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Campholenic aldehyde ozonolysis: a mechanism leading to specific biogenic secondary organic aerosol constituents

In the present study, campholenic aldehyde ozonolysis was performed to investigate pathways leading to specific biogenic secondary organic aerosol (SOA) marker compounds. Campholenic aldehyde, a known α-pinene oxidation product, is suggested to be a key intermediate in the formation of terpenylic acid upon α-pinene ozonolysis. It was reacted with ozone in the presence and absence of an OH radical scavenger, leading to SOA formation with a yield of 0.75 and 0.8, respectively. The resulting oxidation products in the gas and particle phases were investigated employing a denuder/filter sampling combination. Gas-phase oxidation products bearing a carbonyl group, which were collected by the denuder, were derivatised by 2,4-dinitrophenylhydrazine (DNPH) followed by liquid chromatography/negative ion electrospray ionisation time-of-flight mass spectrometry analysis and were compared to the gas-phase compounds detected by online proton-transfer-reaction mass spectrometry. Particle-phase products were also analysed, directly or after DNPH derivatisation, to derive information about specific compounds leading to SOA formation. Among the detected compounds, the aldehydic precursor of terpenylic acid was identified and its presence was confirmed in ambient aerosol samples from the DNPH derivatisation, accurate mass data, and additional mass spectrometry (MS2 and MS3 fragmentation studies). Furthermore, the present investigation sheds light on a reaction pathway leading to the formation of terpenylic acid, involving α-pinene, α-pinene oxide, campholenic aldehyde, and terpenylic aldehyde. Additionally, the formation of diaterpenylic acid acetate could be connected to campholenic aldehyde oxidation. The present study also provides insights into the source of other highly functionalised oxidation products (e.g. m / z 201, C9H14O5 and m / z 215, C10H16O5), which have been observed in ambient aerosol samples and smog chamber-generated monoterpene SOA. The m / z 201 and 215 compounds were tentatively identified as a C9- and C10-carbonyl-dicarboxylic acid, respectively, based on reaction mechanisms of campholenic aldehyde and ozone, as well as detailed interpretation of mass spectral data, in conjunction with the formation of corresponding DNPH derivatives.
Four years of ground-based MAX-DOAS observations of HONO and NO2 in the Beijing area

Ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements of nitrous acid (HONO) and its precursor NO2 (nitrogen dioxide) as well as aerosols have been performed daily in Beijing city centre (39.98° N, 116.38° E) from July 2008 to April 2009 and at the suburban site of Xianghe (39.75° N, 116.96° E) located ~60 km east of Beijing from March 2010 to December 2012. This extensive dataset allowed for the first time the investigation of the seasonal cycle of HONO as well as its diurnal variation in and in the vicinity of a megacity. Our study was focused on the HONO and NO2 near-surface concentrations (0–200 m layer) and total vertical column densities (VCDs) and also aerosol optical depths (AODs) and extinction coefficients retrieved by applying the Optimal Estimation Method to the MAX-DOAS observations. Monthly averaged HONO near-surface concentrations at local noon display a strong seasonal cycle with a maximum in late fall/winter (~0.8 and 0.7 ppb at Beijing and Xianghe, respectively) and a minimum in summer (~0.1 ppb at Beijing and 0.03 ppb at Xianghe). The seasonal cycles of HONO and NO2 appear to be highly correlated, with correlation coefficients in the 0.7–0.9 and 0.5–0.8 ranges at Beijing and Xianghe, respectively. The stronger correlation of HONO with NO2 and also with aerosols observed in Beijing suggests possibly larger role of NO2 conversion into HONO in the Beijing city center than at Xianghe. The observed diurnal cycle of HONO near-surface concentration shows a maximum in the early morning (about 1 ppb at both sites) likely resulting from night-time accumulation, followed by a decrease to values of about 0.1–0.4 ppb around local noon. The HONO / NO2 ratio shows a similar pattern with a maximum in the early morning (values up to 0.08) and a decrease to ~0.01–0.02 around local noon. The seasonal and diurnal cycles of the HONO near-surface concentration are found to be similar in shape and in relative amplitude to the corresponding cycles of the HONO total VCD and are therefore likely driven mainly by the balance between HONO sources and the photolytic sink, whereas dilution effects appear to play only a minor role. The estimation of OH radical production from HONO and O3 photolysis based on retrieved HONO near-surface concentrations and calculated photolysis rates indicate that in the 0–200 m altitude range, HONO is by far the largest source of OH radicals in winter as well as in the early morning at all seasons, while the contribution of O3 dominates in summer from mid-morning until mid-afternoon.
Establishing the contribution of lawn mowing to atmospheric aerosol levels in American suburbs

Green leaf volatiles (GLVs) are a class of wound-induced volatile organic compounds emitted by several plant species. Turf grasses emit a complex profile of GLVs upon mowing, as evidenced by the "freshly cut grass" smell, some of which are readily oxidized in the atmosphere to contribute to secondary organic aerosol (SOA). The contribution of lawn-mowing-induced SOA production may be especially impactful at the urban–suburban interface, where urban hubs provide a source of anthropogenic oxidants and SOA while suburban neighborhoods have the potential to emit large quantities of reactive, mow-induced GLVs. This interface provides a unique opportunity to study aerosol formation in a multicomponent system and at a regionally relevant scale. Freshly cut grass was collected from a study site in Essex Junction, Vermont, and was placed inside a 775 L Teflon experimental chamber. Thermal desorption gas chromatography–mass spectrometry (TD-GC/MS) was used to characterize the emitted GLV profile. Ozone was introduced to the experimental chamber and TD-GC/MS was used to monitor the consumption of these GLVs and the subsequent evolution of gas-phase products, while a scanning mobility particle sizer was used to continuously measure aerosol size distributions and mass loadings as a result of grass clipping ozonolysis. Freshly cut grass was found to emit a complex mixture of GLVs, dominated by extit{cis}-3-hexenyl acetate (CHA) and extit{cis}-3-hexenol (HXL), which were released at an initial rate of 1.8 (± 0.5) μg and 0.07 (± 0.03) μg per square meter of lawn mowed with each mowing. Chamber studies using pure standards of CHA and HXL were found to have aerosol yields of 1.2 (± 1.1)% and 3.3 (± 3.1)%, respectively. Using these aerosol yields and the emission rate of CHA and HXL by grass, SOA evolution by ozonolysis of grass clippings was predicted. However, the measured SOA mass produced from the ozonolysis of grass clippings exceeded the predicted amount, by upwards of ~150%. The ozonolysis of a mixture of CHA and HXL representative of environmental mixing ratios also failed to accurately model the SOA mass produced by grass clippings. The disparity between measured SOA mass and the predicted SOA mass suggests that grass clippings contain other SOA precursors in addition to CHA and HXL. Aerial photographs and geospatial analysis were used to determine the area of turfgrass coverage in a suburban neighborhood, which was then used along with measured SOA production as a function of grass mowed to determine that lawn mowing has the potential to contribute 47 μg SOA per m−2 of lawn to the atmosphere per mowing event by ozonolysis, which cannot be modeled solely by the ozonolysis of CHA, HXL or a representative mixture of the two.
Projections of atmospheric mercury levels and their effect on air quality in the United States

The individual and combined effects of global climate change and emissions changes from 2000 to 2050 on atmospheric mercury levels in the United States are investigated by using the global climate-chemistry model, CAM-Chem, coupled with a mercury chemistry-physics mechanism (CAM-Chem/Hg). Three future pathways from the Intergovernmental Panel on Climate Change (IPCC) Special Report on Emissions Scenarios (SRES) are considered, with the A1FI, A1B and B1 scenarios representing the upper, middle and lower bounds of potential climate warming, respectively. The anthropogenic and biomass burning emissions of mercury are projected from the energy use assumptions in the IPCC SRES report. Natural emissions from both land and ocean sources are projected by using dynamic schemes. TGM concentration increases are greater in the low latitudes than they are in the high latitudes, indicative of a larger meridional gradient than in the present day. In the A1FI scenario, TGM concentrations in 2050 are projected to increase by 2.1–4.0 ng m−3 for the eastern US and 1.4–3.0 ng m−3 for the western US. This spatial difference corresponds to potential increases in wet deposition of 10–14 μg m−2 for the eastern US and 2–4 μg m−2 for the western US. The increase in Hg(II) emissions tends to enhance wet deposition and hence increase the risk of higher mercury entering the hydrological cycle and ecosystem. In the B1 scenario, mercury concentrations in 2050 are similar to present level concentrations; this finding indicates that the domestic reduction in mercury emissions is essentially counteracted by the effects of climate warming and emissions increases in other regions. The sensitivity analyses show that changes in anthropogenic emissions contribute 32–53% of projected changes in mercury air concentration, while the independent contribution by climate change and its induced natural emissions change accounts for 47–68%.
Sensitivity of aerosol retrieval to geometrical configuration of ground-based sun/sky radiometer observations

A sensitivity study of aerosol retrievals to the geometrical configuration of the ground-based sky radiometer observations is carried out through inversion tests. Specifically, this study is focused on principal plane and almucantar observations, since these geometries are employed in AERONET (AErosol RObotic NETwork). The following effects have been analyzed with simulated data for both geometries: sensitivity of the retrieval to variability of the observed scattering angle range, uncertainties in the assumptions of the aerosol vertical distribution, surface reflectance, possible instrument pointing errors, and the effects of the finite field of view. The synthetic observations of radiometer in the tests were calculated using a previous climatology data set of retrieved aerosol properties over three AERONET sites: Mongu (Zambia) for biomass burning aerosol, Goddard Space Flight Center (GSFC; Maryland, USA) for urban aerosol and Solar Village (Saudi Arabia) for desert dust aerosol. The results show that almucantar retrievals, in general, are more reliable than principal plane retrievals in presence of the analyzed error sources. This fact partially can be explained by practical advantages of the almucantar geometry: the symmetry between its left and right branches that helps to eliminate some observational uncertainties and the constant value of optical mass during the measurements, that make almucantar observations nearly independent of the vertical variability of aerosol. Nevertheless, almucantar retrievals present instabilities at high sun elevations due to the reduction of the scattering angle range coverage, resulting in decrease of information content. It is in such conditions that principal plane retrievals show a better stability, as shown by the simulation analysis of the three different aerosol models. The last part of the study is devoted to the identification of possible differences between the aerosol retrieval results obtained from real AERONET data using both geometries. In particular, we have compared AERONET retrievals at the same sites used in the simulation analysis: Mongu (biomass burning), GSFC (urban) and Solar Village (desert dust). Overall, this analysis shows robust consistency between the retrievals from simultaneous observations in principle plane and almucantar All identified differences are within the uncertainties estimated for the AERONET operational aerosol retrieval. The differences in the size distribution are generally under 10% for radii between 0.1 μm and 5 μm, and outside this size range, the differences can be as large as 50%. For the absorption parameters, i.e., single scattering albedo and the imaginary part of the refractive index, the differences are typically under 0.01 and 0.003, respectively. The real part of the refractive index showed a difference of 0.01 for biomass burning and urban aerosol, and a difference of around 0.03 for desert dust. Finally, it should be noted that the whole data set includes only 200 pairs, which have been taken under very stable atmospheric conditions; therefore, in a general case, differences between principal plane (PPL) and almucantar (ALM) are expected to be higher. Though the observed differences between ALM and PPL are rather small, it should be noted that this analysis has been conducted using a limited set of 200 observation pairs selected under stable atmospheric conditions.
Modelling NO2 concentrations at the street level in the GAINS integrated assessment model: projections under current legislation

NO2 concentrations at the street level are a major concern for urban air quality in Europe and have been regulated under the EU Thematic Strategy on Air Pollution. Despite the legal requirements, limit values are exceeded at many monitoring stations with little or no improvement in recent years. In order to assess the effects of future emission control regulations on roadside NO2 concentrations, a downscaling module has been implemented in the GAINS integrated assessment model. The module follows a hybrid approach based on atmospheric dispersion calculations and observations from the AirBase European air quality database that are used to estimate site-specific parameters. Pollutant concentrations at every monitoring site with sufficient data coverage are disaggregated into contributions from regional background, urban increment, and local roadside increment. The future evolution of each contribution is assessed with a model of the appropriate scale: 28 × 28 km grid based on the EMEP Model for the regional background, 7 × 7 km urban increment based on the CHIMERE Chemistry Transport Model, and a chemical box model for the roadside increment. Thus, different emission scenarios and control options for long-range transport as well as regional and local emissions can be analysed. Observed concentrations and historical trends are well captured, in particular the differing NO2 and total NOx = NO + NO2 trends. Altogether, more than 1950 air quality monitoring stations in the EU are covered by the model, including more than 400 traffic stations and 70% of the critical stations. Together with its well-established bottom-up emission and dispersion calculation scheme, GAINS is thus able to bridge the scales from European-wide policies to impacts in street canyons. As an application of the model, we assess the evolution of attainment of NO2 limit values under current legislation until 2030. Strong improvements are expected with the introduction of the Euro 6 emission standard for light duty vehicles; however, for some major European cities, further measures may be required, in particular if aiming to achieve compliance at an earlier time.
A new method for evaluating the impact of vertical distribution on aerosol radiative forcing in general circulation models

The quantification and understanding of direct aerosol forcing is essential in the study of climate. One of the main issues that makes its quantification difficult is the lack of a complete understanding of the role of the vertical distribution of aerosols and clouds. This work aims at reducing the uncertainty of aerosol top-of-the-atmosphere (TOA) forcing due to the vertical superposition of several short-lived atmospheric components, in particular different aerosol species and clouds. We propose a method to quantify the contribution of different parts of the atmospheric column to the TOA forcing as well as to evaluate the contribution to model differences that is exclusively due to different spatial distributions of aerosols and clouds. We investigate the contribution of aerosol above, below and in clouds by using added diagnostics in the aerosol–climate model LMDz. We also compute the difference between the TOA forcing of the ensemble of the aerosols and the sum of the forcings from individual species in clear sky. This difference is found to be moderate for the global average (14%) but can reach high values regionally (up to 100%). Nonlinear effects are even more important when superposing aerosols and clouds. Four forcing computations are performed: one where the full aerosol 3-D distribution is used, and then three where aerosols are confined to regions above, inside and below clouds, respectively. We find that the TOA forcing of aerosols depends crucially on the presence of clouds and on their position relative to that of the aerosol, in particular for black carbon (BC). We observe a strong enhancement of the TOA forcing of BC above clouds, attenuation for BC below clouds, and a moderate enhancement when BC is found within clouds. BC above clouds accounts for only about 30% of the total BC optical depth but for 55% of the forcing, while forcing efficiency increases by a factor of 7.5 when passing from below to above clouds. The different behaviour of forcing nonlinearities for these three components of the atmospheric column encouraged us to develop the method for application to inter-model variability studies by reading 3-D aerosol and cloud fields from different general circulation models (GCMs) into the same model. We apply the method to the comparison of forcing due to the aerosols and clouds distributions of the general circulation models LMDz and SPRINTARS. The different amount of BC above but also within clouds is revealed to play a major role on the differences of cloudy-sky forcings between the two models, which can exceed 100% regionally.
Source apportionment and the role of meteorological conditions in the assessment of air pollution exposure due to urban emissions

As particulate matter (PM) impacts human health, knowledge about its composition, exposure and source apportionment is required. A study of the urban atmosphere in the case of Augsburg, Germany, during winter (31 January–12 March 2010) is thus presented here. Investigations were performed on the basis of aerosol mass spectrometry and further air pollutants and meteorological measurements, including mixing layer height. Organic matter was separated by source apportionment of PM1 with positive matrix factorization (PMF) in three factors: OOA – oxygenated organic aerosol (secondary organic factor), HOA – hydrocarbon-like organic aerosol (traffic factor or primary organic factor) and WCOA – wood combustion organic aerosol (wood combustion factor), which extend the information from black carbon (BC) measurements. PMF was also applied to the particle size distribution (PSD) data of PM2.5 to determine different source profiles and we assigned them to the particle sources: nucleation aerosol, fresh traffic aerosol, aged traffic aerosol, stationary combustion aerosol and secondary aerosol. Ten different temporal phases were identified on the basis of weather characteristics and aerosol composition and used for correlations of all air pollutants and meteorological parameters. While source apportionment from both organic PM composition and PSD agree and show that the main emission sources of PM exposure are road traffic as well as stationary and wood combustion, secondary aerosol factor concentrations are very often the highest ones. The hierarchical clustering analysis with the Ward method of cross-correlations of each air pollutant and PM component and of the correlations of each pollutant with all meteorological parameters provided two clusters: "secondary pollutants of PM1 and fine particles" and "primary pollutants (including CO and benzene) and accumulation mode particles". The dominant meteorological influences on pollutant concentrations are wind speed and mixing layer height which are coupled with a certain wind direction. The compounds of the cluster "secondary pollutants and fine particles" show a negative correlation with absolute humidity, i.e., low concentrations during high absolute humidity and vice versa. The PM10 limit value exceedances originated not only from the emissions but also in combination with specific meteorological conditions. NC3-10 (number concentration of nucleation mode particles) and NC10-30 (Aitken mode particles), i.e., ultrafine particles and the fresh traffic aerosol, are only weakly dependent on meteorological parameters and thus are driven by emissions. The results of this case study provide information about chemical composition and causes of PM exposure during winter time in urban air pollution.
Stratospheric ozone trends and variability as seen by SCIAMACHY from 2002 to 2012

Vertical profiles of the rate of linear change (trend) in the altitude range 15–50 km are determined from decadal O3 time series obtained from SCIAMACHY1/ENVISAT2 measurements in limb-viewing geometry. The trends are calculated by using a multivariate linear regression. Seasonal variations, the quasi-biennial oscillation, signatures of the solar cycle and the El Niño–Southern Oscillation are accounted for in the regression. The time range of trend calculation is August 2002–April 2012. A focus for analysis are the zonal bands of 20° N–20° S (tropics), 60–50° N, and 50–60° S (midlatitudes). In the tropics, positive trends of up to 5% per decade between 20 and 30 km and negative trends of up to 10% per decade between 30 and 38 km are identified. Positive O3 trends of around 5% per decade are found in the upper stratosphere in the tropics and at midlatitudes. Comparisons between SCIAMACHY and EOS MLS3 show reasonable agreement both in the tropics and at midlatitudes for most altitudes. In the tropics, measurements from OSIRIS4/Odin and SHADOZ5 are also analysed. These yield rates of linear change of O3 similar to those from SCIAMACHY. However, the trends from SCIAMACHY near 34 km in the tropics are larger than MLS and OSIRIS by a factor of around two. 1 SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY 2 European environmental research satellite 3 Earth Observing System (EOS) Microwave Limb Sounder (MLS) 4 Optical Spectrograph and InfraRed Imager System 5 Southern Hemisphere ADditional OZonesondes
Modeled global effects of airborne desert dust on air quality and premature mortality

Fine particulate matter is one of the most important factors contributing to air pollution. Epidemiological studies have related increased levels of atmospheric particulate matter to premature human mortality caused by cardiopulmonary disease and lung cancer. However, a limited number of investigations have focused on the contribution of airborne desert dust particles. Here we assess the effects of dust particles with an aerodynamic diameter smaller than 2.5 μm (DU2.5) on human mortality for the year 2005. We used the EMAC atmospheric–chemistry general circulation model at high resolution to simulate global atmospheric dust concentrations. We applied a health impact function to estimate premature mortality for the global population of 30 yr and older, using parameters from epidemiological studies. We estimate a global cardiopulmonary mortality of about 402 000 in 2005. The associated years of life lost are about 3.47 million per year. We estimate the global fraction of the cardiopulmonary deaths caused by atmospheric desert dust to be about 1.8%, though in the 20 countries most affected by dust this is much higher, about 15–50%. These countries are primarily found in the so-called "dust belt" from North Africa across the Middle East and South Asia to East Asia