Iron isotope fractionation during biogeochemical cycle: Information from suspended particulate matter (SPM) in Aha Lake and its tributaries,Guizhou, China

Iron isotope compositions of suspended particulate matters (SPM) collected from the Aha Lake, an artificial lake in the karst area of Yun-Gui Plateau, and its tributaries in summer and winter were investigated for our understanding of the behavior of Fe isotopes during iron biogeochemical cycling in lake. δ⁵⁶Fe values of SPM display statistically negative shift relative to IRMM-014. Samples from the lake display a range from ?1.36‰ to ?0.10‰ in summer and from ?0.30‰ to ?0.07‰ in winter, while river samples vary from ?0.88‰ to 0.07‰ in summer and from ?0.35‰ to ?0.03‰ in winter. The average iron isotope composition of aerosol samples is + 0.10‰, which is very similar to that of igneous rocks (0.09‰). The SPM in most rivers and water column showed seasonal variation in δ⁵⁶Fe value: the δ⁵⁶Fe values of SPM in summer were lower than in winter. The seasonal variation in δ⁵⁶Fe value of the riverine SPM should be ascribed to the change in source of particulate Fe and geochemical process in the watershed: More particulate Fe was leached from soil and produced by weathering of pyrite widely distributed in coal-containing strata. It is suggested that both allochthonous inputs and the redox iron cycling control the variations of δ⁵⁶Fe values for SPM in lake.During summer stratification, an Fe cycle named “ferrous wheel” is established near the redox boundary where the upwardly diffusing Fe(II) is oxidized and the reactive Fe oxides formed will continuously sink back into the reduction zone to complete the cycle. The δ⁵⁶Fe values for SPM reach the minima, ?0.88‰ for DB station and ?1.36‰ for LJK station, just near the redox boundary as a result of the Fe cycling, where a rough 45% to 76% of Fe in these particles was produced by the repetitive cycle. Due to random transportation and diffusion, δ⁵⁶Fe values of the particles near the redox zone distributed into approximately a Gaussian shape. The good negative correlation existed between δ⁵⁶Fe values and Fe/Al ratios for DB station, suggesting that they together can be used as good indicators of the redox-driven Fe transformations.     

Oxygen and Hydrogen Isotopes of Waters in the Ordos Basin,China: Implications for Recharge of Groundwater in the North of Cretaceous Groundwater Basin

Hundreds of precipitation samples collected from meteorological stations in the Ordos Basin from January 1988 to December 2005 were used to set up a local meteoric water line and to calculate weighted average isotopic compositions of modern precipitation. Oxygen and hydrogen isotopes, with averages of ?7.8‰ and ?53.0‰ for δ18O and δD, respectively, are depleted in winter and rich in spring, and gradually decrease in summer and fall, illustrating that the seasonal effect is considerable. They also show that the isotopic difference between south portion and north portion of the Ordos Basin are not obvious, and the isotope in the middle portion is normally depleted. The isotope compositions of 32 samples collected from shallow groundwater (less than a depth of 150 m) in desert plateau range from ?10.6‰ to ?6.0‰ with an average of ?8.4‰ for δ18O and from ?85‰ to ?46‰ with an average of ?63‰ for δD. Most of them are identical with modern precipitation. The isotope compositions of 22 middle and deep groundwaters (greater than a depth of 275 m) fall in ranges from ?11.6‰ to ?8.8‰ with an average of ?10.2‰ for δ18O and from ?89‰ to ?63‰ with an average of ?76‰ for δD. The average values are significantly less than those of modern precipitation, illustrating that the middle and deep groundwaters were recharged at comparatively lower air temperatures. Primary analysis of 14C shows that the recharge of the middle and deep groundwaters started at late Pleistocene. The isotopes of 13 lake water samples collected from eight lakes define a local evaporation trend, with a relatively flat slope of 3.77, and show that the lake waters were mainly fed by modern precipitation and shallow groundwater.     

Iron isotope constraints on the metal source and depositional environment of the Neoproterozoic banded iron- and manganese deposits in Urucum,Brazil

The Urucum area of Brazil hosts a series of Cryogenian ironstones intercalated by oxide-dominated manganese layers. The Urucum iron and manganese formations (IF-MnF) are among the largest sedimentary iron and associated manganese deposits of the Neoproterozoic, however, the depositional model and the source of metals for the IF-MnF in this area are highly controversial. In this study, we performed systematic Fe isotope analysis on fresh and geochemically characterized drill core samples of the Urucum iron and manganese formation deposited in the center of the ancient Urucum graben system. The samples have a large variation in Fe isotope composition, with a δ⁵⁶Fe range of −2.04‰ to +0.75‰, and exhibit a general trend of decreasing δ⁵⁶Fe values with increasing manganese contents. The low δ⁵⁶Fe values of the IF and MnF samples reflect Rayleigh fractionation processes of contineous partial oxidation of aqueous Fe(II) prior to deposition at the sampling site. Using a mixing model and previously published Nd isotope data on the same samples, we estimated that benthic (i.e., porewaters released from submarine sediments in the Urucum basin) Fe fluxes provided 7–50% of total Fe in the Urucum IF-MnF, and the rest of Fe source was from low-temperature hydrothermal vents. Based on combined Fe and Nd isotope data of the Urucum IF-MnF, we propose that low-temperature hydrothermal fluids and benthic fluxes of pore waters were mixed and transported by an upwelling current. The fluid subsequently experienced partial oxidation during the transportation process and became enriched in light Fe isotopes. In the Urucum graben basin, the iron- and manganese-rich oxides deposition occurred progressively under increasingly oxidizing conditions, and such process could have operated repeatedly to produce the alternation of iron and manganese formations. The chemical sediments of the Urucum IF-MnF deposits thus reflect the existence of a sharp redox gradient in the marine environment during the late Cryogenian period.     

The effect of early diagenesis on the Fe isotope compositions of porewaters and authigenic minerals in continental margin sediments

Iron isotope compositions in marine pore fluids and sedimentary solid phases were measured at two sites along the California continental margin, where isotope compositions range from δ⁵⁶Fe = −3.0‰ to +0.4‰. At one site near Monterey Canyon off central California, organic matter oxidation likely proceeds through a number of diagenetic pathways that include significant dissimilatory iron reduction (DIR) and bacterial sulfate reduction, whereas at our other site in the Santa Barbara basin DIR appears to be comparatively small, and production of sulfides (FeS and pyrite) was extensive. The largest range in Fe isotope compositions is observed for Fe(II)_aq in porewaters, which generally have the lowest δ⁵⁶Fe values (minimum: −3.0‰) near the sediment surface, and increase with burial depth. δ⁵⁶Fe values for FeS inferred from HCl extractions vary between ∼−0.4‰ and +0.4‰, but pyrite is similar at both stations, where an average δ⁵⁶Fe value of −0.8 ± 0.2‰ was measured. We interpret variations in dissolved Fe isotope compositions to be best explained by open-system behavior that involves extensive recycling of Feflux. This study is the first to examine Fe isotope variations in modern marine sediments, and the results show that Fe isotopes in the various reactive Fe pools undergo isotopic fractionation during early diagenesis. Importantly, processes dominated by sulfide formation produce high-δ⁵⁶Fe values for porewaters, whereas the opposite occurs when Fe(III)-oxides are present and DIR is a major pathway of organic carbon respiration. Because shelf pore fluids may carry a negative δ⁵⁶Fe signature it is possible that the Fe isotope composition of ocean water reflects a significant contribution of shelf-derived iron to the open ocean. Such a signature would be an important means for tracing iron sources to the ocean and water mass circulation.     

Carbon and Oxygen Isotopic Composition of Surface‐Sediment Carbonate in Bosten Lake (Xinjiang,China) and its Controlling Factors

Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition (δ13C) values of the carbonate sediment (?1‰ to ?2‰) have no relation to the oxygen isotope composition of the carbonate (δ18O) values (?7‰ to ?8‰), with both isotopes showing a low variability. The carbonate content is low (<20%). Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ13C values between approximately +0.5‰ and +3‰, and δ18O values between ?1‰ and ?5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg–calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg–calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.     

Changes to depositional palaeoenvironments within the Qikou depression (Bohaiwan Basin,China): carbon and oxygen isotopes in lacustrine carbonates of the Palaeogene Shahejie Formation

This paper reports the carbon and oxygen isotope compositions of lacustrine carbonate sediments from the Palaeogene Shahejie Formation, Qikou depression, Bohaiwan Basin, with the aim of determining the palaeoenvironmental conditions in the region. Results from Es₂, the second member of the Shahejie Formation, showed values of δ¹³C and δ¹⁸O from –1.2‰ to +2.4‰ (average +0.6‰) and from –6.8‰ to –4.7‰ (average –5.7‰), respectively, suggesting a relatively hot climate attending deposition. The slightly closed nature of the lake, which contains brackish water, resulted in higher carbonate δ¹³C and δ¹⁸O values than in a meteoric environment. The values of δ¹³C and δ¹⁸O preserved within the carbonates of the overlying lower Shahejie I (Es₁) varied between +1.3‰ and +4.9‰ (average +3.2‰) and from ?4.4‰ to ?1.8‰ (average ?3.1‰), respectively, indicating that the climate became colder at that time. Subsequently, a marine transgression caused the salinity of the lake water to increase. The values of δ¹³C and δ¹⁸O were controlled by salinity. The high δ¹³C values were also influenced by the rapid burial of the lake organisms and by algal photosynthesis. Values of δ¹³C and δ¹⁸O from carbonates in upper Es₁ ranged from ?8.0‰ to +11.0‰ (average +10.1‰) and from ?5.0‰ to ?1.5‰ (average ?3.4‰), respectively, indicating a slight increase in the temperature over time. In the closed and reducing environment, extremes in δ¹³C values resulted from biochemical fermentation. The positive δ¹³C excursion recorded in the carbonates of the Shahejie Formation in the Qikou depression indicates that the palaeoclimate underwent a significant transformation during the Eocene and the Oligocene.     

Carbon,oxygen and strontium isotope geochemistry of Proterozoic carbonate rocks of the Vindhyan Basin,central India

Carbon, oxygen and strontium isotope compositions of carbonate rocks of the Proterozoic Vindhyan Supergroup, central India suggest that they can be correlated with the isotope evolution curves of marine carbonates during the latter Proterozoic. The carbonate rocks of the Lower Vindhyan Supergroup from eastern Son Valley and central Vindhyan sections show δ¹³C values of ∼0‰ (V-PDB) and those from Rajasthan section are enriched up to +2.8‰. In contrast, the carbonate rocks of the Upper Vindhyan succession record both positive and negative shifts in δ¹³C compositions. In the central Vindhyan section, the carbonates exhibit positive δ¹³C values up to +5.7‰ and those from Rajasthan show negative values down to –5.2‰. The δ¹⁸O values of most of the carbonate rocks from the Vindhyan Supergroup show a narrow range between –10 and –5‰ (V-PDB) and are similar to the ‘best preserved’ ¹⁸O compositions of the Proterozoic carbonate rocks. In the central Vindhyan and eastern Son Valley sections, carbonates from the Lower Vindhyan exhibit best-preserved ⁸⁷Sr/⁸⁶Sr compositions of 0.7059±6, which are lower compared to those from Rajasthan (0.7068±4). The carbonates with positive δ¹³C values from Upper Vindhyan are characterized by lower ⁸⁷Sr/⁸⁶Sr values (0.7068±2) than those with negative δ¹³C values (0.7082±6). A comparison of C and Sr isotope data of carbonate rocks of the Vindhyan Supergroup with isotope evolution curves of the latter Proterozoic along with available geochronological data suggest that the Lower Vindhyan sediments were deposited during the Mesoproterozoic Eon and those from the Upper Vindhyan represent a Neoproterozoic interval of deposition.     

Stable isotopic compositions of Recent freshwater cyanobacterial carbonates from the British Isles: local and regional environmental controls

Recent (<50 years old) freshwater cyanobacterial carbonates from diverse environments (streams, lakes, waterfalls) throughout Britain and Ireland were analysed for their stable carbon and oxygen isotope compositions. The mean δ¹⁸O value of ?5–9‰ PDB for river and stream data represents calcite precipitation in equilibrium with the mean oxygen isotopic composition of precipitation in central Britain (?7–5‰SMOW) assuming a mean water temperature of 9°C. The mean δ¹⁸O of lake data, ?4–5‰ PDB, is statistically different, reflecting the effects of residence time and/or variations in the oxygen isotopic composition of rainfall. Carbon isotopes have wide variations in both fluviatile and lake data sets (+ 3 to ?12‰ PDB). These variations are principally controlled in the fluviatile samples by contribution of isotopically light ‘soil zone’ carbon relative to isotopically heavier carbon from limestone aquifer rock dissolution. Lake samples have the heaviest carbon isotope values, reflecting a trend toward isotopic equilibrium between atmospheric CO₂ and aqueous HCO^?₃. We infer that isotopic compositions of ancient cyanobacterial carbonates should also record environmental information, although the effects of stabilization and diagenesis on primary δ¹⁸O values will need careful consideration. Primary carbon isotope compositions should be well preserved, although in marine samples values will be buffered by the isotopic composition of aqueous marine bicarbonate.     

Iron isotope compositions of carbonatites record melt generation, crystallization, and late-stage volatile-transport processes

Carbonatites define the largest range in Fe isotope compositions yet measured for igneous rocks, recording significant isotopic fractionations between carbonate, oxide, and silicate minerals during generation in the mantle and subsequent differentiation. In contrast to the relatively restricted range in δ⁵⁶Fe values for mantle-derived basaltic magmas (δ⁵⁶Fe?=?0.0?±?0.1‰), calcite from carbonatites have δ⁵⁶Fe values between ?1.0 and +0.8‰, similar to the range defined by whole-rock samples of carbonatites. Based on expected carbonate-silicate fractionation factors at igneous or mantle temperatures, carbonatite magmas that have modestly negative δ⁵⁶Fe values of ~ ?0.3‰ or lower can be explained by equilibrium with a silicate mantle. More negative δ⁵⁶Fe values were probably produced by differentiation processes, including crystal fractionation and liquid immiscibility. Positive δ⁵⁶Fe values for carbonatites are, however, unexpected, and such values seem to likely reflect interaction between low-Fe carbonates and Fe³⁺-rich fluids at igneous or near-igneous temperatures; the expected δ⁵⁶Fe values for Fe²⁺-bearing fluids are too low to produced the observed positive δ⁵⁶Fe values of some carbonatites, indicating that Fe isotopes may be a valuable tracer of redox conditions in carbonatite complexes. Further evidence for fluid-rock or fluid-magma interactions comes from the common occurrence of Fe isotope disequilibrium among carbonate, oxide, silicate, and sulfide minerals in the majority of the carbonatites studied. The common occurrence of Fe isotope disequilibrium among minerals in carbonatites may also indicate mixing of phenocyrsts from distinct magmas. Expulsion of Fe³⁺-rich brines into metasomatic aureols that surround carbonatite complexes are expected to produce high-δ⁵⁶Fe fenites, but this has yet to be tested.     

Iron isotope fractionation in subduction-related high-pressure metabasites (Ile de Groix,France)

Characterisation of mass transfer during subduction is fundamental to understand the origin of compositional heterogeneities in the upper mantle. Fe isotopes were measured in high-pressure/low-temperature metabasites (blueschists, eclogites and retrograde greenschists) from the Ile de Groix (France), a Variscan high-pressure terrane, to determine if the subducted oceanic crust contributes to mantle Fe isotope heterogeneities. The metabasites have δ⁵⁶Fe values of +0.16 to +0.33‰, which are heavier than typical values of MORB and OIB, indicating that their basaltic protolith derives from a heavy-Fe mantle source. The δ⁵⁶Fe correlates well with Y/Nb and (La/Sm)_PM ratios, which commonly fractionate during magmatic processes, highlighting variations in the magmatic protolith composition. In addition, the shift of δ⁵⁶Fe by +0.06 to 0.10‰ compared to basalts may reflect hydrothermal alteration prior to subduction. The δ⁵⁶Fe decrease from blueschists (+0.19 ± 0.03 to +0.33 ± 0.01‰) to eclogites (+0.16 ± 0.02 to +0.18 ± 0.03‰) reflects small variations in the protolith composition, rather than Fe fractionation during metamorphism: newly-formed Fe-rich minerals allowed preserving bulk rock Fe compositions during metamorphic reactions and hampered any Fe isotope fractionation. Greenschists have δ⁵⁶Fe values (+0.17 ± 0.01 to +0.27 ± 0.02‰) similar to high-pressure rocks. Hence, metasomatism related to fluids derived from the subducted hydrothermally altered metabasites might only have a limited effect on mantle Fe isotope composition under subsolidus conditions, owing to the large stability of Fe-rich minerals and low mobility of Fe. Subsequent melting of the heavy-Fe metabasites at deeper levels is expected to generate mantle Fe isotope heterogeneities.     

The oxygen isotopic composition of phosphate as an effective tracer for phosphate sources in Hongfeng Lake

In order to characterize the oxygen isotopic composition of internal phosphate and explore the possibility of using these data to identify phosphate sources, we measured oxygen isotopic compositions of phosphate (δ¹⁸O_p) in sediment pore water in Hongfeng Lake, a typical deep-water lake in a mountainous area. These data, in combination with δ¹⁸O_p in surface water samples and water column samples, were successfully used to identify phosphate sources. The δ¹⁸O_p value of sediment pore water ranged from 15.2‰ to 15.8‰, with an average value of 15.5‰—the δ¹⁸O_p value of internal phosphate. The δ¹⁸O_p values decreased gradually through the water column from 19.4‰ in surface water to 16.4‰ in deeper water, implying that internal phosphate had more negative δ¹⁸O_p values than external phosphate. This finding was substantiated by horizontal variations in δ¹⁸O_P values, which decreased with increasing distance from inflowing rivers. All collected evidence suggests that external and internal phosphate have distinctly different isotopic signatures and that these signatures have not been considerably altered by biological mediation in Hongfeng Lake. Therefore, δ¹⁸O_P can be used to distinguish phosphate sources. A two-endmember mixing model showed that internal phosphate had an average contribution of 40%, highlighting the influence of internal phosphorus loading on aqueous phosphate and eutrophication. This study illustrates the need to reduce the internal phosphorus load from sediment and provides guidance for nutrient management and in-lake restoration treatment in Hongfeng Lake. The data presented here are limited, but serve to highlight the great potential of δ¹⁸O_p as an effective tracer for identifying phosphate sources. Systematic investigations of the oxygen isotopic compositions of external phosphate, internal phosphate, and phosphate through the water column, in combination with in-lake P biogeochemical cycle study, would be desirable in further research.     

Geochemical characteristics of methane from sediments of the underwater high Posolskaya Bank (Lake Baikal)

The component and carbon isotope compositions were studied in the hydrocabon gases from sediments of the underwater high Posolskaya Bank (Lake Baikal). It was established that sediments of this Baikal area contain methane of microbial (C₁/C₂ >16000; δ¹³C 70 ± 3‰) and thermocatalytic (C₁/C₂ <100; δ¹³C–46 ± 3‰) origin. Some samples represent a gas mixture of thermocatalytic and microbial origin. This gas is characterized by δ¹³C of methane varying from–60 to–70‰ and contains a significant amount of ethane. The main homolog of methane in the thermocatalytic and mixed gas is ethane. Owing to biodegradation, propane and butanes are present in trace amounts.     

Sulphur isotopes in carbonatites and associated silicate rocks from the Superior Province, Canada

Thirty-five S isotope analyses obtained from six carbonatite complexes from the Superior Province, Canadian Shield, ranging in age from 1,897 Ma to 1,093 Ma, have δ³⁴S_CDT values of between ?4.5‰ and +3.4‰. Pyrrhotite, chalcopyrite and pyrite mineral separates were used. Each complex possesses its own distinct range and mean S isotope composition. The range for Schryburt Lake is: ?4.5‰ to ?3.4‰ ( mean?=??3.9‰), for Big Beaver House: ?3.6‰ to ?1.5‰ (mean?=??2.2‰), for Cargill: ?1.5‰–+0.5‰ (mean?=??0.7‰), for Spanish River: ?0.1‰–+0.1‰ (mean?=?0.0‰), and for Firesand River: +1.3‰–+3.4‰ (mean?=?+1.7‰). A single sample from Carb Lake yielded a δ³⁴S_CDT value of +2.8‰. Differences in isotope compositions can be related to isotope effects brought about during melt generation and emplacment, such as variations in fo₂ and temperature. The different S and C isotope data for most complexes, however, suggest that the parental melts could have been generated from a heterogeneous mantle source, although process-driven changes cannot be completely ruled out.     

Iron isotopic systematics of UHP eclogites respond to oxidizing fluid during exhumation

The iron stable isotope compositions (δ⁵⁶Fe) and iron valence states of ultrahigh‐pressure eclogites from Bixiling in the Dabie orogen belt, China, were measured to trace the changes of geochemical conditions during vertical transportation of earth materials, for example, oxygen fugacity. The bulk Fe³⁺/ΣFe ratios of retrograde eclogites, determined by Mössbauer spectroscopy, are consistently higher than those of fresh eclogites, suggesting oxidation during retrograde metamorphism and fluid infiltration. The studied eclogites (five samples) display limited mid‐ocean ridge basalts (MORB)‐like (~0.10‰) δ⁵⁶Fe values, which are indistinguishable from their protoliths, that is, gabbro cumulates formed through differentiation of mantle‐derived basaltic magma. This suggests that Fe isotope fractionation during continental subduction is limited. Garnet separates display limited δ⁵⁶Fe variation ranging from ?0.08 ± 0.07 ‰ to 0.02 ± 0.07‰, whereas coexisting omphacite displays a large variation of δ⁵⁶Fe values from 0.15 ± 0.07‰ to 0.47 ± 0.07‰. Omphacite also has highly variable Fe³⁺/ΣFe ratios from 0.367 ± 0.025 to 0.598 ± 0.024, indicating modification after peak metamorphism. Omphacite from retrograde eclogites has elevated Fe³⁺/ΣFe ratios (0.54–0.60) compared to that from fresh eclogites (~0.37), whereas garnet displays a narrow range of ferric iron content with Fe³⁺/ΣFe ratios from 0.039 ± 0.013 to 0.065 ± 0.022. The homogenous δ⁵⁶Fe values and Fe³⁺/ΣFe ratios of garnet suggest that it survived the retrograde metamorphism and preserved its Fe‐isotopic features and ferric contents of peak metamorphism. Because of similar diffusion rates of Fe and Mg in garnet and omphacite, and constant Δ²⁶Mg_{omphacite‐garnet} values (1.14 ± 0.04‰), equilibrium iron isotope fractionation between garnet and omphacite was probably achieved during peak metamorphism. Elevated Fe³⁺/ΣFe ratios of omphacite from retrograde eclogites and variant Δ⁵⁶Fe_{omphacite‐garnet} values of the studied eclogites (0.13 ± 0.10‰ to 0.48 ± 0.10‰) indicate that oxidized geofluid infiltration resulted in the elevation of δ⁵⁶Fe values of omphacite during retrograde metamorphism.     

The impact of sulfate reduction on the distribution of methylmercury in reservoirs in the city of Guiyang

In this paper, the relationship between sulfate reduction potential and mercury methylation potential was studied in the Aha, Baihua and Hongfeng reservoirs from Guiyang City. The methylmercury (MeHg) concentrations of lake water in the Aha Reservoir were greatly elevated as compared to those of the Hongfeng and Baihua reservoirs, which was correlated with its distinctly high SRB abundance, SO42-, and S2- concentrations. Among the three reservoirs, however, the highest MeHg was observed in in the top several centimenters of pore water profile in the Hongfeng Reservoir where the lowest S2- in pore water occurred. The distributions of MeHg in lake water and pore water showed the highest methylation potential occurred at water-sediment surface for the Aha Reservoir and the in the top several centimenters of sediments for the Hongfeng Reservoir. It is guessed that the highest mercury methylation only occurs at the sites with certain sulfide concentrations.     

Sources of Matter and Ore-Producing Fluid of the Tamunyer Gold–Sulfide Deposit (Northern Urals): Isotope Results

The Tamunyer deposit is a typical example of gold–sulfide mineralization located in the lower lithologic–stratigraphic unit (S₂–D₁) of the Auerbach volcanic–plutonic belt. The latter comprises island–arc andesitic volcano–sediments, volcanics, and comagmatic intrusive formations. Carbonates have demonstrated intermediate values of δ¹³C between marine limestone and mantle. The quartz δ¹⁸O is in the range of 15.3–17.2‰. The δ³⁴S of sulfides from the beresitized volcano-sedimentary rocks and ores varies widely from –7.5 to 12‰. The calculated isotope compositions of H₂O, CO₂, and H₂S of the ore-bearing fluid imply two major sources of matter contributing to ore genesis: local rocks and foreign fluid. The ore-bearing fluid was formed by interaction and isotope equilibration between a deep magmatic fluid and marine carbonates (W/R ~ 1), with the contribution of sulfur from the volcano-sedimentary rocks.     

Sulfur Isotope Variations of Metallic Ore Deposits in the Gyeongsang Basin,South Korea

Many metallic ore deposits of the Late Cretaceous to Early Tertiary periods are distributed in the Gyeongsang Basin. Previous and newly analyzed sulfur isotope data of 309 sulfide samples from 56 ore deposits were reviewed to discuss the genetic characteristics in relation to granitoid rocks. The metallogenic provinces of the Gyeongsang Basin are divided into the Au–Ag(–Cu–Pb–Zn) province in the western basin where the sedimentary rocks of the Shindong and Hayang groups are distributed, Pb–Zn(–Au–Ag–Cu), Cu–Pb–Zn(–Au–Ag), and Fe–W(–Mo) province in the central basin where the volcanic rocks of the Yucheon Group are dominant, and Cu(–Mo–W–Fe) province in the southeastern basin where both sedimentary rocks of the Hayang Group and Tertiary volcanic rocks are present. Average sulfur isotope compositions of the ore deposits show high tendencies ranging from 2.2 to 11.7‰ (average 5.4‰) in the Pb–Zn(–Au–Ag–Cu) province, ?0.7 to 11.5‰ (average 4.6‰) in the Cu–Pb–Zn(–Au–Ag) province, and 3.7 to 11.4‰ (average 7.5‰) in the Fe–W(–Mo) province in relation to magnetite‐series granitoids, whereas they are low in the Au–Ag(–Cu–Pb–Zn) province in relation to ilmenite‐series granitoids, ranging from ?2.9 to 5.7‰ (average 1.7‰). In the Cu(–Mo–W–Fe) province δ³⁴S values are intermediate ranging from 0.3 to 7.7‰ (average 3.6‰) and locally high δ³⁴S values are likely attributable to sulfur derived from the Tertiary volcanic rocks during hydrothermal alteration through faults commonly developed in this region. Magma originated by the partial melting of the ³⁴S‐enriched oceanic plate intruded into the volcanic rocks and formed magnetite‐series granitoids in the central basin, which contributed to high δ³⁴S values of the metallic deposits. Conversely, ilmenite‐series granitoids were formed by assimilation of sedimentary rocks rich in organic sulfur that influenced the low δ³⁴S values of the deposits in the western and southeastern provinces.     

Geological and C–O–S–Pb–Sr isotopic constraints on the origin of the Qingshan carbonate-hosted Pb–Zn deposit,Southwest China

Located in the western Yangtze Block, the Qingshan Pb–Zn deposit, part of the Sichuan–Yunnan–Guizhou Pb–Zn metallogenic province, contains 0.3 million tonnes of 9.86 wt.% Pb and 22.27 wt.% Zn. Ore bodies are hosted in Carboniferous and Permian carbonate rocks, structurally controlled by the Weining–Shuicheng anticline and its intraformational faults. Ores composed of sphalerite, galena, pyrite, dolomite, and calcite occur as massive, brecciated, veinlets, and disseminations in dolomitic limestones.

The C–O isotope compositions of hydrothermal calcite and S–Pb–Sr isotope compositions of Qingshan sulphide minerals were analysed in order to trace the sources of reduced sulphur and metals for the Pb–Zn deposit. δ¹³C_PDB and δ¹⁸O_SMOW values of calcite range from –5.0‰ to –3.4‰ and +18.9‰ to +19.6‰, respectively, and fall in the field between mantle and marine carbonate rocks. They display a negative correlation, suggesting that CO₂ in the hydrothermal fluid had a mixed origin of mantle, marine carbonate rocks, and sedimentary organic matter. δ³⁴S values of sulphide minerals range from +10.7‰ to +19.6‰, similar to Devonian-to-Permian seawater sulphate (+20‰ to +35‰) and evaporite rocks (+23‰ to +28‰) in Carboniferous-to-Permian strata, suggesting that the reduced sulphur in hydrothermal fluids was derived from host-strata evaporites. Ores and sulphide minerals have homogeneous and low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.561 to 18.768, ²⁰⁷Pb/²⁰⁴Pb = 15.701 to 15.920, and ²⁰⁸Pb/²⁰⁴Pb = 38.831 to 39.641) that plot in the upper crust Pb evolution curve, and are similar to those of Devonian-to-Permian carbonate rocks. Pb isotope compositions suggest derivation of Pb metal from the host rocks. ⁸⁷Sr/⁸⁶Sr ratios of sphalerite range from 0.7107 to 0.7136 and (⁸⁷Sr/⁸⁶Sr)_200Ma ratios range from 0.7099 to 0.7126, higher than Sinian-to-Permian sedimentary rocks and Permian Emeishan flood basalts, but lower than Proterozoic basement rocks. This indicates that the ore strontium has a mixture source of the older basement rocks and the younger cover sequence. C–O–S–Pb–Sr isotope compositions of the Qingshan Pb–Zn deposit indicate a mixed origin of the ore-forming fluids and metals.     

Iron Isotope Variations in Coastal Seawater Determined by Multicollector ICP-MS

In this paper, we applied a reliable technique for measuring Fe isotope variations in coastal seawater at nanomolar levels. Iron was directly pre-concentrated from acidified seawater samples onto a nitrilotriacetic acid chelating resin and further purified using anion-exchange resin. Sample recovery, determined using a standard addition method, was essentially quantitative. Iron was then determined using a high-resolution multicollector ICP-MS (Neptune) coupled to an ApexQ desolvation introduction system. The external precision for δ⁵⁶Fe values was 0.11‰ (2s) when using total a Fe quantity between 25 and 100 ng. We initially applied this technique to measure the Fe isotope composition of dissolved Fe from several coastal environments in the north-eastern United States and we observed a range of δ⁵⁶Fe values between -0.9‰ and 0.1‰ relative to the IRMM-14 reference material. Iron isotope compositions of several reference water materials for inter-laboratory comparisons were also reported. Our results suggest that iron in coastal seawater, derived from benthic diagenesis and/or groundwater has negative Fe isotopic signatures that are distinct from other iron sources such as atmospheric deposition and rivers.     

Two pulses of mineralization and genesis of the Zhaxikang Sb–Pb–Zn–Ag deposit in southern Tibet: Constraints from Fe–Zn isotopes

Zhaxikang is one large Sb–Pb–Zn–Ag deposit located in the North Himalaya of southern Tibet. To date, the genesis of this deposit still remains controversial. Here, we present new pyrite Fe and sphalerite Zn isotopic data for the first three stages of mineralization, Fe–Zn isotopic data for Mn–Fe carbonate that formed during the first two stages of mineralization, and Zn isotopic data for the slate wall rocks of the Jurassic Ridang Formation to discuss the genesis of the Zhaxikang deposit. The overall δ⁵⁶Fe and δ⁶⁶Zn values range from −0.80‰ to 0.43‰ and from −0.03‰ to 0.38‰, respectively. The δ⁵⁶Fe values of Mn–Fe carbonates are lighter than those of associated pyrite in six mineral pairs, indicating that the iron carbonates are preferentially enriched in light Fe isotopes relative to pyrite. The sphalerite has lighter δ⁶⁶Zn values than associated Mn–Fe carbonates in three mineral pairs.The δ⁵⁶Fe values of pyrite that formed during the first three stages of mineralization gradually increase from stage 1 (−0.33‰ to −0.09‰) through stage 2 (−0.30‰ to 0.19‰) to stage 3 (0.16‰–0.43‰). In comparison, the sphalerite that formed during these stages has δ⁶⁶Zn values that gradually decrease from stage 1 (0.16‰–0.35‰) through stage 2 (0.09‰–0.23‰) to stage 3 (−0.03‰ to 0.22‰). These data, in conjunction with the observations of hand specimens and thin sections, suggest that the deposit was overprinted by a second pulse of mineralization. This overprint would account for these Fe–Zn isotopic variations as well as the kinetic Rayleigh fractionation that occurred during mineralization. The temporally increasing δ⁵⁶Fe and decreasing δ⁶⁶Zn values recorded in the deposit are also coincident with an increase in alteration, again supporting the existence of two pulses of mineralization. The δ⁵⁶Fe values of the first pulse of ore-forming fluid were calculated using theoretical equations, yielding values of −0.54‰ to −0.34‰ that overlap with those of submarine hydrothermal solutions (−1‰ to 0‰). However, the δ⁵⁶Fe values of the stage 3 pyrite are heavier than those of typical submarine hydrothermal solutions, which suggests that the second pulse of mineralization was probably derived from a magmatic hydrothermal fluid. In addition, the second pulse of ore-forming fluid has brought some Fe and taken away parts of Zn, which results the lighter δ⁶⁶Zn values of sphalerite and heavier δ⁵⁶Fe values of pyrite from the second pulse of mineralization. Overall, the Zhaxikang deposit records two pulses of mineralization, and the overprint by the second pulse of mineralization causes the lighter δ⁶⁶Zn values and heavier δ⁵⁶Fe values of modified samples.