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

Recent progress of including lake subroutines in numerical weather prediction (NWP) models has led to more accurate forecasts. In lake models, one essential parameter is water clarity, parameterized via the light extinction coefficient, K d , for which a global constant value is usually used. We used direct eddy covariance fluxes and basic meteorological measurements coupled with lake water temperature and clarity measurements from a boreal lake to estimate the performance of two lake models, LAKE and FLake. These models represent two 1-D modeling frameworks broadly used in NWP. The results show that the lake models are very sensitive to changes in K d when it is lower than 0.5 m À1. The progress of thermal stratification depended strongly on K d . In dark-water simulations the mixed layer was shallower, longwave and turbulent heat losses higher, and therefore the average water column temperatures lower than in clear-water simulations. Thus, changes in water clarity can also affect the onset of ice cover. The more complex LAKE modeled the seasonal thermocline deepening, whereas it remained virtually constant during summer in the FLake model. Both models overestimated the surface water temperatures by about 1°C and latent heat flux by >30%, but the variations in heat storage and sensible heat flux were adequately simulated. Our results suggest that, at least for humic lakes, a lake-specific, but not time-depending, constant value for K d can be used and that a global mapping of K d would be most beneficial in regions with relatively clear lakes, e.g., in lakes at high altitudes.

Abstract. Freshwaters bring a notable contribution to the global carbon budget by emitting both carbon dioxide (CO 2 ) and methane (CH 4 ) to the atmosphere. Global estimates of freshwater emissions traditionally use a wind-speed-based gas transfer velocity, k CC (introduced by Cole and Caraco, 1998), for calculating diffusive flux with the boundary layer method (BLM). We compared CH 4 and CO 2 fluxes from BLM with k CC and two other gas transfer velocities (k TE and k HE ), which include the effects of water-side cooling to the gas transfer besides shear-induced turbulence, with simultaneous eddy covariance (EC) and floating chamber (FC) fluxes during a 16-day measurement campaign in September 2014 at Lake Kuivajärvi in Finland. The measurements included both lake stratification and water column mixing periods. Results show that BLM fluxes were mainly lower than EC, with the more recent model k TE giving the best fit with EC fluxes, whereas FC measurements resulted in higher fluxes than simultaneous EC measurements. We highly recommend using up-to-date gas transfer models, instead of k CC , for better flux estimates.BLM CO 2 flux measurements had clear differences between daytime and night-time fluxes with all gas transfer models during both stratified and mixing periods, whereas EC measurements did not show a diurnal behaviour in CO 2 flux. CH 4 flux had higher values in daytime than night-time during lake mixing period according to EC measurements, with highest fluxes detected just before sunset. In addition, we found clear differences in daytime and night-time concentration difference between the air and surface water for both CH 4 and CO 2 . This might lead to biased flux estimates, if only daytime values are used in BLM upscaling and flux measurements in general.FC measurements did not detect spatial variation in either CH 4 or CO 2 flux over Lake Kuivajärvi. EC measurements, on the other hand, did not show any spatial variation in CH 4 fluxes but did show a clear difference between CO 2 fluxes from shallower and deeper areas. We highlight that while all flux measurement methods have their pros and cons, it is important to carefully think about the chosen method and measurement interval, as well as their effects on the resulting flux.

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.

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.

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.

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.