超高压液相色谱-串联质谱测定地表水中邻苯二甲酸酯

建立了地表水中6种邻苯二甲酸酯类（PAEs）的液相色谱-串联质谱分析方法。样品直接过膜上样,用超高压液相色谱-串联质谱仪测定地表水中的邻苯二甲酸二甲酯、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、邻苯二甲酸二正辛酯、邻苯二甲酸二（2-乙基己基）酯。结果表明,6种PAEs线性相关性良好,方法最低检出限为0．01～ 0．05μg/L,低、中、高三个浓度的加标回收率在87．4％～106．9％之间。该方法方便、准确、灵敏度高,适合地表水中邻苯二甲酸酯类的监测分析。     

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.     

邻苯二甲酸酯及邻苯二甲酸在碳管上的吸附

以邻苯二甲酸（PA）和邻苯二甲酸二乙酯（DEP）为目标污染物,碳纳米管（CNTs）为吸附剂,通过不同pH值条件下单、双溶质的吸附实验,结合能量分布理论,分析PA对DEP在CNTs上的竞争和取代吸附.结果表明,在同一pH值下,DEP在CNTs上的吸附性强于PA.对于DEP,pH值改变导致的CNTs分散稳定性的变化是影响其吸附的决定因素.对于PA,溶液pH值会影响CNTs的表面电荷及PA的解离程度,两者均会产生影响.双溶质体系下,PA对DEP在CNTs上的吸附存在竞争和取代效应.在不同pH值条件下,PA对DEP在CNTs上的竞争和取代的程度与CNTs的分散稳定性和PA的解离程度有关.基于能量分布的分析表明,虽然PA的加入导致DEP在CNTs上可利用的高能吸附位点数量显著下降,但是其可利用的低能吸附位点数量增加.     

南京市雪水中有机磷阻燃剂的污染特征及健康风险评价

采用超高效液相色谱-串联质谱仪（HPLC-MS/MS）分析了南京雪水中的13种有机磷酸酯阻燃剂（Organophosphate esters,OPEs）,研究了其浓度水平及污染特征,利用主成分分析阐述了OPEs可能的来源,并评估了其健康风险.结果表明,雪水中共检出11种OPEs,11种检出OPEs总浓度水平范围为229.1~1175.0ng/L,平均浓度为746.0ng/L,其中∑₁₁OPEs的最大值区域为商业区和住宅区密集的马群,最小值区域为城郊的化工园区.磷酸三（1,3-二氯-2-丙基）酯（Tris（1,3-dichloropropyl）phosphate,TDCPP）和磷酸三（2-丁氧基乙基）酯（Tris（2-butoxyethyl）phosphate,TBEP）是雪水中主要的OPEs污染单体,两者的贡献率分别为26.6%、20.4%.主成分分析表明雪水中TBEP与磷酸三（2-氯异丙基）酯（Tris（1-chloro-2-propyl）phosphate,TCPP）、磷酸三甲酯（TriMethyl Phosphate,TMP）与磷酸三乙酯（Triethyl phosphate,TEP）两两之间可能存在共同的来源,大气的远距离迁移和干湿沉降可能是雪水中附着OPEs的重要原因.不同人群通过饮水摄入11种OPEs的日均暴露量范围为26.6~39.0ng/（kg·d）,通过饮水摄入的OPEs的非致癌风险和致癌风险均低于理论风险值,研究区内雪水中OPEs所致人体健康风险处于较低水平.     

松花湖表层沉积物中PAHs及PAEs污染特征

松花湖是吉林省面积最大的湖泊和重要水源地,具有防洪排涝、灌溉供水、航运旅游等重要功能.为探究松花湖中PAHs（多环芳烃）和PAEs（邻苯二甲酸酯）的主要污染来源及生物毒性风险,于2017年7月采集松花湖21个表层沉积物样品,采用GC-MS测试16种US EPA（美国环境保护局）优先控制PAHs和6种PAEs的质量分数,并通过统计学方法对调查结果进行分析.结果表明:①松花湖沉积物中w（∑₁₆PAHs）范围为23.1~554.8 ng/g,平均值和中位值分别为172.9和123.2 ng/g,w（∑₁₆PAHs）高值分布在漂河镇和丰满乡附近湖区,主要来源于石油燃烧污染,贡献率为57.9%,其次为煤及生物质燃烧污染、石油泄露污染,贡献率分别为21.1%、21.0%.②松花湖沉积物中w（∑₆PAEs）范围为33.7~2 062.3 ng/g,平均值和中位值分别为240.4和72.7 ng/g,主要成分为DBP（邻苯二甲酸二正丁酯）和DEHP（邻酞酸二辛酯）,w（∑₆PAEs）高值分布在旺起镇附近湖区,其来源主要与城镇生活污染输入有关.③松花湖沉积物中PAHs、PAEs污染生态风险较低,只有部分采样点存在低度潜在生态风险,但旺起镇附近湖区沉积物中的w（DBP）已经临近ERL（效应区间低值）,需加以关注.研究显示,松花湖PAHs、PAEs污染程度较低,为加强松花湖饮用水源地保护,应着重加强交通燃油污染源的风险防控,同时在乡镇附近湖区应加强燃煤和生活污染源的监管力度.      

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.     

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.     

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.     

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.     

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.