Atmospheric Environment (v.44, #28)

Ultrafine particles (UFPs) released from laser printers are electrostatically charged during the working processes of the devices, and the electrostatic force can obviously influence the dynamics of the particles. Due to the measurement difficulty and scarcity of relevant research, this issue was not reported. This study tried to address this issue through experimental measurement of the surface charge of UFPs and numerical investigation on the influence of electrostatic force on the dynamics of UFPs. A test chamber was set up to collect the UFPs, and the Scanning Electron Microscope was used to observe the morphologies of the UFPs. Based on the particle diameter and surface zeta potential, the surface charge of UFPs was calculated. The measurement results gave that particle emitted from laser printers are negatively charged and the average surface charge of particle emissions for four laser printers is in a range of about −4.16 × 10−17 to −6.07 × 10−17 C (∼−260 to −379 e). This paper also discussed the influence of electrostatic force on the dynamics of UFPs. According to the numerical investigation, it was found that, in the absence of electric field, the electrostatic force has to be considered when the surface charge is larger than 1 × 10−16 C and when the UFP is very close to the wall with a distance of less than 0.01 m. These findings will guide constructively in predicting the dispersion and deposition of particles emitted from laser printers.
Keywords: Surface charge; Ultrafine particle; Laser printer; Zeta potential;

Economic damages of ozone air pollution to crops using combined air quality and GIS modelling by Ch. Vlachokostas; S.A. Nastis; Ch. Achillas; K. Kalogeropoulos; I. Karmiris; N. Moussiopoulos; E. Chourdakis; G. Banias; N. Limperi (3352-3361).
This study aims at presenting a combined air quality and GIS modelling methodological approach in order to estimate crop damages from photochemical air pollution, depict their spatial resolution and assess the order of magnitude regarding the corresponding economic damages. The analysis is conducted within the Greater Thessaloniki Area, Greece, a Mediterranean territory which is characterised by high levels of photochemical air pollution and considerable agricultural activity. Ozone concentration fields for 2002 and for specific emission reduction scenarios for the year 2010 were estimated with the Ozone Fine Structure model in the area under consideration. Total economic damage to crops turns out to be significant and estimated to be approximately 43 M€ for the reference year. Production of cotton presents the highest economic loss, which is over 16 M€, followed by table tomato (9 M€), rice (4.2 M€), wheat (4 M€) and oilseed rape (2.8 M€) cultivations. Losses are not spread uniformly among farmers and the major losses occur in areas with valuable ozone-sensitive crops. The results are very useful for highlighting the magnitude of the total economic impacts of photochemical air pollution to the area’s agricultural sector and can potentially be used for comparison with studies worldwide. Furthermore, spatial analysis of the economic damage could be of importance for governmental authorities and decision makers since it provides an indicative insight, especially if the economic instruments such as financial incentives or state subsidies to farmers are considered.
Keywords: Air quality modelling; Ozone; Agricultural production; Yield loss; Damage costs; Mediterranean area;

Ammonia volatilization from crop residues and frozen green manure crops by F.J. de Ruijter; J.F.M. Huijsmans; B. Rutgers (3362-3368).
Agricultural systems can lose substantial amounts of nitrogen (N). To protect the environment, the European Union (EU) has adopted several directives that set goals to limit N losses. National Emission Ceilings (NEC) are prescribed in the NEC directive for nitrogen oxides and ammonia. Crop residues may contribute to ammonia volatilization, but sufficient information on their contribution to the national ammonia volatilization is lacking. Experiments were carried out with the aim to assess the ammonia volatilization of crop residues left on the soil surface or incorporated into the soil under the conditions met in practice in the Netherlands during late autumn and winter.Ammonia emission from residues of broccoli, leek, sugar beet, cut grass, fodder radish (fresh and frozen) and yellow mustard (frozen) was studied during two winter seasons using volatilization chambers. Residues were either placed on top of soil or mixed with soil. Mixing residues with soil gave insignificant ammonia volatilization, whereas volatilization was 5–16 percent of the N content of residues when placed on top of soil.Ammonia volatilization started after at least 4 days. Total ammonia volatilization was related to C/N-ratio and N concentration of the plant material. After 37 days, cumulative ammonia volatilization was negligible from plant material with N concentration below 2 percent, and was 10 percent of the N content of plant material with 4 percent N. These observations can be explained by decomposition of plant material by micro-organisms. After an initial built up of the microbial population, NH4 + that is not needed for their own growth is released and can easily emit as NH3 at the soil surface.The results of the experiments were used to estimate the contribution of crop residues to ammonia volatilization in the Netherlands. Crop residues of arable crops and residues of pasture topping may contribute more than 3 million kg NH3–N to the national ammonia volatilization of the Netherlands, being more than 3 percent of the national emissions in 2005. This contribution should therefore be considered when focusing on the national ceilings for ammonia emissions.
Keywords: Ammonia volatilization; Broccoli; Grass; Green manure crops; Leek;

Estimation of economic costs of particulate air pollution from road transport in China by X.R. Guo; S.Y. Cheng; D.S. Chen; Y. Zhou; H.Y. Wang (3369-3377).
Valuation of health effects of air pollution is becoming a critical component of the performance of cost–benefit analysis of pollution control measures, which provides a basis for setting priorities for action. Beijing has focused on control of transport emission as vehicular emissions have recently become an important source of air pollution, particularly during Olympic games and Post-games. In this paper, we conducted an estimation of health effects and economic cost caused by road transport-related air pollution using an integrated assessment approach which utilizes air quality model, engineering, epidemiology, and economics. The results show that the total economic cost of health impacts due to air pollution contributed from transport in Beijing during 2004–2008 was 272, 297, 310, 323, 298 million US$ (mean value), respectively. The economic costs of road transport accounted for 0.52, 0.57, 0.60, 0.62, and 0.58% of annual Beijing GDP from 2004 to 2008. Average cost per vehicle and per ton of PM10 emission from road transport can also be estimated as 106 US $/number and 3584 US $ t−1, respectively. These findings illustrate that the impact of road transport contributed particulate air pollution on human health could be substantial in Beijing, whether in physical and economic terms. Therefore, some control measures to reduce transport emissions could lead to considerable economic benefit.
Keywords: Economic valuation; Road transport; Particulate air pollution; Beijing;

Verification of diffusive and pumped samplers for volatile organic compounds using a controlled atmosphere test facility by Nicholas A. Martin; Edward J. Leming; Malcolm H. Henderson; Robert P. Lipscombe; John K. Black; Scott D. Jarvis (3378-3385).
There is a requirement to verify the performance of sorbent-based passive or active samplers and to extend their use, where possible, to monitor volatile organic compounds (VOCs) that are known to be photochemical ozone pre-cursors or are relevant to the activities of the petrochemical industry. We report measurements of the 14-day diffusive uptake rates for the VOCs: i-butane (2-methyl propane), n-butane, i-pentane (2-methyl butane), n-pentane, n-hexane, benzene, toluene, and m-xylene (at environmental level concentrations) for industry standard axial samplers (Perkin–Elmer-type samplers) containing the sorbents Carbopack-X, -Z, -B or Tenax-TA. We also present data on back-diffusion, blank levels, and storage for the above sorbents, and describe the simultaneous use of the sorbent Carbopack-X for pumped sampling of certain VOCs. The results were obtained by dosing samplers in a controlled atmosphere test facility (CATFAC) operating under well-defined conditions of concentration, nominal temperature of 20 °C, wind speed of 0.5 m s−1, and relative humidities of 0% and 80%. Field measurements were also obtained to provide supplementary data to support the laboratory study. Results are compared to existing published data, where these are available.
Keywords: Sorbents; Test atmosphere; Diffusive uptake rates; Pumped samplers; Volatile organic compounds; Environmental level;

We investigated chemical and Sr isotopic composition of monthly rainwater collected on Peng-Chia-Yu (PCY) in northern Taiwan. Rainwater 87Sr/86Sr ratios, Na/Cl, Ca/Cl, Sr/Cl, Sr/Ca, NH4/Cl, NO3/Cl, SO4/Cl and Na/Sr, showed clear seasonal cycles, reflecting mixture of loess carbonates (high Ca/Sr and more radiogenic 87Sr/86Sr) and seawater (low Ca/Sr and intermediate 87Sr/86Sr). Model results showed that the former source contributes up to 45% during the winter monsoon period, but seawater is the dominant Sr source in rainwater (>50%) at other times. Two anomalously low 87Sr/86Sr values occurred in July and August 1998, coinciding with the Merapi eruption in Indonesia. Air-mass backward trajectories and the geochemical and isotopic compositions in rainwater and Merapi lava (i.e. Ca/Sr = 100 and 87Sr/86Sr = 0.705400) suggested that the Merapi eruption delivered ash across the western equatorial Pacific to PCY. Aerosols leaching experiments were conducted to examine the impact of the 1998 eruption, demonstrating that only a minor terrestrial signature can be extracted by distilled water, implying rapid dispatch of volcanic gases or high-efficiency dissolution of ash related substance in acidic rains.
Keywords: Peng-Chia-Yu; Rainwater; Sr isotopes; Merapi volcanic eruption;

Mixing and transformation of Asian dust with pollution in the two dust storms over the northern China in 2006 by Wenjie Zhang; Guoshun Zhuang; Kan Huang; Juan Li; Rong Zhang; Qiongzhen Wang; Yele Sun; Joshua S. Fu; Ying Chen; Dongqun Xu; Wei Wang (3394-3403).
To study the mixing and transformation of Asian dust with pollution in the two dust storms over the northern China in 2006, both TSP and PM2.5 samples were collected at three sites of northern China in addition to the dry deposition samples collected in an episode in Beijing. 23 elements, 15 ions, and 16 PAHs in each sample were analyzed. The two dust storms in northern China were observed in April 8–10 (DS1) and April 16–18 (DS2). Compared to DS2, DS1 was weaker and more polluted with stronger mixing between crustal and pollutant aerosols during their long-range transport. The concentrations of pollution species, e.g. pollution elements, ions, and PAHs were higher in DS1 than that in DS2, while the crustal species showed adverse variation. The correlation between chemical species and Al and between PAH(4) and PAH(5,6) further confirmed the stronger chemical transformation and aerosol mixing in DS1 than that in DS2. Back trajectory and chemical analysis revealed that in DS1 the air masses at Beijing were mostly from southern or southwestern direction at lower altitude with much more pollution, while in DS2 the air masses were mostly from the northwestern and northern direction with dust mainly, which explained why there was a stronger mixing of dust with pollution aerosol in DS1 than that in DS2 over Beijing.
Keywords: Dust storm; Pollution; Mixing; Transformation; Long-range transport;

Ozone uptake by citrus trees exposed to a range of ozone concentrations by Silvano Fares; Jeong-Hoo Park; Elena Ormeno; Drew R. Gentner; Megan McKay; Francesco Loreto; John Karlik; Allen H. Goldstein (3404-3412).
The Citrus genus includes a large number of species and varieties widely cultivated in the Central Valley of California and in many other countries having similar Mediterranean climates. In the summer, orchards in California experience high levels of tropospheric ozone, formed by reactions of volatile organic compounds (VOC) with oxides of nitrogen (NOx). Citrus trees may improve air quality in the orchard environment by taking up ozone through stomatal and non-stomatal mechanisms, but they may ultimately be detrimental to regional air quality by emitting biogenic VOC (BVOC) that oxidize to form ozone and secondary organic aerosol downwind of the site of emission. BVOC also play a key role in removing ozone through gas-phase chemical reactions in the intercellular spaces of the leaves and in ambient air outside the plants. Ozone is known to oxidize leaf tissues after entering stomata, resulting in decreased carbon assimilation and crop yield. To characterize ozone deposition and BVOC emissions for lemon (Citrus limon), mandarin (Citrus reticulata), and orange (Citrus sinensis), we designed branch enclosures that allowed direct measurement of fluxes under different physiological conditions in a controlled greenhouse environment. Average ozone uptake was up to 11 nmol s−1  m−2 of leaf. At low concentrations of ozone (40 ppb), measured ozone deposition was higher than expected ozone deposition modeled on the basis of stomatal aperture and ozone concentration. Our results were in better agreement with modeled values when we included non-stomatal ozone loss by reaction with gas-phase BVOC emitted from the citrus plants. At high ozone concentrations (160 ppb), the measured ozone deposition was lower than modeled, and we speculate that this indicates ozone accumulation in the leaf mesophyll.
Keywords: Ozone fluxes; Citrus; Tropospheric ozone; Enclosures; BVOC;

Ammonia emissions from naturally ventilated dairy cattle buildings and outdoor concrete yards in Portugal by José Pereira; Tom H. Misselbrook; David R. Chadwick; João Coutinho; Henrique Trindade (3413-3421).
There is a lack of information on ammonia (NH3) emissions from cattle housing systems in Mediterranean countries, with most published data deriving from NW Europe. An investigation was carried out in NW Portugal to quantify NH3 emissions for the main types of dairy cattle buildings in Portugal, i.e. naturally ventilated buildings and outdoor concrete yards, and to derive robust emission factors (EFs) for these conditions and compare with EFs used elsewhere in Europe. Measurements were made throughout a 12-month period using the passive flux sampling method in the livestock buildings and the equilibrium concentration technique in outdoor yards.The mean NH3 emission factor for the whole housing system (buildings + outdoor yards) was 43.7 g NH3–N LU−1 day−1 and for outdoor concrete yards used by dairy cattle was 26.6 g NH3–N LU−1 day−1. Expressing NH3 emission in terms of the quantity of liquid milk produced gave similar values across the three dairy farms studied (with a mean of 2.3 kg N ton-milk−1 produced) and may have advantages when comparing different farming systems. In dairy houses with outdoor yards, NH3 emissions from the yard area contributed to 69–92% of total emissions from this housing system. Emissions were particularly important during spring and summer seasons from outdoor yards with NH3 emitted in this period accounting for about 72% of annual emissions from outdoor yards. Mean NH3 emission factors derived for this freestall housing system and outdoor concrete yards used by dairy cattle in Portugal were higher than those measured in northern Europe. In addition, values of animal N excretion estimated in this study were greater than official National standard values. If these emissions are typical for Portuguese dairy systems, then the current National inventory underestimates emissions from this source in NW of Portugal, because of the use of lower standard values of N excretion by dairy cattle.
Keywords: Ammonia emissions; Cattle buildings; Emission factors; Natural ventilation; Outdoor yards;

Quantification of self pollution from two diesel school buses using three independent methods by L.-J. Sally Liu; Harish C. Phuleria; Whitney Webber; Mark Davey; Douglas R. Lawson; Robert G. Ireson; Barbara Zielinska; John M. Ondov; Christopher S. Weaver; Charles A. Lapin; Michael Easter; Thomas W. Hesterberg; Timothy Larson (3422-3431).
We monitored two Seattle school buses to quantify the buses’ self pollution using the dual tracers (DT), lead vehicle (LV), and chemical mass balance (CMB) methods. Each bus drove along a residential route simulating stops, with windows closed or open. Particulate matter (PM) and its constituents were monitored in the bus and from a LV. We collected source samples from the tailpipe and crankcase emissions using an on-board dilution tunnel. Concentrations of PM1, ultrafine particle counts, elemental and organic carbon (EC/OC) were higher on the bus than the LV. The DT method estimated that the tailpipe and the crankcase emissions contributed 1.1 and 6.8 μg m−3 of PM2.5 inside the bus, respectively, with significantly higher crankcase self pollution (SP) when windows were closed. Approximately two-thirds of in-cabin PM2.5 originated from background sources. Using the LV approach, SP estimates from the EC and the active personal DataRAM (pDR) measurements correlated well with the DT estimates for tailpipe and crankcase emissions, respectively, although both measurements need further calibration for accurate quantification. CMB results overestimated SP from the DT method but confirmed crankcase emissions as the major SP source. We confirmed buses’ SP using three independent methods and quantified crankcase emissions as the dominant contributor.
Keywords: School bus; Self pollution; PM2.5; Dual tracers; Tailpipe; Crankcase emissions; Cabin air; Exposure;

Influence of roads and inhabited areas on metal concentrations in terrestrial mosses by B. Carvajal; J.R. Aboal; J.A. Fernández; C. Real; A. Carballeira (3432-3441).
The guidelines regarding sampling terrestrial mosses for biomonitoring the atmospheric contamination in a region specifically recommend that sampling close to focal points of contamination (i.e. roads, populated areas, etc.) should be avoided for satisfactory characterization of general patterns of contamination. However, these recommendations cannot always be followed in many parts of the world with dense, highly dispersed populations. The aim of the present study was to determine how the distances between sampling sites (SS) and contamination foci such as roads, isolated houses and urban nuclei affect regular, large-scale sampling networks. Metal concentrations obtained in biennial sampling surveys carried out between 2000 and 2006 in Galicia (NW Spain) were used, and the relative proportions of the concentrations corresponding to small-scale and large-scale processes were calculated. The possible relationship between the mean concentrations corresponding to small-scale processes in the different sampling surveys and the distances from SS to roads, buildings and urban nuclei was established by a GIS. Outliers in the data were identified at many of the SS and frequency statistics revealed the absence of any relationship between the distance to these foci and the concentrations of metals in the moss. The method also revealed many instances of the influence of one or more small-scale contamination foci such as airports and railways (often not considered in the sampling recommendations) on SS. Relocation of such SS would improve the representativeness of the sampling grid.
Keywords: Pseudoscleropodium purum; Highways; Pollution; Biomonitoring; Median polish; Variograms;

Assessment of air quality benefits from national air pollution control policies in China. Part I: Background, emission scenarios and evaluation of meteorological predictions by Litao Wang; Carey Jang; Yang Zhang; Kai Wang; Qiang Zhang; David Streets; Joshua Fu; Yu Lei; Jeremy Schreifels; Kebin He; Jiming Hao; Yun-Fat Lam; Jerry Lin; Nicholas Meskhidze; Scott Voorhees; Dale Evarts; Sharon Phillips (3442-3448).
Under the 11th Five Year Plan (FYP, 2006–2010) for national environmental protection by the Chinese government, the overarching goal for sulfur dioxide (SO2) controls is to achieve a total national emissions level of SO2 in 2010 10% lower than the level in 2005. A similar nitrogen oxides (NOx) emissions control plan is currently under development and could be enforced during the 12th FYP (2011–2015). In this study, the U.S. Environmental Protection Agency (U.S.EPA)’s Community Multi-Scale Air Quality (Models-3/CMAQ) modeling system was applied to assess the air quality improvement that would result from the targeted SO2 and NOx emission controls in China. Four emission scenarios — the base year 2005, the 2010 Business-As-Usual (BAU) scenario, the 2010 SO2 control scenario, and the 2010 NO x control scenario—were constructed and simulated to assess the air quality change from the national control plan. The Fifth-Generation NCAR/Penn State Mesoscale Model (MM5) was applied to generate the meteorological fields for the CMAQ simulations. In this Part I paper, the model performance for the simulated meteorology was evaluated against observations for the base case in terms of temperature, wind speed, wind direction, and precipitation. It is shown that MM5 model gives an overall good performance for these meteorological variables. The generated meteorological fields are acceptable for using in the CMAQ modeling.
Keywords: Air pollution in China; Air quality modeling; Emission control; MM5/CMAQ; 11th FYP;

Assessment of air quality benefits from national air pollution control policies in China. Part II: Evaluation of air quality predictions and air quality benefits assessment by Litao Wang; Carey Jang; Yang Zhang; Kai Wang; Qiang Zhang; David Streets; Joshua Fu; Yu Lei; Jeremy Schreifels; Kebin He; Jiming Hao; Yun-Fat Lam; Jerry Lin; Nicholas Meskhidze; Scott Voorhees; Dale Evarts; Sharon Phillips (3449-3457).
Following the meteorological evaluation in Part I, this Part II paper presents the statistical evaluation of air quality predictions by the U.S. Environmental Protection Agency (U.S. EPA)’s Community Multi-Scale Air Quality (Models-3/CMAQ) model for the four simulated months in the base year 2005. The surface predictions were evaluated using the Air Pollution Index (API) data published by the China Ministry of Environmental Protection (MEP) for 31 capital cities and daily fine particulate matter (PM2.5, particles with aerodiameter less than or equal to 2.5 μm) observations of an individual site in Tsinghua University (THU). To overcome the shortage in surface observations, satellite data are used to assess the column predictions including tropospheric nitrogen dioxide (NO2) column abundance and aerosol optical depth (AOD). The result shows that CMAQ gives reasonably good predictions for the air quality.The air quality improvement that would result from the targeted sulfur dioxide (SO2) and nitrogen oxides (NOx) emission controls in China were assessed for the objective year 2010. The results show that the emission controls can lead to significant air quality benefits. SO2 concentrations in highly polluted areas of East China in 2010 are estimated to be decreased by 30–60% compared to the levels in the 2010 Business-As-Usual (BAU) case. The annual PM2.5 can also decline by 3–15 μg m−3 (4–25%) due to the lower SO2 and sulfate concentrations. If similar controls are implemented for NOx emissions, NOx concentrations are estimated to decrease by 30–60% as compared with the 2010 BAU scenario. The annual mean PM2.5 concentrations will also decline by 2–14 μg m−3 (3–12%). In addition, the number of ozone (O3) non-attainment areas in the northern China is projected to be much lower, with the maximum 1-h average O3 concentrations in the summer reduced by 8–30 ppb.
Keywords: Air pollution in China; Air quality modeling; Emission control; MM5/CMAQ; 11th FYP;

Hydroxyl radical (OH) yields from the ozonolysis of both double bonds for five monoterpenes by Frank Herrmann; Richard Winterhalter; Geert K. Moortgat; Jonathan Williams (3458-3464).
A new method has been applied to determine OH-radical yields from the ozonolysis of both double bonds from five selected, atmospherically relevant monoterpenes, namely terpinolene, α-phellandrene, limonene, α-terpinene and γ-terpinene. While OH-yields for the faster reacting double bond agreed with previous literature values, the yields from the second double bond were determined for the first time and are as follows: limonene 7–10%, terpinolene 39–48%, α-phellandrene 8–11% and α-terpinene 12–14%. Only for γ-terpinene the rate coefficient for the reaction of ozone with the two double bonds was too similar in order to distinguish the OH-yield with this method. In all cases the yield from the second double bond was significantly lower than the first. The reasons for this difference are discussed in terms of the Criegee-intermediate reactions, in particular the number of abstractable H-atoms and the number of possible hydroperoxide products.
Keywords: OH; OH-yield; Ozone; Terpenes; PTR-MS; Ozonolysis;

Indoor smoking ban in public places can reduce secondhand smoke (SHS) exposure. However, smoking in cars and homes has continued. The purpose of this study was to assess particulate matter less than 2.5 μm (PM2.5) concentration in moving cars with different window opening conditions. The PM2.5 level was measured by an aerosol spectrometer inside and outside moving cars simultaneously, along with ultrafine particle (UFP) number concentration, speed, temperature and humidity inside cars. Two sport utility vehicles were used. Three different ventilation conditions were evaluated by up to 20 repeated experiments. In the pre-smoking phase, average in-vehicle PM2.5 concentrations were 16–17 μg m−3. Regardless of different window opening conditions, the PM2.5 levels promptly increased when smoking occurred and decreased after cigarette was extinguished. Although only a single cigarette was smoked, the average PM2.5 levels were 506–1307 μg m−3 with different window opening conditions. When smoking was ceased, the average PM2.5 levels for 15 min were several times higher than the US National Ambient Air Quality Standard of 35 μg m−3. It took longer than 10 min to reach the level of the pre-smoking phase. Although UFP levels had a similar temporal profile of PM2.5, the increased levels during the smoking phase were relatively small. This study demonstrated that the SHS exposure in cars with just a single cigarette being smoked could exceed the US EPA NAAQS under realistic window opening conditions. Therefore, the findings support the need for public education against smoking in cars and advocacy for a smoke-free car policy.
Keywords: Secondhand smoke; Ultrafine particles; PM2.5; Exposure; In-vehicle;