厦门湾沉积物元素地球化学的研究
摘要
本文首次较全面地研究厦门湾九龙江口、厦门西港和同安湾三个海区22个站位表层沉积物样中Al、Ba、Ca、Co、Cr、Cu、Fe、Li、Mg、Mn、Na、Ni、P、Sr、Ti、V、Zn共17种常、微量元素，并对沉积物中元素含量与分布的主要控制因素、赋存形态及分布特征进行了探讨。结果表明：
厦门湾表层沉积物中所研究的多数元素的丰度接近于中国近岸浅海沉积物及福建省土壤平均值，但与长江口、黄河口沉积物相比，元素Zn和Mn有不同程度的富集，而Ca、Sr明显贫化。
九龙江河口区Ca、Sr、Mg等元素含量沿九龙江入海方向逐渐增大；而Al、Fe、Cu、Co等则沿入海方向略呈降低趋势。厦门西港中多数元素的含量分布较为均匀。同安湾沉积物中元素Ba、Co、Cu、Ni、V含量分布相对均匀，元素Ca、Sr、Mg等沿着入海方向呈现增加的趋势。
根据R型聚类分析结果将厦门湾沉积物分为三组：Fe、Al、Cu、Zn等元素为代表的粘土矿物组，以Ca、Mg、Ba、Sr等碱土金属为代表的碳酸盐矿物组和受人为活动的输入影响较大的元素(如元素P等)组。不同站位的Q型聚类分析将厦门湾分为五个元素地球化学分区，即以Fe、Al、Zn、Cu等元素含量高值区为特征的九龙江河口湾区，以元素P含量高值区为特征的同安湾东嘴港区，Ca、Na、Ni等元素含量高值区为特征的同安湾浔江海区，Sr、Ba、Ti等元素含量高值区为特征的厦门湾南部海区和以Co、Cr等元素含量高值区为特征的厦门西港海区。
厦门湾表层沉积物中元素Fe、Ti、Al、Co、Cr、Cu、Li、Ni、P、Zn等主要赋存在残渣态中，而元素Ca、Sr、Mn等主要赋存于非残渣态中。按元素的残渣态所占比例由高到低排序，可得如下结果，Ti＞Al＞Ba＞Fe＞V＞Li＞Zn＞Cu＞Cr＞Ni＞Co＞P＞Sr＞Mn＞Na＞Ca。
厦门湾表层沉积物元素的赋存形态存在不同程度的空间差异。在九龙江
河口区，多数元素在不同站位的赋存形态差异较大，而厦门西港和同安湾差
异较小。Mn、P、Ca、Sr等元素赋存形态的空间差异较大，其余元素差异
较小。
物质来源、沉积物粒度和水动力条件是厦门湾表层沉积物中元素含量、
赋存形态和空间分布等地球化学特征的主要控制因素。
Surface sediment samples collected from 22 stations in three regions of the Xiamen Bay, i.e., Jiulongjiang estuary, Xiamen Western Sea and Tongan Bay, were analyzed for both the major and trace elements(Al.. Fe.. Mn.. Ti.. Ca.. Mg.. Na.. Ba.. Co.. Cr.. Cu.. Li.. Ni.. P.. Sr.. V.. Zn) systemically, for the first time. The sedimentological and geochemical factors that controlled the contents, distribution patterns and the speciation of these elements were evaluated as well. The main results gained here were:
Contents of most elements in the surface sediment samples from Xiamen Bay were similar with those of average coastal sediment of China and the soil of Fujian province, but were generally high in Zn and Mn, low in Ca and Sr, compared to those of changjiang estuary and huanghe estuary.
Spatial distribution patterns of elements: the contents of Ca.. Sr.. Mg in Jiulongjiang estuary increased along the river towards the sea, while the distribution of Al.. Fe.. Cu.. Co showed an opposite trend. The majority of the elements in Xiamen Bay were unanimous in their distribution. The distributions of the elements in Tongan Bay exhibited two trends, Ba.. Co.. Cu.. Ni.. V had no obvious variety; while the contents of Ca.. Sr.. Mg increased from the inner part to the outer part (near the sea) of the bay.
The sediment types in Xiamen bay could be divided into three groups by model R Cluster Analysis: Fe.. Al.. Cu.. Zn appeared to be enriched in mud deposits; alkaline earth elements Ca.. Mg.. Ba.. Sr were
III
7
associated with the carbonate-rich sediments; P, however, did not match those two patterns but instead had a higher content in the sediments influenced by anthropogenic inputs heavily. Based on the regional distributions of elements and the hydraulic environments, the elements of sediments in Xiamen Bay could be divided into three distribution patterns and geochemical regions by model Q Cluster Analysis. The concentrations of elements near the Jiulongjiang estuary were characterized by high Fe~ Al.. Zn~. Cu; Dongzui harbor in Tongan bay had high content of P; high values of Ca.. Na.. Ni appeared in the Xunjiang of the Tongan Bay; the areas in the south of Xiamen Bay showed high values of Sr.. Ba.. Ti; the sediments of the Xiamen Western Sea had high Co.. Cr contents.
A four-stage sequential extraction procedure for determination of the speciation of extractable element, proposed by the Commission of the European Communities Bureau of Reference (BCR), had been applied to the sediments in Xiamen Bay. The results obtained showed that the majority of the elements studied, such as Fe.. Ti.. Al.. Co.. Cr.. Cu.. Li.. Ni.. P.. Zn, in the sediment of Xiamen Bay, were predominate in the residual fraction. On the contrary, Ca.. Sr and Mn were similar, with the residual fraction being of lowest significance. They were extracted in the largest percentage in exchangeable and bound to carbonates fraction. The relative abundance in residual fraction for these element followed the order: Ti> Al> Ba> Fe > V> Li > Zn> Cu> Cr> Ni> Co > P> Sr> Mn> Na> Ca0
The elements bound to different phases in Xiamen Bay behaved
Iv
differently in the level of spatial distributions. The variations in element speciation along the Jiulongjiang estuary were considerably greater than those of Xiamen West Sea and Tongan Bay. Relative to the distribution of other element speciation, the elements, such as Mn~ P~. Ca~. Sr, showed more obvious variation.
The sources, grain sizes and the currents were three major factors controlling the geochemical characteristics, such as the contents, speciation and spatial distribution patterns, of the surface sediments in Xiamen Bay.
厦门湾表层沉积物中所研究的多数元素的丰度接近于中国近岸浅海沉积物及福建省土壤平均值，但与长江口、黄河口沉积物相比，元素Zn和Mn有不同程度的富集，而Ca、Sr明显贫化。
九龙江河口区Ca、Sr、Mg等元素含量沿九龙江入海方向逐渐增大；而Al、Fe、Cu、Co等则沿入海方向略呈降低趋势。厦门西港中多数元素的含量分布较为均匀。同安湾沉积物中元素Ba、Co、Cu、Ni、V含量分布相对均匀，元素Ca、Sr、Mg等沿着入海方向呈现增加的趋势。
根据R型聚类分析结果将厦门湾沉积物分为三组：Fe、Al、Cu、Zn等元素为代表的粘土矿物组，以Ca、Mg、Ba、Sr等碱土金属为代表的碳酸盐矿物组和受人为活动的输入影响较大的元素(如元素P等)组。不同站位的Q型聚类分析将厦门湾分为五个元素地球化学分区，即以Fe、Al、Zn、Cu等元素含量高值区为特征的九龙江河口湾区，以元素P含量高值区为特征的同安湾东嘴港区，Ca、Na、Ni等元素含量高值区为特征的同安湾浔江海区，Sr、Ba、Ti等元素含量高值区为特征的厦门湾南部海区和以Co、Cr等元素含量高值区为特征的厦门西港海区。
厦门湾表层沉积物中元素Fe、Ti、Al、Co、Cr、Cu、Li、Ni、P、Zn等主要赋存在残渣态中，而元素Ca、Sr、Mn等主要赋存于非残渣态中。按元素的残渣态所占比例由高到低排序，可得如下结果，Ti＞Al＞Ba＞Fe＞V＞Li＞Zn＞Cu＞Cr＞Ni＞Co＞P＞Sr＞Mn＞Na＞Ca。
厦门湾表层沉积物元素的赋存形态存在不同程度的空间差异。在九龙江
河口区，多数元素在不同站位的赋存形态差异较大，而厦门西港和同安湾差
异较小。Mn、P、Ca、Sr等元素赋存形态的空间差异较大，其余元素差异
较小。
物质来源、沉积物粒度和水动力条件是厦门湾表层沉积物中元素含量、
赋存形态和空间分布等地球化学特征的主要控制因素。
Surface sediment samples collected from 22 stations in three regions of the Xiamen Bay, i.e., Jiulongjiang estuary, Xiamen Western Sea and Tongan Bay, were analyzed for both the major and trace elements(Al.. Fe.. Mn.. Ti.. Ca.. Mg.. Na.. Ba.. Co.. Cr.. Cu.. Li.. Ni.. P.. Sr.. V.. Zn) systemically, for the first time. The sedimentological and geochemical factors that controlled the contents, distribution patterns and the speciation of these elements were evaluated as well. The main results gained here were:
Contents of most elements in the surface sediment samples from Xiamen Bay were similar with those of average coastal sediment of China and the soil of Fujian province, but were generally high in Zn and Mn, low in Ca and Sr, compared to those of changjiang estuary and huanghe estuary.
Spatial distribution patterns of elements: the contents of Ca.. Sr.. Mg in Jiulongjiang estuary increased along the river towards the sea, while the distribution of Al.. Fe.. Cu.. Co showed an opposite trend. The majority of the elements in Xiamen Bay were unanimous in their distribution. The distributions of the elements in Tongan Bay exhibited two trends, Ba.. Co.. Cu.. Ni.. V had no obvious variety; while the contents of Ca.. Sr.. Mg increased from the inner part to the outer part (near the sea) of the bay.
The sediment types in Xiamen bay could be divided into three groups by model R Cluster Analysis: Fe.. Al.. Cu.. Zn appeared to be enriched in mud deposits; alkaline earth elements Ca.. Mg.. Ba.. Sr were
III
7
associated with the carbonate-rich sediments; P, however, did not match those two patterns but instead had a higher content in the sediments influenced by anthropogenic inputs heavily. Based on the regional distributions of elements and the hydraulic environments, the elements of sediments in Xiamen Bay could be divided into three distribution patterns and geochemical regions by model Q Cluster Analysis. The concentrations of elements near the Jiulongjiang estuary were characterized by high Fe~ Al.. Zn~. Cu; Dongzui harbor in Tongan bay had high content of P; high values of Ca.. Na.. Ni appeared in the Xunjiang of the Tongan Bay; the areas in the south of Xiamen Bay showed high values of Sr.. Ba.. Ti; the sediments of the Xiamen Western Sea had high Co.. Cr contents.
A four-stage sequential extraction procedure for determination of the speciation of extractable element, proposed by the Commission of the European Communities Bureau of Reference (BCR), had been applied to the sediments in Xiamen Bay. The results obtained showed that the majority of the elements studied, such as Fe.. Ti.. Al.. Co.. Cr.. Cu.. Li.. Ni.. P.. Zn, in the sediment of Xiamen Bay, were predominate in the residual fraction. On the contrary, Ca.. Sr and Mn were similar, with the residual fraction being of lowest significance. They were extracted in the largest percentage in exchangeable and bound to carbonates fraction. The relative abundance in residual fraction for these element followed the order: Ti> Al> Ba> Fe > V> Li > Zn> Cu> Cr> Ni> Co > P> Sr> Mn> Na> Ca0
The elements bound to different phases in Xiamen Bay behaved
Iv
differently in the level of spatial distributions. The variations in element speciation along the Jiulongjiang estuary were considerably greater than those of Xiamen West Sea and Tongan Bay. Relative to the distribution of other element speciation, the elements, such as Mn~ P~. Ca~. Sr, showed more obvious variation.
The sources, grain sizes and the currents were three major factors controlling the geochemical characteristics, such as the contents, speciation and spatial distribution patterns, of the surface sediments in Xiamen Bay.
引文
[1] J．P．Riley，G．Skirrow，刘光等译，化学海洋学，第六卷，北京，海洋出版社，1986
[2] 赵一阳，喻德科，黄海沉积物地球化学分析，海洋与湖沼，1983，14(5)432～445
[3] 蓝先洪，黄河，长江和珠江三角洲近代沉积物的沉积化学特征，台湾海峡，1995，14(1)：44-5
[4] 蓝先洪，珠江口沉积物的地球化学研究，中国主要河口的生物地球化学研究，北京，海洋出版社，1996
[5] 刘苍字，邱佩英，王孝京．浙南近岸带沉积物的地球化学特征．海洋通报，1991，10(5)：27～36
[6] A.S. Basaham, M.A. El-Sayed, Distribution and phase association of some major and trace elements in the Arabian gulf sediments, Estuarine Coastal and Shelf Science, 1998, 46:185-194
[7] P.W. Balls, S. Hull, B.S. Miller et al.,Trace metal in Scottish estuarine and coastal sediments, Marine Pollution Bulletin, 1997, 34(1):42～50
[8] 刘素美，张经，沉积物中重金属的归一化处理—以Al为例，东海海洋，1998，16(3)：48-55
[9] J.K. Cochran, D.J. Hirschberg, D.J. wang, et al.,Atmospheric deposition of metals to coastal waters (Long Island Sound, New York, USA): evidence from saltmarsh deposits, Estuarine Coastal Shelf Science, 1998, 46:503-522
[10]马德毅，海洋沉积物的污染指示作用和监测方法，海洋通报，1993，12(5)：89-97
[11]S.D.W. Comber, A.M. Gunn and C. Whalley, Comparison of the partitioning of trace metals in the Humber and Mersey Estuaries, Marine Pollution Bulletin, 1995, 30:851-860
[12] B. Rubio, M.A. Nombela, E Vilas, Geochemistry of major and trace elements in sediments of the Ria de Vigo (NW Spain): an assessment of metal pollution, Marine Pollution Bulletin, 2000, 40(11):968-980
[13] 廖文卓，潘皆再，陈松，九龙江口厦门港沉积物中镉、铜、铅的分布和行为．台湾海峡，1983，2(1)：47-53
[14] 洪华生，洪丽玉，刘琼玉，厦门西海域沉积物柱状样中 Cu，Pb，Zn，Cd 的垂直分布特征，香港与厦门港湾污染沉积物的研究，厦门，厦门大学出版社，1997
[15] 刘素美，于庆，大辽河口重金属的地球化学，中国主要河口的生物地球化学研究，北京，海洋出版社，1996
[16] G. Müller, Schwermetalle in den sedimenten des Rhèins-Vernderungen seitt 1971, Umschan, 1979, 79:778-783
[17] X.D. Li, On L. Campanella, D. D'Orazio, B.M. Petronio, E. Pietrantonio, Proposal for a metal speciation study in sediments, Anal. Dhim. Acta, 1995, 309:387-393
[18] Carmen Izquierdo, Jose Usero and Ignacio Gracia, Speciation of heavy metals in sediments from salt marshes on the Southern Atlantic Coast of Spain, Marine Pollution Bulletin, 1997, 34(2): 123-128
[19] 庄峙厦，洪华生，张珞平等，香港维多利亚港 Cu、Pb、Cd 在各地球化学相中的分布特征，厦门大学学报，1994，33(6)：832-837
[20] 陈松，许爱玉，骆炳坤等，长江口表层沉积物中 Fe，Mn，Zn，Co，Ni 的地球化学特征，台湾海峡，1987，6(1) 13～19
[21] 徐立，洪华生等，台湾海峡南部沉积物中主要金属元素的地球化学，“闽南台湾浅滩渔场上升流生态系研究”，北京，科学出版社，1991
[22] Tessier, P.G.C. Campbell, M. Bisson, Sequential extraction procedure for the speciation of particulated metals, Anal Chem.,1979, 51:844-851
[23] M. Kersten, U. Forstner, Chemical fractionation of heavy metals in anoxic estuarine and coastal sediments, Water Sci. Technol.,1986, 18:121-130
[24] A.M. Ure, Ph. Quevauviller, H. Muntau, et al.,An account of the improvement and harmonization of extraction techniques undertaken under the auspices of the BCR of the commission of the European Communities, Int. J. Environ. Anal. Chem.,1993, 51:135-627
[25] J. Bryn, T. Adnan, Distribution and speciation of heavy metals in surficial sediments from the Tees estuary, north-east English, Marine pollution bulletin, 1997, 34(10):768-779
[26] Michael Hon-wah Lam, Angel Yuk-wai Tjia, Chun-chiu Chan et al.,Speciation study of chromium, copper and nickel in coastal estuarine sediments polluted by domestic and industrial effluents, Marine Pollution Bulletin, 1997, 34(11):949～959
[27] 沈耀琴，厦门港湾表层沉积物中 Fe_2O_3，Al_2O_3，TiO_2含量的分布及相关性，台湾海峡，1987，6(2)：146～151
[28] 黄衍宽，厦门港湾沉积物中几种元素的地球化学行为，厦门市海岛调查研究论文集，郑家麟主编，北京，海洋出版社，1996
[29] 陈水土，阮五崎，九龙江口、厦门西海域磷的生物地球化学研究，Ⅱ表层沉积物中磷形态的分布及在再悬浮过程中的转化，海洋学报，1993，15(6)：47～54
[30] 陈淑美，傅天保，林建云，厦门西港表层沉积物磷的形态和分布，台湾海峡，1991，10(3)：235-239
[2] 赵一阳，喻德科，黄海沉积物地球化学分析，海洋与湖沼，1983，14(5)432～445
[3] 蓝先洪，黄河，长江和珠江三角洲近代沉积物的沉积化学特征，台湾海峡，1995，14(1)：44-5
[4] 蓝先洪，珠江口沉积物的地球化学研究，中国主要河口的生物地球化学研究，北京，海洋出版社，1996
[5] 刘苍字，邱佩英，王孝京．浙南近岸带沉积物的地球化学特征．海洋通报，1991，10(5)：27～36
[6] A.S. Basaham, M.A. El-Sayed, Distribution and phase association of some major and trace elements in the Arabian gulf sediments, Estuarine Coastal and Shelf Science, 1998, 46:185-194
[7] P.W. Balls, S. Hull, B.S. Miller et al.,Trace metal in Scottish estuarine and coastal sediments, Marine Pollution Bulletin, 1997, 34(1):42～50
[8] 刘素美，张经，沉积物中重金属的归一化处理—以Al为例，东海海洋，1998，16(3)：48-55
[9] J.K. Cochran, D.J. Hirschberg, D.J. wang, et al.,Atmospheric deposition of metals to coastal waters (Long Island Sound, New York, USA): evidence from saltmarsh deposits, Estuarine Coastal Shelf Science, 1998, 46:503-522
[10]马德毅，海洋沉积物的污染指示作用和监测方法，海洋通报，1993，12(5)：89-97
[11]S.D.W. Comber, A.M. Gunn and C. Whalley, Comparison of the partitioning of trace metals in the Humber and Mersey Estuaries, Marine Pollution Bulletin, 1995, 30:851-860
[12] B. Rubio, M.A. Nombela, E Vilas, Geochemistry of major and trace elements in sediments of the Ria de Vigo (NW Spain): an assessment of metal pollution, Marine Pollution Bulletin, 2000, 40(11):968-980
[13] 廖文卓，潘皆再，陈松，九龙江口厦门港沉积物中镉、铜、铅的分布和行为．台湾海峡，1983，2(1)：47-53
[14] 洪华生，洪丽玉，刘琼玉，厦门西海域沉积物柱状样中 Cu，Pb，Zn，Cd 的垂直分布特征，香港与厦门港湾污染沉积物的研究，厦门，厦门大学出版社，1997
[15] 刘素美，于庆，大辽河口重金属的地球化学，中国主要河口的生物地球化学研究，北京，海洋出版社，1996
[16] G. Müller, Schwermetalle in den sedimenten des Rhèins-Vernderungen seitt 1971, Umschan, 1979, 79:778-783
[17] X.D. Li, On L. Campanella, D. D'Orazio, B.M. Petronio, E. Pietrantonio, Proposal for a metal speciation study in sediments, Anal. Dhim. Acta, 1995, 309:387-393
[18] Carmen Izquierdo, Jose Usero and Ignacio Gracia, Speciation of heavy metals in sediments from salt marshes on the Southern Atlantic Coast of Spain, Marine Pollution Bulletin, 1997, 34(2): 123-128
[19] 庄峙厦，洪华生，张珞平等，香港维多利亚港 Cu、Pb、Cd 在各地球化学相中的分布特征，厦门大学学报，1994，33(6)：832-837
[20] 陈松，许爱玉，骆炳坤等，长江口表层沉积物中 Fe，Mn，Zn，Co，Ni 的地球化学特征，台湾海峡，1987，6(1) 13～19
[21] 徐立，洪华生等，台湾海峡南部沉积物中主要金属元素的地球化学，“闽南台湾浅滩渔场上升流生态系研究”，北京，科学出版社，1991
[22] Tessier, P.G.C. Campbell, M. Bisson, Sequential extraction procedure for the speciation of particulated metals, Anal Chem.,1979, 51:844-851
[23] M. Kersten, U. Forstner, Chemical fractionation of heavy metals in anoxic estuarine and coastal sediments, Water Sci. Technol.,1986, 18:121-130
[24] A.M. Ure, Ph. Quevauviller, H. Muntau, et al.,An account of the improvement and harmonization of extraction techniques undertaken under the auspices of the BCR of the commission of the European Communities, Int. J. Environ. Anal. Chem.,1993, 51:135-627
[25] J. Bryn, T. Adnan, Distribution and speciation of heavy metals in surficial sediments from the Tees estuary, north-east English, Marine pollution bulletin, 1997, 34(10):768-779
[26] Michael Hon-wah Lam, Angel Yuk-wai Tjia, Chun-chiu Chan et al.,Speciation study of chromium, copper and nickel in coastal estuarine sediments polluted by domestic and industrial effluents, Marine Pollution Bulletin, 1997, 34(11):949～959
[27] 沈耀琴，厦门港湾表层沉积物中 Fe_2O_3，Al_2O_3，TiO_2含量的分布及相关性，台湾海峡，1987，6(2)：146～151
[28] 黄衍宽，厦门港湾沉积物中几种元素的地球化学行为，厦门市海岛调查研究论文集，郑家麟主编，北京，海洋出版社，1996
[29] 陈水土，阮五崎，九龙江口、厦门西海域磷的生物地球化学研究，Ⅱ表层沉积物中磷形态的分布及在再悬浮过程中的转化，海洋学报，1993，15(6)：47～54
[30] 陈淑美，傅天保，林建云，厦门西港表层沉积物磷的形态和分布，台湾海峡，1991，10(3)：235-239
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