深海沉积物中的稀土矿产资源研究进展
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摘要
近年发现,太平洋和印度洋的深海盆地中存在大量富含稀土的深海沉积物。主要类型为多金属软泥、沸石黏土和远洋黏土,其中的全稀土含量(∑REY,∑REE+Y)为400×10-6~2000×10-6,最高可达6600×10-6,重稀土含量(HREE)已达到或超过中国南方离子吸附型矿床的重稀土品位两倍以上,是潜在的新型稀土资源,具有重要的经济价值。目前不少学者对富稀土的深海沉积物进行了大量地球化学及部分矿物学的工作,认为多金属软泥中的稀土元素多赋存于与海底热液作用有关的铁锰氧化物和氢氧化物中,而沸石黏土和远洋黏土中稀土元素的富集则与磷酸盐的混入密切相关,其稀土元素主要存在于与磷灰石成分相当的生物鱼骨屑中。深海黏土的北美页岩标准化稀土配分模式与海水相似,表明其中的稀土元素主要来自于海水,REY富集成矿可能主要受控于磷灰石早期成岩阶段,期间稀土元素未发生分异。尽管近些年对深海沉积物中的稀土元素研究取得了不少成果,但是,对于沉积物中的稀土富集机制及影响因素等问题仍然需要更加深入的研究。作为稀土资源大国,为了争取我国在国际海底稀土资源竞争中的话语权,维护中国的稀土利益,中国应加紧开展相关的稀土资源勘查和潜力评价。
The deep-sea sediments rich in rare earth elements discovered in recent years in the Pacific and Indian Ocean basin are a potential rare earth mineral resource. The metalliferous sediments, zeolite clay and pelagic clay are thought to be the main types of REY-rich sediments with high total REY(REE+Y) content(400×10-6-2000×10-6, the highest up to 6600×10-6) and heavy rare earth content(HREE). The HREE values of the sediments are nearly twice as abundant as those in the southern Chinaion-absorption-type deposits. Previous chemical and mineral studies suggest that Fe/Mn oxide and oxyhydroxide precipitated from hydrothermal activities is the main host of the REY in the metalliferous sediments, while phosphate whose chemical composition is equivalent to apatite(such as fish debris) is the main carrier of rare earth elements in the zeolite clay and pelagic clay. The NASC-normalized REEpatterns of deep-sea sediments are similar to those of seawater, indicating that the rare earth elements of the sediments were taken up from ambient seawater. REY were mainly enriched at the early diagenetic stage of apatite without differentiation. Many achievements have been made about the rare earth elements in deep-sea sediments in recent years. However, the enrichment mechanisms of rare earth elements in deep-sea sediments and influencing factors still need further study. China has been the dominant producer of REE and hosts the most known global reserves. In order to safeguard China's right in the competition for REE in the international seabed and safeguard China's benefit, it is very necessary and critical to search for and evaluate potential marine REE resources.
The deep-sea sediments rich in rare earth elements discovered in recent years in the Pacific and Indian Ocean basin are a potential rare earth mineral resource. The metalliferous sediments, zeolite clay and pelagic clay are thought to be the main types of REY-rich sediments with high total REY(REE+Y) content(400×10-6-2000×10-6, the highest up to 6600×10-6) and heavy rare earth content(HREE). The HREE values of the sediments are nearly twice as abundant as those in the southern Chinaion-absorption-type deposits. Previous chemical and mineral studies suggest that Fe/Mn oxide and oxyhydroxide precipitated from hydrothermal activities is the main host of the REY in the metalliferous sediments, while phosphate whose chemical composition is equivalent to apatite(such as fish debris) is the main carrier of rare earth elements in the zeolite clay and pelagic clay. The NASC-normalized REEpatterns of deep-sea sediments are similar to those of seawater, indicating that the rare earth elements of the sediments were taken up from ambient seawater. REY were mainly enriched at the early diagenetic stage of apatite without differentiation. Many achievements have been made about the rare earth elements in deep-sea sediments in recent years. However, the enrichment mechanisms of rare earth elements in deep-sea sediments and influencing factors still need further study. China has been the dominant producer of REE and hosts the most known global reserves. In order to safeguard China's right in the competition for REE in the international seabed and safeguard China's benefit, it is very necessary and critical to search for and evaluate potential marine REE resources.
引文
Aplin A C.1984.Rare earth element geochemistry of central Pacific ferromanganese encrustations[J].Earth Planetary Science Letters,71:13-22.
Arrhenius G,Bramlette M N,Piciotto E.1957.Localization of radioactive and stable heavy nuclides in ocean sediments[J].Nature,180:85-86.
Balistrieri L,Brewer P G,Murray J W.1981.Scavenging residence time of trace metals and surface chemistry of sinking particals in the deep ocean[J].Deep-Sea Research,28:101-121.
Boyle E A,Edmond J M,Sholkovitz E R.1977.The mechanism of iron removal in estuaries[J].Geochimica et Cosmochimica Acta,41:1313-1324.
Dubinin A V.2000.Geochemistry of Rare Earth Elements in Oceanic Phillipsites[J].Lithology and Mineral Resources,35(2):101-108.
Elderfield H,Pagett R.1986.Rare earth elements in ichthyoliths:variations with redox conditions and depositional environment[J].The Science of the total environment,49:175-197.
Fujinaga K,Yasukawa K,Nakamura K,Machida S,Takaya Y,Ohta J,Araki S,Liu H,Usami R,Maki R,Haraguchi S,Nishio Y,Usui Y,Nozaki t,Yamaki T,Ichiyama Y,Ijiri A,Inagaki f,Machiyama H,Iijima K,Suzuki K,Kato Y.2016.Geochemistry of REY-rich mud in the Japanese Exclusive Economic Zone around Minamitorishina Island[J].Geochemical Journal,50.
Grandjean P,Cappetta H,Michard A,Albarede F.1987.The assessment of REE patterns and143Nd/144Nd ratios in fish remains[J].Earth Planetary Science Letters,84:181-196.
Huang Dasong.2016.Geochemical Characteristics Zeolite Clay from the Central Indian Ocean Basin and the Implications for the Enrichment Process of REY[D].Zhejiang University(in Chinese with English abstract).
Huang Mu,Liu Jihua,Shi Xuefa,Zhu Aimei,Lv Huahua,Hu Limin.2014.Geochemical characteristics and material sources of Rare Earth Elements in sediments from the CC area in the Eastern Pacific Ocean[J].Advances in Marine Science,32(2):175-187.
Hunter K A.1983.The adsorptive properties of sinking particles in the deep ocean[J].Deep-Sea Research,30:669-675.
Jaireth S,Hoatson D M,Miezitis.2014.Geological setting and resources of the major rare-earth-element deposits in Australia[J].Ore Geology Reviews,62:72-128.
Kashiwabara T,Toda R,Fujinaga K,Honma T,Takshashi Y,Kato Y.2014.Determination of host phase of lanthanumin deep-sea REY-rich mud by XAFS and u-XRF using high-energy synchrotron radiation[J].Chem.Lett.,43:199-200.
Kato Y,Fujinaga K,Nakamura K,Takaya Y,Kitamura K,Ohta J,Toda R,Nakashima T,Iwamori H.2011.Deep-sea mud in the Pacific Ocean as a potential resource for Rare-earth elements[J].Nature Geoscience,3:535-539.
Kato Y.2012.The exploitation of the REY-rich deep-sea mud deposit in the EEZ of Japan,Ocean Policy Research Foundation(OPRF),NO.94 Conference(2012/9/18)(in Japanese).
Koeppenkastrop D,De Carlo E H,Roth M.1991.A method toinvestigate the interaction of rare earth elements in aqueous solution with metal oxides[J].J.Radioanal.Nucl.Chem.,152:337-346.
Kon Y,Hoshino M,Sanematsu K,Morita S,Tsunematsu M,Okamoto N,Yano N,Tanaka M,Takagi T.2014.Geochemical characteristics of apatite in heavy REE-rich deep-sea mud from MinamiTorishima area,Southeastern Japan[J].Resource Geology,64(1):47-57.
Liu Jihua.2004.The Geochemistry of REES and Nd isotope in DeepSea Sediments from the Eastern Pacific and Their Geological Implications[D].Graduate School of Chinese Academy of Sciences,2004(in Chinese).
Martin J M,Hogdahl O,Phillippot J C.1976.Rare Earth Element Supply to the Ocean[J].J.Geophys.Res.,81(18):3119-3124.
Mc Arthur J M,Walsh J N.1984.Rare-earth geochemistry of phosphorites[J].Chemical Geology,47:191-220.
Ohta J,Yasukawa K,Machida S,Fujinaga K,Nakamura K,Takaya Y,Iijima K,Suzuki K,Kato Y.2016.Geochemical factors responsible for REY-rich mud in the western North Pacific Ocean:Implications from mineralogy and grain size distributions[J].Geochemical Journal,50.
Oudin E,Cocherie A.1988.Fish debris record the hydrothermal activity in the Atlantis II Deep sediments(Red Sea)[J].Geochimica et Cosmochimica Acta,52:177-184.
Piper D Z.1974.Rare earth elements in ferromanganese nodules and other marine phases[J].Geochimica et Cosmochimica Acta,38:1007-1022.
Rasmussen B.1996.Early-diagenetic REE-phoshate minerals(florencite,gorceixite,crandallite,and xenotime)in marine sandstones:Amajoe sink for oceanic phosphorus[J].American Journal of Science,296:601-632.
Ren Jiangbo,Yao Huiqiang,Zhu Kechao He Gaowen,Deng Xiguang,Wang Haifeng,Liu Jiyong,Fu Piaoer,Yang Shengxiong.2015.Enrichment mechanism of rare earth elements and yttrium in deepsea mud of Clarion-Clipperton Region[J].Earth Science Frontiers,22(4):200-211(in Chinese with Englishabstract).
Shen Huadi.1990.The REE in deep-sea sediments[J].Geochemistry,20(4):340-348(in Chinese with Englishabstract).
Toyoda K,Nakamura Y,Masuda A.1990.Rare earth elements of Pacific pelagic sediments[J].Geochim Cosmochim Acta,54:1093-1103.
Wang Fenlian,He Gaowen,Wang Haifeng,Ran Jiangbo.2016.The elemental association characteristics and the geological significance of REY-rich pelagic sediments in the Central Pacific Ocean[J].Marine Geology Frontiers,32(7):11-18(in Chinese with English abstract).
Wang Fenlian,He Gaowen,Sun Xiaoming,Yang Yang,Zhao Taiping.2016.The host of REE+Y elements in deep-sea sediments from the Pacific Ocean[J].Acta Petrologica Scinica,32(7):2057-2068(in Chinese with English abstract).
Wang Zhonggang,Yu Xueyuan,Zhao Zhenghua.1987.The Geochemistry of Rare Earth Elements[M].Beijing:Science Press(in Chinese).
Wright J,Schrader H,Holser WT.1987.Paleoredox variations in ancient oceans recorded by rare earth elements in fossil apatite[J].Geochimica et Cosmochimica Acta,51,631-644.
Yasukawa K,Liu H J,Fujinaga K,Machida S,Haraguchi S,Ishii T,Nakamura K,Kato Y.2014.Geochemistry and mineralogy of REY-rich mud in the eastern Indian Ocean[J].Journal of Asian Earth Sciences,93:25-36
Zhang Xiaoyu,Deng Han,Zhang Fuyuan,Zhang Weiyan,Du Yong,Jiang Binbin.2013.Enrichment and geochemical characteristics of rare earthelements in deep-sea mud from seamount area of Western Pacific[J].Journal of the Chinese Society of Rare Earths,31(6):729-737(in Chinese with English Abstract).
Zhao Shanrong,Bian Qiujuan,Ling Qicong.2004.Crystallography and Mineralogy[M].Beijing:Higher Education Press,1-441(in Chinese).
Zhu Kechao,Ren Jiangbo,Wang Haifeng,Lu Hongfeng.2015.The enrichment mechanism of REY and geochemical characteristics of REY-rich pelagic clay from the central Pacific[J].Earth Science--China University of Geosciences,40(6):736-744(in Chinese with English Abstract).
黄大松.2016.中印度洋洋盆沸石型深海黏土地球化学特征及其对稀土元素富集过程的指示意义[D].浙江大学硕士学位论文.
黄牧,刘季花,石学法,朱爱美,吕华华,胡利民.2014.东太平洋CC区沉积物稀土元素特征及物源[J].海洋科学进展,32(2):175-187.
黄牧.2013.太平洋深海沉积物稀土元素地球化学特征及资源潜力初步研究[D].国家海洋局第一海洋研究所硕士学位论文.
刘季花.东太平洋沉积物稀土元素和Nd同位素地球化学特征及其环境指示意义[D].中国科学院研究生院,2004.
任江波,姚会强,朱克超,何高文,邓希光,王海峰,刘纪勇,傅飘儿,杨胜雄.2015.稀土元素在东太平洋CC区深海泥中的富集特征及机制[J].地学前缘,22(4):200-211.
沈华悌.1990.深海沉积物中的稀土元素[J].地球化学,20(4):340-348.
王汾连,何高文,孙晓明,杨阳,赵太平.2016.太平洋富稀土深海沉积物中稀土元素赋存载体研究[J].32(7):2057-2068.
王汾连,何高文,王海峰,任江波.2016.中太平洋深海沉积物中元素组合特征及地质意义[J].海洋地质前沿,32(7):11-18.
王中刚,于学元,赵振华.1987.稀土元素地球化学[M].科学出版社.
张霄宇,邓涵,张富元,章伟艳,杜泳,江彬彬.2013.西太平洋海山区深海软泥中稀土元素富集的地球化学特征[J].中国稀土学报,31(6):729-737.
赵珊茸,边秋娟,凌其聪.2004.结晶学与矿物学[M].北京:高等教育出版社,1-441.
朱克超,任江波,王海峰,陆红锋.2015.太平洋中部富REY深海黏土的地球化学特征及REY富集机制[J].地球科学--中国地质大学学报,40(6):736-744.
Arrhenius G,Bramlette M N,Piciotto E.1957.Localization of radioactive and stable heavy nuclides in ocean sediments[J].Nature,180:85-86.
Balistrieri L,Brewer P G,Murray J W.1981.Scavenging residence time of trace metals and surface chemistry of sinking particals in the deep ocean[J].Deep-Sea Research,28:101-121.
Boyle E A,Edmond J M,Sholkovitz E R.1977.The mechanism of iron removal in estuaries[J].Geochimica et Cosmochimica Acta,41:1313-1324.
Dubinin A V.2000.Geochemistry of Rare Earth Elements in Oceanic Phillipsites[J].Lithology and Mineral Resources,35(2):101-108.
Elderfield H,Pagett R.1986.Rare earth elements in ichthyoliths:variations with redox conditions and depositional environment[J].The Science of the total environment,49:175-197.
Fujinaga K,Yasukawa K,Nakamura K,Machida S,Takaya Y,Ohta J,Araki S,Liu H,Usami R,Maki R,Haraguchi S,Nishio Y,Usui Y,Nozaki t,Yamaki T,Ichiyama Y,Ijiri A,Inagaki f,Machiyama H,Iijima K,Suzuki K,Kato Y.2016.Geochemistry of REY-rich mud in the Japanese Exclusive Economic Zone around Minamitorishina Island[J].Geochemical Journal,50.
Grandjean P,Cappetta H,Michard A,Albarede F.1987.The assessment of REE patterns and143Nd/144Nd ratios in fish remains[J].Earth Planetary Science Letters,84:181-196.
Huang Dasong.2016.Geochemical Characteristics Zeolite Clay from the Central Indian Ocean Basin and the Implications for the Enrichment Process of REY[D].Zhejiang University(in Chinese with English abstract).
Huang Mu,Liu Jihua,Shi Xuefa,Zhu Aimei,Lv Huahua,Hu Limin.2014.Geochemical characteristics and material sources of Rare Earth Elements in sediments from the CC area in the Eastern Pacific Ocean[J].Advances in Marine Science,32(2):175-187.
Hunter K A.1983.The adsorptive properties of sinking particles in the deep ocean[J].Deep-Sea Research,30:669-675.
Jaireth S,Hoatson D M,Miezitis.2014.Geological setting and resources of the major rare-earth-element deposits in Australia[J].Ore Geology Reviews,62:72-128.
Kashiwabara T,Toda R,Fujinaga K,Honma T,Takshashi Y,Kato Y.2014.Determination of host phase of lanthanumin deep-sea REY-rich mud by XAFS and u-XRF using high-energy synchrotron radiation[J].Chem.Lett.,43:199-200.
Kato Y,Fujinaga K,Nakamura K,Takaya Y,Kitamura K,Ohta J,Toda R,Nakashima T,Iwamori H.2011.Deep-sea mud in the Pacific Ocean as a potential resource for Rare-earth elements[J].Nature Geoscience,3:535-539.
Kato Y.2012.The exploitation of the REY-rich deep-sea mud deposit in the EEZ of Japan,Ocean Policy Research Foundation(OPRF),NO.94 Conference(2012/9/18)(in Japanese).
Koeppenkastrop D,De Carlo E H,Roth M.1991.A method toinvestigate the interaction of rare earth elements in aqueous solution with metal oxides[J].J.Radioanal.Nucl.Chem.,152:337-346.
Kon Y,Hoshino M,Sanematsu K,Morita S,Tsunematsu M,Okamoto N,Yano N,Tanaka M,Takagi T.2014.Geochemical characteristics of apatite in heavy REE-rich deep-sea mud from MinamiTorishima area,Southeastern Japan[J].Resource Geology,64(1):47-57.
Liu Jihua.2004.The Geochemistry of REES and Nd isotope in DeepSea Sediments from the Eastern Pacific and Their Geological Implications[D].Graduate School of Chinese Academy of Sciences,2004(in Chinese).
Martin J M,Hogdahl O,Phillippot J C.1976.Rare Earth Element Supply to the Ocean[J].J.Geophys.Res.,81(18):3119-3124.
Mc Arthur J M,Walsh J N.1984.Rare-earth geochemistry of phosphorites[J].Chemical Geology,47:191-220.
Ohta J,Yasukawa K,Machida S,Fujinaga K,Nakamura K,Takaya Y,Iijima K,Suzuki K,Kato Y.2016.Geochemical factors responsible for REY-rich mud in the western North Pacific Ocean:Implications from mineralogy and grain size distributions[J].Geochemical Journal,50.
Oudin E,Cocherie A.1988.Fish debris record the hydrothermal activity in the Atlantis II Deep sediments(Red Sea)[J].Geochimica et Cosmochimica Acta,52:177-184.
Piper D Z.1974.Rare earth elements in ferromanganese nodules and other marine phases[J].Geochimica et Cosmochimica Acta,38:1007-1022.
Rasmussen B.1996.Early-diagenetic REE-phoshate minerals(florencite,gorceixite,crandallite,and xenotime)in marine sandstones:Amajoe sink for oceanic phosphorus[J].American Journal of Science,296:601-632.
Ren Jiangbo,Yao Huiqiang,Zhu Kechao He Gaowen,Deng Xiguang,Wang Haifeng,Liu Jiyong,Fu Piaoer,Yang Shengxiong.2015.Enrichment mechanism of rare earth elements and yttrium in deepsea mud of Clarion-Clipperton Region[J].Earth Science Frontiers,22(4):200-211(in Chinese with Englishabstract).
Shen Huadi.1990.The REE in deep-sea sediments[J].Geochemistry,20(4):340-348(in Chinese with Englishabstract).
Toyoda K,Nakamura Y,Masuda A.1990.Rare earth elements of Pacific pelagic sediments[J].Geochim Cosmochim Acta,54:1093-1103.
Wang Fenlian,He Gaowen,Wang Haifeng,Ran Jiangbo.2016.The elemental association characteristics and the geological significance of REY-rich pelagic sediments in the Central Pacific Ocean[J].Marine Geology Frontiers,32(7):11-18(in Chinese with English abstract).
Wang Fenlian,He Gaowen,Sun Xiaoming,Yang Yang,Zhao Taiping.2016.The host of REE+Y elements in deep-sea sediments from the Pacific Ocean[J].Acta Petrologica Scinica,32(7):2057-2068(in Chinese with English abstract).
Wang Zhonggang,Yu Xueyuan,Zhao Zhenghua.1987.The Geochemistry of Rare Earth Elements[M].Beijing:Science Press(in Chinese).
Wright J,Schrader H,Holser WT.1987.Paleoredox variations in ancient oceans recorded by rare earth elements in fossil apatite[J].Geochimica et Cosmochimica Acta,51,631-644.
Yasukawa K,Liu H J,Fujinaga K,Machida S,Haraguchi S,Ishii T,Nakamura K,Kato Y.2014.Geochemistry and mineralogy of REY-rich mud in the eastern Indian Ocean[J].Journal of Asian Earth Sciences,93:25-36
Zhang Xiaoyu,Deng Han,Zhang Fuyuan,Zhang Weiyan,Du Yong,Jiang Binbin.2013.Enrichment and geochemical characteristics of rare earthelements in deep-sea mud from seamount area of Western Pacific[J].Journal of the Chinese Society of Rare Earths,31(6):729-737(in Chinese with English Abstract).
Zhao Shanrong,Bian Qiujuan,Ling Qicong.2004.Crystallography and Mineralogy[M].Beijing:Higher Education Press,1-441(in Chinese).
Zhu Kechao,Ren Jiangbo,Wang Haifeng,Lu Hongfeng.2015.The enrichment mechanism of REY and geochemical characteristics of REY-rich pelagic clay from the central Pacific[J].Earth Science--China University of Geosciences,40(6):736-744(in Chinese with English Abstract).
黄大松.2016.中印度洋洋盆沸石型深海黏土地球化学特征及其对稀土元素富集过程的指示意义[D].浙江大学硕士学位论文.
黄牧,刘季花,石学法,朱爱美,吕华华,胡利民.2014.东太平洋CC区沉积物稀土元素特征及物源[J].海洋科学进展,32(2):175-187.
黄牧.2013.太平洋深海沉积物稀土元素地球化学特征及资源潜力初步研究[D].国家海洋局第一海洋研究所硕士学位论文.
刘季花.东太平洋沉积物稀土元素和Nd同位素地球化学特征及其环境指示意义[D].中国科学院研究生院,2004.
任江波,姚会强,朱克超,何高文,邓希光,王海峰,刘纪勇,傅飘儿,杨胜雄.2015.稀土元素在东太平洋CC区深海泥中的富集特征及机制[J].地学前缘,22(4):200-211.
沈华悌.1990.深海沉积物中的稀土元素[J].地球化学,20(4):340-348.
王汾连,何高文,孙晓明,杨阳,赵太平.2016.太平洋富稀土深海沉积物中稀土元素赋存载体研究[J].32(7):2057-2068.
王汾连,何高文,王海峰,任江波.2016.中太平洋深海沉积物中元素组合特征及地质意义[J].海洋地质前沿,32(7):11-18.
王中刚,于学元,赵振华.1987.稀土元素地球化学[M].科学出版社.
张霄宇,邓涵,张富元,章伟艳,杜泳,江彬彬.2013.西太平洋海山区深海软泥中稀土元素富集的地球化学特征[J].中国稀土学报,31(6):729-737.
赵珊茸,边秋娟,凌其聪.2004.结晶学与矿物学[M].北京:高等教育出版社,1-441.
朱克超,任江波,王海峰,陆红锋.2015.太平洋中部富REY深海黏土的地球化学特征及REY富集机制[J].地球科学--中国地质大学学报,40(6):736-744.