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Atmospheric Environment (v.39, #16)

Editorial board (pp. i).

Chemical characterization of water-soluble organic acids in PM2.5 in Beijing, China by Xiao-Feng Huang; Min Hu; Ling-Yan He; Xiao-Yan Tang (pp. 2819-2827).
Water-soluble organic acids are important components in atmospheric aerosols and can act as cloud condensation nuclei to potentially affect the climate. In this study, a total of 25 PM2.5 samples were collected from summer to winter in 2002–2003 at an urban area in Beijing. C2–C5 dicarboxylic acids and malic, glyoxylic and pyruvic acids were determined using a capillary electrophoresis. Oxalic acid dominated in these acids with seasonal average concentrations of 107–412ngm–3. Malonic and succinic acids were comparable in different seasons, with seasonal average concentrations ranging from 20 to 60ngm–3. Glutaric acid was much less abundant with an average of 10ngm–3. The sum of these seven detected acids accounted for 3–15% of organic carbon content in PM2.5. Seasonal differences of these acids were discussed in terms of their corresponding sources. Correlations of these acids with sulfate and MSA were also investigated to interpret their possible secondary formation pathways.

Keywords: PM; 2.5; Dicarboxylic acids; Oxalic acid; Secondary formation; Precursor


Diurnal and seasonal cycles of ozone precursors observed from continuous measurement at an urban site in Taiwan by K.-L. Kuang-Ling Yang; Chien-Chung Ting; Jia-Lin Wang; Oliver W. Wingenter; Chang-Chuan Chan (pp. 2829-2838).
Hourly measurement of 56 ozone precursors was conducted by a monitoring station located in a metropolitan area in central Taiwan. After nearly a year of continuous operation at this urban site, both diurnal and seasonal cycles of non-methane hydrocarbons (NMHCs) were clearly observed, which were caused by the interplay between source, chemical loss, and meteorology. Selected species representing three different types of major sources, namely, the household fuel leakage, vehicular exhaust and gasoline evaporation, as well as biogenic emissions exhibit dramatic diurnal or seasonal cycles with each displaying its own unique characteristics.Ethane and propane, largely originated from leakage of natural gas or liquefied petroleum gases (LPG), showed concentrations elevating throughout the night and early morning, but began to decrease toward noon as the nocturnal temperature inversion elevated. Because of the lower chemical reactivity and somewhat more constant emissions than other measured target compounds, their diurnal cycles were presumably the direct reflection of the mixing height over the metropolitan area.For compounds originating from vehicular plus evaporative emissions such as benzene, which accounts for most of the monitored compounds, their diurnal cycles were also largely controlled by the variation in the height of temperature inversion.Of all the 56 species monitored, isoprene, an abundant biogenic species largely released by plants, showed distinct diurnal and seasonal cycles different from the other measured NMHCs. Its concentration usually peaked at noon in summer and fell when temperature and solar radiation reached their maximum levels, demonstrating the close relationship of isoprene with photosynthesis.Seasonal variation was also clearly observed for the other NMHCs quantified. With the exception of isoprene, most species show higher average concentration in winter and lower average concentration in summer with the fall values being the intermediate, which presumably is caused by both the seasonal variation in HO abundance and the height of the temperature inversion.

Keywords: Volatile organic compounds (VOCs); Non-methane hydrocarbons (NMHCs); Liquefied petroleum gases (LPG); Temperature inversion


Polycyclic aromatic hydrocarbons and other selected organic compounds in ambient air of Campo Grande City, Brazil by Re-Poppi Nilva Ré-Poppi; Mary Santiago-Silva (pp. 2839-2850).
Fourteen samples of particulate matter and semi-volatile organic compounds were collected during 6 months in the city of Campo Grande, South Mato Grosso State, Brazil. Particle-bound polycyclic aromatic hydrocarbons (PAHs) were collected on Fluoropore PTFE filters and gas-phase PAHs were collected into sorbent tubes with XAD-2 resin. Both types of samples were extracted with a dichloromethane/methanol mixture (4:1v/v), then the extracts were subjected to gas chromatography–mass spectrometry (GC–MS) analysis. PAHs, oxidized PAH (oxy-PAHs), phenols and methoxyphenols were identified by use of GC retention indices and MS files. The average value obtained for the sum of 15 PAHs was 21.05ngm−3 (range: 8.94–62.5ngm−3). The presence of specific tracers and calculations of characteristic ratios (e.g. [Phe]/[Phe]+[Ant]) were used to identify the sources of the emissions of PAHs in the atmospheric samples. Levoglucosan (the anhydride of β-glucose), retene (1-methyl-7-isopropylphenanthrene) and methoxyphenols (derivatives of syringol and guaiacol) and tracers for wood burning were identified. This study demonstrates that biomass burning from the rural zone is the main source of PAHs and emissions of other substances in the investigated site of Campo Grande.

Keywords: PAH; Oxy-PAH; Retention indices; Campo Grande City


NO x emissions from large point sources: variability in ozone production, resulting health damages and economic costs by Denise L. Mauzerall; Babar Sultan; Namsoug Kim; David F. Bradford (pp. 2851-2866).
We present a proof-of-concept analysis of the measurement of the health damage of ozone (O3) produced from nitrogen oxides(NOx=NO+NO2) emitted by individual large point sources in the eastern United States. We use a regional atmospheric model of the eastern United States, the Comprehensive Air quality Model with Extensions (CAMx), to quantify the variable impact that a fixed quantity of NO x emitted from individual sources can have on the downwind concentration of surface O3, depending on temperature and local biogenic hydrocarbon emissions. We also examine the dependence of resulting O3-related health damages on the size of the exposed population. The investigation is relevant to the increasingly widely used “cap and trade� approach to NO x regulation, which presumes that shifts of emissions over time and space, holding the total fixed over the course of the summer O3 season, will have minimal effect on the environmental outcome. By contrast, we show that a shift of a unit of NO x emissions from one place or time to another could result in large changes in resulting health effects due to O3 formation and exposure. We indicate how the type of modeling carried out here might be used to attach externality-correcting prices to emissions. Charging emitters fees that are commensurate with the damage caused by their NO x emissions would create an incentive for emitters to reduce emissions at times and in locations where they cause the largest damage.

Keywords: Surface ozone; NO; x; emissions; Point sources; Health impacts; Mortality; Morbidity; Cap-and-trade


Effects of reactive hydrocarbons on ozone formation in southern Taiwan by C.-C. Chih-Chung Chang; T.-Y. Tai-Yih Chen; C.-Y. Chuan-Yao Lin; C.-S. Chung-Shin Yuan; S.-C. Shaw-Chen Liu (pp. 2867-2878).
Ambient air samples were collected at 13 air quality monitoring stations in Kaohsiung city, Kaohsiung county, and Pingtung county (KKP) to investigate the composition and spatial distribution of C2–C10 non-methane hydrocarbons (NMHCs) in southern Taiwan. Ozone formation potentials (OFPs) of NMHCs were estimated using maximum incremental reactivity (MIR) and kOH method (reactivity of NMHC with OH radical) to assess the relative effects of hydrocarbons on ozone formation. The measurements showed that mixing ratios of toluene, ethene, ethyne, ethane, isopantane and propane were the highest among all measured species at most of the sampling sites. Nevertheless, considering both the photochemical reactivities and mixing ratios of all the measured species, toluene, xylene, ethene and propene were calculated to have the highest OFPs and reactivities. The OFPs and reactivities assessed by the MIR and kOH methods for the four compounds accounted for 54.5% and 39.3% of all the measured species. Larger benefit margin of ozone abatement may be obtained by reducing emissions of a group of key species with high OFPs.2,2-dimethylbutane (22DMC4) was used as an indicator of traffic emissions to distinguish traffic from non-traffic contributions of key species in Kaohsiung metropolitan area. It revealed that the contribution of non-traffic source was significant for toluene, whereas xylene was found to be primarily from the traffic source in Kaohsiung metropolitan area during the sampling periods.

Keywords: Ozone formation potential; Non-methane hydrocarbons; Emission sources


Effect of typhoon on chemical composition of rainwater in Okinawa Island, Japan by Hideaki Sakihama; Akira Tokuyama (pp. 2879-2888).
We have studied the effects of typhoons on the behavior of chemical components of rainwater. Samples were collected at Yona in the northern part of Okinawa Island and analyzed for major cations and anions.The chemical components in rainwater could be classified into three types. Components belonging to type I originated from sea salt (ss-) in which their concentrations in rainwater increased with an increase in maximum wind speed (MWS). Those belonging to type II were non-sea salt (nss-) components in which their concentrations in rainwater decreased with an increase in MWS. Ca2+ and SO42− belonging to type III in which their concentrations in rainwater had no relationship with MWS. To clarify the behaviors of type III components, they were separated into the two fractions: ss- and nss- by assuming that all Na+ ions were supplied from ocean. Each fraction of Ca2+ and SO42− except nss-Ca2+ showed a significant correlation with MWS. Moreover, When MWS was slower than 10–13ms−1, the concentration of nss-SO42− was dominant in rainwater. But, the concentration of ss-SO42− in rainwater became dominant when MWS was faster than 13ms−1. The chemical compositions in rainwater also changed drastically with MWS. Values of Σacid–Σbase ( D value) in rainwater ranged from 1.11 to 62.4μeq l−1 and correlated strongly with pH (5.92 to 4.17). Values of pH during typhoon were higher in contrast to those during non-typhoon weather, which is attributed to the higher decreasing rate of Σacid than Σbase. This result suggests that a typhoon has the ability to remove or dilute pollutants such as NO3− and nss-SO42−.

Keywords: Wind speed; Acid component; Neutralization; Subtropical area


Stability of single particle tracers for differentiating between heavy- and light-duty vehicle emissions by Deborah S. Gross; Alexander R. Barron; Ellen M. Sukovich; Benjamin S. Warren; Julia C. Jarvis; David T. Suess; Kimberly A. Prather (pp. 2889-2901).
To determine the size and chemical composition of particles derived from on-road vehicle emissions, individual particles were sampled continuously with an aerosol time-of-flight mass spectrometer (ATOFMS) at the Caldecott Tunnel in Northern California. In this tunnel, traffic is segregated, such that in theory only light duty vehicle emissions or a mix of heavy- (HDV) and light-duty vehicle (LDV) emissions can be sampled separately. Two studies were carried out, one in November 1997 and a second in July 2000, time periods with average ambient temperatures of 10–15 and 26–32°C, respectively, with the instrument operating at ambient outdoor temperatures. Analysis of the chemical composition of the particles sampled in these studies shows that sampling conditions can strongly impact the determination of suitable markers for identifying particles emitted from different vehicle types during ambient studies. Differences in the results of these two studies are shown to be related to the different ambient temperatures at which the measurements were carried out. Particles sampled from HDV-influenced traffic in the 1997 study were 16 times more likely to have mass spectra containing peaks at both m/ z 128 (naphthalene) and 156 (dimethylnaphthalene/naphthaldehyde) and 51 times more likely to have mass spectra containing peaks at both m/ z 156 and 170 (trimethylnaphthalene/methylnaphthaldehyde) than were particles sampled from the LDV-only traffic tunnel. The peaks corresponding to m/ z 156 and 170 are on average 2 and 4 times more intense in the mass spectra of the HDV-influenced data set than in the LDV-only data set. In contrast, in the 2000 experiment, the peaks at m/ z 128 and 156 were present in ∼1% and ∼2% of the particles, respectively, with no preference for traffic type. These results show the usefulness of naphthalene and its derivatives for identification of the vehicle source of particulate emissions, under appropriate conditions, and highlight the fact that ambient conditions can strongly affect potential marker ions for source apportionment studies, necessitating a combination of controlled laboratory and field measurements for identification of stable marker ions.

Keywords: Aerosol particle; Polycyclic aromatic hydrocarbon; Semivolatile; Vehicle emissions; Diesel


Chemical characteristics of Asian dust aerosol from Hunshan Dake Sandland in Northern China by Tiantao Cheng; Daren Lu; Gengchen Wang; Yongfu Xu (pp. 2903-2911).
Dust aerosol was sampled at three sites in north China along the northern route of the dust events in spring 2001. Mass concentrations and concentrations of the chemical elements associated with aerosols were examined. The average mass concentration of TSP during the field period were 0.545mgm−3 at Sanggen Dalai tall-tower station, 0.366mgm−3 at Sanggen Dalai ground-based station, 0.360mgm−3 at Beijing, and 2.778mgm−3 at Sunite Zuoqi. The average concentrations of PM10 accounted for more than 61% of TSP loadings at all stations. The average concentrations of special crustal elements (Al, Ca, Fe, Mg, Mn) in PM10 accounted for 65–86% of each of their loadings in TSP, and the average concentrations of important pollutant elements (Pb, Zn, Cu) in PM10 accounted for 63–79% of each of their loadings in TSP. During the dusty days with wind speeds rising, the aerosol mass loading severely increased, and the trend of chemical element increasing in dust particles was associated with the aerosol loading ascending. Crustal elements in aerosols were dominated by dust particles. The chemical elements of Ca, Fe, Mg, Mn and Ti in aerosols were derived more from Ca-rich soil than from sandy soil, but Ba and K were opposite. The pollutant elements of Cu, S, Pb, V and Zn associated with aerosols in Hunshan Dake Sandland were affected by the anthropogenic pollutant sources in upwind regions.

Keywords: Dust aerosol; Hunshan Dake Sandland; Aerosol mass concentration; Chemical element concentration


An urban photochemistry study in Santiago de Chile by Rappengluck B. Rappenglück; R. Schmitz; M. Bauerfeind; F. Cereceda-Balic; D. von Baer; H. Jorquera; Y. Silva; P. Oyola (pp. 2913-2931).
During spring time 2002 a field experiment was carried out in the Metropolitan Area of Santiago de Chile at three monitoring sites located along a SW–NE transect that represents upwind, downtown and downwind conditions, respectively. Three consecutive days (30 October–01 November 2002) reflecting different photochemical and meteorological conditions were selected. These days included two workdays and one holiday and thus the effect of different primary emissions could be investigated. A variety of trace gas measurements (O3, NO x, CO, volatile organic compounds (VOC)) were obtained at these sites. Alkanes represent the largest VOC fraction at all sites, followed by aromatics and alkenes, the smallest fractions are represented by the alkynes or isoprene. Regarding reactivity ranking propene equivalent values show that during morning hours, alkenes are the most reactive compounds, at noon, aromatics are dominant, and in the afternoon isoprene becomes important. Alkanes do not contribute more than 20% to the total air mass reactivity despite being present at the higher concentration levels. Regarding liquefied petroleum gas (LPG) impacts, we find a threefold decrease of concentrations at the eastern side of the city—and no significant trend at Downtown Santiago—which we ascribe to a switch to natural gas in the higher income eastern side of town. The generation of ozone impacts above 50ppbv is mainly due to anthropogenic traffic-related hydrocarbons. In addition, traffic emissions are contributing most to the formation of secondary organic aerosols (SOA). A model study was carried out, applying a Lagrange trajectory model coupled with photochemical and aerosol modules. The model results are in good agreement with the observations. Additionally, the relative contribution of the respective hydrocarbons to the ozone production in an air parcel along the trajectory was computed. The model also indicates SOA formation by means of oxidation of higher alkanes, alkenes, and aromatics, the latter being the major contributors to those secondary pollutants.

Keywords: Santiago de Chile; NMHC; Propene-equivalent; RADM2; MADE/SORGAM


The vertical distribution of aerosol over Europe—synthesis of one year of EARLINET aerosol lidar measurements and aerosol transport modeling with LMDzT-INCA by Sarah Guibert; Volker Matthias; Michael Schulz; Jens Bösenberg; Ronald Eixmann; Ina Mattis; Gelsomina Pappalardo; Maria Rita Perrone; Nicola Spinelli; Geraint Vaughan (pp. 2933-2943).
Aerosol extinction vertical profiles measured with Raman lidar in the framework of EARLINET in 2000 are compared to profiles modeled by a general circulation model, LMDzT-INCA, at seven stations in Europe. Comparisons based on individual profiles show moderate correlation between model and data. Averaging aerosol extinction values on larger temporal or spatial scales improves the comparison. Furthermore, we show that the model succeeds to reproduce the mean annual aerosol distribution over Europe. Comparisons of the aerosol vertical distribution in two distinct regions of Europe are presented. For the northern stations, the observed yearly average aerosol extinction coefficient vertical profile and the modeled one show an average bias of 22%. For the southern stations the mean bias is slightly higher (29%). Both model and lidar show different extinction profiles in different parts of Europe, with higher values in upper heights in the South. According to modeled profiles of each aerosol component, this is caused by the presence of dust at altitudes between 2 and 6km. In addition vertical mixing in the South seems to be more effective for the other aerosol components.

Keywords: Aerosol extinction; Vertical profiles; Aerosol composition; Saharan dust; GCM


The influence of south foehn on the ozone mixing ratios at the high alpine site Arosa by Mike Campana; Yingshi Li; Johannes Staehelin; Andre S.H. Prevot; Paolo Bonasoni; Hanspeter Loetscher; Thomas Peter (pp. 2945-2955).
Within 2 years of trace gas measurements performed at Arosa (Switzerland, 2030m above sea level), enhanced ozone mixing ratios were observed during south foehn events during summer and spring (5–10ppb above the median value). The enhancements can be traced back to ozone produced in the strongly industrialized Po basin as confirmed by various analyses. Backward trajectories clearly show advection from this region during foehn. NO y versus O3 correlation and comparison of O3 mixing ratios between Arosa and Mt. Cimone (Italy, 2165masl) suggest that ozone is the result of recent photochemical production (+5.6ppb on average), either directly formed during the transport or via mixing of air processed in the Po basin boundary layer. The absence of a correlation between air parcel residence times over Europe and ozone mixing ratios at Arosa during foehn events is in contrast to a previous analysis, which suggested such correlation without reference to the origin of the air. In the case of south foehn, the continental scale influence of pollutants emission on ozone at Arosa appears to be far less important than the direct influence of the Po basin emissions. In contrast, winter time displays a different situation, with mean ozone reductions of about 4ppb for air parcels passing the Po basin, probably caused by mixing with ozone-poor air from the Po basin boundary layer.

Keywords: Mountains; Ozone; Case study; Trajectories; Trace gases


Simulation of ozone during the August 2003 heat wave and emission control scenarios by R. Vautard; Honore C. Honoré; M. Beekmann; L. Rouil (pp. 2957-2967).
During August 2003, western European countries witnessed an unpreceeded 15-day long heat wave with record temperatures and unusually persistent high-ozone concentrations. In France, about 15000 extra deaths occurred during this period. The study of photochemical smog during this episode is of primary interest since weather conditions were so extreme for western Europe that they provide a worst case scenario for air quality. This episode also provides an interesting benchmark for the evaluation air quality models.We present and evaluate the results of a regional simulation of the episode with the CHIMERE chemistry-transport model. In a reference run, the simulated ozone concentrations are compared to surface observations obtained from 237 monitoring stations in Europe. Statistical scores on diurnal cycle, daily maxima, spatial structure of ozone concentrations, and AOT60 show that the simulated values compare very well with the observed ones, although extreme ozone peaks are underestimated probably due to a lack of model resolution.We describe the simulated impacts on ozone of theoretical emission reduction scenarios. The current European legislation should lead in 2010 to a drastic reduction of health exposure (about half), as measured by the AOT60 indicator, and of the number of 180μgm−3 exceedance hours (74% reduction). “Emergency� scenarios, with an assumed 20% emission reduction throughout Europe, would also be efficient (AOT60 indicator reduced by 28%). Over France, the efficiency of a national emergency scenario would be only about 2/3rd of that of a Europewide scenario. When the reduction starts after a few episode days, the time taken for the reduction to reach its full impact is about 3 days. Finally, it is shown that reduction of NO x emissions is twice as efficient as reduction in volatile organic compounds emissions.

Keywords: Heat wave; Summer 2003; Ozone episode; Emission control scenario; Model evaluation


Meteorologically adjusted urban air quality trends in the Southwestern United States by Erika K. Wise; Andrew C. Comrie (pp. 2969-2980).
Cities in the Southwestern United States (Southwest) are often close to violating tropospheric ozone (ozone) and particulate matter (PM) federal air quality standards, and local climate and weather conditions play a large part in determining whether or not pollutant levels exceed the federally mandated limits and by what magnitude. The Kolmogorov–Zurbenko (KZ) filter method has been used in a number of studies in the Eastern United States to determine meteorological controls on ozone concentrations and to separate out those effects in order to examine underlying trends. The Southwest, however, experiences a different climate regime than other parts of the country, and atmospheric controls on air quality in the region have not been examined in this manner. This paper determines which meteorological variables most influence ozone and PM in the Southwest and examines patterns of underlying pollutant trends due to emissions.Ozone and PM data were analyzed over the time period 1990–2003 for the Southwest's five major metropolitan areas: Albuquerque, NM; El Paso, TX; Las Vegas, NV; Phoenix, AZ; and Tucson, AZ. Results indicate that temperature and mixing height most strongly influence ozone conditions, while moisture levels (particularly relative humidity) are the strongest predictors of PM concentrations in all five cities examined. Meteorological variability typically accounts for 40–70% of ozone variability and 20–50% of PM variability. Long-term ozone trends are highly variable, but records from most stations indicate increasing concentrations over the last decade. Long-term trends in PM concentrations were relatively flat in all five cities analyzed but contained coincident extremes unrelated to meteorology.

Keywords: Air pollution; Kolmogorov–Zurbenko filter; Particulate matter; PM; 10; Tropospheric ozone; Climate; KZ filter; US Southwest; Weather


Measurements of effective Henry's law constants for hydrogen peroxide in concentrated salt solutions by Myeong Y. Chung; Saddam Muthana; Rodhelen N. Paluyo; Alam S. Hasson (pp. 2981-2989).
The solubility of hydrogen peroxide was measured in aqueous salt solutions containing ammonium sulfate, ammonium nitrate, ammonium chloride, and sodium nitrate. Effective Henry's law constants are reported for these salts at 292K for concentrations up to 10M. Salts containing ammonium ions were found to increase the solubility of hydrogen peroxide by up to a factor of two compared to pure water. The data are consistent with a reversible chemical reaction between ammonium ions and hydrogen peroxide. Implications for the aerosol mass loadings of hydrogen peroxide in atmospheric particulate matter and their associated health effects are discussed.

Keywords: Particulate matter; Toxicity; Air pollution; Solubility; Reactive oxygen species (ROS)


Temperature variation of indoor and outdoor radon progeny by H.S. Sahota; K.S. Randhawa; Manmohan Singh; Kulwant Singh (pp. 2991-2994).
The indoor and outdoor radon progeny concentrations were investigated at a semi-hilly area of Pathankot in Punjab using the method of beta particle counting of aerosol samples collected on a glass micro-fiber filter. A linear relation was found between indoor and outdoor equilibrium equivalent concentrations of radon-222 (EECRn) with correlation coefficient ofR=0.9. The indoor and outdoor EECRn levels were also studied as a function of outdoor temperature. The variations with temperature in both cases showed negative correlation with correlation coefficient ofR=-0.66 andR=-0.73, respectively. The ratio of outdoor to indoor EECRn investigated as a function of absolute difference of indoor and outdoor temperatures (| Tin– Tout|) resulted in a correlation coefficient ofR=0.52, which is positive. The indoor EECRn was also estimated from an empirical relation based on transport of inside and outside radon progeny through ventilation. The measured inside EECRn agrees well with the computed value.

Keywords: Radon progeny; EEC; Rn; Correlation coefficient; Temperature variation; Ventilation; Computed indoor levels


On plume meandering in unstable stratification by C.-H. Chun-Ho Liu; Dennis Y.C. Leung (pp. 2995-2999).
Vertical plume meandering of gaseous pollutant is commonly experienced in the daytime atmospheric boundary layer (also know as convective boundary layer, CBL) that arose from the complicated interaction between buoyancy-generated turbulence and gravitational force. It leads to rapid pollutant mixing that cannot be accurately modeled by conventional Gaussian plume model. In the light of explaining the mechanism of plume rises and descents in CBLs, this study employs a direct numerical simulation (DNS) technique to compute the plume behaviors for pollutant emitted from line sources placed parallel to the spanwise direction in an unstably stratified turbulent open channel flow. The DNS results show that the plume meandering is due to the domination of uni-directional mean vertical pollutant fluxes above and below the mean plume height.

Keywords: Convective boundary layer (CBL); Plume rise and descent; Direct numerical simulation (DNS); Gaussian plume model

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