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Based on the analysis of the material composition and mercury(Hg)content in the surface sediments of the Yellow River subaqueous delta, the distribution characteristics and influencing factors of Hg in the region were examined. The results showed that the Hg content in the surface sediments ranged from 15.09 to 53.11µg/kg, with an average content of 36.32µg/kg, which was relatively low compared to other domestic and international marine areas. The Hg content in the sediments exhibited a'low-high-low-high' pattern from the shore to the sea, with peak concentrations observed at the shear front and in the fine-grained sediment areas offshore. Elevated Hg levels were also found in the sediments near Laizhou Bay in the southern region. Hg was primarily derived from natural sources but was also influenced by emissions from human activities. Hydrodynamic conditions played a crucial role in controlling the distribution of Hg, with a tendency for Hg to accumulate in fine-grained sediments. The 'filter' effect of the estuary, especially the shear front, significantly influenced the spatial distribution of Hg and its transport to the open sea. The distribution of Hg was also related to its carriers, such as organic carbon, carbonate minerals, and iron-manganese oxides. These carriers directly bound with Hg, affecting its distribution, and also influenced the properties of the sediments, thus indirectly influencing the distribution of Hg.

, correspAuthors=Ming LIU, 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=Xin-ying CHE, Ming LIU, Fei-yu WANG, Jing-bo CHEN, Xue-shi SUN, De-jiang FAN), CN=ArticleExt(id=1241057240069755075, articleId=1241057233396618068, tenantId=1146029695717560320, journalId=1234093305789726721, language=CN, title=黄河水下三角洲表层沉积物汞(Hg)分布特征及其影响因素, columnId=1234106388268503686, journalTitle=中国环境科学, columnName=环境生态, runingTitle=null, highlight=null, articleAbstract=

基于对黄河水下三角洲表层沉积物的物质组成和汞(Hg)含量的分析,以期了解黄河水下三角洲Hg分布特征及影响因素.结果表明,黄河水下三角洲表层沉积物中的Hg含量介于15.09~53.11µg/kg,平均含量为36.32µg/kg,相较于其他国内外海域较低.沉积物中Hg含量由岸向海呈现“低-高-低-高”的间隔分布,切变锋位置和外海细颗粒沉积区Hg含量出现峰值,南部靠近莱州湾区域沉积物中Hg含量也较高.Hg以自然来源为主,同时受人类活动排放的影响.水动力条件对沉积物中Hg的分布有显著的控制作用,Hg倾向于在细颗粒沉积物中富集,河口的“过滤器”效应尤其是切变锋的作用显著影响了Hg的空间分布和向远海的迁移.沉积物中Hg的分布还与有机碳、碳酸盐矿物和铁锰氧化物等其在沉积物中的赋存载体有关,一方面,这些赋存载体直接与Hg结合影响其在沉积物中的分布,另一方面这些赋存载体还会影响沉积物的性质进而间接影响Hg的分布.

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* 责任作者,正高级实验师,
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车新颖(2000-),男,山东蒙阴人,中国海洋大学硕士研究生,主要从事重金属的沉积源汇过程研究.发表论文2篇..

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车新颖(2000-),男,山东蒙阴人,中国海洋大学硕士研究生,主要从事重金属的沉积源汇过程研究.发表论文2篇..

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车新颖(2000-),男,山东蒙阴人,中国海洋大学硕士研究生,主要从事重金属的沉积源汇过程研究.发表论文2篇..

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环流、水深和切变锋位置改绘自[23]

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The indication of EF to heavy metal enrichment

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轻度中度中重度重度极重度严重
EF<11≤EF<33≤EF<55≤EF<1010≤EF<2525≤EF<50EF≥50
), ArticleFig(id=1241057249175589625, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057233396618068, language=CN, label=表1, caption=

EF指示的重金属富集程度

, figureFileSmall=null, figureFileBig=null, tableContent=
轻度中度中重度重度极重度严重
EF<11≤EF<33≤EF<55≤EF<1010≤EF<2525≤EF<50EF≥50
), ArticleFig(id=1241057249343361793, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057233396618068, language=EN, label=Table 2, caption=

The indication of Er value to heavy metal ecological pollution degree

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较高严重
Er≤4040<Er≤8080<Er≤160160<Er≤320Er>320
), ArticleFig(id=1241057249452413703, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057233396618068, language=CN, label=表2, caption=

Er值指示的重金属生态污染程度

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较高严重
Er≤4040<Er≤8080<Er≤160160<Er≤320Er>320
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The content of major elements and trace elements in the surface sediments

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元素最大值最小值平均值标准偏差变异系数(%)
SiO2(%)68.2045.8156.884.638.14
Al2O3(%)13.269.8711.930.796.61
CaO(%)8.125.056.590.7912.00
MgO(%)3.271.842.650.3111.71
Na2O(%)2.702.082.400.176.23
K2O(%)2.602.052.390.135.49
Fe2O3(%)5.573.134.530.5612.46
MnO(%)0.110.050.090.0115.63
TiO2(%)0.610.550.590.022.80
P2O5(%)0.160.130.150.015.57
Cr(mg/kg)86.5563.4974.115.617.57
Cu(mg/kg)50.2410.6224.668.6335.01
Zn(mg/kg)91.3249.1376.3810.6813.98
Pb(mg/kg)31.2819.2125.903.3212.81
Ni(mg/kg)46.0921.2733.125.1615.59
Cd(mg/kg)0.270.120.190.0423.36
), ArticleFig(id=1241057249674711832, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057233396618068, language=CN, label=表3, caption=

研究区表层沉积物常量元素和微量元素含量

, figureFileSmall=null, figureFileBig=null, tableContent=
元素最大值最小值平均值标准偏差变异系数(%)
SiO2(%)68.2045.8156.884.638.14
Al2O3(%)13.269.8711.930.796.61
CaO(%)8.125.056.590.7912.00
MgO(%)3.271.842.650.3111.71
Na2O(%)2.702.082.400.176.23
K2O(%)2.602.052.390.135.49
Fe2O3(%)5.573.134.530.5612.46
MnO(%)0.110.050.090.0115.63
TiO2(%)0.610.550.590.022.80
P2O5(%)0.160.130.150.015.57
Cr(mg/kg)86.5563.4974.115.617.57
Cu(mg/kg)50.2410.6224.668.6335.01
Zn(mg/kg)91.3249.1376.3810.6813.98
Pb(mg/kg)31.2819.2125.903.3212.81
Ni(mg/kg)46.0921.2733.125.1615.59
Cd(mg/kg)0.270.120.190.0423.36
), ArticleFig(id=1241057249813123875, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057233396618068, language=EN, label=Table 4, caption=

The main mineral composition of the sediments in the study area(%)

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项目石英黏土矿物斜长石钾长石方解石
最大值49.3746.1033.328.9017.72
最小值24.719.666.851.016.26
平均含量36.6925.8619.484.4411.21
), ArticleFig(id=1241057249922175783, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057233396618068, language=CN, label=表4, caption=

研究区沉积物主要矿物组成(%)

, figureFileSmall=null, figureFileBig=null, tableContent=
项目石英黏土矿物斜长石钾长石方解石
最大值49.3746.1033.328.9017.72
最小值24.719.666.851.016.26
平均含量36.6925.8619.484.4411.21
), ArticleFig(id=1241057250022839086, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057233396618068, language=EN, label=Table 5, caption=

Comparison of Hg content in sediments from the study area and other areas

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地区Hg含量(µg/kg)参考文献
黄河水下三角洲36.32本研究
黄河口湿地(2015年)40±20[30]
渤海38.8[31]
黄海24.2
东海32.8
南海166.1
密西西比河33~91[32]
埃及地中海海滩14.938[33]
多瑙河三角洲176[34]
伏尔加河水库1~234[35]
中国黄土元素背景值14.6[36]
中国水系沉积物背景值27[37]
中国土壤环境背景值65[38]
), ArticleFig(id=1241057250102530869, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057233396618068, language=CN, label=表5, caption=

研究区沉积物Hg含量与国内外其他区域含量对比

, figureFileSmall=null, figureFileBig=null, tableContent=
地区Hg含量(µg/kg)参考文献
黄河水下三角洲36.32本研究
黄河口湿地(2015年)40±20[30]
渤海38.8[31]
黄海24.2
东海32.8
南海166.1
密西西比河33~91[32]
埃及地中海海滩14.938[33]
多瑙河三角洲176[34]
伏尔加河水库1~234[35]
中国黄土元素背景值14.6[36]
中国水系沉积物背景值27[37]
中国土壤环境背景值65[38]
), ArticleFig(id=1241057250173834046, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057233396618068, language=EN, label=Table 6, caption=

Comparison of major elements and trace elements in sediments of the study area and Loess

, figureFileSmall=null, figureFileBig=null, tableContent=
项目Na2O(%)MgO(%)Al2O3(%)SiO2(%)K2O(%)CaO(%)TiO2(%)MnO(%)Fe2O3(%)Cr(mg/kg)Ni(mg/kg)Cu(mg/kg)Zn(mg/kg)Cd(mg/kg)Pb(mg/kg)Hg(µg/kg)
研究区**2.402.6511.9356.882.396.590.590.094.5374.1133.1224.6676.380.1925.9036.32
黄土1.642.2713.2157.542.586.870.560.104.3567.3031.0022.5065.400.1021.0014.60
), ArticleFig(id=1241057250257720130, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057233396618068, language=CN, label=表6, caption=

研究区沉积物与黄土*常量元素与微量元素对比

, figureFileSmall=null, figureFileBig=null, tableContent=
项目Na2O(%)MgO(%)Al2O3(%)SiO2(%)K2O(%)CaO(%)TiO2(%)MnO(%)Fe2O3(%)Cr(mg/kg)Ni(mg/kg)Cu(mg/kg)Zn(mg/kg)Cd(mg/kg)Pb(mg/kg)Hg(µg/kg)
研究区**2.402.6511.9356.882.396.590.590.094.5374.1133.1224.6676.380.1925.9036.32
黄土1.642.2713.2157.542.586.870.560.104.3567.3031.0022.5065.400.1021.0014.60
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黄河水下三角洲表层沉积物汞(Hg)分布特征及其影响因素
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车新颖 1 , 刘明 1, 2, * , 王飞宇 1 , 陈竟博 1 , 孙学诗 1, 2 , 范德江 1, 2
中国环境科学 | 环境生态 2025,45(5): 2806-2815
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中国环境科学 | 环境生态 2025, 45(5): 2806-2815
黄河水下三角洲表层沉积物汞(Hg)分布特征及其影响因素
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车新颖1 , 刘明1, 2, * , 王飞宇1, 陈竟博1, 孙学诗1, 2, 范德江1, 2
作者信息
  • 1.中国海洋大学海洋地球科学学院,山东 青岛 266100
  • 2.海底科学与探测技术教育部重点实验室,山东 青岛 266100
  • 车新颖(2000-),男,山东蒙阴人,中国海洋大学硕士研究生,主要从事重金属的沉积源汇过程研究.发表论文2篇..

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* 责任作者,正高级实验师,
Distribution characteristics and influencing factors of Mercury (Hg) in the surface sediment of Yellow River Subaqueous Delta
Xin-ying CHE1 , Ming LIU1, 2, * , Fei-yu WANG1, Jing-bo CHEN1, Xue-shi SUN1, 2, De-jiang FAN1, 2
Affiliations
  • 1.College of Marine Geosciences, Ocean University of China, Qingdao 266100, China
  • 2.Key Laboratory of Submarine Geosciences and Technology, MOE, Ocean University of China, Qingdao 266100, China
出版时间: 2025-05-20
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基于对黄河水下三角洲表层沉积物的物质组成和汞(Hg)含量的分析,以期了解黄河水下三角洲Hg分布特征及影响因素.结果表明,黄河水下三角洲表层沉积物中的Hg含量介于15.09~53.11µg/kg,平均含量为36.32µg/kg,相较于其他国内外海域较低.沉积物中Hg含量由岸向海呈现“低-高-低-高”的间隔分布,切变锋位置和外海细颗粒沉积区Hg含量出现峰值,南部靠近莱州湾区域沉积物中Hg含量也较高.Hg以自然来源为主,同时受人类活动排放的影响.水动力条件对沉积物中Hg的分布有显著的控制作用,Hg倾向于在细颗粒沉积物中富集,河口的“过滤器”效应尤其是切变锋的作用显著影响了Hg的空间分布和向远海的迁移.沉积物中Hg的分布还与有机碳、碳酸盐矿物和铁锰氧化物等其在沉积物中的赋存载体有关,一方面,这些赋存载体直接与Hg结合影响其在沉积物中的分布,另一方面这些赋存载体还会影响沉积物的性质进而间接影响Hg的分布.

黄河水下三角洲  /  汞  /  空间分布  /  影响因素

Based on the analysis of the material composition and mercury(Hg)content in the surface sediments of the Yellow River subaqueous delta, the distribution characteristics and influencing factors of Hg in the region were examined. The results showed that the Hg content in the surface sediments ranged from 15.09 to 53.11µg/kg, with an average content of 36.32µg/kg, which was relatively low compared to other domestic and international marine areas. The Hg content in the sediments exhibited a'low-high-low-high' pattern from the shore to the sea, with peak concentrations observed at the shear front and in the fine-grained sediment areas offshore. Elevated Hg levels were also found in the sediments near Laizhou Bay in the southern region. Hg was primarily derived from natural sources but was also influenced by emissions from human activities. Hydrodynamic conditions played a crucial role in controlling the distribution of Hg, with a tendency for Hg to accumulate in fine-grained sediments. The 'filter' effect of the estuary, especially the shear front, significantly influenced the spatial distribution of Hg and its transport to the open sea. The distribution of Hg was also related to its carriers, such as organic carbon, carbonate minerals, and iron-manganese oxides. These carriers directly bound with Hg, affecting its distribution, and also influenced the properties of the sediments, thus indirectly influencing the distribution of Hg.

Yellow River Subaqueous Delta  /  Mercury  /  spatial distribution  /  influencing factors
车新颖, 刘明, 王飞宇, 陈竟博, 孙学诗, 范德江. 黄河水下三角洲表层沉积物汞(Hg)分布特征及其影响因素. 中国环境科学, 2025 , 45 (5) : 2806 -2815 .
Xin-ying CHE, Ming LIU, Fei-yu WANG, Jing-bo CHEN, Xue-shi SUN, De-jiang FAN. Distribution characteristics and influencing factors of Mercury (Hg) in the surface sediment of Yellow River Subaqueous Delta[J]. China Environmental Science, 2025 , 45 (5) : 2806 -2815 .
汞(Hg)是一种具有强烈神经毒素的元素,且具有持久性、富集性和可迁移性,是生态环境研究的重要指标元素[1-2].近几十年随着人类活动的增强,Hg排放量迅速增加,大气Hg排放比自然水平增加450%,地表水的Hg浓度自工业革命以来已经增至3倍左右[3-6].Hg排放量的增长使得Hg污染问题愈发严重[7-10].
在水生系统中,沉积物通常被认为是陆源排放污染物的最终汇[11].河流三角洲处在岩石圈、大气圈、水圈和生物圈的交互地带,是海陆相互作用非常强烈的区域,同时也是人类活动最为密集的区域[12-13].三角洲独特的环境会使河流输入或者大气沉降等不同方式输入的Hg在此沉积,使其成为重要的汇[14-16];这些Hg在沉积物中积累到一定浓度后,或在外界条件改变后,会从沉积物中重新向水体释放,这种内源性的Hg释放会增加水体中的Hg浓度,对生态环境产生重要影响[17-18].
黄河途经黄土高原,具有显著的水少沙多、水沙异源的特点[19].1885年后黄河由苏北改道大清河注入渤海,大量黄土沉积物在黄河口处沉积,形成了中国面积最大的三角洲以及中国最年轻的河口湿地[20-21].同时,黄河三角洲地下还蕴藏着丰富的石油和天然气资源,兼具生态效益和经济效益,对我国社会发展和生态安全至关重要[22].黄河流域中上游支流众多,人类活动产生的大量污染物通过支流输送进入黄河汇聚到干流的水库中,造成水库中沉积物污染物含量升高,如小浪底水库中Hg含量就高出黄土背景值2~7倍.调水调沙或者洪水时,这些携带高含量Hg的沉积物就会排放入海,在三角洲地区沉积,对该区域的生态环境造成重要影响.然而目前对于黄河水下三角洲沉积物中Hg的分布及其控制因素的研究却尚未见报道.
为此,本文基于2021年5月在黄河水下三角洲采集的表层沉积物样品,开展了其物质组成和Hg含量的分析,查明该区域内表层沉积物Hg含量的空间分布特征,分析沉积物中Hg的来源,探讨了Hg在黄河水下三角洲空间分布的控制因素和影响机制.该研究对于认识大河三角洲Hg等重金属污染物质的源汇过程及环境效应具有重要意义,同时对于黄河三角洲生态保护和可持续发展也具有一定的参考价值.
研究区域位于黄河水下三角洲及邻近海域,包括现行黄河入海口的东汊和北汊以外的海域.于2021年5月开展研究区4个断面共22个站位的现场调查和表层沉积物的采集工作,具体采样站位见图1.表层沉积物使用箱式取样器采集,取表层2cm的样品装入聚乙烯袋中,在船载冰柜内于-20℃下冷冻并用于后续实验分析.
表层沉积物的粒度分析测试使用Malvern公司的Mastersizer 3000型激光粒度仪.取少量沉积物湿样加入H2O2溶液和HCl去除其中的有机质和碳酸盐,反应完全后,离心去除残留的H2O2溶液和HCl,加入适量0.5mol/L的(NaPO36溶液超声振荡使其充分分散后上机测试.仪器测量的粒级间隔为φ/4,重复测试相对误差小于2%.粒度相关参数采用Folk公式进行计算[24].
常量元素的测试采用的仪器为Axios型X射线荧光光谱仪(XRF).取适量烘干并研磨后的样品,加入复合熔剂搅拌均匀并置入铂金坩埚中熔融,冷却后制片并上机测试.
微量元素测试采用的仪器为电感耦合等离子体质谱仪(ICP-MS,NexIon 2000).取适量烘干并研磨后的样品,使用高纯HNO3和HF消解后上机测试.测试过程中,采用国家标准物质水系沉积物(GBW 07309)、近海海洋沉积物(GBW 07314)和空白样品进行质量控制,测试相对标准偏差小于5%.
表层沉积物的有机碳(TOC)含量测试采用TOC-L总有机碳分析仪.取冷藏的表层沉积物样品,加入3mol/L的HCl充分反应除去其中的碳酸盐,之后离心除去剩余的HCl,将处理好的样品于40℃条件下烘干并充分研磨.上机测试时,将样品放入样品舟后推入仪器中,通氧气2min排出内部空气后开始测定,待测出数据后取出样品舟,重复上述步骤继续下一个样品的测量.测试过程采用标准物质葡萄糖和平行样品来进行质量控制,多次测量的相对标准偏差小于5%.
表层沉积物的矿物相分析使用X射线衍射仪(Bruker D8ADVANCE型).具体条件设置为:使用Cu靶Kα射线辐射,管电压/电流为40kV/100mA,步进扫描,步进长度0.02°(2θ),预置时间为0.02s,扫描范围为3°~65°,扫描速度为4°/min.对测试结果采用Jade 6.5软件进行半定量计算分析.
冷冻干燥后的样品采用DMA-80汞分析仪(Milestone Scientific Inc.,USA)开展Hg含量分析测试.分析测试过程中采用中国环境监测站的环境标准(ESS-4,0.021μg/g Hg)和中国物探化探研究所的土壤标准物质(GSS-13)进行质量控制.校准曲线包括8个浓度梯度Hg,每10个样品测量一次标准物质.标准物质和重复样品分析的相对标准偏差在2%~5%.
(1)富集因子(EF)
富集因子是用于定量评价沉积物重金属污染程度与污染来源的重要指标,通过重金属的实测值与背景值的比值,分辨出来源和富集状况[25].其计算公式如下[26]
式中:Me为重金属元素含量,单位为μg/kg,Al2O3为沉积物中测得的Al2O3元素含量,单位为μg/kg,作为标准化元素消除粒度等带来的影响;由于黄河沉积物90%以上来自中游的黄土高原[19],黄河下游河道高程高于两岸,且基本没有支流汇入,因此黄河水下三角洲的沉积物主要来自于黄土,本研究背景值采用黄土中的元素含量作为背景值,Hg的背景值取为14.6 μg/kg.根据EF的大小,将沉积物中重金属的富集程度分为7个等级[27],如表1所示.
(2)潜在生态危害指数
潜在生态危害指数是Hakanson在1980年提出的,广泛应用于评估重金属的生态风险[28],其计算公式为:
式中:Er为Hg的潜在生态危害指数;Tr是根据其生态活性制定的毒性系数,Hg为40;Cr代表Hg的污染指数;Cs是每个样品沉积物中Hg的测量浓度;Cn是地球化学背景浓度,本研究同样使用黄土中Hg的含量作为背景值.根据计算结果将污染程度分为5类[28],如表2所示.
研究区域与采样站位分布图采用ArcGIS 10.8软件绘制;沉积物物质组成、Hg含量等等值线图采用ArcGIS 10.8利用插值法绘制;相关性分析和结果的图形绘制由Origin 2022完成.
根据Folk分类方法,研究区沉积物主要为砂质粉砂和粉砂,极少部分站位为粉砂质砂.如图2所示,各站位的中值粒径范围为7.79~64.10μm,平均为21.40μm,最高值区分布在黄河口北汊外.由陆向海,沉积物粒径呈现高-低-高-低的变化趋势,其中临近现行河口北汊处沉积物粒径最粗,向外到切变锋附近沉积物粒度变细,切变锋外侧沉积物粒径又开始变粗,远海区域沉积物粒径又逐渐变细.粒度组成的结果也说明河口区域粒度粗,切变锋附近和远海沉积物粒度细.
对沉积物进行常量元素和微量元素地球化学分析,共获取了SiO2、Al2O3、CaO、MgO、Na2O、K2O、Fe2O3、MnO、TiO2和P2O5共10种常量元素以及Cr、Cu、Zn、Pb、Ni和Cd 6种微量重金属元素,其含量如表3所示.常量元素中,SiO2的含量最高,平均值达到56.88%,其次为Al2O3,平均含量为11.93%,表明研究区沉积物以硅酸盐和铝硅酸盐矿物为主.微量元素中,Zn的含量最高,Cd的含量最低.各元素中Cu和Cd的变异系数高,与其他微量元素差异较大,说明这两种元素在空间上的分布不均匀,不同站位含量差异较大.
研究区表层沉积物有机碳含量分布如图3所示.沉积物中有机碳含量介于0.11%~0.63%之间,平均含量为0.36%.在河口附近沿岸线有机碳含量较低;切变锋处有机碳含量有所增加;远海细颗粒沉积区沉积物有机碳含量高.
研究区表层沉积物中矿物组成差别较大,其主要矿物组成见表4.石英为研究区平均含量最高的矿物,其高值区与粒度较粗的区域相吻合,表明石英偏向分布在粗颗粒沉积物中,而黏土矿物则与之相反,主要分布在远海细颗粒沉积区中.研究区中碳酸盐矿物主要为方解石,平均含量达到11.21%,远高于其他河口,体现了黄河控制下的物质输送[29].
黄河水下三角洲沉积物中Hg含量介于15.09~53.11μg/kg,平均含量为36.32μg/kg,其中最低值出现在靠近黄河口北汊外的A2-1站位,最高值出现在黄河口东汊外的A5-2站位.由岸向海,沉积物Hg含量呈现“低-高-低-高”的间隔分布,与岸线近乎平行,河口和近岸边含量低,随后在切变锋附近含量升高出现峰值,之后含量开始下降,在远海处含量又开始上升(图4).总体来看,研究区南部靠近莱州湾区域含量更高,临近河口北汊处以及研究区中部Hg含量较低.
从不同断面来看(图5),各个断面变化较为一致,均呈现先增加后降低再增加的趋势(A5断面呈现先增加后降低趋势),最高值出现在切变锋附近的第二站位处.从含量来看,不同断面也有差异,各断面Hg含量平均值分别为31.59,34.89,35.16和44.82μg/kg,南部靠近莱州湾区域Hg含量更高.
与国内外其他区域相比较(表5),黄河水下三角洲沉积物中的Hg含量都处于正常水平或较低水平,低于其他经济发展水平较高的区域.相较于中国黄土元素背景值,黄河水下三角洲沉积物中Hg含量明显升高.相较于中国土壤环境背景值,Hg含量则相对较低.
三角洲沉积物的分布格局和性质一般受控于物源和水动力条件,物源是决定沉积物类型的首要条件.为了解黄河水下三角洲沉积物中Hg的来源,计算了沉积物中Hg的富集因子(EF)和潜在生态危害指数Er,其结果如图6所示.
富集因子结果表明Hg在研究区大部分区域属于轻度富集,切变锋附近及远海站位出现中度富集,潜在生态危害指数的结果和富集因子结果类似,近岸河口区域及切变锋后海域属于中风险,切变锋处和远海区域是较高风险.二者结果类似,表明研究区沉积物中Hg以自然来源为主,但是也受到人类活动的污染.
黄河搬运的泥沙90%以上来自中游黄土高原的侵蚀,这导致黄河泥沙中部分重金属含量与马兰黄土接近[19,39-40].而将黄河水下三角洲沉积物中常量元素与黄土元素背景值进行对比(表6),发现研究区常量元素与黄土非常接近,而几种重金属微量元素则相较于黄土元素含量均有升高,但幅度不大,说明黄土高原的自然风化过程是控制黄河沉积物中重金属浓度的主要因素[41];但是其中的Hg和Cd含量明显不同于黄土,有较为明显的升高,说明除自然来源,也受到了人类活动的影响.
黄河近年来向海的物质输送显著受控于人类活动,全年超过三分之一的水沙在调水调沙期间入海[42-43],这不仅显著的改变了黄河物质的输送格局,而且改变了重金属的输运模式[44].中上游占整个流域面积的90%以上,工农业产生的污染物通过支流输送到黄河干流,汇聚到干流的水库中,调沙期水库沉积物向外排放,成为一年中重金属向海排放的主要时段,如Cu、Pb、Cr、Ni等重金属在这一时期的排放通量占全年的50%左右[44].所以,中上游的人类活动是黄河水下三角洲沉积物中Hg的重要来源.黄河下游由于地形平缓,沉积物不断淤积,难以有污染物通过支流汇入,一般认为对黄河入海物质贡献较少,但也有研究表明,下游地区的人为排放对黄河入海重金属也有贡献,这主要与近几十年来沉积物沿河岸和河床沉积,下游河漫滩改造为耕地有关[44-45].
此外,黄河水下三角洲位于中国东部,是大陆与大洋的交汇区域,同时位于亚洲风尘运输的路径上.在季风的作用下,这些尘土和其中的污染物被向东输送至太平洋.因此黄河三角洲也会沉降大气颗粒物及其携带的Hg等污染物[46].
水动力环境在沉积物的搬运沉积过程中起决定作用,是外部因素对沉积物进行改造的条件[47].黄河三角洲沉积物主要来自于黄河输运的黄土高原的物质,决定了沉积物的性质,包括沉积物的物质组成、矿物含量和元素组成等,而水动力条件则对沉积物的搬运沉积产生重要的影响.
粒度可以反映沉积时的水动力环境,对不同断面的Hg含量和粒度(中值粒径)进行相关性分析,结果如图7所示.根据相关性散点图,A2至A4断面,拟合趋势线的斜率相差不大,均有显著的负相关关系,粒度对Hg含量的影响相差不大;而南部的A5断面,沉积物中Hg含量对粒度的相关性与其他断面明显不同,呈现并不显著的正相关关系.
黄河三角洲是潮控型河口三角洲,潮汐和潮流动力是塑造河口地形及控制沉积物运动的主要动力[48],特别是潮流与地形共同作用形成的潮流切变锋,对沉积物向外扩散具有重要的控制作用.切变锋内侧经过物理、化学和生物等作用,沉积物易发生沉积,难以向外扩散,因此积累大量的细粒沉积物,Hg含量远远高出附近站位,由于落潮切变锋对沉积物具有更强的捕获作用,落潮流对泥沙的搬运作用强于涨潮流,导致泥沙净通量方向为南向,所以研究区南部靠近莱州湾沉积物中Hg含量更高[20,48].在切变锋处达到峰值后,由于切变锋外侧受到环流影响,水动力更强,沉积物中Hg含量降低,这一过程体现了河口作为重金属入海过程中的“过滤器”效应,对Hg等重金属的向海输运起到了拦截和清除作用[23].当然,河口过程虽然拦截了相当部分的沉积物和Hg等重金属元素,但细颗粒的沉积物仍向远海输运,在远海方向,随着水动力的减弱,更细粒的沉积物发生沉积(图2),这部分沉积物因具有较高的比表面积和较强的吸附能力,因此Hg含量又逐渐升高.
河口冲淡水也是控制沉积物分布的因素之一,由于河口处流速大,不利于沉积物沉积,因此在近岸站位Hg含量相对较低,而目前黄河入海口在1996年改道清8汊之后形成了东汊和北汊双槽入海的汊道,北汊是黄河入海径流的主要通道[49],所以此处Hg含量更低.从全年来看,黄河三角洲沉积物具有“夏储冬输”的特征,这与冬季环流的搬运等有关,这也进一步解释研究区南部靠近莱州湾沉积物Hg含量更高.
沉积物中的Hg含量与粒度具有直接的关系,前文中相关性分析结果表明Hg含量与粒度具有显著的相关性,以往也研究发现沉积物中的Hg主要富集在细粒沉积物中.粒度是控制沉积物吸附能力的主要因素,细粒物质具有更大的比表面积,提供了更多的与Hg吸附、络合的反应场所,因此对Hg的结合能力更强[50-52].沉积物中Hg含量受粒度控制影响大,会掩盖其他影响Hg在沉积物中分布的因素.为了解影响沉积物中其他影响Hg分布的控制因素,消除粒度对Hg含量的影响,采用Al归一化方法对Hg含量和有机碳含量、方解石含量、常量元素等进行了处理,Al是铝硅酸盐矿物的主要构成元素,自然状态下性质稳定,受人类活动影响小,迁移能力弱,因此常用作参考元素[53].对归一化后Hg含量、有机碳含量、方解石含量及常量元素、重金属元素进行了相关性分析,结果如图8所示.
图8中可以看出,归一化后Hg含量与有机碳含量、方解石含量都有较高的正相关关系.有机质含有大量的结合位点,可以结合更多的Hg,有机质含量增加,Hg吸附量也会大大增加[54-56],同时有机碳含量还会影响沉积物中金属的流动性,进而影响它们在水体和沉积物之间的分布[57].Hg与方解石和CaO的正相关关系是由于沉积物中碳酸盐对于微量元素的淋溶性和流动性会产生影响[58],黄河三角洲沉积物来自于黄河搬运的黄土高原沉积物,包括原岩风化的产物和孔隙中的次生方解石胶结物,具有粒度细且含量高的特征[59],因此黄河三角洲区域沉积物中的Hg含量受碳酸盐含量的影响明显.常量元素中的MgO常存在于黏土矿物中,MnO、Fe2O3代表了沉积物中的铁锰氧化物,是Hg在沉积物中重要载体,因此三者与Hg具有正相关关系.
6种微量重金属元素中,Ni、Zn、Cd、Pb与Hg具有较为显著的正相关关系,而Cr、Cu的相关性较差.几种重金属元素的空间分布上也体现了这种差异,Ni、Zn、Cd、Pb的分布与Hg较为相似,高值区与低值区的分布界限明显,由岸向海呈现“低-高-低-高”的条带状分布,切变锋附近第二站位达到或接近峰值.前人对这几种重金属在黄河水下三角洲的具体赋存形态也进行了研究,发现除性质稳定的残渣态外,碳酸盐结合态和铁锰氧化物结合态也是这几种重金属的主要赋存形态,几乎超过50%[23].综上所述,Hg在黄河三角洲沉积物中的分布主要受物质来源和水动力的控制,除粒度外,沉积物中Hg的分布主要受有机碳、碳酸盐和铁锰氧化物等赋存载体的影响.
4.1 黄河水下三角洲表层沉积物中Hg含量介于15.09~53.11μg/kg,平均含量为36.32μg/kg,由岸向海,沉积物Hg含量呈现“低-高-低-高”的间隔分布,与岸线近乎平行分布,在切变锋处和外海细颗粒沉积区Hg含量出现峰值,研究区南部靠近莱州湾区域沉积物中Hg含量更高.与其他区域相比,黄河水下三角洲表层沉积物中Hg含量呈现正常或较低水平.
4.2 黄河三角洲沉积物中Hg的来源主要包括自然来源及人类活动的排放.河口冲淡水、潮流切变锋及环流等水动力条件对沉积物中Hg的分布起控制作用,尤其是切变锋显著影响了Hg的分布和向远海的运输;此外,沉积物中Hg的分布还受到有机碳、碳酸盐和铁锰氧化物等赋存载体的控制.
  • 国家自然科学基金资助项目(41606054)
  • 山东省自然科学基金项目(ZR2022MD051)
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2025年第45卷第5期
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  • 接收时间:2024-10-23
  • 首发时间:2026-03-18
  • 出版时间:2025-05-20
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  • 收稿日期:2024-10-23
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国家自然科学基金资助项目(41606054)
山东省自然科学基金项目(ZR2022MD051)
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    1.中国海洋大学海洋地球科学学院,山东 青岛 266100
    2.海底科学与探测技术教育部重点实验室,山东 青岛 266100

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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
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
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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