黄河三角洲地区土壤中有机氯农药的残留特征及风险评价

在黄河三角洲不同区域采集了26个土壤样品,利用GC-MS内标法测定土壤中22种有机氯农药(OCPs)含量,并对其残留特征、污染来源和生态风险进行了分析和评价.研究结果表明,土壤中共检测到19种OCPs,总的OCPs浓度范围为0.01—10.49 ng·g~(-1),平均浓度为1.678 ng·g~(-1).OCPs平均浓度顺序如下:DDTsHCHs氯丹类硫丹类,DDTs类农药的检出率最高,DDTs和HCHs是土壤中OCPs主要的组成成分,研究区土壤中DDTs和HCHs的残留水平低于国内其他地区土壤中含量,也低于规定的土壤阈值和土壤环境质量标准,本研究区土壤未受OCPs的污染.β-HCH和p,p'-DDE分别是HCHs和DDTs的主要组成成分.研究区土壤中OCPs主要来源于历史残留,无新的污染源输入.土壤中TOC和p H值对OCPs的残留存在影响,并且呈现弱的负相关性,不同类型土壤OCPs残留量存在差异,OCPs在树林土壤中的残留含量高于海岸带和原耕地土壤中.风险评价表明研究区土壤中HCHs农药残留量不会对生物产生风险;DDTs类农药对研究区生物存在可能性较小的生态风险,危害性总体较低.     

保安湖鱼体重金属和有机氯农药污染特征及健康风险评价

在湖北保安湖采集主要食用鱼类(团头鲂、鲫鱼、草鱼)样品,通过测定鱼体中的重金属(Cr、Cd、As、Pb、Hg、Cu、Zn)和有机氯农药(六六六(HCHs)、滴滴涕(DDTs))含量,基于不同评估模型分析了这3种鱼的污染特征和健康风险。结果显示,鱼样中Cr、Cu、Zn、As、Cd、Pb和Hg的含量分别为1.03～1.13、0.93～1.66、22.80～31.54、0.08～0.49、0.004～0.007、0.040～0.050和0.03～0.06 mg·kg~(-1);鱼样中HCHs、DDTs的含量为5.94～38.04和5.99～38.38 ng·g~(-1)ww。根据国家规定的有毒有害物质限量标准,团头鲂和鲫鱼中As分别超标0.2和3.9倍;鲫鱼体内HCHs和草鱼体内DDTs含量分别超标0.9和2.8倍;其他鱼样重金属和有机氯农药含量均未超过标准限值。总体来看,鲫鱼重金属严重污染,重金属综合污染程度的顺序是鲫鱼团头鲂草鱼;鲫鱼和草鱼体内有机氯农药(OCPs)达到重度污染,OCPs综合污染程度为草鱼鲫鱼团头鲂; 3种鱼样重金属和OCPs复合暴露条件下健康风险评估结果表明,食用3种鱼肉的致癌风险都大于10-6,即均存在一定的潜在致癌风险,致癌风险概率为鲫鱼草鱼团头鲂,同时,食用鲫鱼还存在非致癌健康风险,其污染来源及有效防治值得进一步研究。     

珠江水产品中滴滴涕和六六六残留特征及风险评价

以珠江河口水生食物链较顶端的鱼类和虾类作为研究对象,利用气相色谱(GC-ECD)法检测分析了有机氯农药滴滴涕(DDTs)和六六六(HCHs)及其单体在这些水生动物体内的残留水平和特征,以期为珠江流域水生生物生态风险评价提供基础资料和科学依据。结果显示,鱼类肌肉中的DDTs含量(以湿质量计)范围为未检出(nd)～42.73μg.kg-1(平均值为7.61μg.kg-1),在虾类肌肉中的含量范围为nd～9.51μg.kg-1(平均值为1.97μg.kg-1);鱼类肌肉中的HCHs含量范围为nd～1.71μg.kg-1(平均值为0.62μg.kg-1),在虾类肌肉中的含量范围为nd～0.86μg.kg-1(平均值为0.56μg.kg-1)。鱼类肌肉中DDTs和HCHs的残留均值高于虾类,而鱼类和虾类体内DDTs的残留量均高于HCHs的残留量。HCHs、DDTs的单体分别以γ-HCH、p,p'-DDT的含量最高,而且近期都有新的污染源输入。所采集的水产品中DDTs、HCHs残留量尚低于我国的无公害水产品质量安全标准要求(GB18406.4),亦低于日本、欧盟等发达国家和地区相关的最大残留限量,因此,DDTs、HCHs通过膳食的暴露暂时不会对该地区的人体健康产生危害。     

辽东半岛海域鱼贝中有机氯农药残留及其风险评估

2011年1月-2012年5月间采集了辽东半岛海域11种鱼类和2种贝类样品,分析了其可食部位中22种有机氯农药的残留量,评估了其中DDTs和HCHs的残留对人体健康的风险。在所调查样品中HCB、HCHs和DDTs是主要的污染物,样品中OCPs残留量为57.12~546.15μg·kg-1。利用污染指数计算法评估,旅顺海域小黄鱼、鳙鱼、中国斗鱼和偏口鱼未受到HCHs的污染,棒花鱼受到HCHs轻度污染,其它鱼种样品均受到重度污染,而对于DDTs,只有鲫鱼未受到污染,其它鱼种样品均受到重度污染。大黄鱼、梭鱼、黑鱼和鳙鱼体内HCHs残留量明显高于国标再残留限值,DDTs残留量符合国标标准。α-HCH、γ-HCH、β-HCH、p,p'-DDE、p,p'-DDD和p,p'-DDT的致癌风险指数范围为0.32×10-6~49.57×10-6,均低于10-4,为可接受的致癌风险;α-HCH、γ-HCH、β-HCH、p,p'-DDE的接触风险指数ERI为0.01×10-3~153.28×10-3,均小于1,为可接受的接触风险,但2012年4月的黑鱼样品上述六种农药的CRI总值高于10-4,存在潜在的致癌风险,因此,建议黑鱼的日均食用量应控制在50 g以下较为安全。     

太湖沉积物柱状样中有机氯农药的垂直分布特征

采用气相色谱质谱法测定了太湖沉积物柱状样品中有机氯农药(OCPs)含量,探讨了沉积柱中有机氯农药的垂直变化特征及可能的来源.研究结果表明:沉积柱中OCPs浓度为0.88—4.73 ng·g-1(干重),平均值为2.17 ng·g-1;DDTs、HCHs、六氯苯的残留量均较高,其中DDTs为0.10—1.32 ng·g-1,平均值为0.57 ng·g-1;HCHs的浓度为0.25—1.99 ng·g-1,平均值为0.65 ng·g-1;六氯苯为0.50—1.35 ng·g-1,平均值为0.92 ng·g-1.3个湖湾的沉积柱表层DDTs含量最高,有明显的表面富集现象,成分分析表明,太湖可能着存在着DDTs类物质的输入.     

吉林松花江沿岸土壤中有机氯农药残留特征及健康风险评价

选用GC/ECD分析吉林市松花江两岸土壤中17种有机氯农药（OCPs）残留情况,并探讨该区土壤中OCPs的残留特征及其可能的健康风险.研究结果表明,17种OCPs均有不同程度的检出,含量较高的组分为六六六（HCHs）、滴滴涕（DDTs）和七氯,总有机氯农药含量为133.15—1263.80 ng.g-1.研究区OCPs...     

黄浦江水相中有机氯农药的污染特征分析

本文研究了黄浦江水相中有机氯农药的浓度分布、组成特征和污染来源;分析黄浦江水体中有机氯农药(OCPs)含量的时空变化;在黄浦江水相样品中,除了甲氧氯在所有样品中均未检出外,其他20种有机氯农药在样品中均被检出,在所有水样中的OCPs浓度范围为0.29—44.7(中值2.19)ng·L~(-1).六六六(HCHs)是主要污染物,其次为滴滴涕(DDTs),浓度分别为0.13—38.3(中值0.92)ng·L~(-1)、0.03—3.28(中值0.63)ng·L~(-1).HCHs呈现出自上游至下游浓度逐渐升高的趋势,DDTs在上、下游无明显的空间分布规律.HCHs、DDTs的浓度均呈现夏季低、冬季高、春秋介于中间的季节性规律.     

华北典型污灌区有机氯农药残留特征及健康风险评价

在我国华北地区由于水资源的匮乏及农业生产的需要,采用污水灌溉与施用有机氯农药(OCPs)结合的农业管理方式普遍存在。大量OCPs则被引入到当地环境中,进而可能对该地区的居民产生潜在的健康风险。本研究分析石家庄市汪洋沟污灌区OCPs的残留状况,探讨污水灌溉条件下土壤-作物系统OCPs残留对土壤质量影响,并评价经口摄入及皮肤接触两种暴露途径下对人体产生的健康风险。结果表明:汪洋沟污灌区地表水、沉积物、土壤和玉米籽粒中检出了14种OCPs,其平均残留浓度分别为36.5 ng·L~(-1)、62.9 ng·g~(-1)、57.3 ng·g~(-1)和27.0 ng·g~(-1),滴滴涕(DDTs)是其最主要的污染物,占OCPs的73%以上,其次是六六六(HCHs)和甲氧滴滴涕。р,р'-DDT是DDTs的最主要成分,其主要来源于污水灌溉或近期DDTs的使用。γ-HCH是环境HCHs残留的主要成分,其主要来源于林丹的输入和使用。此外,在该地区污灌条件下OCPs残留对土壤中C、N循环及有机S的矿化产生一定的负面影响。研究区OCPs残留对人体产生的非致癌风险和致癌风险均不超过控制标准,但经口摄入所引致的非致癌风险应予以关注,其中р,р'-DDT与γ-HCH为主要风险物质。     

太原市小店污灌区地表水中有机氯农药分布

为了研究太原市小店污灌区地表水中有机氯农药(OCPs)分布,沿污灌区引水渠、退水渠及汇入河流采集地表水15个,采用液液萃取-气相色谱电子捕获检测器(LLE-GC-ECD)方法检测水样OCPs含量.检测结果表明,污灌区地表水中,残留OCPs主要为六六六(HCHs)和滴滴涕(DDTs),分别占总OCPs的94.85%和4.28%;HCHs的平均含量顺序为:退水渠>河流>东干渠;DDTs平均含量的高低顺序为:河流>退水渠>东干渠.最后通过SPSS软件进行统计分析发现HCHs主要分布在两条退水渠,其受灌溉退水、退水渠周边生活污水和工业废水排放的影响.     

贵州百花湖水体中有机氯农药的残留及健康风险评价

为了研究贵州百花湖水体中有机氯农药(OCPs)对人体的潜在健康风险,在百花湖及其周边布设8个采样点分别采集水样,采用液液萃取-毛细管气相色谱法对OCPs的残留状况进行测定.结果显示,水样中11种有机氯的总含量范围为15.5～43.8ng·L-1,其中,BHCs和DDTs含量范围分别为3.2～14.6和1.2～7.8 ng·L-1.采用美国国家环境保护局(EPA)推荐的健康风险评价方法的评价结果表明,百花湖水体中OCPs的致癌风险和非致癌风险均低于国际辐射防护委员会(ICRP)推荐的最大可接受风险水平,表明百花湖水体中11种OCPs对人体健康风险处于较低水平.     

Organochlorine pesticides (HCHs and DDTs) in soils along the north coastal areas of the Bohai Sea,China

A systematic survey of organochlorine pesticides (OCPs) including hexachlorocyclohexane isomers (α-HCH, β-HCH, γ-HCH, δ-HCH and ΣHCH) and dichlorodiphenyltrichloroethane metabolites (p,p′-DDT, p,p′-DDE, o,p′-DDT, p,p′-DDD and ∑DDT) in soils along the north coastal areas of the Bohai Sea, China, has been lacking. In this study, 31 representative surface soil samples were collected along the north coastal and riverine areas of the Bohai Sea to characterise the potential for adverse effects of ∑HCH, ∑DDT and their individual isomers and transformation products. Concentrations of ΣHCH and ΣDDT in soils ranged from less than the limit of detection (1 ng · g^?1 dw (mean: 3.5 ng · g^?1 dw) and2 ng · g^?1 dw (mean: 1.7 × 10¹ ng · g^?1 dw), respectively. Compared with studies of OCPs in soils from other locations, concentrations of HCHs and DDTs observed in this study were moderate. Concentrations of OCPs observed in soils were generally less than proposed reference values. HCH residues were a mixture of historical technical HCH and current lindane sources. The pattern of DDTs was consistent with historical releases of technical DDTs. Selected soil physicochemical properties did not explain the sorption and/or partitioning of HCHs or DDTs.     

Organochlorine pesticides in surface soils and sediments from obsolete pesticides dumping site near Lahore city,Pakistan: contamination status and their distribution

Surface soil and sediment samples were collected from the surroundings of Lila stream, which passes through the obsolete pesticides dumping area Kalashah Kaku near Lahore city, to evaluate the residual levels of 19 organochlorine pesticides (OCPs), their distribution and potential sources. OCPs followed the order: ∑ DDT>∑ HCH>dicofol>endrin>heptachlor>dieldrin. Ratios of β to γ-HCH highlighted an old source of technical HCH in the study area, whereas the predominance of p, p′-DDT and p, p′-DDE indicated presence of technical DDT in surface soils. Factor analysis based on principal component analysis identified the origin of OCPs from industrial activities in Kalashah Kaku and waste dumping from Ittehad Chemical Industries via open drains into Lila stream. Greater levels of DDTs and HCHs above quality guideline pose potential exposure risk to biological organisms, safety of agricultural products and human health in the surrounding of Lila stream.     

Concentrations and classification of HCHs and DDTs in soil from the lower reaches of the Jiulong River, China

Soil is an important source to other environmental media and organisms for organochlorine pesticides (OCPs) bioaccumulation. Twenty-four representative surface soil samples were collected from the lower reaches of the Jiulong River, China, in 2009. The concentrations of hexachlorocyclohexane isomers (HCHs) ranged from 0.38 to 39.52 ng·g^?1, with a mean value of 9.51 ng·g^?1. The concentrations of dichlorodiphenyltrichloroethanes (DDTs) and their metabolites were within the ranges of 0.94–700.99 ng·g^?1, with a mean value of 71.17 ng·g^?1. The concentrations of HCHs and DDTs in the soil were lower than the first grade level (50 ng·g^?1) of the Chinese Environmental Quality Standard (GB15618-1995). Hierarchical Cluster Analysis (HCA) and Pearson’s bivariate Correlations Analysis (PCA) were used to analyse the distribution and contamination levels of OCPs in this region. The results showed that DDTs were the major contaminants and there were no significant correlations between various OCPs concentrations and the total organic carbon (TOC) contents. A significant positive correlation was observed between HCHs and DDTs (p<0.01), which indicates that HCHs and DDTs may have similar sources and fate in the study area.     

珠江八大入海口表层沉积物中DDTs和HCHs残留调查

于2010年8月-2011年5月4次采集珠江八大人海口表层沉积物,采用气相色谱-电子捕获（GC—ECD）法分析沉积物中DDTs（p,P’-DDE、P,P’-DDD、0,P’-DDT、P,P-DDT）和HCHs（α-HCH、β-HCH、γ-HCH、δ-HCH）的污染现状。结果显示,珠江8大人海口表层沉积物中DDTs总含量介于1．02—3．08μg·kg-1之间（以干质量计,下同）,平均值为1．91μg·kg-1;HCHs总含量介于0．21—0．41μg·kg-1之间,平均值为0．31μg·kg-1。DDTs平均含量大于HCHs,其中P,P。DDT对污染的贡献最大,含量范围为ND～7．66μg·kg-1,平均值为2．12μg·kg-1。大部分样点伽（α-HCH）／w（γ-HCH）比值小于3,说明研究区α-HCH大都被降解,或者林丹正取代工业HCHs成为珠江口水环境中HCHs输入的主要来源;甜（DDT）／w（DDD＋DDE）比值大于2,表明沉积物中除早期农药残留外,仍然有新的DDTs类农药输入。     

广东北江上游流域农田土壤有机氯农药残留及其分布特征

北江是珠江的重要支流之一,为确定北江上游流域农田土壤有机氯农药（OCPs）的含量、来源以及分布特征,2010年11月,对该区域水稻田、菜地和果园土壤进行了采样、处理以及GC/MS分析。研究结果表明：27种OCPs中,除环氧七氯、狄氏剂、硫丹I、反式九氯、顺式九氯、异狄氏剂醛和甲氧氯外,其余均有不同程度的检出。总OCPs质量分数为2.71～62.4 ng.g-1,平均11.9 ng.g-1;含量最高的为DDTs,其次为硫丹和HCHs,其质量分数范围分别为1.82～60.3、0.103～19.6和nd（未检出）～1.74 ng.g-1;水稻田土壤DDTs的含量与果园相当,但明显高于菜地的残留水平。研究区域OCPs的源分析表明,HCHs主要来自于早期商业HCHs和林丹农药的残留,DDTs源于商业DDTs和三氯杀螨醇农药的残留。北江上游流域农田表层土壤OCPs储存量约为342 kg,其中DDTs 243 kg、硫丹63.7 kg、HCHs 15.0 kg。与国内外同类型报道相比,结合我国GB 15618-1995《土壤环境质量标准》,研究区域土壤OCPs残留的程度较低。     

Residues and sources of organochlorine pesticides in soils of elementary schools and communities in Wenchuan 5.12 Earthquake-affected areas

The disinfectants and pesticides extensively used after Wenchuan 5.12 Earthquake on May 12, 2008 (so-called Wenchuan 5.12 Earthquake), for epidemic prevention purpose can raise great concerns of environmental pollution and potential personal exposure. To investigate the soil pollution caused by the intensive application in earthquake-affected areas, surface soil samples from two elementary schools, two communities and two background areas were collected in Beichuan County and Dujiangyan City once per location in spring and in autumn in 2011 and then analyzed by gas chromatography/mass spectrometry for organochlorine pesticides (OCPs). The results showed serious soil pollution of hexachlorocyclohexanes (HCHs, 0.05–60.05 ng/g) and dichloro-diphenyl-trichloroethane (DDTs, 0.06–35.79 ng/g) in the study areas compared with Wolong Nature Reserve (0.03–0.81 ng/g for HCHs and 0.02–0.40 ng/g for DDTs). The concentrations of most OCPs in soil of Beichuan County (e.g., 0.10–60.05 ng/g for HCHs and 0.17–35.79 ng/g for DDTs) were much higher than those of Dujiangyan City (e.g., 0.05–20.58 ng/g for HCHs and 0.06–10.69 ng/g for DDTs). In Beichuan County, the highest concentrations of HCHs and DDTs were found in the elementary school. In Dujiangyan City, the highest concentrations of HCHs and DDTs were found in the elementary school and the community, respectively. The concentrations of HCHs and DDTs were generally higher in spring than those in autumn. The predominant species (γ-HCH in ∑HCHs and 4,4′-DDT in ∑DDTs) and specific ratios suggested new inputs of lindane and technical DDT in the study areas. Therefore, continuous soil monitoring and possible intervention would be recommended to minimize local residents’ exposure to these toxic chemicals.     

成都城区蔬菜地土壤中农药残留及其分布特征

采用GC-ECD检测、GC/MS-MS确证的方法对成都城区14个区县蔬菜地土壤中23种有机氯农药（OCPs）进行分析,以揭示OCPs的残留现状及其分布特征。结果表明,OCPs残留水平在不同区县间差异很大,变化范围20.18～104.33μg.kg-1之间,近郊区县（双流、龙泉驿、郫县、新都、温江）远低于边缘区县。被检出的18种OCPs中,DDTs、HCHs检出率最高（100%）,残留水平为16.11～99.51、1.31～9.34μg.kg-1,分别占OCPs残留总量质量分数的87.68%、8.15%;六氯苯（HCB）次之（90%）;灭蚁灵、环氧七氯、硫丹Ⅰ和γ-氯丹也有不同程度的检出（44.29%～47.14%）,主要分布在近郊区县;艾氏剂、狄氏剂、异狄氏剂、毒杀芬的检出率较低（32.86%～37.14%）,多分布于彭州、都江堰、大邑、崇州等地。土壤中OCPs的各种异构体、代谢物变化规律显示,DDTs、HCHs残留主要源于早期的使用或大气输入,但不排除金堂、青白江、新津地区近期可能有新的DDTs输入,崇州、彭州、都江堰、大邑地区可能有HCHs输入。     

Characteristics and risk assessment of organochlorine pesticide residues in surface sediments collected at the Qingshitan Reservoir

ABSTRACT

An ultrasonic extraction – gas chromatography – electron capture detector analytical method was used to measure the concentration and types of organochlorine (OC) pesticides in sediment to obtain a better understanding of the characteristics and hidden ecological risks associated with OC pesticide exposure in surface sediment of the Qingshitan Reservoir. Fifteen types of OC pesticides were detected in the sediment, and the sum concentration of these chemicals was in the 149.32–490.19 ng/g range (mean value: 319.39 ng/g). The concentrations of detected OC pesticides occurred in the following order: hexachlorohexanes (HCHs) (mean value: 200.17 ng/g) > DDTs (mean value: 36.92 ng/g) > heptachlors (mean value: 32.74 ng/g) > methoxychlor (mean value: 24.13 ng/g). There was a 100% detection rate for HCH isomers, and their concentrations occurred in the following order: β-HCH > δ-HCH > γ-HCH > α-HCH. β-HCH was the main component of HCHs. Ratios between α-HCH/γ-HCH and β-/(α+γ)-HCH were used to investigate the sources of pollution. Most of the surveyed areas were polluted by lindane, which originated from past pesticide residue usage, and no new inputs of HCHs were found. DDT was the major component of the DDTs, and accounted for 52%–87% of the DDTs. The ratios of (DDE+DDD)/DDT at all sample collection points were less than 1, indicating that degradation rate of DDTs in sediment was low and there was a new input of DDTs in these surveyed areas. The ratio of DDD/DDE was less than 1 at most of the sample collection points, indicating that the degradation of DDT in the sediments primarily took place under aerobic conditions. Comparison of OC pesticide residual levels in the underwater sediment collected at the Qingshitan Reservoir to other states and countries showed the pollution level of these chemicals of the Qingshitan Reservoir was relatively high. The ecological risk was assessed based on guideline values of effects range-low (ERL) and effects range-medium (ERM). The results showed that DDD, DDE, DDTs and endrin residues in the sediment posed a moderate ecological risk, but DDT and γ-HCH showed high ecological risk. These OC pesticides might adversely affect biological systems, and need to be addressed.     

Organochlorine Residues in Coastal Birds From the Vellar River Watershed Areas,Parangipettai, Southern India

Organochlorine contaminants (HCHs, DDTs and PCBs) in the muscle tissues of 12 bird species collected from Vellar River watershed areas (S. India) were determined. the accumulation pattern of organochlorine residues in birds of different feeding groups for HCHs and PCBs was: scavengers > inland piscivores > coastal piscivores > insectivores. the pattern for DDTs was: coastal piscivores > scavengers > insectivores > inland piscivores. Scavengers accumulated all the three organochlorines to a higher degree than the other groups of birds. Marked variations in the accumulation pattern by different species and individuals of birds to the same and different organochlorine residues were observed. the differences in the accumulation pattern of residues in different species of birds with similar feeding habits could be attributed to different feeding areas and because migrants are exposed to contaminants in different geographical locations. HCH residues were generally found in higher concentrations than DDTs, reflecting increasing use of HCH pesticides since banning of DDT for agriculture. Levels of PCBs were lower than in birds in developed countries. Results are discussed in relation to future pest control and industrialisation in India.     

Vertical profiles of organochlorine pesticides in sediment core from Nile river and Manzala lake,Egypt

Residue levels of organochlorine pesticides (DDTs, HCHs, HCB and chlordane compounds) were determined in core samples collected from Nile River near by Cairo and Manzala Lake, Egypt in 1994. Regional difference and vertical profiles were discussed in view of historical reconstruction of environmental pollution by these chemicals. On the basis of estimated sedimentation rate (0.5 to 0.7 cm/year) in Manzala Lake, it seems that discharge of DDTs and CHLs into Egyptian environment increased rapidly from early 1960's and the maximum discharge was recorded in 1980's. However, concentration of HCHs increased continuously up to the present in spite of decreasing of DDTs and CHLs after 1980's. It was revealed that vertical profiles of organochlorine pesticides in sediment core from Manzala Lake are useful to estimate a temporal trend of pesticide use in Egypt.