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Atmospheric Environment (v.40, #3)
Continuous weeklong measurements of personal exposures and indoor concentrations of fine particles for 37 health-impaired North Carolina residents for up to four seasons
by Lance Wallace; Ron Williams; Anne Rea; Carry Croghan (pp. 399-414).
A study of personal exposures and indoor and outdoor concentrations of particles was carried out in 2000–2001 for 37 health-impaired residents of North Carolina. Earlier papers have dealt with the 24-h integrated gravimetric samples; this report adds the continuous data (1-min resolution) using optical scattering devices (personal data RAMs, or pDRs) for personal and indoor measurements. Subjects and their households were sampled for 7 consecutive days in each of four seasons, although not all subjects completed all four seasons. Each subject completed an activity diary with 15-min resolution on each day giving his or her presence in one of six locations and describing activities with the potential for increased exposure to particles. More than 800 person-days and 1.1×106person-min of valid personal exposures and indoor air concentrations were collected.The pDRs compared well with the PM2.5 gravimetric devices, with an R2 of 87% compared to the indoor Harvard impactor (HI), and 70% compared to the personal exposure monitor (PEM). As found in previous studies, (and as expected due to the calibration of these devices with an aerosol of higher density than normal ambient and indoor aerosols), the pDRs overestimated the gravimetric concentrations by 20–50%. Because the correction factor varied by season and by type of sample (indoor vs. personal), no overall correction factor could be applied. The estimated mean increases in exposure during three common activities (cooking, cleaning, and personal care) were 56, 28, and 20μgm−3, respectively. Several less common activities, such as burning food and using a fireplace were found to result occasionally in very high (>1500μgm−3) short-term peaks of exposure. Although households with smoking were ineligible for participation, two households did have significant smoking, and had the highest average personal exposures and indoor concentrations of all the study homes. The diurnal variation of personal exposures and indoor concentrations was bimodal, with peaks occurring between 10 and 11 AM and 5 and 6 PM. The “damping effect� of the home due to air exchange caused the infiltrated outdoor particles to show only a unimodal variation, with a single broad and mild peak occurring between 6 and 10 AM.A method for identifying peak concentrations due to indoor sources and personal activities was developed. Peaks due to personal activities and indoor sources occurred about 23% and 14% of the time, respectively. On average, outdoor particles contributed about half of the total personal exposures and indoor concentrations, but there was wide variation across subjects. These findings using the MIE data were then compared to previously published estimates using measurements of sulfur from the gravimetric data; good agreement ( R2 values from 50% to 65%) was found, providing a measure of validation to both methods. Personal exposures exceeded co-located indoor concentrations by 2–3μgm−3, confirming findings of a small but statistically significant “personal cloud� for PM2.5 made in previous studies using gravimetric 24-h integrating monitors.
Keywords: Personal DataRAM; pDR; PM; 2.5; Cooking; Personal cloud; Optical scattering
Modelling subgrid scale dry deposition velocity of O3 over the Swedish west coast with MM5-PX model
by J.-F. Miao; D. Chen; K. Wyser (pp. 415-429).
A mesoscale meteorological model (MM5) coupled with an advanced land surface model (PX LSM) is used in this study to model high-resolution (2km) dry deposition velocity of ozone over the Swedish west coast, together with a newly revised dry deposition parameterization for air-quality models with emphasis on non-stomatal resistance. The important air-surface exchange processes for air quality (surface fluxes of heat, moisture and momentum) are also simulated by this model. The modelled subgrid scale variability of the dry deposition velocity and its dependence on land use, terrain height and synoptic conditions are investigated. It is found that a systematic difference in the deposition velocity modelled by different resolutions exists, and the difference varies diurnally and daily. The subgrid scale variation is significant, which has a clear impact on the area-averaged deposition velocity. The deposition velocity depends strongly on land use and weather conditions, but not on topography for the area studied. Meteorological conditions at subgrid scales play an important role in determining the deposition velocity. It is also concluded that the dry deposition velocity simulated in this study is reasonable, and that a 6-km resolution would be practically good enough to resolve the inhomogeneity of the surface properties for dry deposition studies in this area. The variation range of dry deposition velocity over different land use categories and the corresponding resistances are outlined. Moreover, the difference in the estimated dry deposition velocitiy between the methods using fractional land use and using dominant land use is compared.
Keywords: Mesoscale meteorological model; Land surface model; Dry deposition; Non-stomatal resistance; Air-surface exchange
Vertical distributions of particles and sulfur gases (volatile sulfur compounds and SO2) over East Asia: Comparison with two aircraft-borne measurements under the Asian continental outflow in spring and winter
by Yayoi Inomata; Yasunobu Iwasaka; Kazuo Osada; Masahiko Hayashi; Ikuko Mori; Mizuka Kido; Keiichiro Hara; Tetsu Sakai (pp. 430-444).
We have presented the vertical distributions, between 0.5 and 5.5km, of particles, volatile sulfur compounds, sulfur dioxide, O3, and fractions of sulfur over the Japan Sea coast, Wakasa Bay, on 23 April 1996 and 28 December 1995. Comparison of these measurements showed that free tropospheric concentrations of particles and short-lived sulfur gases (CS2, H2S, SO2) on 23 April 1996 were significantly higher than those on 28 December 1995. Clustered isentropic backward trajectory analysis and meteorological data indicated that the difference was associated with air mass transport routes and meteorological conditions. On 23 April 1996, coarse size particles (mineral dust particles) were injected over the arid region associated with dust storms. During transport by westerly winds, these coarse size particles were mixed with short-lived sulfur gases injected by convection over an industrial region. The presence of DMS, confined to the boundary layer, indicated that Asian continental outflow can be modified during long-range transport through mixing with marine air in the boundary layer over the Japan Sea. On the other hand, on 28 December 1995, low concentrations of particles and short-lived sulfur gases, measured at altitudes above 3.0km, were due to air mass subsidence. It is likely that some photochemical processing was also due to low concentrations of short-lived sulfur gases.Vertical distributions of O3 concentrations and values of sulfur fraction (SO42−/(SO42−+SO2)) supported this interpretation. There was no significant difference in concentrations of long-lived COS, except for one sample on 23 April 1996. The low COS concentration coincided with significantly high concentrations of CS2, suggesting rapid upward transport of COS depleted air masses from the surface.
Keywords: Particles; Sulfur gases; Weak KOSA; Long-range transport; Vertical distribution
Retrieval of black carbon and specific absorption over Kanpur city, northern India during 2001–2003 using AERONET data
by Sagnik Dey; S.N. Tripathi; Ramesh P. Singh; B.N. Holben (pp. 445-456).
Column-integrated aerosol black carbon (BC) concentration, [BC] has been retrieved over Kanpur (an industrial city in the Gangetic basin, northern India) during 2001–2003 for the first time. [BC] is derived from BC volume fraction and AERONET-retrieved size distribution using Maxwell–Garnett and Bruggeman mixing rules in a mixture of water, BC and (NH4)2SO4. In addition partly absorbing components like organic carbon (OC) and dust are added to the Maxwell–Garnett mixture depending on the season to investigate their role in the retrieval of [BC]. The volume fraction of each component is retrieved by matching the mixture refractive index (real, n( λ) and imaginary, k( λ)) with AERONET-retrieved refractive index. [BC] shows seasonal variations with high values (>10mgm-2) observed during the post-monsoon and winter seasons and low values (<6mgm-2) during the monsoon season. Specific absorption cross-section ( αa) decreases non-linearly with the increase in [BC], however, the decrease becomes linear when other absorbing components are present. Yearly averaged [BC] and αa are 9.99±1.95, 5.52±1.07, 7.9±1.53mgm−2 and 7.9±1.83 and 9.67±3.45, 12.74±2.92m2g−1 for 2001, 2002 and 2003, respectively, using Maxwell–Garnett mixing, which differ by ∼15% from those using Bruggeman mixing. [BC] shows diurnal variation with morning and afternoon peaks and mid-day minimum. The amplitude is subdued as it represents the total column, which is more influenced by anthropogenic activities than by boundary layer dynamics. In order to estimate [BC] accurately, OC has to be considered when the absolute difference between k(0.44μm) and k(1.02μm) becomes higher than 0.0015. The sensitivity of [BC] due to dust n( λ) becomes important during the intense dust loading period. It was found that [BC] is more sensitive to dust k( λ) than dust n( λ), as [BC] increases ∼10–13% for 10% rise in k( λ). Retrieved [BC] shows good agreement with the in situ measurements. Therefore our retrieval can be used as an alternate method to infer BC and OC specific absorption globally.
Keywords: Aerosols; Black carbon; Specific absorption; Internal mixing; Effective medium approximation
Modeling particle deposition from fully developed turbulent flow in ventilation duct
by Bin Zhao; Jun Wu (pp. 457-466).
This paper proposes an improved Eulerian model to predict particle deposition velocity in fully developed turbulent duct flow. The model is modified based on the three-layer model by Lai and Nazaroff (Journal of Aerosol Science, 31, 463–476, 2000), accounting for turbophoresis as well as Brownian diffusion, turbulent diffusion and gravitational settling. An expression relating the turbophoretic velocity to particle relaxation time, friction velocity and the normal distance to the wall surface is presented to model the turbophoresis. Similar with previous one by Lai and Nazaroff, the model only needs to input friction velocity, which makes it easy to apply. The predicted results agree well with measurement data for floor and vertical walls.And then deposition velocity of airborne particles to smooth walls in straight steel ducts is predicted by the modified model. The results agree with the published measured data, especially for floor and vertical walls of ventilation duct. Thus it is expected to be applied for predicting particle deposition in ventilation duct for indoor air quality control or evaluation. Furthermore, the condition to ignore turbophoresis for particle deposition is discussed by comparing the results of the improved model and that of Lai and Nazaroff.
Keywords: Aerosol; Particle; Deposition; Ventilation duct; Indoor air quality (IAQ)
Densities of liquidH+/NH4+/SO42-/NO3-/H2O solutions at tropospheric temperatures
by Micha Semmler; Bei Ping Luo; Thomas Koop (pp. 467-483).
Densities of liquid aqueous solutions of the systemH+/NH4+/SO42-/NO3-/H2O have been determined experimentally at temperatures between 243 and 353K for total solute mass fractions up to 0.6. The new density data, together with additional data from the literature, have been evaluated using a semi-empirical model that is based on a partial molar volume approach. With this model densities of multicomponent solutions can be predicted from parameters determined from binary solutions of the corresponding solutes. Model predictions for ternary or quaternary solutions agree with experimental data to about one percent. The advantages of our approach are that the model can be extended to include additional solutes without a re-parameterization of the existing binary parameters, and that it allows extrapolation to temperatures of the upper troposphere and lower stratosphere.
Keywords: Density; Aerosols; Inorganic aqueous solutions
Three-dimensional pollutant concentration dispersion of a vehicular exhaust plume in the real atmosphere
by J.S. Wang; T.L. Chan; C.S. Cheung; C.W. Leung; W.T. Hung (pp. 484-497).
The pollutant dispersion process from the vehicular exhaust plume has a direct impact on human health, particularly on vehicle drivers and passengers, bicyclists, motorcyclists, pedestrians and people working nearby. A three-dimensional vehicular pollutant dispersion numerical model was developed based on the Reynolds-averaged Navier–Stokes equations coupled with ak–ε turbulence model to simulate the initial pollutant dispersion process of carbon monoxide, CO, from a vehicular exhaust plume in the real atmospheric environment. Since the ambient wind direction and velocity are stochastic and uncontrollable in the real atmospheric environment, a wind-direction–frequency-weighted (WDFW) approach was used to obtain the real pollutant concentration dispersion along with the development of the vehicular exhaust plume. Within the specified sampling period, the ambient windflow conditions are transformed into the corresponding frequencies of wind directions and averaged magnitudes of wind velocities from directions N, E, S or W. Good agreement between the calculated and measured data for two diesel-fuelled vehicles indicates that with the WDFW approach the initial dispersion of pollutant concentration from a vehicular exhaust plume in the real atmospheric environment can be truly reflected. The present study shows that the dispersion process in the near region for the relative concentration of CO, fromRC=0.1 (or 10%) to 1 (or 100%), is less influenced by the ambient wind velocity than by the vehicular exhaust velocity, but it is vice versa in the far region fromRC=0 (or 0%) to 0.1 (or 10%). It implies that the effect of vehicular exhaust exit velocity on the dispersion process is more pronounced than that of ambient wind velocity at the vicinity of the exhaust tailpipe exit, while the effect of ambient wind velocity gradually shows a significant role for the dispersion process along with the development of a vehicular exhaust plume.
Keywords: Vehicular exhaust plume dispersion model; Carbon monoxide; Wind-direction–frequency-weighted (WDFW) approach; Numerical simulation
Heathland vegetation as a bio-monitor for nitrogen deposition and source attribution using δ15N values
by R.A. Skinner; P. Ineson; H. Jones; D. Sleep; I.D. Leith; L.J. Sheppard (pp. 498-507).
The %N and δ15N signals in foliar nitrogen (N) from four heathland species have been monitored in a blanket bog plant community subjected to different experimental inputs of wet and dry N deposition. Interactions with combined additional treatments of phosphorus (P) and potassium (K) were also investigated. Calluna vulgaris, Cladonia portentosa, Sphagnum capillifolium and Hypnum cupressiforme were harvested for15N analysis prior to wet and dry treatment applications and again after 16 months field exposure. A significant increase was observed in both %N and δ15N values for all plant species in response to both wet and dry treatments whilst PK additions also produced significant decreases in foliar %N and associated δ15N values for several of the species sampled. These enrichments in the δ15N signals for post-treatment shoot tissue were attributable to the δ15N signal in the source application, a finding of potential value in using bio-monitors for assessment of N deposition.
Keywords: Calluna; Cladonia; Hypnum; Sphagnum; Delta 15N; Ammonia release; Whim Moss
Lanthanum and lanthanides in atmospheric fine particles and their apportionment to refinery and petrochemical operations in Houston, TX
by Pranav Kulkarni; Shankararaman Chellam; Matthew P. Fraser (pp. 508-520).
A study was conducted in Houston, TX focusing on rare earth elements (REEs) in atmospheric fine particles and their sources. PM2.5 samples were collected from an ambient air quality monitoring site (HRM3) located in the proximity of a large number of oil refineries and petrochemical industries to estimate the potential contributions of emissions from fluidized-bed catalytic cracking operations to ambient fine particulate matter. The elemental composition of ambient PM2.5, several commercially available zeolite catalysts, and local soil was measured after microwave assisted acid digestion using inductively coupled plasma—mass spectrometry. Source identification and apportionment was performed by principal component factor analysis (PCFA) in combination with multiple linear regression. REE relative abundance sequence, ratios of La to light REEs (Ce, Pr, Nd, and Sm), and enrichment factor analysis indicated that refining and petrochemical cat cracking operations were predominantly responsible for REE enrichment in ambient fine particles. PCFA yielded five physically meaningful PM2.5 sources: cat cracking operations, a source predominantly comprised of crustal material, industrial high temperature operations, oil combustion, and sea spray. These five sources accounted for 82% of the total mass of atmospheric fine particles (less carbon and sulfate). Factor analysis confirmed that emissions from cat cracking operations primarily contributed to REE enrichment in PM2.5 even though they comprised only 2.0% of the apportioned mass. Results from this study demonstrate the need to characterize catalysts employed in the vicinity of the sampling stations to accurately determine local sources of atmospheric REEs.
Keywords: Rare earth elements; PM; 2.5; ICP-MS; Factor analysis; Catalyst; Industrial emissions
Regional variations in wet and dry deposition fluxes of trace elements in Japan
by Masahiro Sakata; Kohji Marumoto; Masahiro Narukawa; Kazuo Asakura (pp. 521-531).
The annual wet and dry deposition fluxes of 12 trace elements (i.e., As, Cd, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se and V) were measured on the basis of 1 year of observations (December 2003–November 2004) at 10 sites in Japan. Precipitation and dry deposition (gases and particles) samples were collected every half month using an automatic sampler, which is composed of a precipitation sampler and a water surface sampler for dry deposition. The wet deposition fluxes of Hg, Pb and Se exceeded their dry deposition fluxes at most sites. In contrast, the dry deposition fluxes of Cr, Cu, Mn, Mo, Ni and V were significantly higher than their wet deposition fluxes. The annual wet deposition fluxes of trace elements except for Cu, Mo and Ni were correlated with the annual precipitation amount (P<0.05). In particular, about 70–80% of the variance of the wet deposition fluxes for Hg (r2=0.80), Sb (r2=0.68) and V (r2=0.80) was explained using the precipitation amount. The wet deposition fluxes of As, Cd, Pb and Se at sites on the Japan Sea coast tended to be higher than those expected from the precipitation amount. This suggests a large contribution of their long-range transport from the Asian continent. On the other hand, the regional variations in the dry deposition fluxes of the trace elements were different from those in the wet deposition fluxes. A markedly higher dry deposition fluxes were observed at sites in industrial and urban areas. The relatively high dry deposition fluxes of Cr, Cu, Mn, Ni and Pb suggest that these elements are mainly from electric steel furnaces near the sites, because they are abundant in furnace emission particles. The results of lead isotope analyses indicate that the lead isotope ratios in the dry deposition samples at industrial and urban sites are different from those at other sites. This implies that lead dry deposition at such sites is dominated by emissions from peculiar sources, although whether those sources are the electric steel furnaces is unknown.
Keywords: Bulk deposition; Mercury; Asian continent; Lead isotope ratios; Water surface sampler
A competitive neural network approach for meteorological situation clustering
by Ignacio J. Turias; Gonzalez Francisco J. González; Martin M Luz Martín; Pedro L. Galindo (pp. 532-541).
A complete competitive scheme is proposed in this work in order to perform a classification analysis of meteorological data in the ‘Campo de Gibraltar’ region (in the South of Spain) from 1999 to 2002. The main objectives of the study presented here have been the characterization of the meteorological conditions in the area, using a competitive neural network based on Kohonen learning rule. Standard Principal Component Analysis (PCA) and VARIMAX rotation have allowed interpreting the physical meaning of the classes obtained from the competitive scheme. Quantitative (using three quality indices) and qualitative (from the analysis of the data projection) criteria based on Fisher Discriminant Analysis were introduced to verify the results of the clustering. A randomized procedure is developed to assure the best performance of the models and to select the best model in the experiments. The different experiments developed extracted five classes, which were related to typical meteorological conditions in the area.
Keywords: Artificial intelligence; Cluster analysis; Automated meteorological classification; Artificial neural network; Multivariate techniques
Predicting long-term average concentrations of traffic-related air pollutants using GIS-based information
by Matthias Hochadel; Joachim Heinrich; Ulrike Gehring; Verena Morgenstern; Thomas Kuhlbusch; Elke Link; H.-E. H.-Erich Wichmann; Kramer Ursula Krämer (pp. 542-553).
Global regression models were developed to estimate individual levels of long-term exposure to traffic-related air pollutants. The models are based on data of a one-year measurement programme including geographic data on traffic and population densities. This investigation is part of a cohort study on the impact of traffic-related air pollution on respiratory health, conducted at the westerly end of the Ruhr-area in North-Rhine Westphalia, Germany.Concentrations of NO2, fine particle mass (PM2.5) and filter absorbance of PM2.5 as a marker for soot were measured at 40 sites spread throughout the study region. Fourteen-day samples were taken between March 2002 and March 2003 for each season and site. Annual average concentrations for the sites were determined after adjustment for temporal variation.Information on traffic counts in major roads, building densities and community population figures were collected in a geographical information system (GIS). This information was used to calculate different potential traffic-based predictors: (a) daily traffic flow and maximum traffic intensity of buffers with radii from 50 to 10000m and (b) distances to main roads and highways.NO2 concentration and PM2.5 absorbance were strongly correlated with the traffic-based variables. Linear regression prediction models, which involved predictors with radii of 50 to 1000m, were developed for the Wesel region where most of the cohort members lived. They reached a model fit ( R2) of 0.81 and 0.65 for NO2 and PM2.5 absorbance, respectively. Regression models for the whole area required larger spatial scales and reachedR2=0.90 and 0.82. Comparison of predicted values with NO2 measurements at independent public monitoring stations showed a satisfactory association (r=0.66). PM2.5 concentration, however, was only slightly correlated and thus poorly predictable by traffic-based variables (r<0.3).We concluded that NO2 and soot can be considered truly traffic-related pollutants, and that GIS-based regression models offer a promising approach to assess individual levels of exposure to these pollutants.
Keywords: Exposure; Geographical information system; Particulate matter; Nitrogen dioxide; Pollution mapping
A hierarchical Bayesian approach to the spatio-temporal modeling of air quality data
by A. Riccio; G. Barone; E. Chianese; G. Giunta (pp. 554-566).
The statistical evaluation of an air quality model is part of a broader process, generally referred to as ‘model assessment’, including sensitivity analysis and other tools. The evaluation process is usually implemented through the comparison of model predicted data with point-wise observations. However, this analysis is based on several (implicit) assumptions which are difficult, if not impossible, to assess: e.g.unbiased observations, measurements errors small enough in comparison to the typical usage of observed data, observations representative of the true area-averaged values within each computational cell, numerical model errors small enough in comparison to mis/un-represented physics/chemistry, and so on.In this work we address the problem of the comparison between point measured data and cell-averaged model values. We present a Bayesian approach for the space-time interpolation of measured data and the prediction of cell-averaged values.We used cell-averaged observations to validate the results from the CAMx air quality model. We found that a relevant fraction of the model bias can be explained by the subgrid spatial variability. This analysis may be important in all cases in which one is interested in a model and/or process comparison exercise.
Keywords: Bayesian space-time interpolation; Sub-grid variability; Model evaluation; CAMx model
PCDD/Fs in ambient air: TSP and PM10 sampler comparison
by Martinez Karell Martínez; Esteban Abad; L. Lluís Gustems; Albert Manich; Gomez Rafael Gómez; Xavier Guinart; Hernandez Isabel Hernández; Josep Rivera (pp. 567-573).
In this work, a comparison of TSP and PM10 samplers has been carried out with the purpose of evaluating the compatibility of the PCDD/Fs measurements between them and to comply with the current EC directive (Council directive 1999/30/EC) that regulates the particulate matter content, expressed as PM10 (particulate matter <10μm aerodynamic diameter) in ambient air due to their potential risk for human health.A total of 40 ambient air samples were collected for the analysis of PCDD/Fs from eight locations at different dates, using both TSP and PM10 samplers. Locations with diverse characteristic such as industrial, urban and traffic-affected zones were chosen.The results obtained in this work indicate that PCDD/F levels found using the TSP and PM10 sampling systems are comparable, or those from the latter are a bit lower, but these differences cannot be attributed to the sampling methodology.
Keywords: PCDD/Fs; TSP; PM; 10; Ambient air
Atmospheric pollutant dispersion around an urban area using trace metal concentrations and Pb isotopic compositions in epiphytic lichens
by C. Christophe Cloquet; Jean Carignan; Guy Libourel (pp. 574-587).
Epiphytic lichen samples were collected in and around a city of 300000 inhabitants in NE France to study the dispersion and fallout of Cd, Cu, Zn and Pb. Lichens hanging in small tree branches within a 15km radius from the city centre, together with bus air filter aerosols and unleaded gasoline samples, were analysed to evaluate the relative contribution of anthropogenic metals. On an average, Pb and Cd concentrations and calculated enrichment factors in lichens showed a radial distribution from downtown, decreasing rapidly within 4 or 5km and then less so towards more rural areas, whereas it is more diffuse for Cu and Zn despite the more elevated values close to the city centre. Metal concentrations can be interpreted in the light of major wind directions and/or secondary pollution sources to the atmosphere. Lichens sampled in the city and close to high traffic roads had206Pb/207Pb ratios of about 1.13. This ratio was consistently higher (up to 1.157) for lichens sampled at only five kilometres from the city centre. On the other hand, urban aerosols (on bus air filters) have homogeneous206Pb/207Pb ratios of1.153±0.003. The variation in Pb isotopic composition in lichens can be interpreted as the result of mixing between different industrial sources and old Pb pollution from leaded gasoline combustion re-emitted into the atmosphere. Combining elemental concentrations and isotopic ratios allowed a better understanding of the atmospheric deposition of metals and related sources in urban areas.
Keywords: Isotopic tracing; Biomonitoring; Elementary concentration; Anthropogenic pollution; Lead
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