Characteristics of Individual Particles at a Rural Site in the Eastern United States

To determine the nature of aerosol particles in a rural area of the eastern United States, aerosol samples were collected at Deep Creek Lake, Maryland, on various substrates and analyzed by a scanning electron microscope (SEM) and a transmission electron microscope (TEM). SEM analysis of particles larger than 2.5 μm collected on Nuclepore filters revealed the following: clay minerals, quartz, gypsum, and calcite comprised 50 percent of the particles analyzed; spores, pollen, and plant debris comprised 25 percent; 9 percent were fly ash; 11 percent were sulfates; 5 percent were unidentified. Particles ranging from 0.3 to 2 μm were collected in a cascade impactor on grid-supported carbon films and analyzed by TEM for decomposition rate as well as for reaction with the barium chloride and nitron (C₂₀H₁₆N₄) films that were applied after sampling. The TEM analyses indicated that as much as 95 percent of the particles in the 0.3- to 2-μm diameter range were pure ammonium sulfate or acidic ammonium sulfate; they contained essentially no insoluble or nonvolatile matter. About 5 percent of the particles were fly ash spheres. When replicas of particles collected on Nucleopore filters were analyzed by TEM, we observed agglomerates of particles smaller than 0.1 μm.     

Global Emissions of Nitrogen and Sulfur Oxides from 1860 to 1980

Statistical models have been developed that relate the rate of emissions of a pollutant to the rate of fuel consumption. These relations may be used to estimate emissions in other regions, or at other times, if fuel consumption data are available. This approach has been used to estimate global emissions of nitrogen and sulfur oxides in fossil fuel combustion at ten year intervals from 1860 to 1980. Emissions from each of the populated continents, i.e., North America, South America, Asia, Europe, Africa and Oceania from 1930 to 1980 are also presented. When averaged globally over the 1860 to 1980 period, sulfur emissions increased at the rate of 2.9 percent per year and the nitrogen emissions at the rate of 3.4 percent per year. The ratio of global sulfur emissions to nitrogen emissions has declined steadily; it was nearly 5 in the 19th century and became 3 by 1980. After the second world war, the most rapid increases in emissions have been registered in Asia, South America, and Africa.     

Comparison of Fine Particles and the Relationship between Particle Variations and Meteorology at an Urban Site and a Remote Site in the Eastern United States

Abstract

This study compared the variations in the mass of certain particles at an urban site, Washington, DC, and at a remote site, Shenandoah National Park, VA, in the eastern United States. Seven years (1991-1997) of Interagency Monitoring of Protected Visual Environments (IMPROVE) fine particulate matter (PM_2.5), PM₁₀, coarse fraction, SO₄ ^2?, and total sulfur data were used for this study together with available meteorology/climatology data. Various statistical modeling and analysis procedures, including time series analysis, factor analysis, and regression modeling, were employed. Time series of the constituents were divided into four terms: the long-term mean, the intra-annual perturbation, the interannual perturbation, and the synoptic perturbation. PM_2.5 at the two sites made up ~72% of the total mass for PM₁₀, and the coarse fraction made up the remaining 28%, on average. Thirty-one percent of the PM_2.5 at the DC site and 42% at the Shenandoah site was SO₄ ^2?, based on average data for the entire period. At the DC site, the two main contributors to the constituent mass were the long-term mean and the synoptic perturbation terms, and at the Shenandoah site, they were the long-term mean and the intra-annual perturbation terms. This suggested that the constituent mass at the two sites was affected by very different processes. The terms that provided the principal contribution to the constituent mass at the two sites were studied in detail.

At the DC site, dew point trends, a climate variable, were the primary driver of the 7-year trends for PM_2.5, PM₁₀, the coarse fraction, and total sulfur, and SO₂ emission trends were the primary driver of the trends for SO₄ ^2?. SO₂ emission trends influenced the trends for PM_2.5 and total sulfur, appearing as the second term in the model, but only parameters dealing with climate trends had significant effects on the trends for PM₁₀ and the coarse fraction. At the Shenandoah site, only parameters dealing with climate trends affected long-term particle trends.     

Studies on a New Method of Simultaneously Removing Sulfur Dioxide and Oxides of Nitrogen from Combustion Gases

Simultaneous reduction of SO₂ and NO by catalyzed reaction with carbon monoxide at space rates approaching 10⁴ vol/vol/hr has been shown. The reaction of sulfur dioxide with carbon monoxide results in the formation of carbon dioxide and elemental sulfur. Nitric oxide reacts with carbon monoxide to form carbon dioxide and molecular nitrogen. Metals supported on alumina appear to be the preferred catalysts. Among the effective metals are copper, silver, and palladium. A side reaction of carbon monoxide with elemental sulfur to form carbonyl sulfide requires that the initial amount of carbon monoxide be stoichio-metric for the amount of sulfur dioxide plus nitric oxide present. A furnace employing this method would have to be operated at low excess air, near stoichiometric fuel/air, or possibly slightly on the rich side.     

Precision and Accuracy in the Determination of Sulfur Oxides,Fluoride, and Spherical Aluminosilicate Fly Ash Particles in Project MOHAVE

The precision and accuracy of the determination of particu-late sulfate and fluoride, and gas phase SO₂ and HF are estimated from the results obtained from collocated replicate samples and from collocated comparison samples for high-and low-volume filter pack and annular diffusion denuder samplers. The results of replicate analysis of collocated samples and replicate analyses of a given sample for the determination of spherical aluminosilicate fly ash particles have also been compared. Each of these species is being used in the chemical mass balance source apportionment of sulfur oxides in the Grand Canyon region as part of Project MOHAVE, and the precision and accuracy analyses given in this paper provide input to that analysis. The precision of the various measurements reported here is ±1.8 nmol/m³ and ±2.5 nmol/m³ for the determination of SO₂ and sulfate, respectively, with an annular denuder. The precision is ±0.5 nmol/m³ and ±2.0 nmol/m³ for the determination of the same species with a high-volume or low-volume filter pack. The precision for the determination of the sum of HF(g) and fine particulate fluoride is ±0.3 nmol/m³. The precision for the determination of aluminosilicate fly ash particles is ±100 particles/m³. At high concentrations of the various species, reproducibility of the various measurements is ±10% to ±14% of the measured concentration. The concentrations of sulfate determined using filter pack samplers are frequently higher than those determined using diffusion denuder sampling systems. The magnitude of the difference (e.g., 2-10 nmol sulfate/m³) is small, but important relative to the precision of the data and the concentrations of particulate sul-fate present (typically 5-20 nmol sulfate/m³). The concentrations of SO₂(g) determined using a high-volume cascade impactor filter pack sampler are correspondingly lower than those obtained with diffusion denuder samplers. The concentrations of SO_x (SO₂(g) plus particulate sulfate) determined using the two samplers during Project MOHAVE at the Spirit Mountain, NV, and Hopi Point, AZ, sampling sites were in agreement. However, for samples collected at Painted Desert, AZ, and Meadview, AZ, the concentrations of SO_x and SO₂(g) determined with a high-volume cascade impactor filter pack sampler were frequently lower than those determined using a diffusion denuder sampling system. These two sites had very low ambient relative humidity, an average of 25%. Possible causes of observed differences in the SO₂(g) and sulfate results obtained from different types of samplers are given.     

Environmental Appraisal-Particulate Matter,Oxides of Sulfur,and Sulfuric Acid

The role of particulate matter and oxides of sulfur in degradation of the atmospheric environment is discussed. The Federal Air Quality Criteria for these pollutants are analyzed for their conformance with the requirement of the Clean Air Act of 1967 that they reflect the latest scientific knowledge pertinent to the indication of their effects on health and welfare. Visibility reduction by suspended particulate matter is treated and the bases for the criteria issued in the documents “Air Quality Criteria for Particulate Matter” and “Air Quality Criteria for Sulfur Oxides” are examined. The reactions between particulate matter and gaseous pollutants are discussed, along with the Impact of particulate matter on modifications of weather processes. Local effects, such as precipitation, are considered. The relationship between pollution by particulate matter and cloud formation is discussed, as are persistence of fog and the observation that certain sources of particulate pollution are also sources of ice nuclei.     

Measurements of Rural Sulfur Dioxide and Particle Sulfate: Analysis of CASTNet Data, 1987 through 1996

ABSTRACT

The Clean Air Status and Trends Network (CASTNet) was implemented by the U.S. Environmental Protection Agency (EPA) in 1991 in response to Title IX of the Clean Air Amendments of 1990, which mandated the deployment of a national ambient air monitoring network to track progress of the implementation of emission reduction programs in terms of deposition, air quality, and changes to affected ecosystems. CASTNet evolved from the National Dry Deposition Network (NDDN). CASTNet currently consists of 45 sites in the eastern United States and 28 sites in the West. Each site measures sulfur dioxide (SO₂), nitric acid (HNO₃), particle sulfate (SO₄ ⁼), particle nitrate (NO₃ ^- ), and ozone. Nineteen sites collect precipitation samples. NDDN/CASTNet uses a uniform set of site-selection criteria which provides the data user with consistent measures to compare each site. These criteria also ensure that, to the extent possible, CASTNet sites are located away from local emission sources.

This paper presents an analysis of SO₂ and SO₄ ⁼ concentration data collected from 1987 through 1996 at rural NDDN/CASTNet sites. Annual and seasonal variability is examined. Gradients of SO₂ and SO₄ ⁼ are discussed. The variability of the atmospheric mix of SO₂ and SO₄ ⁼ is explored spatially and seasonally. Data from CASTNet are also compared to SO₂ and SO₄ ⁼ data from concurrent monitoring studies in rural areas.     

Toxicologic Appraisal of Particulate Matter,Oxides of Sulfur,and Sulfuric Acid

An examination of the available toxicological literature indicates that sulfur dioxide itself would be properly classified as a mild respiratory irritant, the main portion of which is absorbed in the upper respiratory tract. The reported industrial experience of symptoms of mild chronic respiratory irritation from exposures at or above 5 ppm is compatible with what would have been predicted on the basis of available toxicological data. The basic physiological response to inhalation of pure SO₂ appears to be a mild degree of bronchoconstriction reflected in a measurable increase in flow resistance. Although the response is highly variable, most individuals tested have responded to 5 ppm and levels of 5 to 10 ppm have upon occasion produced severe bronchospasm in sensitive individuals. This serves to point up the fact that experience with the industrial Threshold Limit Value (5 ppm) is not applicable as a guide for the general population. Although the majority of individuals tested have shown no detectable response to levels of 1 ppm, there are again sensitive individuals who have responded. It is not known whether these individuals would have responded to concentrations lower than this. The response of these more sensitive individuals to 1 ppm would be classified as detectable response, not as severe bronchospasm. An examination of the available toxicological literature also indicates that sulfuric acid and irritant sulfates, to the extent that the latter have been examined, are more potent irritants than sulfur dioxide. This has been demonstrated in studies using morality and lung pathology as criteria as well as in studies using alterations in pulmonary function in experimental animals and human subjects. The irritant potency of these substances is affected by particle size and by relative humidity, which factors are probably interrelated. It is unfortunate that these substances have not been as yet studied in as great detail as has the less irritant sulfur dioxide. There is evidence which cannot be ignored, even though it is based entirely on animal experiments of one investigator, indicating that the presence of particulate material capable of oxidizing sulfur dioxide to sulfuric acid caused a three to fourfold potentiation of the irritant response. The aerosols causing this potentiation were soluble salts of ferrous iron, manganese and vanadium all of which would become droplets upon inhalation. Insoluble aerosols such as carbon, iron oxide fume, triphenylphosphate or fly ash did not cause a potentiation of the irritant action of SO₂ even when used at higher concentrations. The concentrations of SO₂ used in these various experiments were in some cases as low as 0.16 ppm. The catalytic aerosols were used at concentrations of 0.7 to 1 mg/m³ which is above any reported levels of these metals in urban air. If the SO₂ present as an air pollutant remained unaltered until removed by dilution, there would be no evidence in the toxicological literature suggesting that it would be likely to have any effects on man at prevailing levels. Studies of atmospheric chemistry have shown that SO₂ does not remain unaltered in the atmosphere, especially under onditions of high humidity and in the presence of particulate material, but is converted to H₂SO₄. Such a conversion increases its irritant potency. On this basis the toxicological literature combined with the literature of atmospheric chemistry suggest that sulfur dioxide levels be controlled in terms of the potential formation of irritant particles. This means that control measures as far as feasible should be aimed at both SO₂ and particulate material and not against either alone.     

Consistency of Ozone and Nitrogen Oxides Standards at Tropospherically Relevant Mixing Ratios

Abstract

The absolute accuracy and long‐term precision of atmospheric measurements hinge on the quality of the instrumentation and calibration standards. To assess the consistency of the ozone (O₃) and nitrogen oxides (NO_x) standards maintained at the National Institute of Standards and Technology (NIST), these standards were compared through the gas‐phase titration of O3 with nitric oxide (NO). NO and O₃ were monitored using chemiluminescence and UV absorption, respectively. Nitrogen dioxide (NO₂) was monitored directly by laser‐induced fluorescence and indirectly by catalytic conversion to NO, followed by chemiluminescence. The observed equivalent loss of both NO and O₃ and the formation of NO₂ in these experiments was within 1% on average over the range of 40–200 nmol mol^?1 of NO in excess O3, indicating that these instruments, when calibrated with the NIST O₃ and NO standards and the NO₂ permeation calibration system, are consistent to within 1% at tropospherically relevant mixing ratios of O₃. Experiments conducted at higher initial NO mixing ratios or in excess NO are not in as good agreement. The largest discrepancies are associated with the chemiluminescence measurements. These results indicate the presence of systematic biases under these specific conditions. Prospects for improving these experiments are discussed.     

Ancient manuring practices pollute arable soils at the St Kilda World Heritage Site, Scottish North Atlantic

The impact of ancient fertilization practices on the biogeochemistry of arable soils on the remote Scottish island of Hirta, St Kilda was investigated. The island was relatively unusual in that the inhabitants exploited seabird colonies for food, enabling high population densities to be sustained on a limited, and naturally poor, soil resource. A few other Scottish islands, the Faeroes and some Icelandic Islands, had similar cultural dependence on seabirds. Fertilization with human and animal waste streams (mainly peat ash and bird carcases) on Hirta over millennia has led to over-deepened, nutrient-rich soils (plaggen). This project set out to examine if this high rate of fertilization had adversely impacted the soil, and if so, to determine which waste streams were responsible. Arable soils were considerably elevated in Pb and Zn compared to non-arable soils. Using Pb isotope signatures and analysis of the waste streams, it was determined that this pollution came from peat and turf ash (Pb and Zn) and from bird carcases (Zn). This was also confirmed by ¹³C and ¹⁵N analysis of the profiles which showed that soil organic matter was highly enriched in marine-derived C and N compared to non-arable soils. The pollution of such a remote island may be typical of other ‘bird culture’ islands, and peat ash contamination of marginal arable soils at high latitudes may be widespread in terms of geographical area, but less intense at specific locations due to lower population densities than on Hirta.     

Response of Fine Particulate Matter to Emission Changes of Oxides of Nitrogen and Anthropogenic Volatile Organic Compounds in the Eastern United States

Abstract

A three-dimensional chemical transport model (Particulate Matter Comprehensive Air Quality Model with Extensions [PMCAMx]) is used to investigate changes in fine particle (PM_2.5) concentrations in response to 50% emissions changes of oxides of nitrogen (NO_x) and anthropogenic volatile organic compounds (VOCs) during July 2001 and January 2002 in the eastern United States. The reduction of NO_x emissions by 50% during the summer results in lower average oxidant levels and lowers PM_2.5 (8% on average), mainly because of reductions of sulfate (9–11%), nitrate (45–58%), and ammonium (7–11%). The organic particulate matter (PM) slightly decreases in rural areas, whereas it increases in cities by a few percent when NO_x is reduced. Reduction of NO_x during winter causes an increase of the oxidant levels and a rather complicated response of the PM components, leading to small net changes. Sulfate increases (8–17%), nitrate decreases (18– 42%), organic PM slightly increases, and ammonium either increases or decreases a little. The reduction of VOC emissions during the summer causes on average a small increase of the oxidant levels and a marginal increase in PM_2.5. This small net change is due to increases in the inorganic components and decreases of the organic ones. Reduction of VOC emissions during winter results in a decrease of the oxidant levels and a 5–10% reduction of PM_2.5 because of reductions in nitrate (4–19%), ammonium (4–10%), organic PM (12–14%), and small reductions in sulfate. Although sulfur dioxide (SO₂) reduction is the single most effective approach for sulfate control, the coupled decrease of SO₂ and NO_x emissions in both seasons is more effective in reducing total PM_2.5 mass than the SO₂ reduction alone.     

Characterization of Ozone During Consecutive Drought and Wet Years at a Rural West Virginia Site

Ozone concentrations at a rural-remote site in a forested region of north-central West Virginia were monitored during 1988 and 1989, a drought and wet year, respectively. During 1988, the absolute maximum average concentration for a single hour was 156 ppb, while it was only 107 ppb in 1989. Overall, the frequency of high concentrations was greater during 1988; the 120 ppb National Ambient Air Quality Standard was exceeded 17 times. The 7-h period encompassing the highest growing season concentrations for this site over the 2-yr period is 1100- 1759 h EST, rather than the period 0900-1559 h originally used by the National Crop Loss Assessment Network. The 7-h growing season means (0900-1559 h) of 52.6 ppb and 47.1 ppb for 1988 and 1989, respectively, compare well to those reported for the Piedmont/Mountain/Ridge-Valley area, but are higher than those for other surrounding areas. The diurnal ozone patterns, as well as the distribution of concentration ranges and timing of seasonal maxima, suggest that long-range transport of ozone and its precursors probably is an important factor at this site, given its remote and rural character.     

On the Relation Between the Indoor and Outdoor Concentrations of Nitrogen Oxides

Simultaneous measurements were made of the concentrations of NO, NO₂, and CO inside and outside of a building. The building is located in the Los Angeles area, which is heavily polluted by photochemical smog, and the experiments were conducted at a time of the year when the pollutants in question tend to be high. The results shows that there is a direct relationship between the inside and outside concentrations, and that the phase lag between the concentrations depends principally on the ratio of the building volume to the ventilation rate. Although the outside concentrations of the pollutants in question did not follow the same pattern every day, peak concentrations seemed to be related to “rush-hour” traffic. By reducing ventilation rates during these periods, it may be possible to reduce the concentration peaks inside of the building. The building involved in the current study was not located in the immediate vicinity of heavy traffic, and the indoor concentrations of NO, NO₂, and CO did not appear to be very severe when compared to those defined by present air quality standards. Finally, the results support the belief that NO and O₃ do not co-exist indoors except in very small quantities.     

An Epidemiological Appraisal of the Effects of Ambient Air on Health: Particulates and Oxides of Sulfur

This review has attempted to evaluate the present state of our knowledge of the effects on health in man of environmental exposure to oxides of sulfur, sulfates, and particulate matter. There has been a great deal of activity in this field over the last 15 years, and therefore any collation of this material will represent the selected biases of the reviewer. The conclusions reached can be summarized as follows: (1) These pollutants, as they have been measured in epidemiological investigations, can only be considered as indirect indices of general air pollution and in many cases cannot be separated from each other. Therefore, we cannot incriminate a specific source of any one pollutant as the producer of the most harmful substance to reach the ambient air. Conversely, we cannot excuse any specific source of one pollutant because that specific pollutant has not been found to cause disease at a given concentration. The measurements in ambient air are the net results from all sources of pollution in combination with factors influenced by weather and meteorological considerations. (2) Direct effects from acute, high ambient air pollution disasters have been adequately demonstrated. Significant excess mortality has occurred in association with particular air pollution episodes. All of these episodes have occurred during cold weather, and the effects of temperature must also be considered along with elevated levels of smoke and sulfur oxides. (3) Specific working groups exposed to unusually high levels of these pollutants do not demonstrate dramatic effects. This is presumably related to the fact that susceptible people are self-selected out of these environments. (4) Associations between the prevalence of chronic respiratory disease in the general population and specific levels of these air pollutants have been demonstrated. The major thrusts of epidemiological investigations have been to study the effects of chronic exposure to ambient levels of smoke and sulfur dioxide. The studies to date have collected and analyzed point-prevalence data and information obtained from retrospective investigations. Although epidemiological investigations cannot prove a cause-and-effect relationship, the consistency of the results is such that one must conclude that a causal association is likely. In this reviewer’s opinion we have reached the stage at which we no longer need to demonstrate the effect of past exposure to these pollutants. What is needed now is to demonstrate the effects of current and continued exposure. This will require a better understanding of the natural history and pathophysiology of the diseases thought to be associated with chronic exposure to smoke and sulfur dioxide. Because of the nature of chronic respiratory disease, groups of subjects for whom exposure is known, must be followed over extended periods of time. The logical extension of these observations will be the follow-up of large populations for whom exposure has been reduced. Only by studies of this kind may we be able to prove the cause-and-effect relationship which most likely exists.     

Second Generation Chemical Mass Balance Source Apportionment of Sulfur Oxides and Sulfate at the Grand Canyon during the Project MOHAVE Summer Intensive

ABSTRACT

Receptor-based chemical mass balance (CMB) analysis techniques are designed to apportion species that are conserved during pollutant transport using conserved source profiles. The techniques will fail if non-conservative species (or profiles) are not properly accounted for in the CMB model. The straightforward application of the CMB model developed for Project MOHAVE using regional profiles resulted in a significant under-prediction of total sulfate oxides (SO_x, SO₂ plus fine particulate sulfate) for many samples at Meadview, AZ. In addition, for these samples the concentration of the inert tracer emitted from the MOHAVE Power Project (MPP), ocPDCH, was also under-predicted. A second-generation model has been developed which assumes that separation of particles and SO₂ can occur in the MPP plume during nighttime stable plume conditions. This second-generation CMB model accounts for all SO_x present at the various receptor sites. In addition, the concentrations of ocPDCH and the presence of other inert tracers of emission from regional sources are accurately predicted. The major source of SO_x at Meadview was the MPP, but the major source of sulfate at this site was the Las Vegas urban area. At Hopi Point in the Grand Canyon, the Baja California region (Imperial Valley and northwestern Mexico) was the major source of both SO_x and sulfate.     

Assessing the Impacts of Long-Range Sulfur and Nitrogen Deposition on Arctic and Sub-Arctic Ecosystems

For more than a decade, anthropogenic sulfur (S) and nitrogen (N) deposition has been identified as a key pollutant in the Arctic. In this study new critical loads of acidity (S and N) were estimated for terrestrial ecosystems north of 60° latitude by applying the Simple Mass Balance (SMB) model using two critical chemical criteria (Al/Bc = 1 and ANC_le = 0). Critical loads were exceeded in large areas of northern Europe and the Norilsk region in western Siberia during the 1990s, with the more stringent criterion (ANC_le = 0) showing the larger area of exceedance. However, modeled deposition estimates indicate that mean concentrations of sulfur oxides and total S deposition within the Arctic almost halved between 1990 and 2000. The modeled exceeded area is much reduced when currently agreed emission reductions are applied, and almost disappears under the implementation of maximum technically feasible reductions by 2020. In northern North America there was no exceedance under any of the deposition scenarios applied. Modeled N deposition was less than 5 kg ha⁻¹ y⁻¹ almost across the entire study area for all scenarios; and therefore empirical critical loads for the eutrophying impact of nitrogen are unlikely to be exceeded. The reduction in critical load exceedances is supported by observed improvements in surface water quality, whereas the observed extensive damage of terrestrial vegetation around the mining and smelter complexes in the area is mainly caused by direct impacts of air pollution and metals.     

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.     

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.     

Continuous Monitoring of Ultrafine,Fine, and Coarse Particles in a Residence for 18 Months in 1999-2000

Abstract

Continuous monitors were employed for 18 months in an occupied townhouse to measure ultrafine, fine, and coarse particles; air change rates; wind speed and direction; temperature; and relative humidity (RH). A main objective was to document short-term and long-term variation in indoor air concentrations of size-resolved particles (0.01-20 μm) caused by (1) diurnal and seasonal variation of outdoor air concentrations and meteorological variables, (2) indoor sources such as cooking and using candles, and (3) activities affecting air change rates such as opening windows and using fans. A second objective was to test and compare available instruments for their suitability in providing real-time estimates of particle levels and ancillary variables.

Despite different measuring principles, the instruments employed in this study agreed reasonably well for particles less than 10 μm in diameter. The three instruments measuring fine and coarse particles (aerodynamic diameter between 0.3 and 20 μm) agreed to within 30% in their overall estimates of total volume. Two of these instruments employed optical scattering, and the third used an aerodynamic acceleration principle. However, several lines of evidence indicated that the instrument employing aerodynamic acceleration overestimated concentrations for particle diameters greater than 10 μm. A fourth instrument measuring ultrafine and accumulation-mode particles (0.01-1 μm) was operated with two different inlets providing somewhat different particle size ranges. The two inlets agreed in the ultrafine region (<0.1 μm) but diverged increasingly for larger particles (up to 0.445 μm).

Indoor sources affecting ultrafine particle concentrations were observed 22% of the time, and sources affecting fine and coarse particle concentrations were observed 12 and 15% of the time, respectively. When an indoor source was operating, particle concentrations for different sizes ranged from 2 to 20 times the average concentrations when no indoor source was apparent. Indoor sources, such as cooking with natural gas, and simple physical activities, such as walking, accounted for a majority (50-90%) of the ultrafine and coarse particle concentrations, whereas outdoor sources were more important for accumulation-mode particles between 0.1 and 1 um in diameter. Averaged for the entire year and including no periods when indoor sources were apparent, the number distribution was bimodal, with a peak at ~10 nm (possibly smaller), a shallow minimum at ~14 nm, and a second broad peak at ~68 nm. The volume distribution was also bimodal, with a broad peak at ~200 nm, a minimum at ~1.2 μm, and then an upward slope again through the remaining size fractions.

A database was created on a 5-min averaging time basis. It contains more than 90,000 measurements by two of the instruments and approximately 30,000 by the two optical scattering instruments. About 4500 hour-long average air change rates were also calculated throughout the year using a dedicated gas chromatograph with electron capture detection (GC/ECD). At high air change rates [>0.8 air changes per hour (hr^?1)], particle concentrations were either elevated (when no source was present) or depressed (when an indoor source was operating) by factors of up to 2 compared with low air change rates.