δ34S Values Of Sulfate Research Articles

Inorganic sulfur cycles in sediments of the Pearl River Estuary: Processes, mechanisms, and isotopic indicators

The burial of inorganic sulfur is one of the important components in the global sulfur cycle. In this study, the cycling of inorganic sulfide species and the underlying control mechanisms were examined in sediments found in distinct sub-regions of the Pearl River Estuary (PRE). Specifically, the content and isotopic composition of SO42−, acid-volatile sulfides (AVS), and pyrite were determined, along with sedimentary sulfate reduction rates (SRR). The results show that the formation of iron sulfides (such as AVS and pyrite) was mainly controlled by the content of available reactive iron in the sediments of the PRE, and therefore formed mainly in the shallow sediments, with little variation in the deeper parts of the sediments. The δ34S values of AVS and SO42− increased synchronously with depth in the middle and lower part of the sediment, indicating a closed diagenetic environment. In contrast, the δ34S value of pyrite only increased slowly with depth in the case of a small portion of AVS converted to pyrite, which was controlled by the burial time. There are obvious differences in the formation and burial of pyrite in sediments of different sub-regions of the PRE. The surface layer of stations QA and HQ in the upper estuary and brackish coast was an open environment due to sedimentary reworking, and the contents of AVS and pyrite in the sediment was extremely low due to re-oxidation, while the oxidation of 32S-rich H2S also resulted in lower δ34S values of sulfate in the sediment pore water than in the overlying seawater. Station GS in the estuarine mouth had a much higher percentage of AVS converted to pyrite in the sediments than that at stations QA and HQ due to the relatively long burial time. In addition, near the sulfate methane transition zone (SMT), only the estuarine mouth (station GS) produced iron sulfides (AVS) synchronously with the anaerobic oxidation of methane (AOM), and then converted to pyrite gradually; in contrast, the effect of AOM on the formation of iron sulfides in the sediments of the upper estuary and the brackish coast was almost negligible. The results show that the contribution of AOM processes to the final burial of inorganic sulfur is generally small in PRE.

Multiple sulfur isotope systematics of pyrite for tracing sulfate-driven anaerobic oxidation of methane

Sulfate-driven anaerobic oxidation of methane (SD-AOM) is ubiquitous in marine sedimentary environments, governing the global methane budget and the redox evolution of Earth's surface. Tracing SD-AOM and organoclastic sulfate reduction (OSR) from the pyrite archive is key to the reconstruction of SD-AOM activity and paleoenvironmental interpretation. However, discriminating the origins of pyrite – basically SD-AOM and OSR – is commonly challenging due to frequent overlap of δ34Spy values. Multiple sulfur isotopes of pyrite are expected to be an effective tool to distinguish between OSR and SD-AOM, yet variable uncertainties and unknowns remain. Here we investigated the δ34S and Δ33S values of pore-water sulfate and authigenic pyrite from a piston core taken on the continental slope of the South China Sea. A positive Δ33S - δ34S correlation of pore-water sulfate is observed in the upper OSR-dominated zone, resulting in Δ33S and δ34S values of sulfate diffusing into the sulfate-methane transition zone (SMTZ) >0.1‰ and >30‰ larger than the corresponding values of seawater sulfate. A negative Δ33S - δ34S trajectory of pore-water sulfate and pyrite is observed for the SMTZ, agreeing with low sulfur isotope fractionation characteristic for SD-AOM and a diagnostic large Δ33S - δ34S field of SD-AOM-derived pyrite. These findings elucidate that the multiple sulfur isotope systematics of pyrite in methane-bearing sediment depends on (1) mass transport effects of dissolved sulfate and sulfide, (2) the relative contribution of OSR and SD-AOM to the pore-water sulfide and pyrite pools, and (3) the sulfur isotope fractionation during microbial sulfate reduction. Our study highlights the importance of mass transport dynamics on the isotopic composition of pyrite, a factor that needs to be considered in any attempt to reconstruct the origin of early diagenetic pyrite and the paleoenvironmental setting with multiple sulfur isotopes.

Sulfur and oxygen isotope constraints on sulfate sources and neutral rock drainage-related processes at a South African colliery

Understanding the fundamental controls that govern the generation of mine drainage is essential for waste management strategies. Combining the isotopic composition of water (H and O) and dissolved sulfate (S and O) with hydrogeochemical measurements of surface and groundwater, microbial analysis, composition of sediments and precipitates, and geochemical modeling results in this study we discussed the processes that control mine water chemistry and identified the potential source(s) and possible mechanisms governing sulfate formation and transformation around a South African colliery. Compared to various South African water standards, water samples collected from the surroundings of a coal waste disposal facility had elevated Fe2+ (0.9 to 56.9 mg L−1), Ca (33.0 to 527.0 mg L−1), Mg (6.2 to 457.0 mg L−1), Mn (0.1 to 8.6 mg L−1) and SO4 (19.7 to 3440.8 mg L−1) and circumneutral pH. The pH conditions are mainly controlled by the release of H+ from pyrite oxidation and the subsequent dissolution of carbonates and aluminosilicate minerals. The phases predicted to precipitate by equilibrium calculation were green rusts, ferrihydrite, gypsum, ±epsomite. Low concentrations of deleterious metals in solution are due to their low abundance in the local host rocks, and their attenuation through adsorption onto secondary Fe precipitates and co-precipitation at the elevated pH values. The δ34S values of sulfate are enriched (−6.5 ‰ to +5.6 ‰) compared to that of pyrite sampled from the mine (mean −22.5 ‰) and overlap with that of the organic sulfur of coal from the region (−2.5 to +4.9 ‰). The presence of both sulfur reducing and oxidizing bacteria were detected in the collected sediment samples. Combined, the data are consistent with the dissolved sulfate in the sampled waters from the colliery being derived primarily from pyrite probably with the subordinate contribution of organic sulfur, followed by its partial removal through precipitation and microbially-induced reduction.

Mineral dust and fossil fuel combustion dominate sources of aerosol sulfate in urban Peru identified by sulfur stable isotopes and water-soluble ions

High sulfur emissions in the Central Andes have in the past been attributed to active volcanoes and numerous copper smelting facilities in the region. This study evaluates the contribution of these sources on Arequipa, Peru through an evaluation of aerosol sulfate δ34S values and water-soluble ions (WSI). The anthropogenic and natural sources of particulate pollution were determined by aerosol filter sampling from four different locations (urban, suburban, industrial, and rural) providing a view of the spatial variability of aerosols within the city. Sulfate (avg. 2.97 μm/m3) is the most abundant ion species in the aerosols sampled contributing on average 20% of the molar mass. Ion composition profiles between sampling sites are very similar indicating common sources and high contributions of mobilized local surface salt to the aerosols in this desert region. The regional atmospheric chemistry model (RACM) 0-D run for the area confirms that emissions from fuel combustion sources alone cannot account for the high concentrations of sulfate observed. A combination of the RACM results, WSI data, and a Bayesian δ34S isotope mixing model determined that the majority of aerosol sulfates in the area are from mineral dust adding to fossil fuel combustion sources. Mineral dust entrainment in the region is likely elevated by the close proximity of open-pit mining and unpaved roads near the city. Marine organic aerosols and smelting located along the Pacific contribute little to Arequipa's aerosol sulfate concentration. While the influence of volcanic sulfate (9% on average) is low, overall natural sulfate (dust, volcanic, and DMS) accounts for 43% of the aerosol sulfate. Therefore, even though the local environment creates high sulfate background levels, a reduction of sulfate aerosol pollution would be possible if fossil fuel emissions were reduced.

Variability in Sulfur Isotope Records of Phanerozoic Seawater Sulfate

AbstractThe δ34S of seawater sulfate reflects processes operating at the nexus of sulfur, carbon, and oxygen cycles. However, knowledge of past seawater sulfate δ34S values must be derived from proxy materials that are impacted differently by depositional and postdepositional processes. We produced new time series estimates for the δ34S value of seawater sulfate by combining 6,710 published data from three sedimentary archives—marine barite, evaporites, and carbonate‐associated sulfate—with updated age constraints on the deposits. Robust features in multiple records capture temporal trends in the δ34S value of seawater and its interplay with other Phanerozoic geochemical and stratigraphic trends. However, high‐frequency discordances indicate that each record is differentially prone to depositional biases and diagenetic overprints. The amount of noise, quantified from the variograms of each record, increases with age for all δ34S proxies, indicating that postdepositional processes obscure detailed knowledge of seawater sulfate's δ34S value deeper in time.

The abatement of acid rain in Guizhou province, southwestern China: Implication from sulfur and oxygen isotopes

The high frequency of acid rain in southern China has captured public and official concern since 1980s. Subsequently, gas emission reduction measures have been implemented to improve the air quality. Variations in SO2 emission intensities can influence the sulfur and oxygen isotopic compositions of sulfate in rainwater, since atmospheric sulfate is mainly formed via the oxidation of sulfur gases from natural and anthropogenic sources. To evaluate the impacts of emission reduction measures on atmospheric sulfate, the seasonal and long-term trends in stable isotopic compositions of sulfate in rainwater in Guizhou province, southwestern China have been investigated based on rainwater samples collected from June 2016 to June 2018 and literature investigation (2000–2010).The results reveal that coal combustion remains a major contributor to sulfate in rainwater, although its SO2 emission has significantly decreased over the past two decades. The δ34Ssulfate and δ18Osulfate values in rainwater are negatively correlated and have significant seasonal changes. The seasonality in δ34Ssulfate has been interpreted as due to the changes in contributions of dimethyl sulfide and coal combustion, while the seasonal pattern of δ18Osulfate is consistent with that of δ18Owater values, indicating sulfate in rainwater is mainly formed by heterogeneous oxidation of SO2. Combined with the data from previous studies (Xiao and Liu, 2002; Liu, 2007; Xiao et al., 2009; Xiao et al., 2014), we found that the volume weighted mean δ34S values of sulfate in rainwater in Guizhou province show a marked increase between 2001 and 2018, indicating that the 34S-depleted SO2 emission from coal combustion has declined during this period. Furthermore, the synchronous changes in δ34S values, sulfate concentration and pH values of rainwater suggest that the frequency of acid rain in Guizhou province has dropped over the past two decades, which is likely to result from the emission reduction measures taken in Guizhou province.

The impact of diffusive transport of methane on pore-water and sediment geochemistry constrained by authigenic enrichments of carbon, sulfur, and trace elements: A case study from the Shenhu area of the South China Sea

Sulfate-driven anaerobic oxidation of methane (SD-AOM) controls methane release from marine sediments to the ocean. A variety of authigenic precipitates within sediments has been widely used to identify past occurrences of SD-AOM. However, the lack of a systematic evaluation of the formation conditions of these precipitates sometimes impedes the recognition of SD-AOM in past environments characterized by diffusive transport of methane. Carbon, sulfur, and trace element geochemistry of pore-water and sediments was investigated at a site affected by upward methane diffusion in the Shenhu area of the South China Sea. Here, the sulfate-methane transition zone (SMTZ) is located ~7.6 m below the seafloor based on sulfate and methane concentrations. The slope of δ34S vs. δ18O values of sulfate is consistent with diffusive transport of methane. Concentration and isotope profiles of pore-water species point to diffusive rather than advective transport of solutes. Enhanced sulfate reduction inferred from δ34S values of sulfate agrees with the local occurrence of relatively abundant, 34S-enriched iron sulfide minerals. The time required to produce the observed authigenic iron sulfides around the SMTZ is estimated to be ~1.1 ka based on the amount of iron sulfide minerals and the present diffusive flux of sulfate. No enrichment of authigenic carbonate, barium (Ba), and molybdenum (Mo) was detected in the studied sediments. This observation is consistent with the calculation that the current fluxes of pore-water calcium, magnesium, Ba, and Mo are too low to allow for authigenic enrichments. The low fluxes are largely controlled by diffusion, which facilitates the formation of 34S-enriched iron sulfide minerals. The observed enrichment patterns – unlike those of sediments affected by advective seepage – are expected to be prevalent in modern and ancient continental-margin sediments, and may contribute to the identification of past methane-rich zones and overlying SD-AOM zones as sinks for methane in the geological record.

Hydrogeology of the deepest underwater cave in the world: Hranice Abyss, Czechia

Little is known about water mixing in deep underwater cave shafts of hypogene karst. The Hranice Abyss (HA) in Czechia is currently the deepest underwater cave in the world. It shares a thermal and CO2-rich water source with an adjacent spa. Based on chemical and isotope composition, water in the HA is a mixture of shallow and thermal groundwaters. The shallow local groundwater is distinctly different from the adjacent Becva River water in its elemental chemistry and sulfate δ34S values. The thermal water is mixed with 5–10% of modern water, based on tritium content and chlorofluorocarbons. Vertical profiling and deep sampling in the HA showed distinct changes with depth in temperature and TDS. Density-driven flow controls the mixing. In winter, the shallow water of the open HA lake is efficiently cooled; the denser surface water sinks to greater depths, which mixes the water column in the HA. During the summer the shallow water stagnates at the depth of 0–15 m. Periods of stagnation and of accelerated water flow and mixing in the HA perfectly fit with the periodic occurrence of CO2 evasion in the lake and the overall characteristics of the microbial communities, which showed the absence of any functional stratification. Ferric oxyhydroxide precipitation is the major cause for turbidity in the HA. Elevation-specific hydraulic responses of the HA groundwater, caused by the adjacent river’s level pulses, enabled a determination of the points along the river course at which the river is connected to groundwater by karst conduits.

A late Quaternary paleoenvironmental record in sand dunes of the northern Atacama Desert, Chile

AbstractThis paper reports a previously unidentified paleoenvironmental record found in sand dunes of the Atacama Desert, Chile. Long-term aeolian deflation by prevailing onshore winds has resulted in the deposition of sand on the irregular surface of a Miocene-aged anhydrite outcrop. Two deposits ~25 km apart, along the prevailing wind trajectory, were hand excavated then analyzed for vertical (and temporal) changes in physical and chemical composition. Radiocarbon ages of organic matter embedded within the deposits show that rapid accumulation of sediment began at the last glacial maximum and slowed considerably after the Pacific Ocean attained its present post-glacial level. Over this time period, grain sizes are seen to increase while accumulation rates simultaneously decrease, suggesting greater wind speeds and/or a change or decrease in sediment supply. Changes in δ34S values of sulfate in the sediment beginning ~10 ka indicate an increase in marine sources. Similarly, δ2H values from palmitic acid show a steady increase at ~10 ka, likely resulting from aridification of the region during the Holocene. Due to the extreme aridity in the region, these sand dunes retain a well-preserved chemical record that reflects changes in elevation and coastal proximity after the last glacial maximum.

Regional variations of sulfur isotope compositions for metallic deposits in the Taebaeksan Mineralized District, South Korea

Metallic ore deposits of various genetic types are distributed in the Taebaeksan mineralized district in South Korea. The different basements or host rocks for these deposits vary across the northern and southern regions of the district with the Baegunsan Syncline as its center. Previous and newly analyzed sulfur isotope data of 374 sulfide minerals collected from 45 ore deposits were reviewed to compare the genetic characteristics of the two regions. Metallic deposits in the study area were classified into skarn, hydrothermal replacement, and hydrothermal vein based on genetic types and W-Mo, Fe-Cu(-Mo-Pb-Zn), Pb-Zn(-Cu-Au- Ag), and Au-Ag(-Cu-Pb-Zn) deposits with regard to ore species. For each genetic type, average sulfur isotope values were found to be 6.8‰, 7.7‰, and 6.3‰ in the northern region, and 2.3‰, 3.6‰, and 3.5‰ in the southern region, respectively. Average sulfur isotope values for each of the ore species were 11.3‰, 2.6‰, 6.6‰, and 6.9‰ in the northern region, and 1.3‰,–0.2‰, 4.2‰, and 3.3‰ in the southern region, respectively. The results indicate that sulfur isotope compositions for both genetic types and ore species are distinctly higher in the northern region than in the southern region. These differences could be ascribed to different sulfur isotope compositions of basement and host rocks that provided sulfur to ore minerals during the evolution of hydrothermal fluids, though the mineralizing fluids were originated from magmatic source. In the northern region, higher δ34S values of ore sulfurs could be attributed to high δ34S values of sulfate and sulfide in carbonate rocks formed in seawater. On the contrary, lower δ34S values of sulfide minerals in the southern region seem to be attributed to metasedimentary rocks that have lower δ34S values as a result of bacterial sulfate reduction.

Sulfur isotopic fractionation and its implication: Sulfate formation in PM2.5 and coal combustion under different conditions

In order to exactly explore sulfur source and sulfate formation under highly polluted atmosphere, we determined δ34S values of sulfate in PM2.5 and atmospheric SO2 in Nanjing region from 1 to 23 Jan. 2014. The secondary sulfate formation mechanism was discussed based on sulfur isotopic fractionation in the process of SO2 oxidation. Meanwhile, we synchronously studied δ34S values of raw coals used locally as well as sulfur isotopic fractionation during the combustion under coal burning and smoldering. The results show that δ34S average values of SO2 and sulfate in PM2.5 were 1.5‰ and 5.1‰, respectively. δ34S values of sulfate in PM2.5 were consistent with those of coals widely used in Nanjing region and Northern China, indicating coal combustion was an important sulfur source for PM2.5. Sulfur isotopic fractionation factors ranged from 1.0014 to 1.0075, implying that SO2 heterogeneous and homogeneous oxidation were coexisting during the formation of the secondary sulfate. The contribution of SO2 heterogeneous oxidation to sulfate varied from 40.7% to 64.8% during the observation period. δ34S values of coals presented moderately positive sulfur isotopic signatures due to organic sulfur in low sulfur coals were mainly formed by plant assimilation. Besides, the negative relationship between δ34S values of coals and total sulfur contents was also found. In addition, there existed a significant sulfur isotopic fractionation effect during coal combustion. Sulfate in PM2.5 in flue gas enriched 34S, while SO2 in flue gas enriched 32S. There was presence of the difference of δ34S values in PM2.5 and SO2 in flue gas between coal burning and smoldering, which was related to coal property and combustion temperature.

Sulfur isotopic composition of surface snow along a latitudinal transect in East Antarctica

AbstractThe sulfur stable isotopic values (δ34S) of sulfate aerosols can be used to assess oxidation pathways and contributions from various sources, such as marine biogenic sulfur, volcanoes, and sea salt. However, because of a lack of observations, the spatial distribution of δ34S values in Antarctic sulfate aerosols remains unclear. Here we present the first sulfur isotopic values from surface snow samples along a latitudinal transect in eastern Dronning Maud Land, East Antarctica. The δ34S values of sulfate showed remarkably uniform values, in the range of 14.8–16.9‰, and no significant decrease toward the inland part of the transect was noted. These results suggest that net isotopic fractionation during long‐range transport is insignificant. Thus, the δ34S values can be used to infer source contributions. The δ34S values suggest that marine biogenic sulfur is the dominant source of sulfate aerosols, with a fractional contribution of 84 ± 16%.

Source Identification of Sulfur in Uncultivated Surface Soils from Four Chinese Provinces

The analysis of stable isotopes of sulfur (δ34S) is a useful tool for identifying sources of sulfur in soils. Concentrations and sulfur (S) isotopes of water-soluble sulfate (WSS), adsorbed sulfate (AS), residual sulfur (RS), and total sulfur (TS) in uncultivated surface soils of four Chinese provinces were systematically analyzed for identifying sources of S in the soils. Green and healthy mosses (Haplocladium microphyllum) were sampled as bioindicators. The mean WSS concentration (27.8 ± 23.4 mg kg−1) in the surface soils was lower than those of AS (101.4 ± 57.0 mg kg−1) and RS (381.5 ± 256.7 mg kg−1). The mean δ34S values of WSS and AS were very similar (about 2.0%), lower than those of RS (8.0%) and TS (6.1%). A significant linear correlation was found between the δ34S values of AS and WWS (y = 1.0002x – 0.0557, P < 0.0001), indicating that sulfate adsorption in the soils did not markedly fractionate S. All S species in the soils of Guizhou Province were characterized by the lowest δ34S values, consistent with the most 34S-depleted rainwater sulfate reported at Guiyang of Guizhou Province. The δ34S values of sulfate in mosses and rainwater previously reported were significantly linearly correlated with those of both WWS and AS in surface soils, suggesting that atmospheric S input was an important source for soil WSS and AS. However, there were no significant correlations between isotopic composition of rainwater sulfate and RS or TS. The slopes of all these significant linear correlations (soil/rainwater or soil/moss isotopic ratio) were 0.4–0.6, indicating that inorganic sulfate in the surface soils should be a result of mixing of deposited atmospheric sulfate with a more 34S-depleted sulfate component possibly from mineralization of RS.

Sulfur isotope and chemical composition of the rainwater at the Three Gorges Reservoir

Rainwater samples were collected at the Three Gorges Reservoir (TGR) from June 2009 to July 2010 and the pH, major ion concentrations and δ34S values of sulfate were measured. The results indicated that the rain in this region was seriously acidized, 60% of the rain events' pH were lower than 5.0. SO42− and NO3− were the main anions, and their volume weighted mean (VWM) values were 161.9μeq/L and 65.2μeq/L, respectively, which accounted for 71%–99% of the total measured anions. Ca2+ and NH4+ were the major cations with VWM values of 108.3μeq/L and 88.4μeq/L. Sum of Ca2+ and NH4+ accounted for 25%–94% of the total cations. Analysis of the seasonal variations of the pH showed that the rainwater was more acidized in summer than in the other seasons. Investigations of neutralization factors (NFs) indicated that the acidity of rainwater in winter and spring was neutralized by NH4+ and Ca2+. Studies of the origins of major ions showed that SO42− and NO3− were from coal combustion and fossil fuels, and Na+ and Cl− were from sea sources, while Ca2+, Mg2+ and K+ were from the continental sources.The δ34S values of SO42− in rainwater ranged from −2.1‰ to 6.1‰ (mean value of 2.1‰). The δ34S values of SO42− in winter were much higher than those in other seasons. Analysis of the δ34S values vs. SO42− of rainwater combined with air mass trajectory showed that atmospheric sulfur at TGR was mainly associated with coal combustion and fossil fuels. The lower δ34S values in summer at TGR could be explained by higher contribution of biogenic sulfur.

Involvement of magmatic fluids at the Laloki and Federal Flag massive sulfide Cu–Zn–Au–Ag deposits, Astrolabe mineral district, Papua New Guinea: sulfur isotope evidence

We present the first sulfur (S) isotope data of sulfides, sulfates, pyrite in host mudstone, and bulk sulfur of gabbroic rocks from the Laloki and Federal Flag massive Cu–Zn–Au–Ag deposits in the Astrolabe mineral district, Papua New Guinea. Early-stage pyrite–marcasite, chalcopyrite, and sphalerite from Laloki display wide range of δ34S values from −4.5 to +7.0 ‰ (n = 16). Late-stage pyrite, chalcopyrite, and sphalerite have restricted δ34S values of −1.9 to +4.7 ‰ (n = 16). The mineralizing stage these correspond to had moderately saline (5.9–8.4 NaCl eq. wt%) mineralizing fluids of possible magmatic origin. A single analysis of late-stage barite has a value of δ34S +17.9 ‰, which is likely similar to coexisting seawater sulfate. Pyrite from the foot-wall mudstone at Laloki has very light δ34S values of −36.1 to −33.8 ‰ (n = 2), which suggest an organic source for S. Pyrite–marcasite and chalcopyrite from Federal Flag show δ34S values of −2.4 to −1.9 ‰ (n = 2), consistent with a magmatic origin, either leached from intrusive magmatic rocks or derived from magmatic–hydrothermal fluids. The very narrow range and near-zero δ34S values (−1.0 to +0.6 ‰) of bulk gabbroic samples is consistent with mantle-derived magmatic S. Sulfur isotope characteristics of sulfides and sulfates are, however, very similar to base metal sulfide accumulations associated with modern volcanic arcs and sedimented mid-ocean ridges. The most reasonable interpretation is that the range of the sulfide and sulfate δ34S values from both Laloki and Federal Flag massive sulfide deposits is indicative of the complex interaction of magmatic fluids, seawater, gabbroic rocks, and mudstone.

Microbial sulfate reduction within the Iheya North subseafloor hydrothermal system constrained by quadruple sulfur isotopes

Subseafloor hydrothermal systems may host spatially extended and numerically abundant microbial communities sustained by sulfate reduction as one of the important terminal electron accepting metabolisms. In order to estimate microbial sulfate reduction in a subseafloor hydrothermal regime, we analyzed sulfur isotopes (S32/S33/S34/S36) of pore-water sulfate and mineralized sulfide in the upper 100 m of sedimentary sequences at the Iheya North hydrothermal field in the Okinawa Trough recovered in Integrated Ocean Drilling Program Expedition 331 (IODP Exp 331). On the basis of the pore water chemistry and temperature profiles, the subseafloor environment is divided into three hydrogeologic units. In the topmost Unit-1, relatively fresh seawater is recharged, and the bottommost Unit-3 is characterized by predominance of endmember-like high-temperature hydrothermal fluid (>300 °C) underlying the impermeable cap rock layers. Intermediate Unit-2 is subject to mixing between the hydrothermal fluid and seawater. The δ34S values of sulfate in the Unit-2 mixing zone were found to be more 34S-enriched than the values expected from simple mixing model of seawater sulfate in the Unit-1 with the hydrothermal fluid in the Unit-3. The observed SSO434-enrichment and sulfate concentration [SO2−4]-depletion suggest sulfate reduction is taking place below the seafloor. Based on our model calculation, the isotope discrimination (ε34) is estimated to be −21‰. This large isotope discrimination together with slight Δ33S′ enrichment and Δ36S′ depletion reveals that sulfate reduction is caused by microbial processes but not by thermochemical processes. In addition, our numerical simulation points out that sulfate may be reduced prior to presently undergoing mixing with high-temperature fluid, probably within the seawater recharge zone. Despite the abundant input of hydrothermal H2S, mineralized sulfide below 10 m seafloor (mbsf) shows characteristic sulfur isotopic signatures that support the significant contribution of subseafloor microbial sulfate reduction, potentially corresponding to approximately 20% of the total sulfide mineral formation. Active microbial sulfate reduction below the seafloor may be promoted by significant input of seawater to the habitats through the vigorous hydrothermal circulation in vicinity of Iheya North field.

Sulfur isotope and chemical compositions of the wet precipitation in two major urban areas, Seoul and Busan, Korea

The seasonal variations of δ34S together with major ions in snow and rainwater samples were measured in urban areas. Precipitation samples were collected from metropolitan city, Seoul and large port city, Busan, Korea, for about one year from June 2002 to June 2003. The δ34S values of sulfate in precipitation ranged from −4.3‰ to +6.6‰ (mean: 3.72‰) and +1.0‰ to +18.6‰ (mean: 5.55‰) in Seoul and Busan, respectively. Even though both of the study areas have large populations and transportation infrastructure, δ34S values of sulfate in Seoul precipitation originate more from anthropogenic sources relative to that of Busan. The elevated anthropogenic sources in Seoul might be influenced by human activities from surrounding industrial cities, while the scatter of δ34S values in Busan may be influenced by marine air. During the study, δ34S values are high in the fall season and low in the spring season. It may be inferred from this data that spring time δ34S values are affected more by biogenic sources compared to the fall season. As such, Seoul and Busan showed significant differences in chemical compositions, such as δ34S and nss-SO42-. Especially, δ34S values in the Seoul show very good relationship with anthropogenic emissions (e.g., emission from coal combustion) and δ34S values in the Busan may be influenced by sea spray from the oceanic surface micro-layer. This correlation and the δ34S values indicate that the major source in this region is likely to be anthropogenic source in Seoul and sea spray in Busan, rather than traditionally suggested sources such as soil resuspension, stratospheric air intrusion, volcanic emissions, and biogenic emissions.

Pockmark activity inferred from pore water geochemistry in shallow sediments of the pockmark field in southwestern Xisha Uplift, northwestern South China Sea

Pockmarks are widespread on the seabed offshore southwestern Xisha Uplift, northwestern South China Sea. Some of them are so enormous that they are rare worldwide, but their activities were previously poorly known. We collected three gravity-piston cores from this pockmark field, one (C9) from outside, but in close proximity to, a giant pockmark and the other two (C14 and C19) from inside two giant pockmarks. The geochemistry of the pore waters, including SO42−, K+, Ca2+, Mg2+, Sr2+, dissolved inorganic carbon (DIC), δ13CDIC values, and δ34S values of sulfate, was analyzed to elucidate the biogeochemical processes associated with sulfate consumption and to evaluate the current pockmark activity. The sulfate concentration–depth profiles of C9 and C19 are predominantly in response to organoclastic sulfate reduction (OSR), whereas the sulfate concentrations of C14 exhibit three zones of different concentration gradients resulting from varying proportions of contributions from OSR and anaerobic oxidation of methane (AOM). The estimated lower sulfur isotope fractionation factor suggests a higher microbial sulfate reduction rate in C14 than in C9 as a possible consequence of AOM. Based on the sulfate concentration gradient of C14 below 3.7 mbsf, the depth of the sulfate–methane interface (SMI) and the methane diffusive flux in C14 are calculated to be ∼14.3 mbsf and ∼0.0144 mol m−2 yr−1, respectively. The pore-water Mg/Ca and Sr/Ca weight ratios suggest that high Mg-calcite is in equilibrium with respect to pore water or has recently precipitated from pore water in C14. The δ13CDIC values of C9 and C19 are derived from a binary mixture of δ13C from organic matter and of δ13CDIC from bottom water, while DIC from bottom water, OSR, and AOM, concomitant with 13C-enriched DIC from below the SMI possibly all contribute to the DIC pool below 0.66 mbsf in C14. The integrated analysis of pore water geochemistry implies that the pockmark from which C19 was collected may be inactive while the pockmark from which C14 was obtained may currently be sluggish in activity with methane-bearing fluid weakly seeping from subsurface sediments.

Genesis of the Au–Bi–Cu–As, Cu–Mo ± W, and base–metal Au–Ag mineralization at the Mountain Freegold (Yukon, Canada): constraints from Ar–Ar and Re–Os geochronology and Pb and stable isotope compositions

The genesis of mineralized systems across the Mountain Freegold area, in the Dawson Range Cu–Au ± Mo Belt of the Tintina Au province was constrained using Pb and stable isotope compositions and Ar–Ar and Re–Os geochronology. Pb isotope compositions of sulfides span a wide compositional range (206Pb/204Pb, 18.669–19.861; 208Pb/204Pb, 38.400–39.238) that overlaps the compositions of the spatially associated igneous rocks, thus indicating a magmatic origin for Pb and probably the other metals. Sulfur isotopic compositions of sulfide minerals are broadly similar and their δ34S (Vienna-Canyon Diablo Troilite (V-CDT)) values range from −1.4 to 3.6 ‰ consistent with the magmatic range, with the exception of stibnite from a Au–Sb–quartz vein, which has δ34S values between −8.1 and −3.1 ‰. The δ34S values of sulfates coexisting with sulfide are between 11.2 and 14.2 ‰; whereas, those from the weathering zone range from 3.7 to 4.3 ‰, indicating supergene sulfates derived from oxidation of hypogene sulfides. The δ13C (Vienna Peedee Belemnite (VPDB)) values of carbonate range from −4.9 to 1.1 ‰ and are higher than magmatic values. The δ18O (V-SMOW) values of magmatic quartz phenocrysts and magmatic least-altered rocks vary between 6.2 and 10.1 ‰ and between 5.0 and 10.1 ‰, respectively, whereas altered magmatic rocks and hydrothermal minerals (quartz and magnetite) are relatively 18O-depleted (4.2 to 7.9 ‰ and −6.3 to 1.5 ‰, respectively). Hydrogen isotope compositions of both least-altered and altered igneous rock samples are D-depleted (from −133 to −161 ‰ Vienna-Standard Mean Ocean Water (V-SMOW)), consistent with differential magma degassing and/or post-crystallization exchange between the rocks and meteoric ground water. Zircon from a chlorite-altered dike has a U–Pb crystallization age of 108.7 ± 0.4 Ma; whereas, the same sample yielded a whole-rock Ar–Ar plateau age of 76.25 ± 0.53 Ma. Likewise, molybdenite Re–Os model ages range from 75.8 to 78.2 Ma, indicating the mineralizing events are genetically related to Late Cretaceous volcano-plutonic intrusions in the area. The molybdenite Re–Os ages difference between the nearby Nucleus (75.9 ± 0.3 to 76.2 ± 0.3 Ma) and Revenue (77.9 ± 0.3 to 78.2 ± 0.3 Ma) mineral occurrences suggests an episodic mineralized system with two pulses of hydrothermal fluids separated by at least 2 Ma. This, in combination with geological features suggest the Nucleus deposit represents the apical and younger portion of the Revenue–Nucleus magmatic-hydrothermal system and may suggest an evolution from the porphyry to the epithermal environments.

Isotopic characterization of nitrate, ammonium and sulfate in stack PM2.5 emissions in the Athabasca Oil Sands Region, Alberta, Canada

Stable isotope techniques may be a suitable tool for tracing industrial emissions in the atmosphere and the environment provided that the isotopic compositions of industrial emissions are distinct. We determined the isotopic compositions of nitrate, ammonium and sulfate in PM2.5 emitted from two industrial stacks at a large upgrader site in the Athabasca oil sands region (AOSR), northeastern Alberta, Canada, and compared them to the nitrogen and sulfur isotopic compositions of source materials and upgrading by-products. We found distinct isotopic compositions of nitrate and ammonium in PM2.5 compared to those reported for atmospheric nitrate and ammonium in the literature. Nitrate in PM2.5 had δ15N values of 9.4‰ (Stack A) and 16.1 ± 1.2‰ (Stack B) that were significantly enriched in 15N compared to the feedstock materials (∼2.5‰), by-products of upgrading (−0.3–1.3‰), and atmospheric N2 (0‰). δ15N of ammonium in PM2.5 showed a large range with values between − 4.5 to +20.1‰ (Stack B). We report the first measurements of the triple oxygen isotopic composition of industrial emitted nitrate. Nitrate emitted as PM2.5 is not mass-independently enriched in 17O resulting in Δ17O = 0.5 ± 0.9‰ (Stack B) and is therefore distinct from atmospheric nitrate, constituting an excellent indicator of industrial derived nitrate. δ18O values of nitrate in PM2.5 (36.0 and 17.6 ± 1.8‰ for Stack A and B, respectively) were also significantly lower than δ18O values of atmospheric nitrates and hence isotopically distinct. δ34S values of sulfate in PM2.5 were with 7.3 ± 0.3‰ (Stack A) and 9.4 ± 2.0‰ (Stack B) slightly enriched in 34S compared to δ34S in bitumen (4.3 ± 0.3‰) and coke (3.9 ± 0.2‰). δ18O values of sulfate in PM2.5 were 18.9 ± 2.9‰ and 14.2 ± 2.8‰ for Stack A and Stack B, respectively. The isotopic composition of sulfate in PM2.5 was not sufficiently different from δ34S and δ18O values of sulfate in long-range atmospheric deposition in industrial countries to serve as a quantitative indicator for industrial emitted PM2.5. We conclude that δ18O and Δ17O values of nitrate in stack-emitted PM2.5 are excellent, and δ15N values of nitrate and ammonium are suitable indicators for identifying and tracing of PM2.5 nitrate and ammonium emitted from two stacks in the AOSR in the surrounding terrestrial and aquatic ecosystems.