Relation Between Flow and Temporal Variations of Nitrate and Pesticides in Two Karst Springs in Northern Alabama1

Abstract: Two karst springs in the Mississippian Carbonate Aquifer of northern Alabama were sampled between March 1999 and March 2001 to characterize the variability in concentration of nitrate, pesticides, selected pesticide degradates, water temperature, and inorganic constituents. Water temperature and inorganic ion data for McGeehee Spring indicate that this spring represents a shallow flow system with a relatively short average ground‐water residence time. Water issuing from the larger of the two springs, Meridianville Spring, maintained a constant temperature, and inorganic ion data indicate that this water represents a deeper flow system having a longer average ground‐water residence time than McGeehee Spring. Although water‐quality data indicate differing short‐term responses to rainfall at the two springs, the seasonal variation of nitrate and pesticide concentrations generally is similar for the two springs. With the exception of pesticides detected at low concentrations, the coefficient of variation for most constituent concentrations was less than that of flow at both springs, with greater variability in concentration at McGeehee Spring. Degradates of the herbicides atrazine and fluometuron were detected at concentrations comparable to or greater than the parent pesticides. Decreases in concentration of the principal degradate of fluometuron from about July to November indicate that the degradation rate may decrease as fluometuron (demethylfluometuron) moves deeper into the soil after application. Data collected during the study show that from about November to March when recharge rates increase, nitrate and residual pesticides in the soil, unsaturated zone, and storage within the aquifer are transported to the spring discharges. Because of the increase in recharge, fluometuron loads discharged from the springs during the winter were comparable to loads discharged at the springs during the growing season.     

树皮在大气有机氯农药监测中应用的研究进展

有机氯农药(Organochlorine pesticides,OCPs)曾在全世界被大量使用,即使禁用多年,仍能在各种环境介质中被广泛检出,对生态环境和人体健康存在着潜在的威胁。因此OCPs的环境迁移和归趋一直是该领域的研究热点。树皮是一种天然的被动采样器,能够很好的反映出大气有机物长期的污染程度。本文简要论述了树皮作为被动采样器在大气污染物监测研究中应用的优势,并对OCPs在树皮中的残留浓度、特征及影响其富集的因素进行了探讨,最后特别针对具有手性的OCPs在树皮中的对映体选择性特征进行了评述。     

农药内分泌干扰效应研究进展

农药作为农业生产过程中的一类重要生产资料,主要用作杀虫剂、杀菌剂和除草剂等。由于农药的大量使用,目前在各类农产品及各种环境介质中都能被检测到,对饮食健康和环境安全带来潜在危害。研究发现,许多农药为内分泌干扰物,其能够干扰人类和其他生物体的内分泌系统正常功能。本文在总结国内外相关研究的基础上,对农药内分泌干扰效应的作用机理及筛选模型进行总结,对有机氯、有机磷和拟除虫菊酯等各类农药的内分泌干扰效应研究进展进行综述,并提出深入探究农药致毒作用机制和低剂量下多种农药联合毒性是本领域的重要研究方向。     

Utilization of long duration high-volume sampling coupled to SPME-GC-MS/MS for the assessment of airborne pesticides variability in an urban area (Strasbourg,France) during agricultural application

Atmospheric samples have been collected between 14 March and 12 September 2012 on a 2-week basis (15 days of sampling and exchange of traps each 7 days) in Strasbourg (east of France) for the analysis of 43 pesticides. Samples (particle and gas phases) were separately extracted using Accelerated Solvent Extraction (ASE) and pre-concentrated by Solid Phase Micro-Extraction (SPME) before analysis by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Four SPME consecutive injections at distinct temperatures were made in order to increase the sensitivity of detection for the all monitored pesticides. Currently used detected pesticides can be grouped in four classes; those used in maize crops (acetochlor, benoxacor, dicamba, s-metolachlor, pendimethalin, and bromoxynil), in cereal crops (benoxacor, chlorothalonil, fenpropimorph, and propiconazole), in vineyards (tebuconazole), and as herbicides for orchards, meadows of green spaces (2,4-MCPA, trichlopyr). This is in accordance with the diversity of crops found in the Alsace region and trends observed are in accordance with the period of application of these pesticides. Variations observed permit also to demonstrate that the long time sampling duration used in this study is efficient to visualize temporal variations of airborne pesticides concentrations. Then, long time high-volume sampling could be a simple method permitting atmospheric survey of atmospheric contamination without any long analysis time and consequently low cost.     

舟山近岸海域贝类中有机氯农药残留水平及人体健康风险评估

于2012年的7月在舟山群岛新区的海域采集贝类样本,测定了其中的有机氯农药残留量,并进行了人体健康风险评估和安全食用量推算。结果表明,采集的5种贝类样本中,六六六(BHCs)的各组分均未被检出,而滴滴涕(DDTs)在各种样本中均有检出,其中僧帽牡蛎和部分縊蛏样本中DDTs总量超过《海洋生物质量标准》(GB 18421—2001)一类标准(10μg/kg);健康风险评估结果显示,贝类样本中α-BHC、β-BHC、γ-BHC、p,p’-滴滴伊(p,p’-DDE)、p,p’-滴滴滴(p,p’-DDD)、p,p’-DDT的总致癌风险指数均低于10-4,致癌风险均在可接受的安全范围,α-BHC、β-BHC、γ-BHC、p,p’-DDE的总接触风险指数均小于1,接触风险指数未超过危害剂量参考值,人体食用舟山近岸海域的贝类是安全的;按可接受的致癌风险指数进行评估,人体的贝类安全消费量为9.8~138.0g/(kg·d)(按体重计,下同),而按可接受的接触风险指数进行评估,人体的贝类安全消费量在24.6~235.0g/(kg·d)。     

An alternative supercritical fluid extraction system for aqueous matrices and its application in pesticides residue analysis

Abstract

Supercritical fluid extraction (SFE) is a rapid and convenient method for the isolation of organic compounds from environmental samples. This paper describes a supercritical carbon dioxide (CO₂) extraction system that uses a newly designed extraction cell to recover organic compounds from an aqueous matrix. Analysis of the extracts by gas chromatography‐electron capture detector (GC‐ECD) indicated that the herbicide trifluralin (2,6‐dinitro‐N,N‐dipropyl‐4‐trifluoromethylaniline) could be quantitatively extracted by using the SFE system proposed with small amounts of sample. The percentage of recovery obtained with the SFE system described was twice as high as the result obtained using a conventional solid‐phase extraction technique. Extraction by SFE was completed in a short period of time using a simple and low‐cost home‐made system that did not require the use of organic solvents.     

Analytical methods for the determination of alachlor,metolachlor, simazine and atrazine mobility in soils

Abstract

A method for the determination of the mobility of the herbicides, alachlor, metolachlor, simazine and atrazine in soil is described . The method is based on the use of soil thin‐layer chromatography (TLC) and does not require the use of radiolabelled compounds. Soil on the TLC plate after development was separated into various bands, the material in each band was extracted with solvents and analyzed by gas chromatography.     

A novel pretreatment approach for fast determination of organochlorine pesticides in biotic samples

Recent studies have focused on enantiomeric behaviors of chiral organochlorine pesticides (OCPs) in biotic matrix because they provide insights into the biotransformation processes of chiral OCPs. In the present paper, a double in-line column chromatographic method was developed to effectively remove the lipid impurity in different biotic samples for clean-up of OCPs. After an initial Soxhlet extraction of OCPs from the biotic samples by a mixture of acetone and dichloromethane (DCM), dimethyl sulfoxide (DMSO) was directly added to the extract, and low boiling point solvents (acetone and DCM) were then evaporated. OCPs remained in DMSO were eluted via column 1 filled with silicon gel, and subsequently passed through column 2 packed with 15% deactivated florisil. This novel method was characterized by significant time and solvent savings. The recovery rates of α -HCH (hexachlorocyclohexane), β -HCH, γ -HCH and δ -HCH were 78.5 ± 3.1%, 72.4 ± 7.7%, 72 ± 4.0% and 70.0 ± 8.7%, respectively, and 92.5 ± 3.8%, 79.7 ± 6.7% and 83.4 ± 6.5% for 1,1-dichloro-2-(2-chlorophenyl)-2-(4- chlorophenyl) ethylene (o,p′-DDE), 1,1-dichloro-2-(2-chlorophenyl)-2-(4-chloro phenyl)ethane (o,p′-DDD) and 1,1,1-trichloro-2-(2-chlorophenyl)-2-(4-chlorophenyl) ethane (o,p′-DDT), separately. In addition, the separation efficiencies of the target compounds by both achiral and chiral gas chromatographic columns were satisfactory using the established method. Therefore, the double in-line column chromatography was a useful alternative method for pretreatment of OCPs in different biotic samples.     

Residues of organochlorine pesticides and PCBs in some Brazilian municipal solid waste compost

Persistent organic pollutants (POPs), organochlorine pesticides and polychlorinated biphenyls (PCBs), listed as per the Stockholm Convention (α -HCH, β -HCH, γ -HCH, p,p′-DDT, o,p′-DDT, p,p′-DDD, p,p′-DDE, aldrin, endrin, dieldrin, PCBs 28, 52, 118, 138, 153, and 180), were analyzed in municipal solid waste (MSW) compost samples from three different Brazilian composting plants located in three São Paulo State cities: Araras, Araraquara and São Paulo (Vila Leopoldinha). Quantitative and qualitative analyses were carried out using gas chromatography electron capture detection (GC-ECD) and gas chromatography mass spectrometry (GC-MS) (Ion Trap, electron impact ionization), respectively. The samples were analyzed in triplicate and the target POPs were not detected by GC-ECD. Twelve pollutants were identified in two samples when qualitative analysis (GC-MS) was used (β -HCH, γ -HCH, p,p′-DDT, o,p′-DDT, p,p′-DDD, and p,p′-DDE, PCBs 28, 118, 138, 153 and 180). The composting process has advantages such as urban solid waste reduction and landfill life-span increase, however the MSW compost quality, which can be utilized for agricultural purposes, should be evaluated and be controlled. This kind of study is the first step in making available information to answer questions regarding MSW compost for sustainable agricultural use, such as the pollutants accumulation in soil and in groundwater, and plants uptake.     

Pesticide residues in Italian Ready-Meals and dietary intake estimation

The investigations carried out during 2005 by state-run Italian laboratories within the framework of controls seeking pesticide residues monitoring in foodstuffs involve quantifying the levels of such residues in fruit and vegetable produce and their processed products: oil, wine and fruit juices. The Italian Ready-Meal Residue Project, promoted by the pesticides working group of Italian Environmental Agencies, seeks to asses the quantity of pesticides in pre-prepared (ready-to-eat) lunches (comprising a first course, side dish, fruit, bread and wine), and to quantify the amounts consumed and compare with the acceptable daily intake ADIs.The data provided by 16 laboratories which analyzed 50 complete meals in 2005 (samples taken on 8 February, 26 May, 24 October, 21 December 2005) showed residues in 39 lunches, with an average number of 2.4 pesticides in each meal and a maximum of 10 pesticides. The most frequently found substances were: pirimiphos-methyl (20 times), procymidone (17), pyrimethanil (7), iprodione (7), cyprodinil (7), fenitrothion (6), diphenylamine (6), chlorpyrifos (6), metalaxyl (5) and chlorpyrifos-methyl (5).The distribution of residues among each dish of the meal was also examined, and the results showed that: 77.3% of the residues were present in the fruit, 14.9% in the wine, 3.0% in the main course, 2.8% in the bread and 2.1% in the side dish. Assuming that two meals are consumed per day, the daily intake of pesticide residues was calculated on a daily basis, in relation to normal body weight (60 kg for an adult, 40 kg for a teenager, 20 kg for a child) and compared with the ADI values established by the European Union. In the case of adults, the average daily intake of pesticides in relation to ADI was 2.6% with a maximum of 73.3%; for teenagers it was 4.9% with a maximum of 109% and for children it was 9.8% with a peak of 219%.