拟除虫菊酯类农药微生物降解研究进展

拟除虫菊酯类农药是杀虫剂中的第三大类,这类农药残留已成为目前农产品中的主要农药残留类型之一。而微生物在降解农药残留中具有重要的作用,微生物降解技术已成为去除农药残留的绿色生产技术。拟除虫菊酯类农药的微生物降解国内外已有的研究主要集中在降解现象,菌株的分离、鉴定及生理生化特性,酶学,不同光学异构体的降解、降解途径等方面,本文对此进行了较详细的回顾,并对将来的研究方向进行了展望。     

拟除虫菊酯类农药光降解的研究进展

拟除虫菊酯类农药的广泛使用,引起的环境问题及农业生产与日常生活中的安全问题日益突出。本文综述了拟除虫菊酯类农药的光降解行为,包括自然光照降解、紫外光照降解、光催化降解、光照下的微生物降解及辐照降解;探讨了影响光降解的因素,如光照强度、p H、氧气、溶剂、金属离子、腐殖质,及与其他农药的交互作用等。最后,总结了拟除虫菊酯类农药的光降解机理。     

甲氰菊酯在土壤中的降解及对蚯蚓的毒性效应研究

拟除虫菊酯作为全球第三大杀虫剂品种，在农业生产中广泛使用，同时也带来了一系列不利的环境影响。然而，目前有关拟除虫菊酯在土壤环境中的残留行为和风险评估报道较少。以典型拟除虫菊酯类杀虫剂甲氰菊酯(FEN)为研究对象，重点探究其在不同性质土壤中的降解行为以及对典型土壤生物蚯蚓的毒性效应。结果表明，甲氰菊酯在碱性土壤中的降解速度快于酸性土壤，同时在非灭菌土壤中的降解速度为灭菌土壤的4倍。因此，土壤酸碱度和微生物是影响FEN在土壤中降解快慢的主要因素。此外，在降解过程中检测到甲氰菊酯主要代谢物3-苯氧基苯甲酸(3-PBA)的生成。蚯蚓富集结果表明，FEN在蚯蚓体内的含量先升高后降低，最大生物富集因子为0.3。亚急性毒性结果表明，高剂量（5 mg?kg-1）甲氰菊酯暴露14 d后，蚯蚓体内蛋白质含量显著降低（P<0.05），细胞色素P450（CYP450）、羧酸酯酶（CarE）、谷胱甘肽-S-转移酶（GST）、超氧化物歧化酶（SOD）、过氧化氢酶（CAT）活性和丙二醛（MDA）含量均显著增加（P<0.05），同时存在剂量效应，证实土壤中残留的FEN对蚯蚓具有毒性效应。本文对甲氰菊酯在土壤环境中的降解行为研究以及生态毒性风险评估具有重要的指导意义。     

拟除虫菊酯在底泥中的归趋及其生物效应

拟除虫菊酯是一类高疏水性仿生杀虫剂,进入环境中易被颗粒物或油滴吸附,最终聚积在底泥沉积物中;同时它可以随水流或胶体等途径发生迁移,已被研究证实在使用及未使用拟除虫菊酯地区的河流、湖泊底泥中均检测到其残留。本文介绍了底泥中拟除虫菊酯的来源、归趋、生物效应,重点分析了拟除虫菊酯的吸附/解吸、降解作用及湿地生态系统对其归趋的影响;讨论了拟除虫菊酯的水生生物毒性、生物富集作用等生物效应,评述了其疏水性及生物可利用性对其毒性的影响,可为拟除虫菊酯水生生态系统风险评价等研究提供重要参考信息。     

浓硫酸纯化-气相色谱法测定土壤中拟除虫菊酯农药残留

建立了土壤中拟除虫菊酯类农药新的前处理方法。样品以乙腈提取,浓硫酸-乙醇进行纯化,毛细管柱气相色谱法测定土壤中的拟除虫菊酯农药。结果表明:4种菊酯在3种土壤样品中的添加回收率在84.14%～105.51%之间,变异系数为1.24%～5.82%。该方法具有省时、省溶剂、操作简单、纯化效果好、实用性强的特点。     

土壤中多种拟除虫菊酯类农药残留的提取与检测方法

研究建立了土壤中甲氰菊酯、三氟氯氰菊酯、顺式氯菊酯、反式氯菊酯、氯氰菊酯、氟氰戊菊酯、氰戊菊酯和溴氰菊酯8种拟除虫菊酯类农药残留的超声提取-硅胶柱净化-气相色谱(GC)检测方法。以石油醚/丙酮(v/v,2:1)溶液为有机提取剂,超声提取土壤样品,旋转蒸发仪浓缩,经自制硅胶柱以10 ml石油醚/乙酸乙酯(v/v,9:1)溶液进行分离净化并浓缩后用正己烷定容,样品采用气相色谱法FID检测器检测。研究结果表明,该方法对土壤样品中8种拟除虫菊酯的加标回收率较高,平均值在84.9%~101.3%之间。通过实验优化了8种拟除虫菊酯类化合物的分离和测定条件。该提取和检测方法具有简便、快捷、成本低、净化效果和重现性好等特点,适合于土壤中痕量拟除虫菊酯类农药残留的测定。     

拟除虫菊酯类农药的色谱分析法

拟除虫菊酯类杀虫剂具有用量低，效果好，杀虫谱广，对温血动物毒性低等优点，目前广泛用于防治农业害虫。在拟除虫菊酯的研究和生产过程中，在环境影响农药残留调查时都要求提供准确快速的测定方法。但是由于拟除虫菊酯分子结构的特点，它们都包含多个光学异构体，这些异体栖往往又具有不同的生物活性，因此必须解决异构物的分析方法问题，本总结了近年来拟除虫菊酯的气相和液相色谱分析方法进展，并介绍了作自己的工作经验。     

农药污染土壤的微生物修复研究进展

本文介绍了土壤中农药污染的现状与危害,总结了土壤农药污染的微生物修复的历史背景、研究现状,重点介绍了降解农药的微生物与农药污染土壤微生物修复的研究进展,并总结了国内外微生物修复的产业化现状,对土壤农药污染微生物修复进行了预测和展望,指出了需要进一步研究的领域。     

有机磷农药污染土壤的微生物降解研究进展

有机磷农药是目前我国使用量最大的农药之一,严重污染环境和生态系统,并通过食物链在生物体内富集,进而危害人类健康。微生物降解技术具有降解效率高、代谢途径多、无二次污染的优势,是目前清除环境中有机磷农药的主要手段,能有效降低有机磷农药的危害。目前有机磷农药的降解微生物主要是通过实验室纯培养方法获得,与自然生态环境中存在的降解功能性微生物信息差异较大,而利用不可培养方法识别功能性微生物的技术具有广阔的应用前景。本文从有机磷农药的使用情况及引发的环境问题出发,概述了有机磷农药在土壤中的迁移转化途径,稳定同位素探测技术和磁性纳米材料等不可培养方法对有机磷农药降解功能性微生物的识别,微生物降解有机磷农药污染土壤的功能基因、降解途径及降解机理;探讨了植物–微生物联合修复在有机磷农药污染土壤修复中的作用,并分析了环境因子及农药自身性质对有机磷农药降解的影响;最后,讨论了微生物降解技术存在的问题及今后研究方向。     

土壤含水量和胡敏酸对有机氯农药降解的影响

尽管我国从1983年就开始禁用有机氯农药，但环境中仍有大量残留存在。土壤中污染物的残留是吸附、降解和迁移等各种理化作用和生物作用的综合结果，其中降解是制约其残留量的关键过程。大量研究表明，影响土壤中农药降解的主要环境因素包括土壤有机质、土壤温度、土壤pH和土壤含水量等，因为这些因素显著影响着土壤微生物的数量和活性。微生物代谢所需的营养物质有一部分来自农药和土壤有机质，土壤中微生物对其降解起着重要作用。胡敏酸（HA）是土壤有机质的主要组分，因此以HA代表土壤有机质对农药降解的影响是合理的，也有很多关于HA对农药在土壤中吸附等环境行为影响的研究报道。     

Mathematical model for microbial degradation of pesticides in the soil

A theoretical model for the microbial degradation of pesticides in soil is presented. This model takes into account an important soil property, the adsorption capacity, and the probable modification of the soil microflora after the pesticide was introduced into the soil.The main assumptions of the model are that: (1) the degradation takes place simultaneously in two ways, by metabolism and by co-metabolism; (2) the pesticide exhibits a lethal effect on a sensitive fraction of the soil microflora; (3) a fraction of this microflora is insensitive and does not degrade the pesticide; (4) the various fractions of the soil microflora can grow at the expense of both the pesticide and soil carbon (metabolizing microorganisms) or of the soil carbon alone (co-metabolizing, sensitive and insensitive microbial populations).Two numerical examples are given to illustrate the soil adaptation phenomenon.The validity of different hypotheses included in the model when applied to the soil system are discussed by comparing the results of the simulations to some experimental data concerning the modification of the degrading soil microflora or by comparing some physico-chemical and biological parameter values used in the calculations to published values.     

Kinetic Modelling of Pesticidal Degradation and Microbial Growth in Soil

This paper discusses such models for the degradation kinetics of pesticides in soil as the model expressing the degradation rate as a function of two varables:the pesticide concentration and the number of pesticide degrading microorganisms,the model expressing the pesticide concentration as explicit or implicit function of time ,and the model exprssing the pesticide loss rate constants as functions of temperature,These models may interpret the degradation curves with an inflection point.A Kinetic model describing the growth processes of microbial populations in a closed system is reported as well.     

Cross-enhancement of accelerated biodegradation of organophosphorus compounds in soils: Dependence on structural similarity of compounds

Rates of degradation of seven organophosphate nematicides and insecticides were examined in two soils known to show accelerated biodegradation of fenamiphos and one soil known to show accelerated biodegradation of chlorpyrifos. The results indicated that several organophosphate insecticides and one nematicide were susceptible to cross-enhanced degradation in the soil showing accelerated biodegradation of chlorpyrifos. No cross-enhancement was observed in the two soils showing accelerated degradation of fenamiphos. Fumigation resulted in the complete inhibition of pesticide degradation in all soils. The data suggested that the cross-enhancement of selected pesticides in chlorpyrifos-degrading soil was dependent on the structural similarity of the compounds. Mechanisms of degradation of pesticide in soil support this hypothesis, where structurally similar compounds (diazinon, parathion, coumaphos and isazofos) were hydrolysed by microbial activity in chlorpyrifos-degrading soil but the degradation products were accumulated. Enhanced degradation of chlorpyrifos and fenamiphos was found to be stable in the laboratory condition for a period of one year.     

Relationships between microbial biomass and dissipation of 2,4-D and dicamba in soil

A study was conducted to evaluate relationships between microbial biomass and the dissipation of 2,4-D (2,4-dichlorophenoxy acetic acid) and dicamba (2-methoxy-3,6-dichlorobenzoic acid) in soil. We hypothesized that the size of the microbial biomass should be a strong predictor of the pesticide degradation capacity of a particular soil. Soils with a high microbial biomass should have relatively high levels of general microbial activity and should support a diversity of degradation pathways. In this study, we quantified the degradation of 2,4-D and dicamba in a range of soils with different concentrations of microbial biomass. The herbicides 2,4-D and dicamba were added to similar soils collected from five different land use types (home lawn, cornfield, upland hardwood forest, wetland forest, and aquifer material) and incubated for 80 days under laboratory conditions. Herbicide residue and microbial biomass (C and N) analyses were performed 5, 10, 20, 40, and 80 days following herbicide application. Microbial biomass-C and -N and soil organic matter content were positively correlated with dissipation of 2,4-D and dicamba. The results suggest that there are relationships between the size of the soil microbial biomass and the herbicide degradation capacity of an ecosystem. These relationships may be useful for developing approaches for evaluating and predicting the fate of pesticides in different ecosystems.     

Relationships between microbial biomass and dissipation of 2,4-D and dicamba in soil

A study was conducted to evaluate relationships between microbial biomass and the dissipation of 2,4-D (2,4-dichlorophenoxy acetic acid) and dicamba (2-methoxy-3,6-dichlorobenzoic acid) in soil. We hypothesized that the size of the microbial biomass should be a strong predictor of the pesticide degradation capacity of a particular soil. Soils with a high microbial biomass should have relatively high levels of general microbial activity and should support a diversity of degradation pathways. In this study, we quantified the degradation of 2,4-D and dicamba in a range of soils with different concentrations of microbial biomass. The herbicides 2,4-D and dicamba were added to similar soils collected from five different land use types (home lawn, cornfield, upland hardwood forest, wetland forest, and aquifer material) and incubated for 80 days under laboratory conditions. Herbicide residue and microbial biomass (C and N) analyses were performed 5, 10, 20, 40, and 80 days following herbicide application. Microbial biomass-C and -N and soil organic matter content were positively correlated with dissipation of 2,4-D and dicamba. The results suggest that there are relationships between the size of the soil microbial biomass and the herbicide degradation capacity of an ecosystem. These relationships may be useful for developing approaches for evaluating and predicting the fate of pesticides in different ecosystems.     

Short- and long-term effects on soil microorganisms of two potato pesticide spraying sequences with either glufosinate or dinoseb as defoliants

Pesticides applied to potatoes in Swiss integrated farming were evaluated with respect to their cumulative effects on soil microorganisms in a study performed under controlled conditions. Potatoes were treated with a series of herbicides, fungicides and insecticides and were finally defoliated either by hand in the untreated control or with the total herbicides Basta (active ingredient glufosinate) or Super Kabrol (active ingredient dinoseb). Twenty-one and 135 days after the last pesticide application soil samples were collected and analysed for microbial biomass, activity and community level substrate utilisation (CLSU). In the short-term, cumulative pesticide side-effects on microbial biomass and microbial activities averaged 19% for the spraying sequence with glufosinate and 45% for the one with dinoseb. After 135 days these values merely returned to normal. Remarkably, only the CLSU patterns based on Biolog ecoplates showed a lasting effect. We consider this an indication of change in microbial catabolic capabilities that may be due either to induced pesticide degradation capabilities or to a change within the microbial community. Even though this method has drawbacks in comparison to molecular methods of microbial community analysis—in particular because of its culture dependence—it gives a first indication that changes in the microbial community may have occurred. The microbial community structure may then be analysed in more detail with molecular tools. As an additional tool to conventional testing of agrochemicals, microbial community analysis may help in the interpretation of pesticide side-effects and open up new possibilities for their observation.     

Almond organophosphate and pyrethroid use in the San Joaquin Valley and their associated environmental risk

Purpose

The purpose of the present study are to analyze the temporal and spatial trends of the pesticide use on almond crops and assess their associated risk to soil, surface water, and air, and to investigate the impacts of pesticide risk on biodiversity.

Materials and methods

California Pesticide Use Report database was used to determine the organophosphate (OP) and pyrethroid use trends in the San Joaquin Valley for almonds from 1992 to 2005. Environmental potential risk indicator for pesticides model was employed to evaluate associated environmental relative risks in soil and in surface water. Emission potential of pesticide product was used to estimate the air relative risk. Geographical Information System was used to delineate the spatial distribution patterns of environmental risk evaluation in almonds and biodiversity.

Results and discussion

OP pesticide use has been declined in any measurement in almonds. However, a converse result was found for pyrethroid pesticide. Pesticide use trends reflect the profound changes in pest management strategies in the California almond farm community. The model results in this study showed evidence that pyrethroid posed less environmental risks to soil, air, and water resources than OP. The physiochemical properties of pyrethroid reflect a strong tendency to adsorb to organic carbons, and therefore, potentially move off-site attached to sediment. Once in sediments, they can be bioavailable to the aquatic food web. So, more future study on environmental model should address pyrethroid environmental risk on sediment. Ecologists revealed that endangered species diversity has good correlation with total species diversity, so we developed a biodiversity index by using the survey data of endangered and rare animals in California. The results showed a negative relationship between count of animal occurrence and predicted environmental risk. This result would be useful to help conserve California??s biological diversity by providing information to promote agricultural management and land-use decisions.

Conclusions

Pesticide use trend is directly related to environmental risk. Pyrethroid posed less environmental risk than OP in this study. And also, this study got a noticeable result that pesticide uses in intensive agriculture and their associated environmental risks pose negative impacts on biodiversity.     

黄土高原风蚀水蚀交错带沟岸对柠条林地土壤水分的影响

The most serious erosion on the Loess Plateau of China exists in the wind-water erosion crisscross region where the annual precipitation is about 400 mm, the ecological environment is very fragile, and water is the key limiting factor for improving the environment. In this study, changes of soil moisture content for Caragana korshinskii Kom. shrubland in the gully bank of the Loess Plateau were studied using the methods of soil sampling and neutron probe. A typical gully （75 m long, 28 m wide, and 10 m deep） was selected, and six neutron probe access tubes （6 m long） were installed at points 50, 100, 200, 300, 400, and 500 cm from the gully border for obtaining soil moisture data from July to October 2004 at approximately 10 d intervals. Soil samplings were simultaneously carried out for moisture determination at the six points. Results showed that the soil moisture of the shrubland in the gully bank significantly varied between 300 and 400 cm in the horizontal direction and up to 600 cm in vertical direction of the gully. Seasonal changes in soil moisture revealed a curve with a single peak that occurred at the end of August or early September. A linear regression equation was fit for soil water storage and the distance from the gully border, with coefficients depending on rainfall characteristics, sampling point, and time of measurement.     

Degradation of pesticides in biobeds: the effect of concentration and pesticide mixtures

Biobeds aim to create an environment whereby any pesticide spills are retained and then degraded, thus reducing the potential for surface or groundwater contamination. Biobeds may receive high concentrations of relatively complex mixtures of pesticides. The effects of concentration and pesticide interaction on degradation rate were therefore investigated. At concentrations up to 20 times the maximum recommended application rate for isoproturon and chlorothalonil, the rate of degradation in topsoil and biomix decreased with increasing concentration. With the exception of isoproturon at concentrations above 11 mg kg(-1), degradation was quicker in biomix (a composted mixture of topsoil, compost, and wheat straw) than in topsoil. One possible explanation for faster isoproturon degradation in topsoil as compared to biomix may be that previous treatments of isoproturon applied to the field soil as part of normal agricultural practices had resulted in proliferation of microbial communities specifically adapted to use isoproturon as an energy source. Such microbial adaptation could enhance the performance of a biobed. Studies with a mixture of isoproturon and chlorothalonil showed that interactions between pesticides are possible. In biomix, the degradation of either isoproturon or chlorothalonil was unaffected by the presence of the other pesticide, whereas in topsoil, isoproturon DT(50) values increased from 18.5 to 71.5 days in the presence of chlorothalonil. These studies suggest that biobeds appear capable of treating high concentrations of more than one pesticide.