Chemical Composition of Fine Particles in the Tennessee Valley Region

ABSTRACT

Fine particles in the atmosphere have elicited new national ambient air quality standards (NAAQS) because of their potential role in health effects and visibility-reducing haze. Since April 1997, Tennessee Valley Authority (TVA) has measured fine particles (PM_2.5) in the Tennessee Valley region using prototype Federal Reference Method (FRM) samplers, and results indicate that the new NAAQS annual standard will be difficult to meet in this region. The composition of many of these fine particle samples has been determined using analytical methods for elements, soluble ions, and organic and elemental carbon. The results indicate that about one-third of the measured mass is SO₄ ^-2, one-third is organic aerosol, and the remainder is other materials. The fraction of SO₄ ^-2 is highest at rural sites and during summer conditions, with greater proportions of organic aerosol in urban areas throughout the year. Additional measurements of fine particle mass and composition have been made to obtain the short-term variability of fine mass as it pertains to human exposure. Measurements to account for semi-volatile constituents of fine mass (nitrates, semi-volatile organics) indicate that the FRM may significantly under-measure organic constituents. The potentially controllable anthropogenic fraction of organic aerosols is still largely unknown.     

Characterization of Major Chemical Components of Fine Particulate Matter in North Carolina

Abstract

This paper presents measurements of daily sampling of fine particulate matter (PM_2.5) and its major chemical components at three urban and one rural locations in North Carolina during 2002. At both urban and rural sites, the major insoluble component of PM_2.5 is organic matter, and the major soluble components are sulfate (SO₄ ^2?), ammonium (NH₄ ⁺), and nitrate (NO₃ ^?). NH₄ ⁺ is neutralized mainly by SO₄ ^2? rather than by NO₃ ^?, except in winter when SO₄ ^2? concentration is relatively low, whereas NO₃ ^? concentration is high. The equivalent ratio of NH₄ ⁺ to the sum of SO₄ ^2? and NO₃ ^? is <1, suggesting that SO₄ ^2?and NO₃ ^?are not completely neutralized by NH₄ ⁺. At both rural and urban sites, SO₄ ^2?concentration displays a maximum in summer and a minimum in winter, whereas NO₃ ^?displays an opposite seasonal trend. Mass ratio of NO₃ ^? to SO₄ ^2?is consistently <1 at all sites, suggesting that stationary source emissions may play an important role in PM_2.5 formation in those areas. Organic carbon and elemental carbon are well correlated at three urban sites although they are poorly correlated at the agriculture site. Other than the daily samples, hourly samples were measured at one urban site. PM_2.5 mass concen trations display a peak in early morning, and a second peak in late afternoon. Back trajectory analysis shows that air masses with lower PM_2.5 mass content mainly originate from the marine environment or from a continental environment but with a strong subsidence from the upper troposphere. Air masses with high PM_2.5 mass concentrations are largely from continental sources. Our study of fine particulate matter and its chemical composition in North Carolina provides crucial information that may be used to determine the efficacy of the new National Ambient Air Quality Standard (NAAQS) for PM fine. Moreover, the gas-to-particle conversion processes provide improved prediction of long-range transport of pollutants and air quality.     

Calculation of the Charging Rate of Fine Particles by Unipolar Ions

Theories of particle charging based on boundary value solutions to the diffysional equation may not be applicable to electrostatic precipitators where the ion density is rarely more than an order of magnitude greafer than the particle concentration. A new charging equation, based on kinetic theory, is presented which evaluates the charging rate in terms of the probability of collisions between the flust particles and ions. In the presence of an external electric field, the surface of the particle is divided into three charging regions, and separate charging rates are calculated for each region. The total charging rate is the sum of these three individual rates. For large particles and high electric fields, this theory predicts essentially the same charging rate as the classical field charging equation of Rohmann and Pauthenier. For low electric fields, the theory reduces to White’s diffusional charging equation. Agreement is within 25% of Hewitt’s experimental results over the entire range of variables where data are available. For practical charging times, agreement is within 15%.     

Threshold Dependence of Mortality Effects for Fine and Coarse Particles in Phoenix,Arizona

ABSTRACT

Daily data for fine (<2.5 um) and coarse (2.5-10 um) particles are available for 1995-1997 from the U.S. Environmental Protection Agency (EPA) research monitor in Phoenix, AZ. Mortality effects on the 65 and over population were studied for both the city of Phoenix and for a region of about 50 mi around Phoenix. Coarse particles in Phoenix are believed to be natural in origin and spatially homogeneous, whereas fine particles are primarily vehicular in origin and concentrated in the city itself. For this reason, it is natural to focus on city mortality data when considering fine particles, and on region mortality data when considering coarse particles, and most of the results reported here correspond to those assignments.

After allowing for seasonality and long-term trend through a nonlinear (B-spline) trend curve, and also for meteorological effects based on temperature and specific humidity, a regression of mortality was performed on PM using several different measures for PM. Based on a linear PM effect, we found a statistically significant coefficient for coarse particles, but not for fine particles, contrary to what is widely believed about the effects of coarse and fine particles. An analysis of nonlinear pollution-mortality relationships, however, suggests that the true picture is more complicated than that. For coarse particles, the evidence for any nonlinear or threshold-based effect is slight. For fine particles, we found evidence of a threshold, most likely with values in the range of 20-25 ug/m³. We also found some evidence of interactions of the PM effects with season and year.

The main effect here is an apparent seasonal interaction in the coarse PM effect. An attempt was made to explain this in terms of seasonal variation in the chemical composition of PM, but this led to another counterintuitive result: the PM effect is highest in spring and summer, when the anthropogenic concentration of coarse PM is lowest as determined by a principal components analysis. There was no evidence of confounding between the fine and coarse PM effects. Although these results are based on one city and should be considered tentative until replicated in other studies, they suggest that the prevailing focus on fine rather than coarse particles may be an oversimplification. The study also shows that consideration of nonlinear effects can lead to real changes of interpretation and raises the possibility of seasonal effects associated with the chemical composition of PM.     

Radiation Charging: A Novel Way to Charge Fine Particles Electrically

The purpose of this paper is to describe a scheme to electrically charge fine particles using electric and magnetic fields in conjunction with ionizing radiation. Once charged, particulate matter can be removed from the air stream by directly applying a transverse electric field. In addition, since electrostatic forces can assist filtration and wet collection systems, it may be possible to design new and improved filtration and wet scrubber systems using radiation charging. The objectives of this paper are: (1) to present expressions that predict the charge acquired by particles and (2) to present the results of preliminary experiments.     

Indoor Fine Particles: The Role of Terpene Emissions from Consumer Products

Abstract

Consumer products can emit significant quantities of terpenes, which can react with ozone (O₃). Resulting byproducts include compounds with low vapor pressures that contribute to the growth of secondary organic aerosols (SOAs). The focus of this study was to evaluate the potential for SOA growth, in the presence of O₃, following the use of a lime-scented liquid air freshener, a pine-scented solid air freshener, a lemon-scented general-purpose cleaner, a wood floor cleaner, and a perfume. Two chamber experiments were performed for each of these five terpene-containing agents, one at an elevated O₃ concentration and the other at a lower O₃ concentration. Particle number and mass concentrations increased and O₃ concentrations decreased during each experiment. Experiments with terpene-based air fresheners produced the highest increases in particle number and mass concentrations. The results of this study clearly demonstrate that homogeneous reactions between O₃ and terpenes from various consumer products can lead to increases in fine particle mass concentrations when these products are used indoors. Particle increases can occur during periods of elevated outdoor O₃ concentrations or indoor O₃ generation, coupled with elevated terpene releases. Human exposure to fine particles can be reduced by minimizing indoor terpene concentrations or O₃ concentrations.     

Fine Particles and Oxidant Pollution: Developing an Agenda for Cooperative Research

ABSTRACT

This paper describes a background for the North American Research Strategy for Tropospheric Ozone (NARSTO) cooperative program integrating studies of O₃ and PM_{2 5}. It discusses several important aspects for rationalizing NARSTO's trinational investigative approach, including (1) an outlook on the state of knowledge about fine particles in the troposphere and their origins in Canada, Mexico, and the United States; (2) the need for enhancement and strengthening of key field measurements in relation to tropospheric chemistry and a health effects component; and (3) the use of a central theme for advancing air quality modeling using evolving techniques to integrate and guide key process-oriented field campaigns. The importance of organizing a scientific program to acquire “policy-relevant” information is stressed, noting cooperative research directions that address combined PM_2.5 and O₃ issues, illustrated through exploration of hypothetical pathways of PM_2.5 response to choices of O₃ and PM precursor emission reductions. The information needed for PM_2.5 research is noted to intersect in many cases with those of O₃, but diverge in other cases. Accounting for these distinctions is important for developing NARSTO's strategy over the next decade.     

Concentration and Size Distribution of Ultrafine Particles Near a Major Highway

Abstract

Motor vehicle emissions usually constitute the most significant source of ultrafine particles (diameter <0.1 μm) in an urban environment, yet little is known about the concentration and size distribution of ultrafine particles in the vicinity of major highways. In the present study, particle number concentration and size distribution in the size range from 6 to 220 nm were measured by a condensation particle counter (CPC) and a scanning mobility particle sizer (SMPS), respectively. Measurements were taken 30, 60, 90, 150, and 300 m downwind, and 300 m upwind, from Interstate 405 at the Los Angeles National Cemetery. At each sampling location, concentrations of CO, black carbon (BC), and particle mass were also measured by a Dasibi CO monitor, an aethalometer, and a DataRam, respectively. The range of average concentration of CO, BC, total particle number, and mass concentration at 30 m was 1.7?2.2 ppm, 3.4?10.0 μg/m³, 1.3?2.0 × 10⁵/cm³, and 30.2?64.6 μ/m³, respectively.

For the conditions of these measurements, relative concentrations of CO, BC, and particle number tracked each other well as distance from the freeway increased. Particle number concentration (6–220 nm) decreased exponentially with downwind distance from the freeway. Data showed that both atmospheric dispersion and coagulation contributed to the rapid decrease in particle number concentration and change in particle size distribution with increasing distance from the freeway. Average traffic flow during the sampling periods was 13,900 vehicles/hr. Ninety-three percent of vehicles were gasoline-powered cars or light trucks. The measured number concentration tracked traffic flow well. Thirty meters downwind from the freeway, three distinct ultrafine modes were observed with geometric mean diameters of 13, 27, and 65 nm. The smallest mode, with a peak concentration of 1.6 × 10⁵/cm³, disappeared at distances greater than 90 m from the freeway. Ultrafine particle number concentration measured 300 m downwind from the freeway was indistinguishable from upwind background concentration. These data may be used to estimate exposure to ultrafine particles in the vicinity of major highways.     

Measurement of Fine Particles in Diesel Emissions Using a Real-Time Aerosol Monitor

Abstract

A real-time monitoring methodology to determine diesel fine particles in diesel emissions has been evaluated. The range of particle size captured by the monitor was ～0.1 μm to 1 μm. DustTrak real-time monitors were connected to the dilution tunnel of the vehicle exhaust to measure the emissions during the vehicle tests under both dynamic and steady-state driving conditions, and concentration data were recorded every 5 sec. Test variation of the real-time monitoring among different test days was similar to that measured by traditional filter-based gravi-metric method, whereas the repeatability of the monitor data within the same-day tests was better than that of gravimetric method. Correlations between the two methods were established for different fuels tested on a single light duty vehicle. When the emissions from the reference fuel was used to convert the monitor’s response to diesel fuels, the levels determined by the real-time monitor were consistent with those measured by gravimetric method among different fuels tested. Use of the real-time monitor could provide information on the levels of fine particles that is more relevant to the public health than the total particles.     

Ciliary Activity and Pulmonary Retention of Inhaled Dust In Rats Exposed to Sulfur Dioxide

While the ciliary activity in the airways of rats exposed to sulfur dioxide at low concentration has been studied repeatedly, the effects of chronic exposure to realistic levels of sulfur dioxide and particulates has not been determined. This paper describes the response of white albino rats to the inhalation of low concentrations of sulfur dioxide while exposed to relatively high concentrations of an inert dust. Test results indicate that no change is found in the ciliary activity or the relative number of dust cells in the alveolar structure of rats exposed to 1 ppm of sulfur dioxide and 1 mg/m³ of a graphite dust.     

Size and Concentration Measurements of Particles Produced in Commercial Chromium Plating Processes

Abstract

Optical measurements of particle size and concentration were made at the chromium plating tank and exhaust system at a commercial hexavalent chromium plating facility. Particles were examined at three locations in the exhaust system: 1) directly at the hexavalent chromium plating bath surface, 2) at the exit of a cyclone separator located in the exhaust system approximately three to four meters downstream of the bath, and 3) in the exhaust stack, downstream of the induced draft fan and all abatement devices. Particle diameters at the bath surface ranged from 0.3 to 25 μm. Downstream of the cyclone exit and mesh pad filters, particle top sizes were approximately 5 and 0.7 mm, respectively. On a mass basis, the collection efficiency of all abatement devices was 99.997%. Assuming that droplets in the flow consist primarily of water and chromium, correcting the total particle mass flow against water content gives a chromium emission rate of 64,000 μg/hr, which compares favorably with a value of 77,000 μg/hr measured with EPA methods. This initial agreement, which should be validated through additional measurements over a broad range of flow conditions, raises the possibility of continuous monitoring for chromium metal emissions using particle size/mass as a surrogate.     

化学沉降沸石吸附法处理高浓度电镀含锌废水的研究

含锌废水对人体健康和环境具有严重的危害性。处理高浓度的含锌废水时需先进行化学沉降,然后再进行深度处理。试验结果证明,对于含289 mg/L Zn2+的电镀废水,用质量分数为10%的氢氧化钠处理,其投加量为3.7 mL/100 mL,处理后的Zn2+的浓度为6.6 mg/L。再用沸石进行吸附,沸石用量为0.25 g/L,搅拌(110 r/min)50 min,处理后,废水的锌离子去除率最高可达88.8%,剩余Zn2+浓度为0.47 mg/L,远低于《国家污水综合排放标准》(GB 8978-2002)的一级标准。     

Health Effects of Fine Particulate Air Pollution: Lines that Connect

Abstract

Efforts to understand and mitigate the health effects of particulate matter (PM) air pollution have a rich and interesting history. This review focuses on six substantial lines of research that have been pursued since 1997 that have helped elucidate our understanding about the effects of PM on human health. There has been substantial progress in the evaluation of PM health effects at different time-scales of exposure and in the exploration of the shape of the concentration-response function. There has also been emerging evidence of PM-related cardiovascular health effects and growing knowledge regarding interconnected general pathophysiological pathways that link PM exposure with cardiopulmonary morbidity and mortality. Despite important gaps in scientific knowledge and continued reasons for some skepticism, a comprehensive evaluation of the research findings provides persuasive evidence that exposure to fine particulate air pollution has adverse effects on cardiopulmonary health. Although much of this research has been motivated by environmental public health policy, these results have important scientific, medical, and public health implications that are broader than debates over legally mandated air quality standards.     

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.     

Mass and Elemental Composition of Fine and Coarse Particles in Six U.S. Cities

Inhalable particulate matter (IP) samples have been collected in six U.S. cities in conjunction with an air pollution health study. The IP were collected using dichotomous virtual impactors in two size ranges: fine particles (FP) having aerodynamic diameter (d_a) <2.5 μm, and coarse particles (CP) with 2.5 μm < da < 15 μm. The mass measurements were determined by beta-gauge attenuation. The elemental composition of the FP and CP were determined by X-ray fluorescence. The means and distributions for FP and CP and selected elemental data highlight the similarities and differences that exist among these cities in the health study. Examining the temporal variations gives additional information on the meteorology and sources influencing the FP and CP fractions of Inhalable particle mass.

Differences in the concentration (and ratios) of selected elements have indicated the varying presence of crustal, steel industry, automotive, oceanic and fuel combustion sources in these cities. The noted variation in the concentrations and character of ambient aerosols in these cities are pertinent to interpreting differences in population exposures.     

Kinetic Sequential Sampling (KSS) System: An Automated Sampling System for Measuring Vertical Concentration Profiles of Airborne Particles

ABSTRACT

An electronically controlled lift system carrying a realtime particle monitor has been developed for sampling air sequentially, at different heights within the breathing zone. Data are automatically logged at the different receptor levels, for the determination of average vertical concentration profiles of airborne particulate matter. The system is easy to operate, portable, and easily extended to different heights or modified for use with other types of monitors (e.g., a portable CO analyzer). For measuring airborne particle concentrations, a Grimm Dust Monitor 1.104/5 was used. The results of trial runs, which were carried out indoors and in a relatively open semi-rural area, are presented, and applications of the kinetic sequential sampling (KSS) system are discussed.     

Chemical Composition and Source Apportionment of PM25 Particles in the Sihwa Area,Korea

ABSTRACT

To investigate the chemical characteristics of fine particles in the Sihwa area, Korea, atmospheric aerosol samples were collected using a dichotomous PM₁₀ sampler and two URG PM_2.5 cyclone samplers during five intensive sampling periods between February 1998 and February 1999. The Inductively Coupled Plasma (ICP)-Atomic Emission Spectrometry (AES)/ICP-Mass Spectrometry (MS), ion chromatograph (IC), and thermal manganese dioxide oxidation (TMO) methods were used to analyze the trace elements, ionic species, and carbonaceous species, respectively. Backward trajectory analysis, factor analysis, and a chemical mass balance (CMB) model were used to estimate quantitatively source contributions to PM_{2 5} particles collected in the Sihwa area.

The results of PM_2.5 source apportionment using the CMB7 receptor model showed that (NH₄)₂SO₄ was, on average, the major contributor to PM_2.5 particles, followed by nontraffic organic carbon (OC) emission, NH₄NO₃, agricultural waste burning, motor vehicle emission, road dust, waste incineration, marine aerosol, and others. Here, the nontraffic OC sources include primary anthropogenic OC emitted from the industrial complex zone, secondary OC, and organic species from distant sources. The source impact of waste incineration emission became significant when the dominant wind directions were from southwest and west sectors during the sampling periods. It was found that PM_2.5 particles in the Sihwa area were influenced mainly by both anthropogenic local sources and long-range transport and transformation of air pollutants.     

物化技术处理高浓度染料废水的研究进展

由于染料废水具有成分复杂、浓度高、难降解等特点，对其有效处理一直是个难题。因此，综述了国内外的物理法、化学法，特别是高级氧化技术在处理染料废水中的进展情况，并指出物化技术和生物技术相结合的发展趋势。     

The Contribution of Sulfate and Nitrate to Atmospheric Fine Particles During Winter Inversion Fogs in Cache Valley,Utah

Abstract

Air pollutants were collected in Logan, Cache County, UT, in February 1993 during two periods of atmospheric inversion accompanied by fog. The following atmospheric species were determined: (1) gaseous SO₂, NO₂ (semi-quantitatively),HNO3, NH3, and HF; (2) fine particulate SO₄ ⁼, NO₃ ^-, NH₄ ⁺, F–, H⁺, C, Si, S, K, Ca, Ti, Mn, Fe, Ni, Cu, Zn, Pb, Se, Br, and Sr, and; (3) fine particulate mass, which was calculated. The major components of fine particulate matter were carbonaceous material, ammonium nitrate, and ammonium sulfate, while the soil component was small. Calculated, fine particulate mass averaged 80 μg/m³ and reached concentrations as high as 120 μg/m³. SO₂/So_x and NO₂/NO_y mole ratios generally varied between 0.2 and 0.1 during inversions. These ratios also showed moderate but consistent diurnal patterns. The emission inventory for Cache County indicates sources of SO₂ and NO_x but not significant amounts of primary sulfate and nitrate. The observations reported here indicate there is significant conversion of SO₂ and NO_x in the presence of excess oxidants to sulfuric and nitric acid that are neutralized by excess ammonia.