Carbonyl Sulfide Concentrations Research Articles

What kind of corrosion products are “black spots”? —Effects of reduced sulfur compounds on corrosion of bronze artefacts

While deterioration due to the generation of “black spots” is reported, consensus on the specific corrosion products comprising black spots and underlying deterioration mechanisms is lacking. This study investigated the deterioration of copper objects by analysing the black spots that appeared on them and proposes environmental conditions to suppress the appearance of black spots. Bronze artefacts excavated from a marine archaeological site, on which black spots were generated, were closely observed, and investigated. First, X-ray fluorescence and micro-X-ray diffraction analyses were performed on a bronze artefact, from which the black spots were removed, to determine the composition of the artefact. Second, to investigate the composition of the black spots, fine structure analysis of the black spots on the fine fragments of the bronze artefacts was conducted using scanning and transmission electron microscopy, energy dispersive X-ray spectroscopy, and electron diffraction (ED) analysis. The results indicate that the black spots were partially composed of metallic copper and a fine particle mixture of Cu2S and CuSO4. These results imply that the transformation of copper sulfide to metallic copper may have played an important role in the initiation and propagation of black spots. In this study, ED analysis was performed on the microscopic area of the black spots; no amorphous phases were detected, and all observed phases were identified as crystalline materials. To determine the sources of gas-phase sulfur compounds that cause black spots, H2S and carbonyl sulfide (COS) emissions from a spherical clay artefact (a cannon ball with gunpowder excavated from an underwater archaeological site) which was exhibited in the same showcase with the bronze artefacts were analysed via gas chromatography. The concentrations of H2S and COS were 0.462 and 8.636 ppb, respectively; these are significantly higher than those in the lower troposphere. These results indicate that deterioration by black spots occurred because of H2S and COS, which were emitted from the spherical clay artefact excavated from an underwater archaeological site in the exhibition case. In addition, it was confirmed that the inclusion of deoxygenating and dehumidifying agents (RP-AN) in the plastic bag in which the spherical clay artefact was inserted resulted in a significant decrease in the concentration of H2S and COS.

Capture of carbonyl sulfide trace from natural gas by adsorption on zeolitic Nanostructure: Monte Carlo molecular simulation

The economic and environmental challenge for the oil and gas industries is to eliminate carbonyl sulfide (COS) from natural gas selectively. This compound can lead to corrosion and environmental damage, even when it is present in small amounts. The zeolites have been known as the appropriate adsorbent for COS. Grand Canonical Monte Carlo (GCMC) simulation has been used to explore the suitability of zeolite frameworks with different topologies on the adsorption and separation properties of mixtures containing industrial concentrations of COS in order to overcome the experimental tests that are difficult to handle. The adsorption isotherms for pure COS and COS/methane mixture on purely siliceous zeolites such as BEA, FAU, LTL, MFI, and MOR have been recorded at 298 K within a pressure range of 0–100 kPa. MFI zeolite, with its high adsorption capacity and isosteric heat, has been identified as the most suitable candidate for COS adsorption due to its ideal pore size and shape. Examining the density distribution snapshots reveals the preferred locations of zeolites for the COS adsorption. The findings could be systematically used in various case studies, thereby providing insights into selecting the best zeolitic nanostructure for the industrial removal processes of COS.

Spatial and seasonal variability in volatile organic sulfur compounds in seawater and the overlying atmosphere of the Bohai and Yellow seas

Abstract. Volatile organic sulfur compounds (VSCs), including carbon disulfide (CS2), dimethyl sulfide (DMS), and carbonyl sulfide (COS), were surveyed in the seawater of the Bohai and Yellow seas and the overlying atmosphere during spring and summer of 2018 to understand the production and loss of VSCs and their influence factors. The concentration ranges of COS, DMS, and CS2 in the surface seawater were 0.14–0.42, 0.41–7.74, and 0.01–0.18 nmol L−1 during spring and 0.32–0.61, 1.31–18.12, and 0.01–0.65 nmol L−1 during summer, respectively. The COS concentrations exhibited positive correlation with dissolved organic carbon (DOC) concentrations in seawater during summer, which verified the photochemical production of COS from chromophoric dissolved organic matter (CDOM). High DMS concentrations occurred near the Yellow River, Laizhou Bay, and Yangtze River estuary, coinciding with high nitrate and chlorophyll (Chl) a concentrations due to river discharge during summer. The COS, DMS, and CS2 concentrations were the highest in the surface seawater and decreased with the depth. The mixing ratios of COS, DMS, and CS2 in the atmosphere were 255.9–620.2, 1.3–191.2, and 5.2–698.8 pptv during spring and 394.6–850.1, 10.3–464.3, and 15.3–672.7 pptv in summer, respectively. The ratios of mean oceanic concentrations and atmospheric mixing ratios for summer to spring in COS, DMS, and CS2 were 1.8, 3.1, 3.7 and 1.6, 4.6, 1.5, respectively. The ratios of the mean sea-to-air fluxes for summer to spring in COS, DMS, and CS2 were 1.2, 2.1, and 4.3. The sea-to-air fluxes of VSCs indicated that the marginal seas are important sources of VSCs in the atmosphere. The results support a better understanding of the contribution of VSCs in marginal seas.

Release of Sulfur and Chlorine Gas Species during Combustion and Pyrolysis of Walnut Shells in an Entrained Flow Reactor

The release behavior of sulfur and chlorine compounds into the gas phase of walnut shell particles (WNS) is studied with an entrained flow reactor. Experiments are carried out in nitrogen (N2), carbon dioxide (CO2) atmosphere and under air and oxy-fuel conditions at different temperatures (T = 1000–1300 °C) and stoichiometries (λ = 0.8–1.1). A total of 98.7% of fuel-bound sulfur volatilizes as sulfur dioxide (SO2), carbonyl sulfide (COS) and hydrogen sulfide (H2S) in the gas phase in N2 atmosphere at 1000 °C. As hydrogen chloride (HCl), 37.0% of the chlorine is released at this temperature. In CO2 atmosphere, a similar total release of sulfur and chlorine is observed (1000 °C). With each temperature increment, the release of SO2, H2S and HCl in the gas phase decreases (N2 and CO2 atmosphere). SO2 forms the major sulfur component in both atmospheres. In CO2 atmosphere, higher concentrations of COS were detected than in N2 atmosphere. Air and oxy-fuel combustion conditions show significantly lower SO2, COS and HCl concentrations as in N2 and CO2 atmosphere. No H2S is detected in the gas phase during any of the combustion trials.

The Z-2018 emissions inventory of COS in Europe: A semiquantitative multi-data-streams evaluation

The anthropogenic emissions of carbonyl sulfide (COS) and the uptake of this gas by terrestrial vegetation are major drivers of COS concentration variations in the atmosphere since the beginning of the industrial era. The fine spatial resolution (i.e., 0.1° × 0.1°) of the gridded anthropogenic emissions inventory of COS developed by Zumkehr et al. (2018), Z-2018 hereafter, is designed for a use by regional chemistry-transport models. In order to anticipate future applications at the regional scale, we carried out a first semiquantitative assessment of direct and indirect (i.e., from CS2 conversion) COS anthropogenic emissions at the sub-country scale in France using historical governmental data. Better agreement between the two inventories was found for direct emissions of COS by coal power plants, than for indirect sources. The use in this latter case of a sub-country spatial scaling, based on industrial N2O emissions, (1) strongly underestimates fluxes from food casings and cellulosic sponge industrial activities responsible for atmospheric CS2 emissions in France, and (2) considerably overestimates emissions from Paris and surrounding areas, which are free of a rayon industry. A list of food casings and cellulosic sponge industrial sites is provided to produce a more realistic inventory of CS2 sources in Europe. Nevertheless, a cluster analysis of wintertime air masses trajectories, with the atmospheric COS monitoring site of Gif-sur-Yvette (GIF) as end point, suggests that Z-2018 correctly identifies northern Germany and Belgium as sources of anthropogenic COS. In winter, when the wind blows from the NE sector, advection of anthropogenic COS from coal power plants is illustrated by synchronous variations in GIF and at the Trainou tall tower (distant of about 80 km) of a series of atmospheric pollution tracers, especially between COS and sulfates. These observations support the use of SO2 emissions as temporal and sub-country spatial scaling factors of COS emissions by the coal industry.

Global modelling of soil carbonyl sulfide exchanges

Abstract. Carbonyl sulfide (COS) is an atmospheric trace gas of interest for C cycle research because COS uptake by continental vegetation is strongly related to terrestrial gross primary productivity (GPP), the largest and most uncertain flux in atmospheric CO2 budgets. However, to use atmospheric COS as an additional tracer of GPP, an accurate quantification of COS exchange by soils is also needed. At present, the atmospheric COS budget is unbalanced globally, with total COS flux estimates from oxic and anoxic soils that vary between −409 and −89 GgS yr−1. This uncertainty hampers the use of atmospheric COS concentrations to constrain GPP estimates through atmospheric transport inversions. In this study we implemented a mechanistic soil COS model in the ORCHIDEE (Organising Carbon and Hydrology In Dynamic Ecosystems) land surface model to simulate COS fluxes in oxic and anoxic soils. Evaluation of the model against flux measurements at seven sites yields a mean root mean square deviation of 1.6 pmol m−2 s−1, instead of 2 pmol m−2 s−1 when using a previous empirical approach that links soil COS uptake to soil heterotrophic respiration. However, soil COS model evaluation is still limited by the scarcity of observation sites and long-term measurement periods, with all sites located in a latitudinal band between 39 and 62∘ N and no observations during wintertime in this study. The new model predicts that, globally and over the 2009–2016 period, oxic soils act as a net uptake of −126 GgS yr−1 and anoxic soils are a source of +96 GgS yr−1, leading to a global net soil sink of only −30 GgS yr−1, i.e. much smaller than previous estimates. The small magnitude of the soil fluxes suggests that the error in the COS budget is dominated by the much larger fluxes from plants, oceans, and industrial activities. The predicted spatial distribution of soil COS fluxes, with large emissions from oxic (up to 68.2 pmol COS m−2 s−1) and anoxic (up to 36.8 pmol COS m−2 s−1) soils in the tropics, especially in India and in the Sahel region, marginally improves the latitudinal gradient of atmospheric COS concentrations, after transport by the LMDZ (Laboratoire de Météorologie Dynamique) atmospheric transport model. The impact of different soil COS flux representations on the latitudinal gradient of the atmospheric COS concentrations is strongest in the Northern Hemisphere. We also implemented spatiotemporal variations in near-ground atmospheric COS concentrations in the modelling of biospheric COS fluxes, which helped reduce the imbalance of the atmospheric COS budget by lowering soil COS uptake by 10 % and plant COS uptake by 8 % globally (with a revised mean vegetation budget of −576 GgS yr−1 over 2009–2016). Sensitivity analyses highlighted the different parameters to which each soil COS flux model is the most responsive, selected in a parameter optimization framework. Having both vegetation and soil COS fluxes modelled within ORCHIDEE opens the way for using observed ecosystem COS fluxes and larger-scale atmospheric COS mixing ratios to improve the simulated GPP, through data assimilation techniques.

An approach to sulfate geoengineering with surface emissions of carbonyl sulfide

Abstract. Sulfate geoengineering (SG) methods based on lower stratospheric tropical injection of sulfur dioxide (SO2) have been widely discussed in recent years, focusing on the direct and indirect effects they would have on the climate system. Here a potential alternative method is discussed, where sulfur emissions are located at the surface or in the troposphere in the form of carbonyl sulfide (COS) gas. There are two time-dependent chemistry–climate model experiments designed from the years 2021 to 2055, assuming a 40 Tg-Syr-1 artificial global flux of COS, which is geographically distributed following the present-day anthropogenic COS surface emissions (SG-COS-SRF) or a 6 Tg-Syr-1 injection of COS in the tropical upper troposphere (SG-COS-TTL). The budget of COS and sulfur species is discussed, as are the effects of both SG-COS strategies on the stratospheric sulfate aerosol optical depth (∼Δτ=0.080 in the years 2046–2055), aerosol effective radius (0.46 µm), surface SOx deposition (+8.9 % for SG-COS-SRF; +3.3 % for SG-COS-TTL), and tropopause radiative forcing (RF; ∼-1.5 W m−2 in all-sky conditions in both SG-COS experiments). Indirect effects on ozone, methane and stratospheric water vapour are also considered, along with the COS direct contribution. According to our model results, the resulting net RF is −1.3 W m−2, for SG-COS-SRF, and −1.5 W m−2, for SG-COS-TTL, and it is comparable to the corresponding RF of −1.7 W m−2 obtained with a sustained injection of 4 Tg-Syr-1 in the tropical lower stratosphere in the form of SO2 (SG-SO2, which is able to produce a comparable increase of the sulfate aerosol optical depth). Significant changes in the stratospheric ozone response are found in both SG-COS experiments with respect to SG-SO2 (∼5 DU versus +1.4 DU globally). According to the model results, the resulting ultraviolet B (UVB) perturbation at the surface accounts for −4.3 % as a global and annual average (versus −2.4 % in the SG-SO2 case), with a springtime Antarctic decrease of −2.7 % (versus a +5.8 % increase in the SG-SO2 experiment). Overall, we find that an increase in COS emissions may be feasible and produce a more latitudinally uniform forcing without the need for the deployment of stratospheric aircraft. However, our assumption that the rate of COS uptake by soils and plants does not vary with increasing COS concentrations will need to be investigated in future work, and more studies are needed on the prolonged exposure effects to higher COS values in humans and ecosystems.

Light and Water Conditions Co-Regulated Stomata and Leaf Relative Uptake Rate (LRU) during Photosynthesis and COS Assimilation: A Meta-Analysis

As a trace gas involved in hydration during plant photosynthesis, carbonyl sulfide (COS) and its leaf relative uptake rate (LRU) is used to reduce the uncertainties in simulations of gross primary productivity (GPP). In this study, 101 independent observations were collected from 22 studies. We extracted the LRU, stomatal conductance (gs), canopy COS and carbon dioxide (CO2) fluxes, and relevant environmental conditions (i.e., light, temperature, and humidity), as well as the atmospheric COS and CO2 concentrations (Ca,COS and Ca,CO2). Although no evidence was found showing that gs regulates LRU, they responded in opposite ways to diurnal variations of environmental conditions in both mixed forests (LRU: Hedges’d = −0.901, LnRR = −0.189; gs: Hedges’d = 0.785, LnRR = 0.739) and croplands dominated by C3 plants (Hedges’d = −0.491, LnRR = −0.371; gs: Hedges’d = 1.066, LnRR = 0.322). In this process, the stomata play an important role in COS assimilation (R2 = 0.340, p = 0.020) and further influence the interrelationship of COS and CO2 fluxes (R2 = 0.650, p = 0.000). Slight increases in light intensity (R2 = 1, p = 0.002) and atmospheric drought (R2 = 0.885, p = 0.005) also decreased the LRU. The LRU saturation points of Ca,COS and Ca,CO2 were observed when ΔCa,COS ≈ 13 ppt (R2 = 0.580, p = 0.050) or ΔCa,CO2 ≈ −18 ppm (R2 = 0.970, p = 0.003). This study concluded that during plant photosynthesis and COS assimilation, light and water conditions co-regulated the stomata and LRU.

Plant gross primary production, plant respiration and carbonyl sulfide emissions over the globe inferred by atmospheric inverse modelling

Abstract. Carbonyl sulfide (COS), a trace gas showing striking similarity to CO2 in terms of biochemical diffusion pathway into leaves, has been recognized as a promising indicator of the plant gross primary production (GPP), the amount of carbon dioxide that is absorbed through photosynthesis by terrestrial ecosystems. However, large uncertainties about the other components of its atmospheric budget prevent us from directly relating the atmospheric COS measurements to GPP. The largest uncertainty comes from the closure of its atmospheric budget, with a source component missing. Here, we explore the benefit of assimilating both COS and CO2 measurements into the LMDz atmospheric transport model to obtain consistent information on GPP, plant respiration and COS budget. To this end, we develop an analytical inverse system that optimizes biospheric fluxes for the 15 plant functional types (PFTs) defined in the ORCHIDEE global land surface model. Plant uptake of COS is parameterized as a linear function of GPP and of the leaf relative uptake (LRU), which is the ratio of COS to CO2 deposition velocities in plants. A possible scenario for the period 2008–2019 leads to a global biospheric sink of 800 GgS yr−1, with higher absorption in the high latitudes and higher oceanic emissions between 400 and 600 GgS yr−1 most of which is located in the tropics. As for the CO2 budget, the inverse system increases GPP in the high latitudes by a few GtC yr−1 without modifying the respiration compared to the ORCHIDEE fluxes used as a prior. In contrast, in the tropics the system tends to weaken both respiration and GPP. The optimized components of the COS and CO2 budgets have been evaluated against independent measurements over North America, the Pacific Ocean, at three sites in Japan and at one site in France. Overall, the posterior COS concentrations are in better agreement with the COS retrievals at 250 hPa from the MIPAS satellite and with airborne measurements made over North America and the Pacific Ocean. The system seems to have rightly corrected the underestimated GPP over the high latitudes. However, the change in seasonality of GPP in the tropics disagrees with solar-induced fluorescence (SIF) data. The decline in biospheric sink in the Amazon driven by the inversion also disagrees with MIPAS COS retrievals at 250 hPa, highlighting the lack of observational constraints in this region. Moreover, the comparison with the surface measurements in Japan and France suggests misplaced sources in the prior anthropogenic inventory, emphasizing the need for an improved inventory to better partition oceanic and continental sources in Asia and Europe.

Occurrence and emissions of volatile sulfur compounds in the Changjiang estuary and the adjacent East China Sea

Volatile organic sulfur compounds (VSCs) are key components of the oceanic and atmospheric sulfur cycle. Here, we investigated the distributions of three major VSCs, such as carbon disulfide (CS2), dimethyl sulfide (DMS), and carbonyl sulfide (COS), and estimated their sea-to-air fluxes in the Changjiang Estuary and the adjacent East China Sea from July 20 to August 3, 2017. The DMS, COS, and CS2 surface water concentration ranges were 0.22–18.62, 0.06–0.77, and 0.02–0.3 nmol L−1, respectively. The distributions of VSCs were related to environmental and biological factors. In contrast to DMS, COS and CS2 concentrations generally decreased from the estuary to offshore waters. A significant correlation was observed between chlorophyll a and CS2 concentration, suggesting that CS2 production may be related to phytoplankton growth. Moreover, a positive correlation was observed between CS2 and DMS, indicating that they might share similar production pathways. COS was the most abundant VSC in the atmosphere, with an average concentration of 422.9 ± 301.8 ppt, but its distribution was likely influenced by anthropogenic activities. The average COS, DMS, and CS2 sea-to-air fluxes were 0.98 ± 0.98, 4.38 ± 6.42, and 0.05 ± 0.05 μmol m−2 d−1. The Changjiang Estuary and the adjacent East China Sea are important sources of atmospheric VSCs. These results will help us to better understand global VSC cycling between the oceanic atmosphere and bodies of water.

Carbonyl sulfide: comparing a mechanistic representation of the vegetation uptake in a land surface model and the leaf relative uptake approach

Abstract. Land surface modellers need measurable proxies to constrain the quantity of carbon dioxide (CO2) assimilated by continental plants through photosynthesis, known as gross primary production (GPP). Carbonyl sulfide (COS), which is taken up by leaves through their stomates and then hydrolysed by photosynthetic enzymes, is a candidate GPP proxy. A former study with the ORCHIDEE land surface model used a fixed ratio of COS uptake to CO2 uptake normalised to respective ambient concentrations for each vegetation type (leaf relative uptake, LRU) to compute vegetation COS fluxes from GPP. The LRU approach is known to have limited accuracy since the LRU ratio changes with variables such as photosynthetically active radiation (PAR): while CO2 uptake slows under low light, COS uptake is not light limited. However, the LRU approach has been popular for COS–GPP proxy studies because of its ease of application and apparent low contribution to uncertainty for regional-scale applications. In this study we refined the COS–GPP relationship and implemented in ORCHIDEE a mechanistic model that describes COS uptake by continental vegetation. We compared the simulated COS fluxes against measured hourly COS fluxes at two sites and studied the model behaviour and links with environmental drivers. We performed simulations at a global scale, and we estimated the global COS uptake by vegetation to be −756 Gg S yr−1, in the middle range of former studies (−490 to −1335 Gg S yr−1). Based on monthly mean fluxes simulated by the mechanistic approach in ORCHIDEE, we derived new LRU values for the different vegetation types, ranging between 0.92 and 1.72, close to recently published averages for observed values of 1.21 for C4 and 1.68 for C3 plants. We transported the COS using the monthly vegetation COS fluxes derived from both the mechanistic and the LRU approaches, and we evaluated the simulated COS concentrations at NOAA sites. Although the mechanistic approach was more appropriate when comparing to high-temporal-resolution COS flux measurements, both approaches gave similar results when transporting with monthly COS fluxes and evaluating COS concentrations at stations. In our study, uncertainties between these two approaches are of secondary importance compared to the uncertainties in the COS global budget, which are currently a limiting factor to the potential of COS concentrations to constrain GPP simulated by land surface models on the global scale.

Measurement Device for Ambient Carbonyl Sulfide by Means of Catalytic Reduction Followed by Wet Scrubbing/Fluorescence Detection.

A portable chemical analysis system for monitoring ambient carbonyl sulfide (COS) was investigated for the first time. COS is paid attention to from the perspectives of photosynthesis tracer, breath diagnosis marker, and new process-use in the manufacture of semiconductors. Recently, the threshold level value of COS was settled at 5 ppm in volume ratio (ppmv) for workplace safety management. In this work, COS was converted to H2S by a small column packed with alumina catalyzer at 65 °C. Then, the H2S produced was collected in a small channel scrubber to react with fluorescein mercuric acetate (FMA), and the resulting fluorescence quenching was monitored using an LED/photodiode-based miniature detector. The miniature channel scrubber was re-examined to determine its robustness and easy fabrication, and conditions of the catalyzer were optimized. When the FMA concentration used was 1 μM, the limit of detection and dynamic range, which were both proportional to the FMA concentration, were 0.07 and 25 ppbv, respectively. Ambient COS in the background level and even contaminated COS in the nitrogen gas cylinder could be detected. If necessary, H2S was removed selectively by reproducible adsorbent columns. COS concentrations of engine exhaust were measured by the proposed method and by cryo-trap-gas chromatography-flame photometric detection, and the results obtained (0.5–5.9 ppbv) by the two methods agreed well (R2 = 0.945, n = 19). COS in ambient air and exhaust gases was successfully measured without any batchwise pretreatment.

Soil–atmosphere exchange of carbonyl sulfide in a Mediterranean citrus orchard

Abstract. Carbonyl sulfide (COS) is used as a tracer of CO2 exchange at the ecosystem and larger scales. The robustness of this approach depends on knowledge of the soil contribution to the ecosystem fluxes, which is uncertain at present. We assessed the spatial and temporal variations in soil COS and CO2 fluxes in a Mediterranean citrus orchard combining surface flux chambers and soil concentration gradients. The spatial heterogeneity in soil COS exchange indicated net uptake below and between trees of up to 4.6 pmol m−2 s−1 and net emission in sun-exposed soil between rows of up to 2.6 pmol m−2 s−1, with an overall mean uptake value of 1.1±0.1 pmol m−2 s−1. Soil COS concentrations decreased with soil depth from atmospheric levels of ∼450 to ∼100 ppt at 20 cm depth, while CO2 concentrations increased from ∼400 to ∼5000 ppm. COS flux estimates from the soil concentration gradients were, on average, -1.0±0.3 pmol m−2 s−1, consistent with the chamber measurements. A soil COS flux algorithm driven by soil moisture and temperature (5 cm depth) and distance from the nearest tree, could explain 75 % of variance in soil COS flux. Soil relative uptake, the normalized ratio of COS to CO2 fluxes was, on average, -0.4±0.3 and showed a general exponential response to soil temperature. The results indicated that soil COS fluxes at our study site were dominated by uptake, with relatively small net fluxes compared to both soil respiration and reported canopy COS fluxes. Such a result should facilitate the application of COS as a powerful tracer of ecosystem CO2 exchange.

Temporal and spatial distributions of carbonyl sulfide, dimethyl sulfide, and carbon disulfide in seawater and marine atmosphere of the Changjiang Estuary and its adjacent East China Sea

AbstractCarbonyl sulfide (COS), dimethyl sulfide (DMS), and carbon disulfide (CS2) concentrations were determined in seawater and the overlying atmosphere of the Changjiang Estuary and the adjacent area during two cruises from 22 February 2016 to 15 March 2016 and from 03 July 2016 to 25 July 2016. The concentration ranges of COS, DMS, and CS2 in seawater during winter were 121–388 pmol L−1, 0.321–1.59 nmol L−1, and 10.3–46.8 pmol L−1, respectively, and those during summer were 98–346 pmol L−1, 0.397–9.13 nmol L−1, and 13.3–65.4 pmol L−1. The DMS concentration in surface seawater varied seasonally, whereas the COS and CS2 concentrations varied little. The atmospheric mixing ratios of COS, DMS, and CS2 were 459–777 pptv, 5.2–96.8 pptv, and 96.9–164 pptv during winter and 417–644 pptv, 133–365 pptv, and 15.8–89.8 pptv during summer, respectively. A correlation analysis revealed that COS concentration was related to the concentrations of DMS and CS2. The estimated fluxes of COS, DMS, and CS2 were in the range of 1.19–2.06 μg m−2 d−1, 15.11–164.81 μg m−2 d−1, and 0.27‐1.32 μg m−2 d−1 during winter and 0.61–0.97 μg m−2 d−1, 71.76–2511 μg m−2 d−1, and 0.38–1.47 μg m−2 d−1 during summer, respectively. These results indicate that the study area is a sink for COS, but served as a source of atmospheric DMS and CS2 during the study period.

Disentangling the rates of carbonyl sulfide (COS) production and consumption and their dependency on soil properties across biomes and land use types

Abstract. Soils both emit and consume the trace gas carbonyl sulfide (COS) leading to a soil–air COS exchange rate that is the net result of two opposing fluxes. Partitioning these two gross fluxes and understanding their drivers are necessary to estimate the contribution of soils to the current and future atmospheric COS budget. Previous efforts to disentangle the gross COS fluxes from soils have used flux measurements on air-dried soils as a proxy for the COS emission rates of moist soils. However, this method implicitly assumes that COS uptake becomes negligible and that COS emission remains steady while soils are drying. We tested this assumption by simultaneously estimating the soil COS sources and sinks and their temperature sensitivity (Q10); these estimates were based on soil–air COS flux measurements on fresh soils at different COS concentrations and two soil temperatures. Measurements were performed on 27 European soils from different biomes and land use types in order to obtain a large range of physical–chemical properties and identify the drivers of COS consumption and production rates. We found that COS production rates from moist and air-dried soils were not significantly different for a given soil and that the COS production rates had Q10 values (3.96 ± 3.94) that were larger and more variable than the Q10 for COS consumption (1.17 ± 0.27). COS production generally contributed less to the net flux at lower temperatures but this contribution of COS production increased rapidly at higher temperatures, lower soil moisture contents and lower COS concentrations. Consequently, measurements at higher COS concentrations (viz. 1000 ppt) always increased the robustness of COS consumption estimates. Across the range of biomes and land use types COS production rates co-varied with total soil nitrogen concentrations (r = 0.52, P<0.05) and mean annual precipitation (r=0.53, P<0.05), whilst the gross COS uptake rate and the first-order COS hydrolysis rate constant co-varied significantly with the microbial biomass nitrogen (N) content of the soils (r=-0.74 and 0.64, P<0.05 and P<0.05, respectively). Collectively our findings suggest a strong interaction between soil nitrogen and water cycling on COS production and uptake, providing new insights into how to upscale the contribution of soils to the global atmospheric COS budget.

Large historical growth in global terrestrial gross primary production.

Growth in terrestrial gross primary production (GPP)-the amount of carbon dioxide that is 'fixed' into organic material through the photosynthesis of land plants-may provide a negative feedback for climate change. It remains uncertain, however, to what extent biogeochemical processes can suppress global GPP growth. As a consequence, modelling estimates of terrestrial carbon storage, and of feedbacks between the carbon cycle and climate, remain poorly constrained. Here we present a global, measurement-based estimate of GPP growth during the twentieth century that is based on long-term atmospheric carbonyl sulfide (COS) records, derived from ice-core, firn and ambient air samples. We interpret these records using a model that simulates changes in COS concentration according to changes in its sources and sinks-including a large sink that is related to GPP. We find that the observation-based COS record is most consistent with simulations of climate and the carbon cycle that assume large GPP growth during the twentieth century (31% ± 5% growth; mean ± 95% confidence interval). Although this COS analysis does not directly constrain models of future GPP growth, it does provide a global-scale benchmark for historical carbon-cycle simulations.

Radiation and atmospheric circulation controls on carbonyl sulfide concentrations in the marine boundary layer

AbstractA potential closure of the global carbonyl sulfide (COS or OCS) budget has recently been attained through a combination of remote sensing, modeling, and extended surface measurements. However, significant uncertainties in the spatial and temporal dynamics of the marine flux still persist. In order to isolate the terrestrial photosynthetic component of the global atmospheric OCS budget, tighter constraints on the marine flux are needed. We present 6 months of nearly continuous in situ OCS concentrations from the North Atlantic during the fall and winter of 2014–2015 using a combination of research vessel and fixed tower measurements. The data are characterized by synoptic‐scale ∼100 pmol mol−1 variations in marine boundary layer air during transitions from subtropical to midlatitude source regions. The synoptic OCS variability is shown here to be a linear function of the radiation history along an air parcel's trajectory with no apparent sensitivity to the chlorophyll concentration of the surface waters that the air mass interacted with. This latter observation contradicts expectations and suggests a simple radiation limitation for the combined direct and indirect marine OCS emissions. Because the concentration of OCS in the marine boundary layer is so strongly influenced by an air parcel's history, marine and atmospheric concentrations would rarely be near equilibrium and thus even if marine production rates are held constant at a given location, the ocean‐atmosphere flux would be sensitive to changes in atmospheric circulation alone. We hypothesize that changes in atmospheric circulation including latitudinal shifts in the storm tracks could affect the marine flux through this effect.

Detection of intense partial discharge of epoxy insulation in sf6 insulated equipment using carbonyl sulfide

Basin insulators in gas insulated switchgear (GIS) are prone to failure by partial discharge (PD). Insulation diagnosis using gas analysis method has advantages of strong anti-interference ability and high detection precision. This paper reports a new characteristic gas Carbonyl Sulfide (COS) for the detection of PD in epoxy insulators of GIS. The generation of COS is verified by experiments with trace gas detection technique. Experimental results indicate that COS is generated only when the intensity of PD is strong enough to cause flashover on the epoxy insulators. The corresponding production mechanisms of COS have been clarified using quantum chemistry calculations. To assess the PD level using COS, the relationship between discharge power and growth law of the concentration of COS is obtained from the experiments, which indicates that COS could be used as an effective characteristic gas to diagnose epoxy solid insulation of GIS concerning high energy discharge.

Degradation of carbonyl sulfide by Actinomycetes and detection of clade D of β-class carbonic anhydrase.

Carbonyl sulfide (COS) is an atmospheric trace gas and one of the sources of stratospheric aerosol contributing to climate change. Although one of the major sinks of COS is soil, the distribution of COS degradation ability among bacteria remains unclear. Seventeen out of 20 named bacteria belonging to Actinomycetales had COS degradation activity at mole fractions of 30 parts per million by volume (ppmv) COS. Dietzia maris NBRC 15801T and Mycobacterium sp. THI405 had the activity comparable to a chemolithoautotroph Thiobacillus thioparus THI115 that degrade COS by COS hydrolase for energy production. Among 12 bacteria manifesting rapid degradation at 30 ppmv COS, D. maris NBRC 15801T and Streptomyces ambofaciens NBRC 12836T degraded ambient COS (∼500 parts per trillion by volume). Geodermatophilus obscurus NBRC 13315T and Amycolatopsis orientalis NBRC 12806T increased COS concentrations. Moreover, six of eight COS-degrading bacteria isolated from soils had partial nucleotide sequences similar to that of the gene encoding clade D of β-class carbonic anhydrase, which included COS hydrolase. These results indicate the potential importance of Actinomycetes in the role of soils as sinks of atmospheric COS.

Variability of atmospheric carbonyl sulfide at a semi-arid urban site in western India

Atmospheric carbonyl sulfide (COS) is a major precursor for sulfate aerosols that play a critical role in climate regulation. Recent studies have highlighted the importance of COS measurements as a reliable means to constrain biospheric carbon assimilation. In a scenario of limited availability of COS data around the globe, we present gas-chromatographic measurements of atmospheric COS mixing ratios over Ahmedabad, a semi-arid, urban region in western India. These measurements, being reported for the first time over an Indian site, enable us to understand the diurnal and seasonal variation in atmospheric COS with respect to its natural, anthropogenic and photochemical sources and sinks. The annual mean COS mixing ratio over Ahmedabad is found to be 0.83±0.43ppbv, which is substantially higher than free tropospheric values for the northern hemisphere. Inverse correlation of COS with soil and skin temperature, suggests that the dry soil of the semi-arid study region is a potential sink for atmospheric COS. Positive correlations of COS with NO2 and CO during post-monsoon and the COS/CO slope of 0.78pptv/ppbv reveals influence of diesel combustion and tire wear. The highest concentrations of COS are observed during pre-monsoon; COS/CO2 slope of 44.75pptv/ppmv combined with information from air mass back-trajectories reveal marshy wetlands spanning over 7500km2 as an important source of COS in Ahmedabad. COS/CO2 slopes decrease drastically (8.28pptv/ppmv) during post-monsoon due to combined impact of biospheric uptake and anthropogenic emissions.