长江水体多氯联苯和有机氯农药污染特征与通量研究

林明兰; 林田; 徐良; 贺静

doi:10.13198/j.issn.1001-6929.2022.07.07

长江水体多氯联苯和有机氯农药污染特征与通量研究

doi: 10.13198/j.issn.1001-6929.2022.07.07

上海海洋大学海洋生态与环境学院，上海　201306

基金项目: 国家自然科学基金面上项目(No.42076205)

详细信息

作者简介:
林明兰（1997-），福建龙岩人，m200401120@st.shou.edu.cn

通讯作者:
林田(1981-)，男，浙江丽水人，教授，博士，主要从事环境地球化学研究，tlin@shou.edu.cn

中图分类号: X52
计量
- 文章访问数: 261
- HTML全文浏览量: 46
- PDF下载量: 80
- 被引次数: 0
出版历程
- 收稿日期: 2022-03-14
- 修回日期: 2022-06-05

Pollution Characteristics and Fluxes of Polychlorinated Biphenyls and Organochlorine Pesticides in Water of the Yangtze River

College of Marine Ecology and Environment, Shanghai Ocean University, Shanghai 201306, China

Funds: National Natural Science Foundation of China (No.42076205)

摘要

摘要: 河流作为陆源持久性有机污染物(POPs)进入海洋的重要途径，其POPs污染问题备受关注. 为了解我国“十三五”时期长江水体多氯联苯(PCBs)和有机氯农药(OCPs)的污染特征，以2017年11月—2018年11月在长江大通站采集的表层水为研究对象，利用气相色谱-三重四级杆串联质谱仪(GC-MS/MS)测定水体中溶解态、颗粒态PCBs和OCPs的浓度，分析水体中溶解态、颗粒态PCBs和OCPs的污染特征，通过化合物组成特征和比值揭示水体中PCBs、OCPs的来源，估算输出通量，并从污染物浓度、年径流量及输沙量三方面加以比较. 结果表明：大通站水体中溶解态∑₄₁PCBs和∑₉OCPs浓度范围分别为0.059~0.29和0.21~0.52 ng/L，颗粒态∑₄₁PCBs和∑₉OCPs浓度范围分别为0.26~0.88和0.34~0.89 ng/L. 六六六(HCHs)、滴滴涕(DDTs)和氯丹(CHLs)均以历史使用残留为主，而PCBs存在新的输入. PCBs、HCHs和DDTs的总输出通量(溶解态+颗粒态)分别为0.57、0.35和0.29 t/a，远低于其他学者于2009—2015年得到的长江入海PCBs、HCHs和DDTs的年均通量. 研究显示，大通站水体中溶解态、颗粒态PCBs和OCPs的污染特征不同，大通站相对较低的PCBs、HCHs和DDTs的输出通量与长江流域过去10年污染物浓度、年径流量和输沙量的整体降低直接相关，溶解态PCBs、HCHs和DDTs浓度显著降低是重要因素. 研究结果反映了我国“十三五”期间提出的长江经济带“共抓大保护，不搞大开发”和近20年坚持履行《关于持久性有机污染物的斯德哥尔摩公约》的重要成效. 今后应重点关注大通以下至长江河口的污染物跨介质分配和交换通量，以系统揭示长江输出POPs在区域污染物“源汇”关系中扮演的角色.
- 多氯联苯 /
- 有机氯农药 /
- 水体 /
- 通量 /
- 长江
Abstract: River runoff is an important pathway for terrestrial organic matters to enter the ocean, and persistent organic pollutants (POPs) pollution is of particular concern. In order to understand the pollution characteristics of PCBs and organochlorine pesticides (OCPs), including hexachlorocyclohexane (HCHs), dichlorodiphenyltrichloroethane (DDTs) and chlordane (CHLs), in the Yangtze River, water samples were collected at the Datong Station of the Yangtze River during November 2017 to November 2018. The concentrations of dissolved and particulate PCBs, HCHs, DDTs and CHLs were determined by gas chromatography-triple quadrupole tandem mass spectrometer (GC-MS/MS) to discuss compound composition, phase distribution and source. The fluxes were estimated and illustrated by the changes of concentration, annual runoff and sediment load. The results showed that the dissolved concentrations of ∑₄₁PCBs and ∑₉OCPs in surface water of the Datong Station were 0.059-0.29 and 0.21-0.52 ng/L, respectively. Moreover, the particulate concentrations of ∑₄₁PCBs and ∑₉OCPs were 0.26-0.88 and 0.34-0.89 ng/L, respectively. Combined with the comparison of concentration levels in different regions, the compound composition and ratio results indicated that HCHs, DDTs and CHLs were dominated by the historical application of pesticides, but there were new inputs of PCBs. The estimated fluxes of PCBs, HCHs and DDTs from river runoff were 0.57, 0.35 and 0.29 t/a, respectively. The results of this study indicated that the pollution characteristics of dissolved and particulate PCBs and OCPs in water of the Datong Station were different, and the fluxes of PCBs, HCHs and DDTs were significantly lower than those from 2009 to 2015 reported by previous studies, due to the overall reduction in pollutant concentration, annual runoff and sediment load of the Yangtze River over the past decade, and reduced dissolved concentration of PCBs, HCHs and DDTs in water were important factors. It can be said that ‘to set up conservation of the Yangtze River and stop its over development’ proposed during the ‘13^th Five-Year Plan’ period, as well as the implementation of the Stockholm Convention on Persistent Organic Pollutants in the past 20 years have jointly contributed to the decline of flux. In the future, further studies should focus on the profile distribution of POPs and exchange fluxes at the different media interface from Datong to the Yangtze River Estuary, to systematically reveal the role of the Yangtze River runoff output and its implications for the regional POPs cycle.
- polychlorinated biphenyls /
- organochlorine pesticides /
- water /
- flux /
- the Yangtze River

HTML全文

图 1 大通站采样点位

注：底图源自自然资源部(http://bzdt.ch.mnr.gov)下载的《中国地图1∶3200万 32开线划一》. 审图号：GS(2016)1569号.

Figure 1. Sampling site in the Datong Station of the Yangtze River, China

下载: 全尺寸图片幻灯片

图 2 2017年—2018年大通站水体溶解态、颗粒态PCBs与OCPs的浓度及相态分布

Figure 2. The concentrations and distribution of dissolved and particulate PCBs and OCPs at the surface water of the Datong Station from 2017 to 2018

下载: 全尺寸图片幻灯片

图 3 大通站水体OCPs各异构体浓度比值

Figure 3. The isomer ratios of OCPs at the surface water of the Datong Station

下载: 全尺寸图片幻灯片

图 4 大通站水体不同氯代PCBs组成

Figure 4. The composition of PCBs at the surface water of the Datong Station

下载: 全尺寸图片幻灯片

图 5 年径流量、输沙量、污染物浓度和其他因素对2017—2018年大通站和2009—2015年长江口^[13,35-36]HCHs、DDTs、PCBs输出通量差异的影响

Figure 5. Effects of the annual discharge, sediment load, pollutant concentrations as well as other factors on the difference of transportation fluxes of HCHs, DDTs and PCBs between the Datong Station from 2017 to 2018 and the Yangtze River Estuary from 2009 to 2015^[13,35-36]

下载: 全尺寸图片幻灯片

表 1 大通站水体OCPs浓度与其他水体的比较

Table 1. Comparison of the concentrations of OCPs in the Datong Station and those in other rivers and sea areas globally

水域		采样时间	HCHs浓度/(ng/L)	DDTs浓度/(ng/L)	数据来源
国内	厦门港	1998年	3.51~27.8	0.95~2.25	文献[20]
	洞庭湖	2017年	7.38~29.59	10.01~53.04	文献[14]
	珠江口	2000年	39.82~282	43.15~292	文献[21]
	洪湖	2014年	0.50~3.28	0.26~5.51	文献[9]
	长江大通站	2017—2018年	0.155~0.434¹⁾、	0.044~0.081¹⁾、	该研究
	长江大通站	2017—2018年	0.086~0.210²⁾	0.143~0.706²⁾	该研究
国外	西班牙埃布罗河	1995—1996年	0.22~28.58	1.97~6.77	文献[22]
	土耳其伊兹密尔湾	2005年	0.032~0.061¹⁾、	0.01-0.013¹⁾、	文献[23]
	土耳其伊兹密尔湾	2005年	0.006~0.009²⁾	0.006~0.01²⁾	文献[23]
	南波罗的海	2003年	0.18~0.75	0.05~0.32	文献[24]
开放大洋	北太平洋	2017年	0.077~0.532	0.002~0.062	文献[2]
注：1)溶解态；2)颗粒态.

下载: 导出CSV

表 2 大通站水体PCBs与其他水体的比较

Table 2. Comparison of the concentrations of PCBs in the Datong Station and those in other rivers and sea areas globally

水域		采样时间	PCBs浓度/(ng/L)	化合物数目	数据来源
国内	洪湖	2014年	0.16~10.85	7	文献[9]
	松花江	2007—2008年	1.10~14	43	文献[25]
	东洞庭湖	2014年	0.50~2.84	7	文献[9]
	东海	2012年	0.59~1.68	12	文献[26]
	厦门港	1998年	0.08~1.69	12	文献[20]
	长江大通站	2017—2018年	0.059~0.290¹⁾、	41	该研究
	长江大通站	2017—2018年	0.262~0.879²⁾	41	该研究
国外	意大利威尼斯泻湖	2002—2003年	0.250~0.792¹⁾、	49	文献[27]
	意大利威尼斯泻湖	2002—2003年	0.105~1.273²⁾	49	文献[27]
	日本东京湾	2006年	0.04~0.64¹⁾、	209	文献[4]
	日本东京湾	2006年	0.045~0.68²⁾	209	文献[4]
	土耳其伊兹密尔湾	2005年	0.132~0.205¹⁾、	29	文献[23]
	土耳其伊兹密尔湾	2005年	0.118~0.181²⁾	29	文献[23]
开放大洋	北大西洋	2005年	0.0002~0.0057	27	文献[28]
开放大洋	赤道印度洋	2011年	0.0027~0.025	21	文献[29]
注：1)溶解态；2)颗粒态.

下载: 导出CSV

表 3 2017—2018年大通站与2009—2015年长江口^[13,35-36]HCHs、DDTs和PCBs输出通量及污染物浓度、年径流量和输沙量的变化

Table 3. The transportation fluxes, annual discharge, sediment load and average concentrations of HCHs, DDTs and PCBs between the Datong Station from 2017 to 2018 and the Yangtze River Estuary from 2009 to 2015^[13,35-36]

研究区域	输出通量/(t/a)						污染物浓度						年径流量/m³	输沙量/t
	溶解态			颗粒态			溶解态			颗粒态
	PCBs	HCHs	DDTs	PCBs	HCHs	DDTs	PCBs	HCHs	DDTs	PCBs	HCHs	DDTs
长江口	2.7	3.2	1.8	0.52	0.6	4.0	3.1¹⁾	3.5¹⁾	2.0¹⁾	0.24¹⁾	2.5²⁾	16²⁾	9.6×10¹¹	2.5×10⁸
大通站	0.12	0.24	0.050	0.45	0.11	0.24	0.15¹⁾	0.29¹⁾	0.06¹⁾	0.55¹⁾	3.00²⁾	6.70²⁾	8.0×10¹¹	0.83×10⁸
注：颗粒态HCHs和DDTs的浓度(ng/g)由原浓度(ng/L)除以2017—2018年大通站总悬浮颗粒物(TSS)的平均浓度(43.44 mg/L)得到. 1)单位为ng/L；2)单位为ng/g.

下载: 导出CSV

参考文献(38)

[1]	CHEN Y P,ZHAO Y,ZHAO M M,et al.Potential health risk assessment of HFRs, PCBs, and OCPs in the Yellow River Basin[J].Environmental Pollution,2021,275:116648. doi: 10.1016/j.envpol.2021.116648
[2]	WU Z L,LIN T,HU L M,et al.Atmospheric legacy organochlorine pesticides and their recent exchange dynamics in the Northwest Pacific Ocean[J].Science of the Total Environment,2020,727:138408. doi: 10.1016/j.scitotenv.2020.138408
[3]	CAO X H,HUO S L,ZHANG H X,et al.Source emissions and climate change impacts on the multimedia transport and fate of persistent organic pollutants,Chaohu watershed,eastern China[J].Journal of Environmental Sciences,2021,109:15-25. doi: 10.1016/j.jes.2021.02.028
[4]	KOBAYASHI J,SERIZAWA S,SAKURAI T,et al.Spatial distribution and partitioning of polychlorinated biphenyls in Tokyo Bay,Japan[J].Journal of Environmental Monitoring,2010,12(4):838-845. doi: 10.1039/b925541a
[5]	GONG X H,DING Q Q,JIN M,et al.Recording and response of persistent toxic substances (PTSs) in urban lake sediments to anthropogenic activities[J].Science of the Total Environment,2021,777:145977. doi: 10.1016/j.scitotenv.2021.145977
[6]	QADEER A,LIU S,LIU M,et al.Historically linked residues profile of OCPs and PCBs in surface sediments of typical urban river networks,Shanghai:ecotoxicological state and sources[J].Journal of Cleaner Production,2019,231:1070-1078. doi: 10.1016/j.jclepro.2019.05.203
[7]	HAN D M,CURRELL M J.Persistent organic pollutants in China's surface water systems[J].Science of the Total Environment,2017,580:602-625. doi: 10.1016/j.scitotenv.2016.12.007
[8]	CHEN L,XIAO Y C,LI Y Y,et al.Construction of the hydrological condition-persistent organic pollutants relationship in the Yangtze River Estuary[J].Journal of Hazardous Materials,2018,360:544-551. doi: 10.1016/j.jhazmat.2018.08.045
[9]	WEI L F,TADESSE A W,WANG J.Organohalogenated contaminants (OHCs) in surface sediments and water of east Dongting Lake and Hong Lake,China[J].Archives of Environmental Contamination and Toxicology,2019,76(2):157-170. doi: 10.1007/s00244-018-0564-4
[10]	JIN X L,LIU Y,QIAO X C,et al.Risk assessment of organochlorine pesticides in drinking water source of the Yangtze River[J].Ecotoxicology and Environmental Safety,2019,182:109390. doi: 10.1016/j.ecoenv.2019.109390
[11]	YANG Y J,CHEN Z L,ZHANG J L,et al.The challenge of micropollutants in surface water of the Yangtze River[J].Science of the Total Environment,2021,780:146537. doi: 10.1016/j.scitotenv.2021.146537
[12]	GE J,YUN X Y,LIU M X,et al.Distribution,potential source and ecotoxicological risk of polychlorinated biphenyls and polybrominated diphenyl ethers in the surface water of the Three Gorges Dam region of the Yangtze River,China[J].Ecotoxicology (London,England),2014,23(6):978-987. doi: 10.1007/s10646-014-1241-7
[13]	ZHANG L F,SHI S X,DONG L,et al.Concentrations and possible sources of polychlorinated biphenyls in the surface water of the Yangtze River Delta,China[J].Chemosphere,2011,85(3):399-405. doi: 10.1016/j.chemosphere.2011.07.064
[14]	CAO F M,LI Z Z,HE Q,et al.Occurrence,spatial distribution,source,and ecological risk assessment of organochlorine pesticides in Dongting Lake,China[J].Environmental Science and Pollution Research,2021,28(24):30841-30857. doi: 10.1007/s11356-021-12743-x
[15]	FLOEHR T,XIAO H X,SCHOLZ-STARKE B,et al.Solution by dilution?a review on the pollution status of the Yangtze River[J].Environmental Science and Pollution Research,2013,20(10):6934-6971. doi: 10.1007/s11356-013-1666-1
[16]	王金南,孙宏亮,续衍雪,等.关于“十四五”长江流域水生态环境保护的思考[J].环境科学研究,2020,33(5):1075-1080. doi: 10.13198/j.issn.1001-6929.2020.03.22 WANG J N,SUN H L,XU Y X,et al.Water eco-environment protection framework in the Yangtze River Basin during the ‘14^th Five-Year Plan’ period[J].Research of Environmental Sciences,2020,33(5):1075-1080. doi: 10.13198/j.issn.1001-6929.2020.03.22
[17]	王丽婧,李虹,杨正健,等.三峡水库蓄水运行初期(2003—2012年)水环境演变特征的“四大效应”[J].环境科学研究,2020,33(5):1109-1118. doi: 10.13198/j.issn.1001-6929.2020.03.23 WANG L J,LI H,YANG Z J,et al.Four effects of water environment evolution in early period (2003-2012) after impoundment of the Three Gorges Reservoir[J].Research of Environmental Sciences,2020,33(5):1109-1118. doi: 10.13198/j.issn.1001-6929.2020.03.23
[18]	黄德生,陈煌,张莉,等.长江大保护环境与经济可持续发展问题及对策研究[J].环境科学研究,2020,33(5):1284-1292. doi: 10.13198/j.issn.1001-6929.2020.03.42 HUANG D S,CHEN H,ZHANG L,et al.Problems and countermeasures on the sustainable development of environment and economy for Yangtze River conservation[J].Research of Environmental Sciences,2020,33(5):1284-1292. doi: 10.13198/j.issn.1001-6929.2020.03.42
[19]	GAO S H,CHEN J,SHEN Z Y,et al.Seasonal and spatial distributions and possible sources of polychlorinated biphenyls in surface sediments of Yangtze Estuary,China[J].Chemosphere,2013,91(6):809-816. doi: 10.1016/j.chemosphere.2013.01.085
[20]	张祖麟,洪华生,哈里德,等.厦门港表层水体中有机氯农药和多氯联苯的研究[J].海洋环境科学,2000,19(3):48-51. doi: 10.3969/j.issn.1007-6336.2000.03.011 ZHANG Z L,HONG H S,KHALID Maskaoui,et al.Study on organochlorine pesticide and PCBs at surface water in Xiamen Harbour[J].Marine Environmental Science,2000,19(3):48-51. doi: 10.3969/j.issn.1007-6336.2000.03.011
[21]	ZHANG Z,DAI M,HONG H,et al.Dissolved insecticides and polychlorinated biphenyls in the Pearl River Estuary and South China Sea[J].Journal of Environmental Monitoring:JEM,2002,4(6):922-928. doi: 10.1039/b206891p
[22]	FERNÁNDEZ M A,ALONSO C,GONZÁLEZ M J,et al.Occurrence of organochlorine insecticides,PCBs and PCB congeners in waters and sediments of the Ebro River (Spain)[J].Chemosphere,1999,38(1):33-43. doi: 10.1016/S0045-6535(98)00167-2
[23]	ODABASI M,CETIN B,DEMIRCIOGLU E,et al.Air-water exchange of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) at a coastal site in Izmir Bay,Turkey[J].Marine Chemistry,2008,109(1/2):115-129.
[24]	SAPOTA G.Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in seawater of the southern Baltic Sea[J].Desalination,2004,162:153-157. doi: 10.1016/S0011-9164(04)00038-4
[25]	YOU H,DING J,ZHAO X S,et al.Spatial and seasonal variation of polychlorinated biphenyls in Songhua River,China[J].Environmental Geochemistry and Health,2011,33(3):291-299. doi: 10.1007/s10653-010-9341-7
[26]	李敏桥,林田,李圆圆,等.中国东海水体中多氯联苯的浓度及其组成特征[J].海洋环境科学,2019,38(4):589-593. doi: 10.12111/j.mes20190416 LI M Q,LIN T,LI Y Y,et al.Concentration and composition of polychlorinated biphenyls in the water of the East China Sea[J].Marine Environmental Science,2019,38(4):589-593. doi: 10.12111/j.mes20190416
[27]	MORET I,GAMBARO A,PIAZZA R,et al.Determination of polychlorobiphenyl congeners (PCBs) in the surface water of the Venice lagoon[J].Marine Pollution Bulletin,2005,50(2):167-174. doi: 10.1016/j.marpolbul.2004.10.005
[28]	GIOIA R,NIZZETTO L,LOHMANN R,et al.Polychlorinated biphenyls (PCBs) in air and seawater of the Atlantic Ocean:sources,trends and processes[J].Environmental Science & Technology,2008,42(5):1416-1422.
[29]	HUANG Y M,LI J,XU Y,et al.Polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) in the equatorial Indian Ocean:temporal trend,continental outflow and air-water exchange[J].Marine Pollution Bulletin,2014,80(1/2):194-199.
[30]	WANG J X,BI Y H,PFISTER G,et al.Determination of PAH,PCB,and OCP in water from the Three Gorges Reservoir accumulated by semipermeable membrane devices (SPMD)[J].Chemosphere,2009,75(8):1119-1127. doi: 10.1016/j.chemosphere.2009.01.016
[31]	LIU C,YUAN G L,YANG Z F,et al.Levels of organochlorine pesticides in natural water along the Yangtze River,from headstream to estuary,and factors determining these levels[J].Environmental Earth Sciences,2011,62(5):953-960. doi: 10.1007/s12665-010-0580-9
[32]	BAQAR M,SADEF Y,AHMAD S R,et al.Organochlorine pesticides across the tributaries of River Ravi,Pakistan:human health risk assessment through dermal exposure,ecological risks,source fingerprints and spatio-temporal distribution[J].Science of the Total Environment,2018,618:291-305. doi: 10.1016/j.scitotenv.2017.10.234
[33]	夏凡,胡雄星,韩中豪,等.黄浦江表层水体中有机氯农药的分布特征[J].环境科学研究,2006,19(2):11-15. doi: 10.3321/j.issn:1001-6929.2006.02.006 XIA F,HU X X,HAN Z H,et al.Distribution characteristics of organochlorine pesticides in surface water from the huangpu river[J].Research of Environmental Sciences,2006,19(2):11-15. doi: 10.3321/j.issn:1001-6929.2006.02.006
[34]	ZHAO H,CAO Z,LIU X,et al.Seasonal variation,flux estimation,and source analysis of dissolved emerging organic contaminants in the Yangtze Estuary,China[J].Marine Pollution Bulletin,2017,125(1/2):208-215.
[35]	LIN T,GUO Z G,LI Y Y,et al.Air-seawater exchange of organochlorine pesticides along the sediment plume of a large contaminated river[J].Environmental Science & Technology,2015,49(9):5354-5362.
[36]	ZHAO T G,GUO Z G,YAO P,et al.Deposition flux and mass inventory of polychlorinated biphenyls in sediments of the Yangtze River Estuary and inner shelf,East China Sea:implications for contributions of large-river input and e-waste dismantling[J].Science of the Total Environment,2019,647:1222-1229. doi: 10.1016/j.scitotenv.2018.08.076
[37]	HE H,HU G J,SUN C,et al.Trace analysis of persistent toxic substances in the main stream of Jiangsu section of the Yangtze River,China[J].Environmental Science and Pollution Research,2011,18(4):638-648. doi: 10.1007/s11356-010-0414-z
[38]	娄保锋,卓海华,周正,等.近18年长江干流水质和污染物通量变化趋势分析[J].环境科学研究,2020,33(5):1150-1162. doi: 10.13198/j.issn.1001-6929.2020.04.24 LOU B F,ZHUO H H,ZHOU Z,et al.Analysis on alteration of water quality and pollutant fluxes in the Yangtze mainstem during recently 18 years[J].Research of Environmental Sciences,2020,33(5):1150-1162. doi: 10.13198/j.issn.1001-6929.2020.04.24