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Analysis of ΔO2/ΔCO2 ratios for the pollution events observed at Hateruma Island, Japan

Pollution events extracted from the in situ observations of atmospheric CO2 and O2 mixing ratios at Hateruma Island (HAT, 24° N, 124° E) during the period from October 2006 and December 2008 are examined. The air mass origins for the pollution events are categorized by using back trajectory analysis, and the oxidative ratios (OR = −O2:CO2 molar exchange ratio) for selected pollution events are calculated. We find that there is a significant difference in the average oxidative ratios between events from China (OR = 1.14 ± 0.12, n = 25) and Japan/Korea (OR = 1.37 ± 0.15, n = 16). These values are in a good agreement with the national average oxidative ratios for the emissions from fossil fuel burning and cement production (FFBC) in China (ORFFBC = 1.11 ± 0.03) and Korea/Japan (ORFFBC = 1.36 ± 0.02). Compared with the observation, simulations of the atmospheric O2 and CO2 mixing ratios using Lagrangian particle dispersion models do a good job in reconstructing the average oxidative ratio of the pollution events originating in China but tend to underestimate for events originating in Japan/Korea. A sensitivity test suggests that the simulated atmospheric oxidative ratios at HAT are especially sensitive to changes in Chinese fuel mix.
Carbonaceous aerosols in China: top-down constraints on primary sources and estimation of secondary contribution

We simulated elemental carbon (EC) and organic carbon (OC) aerosols in China and compared model results to surface measurements at Chinese rural and background sites, with the goal of deriving "top-down" emission estimates of EC and OC, as well as better quantifying the secondary sources of OC. We included in the model state-of-the-science Chinese "bottom-up" emission inventories for EC (1.92 TgC yr−1) and OC (3.95 TgC yr−1), as well as updated secondary OC formation pathways. The average simulated annual mean EC concentration at rural and background sites was 1.1 μgC m−3, 56% lower than the observed 2.5 μgC m−3. The average simulated annual mean OC concentration at rural and background sites was 3.4 μgC m−3, 76% lower than the observed 14 μgC m−3. Multiple regression to fit surface monthly mean EC observations at rural and background sites yielded the best estimate of Chinese EC source of 3.05 ± 0.78 TgC yr−1. Based on the top-down EC emission estimate and observed seasonal primary OC/EC ratios, we estimated Chinese OC emissions to be 6.67 ± 1.30 TgC yr−1. Using these top-down estimates, the simulated average annual mean EC concentration at rural and background sites was significantly improved to 1.9 μgC m−3. However, the model still significantly underestimated observed OC in all seasons (simulated average annual mean OC at rural and background sites was 5.4 μgC m−3), with little skill in capturing the spatiotemporal variability. Secondary formation accounts for 21% of Chinese annual mean surface OC in the model, with isoprene being the most important precursor. In summer, as high as 62% of the observed surface OC may be due to secondary formation in eastern China. Our analysis points to four shortcomings in the current bottom-up inventories of Chinese carbonaceous aerosols: (1) the anthropogenic source is underestimated on a national scale, particularly for OC; (2) the spatiotemporal distributions of emissions are misrepresented; (3) there is a missing source in western China, likely associated with the use of biofuels or other low-quality fuels for heating; and (4) sources in fall are not well represented, either because the seasonal shifting of emissions and/or secondary formation are poorly captured or because specific fall emission events are missing. In addition, secondary production of OC in China is severely underestimated. More regional measurements with better spatiotemporal coverage are needed to resolve these shortcomings.
Sensitivity to deliberate sea salt seeding of marine clouds – observations and model simulations

Sea salt seeding of marine clouds to increase their albedo is a proposed technique to counteract or slow global warming. In this study, we first investigate the susceptibility of marine clouds to sea salt injections, using observational data of cloud droplet number concentration, cloud optical depth, and liquid cloud fraction from the MODIS (Moderate Resolution Imaging Spectroradiometer) instruments on board the Aqua and Terra satellites. We then compare the derived susceptibility function to a corresponding estimate from the Norwegian Earth System Model (NorESM). Results compare well between simulations and observations, showing that stratocumulus regions off the west coast of the major continents along with large regions over the Pacific and the Indian Oceans are susceptible. At low and mid latitudes the signal is dominated by the cloud fraction. We then carry out geo-engineering experiments with a uniform increase over ocean of 10−9 kg m−2 s−1 in emissions of sea salt particles with a dry modal radius of 0.13 μm, an emission strength and areal coverage much greater than proposed in earlier studies. The increased sea salt concentrations and the resulting change in marine cloud properties lead to a globally averaged forcing of −4.8 W m−2 at the top of the atmosphere, more than cancelling the forcing associated with a doubling of CO2 concentrations. The forcing is large in areas found to be sensitive by using the susceptibility function, confirming its usefulness as an indicator of where to inject sea salt for maximum effect. Results also show that the effectiveness of sea salt seeding is reduced because the injected sea salt provides a large surface area for water vapor and gaseous sulphuric acid to condense on, thereby lowering the maximum supersaturation and suppressing the formation and lifetime of sulphate particles. In some areas, our simulations show an overall reduction in the CCN concentration and the number of activated cloud droplets decreases, resulting in a positive forcing.
Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-Rudich-Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modeled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system and the computational constraints, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmospheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at ~270 K is close to unity (Winkler et al., 2006). Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for efficient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.
Inverse modelling of cloud-aerosol interactions – Part 2: Sensitivity tests on liquid phase clouds using a Markov chain Monte Carlo based simulation approach

This paper presents a novel approach to investigate cloud-aerosol interactions by coupling a Markov chain Monte Carlo (MCMC) algorithm to an adiabatic cloud parcel model. Despite the number of numerical cloud-aerosol sensitivity studies previously conducted few have used statistical analysis tools to investigate the global sensitivity of a cloud model to input aerosol physiochemical parameters. Using numerically generated cloud droplet number concentration (CDNC) distributions (i.e. synthetic data) as cloud observations, this inverse modelling framework is shown to successfully estimate the correct calibration parameters, and their underlying posterior probability distribution. The employed analysis method provides a new, integrative framework to evaluate the global sensitivity of the derived CDNC distribution to the input parameters describing the lognormal properties of the accumulation mode aerosol and the particle chemistry. To a large extent, results from prior studies are confirmed, but the present study also provides some additional insights. There is a transition in relative sensitivity from very clean marine Arctic conditions where the lognormal aerosol parameters representing the accumulation mode aerosol number concentration and mean radius and are found to be most important for determining the CDNC distribution to very polluted continental environments (aerosol concentration in the accumulation mode >1000 cm−3) where particle chemistry is more important than both number concentration and size of the accumulation mode. The competition and compensation between the cloud model input parameters illustrates that if the soluble mass fraction is reduced, the aerosol number concentration, geometric standard deviation and mean radius of the accumulation mode must increase in order to achieve the same CDNC distribution. This study demonstrates that inverse modelling provides a flexible, transparent and integrative method for efficiently exploring cloud-aerosol interactions with respect to parameter sensitivity and correlation.
Reactions of H+(pyridine)m(H2O)n and H+(NH3)1(pyridine)m(H2O)n with NH3: experiments and kinetic modelling

Reactions between pyridine containing water cluster ions, H+(pyridine)1(H2O)n, H+(pyridine)2(H2O)n and H+(NH3)1(pyridine)1(H2O)n (n up to 15) with NH3 have been studied experimentally using a quadrupole time-of-flight mass spectrometer. The product ions in the reaction between H+(pyridine)m(H2O)n (m = 1 to 2) and NH3 have been determined for the first time. It is found that the reaction mainly leads to cluster ions of the form H+(NH3)1(pyridine)m(H2O)n-x, with x = 1 or 2 depending on the initial size of the reacting cluster ion. For a given number of water molecules (from 5 to 15) in the cluster ion, rate coefficients are found to be slightly lower than those for protonated pure water clusters reacting with ammonia. The rate coefficients obtained from this study are used in a kinetic cluster ion model under tropospheric conditions. The disagreement between ambient ground level measurements and previous models are discussed in relation to the results from our model and future experimental directions are suggested.
Microphysical controls on the stratocumulus topped boundary-layer structure during VOCALS-REx

Simulations at a range of resolutions are compared to observations from the South-East Pacific taken during VOCALS-REx. It is found that increased horizontal and vertical resolution make only small improvements to the bulk properties of the simulated cloud and drizzle, but the highest resolution simulation is able to realistically represent mesoscale features in the cloud field. We focus on the highest resolution simulation and demonstrate that a poor representation of the cloud microphysics results in excessive drizzle production. This promotes persistent drizzle induced decoupling of the boundary layer, giving a poor representation of the observed diurnal cycle of stratocumulus. Two simple changes to the microphysics scheme are implemented: a modified autoconversion parametrization and a new representation of the rain drop size distribution. This results in a more realistic simulation of boundary-layer diurnal decoupling, and improvements to the cloud liquid water path and surface drizzle rate.
Atmospheric dust modeling from meso to global scales with the online NMMB/BSC-Dust model – Part 2: Experimental campaigns in Northern Africa

The new NMMB/BSC-Dust model is intended to provide short to medium-range weather and dust forecasts from regional to global scales. It is an online model in which the dust aerosol dynamics and physics are solved at each model time step. The companion paper (Pérez et al., 2011) develops the dust model parameterizations and provides daily to annual evaluations of the model for its global and regional configurations. Modeled aerosol optical depth (AOD) was evaluated against AERONET Sun photometers over Northern Africa, Middle East and Europe with correlations around 0.6–0.7 on average without dust data assimilation. In this paper we analyze in detail the behavior of the model using data from the Saharan Mineral dUst experiment (SAMUM-1) in 2006 and the Bodélé Dust Experiment (BoDEx) in 2005. AOD from satellites and Sun photometers, vertically resolved extinction coefficients from lidars and particle size distributions at the ground and in the troposphere are used, complemented by wind profile data and surface meteorological measurements. All simulations were performed at the regional scale for the Northern African domain at the expected operational horizontal resolution of 25 km. Model results for SAMUM-1 generally show good agreement with satellite data over the most active Saharan dust sources. The model reproduces the AOD from Sun photometers close to sources and after long-range transport, and the dust size spectra at different height levels. At this resolution, the model is not able to reproduce a large haboob that occurred during the campaign. Some deficiencies are found concerning the vertical dust distribution related to the representation of the mixing height in the atmospheric part of the model. For the BoDEx episode, we found the diurnal temperature cycle to be strongly dependant on the soil moisture, which is underestimated in the NCEP analysis used for model initialization. The low level jet (LLJ) and the dust AOD over the Bodélé are well reproduced. The remaining negative AOD bias (due to underestimated surface wind speeds) can be substantially reduced by decreasing the threshold friction velocity in the model.
A-train CALIOP and MLS observations of early winter Antarctic polar stratospheric clouds and nitric acid in 2008

A-train Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) and Microwave Limb Sounder (MLS) observations are used to investigate the development of polar stratospheric clouds (PSCs) and the gas-phase nitric acid distribution in the early 2008 Antarctic winter. Observational evidence of gravity-wave activity is provided by Atmospheric Infrared Sounder (AIRS) radiances and infrared spectroscopic detection of nitric acid trihydrate (NAT) in PSCs is obtained from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). Goddard Earth Observing System Data Assimilation System (GEOS-5 DAS) analyses are used to derive Lagrangian trajectories and to determine temperature-time histories of air parcels. We use CALIOP backscatter and depolarization measurements to classify PSCs and the MLS measurements to determine the corresponding gas-phase HNO3 as a function of temperature. For liquid PSCs the uptake of HNO3 follows the theoretical equilibrium curve for supercooled ternary solutions (STS), but at temperatures about 1 K lower as determined from GEOS-5. In the presence of solid phase PSCs, above the ice frost-point, the HNO3 depletion occurs over a wider range of temperatures (+2 to −7 K) distributed about the NAT equilibrium curve. Rapid gas-phase HNO3 depletion is first seen by MLS from from 23–25 May 2008, consisting of a decrease in the volume mixing ratio from 14 ppbv (parts per billion by volume) to 7 ppbv on the 46–32 hPa (hectopascal) pressure levels and accompanied by a 2–3 ppbv increase by renitrification at the 68 hPa pressure level. The observed region of depleted HNO3 is substantially smaller than the region bounded by the NAT existence temperature threshold. Temperature-time histories of air parcels demonstrate that the depletion is more clearly correlated with prior exposure to temperatures a few kelvin above the frost-point. From the combined data we infer the presence of large-size NAT particles with effective radii >5–7 μm and low NAT number densities <1 × 10−3 cm−3. This denitrification event is observed close to the pole in the Antarctic vortex before synoptic temperatures first fall below the ice frost point and before the widespread occurrence of large-scale NAT PSCs. An episode of mountain wave activity detected by AIRS on 28 May 2008 led to wave-ice formation in the rapid cooling phases over the Antarctic Peninsula and Ellsworth Mountains, seeding an outbreak of NAT PSCs that were detected by CALIOP and MIPAS. The NAT clouds formed at altitudes of 18–26 km in a polar freezing belt and appear to be composed of relatively small particles with estimated effective radii of around 1 μm and high NAT number densities >0.2 cm−3. This NAT outbreak is similar to an event previously reported from MIPAS observations in mid-June 2003.
Satellite constraint for emissions of nitrogen oxides from anthropogenic, lightning and soil sources over East China on a high-resolution grid

Vertical column densities (VCDs) of tropospheric nitrogen dioxide (NO2) retrieved from space provide valuable information to estimate emissions of nitrogen oxides (NOx) inversely. Accurate emission attribution to individual sources, important both for understanding the global biogeochemical cycling of nitrogen and for emission control, remains difficult. This study presents a regression-based multi-step inversion approach to estimate emissions of NOx from anthropogenic, lightning and soil sources individually for 2006 over East China on a 0.25° long × 0.25° lat grid, employing the DOMINO product version 2 retrieved from the Ozone Monitoring Instrument. The inversion is done gridbox by gridbox to derive the respective emissions, taking advantage of differences in seasonality between anthropogenic and natural sources. Lightning and soil emissions are combined together for any given gridbox due to their similar seasonality; and their different spatial distributions are used implicitly for source separation to some extent. The nested GEOS-Chem model for East Asia is used to simulate the seasonal variations of different emission sources and impacts on VCDs of NO2 for the inversion purpose. Sensitivity tests are conducted to evaluate key assumptions embedded in the inversion process. The inverse estimate suggests annual budgets of about 7.1 TgN (±39%), 0.21 TgN (±61%), and 0.38 TgN (±65%) for the a posteriori anthropogenic, lightning and soil emissions, respectively, about 18–23% higher than the respective a priori values. The enhancements in anthropogenic emissions are largest in cities and areas with extensive use of coal, particularly in the north in winter, as evident on the high-resolution grid. Derived soil emissions are consistent with recent bottom-up estimates. They are less than 6% of anthropogenic emissions annually, increasing to about 13% for July. Derived lightning emissions are about 3% of anthropogenic emissions annually and about 10% in July. Overall, anthropogenic emissions are found to be the dominant source of NOx over East China with important implications for nitrogen control.