中国土壤与沉积物中邻苯二甲酸酯污染水平及其吸附研究进展

邻苯二甲酸酯（PAEs）是一类重要的环境激素化合物,具有致畸性、致癌性、致突变性及生殖毒性的特点。在环境中普遍存在,对人体及生态环境的威胁极大,已经引起了人们广泛的关注。吸附作用是影响污染物在土壤及沉积物环境中迁移转化的关键因素之一。分析了近年来我国土壤及沉积物中PAEs的污染现状,归纳了影响PAEs吸附过程的主要因素。我国与世界其他各国的土壤及沉积物的PAEs主要污染组分较为一致,但PAEs污染相对严重。土壤有机质及粘土矿物对PAEs的吸附影响成为了学术界的研究热点。有机质中的腐殖质对PAEs的吸附起着决定作用;腐殖质由胡敏酸、富里酸及胡敏素,部分含有碳黑组成,各组成对PAEs的吸附影响大小不一,相应的吸附机理还有待于深入的研究,而且土壤与沉积物中的溶解性有机物（DOM）对PAEs的吸附双重影响认识还不够。在有机质含量低的土壤中,粘土矿物对PAEs的吸附起着主要作用,然而PAEs的吸附与粘土矿物类型及其表面电场的关系、是否能与水分子竞争表面电场等问题还不甚清楚,需要进一步探索。今后将引入并开发先进的分析测试技术,从土壤及沉积物的有机质组成及微观结构研究其对PAEs的吸附机理。     

城市污泥中邻苯二甲酸酯的好氧降解规律研究

为评价邻苯二甲酸酯类环境激素在环境中的滞留情况,妥善解决城市污泥的处理处置问题,对城市污泥中6种邻苯二甲酸酯的好氧生物降解规律进行了研究。结果表明,邻苯二甲酸酯的好氧生物降解性随烷基链含碳数的增加而降低;其好氧降解过程可用一级动力学模型描述;其好氧生物降解速率常数与烷基链含碳数、降解半衰期与烷基链含碳数、降解速率常数与正辛醇—水分配系数之间存在良好的相关性。     

塑料供水管向自来水中释放邻苯二甲酸酯的规律及影响因素研究

添加邻苯二甲酸酯（PAEs）增塑剂的塑料管道被广泛用于自来水管道系统,存在健康风险.然而,塑料管道是否是自来水中PAEs的污染来源仍了解不足.因此,本文探究了两种常用管材—硬质聚氯乙烯（UPVC）、聚丙烯（PPR）的新管道和人为磨损管道,在不同水力停留时间和余氯浓度下向水样中释放PAEs的规律.结果表明,人为磨损会使管道中PAEs向自来水中的总释放量增多,其中,邻苯二甲酸二丁酯（DBP）最为明显,且人为磨损管道释放PAEs的速率大于新管道.对于不同管材的管道,PPR管道PAEs的释放量小于UPVC管道,因而针对PAEs污染,PPR管道可能比UPVC管道更安全.在所有实验中,添加余氯可使水中PAEs浓度整体更低,且余氯浓度越高,平衡时的PAEs浓度越低,因而 推测PAEs可能会与余氯发生化学反应.本研究揭示了塑料管道作为自来水中PAEs的来源之一,向水体中释放PAEs的规律及影响因素,从而为自来水水质安全的控制提供了新的关注点.     

酞酸酯在模拟海河菹草微宇宙中的消减和分布特征

模拟海河干流水体构建了室内菹草微宇宙,同时设置了无菹草微宇宙为对照,对微宇宙中酞酸二丁酯(DBP)和酞酸二异辛酯(DEHP)的消减和分布特征进行了研究.结果表明,实验过程中,有草组水和沉积物中这2种酞酸酯(PAEs)的浓度始终低于对照组;实验结束时,这2种PAEs主要分布在沉积物中,其次是水中,并且在菹草中也有一定程度的富集,尤其是疏水性较强的DEHP;菹草(以湿重计)对水中DBP和DEHP富集系数(BCF)的平均值分别为22.4 L.kg-1和180.7 L.kg-1;计算得出整个实验过程中,有草微宇宙中DBP和DEHP的降解率分别为输入量的94.2%和60.8%,较对照组(DBP和DEHP分别为91.0%和45.5%)分别提高了4.1和15.3个百分点;有草组DBP和DEHP的残留率分别为输入量的-0.6%和30.7%,而对照组为4.7%和37.7%.可见,菹草体系不仅能够有效增强这2种PAEs的降解作用,还能减少系统残留量,降低内源污染.     

惠州市农业土壤中邻苯二甲酸酯(PAEs)含量的分布特征

用气相色谱法(GC-FID)对地处珠三角地区的惠州市49个农业土壤样品中的16种PAEs化合物进行了测定。结果表明,PAEs的检出率高达100%,其中土壤中PAEs含量范围为183.48～2 037.56 ug/kg,平均600.42 ug/kg,以DnBP、BEHP和DEHP等为主。在3种主要利用类型土壤中,∑PAEs含量高低排序为菜地水田果园。与美国土壤PAEs控制标准相比,惠州土壤中的DnBP、DMP和DEP含量超标,其中DnBP的超标率达85.71%。总体上惠州市农业土壤已受到一定程度的PAEs污染,但同其它地区相比处于较低水平。     

搅拌棒吸附萃取-气相色谱-质谱联用测定海水中邻苯二甲酸酯

为了测定海水中痕量邻苯二甲酸酯,构建并优化了搅拌棒吸附萃取-气相色谱-质谱联用方法.选取邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二(2-乙基己基)酯和邻苯二甲酸二辛酯这6种邻苯二甲酸酯作为研究对象,优化了萃取时间和解析时间等5种因素,通过回收率和相对标准偏差等对SBSE-GC-MS方法进行验证.结果表明,最佳萃取时间为2 h,最佳甲醇添加量为10%,最佳氯化钠添加量为5%,最佳解析时间为50 min,最佳解析溶剂为甲醇∶乙腈=4∶1(体积比).6种邻苯二甲酸酯的峰面积和质量浓度线性对应关系良好,相关性系数均大于0.997,检出限在0.25~174.42 ng·L-1之间,不同质量浓度的回收率均在56.97%~124.22%之间,相对标准偏差在0.41%~14.39%之间.在建立方法的基础上,测定了胶州湾主要河流入海口的样品,结果表明所有采样点均检出邻苯二甲酸酯,邻苯二甲酸二乙酯检出率为100%,质量浓度较大的污染物为邻苯二甲酸二丁酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二(2-乙基己基)酯和邻苯二甲酸二辛酯.     

珠江三角洲典型区域农产品中邻苯二甲酸酯(PAEs)污染分布特征

在珠江三角洲典型区域(中山市、珠海市、东莞市和惠州市)内共采集了131个农产品样品,进行了6种优先控制污染物邻苯二甲酸酯(PAEs)含量水平分析及风险评价.结果表明,珠三角地区农产品样品中6种邻苯二甲酸酯累计含量(∑PAEs)范围为nd~79.86 mg·kg~(-1),平均含量为2.84 mg·kg~(-1),检出率为98.5%.各类农产品中∑PAEs平均含量的顺序依次为蔬菜(3.03 mg·kg~(-1))水稻(2.52 mg·kg~(-1))水果(1.26 mg·kg~(-1)).各城市产区内农产品中∑PAEs平均含量顺序为:珠海(6.53 mg·kg~(-1))东莞(2.59 mg·kg~(-1))惠州(1.53 mg·kg~(-1))中山(1.12 mg·kg~(-1)).农产品中PAEs的主要成分为邻苯二甲酸二正丁酯(DBP)、邻苯二甲酸二(2-乙基)己酯(DEHP)和邻苯二甲酸二正辛酯(DnOP),三者的累计含量占∑PAEs总量的90.8%.其中生菜(珠海)和芥兰(东莞)二者中∑PAEs的总量以及生菜、油麦菜(珠海)样品中DEHP的含量均超过美国和欧洲的建议标准,存在潜在的健康风险.芥兰、生菜等叶菜类蔬菜在14种不同蔬菜样品中的∑PAEs总量较高,而菜心和苋菜的∑PAEs含量最低.蔬菜品种间结构特征和生长环境(大气和土壤)的差异是影响其对PAEs的吸收及在体内累积的主要因素.     

Evaluating the blank contamination and recovery of sample pretreatment procedures for analyzing organophosphorus flame retardants in waters

Organophosphate esters (OPEs), used as flame retardants and plasticizers, are widely present in environmental waters. Development of accurate determination methods for trace OPEs in water is urgent for understanding the fate and risk of this class of emerging pollutants. However, the wide use of OPEs in experimental materials results in blank interference, which influences the accuracy of analytical results. In the present work, blank contamination and recovery of pretreatment procedures for analysis of OPEs in water samples were systematically examined for the first time. Blank contaminations were observed in filtration membranes, glass bottles, solid phase extraction cartridges, and nitrogen blowing instruments. These contaminations could be as high as 6.4–64 ng/L per treatment. Different kinds of membranes were compared in terms of contamination levels left after common glassware cleaning, and a special wash procedure was proposed to eliminate the contamination from membranes. Meanwhile, adsorption of highly hydrophobic OPEs on the inside wall of glass bottles was found to be 42.4%–86.1%, which was the primary cause of low recoveries and was significantly reduced by an additional washing step with acetonitrile. This work is expected to provide guidelines for the establishment of analysis methods for OPEs in aqueous samples.     

Pollution levels and characteristics of phthalate esters in indoor air of offices

The pollution status and characteristics of PAEs (phthalate esters) were investigated in indoor air of offices, and PAEs of both gas-phase and particulate-phase were detected in all the samples. The concentration (sum of the gas phase and the particulate phase) was 4748.24 ng/m³, ranging between 3070.09 and 6700.14 ng/m³. Diethyl phthalate, dibutyl phthalate, and di(2-ethylhexyl) phthalate were the most abundant compounds, together accounting for 70% of the ∑ 6PAEs. Dividing the particulate-phase PAEs into four size ranges (< 2.5, 2.5–5, 5–10, > 10 μm), the result indicated that PAEs in PM_2.5 were the most abundant, with the proportion of 72.64%. In addition, the PAE concentration in PM_2.5 correlated significantly with the total particulate-phase PAEs (R² = 0.85). Thus, the amount of PAEs in PM_2.5 can be estimated from the total amount of particulate-phase PAEs using this proportion. In a comparison between the offices and a newly decorated study room, it was found that pollution characteristics were similar between these two places. Thus, it is implied that the PAE concentration decreased by 50% 2 yr after decorating.     

Delayed neurotoxicity in the wild mallard duckling caused by the organophosphorus insecticides cyanofenphos and leptophos

Abstract

The susceptibility of wild mallard ducklings to the delayed neurotoxic effect of the neurotoxic organophosphorus insecticides cyanofenphos and leptophos was evaluated following a daily dosing regimen. Ducklings were treated daily with either cyanofenphos or with leptophos at different dose levels for 90 days, or until they died, or became paralyzed. A control group of ducklings given corn oil at 1 ml/kg daily for 90 days was used for comparison. All treated birds were observed daily for any clinical signs of neurotoxicity during the course of this study. All of the surviving ducklings that were treated with cyanofenphos at 4 mg/kg/day or leptophos at 10 mg/kg/day developed clinical signs of delayed neurotoxicity after 7 to 11 weeks of intoxication. Symptoms included leg weakness, ataxia, severe ataxia and paralysis. The observed clinical signs were confirmed by histological changes found in the spinal cords of the treated birds. These changes were of the type associated with organophosphorus‐induced delayed neuropathy (OPIDN). These results demonstrate that wild mallard ducklings are susceptible to OPIDN and this avian species can be used in screening organophos‐phorus compounds for such effect.