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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 CO2 during 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 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.

Current climate models disagree on how much carbon dioxide land ecosystems take up for photosynthesis. Tracking the stronger carbonyl sulfide signal could help.

Lack of knowledge still remains on many processes leading to COS atmospheric fluxes, either natural such as the oceanic emissions or the vegetation and soil fluxes, or anthropogenic, from industrial activities and power generation. Moreover, COS atmospheric mixing ratio data are still too sparse to evaluate the estimations of these sources and sinks. This study assesses the anthropogenic and biogenic COS fluxes at the regional scale, in the footprint a measurement site in Western Europe, at a seasonal to diurnal time resolution over half a decade. The continuous time series of COS mixing ratios obtained at the monitoring site of Gif-sur-Yvette (in the Paris area) from August 2014 to December 2019 are compared to simulations with the Lagrangian model FLEXPART, transporting oceanic emissions, biogenic land fluxes from the process-model ORCHIDEE and anthropogenic emissions by two different inventories. The anthropogenic emission inventory based on reported industrial emissions and the characteristics of coal power plants in Europe is consistent with the observations. The flat temporal variability applied to anthropogenic fluxes due to lack of information on industrial and power-generation activity in viscose factories and coal-power plants and the potential mismatches in the representation of the plumes emitted from these hot-spots in the model are the main limitations of this inventory. We find that the net ecosystem COS uptake simulated by ORCHIDEE is underestimated in winter at night, which suggests improvements in the parameterization of the nighttime uptake by plants for COS. [ABSTRACT FROM AUTHOR]

Carbonyl sulfide (OCS) is used to quantify the carbon capture potential of the biosphere because of its direct correlation with CO2 uptake during photosynthesis. However, to constrain the urban biosphere signal, it is necessary to evaluate potential anthropogenic sources. We conducted two sampling campaigns in the Metropolitan Area of Barcelona (AMB), Spain, during May (full COVID lockdown) and October 2020 to measure the spatial distribution and variability of OCS in four urban land uses as follows: built, urban forest, urban park, and peri‐urban agriculture. The OCS background levels determined at Tibidabo (442 m asl) were approximately 484 ± 20 ppt and 407 ± 8 ppt for May and October 2020, respectively, and agreed with other seasonal surveys conducted in Europe during that same period. Averaged emissions were in the range of +Δ12 ± 40 ppt for the city and were +Δ9.4 ± 40.9 ppt for urban +Δ22.1 ± 48 ppt for urban green +Δ20.7 ± 42.9 ppt for agricultural and −Δ4.8 ± 19.6 ppt for forest. The urban values ranged from neutral to above background, suggesting nearby anthropogenic and marine emissions such as +Δ150 ppt in Montjuic, which is downwind of Barcelona's harbor. During the crop‐growing season in May, the agricultural areas consistently showed values below the background (up to −Δ76 ppt in Gavà, uptake) at 7:00 UTC when the land breezes were dominant, while later in the morning, when the sea breeze are developed, the plant sink is masked by the transport of marine emissions. Urban forests located north of Tibidabo showed OCS values up to −Δ70 ppt, suggesting significant uptake by urban forests. We conclude that determining the urban biosphere signal using OCS as a tracer is more complex than expected because the marine and anthropogenic emissions from the port strongly impact the spatial‐temporal distribution of OCS. Plain Language Summary: Carbonyl sulfide (OCS) is a gas used to quantify the carbon capture potential of the biosphere. However, cities have potential anthropogenic OCS sources that can impede a clear constraint of the urban biosphere signal. We conducted two sampling campaigns in the Metropolitan Area of Barcelona (AMB), Spain, during May (full COVID lockdown) and October 2020 to measure the variability of OCS in four urban land uses: built, urban forest, urban park, and peri‐urban agriculture. The OCS background levels determined at Tibidabo (were approximately 484 ± 20 ppt and 407 ± 8 ppt for May and October 2020, respectively). The urban built sites were typically above background, suggesting nearby anthropogenic and marine emissions. During the crop‐growing season, the agricultural areas consistently showed values below the background suggesting plant OCS uptake when the land breezes were dominant, while later in the morning, when the sea breezes developed, the influence of marine emission resulted in values above the background. Urban forests showed significant OCS uptake. We conclude that determining the urban biosphere signal using OCS as a tracer is more complex than expected because the marine and anthropogenic emissions from the port strongly impact the spatial‐temporal distribution of OCS. Key Points: The urban built sites were typically above background, suggesting nearby anthropogenic and marine emissionsAgricultural areas consistently showed values below the background suggesting plant Carbonyl sulfide (OCS) uptake when the land breezes were dominantDetermining urban biosphere signal using OCS is complex because marine and anthropogenic emissions impact its spatial‐temporal distribution [ABSTRACT FROM AUTHOR]

Author(s): Stéphane Blain (corresponding author) [1]; Bernard Quéguiner [1]; Leanne Armand [1]; Sauveur Belviso [2]; Bruno Bombled [2]; Laurent Bopp [2]; Andrew Bowie [3, 4]; Christian Brunet [5]; Corina Brussaard [...]

Data on the presence of iron and chlorophyll-alpha are provided for the Antarctic water tongue and coastal zone of the Antarctic Ocean. Both regions were found to be iron-rich, but the low level of chlorophyll-alpha suggests either heavy copepod grazing pressure and/or an inadequate light-mixing regime; offshore waters, however, supported greater phytoplankton growth due to an improved light-mixing regime.

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 budgets 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 -104 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 land surface model to simulate COS fluxes in oxic and anoxic soils. Evaluation of the model against flux measurements at 7 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. 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 in the tropics 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, marginally improves the latitudinal gradient of atmospheric COS concentrations, after transport by the LMDZ 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 spatio-temporal variations of near-ground atmospheric COS concentrations in the modelling of biospheric COS fluxes, which helped reduce the imbalance of the atmospheric COS budget by lowering COS uptake by soils and vegetation globally (-10% for soil, and -8% for vegetation with a revised mean estimate 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. [ABSTRACT FROM AUTHOR]

Carbonyl Sulphide (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 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 have been evaluated against independent measurements over Northern 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. [ABSTRACT FROM AUTHOR]

Land surface modelers 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 normalized to respective ambient concentrations for each vegetation type (Leaf Relative Uptake, LRU). COS leaf fluxes were then computed from GPP, and the resulting concentrations were transported with an atmospheric model which included all other known COS fluxes as inputs. Modelled COS concentrations could then be compared to COS measurements from the NOAA air sampling tower network. 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 global scale, and 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 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 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 second importance as 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. [ABSTRACT FROM AUTHOR]