根际土壤中DDTs的残留与转化

通过根垫法研究DDT的五种异构体p,p‘-DDE,o,p’-DDD,p,p‘-DDD,o,p‘-DDT,p,p‘-DDT在小麦根际土壤和非根际土壤中的残留量以及DDT,DDD和DDE之间的转化．结果发现,在40d试验期间内,DDT发生缓慢降解,根际土壤中的降解略快于非根际土壤,且差别主要表现在生成DDD的厌氧过程方面．此外,根际土壤中五种DDT的异构体的可提取残留都高于非根际土壤,说明该农药的锁定过程在根际环境相对较弱．     

超声辅助硫酸亚铁活化过碳酸钠降解4种典型DDTs

采用超声波辅助硫酸亚铁活化过碳酸钠(SPC/Fe~(2+))体系降解水中的4种典型有机氯农药DDTs(包括p,p′-DDD、p,p′-DDE、o,p′-DDT、p,p′-DDT),考察超声波功率、过碳酸钠投加量和硫酸亚铁投加量等实验条件对DDTs降解的影响,采用响应面法设计多因素实验,采用二次多项式和逐步回归法拟合DDTs降解率、毒性削减率与实验条件之间的关系,通过模型优化和验证实验获得最佳降解条件,通过GC/MS检测分析DDTs降解产物并推断其降解途径.结果表明,超声波辅助Fe~(2+)/SPC能够在5 min内高效降解DDTs,当超声波功率为30 W、超声5 min、过碳酸钠和硫酸亚铁投加量分别为3.21 g·L~(-1)和0.64 g·L~(-1)时,DDTs总毒性削减率可达98.2%.DDT首先脱氯生成DDE和DDD,再进一步降解生成DDMU等其他物质.     

嗪吡嘧磺隆在土壤和沉积物中的降解

采用室内模拟实验法,测定了嗪吡嘧磺隆在好氧与积水厌气(或厌氧)条件下的土壤降解和水-沉积物降解特性.研究结果表明,嗪吡嘧磺隆在好氧条件下,江西红壤、太湖水稻土、东北黑土中降解速率分别为0.041、0.008、0.004 d-1,积水厌气条件下分别为0.028、0.023、0.005 d-1,不同类型土壤中降解快慢顺序为:江西红壤太湖水稻土东北黑土,在太湖水稻土和东北黑土中积水厌气条件更有利于其降解,且土壤p H值是影响土壤中降解速率的主要因素;水-沉积物降解中,好氧条件下河流与湖泊水-沉积物系统中农药总量的降解速率分别为:0.031、0.032 d-1,厌氧条件下的降解速率分别为0.035、0.041 d-1,湖泊体系的降解速率快于河流体系,厌氧条件下降解速率快于好氧条件,且嗪吡嘧磺隆在水-沉积物体系中主要存在于水体中,系统降解速率主要受水体中的降解速率影响.可见,嗪吡嘧磺隆在中性至碱性土壤中具有较强稳定性,进入水-沉积物系统时主要分布于水体当中,可能会对水体和土壤环境造成一定的污染影响.     

DDT及其衍生物对2种单细胞藻的毒性效应

研究4种不同质量浓度的DDT及其衍生物对2种单细胞藻(Nannochloropsis sp. 和Nannochloropsis. Oculata)生长及细胞活力的影响.将单细胞藻接种于f/2培养液中,接种培养10 d后,再添加各种种类及质量浓度的DDT及其衍生物,其后每隔7 d记数一次,培养周期为38 d,观察并记录单细胞藻的生长状况.单细胞藻的定量方法,参照血球计数板计数法.结果表明,Nannochloropsis sp. 具有较明显的抗性及良好的生长特征,其生长受DDT及其衍生物的影响较小,在p. p′-DDD作用组中,培养36 d后细胞数达到最高(23510细胞数·μL-1),空白对照为23290细胞数·μL-1;而DDT及其衍生物对Nannochloropsis. oculata的生长有一定的抑制作用,抑制作用大小依次为p.p′-DDT,p.p′-DDE,o. p′-DDT,p. p′-DDD;其中,p. p′-DDT的最大抑制质量浓度为5 μg· L-1,p. p′-DDE的最大抑制质量浓度为10 μg·L-1,o. p′-DDT最大抑制作用质量浓度为1 μg·L-1,p. p′-DDD的最大抑制质量浓度为10 μg·L-1.细胞活力的测定采用MTT法,检测结果表明,从第10 d起,Nannochloropsis sp. 就呈现出较高的细胞活力水平.其中p. p′-DDT,p. p′-DDD,p. p′-DDE 对其作用所引起的变化较大,在0.13～0.325 OD范围,o. p′-DDT 引起的变化较小,在0.145～0.237 OD范围,这与该藻具有抗逆性强特性相吻合.加入不同质量浓度的DDT及其衍生物后,从10 17 d起,Nannochloropsis. oculata均呈现出呈较低水平的细胞活力,平均在0.072～0.26 OD范围,但从24 d起出现较高的细胞活力,平均在 0.249～0.408 OD水平,其后呈现逐渐下降的趋势.     

环氟菌胺在土壤和水-沉积物系统中的降解研究

环氟菌胺是一种新型酰胺类杀菌剂,其在环境中的归趋备受关注。采用室内模拟试验方法,研究了环氟菌胺在不同土壤和水-沉积物体系中的降解特性。结果表明,好氧条件下,其在江西红壤、太湖水稻土、东北黑土中降解速率分别为0.007、0.007、0.009 d~(-1),降解半衰期分别为99.0、99.0和77.0 d;积水厌气条件下降解速率为分别为0.004、0.004、0.011 d~(-1),降解半衰期为173、173和63.0 d。不同类型土壤中降解速率大小为江西红壤≈太湖水稻土东北黑土,土壤p H值是影响环氟菌胺在土壤中降解的主要因素。好氧条件下河流与湖泊水-沉积物系统中环氟菌胺总量的降解速率分别为0.032、0.028 d~(-1),降解半衰期分别为21.7和24.8 d;厌氧条件下其降解速率分别为0.028、0.023 d~(-1),降解半衰期分别为24.8和30.1 d。河流体系的降解速率高于湖泊体系,好氧条件下降解速率高于厌氧条件。环氟菌胺在水-沉积物体系中主要存在于沉积物中,系统降解速率主要受沉积物中的降解速率影响。环氟菌胺在土壤中具有较强稳定性,进入水-沉积物系统时主要分布于沉积物中,可能会对水体和土壤环境造成一定的污染。     

手性农药的环境行为研究进展

手性农药由于其对映体选择性,在环境中具有特殊的归宿.研究其环境行为有助于准确评价生态系统和人体健康的风险性.文章综述了手性农药的研究进展,指出高效液相和气质联用法是不同环境介质中手性农约的主要分离分析方法;利用手性农药的对映体分数可研究农约在土壤-大气,水体-大气间的迁移过程;一些手性农药在土壤、水体和动物体内中发生的选择性降解与累积与微生物或特异性的酶有直接关系,可利用此性质修复被污染的土壤;归纳了在手性农约污染环境风险研究中应注意的问题;加强手性农约在环境中的选择性降解动力学、对映体转化及毒理学机制研究,并最终深人到代谢机理、蛋白和基因水平上,阐述产生手性对映体选择性的根源将是未来研究的方向.     

手性有机磷农药在土壤中对映体选择性降解特征

马拉硫磷和丙溴磷是2种常用的有机磷杀虫剂,均有一个手性中心存在2个对映体.采用室内避光培养的方法,在对映体水平上研究了马拉硫磷和丙溴磷在2种土壤中的降解情况.结果表明,2种农药在土壤中的降解均较快,马拉硫磷和丙溴磷的降解半衰期分别为:黄土中3.5 h和21.5 h,红土中4.3 h和29.4 h.进一步的手性测定表明2种农药的降解均存在一定的对映体差异,丙溴磷对映体的选择性明显高于马拉硫磷,在2种土壤中马拉硫磷的左旋对映体降解快于右旋对映体,丙溴磷的右旋体降解快于左旋体.研究有助于深入认识2种有机磷农药在环境中的归趋,并对其生态风险性进行更合理的评估.     

滴滴涕类农药在广东省鱼类中的残留及人体暴露水平初步评价

检测了采自广东省13个城市水产市场和超市的390个鱼样品中滴滴涕类农药(DDT)及其代谢物(包括o,p’-DDE,p,p’-DDE,o,p’-DDD,p,p’-DDD,o,p’-DDT,p,p’-DDT)的残留浓度.鱼体中DDTs的含量为8.7￣18002ng·g-1(脂肪重)或0.1￣698.9ng·g-1(湿重).不同鱼类之间因生活环境和生活习性的不同,而使其DDTs含量存在较大差别.与我国鱼类食品中DDTs的残留标准相比,仅有2个样品中的DDTs含量水平超过此标准,约占样品总数的0.51%,而超过欧盟水产品标准和美国环境保护局(EPA)标准的样品分别占13.8%和30.5%.广东省居民通过鱼类消费每天DDTs的摄入量为30.8ng·kgbodyweight-1·day-1,仅占FAO/WHO每日允许摄入量的0.3%,但高于其他国家或地区.     

土壤类型与污染浓度对漆酶修复DDT污染土壤的影响

具有难降解、高残留特征的DDT至今在土壤中仍有残留,对农产品安全和人体健康有严重影响.本文采用批实验的方法研究了3种不同类型土壤和3个污染水平对漆酶修复DDT污染土壤的影响.研究结果表明,不同类型土壤中DDT各组分及总量(DDTs)的降解率存在显著差异,总体上为水稻土＞菜园土＞赤红壤,对照处理土壤中DDTs的降解率仅为20%左右,加酶处理土壤中则高达50%～65%.对于不同污染水平的DDT污染土壤,土壤中DDT各组分及DDTs的降解率均随着污染水平的提高而增大,多数在不同污染水平之间差异显著.对照处理对不同污染水平土壤中DDTs的降解率仅为15%左右,而加酶处理则高达43.60%～50.53%.     

兰州周边地区土壤典型有机氯农药残留及生态风险

应用Agilent 7890-5975C GC-MSD对兰州及其周边地区16个表层土壤样品中HCHs和DDTs残留水平进行分析,并对兰州周边地区土壤中OCPs的可能来源和生态风险进行了初步研究.结果表明,研究区土壤中HCHs残留范围为8.22×10-2—4.49 ng.g-1,平均值为6.85×10-1ng.g-1;DDTs残留范围为1.41×10-1—120 ng.g-1,平均值为16.9 ng.g-1;DDTs残留较HCHs占优势,约占二者总残留量的96%.α-HCH/γ-HCH比值介于0.18—14,平均值为2.8,推测研究区土壤中HCHs残留源于工业HCHs和林丹的混合源,并且可能存在有周边地区HCHs的大气长距离输送.DDE/DDD比值介于0.35—4.8,平均值为2.1,说明研究区土壤中DDT以有氧方式降解为主;(DDE+DDD)/DDT比值介于0.067—0.69,平均值为0.30,o,p’-DDT/p,p’-DDT比值介于0.091—2.8,平均值为0.60,表明研究区土壤DDTs污染可能主要源于工业源DDTs.与国内其它地区土壤相比,研究区土壤中HCHs和DDTs残留量相对较低;依照国家《土壤环境质量标准》(GB-15618—1995),研究区土壤中HCHs和DDTs残留处于较低水平;研究区土壤中HCHs残留处于较低的生态风险,DDTs残留对于土壤生物和鸟类具有一定的生态风险,而对于哺乳类动物生态风险较低.     

Cattle egrets as a biosentinels of persistent organic pollutants exposure

We investigated selected chlorinated pollutants (β-HCH, γ-HCH, DDDs, DDEs, o,p′-DDT, p,p′-DDT, heptachlor, aldrin, dieldrin, and endrin) in the Lahore and the Sialkot districts of Pakistan, using eggs of cattle egret (Bubulcus ibis) collected during May and June 2007. The pollutant with highest level and frequency was ΣDDT, followed by β-HCH, γ-HCH, heptachlor, aldrin, dieldrin, and endrin in descending order. The concentration(s) were significantly higher in Sialkot heronry for all the pollutants (except p,p′-DDT) than in Lahore. The values for DDTs, β-HCH, γ-HCH, and heptachlor were significantly higher (p < 0.05) in the egg(s) than in sediment(s) and in the chicks’ diet, due to biomagnification. Among DDTs analogues, p,p′-DDD was the major contaminant with >60 % of total DDT burden, reflecting the widespread aged as well as recent use of DDT as well as anaerobic degradation (DDD/DDE > 1 in many cases) in the nearby paddy soils. In few samples, p,p′-DDT/(DDD + DDE) > 0.5 suggested the recent emission patterns from surrounding contaminated areas of demolished DDT units and obsolete pesticide stores. The higher levels of HCHs (i.e., β-HCH) in the samples collected from Sialkot indicate exposure from long-term agricultural use. Overall, concentrations of all studied POPs were less than the threshold levels known to affect reproduction. Nevertheless, total DDTs and/or HCHs burdens in some eggs contained concentrations of greater than what would educe adverse effects on birds. This is among few studies on OCPs exposure to avian species, which provide the evidence of Pakistan’s contribution toward the Global POPs emission.     

DDT isomers and metabolites in the environment: an overview

It is known for decades that the isomeric composition of organic pollutants can be influenced substantially by environmental processes such as biotransformation or transfer between compartments. This accounts also for the pesticide 2,2,-bis(4-chlorophenyl)-1,1,1-trichloroethane, better known as p,p′-DDT, and its accompanied substitution isomer 2-(2-chlorophenyl)-2-(4-chlorophenyl)-1,1,1-trichloroethane (o,p′-DDT). Although many studies followed the environmental fate of DDT, only very few publications reported on quantitative data of both o,p′- and p,p′-isomers. Therefore this condensed review describes evidence for remarkable changes and shifts in o,p′-/p,p′-ratios of DDT-related compounds. The application of isomer-specific analysis remains dominantly on emission source apportionment, for example, to differentiate DDT and dicofol emission. Only very few studies linked observed isomer shifts to aspects of environmental processes, such as (1) volatility from soil to air, (2) environmental stability in soil or (3) bioaccumulation in fishes. Additionally, several studies failed to use isomer-specific interpretation in order to obtain more detailed insight into environmental processes, for example, for observed isomer shifts during air–water fluxes. The o,p′-/p,p′-ratios of DDT and its main metabolite DDD have been detected more or less on the same level, whereas the isomers of the second main metabolite DDE were definitely depleted by the o,p′-isomer in all environmental compartments, indicating a general isomer-specific differentiation during DDT metabolism.     

Accumulation, distribution and transformation of DDT and PCBs by Phragmites australis and Oryza sativa L.: I. Whole plant study

Glasshouse experiments were conducted to determine the accumulation, distribution and transformation of o,p′-DDT, p,p′-DDT and PCBs by common reed (Phragmites australis) and rice (Oryza sativa L.) under hydroponic conditions. The culture solution was spiked with the organic pollutants and samples were collected daily. Analysis of the plants at harvest showed that both species had removed DDT and PCBs from the solution. DDT appeared to have accumulated within P. australis by both passive adsorption and active absorption. Both o,p′-DDT and p,p′-DDT were transformed within P. australis. DDD was the major metabolite and the transformation was mediated by reductive dehalogenation. Plant long-distance transportation systems may be involved in the translocation of PCBs within P. australis and the affinity of the PCBs for lipids is one of the major factors affecting their uptake and translocation within the plants. Similar but less pronounced results were found in O. sativa and suggest that these wetland plants may be used for the plant-mediated remediation of persistent organic pollutants.     

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。     

除草剂苯噻草胺对水稻田土壤微生物种群的影响

以浙江大学华家池校区水稻土为材料,采用室内培养法,研究了不同浓度的外源除草剂苯噻草胺对水稻田土壤可培养微生物种群数量的影响.结果表明:土壤中各微生物类群对不同浓度的苯噻草胺具有各自不同的反应.苯噻草胺能刺激好氧细菌数量增加,但不利于真菌和放线菌的生长.低浓度苯噻草胺刺激水解发酵性细菌(AFB)、产氢产乙酸细菌(HPAB)和产甲烷细菌(MPB)数量的增加,但高浓度苯噻草胺却具有抑制性.在苯噻草胺施用第4周时可强烈刺激反硝化细菌(DNB)数量的增加.苯噻草胺也能刺激厌氧固氮菌(ANFB)数量增加,但这种刺激作用在第2周才出现,而且在培养后期消失.苯噻草胺的短期影响即急性毒性对土壤中可培养微生物的影响较小,比上一代除草剂丁草胺相对安全.图2表1参15     

Organochlorine residues in maternal milk from inhabitants of the Thohoyandou area,South Africa

The presence of organochlorine compounds (OC) such as DDT and their metabolites in the environment have created a significant environmental concern over the years due to adverse effects. Consequently, DDT has been banned in many countries. However, it is still used in some countries including South Africa, particularly for vector-borne disease eradication programmes. Since the presence of DDT and its metabolites may provide an indication of the general exposure and use of these compounds, there was a need for such a study. Human breast milk samples (n = 30) were collected from mothers within the age range of 19–40 years from the Thohoyandou area, South Africa. The liquid–liquid extraction method was used to extract DDT and its metabolites from the samples. The crude extracts were subjected to column chromatography for measurements of OC levels. The concentration ranges of the contaminants were as follows: not detected (ND) to1770 ng g^?1 (2,4′-DDE); ND to 3977 ng g^?1 (4,4′-DDE); ND to 3250 ng g^?1 (2,4′-DDD); ND to 2580 ng g^?1 (4,4′-DDD) and ND to 2847 ng g^?1 (4,4′-DDT). The mean ΣDDE, ΣDDD and ΣDDT obtained from the villages were 1180 ng g^?1, 830 ng g^?1 and 690 ng g^?1, respectively. The total DDT ranged from 820–7473 ng g^?1. The estimated daily intake varied from 260 to 4696 ng g^?1, ND-10551 ng g^?1 and ND-4237 ng g^?1 for DDE, DDD and DDT, respectively. These values are significantly higher than the FAO/WHO acceptable daily intake (ADI) of 20 ng g^?1. The ΣDDT was found to decrease with increasing age of the mothers. The observed high levels of DDE compared to DDT indicated chronic exposure of the mothers to DDT, which is metabolized to DDE and retained in the body.     

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.     

DDT und Metaboliten in Sedimenten Berliner Gewässer

Sediment samples from rivers and lakes of Berlin (Germany) were analysed for their contamination with organic compounds by means of qualitative and quantitative GC/MS analysis. The principal compounds detected were PAH, organotin derivates, several classes of chlorinated, brominated and mixed halogenated compounds and some of their related metabolites. The DDT metabolites DDD, DDE, DDCN, DDMU and DDMS were the most abundant compounds of halogenated pesticides in a wide range of samples. The main metabolite determined was p,p′-DDD, with concentrations up to 1230 μg/kg dw. The parent DDT compound was detected in only a few samples. The acute cytotoxicity of selected DDT-metabolites was determined with the permanent cell line RTG-2 from the gonads of the rainbow trout (Oncorhynchus mykiss). The results indicate a high cytotoxic potential of these metabolites. The oestrogenic potential was determined by the Dot-Blot/RNase-Protection-Assay an the order from o,p′-DDT>p,p′-DDMS>p,p′-DDMU≥p,p′-DDCN. Risk assessments based on chemical analysis of DDT, DDD and DDE alone is not able to estimate the real toxic potential of DDT and its metabolites. The development of a method for bioassay directed assessment seems to be an effective strategy to solve this problem. Especially scarce or not available data of combinatory effects, differences between different trophic levels and their availability to biota and low knowledge about the metabolism in situ as well as the enantioselective characteristics of most chiral DDT metabolites warrant future analyses.     

磺胺嘧啶在水中的微生物降解研究

为了探明磺胺嘧啶在水中的环境行为,通过室内模拟降解实验分别研究了磺胺嘧啶在湖水和猪场废水中的好氧和厌氧微生物降解,考察了供氧方式和有机质含量对磺胺嘧啶微生物降解的影响。结果表明:磺胺嘧啶在猪场废水中厌氧微生物降解速率高于其好氧组,而磺胺嘧啶在湖水中厌氧微生物降解速率低于其好氧组。磺胺嘧啶在湖水和猪场废水中的好氧或厌氧微生物降解均较缓慢,这可能与其较强的抑菌性和微生物的营养状况有关。通过微生物培养还研究了好氧降解时磺胺嘧啶对湖水中微生物种群生长的影响,数据显示:磺胺嘧啶对湖水和猪场废水中细菌的生长具有一定的刺激作用,而对真菌和放线菌的生长影响不明显。     

Pesticide Residues in Water From River Kaveri,South India

The residue levels of presistent chlorinated pesticides such as HCH (hexachlorocyclo-hexane) isomers and DDT (dichlorodiphenyl trichloroethane) compounds were quantified in water samples collected from the River Kaveri and its distributor River Coleroon in Tamil Nadu, South India. HCH showed higher levels in River Kaveri during premonsoon (July to September) and monsoon (October to December) months, reflecting the HCH usage during that season for paddy crops. But in the case of DDT no clear trend in residue level was observed. the α-HCH was detected as the dominant isomer in all the three sampling sites. Among DDT compounds, p,p'-DDT and p,p'-DDE showed higher percentage of the total. International comparison of residue levels revealed that the present values are comparable to the waters from Asian and South East Asian nations, but lower than some samples from other parts of India. the value of DDT is well below the EEC's maximum acceptable concentration for surface waters and lower than the recommended limit of 2000ng 1^-1 in USA water for protection of aquatic life (Water Quality Criteria, 1972).