Article(id=1225012183843619429, tenantId=1146029695717560320, journalId=1149651085930835976, issueId=1224796769733726966, articleNumber=null, orderNo=null, doi=10.12284/hyxb2022186, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1644336000000, receivedDateStr=2022-02-09, revisedDate=1655827200000, revisedDateStr=2022-06-22, acceptedDate=null, acceptedDateStr=null, onlineDate=1769995264254, onlineDateStr=2026-02-02, pubDate=1664553600000, pubDateStr=2022-10-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1769995264254, onlineIssueDateStr=2026-02-02, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1769995264254, creator=13701087609, updateTime=1769995264254, updator=13701087609, issue=Issue{id=1224796769733726966, tenantId=1146029695717560320, journalId=1149651085930835976, year='2022', volume='44', issue='10', pageStart='1', pageEnd='192', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1769943905528, creator=13701087609, updateTime=1769996085810, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1225015629757956162, tenantId=1146029695717560320, journalId=1149651085930835976, issueId=1224796769733726966, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1225015629757956163, tenantId=1146029695717560320, journalId=1149651085930835976, issueId=1224796769733726966, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=63, endPage=79, ext={EN=ArticleExt(id=1225012184103666279, articleId=1225012183843619429, tenantId=1146029695717560320, journalId=1149651085930835976, language=EN, title=Occurrence mechanism of redox sensitive elements in columnar sediments in South Central Okinawa Trough and their environmental implications, columnId=1194652705852465724, journalTitle=Haiyang Xuebao, columnName=Article, runingTitle=null, highlight=null, articleAbstract=

Changes in the content of redox sensitive elements (RSE) in sediments are good surrogate indicators for the redox environment of the overlying water. The RSE in the columnar sediments under complex environmental backgrounds through the grain size, total organic carbon and total nitrogen and its isotopes contents, and redox sensitive elements contents of the two columnar sediments (30 cm) in South Central Okinawa Trough are explored in this paper. And to explore the occurrence mechanism and environmental indication significance. The study found that in addition to the depletion of Cr in the columnar sediments, other RSEs showed different degrees of enrichment. The “grain size effect” has little effect on the RSE content of columnar sediments in the Okinawa Trough; analysis and judgment show that seawater surface productivity is the main factor affecting the redox environment of sediments, and RSE is achieved through the adsorption or desorption of Mn (hydrogen) oxides enrichment and loss. Indicators such as δCe, V/(V+Ni), Ni/Co and V/Cr indicate that the sediment is in an oxic-dysoxic water environment. The Mn element in the sediment diffuses upward in the form of Mn2+ through reduction, and is oxidized and enriched by oxygen-containing interstitial water at 25−30 cm to form a manganese peak. The 0−25 cm columnar sediment is in an oxic water column, and 25−30 cm is in a dysoxic water column.

, correspAuthors=Yanguang Dou, authorNote=null, correspAuthorsNote=null, copyrightStatement=Copyright © 2022 Pratacultural Science. All rights reserved., 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=Xiaoyan Xu, Yanguang Dou, Yong Zhang, Xiaohui Chen, Zhilei Sun, Fenglong Bai, Bin Zhai, Libo Wang, Liang Zou), CN=ArticleExt(id=1225012187513635455, articleId=1225012183843619429, tenantId=1146029695717560320, journalId=1149651085930835976, language=CN, title=冲绳海槽中南部柱状沉积物氧化还原敏感元素赋存机理与环境指示意义, columnId=1149698756456657529, journalTitle=海洋学报, columnName=论文, runingTitle=null, highlight=null, articleAbstract=

沉积物中氧化还原敏感元素(Redox Sensitive Element,RSE)含量变化是上覆水体氧化还原环境良好的替代指标。本文通过冲绳海槽中南部两个柱状沉积物(深度:30 cm)粒度、总有机碳、总氮及其同位素含量和氧化还原敏感元素含量等指标,探究复杂环境背景下冲绳海槽柱状沉积物中RSE的赋存机理与环境指示意义。研究发现,柱状沉积物中除了Cr亏损,其他RSE均显示有不同程度的富集。“粒控效应”对冲绳海槽柱状沉积物的RSE含量影响较小;分析可知,海水表层生产力是影响沉积物氧化还原环境的主要因素,通过Mn(氢)氧化物的吸附或解吸附作用实现RSE的富集与亏损。δCe、V/Cr、Ni/Co和V/(V+Ni)等指标指示沉积物整体处于氧化−弱氧化环境。沉积物中Mn元素通过还原作用以Mn2+形式向上扩散,在25~30 cm处被含氧间隙水氧化富集形成锰峰,指示柱状沉积物0~25 cm处为氧化环境,25~30 cm处为弱氧化环境。

, correspAuthors=窦衍光, authorNote=null, correspAuthorsNote=
窦衍光(1979-),男,研究员,主要从事海洋沉积地球化学研究。E-mail:
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许晓燕(1997-),女,广东省汕头市人,主要从事海洋地质研究。E-mail:

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Laboratory for Marine Mineral Resource, Pilot National Laboratory for Marine Science and Technology (Qingdao), Qingdao 266237, China), AuthorCompanyExt(id=1225368253954961916, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, companyId=1225368253942379002, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=4.青岛海洋科学与技术试点国家实验室 海洋矿产资源评价与探测技术功能实验室,山东 青岛 266237)])], figs=[ArticleFig(id=1225368259290116771, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=EN, label=Fig. 1, caption=Ocean current system[31] and sample location in the Okinawa Trough of the East China Sea, figureFileSmall=OnkthHOAJy6FxcQjpL5xRg==, figureFileBig=Gix97at32HWA6xd5REud6A==, tableContent=null), ArticleFig(id=1225368259394974375, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=CN, label=图1, caption=东海冲绳海槽洋流体系[31]及样品位置, figureFileSmall=OnkthHOAJy6FxcQjpL5xRg==, figureFileBig=Gix97at32HWA6xd5REud6A==, tableContent=null), ArticleFig(id=1225368259927650989, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=EN, label=Fig. 2, caption=Vertical characteristics of component content, average particle size, TOC content, TN content, δ13C value, δ15N value and fm in the columnar sediments of DYBB27 (a) and DYB228 (b), figureFileSmall=cziDupMhlqMAwkVMpPo2Jw==, figureFileBig=99ZLL8gVcPVDbUVpj4/54g==, tableContent=null), ArticleFig(id=1225368260506464946, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=CN, label=图2, caption=DYBB27(a)和DYB228(b)柱状沉积物组分含量、平均粒径、TOC含量、TN含量、δ13C值、δ15N值和海洋自生有机质组分占比(fm)的垂向特征, figureFileSmall=cziDupMhlqMAwkVMpPo2Jw==, figureFileBig=99ZLL8gVcPVDbUVpj4/54g==, tableContent=null), ArticleFig(id=1225368260644876982, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=EN, label=Fig. 3, caption=Vertical characteristics of RSE/Al ratio in the columnar sediments of DYBB27 and DYB228, figureFileSmall=ZF0dTJLBrzb6RxSrv4NVig==, figureFileBig=XS4dcT56XH1DSa43xAQD2g==, tableContent=null), ArticleFig(id=1225368260749734583, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=CN, label=图3, caption=DYBB27和DYB228柱状沉积物中RSE/Al比值的垂向特征, figureFileSmall=ZF0dTJLBrzb6RxSrv4NVig==, figureFileBig=XS4dcT56XH1DSa43xAQD2g==, tableContent=null), ArticleFig(id=1225368260850397883, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=EN, label=Fig. 4, caption=Vertical characteristics of RSEEF in the columnar sediments of DYBB27 and DYB228, figureFileSmall=drcSNz5CWSo7DRDDirc4UA==, figureFileBig=9iU1lO4FO1xFpjaQhw68lg==, tableContent=null), ArticleFig(id=1225368260972032702, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=CN, label=图4, caption=DYBB27和DYB228柱状沉积物RSEEF的垂向特征, figureFileSmall=drcSNz5CWSo7DRDDirc4UA==, figureFileBig=9iU1lO4FO1xFpjaQhw68lg==, tableContent=null), ArticleFig(id=1225368261093667522, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=EN, label=Fig. 5, caption=Variation characteristics of different oxidation indicators in columnar sediments of DYBB27 and DYB228 (Uauth is the content of authigenic uranium), figureFileSmall=HW1grwMSvFPv38anFQrh8Q==, figureFileBig=KhNjrVySl01IGI0OZnOYZg==, tableContent=null), ArticleFig(id=1225368261290799814, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=CN, label=图5, caption=DYBB27和DYB228柱状沉积物不同氧化还原指标的变化特征(Uauth为自生铀含量), figureFileSmall=HW1grwMSvFPv38anFQrh8Q==, figureFileBig=KhNjrVySl01IGI0OZnOYZg==, tableContent=null), ArticleFig(id=1225368261395657413, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=EN, label=Fig. 6, caption=Correlation between silt content and RSE/Al ratios in the columnar sediments of DYBB27 (a) and DYB228 (b)

The value of ordinate a is 1 (Mn/Al), and the other RSE/Al are 4

, figureFileSmall=6/1Rnu2dX0/zlBCxKhSGvg==, figureFileBig=neh+WwT1G6aiT/dMIBw6Iw==, tableContent=null), ArticleFig(id=1225368262888829640, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=CN, label=图6, caption=DYBB27(a)和DYB228(b)柱状沉积物中粉砂含量和RSE/Al比值的相关性

纵坐标a值除了Mn/Al比值为1,其他RSE/Al比值为4

, figureFileSmall=6/1Rnu2dX0/zlBCxKhSGvg==, figureFileBig=neh+WwT1G6aiT/dMIBw6Iw==, tableContent=null), ArticleFig(id=1225368262997881546, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=EN, label=Fig. 7, caption=Correlations of bio-barium (Babio) content with TOC content and RSE/Al ratios in the columnar sediments of DYBB27 (dark blue) and DYB228 (blue), figureFileSmall=FRI8dHKn7EpSaKX9UnOEcQ==, figureFileBig=C+LkswvoAZhwlc2W0NUrDw==, tableContent=null), ArticleFig(id=1225368263123710667, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=CN, label=图7, caption=DYBB27(深蓝色)和DYB228(蓝色)柱状沉积物中生源钡(Babio)与TOC含量和RSE/Al比值的相关性, figureFileSmall=FRI8dHKn7EpSaKX9UnOEcQ==, figureFileBig=C+LkswvoAZhwlc2W0NUrDw==, tableContent=null), ArticleFig(id=1225368263249539791, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=EN, label=Fig. 8, caption=Correlation of Mn/Al ratio and RSE/Al ratios in the columnar sediments of DYBB27 (a) and DYB228 (b), figureFileSmall=UmFly5PUW2S58bgPE0ItUQ==, figureFileBig=Dl1deMnKF3SfxNfza08y1g==, tableContent=null), ArticleFig(id=1225368263383757522, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=CN, label=图8, caption=DYBB27 (a)和DYB228 (b)柱状沉积物中Mn/Al比值和RSE/Al比值的相关性, figureFileSmall=UmFly5PUW2S58bgPE0ItUQ==, figureFileBig=Dl1deMnKF3SfxNfza08y1g==, tableContent=null), ArticleFig(id=1225368263497003732, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=EN, label=Fig. 9, caption=Correlations of Babio content and MnO/Al2O3 ratio, figureFileSmall=tAvTNOemQe8hBcyQ8rqAFQ==, figureFileBig=6rQ9vhsGH9H4BzAiKkOdoQ==, tableContent=null), ArticleFig(id=1225368263614444246, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=CN, label=图9, caption=Babio含量和MnO/Al2O3比值的相关性, figureFileSmall=tAvTNOemQe8hBcyQ8rqAFQ==, figureFileBig=6rQ9vhsGH9H4BzAiKkOdoQ==, tableContent=null), ArticleFig(id=1225368263740273368, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=EN, label=Fig. 10, caption=Distribution of Ni/Co and V/Cr ratios in columnar sediments of DYBB27 and DYB228

Other data are quoted from reference [89]

, figureFileSmall=dQz6qcLoEYJJZkHMq31oDA==, figureFileBig=ZR+UZgLOR5E004nnvfFDkg==, tableContent=null), ArticleFig(id=1225368263857713881, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=CN, label=图10, caption=DYBB27和DYB228柱状沉积物中Ni/Co和V/Cr比值分布

其他数据引自文献[89]

, figureFileSmall=dQz6qcLoEYJJZkHMq31oDA==, figureFileBig=ZR+UZgLOR5E004nnvfFDkg==, tableContent=null), ArticleFig(id=1225368263966765786, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=EN, label=Fig. 11, caption=Correlation of V/(V+Ni) and Mn/(Al×10) ratios in columnar sediments of DYBB27 and DYB228, figureFileSmall=BReuMujMhUM2BVoB8zKqig==, figureFileBig=32md9LSxFQ5Os/6ml9E4xA==, tableContent=null), ArticleFig(id=1225368264038068955, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=CN, label=图11, caption=DYBB27和DYB228柱状沉积物中V/(V+Ni) 和Mn/(Al×10) 比值的相关性, figureFileSmall=BReuMujMhUM2BVoB8zKqig==, figureFileBig=32md9LSxFQ5Os/6ml9E4xA==, tableContent=null), ArticleFig(id=1225368264130343645, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=EN, label=Table 1, caption=

Comparison of AMS14C dating data of sediments from different drillings in the South Central Okinawa Trough

, figureFileSmall=null, figureFileBig=null, tableContent=
样品编号纬度经度水深/m深度/cm距今平均校正年龄/(cal a)参考文献
DYBB2726.196 9°N125.233 8°E1 32329~30140本研究
DYB22826.866 3°N125.955 0°E1 27729~3067.5本研究
MD01240426.656 7°N125.820 8°E1 39714.5749文献[39]
OKT-326.018 0°N125.282 0°E1 792281 090文献[40]
OKI-15126.110 0°N125.520 0°E2 013301 135文献[41]
A727.817 2°N126.968 6°E1 26432~362 690文献[42]
C1428.659 7°N127.320 0°E1 10035~37.5673文献[43]
Oki0226.073 6°N125.200 7°E1 61252~542 891文献[44]
OKT12-226.050 0°N125.340 0°E1 924.53573 147.5文献[45]
), ArticleFig(id=1225368264268755679, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=CN, label=表1, caption=

冲绳海槽中南部不同钻孔沉积物的AMS14C测年数据对比

, figureFileSmall=null, figureFileBig=null, tableContent=
样品编号纬度经度水深/m深度/cm距今平均校正年龄/(cal a)参考文献
DYBB2726.196 9°N125.233 8°E1 32329~30140本研究
DYB22826.866 3°N125.955 0°E1 27729~3067.5本研究
MD01240426.656 7°N125.820 8°E1 39714.5749文献[39]
OKT-326.018 0°N125.282 0°E1 792281 090文献[40]
OKI-15126.110 0°N125.520 0°E2 013301 135文献[41]
A727.817 2°N126.968 6°E1 26432~362 690文献[42]
C1428.659 7°N127.320 0°E1 10035~37.5673文献[43]
Oki0226.073 6°N125.200 7°E1 61252~542 891文献[44]
OKT12-226.050 0°N125.340 0°E1 924.53573 147.5文献[45]
), ArticleFig(id=1225368264423944929, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=EN, label=Table 2, caption=

Correlation analysis of RSE/Al ratio and particle size in the columnar sediments of DYBB27 and DYB228

, figureFileSmall=null, figureFileBig=null, tableContent=
样品指标U/AlV/AlCr/AlNi/AlCo/AlCu/AlFe/AlMn/Al
注:**表示在0.01级别(双尾),相关性显著;*表示在0.05级别(双尾),相关性显著。
DYBB27平均粒径−0.177−0.2830.067−0.0920.285−0.1140.140−0.079
砂粒径0.442*0.281−0.0370.036−0.393*−0.005−0.384*−0.018
粉砂粒径−0.607**−0.196−0.0530.0340.369*0.1980.539**0.129
黏土粒径0.175−0.1250.114−0.0890.058−0.240−0.166−0.137
DYB228平均粒径0.554**−0.198−0.416*−0.245−0.069−0.216−0.335−0.056
砂粒径−0.1000.1280.016−0.203−0.240−0.1930.034−0.259
粉粒粒径−0.440*0.0420.424*0.517**0.375*0.508**0.3400.390*
黏土粒径0.748**−0.197−0.635**−0.538**−0.291−0.027−0.532**−0.293
), ArticleFig(id=1225368264491053795, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=CN, label=表2, caption=

DYBB27和DYB228柱状沉积物RSE/Al比值与粒径的相关性分析

, figureFileSmall=null, figureFileBig=null, tableContent=
样品指标U/AlV/AlCr/AlNi/AlCo/AlCu/AlFe/AlMn/Al
注:**表示在0.01级别(双尾),相关性显著;*表示在0.05级别(双尾),相关性显著。
DYBB27平均粒径−0.177−0.2830.067−0.0920.285−0.1140.140−0.079
砂粒径0.442*0.281−0.0370.036−0.393*−0.005−0.384*−0.018
粉砂粒径−0.607**−0.196−0.0530.0340.369*0.1980.539**0.129
黏土粒径0.175−0.1250.114−0.0890.058−0.240−0.166−0.137
DYB228平均粒径0.554**−0.198−0.416*−0.245−0.069−0.216−0.335−0.056
砂粒径−0.1000.1280.016−0.203−0.240−0.1930.034−0.259
粉粒粒径−0.440*0.0420.424*0.517**0.375*0.508**0.3400.390*
黏土粒径0.748**−0.197−0.635**−0.538**−0.291−0.027−0.532**−0.293
), ArticleFig(id=1225368264574939877, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=EN, label=Table 3, caption=

Correlation analysis of RSE/Al ratios with TOC and BaBio in the columnar sediments of DYBB27 and DYB228

, figureFileSmall=null, figureFileBig=null, tableContent=
样品指标Babio含量/10−6U/AlV/AlCr/AlNi/AlCo/AlCu/Al
注:**表示在0.01级别(双尾),相关性显著;*表示在0.05级别(双尾),相关性显著。
DYBB27TOC含量/%0.147−0.093−0.014−0.0530.1000.182−0.036
Babio含量/10−61−0.0170.686**0387*0.844**0.749**0.248
DYB228TOC含量/%0.206−0.427*0.501**0.1950.0390.3600.447*
Babio含量/10−61−0.282−0.3120.0680.759**0.858**0.383*
), ArticleFig(id=1225368264730129127, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=CN, label=表3, caption=

DYBB27和DYB228柱状沉积物RSE/Al比值与TOC和Babio的相关性分析

, figureFileSmall=null, figureFileBig=null, tableContent=
样品指标Babio含量/10−6U/AlV/AlCr/AlNi/AlCo/AlCu/Al
注:**表示在0.01级别(双尾),相关性显著;*表示在0.05级别(双尾),相关性显著。
DYBB27TOC含量/%0.147−0.093−0.014−0.0530.1000.182−0.036
Babio含量/10−61−0.0170.686**0387*0.844**0.749**0.248
DYB228TOC含量/%0.206−0.427*0.501**0.1950.0390.3600.447*
Babio含量/10−61−0.282−0.3120.0680.759**0.858**0.383*
), ArticleFig(id=1225368264860152554, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=EN, label=Table 4, caption=

Correlation analysis of RSE/Al ratios with Fe/Al and Mn/Al ratios in the columnar sediments of DYBB27 and DYB228

, figureFileSmall=null, figureFileBig=null, tableContent=
站位指标U/AlV/AlCr/AlNi/AlCo/AlCu/Al
注:**表示在0.01级别(双尾),相关性显著;*表示在0.05级别(双尾),相关性显著。
DYBB27Fe/Al−0.677**−0.181−0.006−0.1260.0320.053
Mn/Al−0.2480.666**0.2740.972**0.821**0.361
DYB228Fe/Al−0.672**0.391*0.442*0.153−0.1390.299
Mn/Al−0.333−0.2290.0890.896**0.901**0.529**
), ArticleFig(id=1225368264939844331, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1225012183843619429, language=CN, label=表4, caption=

DYBB27和DYB228柱状沉积物RSE/Al比值与Fe/Al和Mn/Al比值的相关性分析

, figureFileSmall=null, figureFileBig=null, tableContent=
站位指标U/AlV/AlCr/AlNi/AlCo/AlCu/Al
注:**表示在0.01级别(双尾),相关性显著;*表示在0.05级别(双尾),相关性显著。
DYBB27Fe/Al−0.677**−0.181−0.006−0.1260.0320.053
Mn/Al−0.2480.666**0.2740.972**0.821**0.361
DYB228Fe/Al−0.672**0.391*0.442*0.153−0.1390.299
Mn/Al−0.333−0.2290.0890.896**0.901**0.529**
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冲绳海槽中南部柱状沉积物氧化还原敏感元素赋存机理与环境指示意义
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许晓燕 1, 2 , 窦衍光 2, 3, * , 张勇 2, 4 , 陈晓辉 2, 4 , 孙治雷 2, 4 , 白凤龙 2, 4 , 翟滨 2, 4 , 王利波 2, 4 , 邹亮 2, 4
海洋学报 | 论文 2022,44(10): 63-79
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海洋学报 | 论文 2022, 44(10): 63-79
冲绳海槽中南部柱状沉积物氧化还原敏感元素赋存机理与环境指示意义
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许晓燕1, 2 , 窦衍光2, 3, * , 张勇2, 4, 陈晓辉2, 4, 孙治雷2, 4, 白凤龙2, 4, 翟滨2, 4, 王利波2, 4, 邹亮2, 4
作者信息
  • 1.中国地质大学(武汉) 海洋学院,湖北 武汉 430074
  • 2.中国地质调查局青岛海洋地质研究所,山东 青岛 266237
  • 3.青岛海洋科学与技术试点国家实验室 海洋地质过程与环境功能实验室,山东 青岛 266237
  • 4.青岛海洋科学与技术试点国家实验室 海洋矿产资源评价与探测技术功能实验室,山东 青岛 266237
  • 许晓燕(1997-),女,广东省汕头市人,主要从事海洋地质研究。E-mail:

通讯作者:

窦衍光(1979-),男,研究员,主要从事海洋沉积地球化学研究。E-mail:
Occurrence mechanism of redox sensitive elements in columnar sediments in South Central Okinawa Trough and their environmental implications
Xiaoyan Xu1, 2 , Yanguang Dou2, 3, * , Yong Zhang2, 4, Xiaohui Chen2, 4, Zhilei Sun2, 4, Fenglong Bai2, 4, Bin Zhai2, 4, Libo Wang2, 4, Liang Zou2, 4
Affiliations
  • 1. College of Marine Science and Technology, China University of Geosciences (Wuhan), Wuhan 430074, China
  • 2. Qingdao Institute of Marine Geology, China Geological Survey, Qingdao 266237, China
  • 3. Laboratory for Marine Geology, Pilot National Laboratory for Marine Science and Technology (Qingdao), Qingdao 266237, China
  • 4. Laboratory for Marine Mineral Resource, Pilot National Laboratory for Marine Science and Technology (Qingdao), Qingdao 266237, China
出版时间: 2022-10-01 doi: 10.12284/hyxb2022186
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沉积物中氧化还原敏感元素(Redox Sensitive Element,RSE)含量变化是上覆水体氧化还原环境良好的替代指标。本文通过冲绳海槽中南部两个柱状沉积物(深度:30 cm)粒度、总有机碳、总氮及其同位素含量和氧化还原敏感元素含量等指标,探究复杂环境背景下冲绳海槽柱状沉积物中RSE的赋存机理与环境指示意义。研究发现,柱状沉积物中除了Cr亏损,其他RSE均显示有不同程度的富集。“粒控效应”对冲绳海槽柱状沉积物的RSE含量影响较小;分析可知,海水表层生产力是影响沉积物氧化还原环境的主要因素,通过Mn(氢)氧化物的吸附或解吸附作用实现RSE的富集与亏损。δCe、V/Cr、Ni/Co和V/(V+Ni)等指标指示沉积物整体处于氧化−弱氧化环境。沉积物中Mn元素通过还原作用以Mn2+形式向上扩散,在25~30 cm处被含氧间隙水氧化富集形成锰峰,指示柱状沉积物0~25 cm处为氧化环境,25~30 cm处为弱氧化环境。

环境指示意义  /  氧化还原敏感元素  /  Mn(氢)氧化物  /  柱状沉积物  /  冲绳海槽

Changes in the content of redox sensitive elements (RSE) in sediments are good surrogate indicators for the redox environment of the overlying water. The RSE in the columnar sediments under complex environmental backgrounds through the grain size, total organic carbon and total nitrogen and its isotopes contents, and redox sensitive elements contents of the two columnar sediments (30 cm) in South Central Okinawa Trough are explored in this paper. And to explore the occurrence mechanism and environmental indication significance. The study found that in addition to the depletion of Cr in the columnar sediments, other RSEs showed different degrees of enrichment. The “grain size effect” has little effect on the RSE content of columnar sediments in the Okinawa Trough; analysis and judgment show that seawater surface productivity is the main factor affecting the redox environment of sediments, and RSE is achieved through the adsorption or desorption of Mn (hydrogen) oxides enrichment and loss. Indicators such as δCe, V/(V+Ni), Ni/Co and V/Cr indicate that the sediment is in an oxic-dysoxic water environment. The Mn element in the sediment diffuses upward in the form of Mn2+ through reduction, and is oxidized and enriched by oxygen-containing interstitial water at 25−30 cm to form a manganese peak. The 0−25 cm columnar sediment is in an oxic water column, and 25−30 cm is in a dysoxic water column.

environmental implications  /  redox sensitive element  /  Mn (hydrogen) oxide  /  columnar sediments  /  Okinawa Trough
许晓燕, 窦衍光, 张勇, 陈晓辉, 孙治雷, 白凤龙, 翟滨, 王利波, 邹亮. 冲绳海槽中南部柱状沉积物氧化还原敏感元素赋存机理与环境指示意义. 海洋学报, 2022 , 44 (10) : 63 -79 . DOI: 10.12284/hyxb2022186
Xiaoyan Xu, Yanguang Dou, Yong Zhang, Xiaohui Chen, Zhilei Sun, Fenglong Bai, Bin Zhai, Libo Wang, Liang Zou. Occurrence mechanism of redox sensitive elements in columnar sediments in South Central Okinawa Trough and their environmental implications[J]. Haiyang Xuebao, 2022 , 44 (10) : 63 -79 . DOI: 10.12284/hyxb2022186
海洋氧化还原环境研究已成为当前全球变化和国际海洋学研究的一个重要领域[1-3]。海水中溶解氧(Dissolved Oxygen,DO)含量直接关系着海洋生态系统的稳定,与生物的生存与进化息息相关[4]。根据DO含量的不同,沉积环境可分为有氧环境(DO含量>2 ml/L)、弱氧化环境(0.2 ml/L<DO含量<2 ml/L)、缺氧环境(不含DO)或者硫化环境(不含DO,含有H2S)[5-6]。在不同的氧化还原条件下,氧化还原敏感元素(Redox Sensitive Element,RSE)在孔隙水和沉积物之间不断交换,导致沉积物中RSE相对富集或亏损[7]。因此,海洋沉积物中RSE的含量变化可提供有关底层水氧化还原条件的信息。
自1925年Schmidt首次在开阔大洋中层水中发现低氧现象后,许多学者对大陆架近岸海域、河口区等浅水海域以及大洋低氧区的氧化还原沉积环境开展了研究[8-11]。河口和近岸海域低氧区数量和面积快速增多,人类活动造成的陆源输入增加和水体富营养化,被认为是低氧面积扩大的关键因素[8, 12- 13]
利用沉积物RSE的含量变化来研究现代和古海洋氧化还原环境演化已经成为常用的研究手段[14-16]。通常在氧化情况下,RSE以易溶的离子形式存在,当水体氧气降低时,离子被还原成溶解度较低的物质富集于沉积物中[3, 6]。大部分RSE(U、V、Cr、Ni、Cu和Zn等)在弱氧化−缺氧沉积环境富集,Mo在硫化环境富集;Ni、Cu、Zn在硫化环境下还会形成自生硫化物矿物富集到沉积物中[17-20]。然而,在边缘海沉积物中,RSE富集水平并不是受氧化环境的单一影响,也受其他因素的影响,包括沉积粒度、生物扰动、成岩作用、海水表层生产力、Fe-Mn(氢)氧化物循环和陆源输入等[6, 21]。沉积物粒度和有机质的吸附或络合作用、沉积物早期成岩作用和Fe-Mn(氢)氧化物循环的吸附或捕获作用都可能影响沉积物中RSE富集程度[22-24];除此以外,海水表层生产力和陆源输入影响海水有机质的通量,有机质降解耗氧也能间接影响水体的氧化还原环境[20, 25- 26]。因此,RSE的波动有时不能反映原始上覆水体氧化还原环境的变化[25, 27]
冲绳海槽是连接东海陆架和西太平洋的重要过渡带,水文和环流体系相当复杂,其中黑潮流系、黄东海暖流系统以及与太平洋的水体交换都会影响冲绳海槽底层水的通风状况[28-30],同时陆源有机质的输入以及海水表层生产力的变化都会影响水体中溶解氧含量,使得冲绳海槽底层水氧化还原环境非常复杂[31]。目前,关于冲绳海槽沉积物中氧化还原敏感元素的赋存机理与控制因素还不清楚。本文以冲绳海槽中南部两个表层柱状样(30 cm)为研究对象,通过沉积物粒度、总有机碳(Total Organic Carbon, TOC)、总氮(Total Nitrogen, TN)及其同位素含量和氧化还原敏感元素含量等指标,分析RSE垂向变化特征和控制因素,探究复杂环境背景下冲绳海槽柱状沉积物中RSE的赋存机理与环境指示意义。
柱状样DYBB27(26.196 9°N,125.233 8°E)和DYB228(26.866 3°N,125.955 0°E)位于冲绳海槽中南部,水深分别为1 323 m和1 277 m(图1)。柱状样沉积物主要由灰黑色粉砂质黏土组成,含水量低,呈块状结构,个别层位可见生物贝壳。
两个柱状样DYBB27和DYB228分别以每样1 cm间隔取样,各取得30个样品,分别对沉积物样品进行粒度、总有机碳、总氮及其同位素含量和常微量元素含量测试。同时,每个柱状样各取1个有孔虫样品进行AMS14C测年。
AMS14C:在每个柱状样底部29~30 cm处挑取有孔虫样品开展AMS14C测试。将沉积样品测定年龄减去碳库效应年龄即为样品碳库校正年龄,利用程序将碳库校正年龄校准为1950年前的日历年龄,引用计算误差为 1 sigma(1σ)(误差范围为±30 cal a BP),预期值和测量值之间的误差在2 sigma(2σ)以内(误差范围为±60 cal a BP)。该检测由美国Beta实验室完成。
粒度测定:取样间距为1 cm,两个柱状样各取30个样品进行粒度测试分析。首先将0.3~0.6 g样品放入烧杯中,先后加入10 mL 10% H2O2和10 mL 10% HCl除去有机质和钙质成分,静置12 h以上,慢慢倒掉上部液体,加入10 mL 30%的六偏磷酸钠充分分散样品颗粒,并将烧杯放置于超声振荡器上振荡15 min,最后上机测量。使用激光粒度分析仪(型号Mastersizer 2000,英国Malvern)测定,该仪器的测量范围为0.02~2 000 μm,偏差小于1%,重现性:Φ50偏差小于1%。该实验在自然资源部第三海洋研究所实验室完成。
总有机碳、总氮含量测试:取样间距为1 cm,两个柱状样各取30个样品。取一定量的沉积物样品,加入4 mol/L盐酸至过量,反应24 h,用去离子水洗至中性,置于60℃烘箱内烘干,恒重后称量,研磨成粉末后过筛(60目)。准确称量10 mg粉末样品,用4 mm×6 mm锡杯包样,使用元素分析仪(型号:Vario EL Ⅲ,德国Elementar)测定沉积物中总有机碳、总氮含量,测量结果以百分含量(%)表示,测量误差均在小于0.05%标准偏差范围内。该实验在自然资源部第三海洋研究所实验室完成。
δ13C和δ15N测试:取适量上述酸化的样品,使用有机元素分析仪—稳定同位素质谱仪联机(型号Flash EA 1112 HT-Delata V Advantages,美国Thermo)测定,测试精度为±0.2‰。δ13C值以VPDB国际标准作为参考标准,计算公式为
$ \delta^{13}{\rm{C}}_{{\rm{TOC}}}(\text{‰})=[R(^{13}{\rm{C}}/^{12}{\rm{C}}_{{\rm{sample}}})/R(^{13}{\rm{C}}/^{12}{\rm{C}}_{{\rm{VPDB}}})-1]\times 1\;000\text{,} $
式中,R13C/12Csample)为样品的碳同位素丰度比值;R13C/12CVPDB)为国际标准物VPDB(Vienna Peedee Belemnite)的碳同位素丰度比值。
δ15N值以空气中氮气作为参考标准,计算公式为
$ {\delta}^{15}{\rm{N}}(\text{‰})=[R(^{15}{\rm{N}}/^{14}{\rm{N}}_{{\rm{sample}}})/R(^{15}{\rm{N}}/^{14}{\rm{N}}_{{\rm{Air}}}) -1]\times 1\;000\text{,} $
式中,R15N/14Nsample)为样品的氮同位素丰度比值;R15N/14NAir)为空气中氮气的氮同位素丰度比值。该实验在自然资源部第三海洋研究所实验室完成。
常微量元素测定:取样间距为1 cm,两个柱状样各取30个样品。精确称量50 mg沉积物样品,各加入1.5 mL HNO3和HF,在190~200℃环境下消解48 h,然后定容至50 g,上机测试。使用电感耦合原子发射光谱仪(ICP-AES)(型号IRIS Advantage,美国)测定样品中Al2O3、Fe2O3、MgO、CaO、K2O、Na2O、MnO、TiO2、P2O5常量元素的含量,用多接收器等离子体质谱(MC-ICP-MS)(型号Agilent 7500a,德国) 仪器测定U、V、Cr、Zn、Cu、Co、Ni等微量元素的含量。此次常量元素分析中使用国家标样(GSR5、GSR6、GSR9)及空白样进行校正。微量元素分析测试分析中使用国家标样(AGV-2、BHVO-2、BCR-2、RGM-2)进行校正。该实验在同济大学海洋地质国家重点实验室完成。
利用沉积物中δ13C值计算陆源和海洋自生有机质来源的比例,计算公式为
$ \delta ^{13}{\rm{C_{measured}}}=f_{\rm{t}}\delta^{13}{\rm{C_{terrestrial}}}+f_{\rm{m}} \delta^{13}{\rm{C_{marine}}}\text{,} $
式中,ft为陆源输入有机质占总有机质的比例;fm为海洋自生有机质占总有机质的比例,ft+fm=1;δ13Cterrestrial和δ13Cmarine分别为陆源输入和海洋自生有机质的δ13C端元值,计算中分别取−27‰和−20‰[32]
为了排除陆源输入的影响,用标准化元素Al,通过(RSE/Al)sample来评估沉积物中RSE的来源和贡献,剔除非自生部分的影响[21, 33]
通过沉积物中的Al含量来估算陆源钡,从而得出沉积物中生源钡(bio-barium, 简称Babio)的含量,计算公式为
$ \rm Ba_{bio}=Ba_{total}-(Al\times Ba/Al_{alusilicate})\text{,} $
式中,Batotal为总Ba含量,这个公式假设沉积物中所有的铝都是来自铝硅酸盐;Ba/Alalusilicate = 0.007 5,用于估计陆壳Ba的丰度[34]
富集系数是元素分析中的重要参数,可以用来反映沉积物中元素的含量相对于标准背景值的富集程度。计算公式为
$ {\rm{X}}_{{\rm{EF}}}=({\rm{X}}/{\rm{Al}})_{{\rm{sample}}}/({\rm{X}}/{\rm{Al}})_{{\rm{std}}}\text{,}$
式中,(X/Al)sample为测试样品的元素比;(X/Al)std为所选参考标准样品的元素比,选取后太古宙澳大利亚平均页岩(Post-Archean Average Australian Shale,PAAS)的元素比来替代平均页岩值,其中,XEF<1表示亏损,XEF>1显示富集,XEF>3明显富集,XEF>10则属中−强烈富集[21, 33]
铈异常(δCe)用PAAS进行标准化,计算公式[35-36]
$ \delta {\rm{Ce}}=\frac{{{\rm{Ce}}}_{样品}/{\rm{Ce}}_{标准物质}}{\sqrt{({{\rm{La}}}_{样品}/{{\rm{La}}}_{标准物质}) \times {({\rm{Pr}}}_{样品}/{\rm{Pr}}_{标准物质})}} \text{,} $
式中,Ce样品、La样品和Pr样品为样品中稀土元素铈、镧和镨的含量;Ce标准物质、La标准物质和Pr标准物质为PAAS标准物质中稀土元素铈、镧和镨含量。
自生铀(authigenic uranium, 简称Uauth)含量计算公式为[37]
$ \rm U_{auth}=U-Th/3, $
式中,U为样品中微量元素铀的含量;Th为样品中微量元素钍的含量。
通过AMS14C测年结果知,DYBB27和DYB228柱状沉积物29~30 cm处校正后,底部年龄分别为距今140 cal a和距今67.5 cal a,根据计算可知,两个柱状沉积物的沉积速率分别约为0.214 cm/a和0.444 cm/a。
DYBB27柱状沉积物中黏土组分(粒度:0~4 μm)的含量范围为16.79%~26.24%,平均含量为20.81%;粉砂组分(粒度:4~63 μm)的含量范围为65.34%~77.04%,平均含量为73.08%;砂组分(粒度:63~2 000 μm)的含量在0~11.23%之间,平均含量为6.11%;平均粒径值集中在6.44 Φ~7.26 Φ之间(Φ=−log2dd为颗粒直径,单位:mm)。DYB228柱状沉积物中黏土组分的含量范围为16.95%~25.77%,平均含量为21.96%;粉砂组分的含量范围为63.65%~77.03%,平均含量为69.77%;砂组分的含量变化较大,在4.16%~15.13%之间,平均含量为8.27%;平均粒径值集中在6.31 Φ~6.92 Φ之间。两个柱状沉积物平均粒径波动情况相似,在表层0~15 cm波动较小,在15~30 cm波动较大,且都是粉砂的含量占优势,黏土次之,砂最低,具体如图2所示。根据谢帕德分类方法[38],DYBB27柱状沉积物30个样品中,主要为黏土质粉砂(21个)和粉砂(9个)这两种类型,粉砂集中在15~26 cm之间;DYB228主要为黏土质粉砂(27个)和粉砂(3个),粉砂出现在20~24 cm之间。
DYBB27和DYB228柱状沉积物TOC含量、TN含量、δ13C值、δ15N值、海洋自生有机质组分占比(fm)的垂向特征如图2所示,变化趋势相似。DYBB27柱状沉积物中TOC含量的变化范围为0.39%~1.35%,平均值为1.04%;TN含量的变化范围为0.06%~0.18%,平均值为0.15%;δ13C值的变化范围为−30.08‰~−21.14‰,平均值为−22.05‰,在5 cm处出现异常低值−30.08‰;δ15N值的变化范围为−2.90‰~5.36‰,平均值为1.35‰;根据δ13C值计算沉积物中海洋自生有机质组分来源的占比,变化范围为0~83.74%,平均值为72.24%。DYB228柱状沉积物中TOC含量的变化范围为0.35%~1.45%,平均值为1.07%;TN含量的变化范围为0.06%~0.19%,平均值为0.14%;δ13C值的变化范围为−23.23‰~−20.11‰,平均值为−21.66‰;δ15N值的变化范围为−0.71‰~6.04‰,平均值为2.62‰;根据δ13C值计算沉积物中海洋自生有机质组分来源的占比,变化范围为53.93%~98.40%,平均值为76.31%。
DYBB27柱状沉积物U/(Al×103)、V/(Al×104)、Cr/(Al×104)、Ni/(Al×104)、Co/(Al×104)、Cu/(Al×104)、Fe/(Al×103)、Mn/(Al×10)的变化范围分别为3.27~4.55、15.52~16.78、10.01~10.93、5.83~7.27、1.66~2.65、4.00~4.55、4.80~5.67、6.53~122.94;DYB228柱状沉积物U/(Al×103)、V/(Al×104)、Cr/(Al×104)、Ni/(Al×104)、Co/(Al×104)、Cu/(Al×104)、Fe/(Al×103)、Mn/(Al×10)的变化范围分别为3.16~4.87、15.91~17.18、9.92~10.45、6.47~8.49、1.87~3.41、4.47~5.84、4.88~5.54、7.35~95.69。其垂向变化特征如图3所示。
DYBB27柱状沉积物U、V、Cr、Ni、Co、Cu、Fe和Mn的富集系数变化范围分别为1.06~1.47、1.03~1.12、0.91~0.99、1.06~1.32、0.72~1.15、0.80~0.91、0.96~1.13、0.77~14.46;DYB228柱状沉积物U、V、Cr、Ni、Co、Cu、Fe和Mn的富集系数变化范围分别为1.02~1.57、1.06~1.15、0.90~0.95、1.18~1.54、0.81~1.48、0.89~1.17、0.98~1.11、0.87~11.26。其垂向变化特征如图4所示。
整体而言,两个站位的RSE/Al和RSEEF的变化趋势相似,除了Cr,其他RSE均显示有富集现象;最显著的特征是底部25~30 cm处均出现锰含量峰值,约为表层含量的14倍,两个柱状沉积物的富集系数分别为14.46和11.26,属中−强烈富集,在相对应的层位,其他RSE/Al和RSEEF值有一定的增高。
DYBB27和DYB228柱状沉积物中氧化还原指标变化如图5所示,两者垂向变化趋势相似。DYBB27柱状沉积物中δCe(PAAS标准化)的变化范围为0.92~0.98,Uauth的变化范围为−1.92~−0.79,U/Th的变化范围为0.19~0.27,V/(V+Ni)的变化范围为0.69~0.73,Ni/Co的变化范围为2.41~3.50,V/Cr的变化范围1.49~1.61。
DYB228柱状沉积物中δCe的变化范围为0.92~0.97,Uauth的变化范围为−1.79~−0.51,U/Th的变化范围为0.19~0.29,V/(V+Ni)的变化范围为0.66~0.72,Ni/Co的变化范围为2.49~3.61,V/Cr的变化范围1.56~1.68。
为验证本文测年结果的可靠性,将测年结果与冲绳海槽中南部周边已发表的AMS14C测年钻孔数据进行对比,结果如表1所示。DYBB27和DYB228柱状样29~30 cm处距今年龄分别为140 cal a和67.5 cal a,与其他孔同深度对比发现,本研究获得的年龄比周边孔小得多。研究区域周边钻孔在相同层位年龄数据相近,底部距今年龄平均值在1 000 cal a以上,这表明本文的测年数据可能并不准确,因此,本测年结果对于DYBB27和DYB228这两个柱状样的年代框架构建参考意义不大。而通过3.3节和3.4节图3图5两个站位的RSE含量和比值的垂向变化趋势较为一致推测,DYBB27和DYB228柱状沉积物为同时期的沉积物,沉积环境相似,在后续论述中一并讨论。
DYBB27和DYB228两个柱状样整体上以细颗粒沉积物为主,指示了相对低能的沉积环境;以往物源研究表明,现今冲绳海槽细颗粒沉积物以台湾河流沉积物为主,部分来自中国大陆[46-48]。沉积物中元素的含量因吸附作用,受粒径组分和大小的变化而呈现出有规律的变化,即元素含量受“粒控效应”影响[49]。这种现象在两柱状样沉积物RSE含量中也有体现,可能原因是随着粒径变细,沉积物中的黏土矿物组分、有机质组分、Fe-Mn(氢)氧化物组分增加,对RSE的吸附作用增强,RSE含量也随之增加[50]
将DYBB27和DYB228柱状沉积物RSE/Al比值与沉积物粒度组分进行相关性分析,分析结果如表2所示。结果发现,在DYBB27和DYB228柱状沉积物中,V/Al比值与粒径组分均无明显相关性,Co/Al比值均与粉砂组分呈现显著正相关,其他RSE/Al比值在两个样品中存在明显差异。DYBB27沉积物中,U/Al比值与砂组分呈现显著正相关,Fe/Al比值与粉砂组分呈现显著正相关,其他RSE/Al比值(Cr/Al、Ni/Al、Cu/Al和Mn/Al比值)与粒径组分无明显相关性;DYB228沉积物中,U/Al比值与黏土组分呈现显著正相关,Cr/Al、Ni/Al、Cu/Al和Mn/Al比值与粉砂组分呈现显著正相关,而Fe/Al比值与黏土组分呈现显著负相关。其中,RSE/Al比值与粉砂组分存在正相关性的r值在0.369~0.539之间(图6),相关性均较弱。整体而言,沉积物中粉砂组分(4~63 μm)对RSE富集存在一定影响,但“粒控效应”对RSE富集影响不大。有研究发现,冲绳海槽南部陆架和陆坡区多数元素的含量变化范围较大,向海槽方向随沉积物粒径变细,海槽区元素含量相对变化较小,相对稳定[51]。说明“粒控效应”的影响在粒度参数变化大的沉积物中会更为明显,本文中所选择样品本身粒度参数变化不大,反映沉积环境相对稳定,说明“粒控效应”对RSE含量影响不明显。
除了沉积物粒度影响外,冲绳海槽由于陆源输入导致的海水表层生产力变化也会影响沉积物中RSE的富集[25, 52]。DYBB27和DYB228柱状沉积物属于近代沉积,东亚冬季风处于稳定且较弱时期[53-56],海平面跟现今差异很小[57],黑潮主轴稳定在冲绳海槽[39]。沉积物中TOC的埋藏速率在很大程度上受到古海洋生产力的控制。将DYBB27和DYB228柱状沉积物中的RSE/Al比值与TOC含量和生源钡(Babio)含量这两个生产力指标进行相关性分析,结果如表3所示。有研究提出,当沉积物中TOC达到一定含量时(>2%),由于吸附作用影响,TOC与RSE含量存在明显正相关性[33]。本研究中,除了DYB228柱状沉积物中的V和Cu存在弱正相关性,r值分别为0.501和0.447,其他RSE/Al比值与TOC含量没有明显的正相关性,表明有机质吸附或络合作用不是控制研究样品RSE变化的主要因素;且Babio和TOC含量几乎没有相关性(图7a),说明生产力的变化与TOC关系不大,这可能与冲绳海槽有机碳沉降和埋藏过程中的分解作用有关,表层水体中形成的有机碳只有极少部分被保存在海底沉积物中[58-59]。TOC含量主要用于评价近岸、上升流等比较富营养环境的生产力水平变化,开阔外海TOC降解氧化程度高,其含量难以反映生产力的变化[60-61]
海洋沉积物中Babio堆积速率或含量是指示古海洋初级生产力的良好指标[62-64]。尤其在弱氧化和氧化环境中,Babio富集程度与古生产力有一定的正相关性[65]。本研究中,RSE/Al比值和Babio含量相关性显示,Babio含量与Ni/Al和Co/Al在DYBB27和DYB228中均存在显著的正相关关系,r值在0.749~0.858之间(图7b);其他RSE/Al比值与Babio含量在两个站位存在差异,V/Al和Cr/Al比值与Babio含量在DYBB27沉积物中呈显著正相关关系,Cu/Al比值与Babio含量在DYB228沉积物中呈显著正相关关系。表明冲绳海槽中南部沉积物中RSE含量受生产力变化的影响,生产力提高导致大量有机质降解,造成底层水体的低氧。对埃及东北部海相黑色页岩床中的RSE研究有类似的发现,特提斯洋南部存在高产力的上升流导致生产力的提高、有机质再矿化,成为RSE富集的主要因素[20]。此外,阿拉伯海东南部的研究也发现生产力变化是控制南部浅水区氧化还原条件的主导因素,高生产力对应强烈的低氧条件,使得RSE富集[26]
海洋沉积物在堆积埋藏至海底较浅深度的过程中,在沉积颗粒、间隙水以及沉积环境水介质之间发生的一系列物理、化学及生物地球作用的总和即为早期成岩作用[66-67]。有机质的氧化降解是其主要的驱动力[66-67]。在早期成岩作用中,Fe-Mn氧化还原循环对于RSE含量的影响非常重要。沉积物中的Fe和Mn元素受氧化还原条件变化的影响较大[33]。氧化还原敏感元素Mn可作为底水氧化还原环境变化的指标。在弱氧化或缺氧条件下,Mn被还原成Mn2+,从沉积物中浸出;在富氧底水中,Mn又以MnO2的形式沉淀下来[68]。沉积物中Fe(氢)氧化物作为有机质氧化的氧化剂,在弱氧化或缺氧条件下,被还原为Fe2+,Fe2+不稳定,易与其他化学物质HCO3−、HS等反应形成沉淀FeCO3或FeSx,从而保存在沉积物中[69]。Fe-Mn氧化还原循环过程可以影响微量元素的迁移和扩散[18, 70]。在氧化沉积环境中,RSE会被吸附或捕获到Fe-Mn氧化物表面并保存于沉积物中,从而形成RSE与Fe、Mn的正相关关系[33, 71-72]。而当沉积环境处于还原条件时,伴随Fe-Mn氧化物的还原解析,RSE又被重新释放,“清扫”回间隙水中[73]。东海内陆架季节性低氧海区沉积柱中发现RSE/Al比值与Fe/Al和Mn/Al比值具有显著的相关性,指示氧化沉积环境[74]
通过DYBB27和DYB228柱状沉积物中不同元素相关性分析(表4)发现,RSE/Al与Fe/Al比值几乎没有正相关性,仅在DYB228柱状沉积物中与V/Al和Cr/Al表现出正相关性,r值分别为0.391和0.442,表明Fe(氢)氧化物对RSE的吸附或捕获作用的影响很小;RSE/Al(V/Al、Ni/Al、Co/Al和 Cu/Al)比值与Mn/Al比值的正相关性较好(图8),r值在0.529~0.972之间,其中Ni/Al和Co/Al在两个站位均具有较高的相关性,r值在0.821~0.972之间。上层水体溶解态RSE可能是通过与沉积物中Mn(氢)氧化物被捕获或吸附,从而在海洋沉积物中富集,指示整体的氧化沉积环境。王家凯等[75]在南极罗斯海柱状岩心及表层样中同样发现了Ni、Co和Mn同时富集,推测钻孔沉积期为氧化环境,RSE富集是由于锰(氢)氧化物对其捕获或吸附所致。
研究发现DYBB27和DYB228柱状沉积物中,Babio含量和MnO/Al2O3比值都具有明显的正相关性(图9),r值分别为0.830和0.839,说明沉积物中Mn含量与生产力变化密切相关。沉积物间隙水中Fe和Mn主要以扩散的形式在生物扰动层中与水体发生交换,生产力的变化能调节水体中溶解氧(DO)的含量,高Fe、Mn通量指示高生产力的海洋氧化还原环境[76]。生产力的变化会改变水体溶解氧的情况,通过影响间隙水中的Mn通量,来影响进入沉积物中的Mn含量,再通过Mn(氢)氧化物的吸附或还原解析作用来进一步影响RSE在沉积物中的富集程度。且Ni、Cu和Zn作为浮游生物的微量营养元素被浮游生物吸收利用,以有机质为载体进入沉积物中[33]
一般情况下,水体中U6+发生还原作用,变成U4+富集到沉淀中[31]。此时氧化还原电势使得Fe3+还原成易溶的Fe2+,而Fe2+不稳定易被氧化进入沉淀中,因此,Fe与U多呈现出正相关关系[32, 77]。然而,本研究发现,两处沉积物中Fe/Al比值与U/Al比值均呈现负相关关系,r值分别为−0.677和−0.672(表4)。这与常见的研究结果不相符,可能与以下几个原因有关:(1)间隙水中U和Fe含量呈指数负相关关系,这可能使得进入沉积物中的量受限于间隙水中的量而也呈现出负相关关系[69];(2)U对重新氧化作用的响应敏感,容易发生二次氧化[78];(3)U富集受沉积速率的影响,尤其是有机质的沉积速率。当沉积速率较低时,更多的U可以扩散到沉积物中并累积;当深水处于氧化状态且有机质沉降速率较高时,U氧化还原界面可以升高到沉积物−水界面(Sediment Water Interface, SWI)的位置,加速沉积物堆积导致的沉积物中自生铀发生稀释,从而导致该区域的U含量在沉淀中减少,不能反映真实的氧化还原环境[79]。关于U异常的具体原因还有待进一步的研究。
研究发现,RSE易受环境中氧气浓度影响而发生变价,在氧化海水中多以溶解态离子存在,在还原环境中则以低价氧化物、硫化物或有机络合物等形式富集在沉积物中[80-81]。沉积物埋藏之后,RSE几乎不发生迁移,保存了沉积时的组成和含量,所以可以通过计算它们在沉积物或沉积岩中的富集系数来反映出沉积时期的水体氧化还原状态[82-83]。研究发现,除了Cr亏损和Mn在沉积物底部5 cm强烈富集,其他RSE都有不同程度的轻微富集(图4),指示为氧化−弱氧化环境。随着研究的深入,除了单一的RSE含量对环境的指示研究,各学者结合多个RSE,通过综合已有数据进行对比分析,得出一些可以运用的经验。例如,δCe用于衡量Ce相对于La和Pr的分异程度,δCe大于1为正异常,小于1为负异常。变价元素Ce有+3和+4两种价态,其中Ce3+易溶于水,而Ce4+易水解沉淀。在弱氧化或缺氧条件下,以Ce3+形式在水体中稳定存在,Ce异常较弱或不存在;在氧化条件下,Ce3+容易被氧化成溶解度较小的Ce4+,与铁锰铝(氢)氧化物发生共沉淀,此时δCe<1,海水出现Ce负异常现象[84-86]。DYBB27和DYB228柱状沉积物中δCe值变化范围为0.92~0.98(图5),δCe<1,有轻微的Ce负异常,指示氧化−弱氧化环境。
研究发现,沉积物中自生铀(Uauth)和U/Th是判断古海洋氧化还原变化的有效指标。U在氧化条件下以可溶的U6+形式存在,在还原环境下以不溶的U4+富集于沉积物中;Th对氧化还原条件不敏感,以不溶的Th4+形式存在,因此U/Th 值在氧化条件下偏低,此时U/Th<0.75,在缺氧环境中偏高,U/Th>1.25[6, 27]。Wignall和Myers[87]通过测量碎屑沉积物中U和Th含量之间的关系,利用公式Uauth=U–Th/3计算自生铀,认为Uauth小于5×10–6代表氧化环境,大于12×10–6代表缺氧环境,在这之间的值代表弱氧化环境。DYBB27和DYB228柱状沉积物中Uauth变化范围为–1.92~–0.51(图5),都出现异常负值,可能原因具体见4.4节。因此,本研究中U/Th比值对氧化还原沉积环境不具有指示意义,不作讨论。
V在氧化水体中以钒酸根${\rm{HVO}}_4^{2-} $和H2${\rm{VO}}_4^- $的形式存在,在弱还原条件下,V5+被还原为V4+并形成钒酰基VO2+,易与有机金属配位体螯合形成有机络合物或水化物,在缺氧沉积物中富集;Cr在氧化水体中主要以铬酸阴离子${\rm{CrO}}_4^{2-} $的形式存在,在缺氧条件下,Cr6+被还原到Cr3+,可与腐殖酸/富里酸形成复合物,或者吸附于Fe-Mn(氢)氧化物,从而被转移到沉积物中;Ni在氧化环境中主要以溶解的碳酸盐形式(NiCO3)存在或者吸附于腐殖酸/富里酸上,在缺氧环境中,Ni与有机质形成有机络合物可以加速Ni 在沉积物中的富集,硫化环境下Ni以难溶的硫化物形式进入黄铁矿中;相反Co在还原条件下从沉积物中溶解重新进入海水中,使Ni/Co比值增大[33, 88]。水体氧气含量降低时,V、Cr和Ni都是从氧化环境下的溶解态转变为易在还原环境下沉积物中富集的难溶物,因此V/Cr、Ni/Co和V/(V+Ni)比值可作为判别古海洋氧化还原环境的有效参数。Jones和Manning[89]、Tyson和Pearson[90]根据在挪威北海和英国陆上地层获取的193个样品进行RSE含量分析,得出以下经验结论:处于氧化环境的Kimmeridge黏土层和Heather地层以及浅部Draupne地层中,V/Cr<2.00、Ni/Co<5.00,指示富氧环境;大部分地堑深部的Draupne地层沉积形成于永久缺氧的底水环境,此时V/Cr>4.25、Ni/Co>7.00,指示缺氧环境;值在这两者之间则指示弱氧化−弱还原环境。DYBB27和DYB228柱状沉积物中V/Cr的变化范围为1.49~1.68,Ni/Co的变化范围为2.41~3.61,对比上述结论,研究样品V/Cr和Ni/Co比值均指示氧化环境(图10)。Hatch和Leventhal[91]、杨季华等[92]通过对北美黑色页岩的研究得出V/(V+Ni)比值能有效反映沉积环境的氧化还原条件,认为V/(V+Ni)>0.77指示相对还原的沉积环境,V/(V+Ni)<0.6指示相对氧化的沉积环境,介于二者之间则指示弱氧化−弱还原的沉积环境。DYBB27和DYB228柱状沉积物中V/(V+Ni)比值的变化范围为0.66~0.73,据此推测V/(V+Ni)比值指示弱氧化−弱还原环境;且研究发现,在DYBB27和DYB228柱状沉积物中,V/(V+Ni)与Mn/(Al×10)比值均具有很明显的负相关性,r值分别为−0.975和−0.912(图11),表明V/(V+Ni)比值可能与Mn含量所指示的海水表层生产力变化密切相关,而Mn(氢)氧化物的吸附或捕获作用增强可能导致该值偏大。
根据以上RSE比值分析可知,尽管大多数氧化还原敏感元素在还原条件下在海洋沉积物中富集,可以通过多种指标对氧化还原条件进行定性分析,但由于不同指标元素间的反应性、水柱循环、宿主基质的可用性和其他因素存在差异,相对富集率可能会有所不同,含量变化受沉积环境的影响也不同,因此,各示踪指标之间的判别可能出现多解性,指示的沉积环境难免出现一定的差异[92-94]。DYBB27和DYB228柱状沉积物中RSEEF和δCe比值指示氧化−弱氧化环境,V/Cr和Ni/Co比值指示氧化环境,可能偏大的V/(V+Ni)比值指示弱氧化−弱还原环境,结合4.4节可以判断,本研究柱状样沉积环境整体处于氧化−弱氧化环境。
值得注意的是,在浅表层沉积物中,经常观察到Mn的峰值,本研究数据也显示在柱状样25~30 cm处出现Mn的峰值(图3)。Mn在氧化环境下,Mn(氢)氧化物参与有机质的降解过程被还原分解,Mn2+被释放出来,固相中的Mn含量迅速减少。在上部水体处于还原条件时,Mn2+可以扩散进入上覆水中,或者在向上扩散过程中被再次氧化而进入沉积物,在沉积物表层出现Mn的高峰分布[16, 69]。深层的Mn由于还原作用(缺氧环境)被释放出来,之后向上扩散,遇氧化间隙水再次被氧化富集在沉积之中,从而形成Mn的次高峰分布[17]。白海坎达拉克沙湾底部沉积物中也同样出现Mn含量异常高,研究认为是成岩作用的影响:间隙水中的Mn2+含量极高(>500 µmol/L),导致其进入底水,与氧气接触氧化,并合成二氧化锰或氢氧化物,使沉积物表层富集Mn。本研究活跃的成岩氧化还原过程终止于25~30 cm深度,表层沉积物积累的Mn亚稳态残留物易于扩散,使得深层富锰[95]。在Mn峰出现处,发现Co、Ni、Cu和V的含量也相对增多,同样指示了底部水体的氧化−弱氧化环境,与西赤道太平洋的翁通爪哇海台研究相似[96]。本研究认为,Mn在浅表层沉积物中强烈富集,可能与海水生产力提高有关,生产力的变化会改变水体溶解氧的情况,通过影响间隙水中的Mn通量,来影响进入沉积物中的Mn含量[76]。且生产力的提高会导致有机质通量增加,有机质降解耗氧,底部水体进一步发生缺氧现象。
本文基于沉积物粒度、总有机碳、总氮及其同位素和氧化还原敏感元素等指标,通过相关性方法重点分析冲绳海槽中南部柱状沉积物中RSE的赋存机理与环境指示意义,主要结论如下:
(1)冲绳海槽中南部DYBB27和DYB228两个柱状样以细颗粒为主,沉积环境相对稳定,“粒控效应”对RSE富集的影响较小;有机质吸附或络合作用不是RSE变化的主要因素。RSE含量受Fe(氢)氧化物影响较小,而与Mn(氢)氧化物的吸附或捕获作用密切相关。
(2)海水表层生产力变化影响了沉积环境的氧化还原条件,使得Mn(氢)氧化物的吸附或捕获作用增强,进而导致了RSE富集,生产力的提高使得大量有机质降解,造成底层水体的低氧。
(3)DYBB27和DYB228两个柱状样的沉积环境处于氧化−弱氧化环境之间。沉积物中Mn与RSE同时富集,指示整体的沉积环境为氧化环境(0~25 cm)。下部沉积物(25~30 cm)处锰峰的出现指示此处为氧化还原界面,Mn在缺氧环境中发生还原作用,以Mn2+形式向上扩散,遇含氧间隙水发生氧化作用形成MnO2,指示弱氧化环境。
  • 国家自然科学基金(41776077)
  • 国家海洋局国际合作项目(GASI-GEOGEO-04)
  • 中国地质调查局地质调查专项(DD20190205,DD20221710)
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2022年第44卷第10期
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doi: 10.12284/hyxb2022186
  • 接收时间:2022-02-09
  • 首发时间:2026-02-02
  • 出版时间:2022-10-01
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  • 收稿日期:2022-02-09
  • 修回日期:2022-06-22
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国家自然科学基金(41776077)
国家海洋局国际合作项目(GASI-GEOGEO-04)
中国地质调查局地质调查专项(DD20190205,DD20221710)
作者信息
    1.中国地质大学(武汉) 海洋学院,湖北 武汉 430074
    2.中国地质调查局青岛海洋地质研究所,山东 青岛 266237
    3.青岛海洋科学与技术试点国家实验室 海洋地质过程与环境功能实验室,山东 青岛 266237
    4.青岛海洋科学与技术试点国家实验室 海洋矿产资源评价与探测技术功能实验室,山东 青岛 266237

通讯作者:

窦衍光(1979-),男,研究员,主要从事海洋沉积地球化学研究。E-mail:
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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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