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1.
Concentrations and isotopic compositions of Hg and Pb were measured in a sediment core collected from Lake Ballinger, near Seattle, Washington, USA. Lake Ballinger has been affected by input of metal contaminants emitted from the Tacoma smelter, which operated from 1887 to 1986 and was located about 53 km south of the lake. Concentrations and loadings of Hg and Pb in Lake Ballinger increased by as much as three orders of magnitude during the period of smelting as compared to the pre-smelting period. Concentrations and loadings of Hg and Pb then decreased by about 55% and 75%, respectively, after smelting ended. Isotopic compositions of Hg changed considerably during the period of smelting (δ202Hg = −2.29‰ to −0.38‰, mean −1.23‰, n = 9) compared to the pre-smelting period (δ202Hg = −2.91‰ to −2.50‰, mean −2.75‰, n = 4). Variations were also observed in 206Pb/207Pb and 208Pb/207Pb isotopic compositions during these periods. Data for Δ199Hg and Δ201Hg indicate mass independent fractionation (MIF) of Hg isotopes in Lake Ballinger sediment during the smelting and post-smelting period and suggest MIF in the ore smelted, during the smelting process, or chemical modification at some point in the past. Negative values for Δ199Hg and Δ201Hg for the pre-smelting period are similar to those previously reported for soil, peat, and lichen, likely suggesting some component of atmospheric Hg. Variations in the concentrations and isotopic compositions of Hg and Pb were useful in tracing contaminant sources and the understanding of the depositional history of sedimentation in Lake Ballinger. 相似文献
2.
Polymetallic vein-type Zn-Pb deposits are located in the Xiangxi–Qiandong zinc-lead metallogenic belt (XQMB) of the northwestern margin of the Jiangnan Orogen, South China. Ores are mainly found in fault-bounded quartz veins hosted in the upper part of the Banxi Group that consists of low-grade metamorphic sandstone, siltstone with minor tuff interbeds. The Zn-Pb deposits primarily contain sphalerite, galena, chalcopyrite and pyrite, accompanied by quartz and minor calcite. Zinc, lead, copper, indium and gallium are enriched in these ores. Investigation of the ore fluid reveals low temperature (87–262 °C) with scattered salinity (range from 2.73 to 26.64 wt% NaCleqv.). Hydrogen and oxygen isotopic compositions of fluid inclusions in quartz indicate mixing of magmatic hydrothermal fluid and meteoric water (δ18OH2O SMOW = 0.2‰ to 4.2‰; δDH2O SMOW = −126‰ to −80‰). Carbon and oxygen isotopic composition of carbonate samples indicate the magmatic hydrothermal origin of CO32− or CO2 in ore-forming fluid (δ13CPDB = −6.9‰ to −5.7‰, δ18OSMOW = 11.3‰ to 12.7‰). Sulfur and lead isotopic compositions (δ34SVCDT = 8.8–14.2‰ and 206Pb/204Pb = 17.156–17.209, 207Pb/204Pb = 15.532–15.508, 208Pb/204Pb = 37.282–37.546) demonstrate that sulfur sources were relatively uniform, and low radiogenic lead isotopic compositions indicate that ore metals were derived from a relatively unradiogenic source, probably by mixing of mantle with crust. Therefore, polymetallic vein-type Zn-Pb mineralization in this area probably arose from a magmatic-related hydrothermal system, and the deposition of sulfides occurred in response to cooling and boiling of magmatic hydrothermal fluids (high salinity, high δ18OH2O and δDH2O and metal-bearing), and is mainly the result of emplacement into open space and mixing with meteoric water (low salinity, low δ18OH2O and δDH2O). This study provides direct evidence that magmatism was involved in the ore-forming processes of the low temperature metallogenic district, South China, and it raises awareness about the presence of polymetallic vein-type Zn-Pb deposits in the northwest margin of Jiangnan Orogen and their potential as a source of zinc, copper, indium and gallium. 相似文献
3.
The stable carbon isotopic compositions of light hydrocarbon gases adsorbed in near-surface soil and sediments from the Saurashtra basin were characterized for their origin and maturity. Saurashtra is considered geologically prospective for oil and gas reserves; however, a major part of the basin is covered by the Deccan Traps, hindering the exploration of Mesozoic hydrocarbon targets. Surface geochemical prospecting, based on micro-seepage of hydrocarbons from subsurface accumulations, could be advantageous in such areas. In light of this, 150 soil samples were collected from the northwestern part of Saurashtra, around the Jamnagar area, where a thick sedimentary sequence of about 2–3 km exists under 1–1.5 km of Deccan basalt. The concentration of acid desorbed alkane gases from soil samples was found to vary (in ppb) as: methane (C1) = 3–518; ethane (C2) = 0–430; propane (C3) = 0–331; i-butane (iC4) = 0–297; n-butane (nC4) = 2–116; i-pentane (iC5) = 0–31 and n-pentane (nC5) = 0–23, respectively.Fifteen samples with high concentrations of alkane gases were measured for their δ13C1; δ13C2 and δ13C3 compositions using gas chromatography–combustion-isotope ratio mass spectrometry (GC–C-IRMS). The values for methane varied from ? 27 to ? 45.4‰, ethane from ? 20.9 to ? 27.6‰, and propane from ? 20.4 to ? 29.1‰ versus the Vienna PeeDee Belemnite (VPDB). The carbon isotope ratio distribution pattern represents isotopic characteristics pertaining to hydrocarbon gases derived from thermogenic sources. Comparisons of carbon isotopic signatures and compositional variations with the standard carbon isotopic models suggest that hydrocarbon gases found in the shallow depths of the study area are not of bacterial origin but are formed thermally from deeply buried organic matter, likely to be mainly a terrestrial source rock with a partial contribution from a marine source. These gases may have migrated to the near-surface environment, where they represent an admixture of thermally generated hydrocarbon gases from mixed sources and maturity. The maturity scale (δ13C versus Log Ro %) applied to the surface sediment samples of the Jamnagar area indicated the source material to be capable of generating oil and gas. The detection of thermogenic alkane gases in near-surface sediments offers the possibility of hydrocarbons at depth in Saurashtra. 相似文献
4.
This study provides 87Sr/86Sr, δ13C and δ18O data from the best-preserved limestone and dolomite of the Ediacaran carbonate-dominated Khorbusuonka Group of the Olenek Uplift, NE Siberian Craton, as well as detrital zircon geochronological data from both underlying and overlying sandstones. The Maastakh Formation is characterized by 87Sr/86Sr ratios of ca. 0.70822 and δ13C values between + 4.8 and + 6.0‰. 87Sr/86Sr ratios in limestones of the Khatyspyt Formation are fairly uniform, ranging from 0.70783 to 0.70806. The carbon isotopic composition slowly decreases from bottom (+ 3.7‰) to top (− 0.2‰) of section. The Sr isotopic composition of the Turkut Formation varies from 0.70824 to 0.70914, value of δ13C is about zero: − 0.7…+0.7 ‰. The youngest population of detrital zircons from Maastakh Formation indicates that these rocks were formed not later than 630 Ma. U–Pb detrital zircons data of Kessyusa Group has a single peak at about 543 Ma, which is almost identical to the earlier dating. Based on biostratigraphy and isotopic data, the Sr isotopic compositions from the Khatyspyt Formation (87Sr/86Sr = 0.70783–0.70806) represent the composition of seawater at 560–550 Ma. Such low values of 87Sr/86Sr ratio in Ediacaran water were probably caused by the quick opening of Iapetus Ocean. 相似文献
5.
This paper investigated the sources and behaviors of sulfate in groundwater of the western North China Plain using sulfur and oxygen isotopic ratios. The groundwaters can be categorized into karst groundwater (KGW), coal mine drainage (CMD) and pore water (subsurface saturated water in interstices of unconsolidated sediment). Pore water in alluvial plain sediments could be further classified into unconfined groundwater (UGW) with depth of less than 30 m and confined groundwater (CGW) with depth of more than 60 m. The isotopic compositions of KGW varied from 9.3‰ to 11.3‰ for δ34SSO4 with the median value of 10.3‰ (n = 4) and 7.9‰ to 15.6‰ for δ18OSO4 with the median value of 14.3‰ (n = 4) respectively, indicating gypsum dissolution in karst aquifers. δ34SSO4 and δ18OSO4 values of sulfate in CMD ranged from 10.8‰ to 12.4‰ and 4.8‰ to 8.7‰ respectively. On the basis of groundwater flow path and geomorphological setting, the pore water samples were divided as three groups: (1) alluvial–proluvial fan (II1) group with high sulfate concentration (median values of 2.37 mM and 1.95 mM for UGW and CGW, respectively) and positive δ34SSO4 and δ18OSO4 values (median values of 8.8‰ and 6.9‰ for UGW, 12.0‰ and 8.0‰ for CGW); (2) proluvial slope (II2) group with low sulfate concentration (median values of 1.56 mM and 0.84 mM for UGW and CGW, respectively) and similar δ34SSO4 and δ18OSO4 values (median values of 9.0‰ and 7.4‰ for UGW, 10.2‰ and 7.7‰ for CGW); and (3) low-lying zone (II3) group with moderate sulfate concentration (median values of 2.13 mM and 1.17 mM for UGW and CGW, respectively) and more positive δ34SSO4 and δ18OSO4 values (median values of 10.7‰ and 7.7‰ for UGW, 20.1‰ and 8.8‰ for CGW). In the present study, three major sources of sulfate could be differentiated as following: sulfate dissolved from Ordovician to Permian rocks (δ34SSO4 = 10–35‰ and δ18OSO4 = 7–20‰), soil sulfate (δ34SSO4 = 5.9‰ and δ18OSO4 = 5.8‰) and sewage water (δ34SSO4 = 10.0‰ and δ18OSO4 = 7.6‰). Kinetic fractionations of sulfur and oxygen isotopes as a result of bacterial sulfate reduction (BSR) were found to be evident in the confined aquifer in stagnant zone (II3), and enrichment factors of sulfate–sulfur and sulfate–oxygen isotopes calculated by Rayleigh equation were −12.1‰ and −4.7‰ respectively along the flow direction of groundwater at depths of 60–100 m. The results obtained in this study confirm that detailed hydrogeological settings and identification of anthropogenic sources are critical for elucidating evolution of δ34SSO4 and δ18OSO4 values along with groundwater flow path, and this work also provides a useful framework for understanding sulfur cycling in alluvial plain aquifers. 相似文献
6.
The Yangla Cu deposit is the largest Cu skarn deposit in the Jinshajiang tectonic belt. Based on the detailed observation of crosscutting relationships, three mineralization stages (i.e., pre-ore, ore and supergene) have been identified in the Yangla deposit. The pre-ore stage is dominated by prograde skarn. The ore stage is characterized by the precipitation of hydrous silicate minerals, Fe-oxides, Fe-Cu-Mo-sulfides, quartz and calcite, whose mineral assemblages were formed in the early and late sub-ore stages. The early sub-ore stage is marked by retrograde alteration with the deposition of hydrous silicate minerals (e.g., actinolite, epidote and chlorite), Fe-oxides, abundant Fe-Cu-Mo-sulfides, quartz and minor calcite. Whilst, the late sub-ore stage, associated with silicic and carbonate alteration, is represented by widespread thick quartz or calcite veins with disseminated pyrite, chalcopyrite, galena and sphalerite. We present new carbon-oxygen (C-O) isotopic compositions of the ore-hosting marble and hydrothermal calcite of this deposit. The hydrothermal calcite in the Yangla deposit was precipitated from both the early and late sub-ore stages. Calcite I from the early sub-ore stage is anhedral, and occurs as spot in the skarn or locally replaces the skarn minerals. Calcite II from the late sub-ore stage is distinguished by being coarse-grained, subhedral to euhedral and its occurrence in thick veins. Calcite I contains lower δ13CPDB (−7.0‰ to −5.0‰) and δ18OSMOW (7.2‰ to 12.7‰) than Calcite II (δ13CPDB = −4.5‰ to −2.3‰; δ18OSMOW = 10.7‰ to 19.4‰). In the δ13CPDB vs. δ18OSMOW diagram, the Calcite I and Calcite II data fall close to the igneous carbonatite field and between the fields of igneous carbonatite and marine carbonates, respectively. This suggests a dominantly magmatic origin for the early sub-ore fluids, and there might have been increasing carbonate wall rock involvement towards the late sub-ore stage. The ore-hosting marble (δ13CPDB = −4.8‰ to −0.3‰; δ18OSMOW = 10.2‰ to 23.9‰) also shows a positive δ13CPDB vs. δ18OSMOW correlation, which is interpreted to reflect the decreasing alteration intensity during the interactions between the hydrothermal fluids and ore-hosting carbonates. Simulated calculation suggests that both the Calcite I and Calcite II precipitated at 350 °C to 250 °C and 250 °C to 150 °C, respectively. We proposed that CO2 degassing and water/rock interactions were likely the two major processes that precipitated the calcite and led to the observed C-O isotopic features of the Yangla Cu deposit. 相似文献
7.
Determining Ge isotopic compositions of sulfides is important to understand the ore-forming processes. Single step anion-exchange chromatography was previously used to recover Ge from silicates and lignites. We apply this procedure to recover Ge from sulfides before determining Ge isotopic compositions by hydride generation (HG)-MC-ICP-MS. Germanium is quantitatively recovered by the proposed sample preparation method. There are no obvious isotope biases for Ge-bearing solutions containing significant amounts of Cu, Sn, and W. However, δ74Ge values show obvious shifts if the solutions contain high Zn, Pb, and Sb, which is possibly attributed to suppression of germane formation that fractionates Ge isotopes. The long-term reproducibility for Ge standard solution is about ± 0.18‰ for δ74Ge. Spex and Merck standard solutions yield mean δ74Ge values of − 0.70 ± 0.19‰ and − 0.36 ± 0.08‰, respectively. The calculated δ74Ge value (− 5.13‰) of sphalerite standard based on doping experiments is indistinguishable from those of sphalerite without doping (− 5.05‰ and − 5.01‰). Sulfides from the Jinding, Shanshulin, and Tianqiao Pb–Zn deposits in SW China have δ74Ge values of − 4.94‰ to + 2.07‰. The paragenetic sequence of sulfides from the Shanshulin and Tianqiao Pb–Zn deposits is pyrite, sphalerite and galena from early to late. Sulfides from the same ore show a trend of δ74Gepyrite < δ74Gesphalerite < δ74Gegalena, which may be controlled by the kinetic or Rayleigh fractionation. 相似文献
8.
The Maozu Pb–Zn deposit, located on the western margin of the Yangtze Block, southwest China, is a typical carbonate-hosted deposit in the Sichuan–Yunnan–Guizhou Pb–Zn metallogenic province with Pb + Zn reserves of about 2.0 million tonnes grading 4.15 wt.% Pb and 7.25 wt.% Zn. Its ore bodies are hosted in Sinian (635–541 Ma) Dengying Formation dolostone and show stratiform, vein and irregular textures. Ores are composed of sphalerite, galena, pyrite, calcite, dolomite, quartz and fluorite with massive, banded, disseminated and veined structures. The C–O–Sm–Nd isotopic compositions of hydrothermal calcites and S–Pb isotopic compositions of sulfides were analyzed to constrain the origin of the Maozu deposit. δ13CPDB and δ18OSMOW values of hydrothermal calcites range from −3.7‰ to −2.0‰ and +13.8‰ to +17.5‰, respectively, and plot near the marine carbonate rocks field in a plot of δ13CPDB vs. δ18OSMOW, with a negative correlation. It suggests that CO2 in the hydrothermal fluids was mainly originated from marine carbonate rocks, with limited influence from sedimentary organic matter. δ34SCDT values of sulfides range from +9.9‰ to +19.2‰, similar to that of Cambrian to Triassic seawater sulfate (+15‰ to +35‰) and evaporate (+15‰ to +30‰) in the Cambrian to Triassic sedimentary strata. It suggests that reduced sulfur was derived from evaporate in sedimentary strata by thermo chemical sulfate reduction. Sulfides have low radiogenic Pb isotope compositions (206Pb/204Pb = 18.129–18.375, 207Pb/204Pb = 15.640–15.686 and 208Pb/204Pb = 38.220–38.577) that plot in the field between upper crust and the orogenic belt evolution curve in the plot of 207Pb/204Pb vs. 206Pb/204Pb, and similar to that of age corrected Proterozoic basement rocks (Dongchuan and Kunyang Groups). This indicates that ore-forming metals were mainly derived from basement rocks. Hydrothermal calcite yields a Sm–Nd isotopic age of 196 ± 13 Ma, possibly reflecting the timing of Pb–Zn mineralization in the SYG province, younger than the Permian Emeishan mantle plume (∼260 Ma). All data combined suggests that hydrothermal fluids circulated through basement rocks where they picked up metals and migrated to surface, mixed with reduced sulfur-bearing fluids and precipitated metals. Ore genesis of the Maozu deposit is different from known magmatic–hydrothermal, Sedimentary Exhalative or Mississippi Valley-types, which maybe represent a unique ore deposit type, named as the SYG-type. 相似文献
9.
《Gondwana Research》2014,25(3-4):1276-1282
Concentrations of total organic matter (TOC), carbon isotopic compositions of carbonate and organic matter (δ13Ccarb, δ13Corg), and sulfur isotopic compositions of carbonate associated sulfate (δ34Ssulfate) across the Guadalupian–Lopingian (G–L) boundary were analyzed from identical samples of Tieqiao section, Laibin, Guangxi province, South China. The δ13Ccarb values show a positive excursion from − 0.45‰ to the peak of 3.80‰ in the Laibin limestone member of the Maokou Formation, followed by a drastic drop to − 2.60‰ in the lowest Heshan formation, then returned to about 1.58‰. Similar to the trends of the δ13Ccarb values, Δ13Ccarb–org values also show a positive excursion followed by a sharp negative shift. The onset of a major negative carbon isotope excursion postdates the end Guadalupian extinction that indicates subsequent severe disturbance of the ocean–atmosphere carbon cycle. The first biostratigraphic δ34Ssulfate values during the G–L transition exhibit a remarkable fluctuation: a dramatic negative shift followed by a rapid positive shift, ranging from 36.88‰ to − 37.41‰. These sulfate isotopic records suggest that the ocean during the G–L transition was strongly stratified, forming an unstable chemocline separating oxic shallow water from anoxic/euxinic deep water. Chemocline excursions, together with subsequent rapid transgression and oceanic anoxia, were likely responsible for the massive diversity decline of the G–L biotic crisis. 相似文献
10.
Carbon (δ13CPDB) and oxygen (δ18OSMOW) isotopic compositions of auriferous quartz-carbonate veins (QCVs) of gold deposits from Sangli, Kabuliyatkatti, Nagavi, Nabapur and Mysore mining areas developed on the Central Lode system of the Gadag Gold Field (GGF) in the Neoarchaean Gadag schist belt of the Dharwar Craton, southern India have been examined for the first time to understand the origin of the mineralising fluids. In majority of the samples (46 out of 49), δ13Cpdb of carbonates of the QCVs fall in the range from − 2.2‰ to − 9.7‰ and the δ18O values range from 12.0‰ to 30.5‰ SMOW. The calculated fluid δ13C∑ C compositions for these deposits range from − 2.1‰ to − 9.6‰ and δ18OH2O from 6.8‰ to 25.9‰, respectively. Carbonate δ13C and fluid δ13C∑ C compositions of the carbonates of the QCVs of the GGF are not only distinct from the carbon isotope range of marine carbonates or meta-sedimentary carbonates of the Chitradurga schist belt, but are consistent with C-isotope values of magmatic (− 5 ± 3‰, Burrows et al., 1986) and/or mantle (− 6 ± 2‰, Ohmoto, 1986) carbonates. As dissolution/decarbonation reactions during metamorphism of pre-existing carbonate/carbonated rocks produce CO2 with δ13C values similar to or more enriched than parent rock, the carbonate or fluid δ13C ratios of the QCVs (which fall in the compositional range of mantle/magmatic derived CO2 or carbonates) obtained in this work cannot be the result of metamorphism. The present study corroborates our previous reports from Ajjanahalli and G.R. Halli gold deposits (Sarangi et al., 2012) occurring in the vicinity of the southern extension of the same crustal scale shear zone on which all the GGF deposits are located.The age of gold mineralisation in this area has been reported to be 2522 ± 6 Ma by Sarma et al., 2011. Chardon et al. (2011) have proposed large-scale remobilization of the older gneissic basement, as well as, emplacement of juvenile granites between 2559 Ma and 2507 Ma, close to the crustal scale shear zone along the eastern margin of the Chitradurga schist belt. Based on these observations and our isotope studies, it is proposed that gold mineralising fluids were derived from mantle/juvenile magmatic melts and were channelled through crustal scale shear zones to give rise to the gold deposits in the GGF. 相似文献
11.
The Dapingzhang volcanogenic Cu–Pb–Zn sulfide deposit is located in the Lancangjiang tectonic zone within the Sanjiang region, Yunnan province of southwestern China. The deposit occurs within a felsic volcanic dome belonging to a mid-Silurian volcanic belt stretching for more than 100 km from Dapingzhang to Sandashan. The mineralized volcanic rocks are predominantly keratophyre and quartz keratophyre with subordinate spilite. The Dapingzhang deposit is characterized by well-developed vertical zonation with stockwork ores in the bottom, disseminated sulfide ores in the middle, and massive sulfide ores in the top, overlain by a thin layer of chemical sedimentary exhalative rocks (chert and barite). The Re–Os age of the pyrites from the deposit is 417 ± 23 Ma, indistinguishable from the age of the associated felsic volcanic rocks. The associated felsic volcanic rocks are characterized by negative Nb–Ta anomalies and positive εNd(t) values (+ 4.4–+6.5), similar to the coeval calc-alkaline volcanic rocks in the region. This observation supports the interpretation that the felsic volcanic rocks associated with the Dapingzhang deposit are the derivatives of arc basaltic magma by extensive fractional crystallization. The δ34S values of the sulfides from the deposit vary from − 1.24 to + 4.32‰, indicating a predominantly magmatic source for the sulfur. The sulfides are also characterized by homogeneous and relatively low radiogenic Pb isotope compositions (206Pb/204Pb = 18.310–18.656, 207Pb/204Pb = 15.489–15.643 and 208Pb/204Pb = 37.811–38.662), similar to the Pb isotopic compositions of the associated volcanic rocks. The Pb isotopic data indicate that mantle-derived Pb is more prevalent than crust-derived Pb in the deposit. The S–Pb isotopic data indicate that the important ore-forming materials were mainly derived from the associated volcanic rocks. The δ13CPDB and δ18OSMOW values of the associated hydrothermal calcite crystals vary from − 2.3‰ to + 0.27‰ and from + 14.6 to + 24.4‰, respectively. These values are between the mantle and marine carbonate values. The narrow range of the δ13CPDB values for the calcite indicates that carbon-bearing species in the hydrothermal fluids were primarily derived from marine carbonates. The δ18O values for the hydrothermal fluids, calculated from the measured values for quartz, are between − 2.1‰ and + 3.5‰. The corresponding δD values for the fluids range from − 59‰ to − 84‰. The O–H isotopic data indicate mixing between magmatic fluids and seawater in the ore-forming hydrothermal system. Similar to a typical volcanogenic massive sulfide (VMS) deposit, the ore-forming fluids contained both magmatic fluids and heated seawater; the ore metals and regents were derived from the underlying magma as well as felsic country rocks. 相似文献
12.
In this study, we investigated Fe and Li isotope fractionation between mineral separates of olivine pheno- and xenocrysts (including one clinopyroxyene phenocryst) and their basaltic hosts. Samples were collected from the Canary Islands (Teneriffa, La Palma) and some German volcanic regions (Vogelsberg, Westerwald and Hegau). All investigated bulk samples fall in a tight range of Li and Fe isotope compositions (δ56Fewr = 0.06–0.17‰ and δ7Lima = 2.5–5.2‰, assuming δ7Li of the olivine-free matrix is virtually identical to that of the bulk sample for mass balance reasons). In contrast, olivine phenocrysts display highly variable, but generally light Fe and mostly light Li isotope compositions compared to their respective olivine-free basaltic matrix, which was considered to represent the melt (with δ56Feol = ? 0.24 to 0.14‰ and δ7Liol = ? 10.5 to + 6.5‰, respectively). Single olivine crystals from one sample display even a larger range of δ56Feol between ? 0.7 and + 0.1‰. One single clinopyroxene phenocryst displays the lightest Li isotope composition (δ7Licpx = ? 17.7‰), but no Fe isotope fractionation relative to melt. The olivine phenocrysts show variable Mg# and Ni (correlated in most cases) that range between 0.89 and 0.74 and between 300 and 3000 μg/g, respectively. These olivines likely grew by fractional crystallization in an evolving magma. One sample from the Vogelsberg volcano contained olivine xenocrysts (Mg# > 0.89 and Ni > 3000 μg/g), in addition to olivine phenocrysts. This sample displays the highest Li- and the second highest Fe-isotope fractionation between olivine and melt (Δ7Liol-melt = ? 13; Δ56Feol-melt = ? 0.29).Our data, i.e. the variable olivine- at constant whole rock and matrix isotope compositions, strongly indicate disequilibrium, i.e. kinetic Fe and Li isotope fractionation between olivine and melt (for Li also between cpx and melt) during fractional crystallization. Δ7Liol-melt is correlated with the Li partitioning between olivine and melt (i.e. with Liol/Limelt), indicating Li isotope fractionation due to preferential (faster) diffusion of 6Li into olivine during fractional crystallization. Olivine with low Δ7Liol-melt, also have low Δ56Feol-melt, indicating that Fe isotope fractionation is also driven by diffusion of isotopically light Fe into olivine, potentially, as Fe–Mg inter-diffusion. The lowest Δ56Feol-melt (? 0.40) was observed in a sample from Westerwald (Germany) with abundant magnetite, indicating relatively oxidizing conditions during magma differentiation. This may have enhanced equilibrium Fe isotope fractionation between olivine and melt or fine dispersed magnetite in the basalt matrix may have shifted its Fe isotope composition towards higher δ56Fe. The decoupling of Li- and Fe isotope fractionation in cpx is likely due to faster diffusion of Li relative to Fe in cpx, implying that the large investigated cpx phenocryst resided in the magma for only a short period of time which was sufficient for Li- but not for Fe diffusion. The absence of any equilibrium Fe isotope fractionation between the investigated cpx phenocryst and its basaltic host may be related to the similar Fe3 +/Fe2 + of cpx and melt. In contrast to cpx, the generally light Fe isotope composition of all investigated olivine separates implies the existence of equilibrium- (in addition to diffusion-driven) isotope fractionation between olivine and melt, on the order of 0.1‰. 相似文献
13.
Xiaolonghe is a poorly studied greisen-type tin deposit that is hosted by biotite granite in the western Yunnan tin belt. The mineralisation-related metaluminous and weak peraluminous granite is characterised by high Si, Al and K and low Mg, Fe and Ca, with an average A/CNK of 1.02. The granite is enriched in LILEs (K and Rb), LREEs and HFSEs (Zr, Hf, Th, U and Ce) and depleted in Ba, Nb, Sr, P, and Ti, with zircon εHf(t) = − 10.8 to − 7.5 (TDM2 = 1.61–1.82 Ga). These characteristics indicate that the magma was generated by the partial melting of a thickened ancient crust. LA-ICP-MS U–Pb dating of igneous zircon and hydrothermal cassiterite yield ages of 71.4 ± 0.4 Ma and 71.6 ± 4.8 Ma, respectively. The igneous biotite and hydrothermal muscovite samples show Ar–Ar plateau ages of 72.3 ± 0.4 Ma and 70.6 ± 0.2 Ma, respectively. The close temporal relationship between the igneous emplacement and hydrothermal activity suggests that the tin mineralisation was closely linked to the igneous emplacement. The δ18O and δD values for the deposit range from + 3.11‰ to − 4.5‰ and from − 127.3‰ to − 94.7‰, respectively. The hydrothermal calcite C and O isotopic data show a wide range of δ13CPDB values from − 5.7‰ to − 4.4‰, and the δ18OSMOW values range from + 1.4‰ to + 11.2‰. The δ34SV-CDT data range from + 4.8‰ to + 8.9‰ for pyrite, and the 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios range from 18.708 to 18.760, from 15.728 to 15.754 and from 39.237 to 39.341, respectively. The stable isotopic (C–H–O–S–Pb) compositions are all similar to those of magmatic and mantle-derived fluids, which indicate that the ore-forming fluids and materials were mainly derived from magmatic sources that were accompanied by meteoric water. The tin mineralisation in the Xiaolonghe district was closely associated with the Late Cretaceous crustal-melting S-type granites that formed during the subduction of the Neo-Tethys oceanic lithosphere. Combined with the tin deposits in the Southeast Asian tin belt, Tengchong block and Central Lhasa, we interpreted that a giant intermittent tin mineralisation belt should be present along the Asian Neo-Tethys margin. 相似文献
14.
Transition metal isotopes are sensitive geochemical tracers of ore genesis. Here we present MC-ICP-MS analytical data of Cu isotope compositions from the Hongshan-Hongniu Cu deposit in Yunnan province. The δ65Cu values (δ65Cu = [(65Cu/63Cu)sample/(65Cu/63Cu)NIST976 − 1] × 1000) of seven whole-rock quartz monzonite porphyries and twenty-two chalcopyrite samples from the skarn ore-bodies display relatively narrow ranges from −0.15‰ to 0.38‰ and from −0.02‰ to 0.77‰, respectively. The overlap of δ65Cu values indicates a genetic relationship between the quartz monzonite porphyry and skarn ore-bodies. We also evaluate the spatial and temporal variations of Cu isotope compositions in the skarn ore-bodies by comparison with some well-documented porphyry deposits in the world. The quartz monzonite porphyry shows compositional zoning with the inner domain enriched in heavy Cu isotope and the skarn related to the porphyry depleted in heavy Cu isotope. The chalcopyrites that formed during the late stage of mineralization tend to be enriched in heavy Cu isotope, and this feature is analogous to porphyry deposits. The δ65Cu values of the quartz monzonite porphyry show typical features of hypogene mineralization, suggesting a potential scope for deep exploration and development in this deposit. 相似文献
15.
Studies of sulfur and lead isotopic compositions in hydrothermal deposits are an important tool to determine the source and processes of both sulfur and lead, and to understand the origin of hydrothermal ore deposits. Here, the sulfur and lead isotopic compositions of sulfide minerals have been studied for different hydrothermal fields in the East Pacific Rise (EPR), Mid-Atlantic Ridge (MAR), Central Indian Ridge (CIR), Southwest Indian Ridge (SWIR), and North Fiji Basin (NFB). The sulfur isotopic compositions of the studied sulfide samples are variable (δ34S 0.0 to 9.6‰, avg. δ34S 4.7‰; n = 60), being close to the associated igneous rocks (~ 0‰ for, e.g., basalt, serpentinized peridotite), which may reflect the S in the sulfide samples is derived mainly from the associated igneous rocks, and a relatively small proportion (< 36%) of seawater sulfur incorporated into these sulfides during mixing between seawater (δ34S 21‰) and hydrothermal fluid. In contrast for a mixed origin for the source of S, the majority of the lead isotopic compositions (206Pb/204Pb 17.541 ± 0.004 to 19.268 ± 0.001, 207Pb/204Pb 15.451 ± 0.001 to 15.684 ± 0.001, 208Pb/204Pb 37.557 ± 0.008 to 38.988 ± 0.002, n = 21) of the sulfides possess a basaltic Pb isotopic composition, suggesting that the lead in the massive sulfide is mainly leached from local basaltic rocks that host the sub-seafloor hydrothermal systems in sediment-free mid-ocean ridges and mature back-arc basins. Furthermore, sulfide minerals in the super-fast and fast spreading mid-ocean ridges (MORs) exhibit less spread in their the δ34S values compared to sulfides from super-slow, and slow spreading MORs, which is most easily explained as a lesser degree of fluid-rock interaction and hydrothermal fluid-seawater mixing during hydrothermal ore-forming process. Additionally, the S and Pb isotope compositions of sulfides are controlled by the fluid processes for forming seafloor massive sulfide deposits. We demonstrate that the variable sulfur and lead isotopic compositions exhibit a relationship with the sulfur and lead sources, fluid–rock interaction, and fluid–seawater mixing. 相似文献
16.
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
17.
Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH4 gas content and its C isotopes (δ13CCH4), and select isotope tracers (δ11B, 87Sr/86Sr, δ2H, δ18O, δ13CDIC) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH4 was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH4/L. The δ13CCH4 of dissolved CH4 ranged from −42.3‰ to −74.7‰, with the most negative values characteristic of a biogenic source also associated with the highest observed CH4 concentrations, with a possible minor contribution of trace amounts of thermogenic CH4. The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ13CCH4 = −35.4‰ to −41.9‰). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca–HCO3 dominated, (3) TDS > 100 mg/L and Na–HCO3 dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr (87Sr/86Sr = 0.7097–0.7166), C (δ13CDIC = −21.3‰ to −4.7‰), and B (δ11B = 3.9–32.9‰) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO3, and higher-mineralized Na–HCO3 composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS ∼10,000–20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH4 and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale. 相似文献
18.
Marc Peters Harald Strauss Sven Petersen Nicolai-Alexeji Kummer Christophe Thomazo 《Chemical Geology》2011,280(1-2):217-231
The Palinuro volcanic complex and the Panarea hydrothermal field, both located in the Tyrrhenian Sea (Italy), are associated with island arc magmatism and characterized by polymetallic sulfide mineralization. Dissolved sulfide concentrations, pH, and Eh measured in porewaters at both sites reveal a variable hydrothermal influence on porewater chemistry.Multiple sulfur isotopic measurements for disseminated sulfides (CRS: chromium reducible sulfur) extracted from sediments at Palinuro yielded a broad range in δ34S range between ?29.8 and + 10.2‰ and Δ33S values between + 0.015 and + 0.134‰. In contrast, sediments at Panarea exhibit a much smaller range in δ34SCRS with less negative values between ?11.3 and ?1.8‰. The sulfur isotope signatures are interpreted to reflect a mixture between hydrothermal and biogenic sulfide, with a more substantial biogenic contribution at Panarea.Multiple sulfur isotope measurements were performed on sulfides and elemental sulfur from drill core material from the Palinuro massive sulfide complex. δ34S and Δ33S values for pyrite between ?32.8 and ?1.1‰ and between ?0.012 to + 0.042‰, respectively, as well as for elemental sulfur with δ34S and Δ33S values between ?26.7 and ?2.1‰ and between + 0.035 and + 0.109‰, respectively, point to a microbial origin for much of the sulfide and elemental sulfur studied. Moreover, data suggest a coupling of bacterial sulfate reduction, sulfide oxidation and sulfur disproportionation. In addition, δ34S values for barite between + 25.0 and + 63.6‰ are also in agreement with high microbial turnover of sulfate at Palinuro.Although a magmatic SO2 contribution towards the formation of the Palinuro massive sulfide complex is very likely, the activity of different sulfur utilizing microorganisms played a fundamental role during its formation. Thus, porewater and multiple sulfur isotope data reveal differences in the hydrothermal activity at Palinuro and Panarea drill sites and underline the importance of microbial communities for the origin of massive sulfide mineralizations in the hydrothermal subsurface. 相似文献
19.
Olivine, clinopyroxene and orthopyroxene in variably metasomatised peridotite xenoliths from three lithospheric mantle sections beneath the East African Rift in Tanzania (Lashaine, Olmani, Labait) show systematic differences in their average Li concentrations (2.4 ppm, 2.0 ppm and 1.5 ppm, respectively) and intermineral isotopic fractionations, with olivine being heaviest (δ7Li = + 2.3 to + 13.9‰, average + 5.0‰), followed by orthopyroxene (? 4.1 to + 6.5‰, average + 0.8‰) and clinopyroxene (? 6.7 to + 4.1‰, average ? 1.6‰). These features are ascribed to the effects of kinetic Li isotope fractionation combined with different Li diffusivities in mantle minerals.Two main mechanisms likely generate diffusion-driven kinetic Li isotope fractionation in mantle xenoliths (1) Li diffusion from grain boundary melt into minerals during recent metasomatism or entrainment in the host magma and (2) subsolidus intermineral Li-redistribution. The latter can produce both isotopically light (Li-addition) and heavy (Li-loss) minerals and may occur in response to changes in pressure and/or temperature.Modelling shows that non-mantle-like δ7Li in clinopyroxene (< + 2‰), combined with apparent equilibrium olivine-clinopyroxene elemental partitioning in most peridotite xenoliths from all three Tanzanian localities probably reflects incipient Li addition during interaction with the host magma. Low δ7Li (< ? 3‰), combined with high Li concentrations (> 3 ppm) in some clinopyroxene may require very recent (minutes) Li ingress from a Li-rich melt (100s of ppm) having mantle-like δ7Li. This might happen during late fragmentation of some mantle xenoliths caused by a volatile- (and Li-) rich component exsolved from the host basalt. In contrast, high Li concentrations (> 2 ppm) and δ7Li (> 4‰) in olivine from many Labait and Olmani samples are attributed to an older, pre-entrainment enrichment event during which isotopic equilibrium was attained and whose signature was not corrupted during xenolith entrainment. Low Li concentrations and mantle-like isotopic composition of olivine from most Lashaine xenoliths indicate limited metasomatic Li addition.Thus, Li concentrations and isotope compositions of mantle peridotites worldwide may reflect two processes, with olivine mainly preserving a signature of depletion in refractory samples (low Li contents and δ7Li) or of older (precursory) melt addition in metasomatised samples (high Li contents and δ7Li), while non mantle-like, low δ7Li in almost all clinopyroxene can be due to Li ingress during transport in the host magma and/or slow cooling, if the samples were erupted in lavas. In Tanzania, the peridotites experienced rift-related heating prior to entrainment and were quenched upon eruption, so Li ingress is the most likely process responsible for the isotopically light clinopyroxene here. 相似文献
20.
《Ore Geology Reviews》2011,41(1):27-40
Diyadin mineralization is the first reported gold deposit located in a collisional tectonic environment in Eastern Anatolia. The mineralization is related to N–S and N10–20°W-trending fault systems and hosted within the Paleozoic metamorphic basement rocks of the Anatolide–Toride microcontinent. Calc-schist, dolomitic marble and Miocene and Quaternary volcanic rocks comprise the exposed units in the mineralized area. Geochemical signatures, alteration types and host rock characteristics of the Diyadin gold deposit resemble those of Carlin-type deposits. Mineralization is constrained by alteration of overlying volcanic rocks to younger than ~ 14 Ma (K–Ar).Carbon and oxygen stable isotope measurements of carbonate rocks were made on six drill holes (n = 81) with an additional four samples of fresh carbonate rocks from surface outcrops. Background carbonate rocks have δ13CV-PDB ~ 1.8‰ and δ18OV-SMOW ~ 27‰. Isotopically-altered host rock samples have decreased δ18O (down to ~+11.4‰) and variable δ13C (from − 3.6 to + 4.8‰). Postore carbonate veins and cave-fill material have distinctly different isotopic signatures, particularly carbon (from δ13C = + 8.4 to + 9.8‰). Whether this post-ore carbonate is simply very late in mineralization associated with the gold system, or is a completely different, younger system utilizing the same pathways, is unclear at present. Within the host rock sample set, there is no correlation between gold and δ13C, and a weak correlation between gold and δ18O, indicative of water–rock interaction and isotopic alteration. Both the isotopic data and structural mapping suggest that the main upflow zone for the deposit is near the northern portion of the drill fence. Additional data at multiple scales are required to clarify the relationship(s) between fluid flow and mineralization. 相似文献