Leaf Relative Uptake Research Articles

Constraining the budget of atmospheric carbonyl sulfide using a 3-D chemical transport model

Abstract. Carbonyl sulfide (OCS) has emerged as a valuable proxy for photosynthetic uptake of carbon dioxide (CO2) and is known to be important in the formation of aerosols in the stratosphere. However, uncertainties in the global OCS budget remain large. This is mainly due to the following three flux terms: vegetation uptake, soil uptake and oceanic emissions. Bottom-up estimates do not yield a closed budget, which is thought to be due to tropical emissions of OCS that are not accounted for. Here we present a simulation of atmospheric OCS over the period 2004–2018 using the TOMCAT 3-D chemical transport model that is aimed at better constraining some terms in the OCS budget. Vegetative uptake of OCS is estimated by scaling gross primary productivity (GPP) output from the Joint UK Land Environment Simulator (JULES) using the leaf relative uptake (LRU) approach. The remaining surface budget terms are taken from available literature flux inventories and adequately scaled to bring the budget into balance. The model is compared with limb-sounding satellite observations made by the Atmospheric Chemistry Experiment – Fourier Transform Spectrometer (ACE-FTS) and surface flask measurements from 14 National Oceanic and Atmospheric Administration – Earth System Research Laboratory (NOAA-ESRL) sites worldwide. We find that calculating vegetative uptake using the LRU underestimates the surface seasonal cycle amplitude (SCA) in the Northern Hemisphere (NH) mid-latitudes and high latitudes by approximately 37 ppt (35 %). The inclusion of a large tropical source is able to balance the global budget, but further improvement to the SCA and phasing would likely require a flux inversion scheme. Compared to co-located ACE-FTS OCS profiles between 5 and 30 km, TOMCAT remains within 25 ppt (approximately 5 % of mean tropospheric concentration) of the measurements throughout the majority of this region and lies within the standard deviation of these measurements. This provides confidence in the representation of atmospheric loss and surface fluxes of OCS in the model. Atmospheric sinks account for 154 Gg S of the annual budget, which is 10 %–50 % larger than previous studies. Comparing the surface monthly anomalies from the NOAA-ESRL flask data to the model simulations shows a root-mean-square error range of 3.3–25.8 ppt. We estimate the total biosphere uptake to be 951 Gg S, which is in the range of recent inversion studies (893–1053 Gg S), but our terrestrial vegetation flux accounts for 629 Gg S of the annual budget, which is lower than other recent studies (657–756 Gg S). However, to close the budget, we compensate for this with a large annual oceanic emission term of 689 Gg S focused over the tropics, which is much larger than bottom-up estimates (285 Gg S). Hence, we agree with recent findings that missing OCS sources likely originate from the tropical region. This work shows that satellite OCS profiles offer a good constraint on atmospheric sinks of OCS through the troposphere and stratosphere and are therefore useful for helping to improve surface budget terms. This work also shows that the LRU approach is an adequate representation of the OCS vegetative uptake, but this method could be improved by various means, such as using a higher-resolution GPP product or plant-functional-type-dependent LRU. Future work will utilise TOMCAT in a formal inversion scheme to better quantify the OCS budget.

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.

Technical note: Novel estimates of the leaf relative uptake rate of carbonyl sulfide from optimality theory

Abstract. In order to estimate the gross primary productivity (GPP) of terrestrial ecosystems from the canopy uptake of carbonyl sulfide (COS), leaf relative uptake rate (LRU) of COS with respect to carbon dioxide needs to be known a priori. Currently, the variability of LRU between plant species in different biomes of the world is poorly understood, making the choice of an appropriate LRU uncertain and hampering further progress towards developing COS as a tracer of GPP. Here we propose a novel approach for estimating light-saturated LRU based on plant optimality principles, validate it against in situ leaf gas exchange measurements and provide global monthly climatological estimates. The global vegetation season average simulated LRUs fall into the 95 % range of 0.68–1.58 and are thus lower than most other published global estimates. We advocate for these LRU estimates to be adopted by global modellers in order to test to what degree these are compatible with our current understanding of the sources and sinks in the global COS budget.

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 .

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.

Plant gross primary production, plant respiration and carbonyl sulfide emissions over the globe inferred by atmospheric inverse modelling

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.

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.

Influences of light and humidity on carbonyl sulfide-based estimates of photosynthesis

Understanding climate controls on gross primary productivity (GPP) is crucial for accurate projections of the future land carbon cycle. Major uncertainties exist due to the challenge in separating GPP and respiration from observations of the carbon dioxide (CO2) flux. Carbonyl sulfide (COS) has a dominant vegetative sink, and plant COS uptake is used to infer GPP through the leaf relative uptake (LRU) ratio of COS to CO2 fluxes. However, little is known about variations of LRU under changing environmental conditions and in different phenological stages. We present COS and CO2 fluxes and LRU of Scots pine branches measured in a boreal forest in Finland during the spring recovery and summer. We find that the diurnal dynamics of COS uptake is mainly controlled by stomatal conductance, but the leaf internal conductance could significantly limit the COS uptake during the daytime and early in the season. LRU varies with light due to the differential light responses of COS and CO2 uptake, and with vapor pressure deficit (VPD) in the peak growing season, indicating a humidity-induced stomatal control. Our COS-based GPP estimates show that it is essential to incorporate the variability of LRU with environmental variables for accurate estimation of GPP on ecosystem, regional, and global scales.

Large Uptake of Atmospheric OCS Observed at a Moist Old Growth Forest: Controls and Implications for Carbon Cycle Applications

AbstractDiurnal and vertical patterns of carbonyl sulfide (OCS) and CO2 mixing ratios above and within a 60‐m‐tall old‐growth temperate forest are presented. Canopy air from four different heights was sampled in situ using a continuous integrated cavity output spectroscopy analyzer during August–September 2014. Measurements revealed large vertical gradients in OCS, from which we inferred ecosystem fluxes. The diurnal cycle of OCS mixing ratios at all heights exhibited a typical pattern characterized by nighttime drawdown, an early morning minimum, and a maximum of OCS around midday. Daytime increase in the upper canopy is attributed to entrainment of planetary boundary layer air into the canopy. The ecosystem was found to be a large daytime sink of OCS (mean maximum daytime flux ~ −75 pmol · m−2 · s−1). Mean leaf relative uptake (concentration normalized uptake of OCS flux to CO2 uptake) was found to be 6.9. We discuss this high leaf relative uptake in the context of the presence and distribution of epiphytes at the site. While epiphytic uptake of OCS has been studied before, we show for the first time that this may contribute significantly to ecosystem fluxes under humid or moist conditions. We test this theory using a chamber experiment measuring epiphytic fluxes for two species of lichen and one moss species (in situ and in a laboratory). We suggest that the role of epiphytes should be explicitly considered when using OCS as a tracer of ecosystem‐scale photosynthesis in forest ecosystems with abundant epiphytic cover and biomass.

Stomatal control of leaf fluxes of carbonyl sulfide and CO<sub>2</sub> in a <i>Typha</i> freshwater marsh

Abstract. Carbonyl sulfide (COS) is an emerging tracer to constrain land photosynthesis at canopy to global scales, because leaf COS and CO2 uptake processes are linked through stomatal diffusion. The COS tracer approach requires knowledge of the concentration normalized ratio of COS uptake to photosynthesis, commonly known as the leaf relative uptake (LRU). LRU is known to increase under low light, but the environmental controls over LRU variability in the field are poorly understood due to scant leaf scale observations. Here we present the first direct observations of LRU responses to environmental variables in the field. We measured leaf COS and CO2 fluxes at a freshwater marsh in summer 2013. Daytime leaf COS and CO2 uptake showed similar peaks in the mid-morning and late afternoon separated by a prolonged midday depression, highlighting the common stomatal control on diffusion. At night, in contrast to CO2, COS uptake continued, indicating partially open stomata. LRU ratios showed a clear relationship with photosynthetically active radiation (PAR), converging to 1.0 at high PAR, while increasing sharply at low PAR. Daytime integrated LRU (calculated from daytime mean COS and CO2 uptake) ranged from 1 to 1.5, with a mean of 1.2 across the campaign, significantly lower than the previously reported laboratory mean value (∼ 1.6). Our results indicate two major determinants of LRU – light and vapor deficit. Light is the primary driver of LRU because CO2 assimilation capacity increases with light, while COS consumption capacity does not. Superimposed upon the light response is a secondary effect that high vapor deficit further reduces LRU, causing LRU minima to occur in the afternoon, not at noon. The partial stomatal closure induced by high vapor deficit suppresses COS uptake more strongly than CO2 uptake because stomatal resistance is a more dominant component in the total resistance of COS. Using stomatal conductance estimates, we show that LRU variability can be explained in terms of different patterns of stomatal vs. internal limitations on COS and CO2 uptake. Our findings illustrate the stomata-driven coupling of COS and CO2 uptake during the most photosynthetically active period in the field and provide an in situ characterization of LRU – a key parameter required for the use of COS as a photosynthetic tracer.

Assessing canopy performance using carbonyl sulfide measurements.

Carbonyl sulfide (COS) is a tracer of ecosystem photosynthesis that can advance carbon cycle research from leaf to global scales; however, a range of newly reported caveats related to sink/source strength of various ecosystem components hinder its application. Using comprehensive eddy-covariance and chamber measurements, we systematically measure ecosystem contributions from leaf, stem, soil, and litter and were able to close the ecosystem COS budget. The relative contributions of nonphotosynthetic components to the overall canopy-scale flux are relatively small (~4% during peak activity season) and can be independently estimated based on their responses to temperature and humidity. Converting COS to photosynthetic CO2 fluxes based on the leaf relative uptake of COS/CO2 , faces challenges due to observed daily and seasonal changes. Yet, this ratio converges around a constant value (~1.6), and the variations, dominated by light intensity, were found unimportant on a flux-weighted daily time-scale, indicating a mean ratio of daytime gross-to-net primary productivity of ~2 in our ecosystem. The seasonal changes in the leaf relative uptake ratio may indicate a reduction in mesophyll conductance in winter, and COS-derived canopy conductance permitted canopy temperature estimate consistent with radiative skin temperature. These results support the feasibility of using COS as a powerful and much-needed means of assessing ecosystem function and its response to change.

A new model of the global biogeochemical cycle of carbonyl sulfide – Part 2: Use of carbonyl sulfide to constrain gross primary productivity in current vegetation models

Abstract. Clear analogies between carbonyl sulfide (OCS) and carbon dioxide (CO2) diffusion pathways through leaves have been revealed by experimental studies, with plant uptake playing an important role for the atmospheric budget of both species. Here we use atmospheric OCS to evaluate the gross primary production (GPP) of three dynamic global vegetation models (Lund–Potsdam–Jena, LPJ; National Center for Atmospheric Research – Community Land Model 4, NCAR-CLM4; and Organising Carbon and Hydrology In Dynamic Ecosystems, ORCHIDEE). Vegetation uptake of OCS is modeled as a linear function of GPP and leaf relative uptake (LRU), the ratio of OCS to CO2 deposition velocities of plants. New parameterizations for the non-photosynthetic sinks (oxic soils, atmospheric oxidation) and biogenic sources (oceans and anoxic soils) of OCS are also provided. Despite new large oceanic emissions, global OCS budgets created with each vegetation model show exceeding sinks by several hundred Gg S yr−1. An inversion of the surface fluxes (optimization of a global scalar which accounts for flux uncertainties) led to balanced OCS global budgets, as atmospheric measurements suggest, mainly by drastic reduction (up to −50 %) in soil and vegetation uptakes. The amplitude of variations in atmospheric OCS mixing ratios is mainly dictated by the vegetation sink over the Northern Hemisphere. This allows for bias recognition in the GPP representations of the three selected models. The main bias patterns are (i) the terrestrial GPP of ORCHIDEE at high northern latitudes is currently overestimated, (ii) the seasonal variations of the GPP are out of phase in the NCAR-CLM4 model, showing a maximum carbon uptake too early in spring in the northernmost ecosystems, (iii) the overall amplitude of the seasonal variations of GPP in NCAR-CLM4 is too small, and (iv) for the LPJ model, the GPP is slightly out of phase for the northernmost ecosystems and the respiration fluxes might be too large in summer in the Northern Hemisphere. These results rely on the robustness of the OCS modeling framework and, in particular, the choice of the LRU values (assumed constant in time) and the parameterization of soil OCS uptake with small seasonal variations. Refined optimization with regional-scale and seasonally varying coefficients might help to test some of these hypothesis.

Sources and sinks of carbonyl sulfide in an agricultural field in the Southern Great Plains.

Net photosynthesis is the largest single flux in the global carbon cycle, but controls over its variability are poorly understood because there is no direct way of measuring it at the ecosystem scale. We report observations of ecosystem carbonyl sulfide (COS) and CO2 fluxes that resolve key gaps in an emerging framework for using concurrent COS and CO2 measurements to quantify terrestrial gross primary productivity. At a wheat field in Oklahoma we found that in the peak growing season the flux-weighted leaf relative uptake of COS and CO2 during photosynthesis was 1.3, at the lower end of values from laboratory studies, and varied systematically with light. Due to nocturnal stomatal conductance, COS uptake by vegetation continued at night, contributing a large fraction (29%) of daily net ecosystem COS fluxes. In comparison, the contribution of soil fluxes was small (1-6%) during the peak growing season. Upland soils are usually considered sinks of COS. In contrast, the well-aerated soil at the site switched from COS uptake to emissions at a soil temperature of around 15 °C. We observed COS production from the roots of wheat and other species and COS uptake by root-free soil up to a soil temperature of around 25 °C. Our dataset demonstrates that vegetation uptake is the dominant ecosystem COS flux in the peak growing season, providing support of COS as an independent tracer of terrestrial photosynthesis. However, the observation that ecosystems may become a COS source at high temperature needs to be considered in global modeling studies.

Growing season eddy covariance measurements of carbonyl sulfide and CO2 fluxes: COS and CO2 relationships in Southern Great Plains winter wheat

To test the capabilities of newly available instrumentation and to explore the dynamics of carbonyl sulfide (COS) as a proxy for the measurement of canopy-scale gross primary production (GPP), we conducted an experiment to measure the simultaneous net transfer of COS and CO2 between the atmosphere and a growing wheat canopy, senesced wheat, and the harvested field (located in the Southern Great Plains of the U.S.) using the eddy covariance technique. We found that during the growing season, there was a strong uptake of COS by the canopy (roughly between −10 and −40pmolm−2s−1) with a strong diel signal that mirrored net CO2 fluxes. After senescence and over the harvested field, we observed a strong source of COS to the atmosphere (up to +40pmolm−2s−1) that exhibited a weaker diel pattern, again similar to CO2. These results suggest that the dynamics of COS are more complicated than once thought, but that it may still be possible to independently derive canopy-scale GPP from direct COS measurements and to use them as model constraints on the atmospheric carbon cycle. To demonstrate this, we computed an average value of leaf relative uptake (LRU) (the scaling factor between GPP and ratios of the fluxes of COS and CO2 and ratios of the atmospheric concentrations of COS and CO2) that is in good agreement with laboratory results.

Effects of Carbonyl Sulfide and Carbonic Anhydrase on Stomatal Conductance

The potential use of carbonyl sulfide (COS) as tracer of CO(2) flux into the land biosphere stimulated research on COS interactions with leaves during gas exchange. We carried out leaf gas-exchange measurements of COS and CO(2) in 22 plant species representing deciduous and evergreen trees, grasses, and shrubs, under a range of light intensities, using mid-infrared laser spectroscopy. A narrow range in the normalized ratio of the net uptake rates of COS (A(s)) and CO(2) (A(c)), leaf relative uptake (A(s)/A(c) × [CO(2)]/[COS]), was observed, with a mean value of 1.61 ± 0.26, which is advantageous to the use of COS in photosynthesis research. Notably, increasing COS concentrations between 250 and 2,800 pmol mol(-1) (enveloping atmospheric levels) enhanced stomatal conductance (g(s)) to a variable extent in most plants examined (up to a normalized enhancement factor [ f(e) = (g(s-max) - g(s-min))/g(s-min)] of 1). This enhancement was completely abolished in carbonic anhydrase (CA)-deficient antisense lines of both C3 and C4 plants. We suggest that the stomatal response is mediated by CA and may involve hydrogen sulfide formed in the reaction of COS and water with CA. In all species examined, the uptake rates of COS and CO(2) were highly correlated, but there was no relationship between the sensitivity of stomata to COS and the rate of COS uptake (or, by inference, hydrogen sulfide production). The basis for the observed stomatal sensitivity and its variations is still to be determined.

Association between Carbonyl Sulfide Uptake and 18Δ during Gas Exchange in C3 and C4 Leaves

Carbonyl sulfide (COS) and C(18)OO exchange by leaves provide potentially powerful tracers of biosphere-atmosphere CO(2) exchange, and both are assumed to depend on carbonic anhydrase (CA) activity and conductance along the diffusive pathway in leaves. We investigated these links using C(3) and C(4) plants, hypothesizing that the rates of COS and C(18)OO exchange by leaves respond in parallel to environmental and biological drivers. Using CA-deficient antisense lines of C(4) and C(3) plants, COS uptake was essentially eliminated and discrimination against C(18)OO exchange ((18)Δ) greatly reduced, demonstrating CA's key role in both processes. (18)Δ showed a positive linear correlation with leaf relative uptake (LRU; ratio of COS to CO(2) assimilation rates, A(s)/A(c), normalized to their respective ambient concentrations), which reflected the effects of stomatal conductance on both COS and C(18)OO exchange. Unexpectedly, a decoupling between A(s) and (18)Δ was observed in comparing C(4) and C(3) plants, with a large decrease in (18)Δ but no parallel reduction in A(s) in the former. This could be explained by C(4) plants having higher COS concentrations at the CA site (maintaining high A(s) with reduced CA) and a high phosphoenolpyruvate carboxylase/CA activity ratio (reducing (18)O exchange efficiency between CO(2) and water, but not A(s)). Similar A(s) but higher A(c) in C(4) versus C(3) plants resulted in lower LRU values in the former (1.16 ± 0.20 and 1.82 ± 0.18 for C(4) and C(3), respectively). LRU was, however, relatively constant in both plant types across a wide range of conditions, except low light (<191 μmol photon m(-2) s(-1)).

Relationships between carbonyl sulfide (COS) and CO2 during leaf gas exchange

*Carbonyl sulfide (COS) exchange in C(3) leaves is linked to that of CO(2), providing a basis for the use of COS as a powerful tracer of gross CO(2) 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 CO(2) in representative C(3) plants under a range of light intensities, relative humidities and temperatures, CO(2) 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 CO(2) were observed. The mean ratio of COS to CO(2) assimilation flux rates, A(s)/A(c), was c. 1.4 pmol micromol(-1) and the leaf relative uptake (assimilation normalized to ambient concentrations, (A(s)/A(c))(C(a)(c)/C(a)(s))) 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 (H(2)S) produced from COS hydrolysis, and a correlation was observed between A(s) and leaf discrimination against C(18)OO. *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.