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.

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

U.S. national and regional emissions of HFC-134a are derived for 20082012 based on atmospheric observations from ground and aircraft sites across the U.S. and a newly developed regional inverse model. Synthetic data experiments were first conducted to optimize the model assimilation design and to assess model-data mismatch errors and prior flux error covariances computed using a maximumlikelihood estimation technique. The synthetic data experiments also tested the sensitivity of derived national and regional emissions to a range of assumed prior emissions, with the goal of designing a system that was minimally reliant on the prior. We then explored the influence of additional sources of error in inversions with actual observations, such as those associated with background mole fractions and transport uncertainties. Estimated emissions of HFC-134a range from 52 to 61 Gg yr-1 for the contiguous U.S. during 20082012 for inversions using air transport from Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model driven by the 12km resolution meteorogical data from North American Mesoscale Forecast System (NAM12) and all tested combinations of prior emissions and background mole fractions. Estimated emissions for 20082010 were 20% lower when specifying alternative transport from Stochastic Time-Inverted Lagrangian Transport (STILT) model driven by the Weather Research and Forecasting (WRF) meteorology. Our estimates (for HYSPLIT-NAM12) are consistent with annual emissions reported by U.S. Environmental Protection Agency for the full study interval. The results suggest a 1020% drop in U.S. national HFC-134a emission in 2009 coincident with a reduction in transportation-related fossil fuel CO2 emissions, perhaps related to the economic recession. All inversions show seasonal variation in national HFC-134a emissions in all years, with summer emissions greater than winter emissions by 2050%.

National-scale emissions of carbon tetrachloride (CCl4) are derived based on inverse modeling of atmospheric observations at multiple sites across the United States from the National Oceanic and Atmospheric Administration's flask air sampling network. We estimate an annual average US emission of 4.0 (2.0-6.5) Gg CCl4 y(-1) during 2008-2012, which is almost two orders of magnitude larger than reported to the US Environmental Protection Agency (EPA) Toxics Release Inventory (TRI) (mean of 0.06 Gg y(-1)) but only 8% (3-22%) of global CCl4 emissions during these years. Emissive regions identified by the observations and consistently shown in all inversion results include the Gulf Coast states, the San Francisco Bay Area in California, and the Denver area in Colorado. Both the observation-derived emissions and the US EPA TRI identified Texas and Louisiana as the largest contributors, accounting for one- to two-thirds of the US national total CCl4 emission during 2008-2012. These results are qualitatively consistent with multiple aircraft and ship surveys conducted in earlier years, which suggested significant enhancements in atmospheric mole fractions measured near Houston and surrounding areas. Furthermore, the emission distribution derived for CCl4 throughout the United States is more consistent with the distribution of industrial activities included in the TRI than with the distribution of other potential CCl4 sources such as uncapped landfills or activities related to population density (e.g., use of chlorine-containing bleach).

Ozone depleting substances (ODSs) controlled by the Montreal Protocol are potent greenhouse gases (GHGs), as are their substitutes, the hydrofluorocarbons (HFCs). Here we provide for the first time a comprehensive estimate of U.S. emissions of ODSs and HFCs based on precise measurements in discrete air samples from across North America and in the remote atmosphere. Derived emissions show spatial and seasonal variations qualitatively consistent with known uses and largely confirm U.S. Environmental Protection Agency (EPA) national emissions inventories for most gases. The measurement-based results further indicate a substantial decline of ODS emissions from 2008 to 2014, equivalent to ~50% of the CO2-equivalent decline in combined emissions of CO2 and all other long-lived GHGs inventoried by the EPA for the same period. Total estimated CO2-equivalent emissions of HFCs were comparable to the sum of ODS emissions in 2014, but can be expected to decline in the future in response to recent policy measures.

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 CO2 during 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 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.