Spatial and vertical variations of perfluoroalkyl substances in sediments of the Haihe River, China

The levels of six perfluoroalkyl substances(PFASs) in surface sediment and their vertical variations in dated sediment cores from the Haihe River were investigated; studied substances included perfluorooctanoic acid(PFOA),perfluorononanoic acid(PFNA),perfluorooctane sulfonate(PFOS),perfluorodecanoic acid(PFDA),perfluoroundecanoic acid(PFUnA),and perfluorododecanoic acid(PFDoA). Results showed that the total PFAS concentration in surface sediment ranged between 0.52 and 16.33 ng/g dry weight(dw) with an average of3.47 ng/g dw,with PFOS and PFOA as the dominant PFASs. In general,the PFAS concentrations in the mainstream increased from the upper to the lower reaches,except that a drop occurred downstream of the Erdao dam. Although the PFASs in the sediment cores did not show a clear decreasing or increasing trend with depth,the three cores had a similar vertical variation.The PFAS levels were relatively low in the surface sediment,and reached the first high point at8–20 cm as a result of the wide use of PFASs from 1990 to 2000. After that the PFAS levels decreased,and then increased to a second high point at about 40–48 cm,which might be caused by the leaching of PFASs in sediment. Because PFASs have hydrophilic groups and relatively high solubility,the PFASs will transfer from the upper to lower layers of sediment when water infiltration occurs,leading to the fluctuation of PFAS levels in sediment cores. This study suggests that both the temporal variation of sources and transfer processes of PFASs in sediments are important factors influencing the vertical variation of PFASs in sediment cores.     

渤海油气区周边海域PFASs的赋存特征与来源

为了解我国海上油田区域附近PFASs(多氟或全氟化合物)污染状况,本文针对我国渤海油田区所在海域采集了92个海水样品,并对其中19种PFASs及其新型替代品的含量进行了分析。结果表明,渤海油气区周边海水中总PFASs浓度范围为9.33~113ng/L,与中国其他海域相比,渤海油田区周边海水中总PFASs含量较高。传统PFASs中,全氟辛酸(PFOA)是大部分样品中的主要PFASs。新型替代品中,六氟环氧丙烷二聚酸(HFPO-DA)的浓度相对较高,浓度中位数为1.82ng/L,而在所有样品中6:2氯代多氟醚磺酸(6:2Cl-PFESA)均未检出。从区域分布来看,总PFASs浓度较高的油田位于渤海西部。总PFASs含量与离岸距离等影响因素相关性分析表明,渤海油气区附近海水中总PFASs含量与离岸距离显著相关,说明陆源是渤海油气区中PFASs污染的主要来源。     

Occurrence, profiles, and ecotoxicity of poly- and perfluoroalkyl substances and their alternatives in global apex predators: A critical review

Certain poly- and perfluoroalkyl substances (PFASs) exhibit significant bioaccumulation/biomagnification behaviors in ecosystems. PFASs, such as perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorohexanesulfonic acid (PFHxS) and related precursors, have elicited attention from both public and national regulatory agencies, which has resulted in worldwide restrictions on their production and use. Apex predators occupy the top trophic positions in ecosystems and are most affected by the biomagnification behavior of PFASs. Meanwhile, the long lifespans of apex predators also lead to the high body burden of PFASs. The high body burden of PFASs might be linked to adverse health effects and even pose a potential threat to their reproduction. As seen in previous reviews of PFASs, knowledge is lacking between the current stage of the PFAS body burden and related effects in apex predators. This review summarized PFAS occurrence in global apex predators, including information on the geographic distribution, levels, profiles, and tissue distribution, and discussed the trophic transfer and ecotoxicity of PFASs. In the case where legacy PFASs were restricted under international convention, the occurrence of novel PFASs, such as 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA) and perfluoroethylcyclohexane sulfonate (PFECHS), in apex predators arose as an emerging issue. Future studies should develop an effective analytical method and focus on the toxicity and trophic transfer behavior of novel PFASs.     

Source apportionment of perfluoroalkyl substances in surface sediments from lakes in Jiangsu Province, China: Comparison of three receptor models

Receptor models have been proved as useful tools to identify source categories and quantitatively calculate the contributions of extracted sources.In this study,sixty surface sediment samples were collected from fourteen lakes in Jiangsu Province,China.The total concentrations of C_4–C_(14)-perfluoroalkyl carboxylic acids and perfluorooctane sulfonic acid(∑_(12)PFASs) in sediments ranged from 0.264 to 4.44 ng/g dw(dry weight),with an average of 1.76 ng/g dw.Three commonly-applied receptor models,namely principal component analysis-multiple linear regression(PCA-MLR),positive matrix factorization(PMF) and Unmix models,were employed to apportion PFAS sources in sediments.Overall,these three models all could well track the ∑_(12) PFASs concentrations as well as the concentrations explained in sediments.These three models identified consistently four PFAS sources:the textile treatment sources,the fluoropolymer processing aid/fluororesin coating sources,the textile treatment/metal plating sources and the precious metal sources,contributing 28.1%,37.0%,29.7% and 5.3% by PCA-MLR model,30.60%,39.3%,22.4% and 7.7% by PMF model,and 20.6%,52.4%,20.2% and 6.8% by Unmix model to the ∑_(12) PFASs,respectively.Comparative statistics of multiple analytical methods could minimize individual-method weaknesses and provide convergent results to enhance the persuasiveness of the conclusions.The findings could give us a better knowledge of PFAS sources in aquatic environments.     

垃圾填埋与焚烧渗滤液全(多)氟化合物赋存特征

采样分析了来自中国西南地区6个生活垃圾填埋场的渗滤液、3个生活垃圾焚烧厂的渗滤液原液及场内处理出水，发现3种水样中17种全（多）氟化合物（PFAS）浓度分别在1805~43310，7228~16565和55~185ng/L之间；呈现以全氟丁烷羧酸（PFBA）和全氟丁烷磺酸（PFBS）等短链、偶数链PFAS为主的污染特征.对比位于相近地理区域的焚烧厂和填埋场渗滤液，发现两者PFAS组成类似，而前者PFAS浓度与运行时间为2a的填埋场渗滤液相似，高于运行时间较长（15a）的填埋场渗滤液.研究结果将为我国西南地区垃圾渗滤液PFAS赋存现状提供基础信息，并为预防和控制PFAS产品生产和使用带来的环境污染提供重要数据支持.     

Occurrence of perfluoroalkyl substances in matched human serum, urine, hair and nail

The purpose of this study was to determine perfluoroalkyl substances(PFASs) in human serum, urine, hair and nail from general populations, and to investigate the possibility for human urine, hair and nail used as the biomonitoring sample for PFASs exposure. We detected the concentrations of PFHx A, PFOA, PFNA, PFDA, PFUn DA, PFDo A, PFHx S and PFOS in 39 matched human serum, urine, hair and nail samples from Shenzhen in China. The detection frequency and the median level of PFOS were all higher than that of the other PFASs in four matrices. The median concentration of PFOS in serum, urine, hair, and nail were 9.24 ng/mL, 13.96 ng/L, 0.58 ng/g and 0.63 ng/g, respectively. The results of spearman correlation test indicated that nail was an ideal matrix for biomonitoring PFOS rather than human urine and hair in general populations for the non-invasive sampling.     

大连沿海常见海产品PFOS和PFOA的暴露水平调查

文章应用液相色谱-质谱分析方法,对2009年春季大连沿海常见海产品体内PFOS和PFOA的暴露水平进行了调查。鱼、蟹、乌贼和海胆肌肉中PFOS的平均暴露水平分别为0.40 ng/g,0.07 ng/g,0.09 ng/g及0.12 ng/g(湿重),而PFOA的平均暴露水平分别为0.06ng/g,0.01 ng/g,0.06 ng/g及0.10 ng/g(湿重)。鱼类肝脏中PFOS和PFOA的平均暴露水平分别为0.90 ng/g和0.24 ng/g。调查结果表明,大连沿岸常见海产品体内普遍检测到PFOS和PFOA,并且肝脏中PFOS和PFOA暴露水平均高于肌肉组织。通过比较发现,大连沿岸鱼类样品中PFOS的暴露水平低于美、日等国家的沿岸海域鱼类的暴露水平。     

沈阳市降雪中PFOS和PFOA污染现状调查

通过调查降雪中PFOS和PFOA的浓度,阐明了沈阳市大气中PFOS和PFOA的污染状况和污染规律.2006-02-06采集沈阳市区和郊区共计36个采样点的降雪样品,2006-02-25在其中5个采样点再次采集降雪样品.固相萃取融雪水中的PFOS和PFOA,利用LC-MS-SIM法测定样品中PFOS和PFOA浓度.全部样品中均检出PFOS和PFOA.2006-02-06降雪中PFOS和PFOA的浓度几何平均值分别为2.0 ng·L^-1（范围：0.4～46.2 ng·L^-1）和3.6 ng·L^-1（范围：1.6～22.4 ng·L^-1）,95%置信区间分别为1.5～2.8 ng·L^-1和3.1～4.2 ng·L^-1.PFOS和PFOA的最高浓度同时出现在郊区采样点朱尔屯,市中心区2种物质的浓度呈显著正相关.2006-02-25的5个采样点降雪中PFOS和PFOA的浓度几何平均值均为2.2 ng·L^-1.2次降雪中PFOS浓度差异不显著,2006-02-25降雪中PFOA浓度高于2006-02-06.结果表明,沈阳市区和郊区降雪中广泛存在PFOS和PFOA污染,局部区域可能存在共同的PFOS和PFOA污染来源;沈阳地区有较稳定的PFOS来源持续向大气中输送该类物质;PFOS和PFOA的环境行为可能不同.     

甘肃省及其周边地区土壤六氯苯污染特征

2011年3月采集甘肃省及其周边地区城区、农村和背景区三类采样区32个采样点的表层土壤样品,应用GC-MSD对其六氯苯含量进行分析测定.结果表明,研究区土壤六氯苯(HCB)检出率高达96.9%,平均污染水平为1.21ng/g,检出范围为n.d.~11.7ng/g;空间污染特征为:城区>农村>背景;研究区内大部分地区土壤中HCB来源是大气长距离迁移沉降,庆阳地区表现为工业和农业源,西宁、兰州地区主要是工业源,张掖、金昌地区主要是农业源;研究区土壤HCB与土壤有机质含量之间呈显著正相关;对HCB土壤生态系统风险进行初评表明:除庆阳和西宁地区外,其余采样点土壤环境处于相对安全状态.     

东湖表层水体中全氟辛酸和全氟辛磺酸空间分布特征

研究了东湖表层水体中全氟辛酸(PFOA)和全氟辛磺酸(PFOS)的含量及空间分布特征,总量范围为31.1～237ng.L-1,几何平均值为115 ng.L-1,表明整个湖区受到不同程度的PFOS和PFOA污染.全部水样均检出了PFOS和PFOA,峰值达到132和158 ng.L-1,几何平均值分别为60.4和55.0 ng.L-1.湖区东部污染最严重,其次是湖区南部,湖区北部和西部污染程度相对较轻.与PFOS相比,高浓度PFOA分布相对分散,PFOS和PFOA含量之间无显著相关性,表明东湖表层水体中PFOS和PFOA属于多源输入.30个(63%)取样点上PFOS含量超过可能对水生生态系统产生影响的临界数值(43 ng.L-1),20个(42%)取样点上PFOA含量超过美国新泽西洲制定的饮用水标准(40 ng.L-1).     

福建闽江沿岸土壤中多环芳烃含量、来源及健康风险评价

为研究福建省闽江沿岸土壤中多环芳烃(PAHs)的残留状况、潜在来源及健康风险,采集闽江沿岸16个土壤样品,利用气相色谱/质谱(GC/MS)分析其中16种PAHs含量,结果表明:研究区土壤中16种PAHs的总含量为70.70~1667.83μg/kg,平均值为480.28μg/kg,其沿闽江沿岸呈“W”型分布模式,具体表现为城市高于郊区的变化;PAHs以2~3环为主,其中萘(Nap)的含量最高.基于PAHs的特征比值和主成分回归结合分析,研究区土壤中PAHs主要是石化和燃烧混合污染源,其中化石燃料高温燃烧占41.45%,石油源及生物质燃烧占49.34%,煤燃烧占9.21%.PAHs总毒性当量浓度值(TEQ_BaP)为3.10~121.15μg/kg,平均值为36.71μg/kg,37.50%的采样点超过荷兰土壤标准目标参考值(33.00μg/kg),表明闽江沿岸土壤已经受到PAHs不同程度的污染.健康风险评价表明,研究区土壤中PAHs的致癌风险(ILCRs)在10^-8~10^-6间,说明其致癌风险较小.     

Polycyclic aromatic hydrocarbons in soils of Beijing and Tianjin region： Vertical distribution, correlation with TOC and transport mechanism

The contents and distribution of 20 polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatic hydrocarbons (HAHs) were investigated in 16 soil profiles of Beijing and Tianjin region. Transport of high molecular weight PAHs (HMWPAHs) and the correlation between total organic carbon (TOC) and their concentrations were also discussed. The results indicated that highly contaminated sites were located at urban or wastewater irrigation areas and pollutants mainly accumulated in topsoil (< 40 cm), with a sharp content decrease at the vertical boundary of 30–40 cm. Total PAHs/HAHs concentrations in soils from Tianjin were markedly greater than those from Beijing. Even the contents at bottoms of soil profiles in Tianjin were higher than those in topsoils of Beijing soil profile. HMWPAHs dominated the PAH profiles, exhibiting a uniform distribution of pyrogenic origin between topsoils and deep layers. Furthermore, the percentages of HMWPAHs remained relative constant with the depth of soil profiles, which were consistent with the distribution of particulate matter-associated PAHs in the local atmospheric environments. Therefore, HMWPAHs transport with particulates might be the predominant source found in soil profiles.     

Organochlorines in sediments and mussels collected from coastal sites along the Pearl River Delta, South China

IntroductionContaminationofthemarineenvironmentassociatedwithorganochlorineshasreceivedincreasingattentionoverthelastthirtyyears.Particularattentionhasbeenfocusedonthecoastalzoneandestuaries ,especiallynearmetropolitanregion(Sericano ,1990 ) .ThePearlRiverestuarine ,rangefromDayaBayintheeasttoChangshanIslandsinthewest,supportslargepopulationsofmarineorganismsandextensivefisheriesintheSouthChina .Sincethe 1980s ,therehasbeenrapideconomicdevelopmentinthePearlRiverDeltaresultinginexcessivedi…     

Tissue distribution of perfluoroalkyl acids and health status in wild Mozambique tilapia (Oreochromis mossambicus) from Loskop Dam, Mpumalanga, South Africa

This study examined concentrations of 15 perfluoroalkyl acids (PFAAs) in tissues from male Mozambique tilapia (Oreochromis mossambicus) collected at Loskop Dam, Mpumalanga, South Africa in 2014 and 2016. Nine of the 15 PFAAs were detected frequently and were included in statistical analysis and included two of the most commonly known PFAAs, perfluorooctanesulfonic acid (PFOS) (median, 41.6 ng/g) and perfluorooctanoic acid (PFOA) (median, 0.0825 ng/g). Of the tissues measured, plasma (2016 and 2014 median, 22.2 ng/g) contained the highest PFAA burden followed by (in descending order): liver (median, 11.6 ng/g), kidney (median, 9.04 ng/g), spleen (median, 5.92 ng/g), adipose (median, 2.54 ng/g), and muscle (median, 1.11 ng/g). Loskop Dam tilapia have been affected by an inflammatory disease of the adipose tissue known as pansteatitis, so this study also aimed to investigate relationships between PFAA tissue concentrations and incidence of pansteatitis or fish health status. Results revealed that healthy tilapia exhibited an overall higher (p-value < 0.05) PFAA burden than pansteatitis-affected tilapia across all tissues. Further analysis showed that organs previously noted in the literature to contain the highest PFAA concentrations, such as kidney, liver, and plasma, were the organs driving the difference in PFAA burden between the two tilapia groups. Care must be taken in the interpretations we draw from not only the results of our study, but also other PFAA measurements made on populations (human and wildlife alike) under differing health status.     

黄渤海区域水产品中全氟烷基物质的分布特征

选取黄渤海区域水产品生产、消费水平较高的23个城市,采集鱼类、海洋贝类、甲壳类、头足类及海珍品（海参、鲍鱼）等5类水产品共1225个样本,采用超快速液相色谱-串联质谱法测定了23种全氟烷基物质（PFASs）的含量,并分析了黄渤海区域水产品中PFASs的残留水平及分布特征.结果表明,黄渤海区域水产品中PFASs的残留水平具有明显的组分差异、城市分布及品种分布差异等特征.在23种PFASs组分中,共检出20种PFASs,其中全氟辛烷磺酸（PFOS）和全氟辛酸（PFOA）的检出率最高,分别为79.1%和71.7%,且PFOA的质量浓度占比最高（64.5%）,为首要污染组分;在不同采样点样本中,莱州湾近岸的潍坊、滨州和东营,渤海湾近岸的沧州以及辽东湾近岸的营口为PFASs总质量浓度（∑PFASs）较高的城市,残留水平范围为10.2~16.8μg/kg;在不同品种样本中,检出PFASs组分的数量由高到低为：鱼类（20种） > 海洋贝类、甲壳类（18种） > 海珍品（16种） > 头足类（10种）,其中海洋贝类、海珍品样本中检出率最高的是PFOA,鱼类、甲壳类样本中检出率最高的是PFOS,而头足类则是全氟辛烷磺酰胺（PFOSA）;通过计算不同水产品中PFASs各组分的平均含量发现,PFOA、PFOS、全氟十一烷酸（PFUdA）和PFOSA在不同品种中平均含量相对较高,且表现出较为明显的组分差异性;通过计算危害指数（HR）评价人体暴露于PFASs的健康风险,得到PFASs各组分的危害指数均 < 1,说明黄渤海区域水产品中残留的PFASs对消费者的潜在健康风险较低.     

岷江流域全氟化合物的污染特征及排放通量

采用超高效液相色谱串联质谱分析了四川省岷江流域水体中13种全氟化合物（PFASs）的浓度水平.结果表明,岷江流域水相中PFASs的浓度为1.54~30.2ng/L,平均值为（11.2±8.0）ng/L,浓度最高点出现在乐山下游（30.2ng/L）.其中,岷江流域水相中最主要的PFASs为全氟丁烷羧酸（PFBA）,浓度为0.16~28.4ng/L,占总全氟化合物的54.0%~94.1%（都江堰除外）.岷江流域沉积物中PFASs浓度最高点在宜宾三江（岷江、金沙江和长江）汇合处（47.5ng/g dw）,最低值在都江堰（0.334ng/g dw）.其中,主要的PFASs是全氟己烷羧酸（PFHxA）（4.44%~66.9%）和全氟辛烷羧酸（PFOA）（1.52%~77.5%）.岷江流域PFASs的年排放通量为1.443t/a,排放通量最高的为PFBA（1.037t/a）,占总排放通量的71.9%.     

天津市区表层土壤中多氯联苯的污染特征

用GC/ECD分析、GC/MS验证的方法测定了天津市区41个表层(0~10 cm)土壤样品中84种PCB异构体. 结果表明:w(PCBs)为0.82~8.86 ng/g,平均值为3.56 ng/g,其中工业区>路边绿化带>公园. 7种PCB指示异构体的浓度(以w计)范围为0.08~2.05 ng/g,占总量的22.89%,与w(PCBs)具有较好的相关性(R=0.74,P<0.000 1). 5氯联苯和3氯联苯是主要的异构体,分别占总量的28.30%和22.14%. 浓度位居前10位的异构体分别是PCB31/28、PCB201、PCB6、PCB84、PCB92、PCB101、PCB16/32、PCB89、PCB180和PCB12/13. 主成分分析显示,国产变压器油与电容器油、Aro1242、Aro1248、Aro1254、A30和KC300以及现有工业的排放是天津市区表层土壤中PCBs的主要来源. 关键词:多氯联苯(PCBs); 表层土壤; PCB指示异构体; 异构体      

Persistent organochlorine residues in sediments of the Haihe River and Dagu Drainage River in Tianjin, China

Persistent organochlorine compounds were analyzed by means of GC-ECD in surface sediment samples from two selected rivers in Tianjin, Haihe River and Dagu Drainage River. A total of 16 surface sediment sites were selected along the both rivers. The frequency of detection of T-HCH and T-DDT in sediment samples both was up to 100%, which illustrated that the contamination of HCH and DDT was widespread in Haihe and Dagu Drainage Rivers. Results indicated that the concentrations of various pesticides in sediments from Haihe River were in the range of 3.30-75.96 ng/g dw for T-HCH and 1.57-211.57 ng/g dw for T-DDT. Compared with Haihe River, Dagu Drainage River was contaminated by HCHs and DDTs along the all locations and the values of T-HCH and T-DDT residues in sediments ranged from 2.30 to 124.61 ng/g dw and from 11.28 to 237.30 ng/g dw, respectively, The possible pollution sources were analyzed through monitoring results of organochlorine pesticides（OCPs） residues in sediments from the two rivers. The investigation also indicated that HCH was still used as pesticide in Tianjin partial area.     

成都市道路积尘中全氟化合物的污染特征及暴露风险评估

为了解成都市道路积尘中全氟化合物(PFASs)的污染特征及人群暴露风险,采用超高效液相色谱-质谱联用仪分析了成都市道路积尘中12种PFASs的含量水平.成都市道路积尘中PFASs的含量为0. 95～111 ng·g~(-1),平均含量为(25. 6±37. 2)ng·g~(-1),说明存在较大的空间差异性.主干道路上PFASs的总含量显著高于支干道路,支干道路市区含量高于郊区含量.解放路一段、金牛坝路及水碾河路段主要的全氟化合物为全氟丁烷羧酸(PFBA),比例高达95%.而其它道路中主要的PFASs为全氟辛烷羧酸(PFOA,24. 8%)和全氟辛烷磺酸(PFOS,24. 1%),说明不同区域PFASs的污染源存在较大差异.成都市儿童和成人通过道路积尘摄入的PFASs分别为0. 168 ng·(kg·d)-1和0. 028 ng·(kg·d)-1,说明儿童暴露风险高于成人,应加强对儿童健康风险的关注.另外,根据欧盟推荐的每日最大耐受量,道路积尘中PFOS和PFOA的暴露量不会对成都市居民造成即时伤害.     

Levels, distributions, and source identification of organochlorine pesticides in the topsoils in Northeastern China

Seventeen topsoil samples (9 urban, 4 suburban, 3 rural and 1 background) were collected in/around Harbin, a typical city in northeast of China, to measure concentration levels of organocholrine pesticides (OCPs) in topsoil of Northeastern China in 2006. Hexachlorohexanes (HCH), dichlorodiphenyltrichloroethane (DDT), and hexachlorobenzene (HCB) were detected in soil samples with mean concentrations (in pg/g dry weight (dw)) of 7120, 5425, and 1039, respectively. The mean concentrations for other OCPs were very low, 4.8 pg/g dw for chlordane and 3.3 pg/g dw for endosulfan. Source identification analysis reveals that all OCPs found in soil samples were due to historical use of these chemicals or from other source regions through long- and short-range atmospheric transport. DDT was mainly used in the rural sites, whereas the sources of HCB, chlordane and endosulfan were mainly in the urban area. HCH was found almost equally in both urban and rural area. Soil concentrations of all detected OCPs, except HCHs, in and around Harbin were much lower than those in the southeast of China, which is expected since the use of these OCPs in the former was much lower than that in the latter, however higher HCH concentrations in and around Harbin than those found in most places of the Southeast China is not expected. It is suggested that high HCH concentration in soil of Northeast China was most likely due to long-range atmospheric transport (LRAT) from Southeast China and the cold condensation process.