DDTs在土壤中的老化规律及生物有效性

用室内模拟培养的方法研究了DDTs在土壤中的老化行为及其在蚯蚓体内的生物富集规律。结果表明。DDTs在土壤中存在老化现象。此类物质在土壤中的可提取态含量随着老化时间延长逐渐降低，并呈现初始老化速率较快，而后老化速率减慢的趋势。在开始的0—30d，其老化的速率较快，o，p’-DDT、p，p’-DDT、o．p’-DDE、p，p’-DDE和p，p’-DDD在土壤中的老化减少量分别是其添加量的53．5％、52．1％、31．4％、36．0％和38．3％。DDTs在蚯蚓体内的生物富集量和生物富集系数也表现出随时间而逐渐降低的趋势，并呈如下规律：p，p＇-DDE〉p，p’-DDD〉o，p’-DDE〉o，p＇-DDT〉p，p＇-DDT。老化虽然可使DDTs的可提取态含量降低。但仍可以在蚯蚓体内有一定的生物富集，潜在的生态风险依然存在。     

污染土壤中六六六和DDT在温室中的分布特征及动态变化研究

应用PUF材料空气被动采样技术,研究了密闭温室条件下污染土壤中有机氯农药[DDT和六六六（HCH）]含量的动态变化及其向空气中扩散的规律。结果表明：土壤中∑HCHs和∑DDTs总量随着培养时间的延长而降低;空气中HCH和DDT浓度在20d时达到峰值,20d以后浓度逐渐降低。培养60d后,土壤中∑HCHs的浓度随土层深度增加而增加,0~2cm土层中∑HCHs的浓度（9.4±0.69）mg·kg-1显著低于6~8cm土层中的浓度（12.11±0.83）mg·kg-1;∑DDTs在土壤中浓度随土壤层次呈现先升高后降低的变化趋势。在温室条件下有机氯农药的异构体和降解产物的组成也发生一定变化,土壤中HCHs和DDTs在一定程度上被激活,温室条件也可能促进HCHs和DDTs的土-气交换过程;温室环境促进了p,p′-DDT和o,p′-DDT向p,p′-DDD和p,p′-DDE转化,从而增大DDT和HCH的环境风险。     

典型滴滴涕废弃生产场地污染土壤的人体健康风险评估研究

对我国典型滴滴涕(DDT)废弃生产场地的疑似重污染区进行环境调查、污染土壤人体健康风险评估和土壤修复建议目标值计算。结果表明,该场地污水处理池周边的关注污染物主要为p,p’-DDT、p,p’-DDD、p,p’-DDE、1,4-二氯苯、氯仿和氯苯,临近污水处理池北侧和东侧的区域土壤中污染物垂向迁移明显,其他区域土壤污染物主要分布于0～50 cm土层。前5种关注污染物的致癌风险均超过10-6,部分点位p,p’-DDT和氯苯的非致癌危害指数大于1。不确定性分析表明,半挥发性有机物p,p’-DDT、p,p’-DDD和p,p’-DDE经口腔摄入土壤和皮肤接触土壤暴露途径对总风险的贡献率超过98%,挥发性有机物氯苯、1,4-二氯苯和氯仿经吸入室内空气暴露途径对总风险的贡献率高达99%以上。土壤颗粒密度、土壤容重和土壤含水率是敏感参数。p,p’-DDT、p,p’-DDD、p,p’-DDE、氯苯、1,4-二氯苯和氯仿的土壤修复建议目标值分别为5.84、6.19、4.36、36.2、0.55和0.02 mg kg-1。     

安徽省典型城市周边土壤-蔬菜中PAHs的污染特征

研究了安徽省合肥、芜湖和亳州市周边蔬菜地土壤和蔬菜中PAHs的含量及其污染特征。结果表明：安徽省典型蔬菜地土壤中15种PAHs（除萘外）的残留总量在58.2～437.8μg·kg-1之间,三环和四环PAHs占PAHs残留总量的70%以上。胡萝卜、菠菜和茄子体内15种PAHs的含量在23.4～209.1μg·kg-1之间,均值为120.7μg·kg-1,三环和四环PAHs占蔬菜中PAHs富集总量的92.8%～94.4%。不同蔬菜体内8种可疑性致癌PAHs的含量在11.5～17.4μg·kg-1之间,分别占蔬菜中PAHs残留总量的9.80%～13.8%,其中BaP含量在1.69～2.03μg·kg-1之间,低于国家对食品中污染物（BaP）的限量标准（5μg·kg-1）。不同类型PAHs在蔬菜体内的富集系数在0.10～9.20之间,极差达10倍以上,低分子量PAHs在蔬菜体内的富集系数要大于高分子量PAHs。不同PAHs在蔬菜体内的富集系数表现为胡萝卜〉菠菜〉茄子,其中芴在蔬菜体内的富集系数最高。     

作物根系对土壤中老化HCH-DDT的富集作用

在室温条件下,采用盆栽试验方法研究了小麦和玉米作物根系对自然污染土壤中不同水平老化HCH、DDT的富集作用及其影响机制。通过连续提取,将根系富集的有机氯农药分为弱吸着、强吸着和吸收3种不同形态。结果表明,作物对老化HCH、DDT的富集存在选择性。在60d的试验周期内,玉米根系富集的HCH、DDT中55．4％～62．2％为根表强吸着,23．3％～36．9％为根内吸收;而小麦根系中HCH,DDT的73．8％-76．9％被根表强吸着,仅15．4％-20．5％可以进入根系组织内部。不同形态组分中异构体及代谢物的组成比例差异化明显,其中吸收态以β-HCH为主,强吸着态以P,p＇-DDT、p,p＇-DDE和P,p＇-DDD为主。随着土壤污染水平的增加,小麦和玉米根系对HCH、DDT的富集总浓度增加,而生物蓄积系数逆浓度梯度增加,小麦根系的富集能力强于玉米。在控制污染水平的条件下,作物根系对土壤老化HCH、DDT的富集量与其根系比表面积大小和总脂含量极显著正相关,而向根系深层组织运移的过程主要受总脂含量控制。     

福建茶园茶叶中六六六和滴滴涕残留水平及来源分析

运用气相色谱-电子捕获检测器（GC-μECD）分析了福建茶园茶叶中六六六（HCHs）和滴滴涕（DDTs）等有机氯农药（OCPs）的分布、组成和来源。结果表明,∑OCPs浓度为0.764～10.561ng.g-1,永泰最高,福鼎最低,一般而言,老叶中∑OCPs浓度高于嫩叶;∑HCHs浓度为0.373～7.427ng.g-1,永泰最高,政和最低,老叶中HCHs浓度显著高于嫩叶;茶叶中HCHs同系物以γ-HCH为主,占总量的51.3%～94.1%;α-/γ-HCH表明所有茶园均存在林丹的使用或输入,β-（/α＋γ）-HCH表明所有茶园均非HCHs历史污染,可能存在HCHs其他新的来源。∑DDTs浓度为0.123～5.168ng.g-1,政和最高,福鼎最低,老叶和嫩叶中无显著差异;与土壤类似,茶叶中DDTs同系物以p,p′-DDT和o,p′-DDT为主,两者之和占总量的67.3%～96.0%;p,p′-DDE/p,p′-DDT表明,除福鼎、永泰和安溪外,其他茶园均存在工业DDTs的使用或输入;o,p′-DDT/p,p′-DDT表明,除政和外,其他茶园均存在大量的三氯杀螨醇的使用或输入,以安溪较为严重。     

福建茶园土壤六六六和滴滴涕残留水平及来源分析

采用现场采样及室内测试方法,分析了福建茶园土壤中六六六（HCHs）和滴滴涕（DDTs）类有机氯农药（OCPs）的分布、组成和来源。结果表明,∑HCHs和∑DDTs浓度分别为0.251-1.120 ng.g^-1和0.210-2.406 ng.g^-1,属于清洁背景范围;漳浦、福鼎和福州茶园土壤∑OCPs浓度显著高于其他样点。除福州外,其他样点HCH同系物中γ-HCH相对含量最高,占HCHs总量的26.3%-76.3%。DDTs中以o,p′-DDT相对含量最高,为34.7%-60.8%。0-15 cm土壤HCHs和DDTs浓度（分别为0.593 ng.g^-1和1.340 ng.g^-1）均高于15-30 cm（0.451 ng.g^-1和0.862 ng.g^-1）。除福州β-（/α＋γ）-HCH和α-/γ-HCH值较高外,其他样点均较低,表明福州HCHs为历史污染,其他样点均存在HCHs新输入,并可能存在林丹的使用或输入;除福鼎p,p′-DDE/p,p′-DDT值较高外,其他样点均较低,表明除福鼎外其他样点均有DDTs的新输入;o,p′-DDT/p,p′-DDT值均较高,表明可能有大量三氯杀螨醇的使用或输入。     

辽东与山东半岛土壤中有机氯农药残留特征研究

2005—2008年在辽东半岛和山东半岛15个市县采集了265个土壤样品,对其10种有机氯农药进行了分析,研究该地区土壤中硫丹、HCH和DDT残留情况及其空间分布特征。结果表明,山东半岛土壤中硫丹残留量为6.30μg kg-1,为辽东半岛的9倍;HCHs残留量为4.82μg kg-1,为辽东半岛的1.3倍;辽东半岛土壤中DDTs残留量为45.70μg kg-1,为山东半岛的2.5倍。山东半岛α-HCH、p,p′-DDE、p,p′-DDT的检出率均高于80%,辽东半岛β-HCH、p,p′-DDE检出率均高于80%。不同种植方式,辽东半岛土壤OCPs残留量:果园玉米地菜地草地水稻田;山东半岛土壤OCPs残留量:果园菜地玉米地麦田棉田。与国内其他地区相比,该地区硫丹残留量相对较低,HCHs和DDTs残留量超过国家《土壤环境质量标准》(GB15618-2008)一级标准的土壤样品分别占样品总数的4.53%和9.05%。     

Tween 80对DDTs污染场地土壤的增溶洗脱效果研究

以苏南某滴滴涕类化合物（DDTs）污染场地土壤为研究对象,进行实验室批量洗脱试验,研究了环境友好型表面活性剂Tween 80对土壤中DDTs的增溶洗脱效果及其影响因素。结果表明,Tween 80显著地增加了DDTs表观溶解度,在临界胶束浓度（CMC）以上对DDTs的增溶曲线呈指数衰减函数关系,DDTs各组分洗脱量顺序为4,4′-DDT〉4,4′-DDD〉2,4′-DDD〉2,4′-DDT。Tween 80的浓度、洗脱次数及土壤吸附作用共同影响其对DDTs的洗脱效果。去离子水能有效去除土壤中残留Tween 80,Tween 80解吸附率最高可达72.66%,大大降低了Tween 80二次污染土壤的风险。Tween 80增溶和去离子水解吸附联合过程对DDTs洗脱效果产生显著的协同作用。10 000 mg·L^-1浓度条件下Tween 80对DDTs的去除率最高为72%,其次为8 000 mg·L^-1 的Tween 80水溶液,去除率为66.72%。采用8 000 mg·L^-1的Tween 80溶液进行土壤洗涤处理,结合其他修复技术,可能会是修复DDTs污染土壤的有效技术方案之一。     

不同施肥方式下土中有机氯农药的残留特征

Soil samples with three fertilization treatments (no fertilizer, corn straw and farm manure) collected from a Lou soil (Eum-orthic Anthrosol classfied using Chinese Soil Taxonomy) in northwestern China were analysed for residual levels and their characteristics of organochlorine pesticides (α-HCH, β-HCH, γ-HCH, δ-HCH, HCB, o,p'-DDT, p,p'-DDT, o,p'-DDE, p,p'-DDE, p,p'-DDD, a-endosulfan, dieldrin and endrin). Organochlorine pesticides (OCPs) were detected in all soil samples except δ-HCH and their total concentrations ranged from 159.31 ± 9.00 to 179.77 ± 2.58 ng g^-1 with an order of HCHs > DDTs > (dieldrin + endrin) > HCB > α-endosulfan. Among all the compounds, γ-HCH had the highest concentration followed by p,p'-DDE. The residual levels of HCH isomers and DDT as well as their metabolites in soil with different fertilization treatments were in the order of γ-HCH > β-HCH ≈ α-HCH > δ-HCH and p,p'-DDE > p,p'-DDT > o,p'-DDT > p,p'-DDD ≈ o,p'-DDE, respectively. DDE/DDT ratios ranged from 1.59 ±0.13 to 3.35 ± 0.16 and endrin/dieldrin ratios from 1.40 ± 0.06 to 9.20 ± 4.05, both indicating no new occurrence of these pesticides in these soils, while α-HCH/γ-HCH ratios of 0.04 indicated a new input of lindane (almost pure γ-HCH) in the past several years. The farm manure treatments showed lower DDT residues than samples without fertilizer. Also addition of corn straw and farm manure increased soil organic matter content and decreased the soil pH which could retard the degradation of DDT in the soil.     

Accumulation and metabolism of DDT and its metabolites byTetrahymena

Tetrahymena pyriformis readily accumulated DDT and its metabolites from the medium initially containing 1 ppm of each compound. These compounds were accumulated in a decreasing order of DDD, DDE, o,p′-DDT, DDMU, and p,p′-DDT. DDT was metabolized to DDE, o,p′-DDT, and DDMU. DDD was metabolized to DDMU whereas o,p′-DDT, DDE and DDMU were not metabolized. When the organisms were transferred to toxicant free medium excretion of p,p′-DDT and its metabolite occurred in two phases: (a) rapid phase of elimination which was completed during the first 3 h and (b) slow phase of elimination which continued for another 21 h. The implications of these results are discussed.     

天津郊区土壤与作物中有机氯农药残留现状与来源初析

通过在天津塘沽和宁河地区野外实地采样分析,了解研究区域有机氯农药各异构体在土壤及作物各部位的残留水平,并通过特征比值推测其来源。结果表明,塘沽和宁河地区土壤中六六六的残留浓度均值分别为88.76μg·kg^-1与98.46μg·kg^-1,β-HCH占绝对优势而γ-HCH均未在土壤样品中检出,α-HCH手性分析结果显示为非消旋体,均表明土壤中六六六来自历史残留而非新近输入或林丹的使用。塘沽和宁河地区滴滴涕的残留浓度均值分别为30.87μg·kg^-1与1.30μg·kg^-1,亦来自历史残留,在个别点位可能曾使用过三氯杀螨醇。作物样品中六六六与滴滴涕的含量较高,经对数变换的生物富集系数变化范围分别为0.24～0.73与2.02～2.90。六氯苯、七氯、艾氏剂、异艾氏剂、反式氯丹、顺式氯丹、狄氏剂与异狄氏剂在大部分土壤与作物样品中也有不同程度的检出。     

Transformation and form of dichlorodiphenyltrichloroethane (DDT) applied to Moscow soils

The transformation rate and direction of dichlorodiphenyltrichloroethane (DDT) and its forms entering the surface layers of Moscow soils have been analyzed. The DDT transformation rate into metabolites—dichlorodiphenyldichloroethylene (DDE) and dichlor diphenyl dichloroethane (DDD)—is small. In 75% of soils, less than half the initial pesticide is transformed. In 67.5% of soils, formation of DDD predominates in the DDE formation. In soils of the entire area of Moscow, 16% of DDT was transformed into DDE and 23% into DDD. The о,n′-DDT to n,n′-DDT ratio is <0.3 for 95% of soils, and the mean ratio is 0.1, which is typical for application of DDT as a technical product.     

Organochloride insecticide residues in air in Delhi,India

Regular monitoring of air at three different sites, namely, Netaji Nagar, Moti Nagar and Town Hall in the metropolitan city of Delhi, India from June, 1980 to May, 1982 revealed varying levels of residues of DDT and HCH. The concentration of total DDT residues varied from 4 to 232 ng m^?3 with an average of 60 ng m^?3. Total HCH ranged from 0 to 21797 ng m^?3 with an average of 438 ng m^?3. Comparatively higher levels of total DDT (73 ng M^?3) were detected at Moti Nagar, the site near a DDT factory. The total HCH was highest at Town Hall (931 ng m^?3). Normally, higher quantities of the residues of DDT and HCH were detected during October to December. The insecticide residues consisted mainly of p, p′-DDT, p, p′-DDE, o, p′-DDT and p, p′-DDD, α- and γ-HCH. Only p, p′-DDT and p, p′-DDE were detected in all the samples and accounted for the bulk of total DDT. The HCH residues were mainly due to the α-isomer. Generally the concentration of HCH was higher than DDT in the air samples collected during the survey.     

Co-remediation of DDT-contaminated soil using white rot fungi and laccase extract from white rot fungi

Purpose

2,2-Bis(p-chlorophenyl)-1,1,1-trichloroethane (DDT), one of the most widely used organochlorine pesticides in soil, was banned in the 1970s for agricultural use because of its detrimental impacts on wildlife and harmful effects on human health via the food chain. However, high levels of DDT are frequently detected in agricultural soils in China. Considering this situation, this study investigated the use of white rot fungi and laccase derived from white rot fungi to co-remediate DDT-contaminated soil.

Materials and methods

A culture of white rot fungi was used to inoculate soil samples and also to extract laccase from. Soil was contaminated with four components of DDT (p,p′-DDE, o,p′-DDT, p,p′-DDD, and p,p′-DDT). Individual DDT components and the sum of the DDT components (p,p′-DDE, o,p′-DDT, p,p′-DDD, and p,p′-DDT—collectively referred to as DDTs) were both analyzed by GC at various stages during the incubation period. The efficacy of co-remediating DDT-contaminated soil using white rot fungi and laccase was tested by investigating how degradation varied with varying amounts of white rot fungi, sterilizing soil, temperature, soil pH, concentrations of DDT, and concentration of the heavy metal ion Cd²⁺.

Results and discussion

“”It was concluded that the reduction of DDTs in soil using white rot fungi and laccase was higher than reduction using only white rot fungi or laccase by nearly 14 and 16 %, respectively. Five milliliters fungi per 15 g soil and 6 U laccase per gram soil were the optimal application rates for remediation, as shown by a reduction in DDTs of 66.82 %. The difference in the reduction of individual DDT components and DDTs between natural and sterilized soils was insignificant. The optimal temperature and pH in the study were 28 °C and 4.5, respectively. In addition, reduction of individual DDT components and DDTs increased with increasing concentrations of DDT and decreased with increasing concentrations of Cd²⁺.

Conclusions

Compared with the remediation of DDT using only white rot fungi or laccase, the co-remediation of DDT using white rot fungi and laccase degraded DDT in soil more rapidly and efficiently; the highest reduction of DDTs was 66.82 %.     

福州地区不同土地利用类型土壤中六六六和滴滴涕的残留特征

采集福州地区106个表层土壤样品,运用气相色谱-电子捕获检测器（GC-μECD）,分析了不同土地类型土壤中六六六（HCHs）和滴滴涕（DDTs）残留水平、组成特征及来源。结果表明,福州土壤HCHs总浓度为0.581～66.9μg·kg-1,DDTs总浓度为0.782～110μg·kg-1。不同土地利用类型土壤中HCHs残留量为未利用地〉水田〉旱田〉草地〉林地。4种HCHs异构体中,草地、旱田和林地土壤中分别以α-HCH、β-HCH和γ-HCH相对含量最高,水田和未利用地土壤中δ-HCH含量最高。不同土地利用类型土壤中DDTs残留量为未利用地〉旱田〉水田〉林地〉草地,除未利用地土壤中相对含量最高的同系物是p,p′-DDD外,其余4种类型土壤中均是p,p′-DDE相对含量最高。来源分析表明,福州可能有林丹（主要成分为γ-HCH）输入,草地可能还有工业HCHs的输入;未利用地、旱田、林地土壤还存在新的DDTs输入,水田和草地土壤近期无工业DDTs输入;旱田、水田、未利用地可能还有少量三氯杀螨醇的使用或输入。     

河西走廊及兰州地区土壤中典型有机氯农药残留研究

应用Agilent7890-5975CGC-MSD对甘肃省河西走廊及兰州地区17个表层土壤样品中六六六（HCHs）和滴滴涕（DDTs）的残留水平进行分析,并对其来源进行初步解析。研究结果表明：研究区土壤中DDTs残留范围为0.22~53.69ng·g-1,平均值为8.58ng·g-1;HCHs残留范围为0.07~9.16ng·g-1,平均值为1.32ng·g-1;DDTs的残留较HCHs占优势,约占二者总残留量的87%。（DDE＋DDD）/DDT比值介于0.12~0.48之间,平均值为0.27,o,p′-DDT/p,p′-DDT比值在0.11~0.79之间,平均值为0.34,表明研究区土壤中的DDTs主要来源于工业源DDTs残留。α-HCH/γ-HCH介于0.64~15.5间,平均值为3.19,可推断研究区近期内不存在HCHs的使用,土壤中的HCHs残留主要来源于历史上工业HCHs和林丹的共同输入。与国内外其他地区土壤相比,该地区HCHs和DDTs的残留量处于较低水平;依照土壤环境质量标准（GB15618—1995）的要求,研究区各采样点土壤环境处于相对安全的状态。     

北京官厅水库有机氯农药分布特征及健康风险评价

为了研究北京官厅水库中有机氯农药（OCPs）对人体产生的潜在健康危害风险,从位于官厅水库、洋河和妫水河的9个采样点采集了水样和沉积物样品,采用气相色谱法对其中的有机氯农药残留状况进行了测定。结果表明,水样中,17种有机氯化合物的总浓度范围为10．06～87．37ng·L^-1,其中六六六（HCHs,即：α—HCH、β-HCH、γ-HCH和δ-HCH）和滴滴涕（DDTs,即：o,p＇-DDT、p,p’-DDT、p,p＇-DDE和p,p＇-DDD）的含量范围分别为3．93～38．94ng·L^-1和3．71～16．03ng·L^-1,官厅水库及其支流水体受到有机氯农药轻度污染,其周边地区农田排放水是水库中农药的重要来源。沉积物中有机氯农药总含量范围为8．48～24．40ng·g^-1,其中HCHs和DDTs的含量高于其他OCPs的含量,其含量范围分别为1．11～7．73ng·L^-1和2．97～10．52ng·g^-1,沉积物中六六六异构体和滴滴涕类似物的含量组成表明这些农药来自环境中的早期残留。利用健康风险评价模型对官厅水库表层水体中的OCPs所致健康风险的评价结果表明,目前官厅水库中有机氯农药类污染物对人体健康的风险处于较低水平。