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The effects of nitrate on the heterogeneous uptake of sulfur dioxide on hematite

Nitrate is often found to be associated with atmospheric particles. Surface nitrate can change the hygroscopicity of these particles, and thus impact their chemical reactivity. However, the influence of nitrate on heterogeneous reactions of atmospheric trace gases is poorly understood. In this work, the effects of nitrate on heterogeneous conversion of SO2 with hematite at 298 K are investigated using an in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and a White cell coupled with Fourier transform infrared spectroscopy (White cell-FTIR). It is found that nitrate participates in heterogeneous reactions of SO2, accelerates the formation rate of sulfate, and leads to the formation of surface-adsorbed HNO3 and gas-phase N2O and HONO. The results indicate that low to moderate amounts of nitrate significantly enhance the reactivity of hematite–nitrate mixtures, the uptake of SO2, and the formation of sulfate on hematite. For mixtures, the sample containing 24% nitrate exhibits the highest sulfate formation rate, and its corresponding uptake coefficient calculated by geometric surface area is about 5.5 times higher than that of hematite alone. The sample containing 48% nitrate presents the highest Brunauer–Emmett–Teller (BET) uptake coefficient, and the value is about 8 times higher than that of pure hematite. No uptake of SO2 and formation of sulfate are observed on pure nitrate. Evidence presented herein implies a significant contribution of the unreleased HNO3 and HONO in the particles for the conversion of SO2 and the enhanced formation of sulfate in the atmosphere. A possible mechanism for the influence of nitrate on the heterogeneous conversion of SO2 on hematite is proposed, and atmospheric implications based on these results are discussed.
Evaluation of IASI-derived dust aerosol characteristics over the tropical belt

IASI (Infrared Atmospheric Sounder Interferometer)-derived monthly mean infrared (10 μm) dust aerosol optical depth (AOD) and altitude are evaluated against ground-based Aerosol RObotic NETwork of sun photometers (AERONET) measurements of the 500 nm coarse-mode AOD and CALIOP (Cloud-Aerosol Lidar with Orthogonal Polarization) measurements of altitude at 38 AERONET sites (sea and land) within the tropical belt (30° N–30° S). The period covered extends from July 2007 to June 2013. The evaluation goes through the analysis of Taylor diagrams and box-and-whiskers plots, separating situations over oceanic regions and over land. For the AOD, such an evaluation raises the problem of the difference between the two spectral domains used: infrared for IASI and visible for AERONET. Consequently, the two measurements do not share the same metrics. For that reason, AERONET coarse-mode AOD is first "translated" into IASI-equivalent infrared AOD. This is done by the determination, site by site, of an infrared to visible AOD ratio. Because translating visible coarse-mode AOD into infrared AOD requires accurate knowledge of variables, such as the infrared refractive index or the particle size distribution, quantifying the bias between these two sources of AOD is not straightforward. This problem is detailed in this paper, in particular in Appendix A. For the sites over oceanic regions, the overall AOD temporal correlation comes to 0.86 for 786 items (IASI and AERONET monthly mean bins). The overall normalized standard deviation (i.e. ratio of the standard deviation of the test data (IASI) to that of the reference data (AERONET)) is 0.93, close to the desired value of 1. Over land, essentially desert, correlation is 0.74 for 619 items and the normalized standard deviation is 0.86. This slight but significant degradation over land most probably results from the greater complexity of the surface (heterogeneity, elevation) and, to a lesser extent, to the episodic presence of dust within the boundary layer (particularly for sites close to active sources) to which IASI, as any thermal infrared sounder, is poorly sensitive, unlike AERONET. Site by site, disparities appear that are principally due to either the insufficient number of AERONET observations throughout the period considered, to the complexity of the location leading to the mixing of several aerosol types (in the case of the Persian Gulf, for example), to surface heterogeneities (elevation, emissivity, etc.), or to the use of a single aerosol model (called "MITR"). Results using another aerosol model, with a different refractive index, are presented and discussed. Concerning altitude over oceanic regions, correlation is 0.70 for 853 items and the normalized standard deviation is 0.92. A systematic bias of −0.4 km (IASI–CALIOP) is observed, with a standard deviation of 0.48 km. This result is satisfactory, considering the important differences between the two instruments (space–time coverage, definition of the altitude). Altitude results over land, essentially over deserts, are not satisfactory for a majority of sites. The smaller sensitivity of IASI to altitude compared to its sensitivity to AOD, added to the difficulties met for the determination of the AOD over land (surface heterogeneities), explain this result. Work is in progress to solve this difficulty. We conclude that the present results demonstrate the usefulness of IASI data, which are planned to cover a long period of time, as an additional constraint to a better knowledge of the impact of aerosols on the climate system.
Will the role of intercontinental transport change in a changing climate?

Intercontinental transport of atmospheric pollution (ITAP) can offset the impact of local emission control efforts, impact human and ecosystem health, and play a role in climate forcing. This study aims to determine the role of ITAP caused by East Asian anthropogenic emissions (EAAEs) under current and future emission and climate scenarios. The contribution from EAAEs is determined using a "brute force method" in which results from simulations with and without EAAEs are compared. ITAP from East Asia is enhanced in the future due to faster wind speeds aloft and a stronger low pressure center near eastern Russia that facilitate enhanced westerly export in the free troposphere and stronger southerly transport near the surface, increased gaseous precursor emissions, and increased temperatures. As a result, the contribution of ozone (O3) generated by EAAEs to the global average O3 mixing ratio increases by ~0.8 ppb from 1.2 ppb in 2001 to 2.0 ppb in 2050. The contribution of PM2.5 generated by EAAEs to the global PM2.5 level increases by ~0.07 μg m−3 from 0.32 μg m−3 in 2001 to 0.39 μg m−3 in 2050, despite a non-homogenous response in PM2.5 resulting from cloud and radiative feedbacks. EAAEs can increase East Asian biogenic secondary organic aerosol by 10–81%, indicating that it is largely controllable. EAAEs also increase the deposition of nitrogen, black carbon, and mercury both locally and downwind, implying that they may play a role in climate feedbacks and ecosystem health of these regions. These results show that EAAEs have a large impact on global air quality and climate, especially on downwind regions. Such impacts may be enhanced under future climate and emission scenarios, demonstrating a need to synergize global pollution control and climate mitigation efforts.
Greenhouse gas network design using backward Lagrangian particle dispersion modelling − Part 1: Methodology and Australian test case

This paper describes the generation of optimal atmospheric measurement networks for determining carbon dioxide fluxes over Australia using inverse methods. A Lagrangian particle dispersion model is used in reverse mode together with a Bayesian inverse modelling framework to calculate the relationship between weekly surface fluxes, comprising contributions from the biosphere and fossil fuel combustion, and hourly concentration observations for the Australian continent. Meteorological driving fields are provided by the regional version of the Australian Community Climate and Earth System Simulator (ACCESS) at 12 km resolution at an hourly timescale. Prior uncertainties are derived on a weekly timescale for biosphere fluxes and fossil fuel emissions from high-resolution model runs using the Community Atmosphere Biosphere Land Exchange (CABLE) model and the Fossil Fuel Data Assimilation System (FFDAS) respectively. The influence from outside the modelled domain is investigated, but proves to be negligible for the network design. Existing ground-based measurement stations in Australia are assessed in terms of their ability to constrain local flux estimates from the land. We find that the six stations that are currently operational are already able to reduce the uncertainties on surface flux estimates by about 30%. A candidate list of 59 stations is generated based on logistic constraints and an incremental optimisation scheme is used to extend the network of existing stations. In order to achieve an uncertainty reduction of about 50%, we need to double the number of measurement stations in Australia. Assuming equal data uncertainties for all sites, new stations would be mainly located in the northern and eastern part of the continent.
Comparison of IASI water vapor retrieval with H2O-Raman lidar in the framework of the Mediterranean HyMeX and ChArMEx programs

The Infrared Atmospheric Sounding Interferometer (IASI) is a new generation spaceborne passive sensor mainly dedicated to meteorological applications. Operational Level-2 products have been available via the European Organisation for the Exploitation of Meteorological Satellites (EUMETSAT) for several years. In particular, vertical profiles of water vapor measurements are retrieved from infrared radiances at the global scale. Nevertheless, the robustness of such products has to be checked because only a few validations have been reported. For this purpose, the field experiments that were held during the HyMeX and ChArMEx international programs are a very good opportunity. A H2O-Raman lidar was deployed on the Balearic island of Menorca and operated continuously for ~ 6 and ~ 3 weeks during fall 2012 (Hydrological cycle in the Mediterranean eXperiment – HyMeX) and summer 2013 (Chemistry–Aerosol Mediterranean Experiment – ChArMEx), respectively. It measured simultaneously the water vapor mixing ratio and aerosol optical properties. This article does not aim to describe the IASI operational H2O inversion algorithm, but to compare the vertical profiles derived from IASI onboard (meteorological operational) MetOp-A and the ground-based lidar measurements to assess the reliability of the IASI operational product for the water vapor retrieval in both the lower and middle troposphere. The links between water vapor contents and both the aerosol vertical profiles and the air mass origins are also studied. About 30 simultaneous observations, performed during nighttime in cloud free conditions, have been considered. For altitudes ranging from 2 to 7 km, root mean square errors (correlation) of ~ 0.5 g kg−1 (~ 0.77) and ~ 1.1 g kg−1 (~ 0.72) are derived between the operational IASI product and the available lidar profiles during HyMeX and ChArMEx, respectively. The values of both root mean square error and correlation are meaningful and show that the operational Level-2 product of the IASI-derived vertical water vapor mixing ratio can be considered for meteorological and climatic applications, at least in the framework of field campaigns.
The stratospheric response to external factors based on MERRA data using linear multivariate linear regression analysis

The stratosphere is influenced by many external forcings (natural or anthropogenic). There are many studies which are focused on this problem and that is why we can compare our results with them. This study is focused on the variability and trends of temperature and circulation characteristics (zonal and meridional wind component) in connection with different phenomena variation in the stratosphere and lower mesosphere. We consider the interactions between the troposphere–stratosphere-lower mesosphere system and external and internal phenomena, e.g. solar cycle, QBO, NAO or ENSO using multiple linear techniques. The analysis was applied to the period 1979–2012 based on the current reanalysis data, mainly the MERRA reanalysis dataset (Modern Era Retrospective-analysis for Research and Applications) for pressure levels: 1000–0.1 hPa. We do not find a strong temperature signal for solar flux over the tropics about 30 hPa (ERA-40 results) but the strong positive signal has been observed near stratopause almost in the whole analyzed area. This could indicate that solar forcing is not represented well in the higher pressure levels in MERRA. The analysis of ENSO and ENSO Modoki shows that we should take into account more than one ENSO index for similar analysis. Previous studies show that the volcanic activity is important parameter. The signal of volcanic activity in MERRA is very weak and insignificant.
Constraining the N2O5 UV absorption cross section from spectroscopic trace gas measurements in the tropical mid-stratosphere

The absorption cross section of N2O5, σN2O5(λ, T), which is known from laboratory measurements with the uncertainty of a factor of 2 (Table 4-2 in (Jet Propulsion Laboratory) JPL-2011; the spread in laboratory data, however, points to an uncertainty in the range of 25 to 30%, Sander et al., 2011), was investigated by balloon-borne observations of the relevant trace gases in the tropical mid-stratosphere. The method relies on the observation of the diurnal variation of NO2 by limb scanning DOAS (differential optical absorption spectroscopy) measurements (Weidner et al., 2005; Kritten et al., 2010), supported by detailed photochemical modelling of NOy (NOx(= NO + NO2) + NO3 + 2N2O5 + ClONO2 + HO2NO2 + BrONO2 + HNO3) photochemistry and a non-linear least square fitting of the model result to the NO2 observations. Simulations are initialised with O3 measured by direct sun observations, the NOy partitioning from MIPAS-B (Michelson Interferometer for Passive Atmospheric Sounding – Balloon-borne version) observations in similar air masses at night-time, and all other relevant species from simulations of the SLIMCAT (Single Layer Isentropic Model of Chemistry And Transport) chemical transport model (CTM). Best agreement between the simulated and observed diurnal increase of NO2 is found if the σN2O5(λ, T) is scaled by a factor of 1.6 ± 0.8 in the UV-C (200–260 nm) and by a factor of 0.9 ± 0.26 in the UV-B/A (260–350 nm), compared to current recommendations. As a consequence, at 30 km altitude, the N2O5 lifetime against photolysis becomes a factor of 0.77 shorter at solar zenith angle (SZA) of 30° than using the recommended σN2O5(λ, T), and stays more or less constant at SZAs of 60°. Our scaled N2O5 photolysis frequency slightly reduces the lifetime (0.2–0.6%) of ozone in the tropical mid- and upper stratosphere, but not to an extent to be important for global ozone.
Observations of the scale-dependent turbulence and evaluation of the flux–gradient relationship for sensible heat for a closed Douglas-fir canopy in very weak wind conditions

Observations of the scale-dependent turbulent fluxes, variances, and the bulk transfer parameterization for sensible heat above, within, and beneath a tall closed Douglas-fir canopy in very weak winds are examined. The daytime sub-canopy vertical velocity spectra exhibit a double-peak structure with peaks at timescales of 0.8 s and 51.2 s. A double-peak structure is also observed in the daytime sub-canopy heat flux co-spectra. The daytime momentum flux co-spectra in the upper bole space and in the sub-canopy are characterized by a relatively large cross-wind component, likely due to the extremely light and variable winds, such that the definition of a mean wind direction, and subsequent partitioning of the momentum flux into along- and cross-wind components, has little physical meaning. Positive values of both momentum flux components in the sub-canopy contribute to upward transfer of momentum, consistent with the observed sub-canopy secondary wind speed maximum. For the smallest resolved scales in the canopy at nighttime, we find increasing vertical velocity variance with decreasing timescale, consistent with very small eddies possibly generated by wake shedding from the canopy elements that transport momentum, but not heat. Unusually large values of the velocity aspect ratio within the canopy were observed, consistent with enhanced suppression of the horizontal wind components compared to the vertical by the very dense canopy. The flux–gradient approach for sensible heat flux is found to be valid for the sub-canopy and above-canopy layers when considered separately in spite of the very small fluxes on the order of a few W m−2 in the sub-canopy. However, single-source approaches that ignore the canopy fail because they make the heat flux appear to be counter-gradient when in fact it is aligned with the local temperature gradient in both the sub-canopy and above-canopy layers. While sub-canopy Stanton numbers agreed well with values typically reported in the literature, our estimates for the above-canopy Stanton number were much larger, which likely leads to underestimated modeled sensible heat fluxes above dark warm closed canopies.
Links between satellite-retrieved aerosol and precipitation

Many theories have been proposed detailing how aerosols might impact precipitation, predicting both increases and decreases depending on the prevailing meteorological conditions and aerosol type. In convective clouds, increased aerosol concentrations have been speculated to invigorate convective activity. Previous studies have shown large increases in precipitation with increasing aerosol optical depth, concluding an aerosol effect on precipitation. Our analysis reveals that these studies may have been influenced by cloud effects on the retrieved aerosol, as well as by meteorological covariations. We use a regime-based approach to separate out different cloud regimes, allowing for the study of aerosol–cloud interactions in individual cloud regimes. We account for the influence of cloud properties on the aerosol retrieval and make use of the diurnal sampling of the TRMM satellite and the TRMM merged precipitation product to investigate the precipitation development. We find that whilst there is little effect on precipitation at the time of the aerosol retrieval, in the 6 h after the aerosol retrieval, there is an increase in precipitation from cloud in high-aerosol environments, consistent with the invigoration hypothesis. Increases in lightning flash count with increased aerosol are also observed in this period. The invigoration effect appears to be dependent on the cloud-top temperature, with clouds with tops colder than 0 °C showing increases in precipitation at times after the retrieval, as well as increases in wet scavenging. Warm clouds show little change in precipitation development with increasing aerosol, suggesting ice processes are important for the invigoration of precipitation.
Aqueous-phase photooxidation of levoglucosan – a mechanistic study using aerosol time-of-flight chemical ionization mass spectrometry (Aerosol ToF-CIMS)

Levoglucosan (LG) is a widely employed tracer for biomass burning (BB). Recent studies have shown that LG can react rapidly with hydroxyl (OH) radicals in the aqueous phase despite many mass balance receptor models assuming it to be inert during atmospheric transport. In the current study, aqueous-phase photooxidation of LG by OH radicals was performed in the laboratory. The reaction kinetics and products were monitored by aerosol time-of-flight chemical ionization mass spectrometry (Aerosol ToF-CIMS). Approximately 50 reaction products were detected by the Aerosol ToF-CIMS during the photooxidation experiments, representing one of the most detailed product studies yet performed. By following the evolution of mass defects of product peaks, unique trends of adding oxygen (+O) and removing hydrogen (−2H) were observed among the products detected, providing useful information for determining potential reaction mechanisms and sequences. Additionally, bond-scission reactions take place, leading to reaction intermediates with lower carbon numbers. We introduce a data analysis framework where the average oxidation state (OSc) is plotted against a novel molecular property: double-bond-equivalence-to-carbon ratio (DBE/#C). The trajectory of LG photooxidation on this plot suggests formation of polycarbonyl intermediates and their subsequent conversion to carboxylic acids as a general reaction trend. We also determined the rate constant of LG with OH radicals at room temperature to be 1.08 ± 0.16 × 109 M−1 s−1. By coupling an aerosol mass spectrometer (AMS) to the system, we observed a rapid decay of the mass fraction of organic signals at mass-to-charge ratio 60 (f60), corresponding closely to the LG decay monitored by the Aerosol ToF-CIMS. The trajectory of LG photooxidation on a f44–f60 correlation plot matched closely to literature field measurement data. This implies that aqueous-phase photooxidation might be partially contributing to aging of BB particles in the ambient atmosphere.