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This study investigated the susceptibility of karst groundwater from surface pollution. A typical karst spring system (the Chaoshuidong in Yichang, Hubei Province of China) was selected to analyze the contamination characteristics, sources, and transport processes of organochlorine pesticides (OCPs). Water, soil, and sediment samples were collected in four seasons for OCP analysis. The results showed that the average concentrations of OCPs in surface water, spring water, soil and sediment samples from Chaoshuidong system were 8.25ng/L, 5.11ng/L, 15.9ng/g and 12.6ng/g, respectively. OCPs concentrations in the Chaoshuidong system were relatively lower than in other regions, with seasonal fluctuations closely correlated to hydrogeological conditions and OCPs transport dynamics. Composition analysis of hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs)indicated that HCHs were primarily from agricultural inputs of Lindane(γ-HCH) in the water and sediments, while the technical HCH dominated in the soils. DDTs were mainly a mixture of inputs from technical DDT and dicofol pesticide in all three media. The contribution of OCPs from the soils in the recharge area to the upstream surface water and to the spring water was 87.8% and 58.3%, respectively, and the contribution of OCPs from the spring water in the discharge area to the spring sediments was 64.2%. This study demonstrated that OCPs can be rapidly transported from recharge area to discharge area through two primary pathways: surface transport and underground transport, subsequently contaminating water bodies.

, correspAuthors=Wei CHEN, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Pei-pei ZHAO, Jun-wu XIONG, Chao ZHANG, Xiu-wen YANG, Chao-jie QIN, Zhe QIAN, Ya-hui ZHAO, Xue-ming ZHANG, Wei LIU, Shi-hua QI, Wei CHEN), CN=ArticleExt(id=1241049981021377170, articleId=1241049975526838735, tenantId=1146029695717560320, journalId=1234093305789726721, language=CN, title=潮水洞岩溶系统中有机氯农药的时空分布特征,来源与迁移, columnId=1240689621210820752, journalTitle=中国环境科学, columnName=新污染物, runingTitle=null, highlight=null, articleAbstract=

为研究岩溶地下水易受地表污染物影响的问题,选取了湖北宜昌一典型岩溶泉域——潮水洞为研究对象,采集了一年四季的水体.土壤和沉积物样品,分析了有机氯农药(OCPs)在岩溶泉系统中的污染特征,来源及迁移过程.结果表明,潮水洞地表水和泉水中OCPs的平均浓度为8.25ng/L和5.11ng/L,土壤及沉积物中OCPs的平均浓度分别为15.9ng/g和12.6ng/g.与其他地区相比,潮水洞岩溶泉域中OCPs的污染处于较低水平,其季节性变化特点与当地水文地质条件及OCPs迁移过程密切相关.HCHs和DDTs的特征比值溯源结果显示,水体和沉积物中的HCHs主要来源于林丹(γ-HCH)的输入,土壤中的HCHs则主要来源于工业HCHs的输入;DDTs在水体,土壤和沉积物3种介质中都是属于混合来源,即来源于工业DDT和三氯杀螨醇.研究表明,补给区土壤中OCPs对上游地表水中OCPs的贡献率为87.8%,对泉水的贡献率为58.3%,排泄区泉水中OCPs对泉沉积物中OCPs的贡献率为64.2%.OCPs可通过地表迁移和地下迁移两种方式从补给区迁移至排泄区污染水体.

, correspAuthors=陈伟, authorNote=null, correspAuthorsNote=
*责任作者,副教授,
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赵培培(2000-),女,河南平顶山人,中国地质大学(武汉)硕士研究生,主要从事环境地球化学研究..

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赵培培(2000-),女,河南平顶山人,中国地质大学(武汉)硕士研究生,主要从事环境地球化学研究..

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赵培培(2000-),女,河南平顶山人,中国地质大学(武汉)硕士研究生,主要从事环境地球化学研究..

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locations and hydrogeological map of the study area, figureFileSmall=caeEpFJOO6rsEc7kVGYFhA==, figureFileBig=dcXm20bT2Vl8krNYjMxrRQ==, tableContent=null), ArticleFig(id=1241049998763282891, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049975526838735, language=CN, label=图1, caption=研究区采样点位及水文地质图

a.研究区区位,b.样品采样点位分布,c.研究区水文地质平面图,d.研究区水文地质剖面图

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Concentrations of OCPs in different media of Chaoshuidong karst system

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OCPs补给区OCPs含量排泄区OCPs含量
地表水(ng/L)土壤(ng/g)沉积物(ng/g)泉水(ng/L)土壤(ng/g)沉积物(ng/g)
HCHs0.14~4.580.40~3.680.28~14.60.20~4.460.44~2.740.10~0.51
DDTs0.40~6.521.14~34.80.49~27.80.24~5.422.27~21.81.08~5.67
HCB<MDL~0.500.13~0.480.04~0.520.03~0.540.12~0.400.04~0.11
CHLs0.05~1.380.11~0.910.13~3.240.03~1.300.13~1.330.07~0.16
DRINs0.39~1.600.11~2.640.15~2.820.37~1.480.13~0.320.20~0.31
MXC0.04~2.41<MDL~7.030.65~4.060.07~0.831.24~2.610.29~1.69
HEPTs0.02~3.27<MDL~1.160.43~1.800.06~0.310.16~0.470.24~0.36
EDNOs0.03~2.840.02~1.490.29~1.130.05~1.070.20~0.270.22~0.43
23OCPs1.31~21.72.71~47.24.35~56.01.49~15.46.77~25.52.92~9.07
), ArticleFig(id=1241050003641258641, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049975526838735, language=CN, label=表1, caption=

潮水洞岩溶系统各介质中OCPs含量

, figureFileSmall=null, figureFileBig=null, tableContent=
OCPs补给区OCPs含量排泄区OCPs含量
地表水(ng/L)土壤(ng/g)沉积物(ng/g)泉水(ng/L)土壤(ng/g)沉积物(ng/g)
HCHs0.14~4.580.40~3.680.28~14.60.20~4.460.44~2.740.10~0.51
DDTs0.40~6.521.14~34.80.49~27.80.24~5.422.27~21.81.08~5.67
HCB<MDL~0.500.13~0.480.04~0.520.03~0.540.12~0.400.04~0.11
CHLs0.05~1.380.11~0.910.13~3.240.03~1.300.13~1.330.07~0.16
DRINs0.39~1.600.11~2.640.15~2.820.37~1.480.13~0.320.20~0.31
MXC0.04~2.41<MDL~7.030.65~4.060.07~0.831.24~2.610.29~1.69
HEPTs0.02~3.27<MDL~1.160.43~1.800.06~0.310.16~0.470.24~0.36
EDNOs0.03~2.840.02~1.490.29~1.130.05~1.070.20~0.270.22~0.43
23OCPs1.31~21.72.71~47.24.35~56.01.49~15.46.77~25.52.92~9.07
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潮水洞岩溶系统中有机氯农药的时空分布特征,来源与迁移
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赵培培 1, 2 , 熊俊武 1, 2 , 张超 1, 2 , 杨秀雯 1, 2 , 秦超杰 3 , 钱喆 4 , 赵亚辉 1, 2 , 张学明 5 , 刘伟 3 , 祁士华 1, 4 , 陈伟 1, 2, 3, 4, 6, *
中国环境科学 | 新污染物 2025,45(1): 292-301
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中国环境科学 | 新污染物 2025, 45(1): 292-301
潮水洞岩溶系统中有机氯农药的时空分布特征,来源与迁移
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赵培培1, 2 , 熊俊武1, 2, 张超1, 2, 杨秀雯1, 2, 秦超杰3, 钱喆4, 赵亚辉1, 2, 张学明5, 刘伟3, 祁士华1, 4, 陈伟1, 2, 3, 4, 6, *
作者信息
  • 1.中国地质大学(武汉)环境学院,湖北 武汉 430078
  • 2.中国地质大学(武汉)地下水质与健康教育部重点实验室,湖北 武汉 430078
  • 3.中国地质大学(武汉)地质调查研究院,湖北 武汉 430074
  • 4.中国地质大学(武汉)生物地质与环境地质国家重点实验室,湖北 武汉 430078
  • 5.山东省地质矿产勘查开发局第五地质大队,山东 泰安 271000
  • 6.湖北省地质局,资源与生态环境地质湖北省重点实验室,湖北 武汉 430034
  • 赵培培(2000-),女,河南平顶山人,中国地质大学(武汉)硕士研究生,主要从事环境地球化学研究..

通讯作者:

*责任作者,副教授,
Temporal and spatial distribution, sources, and transport of organochlorine pesticides in the Chaoshuidong karst system
Pei-pei ZHAO1, 2 , Jun-wu XIONG1, 2, Chao ZHANG1, 2, Xiu-wen YANG1, 2, Chao-jie QIN3, Zhe QIAN4, Ya-hui ZHAO1, 2, Xue-ming ZHANG5, Wei LIU3, Shi-hua QI1, 4, Wei CHEN1, 2, 3, 4, 6, *
Affiliations
  • 1.School of Environmental Studies, China University of Geosciences, Wuhan 430078, China
  • 2.Key Laboratory of Groundwater Quality and Health, Ministry of Education, China University of Geosciences, Wuhan 430078, China
  • 3.Institute of Geological Survey, China University of Geosciences, Wuhan 430074, China
  • 4.State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430078, China
  • 5.The Fifth Geological Brigade of Shandong Geological and Mineral Exploration and Development Bureau, Tai’an 271000, China
  • 6.Hubei Key Laboratory of Resources and Eco-Environment Geology, Hubei Geological Bureau, Wuhan 430034, China
出版时间: 2025-01-20
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为研究岩溶地下水易受地表污染物影响的问题,选取了湖北宜昌一典型岩溶泉域——潮水洞为研究对象,采集了一年四季的水体.土壤和沉积物样品,分析了有机氯农药(OCPs)在岩溶泉系统中的污染特征,来源及迁移过程.结果表明,潮水洞地表水和泉水中OCPs的平均浓度为8.25ng/L和5.11ng/L,土壤及沉积物中OCPs的平均浓度分别为15.9ng/g和12.6ng/g.与其他地区相比,潮水洞岩溶泉域中OCPs的污染处于较低水平,其季节性变化特点与当地水文地质条件及OCPs迁移过程密切相关.HCHs和DDTs的特征比值溯源结果显示,水体和沉积物中的HCHs主要来源于林丹(γ-HCH)的输入,土壤中的HCHs则主要来源于工业HCHs的输入;DDTs在水体,土壤和沉积物3种介质中都是属于混合来源,即来源于工业DDT和三氯杀螨醇.研究表明,补给区土壤中OCPs对上游地表水中OCPs的贡献率为87.8%,对泉水的贡献率为58.3%,排泄区泉水中OCPs对泉沉积物中OCPs的贡献率为64.2%.OCPs可通过地表迁移和地下迁移两种方式从补给区迁移至排泄区污染水体.

岩溶泉系统  /  有机氯农药  /  多介质迁移  /  污染分布  /  来源解析

This study investigated the susceptibility of karst groundwater from surface pollution. A typical karst spring system (the Chaoshuidong in Yichang, Hubei Province of China) was selected to analyze the contamination characteristics, sources, and transport processes of organochlorine pesticides (OCPs). Water, soil, and sediment samples were collected in four seasons for OCP analysis. The results showed that the average concentrations of OCPs in surface water, spring water, soil and sediment samples from Chaoshuidong system were 8.25ng/L, 5.11ng/L, 15.9ng/g and 12.6ng/g, respectively. OCPs concentrations in the Chaoshuidong system were relatively lower than in other regions, with seasonal fluctuations closely correlated to hydrogeological conditions and OCPs transport dynamics. Composition analysis of hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs)indicated that HCHs were primarily from agricultural inputs of Lindane(γ-HCH) in the water and sediments, while the technical HCH dominated in the soils. DDTs were mainly a mixture of inputs from technical DDT and dicofol pesticide in all three media. The contribution of OCPs from the soils in the recharge area to the upstream surface water and to the spring water was 87.8% and 58.3%, respectively, and the contribution of OCPs from the spring water in the discharge area to the spring sediments was 64.2%. This study demonstrated that OCPs can be rapidly transported from recharge area to discharge area through two primary pathways: surface transport and underground transport, subsequently contaminating water bodies.

karst spring system  /  organochlorine pesticides (OCPs)  /  multi-media transport  /  distribution  /  source appointment
赵培培, 熊俊武, 张超, 杨秀雯, 秦超杰, 钱喆, 赵亚辉, 张学明, 刘伟, 祁士华, 陈伟. 潮水洞岩溶系统中有机氯农药的时空分布特征,来源与迁移. 中国环境科学, 2025 , 45 (1) : 292 -301 .
Pei-pei ZHAO, Jun-wu XIONG, Chao ZHANG, Xiu-wen YANG, Chao-jie QIN, Zhe QIAN, Ya-hui ZHAO, Xue-ming ZHANG, Wei LIU, Shi-hua QI, Wei CHEN. Temporal and spatial distribution, sources, and transport of organochlorine pesticides in the Chaoshuidong karst system[J]. China Environmental Science, 2025 , 45 (1) : 292 -301 .
有机氯农药(OCPs)是一类高效的杀虫剂,具有较高的生物毒性和遗传毒性.虽在20世纪80年代以来各国已陆续禁止OCPs的使用,但它们的全球迁移性和持久性使得其至今仍可以在水体[1-2]、土壤[3-4]及沉积物[1,5-6]环境中广泛检出.这类污染物在进入环境后会通过地表径流和渗透被输送至地表水和地下水[7],从而对生态系统和人类健康构成严重威胁.
特别地,在岩溶地区,地下水作为人类重要的饮用水资源[8],其安全问题尤为重要.但由于岩溶区特殊的水文地质结构,地表污染物能够轻易穿透浅薄土壤通过岩溶裂隙或落水洞等进入含水层[9],这使得岩溶地区的地表水和地下水遭受严重污染[6,10-11],从而对地下水水质和水资源安全构成了严重威胁[12].多年来,对于岩溶地区OCPs的分布与来源已有一定的研究[1,4],但对于OCPs在岩溶区地表和地下环境中的迁移过程尚未得到充分的研究[5].因此,深入研究岩溶地区OCPs的迁移过程,对于全面评估岩溶地下水农药污染的现状,预测其环境风险,制定有效的地下水保护措施具有重要的科学价值和现实意义.
宜昌作为湖北省的典型岩溶区域,长期以农业生产为主[13].潮水洞岩溶泉作为当地重要的饮用水源地之一,具备独立的地下水补给区和排泄区[14].该区域的岩溶地貌特征,如溶洞,地下河以及由地下水排泄形成的岩溶泉,在中国其他岩溶地区亦普遍存在.同时,岩溶地区水体所包括的地表径流和地下暗河[15]也为OCPs等污染物质的迁移提供了共通的途径.因此,本文以宜昌潮水洞岩溶泉域为研究对象,旨在系统地探究OCPs在岩溶泉系统中的迁移过程.分析潮水洞多介质环境中OCPs的浓度,组成和分布特征;解析潮水洞岩溶泉系统中OCPs的来源;从地表和地下两个维度去探究整个岩溶泉系统中OCPs的迁移过程.研究结果将为岩溶区农药污染的防控提供科学依据,为相关部门制定针对性的环境保护政策和实施有效的治理措施提供理论参考.
潮水洞位于湖北省宜昌市点军区潮水河流域(图1(a)~(b)),总体为岩溶槽谷地貌,该地区属于亚热带季风气候,降雨量的季节变化和空间差异明显[16],雨水主要集中在夏季.该流域(图1(c)~(d)出露寒武系下统底部水井沱组(∈1s)到寒武系中统覃家庙组(∈2q)地层,其中,石牌组(∈1sh)作为潮水河流域稳定的隔水层将潮水河流域一分为二,上部石龙洞组(∈1sl)和天河板组(∈1t)为潮水河流域两大主要含水层[17].潮水河流域在降雨补给的雨期和无有效降雨补给的无雨期具有两种不同流量,雨期潮水河总径流量的变化主要取决于降雨量,而无雨期潮水河总径流量的变化则是取决于潮水洞地下水的排泄[14].潮水洞三大主要土壤类型是黄土,紫土和石灰土,pH值在4.8~6.5之间,总有机碳(TOC)含量在15.1~30.0g/kg之间[18].此外,当地土层结构松散,不平整度高,厚度变化在0~4m[11].这些土层特性与潮水洞特殊的水文地质条件使得污染物可快速穿透表层土壤进入地下水,并通过地下暗河及潮水河等多种方式迁移至下游泉水.
于2021年4月(春),7月(夏),10月(秋)和2022年1月(冬)在潮水河流域采集了表层土壤,河流沉积物,地表水,泉水及泉沉积物样品.根据当地水文地质条件,在补给区采集了2个水样(上游地表水样CRW1和下游地表水样CRW2),2个表层土壤样品(CRS1,CRS2),1个表层沉积物样品(CRSD);在排泄区(距补给区约2.5km)采集了1个泉水样品(CDW)及对应的泉沉积物样品(CDSD),并在洞口附近采集1份表层土壤样品(CDS),具体的采样位置及点位信息如图1(b)所示.水样使用经过样品润洗后的2L琥珀色玻璃瓶采集;土样和沉积物样品均用干净的不锈钢铲采集,每个点位的土样均是在50m×50m范围内采集4个方向的土壤样品(0~20cm)混合成复合样品后使用铝箔包裹,沉积物样品则是在对应点位采集3份样品(0~2cm)均匀混合后用干净铝箔包裹,铝箔包裹后的土样和沉积物样品均被密封在干净的聚乙烯密实袋中运回实验室.
分析所用的23种OCPs的标准物质购自o2si Smart Solution(美国),2种回收率指示物四氯间二甲苯(TCmX)和十氯联苯(PCB209)购自Accustandard(美国),内标五氯硝基苯(PCNB)购自Supelco(美国),实验所需的二氯甲烷,正己烷,丙酮,异辛烷等均是色谱纯级,购于美国Thermo Fisher公司;中性氧化铝(100~200目)及无水硫酸钠购自国药集团,层析柱硅胶(100~200目)购自青岛谱科分离材料有限公司.
土壤样品及沉积物样品在进行前处理之前使用冻干机冻干,称量10.0g样品并加入少量无水硫酸钠(经马弗炉450℃烧4h),在样品中加入20ng回收率指示物(TCmX和PCB209)后用160mL二氯甲烷在45℃的水浴锅中索式抽提24h.水样使用1L量筒准确量取置于分液漏斗中,接着向水样(1L)中加入20ng回收率指示物,选用二氯甲烷进行萃取,每次30mL,萃取3次.所有萃取液采用旋转蒸发仪浓缩至5mL左右,加入5mL正己烷进行溶剂置换后继续浓缩至2~3mL.浓缩后的样品经过已去活的硅胶氧化铝层析柱(v/v=2:1)净化去除杂质,并使用正己烷和二氯甲烷混合溶液(v/v=3:2)进行淋洗.淋洗液再经旋转蒸发浓缩至0.5mL,使用异辛烷转移至2mL细胞瓶,用柔和的高纯氮气(>99.999%)将目标溶液吹至0.2mL,加入20ng内标物PCNB冷冻(-20℃)保存至上机.
仪器分析参考黄焕芳等[11]的方法,并在此基础上稍作改进.详细的仪器设置及参数如下:使用气相色谱-电子俘获检测器(GC-ECD,美国Agilent 7890A)进行分析,色谱柱为DB-5MS(30.0m×0.32mm×0.25μm),进样器和检测器温度分别设置为290℃和300℃.升温程序如下:柱温箱温度从100℃开始(平衡时间2min),以6℃/min的速度上升到220℃,以4℃/min的速度上升到250℃,以1℃/min的速度上升到253℃,最后以10℃/min的速度达到290℃,保持15min.使用含有不同浓度的OCPs(10,20,50,100,150,200ng/mL)和100ng/mL的PCNB作为内标的标曲溶液对目标物进行定量分析.
样品前处理和分析过程中严格执行质量控制与质量保证.每批实验设置一个程序空白样品和一个平行样品,并在每天的仪器分析中添加一个质量控制标准样品(100ng/mL)和溶剂空白样品以检查可能的干扰和交叉污染,同时方便进行后期的仪器校正.样品前处理之前加入回收率指示物(TCmX和PCB209)用于监控整个前处理过程的质量,其回收率范围在85%~109%之间,本研究所有的数据均进行过回收率校正.根据3倍信噪比(S/N)计算方法检出限(MDL),水样的方法检出限为0.01~0.02ng/L,土壤和沉积物样品的方法检出限(以干重计)为0.01~0.02ng/g.空白样待测组分均低于检出限,平行样品的相对标准偏差小于20%.
将23种OCPs分为8类:HCB(六氯苯),HCHs(六六六,包括α-HCH,β-HCH,γ-HCH,δ-HCH),DDTs(滴滴涕,包括op’-DDT,pp’-DDT,op’-DDE,pp’-DDE,op’-DDD和pp’-DDD),CHLs(氯丹,包括α-氯丹和β-氯丹),DRINs(包括艾氏剂,狄氏剂,异狄氏剂和异狄氏剂醛),EDNOs(硫丹,包括α-硫丹,β-硫丹和硫丹硫酸盐),HEPTs(包括七氯,环氧七氯),MXC(甲氧滴滴涕).在进行数据统计时,低于MDL的含量数据使用1/2MDL进行统计计算.使用IBM SPSS 27对OCPs结果进行差异性分析(Mann-Whitney检验)并检验不同组分OCPs之间的相关性(Spearman相关性分析),上述两种分析均在显著性水平P=0.05的条件下进行,以确保结果的统计学显著性.在分析OCPs在不同介质中迁移传输时使用多元线性回归(MLRA)对结果进行贡献性定量分析.
研究区水体中23种OCPs均被广泛检出,其中补给区地表水样品中有19种OCPs的检出率达到100%;而排泄区泉水样品中共有21种物质的检出率为100%,泉水样品OCPs的检出率略高于地表水.结合当地水文地质条件,主要有以下3种可能:(1)泉水中的OCPs除了通过地下岩溶管道来自于上游地表水以外,还可能来自于凤凰坪附近的落水洞(图1(c));(2)在非雨季的情况下地下水是潮水河的补给源,泉水在向地表河流输送的过程中OCPs被当地土壤颗粒所吸附,导致地表水中的OCPs检出降低;(3)研究区水体pH值处于中性至弱碱性,且泉水的pH值普遍低于地表水,在弱碱性环境下DDTs更易被降解[19],使得部分样品中DDTs含量低于检出限,最终地表水中OCPs的检出率低于泉水;同时,当地土壤TOC含量呈现出排泄区>补给区下游>补给区上游的趋势,而OCPs亲有机质的特性使得高有机质土壤更易在泉水向地表水补给过程中吸附OCPs,从而导致地表水中OCPs检出率相对较低.
潮水洞系统的水体中23种OCPs的含量如表1所示,其中地表水中总OCPs(∑23OCPs)的浓度在1.31~21.7ng/L之间,平均浓度为8.25ng/L,泉水中∑23OCPs浓度在1.49~15.4ng/L之间,平均值为5.11ng/L.与其他地区OCPs浓度相比,潮水洞系统地表水中∑23OCPs的平均浓度(8.25ng/L)高于洪湖[20](4.06ng/L)和北京通惠河地表水[21](7.86ng/L);但是低于鄱阳湖[22](19.1~117.8ng/L)和大冶湖[23](2.14~45.14ng/L).泉水中∑23OCPs浓度(1.49~15.41ng/L)远低于太湖浅层地下河[24](31.63~1241ng/L)和中国西南部岩溶地区地下水[11](2.58~320ng/L).整体来说,潮水洞的水体受到OCPs的污染相对较轻.
水体中∑23OCPs的时空分布特征如图2所示,可以看出水体中冬季∑23OCPs的浓度明显高于其他3季,夏季地表水(上游2.19ng/L,下游1.96ng/L)和泉水(1.49ng/L)中的∑23OCPs浓度普遍较低.潮水洞属于亚热带季风气候,雨水多集中在5~8月[14],夏季采样期间的降雨使得水体中的OCPs进一步被稀释,导致夏季水体中OCPs的浓度较低.同时,春季补给区上游地表水明显高于下游地表水,主要有以下两个原因:上游地表水DDTs等OCPs在迁移的过程中,易被吸附至土壤颗粒导致其含量降低;采样过程中的降雨也会使地表水中OCPs浓度进一步降低,最终使得上游地表水浓度高于下游地表水.此外,补给区地表水中∑23OCPs的浓度显著高于(P=0.035<0.05)排泄区泉水,这与余悦[1]等人的研究一致,由于OCPs的亲脂疏水性[25],OCPs在从地表环境向地下环境迁移的过程中更易被吸附在固相颗粒上,经过土壤的过滤作用[1]使地表水中∑23OCPs含量高于地下水.
研究区土壤中23种OCPs被广泛检出,补给区土壤中有6种物质的检出率为100%;排泄区土壤中有16种物质的检出率为100%.尽管排泄区土壤中OCPs的总含量远低于补给区,但排泄区土壤中OCPs的检出情况明显高于补给区.这种差异可能是由于多年的累积作用,导致排泄区土壤中OCPs的残留种类比补给区更丰富.潮水洞系统土壤中OCPs的含量如表1所示,补给区土壤中∑23OCPs含量(以干重计,下同)在2.71~47.2ng/g之间,平均值为18.5ng/g,排泄区土壤中∑23OCPs含量在6.77~25.5ng/g之间,平均值为13.3ng/g.
与我国其他地区土壤中OCPs的含量相比,潮水洞土壤中∑23OCPs的含量(均值15.9ng/g)远低于华北地区[26](均值16888ng/g),东北地区[26](均值124.8ng/g)和地下河沿岸土壤[27](均值467.28ng/g);高于西南地区土壤中OCPs含量[26](均值7.6ng/g),与中国农业土壤中OCPs含量报告值[28](均值58.9ng/g),上海城区土壤[29](均值22.33ng/g),中国西南部四川盆地土壤[30](均值15.7ng/g)和淮河中游河岸土壤[31]中OCPs含量(均值19ng/g)处于同一数量级.整体而言,潮水洞土壤中OCPs的含量远低于GB 15618-2018《土壤环境质量 农用地土壤污染风险管控标准(试行)》[32]给出的限值(0.1mg/kg),处于较低水平,污染较轻.
潮水洞土壤中OCPs的时空分布特征如图3(a)所示.从季节上来看,补给区土壤OCPs含量夏季(39.4ng/g)>春季(18.7ng/g)>秋季(9.56ng/g)>冬季(6.17ng/g),排泄区土壤中OCPs含量冬季(25.5ng/g)>夏季(10.6ng/g)>秋季(10.4ng/g)>春季(6.77ng/g).补给区土壤中OCPs在春夏季的含量明显高于秋冬季,主要原因可能是:(1)补给区附近人类活动密集,DDTs被用来控制可传播疾病病媒,虽然DDTs早在1983年就被中国禁用,但是对于疟疾的防治和某些农业活动,可能仍有使用[33];(2)目前DDTs主要是作为三氯杀螨醇的中间体使用,而三氯杀螨醇是在2019年8月起才禁止生产使用,在一些不太发达的农业地区可能仍有含三氯杀螨醇农药的使用,导致DDTs含量在春夏两季较高;(3)2021年Huang等[11]指出在宜昌可能存在HCHs和DDTs等OCPs的非法使用,而研究区潮水洞隶属于宜昌,也非常有可能存在OCPs的非法使用,使得春夏季土壤中OCPs含量远高于秋冬两季.排泄区土壤冬季含量明显高于春夏秋3季,主要是由于冬季温度较低,大气中OCPs倾向于通过沉降作用进入土壤;而春夏秋季由于温度升高,使得OCPs倾向从土壤中向大气中挥发[34].此外,在空间分布上,补给区土壤中的OCPs含量显著高于(P=0.009)排泄区土壤,这一现象主要归因于补给区更为频繁的人类农业活动.由于人类活动的影响,OCPs在补给区土壤中积累,导致其含量明显超过排泄区土壤中的OCPs含量.
研究区沉积物中23种OCPs被广泛检出,补给区中有15种OCPs的检出率为100%;而排泄区沉积物中有13种物质的检出率是100%.潮水洞系统沉积物中∑23OCPs的含量如表1所示,补给区沉积物中∑23OCPs含量(以干重计)在4.35~56.0ng/g之间,平均值为20.2ng/g,排泄区沉积物中∑23OCPs含量在2.92~9.07ng/g之间,平均值为2.51ng/g.
与国内外其他地区沉积物中的OCPs含量进行对比,潮水洞沉积物中的OCPs含量(2.92~56.0ng/g)略高于江苏省地表水环境沉积物[35](0.41~10.62ng/g),低于大多数国内河流湖泊沉积物中OCPs含量,如太湖[36](16.8~61.9ng/g),海河[37](>1620ng/g)等,同时也远低于西班牙的埃布罗河[38](>351ng/g)和印度的戈默蒂河[39](>368.7ng/g).整体而言,潮水洞沉积物中OCPs的含量处于较低水平,污染较轻.
潮水洞系统补给区地表水沉积物和排泄区泉水沉积物中的OCPs时空分布如图3(b)所示,补给区沉积物中OCPs的含量夏季(56.03ng/g)>秋季(14.50ng/g)>冬季(5.73ng/g)>春季(4.35ng/g),夏季OCPs的含量显著高于春秋冬三季,与补给区土壤的季节分布一致,说明地表河流携带土壤颗粒沉积所形成的地表水沉积物中OCPs可能来源于补给区土壤.排泄区泉水沉积物OCPs含量分布并无明显季节性差异,但相对来说秋季含量最高,说明补给区土壤中的OCPs也可通过地下岩溶管道迁移至泉口排出,被吸附至泉沉积物上,且通过地下岩溶管道迁移可能存在时间滞后现象.从空间分布上来看,补给区沉积物中OCPs的含量显著高于(p=0.002)排泄区OCPs的含量.
林丹主要成分是γ-HCH(含量99%以上),工业HCHs是由HCHs的四种异构体组成的混合物.HCHs的来源和残留时间可以通过α-HCH/γ-HCH和β-HCH/(α-HCH+γ-HCH)来指示,其中α-HCH/γ-HCH是用来指示HCHs的来源情况,该比值小于3表明HCHs主要来自于林丹的输入;若比值介于3~7之间,则表明HCHs主要来自于工业HCHs的输入;若比值大于7,则表明HCHs的来源可能是长距离传输或工业HCHs多次循环和降解的结果[40-41].β-HCH/(α-HCH+γ-HCH)的比值则是用来指示HCHs在环境中的残留时间,若该比值大于0.5,则表明HCHs主要是历史残留;若该比值小于0.5,则表明HCHs主要是近期输入.
水体,土壤及沉积物中的HCHs比值见图4(a),可以看出水体和沉积物中分别有83.3%和71.4%的点位α-HCH/γ-HCH的值小于3,说明该地区水体和沉积物中的HCHs主要是来自于林丹的输入;土壤中α-HCH/γ-HCH比值的均值为4.08,表明土壤中HCHs主要来源于工业HCHs的输入.另外,潮水洞水体和土壤中分别有83.3%和66.7%的点位β-HCH/(α-HCH+γ-HCH)大于0.5,说明潮水洞地区水体和土壤中的HCHs都是经过历史降解残留的污染物.由图1(c)-(d)水文地质图可以看到,潮水洞的水体来源除了来自于潮水河之外,还来自于李家坪以及凤凰坪附近的落水洞,早期所使用的农药被当地土壤颗粒吸附,并在受到降雨影响后进入水体通过地下暗河和落水洞迁移至潮水洞附近,这也解释了水体及土壤中HCHs来自历史残留的原因;而沉积物中β-HCH/(α-HCH+γ-HCH)的范围是在0.05~0.54之间,均值为0.26,其中比值小于0.5的占75%,因此研究区的沉积物中HCHs可能来自于近期林丹的输入.主要原因可能是在林丹禁用前后被用来防治虫害的林丹通过地表径流进入水体,从而快速被沉积物所吸附.
环境中DDTs的来源也可通过异构体的比值来指示,其中op’-DDT/pp’-DDT和(DDE+DDD)/DDT分别是用来指示DDTs的来源及残留时间.三氯杀螨醇与工业DDTs的组成有所差异,因此可用op’-DDT/pp’-DDT的值来指示DDTs的来源,若该比值为0.2~0.3,则表明DDTs来源于工业DDTs;若该比值为1.3~9.3,则表明DDTs来源于三氯杀螨醇.而(DDE+DDD)/DDT的比值是用来判断DDTs在环境中的残留时间,若该比值大于0.5,则表明DDTs主要是历史残留;若该比值小于0.5,则表明DDTs主要是近期输入.
水体,土壤和沉积物的DDTs比值见图4(b),可以看出水体和土壤中分别有75%和72.7%的点位(DDE+DDD)/DDT大于0.5,说明潮水洞水体和土壤中的DDTs主要是来自于历史残留;而沉积物中(DDE+DDD)/DDT的比值范围是0.05~0.82之间,均值为0.24,其中85.7%的点位小于0.5,表明沉积物中DDTs主要来自于近期输入.DDTs与HCHs的来源类似,早期当地补给区农业活动频繁使得DDTs进入环境,并随着降雨的作用从土壤进入到岩溶地下水,而地下水中微生物活动较为缓慢[11],导致DDTs可长时间存在于环境中,且潮水洞地表水主要是来自于地下水的补给[14],这也就使得水体和土壤中的DDTs均是来自早期的农药施用,即来源于历史残留;此外,DDT,DDE和DDD的辛醇水分配系数关系为DDT>DDE>DDD[42],沉积物中具有更高的有机质含量和不同类型的无机矿物,DDT相较于DDD和DDE更易被吸附到沉积物颗粒上,也就使得(DDE+DDD)/DDT相对较小,大部分点位小于0.5.另一方面也可能是当地近期使用了DDTs来控制可传播的疾病,DDTs被吸附至沉积物上尚未来得及降解[43].另外,水体,土壤和沉积物中70%以上的点位op’-DDT/pp’-DDT都处于0.3~1.3之间,均值分别为0.88,0.43和0.74,说明DDTs的来源属于混合源,即来自于工业DDTs和三氯杀螨醇两类物质.
在岩溶地区,水体可以通过地表径流和地下岩溶系统两种方式从上游补给区流向下游排泄区,同时随着水体的流动,OCPs也可以完成由上游补给区至下游排泄区的迁移.基于此,本研究将OCPs在不同介质中的迁移过程依据岩溶地区水体流动方式分为地表迁移和地下迁移两个部分.其中地表迁移过程是指上游(对应本研究的地下水的补给区域)的污染物通过地表河流迁移至下游(对应本研究的地下水的排泄区域);地下迁移过程则是指补给区的污染物通过地下岩溶管道或裂隙迁移至排泄区由泉口排出.
在地表迁移过程中,补给区上游土壤被降雨冲刷,携带着土壤颗粒进入上游地表水,土壤中的OCPs在随着地表水流动迁移至下游的过程中与周围土壤以及沉积物进行相应的污染物重新分配,同时在整个流动过程不停地发生冲刷-沉降的物质交换.从图5(a)地表迁移过程中各介质组成上看,水体中DDTs所占比例在迁移过程中明显降低,而土壤和沉积物中DDTs比例显著升高,说明在地表迁移的过程中水体中DDTs大量吸附到土壤颗粒以及沉积物颗粒上从而在固-液界面间达到了新的平衡.此外,来自补给区的污染物可通过发育完善的岩溶裂隙或岩溶管道进入地下,随着地下水的流动迁移至排泄区,由泉口排出[43].从图5(b)地下迁移过程中各介质组成上可以看出地表水上游农田旁土壤-上游地表水-排泄区泉水-排泄区沉积物各污染物的组成相似,表明排泄区OCPs主要来源于补给区的输入.
为了更加深入探讨OCPs的迁移过程,对潮水洞不同介质中OCPs各组分浓度进行Spearman相关性分析,结果如图6所示.结果表明,OCPs在地下迁移过程中,补给区土壤-上游地表水(ρ=0.786),补给区土壤-排泄区泉水(ρ=0.714),排泄区泉水-泉沉积物(ρ=0.833)存在显著的相关性(P<0.05),但上游地表水-泉水不存在显著相关性(P>0.05),结合当地水文地质条件分析,潮水洞泉水中的污染物除了来自于上游地表水,还可能有其他多个来源(如图1(c)中的凤凰坪处落水洞和麻子洞等).在地表迁移的过程中,补给区土壤-上游地表水(ρ=0.786),补给区沉积物-排泄区土壤(ρ=0.881)间存在显著相关性(P<0.05),但上游地表水-下游地表水间不存在显著相关性(P>0.05),结合当地的地形和地表水流向,我们推断是由于地表水在流动过程中,污染物质被吸附到周边的土壤颗粒以及沉积物中,导致水体中OCPs含量降低.同时下游地表水-补给区沉积物不存在显著相关性则是由于沉积物中污染物的来源不仅仅只有地表水,也可能是来源于下游的土壤或者排泄区土壤.
为了定量评价潮水洞系统中OCPs的迁移贡献,我们采用MLRA分别以补给区土壤和排泄区泉水,排泄区泉水和对应沉积物中的OCPs含量作为自变量和因变量评价地下迁移过程中OCPs的迁移贡献;同时分别将补给区土壤和上游地表水,排泄区土壤和补给区沉积物中的OCPs含量作为自变量和因变量来评价地表迁移过程中OCPs的迁移贡献.结果表明补给区土壤中OCPs对泉水的贡献率为58.3%(P=0.027),排泄区泉水中OCPs对泉沉积物的贡献率为64.2%(P=0.086);补给区土壤中OCPs对上游地表水的贡献率为87.8%(P<0.001).相关性分析及MLRA结果表明OCPs可通过地下迁移过程从补给区土壤迁移至泉沉积物,也可通过地表迁移过程从上游地表水迁移下游地表水再至排泄区.
3.1 潮水洞补给区和排泄区的水体,土壤和沉积物中∑23OCPs的浓度相对较低,整体来说,补给区∑23OCPs的浓度显著高于排泄区对应介质中浓度.
3.2 潮水洞区域水体中OCPs的含量,地表水下游>地表水上游>泉水,且三者冬季含量均为最高;潮水洞系统中补给区的土壤和沉积物中的OCPs含量均分别高于排泄区的土壤和沉积物中的含量,且研究区夏季固相介质中OCPs含量相对较高.结合区域的水文地质条件,潮水洞系统中OCPs可能来自于夏季补给区周边的农业活动.
3.3 水体和沉积物中HCHs主要来源于林丹的输入,土壤中的HCHs则主要来源于工业HCHs的输入;DDTs在水体,土壤和沉积物三种介质中都是属于混合来源,即来源于工业DDTs和三氯杀螨醇的混合来源.
3.4 OCPs可以通过地表迁移和地下迁移两种方式快速地从补给区迁移至排泄区,暴露了当地岩溶系统水环境的脆弱性.
  • 国家重点研发计划“场地土壤污染成因与治理技术”重点专项项目(2019YFC1805502)
  • 国家自然科学基金青年项目(41907327)
  • 国家自然科学基金青年项目(42007178)
  • 中国地质调查局地质调查项目(DD2019082)
  • 中国地质大学(武汉)中央高校基本科研业务费特色学科团队专项项目(G1323523063)
  • 资源与生态环境地质湖北省重点实验室开放基金资助项目(HBREGKFJJ-202301)
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  • 接收时间:2024-06-03
  • 首发时间:2026-03-18
  • 出版时间:2025-01-20
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  • 收稿日期:2024-06-03
基金
国家重点研发计划“场地土壤污染成因与治理技术”重点专项项目(2019YFC1805502)
国家自然科学基金青年项目(41907327)
国家自然科学基金青年项目(42007178)
中国地质调查局地质调查项目(DD2019082)
中国地质大学(武汉)中央高校基本科研业务费特色学科团队专项项目(G1323523063)
资源与生态环境地质湖北省重点实验室开放基金资助项目(HBREGKFJJ-202301)
作者信息
    1.中国地质大学(武汉)环境学院,湖北 武汉 430078
    2.中国地质大学(武汉)地下水质与健康教育部重点实验室,湖北 武汉 430078
    3.中国地质大学(武汉)地质调查研究院,湖北 武汉 430074
    4.中国地质大学(武汉)生物地质与环境地质国家重点实验室,湖北 武汉 430078
    5.山东省地质矿产勘查开发局第五地质大队,山东 泰安 271000
    6.湖北省地质局,资源与生态环境地质湖北省重点实验室,湖北 武汉 430034

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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
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红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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