Evidence for short-range transport of atmospheric mercury to a rural,inland site

Atmospheric mercury (Hg) species, including gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate-bound mercury (Hg_p), were monitored near three sites, including a cement plant (monitored in 2007 and 2008), an urban site and a rural site (both monitored in 2005 and 2008). Although the cement plant was a significant source of Hg emissions (for 2008, GEM: 2.20 ± 1.39 ng m^?3, RGM: 25.2 ± 52.8 pg m^?3, Hg_p 80.8 ± 283 pg m^?3), average GEM levels and daytime average dry depositional RGM flux were highest at the rural site, when all three sites were monitored sequentially in 2008 (rural site, GEM: 2.37 ± 1.26 ng m^?3, daytime RGM flux: 29 ± 40 ng m^?2 day^?1). Photochemical conversion of GEM was not the primary RGM source, as highest net RGM gains (75.9 pg m^?3, 99.0 pg m^?3, 149 m^?3) occurred within 3.0–5.3 h, while the theoretical time required was 14–23 h. Instead, simultaneous peaks in RGM, Hg_p, ozone (O₃), nitrogen oxides, and sulfur dioxide in the late afternoon suggested short-range transport of RGM from the urban center to the rural site. The rural site was located more inland, where the average water vapor mixing ratio was lower compared to the other two sites (in 2008, rural: 5.6 ± 1.4 g kg^?1, urban: 9.0 ± 1.1 g kg^?1, cement plant: 8.3 ± 2.2 g kg^?1). Together, these findings suggested short-range transport of O₃ from an urban area contributed to higher RGM deposition at the rural site, while drier conditions helped sustain elevated RGM levels. Results suggested less urbanized environments may be equally or perhaps more impacted by industrial atmospheric Hg emissions, compared to the urban areas from where Hg emissions originated.     

Temporal variability of mercury speciation in urban air

Semi-continuous measurements of ambient mercury (Hg) species were performed in Detroit, MI, USA for the calendar year 2003. The mean (±standard deviation) concentrations for gaseous elemental mercury (GEM), particulate mercury (HgP), and reactive gaseous mercury (RGM) were 2.2±1.3 ng m⁻³, 20.8±30.0, and 17.7±28.9 pg m⁻³, respectively. A clear seasonality in Hg speciation was observed with GEM and RGM concentrations significantly (p<0.001) greater in warm seasons, while HgP concentrations were greater in cold seasons. The three measured Hg species also exhibited clear diurnal trends which were particularly evident during the summer months. Higher RGM concentrations were observed during the day than at night. Hourly HgP and GEM concentrations exhibited a similar diurnal pattern with both being inversely correlated with RGM. Multivariate analysis coupled with conditional probability function analysis revealed the conditions associated with high Hg concentration episodes, and identified the inter-correlations between speciated Hg concentrations, three common urban air pollutants (sulfur dioxide, ozone, and nitric oxides), and meteorological parameters. This analysis suggests that both local and regional sources were major factors contributing to the observed temporal variations in Hg speciation. Boundary layer dynamics and the seasonal meteorological conditions, including temperature and moisture content, were also important factors affecting Hg variability.     

Temporal distribution and potential sources of atmospheric mercury measured at a high-elevation background station in Taiwan

Measurements of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM), and particulate mercury (PHg) have been conducted at Lulin Atmospheric Background Station (LABS) in Taiwan since April 2006. This was the first long-term free tropospheric atmospheric Hg monitoring program in the downwind region of East Asia, which is a major Hg emission source region. Between April 13, 2006 and December 31, 2007, the mean concentrations of GEM, RGM, and PHg were 1.73 ng m^?3, 12.1 pg m^?3, and 2.3 pg m^?3, respectively. A diurnal pattern was observed for GEM with afternoon peaks and nighttime lows, whereas the diurnal pattern of RGM was opposite to that of GEM. Spikes of RGM were frequently observed between midnight and early morning with concurrent decreases in GEM and relative humidity and increases in O₃, suggesting the oxidation of GEM and formation of RGM in free troposphere (FT). Upslope movement of boundary layer (BL) air in daytime and subsidence of FT air at night resulted in these diurnal patterns. Considering only the nighttime data, which were more representative of FT air, the composite monthly mean GEM concentrations ranged between 1.06 and 2.06 ng m^?3. Seasonal variation in nighttime GEM was evident, with lower concentrations usually occurring in summer when clean marine air masses prevailed. Between fall and spring, air masses passed the East Asian continent prior to reaching LABS, contributing to the elevated GEM concentrations. Analysis of GEM/CO correlation tends to support the argument. Good GEM/CO correlations were observed in fall, winter, and spring, suggesting influence of anthropogenic emission sources. Our results demonstrate the significance of East Asian Hg emissions, including both anthropogenic and biomass burning emissions, and their long-range transport in the FT. Because of the pronounced seasonal monsoon activity and the seasonal variation in regional wind field, export of the Asian Hg emissions to Taiwan occurs mainly during fall, winter, and spring.     

Mercury (Hg) emissions from domestic biomass combustion for space heating

Three mercury (Hg) species (gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and fine particulate-bound mercury (PBM_2.5)) were measured in the stack of a small scale wood combustion chamber at 400 °C, in the stack of an advanced wood boiler, and in two areas influenced by wood combustion. The low temperature process (lab-scale) emitted mostly GEM (∼99% when burning wood pellets and ∼95% when burning unprocessed wood). The high temperature wood boiler emitted a greater proportion of oxidized Hg (approximately 65%) than the low temperature system. In field measurements, mean PBM_2.5 concentrations at the rural and urban sites in winter were statistically significantly higher than in warmer seasons and were well correlated with Delta-C concentrations, a wood combustion indictor measured by an aethalometer (UV-absorbable carbon minus black carbon). Overall the results suggest that wood combustion may be an important source of oxidized mercury (mostly in the particulate phase) in northern climates in winter.     

Urban–rural differences in atmospheric mercury speciation

Measurements of gaseous elemental mercury (GEM), particulate mercury (Hg_p), and reactive gaseous mercury (RGM) were concurrently recorded at an urban site in Detroit and a rural site in Dexter, both in Michigan for the calendar year 2004. Their average concentrations (±standard deviation) for the urban area were 2.5 ± 1.4 ng m^?3, 18.1 ± 61.0 pg m^?3, and 15.5 ± 54.9 pg m^?3, respectively, while their rural counterparts were 1.6 ± 0.6 ng m^?3, 6.1 ± 5.5 pg m^?3, and 3.8 ± 6.6 pg m^?3, respectively. The medians of urban-to-rural ratios of Hg concentrations indicate approximately 1-fold, 2-fold, and 3-fold gradients between Detroit and Dexter for GEM, Hg_p, and RGM, respectively. The urban–rural differences in Hg also varied considerably on different temporal scales and with wind flow patterns, which was most evident in RGM. Our results show that while Hg at both sites was impacted by regional sources, meteorological conditions, and photochemical transformations, the extent of variations in the observed urban-to-rural gradients, particularly in RGM, cannot be fully accounted for by these processes. Both analyses of the annual data and case studies indicate that the more variable and episodic nature of Hg, particularly RGM, seen in Detroit compared with Dexter, was the result of direct impact from local anthropogenic sources.     

Source apportionment of emissions from light-duty gasoline vehicles and other sources in the United States for ozone and particulate matter

Federal Tier 3 motor vehicle emission and fuel sulfur standards have been promulgated in the United States to help attain air quality standards for ozone and PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm). The authors modeled a standard similar to Tier 3 (a hypothetical nationwide implementation of the California Low Emission Vehicle [LEV] III standards) and prior Tier 2 standards for on-road gasoline-fueled light-duty vehicles (gLDVs) to assess incremental air quality benefits in the United States (U.S.) and the relative contributions of gLDVs and other major source categories to ozone and PM_2.5 in 2030. Strengthening Tier 2 to a Tier 3-like (LEV III) standard reduces the summertime monthly mean of daily maximum 8-hr average (MDA8) ozone in the eastern U.S. by up to 1.5 ppb (or 2%) and the maximum MDA8 ozone by up to 3.4 ppb (or 3%). Reducing gasoline sulfur content from 30 to 10 ppm is responsible for up to 0.3 ppb of the improvement in the monthly mean ozone and up to 0.8 ppb of the improvement in maximum ozone. Across four major urban areas—Atlanta, Detroit, Philadelphia, and St. Louis—gLDV contributions range from 5% to 9% and 3% to 6% of the summertime mean MDA8 ozone under Tier 2 and Tier 3, respectively, and from 7% to 11% and 3% to 7% of the maximum MDA8 ozone under Tier 2 and Tier 3, respectively. Monthly mean 24-hr PM_2.5 decreases by up to 0.5 μg/m³ (or 3%) in the eastern U.S. from Tier 2 to Tier 3, with about 0.1 μg/m³ of the reduction due to the lower gasoline sulfur content. At the four urban areas under the Tier 3 program, gLDV emissions contribute 3.4–5.0% and 1.7–2.4% of the winter and summer mean 24-hr PM_2.5, respectively, and 3.8–4.6% and 1.5–2.0% of the mean 24-hr PM_2.5 on days with elevated PM_2.5 in winter and summer, respectively.

Implications: Following U.S. Tier 3 emissions and fuel sulfur standards for gasoline-fueled passenger cars and light trucks, these vehicles are expected to contribute less than 6% of the summertime mean daily maximum 8-hr ozone and less than 7% and 4% of the winter and summer mean 24-hr PM_2.5 in the eastern U.S. in 2030. On days with elevated ozone or PM_2.5 at four major urban areas, these vehicles contribute less than 7% of ozone and less than 5% of PM_2.5, with sources outside North America and U.S. area source emissions constituting some of the main contributors to ozone and PM_2.5, respectively.     

Ft. McHenry tunnel study: Source profiles and mercury emissions from diesel and gasoline powered vehicles

During the fall of 1998, the US Environmental Protection Agency and the Florida Department of Environmental Protection sponsored a 7-day study at the Ft. McHenry tunnel in Baltimore, MD with the objective of obtaining PM_2.5 vehicle source profiles for use in atmospheric mercury source apportionment studies. PM_2.5 emission profiles from gasoline and diesel powered vehicles were developed from analysis of trace elements, polycyclic aromatic hydrocarbons (PAH), and condensed aliphatic hydrocarbons. PM_2.5 samples were collected using commercially available sampling systems and were extracted and analyzed using conventional well-established methods. Both inorganic and organic profiles were sufficiently unique to mathematically discriminate the contributions from each source type using a chemical mass balance source apportionment approach. However, only the organic source profiles provided unique PAH tracers (e.g., fluoranthene, pyrene, and chrysene) for diesel combustion that could be used to identify source contributions generated using multivariate statistical receptor modeling approaches. In addition, the study found significant emission of gaseous elemental mercury (Hg⁰), divalent reactive gaseous mercury (RGM), and particulate mercury (Hg(p)) from gasoline but not from diesel powered motor vehicles. Fuel analysis supported the tunnel measurement results showing that total mercury content in all grades of gasoline (284±108 ng L⁻¹) was substantially higher than total mercury content in diesel fuel (62±37 ng L⁻¹) collected contemporaneously at local Baltimore retailers.     

Scientific uncertainties in atmospheric mercury models II: Sensitivity analysis in the CONUS domain

In this study, we present the response of model results to different scientific treatments in an effort to quantify the uncertainties caused by the incomplete understanding of mercury science and by model assumptions in atmospheric mercury models. Two sets of sensitivity simulations were performed to assess the uncertainties using modified versions of CMAQ-Hg in a 36-km Continental United States domain. From Set 1 Experiments, it is found that the simulated mercury dry deposition is most sensitive to the gaseous elemental mercury (GEM) oxidation product assignment, and to the implemented dry deposition scheme for GEM and reactive gaseous mercury (RGM). The simulated wet deposition is sensitive to the aqueous Hg(II) sorption scheme, and to the GEM oxidation product assignment. The inclusion of natural mercury emission causes a small increase in GEM concentration but has little impact on deposition. From Set 2 Experiments, it is found that both dry and wet depositions are sensitive to mercury chemistry. Change in model mercury chemistry has a greater impact on simulated wet deposition than on dry deposition. The kinetic uncertainty of GEM oxidation by O₃ and mechanistic uncertainty of Hg(II) reduction by aqueous HO₂ pose the greatest impact. Using the upper-limit kinetics of GEM–O₃ reaction or eliminating aqueous Hg(II)–HO₂ reaction results in unreasonably high deposition and depletion of gaseous mercury in the domain. Removing GEM–OH reaction is not sufficient to balance the excessive mercury removal caused by eliminating the HO₂ mechanism. Field measurements of mercury dry deposition, better quantification of mercury air-surface exchange and further investigation of mercury redox chemistry are needed for reducing model uncertainties and for improving the performance of atmospheric mercury models.     

Sources of fine particles in the South Coast area,California

PM_2.5 (particulate matter less than 2.5 μm in aerodynamic diameter) speciation data collected between 2003 and 2005 at two United State Environmental Protection Agency (US EPA) Speciation Trends Network monitoring sites in the South Coast area, California were analyzed to identify major PM_2.5 sources as a part of the State Implementation Plan development. Eight and nine major PM_2.5 sources were identified in LA and Rubidoux, respectively, through PMF2 analyses. Similar to a previous study analyzing earlier data (Kim and Hopke, 2007a), secondary particles contributed the most to the PM_2.5 concentrations: 53% in LA and 59% in Rubidoux. The next highest contributors were diesel emissions (11%) in LA and Gasoline vehicle emissions (10%) in Rubidoux. Most of the source contributions were lower than those from the earlier study. However, the average source contributions from airborne soil, sea salt, and aged sea salt in LA and biomass smoke in Rubidoux increased.To validate the apportioned sources in this study, PMF2 results were compared with those obtained from EPA PMF (US EPA, 2005). Both models identified the same number of major sources and the resolved source profiles and contributions were similar at the two monitoring sites. The minor differences in the results caused by the differences in the least square algorithm and non-negativity constraints between two models did not affect the source identifications.     

Improving Source Apportionment of Fine Particles in the Eastern United States Utilizing Temperature-Resolved Carbon Fractions

Abstract

The objectives of this study were to examine the use of carbon fractions to identify particulate matter (PM) sources, especially traffic‐related carbonaceous particle sources, and to estimate their contributions to the particle mass concentrations. In recent studies, positive matrix factorization (PMF) was applied to ambient fine PM (PM_2.5) compositional data sets of 24‐hr integrated samples including eight individual carbon fractions collected at three monitoring sites in the eastern United States: Atlanta, GA, Washington, DC, and Brigantine, NJ. Particulate carbon was analyzed using the Interagency Monitoring of Protected Visual Environments/Thermal Optical Reflectance method that divides carbon into four organic carbons (OC): pyrolized OC and three elemental carbon (EC) fractions. In contrast to earlier PMF studies that included only the total OC and EC concentrations, gasoline emissions could be distinguished from diesel emissions based on the differences in the abundances of the carbon fractions between the two sources. The compositional profiles for these two major source types show similarities among the three sites. Temperature‐resolved carbon fractions also enhanced separations of carbon‐rich secondary sulfate aerosols. Potential source contribution function analyses show the potential source areas and pathways of sulfate‐rich secondary aerosols, especially the regional influences of the biogenic, as well as anthropogenic secondary aerosol. This study indicates that temperature‐resolved carbon fractions can be used to enhance the source apportionment of ambient PM_2.5.     

Modeling an air pollution episode in northwestern United States: Identifying the effect of nitrogen oxide and volatile organic compound emission changes on air pollutants formation using direct sensitivity analysis

Air quality impacts of volatile organic compound (VOC) and nitrogen oxide (NO_x) emissions from major sources over the northwestern United States are simulated. The comprehensive nested modeling system comprises three models: Community Multiscale Air Quality (CMAQ), Weather Research and Forecasting (WRF), and Sparse Matrix Operator Kernel Emissions (SMOKE). In addition, the decoupled direct method in three dimensions (DDM-3D) is used to determine the sensitivities of pollutant concentrations to changes in precursor emissions during a severe smog episode in July of 2006. The average simulated 8-hr daily maximum O₃ concentration is 48.9 ppb, with 1-hr O₃ maxima up to 106 ppb (40 km southeast of Seattle). The average simulated PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) concentration at the measurement sites is 9.06 μg m^?3, which is in good agreement with the observed concentration (8.06 μg m^?3). In urban areas (i.e., Seattle, Vancouver, etc.), the model predicts that, on average, a reduction of NO_x emissions is simulated to lead to an increase in average 8-hr daily maximum O₃ concentrations, and will be most prominent in Seattle (where the greatest sensitivity is??0.2 ppb per % change of mobile sources). On the other hand, decreasing NO_x emissions is simulated to decrease the 8-hr maximum O₃ concentrations in remote and forested areas. Decreased NO_x emissions are simulated to slightly increase PM_2.5 in major urban areas. In urban areas, a decrease in VOC emissions will result in a decrease of 8-hr maximum O₃ concentrations. The impact of decreased VOC emissions from biogenic, mobile, nonroad, and area sources on average 8-hr daily maximum O₃ concentrations is up to 0.05 ppb decrease per % of emission change, each. Decreased emissions of VOCs decrease average PM_2.5 concentrations in the entire modeling domain. In major cities, PM_2.5 concentrations are more sensitive to emissions of VOCs from biogenic sources than other sources of VOCs. These results can be used to interpret the effectiveness of VOC or NO_x controls over pollutant concentrations, especially for localities that may exceed National Ambient Air Quality Standards (NAAQS).

Implications: The effect of NO_x and VOC controls on ozone and PM_2.5 concentrations in the northwestern United States is examined using the decoupled direct method in three dimensions (DDM-3D) in a state-of-the-art three-dimensional chemical transport model (CMAQ). NO_x controls are predicted to increase PM_2.5 and ozone in major urban areas and decrease ozone in more remote and forested areas. VOC reductions are helpful in reducing ozone and PM_2.5 concentrations in urban areas. Biogenic VOC sources have the largest impact on O₃ and PM_2.5 concentrations.     

Quantifying road dust resuspension in urban environment by Multilinear Engine: A comparison with PMF2

Atmospheric PM pollution from traffic comprises not only direct emissions but also non-exhaust emissions because resuspension of road dust that can produce high human exposure to heavy metals, metalloids, and mineral matter. A key task for establishing mitigation or preventive measures is estimating the contribution of road dust resuspension to the atmospheric PM mixture. Several source apportionment studies, applying receptor modeling at urban background sites, have shown the difficulty in identifying a road dust source separately from other mineral sources or vehicular exhausts. The Multilinear Engine (ME-2) is a computer program that can solve the Positive Matrix Factorization (PMF) problem. ME-2 uses a programming language permitting the solution to be guided toward some possible targets that can be derived from a priori knowledge of sources (chemical profile, ratios, etc.). This feature makes it especially suitable for source apportionment studies where partial knowledge of the sources is available.In the present study ME-2 was applied to data from an urban background site of Barcelona (Spain) to quantify the contribution of road dust resuspension to PM₁₀ and PM_2.5 concentrations. Given that recently the emission profile of local resuspended road dust was obtained (Amato, F., Pandolfi, M., Viana, M., Querol, X., Alastuey, A., Moreno, T., 2009. Spatial and chemical patterns of PM₁₀ in road dust deposited in urban environment. Atmospheric Environment 43 (9), 1650–1659), such a priori information was introduced in the model as auxiliary terms of the object function to be minimized by the implementation of the so-called “pulling equations”.ME-2 permitted to enhance the basic PMF solution (obtained by PMF2) identifying, beside the seven sources of PMF2, the road dust source which accounted for 6.9 μg m^?3 (17%) in PM₁₀, 2.2 μg m^?3 (8%) of PM_2.5 and 0.3 μg m^?3 (2%) of PM₁. This reveals that resuspension was responsible of the 37%, 15% and 3% of total traffic emissions respectively in PM₁₀, PM_2.5 and PM₁. Therefore the overall traffic contribution resulted in 18 μg m^?3 (46%) in PM₁₀, 14 μg m^?3 (51%) in PM_2.5 and 8 μg m^?3 (48%) in PM₁. In PMF2 this mass explained by road dust resuspension was redistributed among the rest of sources, increasing mostly the mineral, secondary nitrate and aged sea salt contributions.     

Apportionment of Ambient Primary and Secondary Fine Particulate Matter during a 2001 Summer Intensive Study at the CMU Supersite and NETL Pittsburgh Site

Abstract

Gaseous and particulate pollutant concentrations associated with five samples per day collected during a July 2001 summer intensive study at the Pittsburgh Carnegie Mellon University (CMU) Supersite were used to apportion fine particulate matter (PM_2.5) into primary and secondary contributions using PMF2. Input to the PMF2 analysis included the concentrations of PM_2.5 nonvolatile and semivolatile organic material, elemental carbon (EC), ammonium sulfate, trace element components, gas-phase organic material, and NO_x, NO₂, and O₃ concentrations. A total of 10 factors were identified. These factors are associated with emissions from various sources and facilities including crustal material, gasoline combustion, diesel combustion, and three nearby sources high in trace metals. In addition, four secondary sources were identified, three of which were associated with secondary products of local emissions and were dominated by organic material and one of which was dominated by secondary ammonium sulfate transported to the CMU site from the west and southwest. The three largest contributors to PM_2.5 were sec ondary transported material (dominated by ammonium sulfate) from the west and southwest (49%), secondary material formed during midday photochemical processes (24%), and gasoline combustion emissions (11%). The other seven sources accounted for the remaining 16% of the PM_2.5. Results obtained at the CMU site were comparable to results previously reported at the National Energy Technology Laboratory (NETL), located approximately 18 km south of downtown Pittsburgh. The major contributor at both sites was material transported from the west and southwest. Some difference in nearby sources could be attributed to meteorology as evaluated by HYSPLIT model back-trajectory calculations. These findings are consistent with the majority of the secondary ammonium sulfate in the Pittsburgh area being the result of contributions from distant transport, and thus decoupled from local activity involving organic pollutants in the metropolitan area. In contrast, the major local secondary sources were dominated by organic material.     

The influence of ozone on atmospheric emissions of gaseous elemental mercury and reactive gaseous mercury from substrates

Experiments were performed to investigate the effect of ozone (O₃) on mercury (Hg) emission from a variety of Hg-bearing substrates. Substrates with Hg(II) as the dominant Hg phase exhibited a 1.7 to 51-fold increase in elemental Hg (Hg^o) flux and a 1.3 to 8.6-fold increase in reactive gaseous mercury (RGM) flux in the presence of O₃-enriched clean (50 ppb O₃; 8 substrates) and ambient air (up to ∼70 ppb O₃; 6 substrates), relative to clean air (oxidant and Hg free air). In contrast, Hg^o fluxes from two artificially Hg^o-amended substrates decreased by more than 75% during exposure to O₃-enriched clean air relative to clean air. Reactive gaseous mercury emissions from Hg^o-amended substrates increased immediately after exposure to O₃ but then decreased rapidly. These experimental results demonstrate that O₃ is very important in controlling Hg emissions from substrates. The chemical mechanisms that produced these trends are not known but potentially involve heterogenous reactions between O₃, the substrate, and Hg. Our experiments suggest they are not homogenous gas-phase reactions. Comparison of the influence of O₃ versus light on increasing Hg^o emissions from dry Hg(II)-bearing substrates demonstrated that they have a similar amount of influence although O₃ appeared to be slightly more dominant. Experiments using water-saturated substrates showed that the presence of high-substrate moisture content minimizes reactions between atmospheric O₃ and substrate-bound Hg. Using conservative calculations developed in this paper, we conclude that because O₃ concentrations have roughly doubled in the last 100 years, this could have increased Hg^o emissions from terrestrial substrates by 65–72%.     

Chemical characteristics and source apportionment of PM<Subscript>2.5</Subscript> using PCA/APCS,UNMIX, and PMF at an urban site of Delhi,India

The present study investigated the comprehensive chemical composition [organic carbon (OC), elemental carbon (EC), water-soluble inorganic ionic components (WSICs), and major & trace elements] of particulate matter (PM_2.5) and scrutinized their emission sources for urban region of Delhi. The 135 PM_2.5 samples were collected from January 2013 to December 2014 and analyzed for chemical constituents for source apportionment study. The average concentration of PM_2.5 was recorded as 121.9 ± 93.2 μg m^?3 (range 25.1–429.8 μg m^?3), whereas the total concentration of trace elements (Na, Ca, Mg, Al, S, Cl, K, Cr, Si, Ti, As, Br, Pb, Fe, Zn, and Mn) was accounted for ～17% of PM_2.5. Strong seasonal variation was observed in PM_2.5 mass concentration and its chemical composition with maxima during winter and minima during monsoon seasons. The chemical composition of the PM_2.5 was reconstructed using IMPROVE equation, which was observed to be in good agreement with the gravimetric mass. Source apportionment of PM_2.5 was carried out using the following three different receptor models: principal component analysis with absolute principal component scores (PCA/APCS), which identified five major sources; UNMIX which identified four major sources; and positive matrix factorization (PMF), which explored seven major sources. The applied models were able to identify the major sources contributing to the PM_2.5 and re-confirmed that secondary aerosols (SAs), soil/road dust (SD), vehicular emissions (VEs), biomass burning (BB), fossil fuel combustion (FFC), and industrial emission (IE) were dominant contributors to PM_2.5 in Delhi. The influences of local and regional sources were also explored using 5-day backward air mass trajectory analysis, cluster analysis, and potential source contribution function (PSCF). Cluster and PSCF results indicated that local as well as long-transported PM_2.5 from the north-west India and Pakistan were mostly pertinent.     

Effect of diurnal changes in VOC source strengths on performances of receptor models

Introduction

The effect of diurnal changes in strengths of volatile organic compound (VOC) sources on the performances of positive matrix factorization (PMF) and principal component analysis (PCA) was investigated using ambient measurement results that were taken during daytime and nighttime hours between March 24 and May 14, 2011, within Davutpasa Campus of Yildiz Technical University (Istanbul, Turkey).

Methods

Forty-five VOC species, ranging from C₅ to C₁₁ in volatility, were measured in the samples, 40 of which are included in the analyses. Ambient samples were grouped as daytime, nighttime, and all day datasets, and both PMF and PCA were applied to each dataset. A total of six source groups were extracted from each dataset: solvent use, general industrial paint use, gasoline and diesel vehicle exhausts, and biogenic as well as evaporative emissions. Estimated source contributions showed great diurnal variations.

Results

The results suggested that extraction of possible sources by PCA depends greatly on the number of samples and the strength of the sources, while PMF produced stable results regardless of number of samples and source strengths.

Conclusion

Although PMF was unable to resolve gasoline vehicle and evaporative emissions, it was found to be successful in explaining diurnal fluctuations in source strengths, while the performance of PCA depends on the strength of emission source.     

Wintertime and summertime São Paulo aerosol source apportionment study

A detailed aerosol source apportionment study was performed with two sampling campaigns, during wintertime and summertime in the heavily polluted metropolitan area of São Paulo, Brazil. In addition to 12 h fine and coarse mode filter sampling, several real time aerosol and trace gas monitors were used. PM₁₀ was sampled using stacked filter units that collects fine (d<2.5 μm) and coarse (2.5<d<10 μm) particulate matter, providing mass, black carbon (BC) and elemental concentration for each aerosol mode. The concentration of about 20 elements was determined using the particle induce X-ray emission technique. Real time aerosol monitors provided PM₁₀ aerosol mass (TEOM), organic and elemental carbon (Carbon Monitor 5400, R&P) and BC concentration (Aethalometer). A complex system of sources and meteorological conditions modulates the heavy air pollution of the urban area of São Paulo. The boundary layer height and the primary emissions by motor vehicles controls the strong pattern of diurnal cycles obtained for PM₁₀, BC, CO, NO_x, and SO₂. Absolute principal factor analysis results showed a very similar source pattern between winter and summer field campaigns, despite the different locations of the sampling sites of both campaigns, pointing that there are no significant change in the main air pollution sources. The source identified as motor vehicle represented 28% and 24% of the PM_2.5 for winter and summer, respectively. Resuspended soil dust accounted for 25% and 30%. The oil combustion source represented 18% and 21%. Sulfates accounts for 23% and 17% and finally industrial emissions contributed with 5% and 6% of PM_2.5, for winter and summer, respectively. The resuspended soil dust accounted for a large fraction (75–78%) of the coarse mode aerosol mass. Certainly automobile traffic and soil dust are the main air pollution sources in São Paulo. The sampling and analytical procedures applied in this study showed that it is possible to perform a quantitative aerosol source apportionment in a complex urban area such as São Paulo.     

Preparation of mercury emissions inventory for eastern North America

Point and area inventories of anthropogenic mercury emissions documented by US and Canadian environmental agencies have been aggregated into a single archive for analysis and air pollution modeling work. For 5341 point sources and 1634 aggregated area sources, mercury emissions are apportioned among elemental gaseous [Hg(0)], reactive gaseous[Hg(II)], and particulate [Hg(p)] emissions using speciation factors derived from available monitoring measurements. According to this inventory, 4.82 x 10(5) mol of mercury were emitted in calendar year 1996 in the latitude range 24-51 degrees north, and longitude range 64-91 degrees west, which covers most of North America east of the Mississippi River. Using speciation factors consistent with past emission source studies, we find the relative emission proportions among Hg(0):Hg(II):Hg(p) species are 47:35:18. Maps of the various mercury species' emissions patterns are presented. Gridded emission patterns show local mercury emission extremes associated with individual cement production and municipal incineration facilities, and in contrast to past inventories, population centers do not stand out. Considerable uncertainties are still present in estimating emissions from large point sources, as are methods of apportioning emissions among various mercury species.     

Comparison of receptor models for source apportionment of volatile organic compounds in Beijing, China

Identifying the sources of volatile organic compounds (VOCs) is key to reducing ground-level ozone and secondary organic aerosols (SOAs). Several receptor models have been developed to apportion sources, but an intercomparison of these models had not been performed for VOCs in China. In the present study, we compared VOC sources based on chemical mass balance (CMB), UNMIX, and positive matrix factorization (PMF) models. Gasoline-related sources, petrochemical production, and liquefied petroleum gas (LPG) were identified by all three models as the major contributors, with UNMIX and PMF producing quite similar results. The contributions of gasoline-related sources and LPG estimated by the CMB model were higher, and petrochemical emissions were lower than in the UNMIX and PMF results, possibly because the VOC profiles used in the CMB model were for fresh emissions and the profiles extracted from ambient measurements by the two-factor analysis models were "aged".     

Gaseous mercury capture by coir fibre coated with a metal-halide

ABSTRACT

Toxic gaseous elemental mercury (GEM) is emitted to the atmosphere through a variety of routes at rates estimated at over 5000 tonnes per annum, a large fraction of which is Anthropogenic. It is then widely disbursed atmospherically and eventually deposited, where it is subject to further biogeochemical cycling, including re-emission. Research into capture of point source mercury emissions revolves almost exclusively around the use of activated carbons, various catalytic oxidation substrates, or as a by-product of acidic treatments of flue gas during SOx and NOx reduction methods. GEM is very non-reactive in its native state, but capture rates are greatly enhanced if GEM is first oxidized, or at least where oxidation states play a role at the substrate GEM interface. Little research has been devoted to capture of GEM directly. However, presented here is a novel adaption of coir fibers for use as a substrate in capturing GEM emissions directly. Various coir modifications were investigated, with the most effective being fibers coated with CuI crystals dispersed in a non-crosslinked poly-siloxane matrix. Scanning electron microscopy was used to view surface morphologies, and sorption characteristics were measured using atomic absorption spectroscopy (AAS). These results indicate that coir fibers modified by CuI-[SiO₂] _n show great promise in their ability to efficiently sorb GEM, and could potentially be utilized in a variety of configurations and settings where GEM emissions need to be captured.