Atmospheric Environment (v.143, #C)

Atmospheric outflow of PM2.5 saccharides from megacity Shanghai to East China Sea: Impact of biological and biomass burning sources by Xiang Li; Minxuan Chen; Hoa Phuoc Le; Fengwen Wang; Zhigang Guo; Yoshiteru Iinuma; Jianmin Chen; Hartmut Herrmann (1-14).
In an effort to more fully understand atmospheric outflow of PM2.5-associated saccharide species, we investigated primary saccharides (fructose, glucose, sucrose, and trehalose), saccharide alcohols (arabitol and mannitol), and anhydrosaccharides (levoglucosan and mannosan) in atmospheric aerosols at both a megacity site, Shanghai, and a sea background site, Huaniao Island. The results showed that the saccharide species presented pronounced temporal and spatial variability in the outflow from the megacity to the East China Sea, and varied widely with a total concentration range of 8.6–2400 ng m−3 (283 ng m−3 mean) in Shanghai and 0–1050 ng m−3 (51 ng m−3 mean) in Huaniao Island. Both saccharide species (e.g., levoglucosan and sucrose) showed higher concentrations and a noticeable seasonal gradient during the study period ― there was a high level of levoglucosan in the cold season (161 ng m−3 in winter and 229 ng m−3 in autumn) due to elevated biomass burning activities, and a high level of sucrose in the warm seasons (146 ng m−3 in summer and 145 ng m−3 in spring) due to elevated levels of intense biological aerosols including fungal spores and pollen. The calculated levoglucosan/mannosan (L/M) ratio, which may represent the signature of aerosol particles at the two sites, ranged from 5.2 to 10.9 during the cold season. Back-trajectory analysis results indicated that the saccharides originated from regional sources in East and North China before being transported to the sampling site. Emissions due to biomass burning were estimated to correspond to 46% (mass) of the saccharides quantified in the haze particle samples, whereas biogenic emissions corresponded to 18%, indicating that biomass burning was a considerable aerosol source to the regional atmosphere throughout the year. The results presented here support the theory that levoglucosan could be utilized as a molecular marker for East Asian biomass burning outflow, and sucrose as a molecular marker for airborne pollen grains. The results of this study may help future researchers clarify the aerosol sources, as well as their atmospheric transport pathways over East Asia to the western Pacific Ocean.
Keywords: Atmospheric outflow; PM2.5-associated saccharides; Shanghai; Huaniao island; Long-range transport;

Fast oxidation processes from emission to ambient air introduction of aerosol emitted by residential log wood stoves by Federica Nalin; Benjamin Golly; Jean-Luc Besombes; Charles Pelletier; Robin Aujay-Plouzeau; Stéphane Verlhac; Adrien Dermigny; Amandine Fievet; Nicolas Karoski; Pascal Dubois; Serge Collet; Olivier Favez; Alexandre Albinet (15-26).
Little is known about the impact of post-combustion processes, condensation and dilution, on the aerosol concentration and chemical composition from residential wood combustion. The evolution of aerosol emitted by two different residential log wood stoves (old and modern technologies) from emission until it is introduced into ambient air was studied under controlled “real” conditions. The first objective of this research was to evaluate the emission factors (EF) of polycyclic aromatic hydrocarbons (PAH) and their nitrated and oxygenated derivatives from wood combustion. These toxic substances are poorly documented in the literature. A second objective was to evaluate the oxidation state of the wood combustion effluent by studying these primary/secondary compounds. EFs of Σ37PAHs and Σ27Oxy-PAHs were in the same range and similar to those reported in literature (4–240 mg kg−1). Σ31Nitro-PAH EFs were 2–4 orders of magnitude lower (3.10−2-8.10−2 mg kg−1) due to the low temperature and low emission of NO2 from wood combustion processes. An increase of equivalent EF of PAH derivatives was observed suggesting that the oxidation state of the wood combustion effluent from the emission point until its introduction in ambient air changed in a few seconds. These results were confirmed by the study of both, typical compounds of SOA formation from PAH oxidation and, PAH ratio-ratio plots commonly used for source evaluation.Display Omitted
Keywords: Biomass burning; Emission factors; PAH; Nitro-PAH; Oxy-PAH; Gas/particle partitioning;

The influence of Asian dust outflow on particle microphysical and optical properties at Mt. Tai in central east China by X.J. Shen; J.Y. Sun; Y.M. Zhang; X.Y. Zhang; T.T. Wang; Y.Q. Wang; L. Zhang; R.X. Fan; Y. Zhao; D.Z. Wang (27-38).
An in-situ measurement of the particle number size distribution and optical properties (scattering and absorption coefficients) of PM2.5 was conducted at Mt. Tai, a mountain top station in central east China in the spring of 2011. It was found that the particle size distribution, mass concentration, as well as the optical properties have been modified during the dust periods. The mean mass concentration of PM2.5 during the dust periods was nearly twice of that during the non-dust period. The number and volume size distribution showed a higher concentration in the size range of 0.5–2.5 μm during the dust period, which were identified as dust particles. The absorption coefficient increased by ∼40%, while the scattering coefficient did not show much difference. The single scattering albedo of 0.85 during dust period was also comparable with the value of 0.89 during non-dust period. The Mie model was applied to simulate the aerosol optical properties and validated through a closure study for an intensive dust event. This study quantitatively demonstrated that dust particles contributed to nearly 63% of the scattering coefficient, while the remainder was mainly due to anthropogenic particles on dust days. The dust particles took a lower portion to the absorption, about 40%, indicating the anthropogenic particles still played a more dominant role in absorbing. This study also indicated that although there were only a few tens of dust particles during dust period, they could influence in particle optical properties significantly.
Keywords: Dust aerosol; Size distribution; Scattering and absorption; Mie model;

Wet and dry nitrogen deposition in the central Sichuan Basin of China by Fuhong Kuang; Xuejun Liu; Bo Zhu; Jianlin Shen; Yuepeng Pan; Minmin Su; Keith Goulding (39-50).
Reactive nitrogen (Nr) plays a key role in the atmospheric environment and its deposition has induced large negative impacts on ecosystem health and services. Five-year continuous in-situ monitoring of N deposition, including wet (total nitrogen (WTN), total dissolved nitrogen (WTDN), dissolved organic nitrogen (WDON), ammonium nitrogen (WAN) and nitrate nitrogen (WNN)) and dry (DNH3, DHNO3, DpNH4 +, DpNO3 and DNO2) deposition, had been conducted since August 2008 to December 2013 (wet) and May 2011 to December 2013 (dry) in Yan-ting, China, a typical agricultural area in the central Sichuan Basin. Mean annual total N deposition from 2011 to 2013 was 30.8 kg N ha−1 yr−1, and speculated that of 2009 and 2010 was averaged 28.2 kg N ha−1 yr−1, respectively. Wet and dry N deposition accounted for 76.3% and 23.7% of annual N deposition, respectively. Reduced N (WAN, DNH3 and DpNH4 +) was 1.7 times of oxidized N (WNN, DHNO3, DNO2 and DpNO3 ) which accounted for 50.9% and 30.3% of TN, respectively. Maximum loadings of all N forms of wet deposition, gaseous NH3, HNO3 and particulate NH4 + in dry deposition occurred in summer and minimum loadings in winter. Whether monthly, seasonal or annual averaged, dissolved N accounted for more than 70% of the total. N deposition in the central Sichuan Basin increased during the sampling period, especially that of ammonium compounds, and has become a serious threat to local aquatic ecosystems, the surrounding forest and other natural or semi-natural ecosystems in the upper reaches of the Yangtze River.Display Omitted
Keywords: Air pollution; Wet deposition; Dry deposition; Nitrogen; Agricultural activities;

Lead fluxes and 206Pb/207Pb isotope ratios in rime and snow collected at remote mountain-top locations (Czech Republic, Central Europe): Patterns and sources by Nikoleta Cimova; Martin Novak; Vladislav Chrastny; Jan Curik; Frantisek Veselovsky; Vladimir Blaha; Eva Prechova; Jan Pasava; Marie Houskova; Leona Bohdalkova; Marketa Stepanova; Jitka Mikova; Michael Krachler; Arnost Komarek (51-59).
During three winter seasons (2009–2011), Pb concentrations were measured in precipitation at 10 high-elevation sites in the Czech Republic, close to the borders with Austria, Germany, Poland, and Slovakia. Soluble and insoluble Pb forms were quantified in snow (vertical deposition), and rime (horizontal deposition). The objective was to compare Pb input fluxes into ecosystems via vertical and horizontal deposition, and to identify the residual Pb pollution sources in an era of rapidly decreasing industrial pollution. Lead soluble in diluted HNO3 made up 96% of total Pb deposition, with the remaining 4% Pb bound mainly in silicates. Three times higher concentrations of soluble Pb in rime than in snow, and 2.5 times higher concentrations of insoluble Pb in rime than in snow were associated with slightly different Pb isotope ratios. On average, the 206Pb/207Pb ratios in rime were higher than those in snow. Higher mean 206Pb/207Pb ratios of insoluble Pb (1.175) than in soluble Pb (1.165) may indicate an increasing role of geogenic Pb in recent atmospheric deposition. A distinct reversal to more radiogenic 206Pb/207Pb ratios in snow and rime in 2010, compared to literature data from rain-fed Sphagnum peatlands (1800–2000 A.D.), documented a recent decrease in anthropogenic Pb in the atmosphere of Central Europe. Since the early 1980s, Pb concentrations in snow decreased 18 times in the rural south of the Czech Republic, but only twice in the industrial north of the Czech Republic. Isotope signatures indicated that Pb in today's atmospheric deposition is mainly derived from Mesozoic ores mined/processed in Poland and coal combustion in the Czech Republic and Poland.
Keywords: Lead; Isotopes; Rime; Snow; Atmosphere; Deposition;

The isotopic composition of nitrogen oxides (NOx = NO + NO2) hold potential to trace emissions sources, as well as chemistry in the atmosphere. Passive samplers that collect NOx and NO2 as nitrite could provide a simple and inexpensive means by which to collect samples in a variety of environments, and we report here on several methodological considerations when using Ogawa passive collectors of NOx and NO2 for concentration analysis via colorimetric methods and isotopic analysis via the denitrifier method. Using Ogawa samplers, NOx and NO2 were collected in Providence, RI, USA (41.8°N, 71.4°W) with exposure times of seven, fourteen, twenty-one, and twenty-eight days during summer and winter in an area dominated by vehicle emissions, particularly diesel delivery trucks. Average values were −9.7 ± 0.7‰ for δ15N-NOx and −8.3 ± 0.9‰ for δ15N-NO2 based on duplicate seven, fourteen, twenty-one, and twenty-eight day exposures (n = 8) in summertime, and −11.9 ± 0.7‰ for δ15N-NOx and −6.4 ± 1.4‰ for δ15N-NO2 based on seven, fourteen, twenty-one, and twenty-eight day exposures (n = 7) in wintertime. The oxygen isotopic composition (δ18O, Δ17O) was also determined with averages of: 36.3 ± 2.4‰ for δ18O-NOx (n = 8), 50.5 ± 3.2‰ for δ18O-NO2 (n = 8), 6.2 ± 0.8‰ for Δ17O-NOx and 10.8 ± 0.6‰ for Δ17O-NO2 (n = 4) in summer; and 38.7 ± 2.9‰ for δ18O-NOx and 47.4 ± 1.2‰ for δ18O-NO2 (n = 7), 7.7 ± 1.5‰ for Δ17O-NO2 (n = 4) and 5.3 ± 1.2‰ for Δ17O-NOx (n = 5), in winter. Our isotopic results differ from previous studies that utilized passive samplers and suggest specific nitrogen and oxygen isotopic signatures associated with vehicular emissions. To collect sufficient sample for multiple isotopic analyses (e.g., 10 nmol N for δ15N and δ18O; 50 nmol N for Δ17O) the exposure time for the samplers, even in urban areas, is at least days. This necessarily results in collection of a mixture of local emissions sources, as well as background air that can represent multiple NOx sources. Thus, passive samplers cannot be used to diagnose isotopic signatures unless only exposed to a single emissions source. The oxygen isotopic composition of nitrite (the collection analyte) results determined via the denitrifier method must be corrected in comparison to nitrate isotopic reference materials, resulting in an increase of ∼25‰. Even with this correction, the oxygen isotopic results are lower than what would be expected for ozone-dominated atmospheric chemistry in an urban area, and the oxygen isotopic results for NOx were consistently lower than that found for NO2. We suggest that the oxygen isotopic composition of NO and NO2 were modified upon capture and conversion to nitrite on the passive sampler pads, and does not directly reflect abundances in the atmosphere.
Keywords: Isotopes; Nitrogen oxides; Denitrifier method; Passive samplers; Ogawa pads; Urban air;

Model testing for nitrous oxide (N2O) fluxes from Amazonian cattle pastures by Katharina H.E. Meurer; Uwe Franko; Oliver Spott; C. Florian Stange; Hermann F. Jungkunst (67-78).
Process-oriented models have become important tools in terms of quantification of environmental changes, for filling measurement gaps, and building of future scenarios. It is especially important to couple model application directly with measurements for remote areas, such as Southern Amazonia, where direct measurements are difficult to perform continuously throughout the year. Processes and resulting matter fluxes may show combinations of steady and sudden reactions to external changes. The potent greenhouse gas nitrous oxide (N2O) is known for its sensitivity to e.g. precipitation events, resulting in intense but short-term peak events (hot moments). These peaks have to be captured for sound balancing. However, prediction of the effect of rainfall events on N2O peaks is not trivial, even for areas under distinct wet and dry seasons. In this study, we used process-oriented models in both a pre-and post-measurement manner in order to (a) determine important periods for N2O-N emissions under Amazonian conditions and (b) calibrate the models to Brazilian pastures based on measured data of environment conditions (soil moisture and Corg) and measured N2O-N fluxes. During the measurement period (early wet season), observed emissions from three cattle pastures did not react to precipitation events, as proposed by the models. Here both process understanding and models have to be improved by long-term data in high resolution in order to prove or disprove a lacking of N2O-N peaks. We strongly recommend the application of models as planning tools for field campaigns, but we still suggest model combinations and simultaneous usage.
Keywords: N2O-N fluxes; Modeling; Cattle pasture; Southern Amazonia;

Light absorption characteristics of carbonaceous aerosols in two remote stations of the southern fringe of the Tibetan Plateau, China by Chaoliu Li; Fangping Yan; Shichang Kang; Pengfei Chen; Zhaofu Hu; Shaopeng Gao; Bin Qu; Mika Sillanpää (79-85).
Light absorption characteristics of carbonaceous aerosols are key considerations in climate forcing research. However, in situ measurement data are limited, especially on the Tibetan Plateau (TP) – the Third Pole of the world. In this study, the mass absorption cross section (MAC) of elemental carbon (EC) and water soluble organic carbon (WSOC) of total suspended particles at two high-altitude stations (Lulang station and Everest station) in the Tibetan Plateau (TP) were investigated. The mean MACEC values at 632 nm were 6.85 ± 1.39 m2 g−1 and 6.49 ± 2.81 m2 g−1 at these two stations, both of which showed little seasonal variations and were slightly higher than those of EC of uncoated particles, indicating that the enhancement of MACEC by factors such as coating with organic aerosols was not significant. The mean MACWSOC values at 365 nm were 0.84 ± 0.40 m2 g−1 and 1.18 ± 0.64 m2 g−1 at the two stations. Obvious seasonal variations of high and low MACWSOC values appeared in winter and summer, respectively, mainly reflecting photobleaching of light absorption components of WSOC caused by fluctuations in sunlight intensity. Therefore, this phenomenon might also exists in other remote areas of the world. The relative contributions of radiative forcing of WSOC to EC were 6.03 ± 3.62% and 11.41 ± 7.08% at these two stations, with a higher ratio in winter. As a result, both the contribution of WSOC to radiative forcing of carbonaceous aerosols and its seasonal variation need to be considered in radiative forcing related study.
Keywords: Black carbon; Water soluble organic carbon; Light absorption; The Tibetan Plateau; Seasonal variation;

Air pollution associated with road transport is a major environmental issue in urban areas. Buildings in urban areas are the artificial obstacles to atmospheric flow and cause reduced ventilation for street canyons. For a deep street canyon, there is evidence of the formation of multiple segregated vortices, which generate flow regimes such that pollutants exhibit a significant contrast between these vortices. This results in poor air ventilation conditions at pedestrian level, thereby leading to elevated pollutant levels and potential breaches of air quality limits. The hypothesis of a well-mixed deep street canyon in the practical one-box model approach is shown to be inappropriate. This study implements a simplified simulation of the canyon volume: a coupled two-box model with a reduced chemical scheme to represent the key photochemical processes with timescales similar to and smaller than the turbulent mixing timescale. The two-box model captures the significant pollutant contrast between the lower and upper parts of a deep street canyon, particularly for NO2. Core important parameters (i.e. heterogeneity coefficient, exchange velocity and box height ratio) in the two-box model approach were investigated through sensitivity tests. The two-box model results identify the emission regimes and the meteorological conditions under which NO2 in the lower canyon (i.e. the region of interest for the assessment of human health effects) is in breach of air quality standards. Higher NO2 levels were observed for the cases with higher heterogeneity coefficients (the two boxes are more segregated), with lower exchange velocities (worse ventilation conditions), or with smaller box height ratios (reduced dilution possibly due to secondary smaller eddies in the lower canyon). The performance of a one-box model using the same chemical scheme is also evaluated against the two-box model. The one-box model was found to systematically underestimate NO2 levels compared with those in the lower box of the two-box model for all test scenarios. This underestimation generally tends to worsen for higher heterogeneity coefficients, lower exchange velocities or smaller box height ratios. This study highlights the limitation of the assumption of homogeneity in single box models for street canyon simulation, and the inherent uncertainties that must be borne in mind to appropriately interpret such model output (in particular, that a single-box treatment will systematically underestimate NO2 as experienced at street level).
Keywords: Air pollution; Urban street canyon; Two-box model; Dynamics; Photochemistry;

Trace gases in the atmosphere over Russian cities by Nikolai F. Elansky; Olga V. Lavrova; Andrey I. Skorokhod; Igor B. Belikov (108-119).
Multiyear observational data (obtained at the mobile railroad laboratory in the course of the 1995–2010 TROICA experiments) on the composition and state of the atmosphere were used to study the features of both spatial and temporal variations in the contents of trace gases in the surface air layer over Russian cities. The obtained characteristics of urban air noticeably differ from those obtained at stationary stations. The emission fluxes of NOx, CO, and CH4 and their integral emissions from large cities have been estimated on the basis of observational data obtained at the mobile laboratory. The values of these emission fluxes reflect the state of urban infrastructure. The integral urban emissions of CO depend on the city size and vary from 50 Gg yr−1 for Yaroslavl to 130 Gg yr−1 for Yekaterinburg. For most cities, they agree with the EDGAR v4.2 data within the limits of experimental error. The agreement is worse for the emissions of NOx. The EDGAR v4.2 data on the emissions of CH4 seem to be overestimated.
Keywords: Trace gases; Atmospheric air chemistry; Urban pollution; Emissions; Mobile laboratory;

Impact of meteorological inflow uncertainty on tracer transport and source estimation in urban atmospheres by Donald D. Lucas; Akshay Gowardhan; Philip Cameron-Smith; Ronald L. Baskett (120-132).
A computational Bayesian inverse technique is used to quantify the effects of meteorological inflow uncertainty on tracer transport and source estimation in a complex urban environment. We estimate a probability distribution of meteorological inflow by comparing wind observations to Monte Carlo simulations from the Aeolus model. Aeolus is a computational fluid dynamics model that simulates atmospheric and tracer flow around buildings and structures at meter-scale resolution. Uncertainty in the inflow is propagated through forward and backward Lagrangian dispersion calculations to determine the impact on tracer transport and the ability to estimate the release location of an unknown source. Our uncertainty methods are compared against measurements from an intensive observation period during the Joint Urban 2003 tracer release experiment conducted in Oklahoma City. The best estimate of the inflow at 50 m above ground for the selected period has a wind speed and direction of 4.6 − 2.5 + 2.0  m s−1 and 158.0 − 23 + 16 , where the uncertainty is a 95% confidence range. The wind speed values prescribed in previous studies differ from our best estimate by two or more standard deviations. Inflow probabilities are also used to weight backward dispersion plumes and produce a spatial map of likely tracer release locations. For the Oklahoma City case, this map pinpoints the location of the known release to within 20 m. By evaluating the dispersion patterns associated with other likely release locations, we further show that inflow uncertainty can explain the differences between simulated and measured tracer concentrations.
Keywords: Meteorological inflow uncertainty; Source estimation; Bayesian inversion;

Below-cloud scavenging coefficients for ultrafine particles (UFP) exhibit comparatively large uncertainties in part because of the limited availability of observational data sets from which robust parameterizations can be derived or that can be used to evaluate output from numerical models. Long time series of measured near-surface UFP size distributions and precipitation intensity from the Midwestern USA are used here to explore uncertainties in scavenging coefficients and test both the generalizability of a previous empirical parameterization developed using similar data from a boreal forest in Finland (Laakso et al., 2003) and whether a more parsimonious formulation can be developed. Scavenging coefficients (λ) over an ensemble of 95 rain events (with a median intensity of 1.56 mm h−1) and 104 particle diameter (Dp) classes (from 10 to 400 nm) indicate a mean value of 3.4 × 10−5 s−1 (with a standard error of 1.1 × 10−6 s−1) and a median of 1.9 × 10−5 s−1 (interquartile range: −2.0 × 10−5 to 7.5 × 10−5 s−1). The median scavenging coefficients for Dp: 10–400 nm computed over all 95 rain events exhibit close agreement with the empirical parameterization proposed by (Laakso et al., 2003). They decline from ∼4.1 × 10−5 s−1 for Dp of 10–19 nm, to ∼1.6 × 10−5 s−1 for Dp of 80–113 nm, and show an increasing tendency for Dp > 200 nm.
Keywords: Below-cloud; Particle removal; Wet scavenging; Observational; Aerosol particles;

The Peace River district of Northeastern British Columbia, Canada is a region of natural gas production that has undergone rapid expansion since 2005. In order to assess air quality implications, Willems badge passive diffusive samplers were deployed for six two-week exposure periods between August and November 2013, at 24 sites across the region to assess the ambient concentration of nitrogen dioxide (NO2) and sulfur dioxide (SO2). The highest concentrations of both species (NO2: 9.1 ppb, SO2: 1.91 ppb) during the whole study period (except the 1st exposure period), were observed in Taylor (Site 14), which is consistent with its location near major industrial sources. Emissions from industrial activities, and their interaction with meteorology and topography, result in variations in atmospheric dispersion that can increase air pollution concentrations in Taylor. However, relatively high concentrations of NO2 were also observed near the center of Chetwynd (site F20), indicating the importance of urban emissions sources in the region as well. Observations of both species from the other study sites document the spatial variability and show relatively high concentrations near Fort St. John and Dawson Creek, where unconventional oil and gas development activities are quite high. Although a few sites in Northeastern British Columbia recorded elevated concentrations of NO2 and SO2 during this investigation, the concentrations over the three-month period were well below provincial annual ambient air quality objectives. Nonetheless, given the limited observations in the region, and the accelerated importance of unconventional oil and gas extraction in meeting energy demands, it is imperative that monitoring networks are established to further assess the potential for elevated ambient concentrations associated with industrial emissions sources in the Peace River region.
Keywords: Unconventional oil and gas; Northeastern B.C.; Willems badge; Air quality; Nitrogen dioxide; Sulfur dioxide;

Twelve hour integrated ambient fine particles (PM2.5) were collected over an Van Vihar National Park (VVNP), in Bhopal, Central India. Samples were collected on filter substrates every-other-day for two years (2012 and 2013). In addition to PM2.5 mass concentration, water soluble inorganic ions (WSIIs) were also measured. Further, on-site meteorological parameters including temperature, wind speed, wind direction, relative humidity, rainfall and atmospheric pressure were recorded. During 2012, the average PM2.5 concentration was 40 ± 31 μgm−3 while during 2013 it was 48 ± 50 μgm−3. Further, in about 20% of the samples the 12 h integrated fine PM mass exceeded the daily (24 h) average standards (60 μgm−3). This observation suggests that the PM2.5 mass concentration at the study site is likely to be in violation of the National Ambient Air Quality Standard (NAAQS), India. During the study period the sum of three major ions (SO4 2−, NO3 , and NH4 +) accounted for 19.4% of PM2.5 mass on average. Air parcel back trajectory ensembles revealed that emissions from thermal power plants were likely to be the main regional source of particulate SO4 2− and NO3 measured over VVNP. Further, local traffic activities appeared to have no significant impact on the concentrations of PM2.5 and its WSIIs constituents, as revealed by a day-of-the-week analysis. PM2.5 mass, SO4 2−, NO3 , and NH4 + showed a pronounced seasonal trend with winter (Jan, Feb) and post-monsoon (Oct, Nov, Dec) highs and pre-monsoon (Mar, Apr, May) and monsoon (Jun, Jul, Aug, Sep) lows, during both 2012 and 2013. Further, when the sum of SO4 2− and NO3 constituted greater than 90% of water soluble inorganic anions by mass, they were linearly dependent on one another and moderately anti-correlated (r2 = 0.60). The molar ratios of NH4 + and non-sea salt SO4 2− were examined to understand the aerosol neutralization mechanisms and particulate NO3 formation. An assessment of these ratios and subsequent analyses suggested that in NH4 + rich samples, NO3 and non-sea salt SO4 2− were almost entirely neutralized by NH4 +. In NH4 + poor samples, in addition to NH4 + non-sea salt K+ played a role in acidity neutralization. These observations are unlike those reported for PM10 and total suspended particles (TSP) over other locations in India, where mineral aerosol species (specifically Ca2+) played an important role in neutralizing acidic species. Additionally, both during 2012 and 2013, the aerosol acidity showed a pronounced seasonality - the aerosol was alkaline or near-neutral during the winter and post-monsoon seasons, while during the pre-monsoon and monsoon seasons it was acidic.Display Omitted
Keywords: Van Vihar National Park; Central India; PM2.5 mass; Inorganic ions; Temporal variability; Sulfate; Nitrate and ammonium dependencies; Aerosol acidity;

Temporal variability in the sources and fluxes of CO2 in a residential area in an evergreen subtropical city by L.F. Weissert; J.A. Salmond; J.C. Turnbull; L. Schwendenmann (164-176).
Measurements of CO2 fluxes in temperate climates have shown that urban areas are a net source of CO2 and that photosynthetic CO2 uptake is generally not sufficient to offset local CO2 emissions. However, little is known about the role of vegetation in cities where biogenic CO2 uptake is not limited to a 2–8 months growing season. This study used the eddy covariance technique to quantify the atmospheric CO2 fluxes over a period of 12 months in a residential area in subtropical Auckland, New Zealand, where the vegetation cover (surface cover fraction: 47%) is dominated by evergreen vegetation. Radiocarbon isotope measurements of CO2 were conducted at three different times of the day (06:00–09:00, 12:00–15:00, 01:00–04:00) for four consecutive weekdays in summer and winter to differentiate anthropogenic sources of CO2 (fossil fuel combustion) from biogenic sources (ecosystem respiration, combustion of biofuel/biomass). The results reveal previously unreported patterns for CO2 fluxes, with no seasonal variability and negative (net uptake) CO2 midday fluxes throughout the year, demonstrating photosynthetic uptake by the evergreen vegetation all year-round. The winter radiocarbon measurements showed that 85% of the CO2 during the morning rush hour was attributed to fossil fuel emissions, when wind was from residential areas. However, for all other time periods radiocarbon measurements showed that fossil fuel combustion was not a large source of CO2, suggesting that biogenic processes likely dominate CO2 fluxes at this residential site. Overall, our findings highlight the importance of vegetation in residential areas to mitigate local CO2 emissions, particularly in cities with a climate that allows evergreen vegetation to maintain high photosynthetic rates over winter. As urban areas grow, urban planners need to consider the role of urban greenspace to mitigate urban CO2 emissions.
Keywords: Biogenic CO2; Carbon dioxide fluxes; Eddy covariance; Radiocarbon; Source partitioning; Vegetation;

The horizontal and vertical distributions of aerosol extinction coefficient (AEC) and mass concentration over east China in October 2010 were investigated by using an online-coupled regional climate model and CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations) data. Model performance was evaluated comprehensively against ground observations of meteorological variables and PM10 concentrations and CALIPSO retrieved AEC profiles, which demonstrated a good ability of the model in simulating spatial distribution and evolution of aerosol concentration and optical properties. Severe pollution episodes were found over wide areas of east China during the study period, with the maximum mean PM10 concentration exceeding 200 μg m−3 in the Chongqing district and a part of the lower reaches of the Yellow River on 8–10 October. Both CALIPSO retrievals and model simulations revealed high AEC values (≥1 km−1) often occurred within 2 km above ground over most areas of east China. AEC vertical profile in or in the vicinity of China major cities along CALIPSO orbit track exhibited two typical features: one was AEC reached its maximum (∼4 km−1) near the surface (<200 m) and decreased rapidly to < 0.1 km−1 at altitudes above 1 km, another one was AEC peaked at higher altitudes of about 0.5–1 km with a maximum up to 3 km−1. AEC vertical profile was strongly dependent on vertical distribution of both aerosol concentration, composition and relative humidity. The vertical cross sections over typical regions of east China exhibited a decreasing AEC in magnitude from the continent to the China seas. Over the continent, AEC was either maximum near the surface or peaked at higher altitudes (0.5–1.0 km) due to increases of relative humidity or aerosol concentration in those regions, whereas over the seas of China, AEC profile was characterized by peak values at an altitude around 1 km, mainly due to an elevated relative humidity there, which favored rapid aerosol hygroscopic growth and consequently AEC increase.
Keywords: Online-coupled regional model; CALIPSO; Aerosol extinction coefficient; Aerosol mass concentration; Vertical distribution; East China;

The statistical impact of including the process of wet deposition in dispersion model predictions of the movement of volcanic ash is assessed. Based on hypothetical eruptions of Merapi, Indonesia, sets of dispersion model simulations were generated, each containing four simulations per day over a period of three years, to provide results based on a wide range of atmospheric conditions. While on average dry sedimentation removes approximately 10% of the volcanic ash from the atmosphere during the first 24 h, wet deposition removes an additional 30% during seasons with highest rainfall (December and January) but only an additional 1% during August and September. The majority of the wet removal is due to in-cloud rather than below-cloud collection of volcanic ash particles. The largest uncertainties in the amount of volcanic ash removed by the process of wet deposition result from the choice of user-defined parameters used to compute the scavenging coefficient, and from the definition of the cloud top height. Errors in the precipitation field provided by the numerical weather prediction model utilised here have relatively less impact.Display Omitted
Keywords: Volcanic ash; Wet deposition; Dispersion modelling; HYSPLIT; Merapi; Indonesia;

Calibration of polydimethylsiloxane and XAD-Pocket passive air samplers (PAS) for measuring gas- and particle-phase SVOCs by Joseph O. Okeme; Amandeep Saini; Congqiao Yang; Jiping Zhu; Foppe Smedes; Jana Klánová; Miriam L. Diamond (202-208).
Polydimethylsiloxane (PDMS) has seen wide use as the stationary phase of gas chromatographic columns, a passive sampler in water, and recently as a personal exposure sampler, while styrene divinyl-benzene copolymer (XAD) has been used extensively as a passive air sampler outdoors and indoors. We have introduced PDMS and XAD-Pocket as new indoor passive air samplers (PASs). The XAD-Pocket was designed to maximize the surface area-to-volume ratio of XAD and to minimize obstruction of air flow by the sampler housing. Methods were developed to expedite the use of these PASs for measuring phthalates, novel brominated flame-retardants (NFRs) and polybrominated diphenyl ethers (PBDEs) indoors. Sampling rates, Rs, (m3 day−1), were measured during a 7-week calibration study. Variability within and between analyte groups was not statistically significant. As a result, generic values of 0.8 ± 0.4 and 0.5 ± 0.3 m3 day−1 dm−2 are recommended for PDMS and XAD-Pocket for a 50-day deployment time, respectively. PDMS has a higher uptake rate and is easier to use than XAD-Pocket.
Keywords: Passive sampling; Calibration; PDMS; XAD-Pocket; Phthalates; Flame-retardants;

Source profiles are essential for quantifying the role of volatile organic compound (VOC) emissions in air pollution. This study compiled a database of VOC source profiles in China, with 75 species drawn from five major categories: transportation, solvent use, biomass burning, fossil fuel burning, and industrial processes. Source profiles were updated for diesel vehicles, biomass burning, and residential coal burning by measuring both hydrocarbons and oxygenated VOCs (OVOCs), while other source profiles were derived from the available literature. The OVOCs contributed 53.8% of total VOCs in the profiles of heavy - duty diesel vehicle exhaust and 12.4%–46.3% in biomass and residential coal burning, which indicated the importance of primary OVOCs emissions from combustion-related sources. Taking the national emission inventory from 2008 as an example, we established an approach for assigning source profiles to develop a speciation-specific VOC and OVOC emission inventory. The results showed that aromatics contributed 30% of the total 26 Tg VOCs, followed by alkanes (24%), alkenes (19%) and OVOCs (12%). Aromatics (7.9 Tg) were much higher than in previous results (1.1 Tg and 3.4 Tg), while OVOCs (3.1 Tg) were comparable with the 3.3 Tg and 4.3 Tg reported in studies using profiles from the US. The current emission inventories were built based on emission factors from non-methane hydrocarbon measurements, and therefore the proportions from OVOC emissions was neglected, leading to up to 30% underestimation of total VOC emissions. As a result, there is a need to deploy appropriate emission factors and source profiles that include OVOC measurements to reduce the uncertainty of estimated emissions and chemical reactivity potential.
Keywords: VOC; OVOC; Source profile; Speciated emission inventory; China;

We investigate the relationship between synoptic/local meteorological patterns and PM10 air pollution levels in the metropolitan area of Naples, Italy. We found that severe air pollution crises occurred when the 850 and 500 hpa geopotential heights and their relative temperatures present maximum values above the city. The most relevant synoptic parameter was the 850 hPa geopotential height, which is located about 1500 m of altitude. We compared local meteorological conditions (specifically wind stress, rain amount and thermal inversion) against the urban air pollution levels from 2009 to 2013. We found several empirical criteria for forecasting high daily PM10 air pollution levels in Naples. Pollution crises occurred when (a) the wind stress was between 1 and 2 m/s, (b) the thermal inversion between two strategic locations was at least 3°C/200 m and (c) it did not significantly rain for at least 7 days. Beside these meteorological conditions, severe pollution crises occurred also during festivals when fireworks and bonfires are lighted, and during anomalous breeze conditions and severe fire accidents. Finally, we propose a basic model to predict PM10 concentration levels from local meteorological conditions that can be easily forecast a few days in advance. The synthetic PM10 record predicted by the model was found to correlate with the PM10 observations with a correlation coefficient close to 0.80 with a confidence level greater than 99%. The proposed model is expected to provide reliable information to city officials to carry out practical strategies to mitigate air pollution effects. Although the proposed model equation is calibrated on the topographical and meteorological conditions of Naples, it should be easily adaptable to alternative locations.
Keywords: PM10 metropolitan air pollution; 850 and 500 geopotential height; Local meteorological parameters; Air pollution modeling and forecast;

A new visibility measurement system based on a black target and a comparative trial with visibility instruments by Fanjie Tang; Shuqing Ma; Ling Yang; Chuanyao Du; Yingjie Tang (229-236).
According to Koschmieder's law, a mathematical model of contrast between a single black object and the sky background is established. Based on this principle, we built a black target visiometer system using a photograph of a black object taken with an industrial camera, that has a relatively simple structure and automated operation. In this study, three commercial visibility instruments–a forward scatter meter (CJB-3A) and two atmospheric transmission meters (LT31, VM100)–were compared to the black target visiometer system. Our results show that, within visibility ranges of up to 10 km, 1) all of the instruments agree well at low visibility and agree poorly at a visibility exceeding 5 km; 2) the forward scattering instrument has high bias at low visibility because particle absorption is not included; and 3) the best agreement with the black target method was obtained with the simple transmissometer rather than the forward scatter instrument or the hybrid transmissometer for a visibility range of up to 10 km.
Keywords: Visibility; Black object; Industrial camera; Black target visiometer system;

Evaluating stomatal ozone fluxes in WRF-Chem: Comparing ozone uptake in Mediterranean ecosystems by J.H. Rydsaa; F. Stordal; G. Gerosa; A. Finco; Ø. Hodnebrog (237-248).
The development of modelling tools for estimating stomatal uptake of surface ozone in vegetation is important for the assessment of potential damage induced due to both current and future near surface ozone concentrations. In this study, we investigate the skill in estimating ozone uptake in plants by the Weather Research and Forecasting model coupled with chemistry (WRF-Chem) V3.6.1, with the Wesely dry deposition scheme. To validate the stomatal uptake of ozone, the model simulations were compared with field measurements of three types of Mediterranean vegetation, over seven different periods representing various meteorological conditions. Some systematic biases in modelled ozone fluxes are revealed; the lack of an explicit and time varying dependency on plants’ water availability results in overestimated daytime ozone stomatal fluxes particularly in dry periods. The optimal temperature in the temperature response function is likely too low for the woody species tested here. Also, too low nighttime stomatal conductance leads to underestimation of ozone uptake during night. We demonstrate that modelled stomatal ozone flux is improved by accounting for vapor pressure deficit in the ambient air. Based on the results of the overall comparison to measured fluxes, we propose that additional improvements to the stomatal conductance parameterization should be implemented before applying the modelling system for estimating ozone doses and potential damage to vegetation.
Keywords: Ozone; WRF-Chem; Wesely; Dry deposition; Ozone flux; Vegetation; Ozone uptake;

Chemical and morphological characterization of TSP and PM2.5 by SEM-EDS, XPS and XRD collected in the metropolitan area of Monterrey, Mexico by Lucy T. González; F.E.Longoria Rodríguez; M. Sánchez-Domínguez; C. Leyva-Porras; L.G. Silva-Vidaurri; Karim Acuna-Askar; B.I. Kharisov; J.F. Villarreal Chiu; J.M. Alfaro Barbosa (249-260).
Total suspended particles (TSP) and particles smaller than 2.5 μm (PM2.5) were collected at four sites in the metropolitan area of Monterrey (MAM) in Mexico. The samples were characterized by X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), and Scanning Electron Microscopy (SEM). In order to determine the possible sources of emissions of atmospheric particulate matter, a principal component analysis (PCA) was performed. The XRD results showed that the major crystalline compounds found in the TPS were CaCO3 and SiO2; while in the PM2.5 CaSO4 was found. The XPS analysis showed that the main elements found on the surface of the particles were C, O, Si, Ca, S, and N. The deconvolution carried out on the high-resolution spectra for C1s, S2p and N1s, showed that the aromatics, sulfates and pyrrolic-amides were the main groups contributing to the signal of these elements, respectively. The C-rich particles presented a spherical morphology, while the Ca- and Si-based particles mostly showed a prismatic shape. The PCA analysis together with the results obtained from the characterization techniques, suggested that the main contributors to the CaCO3 particles collected in the PM were most probably produced and emitted into the atmosphere by local construction industries and exploitation of rich-deposits of calcite. Meanwhile, the SiO2 found in the MAM originated from the suspension of geological material abundant in the region, and the carbon particles were mainly produced by the combustion of fossil fuels.Display Omitted
Keywords: Total suspended particles; X-ray photoelectron spectroscopy; Anthropogenic sources;

Face the large electricity demand, thermal power generation still derives the main way of electricity supply in China, account for 78.19% of total electricity production in 2013. Three types of thermal power plants, including coal-fired power plant, coal gangue-fired power plant and biomass-fired power plant, were chosen to survey the source profile, chemical reactivity and emission factor of VOCs during the thermal power generation. The most abundant compounds generated during coal- and coal gangue-fired power generation were 1-Butene, Styrene, n-Hexane and Ethylene, while biomass-fired power generation were Propene, 1-Butenen, Ethyne and Ethylene. The ratios of B/T during thermal power generation in this study was 0.8–2.6, which could be consider as the characteristics of coal and biomass burning. The field tested VOCs emission factor from coal-, coal gangue- and biomass-fired power plant was determined to be 0.88, 0.38 and 3.49 g/GJ, or showed as 0.023, 0.005 and 0.057 g/kg, with the amount of VOCs emission was 44.07, 0.08, 0.45 Gg in 2013, respectively. The statistical results of previous emission inventory, which calculated the VOCs emission used previous emission factor, may overestimate the emission amount of VOCs from thermal power generation in China.
Keywords: Volatile organic compounds; Thermal power generation; Sources profile; Ozone formation potential; Emission factor;

Developing QSPR model of gas/particle partition coefficients of neutral poly-/perfluoroalkyl substances by Quan Yuan; Guangcai Ma; Ting Xu; Bakire Serge; Haiying Yu; Jianrong Chen; Hongjun Lin (270-277).
Poly-/perfluoroalkyl substances (PFASs) are a class of synthetic fluorinated organic substances that raise increasing concern because of their environmental persistence, bioaccumulation and widespread presence in various environment media and organisms. PFASs can be released into the atmosphere through both direct and indirect sources, and the gas/particle partition coefficient (K P) is an important parameter that helps us to understand their atmospheric behavior. In this study, we developed a temperature-dependent predictive model for log K P of PFASs and analyzed the molecular mechanism that governs their partitioning equilibrium between gas phase and particle phase. All theoretical computation was carried out at B3LYP/6-31G (d, p) level based on neutral molecular structures by Gaussian 09 program package. The regression model has a good statistical performance and robustness. The application domain has also been defined according to OECD guidance. The mechanism analysis shows that electrostatic interaction and dispersion interaction play the most important role in the partitioning equilibrium. The developed model can be used to predict log K P values of neutral fluorotelomer alcohols and perfluor sulfonamides/sulfonamidoethanols with different substitutions at nitrogen atoms, providing basic data for their ecological risk assessment.Display Omitted
Keywords: Perfluoroalkyl compounds; Polyfluoroalkyl compounds; Gas/particle partition coefficients; K P; QSPR; Molecular structural descriptors;

Study on the influence of ground and satellite observations on the numerical air-quality for PM10 over Romanian territory by Rodica Claudia Dumitrache; Amalia Iriza; Bogdan Alexandru Maco; Cosmin Danut Barbu; Marcus Hirtl; Simone Mantovani; Oana Nicola; Anisoara Irimescu; Vasile Craciunescu; Alina Ristea; Andrei Diamandi (278-289).
The numerical forecast of particulate matter concentrations in general, and PM10 in particular is a theme of high socio-economic relevance. The aim of this study was to investigate the impact of ground and satellite data assimilation of PM10 observations into the Weather Research and Forecasting model coupled with Chemistry (WRF-CHEM) numerical air quality model for Romanian territory. This is the first initiative of the kind for this domain of interest. Assimilation of satellite information – e.g. AOT's in air quality models is of interest due to the vast spatial coverage of the observations. Support Vector Regression (SVR) techniques are used to estimate the PM content from heterogeneous data sources, including EO products (Aerosol Optical Thickness), ground measurements and numerical model data (temperature, humidity, wind, etc.). In this study we describe the modeling framework employed and present the evaluation of the impact from the data assimilation of PM10 observations on the forecast of the WRF-CHEM model. Integrations of the WRF-CHEM model in data assimilation enabled/disabled configurations allowed the evaluation of satellite and ground data assimilation impact on the PM10 forecast performance for the Romanian territory. The model integration and evaluation were performed for two months, one in winter conditions (January 2013) and one in summer conditions (June 2013).
Keywords: Air quality modeling; WRF-CHEM; PM10; Ground and satellite data assimilation;

Scripted drives: A robust protocol for generating exposures to traffic-related air pollution by Allison P. Patton; Robert Laumbach; Pamela Ohman-Strickland; Kathy Black; Shahnaz Alimokhtari; Paul J. Lioy; Howard M. Kipen (290-299).
Commuting in automobiles can contribute substantially to total traffic-related air pollution (TRAP) exposure, yet measuring commuting exposures for studies of health outcomes remains challenging. To estimate real-world TRAP exposures, we developed and evaluated the robustness of a scripted drive protocol on the NJ Turnpike and local roads between April 2007 and October 2014. Study participants were driven in a car with closed windows and open vents during morning rush hours on 190 days. Real-time measurements of PM2.5, PNC, CO, and BC, and integrated samples of NO2, were made in the car cabin. Exposure measures included in-vehicle concentrations on the NJ Turnpike and local roads and the differences and ratios of these concentrations. Median in-cabin concentrations were 11 μg/m3 PM2.5, 40 000 particles/cm3, 0.3 ppm CO, 4 μg/m3 BC, and 20.6 ppb NO2. In-cabin concentrations on the NJ Turnpike were higher than in-cabin concentrations on local roads by a factor of 1.4 for PM2.5, 3.5 for PNC, 1.0 for CO, and 4 for BC. Median concentrations of NO2 for full rides were 2.4 times higher than ambient concentrations. Results were generally robust relative to season, traffic congestion, ventilation setting, and study year, except for PNC and PM2.5, which had secular and seasonal trends. Ratios of concentrations were more stable than differences or absolute concentrations. Scripted drives can be used to generate reasonably consistent in-cabin increments of exposure to traffic-related air pollution.
Keywords: Car commute; In-cabin; Traffic-related air pollution; In-vehicle exposures; Particulate matter; Nitrogen oxides;

A field measurement based scaling approach for quantification of major ions, organic carbon, and elemental carbon using a single particle aerosol mass spectrometer by Yang Zhou; X.H. Hilda Huang; Stephen M. Griffith; Mei Li; Lei Li; Zhen Zhou; Cheng Wu; Junwang Meng; Chak K. Chan; Peter K.K. Louie; Jian Zhen Yu (300-312).
Single Particle Aerosol Mass Spectrometers (SPAMS) have been increasingly deployed for aerosol studies in Asia. To date, SPAMS is most often used to provide unscaled information for both the size and chemical composition of individual particles. The instrument's lack of accuracy is primarily due to only a fraction of particles being detected after collection, and the instrumental sensitivity is un-calibrated for various chemical species in mixed ambient aerosols. During a campaign from January to April 2013 at a coastal site in Hong Kong, the particle number information and ion intensity of major PM2.5 components collected by SPAMS were scaled by comparing with collocated bulk PM2.5 measurements of hourly or higher resolution. The bulk measurements include PM2.5 mass by a SHARP 5030 Monitor, major ions by a Monitor for Aerosols & Gases in ambient Air (MARGA), and organic carbon (OC) and elemental carbon (EC) by a Sunset OCEC analyzer. During the data processing, both transmission efficiency (scaled with the Scanning Mobility Particle Sizer) and hit efficiency conversion were considered, and component ion intensities quantified as peak area (PA) and relative peak area (RPA) were analyzed to track the performance. The comparison between the scaled particle mass assuming a particle density of 1.9 g cm−3 from SPAMS and PM2.5 concentration showed good correlation (R2 = 0.81) with a slope of 0.814 ± 0.004. Regression analysis results suggest an improved scaling performance using RPA compared with PA for most of the major PM2.5 components, including sulfate, nitrate, potassium, ammonium, OC and EC. Thus, we recommend preferentially scaling these species using the RPA. For periods of high K+ concentrations (>1.5 μg m−3), under-estimation of K+ by SPAMS was observed due to exceeding the dynamic range of the acquisition board. When only applying the hit efficiency correction, data for sulfate, nitrate, ammonium, potassium and OC were in reasonably good correlation (R2 = 0.56–0.79) with the bulk measurements, suggesting semi-quantified data by the hit efficiency correction can be utilized when transmission efficiency correction is not available. More inter-comparisons of this type are needed to assess the inter-instrument variability among different SPAMS instruments.
Keywords: Single particle; PM2.5; Laser ionization; Scaling factor; Ions; OCEC;