农田尾菜发酵过程中农药残留变化特征

基于尾菜中存在农药残留的现状,以设施农业尾菜黄瓜秧为研究对象,采用气相色谱法和超高效液相色谱-串联质谱法检测了尾菜黄瓜秧在静态好氧发酵过程中多菌灵、吡虫啉、哒螨灵等50种农药残留的动态变化,并分析发酵重要影响因子堆高对农药残留消解的影响。结果表明:在尾菜黄瓜秧中共检测出腐霉利、多菌灵、嘧菌酯、苯醚甲环唑、烯酰吗啉、虫螨腈、吡虫啉、啶虫脒和哒螨灵9种农药残留,其中多菌灵平均残留量最高,达11.2 mg/kg,其他8种农药平均残留量在0.042~0.89 mg/kg之间。在发酵的24 d中,不同堆高条件下9种农药的消解规律均符合一级反应动力学方程,但不同农药半衰期差异较大,其中吡虫啉的平均半衰期最长,为28.9 d,多菌灵的平均半衰期最短,为10.2 d;不同堆高处理中农药的消解速率也有差异,总体上在2.5 m堆高下各农药的消解率最高、半衰期最短。本研究结果可为尾菜发酵参数优化、农业废弃物的高效资源化利用以及研发基于尾菜发酵产物的有机蔬菜专用有机肥提供理论支撑。     

不同基质和覆土栽培条件下双孢蘑菇中吡虫啉和咪鲜胺残留差异影响

为了明确吡虫啉和咪鲜胺在双孢蘑菇Agaricus bisporus不同栽培基质中的消解规律,采用在工厂化双孢蘑菇栽培覆土中拌料施药、培养料中喷药两种施药方式开展田间试验,运用QuEChERS净化前处理技术结合超高效液相色谱-串联质谱(UPLC-MS/MS)分析,检测了吡虫啉和咪鲜胺在双孢蘑菇栽培基质和子实体中的残留.结...     

Potential for microbial diuron mineralisation in a small wine‐growing watershed: from treated plots to lotic receiver hydrosystem

BACKGROUND: Since biological degradation processes are known to be a major driver of the natural attenuation of pesticide residues in the environment, microbial communities adapted to pesticide biodegradation are likely to play a key environmental role in reducing pesticide exposure in contaminated ecosystems. The aim of this study was to assess the diuron‐mineralising potential of microbial communities at a small‐scale watershed level, including a diuron‐treated vineyard (pollution source), its associated grass buffer strip (as a river protection area against pesticide runoff) and the lotic receiver hydrosystem (sediments and epilithon), by using radiorespirometry. RESULTS: Comparison of results obtained at different sampling sites (in both soil and aquatic systems) revealed the importance of diuron exposure in the adaptation of microbial communities to rapid diuron mineralisation in the vineyard but also in the contaminated grass strip and in downstream epilithic biofilms and sediments. CONCLUSION: This study provides strong suggestive evidence for high diuron biodegradation potential throughout its course, from the pollution source to the final receiving hydrosystem, and suggests that, after microbial adaptation, grass strips may represent an effective environmental tool for mineralisation and attenuation of intercepted pesticides. Copyright © 2009 Society of Chemical Industry     

Dissipation of acephate, chlorpyrifos, cypermethrin and their metabolites in a humid-tropical vegetable production system

BACKGROUND: High amounts of insecticides are often used in intensive tropical vegetable production systems. Their persistence and residues in vegetables and soils need to be studied to ensure food safety and environmental stability. The dissipation of acephate, chlorpyrifos, cypermethrin and their metabolites was studied in green mustard [Brassica juncea (L.) Coss.] and soils. Two treatments, Impact 75 (acephate) and Agent 505 (cypermethrin plus chlorpyrifos), were applied 4 times at weekly intervals. RESULTS: Dissipation of acephate, chlorpyrifos and cypermethrin in green mustard and topsoils followed first‐order kinetics, with half‐lives of between 1.1 and 3.1 days in green mustard and between 1.4 and 9.4 days in topsoils (26 °C). Higher vapour pressure of insecticides and higher rainfall appeared to stimulate dissipation from the vegetable, with least effect of rainfall on chlorpyrifos. Dissipation rates in the vegetable were faster or similar (cypermethrin) to rates observed for temperate areas. Preharvest intervals of 13, 4 and 3 days were required for acephate, chlorpyrifos, cypermethrin and their metabolites to comply with the tolerance levels. The pesticide dissipation rates in soils varied by less than a factor of 3 between sites. The metabolites methamidophos and TCP derived from acephate and chlorpyrifos amounted to less than 10 and 25% by mass of the parent compounds in soils. Vegetable shading possibly retarded pesticide degradation in soil. CONCLUSION: The dissipation of pesticides and their metabolites in the vegetable was rapid and faster than the dissipation in temperate climates. The degradation rates of pesticides in the soil were equal to or slightly faster than the degradation rates in temperate soils. Copyright © 2008 Society of Chemical Industry     

Efficiency of a bagasse substrate in a biological bed system for the degradation of glyphosate, malathion and lambda-cyhalothrin under tropical climate conditions

BACKGROUND: After the rinsing of spray equipment, the rinsing water contains polluting products. One way to avoid pollution is to bring the rinsing water over a purification system, a biological bed. The system consists of an impermeable tub filled with a biomix substrate that facilitates biodegradation of pesticides. Usually, straw is one component of the biomix. The objective of this study was to assess the efficiency of an unusual substrate, bagasse, a residue of sugar cane, for the degradation of three pesticides, glyphosate, malathion and lambda‐cyhalothrin. RESULTS: Results showed that more than 99% of malathion and glyphosate were degraded in 6 months. In the biological bed, the DT₅₀ value for malathion was 17 days, for glyphosate 33 days and for lambda‐cyhalothrin 43 days. The degradation rate of aminomethylphosphonic acid (AMPA) residues from the degradation of glyphosate was slower than that of the other pesticides (DT₅₀ 69 days). Finally, the innocuousness of the biomix after 6 months of degradation was confirmed by biological tests. CONCLUSIONS: Although the degradation rates of the three pesticides in the present bagasse‐based system were similar to those under temperate conditions, the degradation conditions were improved by comparison with those in soil under the given tropical conditions. Further benefits of this system are pesticide confinement, to avoid their dispersion in the environment by liquids or solids, and a lower overall cost. Finally, possibilities for optimising the bagasse‐based system (e.g. management of the water content and nature of the biomix) are discussed. Copyright © 2008 Society of Chemical Industry     

Degradation and adsorption of terbuthylazine and chlorpyrifos in biobed biomixtures from composted cotton crop residues

BACKGROUND: Biobeds have been well studied in northern Europe, whereas little is known regarding their use in southern Europe. The degradation and adsorption of terbuthylazine (TA) and chlorpyrifos (CP) were studied in three different biomixtures composed of composted cotton crop residues, soil and straw in various proportions, and also in sterilised and non‐sterilised soil. RESULTS: Compost biomixtures degraded the less hydrophobic TA at a faster rate than soil, while the opposite was evident for the more hydrophobic CP. These results were attributed to the rapid abiotic hydrolysis of CP in the alkaline soil (pH 8.5) compared with the lower pH of the compost (6.6), but also to the increasing adsorption (K_d = 746 mL g^?1) and reduced bioavailability of CP in the biomixtures compared with soil (K_d = 17 mL g^?1), as verified by the adsorption studies. CONCLUSIONS: Compost had a dual but contrasting effect on degradation that depended on the chemical nature of the pesticide studied: a positive effect towards TA owing to increasing biodegradation and a negative effect towards CP owing to increasing adsorption. Overall, composted cotton crop residues could be potentially used in local biobed systems in Greece, as they promoted the degradation of hydrophilic pesticides and the adsorption of hydrophobic pesticides. Copyright © 2010 Society of Chemical Industry     

Pesticide degradation in a 'biobed' composting substrate

Pesticides play an important role in the success of modern farming and food production. However, the release of pesticides to the environment arising from non-approved use, poor practice, illegal operations or misuse is increasingly recognised as contributing to water contamination. Biobeds appear to offer a cost-effective method for treating pesticide-contaminated waste. This study was performed to determine whether biobeds can degrade relatively complex pesticide mixtures when applied repeatedly. A pesticide mixture containing isoproturon, pendimethalin, chlorpyrifos, chlorothalonil, epoxiconazole and dimethoate was incubated in biomix and topsoil at concentrations to simulate pesticide disposal. Although the data suggest that interactions between pesticides are possible, the effects were of less significance in biomix than in topsoil. The same mixture was applied on three occasions at 30-day intervals. Degradation was significantly quicker in biomix than in topsoil. The rate of degradation, however, decreased with each additional treatment, possibly due to the toxicity of the pesticide mixture to the microbial community. Incubations with chlorothalonil and pendimethalin carried out in sterile and non-sterile biomix indicated that degradation, rather than irreversible adsorption to the matrix, was the main mechanism responsible for the reduction in recovered residues. Results from these experiments suggest that biobeds offer a viable means of treating pesticide waste.     

Field leaching of pesticides at five test sites in Hawaii: modeling flow and transport

BACKGROUND: Physically based tier‐II models may serve as possible alternatives to expensive field and laboratory leaching experiments required for pesticide approval and registration. The objective of this study was to predict pesticide fate and transport at five different sites in Hawaii using data from an earlier field leaching experiment and a one‐dimensional tier‐II model. As the predicted concentration profiles of pesticides did not provide close agreement with data, inverse modeling was used to obtain adequate reactive transport parameters. The estimated transport parameters of pesticides were also utilized in a tier‐I model, which is currently used by the state authorities to evaluate the relative leaching potential. RESULTS: Water flow in soil profiles was simulated by the tier‐II model with acceptable accuracy at all experimental sites. The observed concentration profiles and center of mass depths predicted by the tier‐II simulations based on optimized transport parameters provided better agreements than did the non‐optimized parameters. With optimized parameters, the tier‐I model also delivered results consistent with observed pesticide center of mass depths. CONCLUSION: Tier‐II numerical modeling helped to identify relevant transport processes in field leaching of pesticides. The process‐based modeling of water flow and pesticide transport, coupled with the inverse procedure, can contribute significantly to the evaluation of chemical leaching in Hawaii soils. Copyright © 2011 Society of Chemical Industry     

Adsorption,desorption and dissipation of metolachlor in surface and subsurface soils

BACKGROUND: Variations in soil properties with depth influence retention and degradation of pesticides. Understanding how soil properties within a profile affect pesticide retention and degradation will result in more accurate prediction by simulation models of pesticide fate and potential groundwater contamination. Metolachlor is more persistent than other acetanilide herbicides in the soil environment and has the potential to leach into groundwater. Reasonably, information is needed about the dissipation and eventual fate of metolachlor in subsoils. The objectives were to evaluate the adsorption and desorption characteristics and to determine the dissipation rates of metolachlor in both surface and subsurface soil samples. RESULTS: Adsorption of metolachlor was greater in the high‐organic‐matter surface soil than in subsoils. Lower adsorption distribution coefficient (K_ads) values with increasing depth indicated less adsorption at lower depths and greater leaching potential of metolachlor after passage through the surface horizon. Desorption of metolachlor showed hysteresis, indicated by the higher adsorption slope (1/n_ads) compared with the desorption slope (1/n_des). Soils that adsorbed more metolachlor also desorbed less metolachlor. Metolachlor dissipation rates generally decreased with increasing soil depth. The first‐order dissipation rate was highest at the 0–50 cm depth (0.140 week^?1) and lowest at the 350–425 cm depth (0.005 week^?1). Degradation of the herbicide was significantly correlated with microbial activity in soils. CONCLUSION: Metolachlor that has escaped degradation or binding to organic matter at the soil surface might leach into the subsurface soil where it will dissipate slowly and be subject to transport to groundwater. Copyright © 2009 Society of Chemical Industry     

Evidence for 2,4‐D mineralisation in Mediterranean soils: impact of moisture content and temperature

BACKGROUND: The 2,4‐D degradation ability of the microbiota of three arable Mediterranean soils was estimated. The impact of soil moisture and temperature on 2,4‐D degradation was investigated. RESULTS: The microbiota of the three soils regularly exposed to 2,4‐D were able rapidly to mineralise this herbicide. The half‐life of 2,4‐D ranged from 8 to 30 days, and maximum mineralisation of ¹⁴C‐2,4‐D ranged from 57 to 71%. Extractable ¹⁴C‐2,4‐D and ¹⁴C‐bound residues accounted for less than 1 and 15% respectively of the ¹⁴C‐2,4‐D initially added. The highest amounts of ¹⁴C‐2,4‐D bound residues were recorded in the soil with the lowest 2,4‐D‐mineralising ability. Although all three soils were able to mineralise 2,4‐D, multivariate analysis revealed that performance of this degrading microbial activity was dependent on clay content and magnesium oxide. Soil temperature affected the global structure of soil microbial community, but it had only a moderate effect on 2,4‐D‐mineralising ability. 2,4‐D‐mineralising ability was positively correlated with soil moisture content. Negligible 2,4‐D mineralisation occurred in all three soils when incubated at 10 or 15% soil moisture content, i.e. within the range naturally occurring under the Mediterranean climate of Algeria. CONCLUSION: This study shows that, although soil microbiota can adapt to rapid mineralisation of 2,4‐D, this microbial activity is strongly dependent on climatic parameters. It suggests that only limited pesticide biodegradation occurs under Mediterranean climate, and that arable Mediterranean soils are therefore fragile and likely to accumulate pesticide residues. Copyright © 2009 Society of Chemical Industry     

Availability and biodegradation of metribuzin in alluvial soils as affected by temperature and soil properties

Herbicide degradation in soils is highly temperature‐dependent. Laboratory incubations and field experiments are usually conducted with soils from the temperate climatic zone. Few data are available for cold conditions and the validation of approaches to correct the degradation rate at low temperatures representative of Nordic environments is scarce. Laboratory incubation studies were conducted at 5, 15 and 28°C to compare the influence of temperature on the dissipation of metribuzin in silt/sandy loam soils in southern and northern Norway and in a sandy loam soil under temperate climate in France. Using ¹⁴C‐labelled metribuzin, sorption and biodegradation were studied over an incubation period of 49 days. Metribuzin mineralisation and total soil organic carbon mineralisation rates showed a positive temperature response in all soils. Metribuzin mineralisation was low, but metabolites were formed and their abundance depended on temperature conditions. The rate of dissipation of ¹⁴C‐metribuzin from soil pore water was strongly dependent on temperature. In Nordic soils with low organic content, metribuzin sorption is rather weak and biodegradation is the most important process controlling its mobility and persistence.     

莠去津微生物降解的研究进展

综述了莠去津降解微生物的筛选方法、降解速度的影响因素、降解机理,并对农药降解微生物的应用前景进行了展望。对降解农药微生物的研究不但可以得到消除莠去津环境污染的菌株和相应的酶制剂,而且对于抗莠去津转基因技术的研究也有促进作用。     

三种有机磷农药在双孢蘑菇及其栽培基质中的残留动态

为明确二嗪磷、毒死蜱和辛硫磷3种有机磷农药在双孢蘑菇栽培过程中的残留动态规律,采用在工厂化双孢蘑菇栽培基质 (覆土和培养料) 中拌料施药的方式,开展了田间试验,运用QuEChERS净化前处理技术结合UPLC-MS/MS分析,检测了3种农药在双孢蘑菇子实体和栽培基质中的残留动态。结果表明:建立的双孢蘑菇子实体、覆土和培养料3种基质中3种有机磷农药的液相色谱-串联质谱检测方法,经验证,在二嗪磷分别以0.000 3、0.003、0.1 mg/kg为添加水平,毒死蜱和辛硫磷分别以0.000 6、0.006、0.1 mg/kg为添加水平下,3种有机磷农药在双孢蘑菇、覆土和培养料3种基质中的平均回收率为76%~108%,相对标准偏差为2.2%~13%。检出限分别为:二嗪磷0.000 1 mg/kg、毒死蜱和辛硫磷均为0.000 2 mg/kg,定量限分别为:二嗪磷0.000 3 mg/kg、毒死蜱0.0006 mg/kg和辛硫磷0.000 6 mg/kg。在2 和10 mg/kg两个施药水平下,二嗪磷、毒死蜱和辛硫磷在双孢蘑菇栽培基质中的消解规律均符合一级反应动力学方程,在培养料中的消解半衰期分别为5.2、10.6、13.6 d和5.6、11.4、12.3 d;在覆土中的消解半衰期分别为25.9、41.7、27.2 d和41.7、48.1、36.8 d,且在培养料中的消解快于在覆土中的。在施药剂量不超过10 mg/kg的条件下,在双孢蘑菇子实体中毒死蜱残留量最高,为0.014 mg/kg,超过了欧盟规定的最大残留限量(MRL)标准,其余均低于现行日本、欧盟和美国规定的MRL值。     

Evaluation of the combined toxicity of 15 pesticides by uniform design

BACKGROUND: Environmental pesticides, including insecticides and herbicides, are frequently encountered as mixtures and threaten non‐target organisms in water. Evaluation of the combined toxicity of diverse pesticides with various concentration combinations is important, especially using limited experimental effort. Uniform design (UD) is one optimal experimental technique that can rationally arrange the concentrations of mixture components so that, with a minimum number of experimental runs, the combined toxicity of multiple pesticide mixtures can be evaluated. RESULTS: The concentration compositions of 18 pesticide mixture points designed by UD covered almost all possible concentration ranges of the mixture components on account of the two merits of ‘space filling’ and ‘multiple levels’. The combined toxicities of 18 mixture rays extended by using the fixed‐ratio ray design (FRRD) from 18 UD mixture points were evaluated by concentration addition (CA) and independent action (IA) models. It was found that the concentration–response curves (CRCs) predicted by CA were, on the whole, located between the 95% confidence intervals of the experimental CRCs, which implied that the combined toxicity of the pesticide mixture rays could be evaluated by CA. The CRCs predicted by IA were very similar to those from CA. CONCLUSION: The model developed from the UD mixture rays can effectively simulate mixtures with arbitrary concentration compositions of 15 pesticides. The CA model can accurately evaluate and predict the combined toxicity of the pesticides, which provides a useful tool for risk assessment of a mixture of multiple pesticides in the aquatic environment. Copyright © 2010 Society of Chemical Industry     

五种农药及其二元、三元组合对人肝癌HepG2细胞的联合毒性

为研究农产品中农药混合污染的联合毒性,选取生菜中应用广泛、广谱性强的5种农药(苯醚甲环唑、氯氰菊酯、烯酰吗啉、氯氟氰菊酯和啶虫脒)及其高频检出的二元、三元农药组合为研究对象,采用CCK-8(Cell Counting Assay Kit-8)法探究农药单剂及混合物对人肝癌HepG2细胞增殖的抑制毒性,基于单个农药剂量效...     

Considering degradation kinetics of pesticides in plant uptake models: proof of concept for potato

BACKGROUND

Degradation kinetics of pesticides in plants are crucial for modeling mechanism-based pesticide residual concentrations. However, due to complex open-field conditions that involve multiple pesticide plant uptake and elimination processes, it is difficult to directly measure degradation kinetics of pesticides in plants. To address this limitation, we proposed a modeling approach for estimating degradation rate constants of pesticides in plants, using potato as a model crop. An operational tool was developed to backward-estimate degradation rate constants, and three pesticides were selected to perform example simulations.

RESULTS

The simulation results of thiamethoxam indicated that the growth dynamics of the potato had a significant impact on the degradation kinetic estimates when the pesticide was applied during the early growth stage, as the size of the potato determined the uptake and elimination kinetics via diffusion. Using mepiquat, we demonstrated that geographical variations in weather conditions and soil properties led to significant differences in the dissipation kinetics in both potato plants and soil, which propagated the variability of the degradation rate constant. Simulation results of chlorpyrifos differed between two reported field studies, which is due to the effect of the vertical distribution of the residue concentration in the soil, which is not considered in the majority of recent studies.

CONCLUSIONS

Our proposed approach is adaptable to plant growth dynamics, preharvest intervals, and multiple pesticide application events. In future research, it is expected that the proposed method will enable region-specific inputs to improve the estimation of the degradation kinetics of pesticides in plants. © 2022 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

Bioconversion of dieldrin by wood‐rotting fungi and metabolite detection

BACKGROUND: Dieldrin is one of the most persistent organochlorine pesticides, listed as one of the 12 persistent organic pollutants in the Stockholm Convention. Although microbial degradation is an effective way to remediate environmental pollutants, reports on aerobic microbial degradation of dieldrin are limited. Wood‐rotting fungi can degrade a wide spectrum of recalcitrant organopollutants, and an attempt has been made to select wood‐rotting fungi that can degrade dieldrin, and to identify the metabolite. RESULTS: Thirty‐four isolates of wood‐rotting fungi were investigated for their ability to degrade dieldrin. Strain YK543 degraded 39.1 ± 8.8% of dieldrin during 30 days of incubation. Phylogenetic analysis demonstrated that strain YK543 was closely related to the fungus Phlebia brevispora Nakasone TMIC33929, which has been reported as a fungus that can degrade chlorinated dioxins and polychlorinated biphenyls. 9‐Hydroxydieldrin was detected as a metabolite in the cultures of strain YK543. CONCLUSION: It is important to select the microorganisms that degrade organic pollutants, and to identify the metabolic pathway for the development of bioremediation methods. Strain YK543 was selected as a fungus capable of degrading dieldrin. The metabolic pathway includes 9‐hydroxylation reported in rat's metabolism catalysed by liver microsomal monooxygenase. This is the first report of transformation of dieldrin to 9‐hydroxydieldrin by a microorganism. Copyright © 2010 Society of Chemical Industry     

The ability of indigenous micro-organisms to degrade isoproturon, atrazine and mecoprop within aerobic UK aquifer systems

The potential for the herbicides isoproturon, atrazine and mecoprop to degrade in the major UK aquifers of chalk, sandstone and limestone was studied using laboratory microcosms spiked at 100 microg litre(-1). Significant mecoprop degradation was only observed in sandstone groundwater samples. Atrazine transformation, based on the formation of metabolites, did occur in most groundwater samples, but only at a rate of 1-3% per year. A potential to degrade isoproturon was observed in groundwater samples from each of the aquifer types, with the most rapid and consistent degradation occurring at the sandstone field site. Biodegradation was confirmed by the formation of monodesmethyl- and didesmethyl-isoproturon. Isoproturon degradation potential rates obtained from the groundwater microcosms could not be correlated with either dissolved organic carbon or numbers of bacteria in the groundwater. It was noted that the ability of the groundwater at a field site to degrade a pesticide was not related to performance of the soil above.     

Implication of human drug transporters to toxicokinetics and toxicity of pesticides

Human membrane drug transporters are recognized as major actors of pharmacokinetics. Pesticides also interact with human drug transporters, which may have consequences for pesticide toxicokinetics and toxicity. The present review summarizes key findings about this topic. In vitro assays have demonstrated that some pesticides, belonging to various chemical classes, modulate drug transporter activity, regulate transporter expression and/or are substrates, thus bringing the proof of concept for pesticide‐transporter relationships. The expected low human concentration of pesticides in response to environmental exposure constitutes a key‐parameter to be kept in mind for judging the in vivo relevance of such pesticide‐transporter interactions and their consequences for human health. Existing data about interactions of pesticides with drug transporters remain, however, rather sparse; more extensive and systematic characterization of pesticide‐transporter relationships, through the use of high throughput in vitro assays and/or in silico methods, is, therefore, required. In addition, consideration of transporter polymorphisms, pesticide mixture effects and physiological and pathological factors governing drug transporter expression may help to better define the in vivo relevance of pesticide‐transporter interactions in terms of toxicokinetics and toxicity for humans. © 2019 Society of Chemical Industry     

Pest management programmes in vineyards using male mating disruption

Israeli vine growers have been reluctant to adopt the mating disruption technique for control of the European vine moth, Lobesia botrana Den. & Schiff. Since the chemically controlled honeydew moth, Cryptoblabes gnidiella Mill., coexists with the European vine moth, growers have maintained that the use of mating disruption would fail to bring about a significant reduction in pesticide use. In this study, the efficacy of mating disruption techniques against C. gnidiella was tested, as well as the effect of these methods on pesticide use and damage to clusters when the method was employed against both of the pests in wine grapes. Comparisons were made between plots treated with (1) L. botrana mating disruption pheromone, (2) L. botrana and C. gnidiella mating disruption pheromones and (3) control plots. A significant difference in the number of clusters infested with the developmental stages of the moths was seen between pheromone-treated plots and controls, while no such difference was observed between plots treated with one versus two pheromones. A similar pattern was observed in the number of insecticide applications; the greatest number of applications was used in control plots, followed by plots treated with L. botrana mating disruption pheromone and by plots treated with pheromones against both pests, in which no pesticides were applied.