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1.
The Biluo Co and Amdo 114 station, northern Tibet, cropping out the Early Toarcian and Middle-Late Tithonian (Jurassic) organic-rich black shales, have been a focus to petroleum geologists in discussing their oil-producing potential. This paper first reports the trace elements and rare earth elements to discuss the paleoenvironments, redox conditions and sedimentary mechanisms of those black shales. Both sections exhibit variation in trace element abundances with concentrations <0.1 ppm to 760 ppm, mostly enriched in V, Cr, Ni, Cu, Zn, Mo, Ba and U. Element ratios of Ni/Co, V/Cr, U/Th and V/(V+Ni) plus U were used to identify redox conditions. The shale-normalized rare earth element (REE) patterns are characterized by the flat-shale type with instable Ce anomalies and very weekly positive Eu anomalies. Positive Ceanom values are significant with values varying between –0.064 and 0.029 in Biluo Co, which may be interpreted as release of REE and input of riverine terrestrial matter with rich Ce (resulting in pH change) during the anoxic conditions. In the middle parts of Amdo 114 station, distinct negative Ceanom values are observed (?0.238 to ?0.111) and associated surface water warming were interpreted as being related to a major sea level rise. In contrast, the formation of the black shales in the lower and upper part of the studied succession took place during a cooler (Ceanom values >–0.10), lower surface water productivity, and lower sea-level stage. Thus, we emphasize the role of different factors that control the formation of local and regional black shales. The most important factors are sea-level fluctuations and increasing productivity.  相似文献   

2.
Rare earth elements in the sedimentary cycle: A summary   总被引：2，自引：0，他引：2  
The relative and absolute concentrations of rare earth elements (REE) in authigenic and biogenic phases of deep-sea sediments are quite different. Competition between these phases for REE has resulted in fractionation from the parent material, the latter consisting predominantly of terrigenous material, but with a contribution from marine volcanism. The strongest feature of this fractionation is a depletion of Ce, relative to La, in CaCO3, opalline silica, phillipsite, phosphorite, barite, and montmorillonitic clays; and a Ce enrichment in Fe/Mn nodules. The distribution of REE in different masses of seawater strongly reflects their fractionation in sediments. Whereas the relative concentration of REE in rivers resembles that of shale, their removal from seawater by authigenic and biogenic phases results in: (1) a decrease of their total concentration; (2) a depletion of Ce; and (3) an enrichment of heavy REE relative to light REE. The order of fractionation for water masses in the Atlantic Ocean is:Antarctic intermediate water > North Atlantic deep water > Antarctic bottom water> shelf water > river water ～ shale.The shale-normalized pattern for the sum of REE in the authigenic and biogenic phases of pelagic sediment and in seawater resembles that of an admixture of shale and basalt corresponding presumably to the realtive inputs from continents and marine volcanism respectively. The estimated rate of accumulation of each REE in the sediment, however, is approximately 12 times the estimated rate of input of REE from these two sources.  相似文献   

3.
扬子东南大陆边缘晚前寒武纪古海洋演化的稀土元素记录   总被引：10，自引：1，他引：9  
伊海生  彭军 《沉积学报》1995,13(4):131-137
本文采用中子活化方法分析了晚震旦～早寒武纪１９件样品的稀土元素组成,发现硅质岩石ＲＥＥ配分形式有着复杂的变化,初步可以划分为五种类型,包括“台地型”、“红海型”、“海水型”及两种特殊的配分形式。剖面上Ｃｅ异常由小到大的演变反映了古海洋底层水由缺氧环境向氧化条件的逐渐转化。正Ｅｕ异常的出现代表了热水沉积事件的存在。  相似文献   

4.
Geochemistry of Rare Earth Elements in the Ocean   总被引：4，自引：0，他引：4  
This work briefly outlines modern ideas on geochemistry of rare earth elements (REE) in the ocean. Sources of REE and chemical properties of these elements, which govern their migration ability in natural processes, are considered. The REE behavior in the river water–seawater mixing zone is analyzed. The fractionation of dissolved and suspended REE in oceanic water in both aerobic and anaerobic conditions is also considered. It is shown that the variability of REE composition in pelagic sediments reflects the fractionation of these elements in the oceanic water as a consequence of material differentiation in the ocean. The REE distribution in terrigenous, authigenic, hydrothermal, and biogenic constituents of sediments, such as clay, bone debris, barite, phillipsite, Fe–Mn oxyhydroxides (ferromanganese nodules and micronodules), Fe–Ca hydroxo-phosphate, diatoms, and foraminifers, is considered.  相似文献   

5.
This study explores the possibility of establishing Nd isotopic variations in seawater over geologic time. Calcite, aragonite and apatite are examined as possible phases recording seawater values of ?Nd. Modern, biogenic and inorganically precipitated calcite and aragonite from marine environments were found to have Nd concentrations of from 0.2 to 70 ppb, showing that primary marine CaCO3 contains little REE and that Nd/Ca is not greatly enhanced relative to seawater during carbonate precipitation. Very young marine limestone and dolomite containing no continental detritus have ~200 ppb Nd. All the carbonates are LREE enriched (?0.16 ≤fSmNd≤?0.45). Modern and very young Atlantic and Pacific carbonates have ?Nd in the range of shallow Atlantic and Pacific seawater respectively, implying that they derive their REE from local seawater. The Nd in well preserved carbonate fossils is ≤4 × 104 ppb, much greater than in their modern counterparts but like the high values found for carbonates in other studies. We believe the high REE contents (at the 500 ppb level) in some detritusfree carbonates are due to REE-rich Fe-hydroxide in/on the carbonate. In favorable cases, such material may record seawater ?Nd values, however introduction of extraneous REE may obscure the original isotopic composition of pure CaCO3 because of its very low intrinsic primary REE abundance.Modern biogenic apatite is also shown to have very low REE content (<150 ppb Nd) but appears to quickly scavenge REE from seawater. Inorganically precipitated apatite from phosphorites has high concentrations of seawater-derived REE. Young phosphorite apatite from the Atlantic and Pacific oceans has ?Nd in the range of the seawater from these oceans. Older apatite samples of similar age from different localities bordering common oceans record similar values of ?Nd(T). Sedimentary apatite has ?Sr(T) values in good agreement with the curves for 87Sr86Sr of seawater as a function of time. Individual conodonts from a single formation yield the same ?Sr(T) and ?Nd(T). Other workers have shown that sedimentary apatite preserves seawater REE patterns. These characteristics suggest that sedimentary apatite can be used to determine ?Nd(T) in ancient seawater. The seawater values so inferred range between ?1.7 and ?8.9 over the last 700 my and lie in the range of modern seawater, showing no evidence for drastic changes. High values of seawater ?Nd(T) in the Triassic and latest Precambrian may correlate with the breakup of large continental landmasses. The initial ?Nd(T) =?15.0 of a 2 AE old phosphorite implies the presence of ~ 1.5 AE old continental crust at 2 AE ago. The approach outlined here can be used to constrain the age of the exposed crust as a function of time.  相似文献   

6.
Geochemical and geochronological studies were conducted on basalts and laterites from the Bolaven Plateau in southern Laos in order to evaluate the mobility and mineralization of REE, Y and Sc during laterization. The basalts are classified into three categories: (i) small volumetric alkali basalt (eruption age: 15.7 Ma), large volumetric olivine tholeiite (1.2 Ma) and quartz tholeiite with olivine tholeiite (younger than 0.5 ± 0.2 Ma). Formation of REE minerals during laterization result in mobilization and fractionation of REE and Y in laterite profiles. Occurrence of florencite‐(Ce) in a laterite profile derived from alkali basalt immobilizes REE (particularly LREE) and this leads the laterites to be enriched in LREE relative to the parent basalt. Few positive Ce anomalies in this profile suggest that florencite‐(Ce) [(Ce)Al3(PO4)2(OH)2] formation was followed by CeO2 precipitation due to the change of redox condition. In tholeiite‐derived laterite profiles, florencite is not recognized and REE and Y tend to be depleted relative to the parent basalts with positive Ce anomalies. This is interpreted as scavenging REE3+ except for Ce4+ from the laterite profile in oxidizing conditions. Sc behaves similarly to Fe during laterization and it is more abundant in the tholeiitic laterite than that in the alkali basaltic laterite. Results of sequential extraction indicate that REE of the alkali basaltic laterite are contained in residual phase, which is dominantly florencite‐(Ce), but they are rarely present in ion‐adsorption phase. It is concluded that basaltic laterites have a low potential of REE resource in terms of low REE contents and a difficulty in REE extraction.  相似文献   

7.
Rare earth elements (REE) concentrations of Archean and Proterozoic chemical sediments are commonly used as proxies to study secular trends in the geochemistry of Precambrian seawater. In addition, similarities in the REE signatures of Archean chemical sediments and modern seawater have led researchers to argue that some Archean rocks originated as biochemical precipitates (i.e., microbial carbonates) in shallow marine (e.g., peritidal) environments. However, terrestrial waters, including river water and groundwater, also commonly exhibit REE fractionation patterns that resemble modern seawater. Here, we present the seawater-like REE data for groundwaters from central México as additional evidence that these patterns are not unique to the marine environment. The shale-normalized REE patterns of the groundwaters are compared to those of modern seawater (open ocean and nearshore), Holocene reefal microbial carbonates and corals, and Archean chemical sediments using statistical means (i.e., ANOVA and Wilcoxon analyses) in order to quantify the similarities and/or differences in the REE patterns. Shale-normalized (SN) Ce anomalies and measures of REE fractionation [i.e., (La/Yb)SN, (Pr/Yb)SN, (Nd/Yb)SN, and (Gd/Yb)SN] of the central México groundwater samples are statistically indistinguishable from those of modern seawater. Moreover, except for differences in the Ce anomalies, which are lacking in Archean chemical sediments, the REE patterns of the central México groundwaters are also statistically similar to REE patterns of Archean chemical sediments, especially those of the 3.45 Ga Strelley Pool Chert. Consequently, we suggest that without additional information, it may be premature to unequivocally conclude that Archean chemical sediments record REE signatures of an Archean ocean.  相似文献   

8.
条带状铁建造(BIF)是形成于前寒武纪海洋中的化学沉积岩,记录了古海洋氧化还原状态的重要信息。华北克拉通广泛分布的新太古代和古元古代BIF,是了解古元古代大氧化事件(GOE)前后古海洋氧化还原环境变化的理想对象。初步研究表明,华北克拉通新太古代BIF主要为磁铁矿型氧化物相和硅酸盐相,极少数出现碳酸盐相;古元古代BIF包括赤铁矿型和磁铁矿型氧化物相、硅酸盐相和碳酸盐相,其中赤铁矿相是古元古代BIF独有的。以上矿物学特征表明,新太古代和古元古代水体的氧化还原条件是不同的。华北克拉通新太古代BIF的稀土元素组成缺乏强烈的负Ce异常,反映同期海水氧含量非常低,为缺氧状态; 但少量BIF也包含有负Ce异常,同时具有较大变化范围的Th/U值,指示新太古代海洋的局部水体氧含量相对较高,呈弱氧化状态。与新太古代BIF相比,古元古代BIF的Ce异常变化较大,包括无异常、正异常和负异常,尤其是赤铁矿相BIF具明显的负Ce异常,表明古元古代水体的氧含量和氧化还原结构已发生了明显变化; 结合华北克拉通BIF的Ni/Co、V/(V+Ni)和Th/U等比值特征,认为古元古代海洋呈次氧化—氧化环境。新太古代BIF 强烈富集重铁同位素,S同位素非质量分馏效应较为明显;而古元古代BIF相对富集轻铁同位素,S同位素非质量分馏效应不明显。综上,新太古代海洋环境整体缺氧,但局部可能存在氧气“绿洲”,暗示光合产氧作用在太古代晚期已经存在;大氧化事件期间及之后的古海洋总体具上部氧化、下部还原的分层特征。  相似文献   

9.
Banded iron formation(BIF)belongs to sedimentary rocks formed in Precambrian marine,which can directly reflect the redox state of the ancient oceans. Mineral composition and geochemistry of BIF can reveal the relative changes of oxygen contents of ancient atmosphere-ocean. The Neoarchean and Paleoproterozoic BIFs widely distributed in the North China Craton(NCC),are the ideal research objects for understanding the changes of the ancient ocean redox environment before and after the Paleoproterozoic Great Oxidation Event(GOE). Our previous studies indicated that the sedimentary facies of the Neoarchean BIF in the NCC are mainly magnetite-type oxide and silicate,with minor carbonate. The sedimentary facies of the Paleoproterozoic BIF are hematite- and magnetite-type oxide,silicate and carbonate,of which the hematite-oxide facies is unique to the Paleoproterozoic BIF. The above mineralogical features suggest that the redox conditions of the Neoarchean and Paleoproterozoic seawater are different. The rare earth element composition of the Neoarchean BIF in the NCC lacks a strong negative Ce anomaly,reflecting that the oxygen content of contemporary seawater is very low and the marine is anoxic. However,a small amount of BIFs in the NCC also present the negative Ce anomalies and a wide range of Th/U ratios,indicating that the local water of the Neoarchean ocean had relatively high oxygen content and was at a weak oxidation state. Compared with the Neoarchean BIFs,the Paleoproterozoic BIFs present a wide range of Ce anomalies(i.e.,no Ce anomalies,positive Ce anomalies and negative Ce anomalies). The hematite-bearing BIF has an obvious negative Ce anomalies,implying that the oxygen content and redox state of Paleoproterozoic seawater changed significantly. Combined with the ratios of Ni/Co,V/(V+Ni)and Th/U of the BIFs in the NCC,the Paleoproterozoic oceans exhibited a suboxidation to oxidation environment. Besides,Neoarchean BIF is strongly enriched in heavy iron isotopes and the non-mass fractionation of S isotope is obvious,whereas the Paleoproterozoic BIF is relatively enriched in light iron isotopes and the non-mass fractionation of S isotope is not obvious. It is summarized that the Neoarchean marine is anoxic,but the oxygen‘oasis' may exist locally,implying that photosynthetic oxygen production already existed in the Late Neoarchean. The ancient ocean presented a layered characteristics during and after the GOE,indicating that the shallow water was generally oxidized and the deep water was reduced.  相似文献   

10.
Geochemical and mineralogical studies were conducted on the 12-m-thick weathering profile of the Kata Beach granite in Phuket, Thailand, in order to reveal the transport and adsorption of rare earth elements (REE) related to the ion-adsorption type mineralization. The parent rock is ilmenite-series biotite granite with transitional characteristics from I type to S type, abundant in REE (592 ppm). REE are contained dominantly in fluorocarbonate as well as in allanite, titanite, apatite, and zircon. The chondrite-normalized REE pattern of the parent granite indicates enrichment of LREE relative to HREE and no significant Ce anomaly. The upper part of the weathering profile from the surface to 4.5 m depth is mostly characterized by positive Ce anomaly, showing lower REE contents ranging from 174 to 548 ppm and lower percentages of adsorbed REE from 34% to 68% compared with the parent granite. In contrast, the lower part of the profile from 4.5 to 12 m depth is characterized by negative Ce anomaly, showing higher REE contents ranging from 578 to 1,084 ppm and higher percentages from 53% to 85%. The negative Ce anomaly and enrichment of REE in the lower part of the profile suggest that acidic soil water in an oxidizing condition in the upper part mostly immobilized Ce4+ as CeO2 and transported REE3+ downward to the lower part of the profile. The transported REE3+ were adsorbed onto weathering products or distributed to secondary minerals such as rhabdophane. The immobilization of REE results from the increase of pH due to the contact with higher pH groundwater. Since the majority of REE in the weathered granite are present in the ion-adsorption fraction with negative Ce anomaly, the percentages of adsorbed REE are positively correlated with the whole-rock negative Ce anomaly. The result of this study suggests that the ion-adsorption type REE mineralization is identified by the occurrence of easily soluble REE fluorocarbonate and whole-rock negative Ce anomaly of weathered granite. Although fractionation of REE in weathered granite is controlled by the occurrence of REE-bearing minerals and adsorption by weathering products, the ion-adsorption fraction tends to be enriched in LREE relative to weathered granite.  相似文献   

11.
The ocean and atmosphere were largely anoxic in the early Precambrian, resulting in an Fe cycle that was dramatically different than today’s. Extremely Fe-rich sedimentary deposits—i.e., Fe formations—are the most conspicuous manifestation of this distinct Fe cycle. Rare Earth Element (REE) systematics have long been used as a tool to understand the origin of Fe formations and the corresponding chemistry of the ancient ocean. However, many earlier REE studies of Fe formations have drawn ambiguous conclusions, partially due to analytical limitations and sampling from severely altered units. Here, we present new chemical analyses of Fe formation samples from 18 units, ranging in age from ca. 3.0 to 1.8 billion years old (Ga), which allow a reevaluation of the depositional mechanisms and significance of Precambrian Fe formations. There are several temporal trends in our REE and Y dataset that reflect shifts in marine redox conditions. In general, Archean Fe formations do not display significant shale-normalized negative Ce anomalies, and only Fe formations younger than 1.9 Ga display prominent positive Ce anomalies. Low Y/Ho ratios and high shale-normalized light to heavy REE (LREE/HREE) ratios are also present in ca. 1.9 Ga and younger Fe formations but are essentially absent in their Archean counterparts. These marked differences in Paleoproterozoic versus Archean REE + Y patterns can be explained in terms of varying REE cycling in the water column.Similar to modern redox-stratified basins, the REE + Y patterns in late Paleoproterozoic Fe formations record evidence of a shuttle of metal and Ce oxides across the redoxcline from oxic shallow seawater to deeper anoxic waters. Oxide dissolution—mainly of Mn oxides—in an anoxic water column lowers the dissolved Y/Ho ratio, raises the light to heavy REE ratio, and increases the concentration of Ce relative to the neighboring REE (La and Pr). Fe oxides precipitating at or near the chemocline will capture these REE anomalies and thus evidence for this oxide shuttle. In contrast, Archean Fe formations do not display REE + Y patterns indicative of an oxide shuttle, which implies an absence of a distinct Mn redoxcline prior to the rise of atmospheric oxygen in the early Paleoproterozoic. As further evidence for reducing conditions in shallow-water environments of the Archean ocean, REE data for carbonates deposited on shallow-water Archean carbonate platforms that stratigraphically underlie Fe formations also lack negative Ce anomalies. These results question classical models for deposition of Archean Fe formations that invoke oxidation by free oxygen at or above a redoxcline. In contrast, we add to growing evidence that metabolic Fe oxidation is a more likely oxidative mechanism for these Fe formations, implying that the Fe distribution in Archean oceans could have been controlled by microbial Fe uptake rather than the oxidative potential of shallow-marine environments.  相似文献   

12.
The hematite mineralization under investigation is located 11 km NE of Sarical (Yavu) village of the Yildizeli town (Sivas Province) in central Turkey. The region is within the Central Anatolian Thrust Zone and is comprised of metamorphic units, ophiolitic rocks and overlying Tertiary volcanic and volcanosedimentary rocks in addition to Neogene terrestrial deposits. The mineralization occurs as lenticular or bedded bodies and is composed chiefly of hematite and a lesser amount of goethite. Quartz, calcite, and dolomite are the gangue minerals. Kaolinite and zeolite are the common alteration products. In this study, geochemical and mineralogical investigations were carried out using an X-ray diffractometer analysis (XRD), Raman spectroscopy, and scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDX). The V/(V + Ni) ratio increases in parallel to the detritic contribution, and when this ratio is less than 0.60, deposition conditions are said to be anoxic. Considering the V/(V + Ni) ratio and Ceanom values of the studied samples, we suggest that the environment is both oxic and anoxic in character. The overall assessment of the field observations, mineral paragenesis, major, trace, and rare earth element (REE) data indicates that the Sarical hematite mineralization is of a hydrothermal-sedimentary type.  相似文献   

13.
晚埃迪卡拉纪全球海洋发生了大面积的缺氧,海洋化学结构呈现明显的非均质性,直接影响了埃迪卡拉型生物的演化与分布。四川盆地发育完整的晚埃迪卡拉系地层,以灯影组巨厚层碳酸盐岩沉积为代表。但是对于该套巨厚层碳酸盐岩沉积时的古海水氧化还原性质备受争议。为了解决这一问题,对川东北地区鹿池剖面的灯影组地层开展了系统的沉积学和稀土元素地球化学分析。该地区灯影组的岩石类型主要为泥微晶白云岩、黏连白云岩、叠层/层纹白云岩,以及溶蚀白云岩,沉积环境为开阔碳酸盐岩台地相。地球化学数据结果显示灯影组碳酸盐岩普遍具有较低的稀土总量(∑REE+Y值为0.4～3.3μg/g)、较低的Mn/Sr值(0.2～2.8)和较高的Fe含量(55.9～1 772.6μg/g)。灯影组的REE+Y配分曲线(经页岩标准化)可划分为四个阶段,且Ce异常指示该地区经历了弱氧化到弱还原再到缺氧状态,表明埃迪卡拉纪晚期海洋浅部水体也发生了缺氧现象。  相似文献   

14.
首次在班公湖-怒江缝合带西段去申拉组中发现了泥质硅质岩,呈2个层位产出。为探讨泥质硅质岩的沉积环境、成因及与班-怒特提斯洋西段构造演化的关系,进行岩石学和地球化学分析,结果显示,第一层位泥质硅质岩Al_2O_3/(Al_2O_3+Fe_2O_3)、Ce/Ce~?、(La/Ce)_N、V/(Ni+V)、Ce/La、Ce_(anom)、Eu_(anom)平均值分别为0.60、0.80、1.24、0.72、1.84、-0.08、0.01,第二层位泥质硅质岩相应比值平均值分别为0.65、0.83、1.16、0.77、1.97、-0.07、0.02。结合泥质硅质岩的Fe_2O_3/TiO2-Al_2O_3/(Al_2O_3+Fe_2O_3)、(La/Ce)N-Al_2O_3/(Al_2O_3+Fe_2O_3)、Hf/3-Th-Ta关系图解,表明第一、二层位泥质硅质岩形成于活动大陆边缘,沉积时水-岩界面为水体分层不强烈的厌氧环境。U-Th、Zn-Ni-Co、La-Ce、La/Yb-REE关系图解和稀土元素特征指示了第一、二层位泥质硅质岩为热水成因,热水活动与玄武岩岩浆活动有关,第二层位泥质硅质岩沉积时热水活动更强烈。去申拉组泥质硅质岩的岩石学、地球化学特征表明,狮泉河地区班-怒特提斯洋至少在早白垩世仍具有一定规模的洋盆,其闭合时间应晚于约109Ma,进一步限定了洋盆的闭合时间。  相似文献   

15.
In this study we have used laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), to produce a high resolution coral record of rare earth elements (REE), Mn and Ba from coastal Porites corals from the Great Barrier Reef of Australia. Validation of the LA-ICP-MS technique indicated that the method provides accurate and reproducible (RSD = 13-18%) analysis of low concentration REE in corals (∼1 to 100 ppb). The REE composition in coral samples was found to closely reflect that of the surrounding seawater and distribution coefficients of ∼1-2 indicated minimal fractionation of the series during incorporation into coral carbonate. To explore the idea that coral records of REE can be used to investigate dissolved seawater composition, we analyzed two coastal corals representing a total of ∼30 yr of growth, including a 10-yr overlapping period. Comparable results were obtained from the two samples, particularly in terms of elemental ratios (Nd/Yb) and the Ce anomaly. Based on this evidence and results from the determination of distribution coefficients, we suggest that useful records of seawater REE composition can be obtained from coral carbonates. When compared to the REE composition of a mid shelf coral, coastal corals showed a significant terrestrial influence, characterized by higher REE concentrations (greater than 10 times) and light REE enrichment. The REE composition of coastal seawater inferred from the coral record was dependent on seasonal factors and the influence of flood waters. REE fractionation displayed a strong seasonal cycle that correlated closely with Mn concentration. We suggest that higher Nd/Yb ratios and higher Mn concentrations in summer result from scavenging of heavy REE by particulate organic ligands and Mn reductive dissolution respectively, both processes displaying higher rates during periods of high primary productivity. The Ce anomaly also displayed a strong seasonal cycle showing an enhanced anomaly during summer and during flood events. This is consistent with the Ce anomaly being primarily controlled by the abundance of Ce oxidizing bacteria. Based on these arguments, we suggest that the coral record of dissolved REE and Mn may be regarded as a useful proxy for biological activity in coastal seawater.  相似文献   

16.
Banded iron formations (BIFs) within the Lvliang region of Shanxi Province, China, are hosted by sediments of the Yuanjiacun Formation, part of the Paleoproterozoic Lvliang Group. These BIFs are located in a zone where sedimentation changed from clastic to chemical deposition, indicating that these are Superior-type BIFs. Here, we present new major, trace, and rare earth element (REE) data, along with Fe, Si, and O isotope data for the BIFs in the Yuanjiacun within the Fe deposits at Yuanjiacun, Jianshan, and Hugushan. When compared with Post Archean Australian Shale (PAAS), these BIFs are dominated by iron oxides and quartz, contain low concentrations of Al2O3, TiO2, trace elements, and the REE, and are light rare earth element (LREE) depleted and heavy rare earth element (HREE) enriched. The BIFs also display positive La, Y, and Eu anomalies, high Y/Ho ratios, and contain 30Si depleted quartz, with high δ18O values that are similar to quartz within siliceous units formed during hydrothermal activity. These data indicate that the BIFs within the Yuanjiacun Formation were precipitated from submarine hydrothermal fluids, with only negligible detrital contribution. None of the BIF samples analyzed during this study have negative Ce anomalies, although a few have a positive Ce anomaly that may indicate that the BIFs within the Yuanjiacun Formation formed during the Great Oxidation Event (GOE) within a redox stratified ocean. The positive Ce anomalies associated with some of these BIFs are a consequence of oxidization and the formation of surficial manganese oxide that have preferentially adsorbed Ho, LREE, and Ce4 +; these deposits formed during reductive dissolution at the oxidation–reduction transition zone or in deeper-level reducing seawater. The loss of Ce, LREE, and Ho to seawater and the deposition of these elements with iron hydroxides caused the positive Ce anomalies observed in some of the BIF samples, although the limited oxidizing ability of surface seawater at this time meant that Y/Ho and LREE/HREE ratios were not substantially modified, unlike similar situations within stratified ocean water during the Late Paleoproterozoic. Magnetite and hematite within the BIFs in the study area contain heavy Fe isotopes (56Fe values of 0.24–1.27‰) resulting from the partial oxidation and precipitation of Fe2 + to Fe3 + in seawater. In addition, mass-independent fractionation of sulfur isotopes within pyrite indicates that these BIFs were deposited within an oxygen-deficient ocean associated with a similarly oxygen-deficient atmosphere, even though the BIFs within the Yuanjiacun Formation formed after initiation of the GOE.  相似文献   

17.
Major, trace, and rare earth element abundances were determined for the southwestern Japanese pelagic chert sequence from the early Late Permian to early Early Triassic to investigate a redox change in deep-sea pelagic environments before and at the Permo-Triassic boundary (PTB) (251 Ma). The sequence was primarily deposited in the deep-sea of the superocean Panthalassa, and then was accreted to Japan in the Middle Jurassic. A remarkable lithostratigraphic change from red chert to siliceous∼carbonaceous claystone through gray chert is observed in this sequence. Constituent elements for these sedimentary rocks are essentially derived from two sources: (1) an ancient seawater via biogenic (mainly radiolarian), hydrothermal, and authigenic materials and (2) an average shale-like terrigenous material. The present measurement demonstrates significant stratigraphic changes of the Ce/Cenon-ter* value (estimated Ce anomaly value of non-terrigenous component, recalculated by subtraction of terrigenous REEs from bulk REEs) and the (Mn/TE)sample/(Mn/TE)PAAS value (excess Mn component other than terrigenous one; TE=terrigenous elements including Ti, Al, Nb, Hf, Th; PAAS=Post-Archean Average Australian Shale) in the Permian chert. The Ce/Cenon-ter* values increase from <0.2 to 1 and the (Mn/TE)sample/(Mn/TE)PAAS values decrease up-section, suggesting that the redox condition of deep-sea open-ocean changed from oxic to suboxic in an interval of approximately 10 Myr. The (∑Fe/TE)sample/(∑Fe/TE)PAAS and (Mn/TE)sample/(Mn/TE)PAAS values of carbonaceous claystone near or at the PTB are less than unity, suggesting that reductive dissolution of iron and manganese occurred under an anoxic condition. This supports the idea of the PTB oceanic anoxia in the superocean Panthalassa. The present data suggest that the anoxic condition prevailed in the deep-sea pelagic regions for an extremely long period, much more than 10 Myr, from the middle Late Permian to early Early Triassic. This long-term development of widespread oceanic anoxia may have been linked to the greatest mass extinction of the Phanerozoic.  相似文献   

18.
《Applied Geochemistry》2000,15(6):695-723
Ground and surface waters collected from two undisturbed Zn–Pb massive sulphide deposits (the Halfmile Lake and Restigouche deposits) and active mines in the Bathurst Mining Camp (BMC), NB, Canada were analysed for the rare earth elements (REE). REE contents are highly variable in waters of the BMC, with higher contents typical of waters with higher Fe and lower pH. There are significant differences between ground- and surface waters and between groundwaters from different deposits. The REE contents of surface waters are broadly similar within and between deposit areas, although there are spatial variations reflecting differences in pH and redox conditions. Surface waters are characterised by strong negative Ce anomalies ([Ce/Ce*]NASC as low as 0.08), produced by oxidation of Ce3+ to Ce4+ and preferential removal of Ce4+ from solution upon leaving the shallow groundwater environment. Groundwaters and seeps typically lack significant Ce anomalies reflecting generally more reducing conditions in the subsurface environment and indicating that Ce oxidation is a rapid process in the surface waters. Deeper groundwaters at the Halfmile Lake deposit are characterised by REE patterns that are similar to the host lithologies, whereas most groundwaters at the Restigouche deposit have LREE-depleted patterns compared to NASC. Halfmile Lake deposit groundwaters have generally lower pH values, whereas Restigouche deposit groundwaters show greater heavy REE-complexation by carbonate ions. Shallow waters at the Halfmile Lake and Stratmat Main Zone deposits have unusual patterns which reflect either the adsorption of light REE onto colloids and fracture-zone minerals and/or precipitation of REE–phosphate minerals. Middle REE-enrichment is typical for ground- and surface waters and is highest for neutral pH waters. The labile portion of stream sediments are generally more middle REE-enriched than total sediment and surface waters indicating that the REE are removed from solution by adsorption to Fe- and Mn-oxyhydroxides in the order middle REE≥light REE>heavy REE.  相似文献   

19.
The paper discusses the mineralogy and geochemistry of altered rocks associated with calcite and dolomite–ankerite carbonatites of the Onguren dyke–vein complex in the Western Transbaikal Region. The alteration processes in the Early Proterozoic metamorphic complex and synmetamorphic granite hosting carbonatite are areal microclinization and riebeckitization; carbonates, phlogopite, apatite, and aegirine occur in the near-contact zones of the dolomite–ankerite carbonatite veins; and silicification is displayed within separated zones adjacent to the veins. In aluminosilicate rocks, microclinization was accompanied by an increasing content of K, Fe3+, Ti, Nb (up to 460 ppm), Th, Cu, and REE; Na, Ti, Fe3+, Mg, Nb (up to 1500 ppm), Zr (up to 2800 ppm), Ta, Th, Hf, and REE accumulated in the inner zone of the riebeckitization column. High contents of Ln Ce (up to 11200 ppm), U (23 ppm), Sr (up to 7000 ppm), Li (up to 400 ppm), Zn (up to 600 ppm), and Th (up to 700 ppm) are typical of apatite–phlogopite–riebeckite altered rock; silicified rock contains up to (ppm): 2000 Th, 20 U, 13000 Ln Ce, and 5000 Ва. Ilmenite and later rutile are the major Nb carriers in alkali altered rocks. These minerals contain up to 2 and 7 wt % Nb2O5, respectively. In addition, ferrocolumbite and aeschynite-(Ce) occur in microcline and riebeckite altered rocks. Fluorapatite containing up to 2.7 wt % (Ln Ce)2O3, monazite-(Ce), cerite-(Ce), ferriallanite-(Ce), and aeschynite-(Ce) are the REE carriers in riebeckite altered rock. Bastnäsite-(Ce), rhabdophane-group minerals, and xenotime-(Y) are typical of silicified rock. Thorite, monazite-(Ce), and rhabdophane-group minerals are the Th carriers.  相似文献   

20.
Sorption of rare earth elements (REEs) and Ce oxidation on natural and synthetic Mn oxides have been investigated by many researchers. Although Mn(II)-oxidizing microorganisms are thought to play an important role in the formation of Mn oxides in most natural environments, Ce oxidation by biogenic Mn oxide and the relevance of microorganisms to the Ce oxidation process have not been well understood. Therefore, in this study, we conducted sorption experiments of REEs on biogenic Mn oxide produced by Acremonium sp. strain KR21-2. The distribution coefficients, Kd(REE), between biogenic Mn oxide (plus hyphae) and 10 mmol/L NaCl solution showed a large positive Ce anomaly and convex tetrad effect variations at pH 3.8, which was consistent with previous works using synthetic Mn oxide. The positive Ce anomaly was caused by oxidation of Ce(III) to Ce(IV) by the biogenic Mn oxide, which was confirmed by analysis of the Ce LIII-edge XANES spectra. With increasing pH, the positive Ce anomaly and convex tetrad effects became less pronounced. Furthermore, negative Ce anomalies were observed at a pH of more than 6.5, suggesting that Ce(IV) was stabilized in the solution (<0.2 μm) phase, although Ce(III) oxidation to Ce(IV) on the biogenic Mn oxide was confirmed by XANES analysis. It was demonstrated that no Ce(III) oxidation occurred during sorption on the hyphae of strain KR21-2 by the Kd(REE) patterns and XANES analysis. The analysis of size exclusion HPLC-ICP-MS showed that some fractions of REEs in the filtrates (<0.2 μm) after sorption experiments were bound to organic molecules (40 and <670 kDa fractions), which were possibly released from hyphae. A line of our data indicates that the negative Ce anomalies under circumneutral pH conditions arose from Ce(III) oxidation on the biogenic Mn oxide and subsequent complexation of Ce(IV) with organic ligands. The suppression of tetrad effects is also explained by the complexation of REEs with organic ligands. The results of this study demonstrate that the coexistence of the biogenic Mn oxide and hyphae of strain KR21-2 produces a specific redox chemistry which cannot be explained by inorganic species.  相似文献   

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