PFOS潜在替代品全氟丁基磺酸钾对不同营养水平水生生物的毒性

全氟丁基磺酸钾(PFBSK)作为全氟辛基磺酸(PFOS)潜在的替代品,极易溶于水,主要存在于水体中,因而其水生毒性的研究十分重要。采用OECD 201、OECD 202、OECD 203和OECD 211标准试验方法,研究了PFBSK对羊角月牙藻(Pseudokirchneriella subcapitata)、大型溞(Daphnia magna)和中国本土鱼种稀有鮈鲫(Gobiocypris rarus)的急性毒性效应以及对大型溞繁殖的影响。组合多终点急慢性水生生物毒性结果：PFBSK的急性毒性终点均大于100 mg·L^-1,大型溞繁殖试验的无观察效应浓度(NOEC)为571 mg·L^-1,最低可观察效应浓度(LOEC)为981 mg·L^-1。按GHS分类导则,PFBSK未表现出急性毒性和慢性毒性。与之相比,PFOS则对水生生物表现出毒性,黑头软口鲦(Pimephales promelas)为最敏感物种,其96 h-LC₅₀为4.7 mg·L^-1;大型溞繁殖试验的NOEC为12 mg·L^-1。按GHS分类导则,属于中等毒性物质。可见,PFBSK较PFOS水生毒性明显降低。     

基于权重敏感度分布研究太湖有机磷农药单一和复合风险

基于实验室能得到的有限毒性数据的物种敏感度分布法(species sensitivity distribution, SSD)很难充分代表特定区域生态系统的物种分布,需要采用考虑生物区系特征进行赋予权重的物种敏感度分布法(weighted species sensitivity distribution,WSSD)。基于太湖物种组成构建WSSD,使用最大累积率(maximum cumulative ratio, MCR)(含风险商法(hazard quotient, HQ))和概率风险评价法(probabilistic risk assessment, PRA)对太湖地区单一和混合有机磷农药的风险进行研究。结果表明,相对于传统SSD方法,加权SSD方法计算的风险商大,且5%生物受影响的概率更大。单一风险评价中,敌敌畏和乐果5%生物受影响的概率超过40%,需要优先控制;最大累积率表明,敌敌畏是复合风险的主要贡献者,单一风险评价中风险较小的马拉硫磷和对硫磷也对复合风险贡献较大,复合暴露风险评价是必要的,混合物的风险商>1,5%生物受复合暴露影响的概率高达90%,有机磷农药复合生态风险不容忽视。     

太湖流域西北部地表水中农药的污染特征及生态风险评价

为研究太湖流域西北部地表水中农药的污染特征、时空分布及生态风险,分别于2019年3月(枯水期)和8月(丰水期)对目标区域的湖泊和重要河流中的农药进行监测分析。采用固相萃取结合高效液相色谱串联质谱法对120个地表水样品中的农药进行分析测定,共检测到7种杀虫剂和5种杀菌剂。整体上,枯水期农药污染较丰水期严重,农药总浓度的平均值分别为191.87 ng·L-1和171.07 ng·L-1。残留最高、分布最广的农药是吡虫啉(浓度范围ND～197.97 ng·L-1,检出率98%)和多菌灵(浓度范围ND～114.44 ng·L-1,检出率97%)。靠近农业区的漕桥河(S5和S6)和锡溧漕河(S36)是重污染区,漕桥河的S6点位是污染最严重的点位。采用风险商指数对农药进行生态风险评估,丰水期地表水中的农药对水生生物的威胁大于枯水期。有机磷类杀虫剂和苯并咪唑类杀菌剂对水生生物具有高风险,需要引起重视。     

啶氧菌酯对斑马鱼的安全性评价及其生物富集行为研究

啶氧菌酯是一种新型的内吸性杀菌剂,本研究对其水生生物的毒性和累积风险进行了评估。啶氧菌酯原药对斑马鱼的急性毒性试验结果显示,96 h-LC₅₀为0.0509 mg a.i. L^-1。设置0.005 mg L^-1(1/100LC₅₀)和0.05 mg L^-1(1/10LC₅₀)2个浓度8 d生物累积试验。在0.005 mg L^-1组,第8天斑马鱼体内啶氧菌酯浓度达到0.48 mg kg^-1,生物富集系数(BCF_{8 d})缓慢增长到80.00。而在0.05 mg L^-1组,第8天斑马鱼体内的啶氧菌酯浓度为5.27 mg kg^-1,BCF_{8 d}值为99.42。研究表明,啶氧菌酯对斑马鱼为有剧毒,同时具有中等生物累积效应。因此在使用过程中,需要考虑其对水生生物的毒性和水生食物链的放大效应。     

氧化乐果和毒死蜱混剂对大鼠雄性生殖功能的联合毒性

为探讨有机磷农药混合物对生物生殖毒性的影响,以模式动物Sprague- Dawley (SD)大鼠为实验材料,采用亚慢性染毒动物实验,利用3×3析因实验设计方法研究了常见有机磷农药——氧化乐果和毒死蜱的联合雄性生殖毒性效应及机理。结果表明：氧化乐果和毒死蜱联合染毒60 d后,附睾系数增加,精子数量和精子活力降低,联合作用呈现协同效应(p<0.05);混配农药能降低睾丸标志酶乳酸脱氢酶(LDH)、酸性磷酸酶(ACP)、碱性磷酸酶(AKP)、γ-谷氨酰转移酶(γ-GT)的活力,对LDH、ACP、γ-GT的联合作用表现为协同作用(p<0.05);混配农药能增加睾丸中促卵泡生成激素(FSH)含量,降低睾酮(T)含量,联合作用表现为协同作用(p<0.05)。通过组织病理学观察,氧化乐果和毒死蜱混合物能引起曲细精管的萎缩、畸形精子增多、生精细胞坏死、胞浆溶解和线粒体空泡化;支持细胞数量减少,出现坏死,精子从支持细胞上脱落,基底膜脱落等损伤。氧化乐果和毒死蜱对大鼠的联合生殖毒性为协同效应,混合后有明显的增毒作用;对睾丸标志酶(LDH、ACP、γ-GT)活力及睾丸性激素水平(FSH、T)的协同影响,是产生联合生殖毒性的机理之一。以上结果提示,对氧化乐果和毒死蜱进行环境健康风险评价时应考虑这种协同作用。     

不同类别农药助剂对蚯蚓(Eisenia foetida)的急性毒性

为评价农药助剂对土壤生物的毒性效应,分别采用滤纸接触法和人工土壤法测定了不同类别农药助剂对赤子爱胜蚓(Eisenia foetida)的急性毒性。结果表明：19种非离子表面活性剂中,烷基酚聚氧乙烯醚与脂肪醇聚氧乙烯醚毒性较高,滤纸法48 h-LC₅₀为7.630～39.65 μg·cm^-2,人工土壤法14 d-LC₅₀为876.5～2786.6 mg·kg^-1,其它类型非离子表面活性剂毒性较低。5种阴离子表面活性剂中,十二烷基硫酸钠、十二烷基苯磺酸钙毒性高于木质素磺酸钠、木质素磺酸钙、亚甲基双萘磺酸钠,滤纸法48 h-LC₅₀为6.575～41.89 μg·cm^-2,人工土壤法14 d-LC₅₀为1195.0～1911.7 mg·kg^-1。13种溶剂中,二甲苯、乙苯、甲苯、正丁醇、环己酮表现出较高的毒性,滤纸法48 h-LC₅₀为6.587～57.62 μg·cm^-2,密封人工土壤法48 h-LC₅₀为181.9～781.5 mg·kg^-1。采用两种方法测得的5种填料高岭土、白炭黑、硅藻土、凹凸棒土和轻质碳酸钙的毒性均较低。由此可见,采用两种方法测得的毒性系统偏差接近,重现性均较好,并且滤纸接触法测得的毒力高于人工土壤法。     

丙硫菌唑对斑马鱼的安全性评价及其生物富集行为研究

丙硫菌唑是一种市场前景非常好的新型广谱杀菌剂。本文研究了丙硫菌唑对水生生物斑马鱼的急性毒性和生物累积风险。通过斑马鱼的急性毒性试验获得丙硫菌唑对斑马鱼的96 h-LC₅₀为2.06 mg a.i. L^-1。随后,采用0.02 mg L^-1 (1/100LC₅₀)和0.2 mg L^-1 (1/10LC₅₀)2个浓度的丙硫菌唑,通过8 d实验,获得其在斑马鱼体内的生物累积效应。在0.02 mg L^-1组中,第8天时,斑马鱼体内的浓度达到0.733 mg kg^-1,生物富集系数(BCF_{8 d})缓慢增长到34.36。而在0.2 mg L^-1组,第8天时,斑马鱼组织内丙硫菌唑浓度为4.198 mg kg^-1, BCF_{8 d}值为19.72。结果表明,丙硫菌唑对斑马鱼的毒性等级为中毒,同时其在斑马鱼体内具有中等生物累积效应。因此,在使用过程中,需要考虑其对水生生物的毒性和水生食物链的放大效应。     

5种有机磷农药的淡水水生生物基准

采用毒性百分数排序法推导了马拉硫磷、乐果、甲基对硫磷、敌敌畏和对硫磷等5种有机磷农药的淡水水生生物基准,得出5种有机磷农药的基准最大浓度(CMC)分别为0.477、1.392、0.247、0.085、0.155μg·L-1;基准连续浓度(CCC)分别为0.030、0.688、0.092、0.056、0.030μg·L-1.将推导出的双值基准与我国地表水环境质量标准比较,结果表明,二者差别较大,我国目前这5种有机磷农药的水质标准可能在一定程度上存在着对水生生物"欠保护"的情况.5种有机磷农药的淡水水生生物基准可为我国淡水水生生物基准的制订提供一定的数据参考.     

不同土壤类型中外源汞对白符跳（Folsomia candida）的毒性研究

参考国际标准化组织(ISO)颁布的跳虫毒性测试方法 ISO11267,分析了汞(Hg)在我国9种典型土壤中对白符跳(Folsomia candida)的急性毒性及繁殖毒性。发现Hg在不同类型土壤中对白符跳的半数致死浓度(LC₅₀)变化为(0.92～1.94) mg·kg^-1,而对白符跳繁殖产生影响的半数效应浓度(EC₅₀)变化范围为(0.98～2.43) mg·kg^-1,产生10%影响的浓度(EC10)变化范围为(0.29～1.40) mg·kg^-1 。将土壤的主要理化性质(pH、OM、CEC)与Hg对白符跳的EC₅₀进行相关性回归分析,发现土壤CEC与EC₅₀呈显著正相关关系(r=0.8624,p<0.01),随着土壤CEC的增大,Hg的EC₅₀值也趋于升高。因此,土壤CEC可能是导致不同类型土壤中汞对白符跳毒性差异的主要因素。本研究结果可为制定基于我国土壤类型的生态筛选值提供基础参考数据。     

应用物种敏感性分布评估微(纳米)塑料对水生生物的生态风险

水环境中的微(纳米)塑料对水生生物具有潜在的危害。为了评估微(纳米)塑料对水生生物的毒性效应及生态风险,本研究在广泛查阅并分析微(纳米)塑料相关毒理学研究数据的基础上,利用物种敏感性分布(Species Sensitivity Distributions,SSD)方法对其中5门10科11种水生生物的急性毒理数据进行曲线拟合;计算对应的5%危害浓度(the hazardous concentration for 5%of the species, HC_5)和潜在影响比例(potential affected fractions, PAF);计算了相应的急性生态效应阀值(predicted no effect concentration, PNEC_(acute)),并比较了各类水生生物对微(纳米)塑料的敏感性及其所受生态风险。结果表明,目前已有数据中微(纳米)塑料对费氏弧菌(Vibrio fischeri)的生态风险最大,对朱氏四爿藻(Tetraselmis chuii)的生态风险最小;基于Reweibull模型对水生生物数据所推导的PNEC_(acute)为0.185μg·L~(-1),约为当前微(纳米)塑料在水体环境中浓度的30%。利用SSD来预测微(纳米)塑料不同暴露浓度下对水生生物的PAF,发现当微(纳米)塑料暴露浓度小于10μg·L~(-1)时,水生生物所受的影响在可接受范围内;当暴露浓度达到1 000μg·L~(-1)时,将有26%的物种受到微(纳米)塑料的危害。此外,利用Rurrlioz软件估算了世界典型淡水与海水水域表层水体中微塑料对水生生物的PAF值,发现其PAF预测值都为0;将各水域微塑料浓度与急性生态效应阀值PNEC_(acute)比较后发现,除太湖外,其他水体环境中微塑料浓度都低于PNEC_(acute),说明如果只考虑微塑料本身的影响,目前世界典型水域表层水中微塑料对水生生物的危害程度大部分都在可接受的范围之内。     

Ecological risk assessment of pesticide residues in Taihu Lake wetland, China

As a major ecosystem type, wetland provides invaluable ecological services. Environmental pollution, especially pesticides pollution should be paid more attention to keep wetlands healthy. Based on the risk quotient method, coupled with a probabilistic risk assessment model, this paper proposed a methodology suitable for ecological risk assessment of pesticide residues for wetland ecosystems. As an important industrializing and ecologically vulnerable area in China, the Taihu Lake wetland was chosen for the case study. The risks of eight pesticides in Taihu Lake wetland were assessed, as single substances and in mixtures. The assessment indicates that risks of the representative species are not significant. In general, the herbicide is found to be more toxic for algae, whereas insecticides pose more risks to zooplankton, insect and fish. For each pesticide in the wetland, the ecological risk it poses is acceptable. But the combined ecological risk posed by mixture can harm more than 10% of species of the wetland ecosystem, mainly dominated by dichlorvos, dimethoate and malathion contributions. These results imply that pesticide residues have been posing pressures on the ecosystem of the Taihu Lake wetland. It is recommended that proper countermeasures should be implemented to reduce the risks.     

极性有机物整合采样技术在监测水环境中农药的应用

明确水环境中农残的污染状况对研究其环境行为和生态风险至关重要。传统主动采样法耗能、耗力且单次采样仅获得瞬时浓度值。被动采样节能、方便且为时间加权平均浓度,利于大规模采样。极性有机物整合采样技术(polar organic chemical integrative sampler,POCIS)是针对极性有机物的被动采样技术,近年来在水环境中农药监测的运用越来越广泛。本文概述了POCIS结构、原理和校正方法,探讨了环境因素(如水流速率、温度、p H、溶解性有机质、盐度和膜污染)、化合物性质及POCIS结构对农药采样速率(Rs)的影响。此外,综述了POCIS在监测水环境中农药的应用,展望了POCIS在该领域中的问题、解决方式及前景。     

太湖入湖河流中精神活性物质污染特征与生态风险

精神活性物质是一类摄入人体后对中枢神经系统具有强烈兴奋或抑制作用的新型污染物,其在水环境中的存在可能对水生生物、水生态系统甚至人体健康产生潜在的危害。为评价太湖中精神活性物质的污染水平和生态风险,利用超高效液相色谱-质谱联用法检测了太湖19条入湖河流中13种典型精神活性物质的质量浓度和空间分布规律。结果表明,在太湖19条入湖河流中除苯甲酰牙子碱(BE)和去甲氯胺酮(NK)外,其余11种目标物均有检出,质量浓度范围为n.d.～43.2 ng·L~(-1)。其中麻黄碱(EPH)的检出率和中间浓度最高,分别为100%和11.0 ng·L~(-1);其次为甲基苯丙胺(METH),检出频率为58%,浓度中值为1.0 ng·L~(-1);苯丙胺(AMP)在东部湖区均未检出。大部分精神活性物质浓度水平较高的河流分布在竺山湾和西太湖,而海洛因(HR)的高值区主要在南太湖。运用风险熵方法对其进行风险评估,结果显示,太湖流域地表水中检出的13种精神活性物质的风险熵值均<0.1,生态风险较低,但其对水生生态系统的长期和综合风险值得关注。     

抗生素与三唑类杀菌剂混合物对羊角月牙藻的长期毒性相互作用研究

地表水中抗生素与农药的混合暴露及其潜在生态与健康风险受到广泛关注。然而,目前关于抗生素与农药混合毒性研究大多仅考虑急性毒性,缺乏其长期毒性相互作用的研究。以较为广泛使用的2种抗生素土霉素(OXY)、环丙沙星(CIP)和1种三唑类杀菌剂农药戊唑醇(TCZ)及其二元混合物为研究对象,以生态系统中初级生产者绿藻(羊角月牙藻)为受试生物,研究目标混合物在暴露时间为96、120、144和168 h的长期毒性相互作用。结果表明,单一物质及其混合物随暴露时间延长而毒性增大;同一暴露时间点的单一污染物毒性大小顺序为OXYTCZCIP;混合物毒性相互作用与浓度、混合物组分和暴露时间三者密切相关;混合体系的拮抗作用均出现在高浓度区域,而中、低浓度区域呈协同作用或加和作用; OXY-CIP与CIPTCZ混合体系的协同作用随着暴露时间延长而协同作用逐渐增大。研究结果对水环境中抗生素与农药复合污染生态风险评估具有重要的现实意义。     

氨基甲酸酯类农药对蛋白核小球藻联合毒性作用特点及机制

氨基甲酸酯类农药广泛应用于农业生产中,其在环境中的残留及其对非靶标生物的毒性作用引起关注。以5种氨基甲酸酯类农药包括残杀威、灭多威、抗蚜威、涕灭威和呋喃丹为研究对象,以蛋白核小球藻为受试生物,应用微板毒性分析法系统测定每种农药及其五元混合物对蛋白核小球藻在不同暴露时间(12、24、48、72和96 h)的生长抑制作用,并同步分析农药对蛋白核小球藻的生理特性如叶绿素含量、蛋白质含量、超氧化物歧化酶(SOD)活性和脂质过氧化物丙二醛(MDA)含量的影响。结果表明,5种农药对蛋白核小球藻的浓度-效应均具有明显的时间依赖性,农药抗蚜威在中低浓度促进绿藻生长,呈现非单调J型浓度-效应曲线(CRC)特征,其余4种农药的CRC呈现经典S型;以半数效应浓度的负对数(p EC50)为毒性大小指标,5种农药在96 h时毒性大小为:呋喃丹(p EC50=3.43)残杀威(p EC50=2.76)抗蚜威(p EC50=2.12)灭多威(p EC50=2.11)涕灭威(p EC50=1.89)。浓度为EC50的5种农药处理后的蛋白核小球藻中叶绿素和蛋白质含量随暴露时间的延长而减少,但不同农药处理的绿藻中叶绿素和蛋白质含量减少率随暴露时间延长变化趋势稍有不同; SOD酶活性随着暴露时间延长逐渐下降,MDA含量逐渐增加,这说明藻细胞受到破坏,脂质过氧化的损害程度超过细胞修复能力,SOD活性被抑制,细胞的抗氧化能力下降,藻细胞内的H2O2不断积累,导致MDA含量升高。五元混合物对蛋白核小球藻的毒性也具有一定的时间依赖性,并表现出刺激作用,即hormesis现象,且混合物毒性与组分浓度比具有良好的线性相关性;暴露于混合物的小球藻均在96 h出现了刺激效应,其叶绿素与蛋白质含量随暴露时间延长不断增加,SOD活性不断升高,MDA含量不断减少;五元混合物均在96 h呈现出拮抗作用,且与混合物的浓度和组分浓度比相关。     

Hematological and biochemical alterations in sprayers occupationally exposed to mixture of pesticides at a mango plantation in Lucknow,India

The aim of this study was to examine the hematological and cholinesterase (ChE) activity levels of pesticide sprayers employed in mango plantations at Lucknow. Fifty-two sprayers from mango plantations who regularly spray mixtures of pesticides including organochlorines (OC), organophosphates (OP), and carbamates were included as exposed group. Twenty residents living close to mango plantations, but not involved in pesticide spraying were taken as controls. Pesticide residues for OC were analyzed in blood by gas chromatography with electron capture detector. There was a significant decrease in acetylcholinesterase and butyrylcholinesterase activities in pesticide sprayers (n?=?52) relative to the control group (n?=?20). A significant difference in the frequency distribution of hematological variations in red blood cell, white blood cell, monocytes, neutrophils, mean corpuscular volume, mean corpuscular hemoglobin, mean corpuscular hemoglobin concentration, and platelet count was observed. Residues of OC pesticides including α-hexachlorocyclohexane (HCH) and total HCH were found to be significantly higher in the blood of sprayers compared to controls. Hematological variations were quantitatively more frequent among the sprayers with 5 years of pesticide exposure compared to the controls and to subjects with less than 5 years of exposure group. Hematological abnormalities in sprayers were correlated with pesticide exposure as evidenced by lower ChE activity as well as the presence of OC pesticides in blood. The poorly controlled use of pesticides in the plantation appeared to have produced sub-clinical intoxication in the sprayers and indicated the need for training and implementation of proper, safer hygiene practices.     

应用物种敏感性分布法分析太湖及天目湖水体的生态风险

采用物种敏感性分布法(SSDs法),应用水生生物急性和慢性毒性数据计算了31种污染物在水中和其中疏水物质在沉积物中的预测无效应浓度(PNECwater和PNECsed),通过收集以往报道的16种污染物在太湖和天目湖的环境浓度,用商值法求得物质的风险商并进行排序.结果发现:蒽、菲、萘、荧蒽、阿特拉津和马拉硫磷在太湖的梅梁湾和五里湖具有很大的生态风险;毒死蜱、三丁基锡氧化物和环己锡虽无环境浓度报道但很有可能具有风险.     

应用物种敏感性分布法对太湖沉积物中多环芳烃的生态风险分析

多环芳烃(PAHs)具有高的疏水性,在水体中优先分布于沉积物.采用物种敏感性分布法(SSDs法),依据水生生物慢性毒性数据计算5%物种危害浓度(HC5);并结合欧盟委员会风险评价技术导则(TGD)进而得到沉积物预测无效应浓度(PNEC-sed),以报道的太湖的沉积物中浓度数据作为预测环境浓度(PECsed);用商值法P...     

Acute toxicity evaluation of triazophos,deltamethrin and their combination on earthworm,Eudrilus eugeniae and its impact on AChE activity

The acute toxicity of three formula grade pesticides namely, triazophos (an organophosphate, OP), deltamethrin (a pyrethroid) and combined pesticide (triazophos?+?deltamethrin) was determined in earthworm, Eudrilus eugeniae. They were exposed to different concentrations of these pesticides for 48 h by paper contact toxicity method. The LC₅₀ values for triazophos, deltamethrin and of combination were determined as 0.076, 0.031 and 0.065?μg/cm², respectively. To study the sublethal effect of these pesticides, E. eugeniae were exposed to 5% and 10% of LC₅₀ of pesticides for 48 h. Morphological alterations such as coiling, clitellar swelling, mucus release and bleeding followed by body segmentation were observed in exposed earthworm. Acetylcholinesterase (AChE) activity assayed in different regions of body segment exhibited a significant (p?<?0.05) decrease in its activity particularly in the pre-clitellar region as compared to other regions. The altered behavioural responses in pesticides exposed earthworms would have been due to decline in AChE activity of the nervous system.     

Human health ambient water quality criteria for 13 heavy metals and health risk assessment in Taihu Lake

• The concentrations of 13 heavy metals in Taihu Lake were analyzed. • Aquatic vegetables intake was first included in deriving human health AWQC. • The human health AWQC for 13 heavy metals in Taihu Lake were derived. • Human health risk assessment for 13 heavy metals were conducted in Taihu Lake. Heavy metals are widely concerning because of their toxicity, persistence, non-degradation and bioaccumulation ability. Human health ambient water quality criteria (AWQC) are specific levels of chemicals that can occur in water without harming human health. At present, most countries do not consider the effects of aquatic vegetables in deriving human health AWQC. Therefore, the intake of aquatic vegetables (Brasenia schreberi) was added to the derivation of human health AWQC and a health risk assessment for 13 heavy metals in Taihu Lake. The human health AWQC (consumption of water, fish and aquatic vegetables) values of 13 heavy metals ranged from 0.04 (Cd) to 710.87 μg/L (Sn), and the intake of B. schreberi had a very significant effect on the human health AWQC for Cu, with a more than 62-fold difference. The hazard quotients of As (2.8), Cd (1.6), Cr (1.4) and Cu (4.86) were higher than the safe level (HQ= 1), indicating that As, Cd, Cr and Cu in Taihu Lake posed a significant health risk. Sensitivity analysis showed that the contribution rate of B. schreberi intake to the human health risk from Cu was 91.6%, and all results indicated that the risk of Cu in B. schreberi to human health should be of particular concern. This study adds the consideration of aquatic vegetable consumption to the traditional method of human health AWQC derivation and risk assessments for the first time, and this approach can promote the development of risk assessments and water quality criteria.