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Different photolysis kinetics at the surface of frozen freshwater vs. frozen salt solutions

Reactions at air-ice interfaces can proceed at very different rates than those in aqueous solution, due to the unique disordered region at the ice surface known as the quasi-liquid layer (QLL) . The physical and chemical nature of the surfacial region of ice is greatly affected by solutes such as sodium halide salts. In this work, we studied the effects of sodium chloride and sodium bromide on the photolysis kinetics of harmine, an aromatic organic compound, in aqueous solution and at the surface of frozen salt solutions above the eutectic temperature. In common with other aromatic organic compounds we have studied, harmine photolysis is much faster on ice surfaces than in aqueous solution, but the presence of NaCl or NaBr – which does not affect photolysis kinetics in solution – reduces the photolysis rate on ice. The rate decreases monotonically with increasing salt concentration; at the concentrations found in seawater, harmine photolysis at the surface of frozen salt solutions proceeds at the same rate as in aqueous solution. These results suggest that the brine excluded to the surfaces of frozen salt solutions is a true aqueous solution, and so it may be possible to use aqueous-phase kinetics to predict photolysis rates at sea ice surfaces. This is in marked contrast to the result at the surface of frozen freshwater samples, where reaction kinetics are often not well-described by aqueous-phase processes.
Unraveling the complex local-scale flows influencing ozone patterns in the southern Great Lakes of North America

This study examines the complexity of various processes influencing summertime ozone levels in the southern Great Lakes region of North America. Results from the Border Air Quality and Meteorology (BAQS-Met) field campaign in the summer of 2007 are examined with respect to land-lake differences and local meteorology using a large array of ground-based measurements, aircraft data, and simulation results from a high resolution (2.5 km) regional air-quality model, AURAMS. Analyses of average ozone mixing ratio from the entire BAQS-Met intensive campaign period support previous findings that ozone levels are higher over the southern Great Lakes than over the adjacent land. However, there is great heterogeneity in the spatial distribution of surface ozone over the lakes, particularly over Lake Erie during the day, with higher levels located over the southwestern end of the lake. Model results suggest that some of these increased ozone levels are due to local emission sources in large nearby urban centers. While an ozone reservoir layer is predicted by the AURAMS model over Lake Erie at night, the land-lake differences in ozone mixing ratios are most pronounced during the night in a shallow inversion layer of about 200 m above the surface. After sunrise, these differences have a limited effect on the total mass of ozone over the lakes and land during the day, though they do cause elevated ozone levels in the lake-breeze air in some locations. The model also predicts a mean vertical circulation during the day with an updraft over Detroit-Windsor and downdraft over Lake St. Clair, which transports ozone up to 1500 m above ground and results in high ozone over the lake. Oscillations in ground-level ozone mixing ratios were observed on several nights and at several ground monitoring sites, with amplitudes of up to 40 ppbv and time periods of 15–40 min. Several possible mechanisms for these oscillations are discussed, but a complete understanding of their causes is not possible given current data and knowledge.
Sources of light-absorbing aerosol in arctic snow and their seasonal variation

Two data sets consisting of measurements of light absorbing aerosols (LAA) in arctic snow together with suites of other corresponding chemical constituents are presented; the first from Siberia, Greenland and near the North Pole obtained in 2008, and the second from the Canadian arctic obtained in 2009. A preliminary differentiation of the LAA into black carbon (BC) and non-BC LAA is done. Source attribution of the light absorbing aerosols was done using a positive matrix factorization (PMF) model. Four sources were found for each data set (crop and grass burning, boreal biomass burning, pollution and marine). For both data sets, the crops and grass biomass burning was the main source of both LAA species, suggesting the non-BC LAA was brown carbon. Depth profiles at most of the sites allowed assessment of the seasonal variation in the source strengths. The biomass burning sources dominated in the spring but pollution played a more significant (though rarely dominant) role in the fall, winter and, for Greenland, summer. The PMF analysis is consistent with trajectory analysis and satellite fire maps.
Temperature thresholds for polar stratospheric ozone loss

Low stratospheric temperatures are known to be responsible for heterogeneous chlorine activation that leads to polar ozone depletion. Here, we discuss the temperature threshold below which substantial chlorine activation occurs. We suggest that the onset of chlorine activation is dominated by reactions on cold binary aerosol particles, without formation of polar stratospheric clouds (PSCs), i.e. without significant uptake of HNO3 from the gas-phase. Using reaction rates on cold binary aerosol, a chlorine activation threshold temperature, TACL, is derived. At typical stratospheric conditions, TACL is similar in value to TNAT the highest temperature at which nitric acid trihydrate (NAT) can theoretically condense to form PSCs. TACL is still in use as parameterization for the threshold temperature for the onset of chlorine activation. However, perturbations can cause TACL to differ from TNAT: TACL is dependent upon H2O, potential temperature, and the sulphate aerosol loading, but unlike TNAT is not dependent upon HNO3. A parameterization of TACL is provided here, allowing it to be calculated over a comprehensive range of stratospheric conditions. Although considering TACL as a proxy for chlorine activation can be no substitute for a detailed model calculation, TACL provides a more accurate description of the temperature conditions necessary for polar ozone depletion than TNAT and can readily be used in place of TNAT.
A decadal regional and global trend analysis of the aerosol optical depth using a data-assimilation grade over-water MODIS and Level 2 MISR aerosol products

Using the ten-year (2000–2009) Data-Assimilation (DA) quality Terra MODIS and MISR aerosol products, as well as 7 years of Aqua MODIS, we studied both regional and global aerosol trends over oceans. This included both operational and data assimilation grade versions of the products. After correcting for what appears to be aerosol signal drift from the radiometric calibration of both MODIS instruments, we found MODIS and MISR agreed on a statistically negligible global trend of ±0.003/per decade. Our study also suggests that AODs over the Indian Bay of Bengal, east coast of Asia, and Arabian Sea show increasing trends of 0.07, 0.06, and 0.06 per decade for MODIS, respectively. These regional trends are considered as significant with a confidence level above 95%. Similar increasing trends were found from MISR, but with less relative magnitude. These trends reflect respective increases in the optical intensity of aerosol events in each region: anthropogenic aerosols over the east coast of China and Indian Bay of Bengal; and a stronger influence from dust events over the Arabian Sea. Negative AOD trends, low in confidence levels, are found off Central America, the east coast of North America, and the west coast of Africa, which indicate that longer periods of observation are necessary to be conclusive.
Aerosol-cloud interaction determined by both in situ and satellite data over a northern high-latitude site

The first aerosol indirect effect over a clean, northern high-latitude site was investigated by determining the aerosol cloud interaction (ACI) using three different approaches; ground-based in situ measurements, combined ground-based in situ measurements and satellite retrievals and using only satellite retrievals. The obtained values of ACI were highest for in situ ground-based data, clearly lower for combined ground-based and satellite data, and lowest for data relying solely on satellite retrievals. One of the key findings of this study was the high sensitivity of ACI to the definition of the aerosol burden. We showed that at least a part of the variability in ACI can be explained by how different investigators have related different cloud properties to "aerosol burden".
Direct satellite observation of lightning-produced NOx

Lightning is an important source of NOx in the free troposphere, especially in the tropics, with strong impact on ozone production. However, estimates of lightning NOx (LNOx) production efficiency (LNOx per flash) are still quite uncertain. In this study we present a systematic analysis of NO2 column densities from SCIAMACHY measurements over active thunderstorms, as detected by the World-Wide Lightning Location Network (WWLLN), where the WWLLN detection efficiency was estimated using the flash climatology of the satellite lightning sensors LIS/OTD. Only events with high lightning activity are considered, where corrected WWLLN flash rate densities inside the satellite pixel within the last hour are above 1 /km2/h. For typical SCIAMACHY ground pixels of 30 × 60 km2, this threshold corresponds to 1800 flashes over the last hour, which, for literature estimates of lightning NOx production, should result in clearly enhanced NO2 column densities. From 2004–2008, we find 287 coincidences of SCIAMACHY measurements and high WWLLN flash rate densities. For some of these events, a clear enhancement of column densities of NO2 could be observed, indeed. But overall, the measured column densities are below the expected values by more than one order of magnitude, and in most of the cases, no enhanced NO2 could be found at all. Our results are in contradiction to the currently accepted range of LNOx production per flash of 15 (2–40)×1025 molec/flash. This probably partly results from the specific conditions for the events under investigation, i.e. events of high lightning activity in the morning (local time) and mostly (for 162 out of 287 events) over ocean. Within the detected coincidences, the highest NO2 column densities were observed around the US Eastcoast. This might be partly due to interference with ground sources of NOx being uplifted by the convective systems. However, it could also indicate that flashes in this region are particularly productive. We conclude that current estimates of LNOx production might be biased high for two reasons. First, we observe a high variability of NO2 for coincident lightning events. This high variability can easily cause a publication bias, since studies reporting on high NOx production have likely been published, while studies finding no or low amounts of NOx might have been rejected as errorneous or not significant. Second, many estimates of LNOx production in literature have been performed over the US, which is probably not representative for global lightning.
Can 3-D models explain the observed fractions of fossil and non-fossil carbon in and near Mexico City?

A 3-D chemistry-transport model has been applied to the Mexico City metropolitan area to investigate the origin of elevated levels of non-fossil (NF) carbonaceous aerosols observed in this highly urbanized region. High time resolution measurements of the fine aerosol concentration and composition, and 12 or 24 h integrated 14C measurements of aerosol modern carbon have been performed in and near Mexico City during the March 2006 MILAGRO field experiment. The non-fossil carbon fraction (fNF), which is lower than the measured modern fraction (fM) due to the elevated 14C in the atmosphere caused by nuclear bomb testing, is estimated from the measured fM and the source-dependent information on modern carbon enrichment. The fNF contained in PM1 total carbon analyzed by a US team (fNFTC) ranged from 0.37 to 0.67 at the downtown location, and from 0.50 to 0.86 at the suburban site. Substantially lower values (i.e. 0.24–0.49) were found for PM10 filters downtown by an independent set of measurements (Swiss team), which are inconsistent with the modeled and known differences between the size ranges, suggesting higher than expected uncertainties in the measurement techniques of 14C. An increase in the non-fossil organic carbon (OC) fraction (fNFOC) by 0.10–0.15 was observed for both sets of filters during periods with enhanced wildfire activity in comparison to periods when fires were suppressed by rain, which is consistent with the wildfire impacts estimated with other methods. Model results show that the relatively high fraction of non-fossil carbon found in Mexico City seems to arise from the combination in about equal proportions of regional biogenic SOA, biomass burning POA and SOA, as well as non-fossil urban POA and SOA. Predicted spatial and temporal variations for fNFOCare similar to those in the measurements between the urban vs. suburban sites, and high-fire vs. low-fire periods. The absolute modeled values of fNFOC are consistent with the Swiss dataset but lower than the US dataset. Resolving the 14C measurement discrepancies is necessary for further progress in model evaluation. The model simulations that included secondary organic aerosol (SOA) formation from semi-volatile and intermediate volatility (S/IVOC) vapors showed improved closure for the total OA mass compared to simulations which only included SOA from VOCs, providing a more realistic basis to evaluate the fNF predictions. fNFOC urban sources of modern carbon are important in reducing or removing the difference in fNF between model and measurements, even though they are often neglected on the interpretation of 14C datasets. An underprediction of biomass burning POA by the model during some mornings also explains a part of the model-measurement differences. The fNF of urban POA and SOA precursors is an important parameter that needs to be better constrained by measurements. Performing faster (≤3 h) 14C measurements in future campaigns is critical to further progress in this area. To our knowledge this is the first time that radiocarbon measurements are used together with aerosol mass spectrometer (AMS) organic components to assess the performance of a regional model for organic aerosols.
Laboratory measurements of trace gas emissions from biomass burning of fuel types from the southeastern and southwestern United States

Vegetation commonly managed by prescribed burning was collected from five southeastern and southwestern US military bases and burned under controlled conditions at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. The smoke emissions were measured with a large suite of state-of-the-art instrumentation including an open-path Fourier transform infrared (OP-FTIR) spectrometer for measurement of gas-phase species. The OP-FTIR detected and quantified 19 gas-phase species in these fires: CO2, CO, CH4, C2H2, C2H4, C3H6, HCHO, HCOOH, CH3OH, CH3COOH, furan, H2O, NO, NO2, HONO, NH3, HCN, HCl, and SO2. Emission factors for these species are presented for each vegetation type burned. Gas-phase nitrous acid (HONO), an important OH precursor, was detected in the smoke from all fires. The HONO emission factors ranged from 0.15 to 0.60 g kg−1 and were higher for the southeastern fuels. The fire-integrated molar emission ratios of HONO (relative to NOx) ranged from approximately 0.03 to 0.20, with higher values also observed for the southeastern fuels. The majority of non-methane organic compound (NMOC) emissions detected by OP-FTIR were oxygenated volatile organic compounds (OVOCs) with the total identified OVOC emissions constituting 61 ± 12% of the total measured NMOC on a molar basis. These OVOC may undergo photolysis or further oxidation contributing to ozone formation. Elevated amounts of gas-phase HCl and SO2 were also detected during flaming combustion, with the amounts varying greatly depending on location and vegetation type. The fuels with the highest HCl emission factors were all located in the coastal regions, although HCl was also observed from fuels farther inland. Emission factors for HCl were generally higher for the southwestern fuels, particularly those found in the chaparral biome in the coastal regions of California.
Assessment of the calibration performance of satellite visible channels using cloud targets: application to Meteosat-8/9 and MTSAT-1R

To examine the calibration performance of the Meteosat-8/9 Spinning Enhanced Visible Infra-Red Imager (SEVIRI) 0.640-μm and the Multi-functional Transport Satellite (MTSAT)-1R 0.724-μm channels, three calibration methods are employed. Total eight months during the 2004–2007 period are used for SEVIRI, and total seven months during the 2007–2008 period are used for MTSAT-1R. First, a ray-matching technique is used to compare Meteosat-8/9 and MTSAT-1R visible channel reflectances with the well-calibrated Moderate Resolution Imaging Spectroradiometer (MODIS) 0.646-μm channel reflectances. Spectral differences of the response function between the two channels of interest are taken into account for the comparison. Second, collocated MODIS cloud products are used as inputs to a radiative transfer model (RTM) to calculate Meteosat-8/9 and MTSAT-1R visible channel reflectances. In the simulation, cloud three-dimensional (3-D) radiative effect associated with subgrid variations is taken into account using the lognormal-independent column approximation (LN-ICA) to minimize the simulation bias caused by the plane-parallel homogeneous assumption. Third, an independent method uses the typical optical properties of deep convective clouds (DCCs) to simulate reflectances of selected DCC targets. Although all three methods are not in perfect agreement, the results suggest that calibration coefficients of Meteosat-8/9 0.640-μm channels are underestimated by 6–7%. On the other hand, the calibration accuracy of MTSAT-1R visible channel appears to be variable with the target reflectance itself because of an underestimate of calibration coefficient (up to 20%) and a non-zero space offset. The results further suggest that the solar channel calibration scheme combining the three methods in this paper can be used as a tool to monitor the calibration performance of visible sensors that are particularly not equipped with an onboard calibration system.