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.     

海河干流及河口地区土壤中有机氯农药的分布特征

以海河干流沿岸及海河河口周边地区为研究区域,采集了31个表层土壤样品,利用加速溶剂萃取（ASE）技术,使用气相色谱-电子捕获检测器（GC-ECD）分析方法测定了样品中的六六六（HCHs）和滴滴涕（DDTs）的含量.结果显示,海河河口地区土壤中HCHs和DDTs的含量范围分别为n.d.～1 728 μg·kg^-1（平均含量为93.9 μg·kg^-1）和n.d.～288 μg·kg^-1（平均含量为34.4 μg·kg^-1）.其中HCHs占优势,约占有机氯农药（OCPs）总残留量的72%.从海河干流到河口地区,OCPs的含量分布呈非均一性,受污染点源的分布影响较大,农药化工企业分布的区域土壤中的有机氯农药含量明显高于其它区域,海河干流区域相对高于河口地区.土壤中有机氯农药的成分分析结果表明,该地区土壤中除个别采样点OCPs仍有新的污染源输入外,大部分点位土壤中的OCPs主要来自于工业点源的历史输入和农业面源即有机氯农药的历史施用.与国内外其他地区土壤相比,该地区土壤中OCPs污染处于较高水平.     

Perfluoroalkyl substances and organochlorine pesticides in sediments from Huaihe watershed in China

Twelve perfluoroalkyl substances （PFASs） and nine organochlorine pesticides （OCPs） were quantified in surface sediments from the Huaihe River, China, along which there are intensive industrial and agricultural activities. Concentrations of PFASs ranged from 0.06 to 0.46 ng/g dry weight （dw）, and concentrations of OCPs ranged from 1.48 to 32.65 ng/g dw. Compared with other areas in China, concentrations of PFASs were lesser than the national mean value, while concentrations of OCPs were moderate. Concentrations of perfluorooctanoic acid （PFOA） and perfluorooctane sulfonate （PFOS） ranged from n.d. （not detected） to 0.03 and n.d. to 0.10 ng/g dw, respectively. Among the three groups of OCPs, mean concentrations of hexachlorocyclohexane and its isomers （HCHs）, dichlorodiphenyltrichloroethane and its metabolites （DDTs） and hexachlorobenzene （HCB） were 5.62 ± 4.35, 2.43 ± 3.12 and 1.55 ± 4.17 ng/g dw, respectively. Concentrations of HCHs and DDTs decreased from upstream to downstream along the mainstream of the Huaihe River. When compared to sediment quality guidelines （SQGs）, concentrations of HCHs, DDTs and HCB would pose adverse biological effects. In general, contamination by PFASs in the upstream of the Huaihe River was more severe than that in the downstream, which was mainly caused by interception from dams, locks and industrial emissions. And OCPs from tributaries, especially the Yinghe River and Wohe River, were higher than those from Huaihe mainstream, and primarily came from historical inputs.     

Phosphorus fractions and its release in the sediments of Haihe River, China

The amounts and forms of phosphorus (P) in surface sediments of Haihe River, Tianjin, North China, were examined using a sequential chemical extraction procedure. Five fractions of sedimentary P, including loosely sorbed P (NH4Cl-P), redox-sensitive P (BD-P), metal oxide bound P (NaOH-P), calcium bound P (HCl-P), and residual P (Res-P) (organic and refractory P), were separately quantified. The results indicated that the contents of di erent P fractions in the sediments varied greatly. The total P (TP) contents ranged from 968 to 2017 mg/kg. Phosphorus contents in NH4Cl-P, BD-P, NaOH-P, and HCl-P ranged from 6.7 to 26.6 mg/kg, 54.5 to 90.2 mg/kg, 185.2 to 382.5 mg/kg, and 252.3 to 425.5 mg/kg, respectively, which represented 1.2%–3.2%, 7.7%–13%, 33.3%–48.9%, and 36.2%–54.2% of the sedimentary inorganic P, respectively. For all the sediment samples, the rank order of P-fractions was Res-P > HCl-P > NaOH-P > BD-P > NH4Cl-P. The highly positive relationship between the amounts of P released from the sediments and those in the NH4Cl-P and BD-P fractions, indicated that NH4Cl-P and BD-P were the main fractions that can release P easily.     

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.     

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.     

Distribution characteristics of poly- and perfluoroalkyl substances in the Yangtze River Delta

In this work, a method was developed and optimized for the analysis of polyfluoroalkyl and/or perfluoroalkyl substances(PFASs) content in surface water and sediment samples with high instrumental response and good separation. Surface water and sediment samples were collected from the Yangtze River Delta(YRD) to analyze the distribution characteristics of perfluoroalkyl carboxylic acids(PFCAs), perfluoroalkane sulfonic acids(PFSAs), perfluoroalkyl phosphonic acids(PFPAs), perfluoroalkyl phosphinic acids(PFPiAs), and polyfluoroalkyl phosphoric acid diesters(di PAPs). The results showed that the total concentrations of PFCAs and PFSAs in YRD varied from 31 to 902 ng/L. PFCAs(≥ 11 carbons) and PFSAs(≥ 10 carbons atoms) were not detected in any surface water samples. The mean concentrations of all PFCAs and PFSAs in surface water from the sampling areas decreased in the following order:Yangtze river(191 ng/L) ≈ Taihu lake(189 ng/L) Huangpu river(122 ng/L) ≈ Qiantang river(120 ng/L) Jiaxing urban river(100 ng/L). Strong significant(p 0.05) correlations between the concentrations of many of the compounds were found in the sampling areas, suggesting a common source for these compounds. Only perfluorooctanoic acid(PFOA) was observed in all sediment samples, at concentrations varying from 0.02 to 1.35 ng/g. Finally, detection rates of two di PAPs were only 8% and 10%, respectively and the concentration of di PAPs was two to three times lower compared to PFCAs and PFSAs.     

海河流域河流生态系统健康评价

随着经济发展,人类活动对河流生态系统的胁迫日益强烈,生态系统健康状况受到严重威胁.本研究以海河流域2010年73个采样点的水质、营养盐和底栖动物指标为例,采用指标体系法,从化学完整性和生物完整性两方面评价了流域内河流生态系统健康.结果表明,海河流域河流生态系统健康状况整体较差,有72.6%的样点处于"极差"健康状态,同时表现出明显的地区集聚效应;河流水质与人类活动强度密切相关;海河流域水体富营养化趋势明显;流域内底栖动物多样性低,清洁物种较少.氨氮、总氮、总磷等营养盐指标是影响河流生态系统健康的关键因子,应从控制上述指标入手,遏制海河流域河流生态系统健康恶化.对于河流生态系统健康评价,多因子的综合评价法优于单因子评价法.     

海河及渤海表层沉积物中多环芳烃的分布与来源

采集海河和渤海表层沉积物样品,测定16种EPA规定多环芳烃.海河∑PAH含量（干重）范围为445～2185 ng·g-1,平均值为964 ng·g-1;渤海∑PAH含量范围为171～290 ng·g-1,平均值为226 ng·g-1.海河塘沽区段和天津市区段沉积物中∑PAH含量比郊区段含量高.LMW/HMW(低分子质量/高分子质量)和异构体比值分析表明,生物质及煤的燃烧为海河表层沉积物中PAHs主要来源;对于渤海湾大部分区域来说,石油污染是其PAHs的主要来源,而热解来源的PAHs主要以生物质及煤的燃烧为主;滨海旅游度假村附近海域因受旅游活动影响而燃烧源的贡献较大.风险评价表明,海河及部分渤海海域存在潜在生态危害,滨海村附近海域存在潜在生态风险可能性较低.     

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%.     

Characterization and distribution of polycyclic aromatic hydrocarbon in sediments of Haihe River, Tianjin, China

In this study sediment samples were collected from 13 sites of Haihe River in Tianjin City, China, sixteen of priority polycyclic aromatic hydrocarbons （PAHs） listed in USEPA were analyzed by means of GC-MS. The total concentrations of PAH ranged from 774.81 to 255371.91 ng/g dw, and two to four rings of PAHs were dominant in sediment samples. Molecular ratios, such as phenanthrene/anthracene, fluoranthene/pyrene and low-molecular-weight PAH/high-molecular-weight PAH, were used to study the possible sources of pollution. It indicated a mixed pattern of parolytic and petrogenic inputs of PAHs in sediments in Haihe River. The petrogenic PAHs may be mainly derived from the leakage of refined products, e.g., gasoline, diesel fuel and fuel oil vehicle traffics or gas stations from urban area. The pyrolytic PAHs might be from the discharge of industrial wastewater and the emission of atmospheric particles from petrochemical factories. In addition, the levels of PAHs in the urban and industrial areas are far beyond the values reported from other rivers and marine systems reported. This situation may be due to polluted discharging from some petrochemical industrial manufactories and worse traffic conditions in Tianjin.     

海河流域农村非点源污染现状及空间特征分析

采用污染排放系数法估算了2008年海河流域农村生活源、畜禽分散养殖、农田化肥流失3个主要农村非点源COD、TN、TP和NH3-N 4种污染物的排放量,并对其排放强度和空间分布特征进行了分析.结果表明,海河流域农村非点源污染源排放COD、TN、TP和NH3-N总量分别为2435826, 3042079, 540568, 1798760t/a,平均排放强度分别为11.10, 13.97, 2.98, 8.28t/(km2·a).海河流域内河北省的3个农村非点源的4种污染物排放量均居首位,农村居民生活源对海河流域非点源污染贡献最大,是流域非点源污染控制最主要的对象;子牙河水系农村非点源污染物排放总量最大,而徒骇马颊河水系排放强度最大,是海河流域内污染最严重的水系,其首要非点源污染源是山东省的农村生活源.流域内非点源污染排放量和排放强度均呈现区域性分布,山区和平原区分别呈现出低污染等级和高污染等级.     

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.     

海河流域水生态功能一级二级分区

水生态功能分区是实现流域水环境"分区、分级、分期和分类"管理的基础.通过分析海河流域的陆地和水生态系统特点,确定了一级二级分区的指标体系,一级分区指标包括地貌类型、径流深、年降水量、年蒸发量,反映水资源供给功能的空间格局特征,共划分了6个一级水生态功能区;二级分区利用植被类型和土壤类型的空间异质性,反映流域生态水文过程及水质净化功能的空间格局特征,共划分了16个二级水生态功能区.最后,通过野外调查各个分区的水生态系统结构和生境差异性(水量、水质、河流生境、水生动植物等),对一级和二级分区结果进行了评价.分区结果能够为海河流域的水质目标管理和区域生态环境建设提供支持,分区方法和指标体系也可以为国内其它类似流域的水生态功能分区提供参考.     

Limitation of spatial distribution of ammonia-oxidizing microorganisms in the Haihe River, China, by heavy metals

The Haihe River is characterized by high ammonia pollution. Therefore, it is necessary to determine how environmental factors, such as heavy metals in the river limit the spatial distribution of ammonia-oxidizing microorganisms. In this study, the relationships between five heavy metals and ammonia-oxidizing microorganisms were studied. The results showed that under high ammonia, low oxygen and high concentrations of suspended particles, ammonia-oxidizing bacteria(AOB) ranged from 101:3 to 104:8 gene copies/mL and ammonia-oxidizing archaea(AOA) ranged from 102:7 to 104:9 gene copies/mL. The average metal concentrations in water were 23.57(Cr), 21.58(Ni), 65.09(Cu), 622.03(Zn) and 10.16(As) μg/L, with those of Zn, Cu and Cr being higher than the US EPA criteria. Scatter plots of microbial abundance and metals indicated that both AOA and AOB were limited by heavy metals, but in different ways. As had an inhibitory effect on AOB, while Ni and Zn promoted AOA, and the other metals investigated showed no significant correlation with microbial abundance. Overall, our results indicated that the effects of heavy metals on ammonia-oxidizing microorganisms in water are complex, and that the final effect is determined by the physiological role of each element in the microorganisms, as well as environmental conditions such as complexation of organic matter, not simply the total metal concentration.     

Association of serum levels of perfluoroalkyl substances with gestational diabetes mellitus and postpartum blood glucose

This study was conducted to examine the association of perfluoroalkyl substance(PFAS)exposure with gestational diabetes mellitus(GDM) risk and postpartum fasting blood glucose.We used a 1:2 matched case–control study with 84 GDM subjects and 168 healthy pregnant women from Beijing, China. The maternal blood was collected at 1–2 days before delivery, and eight linear isomers and fourteen branched isomers were determined in maternal serum.Logistic regression analyses were performed to evaluate the associations after adjusting for potential confounders. The median of the sum of levels of total PFASs was 4.24 ng/m L with a interquartile range(IQR) of 2.82–6.54 ng/m L. Although maternal PFAS exposure was not associated with risk of GDM, significant positive associations were observed between evaluated exposure to specific PFAS congeners and increasing blood glucose. The odds ratio(ORs) of the highest category of postpartum fasting blood glucose for perfluoro-1-metylheptylsulfonat(1 m-PFOS), perfluoro-3/4-metylheptylsulfonat(3 m+4 m-PFOS), perfluoro-5-metylheptylsulfonat(5 m-PFOS), and perfluorohexane sulfonate(PFHx S) were 2.03(95% CI: 1.09–3.77), 1.93(95% CI:1.04–3.58), 2.48(95% CI: 1.33–4.65), and 2.26(95% CI: 1.21–4.21), respectively, suggesting negative effects of maternal exposure to specific PFAS compounds on glucose metabolism.     

海河流域河流耗氧污染变化趋势及氧亏分布研究

耗氧污染是海河流域河流水污染的主要类型,耗氧污染物对河流溶氧的消耗产生的氧亏效应对水生生物产生重大影响.收集海河流域重点水功能区88个监测站点2000—2011年CODCr/CODMn、NH3-N指标,分析河流耗氧污染特征及演变趋势,并基于水质目标(2 mg·L-1)下计算出海河流域河流氧亏量.结果表明,流域河流耗氧污染总体呈现好转趋势,耗氧污染指标(NH3-N、CODCr/CODMn)逐渐降低,I~III类水质站点比例增加,劣V类水质站点数和超标倍数减少;CODMn降低幅度大于NH3-N,主要污染物由COD向NH3-N转化.海河流域重点氧亏区域主要集中于中部平原段和下游滨海段,未氧亏区域多集中于上游山区段;北三河、黑龙港运东与徒骇马颊河水系中部平原段整体处于缺氧区域,子牙河水系中部平原区缺氧现象最为严重,氧亏区域位于石家庄洨河下游、滏阳河艾辛庄下游至献县段及石津总干以南;海河流域内中部平原段河流氧亏的主要贡献仍以COD为主,但氨氮的贡献显著,其中黑龙港运东水系、徒骇马颊河水系和北三河水系,COD耗氧均值都高于5 mg·L-1,在北三河和子牙河水系,氨氮耗氧均值达到了4 mg·L-1.     

海河水环境质量及污染物入海通量

在1993～1997年海河水质监测资料的基础上,计算了各污染因子的污染指数和入海通量.结果表明,海河的污染较严重,各断面的水质等级均在IV级和V级的水平,主要的污染因子为NH₃-N、NO₂-N以及有机物污染.5年间海河的水质有所改善,综合污染指数由1993年的17.21降为1997年的13.39.前4年中污染物的入海通量加大,尤其以COD_Mn、BOD、NH₃-N、NO₃-N和NO₃-N最为严重,分别由1993年的1555、655、337、156和25 t·a^-1上升到1996年8710、4317、2516、1528和188 t·a^-1.而1997年又分别急剧下降至1331、973、572、355和31 t·a^-1,这可能主要是由于海河径流量的变化所引起的.     

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.     

海河流域草地生态系统服务功能及其价值评估

草地生态系统为人类提供了畜产品和生命支持两个方面的多种服务功能,但人们常关注产品提供功能而忽视生命支持功能。研究采用联合国千年生态系统评估框架,构建了海河流域草地生态系统服务功能的评估指标体系,并以2005年为基准年,运用市场价值法、影子价格法等多种方法对海河流域草地生态系统进行经济价值评估。结果表明,海河流域草地面积为6.67×10¹⁰ m²,提供产品、固碳、保持土壤、净化环境等8项服务功能的总价值为2 216.28×10⁸元,单位面积价值为3.32元/(m²·a)。其中,提供产品的价值量最大,占总价值的31.3%,其次是固碳和营养物质保持功能的价值,分别占总价值的26.8%、22.2%。海河流域草地生态系统除了具有重要的产品提供功能外,固碳、营养物质保持等生命支持功能的巨大经济价值也不容忽视,平衡兼顾草地生态系统的产品提供功能和生命支持功能有助于促进海河流域经济社会发展与生态保护的协调。