Passive Sampling for Ozone

The Brigham Young University (BYU) organic sampling system (BOSS) and the high flow rate multi-system BYU organic sampling system (BIG BOSS), which use multichannel diffusion denuder sampling techniques, were both used to collect samples of atmospheric fine particulate organic material. Both systems were used at the Meadview sampling site located at the western boundary of the Grand Canyon National Park in northwestern Arizona for the Project MOHAVE summer intensive sampling program in August 1992. The concentrations of total fine particulate carbonaceous material determined by temperature programmed volatilization for BOSS collocated replicate samples were in agreement with an uncertainty of ±14%. A comparable agreement was seen between the BOSS and BIG BOSS samples. Carbonaceous material collected by the second of two sequential quartz filters was shown to have originated from organic material lost from particles during sampling. About one-half of the fine particulate organic material was lost from particles during sample collection. These semi-volatile organic compounds lost from particles during sampling were characterized by GC/MS analysis. The concentrations of n-alkanes, n-fatty acids, n-fatty methyl esters, and phthalic acid as a function of fine particulate size were obtained for compounds both retained by and lost from particles during sampling. The possible sources of fine particulate semi-volatile organic material collected at Meadview, and the particle size distribution of fine particulate organic material, n-alkanes, n-fatty acids, and n-fatty esters are discussed.     

Generation rates and emission factors of particulate matter and particle-bound polycyclic aromatic hydrocarbons of incense sticks

The generation rates and emission factors of particulate matter and associated polycyclic aromatic hydrocarbons (PAHs) from incense burning were assessed in a laboratory setting. The differences among different segments of the same stick, among different sticks of the same kind of incense, and between two kinds of manually made Chih-Chen incense sticks (A and B) were evaluated. Joss sticks were burned inside a 44 cm long elutriator; personal environmental monitors fitted into the top of the elutriator were used to take PM2.5 and PM10 samples of incense smoke. Samples were analyzed for PAHs by gas chromatography-flame ionization Detector. It was found that particle and associated PAHs were generated approximately at 561 microg/min (geometric standard deviation (GSD) = 1.1) and 0.56 microg/min (GSD = 1.1) from Incense A, and at 661 microg/min (GSD = 1.7) and 0.46 microg/min (GSD = 1.3) from Incense B, respectively. One gram of Incense A emitted about 19.8 mg (GSD = 1.1) particulate matter and 17.1 microg (GSD = 1.2) particulate-phase PAHs, while one gram of Incense B produced around 43.6 mg (GSD = 1.1) of particles and 25.2 microg (GSD = 1.2) of particle-bound PAHs. There were significant differences in emissions between Incenses A and B, although they belong to the same class of incense. A 10-20% variability in emissions was observed in the main part of the manually produced stick, and a larger variation was found at both tips of the combustible part.     

Experimental testing of an annular denuder and filter system to measure gas–particle partitioning of semivolatile bifunctional carbonyls in the atmosphere

An annular denuder and filter-pack system was tested in combination with the use of the in-tube and on-fiber O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA)-derivatization technique to simultaneously sample and measure gaseous and particulate concentrations of semivolatile bifunctional carbonyl compounds in the atmosphere. Ozone was denuded from the sampling air to avoid oxidation and PFBHA was used as the sorbent by coating the sampling denuders and impregnating the filters. The collection efficiency of the system was evaluated under different conditions in photochemical smog chamber experiments and in field samplings of urban and suburban atmospheres. The effects of concentration level, temperature, and humidity on the collection efficiency were assessed. The system showed average collection efficiencies in one denuder from 81% for pyruvic acid and 82% for glyoxylic acid to 87% for hydroxyacetone and dihydroxyacetone. The capacity of the filters to collect the gaseous fraction that cannot be collected in the denuders was also evaluated, and the system allows a correction for this artifact. The application of this method to chamber experiments and field samplings offers an easy-to-apply technique with good results that can be used to evaluate the partition mechanisms of these compounds in the atmosphere.     

Atmospheric Polycyclic Aromatic Hydrocarbons at a Point Source of Emissions. Part A: Identification and Determination of Polycyclic Aromatic Compounds in Airborne Particulate Matter Near a Horizontal Stud Soderberg Plant

Abstract

This paper summarizes the sampling and analytical methods developed to identify and measure polycyclic aromatic hydrocarbons (PAH) and related aromatic compounds near a Horizontal Stud Soderberg plant at Jonquiere, Quebec, Canada. The primary source of PAH is the coal tar pitch used as a binder in Soderberg anodes. Twice a week at a number of sampling sites, airborne particulate matter was collected on glass-fiber filters using a Hi-Vol sampler for a twenty-four hour period. Organics on the filter were Soxhlet extracted with benzene.

Identification was done by gas chromatography-mass spectrometry (GC-MS). The vast majority of compounds present were PAH, but small amounts of alkyl PAH and polycyclic aromatic compounds with heteroatoms such as nitrogen, oxygen and sulfur were also identified. Based on the GC-MS identification, a group of 14 PAH was selected for monitoring. Frequent PAH determinations revealed that the ratio of Benzo(a- )Pyrene to total PAH on the Hi-Vol filters is relatively constant in ambient air from one sampling station to another.     

Survey of polynuclear aromatic compounds in oil refining areas

Air samples in and around refinery areas were collected over a 3-year period. The results of the analysis for polynuclear aromatic compounds listed as priority pollutants by the United States Environmental Protection Agency are presented. The particulate matters in the air were collected on glass fiber filters using high volume samplers. These samples were later Soxhlet extracted with cyclohexane, and then extracted with DMSO/pentane for isolation of the polynuclear aromatic compounds. These extracts were then analyzed using gas chromatography-mass spectrometry for specified polynuclear aromatic compounds. It was found that much higher concentrations of these aromatic compounds were found in one refinery compared to another one. In general, the number of these priority pollutants detected and their concentrations were higher in sites inside the refineries relative to a site outside the refineries.     

Benzo[b]fluoranthene,a Potential Alternative to Benzo[a]pyrene as an Indicator of Exposure to Airborne PAHs in the Vicinity of Söderberg Aluminum Smelters

ABSTRACT

Benzo[b]fluoranthene (B[b]F) was used in relative abundance ratios (RARs), a parameter obtained by dividing the concentration of individual polycyclic aromatic hydrocarbons (PAHs) found in a given sample by the concentration of B[b]F in the same sample. The B[b]F RARs were derived for PAH concentrations measured at stacks and sampling stations in the vicinity of two Söderberg aluminum horizontal stud smelters (HSSs). The samples collected were analyzed by high-performance liquid chromatography using UV and fluorescence detection. A total of 15 PAHs were analyzed, but, due to the inefficiency of the sampling method used in collecting gaseous PAHs, only particulate PAHs were considered. Comparisons between the B[b]F RARs obtained simultaneously at the source (stack) and those obtained at sampling stations at the two smelters showed that B[b]F degrades more slowly than or at the same rate as most other particulate PAHs monitored. Twenty-three months of urban sampling in the vicinity of one of the aluminum HSSs are also presented, and the results indicate that B[b]F is more stable than all other particulate PAHs investigated. Sampling conducted during a smelter shutdown period confirmed that B[b]F was a much better marker of this source than was benzo[a]pyrene (B[a]P), the usual indicator. The remarkable stability of the benzo[k]fluoranthene (B[k]F)/B[b]F ratio is also discussed.     

Molecular composition of organic fine particulate matter in Houston,TX

Organic fine particulate matter collected in Houston, TX between March 1997 and March 1998 was analyzed to determine the concentration of individual organic compounds. Samples from four sites were analyzed including two industrial locations (Houston Regional Monitoring Corporation (HRM-3) site in Channelview and Clinton Drive site near the Ship Channel Turning Basin), one suburban location (Bingle Drive site in Northwest Houston) and one background site (Galveston Island). At the three urban locations, samples were divided into three seasonal sample aggregates (spring, summer and winter), while at the background site a single annual average sample pool was used. Between 10 and 16 individual samples were pooled to get aggregate samples with enough organic carbon mass for analysis. Overall, 82 individual organic compounds were quantified. These include molecular markers which are compounds unique to specific fine particle sources and can be used to track the relative contribution of source emissions to ambient fine particle levels. The differences both spatially and temporally in these tracers can be used to evaluate the variability in emission source strengths.     

Effect of combustion condition on cytotoxic and inflammatory activity of residential wood combustion particles

Residential heating is an important local source of fine particles and may cause significant exposure and health effects in populations. We investigated the cytotoxic and inflammatory activity of particulate emissions from normal (NC) and smouldering (SC) combustion in one masonry heater. The PM_1–0.2 and PM_0.2 samples were collected from the dilution tunnel with a high-volume cascade impactor (HVCI). Mouse RAW 264.7 macrophages were exposed to the PM-samples for 24 h. Inflammatory mediators, (IL-6, TNFα and MIP-2), and cytotoxicity (MTT-test), were measured. Furthermore, apoptosis and cell cycle of macrophages were analyzed. The HVCI particulate samples were characterized for ions, elements and PAH compounds. Assays of elemental and organic carbon were conducted from parallel low volume samples. All the samples displayed mostly dose-dependent inflammatory and cytotoxic activity. SC samples were more potent than NC samples at inducing cytotoxicity and MIP-2 production, while the order of potency was reversed in TNFα production. SC-PM_1–0.2 sample was a significantly more potent inducer of apoptosis than the respective NC sample. After adjustment for the relative toxicity with emission factor (mg MJ^?1), the SC-PM emissions had clearly higher inflammatory and cytotoxic potential than the NC-PM emissions. Thus, operational practice in batch burning of wood and the resultant combustion condition clearly affect the toxic potential of particulate emissions.     

Background concentrations of 18 air toxics for North America

The U.S. Clean Air Act identifies 188 hazardous air pollutants (HAPs), or "air toxics," associated with adverse human health effects. Of these air toxics, 18 were targeted as the most important in a 10-City Pilot Study conducted in 2001 and 2002 as part of the National Air Toxics Trend Sites Program. In the present analysis, measurements available from monitoring networks in North America were used to estimate boundary layer background concentrations and trends of these 18 HAPs. The background concentrations reported in this study are as much as 85% lower than those reported in recent studies of HAP concentrations. Background concentrations of some volatile organic compounds were analyzed for trends at the 95% confidence level; only carbon tetrachloride (CCI4) and tetrachloroethylene decreased significantly in recent years. Remote background concentrations were compared with the one-in-a-million (i.e., 10(6)) cancer benchmarks to determine the possible causes of health risk in rural and remote areas; benzene, chloroform, formaldehyde, and chromium (Cr) fine particulate were higher than cancer benchmark values. In addition, remote background concentrations were found to contribute between 5% and 99% of median urban concentrations.     

Benzo[b]fluoranthene, a potential alternative to benzo[a]pyrene as an indicator of exposure to airborne PAHs in the vicinity of Söderberg aluminum smelters

Benzo[b]fluoranthene (B[b]F) was used in relative abundance ratios (RARs), a parameter obtained by dividing the concentration of individual polycyclic aromatic hydrocarbons (PAHs) found in a given sample by the concentration of B[b]F in the same sample. The B[b]F RARs were derived for PAH concentrations measured at stacks and sampling stations in the vicinity of two S?derberg aluminum horizontal stud smelters (HSSs). The samples collected were analyzed by high-performance liquid chromatography using UV and fluorescence detection. A total of 15 PAHs were analyzed, but, due to the inefficiency of the sampling method used in collecting gaseous PAHs, only particulate PAHs were considered. Comparisons between the B[b]F RARs obtained simultaneously at the source (stack) and those obtained at sampling stations at the two smelters showed that B[b]F degrades more slowly than or at the same rate as most other particulate PAHs monitored. Twenty-three months of urban sampling in the vicinity of one of the aluminum HSSs are also presented, and the results indicate that B[b]F is more stable than all other particulate PAHs investigated. Sampling conducted during a smelter shutdown period confirmed that B[b]F was a much better marker of this source than was benzo[a]pyrene (B[a]P), the usual indicator. The remarkable stability of the benzo[k]fluoranthene (B[k]F)/B[b]F ratio is also discussed.     

Smoke emissions from biomass burning in a Mediterranean shrubland

Gaseous and particulate samples from the smoke from prescribed burnings of a shrub-dominated forest with some pine trees in Lousã Mountain, Portugal, in May 2008, have been collected. From the gas phase Fourier transform infrared (FTIR) measurements, an average modified combustion efficiency of 0.99 was obtained, suggesting a very strong predominance of flaming combustion. Gaseous compounds whose emissions are promoted in fresh plumes and during the flaming burning phase, such as CO₂, acetylene and propene, produced emission factors higher than those proposed for savannah and tropical forest fires. Emission factors of species that are favoured by the smouldering phase (e.g. CO and CH₄) were below the values reported in the literature for biomass burning in other ecosystems. The chemical composition of fine (PM_2.5) and coarse (PM_2.5–10) particles was achieved using ion chromatography (water-soluble ions), instrumental neutron activation analysis (trace elements) and a thermal–optical transmission technique (organic carbon and elemental carbon). Approximately 50% of the particulate mass was carbonaceous in nature with a clear dominance of organic carbon. The organic carbon-to-elemental carbon ratios up to 300, or even higher, measured in the present study largely exceeded those reported for fires in savannah and tropical forests. More than 30 trace elements and ions have been determined in smoke aerosols, representing in total an average contribution of about 7% to the PM₁₀ mass.     

Ions species size distribution in particulate matter associated with VOCs and meteorological conditions over an urban region

Airborne particulate matter (PM10, PM2.5, PM1) and volatile organic compounds (benzene, toluene, m,p-xylene, o-xylene) samples were collected during winter and summer seasons of 2005 at two sites, representing an urban and a suburban region of the Greater Athens Area. Urban site traffic emissions were the major contributor to the concentration of PM2.5, PM10, toluene, and xylenes, while benzene and PM1 concentrations were presented in significant spatial variations. K+, Na+, Mg2+, Ca2+, NO3-, Cl- and SO42- ions were analyzed for the chemical characterization of the collected PM samples. The results showed that Na+ cations and SO42- anions were the dominant species, during winter and summer, respectively, in both sites. The analysis of the synoptic scale and mesoscale atmospheric circulation during the experimental periods demonstrated that the meteorological conditions play a key role, not only in the variation but also in the distribution of the ionic concentrations at the three fractions of particulates and the dominant character (alkaline/acidic/neutral) of the particulates at the two sampling sites.     

In vitro effects of pollutants from particulate and volatile fractions of air samples—day and night variability

Chemicals in air were characterized for potential interference with signaling of estrogen, androgen, and arylhydrocarbon (AhR) receptors, which are known to play an important role in endocrine-disruptive changes in vivo. Previously, effects of this type have been studied mainly in particulate matter in the ambient air from various localities. In this study, both volatile and particulate fractions of air from three sites in Banja Luka region (Bosnia and Herzegovina) were investigated to describe the distribution of endocrine-disrupting contaminants on a small spatial scale. Circadian variability of air pollution was investigated by collecting samples during both day and night. Air samples collected from urban localities at night were more potent in producing the AhR-mediated effects than those collected during daytime. This trend was not observed at the reference rural location. None of the samples showed significant estrogenic or androgenic activity. On the other hand, anti-androgenicity was detected in both particulate and vapor phases, while anti-estrogenicity was detected only in the particulate fraction of air from all localities. The AhR-mediated potencies of samples were associated primarily with non-persistent compounds. Based on the concentrations of 28 individual compounds, PAHs accounted for approximately 30 % of the AhR-mediated potency determined by the bioassay. The results show that there can be a significant difference between levels of bioactive compounds in air between daytime and nighttime.     

Particle Size Distribution of Settled Dust

In 1958, San Bernardino County Air Pollution Control District adopted rules and regulations for the control of dust, fumes and particulate matter. These were taken from ordinances which had been effectively used in other areas. After three years, experience showed that in some instances these rules and regulations should be modified to take into consideration the specific industrial operations in the county. A technical committee was appointed to examine this problem and concluded that a reasonable rule would be one that protects the public from the undesirable effects of dusts, fumes and particulate matter but would not impose an unnecessary burden on industry. Dustfall samples were collected at various locations throughout San Bernardino County and examined for particle-size distribution. In order to obtain reliable data, fairly large samples had to be collected in a short time. A 12 foot square plastic sheet was found suitable for sample collection. Particle size determinations were made with both the coulter counter and the Bahco microparticle classifier. The two methods yielded comparable results. It was found that settled dust particles for all practical considerations were all greater than 30 microns in equivalent diameter. Regulations based on these findings are being developed.     

Application of Computer Controlled High Resolution Mass Spectrometry to the Analysis of Air Pollutants

An AEI-MS9 high resolution mass spectrometer interfaced with a PDP-12 digital computer has been adapted for the multicomponent analysis of air pollutants. Air sampling techniques for particulate and gaseous pollutants have been developed which are compatible with the mass spectrometric system. A single stage impactor has been designed for sampling particulate matter of particle diameters greater than 1–2 μm. The remainder of the particulate matter is collected on a glass fiber filter. Gaseous pollutants are collected on a styrene-divinylbenzene copolymer (Chromosorb 102).

The particulate samples are introduced directly into the mass spectrometer utilizing a temperature programed insertion probe. Gaseous pollutants are desorbed from the copolymer directly into the mass spectrometer by heating. Analysis of composite mass spectral data is facilitated through the use of a digital computer utilizing newly developed computer programs. Final computer output yields qualitative and quantitative results for up to 300 pollutants. Organic pollutants identified in particulate matter include polycyclic aromatic compounds, alkyl chlorides, polychlorinated aromatics, substituted benzenes and organic acids. Composite quantitative results are reported for alkanes and alkenes in the following groups: C₁₅-C₃₀, C₃₀-C₅₀ and Cso-polymeric. Inorganic pollutants identified include As₄O₆, H₂SO_4/ (NH₄)₂SO₄, (NH₄)₂SO₃, NaHSO₄, NH₄NO_3/ NaNO₃, NH₄CI, SeO₂, I₂, elemental sulfur, and elemental cadmium.     

Obtaining polycyclic aromatic hydrocarbon concentration ratios and molecular markers for residential wood combustion: Temuco, a case study

It is known that residential wood combustion (RWC) is an important source of fine particle emissions. The purpose of this work was to characterize the chemical composition of the particulate matter present in the Temuco urban atmosphere during winter, specifically the polycyclic aromatic hydrocarbon (PAH) profile, because PAHs are considered to be among the key compounds in particulate matter toxicity. During the 2008 winter monitoring campaign, samples of particulate matter with aerodynamic diameters of < or = 10 (PM10) and < or = 2.5 (PM2.5) microm were taken on days with contamination episodes. Sixteen U.S. Environmental Protection Agency (EPA) PAH compounds were extracted with toluene and determined by gas chromatography-mass spectrometry (GC-MS). The results show that phenantrene was the predominant compound associated with particulate matter at a concentration range between 300 and 600 ng m(-3), 18 times higher than the second most abundant PAH compound. High-molecular-mass compounds such as dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3,c,d]pyrene were also found, but they were minorities in the set. It was recognized from the PAH concentration ratios of the Temuco atmospheric aerosol that the main contamination source was in fact residential wood combustion; although not all the concentration ratios evaluated match the reported reference values, probably due to the kind of biomass used, the characteristics of Chilean heating appliances and climate.     

Do We Understand Trends in Atmospheric Sulfur Species?

ABSTRACT

Anomalies appear to exist in our understanding of atmospheric sulfur compounds, specifically as evidenced in the time trends of the different chemical forms of these compounds. Trends determined at a number of locations by several different groups seem to indicate that, responding to emission reductions across North America, the concentration of SO₂ in the atmosphere is declining more rapidly than that of aerosol SO₄ ^2-. A number of possible reasons for this discrepancy are examined, but it is not possible to provide a definitive answer at this stage. The intent is to stimulate debate, because shortcomings in our understanding of the processes involved could have profound implications for the credibility of abatement strategies and policies for both acid deposition and fine particulate matter (PM).     

Determination of fine particulate semi-volatile organic material at three eastern U.S. sampling sites

Correct assessment of fine particulate carbonaceous material as a function of particle size is, in part, dependent on the determination of semi-volatile compounds, which can be lost from particles during sampling. This study gives results obtained for the collection of fine particulate carbonaceous material at three eastern U.S. sampling sites [Philadelphia, PA; Shenandoah National Park, VA; and Research Triangle Park (RTP), NC] using diffusion denuder technology. The diffusion denuder samplers allow for the determination of fine particulate organic material with no artifacts, due to the loss of semi-volatile organic particulate compounds, or collection of gas-phase organic compounds by the quartz filter during sampling. The results show that an average of 41, 43, and 59% of fine particulate organic material was lost as volatilized semi-volatile organic material during collection of particles on a filter at Philadelphia, RTP, and Shenandoah, respectively. The particle size distribution of carbonaceous material retained by a filter and lost from a filter during sampling was obtained for the samples collected at Philadelphia and Shenandoah. The carbonaceous material retained by the particles during sampling was found predominantly in particles smaller than 0.4 microm in aerodynamic diameter. In contrast, the semi-volatile organic material lost from the particles during sampling had a mass median diameter of approximately 0.5 microm.     

Elemental analysis of airborne particulates in Chile

Aerosol samples collected in three characteristic Chilean cities-including urban and remote zones-have been analyzed by the PIXE spectroscopic technique. Elemental composition, total suspended particulate matter (TSP), particle size distribution, and the peculiar geographic and meteorological parameters have been included in this study. Santiago--the polluted capital of Chile--registered high TSP indexes and important amounts of hazardous elements in air such as S, V, Cr, Zn, Br and Pb. The atmosphere of Antofagasta city showed marine and mineral activity influence. Results from Chillán city are similar to those from rural environments. Protons and deuterons-provided by the isochronous cyclotron of the University of Chile-were used to excite X-ray radiation from the sample. Signals were processed by an energy dispersive detection system, including a cryogenic Si(Li) detector, electronic for pulse amplification and an analog to digital converter. The absolute elemental concentration of the particulate matter in air was obtained through a fundamental parameter equation. Samples consist of particulate material collected directly on Nuclepore filters or deposited over Kapton foils. Typical elements analyzed were Mg, Al, Si, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Cu, Zn, As, Br and Pb.     

Determination of Fine Particulate Semi-Volatile Organic Material at Three Eastern U.S. Sampling Sites

ABSTRACT

Correct assessment of fine particulate carbonaceous material as a function of particle size is, in part, dependent on the determination of semi-volatile compounds, which can be lost from particles during sampling. This study gives results obtained for the collection of fine particulate carbonaceous material at three eastern U.S. sampling sites [Philadelphia, PA; Shenandoah National Park, VA; and Research Triangle Park (RTP), NC] using diffusion denuder technology. The diffusion denuder samplers allow for the determination of fine particulate organic material with no artifacts, due to the loss of semi-volatile organic particulate compounds, or collection of gas-phase organic compounds by the quartz filter during sampling. The results show that an average of 41, 43, and 59% of fine particulate organic material was lost as volatilized semi-volatile organic material during collection of particles on a filter at Philadelphia, RTP, and Shenandoah, respectively. The particle size distribution of carbonaceous material retained by a filter and lost from a filter during sampling was obtained for the samples collected at Philadelphia and Shenandoah. The carbonaceous material retained by the particles during sampling was found predominantly in particles smaller than 0.4 μm in aerodynamic diameter. In contrast, the semi-volatile organic material lost from the particles during sampling had a mass median diameter of ~0.5 μm.