Search

Carbonyl sulfide (COS), a trace gas in our atmosphere that leads to the formation of aerosols in the stratosphere, is largely taken up by terrestrial ecosystems. Quantifying the biosphere uptake of COS could provide a useful quantity to estimate gross primary productivity (GPP). Some COS sources and sinks still contain large uncertainties, and several top-down estimates of the COS budget point to an underestimation of sources, especially in the tropics. We extended the inverse model TM5-4DVAR to assimilate Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) satellite data, in addition to National Oceanic and Atmospheric Administration (NOAA) surface data as used in a previous study. To resolve possible discrepancies among the two observational data sets, a bias correction scheme is necessary and implemented. A set of inversions is presented that explores the influence of the different measurement streams and the settings of the prior fluxes. To evaluate the performance of the inverse system, the HIAPER Pole-to-Pole Observations (HIPPO) aircraft observations and NOAA airborne profiles are used. All inversions reduce the COS biosphere uptake from a prior value of 1053 GgS a -1 to much smaller values, depending on the inversion settings. These large adjustments of the biosphere uptake often turn parts of Amazonia into a COS source. Only inversions that exclusively use MIPAS observations, or strongly reduce the prior errors on the biosphere flux, maintain the Amazon as a COS sink. Inclusion of MIPAS data in the inversion leads to a better separation of land and ocean fluxes. Over the Amazon, these inversions reduce the biosphere uptake from roughly 300 to 100 GgS a -1 , indicating a strongly overestimated prior uptake in this region. Although a recent study also reported reduced COS uptake over the Amazon, we emphasise that a careful construction of prior fluxes and their associated errors remains important. For instance, an inversion that gives large freedom to adjust the anthropogenic and ocean fluxes of CS2 , an important COS precursor, also closes the budget satisfactorily with much smaller adjustments to the biosphere. We achieved better characterisation of biosphere prior and uncertainty, better characterisation of combined ocean and land fluxes, and better constraint of both by combining surface and satellite observations. We recommend more COS observations to characterise biosphere and ocean fluxes, especially over the data-poor tropics. [ABSTRACT FROM AUTHOR]

Carbonyl sulfide (COS), a trace gas in our atmosphere that leads to the formation of aerosols in the stratosphere, is taken up by terrestrial ecosystems. Quantifying the biosphere uptake of (COS) could provide a useful quantity to estimate Gross Primary Productivity. Some COS sources and sinks still contain large uncertainties, and several top down estimates of the COS budget point to an underestimation of sources especially in the tropics. We extended the inverse model TM5-4DVAR to assimilate MIPAS satellite data, in addition to NOAA surface data as used in a previous study. To resolve possible discrepancies among the two observational datasets, a bias correction scheme was implemented. A set of inversions is presented that explores the influence of the different measurement instruments and the settings of the prior fluxes. To evaluate the performance of the inverse system, the HIAPER Pole-to-Pole Observations (HIPPO) aircraft observations and NOAA airborne profiles are used. All inversions reduce the (COS) biosphere uptake from a prior value of 1053 GgS a-1 to much smaller values, depending on the inversion settings. These large adjustments of the biosphere uptake often turn parts of the Amazonia into a (COS) source. Only inversions that exclusively use MIPAS observations, or strongly reduce the prior errors on the biosphere flux maintain the Amazonia as a COS sink. Assimilating both NOAA surface data and MIPAS data requires a small bias correction for MIPAS data, mostly at higher latitudes, to correct for inconsistencies in the observational data and/or transport model errors. Analysis of the error reduction and posterior correlation between land and ocean fluxes indicates that co-assimilation of NOAA surface observations and MIPAS data better constrains the (COS) budget than assimilation of one individual dataset alone. Our inversions with bias corrections reduce the global biosphere uptake to respectively 570 and 687 GgS a-1, depending on the prior biosphere error. Over the Amazonia, these inversions reduce the biosphere uptake from roughly 300 to 100 GgS a-1, indicating a strongly overestimated prior uptake over the Amazonia. Although a recent study also reported reduced (COS) uptake over the Amazonia, we emphasise that a careful construction of prior fluxes and their associated errors remains important. For instance, an inversion that gives large freedom to adjust the anthropogenic and ocean fluxes of CS2, an important (COS) precursor, also closes the budget satisfactorily with much smaller adjustments to the biosphere. Thus, a better characterisation of biosphere and ocean fluxes by observations is urgently needed, especially over the data-poor tropics. [ABSTRACT FROM AUTHOR]

Carbonyl Sulfide (COS) is a useful tracer to estimate Gross Primary Production (GPP) because it shares part of the uptake pathway with CO2. COS is taken up in plants through hydrolysis, catalyzed by the enzyme carbonic anhydrase (CA), but is not released. The Simple Biosphere model version 4 (SiB4) simulates COS leaf uptake using a conductance approach. SiB4 applies the temperature response of the RuBisCo enzyme (used for photosynthesis) to simulate the COS leaf uptake, but the CA enzyme might respond differently. We introduce a new temperature response function for CA in SiB4, based on enzyme kinetics with an optimum temperature. Moreover, we determine Ball-Berry model parameters for stomatal conductance (gs) using observation-based estimates of COS flux, GPP, and gs along with meteorological measurements in an evergreen needleleaf forest (ENF) and deciduous broadleaf forest (DBF). We find that CA has optimum temperatures of 22 °C (ENF) and 38 °C (DBF) with CA's activation energy as 40 kJ mol-1, which is lower than that of RuBisCo (45 °C), suggesting that air temperature changes can critically affect CA's catalyzation activity. Optimized values for the Ball-Berry offset parameter b0 (ENF: 0.013, DBF: 0.007 mol -2 s-1) are higher (lower) than the original value (0.010 mol m-2 s-1) in the ENF (DBF), and optimized values for the Ball-Berry slope parameter b1 (ENF: 16.36, DBF: 11.43) are higher than the original value (9.0) at both sites. We apply the optimized gCA and gs parameters in SiB4 site simulations, thereby improving the timing and peak of COS assimilation. In addition, we show that SiB4 underestimates the leaf humidity stress under conditions where high VPD should limit gs in the afternoon, thereby overestimating gs. Furthermore, we simulate global COS biosphere fluxes, which show smaller COS uptake in the tropics and larger COS uptake at higher latitudes, corresponding with the updates made to the CA temperature response. This SiB4 update helps resolve gaps in the COS budget identified in earlier studies. Using our optimization and additional observations of COS uptake over various climate and plant types, we expect further improvements in global COS biosphere flux estimates. [ABSTRACT FROM AUTHOR]

Land surface modelers 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 normalized to respective ambient concentrations for each vegetation type (Leaf Relative Uptake, LRU). COS leaf fluxes were then computed from GPP, and the resulting concentrations were transported with an atmospheric model which included all other known COS fluxes as inputs. Modelled COS concentrations could then be compared to COS measurements from the NOAA air sampling tower network. 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 global scale, and 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 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 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 second importance as 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 FROM AUTHOR]

Carbonyl sulfide (COS) has the potential to be used as a climate diagnostic due to its close coupling to the biospheric uptake of CO2 and its role in the formation of stratospheric aerosol. The current understanding of the COS budget, however, lacks COS sources, which have previously been allocated to the tropical ocean. This paper presents a first attempt of global inverse modelling of COS within the 4-Dimensional variational data-assimilation system of the TM5 chemistry transport model (TM5-4DVAR) and a comparison of the results with independent COS observations. We focus on the global COS budget, including COS production from its precursors carbon disulfide (CS2) and dimethyl sulfide (DMS). To this end, we implemented COS uptake by soil and vegetation from an updated biosphere model (SiB4), and new inventories for anthropogenic and biomass burning emissions. The model framework is capable of closing the COS budget by optimizing for missing emissions using NOAA observations in the period 2000-2012. The addition of 432 Gg S a-1 COS is required to obtain a good fit with NOAA observations. This missing source shows little year-to-year variations, but considerable seasonal variations. We found that the missing sources are likely located in the tropical regions, and an overestimated biospheric sink in the tropics cannot be ruled out. Moreover, high latitudes in the Northern Hemisphere require extra COS uptake or reduced emissions. HIPPO aircraft observations, NOAA airborne profiles from an ongoing monitoring program, and several satellite data sources are used to evaluate the optimized model results. This evaluation indicates that COS in the free troposphere remains underestimated after optimization. Assimilation of HIPPO observations slightly improves this model bias, which implies that additional observations are urgently required to constrain sources and sinks of COS. We finally find that the biosphere flux dependency on surface COS mixing ratio may substantially lower the fluxes of the SiB4 biosphere model over strong uptake regions. In planned further studies we will implement this biosphere dependency, and additionally assimilate satellite data with the aim to better separate the role of the oceans and the biosphere in the global COS budget. [ABSTRACT FROM AUTHOR]

Carbonyl sulfide (COS) flux measurements with the eddy covariance (EC) technique are growing in popularity with the recent development in using COS to estimate gross photosynthesis at the ecosystem scale. Flux data intercomparison would benefit from standardized protocols for COS flux data processing. In this study, we analyze how various data processing steps affect the final flux and provide a method for gap-filling COS fluxes. Different methods for determining the lag time between COS mixing ratio and the vertical wind velocity (w) resulted in a maximum of 12 % difference in the cumulative COS flux. Due to limited COS measurement precision, small COS fluxes (below approximately 3 pmol m−2 s−1) could not be detected when the lag time was determined from maximizing the covariance between COS and w. We recommend using a combination of COS and carbon dioxide (CO2) lag times in determining the COS flux, depending on the flux magnitude compared to the detection limit of each averaging period. Different high frequency spectral corrections had a maximum effect of 10 % on COS flux calculations and different detrending methods only 1.2 %. Relative total uncertainty was more than five times higher for low COS fluxes (absolute flux 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, and the low signal-to-noise ratio of COS fluxes that is similar to methane, we recommend a combination of CO2 and methane flux processing protocols for COS EC fluxes. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Soil is a major contributor to the biosphere-atmosphere exchange of carbonyl sulfide (COS) and carbon monoxide (CO). COS is used to improve constraints on terrestrial photosynthesis based on the link between leaf uptake of COS and of CO2, but this use requires the soil COS flux to be well quantified. For CO, soil is a main sink in natural environments that influences the tropospheric CO budget. We measured soil fluxes of COS, CO, and CO2 hourly over the 2015 late growing season in a Scots pine forest in Hyytiälä, Finland. The soil acted as a net sink of COS and CO. Average uptake rates were around 3 pmol m-2 s-1 for COS, and 1 nmol m-2 s-1 for CO, respectively. Soil respiration showed seasonal dynamics controlled by soil temperature, peaking in late August and September with fluxes around 4 μmol m-2 s-1 and dropping to 1-2 μmol m-2 s-1 in October. In contrast, seasonal variations of COS and CO fluxes were weak and mainly driven by soil moisture changes through diffusion limitation. COS and CO fluxes did not appear to respond to temperature, although they both correlated well with soil respiration in specific temperature bins. We found that COS : CO2 and CO : CO2 flux ratios were modulated by temperature, possibly indicating shifts in active COS and CO-consuming microbial groups. Our results show that soil COS and CO uptake do not have strong variations over the late growing season in the boreal forest, and can be well described during the photosynthetically most active period. Well characterized and relatively invariant soil COS fluxes strengthen the case for using COS as a tracer for photosynthesis in this globally important biome. [ABSTRACT FROM AUTHOR]

Carbonyl sulfide (COS) has been suggested as a useful tracer for gross primary production as it is taken up by plants in a similar way as CO2. To explore and verify the application of this novel tracer, it is highly desired to develop the ability to perform continuous and high-precision in situ atmospheric measurements of COS and CO2. In this study we have tested a quantum cascade laser spectrometer (QCLS) for its suitability to obtain accurate and high-precision measurements of COS and CO2. The instrument is capable of simultaneously measuring COS, CO2, CO and H2O after including a weak CO absorption line in the extended wavelength range. An optimal background and calibration strategy was developed based on laboratory tests to ensure accurate field measurements. We have derived water vapor correction factors based on a set of laboratory experiments and found that for COS the interference associated with a water absorption line can dominate over the effect of dilution. This interference can be solved mathematically by fitting the COS spectral line separately from the H2O spectral line. Furthermore, we improved the temperature stability of the QCLS by isolating it in an enclosed box and actively cooling its electronics with the same thermoelectric chiller used to cool the laser. The QCLS was deployed at the Lutjewad atmospheric monitoring station (60 m; 6°21′ E, 53°24′ N; 1 m a.s.l.) in the Netherlands from July 2014 to April 2015. The QCLS measurements of independent working standards while deployed in the field showed a mean difference with the assigned cylinder value within 3.3 ppt COS, 0.05 ppm for CO2 and 1.7 ppb for CO over a period of 35 days. The different contributions to uncertainty in measurements of COS, CO2 and CO were summarized and the overall uncertainty was determined to be 7.5 ppt for COS, 0.23 ppm for CO2 and 3.3 ppb for CO for 1-minute data. A comparison of in situ QCLS measurements with those from concurrently filled flasks that were subsequently measured by the QCLS showed a difference of −9.7 ± 4.6 ppt for COS. Comparison of the QCLS with a cavity ring-down spectrometer showed a difference of 0.12 ± 0.77 ppm for CO2 and −0.9 ± 3.8 ppb for CO. [ABSTRACT FROM AUTHOR]