Geochemical characteristics of pelagic chert sequences across the Permian-Triassic boundary in southwest Japan

Abstract Geochemical characteristics, mainly of major and trace elements and REE (rare earth elements) of bedded chert and shale/mudstone sequences, across the Permian/Triassic boundary in southwest Japan are examined. The boundary is characterized by the disappearance of bedded cherts, and the interval between the Upper Permian cherts and Lower Triassic (probably Smithian) cherts comprises siliceous shales and organic black mudstones. Bedded cherts are characterized by a gradual depletion of chemical elements from Middle to Upper Permian. However, overlying siliceous shales exhibit a clear enrichment in some elements, especially alkaline metals (such as K, Rb and Cs) and Ti, Th, Y, P₂O₅, and REE in comparison with elements of the PAAS (post Archean Australian shales). This indicates that average components of the upper continental crust were transported in the boundary interval, possibly caused by volcanic activity. Ce-negative shifting in NASC (North American Shales Composite)-normalized REE patterns is characteristic of this interval, and could be related to the deposition of siliceous rocks in Ce-depleted seawater. This was probably caused by an invasion of water mass with a Ce-negative anomaly into the previously existing water mass of the Paleo-Tethys. Weak negative Eu-anomalies in this interval are suggestive of plagioclase fractionation caused by acid volcanisms and the LREE/HREE ratios in the interval show a slightly light-REE enrichment. Organic black mudstones are characteristically intercalated in the interval. These rocks are usually regarded as a product of oceanic deterioration, but in pelagic conditions, organic materials were formed by high primary production that resulted from the active upwelling of ocean floor water currents with rich nutrients. This may have been caused by the inferred mixing of water masses of the Paleo-Tethys and of the Panthalassa in Early Triassic time which was regarded as an event synchronous with an increase in volcanic activity on highly matured island arcs and/or continents.     

Distribution of rare earth elements of granitic regolith under the influence of climate

The distribution and anomalies of rare earth elements(REEs) of granitic regolith were studied in Inner Mongolia and Hainan Island, China. One profile showed slight REE enrichment of an upper layer and no obvious light REE/heavy REE(LREE/HREE) fractionation(La_N/Yb_N of 0.9). The second profile was significantly enriched in REEs and enriched in LREEs in the upper portion(La_N/Yb_N1.8). Eu, Ce, and Gd anomalies of the two profiles are different. Slightly negative Eu, Ce, and Gd anomalies in NMG-3-1 indicate slow dissolution of primary minerals and little secondary products; in contrast, a positive Eu anomaly in HN-2 suggests the vegetation cycle may contribute to soil. The Ce anomaly of HN-2 reflects oxidation of Ce and coprecipitation by Fe-and Mn-oxides and organic matter. Correlation between Ce and Gd anomalies in HN-2 suggests Ce and Gd are both influenced by redoxreduction.     

Rare earth element distribution in the Melrose-b howardite: Pre-terrestrial negative Ce anomaly

In order to investigate the genetic nature of the polymict breccia howardite Melrose-b, a whole-rock sample was separated into four fractions after pulverization and the rare earth element (REE) abundances were precisely determined by isotopic dilution in those fractions. Such an investigation shows that the three precipitated fine-particle fractions are depleted in Ce by the same factor (0.62 ～ 0.64) in spite of differences in mineralogy, while the corresponding factor of Ce depletion for the suspended-matter fraction is 0.462; the smaller value indicates a greater depletion in Ce.The weight fraction values of four fractions calculated from the REE abundances are in satisfactory agreement with the actual values. The concentration ratios between plagioclase and mainly pigeonite fractions accord with those observed in similar phases of the Juvinas eucrite [1]. Moreover, the bulk pattern synthesized from the three fine-particle fractions is similar in absolute level to that for the Zmenj howardite [1]. It is concluded that the negative Ce anomaly reflects the effect predating the igneous activity in the parent planetary body.     

The assessment of REE patterns and Nd/Nd ratios in fish remains

The REE content and isotopic composition of Sr and Nd have been determined in fish teeth ranging in age from the Trias to the present and from various localities mostly around the Atlantic. These measurements have been carried out on Selachian and Teleost remains from the same locality in Togo and show no appreciable difference, which suggests, with the help of a mass balance calculation of the Ce anomaly, that diagenetic effects are not responsible for the REE enrichment of biogenic phosphates.One group of fossil teeth has about 3 times the REE abundances of shale and a shale-normalized pattern with a minimum at Sm: it is thought to reflect deposition in the open-sea environment. A second group has REE concentration about 10 times higher than the first group with either a regular light REE enrichment or, more frequently, a maximum in the middle REE, both being probably indicative of deposition in estuarine or near-shore conditions. The shape of the REE spectra and the size of the Ce anomaly can be used semi-quantitatively to determine the depth of deposition. The results presented here on Late Cretaceous/Eocene fish teeth samples from Morocco reflect an increasing influx of deep waters with a lowLa/Yb ratio and strong negative Ce anomaly, which agrees well with the evolution of sediment chemistry and microfauna associations.In contrast, _Nd is typical of the water mass in which the fish debris decayed. Examples of nearly isolated basins identified with Nd isotopes include the South Atlantic prior to the Lutetian (_Nd ≈ −13.5), the Miocene Persian Gulf (_Nd = −3.1), and Bolivia during the Late Cretaceous (_Nd = −12.8). Togo and Guinea-Bissau results suggest that, in the South Atlantic, the meridional oceanic circulation had not started before 45 Ma ago.Combination of REE and_Nd data suggests that the assignment of Jurassic-Cretaceous samples measured so far to open-sea water masses is still ambiguous.     

Ce anomalies in Gough Island lavas — Trace element characteristics of a recycled sediment component

High precision trace element data obtained by inductively coupled plasma mass spectrometry and Sr–Nd isotope analyses are presented for mafic volcanic rocks from Gough Island, South Atlantic. The new data reveal negative Ce anomalies, with Ce/Ce^? values in Gough lavas extending down to ～ 0.92. Ce is only fractionated from other rare earth elements (REE) due to formation of Ce⁴⁺ under oxidizing conditions of near-surface environments while other REE remain trivalent. Ce anomalies in convergent margin magmas have been shown to indicate a contribution of a subducted sediment component. In contrast, Ce anomalies in intra-plate basalts have been attributed to weathering processes, but can be excluded here based on element–element systematics indicating magmatic trends rather than weathering-induced element mobility. Shallow-level contamination by local marine sediments with negative Ce anomaly inherited from seawater can be excluded because Gough lavas with increasingly negative Ce anomalies do not trend towards low Ce/Pb ratios characterizing such sediments. Rather, it is argued that the negative Ce anomalies in Gough Island lavas are consistent with variable amounts of a sediment component in the mantle plume source. Mixtures between estimates of subducting sediment columns with negative Ce anomaly and mantle capable of giving rise to Gough Island magmas without Ce anomalies reproduce the Gough compositional array with the exception of highly fluid-mobile elements. The calculated trace element composition of the deeply recycled sediment in the Gough plume source is depleted in fluid-mobile elements such as Ba and Pb relative to the composition of some present-day subducting sediments. This loss is attributed to the dehydration or flushing of sediment in the subduction factory, consistent with constraints from arc magmas.     

我国非传统矿产资源的实例及其所涉及的科学问题

传统矿产资源随着开采年限的增长而日益减少，寻求新的、非传统的按替资源，是解决人类矿产资源短缺的根本出路，是地球科学家长期肩负的战略性、前瞻性历史使命，我国有许多已经显示出巨大的资源潜力、但传统的矿床学、资源学、矿业技术的理论和方法难以实现其资源价值的地球物质堆积体，可视为典型的非传统矿产资源，包括：1）华南巨量堆积的天然纳米非金属矿物；2）华南微细浸染型金矿床原生矿石中的微粒金；3）西藏冈底斯中段北麓热泉泉华蛋白石中的微粒铯；4）白云鄂博等超大型矿床开采尾矿和选矿尾矿（所谓的“人工堆积矿床”）；5）部分原油和油田水中富集的金和其它金属元素；6）我国南方黑色岩系中特殊赋存状态的贵金属-重金属元素；7）我国西部陆相盆地中的可地浸砂岩型铀矿；8）我国南海和东海海域的天然气水合物；9）我国西南的分散元素矿床，由于非传统矿产资源是受目前理论、技术、经济以及环境等因素的限制尚未被认识或未能开发利用的矿产资源或潜在矿产资源，其所涉及的科学问题往往都具有显著的创新性和前沿性，对我国上述重要的非传统矿产资源而言，其所涉及的关键科学问题包括，天然纳-微米矿物及其特殊性能的成因机制，有机质与金属元素的耦合作用及其对金属富集的宏观与微观控制，等。     

Trace and rare earth element geochemistry of the black and grey shales of the Calabar Flank,Southeastern Nigeria: constraints on the depositional environment and the degree of metal enrichment

This study focuses on the trace and rare earth elements(REE) geochemistry of the Nkporo and Ekenkpon Shales of the Calabar Flank.The main aim is to infer their depositional environment and the degree of their metal enrichment.The shale samples were analyzed using inductively coupled plasma mass spectrometry.The results indicated that the mean concentrations of K,Na,and Fe in Nkporo and Ekenkpon Shales are 1.45,0.4,and 4.17 wt%,and 1.11,0.44,and 5.42 wt%;respectively.The Nkporo Shale is enriched with the following trace elements;PMn Sr Ba Zn Ce Rb Zr VCr Ni and depleted in the following trace elements;Ta GeSb Bi Cd Ag Te In Hg.While the Ekenkpon Shale is enriched with the following trace elements;P Mn Ba Sr VCe Zr Rb Cr Zn Ni and depleted in;Sb Ge Bi Ag Ce Te InHg.The concentration of redox-sensitive elements such as V,Ni,Mo,U,Cu,Cr,Re,Cd,Sb,Ti,Mn,and their ratio V/Mo and U/Mo in the black and grey shale samples show different patterns.The REE obtained from the Nkporo and Ekenkpon Shales were PAAS normalized.The Nkporo Shale showed a slightly flat light rare-earth element(LREE),middle rare-earth element(MREE),and heavy rare earth element(HREE) pattern enrichment.Ce/Ce*ranges from 0.95 to 1.09 in Nkporo Shale and 0.67 to 1.40 in Ekenkpon Shale.The Ekenkpon Shale showed a slight LREE,MREE enrichment,and depleted HREE patterns.The Mn contents and U/Mo ratio in Nkporo and Ekenkpon Shales suggests a poor oxygen transitional environment.The V/Mo and V/(V+Ni) ratios indicated that the Nkporo shales were deposited in an anoxic to suboxic conditions and Ekenkpon shales were also deposited under an anoxic to suboxic conditions.The V/Ni ratio indicated that the organic matter in the Nkporo shale is terrigenous while that of the Ekenkpon shales are both terrigenous and marine in origin.     

江西华齐铜多金属矿区含矿硅质岩的地球化学特征及成因探讨

矿产远景地质调查过程中,在江西华齐铜多金属矿区发现含矿硅质岩。测试分析显示,区内硅质岩贫A l2O3、T iO2,Co、C r等元素含量低,贫ΣREE,δ（Eu）为负异常,δ（C e）为弱正异常,HREE相对富集等热水沉积物的特征。在判别硅质岩形成的系列图解上,样品均指示热水沉积作用和大陆边缘环境,这与S iO2/A l2O3、S iO2/（K2O＋N a2O）、S iO2/M gO、M nO/T iO2、K/R b等特征值所指示的结果相一致。本区硅质岩地球化学特征及其对比结果说明该区域构造演化的复杂性。在元古代华南海槽构造演化中在华夏地块边缘发生断裂拉张,形成断陷盆地,并发生了热水喷流沉积成岩成矿作用。本区硅质岩与成矿关系密切,研究硅质岩对于认识区域构造演化及寻找矿化体具有重要意义。     

Minor elements in perovskite from kimberlites and distribution of the rare earth elements: An electron probe study

We report REE and minor element distributions for perovskites from seven kimberlites (South Africa and U.S.A.). The REE (1.6–6.3 oxides wt.%) are always strongly light REE enriched, often with Ce > La (chondrite-normalized), and show an expected close correlation with whole-rock analyses. Where examined, perovskite contains far more REE than coexisting apatite, by about an order of magnitude. Calculations indicate that iron is mostly present as Fe³⁺ and is low (1.0–2.9 wt.% Fe₂O₃) compared with perovskite from carbonatite complexes such as Oka (4.4 wt.% FeO [3]). In addition to established Nb (0.3–1.7 oxide wt.%), geochemically interesting elements encountered include Zr (up to 1.5 oxide wt.%), Ba and Sr (up to 0.2, 0.4 oxide wt.% respectively). Specific geological applications suggest a possible genetic link between Wesselton pipe and Benfontein Sills kimberlites, and that carbonate-rich dikes in the Premier mine were derived from kimberlites. The overall similarities with incompatible element-rich titanates in veined mantle peridotites suggest a more direct link between kimberlite magmatism and mantle metasomatism.     

Bearing of rare earth patterns of apatites from igneous and metamorphic rocks

Twelve apatite samples from igneous and metamorphic rocks from the Black Forest and igneous rocks from the Kaiserstuhl were analysed for their REE content. The ΣREE range from 0.116 to 1.69 wt.%; the lowest values were found in the metamorphic rocks. All apatites from the various parent rocks show a general enrichment of the lighter rare earths over the heavier and their chondrite-normalized rare earth patterns exhibit a more or less pronounced negative Ce anomaly. This Ce depletion is accompanied by relatively low La and Pr values. In addition, the apatites from igneous rocks from the Black Forest show a marked negative Eu anomaly. An explanation is offered for the simultaneous occurrence of a negative Ce and a negative Eu anomaly in one investigated rock system. The negative Ce anomaly is attributed to the occurrence of phases enriched in Ce (e.g., monazite, allanite) which crystallized prior to or simultaneously with apatite. The negative Eu anomaly in these magmatic apatites most probably is caused by discrimination of Eu²⁺ from the apatite lattice. The result of this discrimination is a selective Eu enrichment in the later crystallizing feldspars, plagioclase and orthoclase. At least in this case, the positive Eu anomaly in feldspars is not a reliable indicator of low oxygen fugacity during their crystallization; the Eu depletion of the earlier crystallized apatites is preferable for this purpose.     

Terminal Ediacaran anoxia in deep-ocean: Trace element evidence from cherts of the Liuchapo Formation,South China

Here we report a detailed trace element study of the cherts from Liuchapo Formation, which is a terminal Ediacaran (551-542 Ma) succession in South China deposited in deep-water basinal setting. The REE of Liuchapo cherts shows similar features as observed for anoxic modern seawater (but not for hydrothermal fluids), characterized by positive La anomaly (La_N/Ce_N = 0.83–1.91, average 1.37), moderately negative Ce anomaly (0.53–1.1, average 0.73), positive Gd anomaly (average 1.08), positive Y anomaly (average 1.21), and depleted LREE and MREE. In addition, the Liuchapo cherts have low ΣREE (3.36–56.13 ppm, average 20.6 ppm), low Al₂O₃, Ti, Th and Zr concentrations, and high Y/Ho ratios (up to 43.9). The redox-sensitive trace elements concentrations in the cherts do not correlate with detrital input proxies. All of these features suggest that the redox-sensitive trace elements in the cherts were authigenically concentrated in water column and their concentrations thus are excellent indicators of ancient redox conditions. Very low Th/U ratios, high V/(V+Ni) and Fe_⊤/Al ratios, enrichments of redox-sensitive trace elements (U, V, Mo), and low concentration of Mn in the cherts imply anoxia in the deep seawater. Our data reveal that the terminal Ediacaran ocean was not completely oxidized and the deep ocean was still anoxic, at least in South China. We propose that although the oxidative events existed in the terminal Ediacaran oceans, decomposition of organic matter prolonged anoxia in the deep ocean. Supported by National Natural Science Foundation of China (Grants Nos. 40532012, 40873007, 40603021) and Chinese Academy of Sciences (Grant No. KZCX3-SW-141)     

Using <Emphasis Type="Italic">in situ</Emphasis> REE analysis to study the origin and diagenesis of dolomite of Lower Paleozoic,Tarim Basin

In situ REE concentrations of various dolomites from Tarim Basin were obtained by LA-ICP-MS analysis, and the data were normalized to standard seawater (Seawater Normalized=SWN). Most of the samples have a ΣREE range of less than 20 ppm. All samples show similar REE_SWN distributions with heavy REE depletion, and positive Ce anomaly, which indicates that they have the same dolomitization fluids (seawater). According to the origin and diagenetic process of dolomite, two types of dolomite are determined and described as follows: 1) syndepositional dolomite, with the highest REE concentrations (more than 20 ppm), the cores of which are more enriched in REE compared with their cortexes, indicating that they underwent the dolomitization of calcareous sediments by hypersaline and subsequent diagenesis decreased the REE content of the cortex because of the low REE concentration of the diagenetic fluids; 2) diagenetic dolomite, which can be subdivided into four groups. (1) burial dolomite which has higher REE concentrations than limestone, but lower than syndepositional dolomite. This shows that pore fluids with high salinity dolomitized the pre-existing limestone; (2) void filling dolomite which has the similar REE patterns with the matrix dolomite. In addition, the Eu anomaly is not obvious, suggesting that the dolomitization fluids originated from the diagenetic fluids; (3) recrystallized dolomite, whose REE concentration was obviously decreased, indicating that the REE concentration was decreased during the recrystallization processes; and (4) hydrothermal altered void-filling dolomite, which has the lowest REE concentration, but obvious positive Eu anomaly, reflecting its hydrothermal activity related origin. Thus, the diverse REE signatures, which were recorded in different dolomites, retain the information of their formation conditions and subsequent diagenetic processes. In situ REE analysis of dolomite is an effective probe into the origin and diagenetic process of dolomite. Supported by National Basic Research Program of China (Grant No. 2005CB422103)     

The Early Paleozoic Tiefosi syn-collisional granite in the northern Dabie Orogen:Geochronological and geochemical constraints

The Tiefosi granitic pluton is located 5 km northwest of Xinyang City,northern Dabie Orogen,and was emplaced in the Proterozoic Qinling Group. SHRIMP zircon U-Pb dating suggests its crystallization at 436 ± 11 Ma. It is composed of monzogranite and syenogranite containing some amounts of muscovite and few mafic minerals. The rocks are characterized by high and restricted SiO2 content,low FeO,Fe2O3 and MgO contents,high K2O/Na2O ratio,and display high-K calc-alkaline and peraluminous (ACNK>1.1) characteristics. They are generally enriched in large ion lithophile elements (LILE) and depleted in high field strength elements (HFSE). They can be divided into three groups in light of rare earth elements (REE) and trace elements. Group I is moderate in ΣREE and characterized by the absence of Eu anom-aly,high (La/Yb)N ratio,and moderate Rb/Sr and Rb/Ba ratios. Group Ⅱ has moderately negative Eu anomaly,low (La/Yb)N ratio and high ΣREE contents,Rb/Sr and Rb/Ba ratios. Group Ⅲ displays positive Eu anomaly,moderate (La/Yb)N ratio,and low ΣREE,Rb/Sr and Rb/Ba ratios. The calculated εNd(440Ma) values of the rocks vary from 8.8 to 9.9 and Nd depleted mantle model ages are about 2.0 Ga,which resemble those of the paragneisses from the Qinling Group. The results indicate that the Tiefosi granite is crust-derived,syn-collisional S-type granite. Generation of Group I was related to low degree melting of the Qinling Group,while Group Ⅱ was formed by fractionational crystallization of plagioclase from Group I magmas,and Group Ⅲ resulted possibly from magma mingling with plagioclase cumulates. The Tiefosi granite was formed within crustal level related to the collision between the North China and South China blocks in the Early Paleozoic time.     

REE and (э)Nd of clay fractions in sediments from the eastern Pacific Ocean: Evidence for clay sources

Clay fractions in the non-calcareous surface sediments from the eastern Pacific were analyzed for clay minerals, REE and 143Nd/144Nd. Montmorillonite/illite ratio (M/I ratio), total REE contents ((REE), LREE/HREE ratio and cerium anomaly (бCe) may effectively indicate the genesis of clay minerals. Clay fractions with M/I ratio >1, бCe (0.85, (REE (400 μg/g, LREE/HREE ratio (4, and REE patterns similar to those of pelagic sediments are terrigenous and autogenetic mixed clay fractions and contain more autogenetic montmorillonite. Clay fractions with M/I ratio <1, бCe=0.86 to 1.5, ΣREE=200 to 350 μg/g, LREE/HREE ratio (6 and REE distribution patterns similar to that of China loess are identified as terrigenous clay fraction. The 143Nd/144Nd ratios or (э)Nd values of clay fractions inherit the features of terrigenous sources of clay minerals. Clay fractions are divided into 4 types according to (э)Nd values. Terrigenous clay minerals of type I with the (э)Nd values of -8 to -6 originate mainly from North American fluvial deposits. Those of type II with the (э)Nd values of -9 to -7 are mainly from the East Asia and North American fluvial deposits. Those of type III with (э)Nd values of -6 to -3 could come from the central and eastern Pacific volcanic islands. Those of type IV with (э)Nd values of -13 to -12 may be from East Asia eolian. The terrigenous and autogenetic mixed clay fractions show patchy distributions, indicating that there are volcanic or hot-spot activities in the eastern Pacific plate, while the terrigenous clay fractions cover a large part of the study area, proving that the terrigenous clay minerals are dominant in the eastern Pacific.     

The origins of rare earths in metalliferous sediments of the Troodos Massif. Cyprus

The ferromanganoan umbers which overlie the uppermost pillow lavas of the Troodos Massif, Cyprus, are strongly enriched in REE relative to normal pelagic clays. Together, the umbers, related ferruginous sediments, and the ochres which are associated with massive cupriferous sulphides located within the lavas, all show light REE enrichment. There is a marked negative Ce anomaly which is characteristic of seawater. Field and chemical data suggest that the REE were incorporated into ferruginous precipitates derived from deep leaching of tholeiitic lavas by seawater. All the metalliferous sediments can be interpreted as related events in the evolution of the Troodos ocean ridge. In contrast, REE patterns of bentonitic clays above the umbers indicate a predominantly continental derivation.     

Negative cerium anomalies in the rare earth element patterns of oceanic ferromanganese nodules

Ferromanganese nodules from the Bauer Basin of the south equatorial Pacific are unlike virtually all oceanic nodules so far analyzed in showing negative Ce anomalies in their REE abundance patterns. In comparison with similarly Cu-Ni-enriched nodules from the north equatorial Pacific they are depleted in REE by 50–80% and are heavy REE enriched relative to intermediate REE. The REE patterns can be accounted for by the input of hydrothermal iron oxyhydroxides and associated REE to the Bauer Basin and the transfer of the REE to the nodules because of diagenetic reactions in the sediment. The excess iron input also is reflected in lower Cu/Ni ratios in the nodules as compared with nodules from the north equatorial zone, apparently because of the larger proportions of a residual Fe phase in the nodules relative to todorokite. Cerium anomalies of the Bauer Basin nodules range from ?0.17 to ?0.29 as compared with +0.33 to +0.07 in the north equatorial Pacific but show a parallel sensitivity of Ce anomaly to Mn/Fe ratios of the nodules. Nodules with the more positive anomalies within each group have the smallest Mn/Fe ratios and have been subjected to the greatest seawater influence whereas nodules with the more negative anomalies have the largest Mn/Fe ratios and have been subjected to the greatest diagenetic influence.     

Geochemistry of the Middle to Late Permian limestones from the marginal zone of an isolated platform (Laibin, South China)

Major, trace and rare earth elements were measured in 27 samples of the Middle to Late Permian limestones from the Tieqiao section located on the marginal zone of an isolated platform (Laibin, South China). Shale-normalized REE+Y patterns of all samples show notably negative Ce anomalies (0.21–0.66, average 0.33), slightly positive Gd anomalies (1.08–1.30, average 1.20), and positive Y anomalies with superchondritic Y/Ho ratios (36–91, average 55), which are consistent with those of modern shallow seawater. Their relative LREEs enrichment with higher Nd_SN/Yb_SN ratios (0.58–1.80) than those of modern shallow seawater (0.21–0.50) suggests complicated sources of REEs for all samples. Compared with geochemical features of sediments influenced by terrigenous particles and hydrothermal fluids, it is concluded that ambient shallow seawater was the primary source of REEs in these limestones. Comparing the indicators of REE+Y elements (ΣREE, Nd_SN/Yb_SN, Ce/Ce*, Gd/Gd*, Eu/Eu* and Y/Ho) in limestones with those in bedded cherts from the Tieqiao section, we consider that limestone and bedded chert have similar sources of REE+Y elements: ambient shallow seawater with more or less hydrothermal fluids. In addition, there is a completely negative correlation between CaCO₃ and SiO₂ contents in limestones and bedded cherts. These results imply that precipitation of CaCO₃ was inhibited by that of SiO₂ which was derived mainly from hydrothermal fluid, especially in bedded cherts from the Tieqiao section.     

Anomalous Gadolinium,Cerium, and Yttrium Contents in the Adige and Isarco River Waters and in the Water of Their Tributaries (Provinces Trento and Bolzano/Bozen,NE Italy)

Rare earth patterns of surface and groundwaters near big cities often show anthropogenic Gd (Gd_ant) anomalies in addition to geogenic Ce and Y anomalies. The Gd_ant anomaly is caused by very stable organic complexes, one of which is gadopentetic acid, Gd‐DTPA. Derivatives of this and similar compounds are used as contrast agents in magnetic resonance imaging (MRI) of the human blood system. The organic Gd complexes are stable enough to pass nearly unaffected through sewage treatment plants and are, thereafter, discharged into surface water systems. Water of the rapidly flowing Isarco/Eisack and Adige/Etsch rivers (Provinces of Trento and Bolzano/Bozen, NE Italy) and their tributaries show remarkable variations in anthropogenic Gd contents (Gd_ant). Low Gd_ant values are found on Monday and Tuesday, whereas high values are observed during the remaining weekdays. Reliable Gd_ant balances are calculated for the river system at the confluence of the Adige and its tributaries. At two places local decrease of Gd_ant indicates exfiltration of groundwater. It is demonstrated that Gd_ant can be used as a reliably conservative tracer to study the water budget in rapidly flowing alpine river systems. The studied different river waters show considerable negative Ce and positive Y anomalies. Negative Ce anomalies are caused by scavenging of Ce(III) by FeO(OH) precipitates and subsequent oxidation to CeO₂. Y anomalies are attributed to less sorption of Y than REE onto particulate matter. Thus, Y moves faster than REE. Both, Ce and Y anomalies, are of geogenic origin.     

青海湖QH1孔晚全新世沉积物稀土元素地球化学与气候环境关系探讨

通过对青海湖QH1孔沉积物稀土元素丰度分布模式及稀土总量(REE)的分析结合沉积物中TOC含量粒度参数的变化特征探讨了稀土元素纵向变化与气候环境之间的关系. 结果表明青海湖沉积物中稀土元素总丰度值不高平均值为63mg/kg不包括Y左右. 总体上表现以半干旱的环境为主导化学风化作用相对微弱. 同时湖泊沉积物具有轻稀土相对富集缓右倾斜型CeEu基本上无明显异常的REE分布模式. 稀土元素与总有机碳TOC粒度之间存在较好的相关性. 分析表明沉积物中REE高值段指示暖湿气候环境REE低值段代表冷干气候环境. 根据稀土元素分布与沉积环境的关系重建了8500aBP以来青海湖区经历4次较大的暖湿-温干-暖偏湿-冷偏干的气候演化过程. 从而得出在高寒半干旱地区的青海湖沉积物中稀土元素对古气候变化具有良好的指示作用.     

Re-Os and Nd isotopes of black shales at the bottom of the Lower Cambrian from the northern Tarim Platform and their comparison with those from the Yangtze Platform

This paper reports Re-Os and Nd isotopes of black shales at the bottom of Lower Cambrian from the northern Tarim Basin and traces source materials of the black shales through isotopes. The average Re/Os, 187Re/188Os, and 187Os/188Os ratios of the black shales at the bottom of Lower Cambrian from the Tarim Basin are 7.18, 5.6438, and 1.9616, respectively. These isotopic ratios suggest the crustal sources of the black shales. The εNd(0) value is -13.17, the εNd(540 Ma) value is -7.32 and the Nd model ages are 1.535 Ga. These parameters in the black shales are quite consistent with those from the basement rocks. Based on the Re-Os and Nd isotopic characteristics of the black shales, we conclude that the continental crust mainly composed of basement rocks is the source material of the black shales. Through comparison of these isotopic parameters with those from the Yangtze Platform, it is clear that the Re-Os isotopic characteristics in the black shales from the Tarim and Yangtze platforms are quite different, which maybe indicates the differences in depositional settings between two platforms. These Re-Os isotopic data provide us with constraints to analyze the genetic relation between the two platforms.