Atmospheric Environment (v.43, #9)

In this work we have compared ground-based measurements of organic carbon (OC) in the fine aerosol (PM2.5) fraction that are reported in peer-reviewed publications as part of both short campaigns and continuous monitoring networks. The comparison provides a quantitative review of global OC measurements for the purpose of establishing the extent to which organic aerosol concentrations are known with sufficient geographic and historical resolution to constrain global climate models. Only North America has sufficient measurements to provide meaningful spatial and temporal trends, although available measurements from China and Japan indicate that the Asian region is the most polluted with OC concentrations of approximately 10 μg m−3. These measurements have a low spatial resolution, with most sites located in highly urban areas within a small geographic region. OC concentrations in North America are approximately 1 μg m−3 and are better characterized spatially, temporally, and historically by continuous monitoring networks established decades ago. OC concentration shows a weakly increasing trend in some regions from 1997 to 2006, although in most regions it has remained effectively constant over the last ten years. Eastern U.S. sites show maximum OC in the winter and western U.S. sites show maximum OC in the summer. There is no correlation at U.S. sites between OC concentration and sulfate, nitrate, or ammonium ions, with R 2  < 0.1 in each case.
Keywords: Organic carbon; Aerosol composition;

This study presents the application of O-(2,3,4,5,6)-pentafluorobenzyl-hydroxylamine hydrochloride (PFBHA) on-fibre derivatisation Solid Phase Microextraction (SPME) to the sampling and quantification of the unsaturated 1,4-dicarbonyl products obtained in the photo-oxidation of furan, 2-methylfuran and 3-methylfuran with HONO: butenedial, 4-oxo-2-pentenal and 2-methylbutenedial, respectively. The use of Proton Transfer Reaction Mass Spectrometry (PTR-MS) is also considered and the advantages of the combined use of both methodologies is discussed. The 1,4 unsaturated dicarbonyl products sampled by SPME were quantified by GC-FID.The experiments were carried out in the EUPHORE outdoor simulation chambers. The results confirm that 1,4-dicarbonyls are the main products of the OH-initiated oxidation of furan and its methylated derivatives, a fact with environmental implications. Molar yields of (1.09 ± 0.41) and (0.90 ± 0.36) were obtained in two experiments of furan photo-oxidation. The yields of 4-oxo-2-pentenal and methylbutenedial were estimated to be (0.60 ± 0.24) and (0.83 ± 0.33) respectively, assuming the same SPME response factor as for butenedial. Furthermore, the unsaturated 1,4-dicarbonyls have also been identified in the chemical characterisation of the aerosols formed in the reactions. The yield of aerosols quantified were (8.5 ± 0.8)% in the photo-oxidation of furan, (1.85 ± 0.18)% in the photo-oxidation of 2-methylfuran and (5.5 ± 0.5)% in the photo-oxidation of 3-methylfuran, at the following concentrations of their precursors: 829 ± 249 ppbV and 748 ± 224 (in two furan experiments), 633 ± 190 in the 2-methylfuran and 641 ± 192 ppbV in the 3-methylfuran experiment.
Keywords: Solid phase microextraction; Furan; Carbonyls; 1,4-Butenedial; 4-Oxo-2-pentenal; 2-Methylbutenedial; Aerosols;

Confronting environmental pressure, environmental quality and human health impact indicators of priority air emissions by Loes M.J. Geelen; Mark A.J. Huijbregts; Henri den Hollander; Ad M.J. Ragas; Hans. A. van Jaarsveld; Dick de Zwart (1613-1621).
This paper evaluates the ranking of 21 priority air pollutants with three indicator schemes: environmental pressure indicator (EPI), environmental quality indicator (EQI), and human health effect indicator (HEI). The EPI and EQI compare the emissions and concentrations with the target emissions and target concentrations, respectively. The HEI comprehends the steps from cause (i.e. national emissions) to effect (i.e. human health effects), and is the total human health burden, expressed in Disability Adjusted Life Years per year of exposure (DALYs year−1). We estimated a health burden in the Netherlands of 41 × 103  DALYs year−1 caused by Dutch air emissions of PM10 and its precursors in the year 2003. The burden due to 17 carcinogenic substances emitted to air, was much lower (140 DALYs year−1). In contrast, when the same substances were evaluated regarding environmental pressure and environmental quality, carbon tetrachloride (pressure) and benzo[a]pyrene (quality) were of highest importance, whereas the importance of PM10 was substantially lower. This result is remarkable, because for the majority of substances evaluated, the target concentrations and target emissions are based on preventing human health damage. The differences in relevance are explained by the different weighting of interests in the indicators. The HEI is based on concentration–response relations, whereas the EPI and EQI also depend on other, policy-based, principles and on technical feasibility. Therefore, to effectively prioritize emission reduction measures in policy-making, substances should not only be evaluated as to whether emission targets and environmental quality targets are reached, but they should be evaluated regarding their human health impact as well. In this context, the HEI is a suitable indicator to evaluate the human health impact.
Keywords: Human health burden; Indicator; Air quality; DALYs; Environmental pressure;

A multi-component data assimilation experiment directed to sulphur dioxide and sulphate over Europe by A.L. Barbu; A.J. Segers; M. Schaap; A.W. Heemink; P.J.H. Builtjes (1622-1631).
Fine particulate matter (PM) is relevant for human health and its components are associated with climate effects. The performance of chemistry transport models for PM, its components and precursor gases is relatively poor. The use of these models to assess the state of the atmosphere can be strengthened using data assimilation. This study focuses on simultaneous assimilation of sulphate and its precursor gas sulphur dioxide into the regional chemistry transport model LOTOS–EUROS using an ensemble Kalman filter. The process of going from a single component setup for SO2 or SO4 to an experiment in which both components are assimilated simultaneously is illustrated. In these experiments, solely emissions, or a combination of emissions and the conversion rates between SO2 and SO4 were considered uncertain. In general, the use of sequential data assimilation for the estimation of the sulphur dioxide and sulphate distribution over Europe is shown to be beneficial. However, the single component experiments gave contradicting results in direction in which the emissions are adjusted by the filter showing the limitations of such applications. The estimates of the pollutant concentrations in a multi-component assimilation have found to be more realistic. We discuss the behavior of the assimilation system for this application. The model uncertainty definition is shown to be a critical parameter. The increased complexity associated with the simultaneous assimilation of strongly related species requires a very careful specification of the experiment, which will be the main challenge in the future data assimilation applications.
Keywords: Data assimilation; Ensemble Kalman filter; LOTOS–EUROS model; Sulphur dioxide; Sulphate;

Comparison of models used for national agricultural ammonia emission inventories in Europe: Litter-based manure systems by B. Reidy; J. Webb; T.H. Misselbrook; H. Menzi; H.H. Luesink; N.J. Hutchings; B. Eurich-Menden; H. Döhler; U. Dämmgen (1632-1640).
Six N-flow models, used to calculate national ammonia (NH3) emissions from agriculture in different European countries, were compared using standard data sets. Scenarios for litter-based systems were run separately for beef cattle and for broilers, with three different levels of model standardisation: (a) standardized inputs to all models (FF scenario); (b) standard N excretion, but national values for emission factors (EFs) (FN scenario); (c) national values for N excretion and EFs (NN scenario). Results of the FF scenario for beef cattle produced very similar estimates of total losses of total ammoniacal-N (TAN) (±6% of the mean total), but large differences in NH3 emissions (±24% of the mean). These differences arose from the different approaches to TAN immobilization in litter, other N losses and mineralization in the models. As a result of those differences estimates of TAN available at spreading differed by a factor of almost 3. Results of the FF scenario for broilers produced a range of estimates of total changes in TAN (±9% of the mean total), and larger differences in the estimate of NH3 emissions (±17% of the mean). The different approaches among the models to TAN immobilization, other N losses and mineralization, produced estimates of TAN available at spreading which differed by a factor of almost 1.7. The differences in estimates of NH3 emissions decreased as estimates of immobilization and other N losses increased. Since immobilization and denitrification depend also on the C:N ratio in manure, there would be advantages to include C flows in mass-flow models. This would also provide an integrated model for the estimation of emissions of methane, non-methane VOCs and carbon dioxide. Estimation of these would also enable an estimate of mass loss, calculation of the N and TAN concentrations in litter-based manures and further validation of model outputs.
Keywords: Inventory; Ammonia; Emission; Emission factor; N-flow model; Total ammoniacal-N (TAN); Solid manure; Agriculture;

Analysis of coupled model uncertainties in source-to-dose modeling of human exposures to ambient air pollution: A PM2.5 case study by Halûk Özkaynak; H. Christopher Frey; Janet Burke; Robert W. Pinder (1641-1649).
Quantitative assessment of human exposures and health effects due to air pollution involve detailed characterization of impacts of air quality on exposure and dose. A key challenge is to integrate these three components on a consistent spatial and temporal basis taking into account linkages and feedbacks. The current state-of-practice for such assessments is to exercise emission, meteorology, air quality, exposure, and dose models separately, and to link them together by using the output of one model as input to the subsequent downstream model. Quantification of variability and uncertainty has been an important topic in the exposure assessment community for a number of years. Variability refers to differences in the value of a quantity (e.g., exposure) over time, space, or among individuals. Uncertainty refers to lack of knowledge regarding the true value of a quantity. An emerging challenge is how to quantify variability and uncertainty in integrated assessments over the source-to-dose continuum by considering contributions from individual as well as linked components. For a case study of fine particulate matter (PM2.5) in North Carolina during July 2002, we characterize variability and uncertainty associated with each of the individual concentration, exposure and dose models that are linked, and use a conceptual framework to quantify and evaluate the implications of coupled model uncertainties. We find that the resulting overall uncertainties due to combined effects of both variability and uncertainty are smaller (usually by a factor of 3–4) than the crudely multiplied model-specific overall uncertainty ratios. Future research will need to examine the impact of potential dependencies among the model components by conducting a truly coupled modeling analysis.
Keywords: Air quality model; Exposure model; Particulate matter; Variability; Uncertainty;

Spatial and chemical patterns of PM10 in road dust deposited in urban environment by F. Amato; M. Pandolfi; M. Viana; X. Querol; A. Alastuey; T. Moreno (1650-1659).
Recent research interest has been focused on road dust resuspension as one of the major sources of atmospheric particulate matter in an urban environment. Given the dearth of studies on the variability of the PM10 fraction of road deposited sediments, our understanding of the main factors controlling this pollutant is incomplete. In the present study a new sampling methodology was devised and applied to collect PM10 deposited mass from 1 m2 of road pavement. PM10 road dust fraction was sampled directly from active traffic lanes at 23 sampling sites during a campaign in Barcelona (Spain) in June 2007. The aim of the study was to gain more insight into the variability of mass and chemistry of road dust in different urban environments, such as the city centre, ring roads, and locations nearby demolition/construction sites. The city centre showed values of PM10 road dust within a range of 3–23 mg m−2, whereas levels reached 24–80 mg m−2 in locations affected by transport of uncovered heavy trucks. The largest dust loads were measured in the proximity of demolition/construction sites and the harbor entry with values up to 328 mg m−2.The city centre road dust profiles (%) were enriched in OC, EC, Fe, S, Cu, Zn, Mn, Cr, Sb, Sn, Mo, Zr, Hf, Ge, Ba, Pb, Bi, SO4 2−, NO3 , Cl and NH4 +, but several crustal components such as Ca, Ti, Na, and Mg were also considerably concentrated. Locations affected by construction and demolition activities had high levels of crustal components such as Ca, Li, Sc, Sr, Rb and also As whereas ring roads, characterized by a higher load of uncovered heavy trucks showed an intermediate composition.Levels of PM10 components per area were also evaluated to quantify the resuspendable amount of each element from 1 m2. In the inner city environment mean values of 1363 μg Ca m−2, 816 μg OC m−2, 239 μg EC m−2, 13 μg Cu m−2, 12 μg Zn m−2, 1.9 μg Sb m−2 and 2.0 μg Pb m−2, in PM10 in all cases, were registered.Moreover the deposited PM load at demolition/construction sites acts as a reservoir or trap for traffic-related particles, which gives rise to large amounts of hazardous pollutants, available for resuspension.
Keywords: PM10 road dust; Resuspension; Deposition; Demolition/construction impact; Uncovered trucks; Levels per m2;

Heterogeneous loss of HO2 by KCl, synthetic sea salt, and natural seawater aerosol particles by Fumikazu Taketani; Yugo Kanaya; Hajime Akimoto (1660-1665).
The HO2 uptake to aerosol particles is potentially significant sink for the HO2 radical in the marine atmosphere. To assess the heterogeneous loss of HO2 on marine aerosol particles, we have investigated the uptake coefficients (γ) of HO2 for submicron aerosol particles of KCl, synthetic sea salt, and natural seawater under ambient conditions (760 Torr and 296 ± 2 K) using an aerosol flow tube (AFT) coupled with a chemical conversion/laser-induced fluorescence (CC/LIF) technique. γ values determined for dry and wet aerosols of KCl were 0.02 ± 0.01 and 0.07 ± 0.03 at 66% and 75% RH, respectively, while γ values for those doped with CuSO4 was 0.55 ± 0.19 at 75% RH. γ values determined for synthetic sea-salt particles were 0.07 ± 0.03, 0.12 ± 0.04 and 0.13 ± 0.04 at 35%, 50%, 75% RH, respectively, while γ values for natural seawater particles were 0.10 ± 0.03, 0.11 ± 0.02 and 0.10 ± 0.03 at 35%, 50%, 75% RH, respectively. We recommend a HO2 uptake coefficient in marine areas of 0.1 for modeling and estimated the contribution of heterogeneous loss of HO2 by sea-salt aerosol particles in marine areas using a box model. Our box-model simulations suggested that daytime maximum HO2 concentrations decreased to 87–94% of the values without heterogeneous loss.
Keywords: HO x radical; Sea-salt aerosol; Uptake coefficient; Atmospheric chemistry; Laboratory study;

The Denver Aerosol Sources and Health (DASH) study: Overview and early findings by S. Vedal; M.P. Hannigan; S.J. Dutton; S.L. Miller; J.B. Milford; N. Rabinovitch; S.-Y. Kim; L. Sheppard (1666-1673).
Improved understanding of the sources of air pollution that are most harmful could aid in developing more effective measures for protecting human health. The Denver Aerosol Sources and Health (DASH) study was designed to identify the sources of ambient fine particulate matter (PM2.5) that are most responsible for the adverse health effects of short-term exposure to PM2.5. Daily 24-h PM2.5 sampling began in July 2002 at a residential monitoring site in Denver, Colorado, using both Teflon and quartz filter samplers. Sampling is planned to continue through 2008. Chemical speciation is being carried out for mass, inorganic ionic compounds (sulfate, nitrate and ammonium), and carbonaceous components, including elemental carbon, organic carbon, temperature-resolved organic carbon fractions and a large array of organic compounds. In addition, water-soluble metals were measured daily for 12 months in 2003. A receptor-based source apportionment approach utilizing positive matrix factorization (PMF) will be used to identify PM2.5 source contributions for each 24-h period. Based on a preliminary assessment using synthetic data, the proposed source apportionment should be able to identify many important sources on a daily basis, including secondary ammonium nitrate and ammonium sulfate, diesel vehicle exhaust, road dust, wood combustion and vegetative debris. Meat cooking, gasoline vehicle exhaust and natural gas combustion were more challenging for PMF to accurately identify due to high detection limits for certain organic molecular marker compounds. Measurements of these compounds are being improved and supplemented with additional organic molecular marker compounds. The health study will investigate associations between daily source contributions and an array of health endpoints, including daily mortality and hospitalizations and measures of asthma control in asthmatic children. Findings from the DASH study, in addition to being of interest to policymakers, by identifying harmful PM2.5 sources may provide insights into mechanisms of PM effect.
Keywords: Air pollution; Particulate matter; Health effects; Mortality; Source apportionment;

A validated 2-D diffusion–advection model for prediction of drift from ground boom sprayers by K. Baetens; Q.T. Ho; D. Nuyttens; M. De Schampheleire; A. Melese Endalew; M.L.A.T.M. Hertog; B. Nicolaï; H. Ramon; P. Verboven (1674-1682).
Correct field drift prediction is a key element in environmental risk assessment of spraying applications. A reduced order drift prediction model based on the diffusion–advection equation is presented. It allows fast assessment of the drift potential of specific ground boom applications under specific environmental wind conditions that obey the logarithmic wind profile. The model was calibrated based on simulations with a validated Computational Fluid Dynamics (CFD) model. Validation of both models against 38 carefully conducted field experiments is successfully performed for distances up to 20 m from the field edge, for spraying on flat pasture land. The reduced order model succeeded in correct drift predictions for different nozzle types, wind velocities, boom heights and spray pressures. It used 4 parameters representing the physical aspects of the drift cloud; the height of the cloud at the field edge, the mass flux crossing the field edge, the settling velocity of the droplets and the turbulence. For the parameter set and range considered, it is demonstrated for the first time that the effect of the droplet diameter distribution of the different nozzle types on the amount of deposition spray drift can be evaluated by a single parameter, i.e., the volume fraction of droplets with a diameter smaller than 191 μm. The reduced order model can be solved more than 4 orders of magnitude faster than the comprehensive CFD model.
Keywords: Spray drift; Pesticide; Lagrangian particle tracking; Computational fluid dynamics; Field sprayer; Nozzle; Droplet; Agriculture;

Heterogeneous light-induced ozone processing on the organic coatings in the atmosphere by Sopheak Net; Laura Nieto-Gligorovski; Sašo Gligorovski; Brice Temime-Rousell; Stephane Barbati; Yannis G. Lazarou; Henri Wortham (1683-1692).
Many of the more recent studies concerning heterogeneous reactions of atmospheric interest, carry, in some cases, much more details but still follow the basic philosophy of the first pioneering studies. Therefore, in this study the accent is put on the additional complexities that arise when the aerosols of interest have more complex compositions. Hence, it is attempted to identify the products following the simultaneous ozone processing and light irradiation on particles coated with 4-phenoxyphenol in the presence of 4-carboxybenzophenone as a photosensitizer. In order to reveal a more complete picture on the fate of these aromatic compounds under controlled experimental conditions, different analytical tools such as gas chromatography coupled to mass spectrometry (GC–MS) and proton transfer reaction-mass spectrometry (PTR-MS) have been applied.Several surface bound products were identified via GC–MS and some of them (phenol, hydroquinone, catechol, 4-hydroxybenzoic acid, benzoic acid, fumaric acid, terephthalic acid, maleic acid, 1,2,4-trihydroxybenzene and 4,4′-oxydiphenol) confirmed with standards. The main volatile secondary products as identified by PTR-MS in this study were formic acid, phenol and p-benzoquinone.A reaction mechanism was proposed and density functional theory calculations were performed in order to elucidate the initial steps of the ozonolysis reaction on 4-phenoxyphenol in the presence of 4-carboxybenzophenone.
Keywords: Aerosol; Irradiation; Surface reaction; Gas chromatography–mass spectrometry; Proton transfer reaction-mass spectrometry; DFT calculations;

A study of the total atmospheric sulfur dioxide load using ground-based measurements and the satellite derived Sulfur Dioxide Index by A.K. Georgoulias; D. Balis; M.E. Koukouli; C. Meleti; A. Bais; C. Zerefos (1693-1701).
We present characteristics of the sulfur dioxide (SO2) loading over Thessaloniki, Greece, and seven other selected sites around the world using SO2 total column measurements from Brewer spectrophotometers together with satellite estimates of the Version 8 TOMS Sulfur Dioxide Index (SOI) over the same locations, retrieved from Nimbus 7 TOMS (1979–1993), Earth Probe TOMS (1996–2003) and OMI/Aura (2004–2006). Traditionally, the SOI has been used to quantify the SO2 quantities emitted during great volcanic eruptions. Here, we investigate whether the SOI can give an indication of the total SO2 load for areas and periods away from eruptive volcanic activity by studying its relative changes as a correlative measure to the SO2 total column. We examined time series from Thessaloniki and another seven urban and non-urban stations, five in the European Union (Arosa, De Bilt, Hohenpeissenberg, Madrid, Rome) and two in India (Kodaikanal, New Delhi). Based on the Brewer data, Thessaloniki shows high SO2 total columns for a European Union city but values are still low if compared to highly affected regions like those in India. For the time period 1983–2006 the SO2 levels above Thessaloniki have generally decreased with a rate of 0.028 Dobson Units (DU) per annum, presumably due to the European Union's strict sulfur control policies. The seasonal variability of the SO2 total column exhibits a double peak structure with two maxima, one during winter and the second during summer. The winter peak can be attributed to central heating while the summer peak is due to synoptic transport from sources west of the city and sources in the north of Greece. A moderate correlation was found between the seasonal levels of Brewer total SO2 and SOI for Thessaloniki, Greece (R  = 0.710–0.763) and Madrid, Spain (R  = 0.691) which shows that under specific conditions the SOI might act as an indicator of the SO2 total load.
Keywords: Sulfur dioxide; Total column; Brewer spectrophotometer; Sulfur Dioxide Index; Satellite observations;

Measurement of gas-phase total peroxides at the summit of Mount Tai in China by Yu Ren; Aijun Ding; Tao Wang; Xinhua Shen; Jia Guo; Jiamin Zhang; Yan Wang; Pengju Xu; Xinfeng Wang; Jian Gao; Jeffrey L. Collett (1702-1711).
Measurement of ambient gas-phase total peroxides was performed at the summit of Mount Tai (Mt. Tai, 1534 m above sea level) in central-eastern China during March 22–April 24 and June 16–July 20, 2007. The hourly averaged concentration of peroxides was 0.17 ppbv (± 0.16 ppbv, maximum: 1.28 ppbv) and 0.55 ppbv (± 0.67 ppbv, maximum: 3.55 ppbv) in the spring and summer campaigns, respectively. The average concentration of peroxides at Mt. Tai, which is in a heavily polluted region, was much lower than hydrogen peroxide measurements made at some rural mountain sites, suggesting that significant removal processes took place in this region. An examination of diurnal variation and a correlation analysis suggest that these removal processes could include chemical suppression of peroxide production due to the scavenging of peroxy and hydroxy radicals by high NOx, wet removal by clouds/fogs rich in dissolved sulfur dioxide which reacts quickly with peroxides, and photolysis. These sinks competed with photochemical sources of peroxides, resulting in different mean concentrations and diurnal pattern of peroxides in the spring and summer. A principal component analysis was conducted to quantify the major processes that influenced the variation of peroxide concentrations. This analysis shows that in the spring photochemical production was an important source of peroxides, and the major sink was scavenging during upslope transport of polluted and humid air from the lower part of the planetary boundary layer (PBL) and wet removal by synoptic scale clouds. During the summer, highly polluted PBL air (with high NOx) was often associated with very low peroxides due to the chemical suppression of HO2 by high NOx and wet-removal by clouds/fogs in this sulfur-rich atmosphere, especially during the daytime. Higher concentrations of peroxides, which often appeared at mid-nighttime, were mainly associated with subsidence of air masses containing relatively lower concentrations of NOy.
Keywords: Photochemical production; Gas-phase peroxides; Principal component analysis; Acid rain; Mt. Tai;