below the treated leaves, and in roots of T–68 compared to Viking. More 2,4-D was bound to alcohol-insoluble cellular constituents of T–68 leaves, stems, and roots. When alcohol-soluble components were fractionated, slightly more 14C water-soluble compounds were found in T–68, indicating further inactivation by glycosylation. No amino acid-2,4-D conjugates were found. The rate of 14CO2 evolution from 14C-2,4-D treated seedlings in T–68 was five times that in Viking. Protein synthesis appeared to be more rapid in T–68 but the relationship to 2,4-D was not clear. In part, 2,4-D resistance in T–68 may result from its ability to inactivate 2,4-D by differential binding and conjugation and by side chain breakdown as indicated by 14CO2 release.

Two nonionic surfactants altered photolysis rates of chlorimuron and metsulfuron in aqueous solutions and on glass slides exposed to sunlight. Photolysis of both herbicides followed first-order kinetics over an 8-day exposure period. Chlorimuron half-lives in solution were 5.8, 3.7, and 2.7 days in the presence of no surfactant, oxysorbic, and octoxynol, respectively. The extrapolated half-life of metsulfuron in solution with no surfactant was 15.7 days, compared to half-lives of 2.9 and 1.5 days in solutions containing oxysorbic or octoxynol, respectively. With the exception of metsulfuron in the absence of a surfactant, rates of chlorimuron and metsulfuron photolysis on glass slides were approximately two- to fourfold slower, and surfactants had little or no effect on herbicide photolysis rates compared to those in aqueous solution. Extrapolated half-lives on glass ranged from 9.9 to 12.5 days for chlorimuron and from 7.6 to 11.7 days for metsulfuron. Presence of oxysorbic or octoxynol did not greatly alter rates of riboflavin-sensitized herbicide photolysis on glass but did increase photolysis rates of metsulfuron in aqueous solution containing riboflavin.

The methyl ester of diclofop {2-[4-(2,4-dichlorophenoxy)phenoxy] propanoic acid} mixed with soil at 1, 2, and 3 ppmw reduced the growth of Bromus species in the greenhouse as follows: downy brome (Bromus tectorum L. ♯ BROTE) more than Japanese brome (Bromus japonicus Thunb. ex Murr. ♯ BROJA) more than cheat (Bromus secalinus L. ♯ BROSE). The decrease in herbicide effect (decay) over time was described better using a second-order equation than a first-order equation. Plant response-herbicide dose relationships were described best with a cubic polynomial equation.

Soybeans [Glycine max (L.) Merr.] are often the replacement crop when cotton (Gossypium hirsutum L.) is abandoned because of stand failure in the southern United States. Injury from cotton herbicides may be reduced if the soybean planting is delayed more than 4 weeks after cotton planting or if the original herbicide-treated area is fully tilled and a new seedbed formed. Planting delay intervals were compared with five cotton preemergence herbicides on Calloway silt loam at one location. Seedbed-preparation methods were included in a similar experiment at two locations on Sharkey silty clay. Herbicides compared were fluometuron [1,1-dimethyl-3-(α,α,α-trifluoro-m-tolyl)urea], norflurazon [4-chloro-5-(methylamino)-2-(α,α,α-trifluoro-m-tolyl)-3(2H)-pyridazinone], cyanazine {2-[[4-chloro-6-(ethylamino)-s-triazin-2-yl] amino]-2-methylpropionitrile}, perfluidone {1,1,1-trifluoro-N-[2-methyl-4-phenylsulfonyl)phenyl] methanesulfonamide}, fluridone {1-methyl-3-phenyl-5-[3-(trifluoromethyl)phenyl]-4(1H)-pyridinone}, and diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea]. Seedbeds compared were no-till and conventional (fully tilled). Soybean planting delays after cotton planting were 20, 29, and 56 days (first year), and 15 and 29 or 15 and 30 days (second year). We found in the 2-yr studies that fluridone severely damaged soybeans both years. Fluometuron and diuron also caused damage the second year when we experienced wet, cool conditions in the spring. Most injury occurred on the clay, with yield reductions occurring even after the 30-day delay. Norflurazon was most injurious at this location. The no-tillage planting method resulted in the least herbicide injury on the silt loam and the conventional tillage method was better on the clay. Detailed studies with fluometuron under incubation conditions showed that degradation was inhibited most by low temperatures and high soil moisture.

Laboratory experiments were conducted to determine the effects of nonionic surfactants and reaction media (water, glass, and corn leaf residue) on photolysis and subsequent phytotoxicity of chlorimuron and metsulfuron residues. Oxysorbic and octoxynol enhanced rates of chlorimuron and metsulfuron photolysis in aqueous solution and on glass slides compared to controls with no surfactant. Enhanced photolysis of chlorimuron by surfactants was greatest on glass, where 93 and 89% loss occurred after 48 h exposure to ultraviolet light in the presence of oxysorbic and octoxynol, respectively, compared to 38% loss with no surfactant. Similarly, surfactant-enhanced metsulfuron photolysis was greatest on glass with 37 and 67% loss after 48 h exposure in the presence of oxysorbic and octoxynol, respectively, compared to 9% loss with no surfactant. Photolysis of herbicides deposited on corn leaf residue was significantly slower than that on glass or in aqueous media at all exposure times and metsulfuron photolysis on corn residue was enhanced by surfactants only after 144 h exposure. Bioassays confirmed that phytotoxicity of photolyzed herbicide residues was negatively correlated (r=-0.94 for chlorimuron and r=-0.92 for metsulfuron) with loss of parent herbicide as measured by liquid chromatography.

Degradation of trifluralin in four soils, each represented at four sites, under field conditions was determined quantitatively and described mathematically. A biexponential equation that resulted from integration of first-order and second-order differential rate equations described degradation data better than the first-order kinetic model for 15 of 25 soil-site combinations. Biexponential model regression coefficients indicated extent of degradation and that degradation is rapid at initially high trifluralin concentrations but slows as concentration decreases. The first-order kinetic model initially underestimated but ultimately overestimated degradation of trifluralin, thereby inferring that a first-order half-life is inadequate for predicting trifluralin persistence.