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Multiple-sulfur isotope effects during photolysis of carbonyl sulfide

Laboratory experiments were carried out to determine sulfur isotope effects during ultraviolet photolysis of carbonyl sulfide (OCS) to carbon monoxide (CO) and elemental sulfur (S0). The OCS gas at 3.7 to 501 mbar was irradiated with or without a N2 bath gas using a 150 W Xe arc lamp. Sulfur isotope ratios for the product S0 and residual OCS were analyzed by an isotope ratio mass-spectrometer with SF6 as the analyte gas. The isotope fractionation after correction for the reservoir effects is −6.8&permil; for the ratio 34S/32S, where product S0 is depleted in heavy isotopes. The magnitude of the overall isotope effect is not sensitive to the addition of N2 but increases to −9.5&permil; when radiation of λ > 285 nm is used. The measured isotope effect reflects that of photolysis as well as the subsequent sulfur abstraction (from OCS) reaction. The magnitude of isotope effects for the abstraction reaction is estimated by transition state theory to be between −18.9 and −3.1&permil; for 34S which gives the photolysis isotope effect as −10.5 to +5.3&permil;. The observed triple isotope coefficients are ln(δ34S + 1)/ln(δ34S + 1) = 0.534 ± 0.005 and ln(δ36S + 1)/ln(δ34S + 1) = 1.980 ± 0.021. These values differ from canonical values for mass-dependent fractionation of 0.515 and 1.90, respectively. The result demonstrates that the OCS photolysis does not produce large isotope effects of more than about 10&permil; for 34S/32S, and can be the major source of background stratospheric sulfate aerosol (SSA) during volcanic quiescence.
Contrasting organic aerosol particles from boreal and tropical forests during HUMPPA-COPEC-2010 and AMAZE-08 using coherent vibrational spectroscopy

We present the vibrational sum frequency generation spectra of organic particles collected in a boreal forest in Finland and a tropical forest in Brazil. These spectra are compared to those of secondary organic material produced in the Harvard Environmental Chamber. By comparing coherent vibrational spectra of a variety of terpene and olefin reference compounds, along with the secondary organic material synthesized in the environmental chamber, we show that submicron aerosol particles sampled in Southern Finland during HUMPPA-COPEC-2010 are composed to a large degree of material similar in chemical composition to synthetic α-pinene-derived material. For material collected in Brazil as part of AMAZE-08, the organic component is found to be chemically complex in the coarse mode but highly uniform in the fine mode. When combined with histogram analyses of the isoprene and monoterpene abundance recorded during the HUMPPA-COPEC-2010 and AMAZE-08 campaigns, the findings presented here indicate that if air is rich in monoterpenes, submicron-sized secondary aerosol particles that form under normal OH and O3 concentration levels can be described in terms of their hydrocarbon content as being similar to α-pinene-derived model secondary organic aerosol particles. If the isoprene concentration dominates the chemical composition of organic compounds in forest air, then the hydrocarbon component of secondary organic material in the submicron size range is not simply well-represented by that of isoprene-derived model secondary organic aerosol particles but is more complex. Throughout the climate-relevant size range of the fine mode, however, we find that the chemical composition of the secondary organic particle material from such air is invariant with size, suggesting that the particle growth does not change the chemical composition of the hydrocarbon component of the particles in a significant way.
Technical Note: A novel approach to estimation of time-variable surface sources and sinks of carbon dioxide using empirical orthogonal functions and the Kalman filter

In this work we propose an approach to solving a source estimation problem based on representation of carbon dioxide surface emissions as a linear combination of a finite number of pre-computed empirical orthogonal functions (EOFs). We used National Institute for Environmental Studies (NIES) transport model for computing response functions and Kalman filter for estimating carbon dioxide emissions. Our approach produces results similar to these of other models participating in the TransCom3 experiment. Using the EOFs we can estimate surface fluxes at higher spatial resolution, while keeping the dimensionality of the problem comparable with that in the regions approach. This also allows us to avoid potentially artificial sharp gradients in the fluxes in between pre-defined regions. EOF results generally match observations more closely given the same error structure as the traditional method. Additionally, the proposed approach does not require additional effort of defining independent self-contained emission regions.
A comparison of different inverse carbon flux estimation approaches for application on a regional domain

We have implemented six different inverse carbon flux estimation methods in a regional carbon dioxide (CO2) flux modeling system for the Netherlands. The system consists of the Regional Atmospheric Mesoscale Modeling System (RAMS) coupled to a simple carbon flux scheme which is run in a coupled fashion on relatively high resolution (10 km). Using an Ensemble Kalman filter approach we try to estimate spatiotemporal carbon exchange patterns from atmospheric CO2 mole fractions over the Netherlands for a two week period in spring 2008. The focus of this work is the different strategies that can be employed to turn first-guess fluxes into optimal ones, which is known as a fundamental design choice that can affect the outcome of an inversion significantly. Different state-of-the-art approaches with respect to the estimation of net ecosystem exchange (NEE) are compared quantitatively: (1) where NEE is scaled by one linear multiplication factor per land-use type, (2) where the same is done for photosynthesis (GPP) and respiration (R) separately with varying assumptions for the correlation structure, (3) where we solve for those same multiplication factors but now for each grid box, and (4) where we optimize physical parameters of the underlying biosphere model for each land-use type. The pattern to be retrieved in this pseudo-data experiment is different in nearly all aspects from the first-guess fluxes, including the structure of the underlying flux model, reflecting the difference between the modeled fluxes and the fluxes in the real world. This makes our study a stringent test of the performance of these methods, which are currently widely used in carbon cycle inverse studies. Our results show that all methods struggle to retrieve the spatiotemporal NEE distribution, and none of them succeeds in finding accurate domain averaged NEE with correct spatial and temporal behavior. The main cause is the difference between the structures of the first-guess and true CO2 flux models used. Most methods display overconfidence in their estimate as a result. A commonly used daytime-only sampling scheme in the transport model leads to compensating biases in separate GPP and R scaling factors that are readily visible in the nighttime mixing ratio predictions of these systems. Overall, we recommend that the estimate of NEE scaling factors should not be used in this regional setup, while estimating bias factors for GPP and R for every grid box works relatively well. The biosphere parameter inversion performs good compared to the other inversions at simultaneously producing space and time patterns of fluxes and CO2 mixing ratios, but non-linearity may significantly reduce the information content in the inversion if true parameter values are far from the prior estimate. Our results suggest that a carefully designed biosphere model parameter inversion or a pixel inversion of the respiration and GPP multiplication factors are from the tested inversions the most promising tools to optimize spatiotemporal patterns of NEE.
Simulating deep convection with a shallow convection scheme

Convective processes profoundly affect the global water and energy balance of our planet but remain a challenge for global climate modeling. Here we develop and investigate the suitability of a unified convection scheme, capable of handling both shallow and deep convection, to simulate cases of tropical oceanic convection, mid-latitude continental convection, and maritime shallow convection. To that aim, we employ large-eddy simulations (LES) as a benchmark to test and refine a unified convection scheme implemented in the Single-column Community Atmosphere Model (SCAM). Our approach is motivated by previous cloud-resolving modeling studies, which have documented the gradual transition between shallow and deep convection and its possible importance for the simulated precipitation diurnal cycle. Analysis of the LES reveals that differences between shallow and deep convection, regarding cloud-base properties as well as entrainment/detrainment rates, can be related to the evaporation of precipitation. Parameterizing such effects and accordingly modifying the University of Washington shallow convection scheme, it is found that the new unified scheme can represent both shallow and deep convection as well as tropical and mid-latitude continental convection. Compared to the default SCAM version, the new scheme especially improves relative humidity, cloud cover and mass flux profiles. The new unified scheme also removes the well-known too early onset and peak of convective precipitation over mid-latitude continental areas.
Enhancement and depletion of lower/middle tropospheric ozone in Senegal during pre-monsoon and monsoon periods of summer 2008: observations and model results

During the summer (8 June through 3 September) of 2008, 9 ozonesondes are launched from Dakar, Senegal (14.75° N, 17.49° W) to investigate ozone (O3) variability in the lower/middle troposphere during the pre-monsoon and monsoon periods. Results during June 2008 (pre-monsoon period) show a reduction in O3 concentrations, especially in the 850–700 hPa layer with Saharan Air Layer (SAL) events. However, O3 concentrations are increased in the 950–900 hPa layer where the peak of the inversion is found and presumably the highest dust concentrations. We also use the WRF-CHEM model to gain greater insights for observations of elevated/reduced O3 concentrations during the pre-monsoon/monsoon periods. In the transition period between 26 June and 2 July in the lower troposphere (925–600 hPa), a significant increase in O3 concentrations occur which we suggest is caused by enhanced biogenic NOx emissions from Sahelian soils following rain events on 28 June and 1 July. During July and August 2008 (monsoon period), with the exception of one SAL outbreak, vertical profiles of O3 are well mixed with concentrations not exceeding 55 ppb between the surface and 550 hPa. The results suggest that during the pre-monsoon period ozone concentrations in the lower troposphere are controlled by the SAL, which destroys ozone through heterogeneous processes. At the base of the SAL we also find elevated levels of ozone, which we attribute to biogenic sources of NOx from Saharan dust that are released in the presence of moist conditions. Once the monsoon period commences, wet and dry deposition become important sinks of ozone in the Sahel with episodes of ozone poor air that is horizontally transported from low latitudes into the Sahel. These results support aircraft chemical measurements and chemical modeling results from the African Monsoon Multidisciplinary Analysis (AMMA) field campaign.
Effect of isoprene emissions from major forests on ozone formation in the city of Shanghai, China

Ambient surface level concentrations of isoprene (C5H8) were measured in the major forest regions located south of Shanghai, China. Because there is a large coverage of broad-leaved trees in this region, high concentrations of isoprene were measured, ranging from 1 to 6 ppbv. A regional dynamical/chemical model (WRF-Chem) is applied for studying the effect of such high concentrations of isoprene on the ozone production in the city of Shanghai. The evaluation of the model shows that the calculated isoprene concentrations agree with the measured concentrations when the measured isoprene concentrations are lower than 3 ppb, but underestimate the measurements when the measured values are higher than 3 ppb. Isoprene was underestimated only at sampling sites near large bamboo plantations, a high isoprene source, indicating the need to include geospatially resolved bamboo distributions in the biogenic emission model. The assessment of the impact of isoprene on ozone formation suggests that the concentrations of peroxy radicals (RO2) are significantly enhanced due to the oxidation of isoprene, with a maximum of 30 ppt. However, the enhancement of RO2 is confined to the forested regions. Because the concentrations of NOx were low in the forest regions, the ozone production due to the oxidation of isoprene (C5H8 + OH → → RO2 + NO → → O3) is low (less than 2–3 ppb h−1). The calculation further suggests that the oxidation of isoprene leads to the enhancement of carbonyls (such as formaldehyde and acetaldehyde) in the regions downwind of the forests, due to continuous oxidation of isoprene in the forest air. As a result, the concentrations of HO2 radical are enhanced, resulting from the photo-disassociation of formaldehyde and acetaldehyde. Because the enhancement of HO2 radical occurs in regions downwind of the forests, the enhancement of ozone production (6–8 ppb h−1) is higher than in the forest region, causing by higher anthropogenic emissions of NOx. This study suggests that the biogenic emissions in the major forests to the south of Shanghai have important impacts on the levels of ozone in the city, mainly due to the carbonyls produced by the continuous oxidation of isoprene in the forest air.
Quantification of the unknown HONO daytime source and its relation to NO2

During the DOMINO (Diel Oxidant Mechanism In relation to Nitrogen Oxides) campaign in southwest Spain we measured simultaneously all quantities necessary to calculate a photostationary state for HONO in the gas phase. These quantities comprise the concentrations of OH, NO, and HONO and the photolysis frequency of NO2, j(NO2) as a proxy for j(HONO). This allowed us to calculate values of the unknown HONO daytime source. This unknown HONO source, normalized by NO2 mixing ratios and expressed as a conversion frequency (% h−1), showed a clear dependence on j(NO2) with values up to 43% h−1 at noon. We compared our unknown HONO source with values calculated from the measured field data for two recently proposed processes, the light-induced NO2 conversion on soot surfaces and the reaction of electronically excited NO2* with water vapour, with the result that these two reactions normally contributed less than 10% (<1% NO2 + soot + hν; and <10% NO2* + H2O) to our unknown HONO daytime source. OH production from HONO photolysis was found to be larger (by 20%) than the "classical" OH formation from ozone photolysis (O(1D)) integrated over the day.
Time-resolved measurements of black carbon light absorption enhancement in urban and near-urban locations of southern Ontario, Canada

In this study a photoacoustic spectrometer (PA), a laser-induced incandescence instrument system (LII) and an Aerosol Mass Spectrometer were operated in parallel for in-situ measurements of black carbon (BC) light absorption enhancement. Results of a thermodenuder experiment using ambient particles in Toronto are presented first to show that LII measurements of BC are not influenced by the presence of non-refractory material thus providing true atmospheric BC mass concentrations. In contrast, the PA response is enhanced when the non-refractory material is internally mixed with the BC particles. Through concurrent measurements using the LII and PA the specific absorption cross-section (SAC) can be quantified with high time resolution (1 min). Comparisons of ambient PA and LII measurements from four different locations (suburban Toronto; a street canyon with diesel bus traffic in Ottawa; adjacent to a commuter highway in Ottawa and; regional background air in and around Windsor, Ontario), show that different impacts from emission sources and/or atmospheric processes result in different particle light absorption enhancements and hence variations in the SAC. The diversity of measurements obtained, including those with the thermodenuder, demonstrated that it is possible to identify measurements where the presence of externally-mixed non-refractory particles obscures direct observation of the effect of coating material on the SAC, thus allowing this effect to be measured with more confidence. Depending upon the time and location of measurement (urban, rural, close to and within a lake breeze frontal zone), 30 min average SAC varies between 9 ± 2 and 43 ± 4 m2 g−1. Causes of this variation, which were determined through the use of meteorological and gaseous measurements (CO, SO2, O3), include the particle emission source, airmass source region, the degree of atmospheric processing. Observations from this study also show that the active surface area of the BC aggregate, which is measured by the LII as the PPS, is an important parameter for inferring the degree of particle collapse of a BC particle. In addition, PPS could be a useful measurement for indicating the importance of recently emitted BC (e.g. from gasoline or diesel engines) relative to the total measured BC in the atmosphere.
Determination of land surface heat fluxes over heterogeneous landscape of the Tibetan Plateau by using the MODIS and in situ data

In this study, a parameterization methodology based on MODIS (Moderate Resolution Imaging Spectroradiometer) and in situ data is proposed and tested for deriving the regional surface reflectance, surface temperature, net radiation flux, soil heat flux, sensible heat flux and latent heat flux over heterogeneous landscape. As a case study, the methodology was applied to the Tibetan Plateau area. Four images of MODIS data (30 January 2007, 15 April 2007, 1 August 2007 and 25 October 2007) were used in this study for the comparison among winter, spring, summer and autumn. The derived results were also validated by using the "ground truth" measured in the stations of the Tibetan Observation and Research Platform (TORP). The results show that the derived surface variables (surface reflectance and surface temperature) and surface heat fluxes (net radiation flux, soil heat flux, sensible heat flux and latent heat flux) in four different seasons over the Tibetan Plateau area are in good accordance with the land surface status. These parameters show a wide range due to the strong contrast of surface features over the Tibetan Plateau. Also, the estimated land surface variables and surface heat fluxes are in good agreement with the ground measurements, and all their absolute percent difference (APD) is less than 10% in the validation sites. It is therefore concluded that the proposed methodology is successful for the retrieval of land surface variables and surface heat fluxes using the MODIS and in situ data over the Tibetan Plateau area. The shortage and further improvement of the methodology were also discussed.