Summary Carbonyl sulphide (COS) is a potential tracer of gross primary productivity (GPP), assuming a unidirectional COS flux into the vegetation that scales with GPP. However, carbonic anhydrase (CA), the enzyme that hydrolyses COS, is expected to be light independent, and thus plants without stomata should continue to take up COS in the dark.We measured net CO 2 (AC) and COS (AS) uptake rates from two astomatous bryophytes at different relative water contents (RWCs), COS concentrations, temperatures and light intensities.We found large AS in the dark, indicating that CA activity continues without photosynthesis. More surprisingly, we found a nonzero COS compensation point in light and dark conditions, indicating a temperature‐driven COS source with a Q 10 (fractional change for a 10°C temperature increase) of 3.7. This resulted in greater AS in the dark than in the light at similar RWC. The processes underlying such COS emissions remain unknown.Our results suggest that ecosystems dominated by bryophytes might be strong atmospheric sinks of COS at night and weaker sinks or even sources of COS during daytime. Biotic COS production in bryophytes could result from symbiotic fungal and bacterial partners that could also be found on vascular plants.

Abstract. Soils both emit and consume the trace gas carbonyl sulfide (COS) leading to a soil–air COS exchange rate that is the net result of two opposing fluxes. Partitioning these two gross fluxes and understanding their drivers are necessary to estimate the contribution of soils to the current and future atmospheric COS budget. Previous efforts to disentangle the gross COS fluxes from soils have used flux measurements on air-dried soils as a proxy for the COS emission rates of moist soils. However, this method implicitly assumes that COS uptake becomes negligible and that COS emission remains steady while soils are drying. We tested this assumption by simultaneously estimating the soil COS sources and sinks and their temperature sensitivity (Q10); these estimates were based on soil–air COS flux measurements on fresh soils at different COS concentrations and two soil temperatures. Measurements were performed on 27 European soils from different biomes and land use types in order to obtain a large range of physical–chemical properties and identify the drivers of COS consumption and production rates. We found that COS production rates from moist and air-dried soils were not significantly different for a given soil and that the COS production rates had Q10 values (3.96 ± 3.94) that were larger and more variable than the Q10 for COS consumption (1.17 ± 0.27). COS production generally contributed less to the net flux at lower temperatures but this contribution of COS production increased rapidly at higher temperatures, lower soil moisture contents and lower COS concentrations. Consequently, measurements at higher COS concentrations (viz. 1000 ppt) always increased the robustness of COS consumption estimates. Across the range of biomes and land use types COS production rates co-varied with total soil nitrogen concentrations (r = 0.52, P<0.05) and mean annual precipitation (r=0.53, P<0.05), whilst the gross COS uptake rate and the first-order COS hydrolysis rate constant co-varied significantly with the microbial biomass nitrogen (N) content of the soils (r=-0.74 and 0.64, P<0.05 and P<0.05, respectively). Collectively our findings suggest a strong interaction between soil nitrogen and water cycling on COS production and uptake, providing new insights into how to upscale the contribution of soils to the global atmospheric COS budget.

The stable oxygen isotope composition of atmospheric CO2 and the mixing ratio of carbonyl sulphide (OCS) are potential tracers of biospheric CO2 fluxes at large scales. However, the use of these tracers hinges on our ability to understand and better predict the activity of the enzyme carbonic anhydrase (CA) in different soil microbial groups, including phototrophs. Because different classes of the CA family (α, β and γ) may have different affinities to CO2 and OCS and their expression should also vary between different microbial groups, differences in the community structure could impact the ‘community-integrated’ CA activity differently for CO2 and OCS. Four soils of different pH were incubated in the dark or with a diurnal cycle for forty days to vary the abundance of native phototrophs. Fluxes of CO2, CO18O and OCS were measured to estimate CA activity alongside the abundance of bacteria, fungi and phototrophs. The abundance of soil phototrophs increased most at higher soil pH. In the light, the strength of the soil CO2 sink and the CA-driven CO2-H2O isotopic exchange rates correlated with phototrophs abundance. OCS uptake rates were attributed to fungi whose abundance was positively enhanced in alkaline soils but only in the presence of increased phototrophs. Our findings demonstrate that soil-atmosphere CO2, OCS and CO18O fluxes are strongly regulated by the microbial community structure in response to changes in soil pH and light availability and supports the idea that different members of the microbial community express different classes of CA, with different affinities to CO2 and OCS.

Abstract. Carbonic anhydrases (CAs) are metalloenzymes present in plants and microorganisms that catalyse the interconversion of CO 2 and water to bicarbonate and protons. Because oxygen isotopes are also exchanged during this reaction, the presence of CA also modifies the contribution of soil and plant CO 18 O fluxes to the global budget of atmospheric CO 18 O. The oxygen isotope signatures (δ 18 O) of these fluxes differ as leaf water pools are usually more enriched than soil water pools, and this difference is used to partition the net CO 2 flux over land into soil respiration and plant photosynthesis. Nonetheless, the use of atmospheric CO 18 O as a tracer of land surface CO 2 fluxes requires a good knowledge of soil CA activity. Previous studies have shown that significant differences in soil CA activity are found in different biomes and seasons, but our understanding of the environmental and ecological drivers responsible for the spatial and temporal patterns observed in soil CA activity is still limited. One factor that has been overlooked so far is pH. Soil pH is known to strongly influence microbial community composition, richness and diversity in addition to governing the speciation of CO 2 between the different carbonate forms. In this study we investigated the CO 2 -H 2 O isotopic exchange rate (k iso ) in six soils with pH varying from 4.5 to 8.5. We also artificially increased the soil CA concentration to test how pH and other soil properties (texture and phosphate content) affected the relationship between k iso and CA concentration. We found that soil pH was the primary driver of k iso after CA addition and that the chemical composition (i.e. phosphate content) played only a secondary role. We also found an offset between the δ 18 O of the water pool with which CO 2 equilibrates and total soil water (i.e. water extracted by vacuum distillation) that varied with soil texture. The reasons for this offset are still unknown.

Abstract. The contribution of photosynthesis and soil respiration to net land-atmosphere carbon dioxide (CO 2 ) exchange can be estimated based on the differential influence of leaves and soils on budgets of the oxygen isotope composition (δ 18 O) of atmospheric CO 2 . To do so, the activity of carbonic anhydrases (CAs), a group of enzymes that catalyse the hydration of CO 2 in soils and plants, needs to be understood. Measurements of soil CA activity typically involve the inversion of models describing the δ 18 O of CO 2 fluxes to solve for the apparent, potentially catalysed, rate of CO 2 hydration. This requires information about the δ 18 O of CO 2 in isotopic equilibrium with soil water, typically obtained from destructive, depth-resolved sampling and extraction of soil water. In doing so, an assumption is made about the soil water pool that CO 2 interacts with, which may bias estimates of CA activity if incorrect. Furthermore, this can represent a significant challenge in data collection given the potential for spatial and temporal variability in the δ 18 O of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by inferring the rate of CO 2 hydration and the δ 18 O of soil water from the relationship between the δ 18 O of CO 2 fluxes and the δ 18 O of CO 2 at the soil surface measured at different ambient CO 2 conditions. This approach was tested through laboratory incubations of air-dried soils that were re-wetted with three waters of different δ 18 O. Gas exchange measurements were made on these soils to estimate the rate of hydration and the δ 18 O of soil water, followed by soil water extraction to allow for comparison. Estimated rates of CO 2 hydration were 6.8-14.6 times greater than the theoretical uncatalysed rate of hydration, indicating that CA were active in these soils. Importantly, these estimates were not significantly different among water treatments, suggesting that this represents a robust approach to assay the activity of CA in soil. As expected, estimates of the δ 18 O of the soil water that equilibrates with CO 2 varied in response to alteration to the δ 18 O of soil water. However, these estimates were consistently more negative than the composition of the soil water extracted by cryogenic vacuum distillation at the end of the gas measurements with differences of up to −3.94 ‰ VSMOW-SLAP. These offsets suggest that, at least at lower water contents, CO 2 -H 2 O isotope equilibration primarily occurs with water pools that are bound to particle surfaces and are depleted in 18 O compared to bulk soil water.