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物探与化探, 2020, 44(5): 1245-1252 doi: 10.11720/wtyht.2020.1531

生态环境调查

北大港湿地东部多环芳烃沉积记录与来源分析

马晗宇,, 申月芳, 杨耀栋

天津市地质矿产测试中心,天津 300191

Sedimentary record and sources analysis of polycyclic aromatic hydrocarbons in eastern Beidagang Wetland

MA Han-Yu,, SHEN Yue-Fang, YANG Yao-Dong

Tianjin Geological and Mineral Resources Testing Center,Tianjin 300191, China

责任编辑: 蒋实

收稿日期: 2019-11-28   修回日期: 2020-03-15   网络出版日期: 2020-10-20

基金资助: 2015年度天津市地质项目 “滨海新区地下水及地质环境调查评价”.  津国土房任[2015]1号

Received: 2019-11-28   Revised: 2020-03-15   Online: 2020-10-20

作者简介 About authors

马晗宇(1986-),男,工程师,毕业于中国地质大学(北京),主要从事水文地质、环境地质、环境地球化学方向的研究工作。Email: mahanyu86@126.com

摘要

利用GC/MS法分析研究了北大港湿地东部沼泽水域沉积物岩芯样中16种多环芳烃(PAHs)含量与组成的垂向分布特征,并对其来源进行了分析。结果表明,沉积物岩芯中PAHs含量在(18.1~821)×10-9 之间,岩芯上段PAHs以5~6环高分子量组分为主,中段和下段则以2~3环组分为主。20世纪50年代以来,北大港湿地PAHs含量显著升高,峰值出现在20世纪50年代中期至60年代中期,比国内多数地区峰值出现时间更早,而20世纪80年代以后PAHs含量再次处于增长态势。根据成分组成和产业发展分析当地不同时期PAHs的来源,20世纪50年代以前,PAHs主要来自于长距离输送和薪柴的低温燃烧,此后则是以湿地周边化石燃料的不完全燃烧为主。北大港湿地的PAHs污染明显受到20世纪50年代以来人类生产活动的影响,化石燃料的不完全燃烧是主要来源,大港油田开采泄漏的影响则不显著。

关键词： 北大港湿地 ; 多环芳烃 ; 沉积记录 ; 来源 ; 垂向分布

Abstract

Polycyclic aromatic hydrocarbons (PAHs) in a sediment core collected from eastern Beidagang Wetland were determined by GC/MS. The ∑PAHs concentration ranges from 18.1×10 -9 to 821×10-9 in the whole sediment core. In the upper core, PAHs are mainly composed of 5~6 rings which are high molecular weight components, while in the middle and lower core PAHs are mainly composed of 2~3 rings of components. Since the 1950s, PAHs content in Beidagang Wetland has increased significantly. The peak appeared from mid 1950s to mid 1960s,earlier than that in most parts of China. PAHs content has been increasing again since the 1980s. According to composition and industrial development, the sources of PAHs in different periods were analyzed. Before the 1950s, PAHs mainly came from long-distance transportation and low-temperature combustion of wood. After 1950s, PAHs mainly came from incomplete combustion of fossil fuels around the wetland. PAHs pollution in Beidagang Wetland has been obviously affected by production activities since the 1950s, the main source of PAHs was incomplete combustion of fossil fuels, while the impact of exploitation leakage in Dagang Oilfield was not significant.

Keywords： Beidagang Wetland ; polycyclic aromatic hydrocarbons ; sedimentary record ; source ; vertical distribution

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本文引用格式

马晗宇, 申月芳, 杨耀栋. 北大港湿地东部多环芳烃沉积记录与来源分析. 物探与化探[J], 2020, 44(5): 1245-1252 doi:10.11720/wtyht.2020.1531

MA Han-Yu, SHEN Yue-Fang, YANG Yao-Dong. Sedimentary record and sources analysis of polycyclic aromatic hydrocarbons in eastern Beidagang Wetland. Geophysical and Geochemical Exploration[J], 2020, 44(5): 1245-1252 doi:10.11720/wtyht.2020.1531

0 引言

多环芳烃(Polycyclic aromatic hydrocarbons,PAHs)是一类广泛存在于环境中的持久性有机物污染物(Persistent organic pollutants,POPs),主要源自人类的生产活动,也是最早被发现和研究的化学致癌物[1]。近年来,中国成为世界上最主要的PAHs排放国[2],PAHs的大量排放给生态环境带来了巨大的压力。

PAHs通常是疏水性的,因此土壤和江河湖海中的沉积物成为了PAHs的主要归宿。对钻孔沉积物的研究,能够重建PAHs污染的历史,反映不同时期人类活动对环境影响的特征与差异。早在20世纪70年代,国外学者就意识到PAHs沉积记录的重要意义[3]。通过对高山湖泊、海洋、水库等沉积物的研究发现,包括欧美、日本在内的发达国家,PAHs峰值通常发生在20世纪80年代以前,最早甚至可追溯至1930年前后[4,5,6,7,8,9,10,11],而国内沉积物中PAHs峰值多出现在1980年以后[12,13,14,15,16,17],体现了我国与发达国家发展阶段的差别。我国近年来对于PAHs沉积记录的研究多集中在中西部湖泊沉积物、草原泥炭层和近岸海底沉积物,而对于东部地区尤其是华北地区的湖泊、湿地研究相对较少。密云水库曾开展过沉积物中PAHs垂向分布研究,但未建立与沉积年代的关系[18]。

北大港湿地位于天津市滨海新区,是华北地区重要的候鸟迁移驿站,具有良好的生物多样性。湿地毗邻大港油田,长期开采原油的历史和周边众多的石化企业易造成PAHs污染,对湿地环境的影响历史值得关注,但目前尚无相关研究的开展。本研究旨在对北大港湿地东部沉积物岩芯中列入EPA优先控制污染物的16种PAHs开展研究工作,对北大港湿地PAHs污染历史及可能来源进行初步的探讨。

1 材料与方法

1.1 样品采集

作为北大港湿地的主要组成部分,北大港水库建立在古潟湖遗迹的基础上,受外来水源、气候降水等因素的影响,水域面积变化较大[19]。研究中采样点位于北大港水库东北角(图1)(坐标N 117°27'49″,E 38°44'15″),多年来为沼泽水域,沉积物受人类扰动相对较小,较好地保留了历史沉积情况。采样点同时邻近大港油田油气开采区,能较好地反映原油开采对湿地中PAHs含量的影响。样品采集于2017年3月,采样工具为手持式沉积柱采样器,所采集沉积物岩芯顶界清晰,上覆水体清澈,未见明显扰动。共采集3根岩芯,岩芯长度为40 cm,各岩芯钻孔间距离在1 m左右。岩芯以2 cm间隔分样,不同岩芯相同深度的样品混合后存放于棕色玻璃瓶内,避光低温(4 ℃)保存,当日送交实验室。

图1

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图1   沉积柱采样点示意

Fig.1   Sampling sites for sediment core


1.2 材料与方法

1.2.1 试剂

研究中所用试剂包括正己烷、二氯甲烷、戊烷、丙酮、环己烷等有机溶剂,均为农残级;无水硫酸钠为分析纯,硅胶吸附剂为层析用。上述试剂使用前均做空白检查,确保不会影响分析结果。

16种PAHs标准混合品包括:萘(Nap)、苊烯(Acy)、苊(Ace)、芴(Flu)、菲(Phe)、蒽(Ant)、荧蒽(Flua)、芘(Pyr)、苯并(a)蒽(BaA)、䓛(Chry)、苯并(b)荧蒽(BbF)、苯并(k)荧蒽(BkF)、苯并(a)芘(BaP)、二苯并(a,h)蒽(DahA)、茚并(1,2,3-cd)芘(INP)、苯并(ghi)苝(BgP)。标准品购于J&K Scientific公司。

1.2.2 样品预处理

采集的沉积物样品剔除石块、植物根等杂质,参考EPA方法(Method 3541)在室温下避光晾干后研磨成细粒并过60目筛。取筛下组分10.0 g,加入适量无水硫酸钠充分混匀,上快速溶剂萃取仪(ASE350)进行萃取,循环两次,静态萃取时间10 min,压力1 500 psi,提取液为1+1丙酮—正己烷溶液(农残级),萃取前加入三联苯、二丁基氯菊酯和2,4,5,6-四氯间二甲苯作为替代物。

提取液经氮吹浓缩至2 mL,加入约4 mL环己烷进行溶剂转换,再次浓缩至2 mL后过硅胶层析净化柱。净化柱结构为1.5 cm无水硫酸钠和10 cm硅胶吸附剂,并用二氯甲烷和正己烷淋洗。加入提取液后,先用25 mL戊烷洗脱并弃去,再用25 mL二氯甲烷—戊烷溶剂洗脱并收集。收集的洗脱液氮吹浓缩至0.5 mL,后用丙酮—正己烷溶剂定容至1.0 mL上机测试。

1.2.3 仪器分析

PAHs测试方法为气相色谱—质谱法(GC/MS),测试仪器为GCMS-QP2010 Ultra气相色谱—质谱仪,外标法定量。16种PAHs检出限为(0.5~1.0)×10-9。气相色谱及质谱分析条件按照《土壤监测规范方法标准 土壤和沉积物多环芳烃的测定 气相色谱—质谱法》(HJ 805-2016)执行。

1.2.4 质量控制

样品分析过程中设置实验室空白样、实验室空白加标样和样品平行样各1组。实验室空白样中16种PAHs均低于检出限,所有样品替代物回收率均在70%~130%之间。取深度18~20 cm段样品作为样品平行样。具体质控信息见表1。

表1   PAHs分析条件及质控信息

Table 1  Information of analysis conditions and quality control for PAHs

PAH检出限/10-9选择离子空白加标回收/%平行偏差/%
萘 Nap0.50128、127、12979.922.2
苊 Ace0.50154、153、15279.710.6
苊烯 Acy0.50152、151、15379.417.3
芴 Flu0.50166、165、16778.38.86
菲 Phe0.50178、179、17678.33.42
蒽 Ant0.50178、179、17680.35.83
荧蒽 Flua0.50202、200、203、101、10081.50.848
芘 Pyr0.50202、200、203、101、10079.55.49
苯并(a)蒽 BaA0.50228、226、229、114、11378.3—
䓛 Chry0.50228、226、229、114、11376.48.23
苯并(b)荧蒽 BbF0.50252、253、250、25181.61.44
苯并(k)荧蒽 BkF0.50252、253、250、25184.22.45
苯并(a)芘 BaP1.00252、253、250、25183.32.17
茚并(1,2,3-cd)芘 INP1.00276、277、275、27477.30.932
二苯并(a,h)蒽 DahA1.00278、276、279、13882.4—
苯并(ghi)苝 BgP1.00276、275、274、13882.62.75

注:“—”代表平行双样中均未检出该组分。

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1.2.5 沉积年代的确定

210Pb、137Cs测年是确定沉积柱年代的常用方法,多数沉积记录研究是利用与PAHs岩芯同时采取的岩芯进行实测,也有部分研究引用了同区域的沉积速率成果[13,20]。本研究中沉积柱样品的沉积速率参考北大港湿地东部沼泽的相关研究结果,沉积速率为0.10~0.29 cm/a[21,22],平均值取0.20 cm/a,据此认为岩芯深度12 cm层段对应20世纪50年代中期,深度22 cm层段对应20世纪初,更深的岩芯则来自于20世纪以前。

2 结果与讨论

2.1 多环芳烃垂向分布与组成特征

在整个沉积柱中,16种EPA优先控制的PAHs有不同程度的检出(表2)。检测结果表明,北大港湿地东部的沉积柱中PAHs总量(∑PAHs)在(18.1~821)×10-9之间,平均值为284×10-9。

表2   沉积柱中多环芳烃浓度统计

Table 2  Concentations of 16 PAHs in the sediment core from eastern Beidagang Wetland

PAH名称浓度范围/10-9平均值/10-9中位值/10-9变异系数
萘 Napnd~16.37.737.720.629
苊 Acend~4.421.390.960.657
苊烯 Acynd~9.812.661.250.970
芴 Flu2.81~44.013.16.121.06
菲 Phe7.98~81.435.136.30.538
蒽 Antnd~7.432.792.810.728
荧蒽 Fluand~56.920.823.70.548
芘 Pyrnd~45.216.616.60.687
苯并(a)蒽 BaAnd~42.210.10.500.477
䓛 Chrynd~99.232.515.01.02
苯并(b)荧蒽 BbFnd~69.119.95.460.648
苯并(k)荧蒽 BkF2.12~91.126.67.921.17
苯并(a)芘 BaP1.25~38.513.510.70.810
茚并(1,2,3-cd)芘 INPnd~61.718.54.751.01
二苯并(a,h)蒽 DahAnd~67.117.61.000.478
苯并(ghi)苝 BgPnd~17647.39.991.05
∑2~3环12.5~14862.360.20.639
∑4环2.25~24479.355.21.04
∑5~6环3.37~50414241.81.26
∑PAHs18.1~8212841980.954

注:nd为未检出。

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总体来看,沉积物岩芯可按PAHs含量的垂向变化划分为3段(图2):下段(深度40~22 cm)、中段(深度22~12 cm)和上段(深度12~0 cm)。下段PAHs含量相对稳定,构成上以2~3环PAHs为主;中段PAHs含量较下段有一定上升,构成上仍以2~3环为主,但4环占比有一定提高;上段PAHs在构成上以5~6环组分为主(图3),含量方面先急剧增加,在12~10 cm处出现峰值,随后有所下降,并在6~0 cm重新表现出上升趋势。

图2

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图2   沉积柱中PAHs垂向分布

Fig.2   Vertical profile of PAHs in sediment core


图3

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图3   沉积柱中不同时期PAHs组成特征

Fig.3   Characteristics of PAHs composition in sediment core at different periods


2.2 不同地区PAHs沉积记录比较

结合PAHs垂向分布规律和沉积速率,可发现不同时期北大港湿地PAHs含量和构成都存在较大差异:以20世纪50年代为界,之前PAHs含量相对较低,构成上以2~3环为主;之后PAHs含量显著升高,构成上以5~6环为主,含量的峰值出现在20世纪50年代中期至60年代中期;在20世纪80年代之后,沉积物中PAHs含量处于增长态势。

本研究和国内外其他地区研究的PAHs沉积记录比较见表3。

表3   不同地区PAHs沉积记录比较

Table 3  Comparison of sedimentary record of PAHs across different areas

研究地区PAHs含量/10-9峰值时段资料来源
北大港湿地东部18.1~82120世纪50年代中期至60年代中期本研究
Cumbria(UK)—1970年左右[4]
Michigan Inland Lakes(USA)—20世纪80年代[5]
Mountain Lakes(Europe)—1960~1980[6]
Northwest Scotland(UK)1719(最大值)1920~1934[7]
Northwestern Mediterranean—1920~1940;1975~1990[8]
Osaka(Japan)4200~260001945~1958[9]
Rhode Island(USA)—1950~1960[10]
Tokyo Bay(Japan)38~200020世纪80年代[11]
渤海湾34.2~2021980年以后[12]
博斯腾湖37.5~184.51990年以后[13]
长江口25.44~567.351990年以后[14]
红枫湖848~37251996年[15]
伶仃洋西岸59~3301990年以后[16]
青海湖496~11722000年以后[17]
澳门近海600~450020世纪60年代[23]
安达曼海(马来西亚)13.2~60.120世纪60年代;20世纪80年代[24]
若尔盖草原36.2~40820世纪60年代[25]

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国内沉积物中PAHs峰值出现时间总体晚于发达国家,但北大港湿地东部沉积物中的峰值出现却早于包括渤海湾在内的国内多数地区,和澳门近海、若尔盖草原峰值时间相当,也和欧洲山地湖泊、美国Rhode岛、日本Osaka地区的峰值时间接近,反映出北大港湿地周边的开发在国内相对较早。20世纪80年代以后,中国经济快速发展,北大港湿地沉积物中PAHs含量也持续上升,与国内的总体趋势一致。

国内部分研究发现,在20世纪50、60年代存在一个相对的PAHs峰值[13,16,23,25],和北大港湿地峰值时段相一致。20世纪50年代末,包括天津地区在内的全国范围大炼钢铁,导致该时期的环境污染严重[26],其中可能也包括PAHs排放量的增加。此外,大港油田成立于1964年,北大港湿地东部的峰值时段还可能与油田的早期勘探开采有关。

2.3 北大港湿地东部多环芳烃来源

PAHs中不稳定的异构体组分会在由不完全燃烧所产生的PAHs中占据主导,因此利用各异构体占比可以初步判断出沉积物中PAHs的来源[27]。常用的异构体组合包括: Ant和Phe、Flua和Pyr、BaA和Chry、INP和BgP。

北大港湿地东部沉积物中不同时期的PAHs比值存在差异(图4)。自20世纪50年代至今,Flua/(Flua+Pyr)均大于0.5,表明PAHs主要来自于煤炭燃烧;INP/(INP+BgP)范围在0.2~0.5,表明PAHs主要来自于石油制品的燃烧。该时期PAHs又以5~6环高分子量组分为主,更倾向于在污染源周边沉降[28]。20世纪50年代以后,北大港湿地周边形成了大港油田和相关的石化产业区,包括煤炭、石油产品在内的化石燃料使用大幅增加,其不完全燃烧成为了湿地中PAHs的主要来源。渤海中部1960年以来沉积物中的PAHs主要来自于石油源,是受到了黄河入海口处胜利油田的影响[15],但同期建成的大港油田却没有使北大港湿地内PAHs表现出石油来源的特征。

图4

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图4   多环芳烃异构体比值分布

Fig.4   PAHs cross-correlations for the ratios of sediment core


20世纪50年代以前,沉积柱中Ant/(Ant+Phe)小于0.1,BaA/(BaA+Chry)则小于0.2,多被认为是PAHs源自于石油制品泄漏的标志[29,30,31]。但在随着大气的长距离迁徙中,Ant和BaA容易发生光化学反应,导致其在异构体中的占比降低,使源解析的结果失真 [8,32],这一点又可以作为PAHs长距离输运的标志[24,33]。该时期沉积物中PAHs以2~3环的低分子量组分为主,通常认为2~3环的PAHs多来自于石油制品,而木柴等燃料的低温燃烧过程也会产生这些组分 [8,17,33]。低分子量的PAHs组分也更容易随大气远距离迁徙。考虑到20世纪50年代以前湿地周边没有大规模油气开采行为,因此推测当时的PAHs源自于全球工业化背景下的长距离输送和周边居民薪柴燃料的低温燃烧更为可信。

20世纪50年代末、60年代初,受大炼钢铁以及大港油田初期勘探开采的影响,北大港湿地周边化石燃料开始大量使用,是当时沉积物中PAHs的主要来源。而同时期国内的博斯腾湖、青海湖和若尔盖草原等地,沉积物中PAHs则以2~3环低分子量组分为主[13,17,25],反映了当时上述地区PAHs源自低温燃烧和远距离输送的可能性更大,也表明了不同地区在当时的PAHs来源差异。

3 结论

通过分析北大港湿地东部沉积柱中多环芳烃的垂直分布和含量特征,重现了该地区多环芳烃的沉积历史。北大港湿地东部沉积物岩芯中PAHs含量为(18.1~821)×10-9。20世纪50年代以来,北大港湿地东部PAHs含量显著升高,峰值出现在20世纪50年代中期至60年代中期,比国内多数地区峰值出现时间更早,而20世纪80年代以后PAHs含量再次处于增长态势。当地不同时期PAHs的来源存在差异,20世纪50年代以前主要来自于长距离输送和薪柴的低温燃烧,此后则是以湿地周边化石燃料的不完全燃烧为主。北大港湿地的PAHs污染明显受到20世纪50年代以来人类生产活动的影响,化石燃料的不完全燃烧是主要来源,大港油田开采泄漏的影响则不显著。

致谢

中国地质大学(北京)刘菲教授、天津大学陈亮副教授在论文撰写期间给予了亲切指导,研究中样品的测试工作由国土资源部天津矿产资源监督检测中心的张岩、展超等同志完成,在此表示衷心感谢。

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[J]. Environmental Science & Technology, 2003,37:4855-4863.

DOI:10.1021/es034514k      URL     PMID:14620810      [本文引用: 2]

The coastal region off Macao is a known depositional zone for persistent organic pollutants (POPs) in the Pearl River Delta and Estuary of southern China and an important gateway for the regional contributions of contamination to the globe. This paper presents a comprehensive assessment of the input sources and transport pathways of polycyclic aromatic hydrocarbons (PAHs) found in the coastal sediments of Macao, based on measurements of 48 2-7 ring PAHs and 7 sulfur/oxygenated (S/O) PAH derivatives in 45 sediment, 13 street dust, and 68 aerosol samples. Total sediment PAHs concentrations ranged from 294 to 12741 ng/g, categorized as moderate contamination compared to other regions of Asia and the world. In addition, the PAH compounds appeared to be bound more strongly to aromatics-rich soot particles than to natural organic matter, implying a prevailing atmospheric transport route for PAHs to Macao's coast. Compositional analysis and principal component analysis (PCA) suggested that different classes of PAHs in the coastal sediments of Macao may have been derived from different input sources via various transport pathways. For example, alkylated and S/O PAHs were likely derived from fossil fuel leakage and transported to sediments by both aerosols particles and street runoff. High-molecular-weight parent PAHs were predominantly originated from automobile exhausts and distributed by direct and indirect atmospheric deposition. Low-molecular-weight parent PAHs, on the other hand, may have stemmed from lower temperature combustion and fossil fuel (such as diesel) spillage from ships and boats and were transported to sediments by river runoff or direct discharge as well as by air-water exchange.

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