广州市公园表层土壤中有机氯农药的分布特征

通过测定广州市典型公园的冬季和夏季表层土壤样品中有机氯农药(OCPs)含量,研究了OCPs的残留现状和潜在生态风险,并与附近地区相比较,结合当地所处的地理位置对土壤中OCPs的分布特征进行了探讨。冬季和夏季土壤中,六六六类(HCHs)的残留水平分别为0.29~6.26 ng/g和0.60~8.07ng/g,平均值分别为2.06和2.44 ng/g;滴滴涕类(DDTs)的残留水平分别为3.27~38.8 ng/g和1.46~35.5 ng/g,平均值分别为12.4和12.5 ng/g。两类OCPs都未超过国家土壤环境质量标准一级自然背景值。较低的α-HCH/γ-HCH比值和γ-HCH>β-HCH,有可能仍有林丹的使用所致。一些公园可能有新的外源DDTs的输入。历史悠久且距离市中心较近的公园土壤中OCPs含量明显偏高。对于大多数新建且相对偏僻的公园而言,表层土壤一般都未见明显的OCPs污染。     

苏南典型地区土壤中有机氯农药残留的空间分布及来源分析

本文研究了江苏张家港市土壤中有机氯农药六六六(HCH)和滴滴涕(DDT)的残留状况,用空间插值和GIS技术分析了其空间分布规律,探讨了潜在来源。结果表明,547个采样点中有21.94%的表层土壤样品中检出HCH,而DDT的检出率为96.16%。HCH在土壤表层的残留均低于《土壤环境质量标准》(GB 15618-1995)的二级标准(500 ng/g),超过一级标准(50ng/g)的也仅占1.46%,DDT则有0.55%的样品超过二级标准。HCH和DDT不同异构体的比值指示土壤中可能有新的来源,但主要还是与历史上的农药施用有关。空间上HCH在南部人为土区的含量要显著高于北部的雏形土区,DDT则相反,这一空间分布格局主要与不同地区的种植历史有关,HCH在人为土区的较高残留可能与历史上水稻种植有关,DDT在北部雏形土区的较高残留则与棉花种植关系较密切。     

表层岩溶带土壤中有机氯农药的分布及来源特征研究——以重庆南川区为例

为了研究有机氯农药(OCPs)在表层岩溶带土壤中的分布趋势、组成特征和来源,采用气相色谱-微池电子捕获检测器(GC-μECD)分析了重庆市南川区水房泉、后沟泉、柏树湾泉、兰花沟泉等典型表层带岩溶泉上覆土层中有机氯农药的浓度。结果显示,总体上表层岩溶带土壤中的OCPs的浓度范围是7.13~323.37ng/g,其中后沟泉、柏树湾泉、兰花沟泉表层土壤中的17种OCPs检出率为100%,水房泉土壤中除p,p'-DDD外其余全部检出,但不同种类有机氯含量差异较大。其中HCHs、DDTs、CHLs、灭蚁灵是主要检出物。研究区内土壤样品中的HCHs来源于工业品HCHs和林丹使用的残留,且由于环境影响,土壤中HCH的同系物组成发生了明显变化。水房泉和柏树湾泉土壤中的DDTs来自于工业DDTs和三氯杀螨醇的混合源,而后沟泉和兰花沟泉土壤中的DDTs可能来自于工业DDTs的使用,而非三氯杀螨醇类型的DDT。对比中国和荷兰的土壤质量标准,柏树湾泉土壤中DDTs浓度接近于荷兰无污染土壤的参考值,兰花沟泉土壤中的DDTs应属于轻度污染,后沟泉土壤中的DDTs和氯丹类化合物污染程度较重,而水房泉土壤为无污染土壤。      

北京市有机氯农药填图与风险评价

采用1个样/km2的密度、1个分析组合样/16km2的方法,对北京市784km2范围内的土壤、大气干湿沉降物、大气颗粒物中HCH、DDT的含量和空间分布特征进行有机氯农药填图.查明2000年北京市地表土壤HCH和DDT的平均含量分别为8.80±11.83ng/g、108.99±301.90ng/g.2006年大气干湿沉降物中HCH和DDT平均含量分别为10.09±9.60ng/g、12.99±13.51ng/g,HCH和DDT的年沉降通量分别为996.57±939.96g/a·km2、1291.53±1342.28g/a·km2.2006年大气颗粒物PM10和PM2.5中的HCH含量分别为0.294±0.205ng/m3和0.217±0.137ng/m3,DDT的平均含量分别为1.037±1.301ng/m3和0.522±0.773ng/m3,显著高于2002-2003年度大气颗粒物中HCH(PM100.01786ng/m3,PM250.01731ng/m3)和DDT(PM100.01672ng/m3,PM2.50.02353ng/m3)的含量,表明北京市或周边地区仍在使用含HCH和DDT化学成分的农药.以2000年北京地表土壤和2006年大气干湿沉降物中HCH和DDT的含量为基础,对2020年土壤中HCH和DDT的时空演变的预测显示,即使干湿沉降物中HCH和DDT的沉降通量每年以5%的速率递减,到2020年土壤中HCH和DDT的环境质量仍不能显著改善,而控制和削减北京及周边地区含HCH和DDT成分农药的使用将是改善北京地表土壤环境质量的关键措施.     

我国南海海鱼中有机氯农药残留分析

建立了凝胶渗透色谱前处理,毛细管气相色谱测定我国南海海鱼中11种有机氯农药的方法。分析了油鲽鱼块、鲷鱼片、银鳕鱼、哈哈鱼块、海鳗鱼中的有机氯农药残留情况,发现在禁用20多年后,六六六(HCHs)、滴滴涕(DDTs)、狄氏剂、环氧七氯在鱼肉中均有不同程度的检出,其中滴滴涕的残留水平最高达到26.73μg/kg。研究发现我国南海海鱼中4种HCH的总残留量高于北京市场上的淡水鱼的残留水平;多数有机氯农药残留污染的平均水平也高于英国和巴西等国鱼类的水平。南海海鱼中有机氯农药残留水平具有指示环境污染的意义。     

柳州岩溶地下河水体有机氯农药分布特征

采用气相色谱(配ECD检测器)对柳州鸡喇和龙寨两条岩溶地下河不同位置水体中18种有机氯农药(OCPs)组分进行分析。结果表明,除异狄氏剂醛外,其余17种OCPs均有不同程度检出,OCPs浓度变化范围为107.68～1101.55ng/L,均值为532.515ng/L。OCPs主要组分为:α-HCH、β-HCH、γ-HCH、δ-HCH、p,p'-DDE、o,p'-DDT、p,p'-DDD、p,p'-DDT、六氯苯、七氯、艾氏剂。其中DDTs和HCHs含量最高,二者之和占到总OCPs的75.8%～96%。对其污染源进行分析,发现地下河水体中DDTs主要源自土壤。HCHs来源相对复杂,可能源于工业品或者长距离大气运输,也可能是近期有林丹的输入使其浓度增高。与国内外各水体相比,本次研究的两条岩溶地下河有机氯农药含量相对较高。      

福建兴化湾水体有机氯农药污染状况

利用气相色谱-电子检测器对福建兴化湾河水和海水中的19种有机氯农药(HCHs、DDTs等)进行的分析结果表明,几种有机氯农药尽管已停止生产多年,但在河水及海水中仍有残留.二者的有机氯农药的质量浓度分别为10.96～56.31,5.78～161.64 ng/L ,同国内外其他港口海区及河流相比,其污染程度相对较低.丰水期河水中DDT的降解产物主要为DDE,而海水中DDT的降解产物主要为DDD.同时,对有机氯农药现状的分析表明,近年来仍有有机氯农药污染的输入,其农药的使用主要集中在六六六和滴滴涕上.     

北京郊区地表水中有机氯农药残留水平及特征

有机氯农药滴滴涕(DDT)、六六六(HCH)等化学性质非常稳定,很难生物降解,对环境及人类健康构成了严重威胁。尽管我国从1983年起已禁止使用,但现在的土壤、水等环境样品中仍有不同程度的检出。水资源是自然环境的主要组成要素,又是农业生产的重要自然资源。以往已有学者对北京部分河流地表水中有机氯农药残留进行过研究,发现存在不同程度水体污染。近年来,经过各方大力控制水体污染和环境治理,北京地区地表水中仍有有机氯农药残留,其残留现状是人们十分关心的重要问题。因此本文选择北京郊区为研究区域,采集了温榆河、北运河、延庆、房山、昌平、顺义等地区地表水,分析了水体中DDTs和HCHs污染物的含量以及分布情况,结果表明DDTs、HCHs在北京郊区地表水中均有不同程度的检出,DDTs含量为ND~1398 ng/L,HCHs含量为387~14642 ng/L。本文同时研究了DDT与其代谢产物DDE、DDD的组成比例以及HCH同分异构体的组成特征,对北京郊区地表水中DDTs和HCHs的污染来源进行了简要分析。     

Pesticides and lipids occurrence in Tangier agricultural soil (northern Morocco)

This study evaluates pesticide occurrence in Tangier agricultural soil (northern Morocco). Soil samples were measured for alpha endosulfan, beta endosulfan, endosulfan sulfate, alpha HCH, beta HCH, gamma HCH, aldrin, dieldrin, endrin, o,p′ DDT, p,p′ DDD, p,p′ DDE and p,p′ DDT. The analyses were performed by gas chromatography coupled with mass spectrometry (GC/MS). Endosulfan isomers (alpha and beta) and endosulfan sulfate were detected in soil samples, in which the beta isomer showed the highest concentrations. Some DDT metabolites (o,p′ DDT and p,p′ DDE) and alpha HCH were also detected in the analyzed soil. The lipid fraction of the soil samples was extracted by accelerated solvent extraction and fractionated using chromatographic techniques. The principal biomarkers obtained were alcohols, esters, ketones, aldehydes, fatty acids and hydrocarbons. Lipid biomarkers were characterized to determine soil organic matter sources. Experimental results showed that the organic matter was mainly of plant origin, although the bacterial contribution was significant.     

广州市海珠区有机氯农药污染状况及其土-气交换

通过在冬夏两季对广州市海珠区表层土壤和空气样品中有机氯农药的采样和分析,对有机氯农药残留现状和潜在生态风险进行了研究。结果表明,土壤中六六六类(HCHs)含量水平在2007年冬季和2008年夏季分别为0.57~8.77 ng/g和0.30~14.9 ng/g,平均值分别为2.87 ng/g和3.04 ng/g,都未超过国家土壤环境质量标准的一级自然背景值。冬季和夏季滴滴涕类(DDTs)含量水平分别为3.69~697.7 ng/g和0.88~263.3 ng/g,平均值分别为85.5 ng/g和39.4 ng/g。海珠区部分地点DDTs超过国家土壤环境质量标准的一级自然背景值。DDTs为该区域表层土壤中主要的有机氯农药残留。在研究区域对逸度模型进行了初步应用。     

Distribution and source of organochlorine pesticides (OCPs) in the sediments of Poyang Lake

The concentrations of typical organochlorine pesticides (OCPs) (DDTs, HCHs, PCP-Na, and HCB) were measured to understand distribution and source of OCPs in surface and columnar sediments of Poyang Lake in 2006. And OCPS concentrations in surface sediment in 2017 were made a comparison with those in 2006 at several same sampling sites. OCPs showed higher concentrations in main stream than in river mouths (entrance of river flow into lake) of the lake. The average concentrations of HCHs and DDTs were 4.63 ± 3.86 and 20.15 ± 26.86 ng/g in surface sediments in 2006, respectively. Concentrations of OCPs in 2017 were lower than in 2006, such as HCHs average 1.98 ± 2.04 ng/g and DDTs average 4.87 ± 1.48 ng/g in 2017, indicating historical residual and degradation. The primary isomers of HCHs and DDTs in the lake were α-HCH, γ-HCH and p,p′-DDD, respectively. HCHs were from historical residual and lindane application. DDTs were from historical residual. PCP-Na total concentrations in surface sediment were 77.36 ng/g in 2006 and 44.04 ng/g in 2017. The concentration of HCB residues in surface sediment was 0.92 ± 0.90 ng/g in 2006 and 0.42 ± 0.38 ng/g in 2017. The concentrations of OCPs in columnar sediments showed annual variations, and the peak concentrations occurred in 1953, 1961, 1974, 1982, and 1995, showing close relations with onset of production OCPs pesticide in 1950s and its later prohibition in 1980s and a large number agricultural cultivated land decrease in 1990s in China. The concentrations of HCB in columnar sediments were average 2.33 ± 1.26 ng/g. OCPs of columnar sediments were from historical residues and lindane input. The main contamination of OCPs was PCP-Na and p,p′-DDD in Poyang Lake. On the whole, the combination of surface samples (0–5 cm in depth) and columnar samples (0–38 cm in depth) in a single study would give insight into OCPs pollution levels in different years (temporal resolution) and in different regions (spatial resolution) in Poyang Lake.     

ΣDDT,PCBs, and HCB in the sediments of Lake Geneva and the upper Rhône River

Eighty surface sediment samples taken in 1978 from Lake Geneva, together with two cores sampled in 1976 and 1980, and 30 samples (1978) from the Rhone River were analyzed for organochlorine compounds. DDT, its metabolites (DDE, TDE), HCB, and PCB were found. No other organochlorine compound was identified at the detection level of 0.5 ppb. DDT metabolites were widespread and indicated residual DDT sources in the Rhone watershed and other minor lake tributaries, particularly on the Swiss coast. DDT levels have declined since an apparent peak usage in 1957. HCB was found in almost all samples. It first appeared about 1962 with consistent usage to the present. Use is widespread with the major source being the Rhône River. PCB was found in all samples at levels comparable to levels in the North American Great Lakes. Sources appear to be diffuse urban/industrial, with major inputs on the Swiss shore between Vevey and Morges. Peak use of PCB occurred in 1972 and was followed by a decline to 1978, with some evidence for a second increase to 1980, the latest sample available. Both HCB and PCB were found at high levels in the most upstream samples of the Rhône River which may be indicative of substantial atmospheric loadings of these two compounds to the Lake Geneva Basin.     

超声提取-固相萃取小柱净化-气相色谱法测定土壤中14种有机氯农药

对土壤中14种有机氯农药的超声提取技术和磺化、固相萃取小柱两种净化方法进行系统研究。结果表明,超声提取节省提取时间,提高分析效率;磺化法和固相萃取小柱法都有净化作用,但磺化法使样品中的艾氏剂、狄氏剂和异狄氏剂全部损失;固相萃取小柱净化当丙酮-正己烷淋洗液体积比为1∶9、淋洗液收集8 mL时回收率>90%,干扰最小。方法检出限为0.63~2.59μg/kg,精密度(RSD,n=7)为1.17%~14.66%,基体加标平均回收率为82.78%~106.94%。方法用于生态地球化学调查评价批量土壤样品的实际分析,检测结果满足评价工作需要。     

沈阳市细河周边农田土壤和大气中有机氯农药和多氯联苯初步研究

在2010年5月调查了沈阳市细河沿岸表层土壤中有机氯农药(OCPs)和多氯联苯(PCBs)的污染现状,评价土壤中OCPs残留的生态风险。沈阳细河沿岸表层土壤中HCHs浓度范围分别为2.32～15.90 ng/g,平均浓度为8.99ng/g。DDTs浓度范围分别为9.06～111.6 ng/g,平均浓度为37.08 ng/g。7种PCBs异构体总平均浓度为1.01ng/g,大部分采样点OCPs和PCBs未超过国家土壤环境质量标准,推断近期可能有林丹的使用但没有新的DDTs污染源输入,但个别地点土壤中的DDTs残留浓度对生态系统健康构成了潜在的威胁。大气蒸汽态HCHs浓度为18.97 ng/m3;DDTs浓度为42.27 ng/m3;PCBs浓度为20.59 ng/m3。研究表明大气长距离传输对该区域的OCPs污染也有较为明显的影响。初步运用逸度概念模型进行分析,发现HCHs和DDTs的逸出方向为从土壤向大气挥发。     

山东烟台地区苹果果园土壤中DDTs和HCHs残留分布特征与来源解析

为研究不同土壤类型中有机氯农药的残留特征、降解程度和来源途径,采集了山东烟台9个不同地质单元苹果园根系土壤和剖面土壤样品,用电子捕获检测器气相色谱法测定其中的滴滴涕(DDTs)和六六六(HCHs)。结果表明,研究区所有类型根系土壤中DDTs和HCHs均未超出《土壤环境质量标准》的二级土壤限值(500 ng/g);土壤中DDTs的残留量及检出率均高于HCHs,DDTs检出率为100%,平均残留量为71.7ng/g,而HCHs的检出率为19.70%,平均残留量为7.9 ng/g;根系土壤中DDTs各异构体平均浓度依次为p,p’-DDT>p,p’-DDE>o,p’-DDT>p,p’-DDD,而HCHs大部分以α-HCH形式存在,部分以β-HCH、γ-HCH存在。不同类型土壤中有机氯农药残留分布特征明显不同:DDTs在棕壤土(臧家庄)中最高(145.5 ng/g),在中粗粒砂土(武宁)中最低(24.1 ng/g);而HCHs在细砂质壤土(蛇窝泊)中最高(27.9ng/g)。各剖面土壤DDTs均在<20 cm层位中残留最高。DDTs和HCHs来源解析表明:研究区土壤为好氧条件;麻砂棕壤(官道和桃村)、黏细壤土(牟平)、细砂质壤土(蛇窝泊)和棕壤土(臧家庄)近年来仍有新的DDTs输入;大部分根系土壤均未发现HCHs新来源,但麻砂棕壤(桃村)在HCHs禁用后可能仍存在林丹的使用。     

Organochlorine residues,eggshell thickness,and nest success in barn owls from the Chesapeake Bay

Eggs of barn owls (Tyto alba) were collected from 18 nests in offshore duck blinds on the Maryland side of the lower Potomac River estuary in 1972 and 1973 and analyzed for organochlorine residues. DDE was found in 100% of the clutches, PCBs in 89%, and dieldrin in 78%. Eggshell thickness was inversely correlated with concentrations of DDE, DDD, and dieldrin residues. Six of the 18 clutches had mean DDE residues above 5 ppm, and eggshell thickness in these six clutches was significantly less (P<0.001) than in the other 12 clutches. The owls produced 1.7 young per active nest in 1973. This rate is slightly below the reproductive rate needed to maintain a stable population. An estimated 15% of the population carried concentrations of organochlorine residues that may have been detrimental to their reproduction. Passerine birds, taken extensively as food by a small proportion of the population, are believed to have been the source of elevated concentrations of organochlorines in these barn owls.     

Concentrations, potential sources and behavior of organochlorines and phenolic endocrine-disrupting chemicals in surficial sediment of the Shaying River, eastern China

Levels and distributions of organochlorine pesticides (OCPs) and phenolic endocrine-disrupting chemicals (EDCs) in surficial sediments of the Shaying River, the largest tributary of the Huaihe River in eastern China, were investigated to understand their relationship with the hydrodynamics. Concentrations of total hexachlorocyclohexane isomers (ΣHCHs) and dichlorodiphenyltrichloroethanes (ΣDDT) were in the range of 26.7–119 and 9.64–214 ng g^?1 with mean values of 104 and 80.7 ng g^?1, respectively. Residues of HCHs in sediments can be considered as originating from the application of both technical mixtures and lindane in the past. According to the spatial distribution of (DDD + DDE)/ΣDDT ratios, the influence of recent DDT inputs was dominant upstream, whereas DDD prevailed downstream, due to anaerobic degradation. Concentrations of total phenolic EDCs (ΣEDCs) including nonylphenol (NP), octylphenol (OP) and bisphenol A (BPA) ranged widely from 425 to 3,953 ng g^?1 with the highest level occurring in the middle reach. This accumulation could be attributed to the retransfer of surficial sediment from upstream, where the main sources are located. Spatial distribution of contaminants indicated that riverine hydrodynamics can significantly affect their behavior and fate in sediment. This evidence was further verified by multivariate statistical techniques such as Cluster Analysis (CA), Principle Component Analysis (PCA) and Discriminant Analysis (DA). The CA identified three distinct clusters reflecting the large complexity of river system like geography setting, hydrodynamic condition, etc. This finding was also confirmed by the DA. Furthermore, a PCA demonstrated that about 80.8 % of total spatial variance can be explained by the first three factors, which also indicated that contaminant spatial distributions are driven by local inputs, biodegradation and riverine hydrodynamics.     

Occurrence and source identification of organochlorine pesticides in the surrounding surface soils of the Ittehad Chemical Industries Kalashah Kaku,Pakistan

Surface soil and sediment samples were collected from the surroundings of the Ittehad Chemical Industries Kalashah Kaku industrial zone to assess residual level of 19 organochlorine pesticides (OCPs) and identify their sources. DDTs and HCHs were most prevalent OCPs and general pattern of contamination followed the order: ∑DDT > ∑HCH > dicofol > endrin > heptachlor > dieldrin > endosulfan II. Total measured concentrations of HCHs (6.38–121.71 ng/g) and DDTs (759.65–1811.98 ng/g) were greater in the soil samples collected from fodder/rice fields irrigated with the factory effluents and in the surrounding of waste disposal site. Ratios of β to γ-HCH highlighted an old mixed source of technical HCH and lindane in surface soils. Predominance of p,p′-DDT and p,p′-DDE among isomers and metabolites showed that large quantity of technical grade DDT is still present in the surrounding surface soils. Six soil samples were categorized as heavy polluted soils (class III category of DDT > 1,000 ng/g), two soil samples into less polluted soil between class I and II (50–500 ng/g) and 28 soil samples as non-polluted (<50 ng/g) according to environmental quality standards for surface soils. Six soil samples were categorized as less polluted between class I and II of HCHs (50–500 ng/g). Greater concentration of DDTs and HCHs above quality guideline poses potential exposure risk to biological organisms, safety of agricultural products and human health in the surrounding of the Ittehad Chemical Industries.     

土壤中25种有机氯农药和多氯联苯的气相色谱分析方法研究

研究了土壤中17种有机氯农药和8种多氯联苯组分的气相色谱分析方法。采用加速溶剂萃取技术提取,优化了萃取条件。提取液用固相萃取技术进行净化,采用20 mL含3%(体积分数)甲苯的正己烷-乙酸乙酯(体积比8∶2)进行淋洗,得到很好的净化效果。方法检出限在0.06~0.27μg/kg,线性范围在1.38~55.2 ng/mL,目标化合物的平均添加回收率在65%~97%,相对标准偏差(RSD,n=6)小于17.11%。方法快速、灵敏、准确,适合批量样品的分析。     

圆盘固相萃取富集-气相色谱法测定地表水中有机氯和有机磷农药

采用环境友好的圆盘固相萃取新技术富集水体中有机氯农药和有机磷农药,分别用微池电子捕获检测器(μECD)和火焰光度检测器(FPD)气相色谱法检测,实现了水中有机氯和有机磷农药残留物的测定。结果表明,16种有机氯农药的平均回收率为64.7%~102%,精密度(RSD,n=6)为2.9%~15%;13种有机磷农药的平均回收率为65.9%~104%,精密度(RSD,n=6)为1.7%~17%。方法快速、灵敏、低污染,可用于水体中多种有机氯农药和有机磷农药的残留分析。