Sulfate δ18O Research Articles

Towards a holistic sulfate-water-O2 triple oxygen isotope systematics

Triple oxygen isotope (∆17O with δ18O) signals of H2O and O2 found in sulfate of oxidative weathering origin offer promising constraints on modern and ancient weathering, hydrology, atmospheric gas concentrations, and bioproductivity. However, interpretations of the sulfate-water-O2 system rely on assuming fixed oxygen-isotope fractionations between sulfate and water, which, contrastingly, are shown to vary widely in sign and amplitude. Instead, here we anchor sulfate-water-O2 triple oxygen isotope systematics on the homogeneous composition of atmospheric O2 with empirical constraints and modeling. Our resulting framework does not require a priori assumptions of the O2- versus H2O‑oxygen ratio in sulfate and accounts for the signals of mass-dependent and mass-independent fractionation in the ∆17O and δ18O of sulfate's O2‑oxygen source. Within this framework, new ∆17O measurements of sulfate constrain ~2.3 Ga Paleoproterozoic gross primary productivity to between 6 and 160 times present-day levels, with important implications for the biological carbon cycle response to high CO2 concentrations prevalent on the early Earth.

Comment on "Correlation of the stratigraphic cover of the Pilbara and Kaapvaal cratons recording the lead up to Paleoproterozoic Icehouse and the GOE" by Andrey Bekker, Bryan Krapež, and Juha A. Karhu, 2020, Earth Science Reviews, https://doi.org/10.1016/j.earscirev.2020.103389

Triple oxygen isotope (∆17O with δ18O) signals of H2O and O2 found in sulfate of oxidative weathering origin offer promising constraints on modern and ancient weathering, hydrology, atmospheric gas concentrations, and bioproductivity. However, interpretations of the sulfate-water-O2 system rely on assuming fixed oxygen-isotope fractionations between sulfate and water, which, contrastingly, are shown to vary widely in sign and amplitude. Instead, here we anchor sulfate-water-O2 triple oxygen isotope systematics on the homogeneous composition of atmospheric O2 with empirical constraints and modeling. Our resulting framework does not require a priori assumptions of the O2- versus H2O‑oxygen ratio in sulfate and accounts for the signals of mass-dependent and mass-independent fractionation in the ∆17O and δ18O of sulfate's O2‑oxygen source. Within this framework, new ∆17O measurements of sulfate constrain ~2.3 Ga Paleoproterozoic gross primary productivity to between 6 and 160 times present-day levels, with important implications for the biological carbon cycle response to high CO2 concentrations prevalent on the early Earth.

Modelling the Effects of Non-Steady State Transport Dynamics on the Sulfur and Oxygen Isotope Composition of Sulfate in Sedimentary Pore Fluids

We present the results of an isotope-enabled reactive transport model of a sediment column undergoing active microbial sulfate reduction to explore the response of the sulfur and oxygen isotopic composition of sulfate under perturbations to steady state. In particular, we test how perturbations to steady state influence the cross plot of δ34S and δ18O for sulfate. The slope of the apparent linear phase (SALP) in the cross plot of δ34S and δ18O for sulfate has been used to infer the mechanism, or metabolic rate, of microbial metabolism, making it important that we understand how transient changes might influence this slope. Tested perturbations include changes in boundary conditions and changes in the rate of microbial sulfate reduction in the sediment. Our results suggest that perturbations to steady state influence the pore fluid concentration of sulfate and the δ34S and δ18O of sulfate but have a minimal effect on SALP. Furthermore, we demonstrate that a constant advective flux in the sediment column has no measurable effect on SALP. We conclude that changes in the SALP after a perturbation are not analytically resolvable after the first 5% of the total equilibration time. This suggests that in sedimentary environments the SALP can be interpreted in terms of microbial metabolism and not in terms of environmental parameters.

Research Advances in Identifying Sulfate Contamination Sources of Water Environment by Using Stable Isotopes.

As the main anion of groundwater, the content of sulfate affects the drinking water safety and ecological security directly. In recent years, with the acceleration of industrialization and urbanization development, the problem of sulfate pollution in water environments is becoming more and more serious. It is critical to effectively identify the sulfate sources of water environment to ensure human health and the benign evolution of water environment. Due to its “fingerprints” feature, the sulfur and oxygen isotopes of SO42− have been widely used to identify sources of sulfate contamination in water environment. However, research advances in tracing sulfate contamination sources of water environment by using stable isotopes are rarely reported. This paper reviewed the research advances of sulfate isotope technology domestically and abroad, which was used to trace the sources of sulfate pollution in water environment, compared different pre-treatment methods for analyzing the δ34S and δ18O of sulfate, and compiled the ranges of typical values of δ34S and δ18O from different potential sources of sulfate contamination. In this review, the limitation of the technique in traceability of sulfate pollution was also discussed, and the future traceability techniques of sulfate pollution were prospected.

The Geochemistry of Englacial Brine From Taylor Glacier, Antarctica

AbstractBlood Falls is a hypersaline, iron‐rich discharge at the terminus of the Taylor Glacier in the McMurdo Dry Valleys, Antarctica. In November 2014, brine in a conduit within the glacier was penetrated and sampled using clean‐entry techniques and a thermoelectric melting probe called the IceMole. We analyzed the englacial brine sample for filterable iron (fFe), total Fe, major cations and anions, nutrients, organic carbon, and perchlorate. In addition, aliquots were analyzed for minor and trace elements and isotopes including δD and δ18O of water, δ34S and δ18O of sulfate, 234U, 238U, δ11B, 87Sr/86Sr, and δ81Br. These measurements were made in order to (1) determine the source and geochemical evolution of the brine and (2) compare the chemistry of the brine to that of nearby hypersaline lake waters and previous supraglacially sampled collections of Blood Falls outflow that were interpreted as end‐member brines. The englacial brine had higher Cl− concentrations than the Blood Falls end‐member outflow; however, other constituents were similar. The isotope data indicate that the water in the brine is derived from glacier melt. The H4SiO4 concentrations and U and Sr isotope suggest a high degree of chemical weathering products. The brine has a low N:P ratio of ~7.2 with most of the dissolved inorganic nitrogen in the form of NH4+. Dissolved organic carbon concentrations are similar to end‐member outflow values. Our results provide strong evidence that the original source of solutes in the brine was ancient seawater, which has been modified with the addition of chemical weathering products.

Assessing redox zones and seawater intrusion in a coastal aquifer in South Korea using hydrogeological, chemical and isotopic approaches

A shallow (<25m), coastal alluvial groundwater system underneath a paddy field in the Yangyang area of South Korea was investigated to examine the occurrence of redox processes. The aquifer is affected by seawater intrusion, and is characterized by a highly reducing environment facilitated by high organic matter in the sediments. Hydrochemical data with δ34S and δ18O of sulfate were examined for depth-specific groundwater from two multilevel samplers that were installed at seaward (YY2) and landward (YY1) locations. Shallow groundwater showed distinct patterns of redox zoning. Evidence of significant bacterial sulfate reduction (BSR) was observed throughout the nearly entire depths of the two boreholes, while at the depths of active seawater intrusion in YY2, conditions suitable for methanogenesis were never reached. Thus, at YY2 the deep zone of intense BSR was overlain by a zone in which methanogenesis occurred in a low-sulfate environment. In contrast, concurrent BSR and methanogenesis in YY1 occurred at depths with high sedimentary organic matter and low dissolved sulfate due to intensive BSR. Considerable BSR in the groundwater representing trapped seawater in a clay layer had resulted in a very strong increase of δ34Ssulfate up to 99.9‰. The inferred sulfur isotopic enrichment factor (ε) for BSR in the lower part of YY2 was −12.3‰, while ε at YY1 was much higher (−45.9‰). In addition, the observed trends of δ18Osulfate at YY1 indicated significant oxygen isotope exchange of sulfate-oxygen with ambient water, likely because of lower cell-specific rates of BSR and higher sulfur isotope fractionation as indicated by the δ34S. In contrast, there was little evidence of oxygen isotope exchange between water and SO42− at YY2. This study indicates that in coastal aquifers with sulfate-reducing activity, δ34S and δ18O of sulfate can reveal zones of active seawater intrusion and of trapped seawater. This study provides an example of the application of sulfur and oxygen isotope data with hydrochemical and hydrogeologic data to interpret complex redox zonation in an organic-rich coastal environment.

The effect of acid rain and altitude on concentration, δ34S, and δ18O of sulfate in the water from Sudety Mountains, Poland

The analyses of sulfate content, δ 34S and δ 18O of dissolved sulfate, and δ 18O of water were carried out in a 14 km 2 crystalline massif located in the Sudety Mountains (SW Poland) to 1) assess the amount of the sulfate delivered to the surface and groundwater systems by modern atmospheric precipitation, 2) determine the effect of altitude on these parameters, and 3) investigate their seasonal variations. In April and November of 2002, August 2003, and March and September of 2005, samples of water were collected from springs and streams of the massif. During these seasons, sulfate contents and δ 18O(SO 4 2−) values varied from 5.80 to 18.00 mg/l and from 3.96 to 8.23‰, respectively, showing distinctively higher values of δ 18O(SO 4 2−) in wet seasons. The δ 34S(SO 4 2−) values had a relatively narrow range from 4.09 to 5.28‰ and were similar to those reported for organic matter in soil and the canopy throughfall in the Sudety Mountains. Sulfate content, δ 34S(SO 4 2−), δ 18O(SO 4 2−), and δ 18O(H 2O) values revealed a remarkable dependence on the altitude. The calculated altitude effects for five season averages of these parameters were − 1.00 mg/l/100 m, − 0.18‰/100 m, − 0.27‰/100 m, and − 0.17‰/100 m, respectively. This dependence on the altitude resulted mainly from the mixing of sulfates of different origins such as anthropogenic sulfate, sulfate produced in the soil within the weathered zone of the massif, and that one from the tree canopy. The oxygen isotope mass balance indicates that, in the study area, about one third of the sulfate delivered to the surface and groundwater by modern precipitation comes from anthropogenic pollution. Further interaction of meteoric water within the weathered rocks causes a continuous decrease of δ 18O(SO 4 2−) values resulting from biological transformation of the sulfate due to plant vegetation and decomposition of organic matter.

Characterising geochemical processes using the δ34S and δ18O of sulfate in groundwater

Characterising geochemical processes using the δ34S and δ18O of sulfate in groundwater