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Gaseous mercury distribution in the upper troposphere and lower stratosphere observed onboard the CARIBIC passenger aircraft

Total gaseous mercury (TGM) was measured onboard a passenger aircraft during monthly CARIBIC flights (Civil Aircraft for Regular Investigation of the Atmosphere Based on an Instrumented Container) made between May 2005 and March 2007 on the routes Frankfurt–São Paulo–Santiago de Chile and back and Frankfurt–Guangzhou–Manila and back. The data provide for the first time an insight into the seasonal distributions of TGM in the upper troposphere and lower stratosphere (UT/LS) of both hemispheres and demonstrate the importance of mercury emissions from biomass burning in the Southern Hemisphere. Numerous plumes were observed in the upper troposphere, the larger of which could be characterized in terms of Hg/CO emission ratios and their probable origins. During the flights to China TGM correlated with CO in the upper troposphere with a seasonally dependent slope reflecting the longer lifetime of elemental mercury when compared to that of CO. A pronounced depletion of TGM was always observed in the extratropical lowermost stratosphere. TGM concentrations there were found to decrease with the increasing concentrations of particles. Combined with the large concentrations of particle bond mercury in the stratosphere observed by others, this finding suggests either a direct conversion of TGM to particle bound mercury or an indirect conversion via a semivolatile bivalent mercury compound. Based on concurrent measurements of SF6 during two flights, the rate of this conversion is estimated to 0.4 ng m−3 yr−1. A zero TGM concentration was not observed during some 200 flight hours in the lowermost stratosphere suggesting an equilibrium between the gaseous and particulate mercury.
Attribution of aerosol light absorption to black carbon, brown carbon, and dust in China – interpretations of atmospheric measurements during EAST-AIRE

Black carbon, brown carbon, and mineral dust are three of the most important light absorbing aerosols. Their optical properties differ greatly and are distinctive functions of the wavelength of light. Most optical instruments that quantify light absorption, however, are unable to distinguish one type of absorbing aerosol from another. It is thus instructive to separate total absorption from these different light absorbers to gain a better understanding of the optical characteristics of each aerosol type. During the EAST-AIRE (East Asian Study of Tropospheric Aerosols: an International Regional Experiment) campaign near Beijing, we measured light scattering using a nephelometer, and light absorption using an aethalometer and a particulate soot absorption photometer. We also measured the total mass concentrations of carbonaceous (elemental and organic carbon) and inorganic particulates, as well as aerosol number and mass distributions. We were able to identify periods during the campaign that were dominated by dust, biomass burning, fresh (industrial) chimney plumes, other coal burning pollution, and relatively clean (background) air for Northern China. Each of these air masses possessed distinct intensive optical properties, including the single scatter albedo and Ångstrom exponents. Based on the wavelength-dependence and particle size distribution, we apportioned total light absorption to black carbon, brown carbon, and dust; their mass absorption efficiencies at 550 nm were estimated to be 9.5, 0.5 (a lower limit value), and 0.03 m2/g, respectively. While agreeing with the common consensus that black carbon is the most important light absorber in the mid-visible, we demonstrated that brown carbon and dust could also cause significant absorption, especially at shorter wavelengths.
Peroxy radicals in the summer free troposphere: seasonality and potential for heterogeneous loss

The sum of peroxy radicals (HO2+ΣiRiO2) and supporting trace gases were measured on the Jungfraujoch (3580 m a.s.l.) during the late summer of 2005. The period was marked by extended times of heavy snow which led to reduction in the observed peroxy radicals during the snowy periods that was greater than the concomitant reduction in j(O1D). In the limit a first order loss rate of 0.0063 s−1 can be derived for the peroxy radical loss in the snowy conditions that could be potentially ascribed to a heterogenous loss process. On snow free days photolysis of HCHO is shown to be a significant peroxy radical source. The seasonal trends of the peroxy radical concentrations have been mapped from the winter to summer transition in line with previous experiments. Net ozone production in late summer at the Jungfraujoch was net neutral to marginally ozone destructive. A value of 28±4 pptv is calculated for the ozone compensation point for the snow free days.
Modelling trends in OH radical concentrations using generalized additive models

During the TORCH campaign a zero dimensional box model based on the Master Chemical Mechanism was used to model concentrations of OH radicals. The model provided a close overall fit to measured concentrations but with some significant deviations. In this research, an approach was established for applying Generalized Additive Models (GAM) to atmospheric concentration data. Two GAM models were fitted to OH radical concentrations using TORCH data, the first using measured OH data and the second using MCM model results. GAM models with five smooth functions provided a close fit to the data with 78% of the deviance explained for measured OH and 83% for modelled OH. The GAM model for measured OH produced substantially better predictions of OH concentrations than the original MCM model results. The diurnal profile of OH concentration was reproduced and the predicted mean diurnal OH concentration was only 0.2% less than the measured concentration compared to 16.3% over-estimation by the MCM model. Photolysis reactions were identified as most important in explaining concentrations of OH. The GAM models combined both primary and secondary pollutants and also anthropogenic and biogenic species to explain changes in OH concentrations. Differences identified in the dependencies of modelled and measured OH concentrations, particularly for aromatic and biogenic species, may help to understand why the MCM model predictions sometimes disagree with measurements of atmospheric species.
Carbonaceous aerosols in Norwegian urban areas

Little is known regarding levels and source strength of carbonaceous aerosols in Scandinavia. In the present study, ambient aerosol (PM10 and PM2.5) concentrations of elemental carbon (EC), organic carbon (OC), water-insoluble organic carbon (WINSOC), and water-soluble organic carbon (WSOC) are reported for a curbside site, an urban background site, and a suburban site in Norway in order to investigate their spatial and seasonal variations. Aerosol filter samples were collected using tandem filter sampling to correct for the positive sampling artefact introduced by volatile and semivolatile OC. Analyses were performed using the thermal optical transmission (TOT) instrument from Sunset Lab Inc., which corrects for charring during analysis. Finally, we estimated the relative contribution of OC from wood burning based on the samples content of levoglucosan. Levels of EC varied by more than one order of magnitude between sites, likely due to the higher impact of vehicular traffic at the curbside and the urban background sites. In winter, the level of particulate organic carbon (OCp) at the suburban site was equal to (for PM10) or even higher (for PM2.5) than the levels observed at the curbside and the urban background sites. This finding was attributed to the impact of residential wood burning at the suburban site in winter, which was confirmed by a high mean concentration of levoglucosan (407 ng m−3). This finding indicates that exposure to primary combustion derived OCp could be equally high in residential areas as in a city center. It is demonstrated that OCp from wood burning (OCwood) accounted for almost all OCp at the suburban site in winter, allowing a new estimate of the ratio TCp/levoglucosan for both PM10 and PM2.5. Particulate carbonaceous material (PCM=Organic matter+Elemental matter) accounted for 46–83% of PM10 at the sites studied, thus being the major fraction.
Methyl chavicol: characterization of its biogenic emission rate, abundance, and oxidation products in the atmosphere

We report measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol was detected simultaneously by three in-situ instruments – a gas chromatograph with mass spectrometer detector (GC-MS), a proton transfer reaction mass spectrometer (PTR-MS), and a thermal desorption aerosol GC-MS (TAG) – and found to be abundant within and above Blodgett Forest. Methyl chavicol atmospheric mixing ratios are strongly correlated with 2-methyl-3-buten-2-ol (MBO), a light- and temperature-dependent biogenic emission from the ponderosa pine trees at Blodgett Forest. Scaling from this correlation, methyl chavicol emissions account for 4–68% of the carbon mass emitted as MBO in the daytime, depending on the season. From this relationship, we estimate a daytime basal emission rate of 0.72–10.2 μgCg−1 h−1, depending on needle age and seasonality. We also present the first observations of its oxidation products (4-methoxybenzaldehyde and 4-methyoxy benzene acetaldehyde) in the ambient atmosphere. Methyl chavicol is a major essential oil component of many plant species. This work suggests that methyl chavicol plays a significant role in the atmospheric chemistry of Blodgett Forest, and potentially other sites, and should be included explicitly in both biogenic volatile organic carbon emission and atmospheric chemistry models.
What would have happened to the ozone layer if chlorofluorocarbons (CFCs) had not been regulated?

Ozone depletion by chlorofluorocarbons (CFCs) was first proposed by Molina and Rowland in their 1974 Nature paper. Since that time, the scientific connection between ozone losses and CFCs and other ozone depleting substances (ODSs) has been firmly established with laboratory measurements, atmospheric observations, and modeling studies. This science research led to the implementation of international agreements that largely stopped the production of ODSs. In this study we use a fully-coupled radiation-chemical-dynamical model to simulate a future world where ODSs were never regulated and ODS production grew at an annual rate of 3%. In this "world avoided" simulation, 17% of the globally-averaged column ozone is destroyed by 2020, and 67% is destroyed by 2065 in comparison to 1980. Large ozone depletions in the polar region become year-round rather than just seasonal as is currently observed in the Antarctic ozone hole. Very large temperature decreases are observed in response to circulation changes and decreased shortwave radiation absorption by ozone. Ozone levels in the tropical lower stratosphere remain constant until about 2053 and then collapse to near zero by 2058 as a result of heterogeneous chemical processes (as currently observed in the Antarctic ozone hole). The tropical cooling that triggers the ozone collapse is caused by an increase of the tropical upwelling. In response to ozone changes, ultraviolet radiation increases, more than doubling the erythemal radiation in the northern summer midlatitudes by 2060.
Spatial heterogeneity of satellite derived land surface parameters and energy flux densities for LITFASS-area

Based on satellite data in different temporal and spatial resolution, the current use of frequency distribution functions (PDF) for surface parameters and energy fluxes is one of the most promising ways to describe subgrid heterogeneity of a landscape. Objective of this study is to find typical distribution patterns of parameters (albedo, NDVI) for the determination of the actual latent heat flux (L.E) determined from highly resolved satellite data within pixel on coarser scale. Landsat ETM+, Terra MODIS and NOAA-AVHRR surface temperature and spectral reflectance were used to infer further surface parameters and radiant- and energy flux densities for LITFASS-area, a 20×20 km2 heterogeneous area in Eastern Germany, mainly characterised by the land use types forest, crop, grass and water. Based on the Penman-Monteith-approach L.E, as key quantity of the hydrological cycle, is determined for each sensor in the accordant spatial resolution with an improved parametrisation. However, using three sensors, significant discrepancies between the inferred parameters can cause flux distinctions resultant from differences of the sensor filter response functions or atmospheric correction methods. The approximation of MODIS- and AVHRR- derived surface parameters to the reference parameters of ETM (via regression lines and histogram stretching, respectively), further the use of accurate land use classifications (CORINE and a new Landsat-classification), and a consistent parametrisation for the three sensors were realized to obtain a uniform base for investigations of the spatial variability. The analyses for 4 scenes in 2002 and 2003 showed that for forest clear distribution-patterns for NDVI and albedo are found. Grass and crop distributions show higher variability and differ significantly to each other in NDVI but only marginal in albedo. Regarding NDVI-distribution functions NDVI was found to be the key variable for L.E-determination.
Vertical advection and nocturnal deposition of ozone over a boreal pine forest

Night-time ozone deposition for a Scots pine forest in Southern Finland was studied at the SMEAR II measurement station by evaluating the turbulent eddy covariance (EC), storage change and vertical advection fluxes. Similarly to night-time carbon dioxide flux, the eddy-covariance flux of ozone was decreasing with turbulence intensity (friction velocity), and storage change of the compound did not compensate the reduction (well-known night-time measurement problem). Accounting for vertical advection resulted in invariance of ozone deposition rate on turbulence intensity. This was also demonstrated for carbon dioxide, verified by independent measurements of NEE by chamber systems. The result highlights the importance of advection when considering the exchange measurements of any scalar. Analysis of aerodynamic and laminar boundary layer resistances by the model approach indicated that the surface resistance and/or chemical sink strength was limiting ozone deposition. The possible aerial ozone sink by known fast chemical reactions with sesquiterpenes and NO explain only a minor fraction of ozone sink. Thus the deposition is controlled either by stomatal uptake or surface reactions or both of them, the mechanisms not affected by turbulence intensity. Therefore invariance of deposition flux on turbulence intensity is expected also from resistance and chemical sink analysis.
Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

Primary aliphatic amines are an important class of nitrogen containing compounds emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with O3 and NO3 have been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large aerosol mass yields (~44% for butylamine) are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (<1% for all amines tested) as detected by an aerosol mass spectrometer (AMS). We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities with elevated nighttime PM loadings, when significant levels of NO3 exist.