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This study used a meta-analysis approach to examine the distribution of three polycyclic aromatic hydrocarbons (Phe, Pyr and BbF) in the surface water of the world's seas as well as the factors that influence them. According to the findings, the Pacific Ocean had significantly greater concentrations of Phe, Pyr and BbF (16.885, 15.787, and 0.642ng/L) than the other oceans. These concentrations were also significantly linked with salinity, temperature, latitude, distance from coast, and chlorophyll. According to the findings, energy consumption and oceanic PAHs had a substantial and positive correlation (P<0.05). The distribution pattern of PAHs in the world's oceans is shown by this study, which offers a scientific foundation for the development of practical methods for the prevention and management of marine pollution.

, correspAuthors=Li-lan ZHANG, 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=Zhi-hui YANG, Li-lan ZHANG, Rui YANG), CN=ArticleExt(id=1241049984271962881, articleId=1241049972955730302, tenantId=1146029695717560320, journalId=1234093305789726721, language=CN, title=全球海洋表层水体中多环芳烃的分布特征, columnId=1234106388268503686, journalTitle=中国环境科学, columnName=环境生态, runingTitle=null, highlight=null, articleAbstract=

本文采用文献调研(Meta-analysis)方法,探讨全球海洋表层水中3种多环芳烃(Phe,Pyr和BbF)的分布特征及其影响因素.研究结果显示,Phe,Pyr和BbF在太平洋浓度(16.885,15.787和0.642ng/L)显著高于其他大洋,且与离岸距离、纬度、叶绿素、温度和盐度等因素显著相关.数据表明,海洋PAHs与能源消耗量显著正相关(P<0.05).本研究揭示了PAHs在全球海洋中的分布规律,为制定有效的海洋污染防控策略提供了科学依据.

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*责任作者,副教授,
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杨志辉(2000-),男,江西萍乡人,重庆大学硕士研究生,主要研究方向为海洋环境中持久性有机污染物..

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杨志辉(2000-),男,江西萍乡人,重庆大学硕士研究生,主要研究方向为海洋环境中持久性有机污染物..

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基于自然资源部标准地图服务网站GS(2016)1665号的标准地图制图,底图边界无修改;(a):Phe;(b):Pyr;(c):BbF;绿色点位表示该站位PAHs浓度排列顺序位于0~25%,蓝色为25%~50%,黄色为50~75%,红色为75~100%;所有站位PAHs浓度均高于检出限

, figureFileSmall=JsLsJsW9vEHcFrikevFxLg==, figureFileBig=/AhjrK2c7fE5UBVfMGTApg==, tableContent=null), ArticleFig(id=1241049993126138013, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049972955730302, language=EN, label=Fig.2, caption=Differences in the oceanic distribution of the three PAHs, figureFileSmall=jyS4WQxgYXc2oZ5dcLuddA==, figureFileBig=TAwO3Uq6ijw76w+HR+i3CQ==, tableContent=null), ArticleFig(id=1241049993381990578, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049972955730302, language=CN, label=图2, caption=3种PAHs大洋分布差异图

图中不同小写字母代表差异显著(P<0.05);(a):Phe;(b):Pyr;(c):BbF

, figureFileSmall=jyS4WQxgYXc2oZ5dcLuddA==, figureFileBig=TAwO3Uq6ijw76w+HR+i3CQ==, tableContent=null), ArticleFig(id=1241049993612677319, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049972955730302, language=EN, label=Fig.3, caption=Differences in the distribution of three PAHs in the Chinese Marginal Sea, figureFileSmall=rlRt/RCyQkxKNXvdYKnKoQ==, figureFileBig=rlYEWPtWa9etgQU+1EJHpw==, tableContent=null), ArticleFig(id=1241049993772060887, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049972955730302, language=CN, label=图3, caption=3种PAHs在中国边缘海分布差异图

(a):Phe;(b):Pyr;(c):BbF

, figureFileSmall=rlRt/RCyQkxKNXvdYKnKoQ==, figureFileBig=rlYEWPtWa9etgQU+1EJHpw==, tableContent=null), ArticleFig(id=1241049994019524838, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049972955730302, language=EN, label=Fig.4, caption=The connection between PAHs and shoreline distance, figureFileSmall=4Z9psWOrifjgwVZDi1m4Eg==, figureFileBig=BCJIYBKMXH0b5Ucrdr8xYw==, tableContent=null), ArticleFig(id=1241049994195685627, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049972955730302, language=CN, label=图4, caption=PAHs与离岸距离的关系, figureFileSmall=4Z9psWOrifjgwVZDi1m4Eg==, figureFileBig=BCJIYBKMXH0b5Ucrdr8xYw==, tableContent=null), ArticleFig(id=1241049994388623624, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049972955730302, language=EN, label=Fig.5, caption=Relationship between the three PAHs and latitude, figureFileSmall=D7OB4JtcxaJnp6GpXcIZZg==, figureFileBig=QReVsqPjDjes+CkyW44Udg==, tableContent=null), ArticleFig(id=1241049994699002140, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049972955730302, language=CN, label=图5, caption=3种PAHs与纬度的关系

(a):Phe;(b):Pyr;(c):BbF

, figureFileSmall=D7OB4JtcxaJnp6GpXcIZZg==, figureFileBig=QReVsqPjDjes+CkyW44Udg==, tableContent=null), ArticleFig(id=1241049994816442662, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049972955730302, language=EN, label=Fig.6, caption=Heat map of chlorophyll, temperature and salinity correlations with PAHs, figureFileSmall=+YVDr59ma4b+pPkkbJADvw==, figureFileBig=grndyDAH+miaWGCx2rJE5A==, tableContent=null), ArticleFig(id=1241049996410278194, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049972955730302, language=CN, label=图6, caption=叶绿素、温度和盐度与PAHs相关性热图, figureFileSmall=+YVDr59ma4b+pPkkbJADvw==, figureFileBig=grndyDAH+miaWGCx2rJE5A==, tableContent=null), ArticleFig(id=1241049997072978251, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049972955730302, language=EN, label=Fig.7, caption=Relationship between global energy consumption and PAHs, figureFileSmall=lgwjr68xzlN20JNwi07Psg==, figureFileBig=dUrr3uoA2FuAMm7gMqCFpw==, tableContent=null), ArticleFig(id=1241049997228167511, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049972955730302, language=CN, label=图7, caption=全球能源消耗量与PAHs的关系

基于自然资源部标准地图服务网站GS(2016)1665号的标准地图制图,底图边界无修改;(a):各国一次能源消耗量;(b):由能源消耗量计算得到的PAHs与海水PAHs浓度关系

, figureFileSmall=lgwjr68xzlN20JNwi07Psg==, figureFileBig=dUrr3uoA2FuAMm7gMqCFpw==, tableContent=null), ArticleFig(id=1241049997488214378, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049972955730302, language=EN, label=Fig.8, caption=Population, GDP and GDP per capita in relation to PAHs, figureFileSmall=42tH9oBaw0La3tPUD7EpWw==, figureFileBig=ixEysJzBBVI9EyZYs04Z5w==, tableContent=null), ArticleFig(id=1241049997672763762, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049972955730302, language=CN, label=图8, caption=人口、GDP和人均GDP与PAHs关系

(a):人口;(b):GDP;(c):人均GDP

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全球海洋表层水体中多环芳烃的分布特征
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杨志辉 1 , 张利兰 1, 2, * , 杨锐 1
中国环境科学 | 环境生态 2025,45(1): 379-389
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中国环境科学 | 环境生态 2025, 45(1): 379-389
全球海洋表层水体中多环芳烃的分布特征
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杨志辉1 , 张利兰1, 2, * , 杨锐1
作者信息
  • 1.重庆大学,三峡库区生态环境教育部重点实验室,重庆 400044
  • 2.重庆大学,煤矿灾害动力学与控制国家重点实验室,重庆 400044
  • 杨志辉(2000-),男,江西萍乡人,重庆大学硕士研究生,主要研究方向为海洋环境中持久性有机污染物..

通讯作者:

*责任作者,副教授,
Distribution characteristics of polycyclic aromatic hydrocarbons in global marine surface waters
Zhi-hui YANG1 , Li-lan ZHANG1, 2, * , Rui YANG1
Affiliations
  • 1.Key Laboratory of Three Gorges Reservoir Region’s Eco-environment, Ministry of Education, Chongqing University, Chongqing 400045, China
  • 2.State Key Laboratory of Coal Mine Disaster Dynamics and Control, Chongqing University, Chongqing 400044, China
出版时间: 2025-01-20
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本文采用文献调研(Meta-analysis)方法,探讨全球海洋表层水中3种多环芳烃(Phe,Pyr和BbF)的分布特征及其影响因素.研究结果显示,Phe,Pyr和BbF在太平洋浓度(16.885,15.787和0.642ng/L)显著高于其他大洋,且与离岸距离、纬度、叶绿素、温度和盐度等因素显著相关.数据表明,海洋PAHs与能源消耗量显著正相关(P<0.05).本研究揭示了PAHs在全球海洋中的分布规律,为制定有效的海洋污染防控策略提供了科学依据.

多环芳烃  /  分布  /  海洋  /  能源

This study used a meta-analysis approach to examine the distribution of three polycyclic aromatic hydrocarbons (Phe, Pyr and BbF) in the surface water of the world's seas as well as the factors that influence them. According to the findings, the Pacific Ocean had significantly greater concentrations of Phe, Pyr and BbF (16.885, 15.787, and 0.642ng/L) than the other oceans. These concentrations were also significantly linked with salinity, temperature, latitude, distance from coast, and chlorophyll. According to the findings, energy consumption and oceanic PAHs had a substantial and positive correlation (P<0.05). The distribution pattern of PAHs in the world's oceans is shown by this study, which offers a scientific foundation for the development of practical methods for the prevention and management of marine pollution.

polycyclic aromatic hydrocarbons  /  distribution  /  oceans  /  energy
杨志辉, 张利兰, 杨锐. 全球海洋表层水体中多环芳烃的分布特征. 中国环境科学, 2025 , 45 (1) : 379 -389 .
Zhi-hui YANG, Li-lan ZHANG, Rui YANG. Distribution characteristics of polycyclic aromatic hydrocarbons in global marine surface waters[J]. China Environmental Science, 2025 , 45 (1) : 379 -389 .
多环芳烃(PAHs)广泛存在于大气[1]、水[2]、土壤[3]和沉积物[4]等各类环境介质中.许多PAHs以其高毒性、致癌性和致突变性而闻名,对人类[5]和其他动物的健康构成严重威胁,并影响生态环境.美国环保署根据PAHs的毒性和流行性,将16种PAHs列入优先控制的污染物名单,以加强其管理和控制[6].
PAHs通过人为来源和自然来源进入水生生态系统.人为来源主要是化石燃料的不完全燃烧、城市径流、石油加工和渗漏或意外漏油等[7-9],构成了PAHs进入水生生态系统的主要来源.随着社会经济趋势的发展,人为来源在时间和空间大尺度上显得尤为突出[10].例如,煤炭、石油和生物质的不完全燃烧过程,促进PAHs的产生[11-12].在全球范围内,据估计,直接使用生物质燃料进行烹饪的人数约有30亿[13],这一庞大的基数导致了大量PAHs被释放到大气中.早在2007年全球大气中排放的16种优控PAHs总量就已达到504Gg[14],并且全球每月大气中的PAHs对海洋的输入量为0.09Tg[15].人为活动产生的PAHs通过大气或洋流的远距离运输[16-18],得以在全球范围内广泛传播,同时海洋与大气之间的相互作用对PAHs在海洋中的分布和浓度起到了重要的调节作用[19-20].使得海洋成为了PAHs的一个关键汇集地[21].相比之下,自然来源的PAHs则相对有限.虽然自然过程如火山爆发、森林火灾等也会释放一定量的PAHs,但其贡献远不及人为活动显著.因此,在探讨海洋中的PAHs时,人为来源的PAHs更应引起重视.
在不同的海域中,PAHs的浓度和分布呈现出各自的特点.太平洋、印度洋和南大洋中Σ23PAHs浓度分别为4,2.7和2.3ng/L,其中三至四环PAHs占据了总浓度的绝大部分,达到了94%[22].而在开阔的大西洋中Σ10PAHs浓度为0.058~1.07ng/L,并且以Phe和Pyr为主[23-24].此外,从北太平洋至北冰洋海水中Σ9PAHs浓度范围为1.8~16ng/L[19].在北极海域中,Σ16PAHs平均浓度为48.5ng/L[25],而在南极海水中Σ16PAHs浓度为0.6~6.3ng/L[26].
海洋中PAHs浓度虽然较低,但由于它们具有生物蓄积性[27]和高毒性,能够沿着食物链进行生物放大,对海洋生物和生态系统都造成严重威胁[28].海洋生态系统是全球最重要的生态系统之一,影响着全球生态系统的稳定和安全,关乎人类的生存和发展.在过去几十年中,城市化导致大量污染物通过河流径流和长距离大气输送排放到海洋生态系统中[29-30],并且随着能源消费结构的优化,更多的可再生能源被利用[31],而不是传统能源(煤炭和石油),这可能会影响PAHs的环境水平.尽管关于海洋水体中PAHs的调查已有许多,大气运输机制被广泛研究[32-33],但鲜有研究在全球规模上讨论海水PAHs分布特征,并将其与能源消耗量相结合.本文基于文献调研,归纳总结海洋表层PAHs的分布特征,揭示其全球规模的分布以及与能源消耗量之间的关系,为海洋中PAHs的风险评价提供更全面的数据支撑,为制定有效的污染防控策略提供科学支持.
本文在Web of science、Elsevier ScienceDirect、SpringerLink和Wiley Oline Library数据库中以海洋(ocean)、多环芳烃(polycyclic aromatic hydrocarbons)和表层水(surface water)为关键词搜索近10a(2013~至今)的文献,对收集的文献进行筛选,剔除支撑材料中没有提供站位确切经纬度或者海水溶解相单体PAHs浓度的文献,并统一PAHs单位(ng/L),共收集23篇文献[26,34-55],总计637个站位,这些数据包括站位的经纬度、叶绿素、温度、盐度和单体PAHs的浓度.选取三环菲(Phenanthrene,Phe,637个站)、四环芘(Pyrene,Pyr,637个站)和五环苯并(b)荧蒽(Benzo(b)fluorene,BbF,250个站)进行分布特征分析,Phe和Pyr因其高毒性以及在环境中的高丰度而被选为目标物质[56],BbF则是因为在收集的五环PAHs中检出率最高.
根据2022年发布的《bp世界能源统计年鉴》中的数据,收集各国一次能源消耗量.
由于数据离散程度大,且部分PAHs浓度小于1ng/L或零值,将PAHs浓度加一处理保证对数处理后数值非负数,并根据对数处理数据绘制图片.为了计算PAHs年排放量,将收集的煤炭和石油消耗量,根据换算系数,统一化为千克标准煤当量(kg ce)[57],由于燃料来源、燃烧设施等条件差异较大,各地区和国家之间的排放因子差异很大,文献中报告的数据不足以编制各个区域内每个国家的排放因子数据库,采用统一的煤的排放因子[58]计算3种PAHs的年排放量(t/a).
式中:LCF分别代表PAHs年排放量、能源消耗量换得到的标准煤当量和煤的排放因子.
使用R 4.3.3绘制纬度与PAHs的关系图,ArcGIS 10.8.1绘制PAHs分布图以及能源消耗量图,其余图片由Origin 2023绘制.统计分析使用SPSS 26和Origin 2023,任何P<0.05都被认为具有统计学意义.
将收集的PAHs浓度从低到高排列四等分,3种PAHs在全球海洋表层海水的分布如图1所示,Phe和Pyr分布于全球五大洋中,其中Phe的浓度范围为0.002~299ng/L,平均值为9.767ng/L;Pyr的浓度范围为0.001~336ng/L,平均值为7.854ng/L;而BbF分布于除印度洋之外的其他大洋中,浓度范围为0.003~10ng/L,平均值为0.781ng/L.3种PAHs在表层海水溶解相中平均浓度排列为Phe>Pyr>BbF,这可能与它们的物理性质有关,PAHs水溶性和蒸气压会随着PAH单体的环数与分子量的增加而降低[59],较高环的PAHs具有较高的辛醇-水分配系数和有机质分配系数,更容易吸附在颗粒物上,因此海水溶解相高环的PAHs浓度较低.
从全球尺度来看,3种PAHs在太平洋区域平均浓度最高(Phe:16.885ng/L,Pyr:15.787ng/L,BbF:0.642ng/L),主要集中于中国边缘海域(红色站位所示).这可能是因为距离陆地较近,有报道称,陆地向沿海水域排放PAHs的速率可达1亿t/a[60],河流输入将PAHs排放到近海水域,因此,与远洋水域相比,近海受到来自陆地源的PAHs污染严重[61].由于PAHs的高水溶性,低分子量的PAHs溶解在水中,并可以通过水团的运动被输送到更远的地区,如温带和极地地区.高分子量的PAHs很少溶于水,并倾向于与颗粒物质结合.因此,远离陆地的站位中PAHs浓度普遍较低(绿色、蓝色站位).全球海洋中PAHs的空间变化清楚地表明了发展中国家对海洋PAHs污染的贡献,与欧洲、北美和澳大利亚相比,亚洲附近的海域PAHs含量更高.而人口的增加、对生物燃料和石油能源的依赖以及缺乏大气中减少PAHs的措施使发展中国家的PAHs排放量激增.在未来几年,城市化和人口增长的加剧将促使PAHs源源不断地进入亚洲、非洲和拉丁美洲的沿海海洋环境中[62],这可能会增加PAHs对海洋生态系统的潜在风险.
海洋约占全球地表面积的71%,主要由太平洋、大西洋、印度洋、北冰洋和南冰洋组成.太平洋是世界上最大的洋,约占海洋总面积的46%;大西洋是世界第二大洋,约占海洋总面积的24%,北面连接北冰洋,南面则以66°S与南冰洋接连;印度洋是世界的第三大洋,位于亚洲、大洋洲、非洲和南极洲之间,约占海洋总面积的20%;北冰洋是世界最小最浅和最冷的大洋;南冰洋是世界第五个被确定的大洋,是世界上唯一完全环绕地球却没有被大陆分割的大洋.了解PAHs在五大洋中分布情况,有助于进一步认识海洋中PAHs分布特征.
图2显示了3种PAHs在五大洋中的分布差异,Phe、Pyr和BbF最高平均浓度均在太平洋,分别为16.885,15.787和0.642ng/L.最低平均浓度出现海域不一致,Phe在大西洋平均浓度最低(0.212ng/L),Pyr在南冰洋平均浓度最低(0.108ng/L),BbF在南冰洋平均浓度最低(0.013ng/L).PAHs浓度在五大洋排列顺序为Phe>Pyr>BbF.单因素方差分析显示,Phe和Pyr在太平洋中浓度显著高于其他四大洋,印度洋、大西洋、北冰洋和南冰洋中浓度分布没有显著差异.不同国家和地区的工业化程度、能源利用方式的差异,可能会影响PAHs的排放量.在太平洋发现3种PAHs的浓度最高,可能受到大陆源的影响,例如来自澳大利亚、东南亚国家和中国的废气和污水排放,携带着PAHs进入海洋[22].研究表明,在中国流出的PAHs总量(8092t)中,有69.9%到达海上环境(4664t)和南海(991t)[63].此外,中国大陆的一次能源消耗量高达157.65EJ,比其他国家高出1~2个数量级,这表明太平洋中PAHs浓度显著高于其他大洋,可能与能源消耗量密切相关.相比之下,在远离人类活动的南冰洋,检测到的PAHs浓度则相对较低.并且发现Phe的平均浓度比大西洋高,这一现象表明,低纬度地区的人类活动排放的PAHs可能通过大气或洋流等途径进行了长距离的传输,最终抵达了南冰洋.
太平洋中PAHs浓度最高,收集的文献中太平洋站位集中于西部(图1),该区域主要为中国边缘海(黄海、东海和南海),它们毗邻中国大陆,是陆地和远洋的重要缓冲带,本文进一步分析3种PAHs在中国边缘海的浓度分布差异.
Phe在黄海浓度范围为0~18.85ng/L,平均值为5.419ng/L,东海浓度范围0~21.61ng/L,平均值为7.978ng/L,南海浓度范围为0.02~299ng/L,平均值为25.715ng/L.Pyr在黄海浓度范围为0.86~30.51ng/L,平均值为4.383ng/L,东海浓度范围0.59~4.786ng/L,平均值为2.55ng/L,南海浓度范围为0~336ng/L,平均值为24.979ng/L.BbF在黄海浓度范围为0~1.63ng/L,平均值为0.456ng/L,在东海的浓度低于检出限,南海浓度范围为0~10ng/L,平均值为0.723ng/L.
3种PAHs在边缘海的浓度分布无显著差异(图3),并且均在南海平均浓度最高,不同的是,Phe在黄海平均浓度最低,Pyr和BbF在东海平均浓度最低.在3个海域内,3种PAHs平均浓度从高到低排列顺序同样为Phe>Pyr>BbF.3种PAHs在南海的分布最多,这可能是因为南海北部毗邻中国工业化程度最高、经济最具活力的地区之一珠江三角洲[64],它包括香港、深圳和广州等大城市.这些地区的污染物可能通过珠江口进入南海.此外,南海还具有季风气候的特点,冬季东北风较强,夏季西南风相对较弱,带来了来自中国和东南亚的空气污染物[65].
对3种PAHs与离岸距离进行线性拟合,结果如图4所示.3种PAHs的浓度与离岸距离均为显著负相关性(P<0.001),这很可能是多重因素综合作用的结果.首先,PAHs的主要来源为陆地的人类活动[66],如化石燃料燃烧及工业排放,使得近岸海域的PAHs浓度相对较高.其次,自然因素如风速和洋流[45]等,是PAHs在海洋环境中扩散和稀释过程的重要因素,可以将陆源PAHs输送至偏远地方.Zhang等[22]发现PAHs浓度随海岸线距离的增加呈现明显的线性下降(P<0.05),表明海水中的PAHs污染受到大陆排放和河流输入的高度影响.当大陆外流的影响增强时,近岸海域中气态PAHs浓度增加,促进PAHs输送至海水中,相反,当远离大陆时,大陆外流的影响减弱,气相PAHs浓度降低,海水中的PAHs过度挥发于大气中,导致在开阔海域发现的较高挥发量[67],降低海水中PAHs浓度.这些原因可能导致PAHs浓度随离岸距离增加而降低.从整体来看,3种PAHs的浓度排序为Phe>Pyr>BbF,这与前文中在全球尺度,五大洋或中国边缘海中PAHs浓度排序一致.与高分子量PAHs相比,低分子量PAHs的辛醇-水分配系数更低,水溶性更高,在海水中被检测到相对较高的丰度[68].相反,高分子量的PAHs由于具有较高的辛醇-水分配系数和较低的亨利定律常数[69],水溶性低,在海洋运输或在大气运输过程中更倾向于与颗粒物结合,并最终沉积到沉积物中[70].这解释了在海水中,随着PAHs环数的增加,浓度递减的现象.
对3种PAHs与纬度进行相关性分析,结果如图5所示.Phe和Pyr的浓度从赤道向两极显著降低(P<0.001),但BbF的浓度从赤道向北极(P=0.15)或者南极(P=0.48)均未发现显著的增减规律.3种PAHs浓度在北半球热带区域(16°N~23.5°N)达到最高值(Phe:299ng/L;Pyr:336ng/L;BbF:10ng/L).这或许可以归因于北半球热带区域的人类活动更为频繁和密集,这些地区往往是工业和交通运输活动的主要集中地,会释放出废水、废气和烟尘等,很可能导致PAHs浓度远高于其他地区.
人类活动排放的PAHs,通过大气和洋流进行区域和全球运输.先前研究表明,在描述和解释受季风影响的中低纬度海洋中PAHs的分布模式时,不能忽视季节性大气输送的影响[2].大气会携带来自陆地的PAHs,在海洋表面与海水进行海-气交换,此过程中,大气干沉积通量取决于悬浮气溶胶中PAHs的浓度,还取决于物理化学性质和环境变量(蒸气压、风速和气溶胶沉积到海面的亲和力)[71].随着纬度的增加,所有PAHs的海-气交换均呈现显著的下降趋势,表明PAHs在低纬度地区的海空交换比高纬度地区更容易[48].洋流是影响陆源PAHs和其他有机污染物在近海迁移和分布的关键驱动因素[72].春季在南向的黄海沿岸洋流和东向长江稀释水的相互作用下,陆源PAHs可到达30°N和125°E左右,甚至延伸至29°N和126°E[17].位于澳大利亚西侧的Leeuwin洋流是全球唯一向极地流动且无上升流的东部边界洋流[73],受其影响,在公海(40~60°S)范围内,三环PAHs呈向南减少的趋势[41].在渺无人烟的南冰洋,其北部边界有南极环极洋流(ACC),连接大西洋、印度洋和太平洋[74].它包含了来自世界不同海洋的混合物,因此南冰洋中的PAHs主要受远距离运输的影响[41].以上研究表明,PAHs浓度随纬度的增加而减少可能受到季风和洋流的影响.
盐度、叶绿素和温度同样会影响海洋PAHs的分布.图6为盐度、叶绿素和温度与PAHs的相关性热图,盐度与BbF具有显著负相关性(P<0.05),叶绿素与Phe、Pyr和Σ3PAHs具有显著负相关性(P<0.05),温度与PAHs具有显著正相关性(P<0.05).由于盐析效应,盐与水分子强烈结合,盐度升高会降低PAHs水溶性[75],可能导致PAHs更多地被悬浮颗粒或沉积物吸收,从而降低海水溶解相中的PAHs浓度.叶绿素浓度是浮游植物生物量的代表,生物因素对于PAHs分布是个不可忽略的因素.在生物降解过程中,三环PAHs可作为唯一碳,稳定降解,而四环PAHs通过共代谢降解[76-77].浮游生物通过摄食颗粒物和排便影响PAHs的传播[78],并能通过垂直运输将颗粒物输送到深海[79],降低表层海水PAHs浓度[80].理论计算表明,温度升高会增加PAHs的水溶性[75],并且在热带季风地区,海水温度的增加,降雨也会增加[81],降雨会将大气环境和降尘中的大部分PAHs冲入水环境[82].此外,大气颗粒物的吸附可以增加PAHs从大气到海洋的输送通量,研究表明大气颗粒物会显著加速PAHs的垂直迁移[54],导致海洋中PAHs浓度升高.
在2021年全球国家的一次能源使用量中,中国,美国和印度的能源使用量排列前三(图7(a)),分别为157.65,92.97和35.43EJ,占全球一次能源使用量比例分别为26.5%,15.6%和6%.对中国而言,石油和煤炭的消耗量在一次能源使用量中的占比是最高的,分别为19.4%和54.7%;印度同样如此,占比分别为26.6%和56.7%;不同的是,石油和天然气的消耗量在美国的一次能源使用量中的占比是最高的,分别为38.0%和32.0%.一次能源中生物质、煤炭和石油燃烧是三个最重要的人为PAHs排放源[83],因此中国和印度一次能源使用量中煤炭和石油的高占比,可能会产生大量的PAHs,导致它们附近海域中PAHs浓度较高.
由能源消耗量计算得到的PAH年排放量与Phe、Pyr和Σ3PAHs具有显著正相关性(图7(b)),表明能源消耗量会显著影响海水PAHs的分布,能源消耗量高的国家会释放更多的PAHs,导致周边海域中PAHs更高.为了量化能源消耗量与海水PAHs浓度的定量关系,基于对数处理的PAHs年排放量与海水中PAHs浓度的一元线性回归模型(r=0.950,P=0.004),将PAHs年排放量换算成能源消耗量,得到对数处理的海水PAHs浓度与能源消耗量的定量关系式如下所示:
式中:表示海水中3种PAHs浓度之和;Ei表示第i种能源消耗量,EJ;ki表示第i种能源的折标煤系数,kg ce/kg;ri表示第i种能源的平均低位发热量,kJ/kg;F表示煤的排放因子,mg/t;n表示能源种类数量.
在大洋尺度范围内,周边国家石油和煤炭能源消耗量高的大洋,其海域中PAHs浓度会相对较高,这进一步证实了能源消耗量是影响海水中PAHs浓度的一个重要因素.然而,在小尺度范围,如海湾、近岸区域等,季风、洋流等因素对海水PAHs分布的影响不可忽视,模型可能无法解释能源消耗量与海水PAHs浓度的关系,需要综合考虑多种因素,并收集更多精细尺度的数据来完善和优化相关模型.
全球范围内,PAHs的来源取决于该国的发展状况和能源结构[84],发达国家能源利用效率的提高有助于减少PAHs的排放,而发展中国家普遍存在的能源危机则会显著增加PAHs的排放[83,85].鉴于能源消耗量与人口和GDP相关,对人口、GDP及人均GDP与海水PAHs浓度进行相关性分析,结果表明人口、GDP及人均GDP不会显著影响海水中PAHs的分布(图8).
已有的研究表明,能源对不同环境中PAHs的分布有显著影响.在巴基斯坦城市大气环境中发现,使用柴油驱动发电机作为替代电源,导致了室内环境中PAHs的高含量,并且天然气车辆转向汽油/柴油驱动车辆也增加了室外PAHs的浓度[86].中国大气PAHs的主要来源为煤炭燃烧和汽车尾气[87].亚洲边缘海域的大气PAHs与陆地排放活动密切相关,受到大陆外流的显著影响[88].它们经过远距离传输,通过海-气交换,进入海洋之中.大陆河流中PAHs主要来源为燃煤和汽车尾气排放[89],经过洋流输送进入海洋.而且,大陆边缘沉积物中的PAHs来源受附近区域不同能量结构下,不同陆源PAHs排放特征的影响[90].沉积物经过再重悬,释放颗粒物,而吸附PAHs颗粒物,经过生物泵、微生物泵和物理泵后分解,PAHs被释放回海水中[91].因此在海洋环境中发现石油或者煤燃烧不仅是边缘海域海水中PAHs的主要来源[92-93],同样也是远洋海水中PAHs主要来源[22].以上研究表明,能源使用量在一定程度上可以影响PAHs在大洋海水内的分布情况.鉴于煤炭燃烧和石油使用是PAHs排放的主要来源之一,并且排放的PAHs可以通过大气传输和河流输送远距离传播进入海洋,因此政策制定者可以积极推动能源结构的优化和转型,鼓励并支持清洁能源(如太阳能、风能、水能等)的开发和利用.特别是在交通和工业部门,通过引入更严格的排放标准、提供清洁能源补贴、建设充电站等措施,以减少PAHs的排放,进而减轻对海洋环境的压力.
探究了全球海洋表层PAHs的分布特征.首先,五大洋中的PAHs分布有所不同,太平洋中的浓度显著高于其他四大洋.其次,Phe、Pyr和BbF随着离岸距离的增加,PAHs的浓度呈现出明显的下降趋势.此外,PAHs的分布与纬度具有显著负相关性,纬度越高,PAHs浓度越低.探究影响海洋中PAHs分布的因素时,盐度、叶绿素和温度显著影响海洋PAHs的分布,而能源消耗量可能是关键因素.这些过程的综合作用共同塑造了海洋中PAHs的分布格局.
本研究虽然对全球海洋表层PAHs的分布特征进行了探究,但仍存在一些不足之处.首先,受限于数据获取和监测站点分布不均等因素,未能全面覆盖全球所有海域,特别是某些偏远海域和深海区域的PAHs分布状况仍缺乏充分了解.这可能导致对全球海洋PAHs污染的整体认识仍存在一定程度的偏差.本研究虽然分析了能源对PAHs分布的影响,但未能充分考虑气候变化、季风和海洋环流等自然因素对PAHs分布的影响.气候变化可能导致海洋环境发生一系列变化,进而影响PAHs的迁移和转化过程.因此,未来研究需要综合考虑自然因素和人类活动对海洋PAHs分布的共同影响.建议加强全球海洋PAHs监测网络建设,提高数据覆盖范围和准确性,综合考虑自然因素和人类活动对海洋PAHs分布的共同影响.加强跨学科合作研究,将气候变化、海洋环流等自然因素纳入研究范围,全面评估其对海洋PAHs分布的影响机制,为制定应对全球气候变化和海洋污染的综合性策略提供有力支撑.
  • 国家自然科学基金资助项目(42177363)
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2025年第45卷第1期
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  • 接收时间:2024-06-06
  • 首发时间:2026-03-18
  • 出版时间:2025-01-20
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  • 收稿日期:2024-06-06
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    1.重庆大学,三峡库区生态环境教育部重点实验室,重庆 400044
    2.重庆大学,煤矿灾害动力学与控制国家重点实验室,重庆 400044

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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
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红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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