Sustained wet-dry cycling on early Mars.

The presence of perennially wet surface environments on early Mars is well documented1,2, but little is known about short-term episodicity in the early hydroclimate3. Post-depositional processes driven by such short-term fluctuations may produce distinct structures, yet these are rarely preserved in the sedimentary record4. Incomplete geological constraints have led global models of the early Mars water cycle and climate to produce diverging results5,6. Here we report observations by the Curiosity rover at Gale Crater indicating that high-frequency wet-dry cycling occurred in early Martian surface environments. We observe exhumed centimetric polygonal ridges with sulfate enrichments, joined at Y-junctions, that record cracks formed in fresh mud owing to repeated wet-dry cycles of regular intensity. Instead of sporadic hydrological activity induced by impacts or volcanoes5, our findings point to a sustained, cyclic, possibly seasonal, climate on early Mars. Furthermore, as wet-dry cycling can promote prebiotic polymerization7,8, the Gale evaporitic basin may have been particularly conducive to these processes. The observed polygonal patterns are physically and temporally associated with the transition from smectite clays to sulfate-bearing strata, a globally distributed mineral transition1. This indicates that the Noachian-Hesperian transition (3.8-3.6 billion years ago) may have sustained an Earth-like climate regime and surface environments favourable to prebiotic evolution.

SO2 and copper tolerance exhibit an evolutionary trade-off in Saccharomyces cerevisiae.

Copper tolerance and SO2 tolerance are two well-studied phenotypic traits of Saccharomyces cerevisiae. The genetic bases of these traits are the allelic expansion at the CUP1 locus and reciprocal translocation at the SSU1 locus, respectively. Previous work identified a negative association between SO2 and copper tolerance in S. cerevisiae wine yeasts. Here we probe the relationship between SO2 and copper tolerance and show that an increase in CUP1 copy number does not always impart copper tolerance in S. cerevisiae wine yeast. Bulk-segregant QTL analysis was used to identify variance at SSU1 as a causative factor in copper sensitivity, which was verified by reciprocal hemizygosity analysis in a strain carrying 20 copies of CUP1. Transcriptional and proteomic analysis demonstrated that SSU1 over-expression did not suppress CUP1 transcription or constrain protein production and provided evidence that SSU1 over-expression induced sulfur limitation during exposure to copper. Finally, an SSU1 over-expressing strain exhibited increased sensitivity to moderately elevated copper concentrations in sulfur-limited medium, demonstrating that SSU1 over-expression burdens the sulfate assimilation pathway. Over-expression of MET 3/14/16, genes upstream of H2S production in the sulfate assimilation pathway increased the production of SO2 and H2S but did not improve copper sensitivity in an SSU1 over-expressing background. We conclude that copper and SO2 tolerance are conditional traits in S. cerevisiae and provide evidence of the metabolic basis for their mutual exclusivity. These findings suggest an evolutionary driver for the extreme amplification of CUP1 observed in some yeasts.

Novel sulfur isotope analyses constrain sulfurized porewater fluxes as a minor component of marine dissolved organic matter.

Marine dissolved organic matter (DOM) is a major reservoir that links global carbon, nitrogen, and phosphorus. DOM is also important for marine sulfur biogeochemistry as the largest water column reservoir of organic sulfur. Dissolved organic sulfur (DOS) can originate from phytoplankton-derived biomolecules in the surface ocean or from abiotically "sulfurized" organic matter diffusing from sulfidic sediments. These sources differ in 34S/32S isotope ratios (δ34S values), with phytoplankton-produced DOS tracking marine sulfate (21‰) and sulfurized DOS mirroring sedimentary porewater sulfide (∼0 to -10‰). We measured the δ34S values of solid-phase extracted (SPE) DOM from marine water columns and porewater from sulfidic sediments. Marine DOMSPE δ34S values ranged from 14.9‰ to 19.9‰ and C:S ratios from 153 to 303, with lower δ34S values corresponding to higher C:S ratios. Marine DOMSPE samples showed consistent trends with depth: δ34S values decreased, C:S ratios increased, and δ13C values were constant. Porewater DOMSPE was 34S-depleted (∼-0.6‰) and sulfur-rich (C:S ∼37) compared with water column samples. We interpret these trends as reflecting at most 20% (and on average ∼8%) contribution of abiotic sulfurized sources to marine DOSSPE and conclude that sulfurized porewater is not a main component of oceanic DOS and DOM. We hypothesize that heterogeneity in δ34S values and C:S ratios reflects the combination of sulfurized porewater inputs and preferential microbial scavenging of sulfur relative to carbon without isotope fractionation. Our findings strengthen links between oceanic sulfur and carbon cycling, supporting a realization that organic sulfur, not just sulfate, is important to marine biogeochemistry.

Shipping regulations lead to large reduction in cloud perturbations.

Global shipping accounts for 13% of global emissions of SO2, which, once oxidized to sulfate aerosol, acts to cool the planet both directly by scattering sunlight and indirectly by increasing the albedo of clouds. This cooling due to sulfate aerosol offsets some of the warming effect of greenhouse gasses and is the largest uncertainty in determining the change in the Earth's radiative balance by human activity. Ship tracks-the visible manifestation of the indirect of effect of ship emissions on clouds as quasi-linear features-have long provided an opportunity to quantify these effects. However, they have been arduous to catalog and typically studied only in particular regions for short periods of time. Using a machine-learning algorithm to automate their detection we catalog more than 1 million ship tracks to provide a global climatology. We use this to investigate the effect of stringent fuel regulations introduced by the International Maritime Organization in 2020 on their global prevalence since then, while accounting for the disruption in global commerce caused by COVID-19. We find a marked, but clearly nonlinear, decline in ship tracks globally: An 80% reduction in SO[Formula: see text] emissions causes only a 25% reduction in the number of tracks detected.

Sulfate-reducing bacteria unearthed: ecological functions of the diverse prokaryotic group in terrestrial environments.

Sulfate-reducing prokaryotes (SRPs) are essential microorganisms that play crucial roles in various ecological processes. Even though SRPs have been studied for over a century, there are still gaps in our understanding of their biology. In the past two decades, a significant amount of data on SRP ecology has been accumulated. This review aims to consolidate that information, focusing on SRPs in soils, their relation to the rare biosphere, uncultured sulfate reducers, and their interactions with other organisms in terrestrial ecosystems. SRPs in soils form part of the rare biosphere and contribute to various processes as a low-density population. The data reveal a diverse range of sulfate-reducing taxa intricately involved in terrestrial carbon and sulfur cycles. While some taxa like Desulfitobacterium and Desulfosporosinus are well studied, others are more enigmatic. For example, members of the Acidobacteriota phylum appear to hold significant importance for the terrestrial sulfur cycle. Many aspects of SRP ecology remain mysterious, including sulfate reduction in different bacterial phyla, interactions with bacteria and fungi in soils, and the existence of soil sulfate-reducing archaea. Utilizing metagenomic, metatranscriptomic, and culture-dependent approaches will help uncover the diversity, functional potential, and adaptations of SRPs in the global environment.

Elucidating the Mechanism on the Transition-Metal Ion-Synergetic-Catalyzed Oxidation of SO2 with Implications for Sulfate Formation in Beijing Haze.

Currently, atmospheric sulfate aerosols cannot be predicted reliably by numerical models because the pathways and kinetics of sulfate formation are unclear. Here, we systematically investigated the synergetic catalyzing role of transition-metal ions (TMIs, Fe3+/Mn2+) in the oxidation of SO2 by O2 on aerosols using chamber experiments. Our results showed that the synergetic effect of TMIs is critically dependent on aerosol pH due to the solubility of Fe(III) species sensitive to the aqueous phase acidity, which is effective only under pH < 3 conditions. The sulfate formation rate on aerosols is 2 orders of magnitude larger than that in bulk solution and increases significantly on smaller aerosols, suggesting that such a synergetic-catalyzed oxidation occurs on the aerosol surface. The kinetic reaction rate can be described as R = k*[H+]-2.95[Mn(II)][Fe(III)][S(IV)] (pH ≤ 3.0). We found that TMI-synergetic-catalyzed oxidation is the dominant pathway of sulfate formation in Beijing when haze particles are very acidic, while heterogeneous oxidation of SO2 by NO2 is the most important pathway when haze particles are weakly acidic. Our work for the first time clarified the role and kinetics of TMI-synergetic-catalyzed oxidation of SO2 by O2 in haze periods, which can be parameterized into models for future studies of sulfate formation.

Single Droplet Tweezer Revealing the Reaction Mechanism of Mn(II)-Catalyzed SO2 Oxidation.

Sulfate aerosol is one of the major components of secondary fine particulate matter in urban haze that has crucial impacts on the social economy and public health. Among the atmospheric sulfate sources, Mn(II)-catalyzed SO2 oxidation on aerosol surfaces has been regarded as a dominating one. In this work, we measured the reaction kinetics of Mn(II)-catalyzed SO2 oxidation in single droplets using an aerosol optical tweezer. We show that the SO2 oxidation occurs at the Mn(II)-active sites on the aerosol surface, per a piecewise kinetic formulation, one that is characterized by a threshold surface Mn(II) concentration and gaseous SO2 concentration. When the surface Mn(II) concentration is lower than the threshold value, the reaction rate is first order with respect to both Mn(II) and SO2, agreeing with our traditional knowledge. But when surface Mn(II) concentration is above the threshold, the reaction rate becomes independent of Mn(II) concentration, and the reaction order with respect to SO2 becomes greater than unity. The measured reaction rate can serve as a tool to estimate sulfate formation based on field observation, and our established parametrization corrects these calculations. This framework for reaction kinetics and parametrization holds promising potential for generalization to various heterogeneous reaction pathways.

Toxic Potencies of Particulate Matter from Typical Industrial Plants Mediated with Acidity via Metal Dissolution.

Acidity is an important property of particulate matter (PM) in the atmosphere, but its association with PM toxicity remains unclear. Here, this study quantitively reports the effect of the acidity level on PM toxicity via pH-control experiments and cellular analysis. Oxidative stress and cytotoxicity potencies of acidified PM samples at pH of 1-2 were up to 2.8-5.2 and 2.1-13.2 times higher than those at pH of 8-11, respectively. The toxic potencies of PM samples from real-world smoke plumes at the pH of 2.3 were 9.1-18.2 times greater than those at the pH of 5.6, demonstrating a trend similar to that of acidified PM samples. Furthermore, the impact of acidity on PM toxicity was manifested by promoting metal dissolution. The dramatic increase by 2-3 orders of magnitude in water-soluble metal content dominated the variation in PM toxicity. The significant correlation between sulfate, the pH value, water-soluble Fe, IC20, and EC1.5 (p < 0.05) suggested that acidic sulfate could enhance toxic potencies by dissolving insoluble metals. The findings uncover the superficial association between sulfate and adverse health outcomes in epidemiological research and highlight the control of wet smoke plume emissions to mitigate the toxicity effects of acidity.

Estimating global agricultural effects of geoengineering using volcanic eruptions.

Solar radiation management is increasingly considered to be an option for managing global temperatures1,2, yet the economic effects of ameliorating climatic changes by scattering sunlight back to space remain largely unknown3. Although solar radiation management may increase crop yields by reducing heat stress4, the effects of concomitant changes in available sunlight have never been empirically estimated. Here we use the volcanic eruptions that inspired modern solar radiation management proposals as natural experiments to provide the first estimates, to our knowledge, of how the stratospheric sulfate aerosols created by the eruptions of El Chichón and Mount Pinatubo altered the quantity and quality of global sunlight, and how these changes in sunlight affected global crop yields. We find that the sunlight-mediated effect of stratospheric sulfate aerosols on yields is negative for both C4 (maize) and C3 (soy, rice and wheat) crops. Applying our yield model to a solar radiation management scenario based on stratospheric sulfate aerosols, we find that projected mid-twenty-first century damages due to scattering sunlight caused by solar radiation management are roughly equal in magnitude to benefits from cooling. This suggests that solar radiation management-if deployed using stratospheric sulfate aerosols similar to those emitted by the volcanic eruptions it seeks to mimic-would, on net, attenuate little of the global agricultural damage from climate change. Our approach could be extended to study the effects of solar radiation management on other global systems, such as human health or ecosystem function.

Triple oxygen isotope evidence for limited mid-Proterozoic primary productivity.

The global biosphere is commonly assumed to have been less productive before the rise of complex eukaryotic ecosystems than it is today1. However, direct evidence for this assertion is lacking. Here we present triple oxygen isotope measurements (∆17O) from sedimentary sulfates from the Sibley basin (Ontario, Canada) dated to about 1.4 billion years ago, which provide evidence for a less productive biosphere in the middle of the Proterozoic eon. We report what are, to our knowledge, the most-negative ∆17O values (down to -0.88‰) observed in sulfates, except for those from the terminal Cryogenian period2. This observation demonstrates that the mid-Proterozoic atmosphere was distinct from what persisted over approximately the past 0.5 billion years, directly reflecting a unique interplay among the atmospheric partial pressures of CO2 and O2 and the photosynthetic O2 flux at this time3. Oxygenic gross primary productivity is stoichiometrically related to the photosynthetic O2 flux to the atmosphere. Under current estimates of mid-Proterozoic atmospheric partial pressure of CO2 (2-30 times that of pre-anthropogenic levels), our modelling indicates that gross primary productivity was between about 6% and 41% of pre-anthropogenic levels if atmospheric O2 was between 0.1-1% or 1-10% of pre-anthropogenic levels, respectively. When compared to estimates of Archaean4-6 and Phanerozoic primary production7, these model solutions show that an increasingly more productive biosphere accompanied the broad secular pattern of increasing atmospheric O2 over geologic time8.

A review on recent advancements in the treatment of polyaromatic hydrocarbons (PAHs) using sulfate radicals based advanced oxidation process.

Polyaromatic hydrocarbons (PAHs) are the most persistent compounds that get contaminated in the soil and water. Nearly 16 PAHs was considered to be a very toxic according US protection Agency. Though its concentration level is low in the environments but the effects due to it, is enormous. Advanced Oxidation Process (AOP) is an emergent methodology towards treating such pollutants with low and high molecular weight of complex substances. In this study, sulfate radical (SO4‾•) based AOP is emphasized for purging PAH from different sources. This review essentially concentrated on the mechanism of SO4‾• for the remediation of pollutants from different sources and the effects caused due to these pollutants in the environment was reduced by this mechanism is revealed in this review. It also talks about the SO4‾• precursors like Peroxymonosulfate (PMS) and Persulfate (PS) and their active participation in treating the different sources of toxic pollutants. Though PS and PMS is used for removing different contaminants, the degradation of PAH due to SO4‾• was presented particularly. The hydroxyl radical (•OH) mechanism-based methods are also emphasized in this review along with their limitations. In addition to that, different activation methods of PS and PMS were discussed which highlighted the performance of transition metals in activation. Also this review opened up about the degradation efficiency of contaminants, which was mostly higher than 90% where transition metals were used for activation. Especially, on usage of nanoparticles even 100% of degradation could be able to achieve was clearly showed in this literature study. This study mainly proposed the treatment of PAH present in the soil and water using SO4‾• with different activation methodologies. Particularly, it emphasized about the importance of treating the PAH to overcome the risk associated with the environment and humans due to its contamination.

Tracing sulfate sources and transformations of surface water using multiple isotopes in a mining-rural-urban agglomeration area.

Rapid urbanization and mining activities are exacerbating sulfate (SO42-) pollution in surface water, and the information on its sources and transformations is crucial for understanding the sulphur cycle in mining areas. In this study, the SO42- in the surface water of Huaibei mining area were monitored and the main sources of pollution and biogeochemical processes were identified using stable isotopes (δD, δ18O-H2O, δ34S-SO42- and δ18O-SO42-) and water chemistry. The results demonstrated the SO42- content in the Huihe River and Linhuan subsidence water area (SWA) is higher than that in other rivers and SWAs, which exceeded the environmental quality standard of surface water. The SO42- content of different rivers and SWAs showed seasonal differences, and the dry season was higher than the wet season. In addition, the SO42- in Tuohe River and Suihe River is primarily caused by urban sewage and agriculture activities, while in Zhonghu and Shuoxihu SWA is mainly contributed by natural evaporate dissolution. Notably, the input of SO42- in the Huihe River and Linhuan SWA caused by mining activities cannot be disregarded. The aerobic environment and isotopic fractionation of surface water indicate that sulfide oxidation is not the major cause of SO42- formation. This work has revealed the multiple sources and transformation mechanisms of SO42-, and provided a reference for the development of comprehensive management and effective remediation strategies of SO42- contamination in surface water around mining areas.

Abundance and sources of particulate polycyclic aromatic hydrocarbons and aromatic acids at an urban site in central China.

We conducted a simultaneous field study of PM2.5-bound particulate polycyclic aromatic hydrocarbons (PAHs) and aromatic acids (AAs) in a polluted city Zhengzhou to explore the concentration, sources and potential conversion pathways between PAHs and AAs in different seasons. The average concentrations of PM2.5, 28PAHs and 8AAs during the sampling period were 77 µg/m3, 75 ng/m3, and 283 ng/m3, respectively. The concentration of both 28PAHs and 8AAs were highest in winter and lowest in summer with ratios of 6.3 and 2.3, respectively. PAHs with 5-7 rings were the main components of PAHs (52%), followed by 4 rings PAHs (30%) and 2-3 rings PAHs (18%). According to the source appointment results obtained by positive matrix factorization, the main sources of PAHs were combustion and vehicle emissions, which account for 37% and 34%, respectively. 8AAs were divided into three groups, including four benzene dicarboxylic acids (B2CAs), three benzene tricarboxylic acids (B3CAs) and one benzene tetracarboxylic acid (B4CA). And interspecies correlation analysis with PM2.5 source markers were used to investigate potential sources. Phthalic acid (o-Ph) was the most abundant specie of 8AAs (157 ng/m3, 55% of 8AAs), which was well correlated with sulfate. Meanwhile, B3CAs and B4CA were highly correlated with sulfate and weakly correlated with levoglucosan, suggesting that secondary formation was their main source. As logical oxidation products of PAHs, o-Ph and B3CAs showed good correlations with a number of PAHs, indicating possible photochemical oxidation pathway by PAHs. In addition, O3, NO2, temperature and relative humidity have positive effects on the secondary formation of B3CAs.

State-of-the-art glycosaminoglycan characterization.

Glycosaminoglycans (GAGs) are heterogeneous acidic polysaccharides involved in a range of biological functions. They have a significant influence on the regulation of cellular processes and the development of various diseases and infections. To fully understand the functional roles that GAGs play in mammalian systems, including disease processes, it is essential to understand their structural features. Despite having a linear structure and a repetitive disaccharide backbone, their structural analysis is challenging and requires elaborate preparative and analytical techniques. In particular, the extent to which GAGs are sulfated, as well as variation in sulfate position across the entire oligosaccharide or on individual monosaccharides, represents a major obstacle. Here, we summarize the current state-of-the-art methodologies used for GAG sample preparation and analysis, discussing in detail liquid chromatograpy and mass spectrometry-based approaches, including advanced ion activation methods, ion mobility separations and infrared action spectroscopy of mass-selected species.

Microbial methane cycling in sediments of Arctic thermokarst lagoons.

Thermokarst lagoons represent the transition state from a freshwater lacustrine to a marine environment, and receive little attention regarding their role for greenhouse gas production and release in Arctic permafrost landscapes. We studied the fate of methane (CH4 ) in sediments of a thermokarst lagoon in comparison to two thermokarst lakes on the Bykovsky Peninsula in northeastern Siberia through the analysis of sediment CH4 concentrations and isotopic signature, methane-cycling microbial taxa, sediment geochemistry, lipid biomarkers, and network analysis. We assessed how differences in geochemistry between thermokarst lakes and thermokarst lagoons, caused by the infiltration of sulfate-rich marine water, altered the microbial methane-cycling community. Anaerobic sulfate-reducing ANME-2a/2b methanotrophs dominated the sulfate-rich sediments of the lagoon despite its known seasonal alternation between brackish and freshwater inflow and low sulfate concentrations compared to the usual marine ANME habitat. Non-competitive methylotrophic methanogens dominated the methanogenic community of the lakes and the lagoon, independent of differences in porewater chemistry and depth. This potentially contributed to the high CH4 concentrations observed in all sulfate-poor sediments. CH4 concentrations in the freshwater-influenced sediments averaged 1.34 ± 0.98 µmol g-1 , with highly depleted δ13 C-CH4 values ranging from -89‰ to -70‰. In contrast, the sulfate-affected upper 300 cm of the lagoon exhibited low average CH4 concentrations of 0.011 ± 0.005 µmol g-1 with comparatively enriched δ13 C-CH4 values of -54‰ to -37‰ pointing to substantial methane oxidation. Our study shows that lagoon formation specifically supports methane oxidizers and methane oxidation through changes in pore water chemistry, especially sulfate, while methanogens are similar to lake conditions.

Microbial sensitivity to temperature and sulfate deposition modulates greenhouse gas emissions from peat soils.

Peatlands are among the largest natural sources of atmospheric methane (CH4 ) worldwide. Microbial processes play a key role in regulating CH4 emissions from peatland ecosystems, yet the complex interplay between soil substrates and microbial communities in controlling CH4 emissions as a function of global change remains unclear. Herein, we performed an integrated analysis of multi-omics data sets to provide a comprehensive understanding of the molecular processes driving changes in greenhouse gas (GHG) emissions in peatland ecosystems with increasing temperature and sulfate deposition in a laboratory incubation study. We sought to first investigate how increasing temperatures (4, 21, and 35°C) impact soil microbiome-metabolome interactions; then explore the competition between methanogens and sulfate-reducing bacteria (SRBs) with increasing sulfate concentrations at the optimum temperature for methanogenesis. Our results revealed that peat soil organic matter degradation, mediated by biotic and potentially abiotic processes, is the main driver of the increase in CO2 production with temperature. In contrast, the decrease in CH4 production at 35°C was linked to the absence of syntrophic communities and the potential inhibitory effect of phenols on methanogens. Elevated temperatures further induced the microbial communities to develop high growth yield and stress tolerator trait-based strategies leading to a shift in their composition and function. On the other hand, SRBs were able to outcompete methanogens in the presence of non-limiting sulfate concentrations at 21°C, thereby reducing CH4 emissions. At higher sulfate concentrations, however, the prevalence of communities capable of producing sufficient low-molecular-weight carbon substrates for the coexistence of SRBs and methanogens was translated into elevated CH4 emissions. The use of omics in this study enhanced our understanding of the structure and interactions among microbes with the abiotic components of the system that can be useful for mitigating GHG emissions from peatland ecosystems in the face of global change.

Stable Isotopic and Metagenomic Analyses Reveal Microbial-Mediated Effects of Microplastics on Sulfur Cycling in Coastal Sediments.

Microplastics are readily accumulated in coastal sediments, where active sulfur (S) cycling takes place. However, the effects of microplastics on S cycling in coastal sediments and their underlying mechanisms remain poorly understood. In this study, the transformation patterns of different S species in mangrove sediments amended with different microplastics and their associated microbial communities were investigated using stable isotopic analysis and metagenomic sequencing. Biodegradable poly(lactic acid) (PLA) microplastics treatment increased sulfate (SO42-) reduction to yield more acid-volatile S and elementary S, which were subsequently transformed to chromium-reducible S (CRS). The S isotope fractionation between SO42- and CRS in PLA treatment increased by 9.1‰ from days 0 to 20, which was greater than 6.8‰ in the control. In contrast, recalcitrant petroleum-based poly(ethylene terephthalate) (PET) and polyvinyl chloride (PVC) microplastics had less impact on the sulfate reduction, resulting in 7.6 and 7.7‰ of S isotope fractionation between SO42- and CRS from days 0 to 20, respectively. The pronounced S isotope fractionation in PLA treatment was associated with increased relative abundance of Desulfovibrio-related sulfate-reducing bacteria, which contributed a large proportion of the microbial genes responsible for dissimilatory sulfate reduction. Overall, these findings provide insights into the potential impacts of microplastics exposure on the biogeochemical S cycle in coastal sediments.

Inhibition of Methylmercury and Methane Formation by Nitrous Oxide in Arctic Tundra Soil Microcosms.

Climate warming causes permafrost thaw predicted to increase toxic methylmercury (MeHg) and greenhouse gas [i.e., methane (CH4), carbon dioxide (CO2), and nitrous oxide (N2O)] formation. A microcosm incubation study with Arctic tundra soil over 145 days demonstrates that N2O at 0.1 and 1 mM markedly inhibited microbial MeHg formation, methanogenesis, and sulfate reduction, while it slightly promoted CO2 production. Microbial community analyses indicate that N2O decreased the relative abundances of methanogenic archaea and microbial clades implicated in sulfate reduction and MeHg formation. Following depletion of N2O, both MeHg formation and sulfate reduction rapidly resumed, whereas CH4 production remained low, suggesting that N2O affected susceptible microbial guilds differently. MeHg formation strongly coincided with sulfate reduction, supporting prior reports linking sulfate-reducing bacteria to MeHg formation in the Arctic soil. This research highlights complex biogeochemical interactions in governing MeHg and CH4 formation and lays the foundation for future mechanistic studies for improved predictive understanding of MeHg and greenhouse gas fluxes from thawing permafrost ecosystems.

Bacterial Sulfate Reduction Facilitates Iodine Mobilization in the Deep Confined Aquifer of the North China Plain.

Bacterial sulfate reduction plays a crucial role in the mobilization of toxic substances in aquifers. However, the role of bacterial sulfate reduction on iodine mobilization in geogenic high-iodine groundwater systems has been unexplored. In this study, the enrichment of groundwater δ34SSO4 (15.56 to 69.31‰) and its significantly positive correlation with iodide and total iodine concentrations in deep groundwater samples of the North China Plain suggested that bacterial sulfate reduction participates in the mobilization of groundwater iodine. Similar significantly positive correlations were further observed between the concentrations of iodide and total iodine and the relative abundance of the dsrB gene by qPCR, as well as the composition and abundance of sulfate-reducing bacteria (SRB) predicted from 16S rRNA gene high-throughput sequencing data. Subsequent batch culture experiments by the SRB Desulfovibrio sp. B304 demonstrated that SRB could facilitate iodine mobilization through the enzyme-driven biotic and sulfide-driven abiotic reduction of iodate to iodide. In addition, the dehalogenation of organoiodine compounds by SRB and the reductive dissolution of iodine-bearing iron minerals by biogenic sulfide could liberate bound or adsorbed iodine into groundwater. The role of bacterial sulfate reduction in iodine mobilization revealed in this study provides new insights into our understanding of iodide enrichment in iodine-rich aquifers worldwide.

Marine Submicron Aerosols from the Gulf of Mexico: Polluted and Acidic with Rapid Production of Sulfate and Organosulfates.

We measured submicron aerosols (PM1) at a beachfront site in Texas in Spring 2021 to characterize the "background" aerosol chemical composition advecting into Texas and the factors controlling this composition. Observations show that marine "background" aerosols from the Gulf of Mexico were highly processed and acidic; sulfate was the most abundant component (on average 57% of total PM1 mass), followed by organic material (26%). These chemical characteristics are similar to those observed at other marine locations globally. However, Gulf "background" aerosols were much more polluted; the average non-refractory (NR-) PM1 mass concentration was 3-70 times higher than that observed in other clean marine atmospheres. Anthropogenic shipping emissions over the Gulf of Mexico explain 78.3% of the total measured "background" sulfate in the Gulf air. We frequently observed haze pollution in the air mass from the Gulf, with significantly elevated concentrations of sulfate, organosulfates, and secondary organic aerosol associated with sulfuric acid. Analysis suggests that aqueous oxidation of shipping emissions over the Gulf of Mexico by peroxides in the particles might potentially be an important pathway for the rapid production of acidic sulfate and organosulfates during the haze episodes under acidic conditions.