Occurrence,Degradation and Fate of Pesticides During Composting

This paper reviews the findings of research reported in the currently available literature regarding the occurrence and transformations of pesticides through the composting process and the use of compost. Part I summarizes the composting process, pesticides and mechanisms of pesticide degradation. Part II reviews research studies concerning the occurrence and fate of pesticides during composting. Investigations of pesticide residues in composting feedstocks and finished compost detected few of the target pesticides. The compounds that were found occurred at low concentrations. The majority of the compounds detected were insecticides in the organochlorine category, including chemicals that have been banned from use in the U.S. for many years. Generally, organophosphate and carbamate insecticides and most herbicides were rarely detected. Comparisons of pesticide concentrations before and after composting also showed organochlorine compounds to be most resistant to biodegradation during composting. With some exceptions, pesticides in other categories decomposed moderately well to very well. Studies that followed the mechanisms of degradation indicate that mineralization accounts for only a small portion of pesticide disappearance. Other prominent fates include partial degradation to secondary compounds, adsorption, humification, and volatilization. In general the research results suggest that the pattern of pesticide degradation during composting is similar to the degradation observed in soils. With a few important distinctions, composting can be considered a biologically active soil environment in which degradation is accelerated. However, as some studies noted, composting does not always speed the degradation of all pesticides. The nature of the pesticide, specific composting conditions and procedures, the microbial communities present, and the duration of composting affect the extent and the mechanisms of degradation.     

Advances in pesticide environmental fate and exposure assessments

Globalization of markets and the growing world population increase threats of invasive and exotic species and place greater demands on food and fiber production. Pest management in both agricultural and nonagricultural settings employs established practices and new biological, chemical, and management technologies. Pesticides are an essential tool in integrated pest management. Without pesticides a significant percentage of food and fiber crops would be lost, infectious diseases would increase, and valuable native habitats would be devastated. Therefore, it is important to understand the environmental fate of pesticides and assess their potential exposure and associated risks to human health and the environment. This paper summarizes the Advances in Pesticide Environmental Fate and Exposure Assessment symposium held at the 231st National Meeting of the American Chemical Society (Atlanta, GA, 2006). The focus of the symposium was to provide current information on advances in pesticide environmental fate and exposure assessments. Thirty papers were presented on advances ranging from subcellular processes to watershed-scale studies on topics including chemical degradation, sorption, and transport; improved methodologies; use of modeling and predictive tools; exposure assessment; and treatment and remediation. This information is necessary to develop more effective pesticide use and management practices, to better understand pesticide fate and associated exposures and risks, to develop mitigation and remediation strategies, and to establish sound science-based regulations.     

Literature Review: Occurrence,Degradation and Fate of Pesticides During Composting: Part II: Occurrence and Fate of Pesticides in Compost and Composting Systems

This paper reviews the findings of research reported in the currently available literature regarding the occurrence and transformations of pesticides through the composting process and the use of compost. Part I summarizes the composting process, pesticides and mechanisms of pesticide degradation. Part II reviews research studies concerning the occurrence and fate of pesticides during composting. Investigations of pesticide residues in composting feedstocks and finished compost detected few of the target pesticides. The compounds that were found occurred at low concentrations. The majority of the compounds detected were insecticides in the organochlorine category, including chemicals that have been banned from use in the U.S. for many years. Generally, organophosphate and carbamate insecticides and most herbicides were rarely detected. Comparisons of pesticide concentrations before and after composting also showed organochlorine compounds to be most resistant to biodegradation during composting. With some exceptions, pesticides in other categories decomposed moderately well to very well. Studies that followed the mechanisms of degradation indicate that mineralization accounts for only a small portion of pesticide disappearance. Other prominent fates include partial degradation to secondary compounds, adsorption, humification, and volatilization. In general the research results suggest that the pattern of pesticide degradation during composting is similar to the degradatiion observed in soils. With a few important distinctions, composting can be considered a biologically active soil environment in which degradation is accelerated. However, as some studies noted, composting does not always speed the degradation of all pesticides. The nature of the pesticide, specific composting conditions and procedures, the microbial communities present, and the duration of composting affect the extent and the mechanisms of degradation.     

岷江下游（五通桥段）土壤污染特征及生态风险评价

为了解岷江下游（五通桥段）土壤污染特征及其生态风险,采用野外采样及室内测试方法分析了岷江下游（五通桥段）103个土壤样品中的农药残留量和重金属含量。结果表明,全部样品中六六六（HcHs）含量符合国家二级标准（500μg·kg-1）,大部分样品中滴滴涕（DDTs）含量符合国家二级标准,有机磷农药（OPPs）杀螟硫磷（60．40％）和溴硫磷（55．45％）超标率较高,重金属cd的地积累指数高达2．79。有机氯农药（OCPs）禁用20a后在区内的降解程度较高,OPPs在土壤中的大量残留是由于农药的无序使用,外源输入是导致重金属污染的主要原因。区内农药残留和重金属污染范围广,复合污染较严重,存在较大的生态风险。     

Contributions of pesticide residue chemistry to improving food and environmental safety: past and present accomplishments and future challenges

The principles of modern pesticide residue chemistry were articulated in the 1950s. Early authors pointed out the advantages of systematizing and standardizing analytical methods for pesticides so that they could be widely practiced and the results could be reproduced from one laboratory to the next. The availability of improved methods has led to a much more complete understanding of pesticide behavior and fate in foods and the environment. Using methods based largely upon gas chromatography (GC) and high-performance liquid chromatography (HPLC) coupled increasingly with mass spectrometry (MS) and MS(n) as the detection tool, residues can be measured at parts per billion levels and below in a variety of food and environmental matrices. Development of efficient extraction and cleanup methods, techniques such as ELISA, efficient sample preparation techniques such as QuEChERS, and automated laboratory and field instrumentation has also contributed to the tools available for use in modern pesticide residue analysis. As a result, great strides have been made in improving food and worker safety and in understanding environmental behavior and fate of pesticides. There are many challenges remaining in the field of pesticide residue chemistry that will continue to stimulate analytical chemists. New chemistries are emerging, often patterned on complex natural products. Analyzing for the parent chemicals and potentially multiple breakdown products will require analytical ingenuity. The development of more sensitive bioassays and knowledge of unintended side effects will challenge residue chemistry as well, as in the case of following the fate of environmental endocrine disruptors associated with some pesticides as well as nonpesticide contaminants from packaging materials and other familiar articles. Continued funding and other resources to ensure better training, international cooperation, and accelerated research and development activities will be a constant need in pesticide residue chemistry as it is for all areas of science that aim to mitigate or eliminate contaminants that can affect human and environmental health and safety.     

Degradation of pesticides in nursery recycling pond waters

Recycling or collection ponds are often used in outdoor container nursery production to capture and recycle runoff water and fertilizers. Waters in recycling ponds generally have high concentrations of nutrients, pesticides, and dissolved organic matter, as well as elevated salinity and turbidity. Little is known about pesticide degradation behavior in the unique environment of nursery recycling ponds. In this study, degradation of four commonly used pesticides diazinon, chlorpyrifos, chlorothalonil, and pendimethalin in waters from two nursery recycling ponds was investigated at an initial pesticide concentration of 50 microg/L. Results showed that the persistence of diazinon and chlorpyrifos appeared to be prolonged in recycling pond waters as compared to surface streamwaters, possibly due to decreased contribution from biotic transformation, while degradation of chlorothalonil and pendimethalin was enhanced. Activation energies of biotic degradation of all four pesticides were lower than abiotic degradation, indicating that microbial transformation was less affected by temperature than chemical transformation. Overall, the pesticide degradation capacity of recycling ponds was better buffered against temperature changes than that of surface streamwaters.     

辐照技术在食品污染物控制方面的研究进展

概述了辐照技术在控制食品真菌毒素、农药、兽药、渔药等方面残留污染的研究现状,并就辐照降解效果、降解机理、降解产物及毒性等内容加以阐述,总结出导致食品污染物降解的原因主要是由于辐照产生的自由基作用于物质结构中键能较低的位点,生成使毒性减小或增大的降解产物,并分析了辐照技术在食品污染物残留控制方面的局限性以及发展方向。     

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.     

Bacterial Community Composition and Genes for Herbicide Degradation in a Stormwater Wetland Collecting Herbicide Runoff

Stormwater wetlands collect and attenuate runoff-related herbicides, limiting their transport into aquatic ecosystems. Knowledge on wetland bacterial communities with respect to herbicide dissipation is scarce. Previous studies showed that hydrological and hydrochemical conditions, including pesticide removal capacity, may change from spring to summer in stormwater wetlands. We hypothesized that these changes alter bacterial communities, which, in turn, influence pesticide degradation capacities in stormwater wetland. Here, we report on bacterial community changes in a stormwater wetland exposed to pesticide runoff, and the occurrence of trz, atz, puh, and phn genes potentially involved in the biodegradation of simazine, diuron, and glyphosate. Based on T-RFLP analysis of amplified 16S rRNA genes, a response of bacterial communities to pesticide exposure was not detected. Changes in stormwater wetland bacterial community mainly followed seasonal variations in the wetland. Hydrological and hydrochemical fluctuations and vegetation development in the wetland presumably contributed to prevent detection of effects of pesticide exposure on overall bacterial community. End point PCR assays for trz, atz, phn, and puh genes associated with herbicide degradation were positive for several environmental samples, which suggest that microbial degradation contributes to pesticide dissipation. However, a correlation of corresponding genes with herbicide concentrations could not be detected. Overall, this study represents a first step to identify changes in bacterial community associated with the presence of pesticides and their degradation in stormwater wetland.     

Remediation of polycyclic aromatic hydrocarbon-contaminated soils using microbes and nanoparticles: A review

Polycyclic aromatic hydrocarbon(PAH) pollution is a global concern because of their toxicity to environment and ecosystem, which induces adverse effects on plants, animals, and humans. Hydrocarbons are mainly released from natural and anthropogenic activities, such as incomplete fuel combustion, leakages in oil pipelines, and the extensive use of pesticides; PAH contaminants include petroleum hydrocarbons(PHCs), halogenated hydrocarbons, chlorophenols, and pesticides. Bioremediation using microo...     

Behavior of Insecticide Chlorpyrifos on Soils and Sediments with Different Organic Matter Content from Provincia de Buenos Aires, República Argentina

Buenos Aires Province (República Argentina) has undergone, in the last years, a great increase in agricultural activities based on the incorporation of new technologies and reduction of diversity to meet the increasing food demand. The increase of intensive agricultural systems in Argentina involves the use of fertilizers and pesticides such as herbicides, insecticides, and fungicides. Chlorpyrifos is one of the insecticides most widely used in these crops and constitutes a risk for human health, birds, and aquatic biota such as macroinvertebrates and fishes. In order to assess the possible contamination that the use of this product may represent for the environment, it is necessary to study its interaction with the different types of soils because fate and transport of environmental pollutants may be influenced by their interactions with soil particles. The behavior of chlorpyrifos was analyzed through the study of the recoveries from spiked solid environmental matrices. A strong dependence with organic matter content was observed along with an important dependence with the initial concentrations employed. Here, we show that chlorpyrifos behavior on solid matrices not only depends on soil chemical composition. A significant dependence of recovery percentages with initial concentrations of the pesticide was evident in all cases. Recovery percentages decreased with an increase of the initial concentration employed, no matter the variations in matrices of chemical compositions.     

Degradation of Prototype Pesticides Submitted to Conventional Water Treatment Conditions: The Influence of Major Parameters

The behavior of several pesticides in aqueous solution, namely bifenthrin, amethrin (pyrethroid insecticides), endosulfan and endosulfan sulfate (organochlorine pesticides), disulfoton, methyl pyrimiphos, and phorate (organophosphorus pesticides), submitted to the conditions typically employed in water treatment stations was investigated. Continuous pesticide depletion was monitored by solid-phase microextraction sampling followed by gas chromatography–mass spectrometry analysis. The influence of major parameters (sodium hypochloride concentration, solution pH, and exposure time to ultraviolet (UV) light) was, thus, adequately established via two complementary approaches: factorial (2³, three variables—two levels) and Doehlert designs. Hence, the sodium hypochloride concentration and the solution pH produced distinct effects depending on the pesticide evaluated (for instance, acidic and basic media caused increasing rates of degradation for the organophosphorus/pyrethroid and organochlorine pesticides, respectively). Conversely, higher rates of degradation were achieved for all of the pesticides investigated when increased exposure times to UV radiation were employed. Finally, the exposure time to UV radiation that lead to complete degradation of disulfoton and endosulfan sulfate (organophosphorus and organochlorine pesticides, respectively) in aqueous media under ordinary conditions employed in water treatment stations was established; disulfoton and endosulfan sulfate were completely degraded after 10 and 40 h, respectively.     

Bioremedial potential of fenamiphos and chlorpyrifos degrading isolates: Influence of different environmental conditions

Previously isolated bacterial strains for chlorpyrifos and fenamiphos degradation were used to examine their potential as bioremedial agents in soils and water containing pesticide residues. Both, chlorpyrifos-degrading Enterobacter sp and fenamiphos-degrading consortium rapidly degraded pesticides when inoculated into natural and sterile water and soils. Degradation rate was slower in lower pH soils in comparison with natural and alkaline soils. Soil organic matter had no impact on pesticide degrading ability of isolates. Soil moisture <40% of maximum water-holding capacity slowed down degradation rate. The bacterial isolates were able to rapidly degrade fenamiphos and chlorpyrifos between 15 and 35 °C but their degradation ability was sharply reduced at 5 and 50 °C. Both groups of bacterial systems were also able to remove a range of pesticide degradation. An inoculum density of 10⁴ cells g⁻¹ of soil was required for initiating rapid growth and degradation. Ageing of pesticide in soils prior to inoculation produced contrasting results. Ageing of fenamiphos had no impact on subsequent degradation by the inoculated consortium. However, degradation of chlorpyrifos by Enterobacter sp after aging resulted in persistence of ∼10% of pesticide in soil matrix. Higher K_oc value of chlorpyrifos may have resulted in a lack of bioavailability of a smaller percentage of chlorpyrifos to degrading bacteria. Overall, this paper confirms bioremedial potential of a fenamiphos degrading consortium and a chlorpyrifos degrading bacterium under different soil and water characteristics.     

Herbicide 2,4-D: A Review of Toxicity on Non-Target Organisms

The intensive use of pesticides has increased exponentially in Brazil and worldwide due to the need to meet the food demands of a growing population. If the management/monitoring of the use of pesticides is adequately performed, it would not compromise the expected benefits or have negative effects on the environment as a whole. In order to examine the information available on herbicide use in Brazil and worldwide, this paper presents a review of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) and its chemical properties, action on target organisms, environmental fate, and toxicity to non-target organisms. This herbicide is a synthetic auxin used to control broad-leaved weeds, and the action in target organisms is well known. Although 2,4-D has been widely used worldwide, many studies have shown that this herbicide induces alterations in non-target organisms. Therefore, ecotoxicology studies are important to assess the risk the herbicides can be to different ecosystems. Thus, it is advised to use this herbicide and other pesticides with caution.     

农药残留的表面增强拉曼光谱快速检测技术研究现状与展望

果蔬农药残留危害人类健康,施药后,农药分布于其表皮和内部组织,果蔬表面农药绝对残留量低、不均匀,直接光谱检测表征难,而表面增强拉曼散射(surface-enhanced Raman scattering,SERS)技术具有分子级检测精度,可以有效扩增信号,在实现微量物质检测方面优势明显。为此,论文综述了国内外表面增强拉曼散射技术的研究现状,特别是详细介绍了通过设计合理的表面增强拉曼基底结构,实现农药残留信号增强的主要技术手段和表面增强拉曼光谱信号分析方法。在此基础上,指出农药残留的表面增强拉曼检测技术研究中的前沿热点问题,探讨并展望了表面增强拉曼技术在农药残留快速检测方面的发展趋势。基于表面增强拉曼的农药高灵敏度、快速检测表征技术,将在农药违禁使用和农药残留超标监管中有广阔应用前景。     

农产品/食品中农药残留快速检测方法研究进展

农药残留的识别和量化通常依赖于气相色谱法、高效液相色谱法、气/液相色谱-质谱联用法以及毛细管电泳法,这些方法需涉及大而贵重的仪器、费时的样品处理以及专门的技术培训。因此,建立在线、高灵敏度、高选择性、简单高效、低成本的农药残留快速检测方法和技术非常重要。该文综述了用于农产品/食品的农药残留分析快速检测方法,主要包括酶抑制法、免疫分析法、光谱法(包括可见/近红外、红外、拉曼和激光诱导击穿光谱等)以及各种生物传感器等,分别介绍了这些方法最新的研究进展,同时分析并总结了这些快速检测方法和技术的基本原理和特点。目前的研究在灵敏度、重复性、准确性方面存在着一些不足,商品化的农药残留检测仪器也比较单一。由于纳米生物技术、分子印迹技术和微流控技术等技术有着巨大的应用潜力,因此特别介绍了这些技术在农药残留分析中的应用。农药残留快速分析技术未来将会朝着检测仪器的小型化和集成化、多通道检测、无线通讯方向发展,提高快速检测方法和仪器的稳定性和可靠性是必然趋势。     

Application of an Air Ionization Device Using an Atmospheric Pressure Corona Discharge Process for Water Purification

Pesticides presently being discharged into the aquatic environment are not only toxic but also only partially biodegradable, they are not easily removed by conventional water treatment plants. Air ionization devices using an atmospheric pressure corona discharge process show great promise in improving degradation of chemical and biological contaminants in water purification plants. In order to assess the effectiveness of this air ionization apparatus, laboratory scale degradation experiments were carried out systematically in a bubble column reactor containing a variety of pesticides such as triazines, carbamates, phenyl urea derivates and chlorophenols relative to the addition of humic acid and inorganic chemicals as well as to pH variation. Chemical oxygen demand (COD) decreased with air ionization treatment and the rate of the biological oxygen demand related to this (BOD/COD) showed improved pesticide biodegradability. Changes in water toxicity were monitored by Daphnia- and Luminescence Bacteria tests. This novel water treatment process is shown to be a potent oxidation technique for persistent organic pollutants such as pesticides.     

化学农药施用技术与粮食安全

化学农药在保证粮食供应方面发挥了重要作用,这是粮食安全的传统意义。但是农药大量投入导致农产品中农药残留超标,影响了粮食安全的另一个方面。化学农药对农产品的负面影响与农药的施用方法有密切的关系。发达国家在改善环境质量、提高农产品品质的同时,建立了完善的农药使用和管理法规,并通过农药施用技术改造,大大提高了农药的利用率,从而基本解决了农药环境污染和农产品农药残留超标的问题。我国在农药施用过程中,由于长期忽视施用质量的提高,加之缺乏相应的管理措施,农药对病虫草害的防治效果一直是以农药的大量投入来保证的,对农产品质量造成了很大的影响。要解决农药的使用问题,首先须通过行政管理和立法限制单位土地面积上农药的施用量,其次建立农户农药购买登记制度,保证农户实际所用农药不会超过允许使用量,最后加强农药施用者的培训,培训合格后发给操作证,持证施用农药。确保这3个环节的落实,可激发农户农药施用技术的改进,使有限投入的农药发挥最大的效用,减少农药用量,缓解农药与环境及农产品质量之间的矛盾     

三唑类农药的微生物降解研究进展

三唑类农药是一种广泛使用的防治植物病害的杀菌剂和植物生长调节剂，可通过抑制麦角甾醇的合成阻碍病原菌的细胞壁形成，从而起到防治作物病害的作用，也能抑制植物赤霉素合成延缓植物生长；但因大范围应用及其难以降解的特性，污染环境和影响人类健康。为给三唑类农药的微生物降解提供参考，基于文献研究，梳理总结了三唑类农药降解菌的种类、影响降解的环境因素和降解机理方面的研究进展，明确了微生物在不同环境中能有效降解三唑类农药，微生物降解技术有望应用于治理三唑类农药造成的环境污染。