Philip M. Fine

Chemical Characterization of Fine Particle Emissions from Fireplace Combustion of Woods Grown in the Northeastern United States

A series of source tests was conducted to determine the chemical composition of fine particle emissions from the fireplace combustion of six species of woods grown in the northeastern United States: red maple, northern red oak, paper birch, eastern white pine, eastern hemlock, and balsam fir. Results include fine particle emission rates for total mass, organic and elemental carbon, ionic species, elemental species including potassium, and over 250 specific organic compounds. The data are intended for use in source-apportionment studies that utilize particulate organic compounds as source-specific tracers. The cellulose pyrolysis product levoglucosan was quantified in each of the wood smokes studied and is thus a good candidate as a molecular tracer for wood combustion in general. Differences in emission rates of specific substituted phenols and resin acids can be used to distinguish between the smoke produced when burning hardwoods versus softwoods. Certain organic compounds, such as betulin from paper birch combustion and juvabione and dehydrojuvabione from balsam fir combustion, are unique to those species and can potentially be utilized to trace particulate emissions back to a specific geographical region where those individual tree species are used for firewood.

Chemical Characterization of Fine Particle Emissions from the Fireplace Combustion of Wood Types Grown in the Midwestern and Western United States

Results are presented from a series of source tests on the fireplace combustion of 10 wood species found in the Midwestern and Western United States: white oak, sugar maple, black oak, American beech, black cherry, white spruce, quaking aspen, douglas fir, ponderosa pine, and pinyon pine. Fine particle emission factors for total mass, organic, and elemental carbon, ionic species, elemental species including potassium, and over 250 individual organic compounds were determined. The data are intended for use in apportionment studies that utilize particulate organic compounds as specific tracers to identify the sources of ambient fine particles. The cellulose pyrolysis products levoglucosan, mannosan, and galactosan were quantified in each of the wood smokes studied; they act as molecular tracers for cellulose from combustion of all wood types. Differences in the emission rates of syringol- and guaiacol-type phenolic compounds from lignin and of resin acids can be used to distinguish between hardwood and soft...

Physical and Chemical Characteristics and Volatility of PM in the Proximity of a Light-Duty Vehicle Freeway

Abstract Volatility properties of ultrafine particles were analyzed next to State Route 110 (Pasadena freeway CA), a light-duty vehicle freeway where heavy-duty traffic is prohibited. In addition, mass concentration and chemical composition of particulate matter (PM) were measured in coarse, accumulation, and ultrafine modes. On weekdays from 17 May to 4 June 2004, measurements were performed in two locations, one very close to the freeway (within 2.5 m from the curb) and one at a distance of about 50 m from the freeway. For measurement of mass and chemical composition, the study employed in each location a micro-orifice uniform deposit impactor (MOUDI) and a modified high-volume sampler. Both instruments sampled with the same size cutpoints: a coarse mode from 2.5 to 10 μm, an accumulation mode from 0.18 to 2.5 μm, and an ultrafine mode of particles less than 0.18 μm in aerodynamic diameter. Alternately, a tandem differential mobility analyzer (TDMA) was used at the two sites. A heater between the two DMAs evaporated volatile material from the monodisperse aerosol, size selected by the first DMA. The second DMA analyzed the losses of volatile components. The ultrafine number concentrations next to the freeway were 46,000 cm−3 on average during the sampling period. The MOUDI ultrafine mass concentration, nitrate, and EC were higher next to the freeway than at the background site farther from the freeway. The other components analyzed in the ultrafine mode had similar concentrations next to the freeway and at the background site. Volatility ranged from about 65% volume losses of 120 nm particles heated to 110°C to 95% of 20 nm particles. The 20 nm aerosol was only internally mixed, whereas increasing nonvolatile fractions were found for 40 nm (6% next to the freeway), 80 nm (20%), and 120 nm (28%) aerosols.

Inferring the Sources of Fine and Ultrafine Particulate Matter at Downwind Receptor Sites in the Los Angeles Basin Using Multiple Continuous Measurements Special Issue of Aerosol Science and Technology on Findings from the Fine Particulate Matter Supersites Program

Recent studies that have found increased health effects of atmospheric ultrafine particulate matter (PM) have refocused attention on particle number rather than particle mass concentrations as a relevant measurement of PM pollution. As part of the Southern California Supersite program, ambient particle characteristics were measured over 13 months at three different sites in the eastern portion of the Los Angeles Basin: Riverside, Rubidoux, and Claremont, CA. The sites represent receptor locations that are influenced by local particle sources as well as advection from the more intense particle sources upwind closer to Downtown Los Angeles. An SMPS/APS tandem system was employed to collect continuous particle size distributions, from which particle number and mass concentrations were calculated. An aethalometer provided continuous particulate elemental carbon (EC) concentrations. Results show no meaningful correlation between particle number and mass, indicating that fine particle standards may not be effective in controlling ultrafine concentrations. Diurnal patterns show a morning traffic peak indicated by increases in particle mass, number, and EC. Afternoon periods in the warmer months are characterized by high number counts while mass and EC remain low, suggesting the formation of new particles by photochemistry. Particle mode diameters range from 30 nm up to above 100 nm, a result not seen in most other studies of particle size distributions in other urban or rural areas where mode diameters are generally less than 50 nm. Evidence is presented that the observed ultrafine particle concentrations and size distributions are influenced by long-range advection and photochemical processes as well as vehicular emissions, which have been previously assumed to dominate day-to-day ultrafine particle levels.

Organic compounds in biomass smoke from residential wood combustion: Emissions characterization at a continental scale

Wood smoke in the atmosphere often accounts for 20–30% of the ambient fine-particle concentrations. In communities where wood is burned for home heating, wood smoke can at times contribute the majority of the atmospheric fine-particle burden. Chemical mass balance receptor models that use organic compounds as tracers can be used to determine the contributions of different emission sources, including wood smoke, to atmospheric fine-particle samples. In order for organic chemical tracer techniques to be applied to communities across the United States, differences in wood smoke composition that arise from differences in the type of wood burned in various regions must be understood. A continental-scale accounting of particulate organic compound emissions from residential wood combustion has been constructed which helps to quantify the regional differences in wood smoke composition that exist between different parts of the United States. Data from a series of source tests conducted on 22 North American wood species have been used to assemble a national inventory of emissions for more than 250 individual organic compounds that are released from wood combustion in fireplaces and wood stoves in the United States. The emission rates of important wood smoke markers, such as levoglucosan, certain substituted syringols and guaiacols, and phytosterols vary greatly with wood type and combustor type. These differences at the level of individual wood type and combustion conditions translate into regional differences in the aggregate composition of ambient wood smoke. By weighting the source test results in proportion to the availability of firewood from specific tree species and the quantities of wood burned in each locale, it is possible to investigate systematic differences that exist between wood smokes from different regions of North America. The relative abundance of 10 major wood smoke components averaged over the emissions inventory in different regions of the United States is computed and then used to illustrate the extent to which wood smoke composition differs from region to region in North America.

Performance evaluation of a recently developed water-based condensation particle counter

This study provides an intercomparison of the performance of a newly developed water-based condensation particle counter (W-CPC) and a more widely used butanol-based CPC (TSI 3022A). Four test aerosols (ammonium nitrate, ammonium sulfate, adipic acid, and glutaric acid) were generated and tested in the laboratory before the instruments were deployed at four field locations (USC/downtown LA, I-710 Freeway, Pacific coast, and Los Angeles International Airport). Both instruments sampled the same incoming aerosol. Selected experiments utilized a differential mobility analyzer to select a particle size upstream of the CPCs. Evaluation of performance was based on the response of the instruments to varying particle composition, concentrations, and size. The results indicated good correlation between the two CPCs, with R2 values ranging from 0.74–0.99. Good agreement was found between the two instruments for particle concentrations between 0 and 40,000 particles/cm3, with W-CPC/TSI 3022A ratios between 0.8 and 1.2. Due to differences in the photometric mode calibration of these instruments, the ratio drops to 0.6–0.8 between 40,000–100,000 particles/cm3. However, the ratio rises again for lab aerosols above 100,000 particles/cm3 to 1.0–1.1. Results of this evaluation show that the W-CPC is a reliable particle– counting technology for particle concentrations encountered downstream of a DMA as well as in some ambient environments (< 40,000 particles/cm3).

Secondary Particulate Matter in the United States: Insights from the Particulate Matter Supersites Program and Related Studies

Abstract Secondary aerosols comprise a major fraction of fine particulate matter (PM2.5) in all parts of the country, during all seasons, and times of day. The most abundant secondary species include sulfate, nitrate, ammonium, and secondary organic aerosols (SOAs). The relative abundance of each species varies in space and time as a function of meteorology, source emissions strength and type, thermodynamics, and atmospheric processing. Transport of secondary aerosols from upwind locations can contribute significantly at downwind receptor sites, especially regionally in the eastern United States, and across a given urbanized area, such as in Los Angeles. Processes governing the formation of the inorganic secondary species (sul-fate, nitrate, and ammonium) are fairly well understood, although the occurrence of nucleation bursts initiated with the formation of ultrafine sulfuric acid particles observed regionally on clean days in the eastern United States was unexpected. Because of the complex nature of organic material in air, much is still to be learned about the sources, formation, and even spatial and temporal distributions of SOAs. For example, a considerable fraction of ambient organic PM is oxidized organic species, many of which still need to be identified, quantified, and their sources and formation mechanisms determined. Furthermore, significant uncertainty (approaching 50% or more) is associated with estimating the SOA fraction of organic material in air with current methods. This review summarizes the findings of the Supersites Program and related studies addressing secondary particulate matter (PM), including spatial and temporal variations of secondary PM and its precursor species, data and methods for determining the primary and secondary fractions of PM mass, and findings on the anthropogenic and natural fractions of secondary PM.

Field evaluation of the versatile aerosol concentration enrichment system (VACES) particle concentrator coupled to the rapid single-particle mass spectrometer (RSMS-3)

A field evaluation of versatile aerosol concentration enrichment system (VACES) coupled to a rapid single- particle mass spectrometer (RSMS-3) was conducted as part of the U. S. Environmental Protection Agency Supersite program in Pittsburgh during March 2002. RSMS- 3 hit rate increases were measured, and possible particle composition changes introduced by the VACES were examined in the single- particle mass spectra. The hit rates increased by 5 - 20 times at particle sizes ranging from 40 to 640 nm. VACES only enhances the hit rate by about a factor of 2 for large particle sizes because the RSMS-3 flow rates for these particles did not match the optimum operating condition of VACES. During the 3 days of measurements most of the particles were a mixture of carbonaceous material and ammonium nitrate with a variation across the spectrum from particles that were mostly carbonaceous to particles that were mostly ammonium nitrate. Both ambient and concentrated carbonaceous and ammonium nitrate composition distributions were indistinguishable with RSMS-3, suggesting that VACES introduces an insignificant artifact for those particles.

Associations between particle number and gaseous co-pollutant concentrations in the Los Angeles Basin.

Abstract Continuous measurements of particle number (PN), particle mass (PM10), and gaseous pollutants [carbon monoxide (CO), nitric oxide (NO), oxides of nitrogen (NOx), and ozone (O3)] were performed at five urban sites in the Los Angeles Basin to support the University of Southern California Childrens Health Study in 2002. The degree of correlation between hourly PN and concentrations of CO, NO, and nitrogen dioxide (NO2) at each site over the entire year was generally low to moderate (r values in the range of 0.1–0.5), with a few notable exceptions. In general, associations between PN and O3 were either negative or insignificant. Similar analyses of seasonal data resulted in levels of correlation with large variation, ranging from 0.0 to 0.94 depending on site and season. Summertime data showed a generally higher correlation between the 24-hr average PN concentrations and CO, NO, and NO2 than corresponding hourly concentrations. Hourly correlations between PN and both CO and NO were strengthened during morning rush-hour periods, indicating a common vehicular source. Comparing hourly particle number concentrations between sites also showed low to moderate spatial correlations, with most correlation coefficients below 0.4. Given the low to moderate associations found in this study, gaseous co-pollutants should not be used as surrogates to assess human exposure to airborne particle number concentrations.

Development and Evaluation of a Compact Facility for Exposing Humans to Concentrated Ambient Ultrafine Particles

This article presents the development and evaluation of a very compact facility for exposing humans to concentrated ambient ultrafine particles (da < 0.15 μm). The human ultrafine particle concentrator (UFPC) operates at an intake flow rate of 1200 liters per minute (LPM). The concentrator is preceded by an ultrafine impactor which separates the accumulation mode from ultrafine mode particles under a very low pressure drop (1.5 kPa), a feature that is essential in enabling human inhalation studies of ultrafine concentrated ambient particulates (CAP). A key feature of the UFPC is a new cooling system, consisting of a programmable refrigerated circulator, which produces the supersaturation that is necessary to grow ultrafine PM to supermicrometer sizes so that they can be concentrated by means of conventional virtual impaction. The new cooling system allows for entirely automated operation of the UFPC. The UFPC was characterized in field experiments, in which the concentration enrichment of ultrafine particles was determined based on their number and mass concentration as well as on chemical composition including elemental carbon (EC), inorganic ions (sulfate and nitrate), and polycyclic aromatic hydrocarbons (PAH). Tests were conducted at minor-to-total flow ratios varying from 2.5–5% (hence at minor flow rates between 30–60 LPM). Measurements with the scanning mobility particle sizer (SMPS) showed a near-ideal increase in number concentrations (corresponding to the ratio of total-to-minor flow rate) of ultrafine particles after enrichment. The concentration enrichment was uniform across the entire particle diameter range of 15–660 nm. Similar results were obtained for EC and PAH concentrations (measured by an Aethalometer). Time-integrated filter-based tests, conducted to characterize the system for ultrafine PM mass and inorganic ion concentrations showed that the average enrichment factor was very close to the ideal values, indicating near-perfect collection efficiency with minimal particle losses.