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Deep subsurface microorganisms constitute over 80 % of Earth's prokaryotic biomass and play an important role in global biogeochemical cycles. Geochemical processes driven by geothermal heating are key factors influencing their biomass and activities, yet their full breadth remains uncaptured. Here, we investigated the microbial community composition and metabolism in microbial-natural-gas-bearing aquifers at temperatures ranging from 38 to 81 °C , situated above nonmicrobial-gas- and oil-bearing sediments at temperatures exceeding 90 °C. Cultivation-based and molecular gene analyses, including radiotracer measurements, of formation water indicated variations in predominant methanogenic pathways across different temperature regimes of upper aquifers: high potential for hydrogenotrophic–methylotrophic, hydrogenotrophic, and acetoclastic methanogenesis at temperatures of 38, 51–65, and 73–81 °C , respectively. The potential for acetoclastic methanogenesis correlated with elevated acetate concentrations with increasing depth, possibly due to the decomposition of sedimentary organic matter. In addition to acetoclastic methanogenesis, in aquifers at temperatures as high as or higher than 65 °C , acetate is potentially utilized by microorganisms responsible for the dissimilatory reduction of sulfur compounds other than sulfate because of their high relative abundance at greater depths. The stable sulfur isotopic analysis of sulfur compounds in water and oil samples suggested that hydrogen sulfide, generated through the thermal decomposition of sulfur compounds in oil, migrates upward and is subsequently oxidized with iron oxides present in sediments, yielding elemental sulfur and thiosulfate. These compounds are consumed by sulfur-reducing microorganisms, possibly reflecting elevated microbial populations in aquifers at temperatures as high as or higher than 73 °C. These findings reveal previously overlooked geothermal-heat-driven geochemical and microbiological processes involved in carbon and sulfur cycling in the deep sedimentary biosphere. [ABSTRACT FROM AUTHOR]

A growing number of general circulation models are adapting interactive sulfur and aerosol schemes to improve the representation of relevant physical and chemical processes and associated feedbacks. They are motivated by investigations of climate response to major volcanic eruptions and potential solar geoengineering scenarios. However, uncertainties in these schemes are not well constrained. Stratospheric sulfate is modulated by emissions of sulfur-containing species of anthropogenic and natural origin, including volcanic activity. While the effects of volcanic eruptions have been studied in the framework of global model intercomparisons, the background conditions of the sulfur cycle have not been addressed in such a way. Here, we fill this gap by analyzing the distribution of the main sulfur species in nine global atmospheric aerosol models for a volcanically quiescent period. We use observational data to evaluate model results. Overall, models agree that the three dominant sulfur species in terms of burdens (sulfate aerosol, OCS, and SO 2) make up about 98 % stratospheric sulfur and 95 % tropospheric sulfur. However, models vary considerably in the partitioning between these species. Models agree that anthropogenic emission of SO 2 strongly affects the sulfate aerosol burden in the northern hemispheric troposphere, while its importance is very uncertain in other regions, where emissions are much lower. Sulfate aerosol is the main deposited species in all models, but the values deviate by a factor of 2. Additionally, the partitioning between wet and dry deposition fluxes is highly model dependent. Inter-model variability in the sulfur species is low in the tropics and increases towards the poles. Differences are largest in the dynamically active northern hemispheric extratropical region and could be attributed to the representation of the stratospheric circulation. The differences in the atmospheric sulfur budget among the models arise from the representation of both chemical and dynamical processes, whose interplay complicates the bias attribution. Several problematic points identified for individual models are related to the specifics of the chemistry schemes, model resolution, and representation of cross-tropopause transport in the extratropics. Further model intercomparison research is needed with a focus on the clarification of the reasons for biases, given the importance of this topic for the stratospheric aerosol injection studies. [ABSTRACT FROM AUTHOR]

New particle formation (NPF) in the free troposphere (FT) is thought to be a significant source of particles over the oceans. The entrainment of particles initially formed in the marine FT is further suspected to be a major contributor to cloud condensation nuclei (CCN) number concentrations in the marine boundary layer (BL). Yet, little is known about the process and, more broadly, about the composition of the marine FT, which remains poorly explored due to access difficulties. Here we report measurements performed in April 2018 at the Maïdo Observatory with a nitrate-based chemical ionization atmospheric pressure interface time-of-flight mass spectrometer, which have allowed the first molecular-level characterization of the remote marine FT composition. A number of molecules and clusters were identified and classified into nine groups according to their chemical composition; among the identified species, the groups containing methanesulfonic acid (MSA) and C2 amines show signals that are on average significantly higher when the site is under conditions representative of the marine FT (compared to the BL). The correlation analysis revealed apparent connections between the signals of the identified compounds and several variables concurrently measured at the site (under FT conditions) or related to air mass history, suggesting that oxalic acid, malonic acid, and observed C2 amines could be of terrestrial origin, with, in addition, a possible marine source for oxalic acid and amines, while iodic acid, sulfur species, and maleic acid have a dominant marine origin. Identification of FT conditions at the site was based on the analysis of the standard deviation of the wind direction; this parameter, which can easily be derived from continuous measurements at the site, is shown in the first part of the study to be a relevant tracer when compared to predictions from the Meso-NH atmospheric model. Similar to other high-altitude sites, FT conditions are mainly encountered at night at Maïdo; therefore, the link to NPF could not be established, and further research is needed to assess the composition of precursors to nanoparticle formation in the marine FT. [ABSTRACT FROM AUTHOR]

To extract climatically relevant chemical signals from the deepest, oldest Antarctic ice, we must first understand the degree to which chemical ions diffuse within solid ice. Volcanic sulfate peaks are the ideal target for such an investigation because they are high amplitude, short duration (~3 years) events with a quasi-uniform structure. Here we present analysis of the EPICA Dome C sulfate record over the last 450 kyr. We identify volcanic peaks and isolate them from the non-sea salt sulfate background to reveal the effects of diffusion: amplitude damping and broadening of peaks in the time domain with increasing depth/age. Sulfate peak shape is also altered by the thinning of ice layers with depth that results from ice flow. Both processes must be simulated to derive effective diffusion rates. This is achieved by running a forward model to diffuse idealised sulfate peaks at different rates while also accounting for ice thinning. Our simulations suggest a median effective diffusion rate of sulfate ions of 2.4 ± 1.7 x 10-7 m2 yr-1 in the Holocene ice, slightly faster than suggested by previous work. The effective diffusion rate observed in deeper ice is significantly lower, and the Holocene ice shows the highest rate of the last 450 kyr. Beyond the Holocene, there is no systematic difference between the effective diffusion rates of glacial and interglacial periods despite variations in soluble ions concentrations, dust loading and ice grain radii. Effective diffusion rates for 40 to 200 ka are relatively constant, on the order of 1 x 10-8 m2 yr-1. Our results suggests that the diffusion of sulfate ions within volcanic peaks is relatively fast initially, perhaps through the inter-connected vein network, but slows significantly after 40 kyr. In the absence of clear evidence for a controlling environmental factor on sulfate diffusivity with depth/age, we hypothesize that the rapid decrease in diffusion rate from the time of deposition to ice of 50 ka age may be due to a switch in the mechanism of diffusion resulting from the changing location of sulfate ions within the ice microstructure. [ABSTRACT FROM AUTHOR]

The formation of secondary sulfate in the atmosphere remains controversial, and it is an urgent need to seek a new method to quantify different sulfate formation pathways. Thus, SO 2 and PM 2.5 samples were collected from 4 to 22 December 2019 in the Nanjing region. Sulfur and oxygen isotopic compositions were synchronously measured to study the contribution of SO 2 homogeneous and heterogeneous oxidation to sulfate. Meanwhile, the correlation of δ18 O values between H 2 O and sulfate from SO 2 oxidation by H 2 O 2 and Fe 3+ / O 2 was simulatively investigated in the laboratory. Based on isotope mass equilibrium equations, the ratios of different SO 2 oxidation pathways were quantified. The results showed that secondary sulfate constituted higher than 80 % of total sulfate in PM 2.5 during the sampling period. Laboratory simulation experiments indicated that the δ18 O value of sulfate was linearly dependent on the δ18 O value of water, and the slopes of linear curves for SO 2 oxidation by H 2 O 2 and Fe 3+ / O 2 were 0.43 and 0.65, respectively. The secondary sulfate in PM 2.5 was mainly ascribed to SO 2 homogeneous oxidation by OH radicals and heterogeneous oxidation by H 2 O 2 and Fe 3+ / O 2. SO 2 heterogeneous oxidation was generally dominant during sulfate formation, and SO 2 oxidation by H 2 O 2 predominated in SO 2 heterogeneous oxidation reactions, with an average ratio around 54.6 %. This study provided an insight into precisely evaluating sulfate formation by combining stable sulfur and oxygen isotopes. [ABSTRACT FROM AUTHOR]

The atmospheric sulfur cycle plays a key role in air quality, climate, and ecosystems, such as pollution, radiative forcing, new particle formation, and acid rain. In this study, we compare the spatially and temporally resolved measurements from the NASA Atmospheric Tomography (ATom) mission with simulations from five AeroCom III models for four sulfur species (dimethyl sulfide (DMS), sulfur dioxide (SO 2), particulate methanesulfonate (MSA), and particulate sulfate (SO 4)). We focus on remote regions over the Pacific, Atlantic, and Southern oceans from near the surface to ∼ 12 km altitude range covering all four seasons. In general, the differences among model results can be greater than 1 order of magnitude. Comparing with observations, model-simulated SO 2 is generally low, whereas SO 4 is generally high. Simulated DMS concentrations near the sea surface exceed observed levels by a factor of 5 in most cases, suggesting potential overestimation of DMS emissions in all models. With GEOS model simulations of tagging emission from anthropogenic, biomass burning, volcanic, and oceanic sources, we find that anthropogenic emissions are the dominant source of sulfate aerosol (40 %–60 % of the total amount) in the ATom measurements at almost all altitudes, followed by volcanic emissions (18 %–32 %) and oceanic sources (16 %–32 %). Similar source contributions can also be derived at broad ocean basins and on monthly scales, indicating the representativeness of ATom measurements for global ocean. Our work presents the first assessment of AeroCom sulfur study using ATom measurements, providing directions for improving sulfate simulations, which remain the largest uncertainty in radiative forcing estimates in aerosol climate models. [ABSTRACT FROM AUTHOR]

Marine sediments can be used to reconstruct the evolution of seawater [SO 42- ] and δ34 S over time, two key parameters that contribute to refine our understanding of the sulfur cycle and thus of Earth's redox state. δ34 S evolution can be measured from carbonates, barites and sulfate evaporites. [SO 42- ] variations can be reconstructed using fluid inclusions in halites, a method that only allows a low-resolution record. Reconstruction of the past sulfur cycle could be improved if carbonates allowed the tracking of both seawater δ34 S and [SO 42- ] variations in a sole, continuous sedimentary repository. However, most primary carbonates formed in the ocean are biogenic, and organisms tend to overprint the geochemical signatures of their carbonates through a combination of processes often collectively referred to as vital effects. Hence, calibrations are needed to allow seawater δ34 S and [SO 42- ] reconstructions based on biogenic carbonates. Because foraminifera are important marine calcifiers, we opted to focus on calcite synthesized by individuals of rosalinid benthic foraminifera cultured in the laboratory under controlled conditions, with varying seawater [SO 42- ] (ranging from 0 to 180 mM). Our experimental design allowed us to obtain foraminiferal asexual reproduction over several generations. We measured bulk carbonate-associated sulfate (CAS) content and sulfur isotopic composition (δ34 S CAS) on samples of tens to hundreds of specimens from a selection of culture media, where [SO 42- ] varied from 5 to 60 mM. Increasing or decreasing [SO 42- ] with respect to modern-day seawater concentration (28 mM) impacted foraminiferal population size dynamics and the total amount of bioprecipitated carbonate. Foraminiferal CAS concentration increased proportionally with [SO 42- ] concentration from 5 mM up to 28 mM and then showed a plateau from 28 to 60 mM. The existence of a threshold at 28 mM is interpreted as the result of a control on the precipitation fluid chemistry that foraminifera exert on the carbonate precipitation loci. However, at high seawater sulfate concentrations (> 40 mM) the formation of sulfate complexes with other cations may partially contribute to the non-linearity of the CAS concentration in foraminiferal tests at high increases in [SO 42- ]. Yet, despite the significant effect of seawater [SO 42- ] on foraminiferal reproduction and on CAS incorporation, the isotopic fractionation between CAS and seawater remains stable through varying seawater [SO 42- ]. Altogether, these results illustrate that CAS in biogenic calcite could constitute a good proxy for both seawater [SO 42- ] and δ34 S and suggests that sulfate likely plays a role in foraminiferal biomineralization and biological activity. [ABSTRACT FROM AUTHOR]

Anthropogenic emissions of aerosols and precursor compounds are known to significantly affect the energy balance of the Earth–atmosphere system, alter the formation of clouds and precipitation, and have a substantial impact on human health and the environment. Global models are an essential tool for examining the impacts of these emissions. In this study, we examine the sensitivity of model results to the assumed height of SO 2 injection, seasonality of SO 2 and black carbon (BC) particulate emissions, and the assumed fraction of SO 2 emissions that is injected into the atmosphere as particulate phase sulfate (SO 4) in 11 climate and chemistry models, including both chemical transport models and the atmospheric component of Earth system models. We find large variation in atmospheric lifetime across models for SO 2 , SO 4 , and BC, with a particularly large relative variation for SO 2 , which indicates that fundamental aspects of atmospheric sulfur chemistry remain uncertain. Of the perturbations examined in this study, the assumed height of SO 2 injection had the largest overall impacts, particularly on global mean net radiative flux (maximum difference of - 0.35 W m -2), SO 2 lifetime over Northern Hemisphere land (maximum difference of 0.8 d), surface SO 2 concentration (up to 59 % decrease), and surface sulfate concentration (up to 23 % increase). Emitting SO 2 at height consistently increased SO 2 and SO 4 column burdens and shortwave cooling, with varying magnitudes, but had inconsistent effects across models on the sign of the change in implied cloud forcing. The assumed SO 4 emission fraction also had a significant impact on net radiative flux and surface sulfate concentration. Because these properties are not standardized across models this is a source of inter-model diversity typically neglected in model intercomparisons. These results imply a need to ensure that anthropogenic emission injection height and SO 4 emission fraction are accurately and consistently represented in global models. [ABSTRACT FROM AUTHOR]

Understanding the composition and sources of atmospheric ultrafine particles (UFPs) is essential in evaluating their exposure risks. It requires long-term measurements with high time resolution, which are scarce to date. We performed near-continuous measurements of UFP composition during four seasons in urban Beijing using a thermal desorption chemical ionization mass spectrometer, accompanied by real-time size distribution measurements. We found that UFPs in urban Beijing are dominated by organic components, varying seasonally from 68 % to 81 %. CHO organics (i.e., molecules containing carbon, hydrogen, and oxygen) are the most abundant in summer, while sulfur-containing organics, some nitrogen-containing organics, nitrate, and chloride are the most abundant in winter. With the increase of particle diameter, the contribution of CHO organics decreases, while that of sulfur-containing and nitrogen-containing organics, nitrate, and chloride increases. Source apportionment analysis of the UFP organics indicates contributions from cooking and vehicle sources, photooxidation sources enriched in CHO organics, and aqueous/heterogeneous sources enriched in nitrogen- and sulfur-containing organics. The increased contributions of cooking, vehicle, and photooxidation components are usually accompanied by simultaneous increases in UFP number concentrations related to cooking emission, vehicle emission, and new particle formation, respectively, while the increased contribution of the aqueous/heterogeneous composition is usually accompanied by the growth of UFP mode diameters. The highest UFP number concentrations in winter are due to the strongest new particle formation, the strongest local primary particle number emissions, and the slowest condensational growth of UFPs to larger sizes. This study provides a comprehensive understanding of urban UFP composition and sources and offers valuable datasets for the evaluation of UFP exposure risks. [ABSTRACT FROM AUTHOR]

The formation of secondary sulfate in the atmosphere remains controversial, and it is urgent to seek for a new method to quantify different sulfate formation pathways. Thus, SO2 and PM2.5 samples were collected from 4 to 22 Dec. 2019 in Nanjing. Sulfur and oxygen isotope compositions were synchronously measured to study the contribution of SO2 homogeneous and heterogeneous oxidation to sulfate. Meanwhile, the correlation of δ18O values between H2O and sulfate from SO2 oxidation by H2O2 and Fe3+/O2 were investigated in the lab. Based on isotope mass equilibrium equations, the ratios of different SO2 oxidation pathways were calculated. The results showed that secondary sulfate constituted higher than 80 % of total sulfate in PM2.5 during the sampling period. Laboratory simulation experiments indicated that δ18O of sulfate was linearly dependent on δ18O of water, and the slopes of linear curves for SO2 oxidation by H2O2 and Fe3+/O2 were 0.43 and 0.65, respectively. The secondary sulfate in PM2.5 was mainly ascribed to SO2 homogeneous oxidation by OH radicals and heterogeneous oxidation by H2O2 and Fe3+/O2. SO2 heterogeneous oxidation was generally dominant during sulfate formation, and the contribution of SO2 heterogeneous oxidation was about 52 %. Especially, SO2 oxidation by H2O2 predominated in SO2 heterogeneous oxidation reactions with an average ratio around 55 %. This study provided an insight into precisely evaluating sulfate formation pathways by combining stable sulfur and oxygen isotopes. [ABSTRACT FROM AUTHOR]

The addition of sulfur (S) to organic matter to form organosulfur compounds is generally thought to protect organic matter from microbial degradation and promote its preservation. While most microbial sulfur cycling occurs in sulfate-rich sediments above the sulfate-methane transition zone, recently discovered active sulfur cycling in deeper sulfate-poor environments may have a yet-unquantified impact on the mineralization of organic matter. Here we investigated the fate of buried S-compounds down to 10-m sediment depth representing the entire ~13.5 kya history of the sulfate-rich alpine Lake Cadagno. Chemical profiles of sulfate and sulfur reveal that these oxidized species are depleted at the sediment surface with the concomitant formation of iron sulfide minerals. An underlying aquifer provides a second source of sulfate and other oxidants to the deepest and oldest sediment layers generating an inverse redox gradient. At both sulfate depletion zones, isotopes of chromium-reducible sulfur (CRS) and humic-bound sulfur are highly negative (−30 to −65 per mil) compared to background sulfate suggesting ongoing microbial sulfur cycling. Interestingly, humic-bound S from intermittent sediment layers within the sulfate-depleted methanogenesis zone consistently exhibits a lower δ34S than CRS in lacustrine deposits but a higher δ34S than CRS in terrestrial deposits, which could possibly be due to different reactivities of organic matter types (lacustrine versus terrestrial origin) to sulfide or the ability of microorganisms to form/degrade organic S. Although sulfate concentrations are extremely low between the sulfate depletion zones, dsrB gene libraries reveal a huge potential for microbial sulfur reduction throughout the sediment column. [ABSTRACT FROM AUTHOR]

The sulfur cycle plays a key role in atmospheric air quality, climate, and ecosystems. In this study, we compare the spatial and temporal distribution of four sulfur-containing species, dimethyl sulfide (DMS), sulfur dioxide (SO2), particulate methanesulfonate (MSA), and particulate sulfate (SO4), that were measured during the airborne NASA Atmospheric Tomography (ATom) mission and simulated by five AeroCom-III models to analyze the budget of sulfur cycle from the models. This study focuses on remote regions over the Pacific, Atlantic, and Southern Oceans from near the ocean surface to ~12-km altitude range, and covers all four seasons. These regions provide us with highly heterogeneous natural and anthropogenic source environments, which is not usually the case for traditional continental studies. We examine the vertical and seasonal variations of these sulfur species over tropical, mid-, and high-latitude regions in both hemispheres. We identify their origins from land versus ocean and from anthropogenic versus natural sources with sensitivity studies by applying tagged tracers linking to emission types and regions. In general, the differences among model results can be greater than one-order of magnitude. Comparing with observations, simulated SO2 is generally low while SO4 is high, and the model-observation agreement is much better in ATom-4 (April–May, 2018). There are much larger DMS concentrations simulated close to the sea surface than observed, indicating that the DMS emissions may be too high from all models. Anthropogenic emissions are the dominant source (40–60 % of the total amount) for atmospheric sulfate simulated at locations and times along the ATom flight tracks at almost every altitude, followed by volcanic emissions (18–32 %) and oceanic sources (16–32 %). Similar source contributions can also be derived at broad ocean basin and monthly scales, indicating that any reductions of anthropogenic sulfur emissions would have global impacts in modern times. [ABSTRACT FROM AUTHOR]

Sulfate aerosol in the stratosphere is an important climate driver, causing solar dimming in the years after major volcanic eruptions. Hence, a growing number of general circulation models are adapting interactive sulfur and aerosol schemes to improve the representation of relevant chemical processes and associated feedbacks. However, uncertainties of these schemes are not well constrained. Stratospheric sulfate is modulated by natural emissions of sulfur-containing species, including volcanic eruptive, and anthropogenic emissions. Model intercomparisons have examined the effects of volcanic eruptions, whereas the background conditions of the sulfur cycle have not been addressed in a global model intercomparison project. Assessing background conditions in global models allows us to identify model discrepancies as they are masked by large perturbations such as volcanic eruptions, yet may still matter in the aftermath of such a disturbance. Here, we analyze the atmospheric burden, seasonal cycle, and vertical and meridional distribution of the main sulfur species among nine global atmospheric aerosol models that are widely used in the stratospheric aerosol research community. We use observational and reanalysis data to evaluate model results. Overall, models agree that the three dominant sulfur species in terms of burdens (sulfate aerosol, OCS, and SO2) make up about 98 % of stratospheric sulfur and 95 % of tropospheric sulfur. However, models vary considerably in the partitioning between these species. Models agree that anthropogenic emission of SO2 strongly affects the sulfate aerosol burden in the Northern Hemispheric troposphere, while its importance is very uncertain in other regions. The total deposition of sulfur varies among models, deviating by a factor of two, but models agree that sulfate aerosol is the main form in which sulfur is deposited. Additionally, the partitioning between wet and dry deposition fluxes is highly model dependent. We investigate the areas of greatest variability in the sulfur species burdens and find that inter-model variability is low in the tropics and increases towards the poles. Seasonality in the southern hemisphere is depicted very similar among models. Differences are largest in the dynamically active northern hemispheric extratropical region, hence some of the differences could be attributed to the differences in the representation of the stratospheric circulation among underlying general circulation models. This study highlights that the differences in the atmospheric sulfur budget among the models arise from the representation of both chemical and dynamical processes, whose interplay complicates the bias attribution. Several problematic points identified for individual models are related to the specifics of the chemistry schemes, model resolution, and representation of cross-tropopause transport in the extratropics. Further model intercomparison research is needed focusing on the clarification of the reasons for biases, given also the importance of this topic for the stratospheric aerosol injection studies. [ABSTRACT FROM AUTHOR]

New particle formation (NPF) in the free troposphere (FT) is thought to be a significant source of particles over the oceans. The entrainment of particles initially formed in the marine FT is further suspected to be a major contributor to cloud condensation nuclei (CCN) number concentrations in the marine boundary layer (BL). Yet, little is known about the process, and more broadly about the composition of the marine FT, which remains poorly explored due to access difficulties. Here we report measurements performed in April 2018 at the Maïdo observatory with a nitrate based chemical ionisation atmospheric pressure interface time-of-flight mass spectrometer, which have allowed the first molecular-level characterisation of the clusters present in the remote marine FT. A number of clusters were identified and classified into 9 groups according to their chemical composition, among which the groups containing methanesulfonic acid (MSA) and C2 amines, which show signals that are on average significantly higher when the site is under conditions representative of the marine FT (compared to the BL). The correlation analysis revealed apparent connections between the signals of the identified compounds and several variables concurrently measured at the site (under FT conditions) or related to air mass history, suggesting that oxalic acid, malonic acid and observed C2 and C4 amines could be of terrestrial origin, with, in addition, a possible marine source for oxalic acid and amines, while iodic acid, sulfur species and maleic acid have a dominant marine origin. Identification of FT conditions at the site was based on the analysis of the standard deviation of the wind direction; this parameter, which can easily be derived from continuous measurements at the site, is shown in the first part of the study to be a relevant tracer when compared to predictions from the Meso-NH atmospheric model. Similar to other high altitude sites, FT conditions are mainly encountered at night at Maïdo and therefore the link to NPF could not be established, and further research is needed to assess the composition of precursors to nanoparticle formation in the marine FT. [ABSTRACT FROM AUTHOR]

Marine emissions of dimethyl sulfide (DMS) and the subsequent formation of its oxidation products methane sulfonic acid (MSA) and sulfuric acid (H2SO4) are well-known natural precursors of atmospheric aerosols, contributing to particle mass and cloud formation over ocean and coastal regions. Despite a long-recognized and well-studied role in the marine troposphere, DMS oxidation chemistry remains a work in progress within many current air quality and climate models, with recent advances exploring heterogeneous chemistry and uncovering previously unknown intermediate species. With the identification of additional DMS oxidation pathways and intermediate species influencing its eventual fate, it is important to understand the impact of these pathways on the overall sulfate aerosol budget and aerosol size distribution. In this work, we update and evaluate the DMS oxidation mechanism of the chemical transport model GEOS-Chem by implementing expanded DMS oxidation pathways into the model. These updates include gas- and aqueous-phase reactions, the formation of the intermediates dimethyl sulfoxide (DMSO) and methane sulphinic acid (MSIA), as well as cloud loss and aerosol uptake of the recently quantified intermediate hydroperoxymethyl thioformate (HPMTF). We find that this updated mechanism collectively decreases the global mean surface-layer gas-phase sulfur dioxide (SO2) mixing ratio by 38 % and enhances sulfate aerosol (SO42-) mixing ratio by 16 %. We further perform sensitivity analyses exploring the contribution of cloud loss and aerosol uptake of HPMTF to the overall sulfur budget. Comparing modeled concentrations to available observations we find improved biases relative to previous studies. To quantify impacts of these chemistry updates on global particle size distributions and mass concentration we use the TOMAS aerosol microphysics module, finding changes in particle formation and growth affect the size distribution of aerosol. With this new DMS-oxidation scheme the global annual mean surface layer number concentration of particles with diameters smaller than 80 nm decreases by 12 %, with cloud loss processes related to HPMTF mostly responsible for this reduction. However, global annual mean number of particles larger than 80 nm increases by 4.5 %, suggesting that the new scheme promotes seasonal particle growth to these sizes capable of acting as cloud condensation nuclei (CCN). [ABSTRACT FROM AUTHOR]

To better understand the production and loss processes of volatile organic sulfur compounds (VSCs) and their influence factors, VSCs including carbon disulfide (CS2), dimethyl sulfide (DMS), and carbonyl sulfide (COS) were surveyed in the seawater and atmosphere of the Bohai and Yellow Seas during spring and summer of 2018. The concentration ranges of COS, DMS, and CS2 in the surface seawater during spring were 0.14-0.42, 0.41-7.74, and 0.01-0.18 nmol L-1, respectively, and 0.32-0.61, 1.31-18.12, and 0.01-0.65 nmol L-1 during summer. COS and CS2 had high concentrations in coastal waters, which may be due to elevated photochemical production rates. High DMS concentrations occurred near the Yellow River, Laizhou Bay, and Yangtze River Estuary coinciding with high nitrate and Chl a concentrations due to river discharge during summer. The depth distributions of COS, DMS, and CS2 were characterized by high concentrations in the surface seawater that decreased with depth. The mixing ratios of COS, DMS, and CS2 in the atmosphere were 255.9-620.2 pptv, 1.3-191.2 pptv, and 5.2-698.8 pptv during spring, and 394.6-850.1 pptv, 10.3-464.3 pptv, and 15.3-672.7 pptv in summer. The mean oceanic/at mospheric concentrations of COS, DMS, and CS2 were 1.8/1.7-, 3.1/4.7-, and 3.7/1.6-fold higher in summer than spring due to the high Chl a concentrations in summer. The mean sea-to-air fluxes of COS, DMS, and CS2 were 1.3-, 2.1-, and 3.0-fold higher in summer than spring. The sea-to-air fluxes of VSCs indicated that these marginal seas are major sources of VSCs in the atmosphere. The results provide help with a better understanding of the control of VSCs distributions in marginal seas. [ABSTRACT FROM AUTHOR]

Solar radiation management through artificially increasing the amount of stratospheric sulfate aerosol is being considered as a possible climate engineering method. To overcome the challenge of transporting the necessary amount of sulfur to the stratosphere, Quaglia and co-workers suggest deliberate emissions of carbonyl sulfide (OCS), a long-lived precursor of atmospheric sulfate. In their paper, published in Atmospheric Chemistry and Physics in 2022, they outline two scenarios with OCS emissions either at the Earth's surface or in the tropical upper troposphere and calculate the expected radiative forcing using a climate model. In our opinion, the study (i) neglects a significantly higher surface uptake that will inevitably be induced by the elevated atmospheric OCS concentrations and (ii) overestimates the net cooling effect of this OCS geoengineering approach due to some questionable parameterizations and assumptions in the radiative forcing calculations. In this commentary, we use state-of-the-art models to show that at the mean atmospheric OCS mixing ratios of the two emissions scenarios, the terrestrial biosphere and the oceans are expected to take up more OCS than is being released to reach these levels. Using chemistry climate models with a long-standing record for estimating the climate forcing of OCS and stratospheric aerosols, we also show that the net radiative forcing of the emission scenarios suggested by Quaglia and co-workers is smaller than suggested and insufficient to offset any significant portion of anthropogenically induced climate change. Our conclusion is that a geoengineering approach using OCS will not work under any circumstances and should not be considered further. [ABSTRACT FROM AUTHOR]

New regulations from the International Maritime Organization (IMO) limiting sulfur emissions from the shipping industry are expected to have large benefits in terms of public health but come with an undesired side effect: an acceleration of global warming as the climate-cooling effects of ship pollution on marine clouds is diminished. Previous work has found a substantial decrease in the detection of ship tracks in clouds after the IMO 2020 regulations went into effect but changes in large-scale cloud properties have been more equivocal. Using a statistical technique that estimates counterfactual fields of what large-scale cloud and radiative properties within an isolated shipping corridor in the southeastern Atlantic would have been in the absence of shipping, we confidently detect a reduction in the magnitude of cloud droplet effective radius decreases within the shipping corridor and find evidence for a reduction in the magnitude of cloud brightening as well. The instantaneous radiative forcing due to aerosol–cloud interactions from the IMO 2020 regulations is estimated as O (1 W m-2) within the shipping corridor, lending credence to global estimates of O (0.1 W m-2). In addition to their geophysical significance, our results also provide independent evidence for general compliance with the IMO 2020 regulations. [ABSTRACT FROM AUTHOR]

Solar radiation management through artificially increasing the amount of stratospheric sulfate aerosol is being considered as a possible climate engineering method. To overcome the challenge of transporting the necessary amount of sulfur to the stratosphere, Quaglia and co-workers suggest deliberate emissions of carbonyl sulfide (OCS), a long-lived precursor of atmospheric sulfate. In their paper, published in Atmospheric Chemistry and Physics in 2022, they outline two scenarios with OCS emissions either at the Earth's surface or in the tropical upper troposphere and calculate the expected radiative forcing using a climate model. In our opinion, the study (i) neglects a significantly higher surface uptake that will inevitably be induced by the elevated atmospheric OCS concentrations and (ii) overestimates the net cooling effect of this OCS geoengineering approach due to some questionable parameterizations and assumptions in the radiative forcing calculations. In this commentary, we use state of the art models to show that at the mean atmospheric OCS mixing ratios of the two emissions scenarios, the terrestrial biosphere and the oceans are expected to take up more OCS than is being released to reach these levels. Using chemistry climate models with a long-standing record for estimating the climate forcing of OCS and stratospheric aerosols, we also show that the net radiative forcing of the emission scenarios suggested by Quaglia and co-workers is smaller than suggested and insufficient to offset any significant portion of anthropogenically induced climate change. Our conclusion is that a geoengineering approach using OCS will not work under any circumstances and should not be considered further. [ABSTRACT FROM AUTHOR]

Anaerobic microbial sulfate reduction and oxidative sulfur cycling have been studied in long sediment cores mainly acquired as part of IODP explorations. The most remarkable observation in many of these studies is the existence of an active sulfur cycle in the deep subsurface sediments that have very low organic carbon content and are presumably refractory. Here we investigate the interstitial sulfate concentrations and sulfur isotope ratios in a 290 m long core collected from the eastern Arabian Sea at a water depth of 2663 m. Continuous decrease in pore water-sulfate concentrations with depth (up to 75 mbsf) coupled with enrichment in δ34SSO4 values suggests organoclastic sulfate reduction (OSR) processes attributed to the activity of sulfate-reducing bacteria (SRB) and retention of labile organic substrates amenable to the SRBs. Below a depth of 75 mbsf, the absence of a further reduction in sulfate concentrations indicates insufficient labile substrate to drive SRB. An increase in sulfate concentrations at the deeper subsurface (below 128.5 mbsf) coupled with decreasing δ34SSO4 values may be attributed to a ferric-oxyhydroxide driven oxidation of Fe-sulfide. This study reveals that even under deep aerobic water columns, organic matter may continue to be a source of labile organic substrates at significantly deeper subsurface. Enhanced sulfate concentrations in the deeper depths may be attributed to the oxidation of sulfides via ferric-oxyhydroxides buried deep within the sediment. A microbiological investigation may reveal further details of the sulfur cycle at the deep surface. [ABSTRACT FROM AUTHOR]

Forest liming is a management tool that has and continues to be used extensively across northern Europe to counteract acidification processes from anthropogenic sulfur and nitrogen (N) deposition. In this study, we quantified how liming affects soil organic carbon (SOC) stocks and attempt to disentangle the mechanisms responsible for the often contrasting processes that regulate net soil carbon (C) fluxes. Using a paired plot experimental design we compared SOC stocks in limed plots with adjacent unlimed control plots at 28 experimental sites to 60 cm soil depth in mature broadleaf and coniferous forests across Germany. Historical soil data from a subset of the paired experiment plots were analyzed to assess how SOC stocks in both control and limed plots changed between 1990 and 2019. Overall, we found that forest floor C stocks have been accumulating over time in the control plots. Liming however largely offset organic layer buildup in the L/O f layer, and forest floor C stocks remained unchanged over time in the limed plots. This, in turn, meant that nutrients remained mobile and were not bound in soil organic matter complexes. Results from the paired plot analysis showed that forest floor C stocks were significantly lower in limed plots than the control (- 34 %, - 8.4 ± 1.7 MgCha-1) but did not significantly affect SOC stocks in the mineral soil, when all sites are pooled together. In the forest floor layers, SOC stocks exhibited an exponential decrease with increasing pH, highlighting how lime-induced improvements in the biochemical environment stimulate organic matter (OM) decomposition. Nevertheless, for both forest floor and mineral soils, the magnitude and direction of the belowground C changes hinged directly on the inherent site characteristics, namely, forest type (conifer versus broadleaf), soil pH, soil texture, and the soil SOC stocks. On the other hand, SOC stock decreases were often offset by other processes that fostered C accumulation, such as improved forest productivity or increased carbon stabilization, which correspondingly translated to an overall variable response by SOC stocks, particularly in the mineral soil. Lastly, we measured soil carbon dioxide (CO2) and soil methane (CH4) flux immediately after a re-liming event at three of the experimental sites. Here, we found that (1) liming doubles CH4 uptake in the long-term; (2) soil organic matter mineralization processes respond quickly to liming, even though the duration and size of the CO2 flush varied between sites; and (3) lime-derived CO2 contributed very little to total CO2 emissions over the measurement period (determined using stable isotope approaches). [ABSTRACT FROM AUTHOR]

There is now substantial literature on climate model studies of equatorial or tropical stratospheric SO 2 injections that aim to counteract the surface warming produced by rising concentrations of greenhouse gases. Here we present the results from the first systematic intercomparison of climate responses in three Earth system models wherein the injection of SO 2 occurs at different latitudes in the lower stratosphere: CESM2-WACCM6, UKESM1.0 and GISS-E2.1-G. The first two use a modal aerosol microphysics scheme, while two versions of GISS-E2.1-G use a bulk aerosol (One-Moment Aerosol, OMA) and a two-moment (Multiconfiguration Aerosol TRacker of mIXing state, MATRIX) microphysics approach, respectively. Our aim in this work is to determine commonalities and differences between the climate model responses in terms of the distribution of the optically reflective sulfate aerosols produced from the oxidation of SO 2 and in terms of the surface response to the resulting reduction in solar radiation. A focus on understanding the contribution of characteristics of models transport alongside their microphysical and chemical schemes, and on evaluating the resulting stratospheric responses in different models, is given in the companion paper. The goal of this exercise is not to evaluate these single-point injection simulations as stand-alone proposed strategies to counteract global warming; instead we determine sources and areas of agreement and uncertainty in the simulated responses and, ultimately, the possibility of designing a comprehensive intervention strategy capable of managing multiple simultaneous climate goals through the combination of different injection locations. We find large disagreements between GISS-E2.1-G and the CESM2-WACCM6 and UKESM1.0 models regarding the magnitude of cooling per unit of aerosol optical depth (AOD) produced, which varies from 4.7 K per unit of AOD in CESM2-WACCM6 to 16.7 K in the GISS-E2.1-G version with two-moment aerosol microphysics. By normalizing the results with the global mean response in each of the models and thus assuming that the amount of SO 2 injected is a free parameter that can be managed independently, we highlight some commonalities in the overall distributions of the aerosols, in the inter-hemispheric surface temperature response and in shifts to the Intertropical Convergence Zone, as well as some areas of disagreement, such as the extent of the aerosol confinement in the equatorial region and the efficiency of the transport to polar latitudes. In conclusion, we demonstrate that it is possible to use these simulations to produce more comprehensive injection strategies in multiple climate models. However, large differences in the injection magnitudes can be expected, potentially increasing inter-model spreads in some stratospheric quantities (such as aerosol distribution) while reducing the spread in the surface response in terms of temperature and precipitation; furthermore, the selection of the injection locations may be dependent on the models' specific stratospheric transport. [ABSTRACT FROM AUTHOR]

The importance of dust heterogeneous oxidation in the removal of atmospheric SO 2 and formation of sulfate aerosols is not adequately understood. In this study, the Fe-, Ti-, and Al-bearing components, Na + , Cl - , K + , and Ca 2+ of the dust surface, were discovered to be closely associated with the heterogeneous formation of sulfate. Regression models were then developed to make a reliable prediction of the heterogeneous reactivity based on the particle chemical compositions. Further, the recognized gas-phase, aqueous-phase, and heterogeneous oxidation routes were quantitatively assessed and kinetically compared by combining the laboratory work with a modelling study. In the presence of 55 µ g m -3 airborne dust, heterogeneous oxidation accounts for approximately 28.6 % of the secondary sulfate aerosols during nighttime, while the proportion decreases to 13.1 % in the presence of solar irradiation. On the dust surface, heterogeneous drivers (e.g. transition metal constituents, water-soluble ions) are more efficient than surface-adsorbed oxidants (e.g. H 2 O 2 , NO 2 , O 3) in the conversion of SO 2 , particularly during nighttime. Dust heterogeneous oxidation offers an opportunity to explain the missing sulfate source during severe haze pollution events, and its contribution proportion in the complex atmospheric environments could be even higher than the current calculation results. Overall, the dust surface drivers are responsible for the significant formation of sulfate aerosols and have profound impacts on the atmospheric sulfur cycling. [ABSTRACT FROM AUTHOR]

Understanding how multiphase processes affect the iron-containing aerosol cycle is key to predicting ocean biogeochemistry changes and hence the feedback effects on climate. For this work, the EC-Earth Earth system model in its climate–chemistry configuration is used to simulate the global atmospheric oxalate (OXL), sulfate (SO 42-), and iron (Fe) cycles after incorporating a comprehensive representation of the multiphase chemistry in cloud droplets and aerosol water. The model considers a detailed gas-phase chemistry scheme, all major aerosol components, and the partitioning of gases in aerosol and atmospheric water phases. The dissolution of Fe-containing aerosols accounts kinetically for the solution's acidity, oxalic acid, and irradiation. Aerosol acidity is explicitly calculated in the model, both for accumulation and coarse modes, accounting for thermodynamic processes involving inorganic and crustal species from sea salt and dust. Simulations for present-day conditions (2000–2014) have been carried out with both EC-Earth and the atmospheric composition component of the model in standalone mode driven by meteorological fields from ECMWF's ERA-Interim reanalysis. The calculated global budgets are presented and the links between the (1) aqueous-phase processes, (2) aerosol dissolution, and (3) atmospheric composition are demonstrated and quantified. The model results are supported by comparison to available observations. We obtain an average global OXL net chemical production of 12.615 ± 0.064 Tg yr -1 in EC-Earth, with glyoxal being by far the most important precursor of oxalic acid. In comparison to the ERA-Interim simulation, differences in atmospheric dynamics and the simulated weaker oxidizing capacity in EC-Earth overall result in a ∼ 30 % lower OXL source. On the other hand, the more explicit representation of the aqueous-phase chemistry in EC-Earth compared to the previous versions of the model leads to an overall ∼ 20 % higher sulfate production, but this is still well correlated with atmospheric observations. The total Fe dissolution rate in EC-Earth is calculated at 0.806 ± 0.014 Tg yr -1 and is added to the primary dissolved Fe (DFe) sources from dust and combustion aerosols in the model (0.072 ± 0.001 Tg yr -1). The simulated DFe concentrations show a satisfactory comparison with available observations, indicating an atmospheric burden of ∼ 0.007 Tg, resulting in an overall atmospheric deposition flux into the global ocean of 0.376 ± 0.005 Tg yr -1 , which is well within the range reported in the literature. All in all, this work is a first step towards the development of EC-Earth into an Earth system model with fully interactive bioavailable atmospheric Fe inputs to the marine biogeochemistry component of the model. [ABSTRACT FROM AUTHOR]

In the low-nutrient, redox-stratified Lake Medard (Czechia), reductive Fe(III) dissolution outpaces sulfide generation from microbial sulfate reduction (MSR) and ferruginous conditions occur without quantitative sulfate depletion. The lake currently has marked overlapping C, N, S, Mn and Fe cycles occurring in the anoxic portion of the water column. This feature is unusual in stable, natural, redox-stratified lacustrine systems where at least one of these biogeochemical cycles is functionally diminished or undergoes minimal transformations because of the dominance of another component or other components. Therefore, this post-mining lake has scientific value for (i) testing emerging hypotheses on how such interlinked biogeochemical cycles operate during transitional redox states and (ii) acquiring insight into redox proxy signals of ferruginous sediments underlying a sulfatic and ferruginous water column. An isotopically constrained estimate of the rates of sulfate reduction (SRRs) suggests that despite high genetic potential, this respiration pathway may be limited by the rather low amounts of metabolizable organic carbon. This points to substrate competition exerted by iron- and nitrogen-respiring prokaryotes. Yet, the planktonic microbial succession across the nitrogenous and ferruginous zones also indicates genetic potential for chemolithotrophic sulfur oxidation. Therefore, our SRR estimates could rather be portraying high rates of anoxic sulfide oxidation to sulfate, probably accompanied by microbially induced disproportionation of S intermediates. Near and at the anoxic sediment–water interface, vigorous sulfur cycling can be fuelled by ferric and manganic particulate matter and redeposited siderite stocks. Sulfur oxidation and disproportionation then appear to prevent substantial stabilization of iron monosulfides as pyrite but enable the interstitial precipitation of microcrystalline equant gypsum. This latter mineral isotopically recorded sulfur oxidation proceeding at near equilibrium with the ambient anoxic waters, whilst authigenic pyrite sulfur displays a 38 ‰ to 27 ‰ isotopic offset from ambient sulfate, suggestive of incomplete MSR and open sulfur cycling. Pyrite-sulfur fractionation decreases with increased reducible reactive iron in the sediment. In the absence of ferruginous coastal zones today affected by post-depositional sulfate fluxes, the current water column redox stratification in the post-mining Lake Medard is thought relevant for refining interpretations pertaining to the onset of widespread redox-stratified states across ancient nearshore depositional systems. [ABSTRACT FROM AUTHOR]

Aerosol indirect radiative forcing (IRF), which characterizes how aerosols alter cloud formation and properties, is very sensitive to the preindustrial (PI) aerosol burden. Dimethyl sulfide (DMS), emitted from the ocean, is a dominant natural precursor of non-sea-salt sulfate in the PI and pristine present-day (PD) atmospheres. Here we revisit the atmospheric oxidation chemistry of DMS, particularly under pristine conditions, and its impact on aerosol IRF. Based on previous laboratory studies, we expand the simplified DMS oxidation scheme used in the Community Atmospheric Model version 6 with chemistry (CAM6-chem) to capture the OH-addition pathway and the H-abstraction pathway and the associated isomerization branch. These additional oxidation channels of DMS produce several stable intermediate compounds, e.g., methanesulfonic acid (MSA) and hydroperoxymethyl thioformate (HPMTF), delay the formation of sulfate, and, hence, alter the spatial distribution of sulfate aerosol and radiative impacts. The expanded scheme improves the agreement between modeled and observed concentrations of DMS, MSA, HPMTF, and sulfate over most marine regions, based on the NASA Atmospheric Tomography (ATom), the Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA), and the Variability of the American Monsoon Systems (VAMOS) Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) measurements. We find that the global HPMTF burden and the burden of sulfate produced from DMS oxidation are relatively insensitive to the assumed isomerization rate, but the burden of HPMTF is very sensitive to a potential additional cloud loss. We find that global sulfate burden under PI and PD emissions increase to 412 Gg S (+ 29 %) and 582 Gg S (+ 8.8 %), respectively, compared to the standard simplified DMS oxidation scheme. The resulting annual mean global PD direct radiative effect of DMS-derived sulfate alone is - 0.11 W m -2. The enhanced PI sulfate produced via the gas-phase chemistry updates alone dampens the aerosol IRF as anticipated (- 2.2 W m -2 in standard versus - 1.7 W m -2 , with updated gas-phase chemistry). However, high clouds in the tropics and low clouds in the Southern Ocean appear particularly sensitive to the additional aqueous-phase pathways, counteracting this change (- 2.3 W m -2). This study confirms the sensitivity of aerosol IRF to the PI aerosol loading and the need to better understand the processes controlling aerosol formation in the PI atmosphere and the cloud response to these changes. [ABSTRACT FROM AUTHOR]

The injection of sulfur into the stratosphere by volcanic eruptions is the dominant driver of natural climate variability on interannual-to-multidecadal timescales. Based on a set of continuous sulfate and sulfur records from a suite of ice cores from Greenland and Antarctica, the HolVol v.1.0 database includes estimates of the magnitudes and approximate source latitudes of major volcanic stratospheric sulfur injection (VSSI) events for the Holocene (from 9500 BCE or 11500 year BP to 1900 CE), constituting an extension of the previous record by 7000 years. The database incorporates new-generation ice-core aerosol records with sub-annual temporal resolution and demonstrated sub-decadal dating accuracy and precision. By tightly aligning and stacking the ice-core records on the WD2014 chronology from Antarctica we resolve long-standing previous inconsistencies in the dating of ancient volcanic eruptions that arise from biased (i.e. dated too old) ice-core chronologies over the Holocene for Greenland. We reconstruct a total of 850 volcanic eruptions with injections in excess of 1 TgS, of which 329 (39 %) are located in the low latitudes with bipolar sulfate deposition, 426 (50 %) are located in the Northern Hemisphere (NH) extratropics and 88 (10 %) are located in the Southern Hemisphere (SH) extratropics. The spatial distribution of reconstructed eruption locations is in agreement with prior reconstructions for the past 2,500 years, and follows the global distribution of landmasses. In total, these eruptions injected 7410 TgS in the stratosphere, for which tropical eruptions accounted for 70 % and NH extratropics for 25 %. A long-term latitudinally and monthly resolved stratospheric aerosol optical depth (SAOD) time series is reconstructed from the HolVol VSSI estimates, representing the first Holocene-scale reconstruction constrained by Greenland and Antarctica ice cores. These new long-term reconstructions of past VSSI and SAOD variability confirm evidence from regional volcanic eruption chronologies (e.g., from Iceland) in showing that the early Holocene (9500-7000 BCE) experienced a higher number of volcanic eruptions (+16 %) and cumulative VSSI (+86 %) compared to the past 2,500 years. This increase coincides with the rapid retreat of ice sheets during deglaciation, providing context for potential future increases of volcanic activity in regions under projected glacier melting in the 21st century. The reconstructed VSSI and SAOD data are available at https://doi.pangaea.de/10.1594/PANGAEA.928646 (Sigl et al., 2021). [ABSTRACT FROM AUTHOR]

A stationary, computationally efficient scheme ChAP 1.0 (Chemical and Aerosol Processes, version 1.0) for the sulfur cycle in the troposphere is developed. This scheme is designed for Earth system models of intermediate complexity (EMICs). The scheme accounts for sulfur dioxide emissions into the atmosphere, its deposition to the surface, oxidation to sulfates, and dry and wet deposition of sulfates on the surface. The calculations with the scheme are forced by anthropogenic emissions of sulfur dioxide into the atmosphere for 1850–2000 adopted from the CMIP5 dataset and by the ERA-Interim meteorology assuming that natural sources of sulfur into the atmosphere remain unchanged during this period. The ChAP output is compared to changes of the tropospheric sulfur cycle simulations with the CMIP5 data, with the IPCC TAR ensemble, and with the ACCMIP phase II simulations. In addition, in regions of strong anthropogenic sulfur pollution, ChAP results are compared to other data, such as the CAMS reanalysis, EMEP MSC-W, and individual model simulations. Our model reasonably reproduces characteristics of the tropospheric sulfur cycle known from these information sources. In our scheme, about half of the emitted sulfur dioxide is deposited to the surface, and the rest is oxidised into sulfates. In turn, sulfates are mostly removed from the atmosphere by wet deposition. The lifetimes of the sulfur dioxide and sulfates in the atmosphere are close to 1 and 5 d, respectively. The limitations of the scheme are acknowledged, and the prospects for future development are figured out. Despite its simplicity, ChAP may be successfully used to simulate anthropogenic sulfur pollution in the atmosphere at coarse spatial scales and timescales. [ABSTRACT FROM AUTHOR]

Aerosol–cloud interactions contribute to the large uncertainties in current estimates of climate forcing. We investigated the effect of aerosol particles on cloud droplet formation by model calculations and aircraft measurements over the Amazon and over the western tropical Atlantic during the ACRIDICON–CHUVA campaign in September 2014. On the HALO (High Altitude Long Range Research) research aircraft, cloud droplet number concentrations (Nd) were measured near the base of clean and polluted growing convective cumuli using a cloud combination probe (CCP) and a cloud and aerosol spectrometer (CAS-DPOL). An adiabatic parcel model was used to perform cloud droplet number closure studies for flights in differently polluted air masses. Model input parameters included aerosol size distributions measured with an ultra-high sensitive aerosol spectrometer (UHSAS), in combination with a condensation particle counter (CPC). Updraft velocities (w) were measured with a boom-mounted Rosemount probe. Over the continent, the aerosol size distributions were dominated by accumulation mode particles, and good agreement between measured and modeled Nd values was obtained (deviations ≲ 10 %) assuming an average hygroscopicity of κ∼0.1 , which is consistent with Amazonian biomass burning and secondary organic aerosol. Above the ocean, fair agreement was obtained assuming an average hygroscopicity of κ∼0.2 (deviations ≲ 16 %) and further improvement was achieved assuming different hygroscopicities for Aitken and accumulation mode particles (κAit=0.8 , κacc=0.2 ; deviations ≲ 10 %), which may reflect secondary marine sulfate particles. Our results indicate that Aitken mode particles and their hygroscopicity can be important for droplet formation at low pollution levels and high updraft velocities in tropical convective clouds. [ABSTRACT FROM AUTHOR]

In the aqueous oligotrophic ecosystem of a post-mining lake (Lake Medard, Czechia), reductive Fe(II) dissolution outpaces sulfide generation from microbial sulfate reduction (MSR), and ferruginous conditions occur without quantitative sulfate depletion. An isotopically constrained estimate of the rates of sulfate reduction (SRR) suggests that despite a high genetic potential, this respiration pathway may be limited by the rather low amounts of metabolizable organic carbon. This points to substrate competition exerted by iron and nitrogen respiring prokaryotes. Yet, the microbial succession across the nitrogenous and ferruginous zones of the bottom water column also indicates sustained genetic potential for chemolithotrophic sulfur oxidation. Therefore, our isotopic SRR estimates could be rather portraying high rates of anoxic sulfide oxidation to sulfate, probably accompanied by microbially induced disproportionation of S intermediates. Near and at the anoxic sediment-water interface, vigorous sulfur cycling can be fuelled by ferric and manganic particulate matter and redeposited siderite stocks. Sulfur oxidation and disproportionation then appear to prevent substantial stabilization of iron monosulfides as pyrite but can enable the interstitial precipitation of small proportions of equant microcrystalline gypsum. This latter mineral isotopically fingerprints sulfur oxidation proceeding at near equilibrium with the ambient anoxic waters, whilst authigenic pyrite-sulfur displays a 38 to 27 ‰ isotopic offset from ambient sulfate, suggestive of incomplete MSR and likely reflective also of an open sulfur cycling system. Pyrite-sulfur fractionation decreases with increased reducible reactive iron in the sediment. In the absence of ferruginous coastal zones today, the current water column redox stratification in the post-mining Lake Medard has scientific value for (i) testing emerging hypotheses on how a few interlinked biogeochemical cycles operated in nearshore paleoenvironments during redox transitional states; and (ii) to acquire insight on how similar early diagenetic redox proxy signals developed in sediments affected by analogue transitional states in ancient water columns. [ABSTRACT FROM AUTHOR]

Understanding how multiphase processes affect the iron-containing aerosol cycle is key to predict ocean biogeochemistry changes and hence the feedback effects on climate. For this work, the EC-Earth Earth system model in its climate-chemistry configuration is used to simulate the global atmospheric oxalate (OXL), sulfate (SO42-), and iron (Fe) cycles, after incorporating a comprehensive representation of the multiphase chemistry in cloud droplets and aerosol water. The model considers a detailed gas-phase chemistry scheme, all major aerosol components, and the partitioning of gases in aerosol and atmospheric water phases. The dissolution of Fe-containing aerosols accounts kinetically for the solution's acidity, oxalic acid, and irradiation. Aerosol acidity is explicitly calculated in the model, both for accumulation and coarse modes, accounting for thermodynamic processes involving inorganic and crustal species from sea salt and dust. Simulations for present-day conditions (2000-2014) have been carried out with both EC-Earth and the atmospheric composition component of the model in standalone mode driven by meteorological fields from ECMWF's ERA-Interim reanalysis. The calculated global budgets are presented and the links between the 1) aqueous-phase processes, 2) aerosol dissolution, and 3) atmospheric composition, are demonstrated and quantified. The model results are supported by comparison to available observations. We obtain an average global OXL net chemical production of 12.61 ± 0.06 Tg yr-1 in EC-Earth, with glyoxal being by far the most important precursor of oxalic acid. In comparison to the ERA-Interim simulation, differences in atmospheric dynamics as well as the simulated weaker oxidizing capacity in EC-Earth result overall in a ~30 % lower OXL source. On the other hand, the more explicit representation of the aqueous-phase chemistry in EC-Earth compared to the previous versions of the model leads to an overall ~20 % higher sulfate production, but still well correlated with atmospheric observations. The total Fe dissolution rate in EC-Earth is calculated at 0.806 ± 0.014 Tg Fe yr-1 and is added to the primary dissolved Fe (DFe) sources from dust and combustion aerosols in the model (0.072 ± 0.001 Tg Fe yr-1). The simulated DFe concentrations show a satisfactory comparison with available observations, indicating an atmospheric burden of ~0.007 Tg Fe, and overall resulting in an atmospheric deposition flux into the global ocean of 0.376 ± 0.005 Tg Fe yr-1, well within the range reported in the literature. All in all, this work is a first step towards the development of EC-Earth into an Earth System Model with fully interactive bioavailable atmospheric Fe inputs to the marine biogeochemistry component of the model. [ABSTRACT FROM AUTHOR]

Anaerobic oxidation of methane (AOM) is one of the major processes limiting the release of the greenhouse gas methane from natural environments. In Lake Kinneret sediments, iron-coupled AOM (Fe-AOM) was suggested to play a substantial role (10-15% relative to methanogenesis) in the methanic zone (>20 cm sediment depth), based on geochemical profiles and experiments on fresh sediments. Apparently, the oxidation of methane is mediated by a combination of mcr gene bearing archaea and aerobic bacterial methanotrophs. Here we aimed to investigate the survival of this complex microbial interplay under controlled conditions. We followed the AOM process during long19 term (~ 18 months) anaerobic slurry experiments of these methanic sediments with two stages of incubations and additions of 13C-labeled methane, multiple electron acceptors and inhibitors. After these incubation stages carbon isotope measurements in the dissolved inorganic pool still showed considerable AOM (3-8% relative to methanogenesis). Specific lipid carbon isotope measurements and metagenomic analyses indicate that after the prolonged incubation aerobic methanotrophic bacteria were no longer involved in the oxidation process, whereas mcr gene bearing archaea were most likely responsible for oxidizing the methane. Humic substances and iron oxides are likely electron acceptors to support this oxidation, whereas sulfate, manganese, nitrate, and nitrite did not support the AOM in these methanic sediments. Our results suggest in the natural lake sediments methanotrophic bacteria are responsible for part of the methane oxidation by the reduction of combined micro levels of oxygen and iron oxides in a cryptic cycle, while the rest of the methane is converted by reverse methanogenesis. After long-term incubation, the latter prevails without bacterial methanotropic activity and with a different iron reduction pathway. [ABSTRACT FROM AUTHOR]

As an important atmosphere constituent, sulfate aerosols exert profound impacts on climate, the ecological environment, and human health. The Tibetan Plateau (TP), identified as the "Third Pole", contains the largest land ice masses outside the poles and has attracted widespread attention for its environment and climatic change. However, the mechanisms of sulfate formation in this specific region still remain poorly characterized. An oxygen-17 anomaly (Δ17O) has been used as a probe to constrain the relative importance of different pathways leading to sulfate formation. Here, we report the Δ17O values in atmospheric sulfate collected at a remote site in the Mt. Everest region to decipher the possible formation mechanisms of sulfate in such a pristine environment. Throughout the sampling campaign (April–September 2018), the Δ17O in non-dust sulfate show an average of 1.7‰±0.5 ‰, which is higher than most existing data on modern atmospheric sulfate. The seasonality of Δ17O in non-dust sulfate exhibits high values in the pre-monsoon and low values in the monsoon, opposite to the seasonality in Δ17O for both sulfate and nitrate (i.e., minima in the warm season and maxima in the cold season) observed from diverse geographic sites. This high Δ17O in non-dust sulfate found in this region clearly indicates the important role of the S(IV)+O3 pathway in atmospheric sulfate formation promoted by conditions of high cloud water pH. Overall, our study provides an observational constraint on atmospheric acidity in altering sulfate formation pathways, particularly in dust-rich environments, and such identification of key processes provides an important basis for a better understanding of the sulfur cycle in the TP. [ABSTRACT FROM AUTHOR]

The coupled biogeochemical cycles of iron and sulfur are central to the long-term biogeochemical evolution of Earth's oceans. For instance, before the development of a persistently oxygenated deep ocean, the ocean interior likely alternated between states buffered by reduced sulfur ("euxinic") and buffered by reduced iron ("ferruginous"), with important implications for the cycles and hence bioavailability of dissolved iron (and phosphate). Even after atmospheric oxygen concentrations rose to modern-like values, the ocean episodically continued to develop regions of euxinic or ferruginous conditions, such as those associated with past key intervals of organic carbon deposition (e.g. during the Cretaceous) and extinction events (e.g. at the Permian–Triassic boundary). A better understanding of the cycling of iron and sulfur in an anoxic ocean, how geochemical patterns in the ocean relate to the available spatially heterogeneous geological observations, and quantification of the feedback strengths between nutrient cycling, biological productivity, and ocean redox requires a spatially resolved representation of ocean circulation together with an extended set of (bio)geochemical reactions. Here, we extend the "muffin" release of the intermediate-complexity Earth system model cGENIE to now include an anoxic iron and sulfur cycle (expanding the existing oxic iron and sulfur cycles), enabling the model to simulate ferruginous and euxinic redox states as well as the precipitation of reduced iron and sulfur minerals (pyrite, siderite, greenalite) and attendant iron and sulfur isotope signatures, which we describe in full. Because tests against present-day (oxic) ocean iron cycling exercises only a small part of the new code, we use an idealized ocean configuration to explore model sensitivity across a selection of key parameters. We also present the spatial patterns of concentrations and δ56Fe and δ34 S isotope signatures of both dissolved and solid-phase Fe and S species in an anoxic ocean as an example application. Our sensitivity analyses show that the first-order results of the model are relatively robust against the choice of kinetic parameter values within the Fe–S system and that simulated concentrations and reaction rates are comparable to those observed in process analogues for ancient oceans (i.e. anoxic lakes). Future model developments will address sedimentary recycling and benthic iron fluxes back to the water column, together with the coupling of nutrient (in particular phosphate) cycling to the iron cycle. [ABSTRACT FROM AUTHOR]

A gas detection system has been developed, characterized, and deployed for pressurized gas-phase sample analyses and near-real-time online measurements. It consists of a cryogenic pre-concentrator (CryoTrap), a gas chromatograph (GC), and a new high-resolution atomic emission detector (AED III HR). Here the CryoTrap–GC–AED instrumental setup is presented, and the performance for iodine (1635 ± 135 counts I atom -1 pptv -1), sulfur (409 ± 57 counts S atom -1 pptv -1), carbon (636 ± 69 counts C atom -1 pptv -1), bromine (9.1 ± 1.8 counts Br atom -1 pptv -1), and nitrogen (28 ± 2 counts N atom -1 pptv -1) emission lines is reported and discussed. The limits of detection (LODs) are in the low parts per trillion by volume range (0.5–9.7 pptv), and the signal is linear to at least 4 orders of magnitude, which makes it a suitable method for diverse volatile organic compound (VOC) measurements in the atmosphere, even in remote unpolluted regions. The new system was utilized in a field study in a boreal forest at Hyytiälä, Finland, in late summer 2016, which made monoterpene measurements possible among other VOCs. Furthermore, pressurized global whole-air samples, collected on board the Lufthansa Airbus A340-600 IAGOS–CARIBIC aircraft in the upper troposphere and lower stratosphere region, were measured with the new setup, providing data for many VOCs, including the long-lived organosulfur compound carbonyl sulfide. [ABSTRACT FROM AUTHOR]

Marine sedimentation rate and bottom-water O2 concentration control the remineralization/sequestration of organic carbon across continental margins; but whether/how they shape microbiome architecture (the ultimate effector of all biogeochemical phenomena), across shelf/slope sediments, is unknown. Here we reveal distinct microbiome structures and functions, amidst comparable pore fluid chemistries, along 300 cm sediment horizons underlying the seasonal (shallow coastal) and perennial (deep sea) oxygen minimum zones (OMZs) of the Arabian Sea, situated across the western-Indian margin (water-depths: 31 m and, 530 and 580 m, respectively). The sedimentary geomicrobiology was elucidated by analyzing metagenomes, metatranscriptomes, and enrichment cultures, and also sedimentation rates measured by radiocarbon and lead excess (210Pbxs); the findings were then evaluated in the light of the other geochemical data available for the cores investigated. Along the perennial- and seasonal-OMZ sediment cores, microbial communities were dominated by Gammaproteobacteria and Alphaproteobacteria, and Euryarchaeota and Firmicutes, respectively. As a perennial-OMZ signature, a cryptic methane production-consumption cycle was found to operate near the sediment-surface (within the sulfate reduction zone); overall diversity, as well as the relative abundances of simple-fatty-acids-requiring anaerobes (methanogens, anaerobic methane-oxidizers, sulfate-reducers and acetogens), peaked in the topmost sediment-layer and then declined via synchronized fluctuations until the sulfate-methane transition zone was reached. The entire microbiome profile was reverse in the seasonal-OMZ sediment horizon. In the perennial-OMZ sediments organic carbon deposited was higher in concentration and marine components-rich, so it potentially degraded readily to simple fatty acids; lower sedimentation rate afforded higher O2 exposure time for organic matter degradation despite perennial hypoxia in the bottom-water; thus, the resultant abundance of reduced carbon substrates sustained multiple inter-competing microbial processes in the upper sediment-layers. Remarkably, the whole geomicrobial scenario was opposite in the sediments of the seasonal/shallow-water OMZ. Our findings create a microbiological baseline for understanding carbon-sulfur cycling across distinct marine depositional settings and water-column oxygenation regimes. [ABSTRACT FROM AUTHOR]

The coupled biogeochemical cycles of iron and sulphur are central to the long-term biogeochemical evolution of Earth's oceans. For instance, before the development of a persistently oxygenated deep ocean, the ocean interior likely alternated between states buffered by reduced sulphur (euxinic) vs. buffered by reduced iron (ferruginous), with important implications for the cycles and hence bioavailability of dissolved iron (and phosphate). Even after atmospheric oxygen concentrations rose to modern-like values, the ocean continued, episodically, to develop regions of euxinic or ferruginous conditions, such as associated with past key intervals of organic carbon deposition (e.g. during the Cretaceous) as well as extinction events (e.g. at the Permian/Triassic boundary). A better understanding of the cycling of iron and sulphur in an anoxic ocean, how geochemical patterns in the ocean relate to the available spatially heterogeneous geological observations, and quantification of the feedback strengths between nutrient cycling, biological productivity, and ocean redox, requires a spatially-resolved representation of ocean circulation together with an extended set of (bio)geochemical reactions. Here, we extend the muffin release of the intermediate-complexity Earth system model cGENIE, to now include an anoxic iron and sulphur cycle, enabling the model to simulate ferruginous and euxinic redox states as well as the precipitation of reduced iron and sulphur minerals (pyrite, siderite, greenalite) and attendant iron and sulphur isotope signatures, which we describe in full. While we cannot make direct model comparison with present-day (oxic) ocean observations, we use an idealized ocean configuration to explore model sensitivity across a selection of key parameters. We also present the spatial patterns of concentrations and δ56Fe isotope signatures of both dissolved and solid-phase Fe species in an anoxic ocean as an example application. Our sensitivity analyses show how the first-order results of the model are relatively robust against the choice default kinetic parameters within the Fe-S system, and that simulated concentrations and reaction rates are comparable to those observed in process analogues for ancient oceans (i.e., anoxic lakes). Future model developments will address sedimentary recycling and benthic iron fluxes back to the water column, together with the coupling of nutrient (in particular phosphate) cycling to the iron cycle. [ABSTRACT FROM AUTHOR]

The methane (CH 4) cycle is a key component of the Earth system that links planetary climate, biological metabolism, and the global biogeochemical cycles of carbon, oxygen, sulfur, and hydrogen. However, currently lacking is a numerical model capable of simulating a diversity of environments in the ocean, where CH 4 can be produced and destroyed, and with the flexibility to be able to explore not only relatively recent perturbations to Earth's CH 4 cycle but also to probe CH 4 cycling and associated climate impacts under the very low-O 2 conditions characteristic of most of Earth's history and likely widespread on other Earth-like planets. Here, we present a refinement and expansion of the ocean–atmosphere CH 4 cycle in the intermediate-complexity Earth system model cGENIE, including parameterized atmospheric O 2 –O 3 –CH 4 photochemistry and schemes for microbial methanogenesis, aerobic methanotrophy, and anaerobic oxidation of methane (AOM). We describe the model framework, compare model parameterizations against modern observations, and illustrate the flexibility of the model through a series of example simulations. Though we make no attempt to rigorously tune default model parameters, we find that simulated atmospheric CH 4 levels and marine dissolved CH 4 distributions are generally in good agreement with empirical constraints for the modern and recent Earth. Finally, we illustrate the model's utility in understanding the time-dependent behavior of the CH 4 cycle resulting from transient carbon injection into the atmosphere, and we present model ensembles that examine the effects of atmospheric p O 2 , oceanic dissolved SO 42- , and the thermodynamics of microbial metabolism on steady-state atmospheric CH 4 abundance. Future model developments will address the sources and sinks of CH 4 associated with the terrestrial biosphere and marine CH 4 gas hydrates, both of which will be essential for comprehensive treatment of Earth's CH 4 cycle during geologically recent time periods. [ABSTRACT FROM AUTHOR]

This study investigates the chemical composition of PM 2.5 collected at a central location in Beijing, China, during winter 2016 and summer 2017. The samples were characterised using direct-infusion negative-nano-electrospray-ionisation ultrahigh-resolution mass spectrometry to elucidate the composition and the potential primary and secondary sources of the organic fraction. The samples from the two seasons were compared with those from a road-tunnel site and an urban background site in Birmingham, UK, analysed in the course of an earlier study using the same method. There were strong differences in aerosol particle composition between the seasons, particularly regarding (poly-)aromatic compounds, which were strongly enhanced in winter, likely due to increased fossil fuel and biomass burning for heating. In addition to the seasonal differences, compositional differences between high- and low-pollution conditions were observed, with the contribution of sulfur-containing organic compounds strongly enhanced under high-pollution conditions. There was a correlation of the number of sulfur-containing molecular formulae with the concentration of particulate sulfate, consistent with a particle-phase formation process. [ABSTRACT FROM AUTHOR]

To explore the potential role of tetrathionate in the sedimentary sulfur cycle, population ecology of microorganisms capable of metabolizing this polythionate was revealed at 15–30 cm resolution along two, ∼3 m long, cores collected from 530 and 580 m below the sea level, off India's west coast, within the oxygen minimum zone (OMZ) of the Arabian Sea. Metagenome analysis along the cores revealed widespread occurrence of genes involved in the formation, oxidation, and reduction of tetrathionate; high diversity and relative abundance were also detected for bacteria that are known to render these metabolisms in vitro. Results of slurry culture of the sediment samples in thiosulfate- or tetrathionate-containing microbial growth media, data obtained via pure-culture isolation, and finally metatranscriptome analyses corroborated the in situ functionality of the tetrathionate-forming, tetrathionate-oxidizing, and tetrathionate-reducing microorganisms. Ion chromatography of pore waters revealed the presence of up to 11.1 µ M thiosulfate in the two cores, whereas tetrathionate remained undetected in spectroscopic assay based on its reaction with cyanide. While thiosulfate oxidation by chemolithotrophic bacteria prevalent in situ is the apparent source of tetrathionate in this ecosystem, high biochemical and geochemical reactivity of this polythionate could be instrumental in its cryptic status in the sulfur cycle. Potential abiotic origin of tetrathionate in the sediment horizon explored could neither be ruled out nor confirmed from the geochemical information available. On the other hand, tetrathionate potentially present in the system can be either oxidized to sulfate or reduced back to thiosulfate/sulfide via chemolithotrophic oxidation and respiration by native bacterial populations, respectively. Up to 2.01 mM sulfide present in the sediment cores may also reduce tetrathionate abiotically to thiosulfate and elemental sulfur. However, in the absence of measured data for O2 or other oxyanions having possibilities of serving as electron acceptors, the biogeochemical modalities of the oxidative half of the tetrathionate cycle remained unresolved. [ABSTRACT FROM AUTHOR]

To explore the potential role of tetrathionate in the sulfur cycle of marine sediments, population ecology of microorganisms capable of metabolizing this polythionate was revealed at 15-30 cm resolution along two, ~ 3-m-long, cores collected from 530 and 580 meters below the sea level, off India's west coast, within the oxygen minimum zone (OMZ) of the Arabian Sea. Metagenome analysis along the two sediment-cores revealed widespread occurrence of genes involved in microbial formation, oxidation, and reduction of tetrathionate; high diversity and relative-abundance was also detected for bacteria that are known to render these metabolisms in vitro. Results of slurry-incubation of the sediment-samples in thiosulfate- or tetrathionate-containing microbial growth media, data obtained via pure-culture isolation, and finally metatranscriptome analyses, corroborated the in situ functionality of tetrathionate-forming, oxidizing, and reducing microorganisms. Geochemical analyses revealed the presence of up to 11.1 μM thiosulfate along the two cores, except a few sample-sites near the sediment-surface. Thiosulfate oxidation by chemolithotrophic bacteria prevalent in situ is the apparent source of tetrathionate in this ecosystem. However, potential abiotic origin of the polythionate can neither be ruled out nor confirmed from the geochemical information currently available for this territory. Tetrathionate, in turn, can be either oxidized to sulfate (via oxidation by the chemolithotrophs present) or reduced back to thiosulfate (via respiration by native bacteria). Up to 2.01 mM sulfide present in the sediment-cores may also reduce tetrathionate abiotically to thiosulfate and elemental sulfur. As tetrathionate was not detected in situ, high microbiological and geochemical reactivity of this polythionate was hypothesized to be instrumental in its cryptic status as a central sulfur cycle intermediate. [ABSTRACT FROM AUTHOR]

This article describes the IFS-AER aerosol module used operationally in the Integrated Forecasting System (IFS) cycle 45R1, operated by the European Centre for Medium-Range Weather Forecasts (ECMWF) in the framework of the Copernicus Atmospheric Monitoring Services (CAMS). We describe the different parameterizations for aerosol sources, sinks, and its chemical production in IFS-AER, as well as how the aerosols are integrated in the larger atmospheric composition forecasting system. The focus is on the entire 45R1 code base, including some components that are not used operationally, in which case this will be clearly specified. This paper is an update to the article that described aerosol forecasts at the ECMWF using cycle 32R2 of the IFS. Between cycles 32R2 and 45R1, a number of source and sink processes have been reviewed and/or added, notably increasing the complexity of IFS-AER. A greater integration with the tropospheric chemistry scheme of the IFS has been achieved for the sulfur cycle and for nitrate production. Two new species, nitrate and ammonium, have also been included in the forecasting system. Global budgets and aerosol optical depth (AOD) fields are shown, as is an evaluation of the simulated particulate matter (PM) and AOD against observations, showing an increase in skill from cycle 40R2, used in the CAMS interim ReAnalysis (CAMSiRA), to cycle 45R1. [ABSTRACT FROM AUTHOR]

We developed an optimal-estimation algorithm to simultaneously retrieve, for the first time, coexisting volcanic gaseous SO2 and sulfate aerosols (SA) from ground-based Fourier transform infrared (FTIR) observations. These effluents, both linked to magmatic degassing process and subsequent atmospheric evolution processes, have overlapping spectral signatures leading to mutual potential interferences when retrieving one species without considering the other. We show that significant overestimations may be introduced in SO2 retrievals if the radiative impact of coexistent SA is not accounted for, which may have impacted existing SO2 long-term series, e.g. from satellite platforms. The method was applied to proximal observations at Masaya volcano, where SO2 and SA concentrations, and SA acidity, were retrieved. A gas-to-particle sulfur partitioning of 400 and a strong SA acidity (sulfuric acid concentration: 65 %) were found, consistent with past in situ observations at this volcano. This method is easily exportable to other volcanoes to monitor magma extraction processes and the atmospheric sulfur cycle in the case of ash-free plumes. [ABSTRACT FROM AUTHOR]

SOCOL-AERv1 was developed as an aerosol–chemistry–climate model to study the stratospheric sulfur cycle and its influence on climate and the ozone layer. It includes a sectional aerosol model that tracks the sulfate particle size distribution in 40 size bins, between 0.39 nm and 3.2 µm. showed that SOCOL-AERv1 successfully matched observable quantities related to stratospheric aerosol. In the meantime, SOCOL-AER has undergone significant improvements and more observational datasets have become available. In producing SOCOL-AERv2 we have implemented several updates to the model: adding interactive deposition schemes, improving the sulfate mass and particle number conservation, and expanding the tropospheric chemistry scheme. We compare the two versions of the model with background stratospheric sulfate aerosol observations, stratospheric aerosol evolution after Pinatubo, and ground-based sulfur deposition networks. SOCOL-AERv2 shows similar levels of agreement as SOCOL-AERv1 with satellite-measured extinctions and in situ optical particle counter (OPC) balloon flights. The volcanically quiescent total stratospheric aerosol burden simulated in SOCOL-AERv2 has increased from 109 Gg of sulfur (S) to 160 Gg S, matching the newly available satellite estimate of 165 Gg S. However, SOCOL-AERv2 simulates too high cross-tropopause transport of tropospheric SO2 and/or sulfate aerosol, leading to an overestimation of lower stratospheric aerosol. Due to the current lack of upper tropospheric SO2 measurements and the neglect of organic aerosol in the model, the lower stratospheric bias of SOCOL-AERv2 was not further improved. Model performance under volcanically perturbed conditions has also undergone some changes, resulting in a slightly shorter volcanic aerosol lifetime after the Pinatubo eruption. With the improved deposition schemes of SOCOL-AERv2, simulated sulfur wet deposition fluxes are within a factor of 2 of measured deposition fluxes at 78 % of the measurement stations globally, an agreement which is on par with previous model intercomparison studies. Because of these improvements, SOCOL-AERv2 will be better suited to studying changes in atmospheric sulfur deposition due to variations in climate and emissions. [ABSTRACT FROM AUTHOR]

Dissimilatory iron reduction is probably one of the oldest types of metabolisms that still participates in important biogeochemical cycles, such as those of carbon and sulfur. It is one of the more energetically favorable anaerobic microbial respiration processes and is usually coupled to the oxidation of organic matter. Traditionally this process is thought to be limited to the shallow part of the sedimentary column in most aquatic systems. However, iron reduction has also been observed in the methanic zone of many marine and freshwater sediments, well below its expected zone and occasionally accompanied by decreases in methane, suggesting a link between the iron and the methane cycles. Nevertheless, the mechanistic nature of this link (competition, redox or other) has yet to be established and has not been studied in oligotrophic shallow marine sediments. In this study we present combined geochemical and molecular evidences for microbial iron reduction in the methanic zone of the oligotrophic southeastern (SE) Mediterranean continental shelf. Geochemical porewater profiles indicate iron reduction in two zones, the uppermost part of the sediment, and the deeper zone, in the layer of high methane concentration. Results from a slurry incubation experiment indicate that the deep methanic iron reduction is microbially mediated. The sedimentary profiles of microbial abundance and quantitative PCR (qPCR) of the mcrA gene, together with Spearman correlation between the microbial data and Fe(II) concentrations in the porewater, suggest types of potential microorganisms that may be involved in the iron reduction via several potential pathways: H2 or organic matter oxidation, an active sulfur cycle, or iron-driven anaerobic oxidation of methane. We suggest that significant upward migration of methane in the sedimentary column and its oxidation by sulfate may fuel the microbial activity in the sulfate methane transition zone (SMTZ). The biomass created by this microbial activity can be used by the iron reducers below, in the methanic zone of the sediments of the SE Mediterranean. [ABSTRACT FROM AUTHOR]

This article describes the IFS-AER aerosol module used operationally in the Integrated Forecasting System (IFS) cycle 45R1, operated by the European Centre for Medium RangeWeather Forecasts (ECMWF) in the framework of the Copernicus Atmospheric Monitoring Services (CAMS). We describe the different parameterizations for aerosol sources, sinks and its chemical production in IFS-AER, as well as how the aerosols are integrated in the larger atmospheric composition forecasting system. The focus is on the entire 45R1 code-base, including some components that are not used operationally, in which case this will be clearly specified. This paper is an update to the Morcrette et al. (2009) article that described aerosol forecasts at ECMWF, using the cycle 32R2 of the IFS. Between cycles 32R2 and 45R1, a number of source and sink processes have been reviewed and/or added, increasing notably the complexity of IFS-AER. A greater integration with the tropospheric chemistry scheme of the IFS has been achieved, for the sulphur cycle as well as for nitrate production. Two new species, nitrate and ammonium, have also been included in the forecasting system. Global budgets and aerosol optical depth (AOD) fields are shown, as well as an evaluation of the simulated Particulate Matter (PM) and AOD against observations, showing an increase in skill from cycle 40R2, used in the CAMS interim Reanalysis (CAMSiRA), to cycle 45R1. [ABSTRACT FROM AUTHOR]

To explore the potential role of tetrathionate in the sulfur cycle of marine sediments, the population ecology of tetrathionate-forming, oxidizing, and respiring microorganisms was revealed at 15-30 cm resolution along two, ~ 3-m-long, cores collected from 530- and 580-mbsl water-depths of Arabian Sea, off India's west coast, within the oxygen minimum zone (OMZ). Metagenome analysis along the two sediment-cores revealed widespread occurrence of the structural genes that govern these metabolisms; high diversity and relative-abundance was also detected for the bacteria known to render these processes. Slurry-incubation of the sediment-samples, pure-culture isolation, and metatranscriptome analysis, corroborated the in situ functionality of all the three metabolic-types. Geochemical analyses revealed thiosulfate (0-11.1 µM), pyrite (0.05-1.09 wt %), iron (9232-17234 ppm) and manganese (71-172 ppm) along the two sediment-cores. Pyrites (via abiotic reaction with MnO2) and thiosulfate (via oxidation by chemolithotrophic bacteria prevalent in situ) are apparently the main sources of tetrathionate in this ecosystem. Tetrathionate, in turn, can be either converted to sulfate (via oxidation by the chemolithotrophs present) or reduced back to thiosulfate (via respiration by native bacteria); 0-2.01 mM sulfide present in the sediment-cores may also reduce tetrathionate abiotically to thiosulfate and elemental sulfur. Notably tetrathionate was not detected in situ - high microbiological and geochemical reactivity of this polythionate is apparently instrumental in the cryptic nature of its potential role as a central sulfur cycle intermediate. Biogeochemical roles of this polythionate, albeit revealed here in the context of OMZ sediments, may well extend to the sulfur cycles of other geomicrobiologically-distinct marine sediment horizons. [ABSTRACT FROM AUTHOR]

We developed an optimal-estimation algorithm to simultaneously retrieve, for the first time, co-emitted volcanic gaseous SO2 and sulphate aerosols (SA) from groundbased FTIR observations. These effluents, both linked to magmatic/degassing and subsequent atmospheric evolution processes, have overlapping spectral signatures leading to mutual potential interferences when retrieving one species without considering the other.We show that significant overestimations may be introduced in SO2 retrievals if the radiative impact of co-existent SA is not accounted for, which may have impacted existing SO2 long-term series, e.g. from satellite platform. The method was applied to proximal observations at Masaya volcano, where SO2 and SA concentrations, and SA acidity were retrieved. A gas-to-particle sulphur partitioning of 400 and a strong SA acidity (sulphuric acid concentration: 65 %) where found, consistently with past in-situ observations at this volcano. This method is easily exportable to other volcanoes, to monitor magma extraction processes and the atmospheric sulphur cycle. [ABSTRACT FROM AUTHOR]

Process-based numerical models are a useful tool for studying marine ecosystems and associated biogeochemical processes in ice-covered regions where observations are scarce. To this end, CSIB v1 (Canadian Sea-ice Biogeochemistry version 1), a new sea-ice biogeochemical model, has been developed and embedded into the Nucleus for European Modelling of the Ocean (NEMO) modelling system. This model consists of a three-compartment (ice algae, nitrate, and ammonium) sea-ice ecosystem and a two-compartment (dimethylsulfoniopropionate and dimethylsulfide) sea-ice sulfur cycle which are coupled to pelagic ecosystem and sulfur-cycle models at the sea-ice–ocean interface. In addition to biological and chemical sources and sinks, the model simulates the horizontal transport of biogeochemical state variables within sea ice through a one-way coupling to a dynamic-thermodynamic sea-ice model (LIM2; the Louvain-la-Neuve Sea Ice Model version 2). The model results for 1979 (after a decadal spin-up) are presented and compared to observations and previous model studies for a brief discussion on the model performance. Furthermore, this paper provides discussion on technical aspects of implementing the sea-ice biogeochemistry and assesses the model sensitivity to (1) the temporal resolution of the snowfall forcing data, (2) the representation of light penetration through snow, (3) the horizontal transport of sea-ice biogeochemical state variables, and (4) light attenuation by ice algae. The sea-ice biogeochemical model has been developed within the generic framework of NEMO to facilitate its use within different configurations and domains, and can be adapted for use with other NEMO-based sub-models such as LIM3 (the Louvain-la-Neuve Sea Ice Model version 3) and PISCES (Pelagic Interactions Scheme for Carbon and Ecosystem Studies). [ABSTRACT FROM AUTHOR]

The biogenic sulfur compounds dimethylsulfide (DMS), dimethylsulfoniopropionate (DMSP) and dimethylsulfoxide (DMSO) are produced and transformed by diverse populations of marine microorganisms and have substantial physiological, ecological and biogeochemical importance spanning organism to global scales. Understanding the production and transformation dynamics of these compounds under shifting environmental conditions is important for predicting their roles in a changing ocean. Here, we report the physiological and biochemical response of Alexandrium minutum, a dinoflagellate with the highest reported intracellular DMSP content, exposed to a 6 day increase in temperature mimicking coastal marine heatwave conditions (+4°C and +12°C). Under mild temperature increases (+4°C), A. minutum growth was enhanced, with no measurable physiological stress response. However, under an acute increase in temperature (+12°C), A. minutum growth declined, photosynthetic efficiency (FV/FM) was impaired, and enhanced oxidative stress was observed. These physiological responses were accompanied by increased DMS and DMSO concentrations followed by decreased DMSP concentrations. At this higher temperature, we observed a cascading stress response in A. minutum, which was initiated 6 h after the start of the experiment by a spike in DMS and DMSO concentrations and a rapid decrease in FV/FM. This was followed by an increase in reactive oxygen species (ROS) and an abrupt decline in DMS and DMSO on day 2 of the experiment. A subsequent decrease in DMSP coupled with a decline in the growth rate of both A. minutum and its associated total bacterial assemblage coincided with a shift in the composition of the A. minutum microbiome. Specifically, an increase in the relative abundance of OTUs matching the genus Oceanicaulis (17.0%), Phycisphaeraceae SM1A02 (8.8%) and Balneola (4.9%) as well as a decreased relative abundance of Maribacter (24.4%), Marinoscillum (4.7%) and Seohaeicola (2.7%), were primarily responsible for differences in microbiome structure observed between temperature treatments. These shifts in microbiome structure are likely to have been driven by either the changing physiological state of A. minutum cells, shifts in biogenic sulfur concentrations, or a combination of both. We suggest that these results point to the significant effect of heatwaves on the physiology, growth and microbiome composition of the red-tide causing dinoflagellate A. minutum, as well as potential implications for biogenic sulfur cycling processes and marine DMS emissions. [ABSTRACT FROM AUTHOR]