大连海域入海污染源中PFASs的赋存、输入通量和季节特征
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摘要
本文对大连海域入海河流和入海排污口中19种PFASs和2种PFOS新型替代品Cl-PFESAs进行了分析,估算其入海通量,并分析了季节变化特征.结果表明,研究区域入海河流中总PFASs的含量范围为9. 85～757 ng·L~(-1)(浓度中位数为74. 7 ng·L~(-1)),与国内外其他河流相比,大连海域入海河流中总PFASs的含量处于中等或较低水平;入海排污口中总PFASs的含量范围为9. 19～801 ng·L~(-1)(浓度中位数为29. 5 ng·L~(-1)).入海河流和入海排污口中PFASs的主要贡献要素为PFOS和PFOA,其中入海河流、市政污水和污水处理厂出水中总PFASs含量未发现明显的季节差异特征,但工业废水中冬季含量显著高于夏季.计算结果显示,大连海域总PFASs入海通量约123 g·d~(-1)(44. 7 kg·a~(-1)),入海河流和入海排污口的贡献相当.全氟/多氟醚类磺酸化合物(Cl-PFESAs)检出率较低,其中8∶2Cl-PFESA均为检出.
Concentrations of 19 PFASs( poly-and perfluoroalkyl substances) in riverwater,coastal wastewater,and effluents from wastewater treatment plants( WWTPs) directly discharged into the Dalian coastal area were measured and their inputs were calculated accordingly. For riverwater samples,the total PFAS concentration ranged from 9. 85 to 757 ng·L~(-1),with a median of 74. 7 ng·L~(-1).For drain outlets,the total PFAS concentration in wastewater ranged from 9. 19 to 801 ng·L~(-1),with a median of 29. 5 ng·L~(-1). PFOS and PFOA were the dominant contributors for the PFASs in both riverwater and wastewater samples in this study. The total PFASs concentration in the industrial wastewater samples collected during the winter were found to be significantly higher than those collected in the summer. However,no seasonal variation was found for other samples. The total PFAS input into the Dalian coastal area was calculated to be 44. 7 kg·a~(-1). The detection frequencies of Cl-PFESAs were low,and no 8∶ 2 Cl-PFESA was detected in all collected samples.
Concentrations of 19 PFASs( poly-and perfluoroalkyl substances) in riverwater,coastal wastewater,and effluents from wastewater treatment plants( WWTPs) directly discharged into the Dalian coastal area were measured and their inputs were calculated accordingly. For riverwater samples,the total PFAS concentration ranged from 9. 85 to 757 ng·L~(-1),with a median of 74. 7 ng·L~(-1).For drain outlets,the total PFAS concentration in wastewater ranged from 9. 19 to 801 ng·L~(-1),with a median of 29. 5 ng·L~(-1). PFOS and PFOA were the dominant contributors for the PFASs in both riverwater and wastewater samples in this study. The total PFASs concentration in the industrial wastewater samples collected during the winter were found to be significantly higher than those collected in the summer. However,no seasonal variation was found for other samples. The total PFAS input into the Dalian coastal area was calculated to be 44. 7 kg·a~(-1). The detection frequencies of Cl-PFESAs were low,and no 8∶ 2 Cl-PFESA was detected in all collected samples.
引文
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[26]王世亮,张丽萍,张鑫,等.泗河水体及污水厂出水中全氟烷基酸类化合物及其前体物空间分布特征[J].环境科学学报,2018,38(4):1459-1557.Wang S L,Zhang L P,Zhang X,et al.Characteristics of spatial distribution of perfluoroalkyl acids(PFAAs)and their precursors in the water samples from the Sihe River and the effluents of wastewater treatment plants[J].Acta Scientiae Circumstantiae,2018,38(4):1549-1557.
[27]王世亮,孙建树,杨月伟,等.典型旅游城市河流水体及污水厂出水中全氟烷基酸类化合物的空间分布及其前体物的转化[J].环境科学,2018,39(12):5494-5502.Wang S L,Sun J S,Yang Y W,et al.Spatial distribution of perfluoroalkyl acids and transformation of their precursors in river water samples and effluents of wastewater treatment plans in a typical tourism city[J].Environmental Science,2018,39(12):5494-5502.
[2]Bowman J S.Fluorotechnology is critical to modern life:the fluoro Council counterpoint to the madrid statement[J].Environmental Health Perspective,2015,123(5):A112-A113.
[3]Benskin J P,Phillips V,St.Louis V L,et al.Source elucidation of perfluorinated carboxylic acids in remote Alpine Lake sediment cores[J].Environmental Science&Technology,2011,45(17):7188-7194.
[4]Butt C M,Berger U,Bossi R,et al.Levels and trends of polyand perfluorinated compounds in the Arctic environment[J].Science of the Total Environment,2010,408(15):2936-2965.
[5]Campo J,Lorenzo M,Pérez F,et al.Analysis of the presence of perfluoroalkyl substances in water,sediment and biota of the Jucar River(E Spain).Sources,partitioning and relationships with water physical characteristics[J].Environmental Research,2016,147:503-512.
[6]Castiglioni S,Valsecchi S,Polesello S,et al.Sources and fate of perfluorinated compounds in the aqueous environment and in drinking water of a highly urbanized and industrialized area in Italy[J].Journal of Hazardous Materials,2015,282:51-60.
[7]Krrman A,Ericson I,van Bavel B,et al.Exposure of perfluorinated chemicals through lactation:levels of matched human milk and serum and a temporal trend,1996-2004,in Sweden[J].Environmental Health Perspective,2006,115(2):226-230.
[8]Giesy J P,Kannan K.Global distribution of perfluorooctane sulfonate in wildlife[J].Environmental Science&Technology,2001,35(7):1339-1342.
[9]Lau C,Anitole K,Hodes C,et al.Perfluoroalkyl acids:a review of monitoring and toxicological findings[J].Toxicological Sciences,2007,99(2):366-394.
[10]孟娣,王潇,王赛赛,等.水体中典型重金属和全氟化合物对水生生物的联合毒性[J].生态毒理学报,2018,13(2):13-22.Meng D,Wang X,Wang S S,et al.Review on combined toxicity of typical heavy metals and perfluorinated compounds in water environment on aquatic organisms[J].Asian Journal of Ecotoxicology,2018,13(2):13-22.
[11]UNEP.SC-4/17:Listing of perfluorooctane sulfonic acid,its salts and perfluorooctane sulfonyl fluoride,COP-4;Stockholm convention on persistent organic pollutants[R].United Nations Environment Programme,2009.
[12]U.S.EPA.Global PFOA Stewardship[EB/OL].http://www.epa.gov/oppt/pfoa,2006.
[13]ECHA.ANNEX XV PROPOSAL FOR A RESTRICTION-Perfluorooctanoic acid(PFOA),PFOA salts and PFOA-related substances,Version 1.0[R].Helsinki,Finland:ECHAEuropean Chemicals Agency.http://echa.europa.eu/documents/10162/e9cddee6-3164-473d-b590-8fcf9caa50e7,2014-10-17/2015-06-02.
[14]Heydebreck F,Tang J H,Xie Z Y,et al.Alternative and legacy perfluoroalkyl substances:differences between European and Chinese river/estuary systems[J].Environmental Science&Technology,2015,49(14):8386-8395.
[15]国务院.国务院关于印发“十三五”生态环境保护规划的通知[R].http://www.gov.cn/zhengce/content/2016-12/05/content_5143290.htm,2016-11-24.
[16]Strynar M,Dagnino S,Mc Mahen R,et al.Identification of Novel Perfluoroalkyl ether carboxylic acids(PFECAs)and sulfonic acids(PFESAs)in natural waters using accurate mass time-of-flight mass spectrometry(TOFMS)[J].Environmental Science&Technology,2015,49(19):11622-11630.
[17]Wang S W,Huang J,Yang Y,et al.First report of a Chinese PFOS alternative overlooked for 30 years:its toxicity,persistence,and presence in the environment[J].Environmental Science&Technology,2013,47(18):10163-10170.
[18]Ruan T,Lin Y F,Wang T,et al.Identification of novel polyfluorinated ether sulfonates as PFOS alternatives in municipal sewage sludge in China[J].Environmental Science&Technology,2015,49(11):6519-6527.
[19]Wang T,Vestergren R,Herzke D,et al.Levels,isomer profiles,and estimated riverine mass discharges of perfluoroalkyl acids and fluorinated alternatives at the mouths of Chinese rivers[J].Environmental Science&Technology,2016,50(21):11584-11592.
[20]Shi Y L,Vestergren R,Zhou Z,et al.Tissue distribution and whole body burden of the chlorinated polyfluoroalkyl ether sulfonic acid F-53B in Crucian Carp(Carassius carassius):evidence for a highly bioaccumulative contaminant of emerging concern[J].Environmental Science&Technology,2015,49(24):14156-14165.
[21]Gebbink W A,Bossi R,Rigét F F,et al.Observation of emerging per-and polyfluoroalkyl substances(PFASs)in Greenland marine mammals[J].Chemosphere,2016,144:2384-2391.
[22]Chen H,Wang X M,Zhang C,et al.Occurrence and inputs of perfluoroalkyl substances(PFASs)from rivers and drain outlets to the Bohai Sea,China[J].Environmental Pollution,2017,221:234-243.
[23]Chen H,Han J B,Zhang C,et al.Occurrence and seasonal variations of per-and polyfluoroalkyl substances(PFASs)including fluorinated alternatives in rivers,drain outlets and the receiving Bohai Sea of China[J].Environmental Pollution,2017,231:1223-1231.
[24]Naile J E,Khim J S,Wang T Y,et al.Perfluorinated compounds in water,sediment,soil and biota from estuarine and coastal areas of Korea[J].Environmental Pollution,2010,158(5):1237-1244.
[25]Zushi Y,Ye F,Motegi M,et al.Spatially detailed survey on pollution by multiple perfluorinated compounds in the Tokyo bay basin of Japan[J].Environmental Science&Technology,2011,45(7):2887-2893.
[26]王世亮,张丽萍,张鑫,等.泗河水体及污水厂出水中全氟烷基酸类化合物及其前体物空间分布特征[J].环境科学学报,2018,38(4):1459-1557.Wang S L,Zhang L P,Zhang X,et al.Characteristics of spatial distribution of perfluoroalkyl acids(PFAAs)and their precursors in the water samples from the Sihe River and the effluents of wastewater treatment plants[J].Acta Scientiae Circumstantiae,2018,38(4):1549-1557.
[27]王世亮,孙建树,杨月伟,等.典型旅游城市河流水体及污水厂出水中全氟烷基酸类化合物的空间分布及其前体物的转化[J].环境科学,2018,39(12):5494-5502.Wang S L,Sun J S,Yang Y W,et al.Spatial distribution of perfluoroalkyl acids and transformation of their precursors in river water samples and effluents of wastewater treatment plans in a typical tourism city[J].Environmental Science,2018,39(12):5494-5502.