Sequestration of organochlorine pesticides in soils of distinct organic carbon content

In the present study, five soil samples with organic carbon contents ranging from 0.23% to 7.1% and aged with technical dichlorodiphenyltrichloroethane (DDT) and hexachlorocyclohexane (HCH) for 15 months were incubated in a sealed chamber to investigate the dynamic changes of the OCP residues. The residues in the soils decreased over the incubation period and finally reached a plateau. Regression analysis showed that degradable fractions of OCPs were negatively correlated with soil organic carbon (SOC) except for α-HCH, while no correlation was found between degradation rate and SOC, which demonstrated that SOC content determines the OCP sequestration fraction in soil. Analysis of the ratio of DDT and its primary metabolites showed that, since it depends on differential sequestration among them, magnitude of (p,p′-DDE + p,p′-DDD)/p,p′-DDT is not a reliable criterion for the identification of new DDT sources.     

Development,validation, and application of a method for the GC-MS analysis of fipronil and three of its degradation products in samples of water,soil, and sediment

A method for the identification and quantification of pesticide residues in water, soil, and sediment samples has been developed, validated, and applied for the analysis of real samples. The specificity was determined by the retention time and the confirmation and quantification of analyte ions. Linearity was demonstrated over the concentration range of 20 to 120 µg L^?1, and the correlation coefficients varied between 0.979 and 0.996, depending on the analytes. The recovery rates for all analytes in the studied matrix were between 86% and 112%. The intermediate precision and repeatability were determined at three concentration levels (40, 80, and 120 µg L^?1), with the relative standard deviation for the intermediate precision between 1% and 5.3% and the repeatability varying between 2% and 13.4% for individual analytes. The limits of detection and quantification for fipronil, fipronil sulfide, fipronil-sulfone, and fipronil-desulfinyl were 6.2, 3.0, 6.6, and 4.0 ng L^?1 and 20.4, 9.0, 21.6, and 13.0 ng L^?1, respectively. The method developed was used in water, soil, and sediment samples containing 2.1 mg L^?1 and 1.2% and 5.3% of carbon, respectively. The recovery of pesticides in the environmental matrices varied from 88.26 to 109.63% for the lowest fortification level (40 and 100 µg kg^?1), from 91.17 to 110.18% for the intermediate level (80 and 200 µg kg^?1), and from 89.09 to 109.82% for the highest fortification level (120 and 300 µg kg^?1). The relative standard deviation for the recovery of pesticides was under 15%.     

纳米TiO2光催化降解有机磷农药的研究

通过实验,探讨了用纳米TiO2光催化处理有机磷农药模拟废水和实际应用的有机磷农药的可行性.实验表明,以测定不同时间PO43-的浓度来衡量有机磷的降解率,并以此来衡量有机磷农药及其中间产物降解的程度是合理的.光催化降解甲胺磷和水胺硫磷的结果,显示了有机磷农药的降解率与其结构有关.实际应用的有机磷农药也可用光催化降解.     

Endosulfan in China 1—gridded usage inventories

Background, aim, and scope  Endosulfan, an organochlorine pesticide (OCP), is genotoxic in mammalian cells and generally considered to be toxic and classified by the World Health Organization and the US Environmental Protection Agency as priority pollutants and a nominator for inclusion in a future iteration of the persistent organic pollutants treaty. Endosulfan is a currently used pesticide and still being used worldwide. The general trend of total global endosulfan use has increased continuously since the first year when this pesticide was applied. It is critical to create national endosulfan usage/emission inventories for China to carry out source–receptor relation analysis, risk assessment, and other research related to endosulfan in this country. Chinese inventories have been published for some OCPs, such as technical HCH and lindane, DDT, and chlordane; for endosulfan, however, there has not been any usage inventory available on any scales (national or provincial), although endosulfan has been widely used since 1994 in this country. This is the first part of the work. The goal of this paper is to quantify the historical production and usage of endosulfan in China and to compile gridded historical usage inventories of endosulfan for this country. Based on these usage inventories, emission and residue inventories will be created, which is the goal of the second part of the work. Materials and methods  Due to the lack of national production and usage information of endosulfan in China, a method to estimate the use of endosulfan was developed. First, information of crops on which endosulfan is applied and average endosulfan use and annual application frequencies of endosulfan on these crops were collected. Secondly, usage of endosulfan on each crop was estimated using the national cropland area for each province from Chinese government reports. Finally, with the help of GIS (geographic information system), the usage data of this insecticide was allocated to a grid system, with a 1/4° longitude by 1/6° latitude resolution, with a size for each grid cell of approximately 25 km by 25 km. Results and discussion  The use of endosulfan in agriculture in China started on cotton in 1994, and on wheat, tea, tobacco, apples, and other fruits in 1998. Endosulfan usage on cotton, wheat, tea, tobacco, and apples in China has been estimated to be approximately 25,700 t between 1994 and 2004. The province with the highest usage of endosulfan is Henan Province, with a total usage reaching 4,000 t, followed by the uses in Xinjiang Autonomous Region (3,200 t), Shandong Province (3,000 t), Hebei Province (2,100 t), and Anhui Province (1,900 t). Gridded usage inventories of endosulfan at a 1/4° longitude by 1/6° latitude resolution have been created, which indicate that the intensive endosulfan use was in the south of Hebei Province, west of Shandong Province, east of Henan Province, north of Anhui Province, east of Jiangsu Province, and some areas in Yunnan Province and Xinjiang Autonomous Region. General agreement has been found between the usage data from our estimation and the small amount of usage data published in China. Conclusions  This is the first national gridded endosulfan usage inventory produced for China. The annual applications of endosulfan from 1994 to 2004 in China were estimated based on the total areas of major crops, on which endosulfan was applied, and spatial distribution of the application was generated at provincial and prefecture levels. With the help of GIS, endosulfan usage based on prefecture was transferred to a 1/4° longitude by 1/6° latitude gridding system. The satisfaction of the inventories was supported by the consistence between the estimation of the annual usage and the reported annual production of endosulfan. Recommendations and perspectives  This gridded endosulfan usage inventory created in this study will be improved upon availability of new information of endosulfan. The usage inventories can be used to create gridded emission and residue inventories for this insecticide. It is believed that this work will pave the way for further endosulfan studies in China and beyond.     

Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in traditional Chinese medicine by gas chromatography with electron capture detection

The Quick Easy Cheap Effective Rugged and Safe multiresidue method (QuEChERS) has been validated for the extraction of 15 organochlorine pesticides (OCPs) in completely different matrices of traditional Chinese medicine (TCM). The method employed a rapid, simple and cost-effective procedure. The spiking levels for the recovery experiments were 0.1, 0.5 and 2.0 mg kg⁻¹. Mean recoveries mostly ranged between 76.0% and 114.0% (96.0% on average), and relative standard deviations (RSD) were generally below 10% (4.72% on average). Based on these results, the methodology has been proven to be highly efficient and robust and thus suitable for monitoring the MRL compliance of a wide range of commodity. The contamination status of 15 OCPs on 80 different TCMs marketed in China, and a total of 400 samples were also performed using a previously validated method. 15 OCPs were benzene hexachloride (BHC, including α-BHC, β-BHC, γ-BHC, δ-BHC), hexachlorobenzene, heptachlor, heptachlor epoxide, aldrin, p, p′-DDE, p, p′-DDD, o, p′-DDT, p, p′-DDT, mirex, endrin, dieldrin. This study indicates that the proposed method is useful for analyzing OCPs in TCM.     

串联四极杆质谱(GC-QqQ-MS/MS)测定土壤中的有机氯农药和多氯联苯

建立了用加速溶剂萃取仪(ASE)萃取、凝胶渗透色谱(GPC)净化、气相色谱/串联四极杆质谱多反应监测、同时测定土壤中17种有机氯农药和19种多氯联苯的方法.加标浓度在3.3μg/kg时的平均回收率在79.6%～93.2%之间,相对标准偏差在2.9%～13.0%之间,定量限在0.01～0.51μg/kg之间.在检测土壤样品中的有机氯农药和多氯联苯残留方面,Gc-QqQ-MS/MS相对于气相色谱/电子捕获检测器(GC-ECD)和GC-MS的选择离子检测(SIM)模式具有非常明显的优势,尤其是在低浓度水平的定性和定量方面.     

碳源对工业污染场地土壤中HCHs和DDTs降解的促进作用

我国对有机氯农药的大量需求使得在农药生产、加工和分装等过程中造成了许多城镇中存在有机氯农药污染场地,限制了土地的后续开发利用.本研究选取3种类型的碳源组成有机修复剂A、B、C,添加到受有机氯工业污染场地土壤中进行微生物降解试验,并对比了3种修复剂的效果.试验过程中,反应体系水分含量为50％,添加零价金属调节氧化还原电位,采用好氧/厌氧交替循环方式进行生物降解.实验结果表明:3种修复剂对HCHs和DDTs的降解都有显著促进作用.与DDTs相比,HCHs较易降解.90 d内,添加修复剂(A、B、C)的处理中∑HCH的浓度分别从73.37~85.71 mg·kg^-1降解到了15.88~38.21 mg·kg^-1.与未添加修复剂的对照相比较,∑HCH的降解率提高了19%~52%,90 d内,ΣHCH的降解率最高可达81%.添加修复剂(A、B、C)的处理中ΣDDT的浓度分别从91.68~119.79 mg·kg^-1降解到了45.1~60.7 mg·kg^-1,相对未添加修复剂的对照试验,∑DDT的降解率提高了39%~45%,30 d内∑DDT的降解率最高可达到51%,但30 d后降解效率无明显增加.就不同类型碳源的促进作用来看,C/N最高,而含水率最低的修复剂B的效果最好,而C/N比最低而含水率最高的修复剂A效果最差.     

有机氯农药污染土壤的Fenton氧化修复研究

研究了Fenton氧化对某实际有机氯农药污染场地土壤的修复效果。结果显示:Fenton氧化能够快速有效地降解污染土壤中的六氯和DDTs。当Fe2+浓度为80 mmol/L,Fe2+与H2O2的摩尔浓度比为1∶5,水土比10∶1时,反应6 h,土壤中六氯和总DDT的去除率分别为:96.7%和78.2%。每方土的修复成本估算为951元。     

青海省西宁市和天峻县大气颗粒物中有机氯农药和类二噁英多氯联苯的水平与分布

本研究测定了青海省西宁市与海西蒙古族藏族自治州天峻县夏、冬两季大气颗粒物中有机氯农药(OCPs)和类二噁英多氯联苯(DL-PCBs)的浓度水平.结果表明,青海省大气颗粒物中OCPs主要为DDTs、HCHs.西宁市DDTs和HCHs的平均水平分别为:35 pg·m-3、5.9 pg·m-3(夏季)和93 pg·m-3、11 pg·m-3(冬季),天峻县DDTs和HCHs的平均水平分别为:83pg·m-3、6.4 pg·m-3(夏季)和28 pg·m-3、6.7 pg·m-3(冬季).与亚洲其它地区相比,青海省大气颗粒物中OCPs处于较低水平.西宁市大气颗粒物中DL-PCBs的平均水平分别为:0.52 pg·m-3(夏季),0.99 pg·m-3(冬季),天峻县为:0.58 pg·m-3(夏季)、0.52 pg·m-3(冬季).西宁市夏、冬两季OCPs的平均水平均大于天峻县,而两地DL-PCBs的平均水平相当.本研究中高原地区DL-PCBs的分布特点及变化规律与极地地区的研究相比存在一定的相似性,而DDTs和HCHs则存在差异性.     

农业生态环境治理与可持续发展

我国是一个农业大国 ,由于长期的农业生产中忽视了对农业生态环境的保护 ,近年来 ,农业环境和农产品污染问题日趋严重 ,耕地环境质量不断下降 ,土地沙化形势十分严峻。农产品有毒有害物质残留问题突出 ,已成为制约农业和农村经济发展的重要因素。针对农业生态环境污染日益加剧的严峻形势 ,必须加大农业生态环境建设和保护力度 ,采取合理措施 ,在农业生产过程中降低化肥和农药的使用和环境造成的污染 ,推广清洁生产应当成为推动新世纪农业进步的发展新模式。与世界其它国家一样 ,合理利用资源和保护生态环境是农业可持续发展的基础。必须实施可持续发展战略 ,大力推广生态农业和生态农村建设 ,调整优化农业生产结构 ,从粗放型向集约型转变 ,以确保 2 1世纪我国农业的可持续发展。