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1.
We report an optimized method for extracting neodymium (Nd) from fossil fish teeth with a single-stage column (125 µl stem volume; LN Resin, Eichrom Industries, Darien Illinois) for isotopic analysis by multi-collector inductively coupled mass spectrometry (MC-ICMPS). Three reference materials (basalt: BCR-2, BHVO-2; phosphate: fossil bone composite) and splits of fossil fish teeth samples previously processed with existing two-stage column methods were processed using the single-stage column method. 143Nd/144Nd values of reference materials agree within error with published values, and the values for fish teeth correspond with sample splits processed with two-stage columns. Precision to ± ～ 0.23 εNd was achieved for 30 ng Nd samples of reference materials, and Nd isotope measurements of fossil fish tooth sample replicates as small as 7 ng Nd were reproducible within long term instrumental uncertainty. We demonstrate the utility of the new method with the first high resolution Nd isotope record spanning the ～ 40.0 Ma middle Eocene Climatic Optimum, which shows an excursion of 0.65 εNd during the peak warming at the study site (Ocean Drilling Program Leg 119, Site 738; 30 kyr sample spacing from 40.3 to 39.6 Ma). LN Resin is already used in standard methods for separating Nd, and Nd isotopes are routinely measured by MC-ICPMS with high efficiency inlet systems. Our innovation is a single, small volume LN Resin column for Nd separation. The streamlined approach results in a 10× increase in sample throughput.  相似文献   

2.
瞿瑗汝  吕逸文  刘盛遨 《地球科学》2021,46(11):4097-4106
锌同位素体系是海洋地球化学研究的新示踪剂,应用于示踪海水中锌元素的来源及其运移过程.海洋沉积物作为锌元素重要的"源"与/或"汇",其锌同位素组成的研究有助于理解海洋锌元素的地球化学循环.海洋沉积物记录了海水组成的信息,可以反演古海水锌同位素组成的变化,前提是理解沉积物与海水之间的分馏.对海水及海洋不同储库锌同位素研究进行系统总结,包括河流输入、热液体系、不同类型海洋沉积物(如富碳酸盐的沉积物、陆源硅酸盐碎屑、硅质沉积物、铁锰结核、贫氧-缺氧沉积物)的锌同位素组成,阐述了海洋沉积物锌同位素组成变化在古气候、古环境重建以及古海洋学等领域的应用以及重要性.   相似文献   

3.
Here we first present samarium (Sm)–neodymium (Nd) isotopic data for the ∼2.5 Ga Wangjiazhuang BIF and associated lithologies from the Wutai greenstone belt (WGB) in the North China Craton. Previous geochemical data of the BIF indicate that there are three decoupled end members controlling REE compositions: high-T hydrothermal fluids, ambient seawater and terrigenous contaminants. Clastic meta-sediment samples were collected for major and trace elements studies in an attempt to well constrain the nature of detrital components of the BIF. Fractionated light rare earth elements patterns and mild negative Eu anomalies in the majority of these meta-sedimentary samples point toward felsic source rocks. Moreover, the relatively low Th/Sc ratios and positive εNd(t) values are similar to those of the ∼2.5 Ga granitoids, TTG gneisses and felsic volcanics in the WGB, further indicating that they are derived from less differentiated terranes. Low Chemical Index of Weathering (CIW) values and features in the A-CN-K diagrams for these meta-sediments imply a low degree of source weathering. Sm–Nd isotopes of the chemically pure BIF samples are characterized by negative εNd(t) values, whereas Al-rich BIF samples possess consistently positive εNd(t) features. Significantly, the associated supracrustal rocks in the study area have positive εNd(t) values. Taken together, these isotopic data also point to three REE sources controlling the back-arc basin depositional environment of the BIF, the first being seafloor-vented hydrothermal fluids (εNd(t) < −2.5) derived from interaction with the underlying old continental crust, the second being ambient seawater which reached its composition by erosion of parts of the depleted landmass (likely the arc) (εNd(t) > 0), the third being syndepositional detritus that received their features by weathering of a nearby depleted source (likely the arc) (εNd(t) > 0).  相似文献   

4.
A first study of REE + Y distribution in a variety of Neoproterozoic (Cryogenian and Ediacaran) carbonates from different settings in the Saldania, Gariep, Damara and West Congo Belts in southwestern and central Africa revealed systematic differences that can be explained by varying palaeoenvironmental factors. The majority of samples display relatively unfractionated, flat shale-normalised REE + Y patterns that cannot be ascribed solely to shale contamination but are interpreted as resulting from the incorporation of near-shore colloids, possibly related to Fe-oxihydroxide scavenging. Only few carbonate units yielded trace element distributions that conform to a typical seawater composition. Those carbonates that were affected by stratiform, syn-sedimentary hydrothermal mineralisation are distinguished by Eu anomalies. Considering the similarity in residence time between REE and carbon, the strong influence of river-born particles on the REE + Y distribution in the analysed carbonates casts considerable doubt over the usefulness of these carbonates for stratigraphic correlation of Neoproterozoic sediment successions based on carbon isotopes.  相似文献   

5.
To constrain the provenance of the Ordos Basin and the evolution history of the Qinling Orogen Belt from the Triassic to the Jurassic, 10 samples from the Dongsheng area and 28 samples from the Yan’an area were analyzed for U–Pb ages and Lu–Hf and Sm–Nd isotopic compositions. The results indicate that Middle Jurassic sediments in the Dongsheng area were derived from the Khondalite Belt, Langshan Mountain and the Yinshan Terrane. Mesozoic sediments in the Yan’an area consist of two parts. One part is derived from the North China Craton (NCC), which has U–Pb age groups of ∼1.8 Ga and ∼2.5 Ga, and Hf model ages of ∼2.8 Ga. The other part is derived from the Qilian–Qinling Orogenic Belt, which has U–Pb age groups of 600–1500 Ma and 100–500 Ma, and Nd and Hf isotopic model ages of less than 2.2 Ga. Combining the U–Pb ages with the Hf and Nd isotopic model ages, Mesozoic detrital zircons with U–Pb age groups of ∼1.8 Ga and ∼2.5 Ga in the Yan’an area are found to also be derived from the Khondalite Belt, Langshan Mountain and the Yinshan Terrane, not from the Trans-China Orogen Belt. From the late–Late Triassic sediments of the Yan’an area, the low average values of the Hf (2.03 Ga) and Nd (2.03 Ga) model ages and the characteristic age population of 600–1500 Ma reveal that the main collision or continental subduction between the NCC and the South China Craton (SCC) occurred in the late–Late Triassic. After the main collision or continental subduction, the proportion of sediments from the Qinling–Qilian Orogenic Belt began to decrease (recorded in the early Jurassic samples), which may be in response to the gradual slowing of the uplift speed of the Qinling Orogenic Belt. In the early-middle Jurassic, the sediments have a main U–Pb age population of 100–500 Ma, low detrital zircon Hf model ages (average value is 1.17 Ga) and low whole rock Nd model ages (average value is 1.13 Ga), which suggests that the Qilian–Qinling Orogenic Belt may have a fast uplift history in the early-middle Jurassic.  相似文献   

6.
The Hf and Nd isotopic evolution of the Musgrave Province, central Australia, is used to constrain the timing of crust formation and lithospheric organisation of Proterozoic Australia. The dataset from this region challenges two widely held tenets of Hf and Nd isotope systematics, namely; that crust formation events can only be identified as periods when crystallisation ages correspond to model ages, and that linear Hf evolution arrays away from depleted mantle (along crustal Lu/Hf or Sm/Nd slopes) reflect reworking of the same source.Hf isotopes in Musgrave Province zircon crystals indicate two major crust formation events at c. 1900 Ma and at 1600–1550 Ma. Although no juvenile rocks or crystals are known from c. 1900 Ma, radiogenic addition into the crust at this time is required to account for consistent Nd and Hf evolution patterns, which show no indication of an initially heterogeneous source. Oxygen isotopes in zircon grains confirm that much of the c. 1900 Ma Hf isotopic signal is not compromised by mixtures. Furthermore, the correspondence between mantle extraction and the commencement of reworking of Archean material supports new crust generation at c. 1900 Ma and a coupling between lower and upper crustal processes. The c. 1900 Ma timing of juvenile addition is dissimilar to that in the Albany–Fraser and Arunta Orogens and may reflect continental arc development on the margin of a southern continent.The general Hf isotopic evolution trend of the Musgrave Province apparently reflects reworking from a dominant c. 1900 Ma source with some additional unradiogenic and radiogenic input through time. However, in the 1220–1050 Ma interval this apparent isotopic evolution contrasts with geological observations that indicate input of voluminous mantle-derived material. Intracontinental rifts and other regions with sustained very-high temperature crustal recycling processes generate magmatic provinces with extreme HFSE-enrichment. This can have a profound influence on isotopic evolution trends, suppressing typical juvenile addition patterns. Isotopic mixture modelling indicates that a significant volume of mantle derived material can be accommodated within HFSE enriched magmas without diverging isotopic signatures from apparent reworking trends. In the Musgrave Province, the crust had become so HFSE enriched during the prolonged Musgrave Orogeny (1220–1150 Ma) that it was insensitive to mantle input, which is estimated to have been as much as 85% during this event.  相似文献   

7.
The behavior of dissolved Hf in the marine environment is not well understood due to the lack of direct seawater measurements of Hf isotopes and the limited number of Hf isotope time-series obtained from ferromanganese crusts. In order to place better constraints on input sources and develop further applications, a combined Nd-Hf isotope time-series study of five Pacific ferromanganese crusts was carried out. The samples cover the past 38 Myr and their locations range from sites at the margin of the ocean to remote areas, sites from previously unstudied North and South Pacific areas, and water depths corresponding to deep and bottom waters.For most of the samples a broad coupling of Nd and Hf isotopes is observed. In the Equatorial Pacific εNd and εHf both decrease with water depth. Similarly, εNd and εHf both increase from the South to the North Pacific. These data indicate that the Hf isotopic composition is, in general terms, a suitable tracer for ocean circulation, since inflow and progressive admixture of bottom water is clearly identifiable.The time-series data indicate that inputs and outputs have been balanced throughout much of the late Cenozoic. A simple box model can constrain the relative importance of potential input sources to the North Pacific. Assuming steady state, the model implies significant contributions of radiogenic Nd and Hf from young circum-Pacific arcs and a subordinate role of dust inputs from the Asian continent for the dissolved Nd and Hf budget of the North Pacific.Some changes in ocean circulation that are clearly recognizable in Nd isotopes do not appear to be reflected by Hf isotopic compositions. At two locations within the Pacific Ocean a decoupling of Nd and Hf isotopes is found, indicating limited potential for Hf isotopes as a stand-alone oceanographic tracer and providing evidence of additional local processes that govern the Hf isotopic composition of deep water masses. In the case of the Southwest Pacific there is evidence that decoupling may have been the result of changes in weathering style related to the buildup of Antarctic glaciation.  相似文献   

8.
This study investigated Holocene and fossil hydrothermal manganese deposits in the Izu-Ogasawara arc. Mineralogically, these deposits comprise 10 Å and 7 Å manganate minerals, and the fossil samples showed higher 10 Å stabilities. Chemical compositions of the Holocene samples are typical of other hydrothermal manganese deposits, including low Fe/Mn ratios, low trace metals, and low rare earth elements. Although the fossil samples generally have similar chemical characteristics, they exhibit significant enrichment in Ni, Cu, Zn, Cd, Ba, REE, Tl, and Pb contents. Furthermore, the chondrite-normalized REE patterns showed more light REE enrichment trends. These chemical characteristics suggest post-depositional uptake of these metals from seawater. U-Th dating of a Holocene hydrothermal manganese deposit from the Kaikata Seamount indicated 8.8 ± 0.94 ka for the uppermost layer and downward growth beneath the seafloor with a growth rate of ca. 2 mm/kyr. This is approximately three orders of magnitude faster than that of hydrogenetic ferromanganese crusts. U-Pb age of a fossil hydrothermal manganese deposit from the Nishi-Jokyo Seamount showed 4.4 ± 1.6 Ma, which was contemporary with basaltic volcanism (5.8 ± 0.3 Ma). Hydrothermal manganese deposits contain high concentrations of high value Mn, but only small amounts of valuable minor metals; their ages constrain the periods of past hydrothermal activity and provide a vector to explore for polymetallic sulfide deposits.  相似文献   

9.
The nature of the lower crust and tectonic setting of the Chinese Altai in the early to middle Paleozoic are still hotly debated. Decoupling between zircon Hf and whole-rock Nd isotopic systems for granites results in different interpretations for the above issues. In order to solve the problem, whole-rock Nd–Hf isotopic analyses were conducted on representative early to middle Paleozoic I-type granite and strongly peraluminous granites and rhyolites from the Chinese Altai. The I-type granites show metaluminous to weakly peraluminous feature and have εNd(t) values ranging from − 2.2 to + 0.8 and εHf(t) from + 3.9 to + 12.9, respectively. The strongly peraluminous granites and rhyolites have similar εNd(t) and εHf(t) values ranging from − 3.0 to + 1.7 and from + 2.1 to + 10.4, respectively. All samples plot above the Terrestrial Array on Nd–Hf isotopic diagram, indicating significant Nd–Hf isotopic decoupling in the magma sources. These samples show flatten HREE pattern and have Lu/Hf ratios similar to the average crust, suggesting that Nd–Hf isotopic decoupling was not originated from an ancient basement with elevated Lu/Hf ratios. The observed isotopic decoupling is similar to those modern island arcs, such as the Lesser Antilles and Sunda, where Nd selectively enriched over Hf due to metasomatism in the mantle wedge and consequently resulted in decoupling between the Sm–Nd and Lu–Hf isotopic systems. Our results, combined with the available data, show that prolonged subduction and crust–mantle interaction caused the Nd–Hf isotopic decoupling in the lithospheric mantle beneath the Chinese Altai. The crust of the Chinese Altai was extracted from the lithospheric mantle and inherited the Nd–Hf isotopic decoupling feature. Therefore, the Hf, rather than Nd, isotopic data more faithfully reflect the nature of the lower crust that was quite juvenile in the Paleozoic, and the Chinese Altai represents an early Paleozoic magmatic arc possibly built near western Mongolia.  相似文献   

10.
We present hafnium (Hf) and neodymium (Nd) isotopic compositions and concentrations in surface waters of the eastern Atlantic Ocean between the coast of Spain and South-Africa. These data are complemented by Hf and Nd isotopic and concentration data, as well as rare earth element (REE) concentrations, in Saharan dust.Hafnium concentrations range between a maximum of 0.52 pmol/kg in the area of the Canary Islands and a minimum value of 0.08 pmol/kg in the southern Angola Basin. Neodymium concentrations also show a local maximum in the area of the Canary Islands (26 pmol/kg) but are even higher between ∼20°N and ∼4°N reaching maximum concentrations of 35 pmol/kg. These elevated concentrations provide evidence of inputs from weathering of the Canary Islands and from the partial dissolution of dust from the Sahara/Sahel region. The inputs from ocean island weathering are also reflected in radiogenic Hf and Nd isotopes.The Hf isotopic compositions of dust samples themselves are highly variable, ranging between εHf = −20 and −0.6. The combined Hf and Nd isotopic compositions of dust plot close to the “terrestrial array” during periods of appreciable dust load in the atmosphere. During low atmospheric dust loading combined Hf and Nd isotopic compositions similar to seawater are observed. Most of the variability can be explained in terms of variable degrees of zircon loss from the dust samples, which in turn is linked to sorting during atmospheric transport to the eastern Atlantic Ocean and possibly presorting by sedimentary redistribution on the continent. In addition, increasing relative proportions of radiogenic clay minerals with decreasing grain size may contribute to the radiogenic Hf isotopic compositions observed.While the Nd isotopic composition in the surface ocean reflects the Nd isotopic composition of the Saharan dust adjacent to the Sahara/Sahel region, the release of Hf from that dust appears to be incongruent and results in surface ocean Hf isotopic compositions which are ∼10 εHf more radiogenic than the bulk dust. Radiogenic Hf appears to be released from clays and possibly from trace apatite. Rare earth element patterns of dust samples indicate the presence of apatite but provide no evidence for ferromanganese grain coatings, suggesting that such coatings are insignificant in the release of Hf and Nd from Saharan dust to the surface ocean.The Nd isotopic composition of the surface waters becomes less radiogenic south of the equator, most likely reflecting the release of Nd from Congo river sediments. The release of Hf from Saharan dust and the Congo river sediments, however, does not produce distinct Hf isotopic signatures in the surface ocean, implying that the mobile fraction of Hf integrated over large continental areas is isotopically uniform. The Hf isotopic uniformity in the surface ocean means that the limited variability in deep water isotopic compositions is consistent with a short deep water residence time and reflects homogenous continental inputs rather than efficient deep water homogenization.  相似文献   

11.
The Sr–Nd–Hf isotopic compositions of both saprolites and parent rocks of a profile of intensively weathered Neogene basalt in Hainan, South China are reported in this paper to investigate changes of isotopic systematics with high masses. The results indicate that all these isotopic systematics show significant changes in saprolites compared to those in corresponding parent rocks. The 87Sr/86Sr system was more seriously affected by weathering processes than other isotope systems, with εSr drifts 30 to 70 away from those of the parent rocks. In the upper profile (> 2.2 m), the Sr isotopes of the saprolites show an upward increasing trend with εSr changing from ~ 50 at 2.2 m to ~ 70 at 0.5 m, accompanying a upward increasing of Sr concentrations, from ~ 10 μg/g to ~ 25 μg/g. As nearly all the Sr of the parent rock has been removed during intensive weathering in this profile, the upward increasing of Sr concentrations in the upper profile suggests import of extraneous Sr. Rainwater in this region, which enriches in Sr (up to 139 μg/L) from seawater, may be the important extraneous source. Thus, the Sr isotopes of the saprolites in the upper profile may be mainly influenced by import of extraneous materials, and the Sr isotopic characteristics may not be retained. In contrast, the εNd and εHf of the saprolites drift only 0–2.6 and 0–3.7 away from the parent rocks, respectively. The negative drifts of the εNd and εHf are coupled with Nd and Hf losses in the saprolites; i.e., larger proportions of Nd and Hf loss correspond to lower εNd and εHf. Compared with the relative high Nd and Hf concentrations of the saprolites, the contributions of extraneous Nd and Hf both from wet and dry deposits of aeolian input are negligible. Thus, the εNd and εHf changes in the profile are mainly resulted from consecutive removal of the Nd and Hf. Calculation indicates that the 143Nd/144Nd and 176Hf/177Hf ratios in saprolites are all significantly lower than their initial values in the parent rock. Simply removing part of the Nd and Hf by incongruent decomposing some of the minerals may not account for this. Fractionation should be happen, which 143Nd and 176Hf may be preferentially removed from the profile relative to 144Nd and 177Hf during intensive chemical weathering, resulting in lower 143Nd/144Nd and 176Hf/177Hf ratios in saprolites relative to the parent rock, even though details for this process is not known. A positive correlation is observed between the εNd and εHf of the saprolites. Interestingly, the saprolites with a net loss of Nd and Hf in the upper profile show good positive correlation, and the regression line parallels the terrestrial array. By contrast, saprolites with a net gain of Nd and Hf in the lower profile generally show higher εHf values at a given εNd value, and the regression line between these εNd and εHf appears to parallel the seawater array. This supports the hypothesis that the contribution of continental Hf from chemical weathering release is the key to the obliquity of the seawater array away from the terrestrial array of the global εNd and εHf correlation. Our results also indicate that caution is needed when using εSr, εNd, and εHf to trace provenances for sediments and soils.  相似文献   

12.
海洋Nd同位素演化及古洋流循环示踪研究   总被引：2，自引：0，他引：2       下载免费PDF全文
海洋Nd同位素演化已经成为示踪陆源风化输入和洋流循环改变的最重要的手段之一,得到了越来越多的应用,并取得了许多重要的成果。海水的Nd同位素组成主要受陆源输入物质控制,热液输入几乎可以忽略。由于Nd在海洋中的停留时间(约500～1000a)略小于海水的平均混合时间(约1500a),且各洋盆有不同的Nd同位素风化输入,因此现代各大洋海水具有不同的Nd同位素组成。在陆源输入稳定的情况下,可以利用海水的Nd同位素组成和演化来示踪水体的混合或洋流循环的改变。目前主要依靠对海洋中水成铁锰结壳、海洋钙质有孔虫壳体、磷酸质鱼骨头或鱼牙齿化石以及沉积物中铁锰氧化物组分等的研究来恢复和反演古海水的Nd同位素组成和演化。4种分析材料各有其优缺点。其中,通过对水成铁锰结壳的Nd同位素分析,基本建立了各大洋新生代以来的主要洋流的Nd同位素组成的长尺度演化。通过有孔虫壳体、鱼化石碎片和沉积物中Fe-Mn氧化物组分可以进行高时间分辨率的古海水Nd同位素演化示踪。利用海水Nd同位素演化可以示踪古洋流通道的开启或闭合,以及获得水体交换的直接信息,为研究构造运动与气候变化之间的关系提供指示。同时,将海水Nd同位素演化与气候变化的指标结合起来,可以用于示踪各种气候条件下洋流循环的改变,将洋流循环的改变与气候变化联系起来,研究两者之间的成因关系。对表层水体的Nd同位素组成的研究则可以示踪不同气候条件下大陆陆源风化输入的改变。  相似文献   

13.
《Gondwana Research》2013,23(3-4):1102-1109
Conodonts collected from sections near the small towns of Thong Pha Phum and Mae Sariang in the westernmost part of Thailand are used to reconstruct the neodymium (Nd) isotopic composition of seawater during the Late Devonian. The study provides the first Devonian seawater signatures recognized within the Australian shelf of northeastern Gondwana and the adjacent Paleotethys Ocean. At Thong Pha Phum site, the seawater was characterized by very low εNd values (from − 13.1 to − 18.2) and very high Sm/Nd ratios (between 0.36 and 0.66). In contrast, the seawater at the Mae Sariang site was characterized by much more radiogenic signatures (εNd values from − 8.7 to − 11.1) and uniform, low Sm/Nd ratios (between 0.20 and 0.23). Extremely low εNd values recognized at Thong Pha Phum attest to a passive margin continental setting and a paleogeographic position very close to a continental area where Paleoproterozoic and Neoarchean rocks were eroded. Thus, the isotopic data provide strong evidence that during Late Devonian time the Sibumasu terrane was situated in the proximity to the Archean cratons of Western Australia, presumably adjacent to the Carnarvon intracratonic basin. Moreover, Sibumasu may not have been situated in an outboard position on the shelf, as previously suggested, but could have been directly attached to the Australian continental crust. By contrast, low and uniform Sm/Nd ratios of seawater at Mae Sariang resemble those of the Variscan and the present-day oceanic seawaters. Therefore, a pelagic setting within the Paleotethys Ocean is postulated for the Mae Sariang succession. This conclusion is also constrained by minor temporal changes in εNd values and suggests that the Paleozoic of Mae Sariang is not part of the Sibumasu terrane but belongs to the Inthanon Zone.  相似文献   

14.
Deep-sea corals have been shown to be useful archives of rapid changes in ocean chemistry during the last glacial cycle. Their aragonitic skeleton can be absolutely dated by U-Th data, freeing radiocarbon to be used as a water-mass proxy. For certain species of deep-sea corals, the growth rate allows time resolution that is comparable to ice cores. An additional proxy is needed to exploit this opportunity and turn radiocarbon data into rates of ocean overturning in the past.Neodymium isotopes in seawater can serve as a quasi-conservative water-mass tracer and initial results indicate that deep-sea corals may be reliable archives of seawater Nd isotopes. Here we present a systematic study exploring Nd isotopes as a water-mass proxy in deep-sea coral aragonite. We investigated five different genera of modern deep-sea corals (Caryophyllia, Desmophyllum, Enallopsamia, Flabellum, Lophelia), from global locations covering a large potential range of Nd isotopic compositions. Comparison with ambient seawater measurements yields excellent agreement and suggests that deep-sea corals are reliable archives for seawater Nd isotopes.A parallel study of Nd concentrations in these corals yields distribution coefficients for Nd between seawater and coral aragonite of 1-10, omitting one particular genus (Enallopsamia). The corals and seawater did however not come from exactly the same location, and further investigations are needed to reach robust conclusions on the incorporation of Nd into deep-sea coral aragonite.Lastly, we studied the viability of extracting the Nd isotope signal from fossil deep-sea corals by carrying out stepwise cleaning experiments. Our results show that physical removal of the ferromanganese coating and chemical pre-cleaning have the highest impact on Nd concentrations, but that oxidative/reductive cleaning is also needed to acquire a seawater Nd isotope signal.  相似文献   

15.
The Early Cambrian black shale sequence of the Niutitang Formation in South China hosts a synsedimentary, organic carbon-rich, polymetallic sulfide layer with extreme metal concentrations, locally mined as polymetallic Ni–Mo–PGE–Au ore. In combination with previously reported data, we present Mo isotope, platinum-group element (PGE), and trace and rare-earth element (REE) data for the polymetallic sulfide ores and host black shales from four mine sites (Dazhuliushui and Maluhe in Guizhou Province, and Sancha and Cili in Hunan Province, respectively), several hundred kilometers apart. The polymetallic sulfide ores have consistently heavy δ98/95Mo values of 0.94 to 1.38‰ (avg. 1.13 ± 0.14‰, 1σ, n = 11), and the host black shale and phosphorite have slightly more variable δ98/95Mo values of 0.81‰ to 1.70‰ (n = 14). This latter variation is due to variable paleoenvironmental conditions from suboxic to euxinic, and partly closed-system fractionation in isolated marine sedimentary basins. Both the polymetallic sulfides and host black shales show PGE distribution patterns similar to that of present-day seawater, but different from those of ancient submarine-hydrothermal deposits and modern submarine hydrothermal fluids. The polymetallic sulfide bed has a generally consistent metal enrichment by a factor of 107 compared to present-day seawater. PAAS-normalized REE + Y patterns of the polymetallic sulfide bed are characterized by a remarkably positive Y anomaly, consistent with an origin of the REE predominantly from seawater. Small positive Eu anomalies in some of the sulfide ores could reflect minor hydrothermal components involved. The Mo isotope, PGE, and trace and rare-earth element geochemical data suggest that metals in the polymetallic Ni–Mo–PGE–Au sulfide ore layer were scavenged mostly from Early Cambrian seawater, by both in-situ precipitation and local re-deposition of sulfide clasts.  相似文献   

16.
The Bayan Obo Fe–REE–Nb deposit is the world's largest rare earth element (REE) resource and with the increasing focus on critical metal resources has become a focus of global interest. The deposit is hosted in the Palaeoproterozoic Bayan Obo Group, mainly concentrated in the H8 dolomite marble. The ores consist of light REE enriched monazite and bastnäsite, with a wide array of other REE minerals. Niobium mineralisation is hosted primarily in aeschynite and pyrochlore, although there are a wide range of other Nb-minerals. The origin of the host dolomite and ore bodies has been a subject of intense debate. The host dolomite has been proposed to be both of sedimentary origin and an igneous carbonatite. Carbonatite dykes do occur widely in the area, and consideration of the textural, geochemical and isotopic composition of the dolomite suggests an origin via intrusion of magmatic carbonatite into meta-sedimentary marble, accompanied by metasomatism. The origin of the ore bodies is complex, indicated most strongly by an ~ 1 Ga range in radiometric age determinations. Compilation of available data suggests that the ores were originally formed around 1.3 Ga (Sm–Nd isochron ages; Th–Pb ages of zircon), close in time to the intrusion of the carbonatite dykes. The ores were subsequently subjected to several stages of deformation and hydrothermal overprint, culminating in deformation, metamorphism and fluid flow related to the Caledonian subduction of the Mongolian Plate under the North China Craton from ~ 450 to 420 Ma (Th–Pb ages of monazite). This stage resulted in the formation of the strong foliation (‘banding’) of the ore. The presence of undeformed veins with alkali mineral fills, and the overprinting of the foliation by Nb minerals suggest that secondary fluid flow events may also have contributed to the metal endowment of the deposits, as well as remobilising the original Fe and REE mineralisation. The alteration mineralogy and geochemistry of the ores are comparable to those of many REE mineralised carbonatites. Initial Nd isotope ratios at 450 Ma, however, suggest crustal sources for the metals. These conflicting lines of evidence can be reconciled if a (at least) two stage isotopic evolution is accepted for the deposits, with an original mantle-sourced, carbonatite-related metal accumulation forming around 1.3 Ga with εNd close to 0. The ore was remobilised, with associated re-equilibration of Th–Pb isotope systematics during deformation at ~ 450 Ma. A further stage of alkaline hydrothermal fluid was responsible for Nb mineralisation at this stage. The complex geological history, with multiple stages of alkaline, high field strength element-rich, metasomatic fluid flow, is probably the main reason for the exceptional metal endowment of the Bayan Obo area.  相似文献   

17.
The Bilong Co oil shale zone is located in the South Qiangtang depression. This zone, together with the Shengli River-Changshe Mountain oil shale zone in the North Qiangtang depression, northern Tibet plateau, represents the potentially largest marine oil shale resource in China. Seventeen samples including oil shale and micritic limestone were collected from the Bilong Co oil shale area to determine the concentrations, distribution patterns, occurrences and origins of platinum group elements (PGEs) in marine oil shale. The oil shale samples from the Bilong Co area exhibit very low total PGE contents ranging from 1.04 to 2.96 ng/g with a weighted mean value of 1.686 ng/g, while the micritic limestone samples from the Bilong Co area exhibit a little lower PGE value ranging from 0.413 to 1.11 ng/g. PGEs in oil shale samples are characterized by high contents in Pd (average 0.79 ng/g), Os (average 0.123 ng/g) and Pt (average 0.644 ng/g) compared with Ru (average 0.068 ng/g), Rh (average 0.033 ng/g) and Ir (average 0.026 ng/g). The highest values for individual PGEs are not uniformly distributed in the section. Clearly, the PGEs are generally enriched in the oil shale samples near the boundary between micritic limestone and oil shale.The individual PGEs in oil shale samples from the Bilong Co area exhibit various modes of occurrence. Ruthenium and Pt occur mainly in pyrite, while Pd is associated mainly with organic matter and Mg-minerals. Rhodium and Os are controlled mainly by pyrite and organic matter. Iridium is present mainly in other Fe-bearing minerals, rather than pyrite. The PGEs in the Bilong Co oil shale are mainly of seawater origin and possibly influenced by terrigenous supply.  相似文献   

18.
Rare earth element (REE) mineralization is hosted within Neoproterozoic alkaline metaigneous rocks in the northwestern part of the Okcheon Metamorphic Belt (OMB), a polymetamorphosed fold-and-thrust belt transecting the Paleoproterozoic Gyeonggi and Yeongnam Massifs in the southern Korean Peninsula. The principal carrier phase of REEs is allanite. Allanite grains can be subdivided into several types based on the texture and mineral assemblage including quartz, K-feldspar, biotite, britholite, apatite, fergusonite, andradite, magnetite, zircon, titanite and fluorite. Electron microprobe analysis of allanite clearly distinguishes sample-to-sample variations in total REEs, Ca, Al, Fe and Y but the textural varieties from each rock sample do not show marked differences in those elements. Sensitive high-resolution ion microprobe dating of allanite and zircon reveals a complex history of multistage mineralization. Allanite grains from REE ores yielded Late Ordovician (444.6 ± 8.0 Ma), Permian to Triassic (ca. 300–220 Ma) and Early Jurassic (199–183 Ma) 208Pb/232Th ages. These multiple age components often coexist in single grains showing slight differences in backscattered electron brightness. The Ordovician components have distinctly higher Th/U than the younger domains in the same rock sample. The cores and rims of zircon from a syenite hosting REE ore bodies yielded Neoproterozoic (858.2 ± 6.3 Ma) and Early Jurassic (ca. 190 Ma) 206Pb/238U ages, respectively. The Early Jurassic ages (194–187 Ma) also obtained from zircon grains from granites taken from dykes occurring close to the ores and a drill core indicate the correspondence between granitic magmatism and REE mineralization. The Neoproterozoic zircon inheritance (weighted mean = 853.9 ± 3.8 Ma) in these granites is in sharp contrast to the dominant Paleoproterozoic inherited zircon from the widespread earliest Middle Jurassic granites enclosing the mineralized zone. The geotectonic significance of the Late Ordovician event recorded in the allanite, as well as in detrital zircon from the OMB, is still unclear but its temporal coincidence with intraplate volcanism and arc-related igneous activity, respectively, reported from the southwestern edge of the adjacent Taebaeksan Basin and the southwestern Gyeonggi Massif is noteworthy. The following Permian–Triassic and Early Jurassic mineralization events are probably linked to the continental suturing between the North and South China blocks and subsequent post-orogenic magmatism, and arc magmatism resulting from the paleo-Pacific plate subduction, respectively. Sub-grain Sm–Nd isotopic analyses of allanite by laser ablation multiple collector ICPMS yielded initial εNd values plotting along the Nd isotopic evolution path of the Neoproterozoic metaigneous rocks, indicating that REEs originating from the host rock have been recycled during multistage mineralization events. The profound differences in inherited zircon ages and Nd isotopic compositions between the Early and Middle Jurassic granites may reflect the presence of a major thrust-bounded crustal structure beneath the OMB.  相似文献   

19.
Geochemical characteristics of marine sediment from the southern Drake Passage were analyzed to reconstruct variations in sediment provenance and transport paths during the late Quaternary. The 5.95 m gravity core used in this study records paleoenvironmental changes during the last approximately 600 ka. Down-core variations in trace element, rare earth element, and Nd and Sr isotopic compositions reveal that sediment provenance varied according to glacial cycles. During glacial periods, detrital sediments in the southern Drake Passage were mostly derived from the nearby South Shetland Islands and shelf sediments. In contrast, interglacial sediments are composed of mixed sediments, derived from both West Antarctica and East Antarctica. The East Antarctic provenance of the interglacial sediments was inferred to be the Weddell Sea region. Sediment input from the Weddell Sea was reduced during glacial periods by extensive ice sheets and weakened current from the Weddell Sea. Sediment supply from the Weddell Sea increased during interglacial periods, especially those with higher warmth such as MIS 5, 9, and 11. This suggests that the influence of deep water from the Weddell Sea increases during interglacial periods and decreases during glacial periods, with the degree of influence increasing as interglacial intensity increases.  相似文献   

20.
Deep-sea sediments can contain relatively high concentrations of rare earth elements and yttrium (REY), with a growing interest in their exploitation as an alternative to land-based REY resources. To understand the processes that lead to enrichment of the REY in deep-sea sediments, we have undertaken a detailed geochemical study of sediments recovered from the Atlantic Ocean, on a transect along ~ 24°N that includes the deep Nares Abyssal Plain and the Canary and North America Basins.Total REY concentrations (ΣREY) range from 7.99 to 513 ppm, and total concentrations of the heavy REY (Eu - Lu) range from 0.993 to 56.3 ppm. REY concentrations are highest in slowly accumulating pelagic red clays, especially in samples that contain ferromanganese micronodules. Factor analysis reveals that hydrogenous Fe- and Mn-(oxyhydr)oxides are the primary REY carrier phase in the red clays. In situ analysis of individual micronodules confirms that they have high ΣREY (up to 3620 ppm). REY concentrations are higher in micronodules that have a hydrogenous source, characterised by higher Fe/Mn, compared to micronodules that have a diagenetic source.The ΣREY content of North Atlantic deep-sea sediments is ~ 4 times lower than in Pacific deep-sea sediments. We calculate that the area of seafloor required to extract ~ 10% of the global annual REY demand is ~ 100 km2, assuming removal of the upper 1 m of sediment.  相似文献   

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