贵州道坨锰矿菱锰矿的稀土元素特征
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摘要
贵州道坨锰矿是2010年发现的一个大型碳酸锰矿床,含矿层位为南华系大塘坡组底部的含锰黑色页岩,主要含锰矿物为菱锰矿。通过对锰矿石全岩与提取出的菱锰矿进行稀土元素对比分析发现:(1)不同Mn含量的锰矿石的∑REE在(171.84~243.08)×10-6之间,提取的菱锰矿的∑REE在(32.52~135.69)×10-6之间,菱锰矿的∑REE占全岩∑REE的比例从15%到80%不等。菱锰矿的∑REE随着锰含量的升高而升高,且稀土元素配分模式都呈轻稀土含量少,中稀土富集,重稀土相对中稀土减少的"帽"式配分模式,而全岩的配分模式基本是平坦的直线型。随着全岩中Mn含量的升高,全岩和菱锰矿的配分模式越来越相似;(2)菱锰矿的δCe值在1左右,且随着Mn含量的升高。δCe值变大,这可能是因为Ce在锰氧化物或氢氧化物逐渐沉积富集的过程中,逐渐地被吸附,而造成了异常值的逐渐增大,说明菱锰矿的形成经过了锰氧化物或氢氧化物的阶段;(3)分别比较菱锰矿中Mn和P与轻、中、重稀土的相关性,Mn与中稀土的相关性最差,而P与中稀土的相关性最好。因此菱锰矿所表现出的中稀土富集的现象可能是其中的磷酸盐引起的,而磷酸盐与菱锰矿的共存可能是因为当时环境中磷与锰的分离不彻底造成的。
The Daotuo manganese deposit in Guizhou is a large-scale carbonate manganese deposit discovered in2010 and hosted in the manganese-bearing black shales with rhodochrosite as the main manganese-bearing mineral at the base of the Nanhuan Datangpo Formation. The results of research in this study are generalized as follows.( 1) The ΣREE contents range between 171. 84 × 10- 6and 243. 08 × 10- 6for the manganese ores with different manganese contents; 32. 52 × 10-6and 135. 69 × 10-6for the selected rhodochrosite in which the ΣREE contents amount to 15% and 80% of the whole manganese-bearing rocks,and ΣREE contents in rhodochrosite tend to increase with the increase of manganese contents. The REE distribution patterns for the rhodochrosite exhibit the"cap"-type distribution patterns showing low LREE contents,enriched MREE contents and relatively lower HREE contents than MREE contents,while almostly smooth straight distribution patterns for the whole manganese-bearing rocks.( 2) The δCe values equal to about 1,and increase with the increase of Mn contents,indicating the gradual absorption of the element Ce during the deposition and enrichment of the manganese oxides and hydroxides.( 3)There is no correlation between Mn and MREE,and a good correlation between P and MREE. It is inferred that the MREE enrichment in rhodochrosite may be caused by the phosphates,and coexistence of the phosphates and rhodochrosite may be ascribed to the incomplete separation of the elements P and Mn in the depositional environments at that time.
The Daotuo manganese deposit in Guizhou is a large-scale carbonate manganese deposit discovered in2010 and hosted in the manganese-bearing black shales with rhodochrosite as the main manganese-bearing mineral at the base of the Nanhuan Datangpo Formation. The results of research in this study are generalized as follows.( 1) The ΣREE contents range between 171. 84 × 10- 6and 243. 08 × 10- 6for the manganese ores with different manganese contents; 32. 52 × 10-6and 135. 69 × 10-6for the selected rhodochrosite in which the ΣREE contents amount to 15% and 80% of the whole manganese-bearing rocks,and ΣREE contents in rhodochrosite tend to increase with the increase of manganese contents. The REE distribution patterns for the rhodochrosite exhibit the"cap"-type distribution patterns showing low LREE contents,enriched MREE contents and relatively lower HREE contents than MREE contents,while almostly smooth straight distribution patterns for the whole manganese-bearing rocks.( 2) The δCe values equal to about 1,and increase with the increase of Mn contents,indicating the gradual absorption of the element Ce during the deposition and enrichment of the manganese oxides and hydroxides.( 3)There is no correlation between Mn and MREE,and a good correlation between P and MREE. It is inferred that the MREE enrichment in rhodochrosite may be caused by the phosphates,and coexistence of the phosphates and rhodochrosite may be ascribed to the incomplete separation of the elements P and Mn in the depositional environments at that time.
引文
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[19]王剑.华南新元古代裂谷盆地沉积演化——兼论与Rodinia解体的关系[M].北京:地质出版社,2000.1-146.
[20]覃英,安正泽,王佳武,李代平.贵州松桃锰矿整装勘查区道坨隐伏超大型锰矿床的发现及地质特征[J].矿产勘查,2013,4(4):345-355.
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[27]解启来,陈多福,漆亮,陈先沛.贵州瓮安陡山沱组磷块岩的稀土元素地球化学特征与沉积古环境[J].矿物学报,2003,23(4):289-295.
[28]ILYIN A V.Rare earth geochemistry of“old”phosphorites and probability of syngenetic precipitation and accumulation of phosphate[J].Chemical Geology,1998,144:243-256.
[29]侯宗林等.扬子地台周边锰矿[M].北京:冶金工业出版社,1997.260-270.
[2]高兴基,朱育群等.松桃地区早震旦世大塘坡期锰矿成矿地质条件及找矿方向[R].贵州省地质矿产局一O三地质大队,1985.
[3]陈多福,陈先沛.贵州省松桃热水沉积锰矿的地质地球特征[J].沉积学报,1992,12(4):35-431.
[4]解启来,陈多福,陈先沛.贵州松桃锰矿沉积有机质特征研究[J].沉积学报,1999,17(2):280-283
[5]杨瑞东,欧阳自远,朱立军,王世杰,姜立君,张位花,高慧.早震旦世大塘坡期锰矿成因新认识[J].矿物学报,2002,22(4):329-334.
[6]杨绍祥,劳可通.湘西北锰矿床成矿模式研究—以湖南花垣民乐锰矿床为例[J].沉积与特提斯地质,2006,26(2):72-80.
[7]覃英,周琦,张遂.黔东北地区南华纪锰矿基本特征[J].贵州地质,2005,22(4):246-251.
[8]周琦,杜远生,王家生,彭加强.黔东北地区南华系大塘坡组冷泉碳酸盐岩及其意义[J].地球科学—中国地质大学学报,2007,32(3):339-346.
[9]周琦,杜远生等.贵州松桃大塘坡地区南华纪早期冷泉碳酸盐岩地质地球化学特征[J].地球科学—中国地质大学学报,2007,32(6):845-852.
[10]张飞飞,朱祥坤,高兆富,程龙,彭乾云,杨德智.黔东北西溪堡锰矿的沉淀形式与含锰层位中黄铁矿异常高34S值的成因[J].地质论评,2013,59(2):274-286.
[11]张飞飞,闫斌,郭跃玲,朱祥坤,周琦,杨德智.湖北古城锰矿的沉淀形式及其古环境意义[J].地质学报,2013,87(2):245-258.
[12]朱祥坤,彭乾云,张仁彪,安正泽,张飞飞,闫斌,李津,高兆富,覃英,潘文.贵州省松桃县道坨超大型锰矿床地质地球化学特征[J].地质学报,2013,87(9):1335-1348.
[13]陈多福,陈先沛.贵州省松桃热水沉积锰矿的地质地球化学特征[J].沉积学报,1992,10(4):35-43.
[14]谭满堂,鲁志雄,张嫣.鄂西地区南华系大塘坡期锰矿成因浅析—以长阳古城锰矿为例[J].资源环境与工程,2009,23(2):108-113.
[15]杨瑞东,高军波,程玛莉,魏怀瑞,许利群,文雪峰,魏晓.贵州从江高增新元古代大塘坡组锰矿沉积地球化学特征[J].地质学报,2010,84(12):1781-1790.
[16]何志威,杨瑞东,高军波,程伟,黄建国.贵州省松桃杨家湾锰矿含锰岩系地质地球化学特征[J].现代地质,2013,27(3):593-602.
[17]陈祎,张均,刘安璐,王中群.贵州松桃千公坪锰矿地质地球化学特征[J].矿物岩石地球化学通报,2014,33(2):1-10.
[18]皮道会,刘丛强,邓海琳,Graham Shields.贵州遵义牛蹄塘组黑色岩系有机质的稀土元素地球化学研究[J].矿物学报,2008,28(3):303-310.
[19]王剑.华南新元古代裂谷盆地沉积演化——兼论与Rodinia解体的关系[M].北京:地质出版社,2000.1-146.
[20]覃英,安正泽,王佳武,李代平.贵州松桃锰矿整装勘查区道坨隐伏超大型锰矿床的发现及地质特征[J].矿产勘查,2013,4(4):345-355.
[21]覃英,王佳武,李代平,蒋天锐.黔东南地区南华纪锰矿地质地球化学特征[J].地质与勘探,2013,49(6):1060-1069.
[22]茹廷锵等.广西锰矿地质[M].北京:地质出版社,1992.28-32.
[23]岩石矿物分析编写组.岩石矿物分析第一分册(第三版)[M].北京:地质出版社,1991.315-317.
[24]韩吟文,马振东等.地球化学[M].北京:地质出版社,2003.200-202.
[25]MCLENNAN S M.Rare earth elements in sedimentary rocks;influence of provenance and sedimentary processes[J].Reviews in Mineralogy and Geochemistry,1989,21(1):169-200.
[26]蔡毅华.太平洋富钴结壳的生长与元素富集机理[D].厦门:厦门大学博士学位论文,2002.
[27]解启来,陈多福,漆亮,陈先沛.贵州瓮安陡山沱组磷块岩的稀土元素地球化学特征与沉积古环境[J].矿物学报,2003,23(4):289-295.
[28]ILYIN A V.Rare earth geochemistry of“old”phosphorites and probability of syngenetic precipitation and accumulation of phosphate[J].Chemical Geology,1998,144:243-256.
[29]侯宗林等.扬子地台周边锰矿[M].北京:冶金工业出版社,1997.260-270.