Size distribution and anthropogenic sources apportionment of airborne trace metals in Kanazawa,Japan

Aerosol samples were collected from Kanazawa, Japan to examine the size distribution of 12 elements and to identify the major sources of anthropogenic elements. Key emission sources were identified and, concentrations contributed from individual sources were estimated as well. Concentrations of elements V, Ca, Cd, Fe, Ba, Mg, Mn, Pb, Sr, Zn, Co and Cu in aerosols were determined with ICP-MS. The results showed that Ca, Mg, Sr, Mn, Co and Fe were mainly associated with coarse particles (>2.1 μm), primarily from natural sources. In contrast, the elements Zn, Ba, Cd, V, Pb and Cu dominated in fine aerosol particles (<2.1 μm), implying that the anthropogenic origin is the dominant source. Results of the factor analysis on elements with high EF_Crust values (>10) showed that emissions from waste combustion in incinerators, oil combustion (involving waste oil burning and oil combustion in both incinerators and electricity generation plants), as well as coal combustion in electricity generation plants were major contributors of anthropogenic metals in the ambient atmosphere in Kanazawa. Quantitatively estimated sum of mean concentrations of anthropogenic elements from the key sources were in good agreement with the observed values. Results of this study elucidate the need for making pollution control strategy in this area.     

Chemical and strontium isotope characterization of rainwater in Beijing,China

Major ion concentrations and Sr isotope ratios (⁸⁷Sr/⁸⁶Sr) were measured in rainwater samples collected at an urban site in Beijing over a period of one year. The pH value and major ion concentrations of samples varied considerably, and about 50% of the rainwater studied here were acidic rain with pH values less than 5.0. Ca²⁺ and NH₄⁺ were the dominant cations in rainwaters and their volume weighted mean (VWM) values were 608 μeq l^?1 (14–1781 μeq l^?1) and 186 μeq l^?1 (48–672 μeq l^?1), respectively. SO₄^2? was the predominant anion with VWM value of 316 μeq l^?1 (65–987 μeq l^?1), next was NO₃^? with VWM value of 109 μeq l^?1 (30–382 μeq l^?1).Using Na as an indicator of marine origin, and Al for the terrestrial inputs, the proportions of sea salt and terrestrial elements were estimated from elemental ratios. More than 99% of Ca²⁺ and 98% of SO₄^2? in rainwater samples are non-sea-salt origin. The ⁸⁷Sr/⁸⁶Sr ratios were used to characterize the different sources based on the data sets of this study and those from literatures. Such sources include sea salts (⁸⁷Sr/⁸⁶Sr～0.90917), soluble soil dust minerals originating from either local or the desert and loess areas (～0.7111), and anthropogenic sources (fertilizers, coal combustion and automobile exhausts). The high concentrations of alkaline ions (mainly Ca²⁺) in Beijing atmosphere have played an important role to neutralize the acidity of rainwater. However, it is worth noting that there is a remarkable acidification trend of rainwater in Beijing recent years.     

An industrial emissions inventory of calcium for Europe

The base cations calcium, magnesium and potassium, have been observed to be declining in air and precipitation in both Europe and North America. There is good evidence that this is the result of declining emissions of fly ash from industrial plant, as a result of increased abatement and industrial decline. This may have the effect of offsetting the effects of declines in acidic emissions, in terms of net deposited acidity. In order to reconcile source strengths of base cations, an industrial emissions inventory of calcium, the dominant base cation in air and precipitation, has been compiled. The main sources identified were: cement plants; iron and steel plants; and coal combustion from both large and small boilers. The overall emission was calculated to be between approximately 750 and 800 ktonnes Ca yr^-1. The dominant source was coal combustion from domestic and small boilers. Of the point sources, cement production dominated over coal combustion, and iron and steel plant. The emission factors used are very uncertain, which gives the inventory a large uncertainty. Furthermore, the emissions are compiled on a base year of 1990, and large changes have taken place in the industrial structuring of the largest contributing countries. Despite the uncertainties, the compilation of the inventory represents a vital first step in understanding the sources of deposited calcium and its effect on net deposited acidity.     

Inventory of aerosol and sulphur dioxide emissions from India: I—Fossil fuel combustion

A comprehensive, spatially resolved (0.25°×0.25°) fossil fuel consumption database and emissions inventory was constructed, for India, for the first time. Emissions of sulphur dioxide and aerosol chemical constituents were estimated for 1996–1997 and extrapolated to the Indian Ocean Experiment (INDOEX) study period (1998–1999). District level consumption of coal/lignite, petroleum and natural gas in power plants, industrial, transportation and domestic sectors was 9411 PJ, with major contributions from coal (54%) followed by diesel (18%). Emission factors for various pollutants were derived using India specific fuel characteristics and information on combustion/air pollution control technologies for the power and industrial sectors. Domestic and transportation emission factors, appropriate for Indian source characteristics, were compiled from literature. SO₂ emissions from fossil fuel combustion for 1996–1997 were 4.0 Tg SO₂ yr⁻¹, with 756 large point sources (e.g. utilities, iron and steel, fertilisers, cement, refineries and petrochemicals and non-ferrous metals), accounting for 62%. PM_2.5 emitted was 0.5 and 2.0 Tg yr⁻¹ for the 100% and the 50% control scenario, respectively, applied to coal burning in the power and industrial sectors. Coal combustion was the major source of PM_2.5 (92%) primarily consisting of fly ash, accounting for 98% of the “inorganic fraction” emissions (difference between PM_2.5 and black carbon+organic matter) of 1.6 Tg yr⁻¹. Black carbon emissions were estimated at 0.1 Tg yr⁻¹, with 58% from diesel transport, and organic matter emissions at 0.3 Tg yr⁻¹, with 48% from brick-kilns. Fossil fuel consumption and emissions peaked at the large point industrial sources and 22 cities, with elevated area fluxes in northern and western India. The spatial resolution of this inventory makes it suitable for regional-scale aerosol-climate studies. These results are compared to previous studies and differences discussed. Measurements of emission factors for Indian sources are needed to further refine these estimates.     

Heavy metal distribution in dust from elementary schools in Hermosillo,Sonora, México

The city of Hermosillo, Sonora in northern Mexico was investigated for its heavy metals content. Samples of sedimented dust in roofs from 25 elementary schools were analyzed for their contents of Ni, Cr, Zn, Cd, Co, Ba, V, Pb, Fe and Cu after digestion with nitric acid. The results of the analysis were used to determine spatial distribution and magnitude of heavy metals pollution. The results of this study reveal that heavy metals distribution is different in two areas of the city. The southern area contains higher concentrations of heavy metals than the northcentral area. The mean level of Cd in exterior dust is 5.65 mg kg⁻¹ in the southern area whereas the mean level of Cd is 2.83 mg kg⁻¹ in the northcentral area. Elevated concentrations of Zn (2012 mg kg⁻¹), Pb (101.88 mg kg⁻¹), Cr (38.13 mg kg⁻¹) and Cd (28.38 mg kg⁻¹) in roof dust were found in samples located near industrial areas. Principal component analysis (PCA) was applied to the data matrix to evaluate the analytical results and to identify the possible pollution sources of metals. PCA shows two main sources: (1) Pb, Cd, Cr and Zn are mainly derived from industrial sources, combined with traffic sources; (2) Fe, Co and Ba are mainly derived from natural sources. V and Ni are highly correlated and possibly related to fuel combustion processes. Enrichment factors were calculated, which in turn further confirms the source identification. Ba and Co are dominantly crustal. Anthropogenically added Cd, Pb, Zn and Cr show maximum enrichment relative to the upper continental crustal component. The distribution of the heavy metals in dust does not seem to be controlled only by the topography of the city, but also by the location of the emission sources.     

Ozone episodes in urban Hong Kong 1994–1999

Summer pollution episodes in Hong Kong are related to the passage of tropical storms close to the territory. Between 1994 and 1999, there were six territory-wide ozone episodes in Hong Kong during which the Hong Kong Air Quality Objective for ozone (240 μg m⁻³, 1 h) was violated. The maximum O₃ concentration for the period was 334 μg m⁻³ recorded in August 1999. Synoptically, tropical storms were in the vicinity on all the episode days. Northwesterly/westerly winds induced by the storms are believed to cause ozone precursor emissions from local power plants in the western part of Hong Kong to impact the territory, and at the same time allowing the import of emissions from upwind sources along the mainland coast. Other important meteorological factors that contribute to the occurrence of the episode events include: stable atmospheres, morning break-up of nocturnal inversions, low winds, strong solar radiation and high temperatures. Trajectory analysis of airflows at 850 hPa confirms the long-range pollutant transport. The strong correlation between non-sea-salt sulphate (NS-SO₄) and selenium for the summer of 1999 indicates that the main source of high levels of NS-SO₄ in summer in Hong Kong is coal combustion. The correlation between arsenic (As) and vanadium (V) for the summers of 1996–1999 suggests a concomitant influence of coal and residual oil combustion in the region.     

Air pollutants in rural homes in Guizhou,China – Concentrations,speciation, and size distribution

Several types of fuels, including coal, fuel wood, and biogas, are commonly used for cooking and heating in Chinese rural households, resulting in indoor air pollution and causing severe health impacts. In this paper, we report a study monitoring multiple pollutants including PM₁₀, PM_2.5, CO, CO₂, and volatile organic compounds (VOCs) from fuel combustion at households in Guizhou province of China. The results showed that most pollutants exhibited large variability for different type of fuels except for CO₂. Among these fuels, wood combustion caused the most serious indoor air pollution, with the highest concentrations of particulate matters (218～417 μg m^?3 for PM₁₀ and 201～304 μg m^?3 for PM_2.5), and higher concentrations of CO (10.8 ± 0.8 mg m^?3) and TVOC (about 466.7 ± 337.9 μg m^?3). Coal combustion also resulted in higher concentrations of particulate matters (220～250 μg m^?3 for PM₁₀ and 170～200 μg m^?3 for PM_2.5), but different levels for CO (respectively 14.5 ± 3.7 mg m^?3 for combustion in brick stove and 5.5 ± 0.7 mg m^?3 for combustion in metal stove) and TVOC (170 mg m^?3 for combustion in brick stove and 700 mg m^?3 for combustion in metal stove). Biogas was the cleanest fuel, which brought about the similar levels of various pollutants with the indoor case of non-combustion, and worth being promoted in more areas. Analysis of the chemical profiles of PM_2.5 indicated that OC and EC were dominant components for all fuels, with the proportions of 30～48%. A high fraction of SO₄^2? (31～34%) was detected for coal combustion. The cumulative percentages of these chemical species were within the range of 0.7～1.3, which was acceptable for the assessment of mass balance.     

Recreational atmospheric pollution episodes: Inhalable metalliferous particles from firework displays

The use of fireworks creates an unusual and distinctive anthropogenic atmospheric pollution event. We report on aerosol samples collected during Las Fallas in Valencia, a 6-day celebration famous for its firework displays, and add comparative data on firework- and bonfire-contaminated atmospheric aerosol samples collected from elsewhere in Spain (Barcelona, L’Alcora, and Borriana) and during the Guy Fawkes celebrations in London. Specific high-profile official firework events during Las Fallas included the afternoon Mascletà and the nightly aerial displays (especially in the climactic final 2 days of the fiesta) and were accompanied by pollution spikes in suspended particles, NO, SO₂, and the creation and dispersal of an aerosol cloud enriched in a range of metallic elements. Notable metal aerosol concentration increases recorded during Las Fallas were potassium (from 500 to 5900 ng m⁻³), aluminium (as Al₂O₃ from around 600 to 2200 ng m⁻³), titanium (from 200 to 700 ng m⁻³), magnesium (from 100 to 500 ng m⁻³), lead (from 17 to 379 ng m⁻³), barium (from 39 to 322 ng m⁻³), strontium (from 3 to 112 ng m⁻³), copper (from 12 to 71 ng m⁻³), and antimony (from 1 to 52 ng m⁻³). Firework-contaminated aerosols of similarly metalliferous composition were also identified at the other monitoring sites, although different sites show variations attributable to other sources such as bonfires and local industry. Unusual levels of the trace elements Ba, Sr and (to a lesser extent) Cu, always in proportions with Ba dominant, along with strongly enhanced K, Pb, and Sb, are identified as being particularly characteristic of firework aerosols. Although firework-related recreational pollution episodes are transient in nature, they are highly concentrated, contribute significantly to total annual metal emissions, and are on average fine enough to be easily inhaled and a health risk to susceptible individuals.     

Mass levels,crustal component and trace elements in PM10 in Palermo,Italy

Results concerning the levels and elemental compositions of daily PM₁₀ samples collected at four air quality monitoring sites in Palermo (Italy) are presented. The highest mean value of PM₁₀ concentrations (46 μg m⁻³, with a peak value of 158 μg m⁻³) was recorded at the Di Blasi urban station, and the lowest at Boccadifalco station (25 μg m⁻³), considered as a sub-urban background station. Seventeen elements (Al, As, Ba, Co, Cr, Cu, Fe, Li, Mn, Mo, Ni, Pb, Sb, Sr, U, V, Zn) were measured by ICP-MS. Al and Fe showed the highest concentrations, indicating the significant contribution of soil and resuspended mineral particles to atmospheric PM₁₀. Ba, Cr, Cu, Mn, Mo, Ni, Pb, Sb, V and Zn had higher concentrations at the three urban sampling sites than at the sub-urban background station. Besides soil-derived particles, an R-mode cluster analysis revealed a group of elements, Mo, Cu, Cr, Sb and Zn, probably related to non-exhaust vehicle emission, and another group, consisting of Ba, As and Ni, which seemed to be associated both with exhaust emissions from road traffic, and other combustion processes such as incinerators or domestic heating plants. The results also suggest that Sb, or the association Sb–Cu–Mo, offers a way of tracing road traffic emissions.     

Identification of sources affecting fog formation using receptor modeling approaches and inventory estimates of sectoral emissions

Positive matrix factorization (PMF) was used to identify factors affecting fog formation in Kanpur during the ISRO-GBP land campaign-II (LC-II) in December 2004. PMF predicted factors were validated by contrasting the emission strength of sources in the foggy and clear periods, using a combination of potential source contribution function (PSCF) analysis and quantitative emission inventory information. A time series aerosol chemical data set of 29 days and 12 species was decomposed to identify 4-factors: Secondary species, Biomass burning, Dust and Sea salt. PMF predicted particle mass with a satisfactory goodness-of-fit (slope of 0.83 ± 0.17 and R² of 0.8), and strong species within 11–12% relative standard deviation. Mean contributions of anthropogenic factors were significantly higher during the foggy period for secondary species (2.9 ± 0.3) and biomass burning (1.2 ± 0.09) compared to the clear period. Local sources contributing to aerosols that mediated fog events at Kanpur, based on emissions in a 200 km × 200 km area around Kanpur city were thermal power plants and transportation (SO₂) and biofuel combustion (BC and OM). Regional scale sources influencing emissions during the foggy period, in probable source regions identified by PSCF included thermal power plants, transportation, brick kilns and biofuel combustion. While biofuel combustion and transportation are distributed area sources, individual point sources include coal-fired thermal power plants located in Aligarh, Delhi, Ghaziabad, Jhansi, Kanpur, Rae Bareli and Rupnagar and brick kilns located in Allahabad, Agra, Farrukhabad, Ghaziabad, Kanpur, Ludhiana, Lucknow and Rae Bareli. Additionally, in the foggy period, large areas of probable source regions lay outside India, implying the significance of aerosol incursion from outside India.     

Characteristics of vertical profiles and sources of PM2.5, PM10 and carbonaceous species in Beijing

In August 2003 during the anticipated month of the 2008 Beijing Summer Olympic Games, we simultaneously collected PM₁₀ and PM_2.5 samples at 8, 100, 200 and 325 m heights up a meteorological tower and in an urban and a suburban site in Beijing. The samples were analysed for organic carbon (OC) and elemental carbon (EC) contents. Particulate matter (PM) and carbonaceous species pollution in the Beijing region were serious and widespread with 86% of PM_2.5 samples exceeding the daily National Ambient Air Quality Standard of the USA (65 μg m⁻³) and the overall daily average PM₁₀ concentrations of the three surface sites exceeding the Class II National Air Quality Standard of China (150 μg m⁻³). The maximum daily PM_2.5 and PM₁₀ concentrations reached 178.7 and 368.1 μg m⁻³, respectively, while those of OC and EC reached 22.2 and 9.1 μg m⁻³ in PM_2.5 and 30.0 and 13.0 μg m⁻³ in PM₁₀, respectively. PM, especially PM_2.5, OC and EC showed complex vertical distributions and distinct layered structures up the meteorological tower with elevated levels extending to the 100, 200 and 300 m heights. Meteorological evidence suggested that there exist fine atmospheric layers over urban Beijing. These layers were featured by strong temperature inversions close to the surface (<50 m) and more stable conditions aloft. They enhanced the accumulation of pollutants and probably caused the complex vertical distributions of PM and carbonaceous species over urban Beijing. The built-up of PM was accompanied by transport of industrial emissions from the southwest direction of the city. Emissions from road traffic and construction activities as well as secondary organic carbon (SOC) are important sources of PM. High OC/EC ratios (range of 1.8–5.1 for PM_2.5 and 2.0–4.3 for PM₁₀) were found, especially in the higher levels of the meteorological tower suggesting there were substantial productions of SOC in summer Beijing. SOC is estimated to account for at least 33.8% and 28.1% of OC in PM_2.5 and PM₁₀, respectively, with higher percentages at the higher levels of the tower.     

Characterization,identification of road dust PAHs in central Shanghai areas,China

Road dust samples were collected from central Shanghai in winter (January) and summer (August), respectively. Sixteen polycyclic aromatic hydrocarbons (PAHs) in the United States Environmental Protection Agency (USEPA) priority-controlled list were determined by GC/MS. Total PAH (t-PAH) concentrations in winter samples ranged from 9176 to 32,573 ng g⁻¹ with a mean value of 20,648 ng g⁻¹, while they varied from 6875 to 27,766 ng g⁻¹ in summer with an average of 14,098 ng g⁻¹. Spatial variation showed that city park (CP) samples had the lowest t-PAH concentration, while industrial area (ID) and traffic area (TR) and commercial area (CO) were the most polluted, in both seasons. PAH homologues concentrations were getting higher with the more rings and higher molecular weight (HMW) in all areas. The study of effective factors showed that grain size was only a minor factor influencing the accumulation of PAHs, whereas total organic carbon (TOC) was found to be closely correlated with t-PAH concentration. Prevailing winds could directly affect on the spatial distribution of PAHs. Chemical source apportionment studies took the form of principal component analysis (PCA), followed by compositional analysis. It was demonstrated that road dust PAHs in central Shanghai mainly came from the mixing of traffic and coal combustion. The contribution percentages of pyrogenic and petrogenic sources were respectively 71.0% and 11.4% in winter, while they were, 64.9% and 14.1% in summer, respectively. Road dust PAHs in Shanghai city mostly came from local sources.     

Urban and rural ultrafine (PM0.1) particles in the Helsinki area

In June 1996–June 1997 Berner low-pressure impactors were used at an urban and at a rural site in the Helsinki area for sampling ultrafine particles (UFP, PM_0.1). Ten sample pairs, each pair measured simultaneously, were collected in the size range of 0.03–15 μm of particle aerodynamic diameter. More than 40 chemical components were measured. Surprisingly, the average UFP mass concentration was higher at the rural site (520 ng/m³) than at the urban site (490 ng/m³). The average chemical composition of UFP was similar at the two sites. The most abundant of the measured components were sulphate (32 and 40 ng/m³ for the urban and rural sites, respectively), ammonium (22 and 25 ng/m³), nitrate (4 and 11 ng/m³) and the Ca²⁺ ion (5 and 7 ng/m³). The most important metals at both sites were Ca, Na, Fe, K and Zn with concentrations between 0.7 and 5 ng/m³. Of the heavy metals, Ni, V, Cu, and Pb were important with average ultrafine concentrations between about 0.1 and 0.2 ng/m³. Also the organic anions oxalate (urban 2.1 ng/m³ and rural 1.9 ng/m³) and methanesulphonate (1.3 and 1.7 ng/m³) contributed similarly at both sites. The measured species accounted for only about 15–20% of the total ultrafine mass. The fraction that was not measured includes mainly carbonaceous material and water. It was estimated that the amount of water was about 10% (50 ng/m³) and that of carbonaceous material about 70% (350 ng/m³) at both sites. Aitken modes were observed for most components with the average mass mean mode diameters being between about 0.06 and 0.12 μm. The average concentrations in the Aitken mode differed clearly from those in the UFP for several components.The average contribution of ultrafine mass to the fine particle mass (PM_2.5) was about 7% at the urban site and 8.5% at the rural site. At both sites the contribution of ultrafine to fine was especially high for Se, Ag, B, and Ni (10–20%) and at the rural site also for Co (20%), Ca²⁺ (16%) and Mo (11%). Enrichment in the ultrafine particles suggests that local sources may exist for these elements.Aitken modes turned out to be useful indicators of local sources for several components. The Aitken modes of Ba, Ca, Mg and Sr were similar in several samples, suggesting a common local combustion source for these elements, possibly traffic exhaust. Co, Fe, Mo and Ni formed another group of elements often having similar Aitken modes, the likely source being combustion of heavy fuel oil.     

Dry deposition and foliar leaching of mercury and selected trace elements in deciduous forest throughfall

The estimated annual throughfall deposition flux of Hg in a northern mixed-hardwood forest in the Lake Huron Watershed was 10.5±1.0 μg m⁻² compared to an annual precipitation Hg flux of 8.7±0.5 μg m⁻² (June 1996–June 1997). The source of this additional Hg in throughfall is often attributed to wash-off of dry deposition, but foliar leaching of Hg may also be important. To determine the influence of both dry deposition and foliar leaching of Hg and other elements in throughfall, we measured a suite of trace elements (Hg, Al, Mg, V, Mn, Cu, Zn, As, Rb, Sr, Cd, Ba, La, Ce, and Pb) in throughfall, precipitation, and ambient air samples from a northern mixed-hardwood forest. Based on a multiple linear regression model, dry deposition had the most important influence on Hg, Al, La, Ce, V, As, Cu, Zn, Cd, and Pb fluxes while foliar leaching strongly influenced Mg, Mn, Rb, Sr, and Ba fluxes in net throughfall. The Hg dry deposition flux was estimated using gaseous and aerosol Hg measurements and modeled deposition velocities. The calculated dry deposition flux (∼12–14 μg m⁻²) of Hg to the canopy indicated that atmospheric deposition of Hg could easily account for all of the Hg deposited in net throughfall (1.9±0.1 μg m⁻²). Although there is a large uncertainty associated with these techniques, the modeling estimates indicate that atmospheric Hg may account for all of the Hg deposited in litterfall (11.4±2.8 μg m⁻²).     

Establishment of a database of emission factors for atmospheric pollutants from Chinese coal-fired power plants

Field measurements and data investigations were conducted for developing an emission factor database for inventories of atmospheric pollutants from Chinese coal-fired power plants. Gaseous pollutants and particulate matter (PM) of different size fractions were measured using a gas analyzer and an electric low-pressure impactor (ELPI), respectively, for ten units in eight coal-fired power plants across the country. Combining results of field tests and literature surveys, emission factors with 95% confidence intervals (CIs) were calculated by boiler type, fuel quality, and emission control devices using bootstrap and Monte Carlo simulations. The emission factor of uncontrolled SO₂ from pulverized combustion (PC) boilers burning bituminous or anthracite coal was estimated to be 18.0S kg t^?1 (i.e., 18.0 × the percentage sulfur content of coal, S) with a 95% CI of 17.2S–18.5S. NO_X emission factors for pulverized-coal boilers ranged from 4.0 to 11.2 kg t^?1, with uncertainties of 14–45% for different unit types. The emission factors of uncontrolled PM_2.5, PM₁₀, and total PM emitted by PC boilers were estimated to be 0.4A (where A is the percentage ash content of coal), 1.5A and 6.9A kg t^?1, respectively, with 95% CIs of 0.3A–0.5A, 1.1A–1.9A and 5.8A–7.9A. The analogous PM values for emissions with electrostatic precipitator (ESP) controls were 0.032A (95% CI: 0.021A–0.046A), 0.065A (0.039A–0.092A) and 0.094A (0.0656A–0.132A) kg t^?1, and 0.0147A (0.0092–0.0225A), 0.0210A (0.0129A–0.0317A), and 0.0231A (0.0142A–0.0348A) for those with both ESP and wet flue-gas desulfurization (wet-FGD). SO₂ and NO_X emission factors for Chinese power plants were smaller than those of U.S. EPA AP-42 database, due mainly to lower heating values of coals in China. PM emission factors for units with ESP, however, were generally larger than AP-42 values, because of poorer removal efficiencies of Chinese dust collectors. For units with advanced emission control technologies, more field measurements are needed to reduce emission factor uncertainties.     

Compound specific carbon and hydrogen stable isotope analyses of volatile organic compounds in various emissions of combustion processes

This study presents carbon (δ¹³C) and hydrogen (δD) isotope values of volatile organic compounds (VOCs) in various emission sources using thermal desorption–gas chromatography–isotope ratio mass spectrometry (TD–GC–irMS). The investigated VOCs ranged from C6 to C10. Samples were taken from (i) car exhaust emissions as well as from plant combustion experiments of (ii) various C3 and (iii) various C4 plants. We found significant differences in δ values of analysed VOCs between these sources, e.g. δ¹³C of benzene ranged between (i) −21.7 ± 0.2‰, (ii) −27.6 ± 1.6‰ and (iii) −16.3 ± 2.2‰, respectively and δD of benzene ranged between (i) −73 ± 13‰, (ii) −111 ± 10‰ and (iii) −70 ± 24‰, respectively. Results of VOCs present in investigated emission sources were compared to values from the literature (aluminium refinery emission). All source groups could be clearly distinguished using the dual approach of δ¹³C and δD analysis. The results of this study indicate that the correlation of compound specific carbon and hydrogen isotope analysis provides the potential for future research to trace the fate and to determine the origin of VOCs in the atmosphere using thermal desorption compound specific isotope analysis.     

Quantifying the sources of hazardous elements of suspended particulate matter aerosol collected in Yokohama,Japan

We analyzed metals (Mg, Al, Ca, V, Cr, Mn, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Ag, Cd, Cs, Ba, Pb and Bi), water-soluble ions (Na⁺, NH₄⁺, K⁺, Ca²⁺, Cl^?, NO₃^? and SO₄^2?) and carbonaceous mass (EC and OC) in SPM aerosol samples using an ICP-MS, ion chromatograph and CHN corder, respectively. The SPM samples were collected from 1999 to 2005 at two locations (urban site A and industrial site B) of Yokohama, Japan with concentrations in mean and ranges of 34.2 and 19.7–50.3 μg m^?3 and 22.9 and 12.7–35.1 μg m^?3 for the respective location. Source apportionment of SPM aerosol was conducted appropriately for the first time to these locations employing PCA-APCS technique. Major sources of SPM at site A were a) crustal source, b) urban origin, c) undefined, and d) mineral rock. At site B, the sources were predicted as a) urban origin, b) undefined, c) crustal source, and d) secondarily formed aerosol. The tracers and nature of the source related to urban origin at both sites were similar but retaining different source strength. Secondarily formed aerosol was quite unique at site B. However, mineral rock was remarkable at site A.     

Sphagnum mosses as archives of recent and past atmospheric lead deposition in Switzerland

Sphagnum mosses received from a herbarium and collected recently from a peat bog surface, were used to assess the isotopic character of past and recent atmospheric Pb deposition in Switzerland and to constrain possible Pb sources. Lead removed from the moss surface was isotopically similar to that measured in the corresponding solid plant, suggesting that neither preservative actions for the herbarium samples nor dust had affected the isotopic composition of the samples. The addition of HCl to aqueous extracts to remove surface particles from the plants released more Pb compared to H₂O alone. The changes in isotope ratios between Sphagnum collected during the past c. 130 yr were significantly greater than the small fluctuations between and among species collected at any one time. Three isotope ratio plots and emission inventories indicated that the most likely source of atmospheric Pb was coal-burning at the turn of the century, fly ash from waste incineration until approximately 1950, and gasoline combustion after that. The pollution record derived from the Sphagnum plants is in good agreement with other archives from Switzerland (peat, sediment, ice) and with other herbarium records in Europe.     

Identification,abundance and seasonal variation of anthropogenic organic aerosols from a mega-city in China

PM_2.5 aerosols were collected in Nanjing, a typical mega-city in China, during summer and winter 2004 and were characterized for aromatic and cyclic compounds using a GC/MS technique to understand the air pollution problem. They include polycyclic aromatic hydrocarbons (PAHs), hopanes, phthalates and hydroxy-PAHs (OH-PAHs). PAHs, hopanes and OH-PAHs presented higher concentrations in winter (26–178, 3.0–18, and 0.013–0.421 ng m⁻³, respectively) than in summer (12–96, 1.6–11, and 0.029–0.171 ng m⁻³, respectively) due to an enhanced coal burning for house heating and atmospheric inversion layers developed in the cold season. In contrast, phthalates are more abundant in summer (109–368 ng m⁻³, average 230 ng m⁻³) than in winter (33–390 ng m⁻³, average 170 ng m⁻³) due to an enhanced evaporation from plastics during the hot season and the subsequent deposition on the pre-existing particles. Generally, all the identified compounds showed higher concentrations in nighttime than in daytime due to inversion layers and increased emissions from heavy-duty trucks at night. PAHs, hopanes and phthalates in Nanjing aerosols are 5–100 times more abundant than those in Los Angeles, USA, indicating a serious air pollution problem in the city. Concentrations of OH-PAHs are 1–3 orders of magnitude less than their parent PAHs and comparable to those reported from other international cities. Source identification using diagnostic ratios of the organic tracers suggests that PAHs in Nanjing urban area are mainly derived from coal burning, whereas hopanes are more attributable to traffic emissions.     

Source contributions to carbonaceous aerosols in the Tennessee Valley Region

Sources of carbonaceous aerosols collected from three sites of Chattanooga, TN (CH), Muscle Shoals, AL (MS), and Look Rock, TN (LR) in the Tennessee Valley Region (TVR) were apportioned using both organic tracer-based chemical mass balance (CMB) modeling and radiocarbon (¹⁴C) measurement and the results were compared. Eight sources were resolved by CMB, among which wood combustion (averaging 0.92 μg m⁻³) was the largest contributor to primary organic carbon (OC) concentrations, followed by gasoline exhaust (0.35 μg m⁻³), and diesel exhaust (0.18 μg m⁻³). The identified primary sources accounted for 43%, 71%, and 14% of measured OC at CH, MS, and LR, respectively. Contributions from the eight primary sources resolved by CMB could explain 107±10% of ambient elemental carbon (EC) concentrations, with diesel exhaust (66±32%) and wood combustion (37±33%) as the most important contributors. The fossil fractions in total carbon determined by ¹⁴C measurements were in reasonably good agreement with that in primary (OC+EC) carbon apportioned by CMB in the MS winter samples. The comparison between the ¹⁴C and CMB results revealed that contemporary sources dominated other OC in the TVR, especially in summertime (84% contemporary).