泥灰岩中自生方解石的稀土元素酸溶方法研究

碳酸盐岩稀土元素是沉积环境示踪的理想参数,但由于自生沉积碳酸盐矿物的稀土元素含量远低于陆源黏土等其他矿物,在样品处理过程中少量陆源黏土矿物的溶解,将影响沉积环境的示踪。因此,如何在样品处理过程中避免陆源黏土矿物中稀土元素的释放,从而获得海洋环境自生沉淀形成的碳酸盐矿物中的元素方法非常重要。本文应用地层中常见的同一泥灰岩样品,分别用5%醋酸、5%盐酸、2%和5%硝酸浸取,采用0.5 h、1 h、2 h、3 h、6 h和24 h的反应时间,用X射线衍射法（XRD）分析酸不溶残渣矿物组成、电感耦合等离子体原子发射光谱法（ICP-AES）测定酸可溶相溶液的主元素和微量元素含量、电感耦合等离子体质谱法（ICP-MS）测定酸可溶相溶液的稀土元素含量,结果表明所有酸溶均可完全溶解泥灰岩中的方解石矿物,并有少量黏土发生溶解,导致稀土总量和Ce/Ce＊增高,但对Eu/Eu＊、LaN/YbN和Gd/Gd＊等参数没有影响。泥灰岩中自生方解石的稀土元素理想溶样条件是5%醋酸反应1 h以内,溶液的ICP-MS分析结果适用于示踪沉积环境的氧化还原条件。     

中国西北地区石炭系泥岩稀土元素地球化学特征及其地质意义

详细研究了中国西北地区石炭系泥岩的稀土元素地球化学特征。各样品稀土总量为18 86× 10 -6～ 6 2 0 4× 10 -6,变化较大 ,其中祁连地区REE总量为 76 49× 10 -6～ 6 2 0 4×10 -6,甘肃永昌煤山子剖面的稀土总量最高 ,新疆北部地区泥岩和灰岩 (泥灰岩 )的稀土总量均较低。各泥岩样品的轻稀土富集 ,Eu负异常 ,δEu介于 0 44～ 0 90之间 ,δCe部分为正异常 (>1) ,部分为负异常 (<1)。研究区样品的Sm含量与北美页岩样品相比为正异常 ,Dy出现负异常的样品较多。根据稀土元素δCe和Ceanow的变化 ,反映当时新疆北部地区水介质环境大部分为缺氧的还原条件 ;祁连地区为海陆过渡环境 ,部分为氧化条件 ,另一部分为缺氧的还原条件 ,这与其他相标志所显示的结果是一致的。根据稀土元素组合及比值的变化 ,显示物源区母岩为花岗岩和玄武岩的混合来源 ,稀土分布模式均为轻稀土富集、重稀土亏损型 ,重稀土配分曲线较为平坦 ,显示源岩为粘土岩、花岗岩和中性岩的混合来源。     

Rare earth elements of seep carbonates: Indication for redox variations and microbiological processes at modern seep sites

At marine seeps, methane is microbially oxidized resulting in the precipitation of carbonates close to the seafloor. Methane oxidation leads to sulfate depletion in sediment pore water, which induces a change in redox conditions. Rare earth element (REE) patterns of authigenic carbonate phases collected from modern seeps of the Gulf of Mexico, the Black Sea, and the Congo Fan were analyzed. Different carbonate minerals including aragonite and calcite with different crystal habits have been selected for analysis. Total REE content (ΣREE) of seep carbonates varies widely, from 0.1 ppm to 42.5 ppm, but a common trend is that the ΣREE in microcrystalline phases is higher than that of the associated later phases including micospar, sparite and blocky cement, suggesting that ΣREE may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates often show different Ce anomalies even in samples from a specific site, suggesting that the formation conditions of seep carbonates are variable and complex. Overall, our results show that apart from anoxic, oxic conditions are at least temporarily common in seep environments.     

Flat rare earth element patterns as an indicator of cumulate processes in the Lesser Qinling carbonatites, China

The Lesser Qinling carbonatite dykes are mainly composed of calcites. They are characterized by unusually high heavy rare earth element concentrations (HREE; e.g. Yb > 30 ppm) and flat to weakly light rare earth element (LREE) enriched chondrite-normalized patterns (La/Yb_n = 1.0–5.5), which is in marked contrast with all other published carbonatite data. The trace element contents of calcite crystals were measured in situ by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Some crystals show reduced LREE from core to rim, whereas their HREE compositions are relatively constant. The total REE contents and chondrite-normalized REE patterns from the cores of carbonate crystals are similar to those of the whole rock. The carbon and oxygen isotopic compositions of calcites fall within the range of primary, mantle-derived carbonatites. The initial Sr isotopic compositions (0.70480–0.70557) of calcites are consistent with an EM1 source or mixing between HIMU and EM1 mantle sources. However these sources cannot produce carbonatite parental magmas with a flat or slightly LREE enrichment pattern by low degrees of partial melting. Analyses of carbonates from other carbonatites show that carbonates have nearly flat REE pattern if they crystallize from a LREE enriched carbonatite melt. This implies that when carbonates crystallize from a carbonatite melt the calcite/melt partition coefficients (D) for HREE are much greater than the D for the LREE. The nearly flat REE patterns of the Lesser Qinling carbonatites can be explained if they are carbonate cumulates that contain little trapped carbonatite melt. Strong enrichment of HREE in the carbonatites may require their derivation by small degrees of melting from a garnet-poor source.     

Rare earth element geochemistry of Late Devonian reefal carbonates, Canning Basin, Western Australia: confirmation of a seawater REE proxy in ancient limestones

Rare earth element and yttrium (REE+Y) concentrations were determined in 49 Late Devonian reefal carbonates from the Lennard Shelf, Canning Basin, Western Australia. Shale-normalized (SN) REE+Y patterns of the Late Devonian samples display features consistent with the geochemistry of well-oxygenated, shallow seawater. A variety of different ancient limestone components, including microbialites, some skeletal carbonates (stromatoporoids), and cements, record seawater-like REE+Y signatures. Contamination associated with phosphate, Fe-oxides and shale was tested quantitatively, and can be discounted as the source of the REE+Y patterns. Co-occurring carbonate components that presumably precipitated from the same seawater have different relative REE concentrations, but consistent REE+Y patterns. Clean Devonian early marine cements (n = 3) display REE+Y signatures most like that of modern open ocean seawater and the highest Y/Ho ratios (e.g., 59) and greatest light REE (LREE) depletion (average Nd_SN/Yb_SN = 0.413, SD = 0.076). However, synsedimentary cements have the lowest REE concentrations (e.g., 405 ppb). Non-contaminated Devonian microbialite samples containing a mixture of the calcimicrobe Renalcis and micritic thrombolite aggregates in early marine cement (n = 11) have the highest relative REE concentrations of tested carbonates (average total REE = 11.3 ppm). Stromatoporoid skeletons, unlike modern corals, algae and molluscs, also contain well-developed, seawater-like REE patterns. Samples from an estuarine fringing reef have very different REE+Y patterns with LREE enrichment (Nd_SN/Yb_SN > 1), possibly reflecting inclusion of estuarine colloidal material that contained preferentially scavenged LREE from a nearby riverine input source. Hence, Devonian limestones provide a proxy for marine REE geochemistry and allow the differentiation of co-occurring water masses on the ancient Lennard Shelf. Although appropriate partition coefficients for quantification of Devonian seawater REE concentrations from out data are unknown, hypothetical Devonian Canning Basin seawater REE patterns were obtained with coefficients derived from modern natural proxies and experimental values. Resulting Devonian seawater patterns are slightly enriched in LREE compared to most modern seawaters and suggest higher overall REE concentrations, but are very similar to seawaters from regions with high terrigenous inputs. Our results suggest that most limestones should record important aspects of the REE geochemistry of the waters in which they precipitated, provided they are relatively free of terrigenous contamination and major diagenetic alteration from fluids with high, non-seawater-like REE contents. Hence, we expect that many other ancient limestones will serve as seawater REE proxies, and thereby provide information on paleoceanography, paleogeography and geochemical evolution of the oceans.     

碳酸盐岩中碳酸盐矿物稀土元素分析方法进展

碳酸盐岩中测定碳酸盐矿物的稀土元素主要有酸溶-ICP-MS和LA-ICP-MS方法.酸溶-ICP-MS方法用盐酸、硝酸溶解碳酸盐矿物,但也能溶解部分非碳酸盐矿物,而影响分析结果;用醋酸溶样可避免非碳酸盐矿物的干扰,但可能没有溶样完全,同样影响分析结果.LA-ICP-MS是应用激光对碳酸盐矿物进行原位剥蚀,将蒸发物导入ICP-MS进行分析,对不合粘土等的碳酸盐矿物最有效,由于激光束光斑较大,且碳酸盐岩中普遍含有微小的粘土矿物,可能也存在不确定性.总体而言,酸溶-ICP-MS和LA-ICP-MS获得的稀土元素页岩标准化配分模式及主要参数相似,均可用于沉积环境的示踪.     

羌塘盆地角木日地区二叠系碳酸盐岩元素地球化学特征及其对古沉积环境的指示

对采自羌塘盆地角木日地区的二叠系碳酸盐岩,包括下二叠统展金组白云岩和中二叠统龙格组灰岩进行了元素地球 化学分析,并讨论了其对古沉积环境的指示意义。结果表明,样品Y/Ho比值平均为45.14,Gd表现为轻微Gd正异常,符合 海相灰岩特征;SiO2和Al2O3的平均含量较低,反映研究区陆源物质的侵入较为有限。碳酸盐岩中ΣREE含量较低,稀土元 素分异程度整体较弱,轻稀土元素相对重稀土元素呈轻微富集特征,Ce,Eu均具有明显负异常,结合V/Cr,V/(V+Ni),Sr/ Ba及Sr/Ca等微量元素含量及比值特征认为,研究区早-中二叠世沉积期海水总体呈氧化环境。纵向上龙格组顶部表现出氧 化性增强、盐度增大的趋势,推测可能与当时水体变浅有关,与早二叠世晚期研究区构造应力由拉张向挤压的变化有密切 关系。     

海底热液系统高温流体的稀土元素组成及其控制因素

研究稀土元素在流体中的地球化学行为及其控制因素,对利用稀土示踪与流体有关的地球化学过程具有重要意义。海底高温流体稀土组成研究表明,不同背景、岩性热液系统喷口流体的稀土含量差别较大,与海水之间可达几个数量级,但配分模式却非常类似,即普遍具有LREE富集、高的正Eu异常特征。流体的稀土组成与岩石或矿物的蚀变程度、结构构造有关,同时受流体的温压、pH值、Eh值、络合介质种类等因素的影响,其配分模式是流体循环、迁移过程中络合、吸附、矿物沉淀等不同因素共同作用而再次调整的结果。正Eu异常作为高温流体的特征标志,可以用来示踪与高温流体有关的地球化学作用过程,同时Y/Ho比值、负Ce异常可以用来示踪与流体/海水混合有关的化学过程。     

Trace element geochemistry of the Mt Vulture carbonatites,southern Italy

The Mt Vulture carbonatites are the only carbonatite occurrence in the southern Apennines. We present new trace element data for these rocks in order to evaluate the factors influencing rare earth element (REE) and other trace element fractionations and their REE grade. This study focuses on massive hyalo-alvikites from two lava flows and one dike, which have different relative abundances of silicate and carbonate (i.e. Si/Ca). These differences are also evident from CaO/(CaO + MgO + FeO(T) + MnO) and Sr/Ba ratios. The REE grade of the Mt Vulture carbonatites is very similar to that of the global average for calcio-carbonatites. R-mode factor analysis shows that most of the trace element variance reflects the relative roles of carbonate and silicate minerals in influencing trace element distributions. Silicates largely control heavy rare earth element (HREE), transition metal, Zr, and Th abundances, whereas carbonate minerals control light rare earth element (LREE), Ba, and Pb abundances. In addition, apatite influences LREE concentrations. Increasing silica contents are accompanied by decreases in (La/Yb)N and (La/Sm)N ratios and less marked LREE enrichment. In contrast, higher carbonate contents are associated with increases in (La/Yb)N and (La/Sm)N. The Si/Ca ratio has little influence on Eu anomalies and middle rare earth element (MREE) to HREE fractionations. Apatite has a negligible effect on inter-REE fractionations amongst the carbonatites.     

碳酸盐(岩)的稀土元素特征及其古环境指示意义

稀土元素主要通过交代碳酸盐矿物的Ca^{2+0进入碳酸盐格架,所以沉积碳酸盐(岩}的稀土元素特征能够很好的指示沉积流体来源和古环境。常用的稀土元素指标包括稀土元素总量(ΣREE)、稀土元素配分型式、以及La、Ce、Eu、Gd和Y等元素的异常指数。碳酸盐(岩)的稀土元素含量可能受到硅酸盐矿物、Fe-Mn氧化物/氢氧化物和磷酸盐等非碳酸盐组分以及成岩蚀变作用的影响。因此,在分析过程中,我们只有排除这些影响因素,才能用碳酸盐(岩)的稀土元素指标来探讨流体来源和古环境。这要求我们采集新鲜剖面上的样品,并用适当浓度的弱酸进行分步溶样,提取适当的组分,避免样品中的非碳酸盐组分干扰原始沉积组分的稀土元素特征。不同的沉积水体和沉积相下形成的碳酸盐(岩)具有不同的稀土元素特征:从太古宙到全新世的海相碳酸盐(岩)记录了LREE亏损、La正异常和高Y/Ho值的稀土元素特征;海底孔隙水的稀土元素特征则受氧化-还原条件、离子络合形式、孔隙流体来源的制约;热液流体具有LREE富集、Eu正异常的稀土元素特征;河水和湖泊有相对平坦的稀土元素特征。因此,碳酸盐(岩)的稀土元素特征具有重要的古环境指示意义。     

羌塘盆地那底岗日地区布曲组碳酸盐岩烃源岩稀土元素分布特征及意义

对采自羌塘盆地那底岗日地区布曲组碳酸盐岩烃源岩进行了稀土元素地球化学研究,分析结果表明:海相碳酸盐岩烃源岩稀土总量(∑REE)最大值75.21μg/g,最小值20.58μg/g,平均值为36.67μg/g.稀土元素北美页岩标准化后具有相对富集轻稀土,亏损重稀土的特点.布曲组碳酸盐岩烃源岩Ce/Ce*值为0.83～0.9...     

川东三叠系飞仙关组碳酸盐岩的阴极发光特征与成岩作用

四川盆地东部三叠系飞仙关组是近年来我国发现的重要天然气储层, 高孔隙度、高渗透率的碳酸盐储层都分布于白云岩地层中, 因而碳酸盐的成岩作用, 尤其是白云岩化作用和白云岩的成因为石油地质学家和沉积学家高度关注.对四川盆地东部罗家寨构造三叠系飞仙关组42个碳酸盐岩样品进行了阴极发光分析, 结合与之有关的Mn、Fe、Mg元素分析和岩石学研究, 讨论了包括白云岩化作用在内的碳酸盐岩成岩过程中可能的成岩流体性质及来源.四川盆地东部三叠系飞仙关组碳酸盐岩普遍具有很弱的阴极发光性, 这与其很低的Mn、Fe含量有关, 说明沉积期后非海相流体对飞仙关组碳酸盐岩的影响非常有限, 海源流体在成岩过程中发挥了主导作用; 不同石灰岩类型和不同白云岩类型仍然具有不同的阴极发光性, 成岩组分含量越高的碳酸盐岩, 或者说与沉积期后流体(主要是孔隙流体) 关系越密切的碳酸盐岩的阴极发光强度越低, 说明随着埋藏成岩作用的进行, 四川盆地东部三叠系碳酸盐岩孔隙流体受海源流体的影响是逐渐增强的; 阴极发光分析结果表明, 作为四川盆地东部主要储集岩的结晶白云岩形成机制与埋藏过程中的深循环流体有关, 这种深循环流体没有或很少穿越铝硅酸盐地层, 但穿越了三叠系内部的某些海相地层, 这些海相地层可能是广泛存在于四川盆地三叠系的蒸发盐地层, 由蒸发盐成岩过程提供的海源流体参与了结晶白云岩的白云岩化作用.      

REE Geochemical Study of the Permian—Triassic Marine Sedimentary Environment in Guizhou Province

This paper deals with the REE geochemical characteristics of Permian-Triassic marine carbonate rocks in Guizhou Province.It is found that there are two broad categories of strati-graphic units in the region studied in accordance with their ΣREE contents and REE distribu-tion patterns: one is characterized by LREE enrichment and slight Ce depletion,with the REE distribution patterns similar to those of North American shales,and the other featrures relative HREE enrichment and relatively remarkable Ce depletion,with the REE distribution patterns close to those of pelagic sediments.In terms of their different ΣREE contents,five types of stratigraphic units can be distinguished.Incorporation of detrital minerals,REE complexing ca-pability,oxidation-reduction conditions of the media are the main factors affecting the REE com-position and REE distribution patterns of marine carbonate rocks in the region studied.In the light of REE geochemical characteristics of carbonate rocks,coupled with sedimentary facies analysis,this paper discusses the characteristics of the Permian-Triassic marine sedimentary environment in Guizhou Province and its evolutional rules.     

西藏高原沱沱河盆地渐新世-中新世湖相碳酸盐岩稀土元素地球化学特征与正铕异常成因初探

对采自沱沱河盆地通天河剖面渐新世雅西措群和中新世五道梁群地层中的湖相灰岩和白云岩样品进行了稀土元素和微量元素分析。研究结果表明,湖相碳酸盐岩稀土元素总量（∑REE）变化于36.23×10-6～189.64×10-6,28件样品平均值为78.58×10-6。稀土元素的页岩标准化配分形式具有中组稀土富集的特点,正铕异常极为明显,在渐新统与中新统界线处Eu/Eu*比达到最大值7.15,这也是首次在陆地湖泊沉积记录中观察到的正Eu异常。根据稀土元素的分布以及Eu与Ba含量的同步变化特点,提出该区湖相碳酸盐岩中Eu的异常富集可能与湖底喷流热水有关。      

东海盆地丽水凹陷古新统沉积岩的稀土元素地球化学特征

采用等离子体质谱分析法测试了东海盆地丽水凹陷古新统砂泥岩样品的稀土元素含量,结果表明,稀土总量在82 2×10-6～182×10-6之间,平均为144×10-6;w(LREE)/w(HREE)比值在4 54～10 02之间,平均为8 67,相对富集LREE;Eu基本为负异常,δEu在0 59～1 03之间,平均为0 73;δCe在0 92～1 09之间,平均为0 98,Ce正常或具微弱的负异常;(w(La)/w(Yb))N在8 23～11 61之间,样品的分布曲线为轻稀土元素富集、重稀土元素亏损型。样品稀土元素的地球化学特征反映当时丽水凹陷为海陆交替的沉积环境,水介质环境为缺氧的还原条件,盆地类型应为稳定的克拉通盆地,物源区母岩主要为花岗岩。     

西秦岭中志留统含铀岩系中硅质岩的岩石学、地球化学及其成因

根据产状和成因,本文将西秦岭中志留统含铀岩系中的硅质岩分为,(1) 成岩过程中硅化交代碳酸盐岩所形成的硅质岩,产于碳酸盐岩和泥质岩类所组成的透镜层的顶部或碳酸盐岩层内;(2) 早期成岩阶段形成的纹层状硅质岩,主要产于碳酸盐岩和泥质岩透镜层底部或呈薄层夹于粉砂岩、泥质岩层中。根据沉积环境分析及硅质岩的化学成分、REE分布模式和氧同位素组成,提出本区硅质岩形成于受大气淡水影响的局限浅海环境。     

Rare earth elements in seep carbonates as tracers of variable redox conditions at ancient hydrocarbon seeps

Marine hydrocarbon seeps are dynamic systems, which are typically reflected in complex lithologies of limestones forming at these sites. In order to test if seep limestones with their multiple generations of carbonate phases reflect variable redox conditions, the rare earth element (REE) patterns of limestones from five ancient hydrocarbon-seep localities, Hollard Mound (Middle Devonian), Iberg (Mississippian), Beauvoisin (Oxfordian), Canyon and Satsop River (Oligocene), and Marmorito (Miocene) have been investigated. The total REE contents vary widely (0.3–43.7 p.p.m.). Early microcrystalline phases tend to show higher contents than spatially associated later phases (microspar, sparite, and blocky cement). The shale-normalized REE patterns of the carbonates show both negative and positive Ce anomalies even for individual deposits, suggesting that the redox conditions varied significantly. It is apparent that in addition to anoxic conditions, oxic conditions were common in some ancient seep environments. Intermittent oxygenation is presumed to have resulted from abrupt changes in fluid flow.     

渝东地区寒武系第四阶龙王庙组古环境演化的稳定同位素与主、微量元素证据

寒武系第四阶是生命演化史上重要的时间节点.渝东地区寒武系第四阶龙王庙组以碳酸盐岩为主要岩石类型,地层中、下部混积岩发育,生物化石发育程度低.∑（CaO+MgO+LOI）含量分布范围广（74.64%~99.18%）,Na₂O、K₂O、Fe₂O₃与MnO含量较高（平均值分别为0.20%、0.27%、0.27%和0.014%）,∑（SiO₂+Al₂O₃+Fe₂O₃+P₂O₅+TiO₂）在地层中下部具较高含量（最大值24.00%）;Sr元素含量较低（135×10-6~407×10-6）,∑REE+Y在地层中部含量较高,∑LREE/∑HREE分布在2~4,具显著正铈异常（δCe=5.6~6.2）,配分曲线为平缓右倾模式.全岩与方解石的δ13C值分别为-1.5‰~1.1‰ VPDB、-3.4‰ ~+0.5‰ VPDB,δ18O值分别为-9.7‰ ~-3.5‰ VPDB、-9.8‰~-5.0‰ VPDB;垂向上,两者的δ13C值在地层中下部均以负值为主,中上部多为正值.依据δ13C、δ18O、MgO/CaO（0.03%~0.12%）、100×MgO/Al₂O₃（93.1~4 715.4）、B_校（278.7~1 494.2）、Sr/Ba（4.05~58.25）、1 000×Sr/Ca（5.41~14.43）、V/（V+Ni）（0.61~0.78）及U/Th（0.21~1.45）等与沉积环境的关系,推断龙王庙期水体温度在17~25℃,属半咸水-咸水环境;水体深度在早-中期波动频繁;以贫氧-缺氧环境为主,在早-中期、末期为阶段性富氧环境.整体上龙王庙组沉积早-中期受河流注入影响较为明显、陆源碎屑供给充足,具海陆过渡环境特征,沉积中后期为稳定的海相环境.咸水、缺氧的条件及海平面波动频繁并伴有大量陆源碎屑注入所产生的环境压力,是引发渝东地区寒武系第四阶生物消亡的主要环境因素.      

中国东部大陆尺度地球化学走廊带碳酸盐岩稀土元素分布特征与影响因素

碳酸盐岩是地球表层岩石圈的重要组成部分,其化学组成可提供沉积环境与海洋水体演化等信息,然而,前人对碳酸盐岩中稀土等元素的分布与变化特征关注不足。本文选择穿越中国东部6个一级大地构造单元的3条地球化学走廊带,系统采集了582件碳酸盐岩地层样品,并准确分析了包括稀土元素(REE)在内的81项指标的含量。结果表明,中国东部地球化学走廊带碳酸盐岩稀土元素(REE＋Y)总量为(0.59～183)×10-6,均值为24.0×10-6,纯净碳酸盐岩(CMC含量≥99％)均值为4.80×10-6。PAAS标准化后其显示具有轻稀土相对于中稀土和重稀土略亏损、δEu轻微正异常、δCe中度负异常等特征。白云岩中稀土含量、LREE/HREE值一般低于石灰岩;砂泥质含量相近时,前中生代各时代碳酸盐岩稀土分布模式相差不大,各构造单元稀土分布特征基本相似;与其他时代相比,中生代及中新元古代碳酸盐岩具有相对较平坦的稀土分布模式。研究表明,碳酸盐岩中稀土分布受碎屑物质影响明显,表现为稀土元素含量与碳酸根负相关,与碎屑物质相关元素(Si、Ti、Rb、Cs、Th、Zr等)、黏土相关元素(Al、Fe、K等)等正相关。成岩过程及白云化过程对较纯净碳酸盐岩中稀土分布特征影响不明显。我国古生代纯净碳酸盐岩分布模式受控于海相环境,其分布模式与现今海水相近;中生代纯净石灰岩受到陆相或海陆交互相的影响,具有较平坦的稀土分布模式。氧化还原条件对δCe的影响较δEu更为明显,δCe值受海相环境控制,极端正异常值(δCe＞1.3)受到还原环境或/和热液影响。若假定海水中REE自中元古代至今无太大变化,各时代稀土元素分配系数均值介于103.55～102.39,分配系数差异是造成碳酸盐岩中轻稀土亏损、Ce负异常及Y正异常的主要原因。微生物(席)可富集稀土等金属元素并改变沉积环境,这可能是造成中新元古界碳酸盐岩较平坦的稀土分布模式的主要原因。     

http://www.sciencedirect.com/science/article/pii/S1674987110000125

<正>Carbonatites are commonly related to the accumulation of economically valuable substances such as REE.Cu,and P.The debate over the origin of carbonatites and their relationship to associated silicate rocks has been ongoing for about 45 years.Worldwide,the rocks characteristically display more geochemical enrichments in Ba,Sr and REE than sedimentary carbonate rocks.However,carbonatite's geochemical features are disputed because of secondary mineral effects.Rock-forming carbonates from carbonatites at Qinling.Panxi region,and Bayan Obo in China show REE distribution patterns ranging from LREE enrichment to flat patterns.They are characterized by a Sr content more than 10 times higher than that of secondary carbonates.The coarse- and fine-grained dolomites from Bayan Obo H8 dolomite marbles also show similar high Sr abundance,indicating that they are of igneous origin.Some carbonates in Chinese carbonatites show REE(especially HREE) contents and distribution patterns similar to those of the whole rocks.These intrusive carbonatites display lower platinum group elements and stronger fractionation between Pt and Ir relative to high-Si extrusive carbonatite.This indicates that most intrusive carbonatites may be carbonate cumulates.Maoniuping and Daluxiang in Panxi region are large REE deposits.Hydrothermal fluorite ore veins occur outside of the carbonatite bodies and are emplaced in wallrock syenite.The fiuorite in Maoniuping has Sr and Nd isotopes similar to carbonatite.The Daluxiang fiuorite shows Sr and REE compositions different from those in Maoniuping.The difference is reflected by both the carbonatites and rock-forming carbonates,indicating that REE mineralization is related to carbonatites.The cumulate processes of carbonate minerals make fractionated fluids rich in volatiles and LREE as a result of low partition coefficients for REE between carbonate and carbonatite melt and an increase from LREE to HREE.The carbonatite-derived fluid has interacted with wallrock to form REE ore veins.The amount of carbonatite dykes occurring near the Bayan Obo orebodies may support the same mineralization model,i.e.that fluids evolved from the carbonatite dykes reacted with H8 dolomite marble,and thus the different REE and isotope compositions of coarse- and fine-grained dolomite may be related to reaction processes.