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1.
Iron, Cu and Zn stable isotope systems are applied in constraining a variety of geochemical and environmental processes. Secondary reference materials have been developed by the Institute of Geology, Chinese Academy of Geological Sciences (CAGS), in collaboration with other participating laboratories, comprising three solutions (CAGS‐Fe, CAGS‐Cu and CAGS‐Zn) and one basalt (CAGS‐Basalt). These materials exhibit sufficient homogeneity and stability for application in Fe, Cu and Zn isotopic ratio determinations. Reference values were determined by inter‐laboratory analytical comparisons involving up to eight participating laboratories employing MC‐ICP‐MS techniques, based on the unweighted means of submitted results. Isotopic compositions are reported in per mil notation, based on reference materials IRMM‐014 for Fe, NIST SRM 976 for Cu and IRMM‐3702 for Zn. Respective reference values of CAGS‐Fe, CAGS‐Cu and CAGS‐Zn solutions are as follows: δ56Fe = 0.83 ± 0.07 and δ57Fe = 1.20 ± 0.13, δ65Cu = 0.57 ± 0.06, and δ66Zn = ?0.79 ± 0.12 and δ68Zn = ?1.65 ± 0.24, respectively. Those of CAGS‐Basalt are δ56Fe = 0.15 ± 0.07, δ57Fe = 0.22 ± 0.10, δ65Cu = 0.12 ± 0.08, δ66Zn = 0.17 ± 0.13, and δ68Zn = 0.34 ± 0.26 (2s).  相似文献   

2.
Isotope ratios of heavy elements vary on the 1/10000 level in high temperature materials, providing a fingerprint of the processes behind their origin. Ensuring that the measured isotope ratio is precise and accurate depends on employing an efficient chemical purification technique and optimised analytical protocols. Exploiting the disparate speciation of Cu, Fe and Zn in HCl and HNO3, an anion exchange chromatography procedure using AG1‐×8 (200–400 mesh) and 0.4 × 7 cm Teflon columns was developed to separate them from each other and matrix elements in felsic rocks, basalts, peridotites and meteorites. It required only one pass through the resin to produce a quantitative and pure isolate, minimising preparation time, reagent consumption and total analytical blanks. A ThermoFinnigan Neptune Plus MC‐ICP‐MS with calibrator‐sample bracketing and an external element spike was used to correct for mass bias. Nickel was the external element in Cu and Fe measurements, while Cu corrected Zn isotopes. These corrections were made assuming that the mass bias for the spike and analyte element was identical, and it is shown that this did not introduce any artificial bias. Measurement reproducibilities were ± 0.03‰, ± 0.04‰ and ± 0.06‰ (2s) for δ57Fe, δ65Cu and δ66Zn, respectively.  相似文献   

3.
In this study the homogeneity of the zinc isotopic composition in the NIST SRM 683 reference material was examined by measuring the Zn isotopic signature in microdrilled sample powders from two metal nuggets. Zinc was purified using AG MP‐1M resin and then measured by MC‐ICP‐MS. Instrumental mass bias was corrected using the “sample‐standard bracketing” method and empirical external normalisation with Cu doping. After evaluating the potential effects of varying acid mass fractions and different matrices, high‐precision Zn isotope data were obtained with an intermediate measurement precision better than ± 0.05‰ (δ66Zn, 2s) over a period of 5 months. The δ66ZnJMC‐Lyon mean values of eighty‐four and fourteen drilled powders from two nuggets were 0.11 ± 0.02‰ and 0.12 ± 0.02‰, respectively, indicating that NIST SRM 683 is a good isotopic reference material with homogeneous Zn isotopes. The Zn isotopic compositions of seventeen rock reference materials were also determined, and their δ66Zn values were in agreement with most previously published data within 2s. The δ66Zn values of most of the rock reference materials analysed were in the range 0.22–0.36‰, except for GSP‐2 (1.07 ± 0.06‰, n = 12), NOD‐A‐1 (0.96 ± 0.03‰, n = 6) and NOD‐P‐1 (0.78 ± 0.03‰, n = 6). These comprehensive data should serve as reference values for quality assurance and interlaboratory calibration exercises.  相似文献   

4.
Copper and Zn metals are produced in large quantities for different applications. During Cu production, large amounts of Cu and Zn can be released to the environment. Therefore, the surroundings of Cu smelters are frequently metal-polluted. We determined Cu and Zn concentrations and Cu and Zn stable isotope ratios (δ65Cu, δ66Zn) in three soils at distances of 1.1, 3.8, and 5.3 km from a Slovak Cu smelter and in smelter wastes (slag, sludge, ash) to trace sources and transport of Cu and Zn in soils. Stable isotope ratios were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in total digests. Soils were heavily contaminated with concentrations up to 8087 μg g−1 Cu and 2084 μg g−1 Zn in the organic horizons. The δ65Cu values varied little (−0.12‰ to 0.36‰) in soils and most wastes and therefore no source identification was possible. In soils, Cu became isotopically lighter with increasing depth down to 0.4 m, likely because of equilibrium reactions between dissolved and adsorbed Cu species during transport of smelter-derived Cu through the soil. The δ66ZnIRMM values were isotopically lighter in ash (−0.41‰) and organic horizons (−0.85‰ to −0.47‰) than in bedrock (−0.28‰) and slag (0.18‰) likely mainly because of kinetic fractionation during evaporation and thus allowed for separation of smelter-Zn from native Zn in soil. In particular in the organic horizons large variations in δ66Zn values occur, probably caused by biogeochemical fractionation in the soil-plant system. In the mineral horizons, Zn isotopes showed only minor shifts to heavier δ66Zn values with depth mainly because of the mixing of smelter-derived Zn and native Zn in the soils. In contrast to Cu, Zn isotope fractionation between dissolved and adsorbed species was probably only a minor driver in producing the observed variations in δ66Zn values. Our results demonstrate that metal stable isotope ratios may serve as tracer of sources, vertical dislocation, and biogeochemical behavior in contaminated soil.  相似文献   

5.
The Saishitang–Rilonggou Ore Field (SROF), which includes the Saishitang, Tongyugou, and Rilonggou ore deposits as well as other scattered occurrences, is located in the Elashan region in Qinghai Province, and is a significant Cu–Sn ore field in NW China. These ores are hosted in stratiform skarn deposits with the main metals being Cu and Sn, as well as Zn, Pb, Au, Ag, and trace elements (e.g. Ga, Ge, Se, and In). Bulk‐rock geochemical analyses of 50 ore samples from the three deposits show that In contents in the Saishitang deposit range from 0.03 to 39 ppm (average 12.7 ppm, n = 19), with 1000 In/Zn values that vary from >0.01 to 29.83 (average 4.29). Indium contents in the Tongyugou deposit vary from 7.51 to 131 ppm (average 28.37 ppm, n = 13), with 1000 In/Zn values from 0.74 to 48 (average 17.55). Finally, indium contents in the Rilonggou deposit vary from 0.73 to 120 ppm (average 36.15 ppm, n = 18), with 1000 In/Zn values from 0.33 to 47 (average 8.52). Indium is hosted mainly in sphalerite, while some other In‐bearing minerals (e.g., roquesite, stannoidite, and stannite) are present locally within the ore field. Roquesite, which replace or fill bornite, occurs in bornite‐rich ores in the Saishitang deposit. This is the first reported Chinese locality of roquesite. Based on previously reported Zn resources, a total of 136 tons of In is calculated to be hosted in the SROF, with 30, 66, and 40 tons of In attributed to the Saishitang, Tongyugou, and Rilonggou deposits, respectively. The differences in indium contents among the deposits and their respective geological histories and characteristics suggest that the origin of indium relates to volcanogenic metallogenesis in an early Permian volcano‐sedimentary basin. Based on the evaluation of In resources, future mining operations should include the recovery of indium in the Tongyugou and Rilonggou deposits.  相似文献   

6.
The Jinding Zn–Pb deposit located in the Mesozoic-Cenozoic Lanping Basin of southwest China has ore reserves of ∼ 220 Mt with an average grade of 6.1% Zn and 1.3% Pb. The mineralization is hosted by sandstone in the Early Cretaceous Jingxing Formation and limestone breccia in the Paleocene Yunlong Formation. Mineralization in both types of host rocks is characterized by a paragenetic sequence beginning with marcasite–sphalerite (Stage 1) followed by pyrite–marcasite–sphalerite–galena (Stage 2), and then galena–sphalerite–pyrite–sulfate–carbonate (Stage 3). Pyrite from these stages have different δ33S compositions with pyrite from Stage 1 averaging − 9.6‰, Stage 2 averaging − 8.9‰, and Stage 3 averaging + 0.3‰. Sphalerite hosted by the sandstone has similar δ66Zn values ranging from 0.10 to 0.30‰ in all stages of the mineralization, but sphalerite samples from the limestone breccia-hosted ore show variable δ66Zn values between − 0.03 and 0.20‰. Our data on sphalerite precipitated during the earlier stages of mineralization has a constant δ66Zn value and cogenetic pyrite displays a very light sulfur isotope signature, which we believe to reflect a sulfur source that formed during bacterial sulfate reduction (BSR). The Stage 3 sphalerite and pyrite precipitated from a late influx of metal-rich basinal brine, which had a relatively constant variable δ66Zn isotopic composition due to open system isotope fractionation, and a near zero δ33S composition due to the influence of abiotic thermochemical sulfate reduction from observed sulfates in the host rock.  相似文献   

7.
Stable Zn isotopes may be applied to trace the source of ore-forming metals in various types of PbZn deposits. To test this application, Zn and Pb isotope systematics for sulfides and associated basement rocks as well as FeMn carbonates (gangue) from the Zhaxikang PbZn deposit in South Tibet have been analyzed. The basement in this region includes metamorphosed mafic to felsic rocks (dolerite, quartz diorite, rhyolite porphyry, pyroclastics and porphyritic monzogranite). These rocks have similar δ66Zn values of 0.33 to 0.37‰, with an average value of 0.36 ± 0.03‰ (2σ), except for the more evolved porphyritic monzogranite that has a heavier value of 0.49‰. FeMn carbonates are present as hydrothermal veins and were probably precipitated from magmatic fluids. They have an average δ66Zn value of 0.27 ± 0.05‰, which is slightly lighter than the basement rocks, possibly representing δ66Zn isotopic compositions of the hydrothermal fluids. Sphalerite and galena have similar Zn isotopic compositions with δ66Zn ranging from 0.03 to 0.26‰ and 0.21 to 0.28‰, respectively. Considering the Zn isotope fractionation factor between sphalerite and fluids of − 0.2‰ at ~ 300 °C as reported in literature, hydrothermal fluids from which these sulfides precipitated will have δ66Zn values of ca. 0.39 ± 0.10‰, which are consistent with the values of basement rocks and the FeMn carbonates. This similarity supports a magmatic-hydrothermal origin of the Zhaxikang PbZn deposit. Both Pb and S isotopes in these sphalerite and galena show large variations and are consistent with being derived from a mixture of basement and sedimentary rocks in various proportions. Zn isotopic compositions of the sulfides significantly extend the range of regional basement rocks, suggesting that sedimentary rocks (e.g., shales) are also a significant source of Zn. However, the Zn isotopic compositions of sphalerite and galena differ from those of marine carbonates and those of typical SEDEX-type deposits (e.g. Kelley et al., 2009), confirming a magmatic-hydrothermal model. Combined with regional geological observations and the age constraints of ~ 20 Ma (Zheng et al., 2012, 2014), the results of our investigation indicate that the Zhaxikang PbZn deposit is most likely a magmatic-hydrothermal deposit.  相似文献   

8.
We studied zinc and sulfur isotopes and the chemical composition of sphalerite samples from Picos de Europa (Aliva mine) and sphalerite and hydrozincite samples from La Florida mine, two carbonate-hosted Mississippi Valley-type (MVT) deposits located in northern Spain; despite being close, they are hosted in carbonatic rocks of different ages, Lower Carboniferous and Lower Cretaceous, respectively. The two generations of sphalerite at Picos de Europa show different δ66Zn values (stage 1 sphalerite +0.24 per mil and stage 2 sphalerite from ?0.75 to +0.08 per mil). Both generations also differ in the sulfur isotope composition (stage 1 has δ34S?=?+6.6 and stage 2 has δ34S?=??0.9 to +2.9 per mil) and the chemical composition (stage 1 sphalerite, compared to stage 2 sphalerite, is significantly enriched in Pb, As, Mn, Sb, slightly enriched in Ag, Ni, and Cu and depleted in Co, Ga, Tl, Te, Ge, and Sn). We suggest that Zn isotope fractionation was controlled predominantly by pH and T changes. High Zn isotope values reflect rapid precipitation of sphalerite from higher-temperature acidic fluids that carried Zn mostly as chloride species after interaction with carbonate rocks while lower Zn isotope values most likely resulted from a longer precipitation process from fluid at higher pH and decreasing T that carried dominantly Zn sulfide species. At La Florida, sphalerite samples show light 66Zn-depleted signatures with δ66Zn values from ?0.80 to ?0.01 per mil (mostly between ?0.80 and ?0.24 per mil) and δ34S values from +10.7 to +15.7 per mil without any relationship between the δ66Zn and δ34S values. Here, the variation in Zn isotope values is interpreted as related to mixing of fluids from two reservoirs. The Zn was carried by a single deep-seated and higher T (~250–320 °C) fluid, and precipitation took place after mixing with a connate S-rich fluid in a system with mH2S?>?mZn2+ as a result of change in pH, T, and Zn predominant species. The light δ66Zn accompanied by heavy δ34S values resulted from fractionation of Zn aqueous sulfides at near-neutral pH and decreasing T. Hydrozincite samples show much heavier δ66Zn values (+0.21 to +0.33 per mil), consistent with fractionation during supergene processes.  相似文献   

9.
The Mike Horse Mine tailings dam in western Montana was partially breached in 1975 due to heavy rainfall and a failed drainage bypass. Approximately 90,000 tons of metal and arsenic-enriched tailings flowed into Beartrap Creek and the Blackfoot River. The spatial distribution of trace elements As, Cd, Cu, Mn, Pb, and Zn in floodplain alluvium of the upper Blackfoot River were examined along 20 transects in the upper 105 river kilometers downstream from the tailings dam. Trace element concentrations decrease with distance from the failed dam, with As reaching background concentrations 15 km from the Mike Horse dam, Cd and Pb at 21 km, Cu at 31 km, and Mn and Zn at 37 km. Distance from the Mike Horse tailings dam and mine area is the dominating factor in explaining trace element levels, with R 2 values ranging from 0.67 to 0.89. Maximum floodplain trace element concentrations in the upper basin exceed US. EPA ecological screening levels for plants, birds and other mammals, and reflect adverse hazard quotients for exposure to As and Mn for ATV/motorcycle use. Trace element concentrations in channel bank and bed alluvium are similar to concentrations in floodplain alluvium, indicating active transport of trace elements through the river and deposition on the floodplain. The fine fraction (<2 mm) of floodplain alluvium is dominated by sand-sized particles (2.0–0.05 mm), with Cu and Mn significantly correlated with silt-sized (0.05–0.002 mm) alluvium. Ongoing remediation in the headwaters area will not address metal contamination stored downstream in the channel banks and on the floodplain. Additionally, some trace elements (Cu, Mn and Zn) were conveyed farther downstream than were others (As, Cd, Pb).  相似文献   

10.
Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ66Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ66Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ66Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe2O4)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ66Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ66Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ66Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.  相似文献   

11.
We report Zn isotopic ratios (δ66Zn) of river suspended particulate matter (SPM) and floodplain deposits (FD) from the Seine basin, France, with a precision ?0.05‰. A decrease in δ66Zn from 0.30‰ to 0.08‰ is observed in SPM from the upstream to downstream parts of the fluvial system, associated with an increase in Zn concentration from 100 ppm to 400 ppm. The Zn/Al of SPM at the river mouth is up to five times greater than the Zn/Al of the natural background, and by normalizing to the later value we define a Zn enrichment factor. Suspended sediments from a temporal series of samples collected in Paris display a similar variation in δ66Zn of between 0.08‰ and 0.26‰, while showing an inverse relationship between the Zn enrichment factor and δ66Zn. The amount of Zn transported as suspended load varies from 10% to 90%, as a function of increasing discharge. The δ66Zn of SPM and the dissolved load are correlated, suggesting that adsorption processes are probably not the dominant process by which the Zn enrichment of SPM takes place. Instead, we interpret our data as reflecting the mixture of two main populations of suspended particles with distinct δ66Zn. The first is characteristic of natural silicate particles transported by erosion processes to the river, while the second likely represents anthropogenic particles derived from wastewater treatment plants or combined sewer overflows. Based on isotopic ratios, we calculate that 70% of Zn in SPM of the Seine River in Paris is of anthropogenic origin.  相似文献   

12.
Historically, a significant level of mining activity has taken place in the batholite-related metalogenic enclave of Linares (Jaén province, Spain), associated with Pb–Ag, Cu, Zn and Fe sulphides and Ba sulphate mineralization, though mining here has now been abandoned. Additionally, the area features a significant amount of urban, industrial and agricultural activities. These considerations, taken together, explain the need to assess the levels of concentration of trace elements and to determine their relationship with geogenic and anthropogenic factors. For geochemical characterisation of the soil, the region has been divided into 126 grid squares with an area of 1 km2. For each grid square, 32 trace elements have been analysed. Elemental concentrations of Cu, Pb, Zn, As and Mn have been included in statistical analyses. According to the reference levels established by the Regional Government (Junta de Andalucía), soils in a large part of the study area require amendment applications. The comparison of the mean content for each grid square with the reference levels reveals a significant degree of contamination of the soil by Cu (719 mg kg−1), Pb (22,964 mg kg−1) and As (100 mg kg−1) in those grid squares affected by metallurgic activities. By means of factor analysis, four scores have been identified which together account for 80% of the variance observed. The first score is highly correlated with the logarithms of the variables Fe, Th, La, Ti, Al, Na, K, Zr, Y, Nb, Be and Sc. It is a “natural” factor that indicates the type of soil matrix (fundamentally granites and, to a lesser degree, Triassic materials). The second score shows high correlation with the logarithms of the variables Mo, Cu, Pb, Zn, Ag, Co, Mn, As, Cd, Sb, Ba, W and Sn, and is the “metallization” factor related to the mineralization that has been exploited. The third score is mainly determined by the logarithms of the variables Sr, Ca and Mg. This is a “natural” factor that indicates a type of carbonate soil matrix (Miocene). Finally, the fourth factor groups the logarithms of the variables Ni, V and Cr, elements that are associated with the combustion of fossil fuels. Analysis of the patterns of each of the factors identified enabled achieving a global characterisation of the study area. Cluster analysis of the observations showed there to be five clusters relating to the grid squares, differentiated by lithologies and degrees of contamination. These clusters are used to determine the background of granite and to calculate the anomalous load.  相似文献   

13.
The Triassic carbonate rocks in Northern Tunisia (Nappes, Domes, Jurassic Mountains zones), consist of massive carbonates, clays and gypsum with authigenic minerals. These are associated with several Pb–Zn deposits and occurrences. At Jebel Ichkeul, Bechateur and Oum Edeboua, these Triassic carbonates exhibit enrichment in Pb (0.32 to 228 ppm), Zn (17 to 261 ppm), Cd (5 to 6 ppm) and Co (0.3 to 89.5 ppm), with respect to their average contents in crustal carbonates. The enrichment is more pronounced at Oum Edeboua (near the ore zone). Permeability is one of the most effective factors of dispersion of metallic trace elements, causing the development of geochemical halos. The genetic relationship of the Triassic carbonate rocks with the ore deposits was controlled by diapirism and tectonic movements, which favored mineralization along the Triassic‐cover contact as well as the remobilization of metals from the mineralized rocks. Analysis of metallic trace elements in Triassic rocks provides clues to the presence of possible mineral deposits. These could be effectively used for both geochemical interpretation and mineral exploration. Carbon and O‐isotope data (– 9.3‰ < δ13C < +3‰; +21.9 < δ18O < +31‰) suggest that the Triassic carbonates of all study areas have marine carbonates as their origin; some of them show significantly lower δ18O values indicating some exchange with hydrothermal fluids. Calcites associated with mineralization at Oum Edeboua have δ13C of –6.2‰ to –8.22‰ and δ18O of +24.88‰ to +25‰. The C‐isotope compositions of these calcites are 13C depleted, indicating an organic origin.  相似文献   

14.
Active and abandoned mine activities constitute the sources of deterioration of water and soil quality in many parts of the world, particularly in the African Copperbelt regions. The accumulation in soils and the release of toxic substances into the aquatic ecosystem can lead to water resources pollution and may place aquatic organisms and human health at risk. In this study, the impact of past mining activity (i.e., abandoned mine) on aquatic ecosystems has been studied using ICP-MS analysis for trace metals and Rare Earth Elements (REE) in sediment samples from Lubumbashi River (RL) and Tshamilemba Canal (CT), Katanga, Democratic Republic of the Congo (DRC). Soil samples from surrounding CT were collected to evaluate trace metal and REE concentrations and their spatial distribution. The extent of trace metal contamination compared to the background area was assessed by Enrichment Factor (EF) and Geoaccumulation Index (Igeo). Additionally, the trace metal concentrations probable effect levels (PELs) for their potential environmental impact was achieved by comparing the trace metal concentrations in the sediment/soil samples with the Sediment Quality Guidelines (SQGs). Spearman's Rank-order correlation was used to identify the source and origin of contaminants. The results highlighted high concentrations of trace metals in surface sediments of CT reaching the values of 40152, 15586, 610, 10322, 60704 and 15152 mg kg−1 for Cu, Co, Zn, Pb, Fe and Mn, respectively. In the RL, the concentrations reached the values of 24093, 2046, 5463, 3340, 68290 and 769 mg kg−1 for Cu, Co, Zn, Pb, Fe and Mn, respectively. The ΣREE varied from 66 to 218 and 142–331 mg kg−1 for CT and RL, respectively. The soil samples are characterized by variable levels of trace metals. The EF analysis showed “extremely severe enrichment” for Cu and Co. However, no enrichment was observed for REE. Except for Mo, Th, U, Eu, Mo, Ho and Tm for which Igeo is classified as “moderately polluted and/or unpolluted”, all elements in different sites are classified in the class 6, “extremely polluted”. The trace metal concentrations in all sampling sites largely exceeded the SQGs and the PELs for the Protection of Aquatic Life recommendation. Cu and Co had positive correlation coefficient values (r = 0.741, P < 0.05, n = 14). This research presents useful tools for the evaluation of water contamination in abandoned and active mining areas.  相似文献   

15.
The concentrations of mercury (Hg) and other trace metals (Ni, Cu, Zn, Mo, Ba, Re, U) and the Hg isotopic composition were examined across a dramatic redox and productivity transition in a mid-Pleistocene Mediterranean Sea sapropel sequence. Characteristic trace metal enrichment in organic-rich layers was observed, with organic-rich sapropel layers ranging in Hg concentration from 314 to 488 ng/g (avg = 385), with an average enrichment in Hg by a factor of 5.9 compared to organic-poor background sediments, which range from 39 to 94 ng/g Hg (avg = 66). Comparison of seawater concentrations and sapropel accumulations of trace metals suggests that organic matter quantitatively delivers Hg to the seafloor. Near complete scavenging of Hg from the water column renders the sapropel Hg isotopic composition representative of mid-Pleistocene Mediterranean seawater. Sapropels have an average δ202Hg value of −0.91‰ ± 0.15‰ (n = 5, 1 SD) and Δ199Hg value of 0.11‰ ± 0.03‰ (n = 5, 1 SD). Background sediments have an average δ202Hg of −0.76‰ ± 0.16‰ (n = 5, 1 SD) and Δ199Hg of 0.05‰ ± 0.01‰ (n = 5, 1 SD), which is indistinguishable from the sapropel values. We suggest that the sapropel isotopic composition is most representative of the mid-Pleistocene Tyrrhenian Sea.  相似文献   

16.
High-precision Zn isotopic variations are reported for carbonaceous chondrites (CC), equilibrated (EOC) and unequilibrated (UOC) ordinary chondrites, iron meteorites from the IAB-IIICD (nonmagmatic) and IIIA (magmatic) groups, and metal from the Brenham pallasite. For irons, δ65Cu values are also reported. Data have also been obtained on a coarse-grained type-B calcium-, aluminum-rich refractory inclusion (CAI) from Allende and on acid leaches of Allende (CV3), Krymka (LL3), and Charsonville (H6). Variations expressed as δ66Zn (deviation in parts per thousand of 66Zn/64Zn in samples relative to a standard) spread over a range of 0.3‰ for carbonaceous chondrites, 2‰ for ordinary chondrites, and 4‰ for irons.The measured 66Zn/64Zn, 67Zn/64Zn, and 68Zn/64Zn ratios vary linearly with mass difference and define a common isotope fractionation line with terrestrial samples, which demonstrates that Zn was derived from an initially single homogeneous reservoir. The δ66Zn values are correlated with meteorite compositions and slightly decrease in the order CI, CM, CV-CO, and to UOC. The isotopically light Zn of Allende CAI and the acid-resistant residues of Allende and Krymka show that the light component is associated with refractory material, presumably minerals from the spinel-group. This, together with the reverse correlation between relative abundances of light Zn isotopes and volatile element abundances, suggests that Zn depletion in planetary bodies with respect to CI cannot be ascribed to devolatilization of CI-like material. These observations rather suggest that refractory material reacted with a gas phase enriched in the lighter Zn isotopes. Alternatively, chondrules with their associated rims should carry a light Zn isotopic signature. The δ66Zn values of unequilibrated chondrites are rather uniform, whereas equilibrated chondrites show distinctly more isotopic variability.The values of δ65Cu-δ66Zn in irons define two trends. The moderate and positively correlated Cu and Zn isotope variations in IIIA and pallasite samples probably reflect crystallization of silicate, sulfide, and solid metal from the liquid metal. The range of δ66Zn values of the IAB-IIICD group is large (>3‰) and contrasts with the moderate fractionation of Cu isotopes. We interpret this feature and the negative δ66Zn-δ65Cu correlation as reflecting mixing, possibly achieved by percolation, between metals from a regolith devolatilized at low temperature (enriched in heavy zinc) and metallic liquids formed within the parent body.  相似文献   

17.
The Upper Cretaceous Nakhlak epigenetic vein-type Pb(Ag) deposit is located 55 km northeast of the town of Anarak in Isfahan Province, Iran. The deposit contains 7 Mt of galena-barite ore with an average grade of 8.33% Pb, 0.38% Zn, and 72 ppm Ag. The ore mineralization occurs as stratabound, epigenetic, steeply dipping, east-west–trending veins in faulted- or fracture-controlled Upper Cretaceous Sadar carbonates. Galena and barite are the primary minerals. Minor sphalerite, tennantite-tetrahedrite, pyrite, and chalcopyrite occur as inclusions in galena. Cerussite with minor amounts of anglesite and plattnerite formed in the oxidized supergene zone. The ore and ore-related minerals were deposited in the hydrothermally dolomitized carbonate host rock containing saddle-shaped dolomite. Geochemically, the dolomitized carbonate host rocks are enriched in MgO, Fe2O3, MnO, Pb, Zn, and Ba, but depleted in CaO. The galena concentrate contains high values of Ag (932 ppm), Sb (342 ppm), Cu (422 ppm), As (91 ppm), and Zn (296 ppm); the presence of these trace elements indicates a low-temperature type of galena mineralization. This interpretation is corroborated by fluid inclusions containing 12.98 wt.% NaCl equivalent salinity; the inclusions homogenize at the low temperature of about 152.1 °C. The similarity between δ34S(V-CDT) values in Nakhlak barite and Permian–Triassic δ34S marine sulfate values indicates that the Nakhlak sulfur was probably provided from evaporates of Permian–Triassic age. The δ34S(V-CDT) values of galena and barite samples occupy the ranges of − 1.04‰ to + 8.62‰ and + 10.95‰ to + 13.71‰, respectively, and are similar to Mississippi Valley–type (MVT) deposits. The low-temperature basinal fluids, evaporate-originated sulfur, and fault- or fracture-controlled galena-rich veins in the Nakhlak deposit resemble the type of geological features documented in Pb-rich MVT deposits.  相似文献   

18.
Zhang  Hongjie  Fan  Haifeng  Xiao  Chaoyi  Wen  Hanjie  Ye  Lin  Huang  Zhilong  Zhou  Jiaxi  Guo  Qingjun 《中国地球化学学报》2019,38(5):642-653

The Sichuan–Yunnan–Guizhou (SYG) metallogenic province of southwest China is one of the most important Zn–Pb ore zones in China, with ~ 200 Mt Zn–Pb ores at mean grades of 10 wt.% Zn and 5 wt.% Pb. The source and mechanism of the regional Zn–Pb mineralization remain controversial despite many investigations that have been conducted. The Wusihe Zn–Pb deposit is a representative large-scale Zn–Pb deposit in the northern SYG, which mainly occurs in the Dengying Formation and yields Zn–Pb resources of ~ 3.7 Mt. In this paper, Zn and S isotopes, and Fe and Cd contents of sphalerite from the Wusihe deposit were investigated in an attempt to constrain the controls on Zn and S isotopic variations, the potential sources of ore-forming components, and the possible mineralization mechanisms. Both the δ66Zn and δ34S values in sphalerite from the Wusihe deposit increase systematically from the bottom to the top of the strata-bound orebodies. Such spatial evolution in δ66Zn and δ34S values of sphalerite can be attributed to isotopic Rayleigh fractionation during sphalerite precipitation with temperature variations. The strong correlations between the Zn–S isotopic compositions and Fe–Cd concentrations in sphalerite suggest that their variations were dominated by a similar mechanism. However, the Rayleigh fractionation mechanism cannot explain the spatial variations of Fe and Cd concentrations of sphalerite in this deposit. It is noted that the bottom and top sphalerites from the strata-bound orebodies document contrasting Zn and S isotopic compositions which correspond to the Zn and S isotopic characteristics of basement rocks and host rocks, respectively. Therefore, the mixing of two-source fluids with distinct Zn–S isotopic signatures was responsible for the spatial variations of Zn–S isotopic compositions of sphalerite from the Wusihe deposit. The fluids from basement rocks are characterized by relatively lighter Zn (~ 0.2 ‰) and S (~ 5 ‰) isotopic compositions while the fluids from host rocks are marked by relatively heavier Zn (~ 0.6 ‰) and S (~ 15 ‰) isotopic compositions.

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19.
Two quartz samples of igneous origin, UNIL‐Q1 (Torres del Paine Intrusion, Chile) and BGI‐Q1 (Shandong province, China), were calibrated for their oxygen isotope composition for SIMS measurements. UNIL‐Q1 and BGI‐Q1 were evaluated for homogeneity using SIMS. Their reference δ18O values were determined by CO2 laser fluorination. The average δ18O value found for UNIL‐Q1 is 9.8 ± 0.06‰ and that for BGI‐Q1 is 7.7 ± 0.11‰ (1s). The intermediate measurement precision of SIMS oxygen isotope measurements was 0.32–0.41‰ (2s; UNIL‐Q1) and 0.40–0.48‰ (2s; BGI‐Q1), respectively. While less homogeneous in its oxygen isotope composition, BGI‐Q1 is also suitable for SIMS trace element measurements.  相似文献   

20.
In order to avoid the pollution of trace metals in marine environment, it is necessary to establish the data and understand the mechanisms influencing the distribution of trace metals in marine environment. The concentration of heavy metals (Fe, Mn, Cr, Cu, Ni, Pb, Zn, Co and Cd) were studied in sediments of Ennore shelf, to understand the metal contamination due to heavily industrialized area of Ennore, south-east coast of India. Concentration of metals shows significant variability and range from 1.7 to 3.7% for Fe, 284–460 μg g−1 for Mn, 148.6–243.2 μg g−1 for Cr, 385–657 μg g−1 for Cu, 19.8–53.4 μg g−1 for Ni, 5.8–11.8 μg g−1 for Co, 24.9–40 μg g−1 for Pb, 71.3–201 μg g−1 for Zn and 4.6–7.5 μg g−1 for Cd. For various metals the contamination factor (CF) and geoaccumulation index (I geo) has been calculated to assess the degree of pollution in sediments. The geoaccumulation index shows that Cd, Cr and Cu moderately to extremely pollute the sediments. This study shows that the major sources of metal contamination in the Ennore shelf are land-based anthropogenic ones, such as discharge of industrial wastewater, municipal sewage and run-off through the Ennore estuary. The intermetallic relationship revealed the identical behavior of metals during its transport in the marine environment.  相似文献   

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