Mary E. Whelan

Atmospheric carbonyl sulfide sources from anthropogenic activity: Implications for carbon cycle constraints

Carbonyl sulfide (COS) has recently emerged as an atmospheric tracer of gross primary production. All modeling studies of COS air-monitoring data rely on a climatological anthropogenic inventory that does not reflect present conditions or support interpretation of ice core and firn trends. Here we develop a global anthropogenic inventory for the years 1850 to 2013 based on new emission measurements and material-specific data. By applying methods from a recent regional inventory to global data, we find that the anthropogenic source is similar in magnitude to the plant sink, confounding carbon cycle applications. However, a material-specific approach results in a current anthropogenic source that is only one third of plant uptake and is concentrated in Asia, supporting carbon cycle applications of global air-monitoring data. Furthermore, changes in the anthropogenic source alone cannot explain the century-scale mixing ratio growth, which suggests that ice and firn data may provide the first global history of gross primary production.

Carbonyl sulfide produced by abiotic thermal and photodegradation of soil organic matter from wheat field substrate

Carbonyl sulfide (COS) is a reduced sulfur gas that is taken up irreversibly in plant leaves proportionally with CO2, allowing its potential use as a tracer for gross primary production. Recently, wheat field soil at the Southern Great Plains Atmospheric Radiation Measurement site in Lamont, Oklahoma, was found to be a measureable source of COS to the atmosphere. To understand the mechanism of COS production, soil and root samples were collected from the site and incubated in the laboratory over a range of temperatures (15–34°C) and light conditions (light and dark). Samples exhibited mostly COS net uptake from the atmosphere in dark and cool ( 25°C), consistent with field observations, and at a lower temperature (19°C) when a full spectrum lamp (max wavelength 600 nm) was applied. Sterilized soil and root samples yielded only COS production that increased with temperature, supporting the hypothesis that (a) COS production in these samples is abiotic, (b) production is directly influenced by temperature and light, and (c) some COS consumption in soil and root samples is biotic.

Large variability in ecosystem models explains uncertainty in a critical parameter for quantifying GPP with carbonyl sulphide

Regional gross primary productivity (GPP) estimates are crucial to estimating carbon-climate feedbacks but are highly uncertain with existing methods. An emerging approach uses atmospheric carbonyl sulphide (COS) as a tracer for carbon dioxide: COS plant uptake is simulated by scaling GPP. A critical parameter for this method is leaf-scale relative uptake (LRU). Plant chamber and eddy covariance studies find a narrow range of LRU values but some atmospheric modelling studies assign values well outside this range. Here we study this discrepancy by conducting new regional chemical transport simulations for North America using the underlying data from previous studies. We find the wide range of ecosystem model GPP estimates can explain the discrepancy in LRU values. We also find that COS concentration uncertainty is more sensitive to GPP uncertainty than to LRU parameter uncertainty. These results support the COS tracer technique as a useful approach for constraining GPP estimates.

Assessing a New Clue to How Much Carbon Plants Take Up

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

Plant Uptake of Atmospheric Carbonyl Sulfide in Coast Redwood Forests

Author(s): Campbell, JE; Whelan, ME; Berry, JA; Hilton, TW; Zumkehr, A; Stinecipher, J; Lu, Y; Kornfeld, A; Seibt, U; Dawson, TE; Montzka, SA; Baker, IT; Kulkarni, S; Wang, Y; Herndon, SC; Zahniser, MS; Commane, R; Loik, ME | Abstract: ©2017. American Geophysical Union. All Rights Reserved. The future resilience of coast redwoods (Sequoia sempervirens) is now of critical concern due to the detection of a 33% decline in California coastal fog over the 20th century. However, ecosystem-scale measurements of photosynthesis and stomatal conductance are challenging in coast redwood forests, making it difficult to anticipate the impacts of future changes in fog. To address this methodological problem, we explore coastal variations in atmospheric carbonyl sulfide (COS or OCS), which could potentially be used as a tracer of these ecosystem processes. We conducted atmospheric flask campaigns in coast redwood sites, sampling at surface heights and in the canopy (~70 m), at the University of California Landels-Hill Big Creek Reserve and Big Basin State Park. We simulated COS atmosphere-biosphere exchange with a high-resolution 3-D model to interpret these data. Flask measurements indicated a persistent daytime drawdown between the coast and the downwind forest (45 ± 6 ppt COS) that is consistent with the expected relationship between COS plant uptake, stomatal conductance, and gross primary production. Other sources and sinks of COS that could introduce noise to the COS tracer technique (soils, anthropogenic activity, nocturnal plant uptake, and surface hydrolysis on leaves) are likely to be small relative to daytime COS plant uptake. These results suggest that COS measurements may be useful for making ecosystem-scale estimates of carbon, water, and energy exchange in coast redwood forests.

Soil exchange rates of COS and CO 18 O differ with the diversity of microbial communities and their carbonic anhydrase enzymes

Differentiating the contributions of photosynthesis and respiration to the global carbon cycle is critical for improving predictive climate models. Carbonic anhydrase (CA) activity in leaves is responsible for the largest biosphere-atmosphere trace gas fluxes of carbonyl sulfide (COS) and the oxygen-18 isotopologue of carbon dioxide (CO18O) that both reflect gross photosynthetic rates. However, CA activity also occurs in soils and will be a source of uncertainty in the use of COS and CO18O as carbon cycle tracers until process-based constraints are improved. In this study, we measured COS and CO18O exchange rates and estimated the corresponding CA activity in soils from a range of biomes and land use types. Soil CA activity was not uniform for COS and CO2, and patterns of divergence were related to microbial community composition and CA gene expression patterns. In some cases, the same microbial taxa and CA classes catalyzed both COS and CO2 reactions in soil, but in other cases the specificity towards the two substrates differed markedly. CA activity for COS was related to fungal taxa and β-D-CA expression, whereas CA activity for CO2 was related to algal and bacterial taxa and α-CA expression. This study integrates gas exchange measurements, enzyme activity models, and characterization of soil taxonomic and genetic diversity to build connections between CA activity and the soil microbiome. Importantly, our results identify kinetic parameters to represent soil CA activity during application of COS and CO18O as carbon cycle tracers.

Ecosystem fluxes of carbonyl sulfide in an old-growth forest: temporal dynamics and responses to diffuse radiation and heat waves

Carbonyl sulfide (OCS) has recently emerged as a tracer for terrestrial carbon uptake. While physiological studies relating OCS fluxes to leaf stomatal dynamics have been established at leaf and branch scales and incorporated into global carbon cycle models, the quantity of data from ecosystem-scale field studies remains limited. In this study, we employ established theoretical relationships to infer ecosystem-scale plant OCS uptake from mixing ratio measurements. OCS fluxes showed a pronounced diurnal cycle, with maximum uptake at midday. OCS uptake was found to scale with independent measurements of CO2 fluxes over a 60 m tall old-growth forest in the Pacific Northwest of the US (454913.76 N, 1215706.88W) at daily and monthly timescales under mid–high light conditions across the growing season in 2015. OCS fluxes were strongly influenced by the fraction of downwelling diffuse light. Finally, we examine the effect of sequential heat waves on fluxes of OCS, CO2, and H2O. Our results bolster previous evidence that ecosystem OCS uptake is strongly related to stomatal dynamics, and measuring this gas improves constraints on estimating photosynthetic rates at the ecosystem scale.