Contamination Characteristics and Degradation Behavior of Low-Density Polyethylene Film Residues in Typical Farmland Soils of China

Low-density polyethylene (LDPE) film residues left in farmlands due to agricultural activities were extensively investigated to evaluate the present pollution situation by selecting the typical areas with LDPE film application, including Harbin, Baoding, and Handan of China. The survey results demonstrated that the film residues were ubiquitous within the investigaed areas and the amount reached 2400–8200 g ha^?1. Breakage rates of the film residues were almost at the same level in the studied fields. There were relatively small amounts of film residues remaining in neighboring farmland fields without application of LDPE film. The studies showed that the sheets of LDPE residues had the same oxidative deterioration, which was probably due to photodegradation instead of biodegradation. The higher molecular weight components of the LDPE film gradually decreased, which were reflected by the appearance of some small flakes detached from the film bodies. LDPE films in the investigated fields gradually deteriorated and the decomposing levels developed with their left time increasing. The degradation behaviors of LDPE films were confirmed by using Fourier transform infrared (FTIR), scanning electron microscopic (SEM), and gel permeation chromatography analyses.     

Simple analytical method for determination of pesticide residues in human serum by liquid chromatography tandem mass spectrometry

The aim of this study was to develop an analytical method for the determination of residues of organophosphorus and carbamate pesticides which are widely used in Tunisia. This method involves a liquid-liquid extraction procedure followed by liquid chromatography tandem mass spectrometry (LC/MS/MS) for the identification and quantification of compounds. Ionization of molecules was performed by the electrospray mode. Multiple reactions monitoring (MRM) was the acquisition mode used for the monitoring of two MS/MS transitions for each compound. The average recoveries obtained, at three different fortification levels, ranged between 65% and 106% for most of the pesticides studied, except for methamidophos (lower than 25%).The linearity of the method was in the range of 5 to 50 μ g/L with a correlation coefficient from 0.995 to 0.999, depending on the analyte. The estimated limit of detection and limit of quantification were 2 μ g/L and 5 μ g/L, respectively. The precision of the analytical procedure was satisfactory and the coefficients of variation, evaluated at three concentration levels were lower than 15% for most pesticides studied. The application of the method was investigated in a population of agricultural workers chronically exposed to various pesticides some of which, such as carbofuran, carbendazim, methomyl and pirimicarb, were detected in some serum samples.     

Review of advances in the thin layer chromatography of pesticides: 2008–2010

Techniques and applications of thin layer chromatography (planar chromatography) for the separation, detection, qualitative and quantitative determination, and preparative isolation of pesticides and their metabolites and other related compounds are reviewed for the period from November 1, 2008 to November 1, 2010. Analyses are described for a variety of samples types and pesticide classes. In addition to references on residue analysis, studies such as pesticide structure-retention relationships, identification and characterization of plant pesticides and synthesized pesticides, metabolism, degradation, mobility, identification of biomarkers for detection of herbicide effects in plants, and lipophilicity are covered.     

Urinary dialkyl phosphate levels before and after first season chlorpyrifos spraying amongst farm workers in the Western Cape,South Africa

The study investigated urinary levels of dialkyl phosphates resulting from pesticide exposure amongst 40 farm workers. Workers were tested (urinary dialkyl phosphate levels, anthropometry, short exposure questionnaire) before and after the first day of seasonal chlorpyrifos spraying. Median baseline urinary dialkyl phosphates was high amongst both non-applicators (1587.5 μg/g creatinine, n = 8) and applicators (365.6 μg/g creatinine, n = 9). There was not much evidence of an increase in post-spray dialkyl phosphates levels from pre-spray levels amongst both applicators and non-applicators. Hours mixing, spraying, driving a tractor and hours worked by non-applicators were not significantly associated with an increase in post-spray dialkyl phosphate levels, adjusting for age, height, weight, gender, use of empty pesticide containers and self-reported kidney problems. Past applicator status was weakly positively associated with pre-spray dialkyl phosphate levels adjusting for age, height, weight, and gender, self-reported kidney problems, smoking and alcohol (β= 1019.5, p = 0.307, R²= 0.28). The high dialkyl phosphate levels call for an epidemiological investigation into the health effects of organophosphorous pesticides.     

Determination of 28 pesticides applied on two tomato cultivars with a different surface/weight ratio of the berries,using a multiresidue GC-MS/MS method

The behavior of 28 pesticides on two tomato cultivars with a different surface/weight (S/W) ratio of the berries (S/W, Birikino vs. Tombola) was studied, in order to provide appropriate indications about their persistence on crops reaching the pre-harvest interval (PHI). Quantitative analysis was performed using a GC MS/MS method. Birikino cv. (BIR) was a “cherry type tomato” with a double S/W ratio compared with Tombola cv. (TOM). The results showed a different pesticide behavior. Azoxystrobin, Boscalid, Bupirimate, Difenoconazole, Etofenprox, Iprodione, Mepanipyrim, Myclobutanil, Tebuconazole, Zoxamide, Metalaxyl M, Pyrimethanil, Tetraconazole, Benalaxyl, Cyprodinil, Fenamidone, Famoxadone and Fludioxonil immediately after treatments showed residues on BIR higher than TOM, and this behavior is consistent with its greater exposed surface. BIR showed higher decay rates of these pesticides during the whole trial, nevertheless residue averages remained higher than TOM reaching the time of harvest. Residues at the PHI were all below their Maximum Residue Levels (MRLs), but data indicated that they could exceed their legal limits especially if the above-mentioned active ingredients were employed more than once per crop cycle on cherry type tomatoes. As regards to Chlorpyrifos, Chlorpyrifos methyl, Triadimenol, Pyridaben and Tebufenpyrad, no different residual behavior related to S/W ratio of the cultivars was observed. Even in this case, residues at the PHI were all below MRLs. As for Cyfluthrin, Deltamethrin, Lambda cyhalothrin, Etoxazole and Cyproconazole, residues were lower than the limit of quantitation (LOQ) of the analytical method just after the treatment, according to their low doses of employment.     

Degradation of ethylenethiourea pesticide metabolite from water by photocatalytic processes

In this study, photocatalytic (photo-Fenton and H₂O₂/UV) and dark Fenton processes were used to remove ethylenethiourea (ETU) from water. The experiments were conducted in a photo-reactor with an 80 W mercury vapor lamp. The mineralization of ETU was determined by total organic carbon analysis, and ETU degradation was qualitatively monitored by the reduction of UV absorbance at 232 nm. A higher mineralization efficiency was obtained by using the photo-peroxidation process (UV/H₂O₂). Approximately 77% of ETU was mineralized within 120 min of the reaction using [H₂O₂]₀ = 400 mg L^?1. The photo-Fenton process mineralized 70% of the ETU with [H₂O₂]₀ = 800 mg L^?1 and [Fe²⁺] = 400 mg L^?1, and there is evidence that hydrogen peroxide was the limiting reagent in the reaction because it was rapidly consumed. Moreover, increasing the concentration of H₂O₂ from 800 mg L^?1 to 1200 mg L^?1 did not enhance the degradation of ETU. Kinetics studies revealed that the pseudo-second-order model best fit the experimental conditions. The k values for the UV/H₂O₂ and photo-Fenton processes were determined to be 6.2 × 10^?4 mg L^?1 min^?1 and 7.7 × 10^?4 mg L^?1 min^?1, respectively. The mineralization of ETU in the absence of hydrogen peroxide has led to the conclusion that ETU transformation products are susceptible to photolysis by UV light. These are promising results for further research. The processes that were investigated can be used to remove pesticide metabolites from drinking water sources and wastewater in developing countries.     

百菌清农药残留的SPE-GC检测

对环境水样中百菌清农药残留进行了SPE-GC分析方法研究。环境水样通过Florisil柱富集、净化,3 mL乙酸乙酯洗脱,GC-ECD进行分析检测。实验表明,百菌清农药残留在0.01~10 mg/L范围内线性关系良好,相关系数为0.9993。外标法定量,检出限为0.0035 mg/L,对实际水样进行加标回收,回收率范围在93.47%~100.14%之间,6次重复测定相对标准偏差在3.97%~4.96%之间,并将方法应用于周边环境地表水的检测。该方法具有简便,快速,准确,灵敏度高等特点,能满足环境水样中农药残留分析要求。     

某废弃农药生产场地地下水挥发性有机物污染健康风险评价

对常州某废弃农药生产场地地下水中挥发性有机物污染状况和健康风险进行了调查评价。结果表明,该场地地下水中挥发性有机物污染以苯系物、氯代苯类和氯代烃类为主;部分点位地下水健康风险评价结果超出可接受范围,可能危害人体。     

AgInput: An Agricultural Nutrient and Pesticide Source Model

Agriculture can be a major nonpoint source (NPS) of nutrient and pesticide contamination in the environment. Available databases do not provide accurate and dynamic data on fertilizer and pesticide application, which limits the ability of complex watershed models to simulate contaminant loads into impaired water bodies. A model for estimating agricultural nutrient and pesticide input for watershed modeling has been developed. Climate, soils, and major agricultural operations are considered within the model, so that it can be adapted to any watershed or subregion within a watershed. The timing of the agricultural operations is a function of the weather data, providing realistic results at daily, monthly, or annual application rates. The model also predicts irrigation demand and biomass production, which can be used to calibrate the model. Model output can be used in any watershed model that considers agricultural land uses. Two case studies were evaluated, using grape vineyards in the Napa River and strawberry production in Newport Bay as examples. The predicted time to maturity corresponded well with actual data. Irrigation and fertilizer needs were very sensitive to weather input. Although the model can generate weather from long-term averages, the simulated results are best when at least observed precipitation and temperature are provided, to capture extreme events. The model has data for 98 crops and 126 pesticides, based on the California Department of Pesticide Regulation database. The databases are easily modifiable by the user to adapt them to local conditions. The output from AgInput is much needed for watershed modeling and for development of total maximum daily loads (TMDLs), based on realistic targets of irrigation, nutrient, and pesticide inputs. The model is available for free download at .     

在线固相萃取-HPLC法测定公共绿地土壤中新烟碱类农药残留

土壤样品经二氯甲烷-乙腈混合溶液超声提取后,用PEP固相萃取柱在线净化,再用HPLC法测定样品中吡虫啉、啶虫脒、噻虫嗪、噻虫啉、烯啶虫胺等5种新烟碱类农药残留。通过优化试验条件,使该方法在0.01 mg/L~2.00 mg/L范围内线性良好,当取样量为3.00 g时,方法检出限为0.002 mg/kg~0.003 mg/kg。8种土壤样品3个质量比水平的加标回收率为72.5%~119%,RSD均低于9.6%。