Article(id=1200377936680448422, tenantId=1146029695717560320, journalId=1149651085930835976, issueId=1200377931454337399, articleNumber=null, orderNo=null, doi=10.12284/hyxb2023172, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1678204800000, receivedDateStr=2023-03-08, revisedDate=1680105600000, revisedDateStr=2023-03-30, acceptedDate=null, acceptedDateStr=null, onlineDate=1764122001999, onlineDateStr=2025-11-26, pubDate=1711814400000, pubDateStr=2024-03-31, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1764122001999, onlineIssueDateStr=2025-11-26, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1764122001999, creator=13701087609, updateTime=1764122001999, updator=13701087609, issue=Issue{id=1200377931454337399, tenantId=1146029695717560320, journalId=1149651085930835976, year='2024', volume='46', issue='3', pageStart='1', pageEnd='110', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=0, articleOrder=1, issueType=-1, specialIssue=null, createTime=1764122000799, creator=13701087609, updateTime=1764122116527, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1200378416919859276, tenantId=1146029695717560320, journalId=1149651085930835976, issueId=1200377931454337399, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1200378416919859277, tenantId=1146029695717560320, journalId=1149651085930835976, issueId=1200377931454337399, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=33, endPage=53, ext={EN=ArticleExt(id=1200377937057935794, articleId=1200377936680448422, tenantId=1146029695717560320, journalId=1149651085930835976, language=EN, title=Geochemical characteristics of water and soil environment and its environmental indicating significances since the Pleistocene in the northern flank of the Changjiang River Delta, columnId=null, journalTitle=Haiyang Xuebao, columnName=null, runingTitle=null, highlight=null, articleAbstract=

The coastal plain of Jiangsu Province is a fragile zone of water resources in Jiangsu Province, and groundwater salinization has become a serious ecological problem. In order to analyze the groundwater recharge and its salinity sources in the north flank of the Changjiang River Delta since Pleistocene, a 275 m deep well HYRD1 was deployed and the whole hole was continuously collected with easily soluble salt samples, geotechnical samples and water samples. Surface water, shallow and deep groundwater, and seawater samples were collected in the area. The hydrochemical characteristics of Well HYRD1 high-precision porewater were obtained by using soluble salt index combined with geotechnical index (water content, wet density, specific gravity). In order to analyze the groundwater recharge and its salt source since Pleistocene, Piper trilinear diagram, Gibbs diagram and ion ratio method were used in combination with δD and δ18O data and 14C data. The results show that the salinity of Well HYRD1 soil is mainly NaCl, and the percentage of saline soil is 25%. The saline soils are mainly distributed in the Qp3 aquitard, Qp2 stratum and the upper part of Qp1 stratum. The water chemistry type of porewater is Cl-Na type (only the lower section of Qp1 is HCO$_3^- $-Ca·Na at individual points), 7% of brackish water, 49% of saline water and 44% of haline water. The brackish water is mainly distributed in the sand layer of the lower section of Qp1. The δ18O and δD of diving indicate that the source of diving is atmospheric precipitation and is subject to a relatively strong evaporation effect. The δ18O and δD of the aquitard pore water and pressurized water are located near the standard seawater dilution line, and the trend of δ18O and δD decreases with the increase of depth, which indicates that the porewater is subjected to the mixing effect of seawater decreases with the increase of depth. Calcareous nodules are mostly seen in the Qp1 aquitard, indicating that the Qp1 aquitard was subjected to strong evaporation after soil formation. The salinity of the upper part of Well HYRD1 Qp1 and the overlying strata is mainly from the 5th stage sea erosion, evaporite and silicate weathering dissolution. The salinity of the lower part of Qp1 is mainly from the crustal source. The groundwater chemistry is influenced by water-rock action, evaporation concentration and human activities.

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江苏沿海平原是江苏省域水资源脆弱带,地下水咸化已成为较为严重的生态环境问题。为了解析长江三角洲北翼地区更新世以来地下水的补给及其盐分来源,布设一口275 m的深井HYRD1,全孔连续采集易溶盐样品、土工样品、水样。在区域采集地表水、浅层与深层地下水、海水样品。采用易溶盐指标结合土工指标(含水率、湿密度、比重)获取了HYRD1高精度孔隙水的水化学特征。采用Piper三线图、Gibbs图、离子比值法等结合δD、δ18O数据、14C测年数据解析了更新世以来地下水的补给及其盐分来源。结果表明:土体盐分主要为NaCl,盐渍土占比为25%。盐渍土主要分布在Qp3弱透水层、Qp2地层与Qp1上段地层。孔隙水水化学类型为Cl−Na型(仅Qp1下段个别点为${{\rm{HCO}}^-_3}- $$ {\rm{Ca}}\cdot {\rm{Na}}$),微咸水占比7%,咸水占比49%,盐水占比44%。微咸水主要分布在Qp1下段砂层中。潜水的δ18O、δD说明潜水来源为大气降水,且受到了较为强烈的蒸发作用。弱透水层孔隙水、承压水的δ18O、δD投点位于标准海水稀释线附近,且随着深度的增加,δ18O、δD有减小趋势,说明海水混合作用随着深度的增加而减小。Qp1弱透水层多见钙质结核,说明了Qp1地层成土后受到了强烈的蒸发作用。HYRD1 Qp1上段及上覆地层盐分主要来源于5期海侵、蒸发盐岩与硅酸盐风化溶解,Qp1下段地层盐分主要来源为地壳源。地下水化学成分受到了水岩作用、蒸发浓缩作用与人类活动等的影响。

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苟富刚(1985—),男,高级工程师,主要从事特殊土与环境地质方面的研究工作。E-mail:

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苟富刚(1985—),男,高级工程师,主要从事特殊土与环境地质方面的研究工作。E-mail:

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苟富刚(1985—),男,高级工程师,主要从事特殊土与环境地质方面的研究工作。E-mail:

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Statistics and classification of soil layers according to salt content

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层位含盐量/%按含盐量分类统计/%
最小值最大值平均值非盐渍土弱盐渍土
潜水(Qh,粉土、粉质黏土)0.140.170.151000
弱透水层(Qh0.450.450.450100
微承压水(Qh0.160.250.211000
弱透水层(Qp30.200.590.383367
砂层(Qp30.080.240.151000
弱透水层(Qp20.490.580.530100
砂层(Qp20.090.460.267228
弱透水层(Qp1上段)0.200.490.351090
砂层(Qp1上段)0.090.460.26892
弱透水层(Qp1下段)0.060.150.111000
砂层(Qp1下段)0.040.070.051000
), ArticleFig(id=1200377951268237965, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1200377936680448422, language=CN, label=表1, caption=

土层按含盐量统计与分类

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层位含盐量/%按含盐量分类统计/%
最小值最大值平均值非盐渍土弱盐渍土
潜水(Qh,粉土、粉质黏土)0.140.170.151000
弱透水层(Qh0.450.450.450100
微承压水(Qh0.160.250.211000
弱透水层(Qp30.200.590.383367
砂层(Qp30.080.240.151000
弱透水层(Qp20.490.580.530100
砂层(Qp20.090.460.267228
弱透水层(Qp1上段)0.200.490.351090
砂层(Qp1上段)0.090.460.26892
弱透水层(Qp1下段)0.060.150.111000
砂层(Qp1下段)0.040.070.051000
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Statistics and classification of pore water according to mineralization degree

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层位矿化度/(g·L-1)各类型占比/%
最小值最大值平均值微咸水咸水盐水
潜水(Qh,粉土、粉质黏土)4.676.65.71-100-
弱透水层(Qh19.2719.2719.27-0100
微承压水(Qh7.3611.318.88-8614
弱透水层(Qp35.9117.4612.2-5050
I承压水(Qp33.088.536.07-100-
弱透水层(Qp221.2827.6323.9-0100
II承压水(Qp24.9121.2711.37-4555
弱透水层(Qp1上段)8.1618.1413.23-1585
III承压水(Qp1上段)4.3332.4111.44-5050
弱透水层(Qp1下段)2.776.064.362278-
III承压水(Qp1下段)1.783.012.148020-
), ArticleFig(id=1200377951461175953, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1200377936680448422, language=CN, label=表2, caption=

孔隙水按照矿化度统计与分类

, figureFileSmall=null, figureFileBig=null, tableContent=
层位矿化度/(g·L-1)各类型占比/%
最小值最大值平均值微咸水咸水盐水
潜水(Qh,粉土、粉质黏土)4.676.65.71-100-
弱透水层(Qh19.2719.2719.27-0100
微承压水(Qh7.3611.318.88-8614
弱透水层(Qp35.9117.4612.2-5050
I承压水(Qp33.088.536.07-100-
弱透水层(Qp221.2827.6323.9-0100
II承压水(Qp24.9121.2711.37-4555
弱透水层(Qp1上段)8.1618.1413.23-1585
III承压水(Qp1上段)4.3332.4111.44-5050
弱透水层(Qp1下段)2.776.064.362278-
III承压水(Qp1下段)1.783.012.148020-
), ArticleFig(id=1200377951574422163, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1200377936680448422, language=EN, label=Table 3, caption=

Statistical of water chemistry type classification (%)

, figureFileSmall=null, figureFileBig=null, tableContent=
层位Cl-Na-BCl-Na-CCl·HCO3-Na-BCl·SO4-Na-BCl·SO4-Na-CCl·SO4-Na·Ca-B
潜水(Qh,弱透水层)75-25---
弱透水层(Qh-100----
微承压水(Qh7214-14--
弱透水层(Qp35050----
I承压水(Qp3100----
弱透水层(Qp2-100----
II承压水(Qp241554---
弱透水层(Qp1上段)2179----
III承压水(Qp1上段)5046--4-
弱透水层(Qp1下段)56-33--11
III承压水(Qp1下段)20-80---
), ArticleFig(id=1200377951708639892, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1200377936680448422, language=CN, label=表3, caption=

水化学类型划分统计(%)

, figureFileSmall=null, figureFileBig=null, tableContent=
层位Cl-Na-BCl-Na-CCl·HCO3-Na-BCl·SO4-Na-BCl·SO4-Na-CCl·SO4-Na·Ca-B
潜水(Qh,弱透水层)75-25---
弱透水层(Qh-100----
微承压水(Qh7214-14--
弱透水层(Qp35050----
I承压水(Qp3100----
弱透水层(Qp2-100----
II承压水(Qp241554---
弱透水层(Qp1上段)2179----
III承压水(Qp1上段)5046--4-
弱透水层(Qp1下段)56-33--11
III承压水(Qp1下段)20-80---
), ArticleFig(id=1200377951800914581, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1200377936680448422, language=EN, label=Table 4, caption=

Correlation analysis of contents of total dissolved solids (TDS), Cl-, Na+ in porewater with the contents of salt, Cl-, Na+ in the soluble salt index

, figureFileSmall=null, figureFileBig=null, tableContent=
指标土体孔隙水
含盐量Na+Cl-TDSNa+K+Ca2+Mg2+$ {{\rm {HCO}_3^-}}$Cl-$ {{\rm {SO}}_4^{2-}} $
  注: **表示在0.01水平(双侧)上显著相关,发生概率为99%;*表示在0.05水平(双侧)上显著相关,发生概率为95%。
土体含盐量1.000
Na+0.988**1.000
Cl-0.992**0.975**1.000
孔隙水TDS0.798**0.810**0.773**1.000
Na+0.776**0.808**0.747**0.990**1.000
K+0.380**0.369**0.357**0.662**0.621**1.000
Ca2+0.572**0.467**0.615**0.483**0.381**0.214*1.000
Mg2+0.663**0.574**0.674**0.648**0.549**0.570**0.762**1.000
$ {{\rm {HCO}_3^-}}$-0.207*-0.174-0.267**0.0850.1090.044-0.212*-0.299**1.000
Cl-0.843**0.850**0.833**0.989**0.976**0.631**0.542**0.684**-0.0181.000
$ {{\rm {SO}}_4^{2-}}$0.567**0.579**0.498**0.853**0.842**0.674**0.258**0.558**0.1038670.789**1.000
), ArticleFig(id=1200377951901577879, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1200377936680448422, language=CN, label=表4, caption=

孔隙水中的溶解性总固体(TDS)、Cl-、Na+含量与易溶盐指标中的含盐量、Na+、Cl-含量的相关性分析

, figureFileSmall=null, figureFileBig=null, tableContent=
指标土体孔隙水
含盐量Na+Cl-TDSNa+K+Ca2+Mg2+$ {{\rm {HCO}_3^-}}$Cl-$ {{\rm {SO}}_4^{2-}} $
  注: **表示在0.01水平(双侧)上显著相关,发生概率为99%;*表示在0.05水平(双侧)上显著相关,发生概率为95%。
土体含盐量1.000
Na+0.988**1.000
Cl-0.992**0.975**1.000
孔隙水TDS0.798**0.810**0.773**1.000
Na+0.776**0.808**0.747**0.990**1.000
K+0.380**0.369**0.357**0.662**0.621**1.000
Ca2+0.572**0.467**0.615**0.483**0.381**0.214*1.000
Mg2+0.663**0.574**0.674**0.648**0.549**0.570**0.762**1.000
$ {{\rm {HCO}_3^-}}$-0.207*-0.174-0.267**0.0850.1090.044-0.212*-0.299**1.000
Cl-0.843**0.850**0.833**0.989**0.976**0.631**0.542**0.684**-0.0181.000
$ {{\rm {SO}}_4^{2-}}$0.567**0.579**0.498**0.853**0.842**0.674**0.258**0.558**0.1038670.789**1.000
), ArticleFig(id=1200377951985463960, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1200377936680448422, language=EN, label=Table 5, caption=

Fitting equation for the relationship between porewater total dissolved solids (TDS) content and the contents of salt, Na+ and Cl- in the soil

, figureFileSmall=null, figureFileBig=null, tableContent=
层位拟合关系式x相关系数编号
全孔y = 0.011 1x + 2.103 6Na+0.810(4)
全孔y = 0.006 4x + 3.277 4Cl-0.773(5)
全孔y = 36.282x + 1.887 1含盐量0.796(6)
Qhy = 0.007x + 2.136 5Cl-0.883(7)
Qp1y = 0.005 7x + 3.776 4Cl-0.778(8)
Qp1上段y = 0.006 5x + 4.706Cl-0.660(9)
Qp1下段y = 0.006 7x + 1.365Cl-0.937(10)
Qh y = 0.013 5x - 0.333 8Na+0.858(11)
Qp1y = 0.009 9x + 2.465 7Na+0.827(12)
Qp1上段y = 0.011 8x + 3.129 3Na+0.726(13)
Qp1下段y = 0.010 9x + 0.874Na+0.930(14)
Qhy = 39.926x - 0.006 9含盐量0.917(15)
Qp1y = 32.154x + 2.502 3含盐量0.810(16)
Qp1上段y = 37.664x + 3.118 9含盐量0.693(17)
Qp1下段y = 37.693x + 0.209 8含盐量0.998(18)
), ArticleFig(id=1200377952060961434, tenantId=1146029695717560320, journalId=1149651085930835976, articleId=1200377936680448422, language=CN, label=表5, caption=

孔隙水溶解性总固体(TDS)含量与土体中含盐量、Na+、Cl-含量关系拟合式

, figureFileSmall=null, figureFileBig=null, tableContent=
层位拟合关系式x相关系数编号
全孔y = 0.011 1x + 2.103 6Na+0.810(4)
全孔y = 0.006 4x + 3.277 4Cl-0.773(5)
全孔y = 36.282x + 1.887 1含盐量0.796(6)
Qhy = 0.007x + 2.136 5Cl-0.883(7)
Qp1y = 0.005 7x + 3.776 4Cl-0.778(8)
Qp1上段y = 0.006 5x + 4.706Cl-0.660(9)
Qp1下段y = 0.006 7x + 1.365Cl-0.937(10)
Qh y = 0.013 5x - 0.333 8Na+0.858(11)
Qp1y = 0.009 9x + 2.465 7Na+0.827(12)
Qp1上段y = 0.011 8x + 3.129 3Na+0.726(13)
Qp1下段y = 0.010 9x + 0.874Na+0.930(14)
Qhy = 39.926x - 0.006 9含盐量0.917(15)
Qp1y = 32.154x + 2.502 3含盐量0.810(16)
Qp1上段y = 37.664x + 3.118 9含盐量0.693(17)
Qp1下段y = 37.693x + 0.209 8含盐量0.998(18)
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长江三角洲北翼更新世以来的水土环境地球化学特征及其环境指示意义
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苟富刚 1, 2 , 龚绪龙 1, 2 , 刘源 1, 2
海洋学报 | 论文 2024,46(3): 33-53
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海洋学报 | 论文 2024, 46(3): 33-53
长江三角洲北翼更新世以来的水土环境地球化学特征及其环境指示意义
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苟富刚1, 2 , 龚绪龙1, 2, 刘源1, 2
作者信息
  • 1.江苏省地质调查研究院,江苏 南京 210049
  • 2.自然资源部地裂缝地质灾害重点实验室,江苏 南京 210049
  • 苟富刚(1985—),男,高级工程师,主要从事特殊土与环境地质方面的研究工作。E-mail:

Geochemical characteristics of water and soil environment and its environmental indicating significances since the Pleistocene in the northern flank of the Changjiang River Delta
Fugang Gou1, 2 , Xulong Gong1, 2, Yuan Liu1, 2
Affiliations
  • 1. Geological Survey of Jiangsu Province, Nanjing 210049, China
  • 2. Key Laboratory of Earth Fissures Geological Disaster, Ministry of Natural Resources, Nanjing 210049, China
出版时间: 2024-03-31 doi: 10.12284/hyxb2023172
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江苏沿海平原是江苏省域水资源脆弱带,地下水咸化已成为较为严重的生态环境问题。为了解析长江三角洲北翼地区更新世以来地下水的补给及其盐分来源,布设一口275 m的深井HYRD1,全孔连续采集易溶盐样品、土工样品、水样。在区域采集地表水、浅层与深层地下水、海水样品。采用易溶盐指标结合土工指标(含水率、湿密度、比重)获取了HYRD1高精度孔隙水的水化学特征。采用Piper三线图、Gibbs图、离子比值法等结合δD、δ18O数据、14C测年数据解析了更新世以来地下水的补给及其盐分来源。结果表明:土体盐分主要为NaCl,盐渍土占比为25%。盐渍土主要分布在Qp3弱透水层、Qp2地层与Qp1上段地层。孔隙水水化学类型为Cl−Na型(仅Qp1下段个别点为${{\rm{HCO}}^-_3}- $$ {\rm{Ca}}\cdot {\rm{Na}}$),微咸水占比7%,咸水占比49%,盐水占比44%。微咸水主要分布在Qp1下段砂层中。潜水的δ18O、δD说明潜水来源为大气降水,且受到了较为强烈的蒸发作用。弱透水层孔隙水、承压水的δ18O、δD投点位于标准海水稀释线附近,且随着深度的增加,δ18O、δD有减小趋势,说明海水混合作用随着深度的增加而减小。Qp1弱透水层多见钙质结核,说明了Qp1地层成土后受到了强烈的蒸发作用。HYRD1 Qp1上段及上覆地层盐分主要来源于5期海侵、蒸发盐岩与硅酸盐风化溶解,Qp1下段地层盐分主要来源为地壳源。地下水化学成分受到了水岩作用、蒸发浓缩作用与人类活动等的影响。

沉积环境  /  含盐特征  /  易溶盐  /  孔隙水  /  弱透水层  /  沿海含水层

The coastal plain of Jiangsu Province is a fragile zone of water resources in Jiangsu Province, and groundwater salinization has become a serious ecological problem. In order to analyze the groundwater recharge and its salinity sources in the north flank of the Changjiang River Delta since Pleistocene, a 275 m deep well HYRD1 was deployed and the whole hole was continuously collected with easily soluble salt samples, geotechnical samples and water samples. Surface water, shallow and deep groundwater, and seawater samples were collected in the area. The hydrochemical characteristics of Well HYRD1 high-precision porewater were obtained by using soluble salt index combined with geotechnical index (water content, wet density, specific gravity). In order to analyze the groundwater recharge and its salt source since Pleistocene, Piper trilinear diagram, Gibbs diagram and ion ratio method were used in combination with δD and δ18O data and 14C data. The results show that the salinity of Well HYRD1 soil is mainly NaCl, and the percentage of saline soil is 25%. The saline soils are mainly distributed in the Qp3 aquitard, Qp2 stratum and the upper part of Qp1 stratum. The water chemistry type of porewater is Cl-Na type (only the lower section of Qp1 is HCO$_3^- $-Ca·Na at individual points), 7% of brackish water, 49% of saline water and 44% of haline water. The brackish water is mainly distributed in the sand layer of the lower section of Qp1. The δ18O and δD of diving indicate that the source of diving is atmospheric precipitation and is subject to a relatively strong evaporation effect. The δ18O and δD of the aquitard pore water and pressurized water are located near the standard seawater dilution line, and the trend of δ18O and δD decreases with the increase of depth, which indicates that the porewater is subjected to the mixing effect of seawater decreases with the increase of depth. Calcareous nodules are mostly seen in the Qp1 aquitard, indicating that the Qp1 aquitard was subjected to strong evaporation after soil formation. The salinity of the upper part of Well HYRD1 Qp1 and the overlying strata is mainly from the 5th stage sea erosion, evaporite and silicate weathering dissolution. The salinity of the lower part of Qp1 is mainly from the crustal source. The groundwater chemistry is influenced by water-rock action, evaporation concentration and human activities.

sedimentary environment  /  saline characteristics  /  soluble salts  /  porewater  /  aquitard  /  coastal aquifers
苟富刚, 龚绪龙, 刘源. 长江三角洲北翼更新世以来的水土环境地球化学特征及其环境指示意义. 海洋学报, 2024 , 46 (3) : 33 -53 . DOI: 10.12284/hyxb2023172
Fugang Gou, Xulong Gong, Yuan Liu. Geochemical characteristics of water and soil environment and its environmental indicating significances since the Pleistocene in the northern flank of the Changjiang River Delta[J]. Haiyang Xuebao, 2024 , 46 (3) : 33 -53 . DOI: 10.12284/hyxb2023172
研究区位于长江三角洲北翼滨海地区,研究区是长江、淮河、黄河等大河与海洋相互作用下形成的广袤平原,受到多次海侵海退的影响,海陆相地层交互沉积。江苏沿海平原是江苏省域水资源量最欠缺的地区,也是省域水资源脆弱带,水资源压力日益增长[1]。自20世纪70年代开始,研究区大量开采深层地下水,III、IV承压水水位持续下降,形成多个水位漏斗(如东漏斗与海门漏斗等),出现地面沉降与深层地下水咸化现象[23]。深层地下水开采后形成降落漏斗后,浅层地下水所在的载体(盐分等)通过水头压力差自弱透水层向砂层越流,促使深层地下水与浅层地下水强烈混合,造成深层地下水同位素测试的年龄数据较小或差异较大,局部出现含水层地下水“年龄倒转”的现象[45]。研究区部分深层地下水现氚水[6]。江苏沿海地区含水砂层与其孔隙水含盐指标呈线性正相关,土体中Cl含量与孔隙水溶解性总固体(Total Dissolved Solids,TDS)回归分析建立的模型相关性最高[3, 7]。深层地下水总体呈咸化趋势,且水土含盐特征具有一致性[7]
水化学方法能够很好地识别含水层地下水的补给过程和盐分来源[813],同位素作为地下水来源的示踪剂被广泛应用于地下水循环研究[1418]。地下水的环境同位素(δD、δ18O、3H、14C)被广泛用于研究地下水的循环过程及其形成年代[19]。众多学者采用δD、δ18O和水化学系数开展过研究区地下水补给源、水化学演化的相关研究[2, 20]14C同位素测年结果显示江苏沿海地区深层地下水中的盐分与含水介质不属于同生关系,其晚于含水介质的形成时间[2122]。江苏滨海平原浅层孔隙水的盐分主要来源于全新世海水,深层微咸水与咸水的盐分主要源于淋滤海相地层中的盐分[21]
弱透水层是地下水的重要载体,在沉积物中的占比远远大于含水砂层,占比高达70%[23]。根据研究区钻孔揭露的新近纪地层弱透水层占比高达88%,更新世以来的弱透水层仅占比37%,这主要与长江的贯通以及现代环流的形成有关。长江贯通的时间争议较大,根据研究区多个钻孔揭示的结果,自更新世起,研究区砂层分布明显增加,即自早更新世起长江物源显著影响研究区。现代环流自距今7.0 ka形成,苏北沿岸流也对研究区全新世土体沉积有显著影响。弱透水层释水量占据地下水开采量的重要组成部分[24],据不完全统计,最高约为41.3%[25]。在人类活动强烈的干预下,如地下水超采,促使孔隙水压力减小,含水层骨架系统压力增加,出现了弱透水层压密释水现象,孔隙水可能携带自身的盐分等补给相邻的含水层[2627]。其次,研究区据海岸距离仅2 km,沿海地区地下水位下降,含水层与相邻海水的水头差增加,可能发生水平方向,甚至是垂直方向的海水入侵问题,进而影响到储备层(弱透水层)孔隙水的水质。弱透水层与含水层相比,由于弱透水层渗透性极低,孔隙水的提取及水力参数获取技术存在要求高、测试难度大、运移规律复杂等原因,研究进展相对缓慢,且研究成果多集中在浅层的包气带或者饱水带。因此,目前有关研究区弱透水层孔隙水水化学特征的研究较少,仅有少量浅部土体含盐特征的相关研究[2830]。文献[3132]建立了研究区100 m以浅土体工程地质层序,并进行了100 m以浅土体含盐特征及其沉积环境分析。目前江苏沿海平原有关地下水演化循环的相关研究主要集中在浅层地下水,对深层地下水的形成、演化以及溶质运移规律研究较少。
目前,有关江苏滨海地区在高强度开发深层地下水的条件下,对含水层系统结构及水质如何响应缺乏系统认识。为此,本研究布设一口深度为275 m的井(HYRD1),采用一孔多成技术,进行了第III承压水层位(上段与下段)成井。本研究采用绘制水文地质剖面的方法,与区域地层资料进行对比,对HYRD1含水层系统进行划分。全孔深度范围内采集易溶盐样品、两个成井层位水样、土工样品(用来测试渗透指标、含水率、湿密度与比重等),为土体含盐指标与孔隙水水化学指标转化提供基础指标。同时在研究区域采集不同层位地下水样品,进行同位素δ18O、δD、14C以及水质全分析。本次将弱透水层与含水砂层作为一个有机整体进行研究,采用水化学特征与同位素(δ18O、δD、14C)数据,识别地下水补给来源和盐分来源,以期确定更新世以来的地下水所赋含的环境指纹特征,揭示其咸化机制,为指导研究区地下水合理开发利用提供理论依据。
研究区位于长江三角洲北翼(图1),隶属扬子地层区下扬子地层分区[25]。研究区地面标高一般为3~4 m,第四纪松散层厚度普遍超过了200 m。根据钻探与物探解译结果,HYRD1 第四纪地层厚度为275 m,基岩埋深介于600~700 m。岩性以粉砂、细砂、粉质黏土为主(图2),海陆相地层相间分布。哈承佑和赵继昌[33]对第四纪地层与含水层系统做过划分,将含水层组(砂层)自上而下,划分为潜水、I、II、III、IV承压水。潜水含水层、I、II承压含水层易受到降水补给且水力联系紧密,因此,将这3个含水层组归为浅层含水系统(图3)。III、IV承压含水层更新能力弱,将其归为深层含水系统。
根据绘制的水文地质剖面结合区域第四纪地层剖面,进行区域地层对比。再结合区域土体AMS14C测年、光释光测年、环境磁参数测试以及粒度分析结果,把HYRD1全新统(Qh)的底界定在30.0 m。上更新统(Qp3)的底界定在74.2 m;中更新统(Qp2)的底界定在168.1 m;下更新统(Qp1)的底界定在275 m。其中,Qh、Qp3、Qp2地层赋存的孔隙水为浅层水,Qp1以及下伏土层赋存的孔隙水为深层水。本文以上述划分的含水层系统为基础进行更新世以来土体盐分、孔隙水水化学特征及其环境指示分析。
在HYRD1采集易溶盐样品112件(图3)。采样深度为0~275 m,平均间距为2.5 m。对所采土样进行全盐量、易溶盐8大离子(${\rm{Cl}}^-$${\rm{HCO}}_3^-$${\rm{SO}}_4^{2-}$${\rm{CO}}_3^{2- }$${\rm{Na}}^+$${\rm{K}}^+$${\rm{Ca }}^{2+}$${\rm{Mg}}^{2+}$)和pH测试。
易溶盐测试样品制备需要经过烘干、研磨、过筛等步骤,再以1∶5比例混合的土水经过溶解、浸提(时间为3 min)、抽虑等步骤获得测试水溶液。测试方法见文献[31, 34]。
盐渍土分类参考文献[35]。目前一般采用0.l kg土中Cl${\rm{SO}}_4^{{2-}} $含量的比值作为分类标准,根据式(1)计算结果结合文献[35]进行分类。
$ {R_1} = \frac{{c{\text{(C}}{{\text{l}}^{{ - }}}{\text{)}}}}{{2c(\rm{SO}_4^{2-})}}\text{,} $
式中,各离子浓度为在100 g土中所含毫摩尔数。
R1 ≤ 0.3时为硫酸盐渍土,当0.3 < R1 ≤ 1时为亚硫酸盐渍土,当1 < R1 ≤ 2时为亚氯盐渍土,当R1 > 2时为氯盐盐渍土。根据文献[35],对于亚氯盐渍土与氯盐,含盐量小于0.3%的为非盐渍土,含盐量大于等于0.3%且小于1%的为弱盐渍土;含盐量大于等于1.0%且小于5.0%的为中盐渍土;含盐量大于等于5.0%且小于8.0%的为强盐渍土;含盐量大于等于8.0%的为超盐渍土。
土体易溶盐样品获取方便,测试分析已规范化,但这一指标应用起来非常不方便。因为现有进行沉积环境演化分析的方法大多都是基于土体孔隙水化学特征。土体孔隙水提取方法可归并为两类:原位提取技术与室内提取技术。原位提取技术包括吸气引液法(主要针对弱透水层)与渗析法,这两种方法操作不便且成本高。室内提取技术包括浸提法、离心法、压榨法和真空蒸馏法,一般主要针对弱透水层。本文提出了一种推演土体孔隙水水化学组分的方法,可以根据土体中的易溶盐指标结合土体基本物理指标(天然含水率、湿密度、颗粒比重)计算出孔隙水矿化度和孔隙水中${\rm{Cl}}^-$${\rm{HCO}}_3^-$${\rm{SO}}_4^{2-}$${\rm{CO}}_3^{2- }$${\rm{Na}}^+$${\rm{K}}^+$${\rm{Ca }}^{2+}$${\rm{Mg}}^{2+}$等浓度[36]。与传统成井来获取含水砂层孔隙水水化学特征相比,该方法可以连续获取不同层位土体孔隙水水化学特征。
孔隙水矿化度(MOW,单位:g/L)和Cl离子浓度(${{{\rm{MO}}}}{{{{\rm{W}}}}_{{\rm{Cl}}^ - }} $,单位:g/L)的计算公式为
$ {{\rm{MOW}}=}\frac{{\rho }_{{\rm{d}}}\times {S}}{(\rho -{\rho }_{{\rm{d}}})/{\rho }_{{\rm{w}}}/1\;000} \text{,} $
$ {{{\rm{MO}}}}{{{{\rm{W}}}}_{{\rm{Cl}}^ - }}= \frac{{{{{S}}_{{\rm{C}}{{\rm{l}}^ - }}} \times {\rho _{\rm{w}}} \times {10}^ {- 3}}}{{\rho /{\rho _{\rm{d}}}-1}} \text{,} $
式中,S为土体含盐量(%);$S_{{\rm{Cl}}^ -}$为测试报告给出的土体中易溶盐Cl离子含量(单位:mg/kg);ρd为干密度(单位:g/cm3);ρ为湿密度(单位:g/cm3);ρw为4℃时水的密度(单位:g/cm3)。其他离子(${\rm{HCO}}_3^-$${\rm{SO}}_4^{2-}$${\rm{CO}}_3^{2- }$${\rm{Na}}^+$${\rm{K}}^+$${\rm{Ca }}^{2+}$${\rm{Mg}}^{2+}$)浓度也可参考式(3)计算。
孔隙水水化学类型分类参考舒卡列夫分类。矿化度小于1 g/L为淡水,1~3 g/L为微咸水,3~10 g/L为咸水,10~50 g/L为盐水,大于50 g/L为卤水[37]
弱透水层δD与δ18O测试样品的获取采用真空蒸馏法。含水砂层测试样品获取要保证洗井1 h以上,采用聚乙烯瓶装取,3H样品样瓶留1/3顶空,其他测试样品不留顶空。δD分析精度优于±1‰,δ18O分析精度优于±0.2‰,采用质谱法。14C测试精度为0.3 pMC(pMC代表碳百分比),采用加速质谱法。3H测试精度优于±2 TU(TU为氚的最小浓度单位),采用液体闪烁计数法。
矿物成分分析采用X’Pert PRO X射线衍射仪(HX041),参照SY/T 5163−2010进行测试分析[38]。ZK1孔AMS 14C测年材料为碳屑,ZK2孔测年材料为贝壳,送往北京大学14C实验室开展AMS 14C测年,送样3件。ZK1、ZK2孔光释光测年材料为粉细砂,送往中国地质科学院水文地质环境地质研究所进行测定,送样8件。古地层测定:ZK2全孔采样,并进行磁倾角、磁化率的测定,绘制古地磁标准极性柱(GPTS)。
对HYRD1土层含盐特征按沉积时代与岩性进行统计(图3)。HYRD1土体盐分主要为NaCl,盐土类型为氯盐渍土类型,仅1个更新统下段的样品为亚氯盐土类型,且未达到盐渍土级别。易溶盐中各离子含量(单位:mg/kg,平均值)从高到低依次为${\rm{Cl}}^-$${\rm{Na}}^+$${\rm{SO}}_4^{2-}$${\rm{HCO}}_3^-$${\rm{Ca }}^{2+}$${\rm{Mg}}^{2+}$${\rm{K}}^+$${\rm{CO}}_3^{2- }$。含盐量介于0.04%~0.59%之间,平均值为0.23%,变异系数为0.552。整体来看,HYRD1含盐量较高,盐渍土占比为25%。盐渍土主要分布在Qp3弱透水层、Qp2地层与Qp1上段地层。Qp1上段上覆地层易溶盐均是Cl与Na+含量最高,Qp1下段砂层易溶盐Cl${\rm{HCO}}_3^-$含量最高。各层土含盐特征统计结果见表1
HYRD1弱透水层占比37%,不能采用传统成井方法进行弱透水层孔隙水的获取,采用式(2)与式(3)计算的孔隙水矿化度与离子浓度,计算的孔隙水水化学特征与HYRD1成井获取水化学特征一致,说明该方法切实可行。弱透水层与含水砂层相比,由于其结构与物质组成的特殊性,渗透性低,其孔隙水保留了土体沉积时期的古环境信息,可以根据弱透水层孔隙水水化学特征来分析沉积环境。
对HYRD1孔隙水水化学特征按沉积时代与岩性进行统计。进行不同层位的孔隙水水化学特征的最小值、最大值、平均值和变异系数统计分析,并参考舒卡列夫分类进行孔隙水水化学类型的分类。分类中A代表矿化度小于1.5 g/L,B代表矿化度介于1.5~10 g/L,C代表矿化度介于10~40 g/L,D代表矿化度介于大于40 g/L[37]
HYRD1孔隙水矿化度介于1.78~32.41 g/L之间,平均值为10.34 g/L。采用矿化度进行水化学分类,按矿化度从高到低,微咸水占比7%,咸水占比49%,盐水占比44%。微咸水仅出现在Qp1下段地层中(图4表2)。各层孔隙水水化学类型以Cl−Na−B与Cl−Na−C为主(共计6类,表3),还出现了Cl·HCO3−Na−B、Cl·SO4−Na−B、Cl·SO4−Na−C和Cl·SO4−Na·Ca−B类型。
选择最主要的易溶盐指标中的含盐量、Na+、Cl含量与孔隙水的TDS、Na+、Cl含量等进行相关性分析。${\rm{CO}}^{2-}_3$离子含量低,不参与相关性分析。根据表4可以看出HYRD1的TDS与土体易溶盐指标中的含盐量、Na+、Cl含量相关性差异不大,TDS与易溶盐中的Na+含量相关性最高,相关性为0.810。
表5展示了孔隙水TDS与土体中含盐量、Na+含量、Cl含量关系拟合式[式(4)至式(18)],TDS单位为g/L,含盐量以百分数表示,Na+、Cl含量单位为mg/kg。根据表5中的预测模型,可以采用土体中的含盐特征指标预测土体孔隙水的TDS值。表5中的拟合关系式均在0.01水平(双侧)上显著相关。进行HYRD1 数据的整体拟合,TDS与易溶盐中的Na+含量相关性最高[式(4)]。不同沉积单元的数据拟合不区分含水砂层孔隙水与弱透水层孔隙水。不同层位孔隙水TDS与土体易溶盐指标的拟合式相关性差异较大。Qp1下段地层赋存的孔隙水TDS与其含盐量的相关性最高[式(18)],Qp1上段地层赋存的孔隙水TDS与Cl含量的相关性最低[式(9)]。TDS与土体易溶盐指标的拟合式相关性均是Qp1下段地层赋存的孔隙水 > Qh地层赋存的孔隙水 > Qp3、Qp2下段地层赋存的孔隙水 > Qp1上段地层赋存的孔隙水。利用该模型可以免去含水率、湿密度、比重的测试,直接根据土体易溶盐中的单一离子就可以预测TDS,节约了成本。
研究区潜水氚浓度为2.4~5.2 TU,平均值为3.8 TU。根据氚浓度的测试结果,推测潜水来源为次现代水与现代补给水的混合。微承压水的氚浓度为0.5~1.4 TU,考虑到测试不确定度,认为其为次现代水,补给时期在1952年以前,这就说明60年内的大气降水并未渗入到20 m以下[2]
14C可以用于测量上限达30 000年的地下水,被广泛应用于深层地下水的年代确定。应用Vogel模型、Tamers模型、CMB-chem模型以及F-G模型[39]14C测年数据进行校正,校正结果见图5
I承压水14C浓度介于24.9~44.7 pMC之间,13C值为−25.7‰~−9.6‰。II承压水14C浓度介于14.3~41.7 pMC之间,13C值为−21.2‰~−15.6‰。I承压水14C年龄介于9 100~10 400 a之间,II承压水14C年龄介于8 400~15 000 a之间(图5)。I承压水与II承压水年龄有重叠的部分,都接受全新世早期或末次冰期后期的补给,表明二者之间有较为密切的水力联系。
III承压水14C浓度介于3.1~9.1 pMC之间,13C值为−17.2‰~−10.3‰。III承压水14C年龄介于14 900~27 700 a之间,为古水,二者接受晚更新世末期的降水补给。III承压水14C年龄大体上自西向东逐渐增大,体现了补给区位于研究区西侧。
14C年龄计算的III承压水的平均径流速度约为5 m/a,即 14 mm/d,与根据流场计算的结果(12 mm/d)相近。III承压水在HYRD1位置漏斗的年龄等值线分布明显,较南部海门漏斗稀疏,说明HYRD1附近的径流速度较南部海门−南通市区一带要快,这与III承压水的流场分布是相符的,北部水力坡度大,渗流速度快。总体来讲,III承压水在HYRD1附近年龄较小,且水位较高,可更新能力较强,开发利用潜力大。
潜水(TDS > 1 g/L)样点δ18O介于−7.10‰~−4.74‰之间,平均值为−6.06‰。δD介于−46.7‰~−34.1‰之间,平均值为−39.8‰。潜水的δ18O值接近或大于现代地下水的δ18O值。东部受海水入侵影响,18O、D向入海口方向逐渐富集。选用南京站大气降水氢氧稳定同位素监测数据,建立研究区当地大气降水线(LMWL)[40]。GMWL为全球大气降水线[41],CMWL为中国大气降水线[42]。潜水中的δ18O与δD线性拟合的斜率为5.76,相关系数为0.969,斜率小于GMWL和LMWL(图6)。拟合线大致与GMWL、LMWL重合,位于LMWL线与海水稀释线之间,远离海水,说明潜水样点受到了蒸发作用的影响,主要受大气降水补给。研究区离海洋较近,受太平洋季风的影响,海洋水汽是其降水的主要来源,拟合线截距偏高也反映了区域湿润多雨的气候特点[6]
弱透水层(Qp3)孔隙水δ18O介于−5.36‰~−1.96‰之间,δD介于−37.34‰~−14.00‰之间。弱透水层(Qp2)孔隙水δ18O介于−5.23‰~−1.90‰之间,δD介于−37.28‰~−17.95‰之间。海水中的δ18O、δD具有明显富集的特征,分别为−1.21‰、−8.5‰。12 000~60 000 a BP的玉木冰期(Qp3δ18O值比现在低约10‰[43],古地下水中的δ18O能够反映更新世冰期到全新世间冰期的气候变化。弱透水层(Qp3)孔隙水δ18O、δD的投点位于标准海水稀释线附近,说明弱透水层(Qp3)孔隙水受到了大气降水与海水的混合补给(混合作用)。弱透水层(Qp2)孔隙水δ18O、δD的投点位于标准海水稀释线附近(偏下方),说明弱透水层(Qp2)孔隙水受到了大气降水与海水的混合补给(混合作用)、蒸发浓缩作用。
研究区由于I、II承压含水层之间的弱透水层有大范围的缺失,因此将这两层水一起讨论。I承压水上覆厚度稳定的弱透水层,I、II承压水与微承压水、潜水水力联系较差。I承压水δ18O介于−5.81‰~−1.00‰之间,δD介于−41.1‰~−9.1‰之间;II承压水δ18O介于−6.31‰~−3.10‰之间、δD介于−41.4‰~−17.4‰之间,位于大气降水与海水端源之间。I、II承压水样点均分布在LMWL和GWML下方,标准海水稀释线附近(偏下方),说明I、II承压水样受到了大气降水与海水的混合补给以及蒸发浓缩作用。
HYRD1弱透水层(Qp1)孔隙水δ18O介于−6.75‰~−4.15‰之间,δD介于−49.25‰~−31.13‰之间。研究区地下水形成年龄越老,δ18O值越偏负。弱透水层(Qp1)孔隙水δ18O、δD明显较弱透水层(Qp2、Qp3)孔隙水偏负,δ18O、δD位于当地潜水下方,标准海水稀释线下方,说明弱透水层(Qp1)孔隙水补给源主要为淡水(大气降水),蒸发浓缩作用强烈。弱透水层(Qp1)多见钙质结核,说明成土后受到了较为强烈的蒸发作用。
矿化度大于1 g/L的III承压水,δ18O介于−6.91‰~−5.22‰之间,δD介于−6.85‰~−5.23‰之间,δ18O与δD位于当地潜水下方,标准海水稀释线下方,指示大气降水是III承压水最重要的补给源,并且受到了显著的蒸发作用影响。由于III承压含水层顶板埋深在150 m以下,承压水不受现代蒸发作用影响。目前III承压水(Qp1上段)受到富集δ18O、δD的咸水端元混入。根据研究区马塘镇水位降落漏斗区的δD、δ18O同位素数据,应用二端元法计算漏斗区补给III承压水的浅层地下水比例约为20%[6]
水化学三线图可以进行水化学类型分类及其演化特征分析[44],水化学类型可以划分为6类(图7a)。仅HYRD1孔隙水(Qp1下段)3个样点水化学类型为HCO$_3^- $−Ca·Na,其中两个样点为弱透水层。其余HYRD1孔隙水水化学类型均为Cl−Na型。地下水的溶质迁移主要包括扩散和对流两个过程[式(19)],弱透水层孔隙水溶质运移以扩散为主[45]。弱透水层孔隙水与水溶液扩散相比,饱和低渗透性介质溶质的扩散过程更为复杂,速度也相对缓慢,而且黏性土具有一定的吸附性,对溶质的扩散存在一定的阻滞作用。根据承压水14C测年结果,I、II承压水补给来源为早全新世与晚更新世的降水,III承压水补给来源为晚更新世的降水,II、III承压水已被替换为晚更新世的降水。弱透水层孔隙水溶质运移以扩散为主,还保留土体沉积时的古环境信息。
$ \frac{\partial {C}}{\partial {\textit{z}}}\left(\theta D\frac{\partial {C}}{\partial {\textit{z}}}\right)-\frac{\partial (v \theta {C})}{\partial {\textit{z}}}=\theta \frac{\partial {C}}{\partial t} \text{,} $
式中,C为孔隙水溶质的含量(单位:mg/L);t为溶质运移时间变量(单位:a);v为平均孔隙水流速(单位:m/s);z为溶质运移的距离变量(单位:m);θ为多孔介质的孔隙度;D为溶质运移的水动力弥散系数(单位:m2/s)。Dθ的乘积为有效扩散系数(单位:m2/s),一般用De表示。
当海水入侵时,水土会发生Na−Ca交换,沿着式(20)向右发生反应,表现为Na+被吸附;同时发生CaCO3沉淀、白云石化[式(21)向右反应]与去白云石化[式(21)向左反应],${\rm{SO}}_4^{2-}$减少(图7b)。QP1绝大部分孔隙水中的${\rm{SO}}_4^{2-} $均位于理论混合曲线的下方,即${\rm{SO}}_4^{2-} $大量被消耗,推测与有机质的硫酸盐矿化有关。
$ {\rm{2Na^+ + Ca}}\chi ^2 \rightleftharpoons {\rm{2Na}}\chi + {\rm{Ca^{2+}}}\text{,} $
$ {\rm{2CaCO_3 + Mg^{2+}}} \rightleftharpoons {\rm{CaMg(CO_3)_2 + Ca^{2+}}}. $
土体(Qp1上段)孔隙水及其以上孔隙水均位于菱形图标中理论混合曲线的下方或附近。土体(Qp1下段,图7c)孔隙水主要位于菱形图标中理论混合曲线的下方,仅两个点位于混合线上方。浅部的潜水受到淡水淋滤的作用最为明显。I承压水受到的淡水淋滤作用较弱透水层(Qp3)孔隙水强烈。这与弱透水层颗粒较细,地下水径向流动较弱有关。II、III承压水、弱透水层(Qp2、Qp3)孔隙水受到淡水淋滤的作用区分不明显。
各孔隙水中Ca2+、Mg2+均位于当地淡水与海水的理论混合曲线下方,仅弱透水层(Qh)中Ca2+、Mg2+位于理论混合曲线附近。推测与Na−Ca、Na−Mg交换等水岩作用以及Ca2+、Mg2+饱和沉淀有关。
浅部弱透水层(Qh)、弱透水层(Qh中部)中Cl位于当地淡水与海水的理论混合曲线上方(两个点紧靠混合曲线上方)。微承压水(Qh)、弱透水层(Qp3)孔隙水、II承压水中Cl位于当地淡水与海水的理论混合曲线附近。III承压水(Qp1)孔隙水位于当地淡水与海水的理论混合曲线附近或上方。弱透水层(Qp1)孔隙水位于当地淡水与海水的理论混合曲线附近或上方。III承压水(Qp1)位于当地淡水与海水的理论混合曲线下方或附近。结合图7b,理论线下一般表示海水入侵,理论线上表示淋滤。
除了潜水、弱透水层(Qp1下段)孔隙水,HYRD1孔隙水均受到海水混合作用的显著影响。大气降水及地表河流的入渗补给作用仅限潜水、微承压水,对I、II、III承压水地下水水化学特征及盐分来源影响有限。当淡水淋滤时,CaCO3与CO2、有机质发生反应,表现为CaCO3的溶解。式(22)与式(23)的反应主要发生在浅表沉积单元,淋滤的最终方向为初级碱性水。
$ {\rm{CaCO_3 + CO_2 + H_2O}}\to {\rm{2HCO_3^- + Ca^{2+}}}\text{,} $
$ {\rm{ CaCO_3 + CH_2O + O_2}}\to {\rm{2HCO_3^- + Ca^{2+}.}} $
海水中各离子含量稳定,离子比值一般为定值,标准海水Na/Cl含量比平均值为0.58。地下水中Na/Cl是表征Na+富集程度的一个水文地球化学参数,可追溯海岸带地下水的成因,Na/Cl值接近海水表明地下水盐分主要来源于海洋[46]。Cl、Na+、Mg2+是海水中的主要成分,根据Na−Cl关系图,绝大部分样品点(除了弱透水层Qp1孔隙水个别点)位于海水比值线上方(图8),这与钠长石碳酸盐风化[式(24)]及水岩作用有关。
$ \begin{split}&{\rm{ 4Na(AlSi_3 O_8) + 4CO_2 + 6H_2O}}\to {\rm{4Na^+}} + 4{\rm{HCO}}_3^- +\\& {\rm{Al}}_4({\rm{Si}}_4{\rm{O}}_{10})({\rm{OH}})_8 + 8{\rm{SiO}}_2. \end{split}$
钠长石碳酸盐风化后释放Na+进入孔隙水。同时,富含钠的黏土矿物吸附来自海水中的Ca2+[式(20)]、Mg2+,将黏土矿物中的Na+释放到孔隙水中,Ca2+、Mg2+离子被黏土矿物吸附进而固定起来,因此孔隙水中Na+增加。
根据Mg−Cl关系图,绝大部分样品点位于海水比值线下方(图8),这与富含钠的黏土矿物吸附来自孔隙水中的Mg2+有关。此外,弱透水层有机质丰富,有机质通过硫酸盐还原作用产生了矿化[式(25)],产生了大量${\rm{HCO}}_3^- $[47],有助于Mg2+饱和沉淀。
$ {\rm{2CH_2O+ SO_4^{2-}}}\to {\rm{2HCO_3^-+H_2S.}} $
根据Ca−Cl关系图,绝大部分样品点位于海水比值线上方(图8),这与钙长石碳酸盐风化[式(26)]有关,钙长石碳酸盐风化后补给Ca2+给孔隙水。
$ \begin{split}&\quad\\[-10pt]&{\rm{2Ca(AlSi_3O_8) + 4CO_2 + 6H_2O}}\to 2{\rm{Ca}}^{2+} +\\&4{\rm{HCO}}_3^- + {\rm{Al}}_4({\rm{Si}}_4{\rm{O}}_{10})({\rm{OH}})_8 + {\rm{8SiO}}_2. \end{split}$
根据K−Cl关系图,绝大部分样品位于海水比值线上方(图8),这主要与钾长石碳酸盐风化[式(27)]及K+的负水合效应有关[48],钾长石碳酸盐风化后释放K+进入孔隙水。
$\begin{split}& {\rm{4K(AlSi_3O_8) + 4CO_2 + 6H_2O}}\to 4{\rm{K}}^+ + 4{\rm{HCO}}_3^- +\\& {\rm{Al}}_4({\rm{Si}}_4{\rm{O}}_{10})({\rm{OH}})_8 + 8{\rm{SiO}}_2.\end{split} $
在地下水化学过程研究中经常使用γ[(Ca2+ + Mg2+) − (${\rm{HCO}}_3^- $ + ${\rm{SO}}_4^{2-} $)]与γ[(Na+ + K+) − Cl]之间的离子当量关系,探讨溶解作用与水岩作用对地下水化学成分的影响[49]。如没有发生阳离子交换,仅依靠岩石溶解反应补给,则绘制的散点应该集中在图9的原点(0,0)附近;当二者之间的斜率接近于−1,表明交换吸附反应是水体中阳离子浓度变化的重要原因。研究区地下水的投点基本沿斜率为−1的直线分布,说明地下水盐分与其赋存载体间发生了显著的阳离子交换反应。事实上,孔隙水中的阳离子与黏土矿物的阳离子之间的交换取决于金属阳离子的键能,Ca2+、Mg2+的键能高于K+、H+、Na+的键能[50]
弱透水层孔隙水的投点相较砂层孔隙水离散。低矿化度的弱透水层孔隙水的投点主要分布在右下角象限(图9)。Qp2弱透水层除外,这主要与Qp2弱透水层较薄,Qp2弱透水层对上覆的厚层砂层孔隙水中的盐分产生了吸附作用,即表现为长石矿物的风化溶解或阳离子离子交换,黏土矿物对孔隙水中的Ca2+ + Mg2+产生了吸附并将其固定,释放Na+ + K+。高矿化度的弱透水层孔隙水的投点主要分布在左上角象限,即表现为Na+ + K+的吸收,Ca2+ + Mg2+的释放,这主要因为高矿化度水体中的盐分一般受海侵时长与范围等控制。
砂层孔隙水的投点主要分布在右下角象限(图9),即表现为长石矿物的风化溶解,释放Na+ + K+;黏土矿物对Ca2+ + Mg2+产生了吸附作用[51],同时释放Na+ + K+。在这种情况下,Cl${\rm{SO}}_4^{2-}$含量保持不变,阳离子交换导致Na+升高和Ca2+、Mg2+浓度下降。另外,下段III承压水(低矿化度)有向原点(0,0)逼近的趋势,这说明阳离子交换作用有减小的趋势,蒸发盐岩溶解作用越来越重要。
Gibbs图(图10)可以用来分析水化学成因,采用TDS(纵轴,对数)与Na+/(Na+ + Ca2+)的质量浓度比值(横轴)进行投点,以及采用TDS与Cl/(Cl + HCO$_3^- $)进行投点,可以分析孔隙水中主要离子的控制因素:大气降水作用、岩石风化作用、蒸发结晶作用[52]。钠长石显著地风化可以引起Na+${\rm{HCO}}_3^- $浓度升高,导致Na+/(Na+ + Ca2+)的比值增大和Cl/(Cl + ${\rm{HCO}}_3^-$)的比值变小,从而形成研究区Gibbs图存在诸多散点的现象。当地淡水(图10)以及Qp1下段地层孔隙水的Gibbs图存在个别散点现象。
当地淡水样品(潜水与地表水)更靠近岩石风化作用区,表明控制浅表水水化学特征的是岩石风化作用,还受蒸发结晶作用影响。HYRD1样品投点绝大部分位于模型的右上端且靠近海水(图10),表明研究区地下水盐分主要受控于蒸发结晶作用、海水浸渍、海水入侵以及通过水头差溶滤海相地层中的盐分补给到深层地下水。微承压水较潜水接近海水。弱透水层(Qh)孔隙水较微承压水接近海水。弱透水层(Qp3)孔隙水较I承压水接近海水。弱透水层(Qp2)孔隙水较II承压水接近海水。II承压水较I承压水接近海水。根据区域地层对比结果,Qp1地层为陆相沉积;中更新世海侵到达现南通市区一带,形成了以陆相地层为主,间隔海相地层。弱透水层(Qp2)投点位于海水附近,说明孔隙水盐分主要来源于海水入侵或上部海相地层中的盐分通过越流补给。弱透水层(Qp1上段)孔隙水投点分布范围广,大部分点与上段III承压水重合(图10),部分点甚至与海水重合,说明上段III承压水受到了较为严重的海水入侵。下段III承压水明显偏离海水,弱透水层(Qp1下段)孔隙水较下段III承压水接近海水,说明弱透水层具有较强的离子吸附作用。
根据图11,孔隙水盐分主要受蒸发盐岩溶解与硅酸盐岩风化溶解补给,基本上不受到碳酸盐岩风化溶解补给。Qp1上段及其上覆地层孔隙水水化学类型均为Cl−Na型,Qp1下段孔隙水开始出现HCO$_3^- $−Ca·Na型,表明盐分来源有所不同。Qp1上段及其上覆地层孔隙水水化学特征明显受海侵影响。Qp1下段的蒸发盐岩来源主要为地壳源,即蒸发盐岩的物质来源主要为岩石的风化。蒸发盐岩溶解补给是孔隙水中盐分的主要来源之一,尤其是高矿化度水体,这种现象与区域构造沉降有关。上新世中期以来,因青藏高原的快速隆起,陆内盆地因伸展而凹陷。进入更新世以后,苏北凹陷带的地面高程基本上与南部长江三角洲一致,即与第四纪地层厚度基本一致(图12图13),早更新世沉降速率可以达到0.3 m/ka,之后一直保持沉降;进入晚更新世以来,沉降速率进一步提高,可达2.26 m/ka[53]。保守估计,第四纪地层累计沉积量可达200 m以上。研究区地势低洼,水体蒸发强烈,导致历史时期的地层中富集大量陆相沉积的蒸发盐岩,以及第四纪以来海退过程中残留的蒸发盐岩。
根据区域地层对比,更新世早期为湖泊相沉积,中晚期河流作用加强。早更新世中期海侵范围仅分布在江苏盐城北部的滨海地区,因此Qp1地层为陆相沉积。中更新世早期海侵(MIS19)也对研究区盐分补给起到了重要作用,对地层(Qp1上段)的孔隙水盐分起到了关键作用。受MIS19、MIS11、MIS5、MIS3与MIS1海侵影响(图12图13[5455],中更新世发育海陆相间地层,晚更新世发育两套海相地层,全新世发育一套海相地层,沉积环境为海湾、滨海或潟湖相,地下水中的盐分主要来自这5期的海水浸渍。此外,研究区地形广阔平坦且濒临大海,土体长期遭受海水入侵及高矿化度潜水共同作用。研究区是较早发现海水入侵的地区[56]。1980−2010年中国近海冬季海平面平均上升速率为3.1 mm/a[57],导致滨海地区海水入侵。三峡调蓄后长江河口地区0~20 cm土体盐分增量约为10%[2930]。研究区濒临大海,浅表地下水受海洋气溶胶所携带的盐分补给。潜水水位季节性变动,HYRD1附近潜水的流向垂直海岸线,自陆向海方向流动。研究区I、II承压水由于水质较差,开发利用较少,水位基本保持稳定,自陆向海方向流动。自20世纪70年代开始,III承压水被大量开采,在如东县与如皋市的中间地带形成了沉降漏斗中心,地下水位高程最低达到−35 m。HYRD1受如东漏斗影响。2001−2008年如东漏斗中心的水位降速为1.91 m/a。受控于如东漏斗,HYRD1附近的浅层地下水与其载体中的盐分越流补给深层水,现深层水已出现咸化趋势。根据区域水文地质剖面对比,近50年来HYRD1 III承压水(下段,砂层)TDS增长了4.6倍。
Cl是海水中最主要的稳定常量元素,是反映土体是否被海水浸染最为敏感的因素[46]。根据式(28)混合模型[58],HYRD1孔隙水混合比fi数值介于1.7%~83.6%之间,平均值为27.5%。fi的低值(平均值3.6%)出现在下段III承压水。fi的高值(平均值67.0%)出现在II承压水(弱透水层),这主要由于I、II承压水之间缺少良好的隔水层,II承压水所赋存的载体(弱透水层)厚度薄,对含水层孔隙水中的离子产生了吸附聚集。除了潜水受大气降水等作用的影响,潜水层下伏的孔隙水,处于同一时期内的均是弱透水层赋存的孔隙水TDS均大于含水砂层孔隙水TDS。
$ f_i=(C_{{\rm{Cl,\;samp}}}-C_{{\rm{Cl,\;d}}})/(C_{{\rm{Cl,\;sea}}}-C_{{\rm{Cl,\;d}}}) \text{,} $
式中,fi为实际混合比例(海水与淡水混合比例,%);CCl, samp为孔隙水中Cl离子含量(单位:mg/L);CCl, d为研究区淡水端元的Cl离子含量(单位:mg/L);CCl, sea为标准海水中Cl离子含量(单位:mg/L)。
HYRD1 fi的数值(平均值)远小于100%,说明HYRD1孔隙水中的盐分来源,除了海盐源外,还受水岩作用、沉积母质原有盐分溶解、雨水携带的气溶胶等的补给。其补给路径包括降水入渗、溶滤、离子交换、蒸发浓缩、海水入侵等[5960]。根据衍射试验数据,Qh、Qp3弱透水层原生矿物以石英(56%,平均含量)和长石(12%)为主,黏土矿物以伊利石(17%)和绿泥石(9%)为主,黏土矿物主要由铝硅酸盐矿物(长石)经化学风化所形成。QP2、Qp1弱透水层原生矿物含量稍有降低,黏土矿物含量稍有增加,黏土矿物以伊利石、蒙脱石为主,见坡缕石。Qp1上段及其以上地层赋存的孔隙水中海盐源占比为11%~67%,地壳源占比为33%~89%。Qp1下段地层孔隙水中的盐分主要来自钠长石碳酸盐风化与蒸发盐岩溶解,即地壳源,占比为91%~96%。
(1)更新世以来的土体含盐量介于0.04%~0.59%,平均值为0.23%。盐渍土占比为25%,盐渍土主要分布在Qp3弱透水层、Qp2地层与Qp1上段地层。HYRD1孔隙水矿化度介于1.78~32.41 g/L之间,平均值为10.34 g/L,Qp1上段及其上覆地层孔隙水水化学类型均为Cl−Na型,Qp1下段出现了${\rm{HCO}}_3^- $−Ca·Na。微咸水占比7%,咸水占比49%,盐水占比44%。水土含盐特征具有高线性相关,整体拟合以TDS与易溶盐中的Na+相关性最高。不同层位的拟合以TDS与含盐量相关性最高。
(2)潜水δ18O、δD的投点位于LMWL下方,GMWL、CMWL附近,偏离海水,说明潜水来源为大气降水,且受到了较为强烈的蒸发作用。弱透水层孔隙水、承压水δ18O、δD的投点位于LMWL、GMWL、CMWL下方,标准海水稀释线附近,且随着深度的增加,δ18O、δD进一步变负,即偏离海水,说明海水混合作用随着深度的增加而减小。Qp1弱透水层多见钙质结核,说明了成土后土体受到了强烈的蒸发作用。潜水来源为次现代水与现代补给水的混合。I、II承压水都接受全新世早期或末次冰期后期的补给,III承压水接受晚更新世末期的降水补给。
(3)HYRD1 Qp1上段及其上覆地层受到MIS19、MIS11、MIS5、MIS3、MIS1海侵的影响,地下水中的盐分主要来自这5期的海水浸渍(海盐源)、蒸发盐岩与钠长石碳酸盐风化溶解。Qp1下段地层孔隙水中的盐分主要来自蒸发盐岩与钠长石碳酸盐风化溶解。此外,研究区地形广阔平坦且近海,土体长期遭受海水入侵及高矿化度潜水共同作用;浅表地下水受海洋气溶胶所携带的盐分补给。HYRD1位于如东漏斗外缘,浅层水与其载体中的盐分通过越流补给深层水,现深层已出现咸化趋势。近50年来 HYRD1 III承压水(下段,砂层)TDS增长了4.6倍。
  • 中国地质调查局项目(1212011220005)
  • 国家自然科学基金项目(42007402)
  • 国家自然科学基金项目(41772327)
  • 江苏地质勘查项目(苏财资环〔2022〕27号)
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2024年第46卷第3期
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doi: 10.12284/hyxb2023172
  • 接收时间:2023-03-08
  • 首发时间:2025-11-26
  • 出版时间:2024-03-31
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  • 收稿日期:2023-03-08
  • 修回日期:2023-03-30
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中国地质调查局项目(1212011220005)
国家自然科学基金项目(42007402)
国家自然科学基金项目(41772327)
江苏地质勘查项目(苏财资环〔2022〕27号)
作者信息
    1.江苏省地质调查研究院,江苏 南京 210049
    2.自然资源部地裂缝地质灾害重点实验室,江苏 南京 210049
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2种不同金属材料的力学参数

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属数
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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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