Carbonyl Sulfide Fluxes Research Articles

Root and rhizosphere contribution to the net soil COS exchange

Background and aimsPartitioning the measured net ecosystem carbon dioxide (CO2) exchange into gross primary productivity (GPP) and ecosystem respiration remains a challenge, which scientists try to tackle by using the properties of the trace gas carbonyl sulfide (COS). Its similar pathway into and within the leaf makes it a potential photosynthesis proxy. The application of COS as an effective proxy depends, among other things, on a robust inventory of potential COS sinks and sources within ecosystems. While the soil received some attention during the last couple of years, the role of plant roots is mostly unknown. In our study, we investigated the effects of live roots on the soil COS exchange.MethodsAn experimental setup was devised to measure the soil and the belowground plant parts of young beech trees observed over the course of 9 months.ResultsDuring the growing season, COS emissions were significantly lower when roots were present compared to chambers only containing soil, while prior to the growing season, with photosynthetically inactive trees, the presence of roots increased COS emissions. The difference in the COS flux between root-influenced and uninfluenced soil was fairly constant within each month, with diurnal variations in the COS flux driven primarily by soil temperature changes rather than the presence or absence of roots.ConclusionWhile the mechanisms by which roots influence the COS exchange are largely unknown, their contribution to the overall ground surface COS exchange should not be neglected when quantifying the soil COS exchange.

Sources and sinks of carbonyl sulfide inferred from tower and mobile atmospheric observations in the Netherlands

Abstract. Carbonyl sulfide (COS) is a promising tracer for the estimation of terrestrial ecosystem gross primary production (GPP). However, understanding its non-GPP-related sources and sinks, e.g., anthropogenic sources and soil sources and sinks, is also critical to the success of the approach. Here we infer the regional sources and sinks of COS using continuous in situ mole fraction profile measurements of COS along the 60 m tall Lutjewad tower (1 m a.s.l.; 53∘24′ N, 6∘21′ E) in the Netherlands. To identify potential sources that caused the observed enhancements of COS mole fractions at Lutjewad, both discrete flask samples and in situ measurements in the province of Groningen were made from a mobile van using a quantum cascade laser spectrometer (QCLS). We also simulated the COS mole fractions at Lutjewad using the Stochastic Time-Inverted Lagrangian Transport (STILT) model combined with emission inventories and plant uptake fluxes. We determined the nighttime COS fluxes to be -3.0±2.6 pmol m−2 s−1 using the radon-tracer correlation approach and Lutjewad observations. Furthermore, we identified and quantified several COS sources, including biodigesters, sugar production facilities and silicon carbide production facilities in the province of Groningen. Moreover, the simulation results show that the observed COS enhancements can be partially explained by known industrial sources of COS and CS2, in particular from the Ruhr Valley (51.5∘ N, 7.2∘ E) and Antwerp (51.2∘ N, 4.4∘ E) areas. The contribution of likely missing anthropogenic sources of COS and CS2 in the inventory may be significant. The impact of the identified sources in the province of Groningen is estimated to be negligible in terms of the observed COS enhancements. However, in specific conditions, these sources may influence the measurements in Lutjewad. These results are valuable for improving our understanding of the sources and sinks of COS, contributing to the use of COS as a tracer for GPP.

Optimizing the carbonic anhydrase temperature response and stomatal conductance of carbonyl sulfide leaf uptake in the Simple Biosphere model (SiB4)

Abstract. Carbonyl sulfide (COS) is a useful tracer to estimate gross primary production (GPP) because it shares part of the uptake pathway with CO2. COS is taken up in plants through hydrolysis, catalyzed by the enzyme carbonic anhydrase (CA), but is not released. The Simple Biosphere model version 4 (SiB4) simulates COS leaf uptake using a conductance approach. SiB4 applies the temperature response of the RuBisCo enzyme (used for photosynthesis) to simulate the COS leaf uptake, but the CA enzyme might respond differently to temperature. We introduce a new temperature response function for CA in SiB4, based on enzyme kinetics with an optimum temperature. Moreover, we determine Ball–Woodrow–Berry (BWB) model parameters for stomatal conductance (gs) using observation-based estimates of COS flux, GPP, and gs along with meteorological measurements in an evergreen needleleaf forest (ENF) and deciduous broadleaf forest (DBF). We find that CA has optimum temperatures of 20 ∘C (ENF) and 36 ∘C (DBF), which is lower than that of RuBisCo (45 ∘C), suggesting that canopy temperature changes can critically affect CA's catalyzation activity. Optimized values for the BWB offset parameter are similar to the original value (0.010 ± 0.003 mol m−2 s−1), and optimized values for the BWB slope parameter (ENF: 16.4, DBF: 11.4) are higher than the original value (9.0) at both sites. The optimization reduces prior errors on all parameters by more than 50 % at both stations. We apply the optimized gi and gs parameters in SiB4 site simulations, thereby improving the timing and peak of COS assimilation. In addition, we show that SiB4 underestimates the leaf humidity stress under conditions where high vapor pressure deficit (VPD) should limit gs in the afternoon, thereby overestimating gs. Furthermore, global COS biosphere sinks with optimized parameters show smaller COS uptake in regions where the air temperature is over 25 ∘C, mostly in the tropics, and larger uptake in regions where the temperature is below 25 ∘C. This change corresponds with reported deficiencies in the global COS fluxes, such as missing sinks at high latitudes and required sources in the tropics. Using our optimization and additional observations of COS uptake over various climate and plant types, we expect further improvements in global COS biosphere flux estimates.

Carbon and Water Fluxes of the Boreal Evergreen Needleleaf Forest Biome Constrained by Assimilating Ecosystem Carbonyl Sulfide Flux Observations

AbstractGross primary production (GPP) by boreal forests is highly sensitive to environmental changes. However, GPP simulated by land surface models (LSMs) remains highly uncertain due to the lack of direct photosynthesis observations at large scales. Carbonyl sulfide (COS) has emerged as a promising proxy to improve the representation of GPP in LSMs. Because COS is absorbed by vegetation following the same diffusion pathway as CO2 during photosynthesis and not emitted back to the atmosphere, incorporating a mechanistic representation of vegetation COS uptake in LSMs allows using COS observations to refine GPP representation. Here, we perform ecosystem COS flux and GPP data assimilations to constrain the COS‐ and GPP‐related parameters in the ORCHIDEE LSM for boreal evergreen needleleaf forests (BorENF). Assimilating ecosystem COS fluxes at Hyytiälä forest increases the simulated net ecosystem COS uptake by 14%. This increase largely results from changes in the internal conductance to COS, highlighting the need to improve the representation of COS internal diffusion and consumption. Moreover, joint assimilation of ecosystem COS flux and GPP at Hyytiälä improves the simulated latent heat flux, contrary to the GPP‐only data assimilation, which fails to do so. Finally, we scaled this assimilation framework up to the boreal region and find that the joint assimilation of COS at Hyytiälä and GPP fluxes at 10 BorENF sites increases the modeled vegetation COS uptake up to 18%, but not GPP. Therefore, this study encourages the use of COS flux observations to inform GPP and latent heat flux representations in LSMs.

On the variability of the leaf relative uptake rate of carbonyl sulfide compared to carbon dioxide: Insights from a paired field study with two soybean varieties

Carbonyl sulfide (COS) has been proposed as a promising tracer for the estimation of the gross primary productivity (GPP) from ecosystem to global scale in recent years. Despite substantial work at spatial scales from leaf to regions, the uncertainty of COS-based GPP estimates are poorly known compared to widely used GPP estimates derived from the net ecosystem CO2 exchange. One key uncertainty in this context is the leaf relative uptake (LRU) of the COS with respect to the GPP, which must be known a priori. To investigate the influence of environmental factors, like drought, on the variability of the LRU, we conducted an experiment using ecosystem flux measurements of COS, CO2 and H2O from two eddy covariance towers above a soybean field, growing a commercial cultivar and a chlorophyll deficient mutant variety, in two separate plots. Our findings suggest that the LRU does not only differ between plant varieties due to differences in the ratio of the internal to ambient CO2 mole fraction and the internal resistance to COS, but also changes in response to drought. We also found the internal resistance to COS uptake to be a significant factor in controlling the total COS flux for both varieties, but more so for the commercial cultivar. Our study indicates that species-specific differences in the LRU need to be investigated further, and that environmental stress might complicate the usage of COS as a tracer for predicting GPP at ecosystem and global scale.

Intercomparison of Atmospheric Carbonyl Sulfide (TransCom‐COS; Part One): Evaluating the Impact of Transport and Emissions on Tropospheric Variability Using Ground‐Based and Aircraft Data

AbstractWe present a comparison of atmospheric transport model (ATM) simulations for carbonyl sulfide (COS), within the framework of the atmospheric tracer transport model intercomparison project “TransCom‐COS.” Seven ATMs participated in the experiment and provided simulations of COS mixing ratios over the years 2010–2018, using state‐of‐the‐art surface fluxes for various components of the COS budget: biospheric sink, oceanic source, sources from fire and industry. The main goal of TransCom‐COS is to investigate the impact of the transport uncertainty and emission distribution in simulating the spatio‐temporal variability of tropospheric COS mixing ratios. A control case with seasonal surface fluxes of COS was constructed. The results indicate that the COS mixing ratios are underestimated by at least 50 parts per trillion (ppt) in the tropics, pointing to a missing tropical source. In summer, the mixing ratios are overestimated by at least 50 ppt above 40°N, pointing to a likely missing sink in the high northern latitudes. Regarding the latitudinal profile, the model spread is greater than 60 ppt above 40°N in boreal summer. Regarding the seasonal amplitude, the model spread reaches 50 ppt at 6 out of 15 sites, compared to an observed seasonal amplitude of 100 ppt. All models simulated a too late minimum by at least 2–3 months at two high northern‐latitude sites, likely owing to errors in the seasonal cycle in the ocean emissions. This study highlighted the shortcomings in the COS global budget that need to be resolved before using COS as a photosynthesis tracer.

Simulating canopy carbonyl sulfide uptake of two forest stands through an improved ecosystem model and parameter optimization using an ensemble Kalman filter

The uptake of carbonyl sulfide (COS) by plant canopy closely correlated with photosynthetic CO2 uptake as they share the same diffusion pathway. Process-based ecosystem models have been used to simulate the CO2, H2O and COS fluxes between terrestrial ecosystems and atmosphere. Some model parameters often vary seasonally and interannually. In this study, the hourly Boreal Ecosystem Productivity Simulator (BEPS) was first improved to simulate the canopy COS uptake rate. Then, an ensemble Kalman filter was designed to optimize the key parameters of the hourly BEPS model, considering the errors in the input, parameters and measurements. The optimized parameters include leaf maximum carboxylation rate at 25 °C at top of canopy (Vcmax250) and a calibration term (α) used to scale the apparent conductance for COS uptake from the intercellular airspace (gcos) to Vcmax. The fluxes of gross primary productivity (GPP), latent heat (LE) and COS uptake by canopy (Fcos_veg) measured using eddy covariance method at a temperate deciduous forest during 2012–2013 and a boreal conifer forest during 2013–2017 were used for data assimilation. Parameters were optimized daily and presented as 10-day averages. It was found that the parameters showed considerable seasonally and interannually variations. With parameter optimization using EnKF, the improved hourly BEPS model could explain 86%, 68% and 55% of variations in measured daily GPP, LE and Fcos_veg at US-Ha1 site during 2012 and 2013 and captured 90%, 74% and 69% of variations in the measured GPP, LE and Fcos_veg at FI-Hyy site during 2013–2017, respectively. The simulated daily Fcos_veg with the parameters optimized using EnKF could capture the day-to-day variations of Fcos_veg at the two studied sites and performed better than the simulations with calibrated parameter values. Further efforts were required to investigate the impacts of model structure and different parameter optimization methods on the optimized parameter values.

Intercomparison of methods to estimate gross primary production based on CO2 and COS flux measurements.

Separating the components of ecosystem-scale carbon exchange is crucial in order to develop better models and future predictions of the terrestrial carbon cycle. However, there are several uncertainties and unknowns related to current photosynthesis estimates. In this study, we evaluate four different methods for estimating photosynthesis at a boreal forest at the ecosystem scale, of which two are based on carbon dioxide (CO2) flux measurements and two on carbonyl sulfide (COS) flux measurements. The CO2-based methods use traditional flux partitioning and artificial neural networks to separate the net CO2 flux into respiration and photosynthesis. The COS-based methods make use of a unique 5-year COS flux data set and involve two different approaches to determine the leaf-scale relative uptake ratio of COS and CO2 (LRU), of which one (LRUCAP) was developed in this study. LRUCAP was based on a previously tested stomatal optimization theory (CAP), while LRUPAR was based on an empirical relation to measured radiation.For the measurement period 2013–2017, the artificial neural network method gave a GPP estimate very close to that of traditional flux partitioning at all timescales. On average, the COS-based methods gave higher GPP estimates than the CO2-based estimates on daily (23% and 7% higher, using LRUPAR and LRUCAP, respectively) and monthly scales (20% and 3% higher), as well as a higher cumulative sum over 3 months in all years (on average 25% and 3% higher). LRUCAP was higher than LRU estimated from chamber measurements at high radiation, leading to underestimation of midday GPP relative to other GPP methods. In general, however, use of LRUCAP gave closer agreement with CO2-based estimates of GPP than use of LRUPAR. When extended to other sites, LRUCAP may be more robust than LRUPAR because it is based on a physiological model whose parameters can be estimated from simple measurements or obtained from the literature. In contrast, the empirical radiation relation in LRUPAR may be more site-specific. However, this requires further testing at other measurement sites.

Leaf relative uptake of carbonyl sulfide to CO2 seen through the lens of stomatal conductance-photosynthesis coupling.

Carbonyl sulfide (COS) has emerged as a multi-scale tracer for terrestrial photosynthesis. To infer ecosystem-scale photosynthesis from COS fluxes often requires knowledge of leaf relative uptake (LRU), the concentration-normalized ratio between leaf COS uptake and photosynthesis. However, current mechanistic understanding of LRU variability remains inadequate for deriving robust COS-based estimates of photosynthesis. We derive a set of closed-form equations to describe LRU responses to light, humidity and CO2 based on the Ball-Berry stomatal conductance model and the biochemical model of photosynthesis. This framework reproduces observed LRU responses: decreasing LRU with increasing light or decreasing humidity; it also predicts that LRU increases with ambient CO2 . By fitting the LRU equations to flux measurements on a C3 reed (Typha latifolia), we obtain physiological parameters that control LRU variability, including an estimate of the Ball-Berry slope of 7.1 without using transpiration measurements. Sensitivity tests reveal that LRU is more sensitive to photosynthetic capacity than to the Ball-Berry slope, indicating stomatal response to photosynthesis. This study presents a simple framework for interpreting observed LRU variability and upscaling LRU. The stoma-regulated LRU response to CO2 suggests that COS may offer a unique window into long-term stomatal acclimation to elevated CO2 .

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.

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.

Long-term fluxes of carbonyl sulfide and their seasonality and interannual variability in a boreal forest

Abstract. The seasonality and interannual variability of terrestrial carbonyl sulfide (COS) fluxes are poorly constrained. We present the first easy-to-use parameterization for the net COS forest sink based on the longest existing eddy covariance record from a boreal pine forest, covering 32 months over 5 years. Fluxes from hourly to yearly scales are reported, with the aim of revealing controlling factors and the level of interannual variability. The parameterization is based on the photosynthetically active radiation, vapor pressure deficit, air temperature, and leaf area index. Wavelet analysis of the ecosystem fluxes confirmed earlier findings from branch-level fluxes at the same site and revealed a 3 h lag between COS uptake and air temperature maxima at the daily scale, whereas no lag between radiation and COS flux was found. The spring recovery of the flux after the winter dormancy period was mostly governed by air temperature, and the onset of the uptake varied by 2 weeks. For the first time, we report a significant reduction in ecosystem-scale COS uptake under a large water vapor pressure deficit in summer. The maximum monthly and weekly median COS uptake varied by 26 % and 20 % between years, respectively. The timing of the latter varied by 6 weeks. The fraction of the nocturnal uptake remained below 21 % of the total COS uptake. We observed the growing season (April–August) average net flux of COS totaling −58.0 g S ha−1 with 37 % interannual variability. The long-term flux observations were scaled up to evergreen needleleaf forests (ENFs) in the whole boreal region using the Simple Biosphere Model Version 4 (SiB4). The observations were closely simulated using SiB4 meteorological drivers and phenology. The total COS uptake by boreal ENFs was in line with a missing COS sink at high latitudes pointed out in earlier studies.

Evaluation of carbonyl sulfide biosphere exchange in the Simple Biosphere Model (SiB4)

Abstract. The uptake of carbonyl sulfide (COS) by terrestrial plants is linked to photosynthetic uptake of CO2 as these gases partly share the same uptake pathway. Applying COS as a photosynthesis tracer in models requires an accurate representation of biosphere COS fluxes, but these models have not been extensively evaluated against field observations of COS fluxes. In this paper, the COS flux as simulated by the Simple Biosphere Model, version 4 (SiB4), is updated with the latest mechanistic insights and evaluated with site observations from different biomes: one evergreen needleleaf forest, two deciduous broadleaf forests, three grasslands, and two crop fields spread over Europe and North America. We improved SiB4 in several ways to improve its representation of COS. To account for the effect of atmospheric COS mole fractions on COS biosphere uptake, we replaced the fixed atmospheric COS mole fraction boundary condition originally used in SiB4 with spatially and temporally varying COS mole fraction fields. Seasonal amplitudes of COS mole fractions are ∼50–200 ppt at the investigated sites with a minimum mole fraction in the late growing season. Incorporating seasonal variability into the model reduces COS uptake rates in the late growing season, allowing better agreement with observations. We also replaced the empirical soil COS uptake model in SiB4 with a mechanistic model that represents both uptake and production of COS in soils, which improves the match with observations over agricultural fields and fertilized grassland soils. The improved version of SiB4 was capable of simulating the diurnal and seasonal variation in COS fluxes in the boreal, temperate, and Mediterranean region. Nonetheless, the daytime vegetation COS flux is underestimated on average by 8±27 %, albeit with large variability across sites. On a global scale, our model modifications decreased the modeled COS terrestrial biosphere sink from 922 Gg S yr−1 in the original SiB4 to 753 Gg S yr−1 in the updated version. The largest decrease in fluxes was driven by lower atmospheric COS mole fractions over regions with high productivity, which highlights the importance of accounting for variations in atmospheric COS mole fractions. The change to a different soil model, on the other hand, had a relatively small effect on the global biosphere COS sink. The secondary role of the modeled soil component in the global COS budget supports the use of COS as a global photosynthesis tracer. A more accurate representation of COS uptake in SiB4 should allow for improved application of atmospheric COS as a tracer of local- to global-scale terrestrial photosynthesis.

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.

Seasonal dynamics of the COS and CO<sub>2</sub> exchange of a managed temperate grassland

Abstract. Gross primary productivity (GPP), the CO2 uptake by means of photosynthesis, cannot be measured directly on the ecosystem scale but has to be inferred from proxies or models. One newly emerged proxy is the trace gas carbonyl sulfide (COS). COS diffuses into plant leaves in a fashion very similar to CO2 but is generally not emitted by plants. Laboratory studies on leaf level gas exchange have shown promising correlations between the leaf relative uptake (LRU) of COS to CO2 under controlled conditions. However, in situ measurements including daily to seasonal environmental changes are required to test the applicability of COS as a tracer for GPP at larger temporal scales. To this end, we conducted concurrent ecosystem-scale CO2 and COS flux measurements above an agriculturally managed temperate mountain grassland. We also determined the magnitude and variability of the soil COS exchange, which can affect the LRU on an ecosystem level. The cutting and removal of the grass at the site had a major influence on the soil flux as well as the total exchange of COS. The grassland acted as a major sink for CO2 and COS during periods of high leaf area. The sink strength decreased after the cuts, and the grassland turned into a net source for CO2 and COS on an ecosystem level. The soil acted as a small sink for COS when the canopy was undisturbed but also turned into a source after the cuts, which we linked to higher incident radiation hitting the soil surface. However, the soil contribution was not large enough to explain the COS emission on an ecosystem level, hinting at an unknown COS source possibly related to dead plant matter degradation. Over the course of the season, we observed a concurrent decrease in CO2 and COS uptake on an ecosystem level. With the exception of the short periods after the cuts, the LRU under high-light conditions was rather stable and indicated a high correlation between the COS flux and GPP across the growing season.

Towards standardized processing of eddy covariance flux measurements of carbonyl sulfide

Abstract. Carbonyl sulfide (COS) flux measurements with the eddy covariance (EC) technique are becoming popular for estimating gross primary productivity. To compare COS flux measurements across sites, we need standardized protocols for data processing. In this study, we analyze how various data processing steps affect the calculated COS flux and how they differ from carbon dioxide (CO2) flux processing steps, and we provide a method for gap-filling COS fluxes. Different methods for determining the time lag between COS mixing ratio and the vertical wind velocity (w) resulted in a maximum of 15.9 % difference in the median COS flux over the whole measurement period. Due to limited COS measurement precision, small COS fluxes (below approximately 3 pmol m−2 s−1) could not be detected when the time lag was determined from maximizing the covariance between COS and w. The difference between two high-frequency spectral corrections was 2.7 % in COS flux calculations, whereas omitting the high-frequency spectral correction resulted in a 14.2 % lower median flux, and different detrending methods caused a spread of 6.2 %. Relative total uncertainty was more than 5 times higher for low COS fluxes (lower than ±3 pmol m−2 s−1) than for low CO2 fluxes (lower than ±1.5 µmol m−2 s−1), indicating a low signal-to-noise ratio of COS fluxes. Due to similarities in ecosystem COS and CO2 exchange, we recommend applying storage change flux correction and friction velocity filtering as usual in EC flux processing, but due to the low signal-to-noise ratio of COS fluxes, we recommend using CO2 data for time lag and high-frequency corrections of COS fluxes due to the higher signal-to-noise ratio of CO2 measurements.

Soil COS Exchange: A Comparison of Three European Ecosystems

AbstractThe potential of carbonyl sulfide (COS) flux measurements as an additional constraint for estimating the gross primary production depends, among other preconditions, on our understanding of the soil COS exchange and its contribution to the overall net ecosystem COS flux. We conducted soil chamber measurements of COS, with transparent chambers, in three different ecosystems across Europe. The in situ measurements were followed by laboratory measurements of soil samples collected at the study sites. The soil samples were exposed to UV radiation to investigate the role of photo‐degradation for COS exchange. In situ and laboratory measurements revealed pronounced intersite and intrasite variability of COS exchange. In situ COS fluxes were primarily governed by radiation in the savannah‐like grassland (SAV), soil temperature and intrasite heterogeneity in the deciduous broadleaf forest, and soil water content and intrasite heterogeneity in the evergreen needleleaf forest. The soil of the ecosystem with the highest light intensity incident on the soil surface, SAV, was a net source for COS, while the soils of the other two ecosystems were COS sinks. UV radiation increased COS emissions and/or reduced COS uptake from all soil samples under laboratory conditions. The impact of UV on the COS flux differed between soil samples, with a tendency toward a stronger response of the COS flux to UV radiation exposure in samples with higher soil organic matter content. Our results emphasize the importance of photo‐degradation for the soil COS flux and stress the substantial spatial variability of soil COS exchange in ecosystems.

Seasonal Evolution of Canopy Stomatal Conductance for a Prairie and Maize Field in the Midwestern United States from Continuous Carbonyl Sulfide Fluxes

AbstractThere are inherent challenges in scaling stomatal conductance (g ) from leaf to canopy particularly over seasonal time scales when species distribution and canopy structure evolve. We address this gap using carbonyl sulfide (OCS) and CO fluxes from a predominantly C3 prairie and C4 maize field in the midwestern United States. The g derived from OCS fluxes captured a transition in the stomatal limitation on gross primary productivity (GPP) through the growing season as well as seasonally persistent g dynamics such as temperature optimum and a positive response of nighttime g to vapor pressure deficit. Near the termination of the prairie growing season, we observed a decrease in the relative OCS to CO flux that we hypothesize emerged from a rising contribution of C4 plants to productivity. The results show how plot‐scale OCS and CO fluxes can be used as a trace gas diagnostic for transitions in the limiting factors for community GPP.

A top-down approach of sources and non-photosynthetic sinks of carbonyl sulfide from atmospheric measurements over multiple years in the Paris region (France).

Carbonyl sulfide (COS) has been proposed as a proxy for carbon dioxide (CO2) taken up by plants at the leaf and ecosystem scales. However, several additional production and removal processes have been identified which could complicate its use at larger scales, among which are soil uptake, dark uptake by plants, and soil and anthropogenic emissions. This study evaluates the significance of these processes at the regional scale through a top-down approach based on atmospheric COS measurements at Gif-sur-Yvette (GIF), a suburban site near Paris (France). Over a period of four and a half years, hourly measurements at 7 m above ground level were performed by gas chromatography and combined with 222Radon measurements to calculate nocturnal COS fluxes using the Radon-Tracer Method. In addition, the vertical distribution of COS was investigated at a second site, 2 km away from GIF, where a fast gas analyzer deployed on a 100 m tower for several months during winter 2015-2016 recorded mixing ratios at 3 heights (15, 60 and 100 m). COS appears to be homogeneously distributed both horizontally and vertically in the sampling area. The main finding is that the area is a persistent COS sink even during wintertime episodes of strong pollution. Nighttime net uptake rates ranged from -1.5 to -32.8 pmol m-2 s-1, with an average of -7.3 ± 4.5 pmol m-2 s-1 (n = 253). However, episodes of biogenic emissions happened each year in June-July (11.9 ± 6.2 pmol m-2 s-1, n = 24). Preliminary analyses of simulated footprints of source areas influencing the recorded COS data suggest that long-range transport of COS from anthropogenic sources located in Benelux, Eastern France and Germany occasionally impacts the Paris area during wintertime. These production and removal processes may limit the use of COS to assess regional-scale CO2 uptake in Europe by plants through inverse modeling.

Reviews and syntheses: Turning the challenges of partitioning ecosystem evaporation and transpiration into opportunities

Abstract. 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.