Abstract. The climate active trace-gas carbonyl sulfide (OCS) is the most abundant sulfur gas in the atmosphere. A missing source in its atmospheric budget is currently suggested, resulting from an upward revision of the vegetation sink. Tropical oceanic emissions have been proposed to close the resulting gap in the atmospheric budget. We present a bottom-up approach including (i) new observations of OCS in surface waters of the tropical Atlantic, Pacific and Indian oceans and (ii) a further improved global box model to show that direct OCS emissions are unlikely to account for the missing source. The box model suggests an undersaturation of the surface water with respect to OCS integrated over the entire tropical ocean area and, further, global annual direct emissions of OCS well below that suggested by top-down estimates. In addition, we discuss the potential of indirect emission from CS 2 and dimethylsulfide (DMS) to account for the gap in the atmospheric budget. This bottom-up estimate of oceanic emissions has implications for using OCS as a proxy for global terrestrial CO 2 uptake, which is currently impeded by the inadequate quantification of atmospheric OCS sources and sinks.

Climate change is altering oceanic conditions in a complex manner, and the concurrent amendment of multiple properties will modify environmental stress for primary producers. So far, global modelling studies have focused largely on how alteration of individual properties will a ect marine life. Here, we use global modelling simulations in conjunction with rotated factor analysis to express model projections in terms of regional trends in concomitant changes to biologically influential multistressors. Factor analysis demonstrates that regionally distinct patterns of complex oceanic change are evident globally. Preliminary regional assessments using published evidence of phytoplankton responses to complex change reveal a wide range of future responses to interactive multi-stressors with <20-300% shifts in phytoplankton physiological rates, and many unexplored potential interactions. In a future ocean, provinces will encounter di erent permutations of change that will probably alter the dominance of key phytoplankton groups and modify regional productivity, ecosystem structure and biogeochemistry. Consideration of regionally distinct multi-stressor patterns can help guide laboratory and field studies as well as the interpretation of interactive multi-stressors in global models.M ultiple lines of evidence, ranging from time-series observations to climate modelling experiments, demonstrate the ongoing role of climate change in modifying many ocean properties such as temperature, salinity and pH (refs 1-3). Coupled ocean-atmosphere-land Earth system models link present-day evidence of a changing ocean 3 with that of a future ocean by providing detailed projections of how climate change will continue to alter concurrently a range of characteristics, for example, enhanced vertical density stratification in the upper ocean, over the coming decades 4 . The effect of changing conditions on marine life has been explored in detail using manipulation experiments in which individual oceanic properties such as pH are perturbed on the basis of future climate change modelling projections 5 . Initial global modelling studies concentrated on the potential impact of a subset of processes on planktonic organisms, for example, changes in temperature, nutrients and stratification on phytoplankton growth 4 or ocean acidification on calcification 6 . Recently, coupled Earth system model studies have begun to focus more on the complexity of these climate-change-mediated environmental changes, including the overlapping effects of warming, acidification and/or hypoxia and their influence on ocean biogeochemistry 2,7 . The goal of our study is a new framework for interpreting and visualizing coupled Earth system model results and helping design future laboratory and field experiments.Two complementary approaches have been taken by modellers investigating how changing oceanic conditions will alter phytoplankton productivity and the resulting biogeochemical signatures 8,9 . A number of coupled Earth models incorporate phytoplankton-zooplankton ...

Abstract. For the past decade, observations of carbonyl sulfide (OCS or COS) have been investigated as a proxy for carbon uptake by plants. OCS is destroyed by enzymes that interact with CO2 during photosynthesis, namely carbonic anhydrase (CA) and RuBisCO, where CA is the more important one. The majority of sources of OCS to the atmosphere are geographically separated from this large plant sink, whereas the sources and sinks of CO2 are co-located in ecosystems. The drawdown of OCS can therefore be related to the uptake of CO2 without the added complication of co-located emissions comparable in magnitude. Here we review the state of our understanding of the global OCS cycle and its applications to ecosystem carbon cycle science. OCS uptake is correlated well to plant carbon uptake, especially at the regional scale. OCS can be used in conjunction with other independent measures of ecosystem function, like solar-induced fluorescence and carbon and water isotope studies. More work needs to be done to generate global coverage for OCS observations and to link this powerful atmospheric tracer to systems where fundamental questions concerning the carbon and water cycle remain.

Abstract. For the past decade, observations of carbonyl sulfide (OCS or COS) have been investigated as a proxy for carbon uptake by plants. OCS is destroyed by enzymes that interact with CO 2 during 25 photosynthesis, namely carbonic anhydrase (CA) and RuBisCO, where CA is the more important. The majority of sources of OCS to the atmosphere are geographically separated from this large plant sink, whereas the sources and sinks of CO 2 are co-located in ecosystems. The drawdown of OCS can therefore be related to the uptake of CO 2 without the added complication of co-located emissions comparable in magnitude. Here we review the state of our understanding of the global OCS cycle and 30 its applications to ecosystem carbon cycle science. OCS uptake is correlated well to plant carbon uptake, especially at the regional scale. OCS can be used in conjunction with other independent measures of ecosystem function, like solar-induced fluorescence and carbon and water isotope studies.More work needs to be done to generate global coverage for OCS observations and to link this powerful Biogeosciences Discuss., https://doi

Abstract. The first concerted multi-model intercomparison of halogenated very short-lived substances (VSLS) has been performed, within the framework of the ongoing Atmospheric Tracer Transport Model Intercomparison Project (TransCom). Eleven global models or model variants participated (nine chemical transport models and two chemistry–climate models) by simulating the major natural bromine VSLS, bromoform (CHBr3) and dibromomethane (CH2Br2), over a 20-year period (1993–2012). Except for three model simulations, all others were driven offline by (or nudged to) reanalysed meteorology. The overarching goal of TransCom-VSLS was to provide a reconciled model estimate of the stratospheric source gas injection (SGI) of bromine from these gases, to constrain the current measurement-derived range, and to investigate inter-model differences due to emissions and transport processes. Models ran with standardised idealised chemistry, to isolate differences due to transport, and we investigated the sensitivity of results to a range of VSLS emission inventories. Models were tested in their ability to reproduce the observed seasonal and spatial distribution of VSLS at the surface, using measurements from NOAA's long-term global monitoring network, and in the tropical troposphere, using recent aircraft measurements – including high-altitude observations from the NASA Global Hawk platform. The models generally capture the observed seasonal cycle of surface CHBr3 and CH2Br2 well, with a strong model–measurement correlation (r  ≥  0.7) at most sites. In a given model, the absolute model–measurement agreement at the surface is highly sensitive to the choice of emissions. Large inter-model differences are apparent when using the same emission inventory, highlighting the challenges faced in evaluating such inventories at the global scale. Across the ensemble, most consistency is found within the tropics where most of the models (8 out of 11) achieve best agreement to surface CHBr3 observations using the lowest of the three CHBr3 emission inventories tested (similarly, 8 out of 11 models for CH2Br2). In general, the models reproduce observations of CHBr3 and CH2Br2 obtained in the tropical tropopause layer (TTL) at various locations throughout the Pacific well. Zonal variability in VSLS loading in the TTL is generally consistent among models, with CHBr3 (and to a lesser extent CH2Br2) most elevated over the tropical western Pacific during boreal winter. The models also indicate the Asian monsoon during boreal summer to be an important pathway for VSLS reaching the stratosphere, though the strength of this signal varies considerably among models. We derive an ensemble climatological mean estimate of the stratospheric bromine SGI from CHBr3 and CH2Br2 of 2.0 (1.2–2.5) ppt,  ∼  57 % larger than the best estimate from the most recent World Meteorological Organization (WMO) Ozone Assessment Report. We find no evidence for a long-term, transport-driven trend in the stratospheric SGI of bromine over the simulation period. The transport-driven interannual variability in the annual mean bromine SGI is of the order of ±5 %, with SGI exhibiting a strong positive correlation with the El Niño–Southern Oscillation (ENSO) in the eastern Pacific. Overall, our results do not show systematic differences between models specific to the choice of reanalysis meteorology, rather clear differences are seen related to differences in the implementation of transport processes in the models.

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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.

LabileCompounds that experience rapid turnover within hours to days of release and do not accumulate. Environmentally persistentCompounds that resist rapid microbial degradation, accumulating on land and in the ocean for centuries to millennia.