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Comparison of several wood smoke markers and source apportionment methods for wood burning particulate mass

Residential wood combustion has only recently been recognized as a major contributor to air pollution in Switzerland and in other European countries. A source apportionment method using the aethalometer light absorption parameters was applied to five winter campaigns at three sites in Switzerland: a village with high wood combustion activity in winter, an urban background site and a highway site. The particulate mass from traffic (PMtraffic) and wood burning (PMwb) emissions obtained with this model compared fairly well with results from the 14C source apportionment method. PMwb from the model was also compared to well known wood smoke markers such as anhydrosugars (levoglucosan and mannosan) and fine mode potassium, as well as to a marker recently suggested from the Aerodyne aerosol mass spectrometer (mass fragment m/z 60). Additionally the anhydrosugars were compared to the 14C results and were shown to be comparable to literature values from wood burning emission studies using different types of wood (hardwood, softwood). The levoglucosan to PM<sb>wb ratios varied much more strongly between the different campaigns (4–13%) compared to mannosan to PMwb with a range of 1–1.5%. Possible uncertainty aspects for the various methods and markers are discussed.
Aqueous-phase ozonolysis of methacrolein and methyl vinyl ketone: a potentially important source of atmospheric aqueous oxidants

Recent studies indicate that isoprene and its gas-phase oxidation products could contribute a considerable amount of aerosol through aqueous-phase acid-catalyzed oxidation with hydrogen peroxide (H2O2), although the source of H2O2 is unclear. The present study revealed a potentially important route to the formation of aqueous oxidants, including H2O2, from the aqueous-phase ozonolysis of methacrolein (MAC) and methyl vinyl ketone (MVK). Laboratory simulation was used to perform the atmospheric aqueous-phase ozonolysis at different pHs and temperatures. Unexpectedly high molar yields of the products, including hydroxylmethyl hydroperoxide (HMHP), formaldehyde (HCHO) and methylglyoxal (MG), of both of these reaction systems have been seen. Moreover, these yields are almost independent of pH and temperature and are as follows: (i) for MAC–O3, 70.3±6.3% HMHP, 32.3±5.8% HCHO and 98.6±5.4% MG; and (ii) for MVK–O3, 68.9±9.7% HMHP, 13.3±5.8% HCHO and 75.4±7.9% MG. A yield of 24.2±3.6% pyruvic acid has been detected for MVK–O3. HMHP is unstable in the aqueous phase and can transform into H2O2 and HCHO with a yield of 100%. We suggest that the aqueous-phase ozonolysis of MAC and MVK can contribute a considerable amount of oxidants in a direct and indirect mode to the aqueous phase and that these compounds might be the main source of aqueous-phase oxidants. The formation of oxidants in the aqueous-phase ozonolysis of MAC and MVK can lead to substantial aerosol formation from the aqueous-phase acid-catalyzed reaction of H2O2 with MAC, even if there are no other sources of oxidants.
The measurement of aerosol optical properties at a rural site in Northern China

Atmospheric aerosols constitute one of the largest sources of uncertainty in the estimation of radiative forcing for climate. From April 2003 to January 2005, in situ measurements of aerosol optical properties were conducted at a rural site in Northern China, Shangdianzi Global Atmosphere Watch (GAW) regional station (SDZ), about 150 km from Beijing. Mean values (standard deviation, S.D.) of scattering and absorption coefficients for the entire period are 174.6 Mm−1 (189.1 Mm-1) and 17.5 Mm−1 (13.4 Mm-1), respectively. These values are approximately one third of the reported values for scattering coefficients and one fifth of those for absorption coefficients obtained in the Beijing urban area. The mean single scattering albedo (SSA) for the entire period was estimated as 0.88 (0.05), which is about 0.07 higher than the values reported for the Beijing urban area, and also higher than the values (0.85) used in a reported climate simulation for China and India. Both the absorption and scattering coefficients showed a seasonal cycle with the lowest values in winter, while the highest values occurred in summer for absorption coefficients and in fall for scattering coefficients. The mean SSA values were lowest in spring and highest in winter. The daily variations of aerosol absorption and scattering coefficients were strongly influenced by synoptic changes throughout the observation period. A trajectory cluster analysis was applied to discern the source characteristics of aerosol optical properties for different air masses. The cluster-mean aerosol scattering coefficients, absorption coefficients and SSA were all high when the air masses moved from SW and SE-E directions to the site and aerosols were influenced with heavy pollution from the dense population centers and industrial areas. The cluster-mean SSA for air masses coming from the polluted areas was not only higher than those with trajectories from the "clean" directions, but also higher than the reported values for the regions with high pollution emissions (such as the Beijing urban area). This fact might reflect the substantial secondary aerosol production during transport. The characteristics of aerosol optical properties measured at this rural site suggest significant impacts of human activities on the regional aerosol.
The influence of European pollution on ozone in the Near East and northern Africa

We present a modeling study of the long-range transport of pollution from Europe, showing that European emissions regularly elevate surface ozone by as much as 20 ppbv in summer in northern Africa and the Near East. European emissions cause 50–150 additional violations per year (i.e. above those that would occur without European pollution) of the European health standard for ozone (8-h average >120 μg/m3 or ~60 ppbv) in northern Africa and the Near East. We estimate that European ozone pollution is responsible for 50 000 premature mortalities globally each year, of which the majority occurs outside of Europe itself, including 37% (19 000) in northern Africa and the Near East. Much of the pollution from Europe is exported southward at low altitudes in summer to the Mediterranean Sea, northern Africa and the Near East, regions with favorable photochemical environments for ozone production. Our results suggest that assessments of the human health benefits of reducing ozone precursor emissions in Europe should include effects outside of Europe, and that comprehensive planning to improve air quality in northern Africa and the Near East likely needs to address European emissions.
Biogenic nitrogen oxide emissions from soils: impact on NOx and ozone over west Africa during AMMA (African Monsoon Multidisciplinary Analysis): observational study

Chemical and meteorological parameters measured on board the Facility for Airborne Atmospheric Measurements (FAAM) BAe 146 Atmospheric Research Aircraft during the African Monsoon Multidisciplinary Analysis (AMMA) campaign are presented to show the impact of NOx emissions from recently wetted soils in West Africa. NO emissions from soils have been previously observed in many geographical areas with different types of soil/vegetation cover during small scale studies and have been inferred at large scales from satellite measurements of NOx. This study is the first dedicated to showing the emissions of NOx at an intermediate scale between local surface sites and continental satellite measurements. The measurements reveal pronounced mesoscale variations in NOx concentrations closely linked to spatial patterns of antecedent rainfall. Fluxes required to maintain the NOx concentrations observed by the BAe-146 in a number of cases studies and for a range of assumed OH concentrations (1×106 to 1×107 molecules cm−3) are calculated to be in the range 8.4 to 36.1 ng N m−2 s−1. These values are comparable to the range of fluxes from 0.5 to 28 ng N m−2 s−1 reported from small scale field studies in a variety of non-nutrient rich tropical and sub-tropical locations reported in the review of Davidson and Kingerlee (1997). The fluxes calculated in the present study have been scaled up to cover the area of the Sahel bounded by 10 to 20 N and 10 E to 20 W giving an estimated emission of 0.03 to 0.30 Tg N from this area for July and August 2006. The observed chemical data also suggest that the NOx emitted from soils is taking part in ozone formation as ozone concentrations exhibit similar fine scale structure to the NOx, with enhancements over the wet soils. Such variability can not be explained on the basis of transport from other areas. Delon et al. (2008) is a companion paper to this one which models the impact of soil NOx emissions on the NOx and ozone concentration over West Africa during AMMA. It employs an artificial neural network to define the emissions of NOx from soils, integrated into a coupled chemistry-dynamics model. The results are compared to the observed data presented in this paper. Here we compare fluxes deduced from the observed data with the model-derived values from Delon et al. (2008).
CUACE/Dust – an integrated system of observation and modeling systems for operational dust forecasting in Asia

An integrated sand and dust storm (SDS) forecasting system – CUACE/Dust (Chinese Unified Atmospheric Chemistry Environment for Dust) has been developed, which consists of a comprehensive dust aerosol module with emission, dry/wet depositions and other atmospheric dynamic processes, and a data assimilation system (DAS) using observational data from the CMA (China Meteorological Administration) ground dust monitoring network and retrieved dust information from a Chinese geostationary satellite – FY-2C. This is the first time that a combination of surface network observations and satellite retrievals of the dust aerosol has been successfully used in the real time operational forecasts in East Asia through a DAS. During its application for the operational SDS forecasts in East Asia for spring 2006, this system captured the major 31 SDS episodes observed by both surface and satellite observations. Analysis shows that the seasonal mean threat score (TS) for 0–24 h forecast over the East Asia in spring 2006 increased from 0.22 to 0.31 by using the DAS, a 41% enhancement. The time series of the forecasted dust concentrations for a number of representative stations for the whole spring 2006 were also evaluated against the surface PM10 monitoring data, showing a very good agreement in terms of the SDS timing and magnitudes near source regions where dust aerosols dominate. This is a summary paper for a special issue of ACP featuring the development and results of the forecasting system.
Receptor modeling of C2–C7 hydrocarbon sources at an urban background site in Zurich, Switzerland: changes between 1993–1994 and 2005–2006

Hourly measurements of 13 volatile hydrocarbons (C2–C7) were performed at an urban background site in Zurich (Switzerland) in the years 1993–1994 and again in 2005–2006. For the separation of the volatile organic compounds by gas-chromatography (GC), an identical chromatographic column was used in both campaigns. Changes in hydrocarbon profiles and source strengths were recovered by positive matrix factorization (PMF). Eight and six factors could be related to hydrocarbon sources in 1993–1994 and in 2005–2006, respectively. The modeled source profiles were verified by hydrocarbon profiles reported in the literature. The source strengths were validated by independent measurements, such as inorganic trace gases (NOx, CO, SO2), methane (CH4), oxidized hydrocarbons (OVOCs) and meteorological data (temperature, wind speed etc.). Our analysis suggests that the contribution of most hydrocarbon sources (i.e. road traffic, solvents use and wood burning) decreased by a factor of about two to three between the early 1990s and 2005–2006. On the other hand, hydrocarbon losses from natural gas leakage remained at relatively constant levels (−20%). The estimated emission trends are in line with the results from different receptor-based approaches reported for other European cities. Their differences to national emission inventories are discussed.
Dependence of cloud properties derived from spectrally resolved visible satellite observations on surface temperature

Cloud climate feedback constitutes the most important uncertainty in climate modelling, and currently even its sign is still unknown. In the recently published report of the intergovernmental panel on climate change (IPCC), 6 out of 20 climate models showed a positive and 14 a negative cloud radiative feedback in a doubled CO2 scenario. The radiative budget of clouds has also been investigated by experimental methods, especially by studying the relation of satellite observed broad band shortwave and longwave radiation to sea surface temperature. Here we present a new method for the investigation of the dependence of cloud properties on temperature changes, derived from spectrally resolved satellite observations in the visible spectral range. Our study differs from previous investigations in three important ways: first, we directly extract cloud properties (effective cloud fraction and effective cloud top height) and relate them to surface temperature. Second, we retrieve the cloud altitude from the atmospheric O2 absorption instead from thermal IR radiation. Third, our correlation analysis is performed using 7.5 years of global monthly anomalies (with respect to the average of the same month for all years). For most parts of the globe (except the tropics) we find a negative correlation of effective cloud fraction versus surface-near temperature. In contrast, for the effective cloud top height a positive correlation is found for almost the whole globe. Both findings might serve as an indicator for an overall positive cloud radiative feedback. Another peculiarity of our study is that the cloud-temperature relationships are determined for fixed locations (instead to spatial variations over selected areas) and are based on the "natural" variability over several years (instead the anomaly for a strong El-Nino event). From a detailed comparison to cloud properties from the International Satellite Cloud Climatology Project (ISCCP), in general good agreement is found. However, also systematic differences occurred indicating that our results provide independent and complementary information on cloud properties. Climate models should thus aim to reproduce our findings. Recommendations for the development of a "processor" to convert model results into the cloud sensitive quantities observed by the satellite are given.
Experimental studies on particle emissions from cruising ship, their characteristic properties, transformation and atmospheric lifetime in the marine boundary layer

Particle emissions from ship engines and their atmospheric transformation in the marine boundary layer (MBL) were investigated in engine test bed studies and in airborne measurements of expanding ship plumes. During the test rig studies, detailed aerosol microphysical and chemical properties were measured in the exhaust gas of a serial MAN B&W seven-cylinder four-stroke marine diesel engine under various load conditions. The emission studies were complemented by airborne aerosol transformation studies in the plume of a large container ship in the English Channel using the DLR aircraft Falcon 20 E-5. Observations from emission studies and plume studies combined with a Gaussian plume dispersion model yield a consistent picture of particle transformation processes from emission to atmospheric processing during plume expansion. Particulate matter emission indices obtained from plume measurements are 8.8±1.0×1015(kg fuel)−1 by number for non-volatile particles and 174±43 mg (kg fuel)−1 by mass for Black Carbon (BC). Values determined for test rig conditions between 85 and 110% engine load are of similar magnitude. For the total particle number including volatile compounds no emission index can be derived since the volatile aerosol fraction is subject to rapid transformation processes in the plume. Ship exhaust particles occur in the size range Dp<0.3 μm, showing a bi-modal structure. The combustion particle mode is centred at modal diameters of 0.05 μm for raw emissions to 0.10 μm at a plume age of 1 h. The smaller-sized volatile particle mode is centred at Dp≤0.02 μm. From the decay of ship exhaust particle number concentrations in an expanding plume, a maximum plume life time of approx. 24 h is estimated for a well-mixed marine boundary layer.
Biogenic nitrogen oxide emissions from soils – impact on NOx and ozone over West Africa during AMMA (African Monsoon Multidisciplinary Experiment): modelling study

Nitrogen oxide biogenic emissions from soils are driven by soil and environmental parameters. The relationship between these parameters and NO fluxes is highly non linear. A new algorithm, based on a neural network calculation, is used to reproduce the NO biogenic emissions linked to precipitations in the Sahel on the 6 August 2006 during the AMMA campaign. This algorithm has been coupled in the surface scheme of a coupled chemistry dynamics model (MesoNH Chemistry) to estimate the impact of the NO emissions on NOx and O3 formation in the lower troposphere for this particular episode. Four different simulations on the same domain and at the same period are compared: one with anthropogenic emissions only, one with soil NO emissions from a static inventory, at low time and space resolution, one with NO emissions from neural network, and one with NO from neural network plus lightning NOx. The influence of NOx from lightning is limited to the upper troposphere. The NO emission from soils calculated with neural network responds to changes in soil moisture giving enhanced emissions over the wetted soil, as observed by aircraft measurements after the passing of a convective system. The subsequent enhancement of NOx and ozone is limited to the lowest layers of the atmosphere in modelling, whereas measurements show higher concentrations above 1000 m. The neural network algorithm, applied in the Sahel region for one particular day of the wet season, allows an immediate response of fluxes to environmental parameters, unlike static emission inventories. Stewart et al (2008) is a companion paper to this one which looks at NOx and ozone concentrations in the boundary layer as measured on a research aircraft, examines how they vary with respect to the soil moisture, as indicated by surface temperature anomalies, and deduces NOx fluxes. In this current paper the model-derived results are compared to the observations and calculated fluxes presented by Stewart et al (2008).