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Vertical structure of MJO-related subtropical ozone variations from MLS, TES, and SHADOZ data

Tian et al. (2007) found that the MJO-related total column ozone (O3) anomalies of 10 DU (peak-to-trough) are mainly evident over the subtropics and dynamically driven by the vertical movement of the subtropical tropopause layer. It was then hypothesized that the subtropical total column O3 anomalies are primarily associated with the O3 variability in the stratosphere rather the troposphere. In this paper, we investigate the vertical structure of MJO-related subtropical O3 variations using the vertical O3 profiles from the Aura Microwave Limb Sounder (MLS) and Tropospheric Emission Spectrometer (TES), as well as in-situ measurements by the Southern Hemisphere Additional Ozonesondes (SHADOZ) project. Our analysis indicates that the subtropical O3 anomalies maximize approximately in the lower stratosphere (60–100 hPa). Furthermore, the spatial-temporal patterns of the subtropical O3 anomalies in the lower stratosphere are very similar to that of the total column. In particular, they are both dynamically driven by the vertical movement of subtropical tropopause. The subtropical partial O3 column anomalies between 30–200 hPa accounts for more than 50 % of the total O3 column anomalies. TES measurements show that at most 27 % of the total O3 column anomalies are contributed by the tropospheric components. This indicates that the subtropical total column O3 anomalies are mostly from the O3 anomalies in the lower stratosphere, which supports the hypothesis of Tian et al. (2007). The strong connection between the intraseasonal subtropical stratospheric O3 variations and the MJO implies that the stratospheric O3 variations may be predictable with similar lead times over the subtropics. Future work could involve a similar study or an O3 budget analysis using a sophisticated chemical transport model in the near-equatorial regions where the observed MJO signals of total column O3 are weak.
Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis

The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007)−((4±5)×10−5) T(°C). The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq = (1.0167±0.0019)−((8.7±3.5) ×10−5)T(°C). The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilibria of S(IV) in solution, which is the reason that there is no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.9894±0.0043) at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S/32S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes. The results presented in this study will be particularly useful to determine the importance of the transition metal-catalysed oxidation pathway compared to other oxidation pathways, but other main oxidation pathways can not be distinguished based on stable sulfur isotope measurements alone.
Observation and modeling of the evolution of Texas power plant plumes

During the second Texas Air Quality Study 2006 (TexAQS II), a full range of pollutants was measured by aircraft in eastern Texas during successive transects of power plant plumes (PPPs). A regional photochemical model is applied to simulate the physical and chemical evolution of the plumes. The observations reveal that SO2 and NOy were rapidly removed from PPPs on a cloudy day but not on the cloud-free days, indicating efficient aqueous processing of these compounds in clouds. The model reasonably represents observed NOx oxidation and PAN formation in the plumes, but fails to capture the rapid loss of SO2 (0.37 h−1) and NOy (0.24 h−1) in some plumes on the cloudy day. Adjustments to the cloud liquid water content (QC) and the default metal concentrations in the cloud module could explain some of the SO2 loss. However, NOy in the model was insensitive to QC. These findings highlight cloud processing as a major challenge to atmospheric models. Model-based estimates of ozone production efficiency (OPE) in PPPs are 20–50 % lower than observation-based estimates for the cloudy day.
Acid-yield measurements of the gas-phase ozonolysis of ethene as a function of humidity using Chemical Ionisation Mass Spectrometry (CIMS)

Gas-phase ethene ozonolysis experiments were conducted at room temperature to determine formic acid yields as a function of relative humidity (RH) using the integrated EXTreme RAnge chamber-Chemical Ionisation Mass Spectrometry technique, employing a CH3I ionisation scheme. RHs studied were <1, 11, 21, 27, 30 % and formic acid yields of (0.07±0.01) and (0.41±0.07) were determined at <1 % RH and 30 % RH respectively, showing a strong water dependence. It has been possible to estimate the ratio of the rate coefficient for the reaction of the Criegee biradical, CH2OO with water compared with decomposition. This analysis suggests that the rate of reaction with water ranges between 1×10−12–1×10−15 cm3 molecule−1 s−1 and will therefore dominate its loss with respect to bimolecular processes in the atmosphere. Global model integrations suggest that this reaction between CH2OO and water may dominate the production of HC(O)OH in the atmosphere.
Have primary emission reduction measures reduced ozone across Europe? An analysis of European rural background ozone trends 1996–2005

National and European legislation over the past 20 yr, and the modernisation or removal of industrial sources, have significantly reduced European ozone precursor emissions. This study quantifies observed and modelled European ozone annual and seasonal linear trends from 158 harmonised rural background monitoring stations over a constant time period of a decade (1996–2005). Mean ozone concentrations are investigated, in addition to the ozone 5th percentiles as a measure of the baseline or background conditions, and the 95th percentiles that are representative of the peak concentration levels. This study aims to characterise and quantify surface European ozone concentrations and trends and assess the impact of the changing anthropogenic emission tracers on the observed and modelled trends. Significant (p<0.1) positive annual trends in ozone mean, 5th and 95th percentiles are observed at 54 %, 52 % and 45 % of sites respectively (85 sites, 82 sites and 71 sites). Spatially, sites in central and north-western Europe tend to display positive annual ozone trends in mean, 5th and 95th percentiles. Significant negative annual trends in ozone mean 5th and 95th percentiles are observed at 11 %, 12 % and 12 % of sites respectively (18 sites, 19 sites and 19 sites) which tend to be located in the eastern and south-western extremities of Europe. European-averaged annual trends have been calculated from the 158 sites in this study. Overall there is a net positive annual trend in observed ozone mean (0.16±0.02 ppbv yr−1 (2σ error)), 5th (0.13±0.02 ppbv yr−1) and 95th (0.16±0.03 ppbv yr−1) percentiles, representative of positive trends in mean, baseline and peak ozone. Assessing the sensitivity of the derived overall trends to the constituent years shows that the European heatwave year of 2003 has significant positive influence and 1998 the converse effect; demonstrating the masking effect of inter-annual variability on decadal based ozone trends. The European scale 3-D CTM CHIMERE was used to simulate hourly O3 concentrations for the period 1996–2005. Comparisons between the 158 observed ozone trends to those equivalent sites extracted from regional simulations by CHIMERE better match the observed increasing annual ozone (predominantly in central and north-western Europe) for 5th percentiles, than for mean or 95th ozone percentiles. The European-averaged annual ozone trend in CHIMERE 5th percentiles (0.13±0.01 ppbv yr−1) matches the corresponding observed trend extremely well, but displays a negative trend for the 95th percentile (−0.03±0.02 ppbv yr−1) where a positive ozone trend is observed. Inspection of the EU-averaged monthly means of ozone shows that the CHIMERE model is overestimating the summer month O3 levels. In comparison to trends in EMEP emissions inventories, with the exception of Austria-Hungary, we do not find that anthropogenic NOx and VOC reductions have a substantial effect on observed annual mean O3 trends in the rest of Europe. On a ten year time-scale presented in this study, O3 trends related to anthropogenic NOx and VOC reductions are being masked as a result of a number of factors including meteorological variability, changes in background ozone and shifts in source patterns.
Bulk microphysical properties of semi-transparent cirrus from AIRS: a six year global climatology and statistical analysis in synergy with geometrical profiling data from CloudSat-CALIPSO

This article presents a retrieval method and a statistical analysis of the bulk microphysical properties of semi-transparent ice clouds using the Atmospheric Infrared Sounder (AIRS). The method relies on spectral differences of cirrus emissivities in the 8–12 μm range and is sensitive to the effective ice crystal diameter (De) and ice water path (IWP) of up to 85 μm and 120 g m−2, respectively. An indication of the most frequent ice crystal habit in the cirrus has been obtained by using separately single scattering properties of column-like and aggregate-like ice crystals in the simulations. Uncertainties due to hypotheses on atmospheric parameters and ice crystal single scattering properties are discussed and the cirrus emissivity and temperature range for the applicability of the method are determined. To be sure that the cirrus only includes ice crystals, one has to restrict the cloud temperature range to Tcld<230 K. On a global scale, these semi-transparent ice clouds (cirrus) represent about 25% of all high clouds and are mainly encountered in the midlatitudes during winter and in the tropics, with an average De and IWP of 52 μm and 27 g m−2, respectively. A comparison with bulk microphysical properties from the TIROS-N Operational Vertical Sounder (TOVS) shows an agreement on global mean values. The addition of spectral information revealed improvements at the limits of the cirrus emissivity range. Collocated Radar-Lidar Geometrical Profiling (GEOPROF) data have been used to study the vertical structure of these clouds and to infer average ice water content (IWC) for cirrus with a small vertical extent. This allowed us to compare and contrast parameterizations of De as functions of IWC and IWP, respectively.
A high-resolution emission inventory of primary pollutants for the Huabei region, China

Huabei, located between 32° N and 42° N, is part of eastern China and includes administratively the Beijing and Tianjin Municipalities, Hebei and Shanxi Provinces, and Inner-Mongolia Autonomous Region. Over the past decades, the region has experienced dramatic changes in air quality and climate, and has become a major focus of environmental research in China. Here we present a new inventory of air pollutant emissions in Huabei for the year 2003 developed as part of the project Influence of Pollution on Aerosols and Cloud Microphysics in North China (IPAC-NC). Our estimates are based on data from the statistical yearbooks of the state, provinces and local districts, including major sectors and activities of power generation, industrial energy consumption, industrial processing, civil energy consumption, crop straw burning, oil and solvent evaporation, manure, and motor vehicles. The emission factors are selected from a variety of literature and those from local measurements in China are used whenever available. The estimated total emissions in the Huabei administrative region in 2003 are 4.73 Tg SO2, 2.72 Tg NOx (in equivalent NO2), 1.77 Tg VOC, 24.14 Tg CO, 2.03 Tg NH3, 4.57 Tg PM10, 2.42 Tg PM2.5, 0.21 Tg EC, and 0.46 Tg OC. For model convenience, we consider a larger Huabei region with Shandong, Henan and Liaoning Provinces included in our inventory. The estimated total emissions in the larger Huabei region in 2003 are: 9.55 Tg SO2, 5.27 Tg NOx (in equivalent NO2), 3.82 Tg VOC, 46.59 Tg CO, 5.36 Tg NH3, 10.74 Tg PM10, 5.62 Tg PM2.5, 0.41 Tg EC, and 0.99 Tg OC. The estimated emission rates are projected into grid cells at a horizontal resolution of 0.1° latitude by 0.1° longitude. Our gridded emission inventory consists of area sources, which are classified into industrial, civil, traffic, and straw burning sectors, and large industrial point sources, which include 345 sets of power plants, iron and steel plants, cement plants, and chemical plants. The estimated regional NO2 emissions are about 2–3% (administrative Huabei region) or 5% (larger Huabei region) of the global anthropogenic NO2 emissions. We compare our inventory (IPAC-NC) with the global emission inventory EDGAR-CIRCE and the Asian emission inventory INTEX-B. Except for a factor of 3 lower EC emission rate in comparison with INTEX-B, the biases of the total emissions of most primary air pollutants in Huabei estimated in our inventory, with respect to EDGAR-CIRCE and INTEX-B, generally range from −30% to +40%. Large differences up to a factor of 2–3 for local emissions in some areas (e.g. Beijing and Tianjin) are found. It is recommended that the inventories based on the activity rates and emission factors for each specific year should be applied in future modeling work related to the changes in air quality and atmospheric chemistry over this region.
ANISORROPIA: the adjoint of the aerosol thermodynamic model ISORROPIA

We present the development of ANISORROPIA, the discrete adjoint of the ISORROPIA thermodynamic equilibrium model that treats the Na+-SO42−- HSO4−-NH4+ -NO3−-Cl−-H2O aerosol system, and we demonstrate its sensitivity analysis capabilities. ANISORROPIA calculates sensitivities of an inorganic species in aerosol or gas phase with respect to the total concentrations of each species present with less than a two-fold increase in computational time over the concentration calculations. Due to the highly nonlinear and discontinuous solution surface of ISORROPIA, evaluation of the adjoint required a new, complex-variable version of the model, which determines first-order sensitivities with machine precision and avoids cancellation errors arising from finite difference calculations. The adjoint is verified over an atmospherically relevant range of concentrations, temperature, and relative humidity. We apply ANISORROPIA to recent field campaign results from Atlanta, GA, USA, and Mexico City, Mexico, to characterize the inorganic aerosol sensitivities of these distinct urban air masses. The variability in the relationship between fine mode inorganic aerosol mass and precursor concentrations shown has important implications for air quality and climate.
Gas-particle partitioning of atmospheric Hg(II) and its effect on global mercury deposition

Atmospheric deposition of Hg(II) represents a major input of mercury to surface environments. The phase of Hg(II) (gas or particle) has important implications for deposition. We use long-term observations of reactive gaseous mercury (RGM, the gaseous component of Hg(II)), particle-bound mercury (PBM, the particulate component of Hg(II)), fine particulate matter (PM2.5), and temperature (T) at five sites in North America to derive an empirical gas-particle partitioning relationship log10(K−1) = (10±1)–(2500±300)/T where K = (PBM/PM2.5)/RGM with PBM and RGM in common mixing ratio units, PM2.5 in μg m−3, and T in K. This relationship is within the range of previous work but is based on far more extensive data from multiple sites. We implement this empirical relationship in the GEOS-Chem global 3-D Hg model to partition Hg(II) between the gas and particle phases. The resulting gas-phase fraction of Hg(II) ranges from over 90 % in warm air with little aerosol to less than 10 % in cold air with high aerosol. Hg deposition to high latitudes increases because of more efficient scavenging of particulate Hg(II) by precipitating snow. Model comparison to Hg observations at the North American surface sites suggests that subsidence from the free troposphere (warm air, low aerosol) is a major factor driving the seasonality of RGM, while elevated PBM is mostly associated with high aerosol loads. Simulation of RGM and PBM at these sites is improved by including fast in-plume reduction of Hg(II) emitted from coal combustion and by assuming that anthropogenic particulate Hg(p) behaves as semi-volatile Hg(II) rather than as a refractory particulate component. We improve the simulation of Hg wet deposition fluxes in the US relative to a previous version of GEOS-Chem; this largely reflects independent improvement of the washout algorithm. The observed wintertime minimum in wet deposition fluxes is attributed to inefficient snow scavenging of gas-phase Hg(II).
Abiotic and biotic control of methanol exchanges in a temperate mixed forest

Methanol exchanges over a mixed temperate forest in the Belgian Ardennes were measured for more than one vegetation season using disjunct eddy-covariance by a mass scanning technique and Proton Transfer Reaction Mass Spectrometry (PTR-MS). Half-hourly methanol fluxes were measured in the range of −0.6 μg m−2 s−1 to 0.6 μg m−2 s−1, and net daily methanol fluxes were generally negative in summer and autumn and positive in spring. On average, the negative fluxes dominated (i.e. the site behaved as a net sink), in contrast to what had been found in previous studies. An original model describing the adsorption/desorption of methanol in water films present in the forest ecosystem and the methanol degradation process was developed. Its calibration, based on field measurements, predicted a mean methanol degradation rate of −0.0074 μg m−2 s−1 and a half lifetime for methanol in water films of 57.4 h. Biogenic emissions dominated the exchange only in spring, with a standard emission factor of 0.76 μg m−2 s−1. The great ability of the model to reproduce the long-term evolution, as well as the diurnal variation of the fluxes, suggests that the adsorption/desorption and degradation processes play an important role in the global methanol budget. This result underlines the need to conduct long-term measurements in order to accurately capture these processes and to better estimate methanol fluxes at the ecosystem scale.