青岛近海沉积物中多环芳烃、多氯联苯和有机氯农药的含量和分布特征

利用气相色谱/质谱方法对青岛近海表层沉积物中多环芳烃(PAHs)、多氯联苯(PCBs)和有机氯农药(OCPs)进行了测定,并分析了PAHs、PCBs和OCPs的分布特征.结果表明,PAHs、PCBs和OCPs的均值分别为684.80、6.87和13.52ng·g-1,含量变化均呈近岸高、远岸低的分布规律.燃料的高温燃烧排放对本研究海域沉积物中PAHs有较大贡献;PCBs主要来源于工业及生活排放,但已受到控制;沉积物中HCHs存在工业和农业双重污染源输入,DDT主要是由于历史上使用农药造成,且在表层沉积物中受到好氧微生物降解.与国内外同类研究结果相比,调查海域沉积物中PAHs、PCBs和OCPs的污染程度及生态风险均处于较低水平.     

北京东南化工区土壤有机氯农药污染特征和分布规律

采集北京原东南化工区表层土壤样品,测定了土壤有机氯农药(滴滴涕、六六六和六氯苯)残留浓度,结果表明化工区土壤有机氯农药浓度较高,滴滴涕和六六六平均浓度高达5470ng/g和2110ng/g,比一般农业和城市土壤中的浓度高出很多;某些点位甚至超过国家土壤三级标准,高浓度的点位主要集中在原农药厂的生产车间和存储点。六氯苯由于来源和挥发性跟滴滴涕和六六六不同,所以六氯苯残留在化工区土壤中的分布相对比较均匀。化工区土壤滴滴涕和六六六的异构体组成特征表明工业区土壤的有机氯农药降解速度较慢,滴滴涕残留来源于工业滴滴涕和三氯杀螨醇,而六六六主要来源于工业六六六。化工区的有机氯农药污染主要来自于原农药厂的生产和存储,重污染点位对周围化工厂的有机氯残留有一定的影响。由于高残留浓度和较低的降解速度,化工区土壤有机氯农药残留的环境风险值得进一步关注。     

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.     

珠江三角洲4种代表性土壤/沉积物中自由态与结合态有机氯农药的含量与分布特征

有机氯农药在土壤/沉积物中主要以自由态和结合态存在.本研究选取珠江三角洲地区4种代表不同沉积环境的典型土壤/沉积物样品,先采用碱萃取、盐酸/氢氟酸去矿物等方法对样品进行了组分分离,再采用有机溶剂萃取法对不同组分中自由态和结合态有机氯农药进行了系统分析.结果显示,4种土壤/沉积物总有机氯农药含量为20.96～134.22 μg·kg^-1,其中HCHs总含量为5.66～22.87　μg·kg^-1,DDTs总含量为1.51～11.70　μg·kg^-1,β-HCH、七氯、艾氏剂、异狄氏剂、硫丹硫酸盐和甲氧滴滴涕等6种农药为主要成分,占总有机氯农药的53.56%～77.26%.自由态有机氯农药含量为8.46～88.45　μg·kg^-1,占总有机氯农药的40.37%～65.90%.结合态有机氯农药含量为11.46～45.77　μg·kg^-1,占总有机氯农药的34.10%～59.63%,主要存在于土壤/沉积物的腐殖酸和胡敏素组分,反映了环境中结合态有机氯农药的大量存在.自由态DDT和HCH类有机氯农药的分布情况表明,4种样品均没有新鲜HCH类农药输入而部分样品仍有新鲜DDT类农药输入.结合态有机氯农药在腐殖酸和胡敏素间的分布与有机质碳含量相关,占总有机碳57.71%～80.55%的胡敏素结合了94.78%～97.48%的结合态有机氯农药.风险评价结果表明,部分游离态有机氯农药如γ-HCH、艾氏剂、异狄氏剂、DDT类农药可能存在一定的生态风险.由于单个化合物的总量要比自由态高出约1～30倍,同时结合态农药在一定条件下有释放到环境的可能,因此有机氯农药的环境风险评价和环境标准建立均需考虑结合态有机氯农药.     

Project tocoen. The fate of selected organic pollutants in the environment—iv. soil,earthworms and vegetation 1988

The samples of soils, earthworms and vegetation (needles, lichens, mosses) were collected for the realization of Project TOCOEN (Toxic Organic Compounds in the ENvironment). The samples were collected from three TOCOEN model areas in Czechoslovakia—one city and two rural areas. The samples were analyzed for polycyclic aromatic hydrocarbons (PAHs), chlorinated pesticides (C1‐PEST) and polychlorinated biphenyls (PCBs).     

有机磷农药对蛋白核小球藻的毒性相互作用研究

水体中农药复合污染产生的毒性效应具有潜在风险。为系统考察有机磷农药(OPs)混合物对淡水生态系统中绿藻的联合毒性效应,以马拉硫磷(MIT)、敌敌畏(DDVP)、敌百虫(TRC)、乐果(DIT)和氧乐果(OMT)等5种OPs作为混合物组分,运用直接均分射线法设计9组二元混合物体系共45条混合物射线。利用96孔微板测定5种OPs及其二元混合物对蛋白核小球藻(C. pyrenoidosa)的生长抑制毒性,通过基于置信区间的组合指数法分析混合物的联合毒性及毒性相互作用。结果表明,以p EC50为毒性指标,5种OPs对C. pyrenoidosa的毒性大小顺序为:TRCMITDDVPOMTDIT,OPs对C. pyrenoidosa的毒性大小受其中心磷原子的电正性影响;因混合组分的不同,部分OPs混合物对C. pyrenoidosa的联合毒性依赖于组分浓度比; OPs混合物对C. pyrenoidosa的毒性相互作用以加和为主,部分发生拮抗作用,发生拮抗作用的混合体系具有低效应区域呈加和作用,高效应区域呈拮抗作用的规律;与MIT混合的体系均有发生拮抗作用,且依赖于MIT浓度,MIT浓度比例越高,拮抗作用越强,OPs混合物的毒性相互作用与组分浓度比相关; OPs混合物的毒性相互作用组分浓度比依赖性与其联合毒性的组分浓度比依赖性规律不相关。     

Enantioselectivity in environmental risk assessment of modern chiral pesticides

Chiral pesticides comprise a new and important class of environmental pollutants nowadays. With the development of industry, more and more chiral pesticides will be introduced into the market. But their enantioselective ecotoxicology is not clear. Currently used synthetic pyrethroids, organophosphates, acylanilides, phenoxypropanoic acids and imidazolinones often behave enantioselectively in agriculture use and they always pose unpredictable enantioselective ecological risks on non-target organisms or human. It is necessary to explore the enantioselective toxicology and ecological fate of these chiral pesticides in environmental risk assessment. The enantioselective toxicology and the fate of these currently widely used pesticides have been discussed in this review article.     

Modeling Parent and Metabolite Fate and Transport in Subsurface Drained Fields With Directly Connected Macropores1

Abstract: Few studies exist that evaluate or apply pesticide transport models based on measured parent and metabolite concentrations in fields with subsurface drainage. Furthermore, recent research suggests pesticide transport through exceedingly efficient direct connections, which occur when macropores are hydrologically connected to subsurface drains, but this connectivity has been simulated at only one field site in Allen County, Indiana. This research evaluates the Root Zone Water Quality Model (RZWQM) in simulating the transport of a parent compound and its metabolite at two subsurface drained field sites. Previous research used one of the field sites to test the original modification of the RZWQM to simulate directly connected macropores for bromide and the parent compound, but not for the metabolite. This research will evaluate RZWQM for parent/metabolite transformation and transport at this first field site, along with evaluating the model at an additional field site to evaluate whether the parameters for direct connectivity are transferable and whether model performance is consistent for the two field sites with unique soil, hydrologic, and environmental conditions. Isoxaflutole, the active ingredient in BALANCE^® herbicide, was applied to both fields. Isoxaflutole rapidly degrades into a metabolite (RPA 202248). This research used calibrated RZWQM models for each field based on observed subsurface drain flow and/or edge of field conservative tracer concentrations in subsurface flow. The calibrated models for both field sites required a portion (approximately 2% but this fraction may require calibration) of the available water and chemical in macropore flow to be routed directly into the subsurface drains to simulate peak concentrations in edge of field subsurface drain flow shortly after chemical applications. Confirming the results from the first field site, the existing modification for directly connected macropores continually failed to predict pesticide concentrations on the recession limbs of drainage hydrographs, suggesting that the current strategy only partially accounts for direct connectivity. Thirty‐year distributions of annual mass (drainage) loss of parent and metabolite in terms of percent of isoxaflutole applied suggested annual simulated percent losses of parent and metabolite (3.04 and 1.31%) no greater in drainage than losses in runoff on nondrained fields as reported in the literature.     

江汉平原典型土壤环境中有机磷农药的分布特征及影响因素

为了研究江汉平原土壤中有机磷农药（OPPs）的分布特征,项目组于2015年9月在地下水监测场所在区域,采集了78个剖面土和7个表层土土样,通过气相色谱-氮磷检测器（GC-NPD）分析OPPs的含量,研究江汉平原土壤中OPPs的分布特征.结果表明,研究区土壤普遍存在OPPs,其中地表土中OPPs的含量范围为89.80~193.85 ng·g^-1,平均值为140.05 ng·g^-1;剖面土中OPPs的整体含量范围为19.81~138.28 ng·g^-1,平均值为40.99 ng·g^-1.地表土和剖面土中OPPs主要检出成分均为甲胺磷、氧化乐果、二嗪农和喹硫磷等,并且根据美国土壤农药残留限量标准,研究区土壤中10种OPPs的残留量已对农产品的安全构成威胁.研究区剖面土中∑OPPs分布为：水平方向,沿河农田剖面土 > 沿河非农田剖面土 > 中部农田剖面土,即：GS1-1 > GS4 > GS2 > GS3;垂直方向,大部分剖面土随着深度的增加整体上呈先减小后增大的趋势;研究区土壤中OPPs的分布受多种因素的影响：农业生产过程中施用OPPs的量、土壤对OPPs的吸附、解吸附作用、地下水的垂直运动、研究区的地形环境、土壤有机质的含量等.     

微波萃取-气相色谱/质谱法测定土壤中的有机氯农药

通过微波萃取提取土壤中的有机氯农药,萃取溶液经浓硫酸脱色、佛罗里硅土柱净化,最后用气相色谱/质谱法分析.以石英砂为基体进行加标回收测定,有机氯农药的回收率在75.5%～103%之间,检出限为0.01μg/kg.