Environmental fate of herbicides trifluralin, metazachlor, metamitron and sulcotrione compared with that of glyphosate, a substitute broad spectrum herbicide for different glyphosate-resistant crops

The introduction of crops resistant to the broad spectrum herbicide glyphosate, N-(phosphonomethyl)glycine, may constitute an answer to increased contamination of the environment by herbicides, since it should reduce the total amount of herbicide needed and the number of active ingredients. However, there are few published data comparing the fate of glyphosate in the environment, particularly in soil, with that of substitute herbicides. The objective of this study is to compare the fate of glyphosate in three soils with that of four herbicides frequently used on crops that might be glyphosate resistant: trifluralin, alpha,alpha,alpha-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine, and metazachlor, 2-chloro-N-(pyrazol-1-ylmethyl)acet-2',6'-xylidide for oilseed rape, metamitron, 4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazin-5-one for sugarbeet and sulcotrione, 2-(2-chloro-4-mesylbenzoyl)cyclohexane-1,3-dione for maize. The distribution of herbicides between the volatilized, mineralized, extractable and non-extractable fractions was studied, along with the formation of their metabolites in laboratory experiments using 14C-labelled herbicides, over a period of 140 days. The main dissipation pathways were mineralization for glyphosate and sulcotrione, volatilization for trifluralin and non-extractable residues formation for metazachlor and metamitron. The five herbicides had low persistence. Glyphosate had the shortest half-life, which varied with soil type, whereas trifluralin had the longest. The half-lives of metazachlor and sulcotrione were comparable, whereas that of metamitron was highly variable. Glyphosate, metazachlor and sulcotrione were degraded into persistent metabolites. Low amounts of trifluralin and metamitron metabolites were observed. At 140 days after herbicide applications, the amounts of glyphosate and its metabolite residues in soils were the lowest in two soils, but not in the third soil, a loamy sand with low pH. The environmental advantage in using glyphosate due to its rapid degradation is counterbalanced by accumulation of aminomethylphosphonic acid specifically in the context of extensive use of glyphosate.     

Influence of temperature on the volatilization of triallate and terbutryn from two soils

The rate of volatilization of the formulated herbicides triallate and terbutryn was studied in a volatilization chamber under controlled laboratory conditions using two soils with sand and loam textures, respectively. The influence of the most relevant experimental variables was investigated by measuring the amount of volatilized herbicides after their incorporation to the soils. The effect of soil temperature was studied in the range from 5 °C to 25 °C. Initial soil water content was fixed at field capacity depending on the physical characteristics of each soil. The volatilized herbicide was trapped in C18 cartridges during different time intervals and analyzed by HPLC. The volatilization losses for triallate ranged from 7 to 58%, whereas the losses for terbutryn ranged from 1 to 6%. Sorption and volatilization resulted in two coupled effects of major importance in these experiments: the sorption process was favoured as temperature decreased, whereas volatilization increased as temperature increased. © 2000 Society of Chemical Industry     

苗期水分管理对水稻分蘖及除草剂控草效应的影响

稻田除草剂大量及高频使用对农作物安全、土壤及水体环境构成了严重威胁,使得除草剂减量使用刻不容缓。水稻机插田药后长时间保水可显著抑制杂草,以此可减少除草剂用量,但长时间保水会导致水稻发育受限。盆栽试验表明,无论是否喷施除草剂30%苄嘧·丙草胺乳油,杂草发生随保水时长增加而减少,且喷施除草剂对杂草防除具显著效果。田间试验表明,稻田施用30%苄嘧·丙草胺乳油100 mL/667m~2后,药后保水7 d时的水稻分蘖及抑草的综合效应达到最佳。     

Effect of trickle irrigation on soil-applied herbicides*

The effect of trickle irrigation on the activity, leaching and distribution in the soil of herbicides, was studied in a model specially constructed for simulating trickle irrigation in the field, and also under field conditions. The pattern of movement of a soil-applied herbicide in the soil under trickle irrigation paralleled, to some extent, that of the trickle water itself, but total herbicide movement was less than that of the water. Both water and herbicide distribution in the soil formed the shape of a hemisphere or cone under the trickle nozzle, the exact shape of which was determined by the soil characteristics (a narrow cone in a light soil and a wide cone in a heavy soil); cone size was determined by the amount of trickle water. Bioassays with susceptible test plants showed that effective weed control could be expected with either simazine or GS-14259 (2-t-butylamino-4-ethylamino-6-methoxy-s-triazine =‘Caragard') only in the areas wetted by the trickle nozzle. The results showed that the pattern of distribution in the soil of simazine and GS-14259 was similar, but there were quantitative differences in their final spread.     

Sorption-desorption of flucarbazone and propoxycarbazone and their benzenesulfonamide and triazolinone metabolites in two soils

Sorption-desorption interactions of pesticides with soil determine the availability of pesticides in soil for transport, plant uptake and microbial degradation. These interactions are affected by the physical and chemical properties of the pesticide and soil and, for some pesticides, their residence time in the soil. While sorption-desorption of many herbicides has been characterised, very little work in this area has been done on herbicide metabolites. The objective of this study was to characterise sorption-desorption of two sulfonylaminocarbonyltriazolinone herbicides, flucarbazone and propoxycarbazone, and their benzenesulfonamide and triazolinone metabolites in two soils with different physical and chemical properties. K(f) values for all four chemicals were greater in clay loam soil, which had higher organic carbon and clay contents than loamy sand. K(f-oc) ranged from 29 to 119 for the herbicides and from 42 to 84 for the metabolites. Desorption was hysteretic in every case. Lower desorption in the more sorptive system might indicate that hysteresis can be attributed to irreversible binding of the molecules to soil surfaces. These data show the importance of characterisation of both sorption and desorption of herbicide residues in soil, particularly in the case of prediction of herbicide residue transport. In this case, potential transport of sulfonylaminocarbonyltriazolinone herbicide metabolites would be overpredicted if parent chemical soil sorption values were used to predict transport.     

The relative movement and persistence in soil of chlorsulfuron, metsulfuron-methyl and triasulfuron

Summary. Adsorption and degradation rates of triasulfuron in 8 different soils were negatively correlated with soil pH and were generally lower in subsoils than in soils from the plough layer. The half-life at 20°C varied from 33 days in a top soil at pH 5·8 to 120 days in a subsoil at pH 7·4. Adsorption distribution coefficients in these two soils were 0·55 and 0·19, respectively. Movement and persistence of residues of chlorsulfuron, triasulfuron and metsulfuron-methyl were compared in a field experiment prepared in spring 1987. Triasulfuron was less mobile in the soil than the other two compounds. Residues of all three herbicides were largely confined to the upper 40–50 cm soil 148 days after application. With an initial dose of 32 g ha⁻¹, residues in the surface soil layers were sufficient to affect growth of lettuce and sugar-beet sown approximately one year after application. Laboratory adsorption and degradation data were used with appropriate weather data in a computer model of herbicide transport in soil. The model gave good predictions of total soil residues during the first five months following application, and also predicted successfully the maximum depth of penetration of the herbicides into the soil during this period. However, more herbicide was retained close to the soil surface than was predicted by the model. The model predicted extensive movement of the herbicides in the soil during winter but did not predict that residues sufficient to affect crop growth could be present in the upper 15–20 cm soil after one year.     

Influence of herbicide-resistant canola on the environmental impact of weed management

The growth of herbicide-resistant canola varieties increased from 10% of the canola area in Canada in 1996, when the technology was first introduced, to 80% in 2000. From 1995 to 2000, the amount of herbicide active ingredient applied per hectare of canola declined by 42.8% and the Environmental Impact (EI) per hectare, calculated using the Environmental Impact Quotient for individual herbicides and the amounts of active ingredients applied, declined 36.8%. The amount of herbicide active ingredient per hectare applied to conventional canola was consistently higher than that applied to herbicide-resistant canola each year between 1996 and 2000. Similarly, the EI of herbicide use per hectare in conventional canola was higher than that of herbicide-resistant canola during the same time period. Since 1996, herbicide use has shifted from broadcast applications of soil-active herbicides to post-emergence applications of herbicides with broad-spectrum foliar activity. The decline in herbicide use and EI since the introduction of herbicide-resistant varieties was due to increased use of chemicals with lower application rates, a reduced number of applications and a decreased need for herbicide combinations.     

Sorption/desorption behaviour of sulfonylurea herbicides as affected by the addition of fresh and composted olive cake to soil

The olive industry generates residues which can be applied as amendments to soils in their original form (olive cake) or after composting or vermicomposting processes. The addition, fresh or incubated, of these amendments to soil and of their different organic fractions was studied in relation to the sorption/desorption of three sulfonylurea herbicides, bensulfuron‐methyl, chlorsulfuron and prosulfuron. Herbicide sorption was low or very low, slightly promoted by the addition of the agricultural by‐products, especially olive cake, and mainly affected by pH of the soil solution, with the organic carbon content having no significant effect on herbicide retention. Desorption was only reduced when fresh olive cake was added. The incubation of soil and amendments for 3 months did not modify herbicide sorption, but made desorption reversible except for olive cake. The transformation of the organic matter of the amendments due to humification and maturity processes are likely to be responsible for this behaviour. Different organic fractions were removed to assess the influence of each fraction on sulfonylurea sorption. Only the removal of all studied organic fractions increased herbicide sorption, revealing the role of humin and mineral fractions in this process. Therefore, the use of organic amendments is not useful for reducing the risk of movement of ionisable molecules in soil.     

Evaluation of a simulation model for prediction of herbicide movement and persistence in soil

The movement and persistence of residues of propyzamide, linuron, isoxaben and R-40244 were measured in a sandy loam soil in field experiments prepared in spring and autumn. None of the herbicides moved to depths greater than 12 cm in the soil during the winter period, following application in autumn, and none moved more than 6 cm in the soil, following application in spring. The general order of persistence of total soil residues was isoxaben > linuron = R-40244 > propyzamide. Appropriate constants to describe the moisture and temperature dependence of degradation were derived from laboratory incubation experiments and used with measurements of the strengths of adsorption of the different herbicides by the soil, in a computer model of herbicide movement. The model, in general, gave good predictions of total soil residues, but overestimated herbicide movement, particularly in winter. Measurements of herbicide desorption from the soil at intervals, during a laboratory incubation experiment, demonstrated an apparent increase in the strength of adsorption with time. When appropriate allowance was made for these changes in adsorption in the computer model, improved predictions of the vertical distribution of the herbicide residues were obtained.     

喷雾助剂对茎叶处理除草剂的增效机制及应用研究进展

农田草害的发生严重影响了农业生产和发展,使用除草剂进行化学防治是目前最省时省力和防除效果最好的除草方法.其中,茎叶处理除草剂因其具有不受土壤环境影响、按草施药、灵活和选择性高等优点,应用范围更广.然而,茎叶处理除草剂在喷雾施药过程中由于受到杂草叶片界面特性的影响,常出现药液迸溅、滚落、难以渗透等现象,导致除草剂用量增大...     

The comparative behaviour of simazine and terbacil in soils

Adsorption of simazine (2-chloro-4,6-bisethyl-amino-1,3,5-triazine) was 2.2–4 times greater than that of terbacil (5-chloro-6-methyl-3-t-butyl-uracil) in the same soils and adsorption of both herbicides was 2–4 times greater in the topsoils than subsoils. Adsorption was inversely correlated with herbicide movement in a thick-layer chromatography system. One year after application of 3 kg/ha to field plots, simazine residues were highest near the soil surface, whereas terbacil residues increased with soil depth in the sandy and sandy loam soils. Total residues recovered from the upper 25 cm of soils was 5% or less of the simazine originally applied, and 10% or less of the applied terbacil. In an oat seedling bio-assay, the GR₅₀ values were generally 1.5–3 times higher for simazine than for terbacil in the same soils.     

Relationships between substituted urea herbicides and soil urease activity

Fenuron, monuron, diuron, siduron, linuron and neburon were tested for their inhibition of soil urease activity in order to investigate relationships between fertilizers and herbicides. The inhibition of urea hydrolysis in the selected soils was 10–33% for fenuron, 10–39% for monuron, 10–35% for diuron, 8–38% for siduron, 9–36% for linuron and 12–30% for neburon. In the field greater effects might be expected since the fertilizer/herbicide ratio would be lower than the one considered here. Some agronomic aspects of the relationship between fertilizers and herbicides are discussed.     

Phytotoxicity of four herbicides in different synthetic soils

The relative phytotoxicity of four soil-applied herbicides, benzthiazuron, cycloate, delachlor, and pyrazon, used for sugar beet (Beta vulgaris L.), was tested on a dilution series of peat, Newe Ya’ar clay soil and Hamadia calcareous clay soil mixed with sand, and of Newe Ya’ar clay soil mixed with lime. The phytotoxicity was assessed with oats (Avena sativa L. cv. Mulga). Cycloate was the most potent herbicide of the four, except in soils with high organic matter ( ?11%), where delachlor was more active. Benzthiazuron was the least phytotoxic herbicide in the peat + sand mixtures, but it was more active than pyrazon in lighter soils of the Newe Ya’ar series. The addition of sand to the peat and the soils increased the phytotoxicity of all herbicides. The addition of lime to Newe Ya’ar clay soil decreased the phytotoxicity of benzthiazuron and pyrazon but not of delachlor.     

Evidence for the Accelerated Degradation of Isoproturon in Soils

The herbicide isoproturon was degraded rapidly in a sandy loam soil under laboratory conditions (incubation temperature, 15°C; soil moisture potential, -33 kPa). Degradation was inhibited following treatment of the soil with the antibiotic chloramphenicol, but unaffected by treatment with cycloheximide, thus indicating an involvement of soil bacteria. Rapid degradation was not observed with other phenylurea herbicides, such as diuron, linuron, monuron or metoxuron incubated in the same soil under the same experimental conditions. Three successive applications of isoproturon to ten soils differing in their physicochemical properties and previous cropping history induced rapid degradation of the herbicide in most of them under laboratory conditions. There were, however, no apparent differences in ease of induction of rapid degradation between soils which had been treated with isoproturon for the last five years in the field and those with no pre-treatment history. A mixed bacterial culture able to degrade isoproturon in liquid culture was isolated from a soil in which the herbicide degraded rapidly.     

Herbicide sorption to concrete and asphalt

In order to accurately predict the fate and behaviour of herbicides following application to hard surfaces, an understanding of the processes involved is required. Previous studies have demonstrated that herbicides with a low soil organic carbon partition coefficient (K(oc)) are preferentially removed from concrete and asphalt surfaces. It is possible, therefore, that sorption may play a role in retaining herbicides to hard surfaces. This study provides an indication of the extent to which herbicides may sorb to concrete and asphalt, and examines the results in the light of other research to identify the significance of sorption in describing herbicide losses after application. There was measurable sorption of herbicides to concrete and asphalt although this was limited compared with that to soils, especially for concrete. An exponential relationship between experimentally derived values of K(p) and literature values of K(oc) for asphalt was established (r(2) = 0.931); there was a weaker relationship for concrete (r(2) = 0.606). The experimentally derived K(p) values could be used to enhance the prediction of herbicide loss to receiving waters following application. It is probable that the fate of herbicides applied to concrete and asphalt surfaces depends more heavily on physical processes than is the case in soils.     

Effects of microbial inhibitors on the degradation rates of metamitron,metazachlor and metribuzin in soil

Rates of carbon dioxide evolution and degradation rates of metamitron, metazachlor and metribuzin were measured in two soils in the presence of three microbial inhibitors. The nonselective microbial inhibitor sodium azide reduced both carbon dioxide evolution and the rate of loss of all three herbicides in both soils, although the reduction in degradation rate of metamitron was small. The antibacterial antibiotic novobiocin enhanced carbon dioxide evolution from both soils but had variable effects on the rates of herbicide degradation. It inhibited degradation of metazachlor and metribuzin, and in one of the soils its effects on metazachlor degradation were similar to those of sodium azide. Novobiocin inhibited degradation of metamitron to a small extent in one soil only. The antifungal antibiotic cycloheximide also enhanced carbon dioxide evolution from both soils. In general, its effects on herbicide degradation were similar to those of novobiocin, although the extent of inhibition was usually less pronounced. The results are discussed in terms of the relative involvement of microorganisms in degradation of the three herbicides.     

Studies on the effects of herbicides on soil nitrification,II

The effects of selected herbicides have been studied on the following parameters of soil nitrification processes: the rates of nitrate and nitrite formation from ammonia in freshly perfused soils and in soils previously saturated with nitrifying organisms in an improved perfusion apparatus; the rates of oxygen consumption and of oxidation of ammonia and nitrite in washed cell suspensions of Nitrosomonas europaea and Nitrobacter winogradskii, respectively; the rates of growth of those two organisms in newly established cultures; the rates of oxygen uptake by soil enriched in nitrifying organisms; the rates of proliferation of nitrifying populations in freshly perfused soil. ID50 values were computed for all parameters and herbicides studied. On average, the most sensitive parameters were the metabolism and growth of the two organisms in pure culture, while the least sensitive were the corresponding measures in the soil environment. Similarly, herbicides fell into four distinct groups. The most toxic were the formulated octanoates of bromoxynil and ioxynil (NPH1320 and Totril, respectively); next in order of toxicity were chlorbufam, phenmedipham, formulated oxadiazon, formulated legurame, ioxynil, formulated trifluralin, and bromoxynil; low toxicity was shown by terbacil, dicamba, and tricamba, whereas asulam and the related experimental herbicide MB9555 showed activity on some parameters at the very highest concentrations only. Comparisons of soil with pure-culture parameters showed that the relative toxicities of herbicides to Nitrosomonas in culture bore little relationship to those in soil. The inhibitions of Nitrobacter proliferations in soil on the other hand were correlated with the inhibitions of growth and metabolism in pure culture. Within these overall effects, individual herbicides showed marked differential actions on various parameters. Thus, the formulated octanoates of bromoxynil and ioxynil were extremely toxic to the growth of nitrifying organisms in culture, an action probably due to an unknown formulation component. Relative to other herbicides, bromoxynil and ioxynil were more effective on nitrification processes in the soil environment. Both in culture and in the soil, Nitrobacter is more sensitive than Nitrosomonas to these four herbicides. Legurame and oxadiazon are relatively more toxic to Nitrosomonas in culture, but this differential action is not demonstrable in the soil. Dicamba, tricamba, trifluralin, and chlorbufam are more toxic to Nitrobacter than to Nitrosomonas in the soil environment. Formulated trifluralin seems to exert a stimulating action on the growth of nitrifying organisms, but only in the soil; suppression of antagonistic organisms is suggested as a possible cause. Extrapolation of these results to the field situation suggests that the only herbicide which might cause small inhibitions of nitrification at field rates is terbacil, which is disproportionately toxic at low concentrations. At rates somewhat in excess of normal, the formulated octanoates of bromoxynil and ioxynil and possibly dicamba and oxadiazon could also cause small inhibitions.     

Persistence and movement of ethofumesate in soil*

Persistence of ethofumesate [(±)2-ethoxy-2.3-dihydro-3,3-dimethylbenzofuran-5-yl-methansulphonate] in soil was associated with soil temperature. Ethofumesate applied at 4.5 kg/ha in November persisted about twice as long in soil as that applied the following March. In another field study, 88–91% of the herbicide had dissipated after 24 weeks in sandy loam soil, compared to 72–77% in loam soil when it was applied at rates of 2.2, 3.4, 4.5, and 9.0 kg/ha. The rate of degradation was independent of the initial rate of chemical applied. The time required for 50% of the herbicide to dissipate in sandy loam and loam soils was 7.7 and 12.6 weeks, respectively. The movement of ethofumesate in these two soils over a 24-weeks sampling period was confined mainly to the upper 7.5 cm of the soil profile.     

Processes affecting herbicide action in soil

The main processes which affect herbicide action in soil are considered to be the extent to which the herbicide is adsorbed by soil particles, the rate of absorption of the herbicide solution by plant roots and the rate at which the herbicide is lost from the soil by decomposition, evaporation or leaching. An attempt is made to show how these factors are interrelated and the possible use of mathematical models to optimise the performance of herbicides is briefly discussed.     

Predicted impact of transgenic, herbicidetolerant corn on drinking water quality in vulnerable watersheds of the mid-western USA

In the intensely farmed corn-growing regions of the mid-western USA, surface waters have often been contaminated by herbicides, principally as a result of rainfall runoff occurring shortly after application of these to corn and other crops. In some vulnerable watersheds, water quality criteria for chronic human exposure through drinking water are occasionally exceeded. We selected three settings representative of vulnerable corn-region watersheds, and used the PRZM-EXAMS model with the Index Reservoir scenario to predict corn herbicide concentrations in the reservoirs as a function of herbicide properties and use pattern, site characteristics and weather in the watersheds. We compared herbicide application scenarios, including broadcast surface pre-plant atrazine and alachlor applications with a glyphosate pre-plant application, scenarios in which losses of herbicides were mitigated by incorporation or banding, and scenarios in which only glyphosate or glufosinate post-emergent herbicides were used with corn genetically modified to be resistant to them. In the absence of drift, in almost all years a single runoff event dominates the input into the reservoir. As a result, annual average pesticide concentrations are highly correlated with annual maximum daily values. The modeled concentrations were generally higher than those derived from monitoring data, even for no-drift model scenarios. Because of their lower post-emergent application rates and greater soil sorptivity, glyphosate and glufosinate loads in runoff were generally one-fifth to one-tenth those of atrazine and alachlor. These model results indicate that the replacement of pre-emergent corn herbicides with the post-emergent herbicides allowed by genetic modification of crops would dramatically reduce herbicide concentrations in vulnerable watersheds. Given the significantly lower chronic mammalian toxicity of these compounds, and their vulnerability to breakdown in the drinking water treatment process, risks to human populations through drinking water would also be reduced.