Sulfate Input Research Articles

Response of sulfate concentration to eutrophication on spatio-temporal scale in freshwater lakes

The dramatical increase of sulfur concentration in eutrophic lakes, especially sulfate (SO42−), has brought attention to the impact on the lake ecosystem; however, the mechanisms driving the intensification of eutrophication and the role of SO₄2− concentrations remain poorly understood. To assess the impact of eutrophication on SO42− dynamics in lakes, this study monitored SO42− concentrations in water and sediments across seven lakes with varying trophic statuses on a spatial scale, and in the eutrophic Lake Taihu over one year on a temporal scale, as well as a series of microcosms with different initial SO42− concentrations. Exogenous sulfur input is the primary driver of increased SO42− concentrations in lakes, the highest SO42− concentration in overlying water was 100 mg/L, as well as which reached 310.9 mg/L in sediment. The concurrent input of nutrients such as nitrogen and phosphorus exacerbated eutrophication, resulting in the destabilization of the sulfur cycle. Eutrophication promoted the SO42− concentration on the spatio-temporal scale, especially in sediment, and trophic lake index (TLI) showed a positive correlation with the SO42− in sediments (R2 = 0.99; 0.88). The SO42− concentration in water and TLI showed a nonlinear correlation on the temporal scale (R2 = 0.44), and showed a positive correlation on the spatial scale (R2 = 0.49). Microscopic experiments demonstrate that the anaerobic environment created by cyanobacteria decomposition induced sulfate reduction and significantly reduces SO42− concentrations. Concurrently, the anaerobic environment facilitates the coupling of iron reduction with sulfate reduction, leading to a substantial increase in Acid Volatile Sulfides (AVS) in the sediment. These findings reveal that eutrophication has a dual effect on the dynamic change of SO42− concentrations in overlying water, which is helpful to accurately evaluate and predict the change of SO42− concentrations in lakes.

Exploring soil nitrogen and sulfur dynamics: implications for greenhouse gas emissions on the Qinghai-Tibet Plateau.

The Qinghai-Tibet Plateau is particularly vulnerable to the effects of climate change and disturbances caused by human activity. To better understand the interactions between soil nitrogen and sulfur cycles and human activities on the plateau, the distribution characteristics of soil nitrogen and sulfur density and their influencing factors for three soil layers in Machin County at depths of 0-20cm, 0-100cm, and 0-180cm are discussed in this paper. The results indicated that at depths of 0-180cm, soil nitrogen density in Machin County varied between 1.36 and 16.85kg/m2, while sulfur density ranged from 0.37 to 4.61kg/m2. The effects of three factors-geological background, land use status, and soil type-on soil nitrogen and sulfur density were all highly significant (p < 0.01). Specifically, natural factors such as soil type and geological background, along with anthropogenic factors including land use practices and grazing intensity, were identified as decisive in causing spatial variations in soil nitrogen and sulfur density. Machin County on the Tibetan Plateau exhibits natural nitrogen and sulfur sinks; However, it is crucial to monitor the emissions of N2O and SO2 into the atmosphere from areas with high external nitrogen and sulfur inputs and low fertility retention capacities, such as bare land. On this basis, changes in the spatial and temporal scales of the nitrogen and sulfur cycles in soils and their source-sink relationships remain the focus of future research.

Identification of Anthropogenic and Natural Inputs of Sulfate into River System of Carbonate Zn-Pb Mining Area in Southwest China: Evidence from Hydrochemical Composition, δ34SSO4 and δ18OSO4

The release of pollutants from lead-zinc mining areas poses a significant threat to the environment, making pollution tracing crucial for environmental protection. However, the complexity of carbonate mining areas makes tracing these pollutants challenging. This study used δ34SSO4 and δ18OSO4 isotopes combined with the Stable Isotope Mixing Models in R (SIMMR) to assess anthropogenic sulfate sources in the Daliangzi mining area. The river water types were mainly Ca2+-Mg2+-HCO3−, and SO42−, which are significantly influenced by dolomite dissolution. The δ34SSO4 values ranged from 6.47‰ to 17.96‰ and the δ18OSO4 values ranged from −5.66‰ to 13.98‰. The SIMMR results showed that evaporite dissolution in tributaries, driven by gypsum, contributed 31% of sulfate, while sulfide oxidation, sewage, and atmospheric deposition contributed 19%, 18%, and 24%, respectively. The tailings pond near Xincha Creek has a higher sulfate release potential than the processing plant near Cha Creek. In the mainstream, sulfide oxidation contributed 25%, primarily from mine drainage. Anthropogenic sources, including sulfide oxidation, fertilizers, and sewage, made up about 50% of the total sulfate, with sulfide oxidation accounting for half of this input. The strong correlation between the Zn and SO42− concentrations (R2 = 0.82) and between the Zn and the contribution from the sulfide oxidation (R2 = 0.67) indicates their co-release during sulfide oxidation, making SO42− a proxy for tracing Zn sources. This study highlights the utility of δ34SSO4 and δ18OSO4 with SIMMR in tracing anthropogenic inputs and underscores the significant impact of mining on river systems and the sulfur cycle.

Characterization and stable isotopic fingerprinting of mine seepage in hyperarid environments: An example of the Namib Lead & Zinc mine, Namibia

Mine drainage at the Namib Lead & Zinc mine in the hyperarid environment of the Namib Desert close to Swakopmund, Namibia, has been investigated using mineralogical, hydrochemical, and isotopic methods. The principal ore minerals are galena and sphalerite. Mine drainage is neutral due to the reactions with the marble gangue rock. Mine water seepage is of the Na-Ca-Cl-SO4 type and sources of dissolved ions are likely halite and gypsum in the unsaturated zone above the mine. Concentrations of dissolved metals are relatively low, and the principal attenuation mechanism of metals is probably their adsorption on ferric minerals because equilibrium of the seepage water with secondary minerals that host the metals is not attained. Based on strongly enriched δ2H (up to 13.27 ‰) and δ18O (up to 4.5 ‰) values, seepage water originates from advective fog and is strongly evaporated after the fog deposition. The high δ13C(DIC) values indicate equilibrium with carbonates and CO2 de-gassing. The δ34S(SO4) values are enriched in shallower depths, probably because of pedogenic gypsum dissolution and then the δ34S values decrease with depth, probably due to the increasing input of sulfur from sulfides. Mine drainage at the Namib Lead & Zinc mine does not represent any risk for the environment due to its neutral character and relatively low seepage water volumes caused by high degree of aridity.

Marine sulfate sulfur isotopic evidence for enhanced terrestrial weathering and expansion of oceanic anoxia during the Devonian-Carboniferous transition

The Hangenberg mass extinction during the Devonian-Carboniferous (D-C) transition represents one of the largest biodiversity losses of the Phanerozoic, while the underlying cause remains controversial. An improved understanding of the contemporaneous sulfur cycle can provide insights into the latest Devonian environmental changes that potentially affected marine biotas. Here, we report on a high-resolution chemostratigraphic study of the sulfur isotopic composition of carbonate-associated sulfate (CAS) through the D-C transition in the Long'an and Qilinzhai sections of South China. The δ34SCAS profiles exhibit a long-term (i.e., >105 yr) negative excursion from +19.0‰ in the upper Lower Si. praesulcata Zone to +13.0‰ in the middle Upper Si. praesulcata Zone, and terminated with a recovery to 20.3‰ in the lower Si. sulcata – Si. duplicata zones, representing a depositional interval of ∼0.9 Myr. In addition, this long-term negative excursion is punctuated by episodic sharp negative shifts. The negative δ34SCAS excursion coincided with the end-Devonian biotic crisis, a positive shift in carbonate δ13C, and negative shifts in bulk-sediment δ15N values and I/Ca ratios. Increasing organic carbon burial indicated by the positive shift in δ13C precludes decreased pyrite burial as an explanation for the negative shift of δ34SCAS, supported by intensified marine anoxia revealed by the negative shifts in δ15N and I/Ca. We attribute the long-term negative shift in δ34SCAS to enhanced inputs of 34S-depleted riverine sulfate in conjunction with low seawater sulfate concentrations within the semi-restricted Yangtze Sea, whereas the transient negative spikes in δ34SCAS were possibly caused by episodic upwelling and oxidation of H2S in expanded oceanic oxygen-minimum zones. In conjunction with the positive shift in δ13C, the negative shift in δ34SCAS supports a significant role for enhanced subaerial weathering in intensifying marine anoxia and triggering the biotic crises that occurred during the latest Devonian, the most likely driver of which was the spread of vascular (especially seed-bearing) land plants.

Integrating Tide‐Driven Wetland Soil Redox and Biogeochemical Interactions Into a Land Surface Model

AbstractRedox processes, aqueous and solid‐phase chemistry, and pH dynamics are key drivers of subsurface biogeochemical cycling and methanogenesis in terrestrial and wetland ecosystems but are typically not included in terrestrial carbon cycle models. These omissions may introduce errors when simulating systems where redox interactions and pH fluctuations are important, such as wetlands where saturation of soils can produce anoxic conditions and coastal systems where sulfate inputs from seawater can influence biogeochemistry. Integrating cycling of redox‐sensitive elements could therefore allow models to better represent key elements of carbon cycling and greenhouse gas production. We describe a model framework that couples the Energy Exascale Earth System Model (E3SM) Land Model (ELM) with PFLOTRAN biogeochemistry, allowing geochemical processes and redox interactions to be integrated with land surface model simulations. We implemented a reaction network including aerobic decomposition, fermentation, sulfate reduction, sulfide oxidation, methanogenesis, and methanotrophy as well as pH dynamics along with iron oxide and iron sulfide mineral precipitation and dissolution. We simulated biogeochemical cycling in tidal wetlands subject to either saltwater or freshwater inputs driven by tidal hydrological dynamics. In simulations with saltwater tidal inputs, sulfate reduction led to accumulation of sulfide, higher dissolved inorganic carbon concentrations, lower dissolved organic carbon concentrations, and lower methane emissions than simulations with freshwater tidal inputs. Model simulations compared well with measured porewater concentrations and surface gas emissions from coastal wetlands in the Northeastern United States. These results demonstrate how simulating geochemical reaction networks can improve land surface model simulations of subsurface biogeochemistry and carbon cycling.

Spatial gradients and molecular transformations of DOM, DON and DOS in human-impacted estuarine sediments

Dissolved organic matter (DOM) constitutes the most active fraction in global carbon pools, with estuarine sediments serving as significant repositories, where DOM is susceptible to dynamic transformations. Anthropogenic nitrogen (N) and sulfur (S) inputs further complicate DOM by creating N-bearing DOM (DON) and S-bearing DOM (DOS). This study delves into the spatial gradients and transformation mechanisms of DOM, DON, and DOS in Pearl River Estuary (PRE) sediments, China, using combined techniques of UV–visible spectroscopy, Excitation–emission matrix (EEM) fluorescence spectroscopy, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), and microbial high-throughput sequencing. Results uncovered a distinct spatial gradient in DOM concentration, aromaticity (SUVA254), hydrophobicity (SUVA260), the content of substituent groups including carboxyl, carbonyl, hydroxyl and ester groups (A253/A203) of chromophoric DOM (CDOM), and the abundances of tyrosine/tryptophan-like protein and humic-like substances in fluorophoric DOM (FDOM). These all decreased from upper to lower PRE, accompanied by a decrease in O3S and O5S components, indicating seaward reduction in the contribution of terrestrial OM, especially anthropogenic inputs. Additionally, sediments exhibited a reduction in molecular diversity (number of formulas) of DOM, DON, and DOS from upper to lower PRE, with molecules tending towards a lower nominal oxidation state of carbon (NOSC) and higher bio-reactivity (MLBL), molecular weight (m/z) and saturation (H/C). While molecular composition of DOM remained similar in PRE sediments, the relative abundance of lignin-like substances decreased, with a concurrent increase in protein-like and lipid-like substances in DON and DOS from upper to lower PRE. Mechanistic analysis identified the joint influence of terrestrial OM, anthropogenic N/S inputs, and microbial processes in shaping the spatial gradients of DOM, DON, and DOS in PRE estuarine sediments. This study contributes valuable insights into the intricate spatial gradients and transformations of DOM, DON, and DOS within human-impacted estuarine sediments.

Geochemical Characteristics of Mesoproterozoic Source Rocks in North China: Insights for Organic Matter Enrichment and Thermal Evolution

In recent years, the exploration of oil and gas in China’s Precambrian strata has garnered significant attention, leading to notable advancements in exploration play assessment. However, there is a dearth of published literature on Proterozoic source rocks’ organic sources, sedimentary environments, marine hydrochemistry, and other attributes. This study focuses on investigating potential source rocks within the Hongshuizhuang and Xiamaling Formations in the Jibei Depression of North China. A comprehensive analysis was conducted to evaluate hydrocarbon generation characteristics, using hydrocarbon biomarkers and polar compounds as geochemical indicators for precursor biota and maturity levels. The results indicate high organic matter abundance with predominantly type I-II1 organic matter composition in the studied source rocks. These samples are at an immature–low mature stage, with the potential for primarily generating aromatic crude oil. The parent material is mainly attributed to lower aquatic organisms, such as bacteria and algae. The sedimentary environment exhibits marine facies, characterized by high evaporation rates, salinity levels, and strong euxinic conditions, that led to sulfur incorporation into the organic matter matrix. It should be noted that correlations between biomarker parameters and maturity may not be fully applicable to ancient source rocks; however, the methyldibenzothiophene ratio (MDR) demonstrates a strong correlation with Tmax. The compounds and their total monoisotope ions abundance (TMIA) were primarily identified and analyzed using FT–ICR MS. It was observed that these compounds were influenced by the depositional environment and organic matter maturity. Importantly, it was clearly demonstrated that the DBE and carbon number range of CH compounds gradually increased with maturity, due to the removal of N, S, and O functional groups. Specifically, N1 compounds predominantly consisted of carbazoles with short alkyl side chains which readily converted into N1Ox compounds. On the other hand, O1 compounds mainly comprised benzofurans with low abundance, indicating a reducing sedimentary environment, as suggested by their low TMIA values. Furthermore, S1 compounds were primarily thiophenes whose DBE range and carbon number increased with maturity, possibly suggesting an abiotic input of inorganic sulfur. Notably, the maturity indices (MAT) proved suitable for Mesoproterozoic source rocks while exhibiting strong linear relationships.

Geochemical evolution of geothermal waters in the Pearl River Delta region, South China: Insights from water chemistry and isotope geochemistry

The Pearl River Delta (PRD) region in South China is abundant of geothermal water resources whereas geochemical evolution of the geothermal water is still poorly understood. In this study, geothermal water is sampled to investigate the provenance of CO2 and sulphate, residence time, recharge elevation, circulation depth, and water-interaction processes by analyzing chemistry of major ions and isotope geochemistry. The range of δ13C and content of bicarbonate reveal multiple sources of soil CO2, carbonate rocks, and small amounts of mantle CO2. The δ34S ratio and sulphate concentration are attributed to evaporites dissolution, input of atmospheric sulphur, seawater intrusion, and oxidation of pyrite. The residence time of up to 21.01 ka for geothermal water likely suggests the earliest precipitation recharge during the Late Pleistocene. Mountains or/and hills at an altitude of 300–760 m in north PRD region are currently the major recharge areas for the geothermal water which can circulate at the depths of up to 3000–4800 m along regional structures. The isotopic and hydrochemical analysis confirms that extensive water interaction with silicate rock, carbonate rock and evaporite, evaporation-crystallization process, and cation exchange are the key mechanisms that control the geochemical evolution of geothermal water in the PRD geothermal system.

Effect of sulfate on arsenic migration and transformation in micro-cosmic experiments simulating mangrove sediment environment

Fragile mangrove wetlands are threatened by sea level rise, which results in the introduction of increased sulfate concentrations into mangrove sediment. Mangroves are also susceptible to heavy metal contamination, such as arsenic (As) contamination. However, little is known about whether sulfate affects the bioavailability of As in mangrove sediment. This study focuses on the effects of sulfate on arsenic mobilization and transformation in As-contaminated mangrove sediment, and modeled changes in sulfate concentration, As contamination levels, and pH conditions. The As release from sediment treated with sulfate (30 mM) significantly decreased (P < 0.05). In the moderate arsenic-contaminated sediment, the mean arsenic release was 181.95 ± 33.05 μg kg−1 without sulfate and 157.55 ± 40.98 μg kg−1 with sulfate. In addition, the release of As was affected by both pH and sulfate when pH conditions were changed. Arsenic release was promoted at pH 11 (P < 0.05), but sulfate still mitigating As release at this pH value (P < 0.001). Furthermore, the release of As after sulfate input was always accompanied by the release of iron (Fe) and aluminum (Al). Sulfate altered the distribution of forms of As in the sediment, with a significant increase in the proportion of strongly adsorbed As and silicate-bound states of As. Overall, sulfate intrusion mitigates As release, but it also increases the bioavailability of As in the sediment. This fact makes the toxic element most susceptible to long-term mobilization via biological processes. Therefore, the effect of persistent sulfate intrusion caused by sea level rise on toxic elements in mangrove sediment deserves long-term attention. The significance of this study is that it contributes to understanding the behavior of heavy metals in coastal wetland ecosystems affected by sea level rise.

Variability of sulfur and oxygen isotope values within wet precipitation and its correlation with diminished anthropogenic sulfur dioxide (SO2) emission

Atmospheric sulfate (SO42−) aerosols have the capacity to scatter solar radiation, thus exerting a cooling effect on the climate. It is widely acknowledged that SO42− deposition significantly contributes to ecosystem effect in aquatic and terrestrial environments worldwide. Over the course of several decades, considerable efforts have been undertaken to mitigate anthropogenic sulfur dioxide (SO2) emissions in China, leading to remarkably low SO2 concentrations. Nevertheless, the implications of reduced anthropogenic SO2 emission on atmospheric sulfate transformation and compositions of isotope values (δ34S-SO42–, δ18O-SO42–) remain inadequately understood. To address this knowledge gap, we conducted multiple rainfall sampling instances between 2010 and 2022 (n = 191), encompassing the period of transitioning anthropogenic SO2 emission from high to low levels. Remarkably, we observed a significant reduction in the volume-weighted mean value (VWMV) of SO42− concentrations, declining from 20.86 mg L−1 in 2010 to 2.41 mg L−1 in 2022, and the VWMV of SO42−/NO3− molar ratios also decreased from 12.90 in 2010 to 0.55 in 2022, reflecting the synchronously decreasing annual SO2 emissions and annual SO2 concentrations from 2010 to 2022. In contrast to the declining trends in VWMV of SO42− concentrations, the VWMV of δ34S-SO42– values exhibited a different pattern from 6.6‰ in 2010 to −0.1‰ in 2017 and slightly increased to 2.5‰ in 2022. Furthermore, the VWMV of δ18O-SO42– values demonstrated an increase from 8.8‰ in 2010 to 14.5‰ in 2018, but subsequently decreased to 5.4‰ in 2022. We attributed the sharply dropping VWMV of δ34S-SO42– values to the reduction in the input of primary sulfate with enriched δ34S-SO42– values. The strict desulfurization reduced SO2 emissions, leading to oxidation of these trace SO2 with negative δ34S values, resulting in low sulfate concentrations and negative δ34S-SO42– values. In addition, the monthly average δ18O-SO42– values exhibited a positive correlation with monthly mean δ18O-H2O values (p < 0.05), strongly indicating the water incorporation during SO2 heterogeneous oxidation. More importantly, during spring rainfall, positive δ18O-SO42– values but relatively negative δ34S-SO42– values were influenced by SO2 heterogeneous oxidation facilitated by air oxygen catalyzed under metal ions in dry weather condition, attributed to the low relative humidity (RH) coupled with high deuterium excess (dexcess) values. Conversely, in summer, negative δ18O-SO42– values but relatively positive δ34S-SO42– values resulted from the SO2 heterogeneous oxidation with H2O2 due to high RH and low dexcess values. Moreover, the VWMV of δ18O-H2O exhibited variations from −3.7‰ in 2019 to −9.7‰ in 2021, and displayed a positive correlation with annual temperature (p < 0.01) and a negative correlation with annual precipitation (p < 0.05), making it a valuable indicator of climate change alongside δ18O-SO42– values. Our findings underscore the importance of continued monitoring of atmospheric wet depositions in response to changes in anthropogenic SO2 emission activities. Furthermore, they highlight the substantial impact of variations in δ34S values of SO2 and primary sulfate on rainwater sulfate concentrations and isotope values.

Modeling the behavior of sulfur in magmatic systems from source to surface: Application to Whakaari/White Island, Aotearoa New Zealand, and Etna, Italy

Our understanding of the role of volcanoes in the global sulfur cycle and how volcanic gas emissions can be used to monitor volcanoes is limited by the complex interactions between hydrothermal systems and volcanic sulfur emissions. Hydrothermal systems influence the amount and speciation of volcanogenic sulfur, which is ultimately released to the surface and atmosphere via a range of physicochemical processes. To understand the effect of the hydrothermal system on surface emissions, we model the magmatic-hydrothermal systems at Whakaari/White Island, Aotearoa New Zealand, and Etna, Italy. We quantify the magmatic sulfur inputs using mass balance and MELTS modeling (thermodynamic model of crystallization); model the effects of degassing using Sulfur_X (an empirical model of melt-gas equilibria); and model the influence of the hydrothermal system using CHIM-XPT and EQ3/6 (thermodynamic and kinetic models of gas+water±rock reactions), which we compare to measured plume and fumarole compositions. We find that the sulfur inputs can broadly equal sulfur outputs over long timescales. However, the hydrothermal system can modulate the total mass of sulfur released and its H2S/SO2 ratio on shorter timescales, especially as the system evolves from water- to gas-dominated through the development of dry, gas-dominated pathways.

Comparative study on the sulfation of spent lithium-ion battery under different sulfur inputs: Extraction efficiency, SO2 emission and mechanism

The recovery of valuable metals from spent lithium-ion batteries (LIBs) is of utmost significance for environmental protection and alleviating resource shortages. Traditional sulfation roasting techniques were accused of their unsustainability and negative environmental impact, such as the consumption of expensive sulfation reagents and the emission of SO2. This study compared the performance of cobalt-lithium co-sulfation and selective sulfation processes under high and low sulfur input conditions with waste ferrous sulfate as sulfation reagent. The results revealed that selective roasting can efficiently achieve lithium separation without SO2 emission. Additionally, a sulfation roasting mechanism for SO2 emission-free conditions under low sulfur input was proposed. At 650 °C, spent lithium cobaltate (LCO) was sulfated via ion exchange with FeSO4 and gas-solid reactions with SO2, and the lithium in the outer layer was selectively sulfated. Partially sulfated CoSO4 was then served as a sulfation agent to sulfate the unreacted LCO at 800 °C, allowing the sulfur element to be fully recovered and recycled in the form of Li2SO4. By comparing the co-sulfation and selective sulfation processes, an efficient and eco-friendly method for recovering metals from spent lithium-ion batteries was established.

Significant influence of water diversion and anthropogenic input on riverine sulfate based on sulfur and oxygen isotopes

The transportation of dissolved sulfate (SO42-) to the ocean via river systems plays a critical role in the global sulfur cycle. However, the increasing anthropogenic input has made it challenging to quantify the various pristine contributions accurately. The riverine sulfur and oxygen isotopes of sulfates (δ34SSO4 and δ18OSO4) and the advantages of the Markov-Chain Monte Carlo model were used to distinguish the anthropogenic input in Fenhe River, a tributary of the Yellow River. The SO42- concentrations and δ34SSO4 and δ18OSO4 values of the mainstream river were normally distributed with minor seasonal variations (P > 0.05). However, the upstream riverine SO42- concentrations were significantly altered by the water diversion from the Yellow River. The midstream and downstream sections exhibited a continuous increase in the riverine SO42- concentration and δ34SSO4 and δ18OSO4 values during both seasons. The coal mining drainage significantly impacted the tributaries near coal mining activities, and chemical fertilizers and sewage contributed more sulfate in the midstream and downstream sections. The yearly sulfate flux of the Fenhe River accounted for 4.2% of that of Yellow River, among which over 60% was from anthropogenic sources. The average δ34SSO4 and δ18OSO4 values had elevated to 11.0‰ and 6.0‰, respectively, due to the extensive input of anthropogenic sulfate. Our findings confirm the utility of δ34SSO4 and δ18OSO4 for tracing anthropogenic input and underscore its impacts on river systems and the global sulfur cycle.

An approach to evaluating the impact of contaminants on flux deposition in gas turbines

AbstractGas turbines are a key part of many countries’ power generation portfolios, but components such as blades can suffer from hot corrosion attack, which can decrease component lifetimes. Corrosion is driven by impurity levels in the fuel and air (e.g., species containing sulphur and/or alkali metals) and depends on environmental conditions (e.g., air pollution, seawater droplets), that can lead to formation of harmful species in the gas. Understanding and determining the deposition flux of such contaminants is crucial for understanding the problem. Thermodynamic simulations were used to determine types and amounts of potentially corrosive contaminants, this was followed by deposition fluxes calculations. An operating scenario, based upon an offshore platform was evaluated. The effectiveness of different filtration systems has been evaluated. The impurity levels of alkali metals, such as sodium, greatly impacts the calculated deposition flux of species linked to corrosion attack. The presence of Na2SO4, and K2SO4 was found, at temperature representative of stage 2 nozzle guide vanes. Lowering sulphur input (from fuel or air) can be an efficient way to decrease deposition, attention must also be paid to lowering the amount of alkali metal entering the gas turbine, which can be lowered by the filtration systems’ correct use.

Effects of fungicide application on physiological and molecular responses of grapevine (Vitis vinifera L.): a comparison between copper and sulphur fungicides applied alone and in combination with novel fungicides.

Chemical products against fungi and oomycetes pose serious environmental issues. In the last decade, the use of less impacting active ingredients was encouraged to reduce chemical inputs in viticulture. In this study, the effect of different antifungal compounds on grapevine agronomic, physiological, and molecular responses in the vineyard was evaluated in addition to protection against powdery and downy mildews. In two years and in two Vitis vinifera cultivars (Nebbiolo and Arneis), a conventional crop protection approach, based on traditional fungicides (sulphur and copper), was compared to combined strategies. A well-known resistance inducer (potassium phosphonate), Bacillus pumilus strain QST 2808 and calcium oxide, both active ingredients whose biological interaction with grapevine is poorly characterized, were applied in the combined strategies in association with chemical fungicides. Despite a genotype effect occurred, all treatments optimally controlled powdery and downy mildews, with minimal variations in physiological and molecular responses. Gas exchange, chlorophyll content and photosystem II efficiency increased in treated plants at the end of season, along with a slight improvement in the agronomic performances, and an activation of molecular defence processes linked to stilbene and jasmonate pathways. The disease control strategies based on potassium phosphonate, Bacillus pumilus strain QST 2808 or calcium oxide combined with traditional chemical compounds did not cause severe limitations in plant ecophysiology, grape quality and productive yields. The combination of potassium phosphonate and calcium oxide with traditional fungicides can represent a valuable strategy for reducing copper and sulphur inputs in the vineyards, including those organically managed. This article is protected by copyright. All rights reserved.

Heterogeneous sulfide reoxidation buffered oxygen release in the Ediacaran Shuram ocean

Ediacaran (∼635–539 Ma) carbonate rocks record the largest negative carbonate-carbon isotope excursion in Earth history, termed the Shuram Excursion (SE). This event has been attributed to anaerobic oxidation of dissolved organic carbon as a result of enhanced weathering inputs of sulfate to the ocean during the amalgamation of Gondwana. However, the effect of carbon–sulfur cycle interplay on the net redox state of the ocean–atmosphere system remains unclear, impeding our understanding of the co-evolution of life and the environment during the Ediacaran. Here, we generate high-resolution records of paired sulfate sulfur and oxygen isotopes, in addition to phosphorus concentrations, for the SE interval in South Australia (Parachilna Gorge) and South China (Jiulongwan and Xiang’erwan sections, Three Gorges), and we evaluate these data in the context of COPSE biogeochemical model simulations to assess net long-term redox changes. Our results support widespread H2S reoxidation in shelf areas during the SE, which would have buffered the net release of oxygen sourced from the burial of organic carbon and pyrite. Varying degrees of H2S reoxidation on different cratons likely contributed significantly to high spatial heterogeneity in both local oceanic redox state and nutrient availability, which characterized local oxygen-deficient conditions in an overall oxygenated SE shelf ocean, and likely affected the distribution of the Ediacaran Biota. Our study highlights the important role of H2S reoxidation in the coevolution of marine redox conditions and complex life during the critical Ediacaran period.

Greigite formation in aqueous solutions: Critical constraints into the role of iron and sulphur ratios, pH and Eh, and temperature using reaction pathway modelling

Greigite forms as an intermediate phase along the pyrite reaction pathway. Despite being considered metastable, it is observed in numerous shallow natural systems, suggesting it could be a unique proxy for diagenetic and environmental conditions. We use thermodynamic reaction pathway modelling in PHREEQC software, to understand the role of iron and sulphur ratios, pH and Eh, and temperature on the formation and retention of greigite in aqueous solutions. With newly available experimental thermodynamic properties, this work identifies the chemical boundary conditions for greigite formation in aqueous solutions. Greigite precipitation is likely favourable in anoxic and alkaline aqueous solutions at or below 25 °C. Our numerical experiments show that greigite is closer to saturation in iron-rich solutions with minor sulphur input. Greigite precipitation in strongly alkaline solutions suggest polysulfides and ferric iron-bearing minerals may be favourable reactants for its formation. Greigite precipitates at iron and sulphur concentrations that are over two orders of magnitude greater than iron sulphide-hosted natural porewaters. This disparity between model and field observations suggest microenvironments within bulk solutions may be important for greigite formation and retention. These constraints suggest greigite is more likely to form alongside pyrite in shallow, non-steady state aqueous solutions.

Optical In Situ Monitoring of Acid Mine Drainage Remediation: Laboratory and Model Investigation

AbstractA permeable reactive barrier (PRB) can be deployed to remediate acid mine drainage. The performance of a PRB material under different boundary conditions (pH, flow velocity, and sulfate concentration) was investigated in a series of column experiments applying in‐situ optical sensing methods for pH and oxygen detection. The reactive material consisted of organic components (compost, wood, and coconut shell) mixed with calcium carbonate and fine gravel. The input concentrations were around 1000 mg/L for iron and 3000 mg/L for sulfate, and the pH value was 6.2. The remediation efficiency of iron was 14.6% and of sulfate 15.2%, but was expected to scale up when moving to a field‐site PRB with greater thickness. The iron and sulfate removal was influenced by decreasing the flow velocity and increasing the sulfate input concentration and the pH value. In an experiment with low pH boundary conditions (pH = 2.2), acidity was neutralized in the PRB by calcium carbonate during an experiment duration of 47 days. The modeling program MIN3P was used to create a simulation of the laboratory experiments. This helps to design parameters, for example, the residence time in the PRB, which is necessary for close to 100% remediation efficiency. This study shows the application of optical oxygen and pH monitoring in PRBs. In this context, they can be used to monitor the stability of a PRB for the remediation of acid mine drainage (AMD).

Mercury and Sulfur Redox Cycling Affect Methylmercury Levels in Rice Paddy Soils across a Contamination Gradient.

Methylmercury (MeHg) contamination in rice via paddy soils is an emerging global environmental issue. An understanding of mercury (Hg) transformation processes in paddy soils is urgently needed in order to control Hg contamination of human food and related health impacts. Sulfur (S)-regulated Hg transformation is one important process that controls Hg cycling in agricultural fields. In this study, Hg transformation processes, such as methylation, demethylation, oxidation, and reduction, and their responses to S input (sulfate and thiosulfate) in paddy soils with a Hg contamination gradient were elucidated simultaneously using a multi-compound-specific isotope labeling technique (200HgII, Me198Hg, and 202Hg0). In addition to HgII methylation and MeHg demethylation, this study revealed that microbially mediated reduction of HgII, methylation of Hg0, and oxidative demethylation-reduction of MeHg occurred under dark conditions; these processes served to transform Hg between different species (Hg0, HgII, and MeHg) in flooded paddy soils. Rapid redox recycling of Hg species contributed to Hg speciation resetting, which promoted the transformation between Hg0 and MeHg by generating bioavailable HgII for fuel methylation. Sulfur input also likely affected the microbial community structure and functional profile of HgII methylators and, therefore, influenced HgII methylation. The findings of this study contribute to our understanding of Hg transformation processes in paddy soils and provide much-needed knowledge for assessing Hg risks in hydrological fluctuation-regulated ecosystems.