Sorption–desorption of 'aged' isoxaflutole and diketonitrile degradate in soil

Isoxaflutole is a relatively new herbicide used for weed control in maize. The objective of this research was to increase the understanding of the behaviour and environmental fate of isoxaflutole and its diketonitrile (DKN) degradate in soil, including determination of the strength of sorption to soil and whether sorption is affected by ageing. In sandy loam (SL) and silty clay (SiCl) soils, ¹⁴C‐isoxaflutole was found to dissipate rapidly after application to soil; recovery ranged from ～42% to 68% at week 0, and recovery had decreased to <10% at week 12. Decreases in ¹⁴C isoxaflutole residues over time in SL and SiCl soils are consistent with hydrolysis of isoxaflutole and formation of bound DKN residues in the soil. DKN recovery from freshly treated SiCl and SL soils was 41% to 52%. After a 12‐week incubation in SL soil at pH 7.1 and 8.0, recoveries were similar, ～40%. However, at week 12 in SL soil pH 5.7, DKN recovery decreased to ～28%. DKN recovery in SiCl soil at week 12 was <10%. Increases in sorption of DKN in SL at pH 5.7 and SiCl soil over time indicate that the DKN degradate is tightly bound to the soil and sorption is affected by soil pH and soil type. Sorption of ¹⁴C‐DKN in the SiCl soil more than doubled with ageing compared with the lower K_d sorption coefficient values of the SL soils. In the SiCl soil at time 0, the K_d was 0.6; at 1 week, K_d increased to 2; and at the end of the 12‐week incubation period, K_d was 4.5. This strong binding of DKN to the soil may be due to chelate formation in the interlayer of the clay.     

Pedotransfer functions for isoproturon sorption on soils and vadose zone materials

BACKGROUND: Sorption coefficients (the linear K_D or the non‐linear K_F and N_F) are critical parameters in models of pesticide transport to groundwater or surface water. In this work, a dataset of isoproturon sorption coefficients and corresponding soil properties (264 K_D and 55 K_F) was compiled, and pedotransfer functions were built for predicting isoproturon sorption in soils and vadose zone materials. These were benchmarked against various other prediction methods. RESULTS: The results show that the organic carbon content (OC) and pH are the two main soil properties influencing isoproturon K_D. The pedotransfer function is K_D = 1.7822 + 0.0162 OC^1.5 ? 0.1958 pH (K_D in L kg^?1 and OC in g kg^?1). For low‐OC soils (OC < 6.15 g kg^?1), clay and pH are most influential. The pedotransfer function is then K_D = 0.9980 + 0.0002 clay ? 0.0990 pH (clay in g kg^?1). Benchmarking K_D estimations showed that functions calibrated on more specific subsets of the data perform better on these subsets than functions calibrated on larger subsets. CONCLUSION: Predicting isoproturon sorption in soils in unsampled locations should rely, whenever possible, and by order of preference, on (a) site‐ or soil‐specific pedotransfer functions, (b) pedotransfer functions calibrated on a large dataset, (c) K_OC values calculated on a large dataset or (d) K_OC values taken from existing pesticide properties databases. Copyright © 2011 Society of Chemical Industry     

Influence of the physical and chemical properties of soil on the retention process of isoxaflutole and its two main derivatives

Isoxaflutole is a new pre‐emergence herbicide for use in maize and sugarcane. Its two main derivatives are a diketonitrile derivative, the 2‐cyano‐3‐cyclopropyl‐1‐(2‐methanesulfonyl‐4‐trifluoromethylphenyl)propan‐1,3‐dione, named DKN, and a benzoic acid derivative, the 2‐methanesulfonyl‐4‐trifluoromethylbenzoic acid, named BA. The adsorption/desorption processes have never been studied for isoxaflutole (IFT) at high concentrations nor for BA, and the present work aimed at completing the knowledge of the behaviour of these three molecules in conditions close to those encountered in the context of agricultural use. The adsorption/desorption study was conducted on seven soils of different physical and chemical properties, using the batch equilibrium technique. During the experiments, IFT was chemically converted into DKN in a continuous manner. This reaction appeared to be dependent on the pH of the soil and was taken into account in the calculations of the adsorbed and desorbed amounts. The adsorption isotherms obtained were predominantly C‐shaped for IFT and DKN and S‐shaped for BA, but some differences appeared on a few soils. They fitted well the Freundlich equation, and the values of the Freundlich coefficient K_fa showed that, whatever the soil, IFT was more adsorbed than its two derivatives. The main parameter influencing the adsorption of IFT appeared to be the organic matter content, whereas this effect was not evident for DKN and BA. No correlation was found between the extent of adsorption and either clay content or pH of the soil, for the three molecules.     

Bromoxynil degradation in a Mississippi silt loam soil

BACKGROUND: The objectives of these laboratory experiments were: (1) to assess bromoxynil sorption, mineralization, bound residue formation and extractable residue persistence in a Dundee silt loam collected from 0–2 cm and 2–10 cm depths under continuous conventional tillage and no‐tillage; (2) to assess the effects of autoclaving on bromoxynil mineralization and bound residue formation; (3) to determine the partitioning of non‐extractable residues; and (4) to ascertain the effects of bromoxynil concentration on extractable and bound residues and metabolite formation. RESULTS: Bromoxynil K_d values ranged from 0.7 to 1.4 L kg^?1 and were positively correlated with soil organic carbon. Cumulative mineralization (38.5% ± 1.5), bound residue formation (46.5% ± 0.5) and persistence of extractable residues (T_1/2 < 1 day) in non‐autoclaved soils were independent of tillage and depth. Autoclaving decreased mineralization and bound residue formation 257‐fold and 6.0‐fold respectively. Bromoxynil persistence in soil was rate independent (T_1/2 < 1 day), and the majority of non‐extractable residues (87%) were associated with the humic acid fraction of soil organic matter. CONCLUSIONS: Irrespective of tillage or depth, bromoxynil half‐life in native soil is less than 1 day owing to rapid incorporation of the herbicide into non‐extractable residues. Bound residue formation is governed principally by biochemical metabolite formation and primarily associated with soil humic acids that are moderately bioavailable for mineralization. These data indicate that the risk of off‐site transport of bromoxynil residues is low owing to rapid incorporation into non‐extractable residues. Published 2009 by John Wiley & Sons, Ltd     

The behavior of clomazone in the soil environment

BACKGROUND: Clomazone is a herbicide used to control broadleaf weeds and grasses. Clomazone use in agriculturally important crops and forests for weed control has increased and is a potential water contaminant given its high water solubility (1100 µg mL^?1). Soil sorption is an environmental fate parameter that may limit its movement to water systems. The authors used model rice and forest soils of California to test clomazone sorption affinity, capacity, desorption, interaction with soil organic matter and behavior with black carbon. RESULTS: Sorption of clomazone to the major organic matter fraction of soil, humic acid (HA) (K_d = 29–87 L kg^?1), was greater than to whole soils (K_d = 2.3–11 L kg^?1). Increased isotherm non‐linearity was observed for the whole soils (N = 0.831–0.893) when compared with the humic acids (N = 0.954–0.999). Desorption isotherm results showed hysteresis, which was greatest at the lowest solution concentration of 0.067 µg mL^?1 for all whole soils and HA extracts. Aliphatic carbon content appeared to contribute to increased isotherm linearity. CONCLUSION: The results indicate that clomazone does not sorb appreciably to sandy or clay soils. Its sorption affinity and capacity is greater in humic acid, and consequently clomazone has difficulty desorbing from soil organic matter. Sorption appears to follow processes explained by the dual‐mode model, the presence of fire residues (black carbon) and a recently proposed sorption mechanism. Copyright © 2009 Society of Chemical Industry     

Some physicochemical and environmental factors affecting transformation rates and sorption of the herbicide metamitron in soil

In addition to the molecular structure of a pesticide, environmental conditions may influence its persistence through their effect on the growth and activity of pesticide-degrading micro-organisms. As a result, transformation rates may decrease rapidly when a compound is leached into subsoil. Metamitron sorption isotherms were determined and incubation series were set up for a sandy loam soil, simulating single and combination effects that occur during transport of metamitron into subsoils. K_OC values increased with increasing depth from 185 to 700 litre kg⁻¹. A combination of conditions that are unfavourable for microbial activity, such as low temperature (5°C), low concentrations (0·5 mg kg⁻¹) and a large sorbed fraction (K_OC = 700) resulted in half-lives of over one year. Oxygen inhibition decreased the transformation rate of metamitron from 0·058 to 0·019 day⁻¹. In order of significance, the transformation of metamitron appears to be a function of temperature, oxygen availability and sorption to organic carbon. Increasing doses did not change transformation rates significantly, although different transformation pathways were observed.     

Behaviour of the insecticides ethoprophos and carbofuran during soil—water transport

The movement of the organophosphate nematicide-insecticide ethoprophos (ethoprop; O-ethyl S,S-dipropyl phosphorodithioate) and the carbamate insecticide-nematicide carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yI methylcarbamate) was studied under steady-state flow in small-scale laboratory soil columns. Miscible displacement column experiments, mass balance calculations, and batch incubation studies furnished information on insecticide sorption and degradation processes that occur during transport through soil. Miscible displacement studies demonstrated that ethoprophos degradation could be described as first-order and that both insecticides exhibited non-equilibrium sorption. Both batch and miscible displacement results showed ethoprophos to be more strongly sorbed by soil than carbofuran. Measured equilibrium sorption coefficients were 1.29 cm³ g^?1 for ethoprophos and 0.29 cm³ g^?1 for carbofuran on a Riverhead soil (0.011 organic carbon fraction); 035 cm³ g^?1 for carbofuran on Valois soil (0.016 organic carbon fraction); and 2.38 cm³ g^?1 for ethoprophos on Rhinebeck soil (0.031 organic carbon fraction). Two solutions to the convection-dispersion equation, one that incorporated equilibrium sorption and another (bicontinuum model) that included a non-equilibrium sorption term, allowed quantitative evaluation of transport processes. The bicontinuum model used in conjunction with experimental batch and mass balance techniques provided estimates of insecticide sorption and degradation parameters.     

Weed interference in maize, cowpea and maize/cowpea intercrop in a subhumid tropical environment. III. Influence of land preparation

The influence of no-tillage and conventional tillage on the outcome of early weed interference in maize (Zea mays L., cv. TZB), cowpea [Vigna unguiculata (L.) Walp, cv. VITA-5] and their intercrop at populations of 40000, 50 000 and 30 000 + 40 000 plants ha^?1 was investigated on a loamy sand Oxic Ustropept in a subhumid tropical environment between April and July 1980. Both tillage treatments received 60 kg N, 30 kg P₂O₅ and 30 kg K₂O ha^?1. Although the weed spectrum was wider under no-tillage, weed weight was only 52% of the weight recorded under conventional tillage 6 weeks after sowing and the average food energy yield reductions caused were 28 and 65%, respectively. Cropping pattern had no effect on plot weediness. With minimum or no weed interference, maize performance was better in conventional than no-tillage but worse with prolonged weed interference. Cowpea responded more to weed interference than to tillage practice. Regardless of tillage practice and weed interference duration (up to 6 weeks) after sowing, maize monoculture produced the highest food energy yield, followed by maize/cowpea intercrop and cowpea monoculture in that order.     

Role of sorption and degradation in the herbicidal function of isoxaflutole

BACKGROUND: The fate of isoxaflutole (IFT) in soil is closely related to soil sorption. Sorption and transformation of IFT were investigated in laboratory incubations with four soils, and these results were used to interpret greenhouse studies using IFT to control several weed species. RESULTS: Degradation proceeded by previously observed pathways to form diketonitrile (DKN) and benzoic acid (BA) derivatives, as well as traces of unidentified products. Over the course of the incubation, DKN was the dominant active form of the herbicide present in the experimental system, and was thus critical to the soil activity of the herbicide for weed control. CONCLUSION: Control of most weed species appeared to be a function of both sorption and biodegradation of DKN, with greatest weed control being observed in soils in which a significant portion of the DKN that was formed persisted and remained bioavailable over the course of the incubation. Copyright © 2009 Society of Chemical Industry     

Fate of fluroxypyr in soil

Batch adsorption K_oc values of fluroxypyr-methylheptyl ester (20000 1kg^?1) and fluroxypyr (74 1kg^?1) indicate increased mobility after hydrolysis of the ester to fluroxypyr. After 1 to 2 weeks incubation time in four soils, desorption K_oc values of fluroxypyr were 100-200 1kg^?1 but increased to 400-700 1kg^?1 after 8 weeks. The increase in desorption K_oc was related to incubation time and not to concentration, and it was interpreted as an entrapment of the fluroxypyr within the soil organic matter. Similar increases in desorption K_oc with incubation time were noticed for pyridinol and methoxypyridine metabolites of fluroxypyr. K_oc values also increased along the metabolic sequence fluroxypyr/pyridinol/methoxypyridine, with maximum K_oc values of 3000-4000 1 kg^?1 for the methoxypyridine metabolite. Hence mobility of the fluroxypyr aromatic ring strongly decreases with increased residence time in the soil.     

Sorption of isoxaflutole by five different soils varying in physical and chemical properties

Isoxaflutole is a new pre-emergence corn herbicide which controls both grass and broadleaf weeds. Experiments were performed in the laboratory to study the sorption of isoxaflutole in five different soils (Moorhead, MN; East Monroe, CO; Ellendale, MN; South Deerfield, MA; and Chelsea, MI) using the batch equilibration technique. Total initial isoxaflutole solution concentrations for each soil were 0.05, 0.15, 0.3. 0.8, 1.5, 2.0 and 4.0 mg litre⁻¹. Analysis of [ring-¹⁴C] isoxaflutole was performed using liquid scintillation counting, and sorption data were fitted with the Freundlich model. Isotherms of isoxaflutole in all the soils were non-linear as depicted by the exponent (n < 1.0), indicating differential distribution of sorption site energies in various soils. Since the isotherms were non-linear the data fit Freundlich's isotherm well, as was indicated by high values of the regression coefficient (r²). The Freundlich sorption coefficient ranged from 0.555 to 50.0 (litre ⁿmg ^l−nkg⁻¹). Multiple regression of the sorption constant, K_F against selected soil properties indicated that organic matter content was the best single predictor of isoxaflutole sorption (r² = 0.999) followed by soil pH (r² = 0.954). Clay content of the soils did not have a high correlation with K_F values (r² = 0.453), while the sorption of isoxaflutole was not influenced by the Ca²⁺ concentration in the soil solution. Isoxaflutole sorption increased with an increase in organic matter content of soils. Sorption of isoxaflutole decreased as the soil pH increased from 4.5 to 8.5, which was depicted by the reduction of K_F values. Sorption of isoxaflutole to the soils varied with differences in binding energies. At a particular net energy value (E*), the corresponding site energy distribution [F(E*)] values followed the order, Chelsea, MI > Moorhead, MN > East Monroe, CO > South Deerfield, MA > Ellendale, MN. The negative magnitude of Gibbs free energy of sorption (ΔG ^x) indicates the spontaneity of the given sorption process in the soils from Moorhead, MN; East Monroe, CO and Chelsea, MI. © 1999 Society of Chemical Industry     

耕作方式对旱地麦田土壤团聚体及其碳氮组分分布的影响

为明确蓄水保墒耕作方式下旱地麦田土壤团聚体稳定性、有机碳及碳组分和全氮及氮组分在不同粒径团聚体组分中的分布特征,深入了解不同耕作方式下土壤碳氮固持机制,以连续3 a(2017—2020年)实施不同耕作方式(免耕、深松、深翻)后冬小麦收获期0～20 cm土壤为研究对象,采用湿筛法测算土壤团聚体的构成与稳定性(R_0.25,>0.25 mm团聚体含量;MWD,平均重量直径;GMD,几何平均直径),并测定各粒径团聚体有机碳(SOC)和碳组分(重组有机碳,HFOC;轻组有机碳,LFOC;易氧化有机碳,EOC;可溶性有机碳,DOC;颗粒有机碳,POC)含量、全氮(TN)和氮组分(硝态氮,NO^-₃-N;铵态氮,NH⁺₄-N;可溶性有机氮,SON)含量,分析了碳氮组分的相关关系。结果显示：(1)免耕和深松处理>2 mm团聚体土壤比例较深翻处理分别提高8.8%和22.1%,免耕有利于增加<0.053 mm粉黏粒比例,较深松和深翻处理分别提高46.4%和27.7%。深松处理较深翻...     

Partitioning of etofenprox under simulated California rice‐growing conditions

BACKGROUND: The pyrethroid insecticide etofenprox is of current interest to rice farmers in the Sacramento Valley owing to its effectiveness against the rice water weevil, Lissorhoptrus oryzophilus Kuschel. This study aimed to describe the partitioning of etofenprox under simulated rice field conditions by determining its Henry's law constant (H) (an estimate of volatilization) and organic carbon‐normalized soil–water distribution coefficient (K_oc) at representative field temperatures. A comparison of etofenprox and λ‐cyhalothrin is presented using a level‐1 fugacity model. RESULTS: Experimental determination of H revealed that etofenprox partitioned onto the apparatus walls and did not significantly volatilize; the maximum value of H was estimated to be 6.81 × 10^?1 Pa m³ mol^?1 at 25 °C, based on its air and water method detection limits. Calculated values for H ranged from 5.6 × 10^?3 Pa m³ mol^?1 at 5 °C to 2.9 × 10^?1 Pa m³ mol^?1 at 40 °C, based on estimated solubility and vapor pressure values at various temperatures. Log K_oc values (at 25 °C) were experimentally determined to be 6.0 and 6.4 for Princeton and Richvale rice field soils, respectively, and were very similar to the values for other pyrethroids. Finally, temperature appears to have little influence on etofenprox sorption, as the log K_oc for the Princeton soil at 35 °C was 6.1. CONCLUSION: High sorption coefficients and relatively insignificant desorption and volatilization of etofenprox suggest that its insolubility drives it to partition from water by sorbing to soils with high affinity. Offsite movement is unlikely unless transported in a bound state on suspended sediments. Copyright © 2009 Society of Chemical Industry     

The effect of maize residues and tillage on emergence of Setaria faberi, Abutilon theophrasti, Amaranthus retroflexus and Chenopodium album

Tillage and maize (Zea mays L.) residues at up to four times the base level had variable effects on the emergence of four annual weed species in the field. Environmental conditions varied during the three years of the research and interacted with residue and tillage to govern seedling emergence. When tillage affected Setaria faberi Herrm., emergence was greater in untillcd than tilled plots. The effect of residues varied among years. Abutilon theophrasti Medik, emergence from tilled soil was greater than from untilled soil in two of three years. Maize residue at two or four times the base levei reduced emergence. Amaranthus retroflexus L. emergence was often greater from untilled than tilled soil. The effect of maize residues on this species was dependent on tillage and precipitation. Chenopodium album L. emergence was affected by tillage and residues but differences over the three years were inconsistent. Results of this research indicate that tillage and residues interact with weed species, precipitation and other factors to regulate seedling emergence. The reduced soil disturbance and minimal weed seed burial associated with the elimination of tillage appear to have a greater impact on weed population dynamics than surface residues in non-tillage maize production systems.     

Acetochlor sorption and degradation in limestone subsurface and aquifers

BACKGROUND: Acetochlor, introduced on the market in 1994, is used extensively worldwide, but sorption and degradation studies, including subsurface, are scarce, and there appear to be no such studies with aquifer sediment according to the present mini‐review. Sorption, degradation and mineralisation of acetochlor were investigated in heterogeneous limestone down to 43 m below surface (mbs) in four European aquifers (1.7–59 mbs), both aerobic and anaerobic. RESULTS: Sorption revealed K_d values of 3.39–4.96 L kg^?1 in topsoil, < 0.01–2.02 L kg^?1 in heterogeneous limestone, 0.06–0.72 L kg^?1 in aerobic aquifers and 1.03–4.60 L kg^?1 in microaerobic or anaerobic aquifers. The mineralisation half‐lives in the samples from 0.0–0.6 mbs were 0.8–2.1 years and 4.7–95 years in the unsaturated limestone samples from 1–43 mbs. Out of 22 samples from four different European aquifers, acetochlor was mineralised in five samples (half‐lives of 9–19 years), all from the same aquifer and core section (19.25–19.53 mbs). CONCLUSION: Sorption was weak in limestone and aerobic sandy aquifers, and strong in topsoils and in reduced sandy aquifers. Redox conditions controlled the extent of acetochlor sorption in aquifers, as reduced conditions induced increased sorption. Acetochlor was mineralised in deep subsurface, though slowly, and, as mineralisation is the only true removal mechanism in natural attenuation, even slow mineralisation in aquifers with long residence times can have a significant impact. Copyright © 2010 Society of Chemical Industry     

Sorption of ionisable organic compounds by field soils. Part 1: Acids

Sorption of different classes of weak organic acids was measured using soils with a range of pH values, taken from long-term field experiments that had received different amounts of lime. Non-ionisable compounds were used to demonstrate that the soils of different pH used in the experiments have similar sorptive properties. Values of the sorption coefficients for chloride ion were negative at all pHs except one. Sorption of moderately polar, monobasic, weak acids was weak in acidic soils and very weak in neutral and alkaline soils where they were predominantly dissociated. A lipophilic weak acid was strongly sorbed even at high pH. A model is presented which estimates soil/water distribution coefficients, at any soil pH, from lipophilicity and pK_a of the acid and organic matter content of the soil. The model was derived using sorption measured for substituted phenoxyacetic acids. Sorption values calculated using the model were compared with values measured for chlorsulfur on and showed useful agreement. Dibasic acids were strongly sorbed, probably by the mechanism of ligand exchange, if they were chelating agents with potential to form 5- or 6-membered rings with an acceptor atom. Phenylphosphonic acid was strongly sorbed, being a strong monodentate ligand.     

The persistence and activity of insecticide spary deposits on woven polypropylene fabric

Wettable powder formulations of the organophosphorus insecticides, fenitrothion and pirimiphos-methyl, and the pyrethroids, permethrin and deltamethrin, have been compared for persistence and activity on woven polypropylene fabric; the residues produced in maize kept under the test sheets have also been measured. The test insects were Sitophilus oryzue (L.) and Tribolium custuneum (Herbst). Permethrin at 41 and 83 mg m^?2 was completely effective for the full 12 weeks of the experiment. Deltamethrin at 6.2 and 12.5 mg m^?2 was almost equally effective but after 4 weeks the deposit was slower acting against S. oryzae. The organophosphorus compounds were effective only up to 2 weeks at 250 mg m^?2 and up to 4 weeks at 500 mg m^?2. No residues could be detected under the pyrethroids but the organophosphorus insecticides gave residues of 2–4 mg kg^?1 on a thin layer of grain. This residue was biologically effective against the test insects.     

Behaviour of bentazon as influenced by water and tillage management in rice‐growing conditions

Bentazon is a widely used herbicide in rice agroecosystems that has commonly been found in water resources. To assess how tillage and water regimes affect sorption/desorption, dissipation and leaching of bentazon in Mediterranean rice‐growing conditions, field experiments were carried out using tillage and flooding (TF), tillage and sprinkler irrigation (TS), no‐tillage and sprinkler irrigation (NTS) and long‐term no‐tillage and sprinkler irrigation (NTS7). After 3 years, the K_d values in TS were 2.3, 1.6 and 1.7 times lower than the values in NTS7, NTS and TF respectively. Greater sorption of bentazon was related to higher contents in total organic carbon and, although to a lesser extent, in humic acids and dissolved organic carbon. The persistence of bentazon was significantly greater under anaerobic (half‐life DT₅₀ = 94.1–135 days) than under aerobic (DT₅₀ = 42.4–91.3 days) incubation conditions for all management regimes. Leaching losses of bentazon were reduced from 78 and 74% in TS and TF to 61 and 62% in NTS7 and NTS respectively. The mid‐ and long‐term implementation of sprinkler irrigation in combination with no‐tillage could be considered a management system that is effective at reducing water contamination by bentazon in Mediterranean rice‐growing agroecosystems. © 2017 Society of Chemical Industry