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The characteristics and origins of carbonaceous aerosol at a rural site of PRD in summer of 2006

Both organic carbon (OC) and elemental carbon (EC) were measured during PRIDE-PRD 2006 summer campaign by using a semi-continuous thermal-optical carbon analyzer at a rural site, Back Garden (BG), which is located 50 km to the northwest of Guangzhou City. Together with the online EC/OC analyzer, various kinds of instruments related to aerosol chemical properties were employed here, which provided a good opportunity to check data quality. The concentrations of OC correlated well with the mass of organic matter (OM) and water soluble organic carbon (WSOC), implying the reliability of the data measured in this campaign. The average OC concentrations in fine particle for three typical periods during the campaign (local emission influence, typhoon and precipitation and normal days) were 28.1 μgC m−3, 4.0 μgC m−3 and 5.7 μgC m−3, respectively; and EC were 11.6 μgC m−3, 1.8 μgC m−3, and 3.3 μgC m−3, respectively. The diurnal patterns of EC and OC during the campaign were higher at night and in early morning than daytime, which was probably caused by the primary emission and accumulation in the occurrence of low boundary layer. Compared with the constant diurnal enhancement ratios of EC, the enhancement ratio of OC (OC versus (CO-CObackground)) kept in a relative high level in the afternoon, with a similar diurnal profile to oxygenated organic aerosol (OOA), due to the strong photochemical formation of OC. Here, a modified EC tracer method was used to estimate the formation of secondary organic carbon (SOC). These results showed that the average SOC concentration (normal days) at BG site was about 2.0 ± 2.3 μgC m−3, and the SOC fraction in OC could reach up to 80% with the average of 47%. The modified approach in this study proved to be effective and reliable for SOC estimation based on good correlations between estimated SOC versus OOA or WSOC, and estimated POC versus hydrocarbon-like organic aerosol (HOA).
Validation of TES methane with HIPPO aircraft observations: implications for inverse modeling of methane sources

We validate satellite methane observations from the Tropospheric Emission Spectrometer (TES) with 151 aircraft vertical profiles over the Pacific from the HIAPER Pole-to-Pole Observation (HIPPO) program. We find that a collocation window of ±750 km and ±24 h does not introduce significant error in comparing TES and aircraft profiles. We validate both the TES standard product (V004) and an experimental product with two pieces of information in the vertical (V005). We determine a V004 mean bias of 65.8 ppb and random instrument error of 43.3 ppb. For V005 we determine a mean bias of 42.3 ppb and random instrument error of 26.5 ppb in the upper troposphere, and mean biases (random instrument errors) in the lower troposphere of 28.8 (28.7) and 16.9 (28.9) ppb at high and low latitudes respectively. Even when V005 cannot retrieve two pieces of information it still performs better than V004. An observation system simulation experiment (OSSE) with the GEOS-Chem chemical transport model (CTM) and its adjoint shows that TES V004 has only limited value for constraining methane sources. Our successful validation of V005 encourages its production as a standard retrieval to replace V004.
Coupling processes and exchange of energy and reactive and non-reactive trace gases at a forest site – results of the EGER experiment

To investigate the energy, matter and reactive and non-reactive trace gas exchange between the atmosphere and a spruce forest in the German mountain region, two intensive measuring periods were conducted at the FLUXNET site DE-Bay (Waldstein-Weidenbrunnen) in September/October 2007 and June/July 2008. They were part of the project "ExchanGE processes in mountainous Regions" (EGER). Beyond a brief description of the experiment, the main focus of the paper concerns the coupling between the trunk space, the canopy and the above-canopy atmosphere. Therefore, relevant coherent structures were analyzed for different in- and above canopy layers, coupling between layers was classified according to already published procedures, and gradients and fluxes of meteorological quantities as well as concentrations of non-reactive and reactive trace compounds have been sorted along the coupling classes. Only in the case of a fully coupled system, it could be shown, that fluxes measured above the canopy are related to gradients between the canopy and the above-canopy atmosphere. Temporal changes of concentration differences between top of canopy and the forest floor, particularly those of reactive trace gases (NO, NO2, O3, and HONO) could only be interpreted on the basis of the coupling stage. Consequently, only concurrent and vertically resolved measurements of micrometeorological (turbulence) quantities and fluxes (gradients) of trace compounds will lead to a better understanding of the forest-atmosphere interaction.
Source-receptor relationships for speciated atmospheric mercury at the remote Experimental Lakes Area, northwestern Ontario, Canada

Source-receptor relationships for speciated atmospheric mercury measured at the Experimental Lakes Area (ELA), northwestern Ontario, Canada were investigated using various receptor-based approaches. The data used in this study include gaseous elemental mercury (GEM), mercury bound to fine airborne particles (<2.5 μm) (PHg), reactive gaseous mercury (RGM), major inorganic ions, sulphur dioxide, nitric acid gas, ozone, and meteorological variables, all of which were measured between May 2005 and December 2006. The source origins identified were related to transport of industrial and combustion emissions (associated with elevated GEM), photochemical production of RGM (associated with elevated RGM), road-salt particles with absorption of gaseous Hg (associated with elevated PHg and RGM), crustal/soil emissions, and background pollution. Back trajectory modelling illustrated that a remote site, like ELA, is affected by distant Hg point sources in Canada and the United States. The sources identified from correlation analysis, principal components analysis and K-means cluster analysis were generally consistent. The discrepancies between the K-means and Hierarchical cluster analysis were the clusters related to transport of industrial/combustion emissions, photochemical production of RGM, and crustal/soil emissions. Although it was possible to assign the clusters to these source origins, the trajectory plots for the Hierarchical clusters were similar to some of the trajectories belonging to several K-means clusters. This likely occurred because the variables indicative of transport of industrial/combustion emissions were elevated in at least two or more of the clusters, which means this Hg source was well-represented in the data.
The adsorption of peroxynitric acid on ice between 230 K and 253 K

Peroxynitric acid uptake to ice and snow has been proposed to be a major loss process from the atmosphere with impacts on the atmospheric oxidation capacity. Here we present results from a laboratory study on the interaction of peroxynitric acid with water ice at low concentration. Experiments were performed in a coated wall flow tube at atmospheric pressure and in the environmentally relevant temperature range of 230 K to 253 K. The interaction was found to be fully reversible and decomposition was not observed. Analysis based on the Langmuir adsorption model showed that the partitioning of peroxynitric acid to ice is orders of magnitude lower than of nitric acid and similar to nitrous acid partitioning behavior. The partition coefficient (KLinC) and its temperature dependency can be described by 3.74 × 10−12 × e(7098/T) [cm]. Atmospheric implications are discussed and show that the uptake to cirrus clouds or to snow-packs in polar areas is an important sink for peroxynitric acid in the environment.
Transport and mixing patterns over Central California during the carbonaceous aerosol and radiative effects study (CARES)

We describe the synoptic and regional-scale meteorological conditions that affected the transport and mixing of trace gases and aerosols in the vicinity of Sacramento, California during June 2010 when the Carbonaceous Aerosol and Radiative Effects Study (CARES) was conducted. The meteorological measurements collected by various instruments deployed during the campaign and the performance of the chemistry version of the Weather Research and Forecasting model (WRF-Chem) are both discussed. WRF-Chem was run daily during the campaign to forecast the spatial and temporal variation of carbon monoxide emitted from 20 anthropogenic source regions in California to guide aircraft sampling. The model is shown to reproduce the overall circulations and boundary-layer characteristics in the region, although errors in the upslope wind speed and boundary-layer depth contribute to differences in the observed and simulated carbon monoxide. Thermally-driven upslope flows that transported pollutants from Sacramento over the foothills of the Sierra Nevada occurred every afternoon, except during three periods when the passage of mid-tropospheric troughs disrupted the regional-scale flow patterns. The meteorological conditions after the passage of the third trough were the most favorable for photochemistry and likely formation of secondary organic aerosols. Meteorological measurements and model forecasts indicate that the Sacramento pollutant plume was likely transported over a downwind site that collected trace gas and aerosol measurements during 23 time periods; however, direct transport occurred during only eight of these periods. The model also showed that emissions from the San Francisco Bay area transported by intrusions of marine air contributed a large fraction of the carbon monoxide in the vicinity of Sacramento, suggesting that this source likely affects local chemistry. Contributions from other sources of pollutants, such as those in the Sacramento Valley and San Joaquin Valley, were relatively low. Aerosol layering in the free troposphere was observed during the morning by an airborne Lidar. WRF-Chem forecasts showed that mountain venting processes contributed to aged pollutants aloft in the valley atmosphere that are then entrained into the growing boundary layer the subsequent day.
South African EUCAARI measurements: seasonal variation of trace gases and aerosol optical properties

In this paper we introduce new in situ observations of atmospheric aerosols, especially chemical composition, physical and optical properties, on the eastern brink of the heavily polluted Highveld area in South Africa. During the observation period between 11 February 2009 and 31 January 2011, the mean particle number concentration (size range 10–840 nm) was 6310 cm3 and the estimated volume of sub-10 μm particles 9.3 μm3 m−3. The aerosol absorption and scattering coefficients at 637 nm were 8.3 Mm−1 and 49.5 Mm−1, respectively. The mean single-scattering albedo at 637 nm was 0.84 and the Ångström exponent of scattering was 1.5 over the wavelength range 450–635 nm. The mean O3, SO2, NOx and H2S-concentrations were 37.1, 11.5, 15.1 and 3.2 ppb, respectively. The observed range of concentrations was large and attributed to the seasonal variation of sources and regional meteorological effects, especially the anticyclonic re-circulation and strong winter-time inversions. In a global context, the levels of gases and particulates were typical for continental sites with strong anthropogenic influence, but clearly lower than the most polluted areas of south-eastern Asia. Of all pollutants observed at the site, ozone is the most likely to have adverse environmental effects, as the concentrations were high also during the growing season. The measurements presented here will help to close existing gaps in the ground-based global atmosphere observation system, since very little long-term data of this nature is available for southern Africa.
Quantification of diesel exhaust gas phase organics by a thermal desorption proton transfer reaction mass spectrometer

A new approach was developed to measure the total abundance of long chain alkanes (C12 and above) in urban air using thermal desorption with a proton transfer reaction mass spectrometer (PTR-MS). These species are emitted in diesel exhaust and may be important precursors to secondary organic aerosol production in urban areas. Long chain alkanes undergo dissociative proton transfer reactions forming a series of fragment ions with formula CnH2n+1. The yield of the fragment ions is a function of drift conditions. At a drift field strength of 80 Townsends, the most abundant ion fragments from C10 to C16 n-alkanes were m/z 57, 71 and 85. The PTR-MS is insensitive to n-alkanes less than C8 but displays an increasing sensitivity for larger alkanes. Higher drift field strengths yield greater normalized sensitivity implying that the proton affinity of the long chain n-alkanes is less than H2O. Analysis of diesel fuel shows the mass spectrum was dominated by alkanes (CnH2n+1), monocyclic aromatics, and an ion group with formula CnH2n−1 (m/z 97, 111, 125, 139). The PTR-MS was deployed in Sacramento, CA during the Carbonaceous Aerosols and Radiative Effects Study field experiment in June 2010. The ratio of the m/z 97 to 85 ion intensities in ambient air matched that found in diesel fuel. Total diesel exhaust alkane concentrations calculated from the measured abundance of m/z 85 ranged from the method detection limit of ~1 μg m−3 to 100 μg m−3 in several air pollution episodes. The total diesel exhaust alkane concentration determined by this method was on average a factor of 10 greater than the sum of alkylbenzenes associated with spark ignition vehicle exhaust.
The MIPAS HOCl climatology

Monthly zonal mean HOCl measurements by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) are presented for the period from June 2002 to March 2004. Highest molar mixing ratios are found at pressure levels between 6 and 2 hPa, whereby largest mixing ratios occasionally exceed 200 ppt. The mixing ratio maximum is generally higher at lower altitudes in the summer hemisphere than in the winter hemisphere except for chlorine activation conditions in polar vortices, where enhanced HOCl abundances are also found in the lower stratosphere below about 10 hPa. During nighttime the maximum is found at higher altitudes than during daytime. Particularly low values (below 80 ppt) during daytime are found in subpolar regions in the winter hemisphere where HOCl photolysis is still strong but where HOCl precursors are less abundant than at other latitudes. The Antarctic polar winter HOCl distribution in 2002, the year of the split of the southern polar vortex, resembles northern polar winters rather than other southern polar winters. Increased HOCl amounts in response to the so-called Halloween solar proton event in autumn 2003 affect the representativeness of data recorded during this particular episode. Calculations with the EMAC model reproduce the measured HOCl distribution reasonably well. MIPAS measurements confirm that the reaction rate constants for HO2 + ClO &longrightarrow; HOCl + O2 from the most recent JPL recommendation allow much more realistic modelling of HOCl than reaction rate constants from earlier recommendations. Modeled HOCl mixing ratios, however, are still too low except in the polar winter stratosphere where the model overestimates the HOCl abundance.
Temporal trend and sources of speciated atmospheric mercury at Waliguan GAW station, Northwestern China

Measurements of speciated atmospheric mercury were conducted at a remote mountain-top station (Waliguan (WLG) Baseline Observatory) at the edge of northeastern part of the Qinghai-Xizang Plateau, Western China. Mean concentrations of total gaseous mercury (TGM), particulate bound mercury (PBM), and gaseous oxidized mercury (GOM) during the whole sampling campaign were 1.98±0.98 ng m−3, 19.4±18.1 pg m−3, and 7.4±4.8 pg m−3, respectively. Levels of speciated Hg at WLG were slightly higher than those reported from remote areas of North America and Europe. Both regional sources and long-rang transport played important roles in the distribution of atmospheric TGM and PBM at WLG, whereas GOM showed major links to the regional sources, likely as well as the in-situ productions via photochemical processes. Regional sources for speciated Hg were mostly located to the east of WLG, which is the most industrial and urbanized areas of Qinghai province. Potential source contribution function (PSCF) results showed that eastern Gansu, western Ningxia and Shanxi Province were likely the potential source regions of WLG, with good accordance with locations of urban areas and industrial centers. Moreover, we found that Northern India may be a significant source region for WLG during the sampling campaign, and this is the first published evidence suggesting long-range transport of atmospheric Hg from India to the Northeastern Tibetan Plateau. Seasonal and diurnal variations of TGM were in contrast to most of the previous studies in China, with relatively higher levels in warm seasons and night, respectively. The temporal trend of TGM also highlighted the impact of long-range transport on the distribution of TGM in ambient air at WLG.