Characterization of chemical species in atmospheric aerosols in a metropolitan basin

Ambient PM10 aerosol samples were collected from Taiwan's Taichung metropolitan basin between October 1997 and January 1998, and their chemical characteristics studied. The average mass concentration of PM10 was 109.0 +/- 54.1 microg/m3. Carbonaceous materials, sulfate, nitrate, and ammonium were the most important contributors to the PM10 component. On average, 64% of the PM10 was made up of fine particles. During PM10 episodes, average wind speed was 0.7 m/s and relative humidity was high, 83% on average, probably giving rise to stagnation of air pollutants and their entrapment close to the surface. With relative humidity < 70%, NO3-, NH4+, SO4(2-), carbonaceous materials, and PM10 mass showed high correlation with maximum hourly average ozone (O3M). Variation in atmospheric humidity may affect the gas-to-particle interactions of S and N species. The most significant contribution to PM10 in the Taichung urban basin was from the photochemical formation of secondary aerosols and carbonaceous materials in the atmospheric environment.     

Evaluations of the chemical mass balance method for determining contributions of gasoline and diesel exhaust to ambient carbonaceous aerosols

The US. Department of Energy Gasoline/Diesel PM Split Study was conducted to assess the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the relative contributions of emissions from gasoline (or spark ignition [SI]) and diesel (or compression ignition [CI]) engines to ambient concentrations of fine particulate matter (PM2.5) in California's South Coast Air Basin (SOCAB). In this study, several groups worked cooperatively on source and ambient sample collection and quality assurance aspects of the study but worked independently to perform chemical analysis and source apportionment. Ambient sampling included daily 24-hr PM2.5 samples at two air quality-monitoring stations, several regional urban locations, and along freeway routes and surface streets with varying proportions of automobile and truck traffic. Diesel exhaust was the dominant source of total carbon (TC) and elemental carbon (EC) at the Azusa and downtown Los Angeles, CA, monitoring sites, but samples from the central part of the air basin showed nearly equal apportionments of CI and SI. CI apportionments to TC were mainly dependent on EC, which was sensitive to the analytical method used. Weekday contributions of CI exhaust were higher for Interagency Monitoring of Protected Visual Environments (IMPROVE; 41+/-3.7%) than Speciation Trends Network (32+/-2.4%). EC had little effect on SI apportionment. SI apportionments were most sensitive to higher molecular weight polycyclic aromatic hydrocarbons (indeno[123-cd]pyrene, benzo(ghi)perylene, and coronene) and several steranes and hopanes, which were associated mainly with high emitters. Apportionments were also sensitive to choice of source profiles. CI contributions varied from 30% to 60% of TC when using individual source profiles rather than the composites used in the final apportionments. The apportionment of SI vehicles varied from 1% to 12% of TC depending on the specific profile that was used. Up to 70% of organic carbon (OC) in the ambient samples collected at the two fixed monitoring sites could not be apportioned to directly emitted PM emissions.     

The use of chemical and statistical methods to identify sources of selected elements in ambient air aerosols in Karachi,Pakistan

Concentrations of 23 elements plus NO₃⁻, SO₄²⁻ and Cl⁻ were determined for samples collected continuously every 3 or 6 h during 22–27 July, 1985 at a suburban site in Karachi, Pakistan. Concentrations of lithophilic elements and several anthropogenic elements were ~ 80 % higher during daytime than at night. These elevated levels were attributed to daytime increases in wind velocity and anthropogenic activity. Factor analysis showed that ~ 50% of the variance was associated with soil, and ~ 14 % each with oceanic Na and Cl⁻, anthropogenic Sb and Pb, and Zn, Se and SO₄²⁻. A cement (limestone/dolomite) factor was not separated even though Ca and Mg concentrations were unusually high and a cement factory was located nearby. This led to an investigation of a chemical approach to determine the sources. Concentrations of Na, Mg and Ca were determined in water-extracts of the samples. Assuming soluble Na (~ 92 % of total) to be sea derived, marine components of Mg, SO₄²⁻, Ca and Br were determined. Solubility considerations were then used to reveal the cement source and apportion the aerosol sources. On the average, approximately 48 % of the total aerosol mass could be accounted for by the ‘cement’ and ‘soil’ components; about 12 % by the ‘sea salt’, about 3% by the ‘fossil fuel’ SO₄²⁻ (as (NH₄)₂SO₄); about 1 % by the NO₃⁻ (as NH₄NO₃); the remaining 36 % of the aerosol mass was unassigned.     

Measurement of organic mass to organic carbon ratio in ambient aerosol samples using a gravimetric technique in combination with chemical analysis

Organic materials make up a significant fraction of ambient particulate mass. It is important to quantify their contributions to the total aerosol mass for the identification of aerosol sources and subsequently formulating effective control measures. The organic carbon (OC) mass can be determined by an aerosol carbon analyzer; however, there is no direct method for the determination of the mass of organic compounds, which also contain N, H, and O atoms in addition to C. The often-adopted approach is to estimate the organic mass (OM) from OC multiplying by a factor. However, this OC-to-OM multiplier was rarely measured for a lack of appropriate methods for OM. We report here a top-down approach to determine OM by coupling thermal gravimetric and chemical analyses. OM is taken to be the mass difference of a filter before and after heating at 550 °C in air for 4 h minus mass losses due to elemental carbon (EC), volatile inorganic compounds (e.g., NH₄NO₃), and loss of aerosol-associated water that arise from the heating treatment. The losses of EC and inorganic compounds are determined through chemical analysis of the filter before and after the heating treatment. We analyzed 37 ambient aerosol samples collected in Hong Kong during the winter of 2003, spring of 2004, and summer of 2005. A value of 2.1±0.3 was found to be the appropriate factor to convert OC to OM in these Hong Kong aerosol samples. If the dominant air mass is classified into two categories, then an OM-to-OC ratio of 2.2 was applicable to aerosols dominated by continent-originated air mass, and 1.9 was applicable to aerosols dominated by marine air mass.     

Observational and modeling studies of chemical species concentrations as a function of raindrop size

The Guttalgor method has been used to determine the chemical species concentrations in size-selected raindrops in nine rain events at Hong Kong from 1999 to 2001. The curve (concentration against raindrop radius) patterns for all the species are similar but depend on the starting time of sampling within a rain event. In these plots, the maximum concentration occurs at the same range of droplet radius, irrespective of the species, and this indicates the importance of coalescence and breakup processes. The maximum is located at a smaller droplet radius than was found in previous studies in Germany. All results show almost constant concentrations with size for large raindrops, and these indicate the in-cloud contributions. The pH of raindrops of similar size is linearly correlated with a function of the sulfate, nitrate, acetate, formate, calcium and ammonium ion species concentrations. Within a single raindrop, chloride depletion is not significant, and sulfate, ammonium and hydrogen ions are found in ratios compatible with the precursor solid-phase mixture of ammonium sulfate and ammonium bisulphate. When simulated by a below-cloud model, good agreement between the modeled and measured sodium and sulfate concentrations has been found. Below-cloud sulfur dioxide scavenging contributes at most 60% of the sulfate concentration in a single raindrop.     

ATR-FTIR characterization of organic functional groups and inorganic ions in ambient aerosols at a rural site

An Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopic method was used to measure organic functional groups and inorganic ions at Tonto National Monument (TNM), an Interagency Monitoring of Protected Visual Environments (IMPROVE) sampling site in a rural area near Phoenix, Arizona. Functional groups and ions from common aerosol compound classes such as aliphatic and aromatic CH, methylene, methyl, aldehydes/ketones, carboxylic acids, ammonium sulfate and nitrate as well as functional groups from difficult to measure compound classes such as esters/lactones, acid anhydrides, carbohydrate hydroxyl and ethers, amino acids, and amines were quantified. On average, ～33% of the PM_1.0 mass was composed of organic aerosol. The average (standard deviation) composition of the organic aerosol at TNM was 34% (6%) biogenic functional groups, 21% (5%) oxygenated functional groups, 28% (7%) aliphatic hydrocarbon functional groups (aliphatic CH, methylene and methyl) and 17% (1%) aromatic hydrocarbon functional groups. Compositional analysis, functional group correlations, and back trajectories were used to identify three types of events with source signatures: primary biogenic-influenced, urban-influenced, and regional background. The biogenic-influenced event had high concentrations of amino acids and carbohydrate hydroxyl and ether, as well as aliphatic CH and aromatic CH functional groups and qualitatively high levels of silicate. The urban-influenced events had back trajectories traveling directly from the Phoenix area and high concentrations of hydrocarbons, oxygenated functional groups, and inorganic ions. This aerosol characterization suggests that both primary emissions in Phoenix and secondary formation of aerosols from Phoenix emissions had a major impact on the aerosol composition and concentration at TNM. The regional background source had low concentrations of all functional groups, but had higher concentrations of biogenic functional groups than the urban source.     

Satellite observations of the seasonal cycles of absorbing aerosols in Africa related to the monsoon rainfall, 1995–2008

The link between the African Monsoon systems and aerosol loading in Africa is studied using multi-year satellite observations of UV-absorbing aerosols and rain gauge measurements.The main aerosol types occurring over Africa are desert dust and biomass burning aerosols, which are UV-absorbing. The abundance of these aerosols over Africa is characterised in this paper using residues and Absorbing Aerosol Index (AAI) data from Global Ozone Monitoring Experiment (GOME) on board ERS-2 and SCanning Imaging Absorption SpectroMeter for Atmospheric ChartograpHY (SCIAMACHY) on board Envisat.Time series of regionally averaged residues from 1995 to 2008 show the seasonal variations of aerosols in Africa. Zonally averaged daily residues over Africa are related to monthly mean precipitation data and show monsoon-controlled atmospheric aerosol loadings. A distinction is made between the West African Monsoon (WAM) and the East African Monsoon (EAM), which have different dynamics, mainly due to the asymmetric distribution of land masses around the equator in the west. The seasonal variation of the aerosol distribution is clearly linked to the seasonal cycle of the monsoonal wet and dry periods in both studied areas.The residue distribution over Africa shows two distinct modes, one associated with dry periods and one with wet periods. During dry periods the residue varies freely, due to aerosol emissions from deserts and biomass burning events. During wet periods the residue depends linearly on the amount of precipitation, due to scavenging of aerosols and the prevention of aerosol emissions from the wet surface. This is most clear over east Africa, where the sources and sinks of atmospheric aerosols are controlled directly by the local climate, i.e. monsoonal precipitation. Here, the wet mode has a mean residue of ?1.4 and the dry mode has a mean residue of ?0.3. During the wet modes a reduction of one residue unit for every 160 mm monthly averaged precipitation was found. Shielding effects due to cloud cover may also play a role in the reduction of the residue during wet periods.A possible influence of aerosols on the monsoon, via aerosol direct and indirect effects, is plausible, but cannot directly be deduced from these data.     

Source apportionment methods applied to the determination of the origin of ambient aerosols that affect visibility in forested areas

An aerosol characterization, visibility, and receptor modeling study was conducted in the Shenandoah Valley, VA between 14 July and 15 August 1980. The objectives of this study were to: (1) determine the origin of the ambient particles, (2) determine the major chemical species contributing to the light extinction coefficient, (3) evaluate analytical methods to characterize aerosols and (4) provide data for comparison with chemical composition of aerosols collected in the Great Smoky Mountains and in the Abastumani Mountains of Georgian Soviet Socialist Republic. The average sulfate concentrations measured in fine particles (<2.5μm) at these three locations were: 12.0μgm⁻³ at Great Smoky Mountains; 13.6 μg m⁻³ at Shenandoah Valley, and 4.6 μg m⁻³ at Abastumani Mountains; the fractions of sulfate in the fine particle mass concentrations at each site were 0.50,0.50 and 0.38, respectively. For the two studies in the United States, the fine particle sulfate during sulfate maxima was mostly in the form of ammonium acid sulfate. Factor analysis of the fine aerosol composition measured in the Shenandoah Valley yielded a persistent factor containing large loadings on mass, SO²⁻₄, S, NH⁺₄, H⁺, Se and total nitrate (sum of particulate nitrate and nitric acid), which is characteristic of coal-fired sources. This factor analysis grouping along with additional emissions information suggests that coal-fired power plants are the principal source of sulfate and nitrate.     

FTIR transmission spectrometry for the nondestructive determination of ammonium and sulfate in ambient aerosols collected on teflon filters

Fourier transform infrared (FTIR) transmission spectrometry has been used to determine ammonium and sulfate in ambient aerosol particles collected on Teflon filters. Integrated absorbance as well as maximum absorbance values for ammonium and sulfate are linearly related to X-ray fluorescence measurements of total sulfur. Apparent detection limits of 1.4 μg m⁻³ for sulfate and 0.5 μg m⁻³ for ammonium (for sample volumes of 21.6 m³) were estimated for samples from Topeka, Kansas; Portage, Wisconsin; Steubenville, Ohio; and Charlottesville, Virginia. The apparent detection limits were essentially independent of sample loading over the range of 0–20 μg m⁻³ of total sulfur. The FTIR transmission measurements of these samples are very precise e.g. repetitive measurements vary ± 0.2% and blank variability is 0.13 μg m⁻³ and 0.20 μg m⁻³ in terms of sulfate and ammonium, respectively. Contributions to analytical uncertainty include 5–8% uncertainties in X-ray fluorescence measurements for total sulfur and the influence of unspecified site-dependent sample characteristics. The method offers the significant advantages of nondestructive analysis, no sample preparation, molecular speciation and rapid analysis.     

Measurements of the photochemical production of aerosols in ambient air near a freeway for a range of SO2 concentrations

The formation and growth of photochemically produced aerosol particles were studied for initially particle-free ambient air collected downwind from a freeway in two 14 m³ transparent Teflon bags exposed to natural sunlight for SO₂ concentrations ranging from 0.006 to 0.067 ppm, by volume. Using a Thermo Systems Electrical Aerosol Analyzer, the concentration and size distribution of aerosol particles from 0.0056 to 0.36 μm dia. was measured as a function of time. The volumetric conversion rate of material from the vapor to the condensed phase was found to be a linear function of the initial SO₂ concentration and directly proportional to the initial non-methane hydrocarbon concentration in the bags. Filter samples of the photochemically produced aerosol particles were analyzed for sulfate, nitrate and nitrite. The sulfate and nitrate formation rates ranged from 0.72 to 2.6 μg m⁻³ h⁻¹ and 0.76 to 3.2 μg m⁻³ h⁻¹, respectively, while the nitrite formation rate ranged from 0.008 to 0.038 μg m⁻³ h⁻¹. The overall rate of SO₂ to sulfate conversion was estimated to range from 0.55 to 1.3% h⁻¹. X-ray photoelectron spectroscopy was used to determine the chemical states of sulfur, nitrogen and carbon on the surface of the filter samples. Sulfur was found in the form of SO²⁻₄, as well as chemisorbed SO₂ and SO₃. Nitrogen was present as NO⁻₃ and as two reduced forms identified as amines or amides, and carbon was present as either elemental carbon or as paraffinic hydrocarbon.     

沸石颗粒在污泥絮体中的形态及其对污泥泥水分离的影响

投加沸石粉提高了活性污泥的泥水分离性能。通过对沸石颗粒表面生物膜和投加了沸石粉的活性污泥絮体生长过程及成熟形态的微观观察,结果表明沸石颗粒不仅可以作为微生物载体长成生物膜,而且成为菌胶团核心和污泥絮体骨架,改善了污泥絮体的颗粒结构,从而增强了絮体强度,提高了絮体密度,降低了污泥塑性。研究结果表明沸石粉适宜的投加量为4g/L;在活性污泥中投加4g/L沸石粉后,SVI从193降低到155,污泥比阻从27.36×1012m/kg降低到5.67×1012m/kg;在沸石粉含量小于10g/L时,随着沸石粉含量的增加,污泥呈现压缩沉淀时界面沉速和出现压缩沉淀的时间持续减小。     

Effect of ambient air pollution on tuberculosis risks and mortality in Shandong,China: a multi-city modeling study of the short- and long-term effects of pollutants

Environmental Science and Pollution Research - Few studies conducted in China have assessed the effects of ambient air pollution exposure on tuberculosis (TB) risk and mortality, especially with a...     

The sensitivity of PM2.5 source-receptor relationships to atmospheric chemistry and transport in a three-dimensional air quality model

Air quality model simulations constitute an effective approach to developing source-receptor relationships (so-called transfer coefficients in the risk analysis framework) because a significant fraction of particulate matter (particularly PM2.5) is secondary (i.e., formed in the atmosphere) and, therefore, depends on the atmospheric chemistry of the airshed. In this study, we have used a comprehensive three-dimensional air quality model for PM2.5 (SAQM-AERO) to compare three approaches to generating episodic transfer coefficients for several source regions in the Los Angeles Basin. First, transfer coefficients were developed by conducting PM2.5 SAQM-AERO simulations with reduced emissions of one of four precursors (i.e., primary PM, sulfur dioxide (SO2), oxides of nitrogen (NOx), and volatile organic compounds) from each source region. Next, we calculated transfer coefficients using two other methods: (1) a simplified chemistry for PM2.5 formation, and (2) simplifying assumptions on transport using information limited to basin-wide emission reductions. Transfer coefficients obtained with the simplified chemistry were similar to those obtained with the comprehensive model for VOC emission changes but differed for NOx and SOz emission changes. The differences were due to the parameterization of the rates of secondary PM formation in the simplified chemistry. In 90% of the cases, transfer coefficients estimated using only basin-wide information were within a factor of two of those obtained with the explicit source-receptor simulations conducted with the comprehensive model. The best agreement was obtained for VOC emission changes; poor agreement was obtained for primary PM2.5.     

Integrated biomonitoring of air quality with plants and lichens: a case study on ambient ozone from central Italy

A biennial integrated survey, based on the use of vascular plants for the bioindication of the effects of tropospheric ozone together with the use of automatic analysers of ozone, as well as the mapping of lichen biodiversity was performed in the area of Castelfiorentino (Tuscany, central Italy). Photochemically produced ozone proved to be a fundamental presence during the warm season, with maximum hourly means reaching 114 ppb, exceeding the information threshold as fixed by EU: the use of supersensitive tobacco Bel-W3 confirmed the opportunity of carrying out detailed cost-effective monitoring surveys. The potential for didactical and educational implications of this methodology are appealing. Critical levels set up for the protection of vegetation have exceeded considerably. The comparison of biomass productivity in sensitive and resistant individuals (NC-S and NC-R white clover clones, in the framework of an European network) provided evidence that ambient ozone levels are associated with relevant reduction (up to 30%) in the performance of sensitive material; effects on flowering were also pronounced. The economic assessment of such an impact deserves attention. Mapping of epiphytic lichen biodiversity – which has been used to monitor air quality worldwide – was not related to ozone geographical distribution as depicted by tobacco response.     

Simulation of aerosols and gas-phase species over Europe with the Polyphemus system. Part II: Model sensitivity analysis for 2001

This paper presents a multi-pollutant sensitivity study of an air quality model over Europe with a focus on aerosols. Following the evaluation presented in the companion paper, the aim here is to study the sensitivity of the model to input data, mathematical parameterizations and numerical approximations. To that end, 30 configurations are derived from a reference configuration of the model by changing one input data set, one parameterization or one numerical approximation at a time. Each of these configurations is compared to the same reference simulation over two time periods of the year 2001, one in summer and one in winter. The sensitivity of the model to the different configurations is evaluated through a statistical comparison between the simulation results and through comparisons to available measurements. The species studied are ozone (O₃), nitrogen dioxide (NO₂), sulfur dioxide (SO₂), ammonia (NH₃), coarse and fine aerosol particles (PM_c and PM_2.5), sulfate, nitrate, ammonium, chloride and sodium.For all species, the modeled concentrations are very sensitive to the parameterization used for vertical turbulent diffusion and to the number of vertical levels. For the other configurations considered in this work, the sensitivity of the modeled concentration to configuration choice varies with the species and the period of the year. O₃ is impacted by options related to boundary conditions. PM_c is sensitive to sea-salt related options, to options influencing deposition and to options related to mass transfer between gas and particulate phases. PM_2.5 is sensitive to a larger number of options than PM_c: sea-salt, boundary conditions, heterogeneous reactions, aqueous chemistry and gas/particle mass transfer. NO₂ is strongly influenced by heterogeneous reactions. Nitrate shows the highest variability of all species studied. As with NO₂, nitrate is strongly sensitive to heterogeneous reactions but also to mass transfer, thermodynamic related options, aqueous chemistry and computation of the wet particle diameter. While SO₂ is mostly sensitive to aqueous chemistry, sulfate is also sensitive to boundary conditions and, to a lesser extent, to heterogeneous reactions. As with nitrate, ammonium is largely impacted by the different configuration choices, although the sensitivity is slightly lower than for nitrate. NH₃ is sensitive to aqueous chemistry, mass transfer and heterogeneous reactions. Chloride and sodium are impacted by sea-salt related options, by options influencing deposition and by options concerning the aqueous-phase module.     

Effects of basin topography and monsoon conditions on transport and occurrence of atmospheric PCDD/Fs in the Taichung Basin

Background, aim, and scope  

Topographical and meteorological factors, such as monsoons, can drastically affect ambient dioxin levels. In order to better understand these phenomena, four sampling lines (comprising 16 sampling sites) were selected in accordance with the topographical characteristics and the transport paths of the Taichung Basin.     

Utilizing the Chemical Mass Balance and Positive Matrix Factorization models to determine influential species and examine possible rotations in receptor modeling results

Data from two of the United States Environmental Protection Agency's Speciation Trends Network fine particulate matter sites within Chicago, Illinois were used to examine the influence that the results and profiles of the Chemical Mass Balance (CMB) receptor model have on the source contributions and profiles of the Positive Matrix Factorization (PMF) model. This was accomplished using the target shape technique, which utilizes a priori information from the CMB source profiles inputted into the PMF model. The target shape methodology involves inputting specific information for the source profiles into the PMF model as it is resolving source profile and contribution matrices. The target shape results demonstrated it is possible to determine in both the CMB and PMF source profiles those species, which do not influence the solutions of either model.A second method utilizing information from the CMB results was used to impose a condition where the Motor Vehicles source never had a zero contribution as was applied to the CMB model. This involved utilizing an edge rotation to rotate the PMF results to yield a different solution without worsening the fit of the original results. The purpose of this work is to achieve a rotation, which produced a PMF solution where all of the Motor Vehicles contributions were greater than zero. Comparing the rotated Motor Vehicles and Sulfates source contributions in PMF to those obtained from CMB showed a better correlation between the PMF Motor Vehicles contributions to the original CMB results than those prior to rotation.     

Accumulated sediments in a detention basin: chemical and microbial hazard assessment linked to hydrological processes

Accumulated sediments in a 32,000-m³ detention basin linked to a separate stormwater system were characterized in order to infer their health hazards. A sampling scheme of 15 points was defined according to the hydrological behaviour of the basin. Physical parameters (particle size and volatile organic matter content) were in the range of those previously reported for stormwater sediments. Chemical analyses on hydrocarbons, PAHs, PCBs and heavy metals showed high pollutant concentrations. Microbiological analyses of these points highlighted the presence of faecal indicator bacteria (Escherichia coli and intestinal enterococci) and actinomycetes of the genus Nocardia. These are indicative of the presence of human pathogens. E. coli and enterococcal numbers in the sediments were higher at the proximity of the low-flow gutter receiving waters from the catchment. These bacteria appeared to persist over time among urban sediments. Samples highly contaminated by hydrocarbons were also shown to be heavily contaminated by these bacteria. These results demonstrated for the first time the presence of Nocardial actinomycetes in such an urban context with concentrations as high as 11,400 cfu g^?1.