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Carbonyl sulfide (COS), an organosulfur compound commonly present in industrial gases, poses significant challenges for environmental protection and industrial processes due to its toxicity. This paper reviews recent advancements in the development of catalysts for COS hydrolysis, emphasizing the effects of various supports and active components on catalyst performance, as well as the mechanisms underlying the hydrolysis reaction. Traditional supports like γ-Al2O3 demonstrate high activity for COS hydrolysis but are susceptible to deactivation. In contrast, novel supports such as activated carbon, TiO2, and ZrO2 have garnered attention for their unique structures and properties. The incorporation of active components, including alkali metals, alkaline earth metals, transition metals, and rare earth metals, significantly enhances the hydrolysis efficiency and resistance to deactivation of the catalysts. Additionally, this paper outlines three primary mechanisms for COS hydrolysis: the alkali-catalyzed mechanism, the Langmuir–Hinshelwood model, and the Eley–Rideal model mechanism, as well as the thiocarbonate intermediate mechanism, which collectively elucidate the conversion of COS into the H2S and CO2 catalyzed by these systems. Future research efforts will concentrate on developing high-activity, high-stability, and cost-effective COS hydrolysis catalysts, along with a more in-depth exploration of the reaction mechanisms to facilitate the efficient removal of COS from industrial emissions.

Carbonyl sulfide (COS) exchange in C₃ leaves is linked to that of CO₂, providing a basis for the use of COS as a powerful tracer of gross CO₂ fluxes between plants and the atmosphere, a critical element in understanding the response of the land biosphere to global change. Here, we carried out controlled leaf-scale gas-exchange measurements of COS and CO₂ in representative C₃ plants under a range of light intensities, relative humidities and temperatures, CO₂ and COS concentrations, and following abscisic acid treatments. No 'respiration-like' emission of COS or detectable compensation point, and no cross-inhibition effects between COS and CO₂ were observed. The mean ratio of COS to CO₂ assimilation flux rates, As/Ac, was c. 1.4 pmol μmol⁻¹ and the leaf relative uptake (assimilation normalized to ambient concentrations, (As/Ac)(Cac/Cas)) was 1.6-1.7 across species and conditions, with significant deviations under certain conditions. Stomatal conductance was enhanced by increasing COS, which was possibly mediated by hydrogen sulfide (H₂S) produced from COS hydrolysis, and a correlation was observed between As and leaf discrimination against C¹⁸OO. The results provide systematic and quantitative information necessary for the use of COS in photosynthesis and carbon-cycle research on the physiological to global scales.

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. Actinomycetes degraded 30 ppmv COS, some bacteria emitted COS in ambient air, and Mycobacterium spp. and Williamsia sp. had partial nucleotide sequences of clade D gene of β-class carbonic anhydrase.

Knowledge related to sulfur isotope ratios of carbonyl sulfide (OCS or COS), the most abundant atmospheric sulfur species, remains scarce. An earlier method developed for sulfur isotopic analysis for OCS using S+ fragmentation by an isotope ratio mass spectrometer is inapplicable for ambient air samples because of the large samples required (approx. 500 L of 500 pmol mol-1 OCS). To overcome this difficulty, herein we present a new sampling system for collecting approximately 10 nmol of OCS from ambient air coupled with a purification system. Salient system features are (i) accommodation of samples up to 500 L (approx. 10 nmol) of air at 5 L min-1; (ii) portability of adsorption tubes (1/4 in. (0.64 cm) outer diameter, 17.5 cm length, approximately 1.4 cm3 volume) for preserving the OCS amount and δ34S(OCS) values at -80 ∘C for up to 90 days and 14 days; and (iii) purification OCS from other compounds such as CO2. We tested the OCS collection efficiency of the systems and sulfur isotopic fractionation during sampling. Results show precision (1σ) of δ34S(OCS) values as 0.4 ‰ for overall procedures during measurements for atmospheric samples. Additionally, this report presents diurnal variation of δ34S(OCS) values collected from ambient air at the Suzukakedai campus of the Tokyo Institute of Technology located in Yokohama, Japan. The observed OCS concentrations andδ34S(OCS) values were, respectively, 447–520 pmol mol-1 and from 10.4 ‰ to 10.7 ‰ with a lack of diurnal variation. The observed δ34S(OCS) values in ambient air differed greatly from previously reported values of δ34S(OCS) = (4.9±0.3) ‰ for compressed air collected at Kawasaki, Japan, presumably because of degradation of OCS in cylinders and collection processes for that sample. The difference of atmospheric δ34S(OCS) values between 10.5 ‰ in Japan (this study) and ∼13 ‰ recently reported in Israel or the Canary Islands indicates that spatial and temporal variation of δ34S(OCS) values is expected due to a link between anthropogenic activities and OCS cycles. The system presented herein is useful for application of δ34S(OCS) for investigation of OCS sources and sinks in the troposphere to elucidate its cycle.

Due to the important roles of carbonyl sulfide (COS) and carbon disulfide (CS2) in atmospheric chemistry, this study was designed to determine different proportions of COS and CS2 fluxes contributed from different sources, i.e., vegetation, soil and roots, at monthly and hourly timescales in the arid area in Xinjiang, China. Results indicated that the seasonal net uptake of COS by vegetation was predominant in the growing season. The CS2 fluxes from vegetation and soils had no significant seasonal variations compared with COS. The exchange rates of COS and CS2 have been found to be stimulated by the addition of nutrients in the form of urea fertilizer. Compared with the results of plots that were treated only with nitrogen, the treatments with both nitrogen and sulfur displayed no significant difference in the exchange fluxes. The results of compartment experiments indicated that the aboveground plants had the highest uptake of COS and had a vital role in the uptake of COS during the main growth period. The shares of COS emissions from the soil and roots increased to 6–17% and 55–58%, respectively, in the total COS fluxes when conditions, such as drought and senescence, were unfavorable for the developmental of vegetation. Observations of the preliminary diurnal fluxes indicated that the fluxes that occurred at night, with contributions from soils and plants, accounted for 27% of the total daily uptake of COS uptake. These quantitative results may be reasonably accounted for the use of COS as a promising tracer to obtain independent constraints on terrestrial carbon exchange at regional to global scales for their response to special environmental conditions in semiarid area.

Mid-infrared dual-comb spectroscopy has the potential to supplant conventional Fourier-transform spectroscopy in applications requiring high resolution, accuracy, signal-to-noise ratio and speed. Until now, mid-infrared dual-comb spectroscopy has been limited to narrow optical bandwidths or low signal-to-noise ratios. Using digital signal processing and broadband frequency conversion in waveguides, we demonstrate a mid-infrared dual-comb spectrometer covering 2.6 to 5.2 µm with comb-tooth resolution, sub-MHz frequency precision and accuracy, and a spectral signal-to-noise ratio as high as 6,500. As a demonstration, we measure the highly structured, broadband cross-section of propane from 2,840 to 3,040 cm−1, the complex phase/amplitude spectra of carbonyl sulfide from 2,000 to 2,100 cm−1, and of a methane, acetylene and ethane mixture from 2,860 to 3,400 cm−1. The combination of broad bandwidth, comb-mode resolution and high brightness will enable accurate mid-infrared spectroscopy in precision laboratory experiments and non-laboratory applications including open-path atmospheric gas sensing, process monitoring and combustion.

Evaporation (E) and transpiration (T) respond differently to ongoing changes in climate, atmospheric composition, and land use. It is difficult to partition ecosystem-scale evapotranspiration (ET) measurements into E and T, which makes it difficult to validate satellite data and land surface models. Here, we review current progress in partitioning E and T and provide a prospectus for how to improve theory and observations going forward. Recent advancements in analytical techniques create new opportunities for partitioning E and T at the ecosystem scale, but their assumptions have yet to be fully tested. For example, many approaches to partition E and T rely on the notion that plant canopy conductance and ecosystem water use efficiency exhibit optimal responses to atmospheric vapor pressure deficit (D). We use observations from 240 eddy covariance flux towers to demonstrate that optimal ecosystem response to D is a reasonable assumption, in agreement with recent studies, but more analysis is necessary to determine the conditions for which this assumption holds. Another critical assumption for many partitioning approaches is that ET can be approximated as T during ideal transpiring conditions, which has been challenged by observational studies. We demonstrate that T can exceed 95 % of ET from certain ecosystems, but other ecosystems do not appear to reach this value, which suggests that this assumption is ecosystem-dependent with implications for partitioning. It is important to further improve approaches for partitioning E and T, yet few multi-method comparisons have been undertaken to date. Advances in our understanding of carbon–water coupling at the stomatal, leaf, and canopy level open new perspectives on how to quantify T via its strong coupling with photosynthesis. Photosynthesis can be constrained at the ecosystem and global scales with emerging data sources including solar-induced fluorescence, carbonyl sulfide flux measurements, thermography, and more. Such comparisons would improve our mechanistic understanding of ecosystem water fluxes and provide the observations necessary to validate remote sensing algorithms and land surface models to understand the changing global water cycle.

Metal-free and controlled synthesis of sulfur-containing polymer is still a big challenge in polymer chemistry. Here, we report a metal-free, living copolymerization of carbonyl sulfide (COS) with epoxides via the cooperative catalysis of organic Lewis pairs including bases (e.g.: phosphazene, amidine, and guanidine) and thioureas as hydrogen-bond donors, afford well-defined poly(monothiocarbonate)s with 100% alternating degree, >99% tail-to-head content, controlled molecular weights (up to 98.4 kg/mol), and narrow molecular weight distributions (1.13–1.23). The effect of the types of Lewis pairs on the copolymerization of COS with several epoxides is investigated. The turnover frequencies (TOFs) of these Lewis pairs are as high as 112 h −1 at 25 °C. Kinetic and mechanistic results suggest that the supramolecular specific recognition of thiourea to epoxide and base to COS promote the copolymerization cooperatively. This strategy provides commercially available Lewis pairs for metal-free synthesis of sulfur-containing polymers with precise structure. Sulfur-containing polymers are useful commodities, but there is still a big challenge to produce such polymers in a controlled fashion. Here the authors show a metal-free living copolymerization between carbonyl sulfide and epoxides via cooperative catalysis.

Carbonyl sulfide (COS) has the potential to be used as a climate diagnostic due to its close coupling to the biospheric uptake of CO2 and its role in the formation of stratospheric aerosol. The current understanding of the COS budget, however, lacks COS sources, which have previously been allocated to the tropical ocean. This paper presents a first attempt at global inverse modelling of COS within the 4-dimensional variational data-assimilation system of the TM5 chemistry transport model (TM5-4DVAR) and a comparison of the results with various COS observations. We focus on the global COS budget, including COS production from its precursors carbon disulfide (CS2) and dimethyl sulfide (DMS). To this end, we implemented COS uptake by soil and vegetation from an updated biosphere model (Simple Biosphere Model – SiB4). In the calculation of these fluxes, a fixed atmospheric mole fraction of 500 pmol mol−1 was assumed. We also used new inventories for anthropogenic and biomass burning emissions. The model framework is capable of closing the COS budget by optimizing for missing emissions using NOAA observations in the period 2000–2012. The addition of 432 Gg a−1 (as S equivalents) of COS is required to obtain a good fit with NOAA observations. This missing source shows few year-to-year variations but considerable seasonal variations. We found that the missing sources are likely located in the tropical regions, and an overestimated biospheric sink in the tropics cannot be ruled out due to missing observations in the tropical continental boundary layer. Moreover, high latitudes in the Northern Hemisphere require extra COS uptake or reduced emissions. HIPPO (HIAPER Pole-to-Pole Observations) aircraft observations, NOAA airborne profiles from an ongoing monitoring programme and several satellite data sources are used to evaluate the optimized model results. This evaluation indicates that COS mole fractions in the free troposphere remain underestimated after optimization. Assimilation of HIPPO observations slightly improves this model bias, which implies that additional observations are urgently required to constrain sources and sinks of COS. We finally find that the biosphere flux dependency on the surface COS mole fraction (which was not accounted for in this study) may substantially lower the fluxes of the SiB4 biosphere model over strong-uptake regions. Using COS mole fractions from our inversion, the prior biosphere flux reduces from 1053 to 851 Gg a−1, which is closer to 738 Gg a−1 as was found by Berry et al. (2013). In planned further studies we will implement this biosphere dependency and additionally assimilate satellite data with the aim of better separating the role of the oceans and the biosphere in the global COS budget.

Terrestrial photosynthesis, or gross primary production (GPP), is the largest carbon flux in the biosphere, but its global magnitude and spatiotemporal dynamics remain uncertain 1 . The global annual mean GPP is historically thought to be around 120 PgC yr −1 (refs.  2 – 6 ), which is about 30–50 PgC yr −1 lower than GPP inferred from the oxygen-18 ( 18 O) isotope 7 and soil respiration 8 . This disparity is a source of uncertainty in predicting climate–carbon cycle feedbacks 9 , 10 . Here we infer GPP from carbonyl sulfide, an innovative tracer for CO 2 diffusion from ambient air to leaf chloroplasts through stomata and mesophyll layers. We demonstrate that explicitly representing mesophyll diffusion is important for accurately quantifying the spatiotemporal dynamics of carbonyl sulfide uptake by plants. From the estimate of carbonyl sulfide uptake by plants, we infer a global contemporary GPP of 157 (±8.5) PgC yr −1 , which is consistent with estimates from 18 O (150–175 PgC yr −1 ) and soil respiration ( 149 − 23 + 29  PgC yr −1 ), but with an improved confidence level. Our global GPP is higher than satellite optical observation-driven estimates (120–140 PgC yr –1 ) that are used for Earth system model benchmarking. This difference predominantly occurs in the pan-tropical rainforests and is corroborated by ground measurements 11 , suggesting a more productive tropics than satellite-based GPP products indicated. As GPP is a primary determinant of terrestrial carbon sinks and may shape climate trajectories 9 , 10 , our findings lay a physiological foundation on which the understanding and prediction of carbon–climate feedbacks can be advanced. An analysis of the effect of mesophyll diffusion on the dynamics of the uptake of carbonyl sulfide by plants estimates global contemporary gross primary productivity to be 157 (±8.5) petagrams of carbon per year.