Dark Production: A Significant Source of Oceanic COS

Carbonyl sulfide (COS) in air and dissolved in seawater was determined during a cruise in August 1999 in the Sargasso Sea in the northwest Atlantic Ocean. Dissolved concentrations at the sea surface displayed only a weak diel cycle with a mean of 8.6 ± 2.8 pmol dm−3 owing to low abundance of photochemical precursors and high temperatures causing rapid hydrolysis. Depth profiles measured over the oceanic mixed layer revealed significant vertical gradients of COS concentration with higher values at the surface, suggesting that the rate of photochemical production at the surface exceeds the rate of vertical mixing. The mean atmospheric mixing ratio was 486 ± 40 ppt, and calculated sea-air fluxes ranged from 0.03 to 0.8 g COS km−2 d−1. COS dark production, estimated from the predawn COS concentration at the surface and the hydrolysis constant, contributed significantly to the total amount of COS produced. A strong temperature dependence of the COS dark production rate q was found by comparing previously published values. The data further indicate an approximately first-order relationship between q and chromophoric dissolved organic matter (CDOM) absorbance at 350 nm, a350, which is used as a proxy for the CDOM content of the water but is likely to covary with other parameters, such as biological activity, that could also affect COS dark production. Together with known functions for COS hydrolysis and solubility, the parameterization of dark production as a function of temperature and a350 allows for the prediction of COS concentrations and saturation ratios as a function of physical and optical seawater properties in the absence of photoproduction. This is used to estimate a lower limit of 0.056 Tg COS yr−1 to the annual COS flux from the ocean to the atmosphere

Heterogeneous chlorine activation on stratospheric aerosols and clouds in the Arctic polar vortex

Chlorine activation in the Arctic is investigated by examining different parameterizations for uptake coefficients on stratospheric aerosols, high-resolution in-situ measurements and vortex-wide satellite observations. The parameterizations for heterogeneous chemistry on liquid aerosols are most sensitive to temperature with the reaction rates doubling for every 1 K increase in temperature. However, differences between the currently available parameterizations are negligible. For Nitric Acid Trihydrate particles (NAT) the major factors of uncertainty are the number density of nucleated particles and different parameterizations for heterogeneous chemistry. These two factors induce an uncertainty that covers several orders of magnitude on the reaction rate. Nonetheless, since predicted reaction rates on liquid aerosols always exceed those on NAT, the overall uncertainty for chlorine activation is small. In-situ observations of ClO<sub>x</sub> from Arctic winters in 2005 and 2010 are used to evaluate the heterogeneous chemistry parameterizations. The conditions for these measurements proved to be very different between those two winters with HCl being the limiting reacting partner for the 2005 measurements and ClONO<sub>2</sub> for the 2010 measurements. Modeled levels of chlorine activation are in very good agreement with the in-situ observations and the surface area provided by Polar Stratospheric Clouds (PSCs) has only a limited impact on modeled chlorine activation. This indicates that the parameterizations give a good representation of the processes in the atmosphere. Back-trajectories started on the location of the observations in 2005 indicate temperatures on the threshold for PSC formation, hence the surface area is mainly provided by the background aerosol. Still, the model shows additional chlorine activation during this time-frame, providing cautionary evidence for chlorine activation even in the absence of PSCs. Vortex-averaged satellite observations by the MLS instrument also show no definite connection between chlorine activation and PSC formation. The inter -and intra-annual variability of vortex-average HCl and HNO<sub>3</sub> based on MLS observations is examined for the Arctic winters 2004/2005 to 2010/2011. These observations show that removal of HCl and HNO<sub>3</sub> from the gas-phase are not correlated. HNO<sub>3</sub> loss exhibits great inter-annual variability depending on prevailing temperatures while HCl loss is continuous through December without considerable inter- or intra-annual variability. Only the recovery of HCl in late winter depends on the level of denitrification. Hence, the occurrence of HNO<sub>3</sub> containing PSC particles does not seem to have a significant effect on the speed of initial chlorine activation on a vortex-wide scale

Combined assimilation of NOAA surface and MIPAS satellite observations to constrain the global budget of carbonyl sulfide

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.</p

Combined assimilation of NOAA surface and MIPAS satellite observations to constrain the global budget of carbonyl sulfide

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

Reconciliation of essential process parameters for an enhanced predictability of Arctic stratospheric ozone loss and its climate interactions

Significant reductions in stratospheric ozone occur inside the polar vortices each spring when chlorine radicals produced by heterogeneous reactions on cold particle surfaces in winter destroy ozone mainly in two catalytic cycles, the ClO dimer cycle and the ClO/BrO cycle. Chlorofluorocarbons (CFCs), which are responsible for most of the chlorine currently present in the stratosphere, have been banned by the Montreal Protocol and its amendments, and the ozone layer is predicted to recover to 1980 levels within the next few decades. During the same period, however, climate change is expected to alter the temperature, circulation patterns and chemical composition in the stratosphere, and possible geo-engineering ventures to mitigate climate change may lead to additional changes. To realistically predict the response of the ozone layer to such influences requires the correct representation of all relevant processes. The European project RECONCILE has comprehensively addressed remaining questions in the context of polar ozone depletion, with the objective to quantify the rates of some of the most relevant, yet still uncertain physical and chemical processes. To this end RECONCILE used a broad approach of laboratory experiments, two field missions in the Arctic winter 2009/10 employing the high altitude research aircraft M55-Geophysica and an extensive match ozone sonde campaign, as well as microphysical and chemical transport modelling and data assimilation. Some of the main outcomes of RECONCILE are as follows: (1) vortex meteorology: the 2009/10 Arctic winter was unusually cold at stratospheric levels during the six-week period from mid-December 2009 until the end of January 2010, with reduced transport and mixing across the polar vortex edge; polar vortex stability and how it is influenced by dynamic processes in the troposphere has led to unprecedented, synoptic-scale stratospheric regions with temperatures below the frost point; in these regions stratospheric ice clouds have been observed, extending over >106km2 during more than 3 weeks. (2) Particle microphysics: heterogeneous nucleation of nitric acid trihydrate (NAT) particles in the absence of ice has been unambiguously demonstrated; conversely, the synoptic scale ice clouds also appear to nucleate heterogeneously; a variety of possible heterogeneous nuclei has been characterised by chemical analysis of the non-volatile fraction of the background aerosol; substantial formation of solid particles and denitrification via their sedimentation has been observed and model parameterizations have been improved. (3) Chemistry: strong evidence has been found for significant chlorine activation not only on polar stratospheric clouds (PSCs) but also on cold binary aerosol; laboratory experiments and field data on the ClOOCl photolysis rate and other kinetic parameters have been shown to be consistent with an adequate degree of certainty; no evidence has been found that would support the existence of yet unknown chemical mechanisms making a significant contribution to polar ozone loss. (4) Global modelling: results from process studies have been implemented in a prognostic chemistry climate model (CCM); simulations with improved parameterisations of processes relevant for polar ozone depletion are evaluated against satellite data and other long term records using data assimilation and detrended fluctuation analysis. Finally, measurements and process studies within RECONCILE were also applied to the winter 2010/11, when special meteorological conditions led to the highest chemical ozone loss ever observed in the Arctic. In addition to quantifying the 2010/11 ozone loss and to understand its causes including possible connections to climate change, its impacts were addressed, such as changes in surface ultraviolet (UV) radiation in the densely populated northern mid-latitudes

Reconciliation of essential process parameters for an enhanced predictability of Arctic stratospheric ozone loss and its climate interactions : (RECONCILE) ; activities and results

The international research project RECONCILE has addressed central questions regarding polar ozone depletion, with the objective to quantify some of the most relevant yet still uncertain physical and chemical processes and thereby improve prognostic modelling capabilities to realistically predict the response of the ozone layer to climate change. This overview paper outlines the scope and the general approach of RECONCILE, and it provides a summary of observations and modelling in 2010 and 2011 that have generated an in many respects unprecedented dataset to study processes in the Arctic winter stratosphere. Principally, it summarises important outcomes of RECONCILE including (i) better constraints and enhanced consistency on the set of parameters governing catalytic ozone destruction cycles, (ii) a better understanding of the role of cold binary aerosols in heterogeneous chlorine activation, (iii) an improved scheme of polar stratospheric cloud (PSC) processes that includes heterogeneous nucleation of nitric acid trihydrate (NAT) and ice on non-volatile background aerosol leading to better model parameterisations with respect to denitrification, and (iv) long transient simulations with a chemistry-climate model (CCM) updated based on the results of RECONCILE that better reproduce past ozone trends in Antarctica and are deemed to produce more reliable predictions of future ozone trends. The process studies and the global simulations conducted in RECONCILE show that in the Arctic, ozone depletion uncertainties in the chemical and microphysical processes are now clearly smaller than the sensitivity to dynamic variability

Measurement report: Carbonyl sulfide production during dimethyl sulfide oxidation in the atmospheric simulation chamber SAPHIR

Carbonyl sulfide (OCS), the most abundant sulfur gas in the Earth's atmosphere, is a greenhouse gas, a precursor to stratospheric sulfate aerosol, and a proxy for terrestrial CO2 uptake. Estimates of important OCS sources and sinks still have significant uncertainties and the global budget is not considered closed. One particularly uncertain source term, the OCS production during the atmospheric oxidation of dimethyl sulfide (DMS) emitted by the oceans, is addressed by a series of experiments in the atmospheric simulation chamber SAPHIR in conditions comparable to the remote marine atmosphere. DMS oxidation was initiated with OH and/or Cl radicals and DMS, OCS, and several oxidation products and intermediates were measured, including hydroperoxymethyl thioformate (HPMTF), which was recently found to play a key role in DMS oxidation in the marine atmosphere. One important finding is that the onset of HPMTF and OCS formation occurred faster than expected from the current chemical mechanisms. In agreement with other recent studies, OCS yields between 9 % and 12 % were observed in our experiments. Such yields are substantially higher than the 0.7 % yield measured in laboratory experiments in the 1990s, which is generally used to estimate the indirect OCS source from DMS in global budget estimates. However, we do not expect the higher yields found in our experiments to directly translate into a substantially higher OCS source from DMS oxidation in the real atmosphere, where conditions are highly variable, and, as pointed out in recent work, heterogeneous HPMTF loss is expected to effectively limit OCS production via this pathway. Together with other experimental studies, our results will be helpful to further elucidate the DMS oxidation chemical mechanism and in particular the paths leading to OCS formation.</p

Low atmospheric CO2 levels during the Little Ice Age due to cooling-induced terrestrial uptake

Low atmospheric carbon dioxide (CO2) concentration during the Little Ice Age has been used to derive the global carbon cycle sensitivity to temperature. Recent evidence confirms earlier indications that the low CO2 was caused by increased terrestrial carbon storage. It remains unknown whether the terrestrial biosphere responded to temperature variations, or there was vegetation re-growth on abandoned farmland. Here we present a global numerical simulation of atmospheric carbonyl sulfide concentrations in the pre-industrial period. Carbonyl sulfide concentration is linked to changes in gross primary production and shows a positive anomaly during the Little Ice Age. We show that a decrease in gross primary production and a larger decrease in ecosystem respiration is the most likely explanation for the decrease in atmospheric CO2 and increase in atmospheric carbonyl sulfide concentrations. Therefore, temperature change, not vegetation re-growth, was the main cause of the increased terrestrial carbon storage. We address the inconsistency between ice-core CO2 records from different sites measuring CO2 and δ13CO2 in ice from Dronning Maud Land (Antarctica). Our interpretation allows us to derive the temperature sensitivity of pre-industrial CO2 fluxes for the terrestrial biosphere (γL = -10 to -90 Pg C K-1), implying a positive climate feedback and providing a benchmark to reduce model uncertainties