Exploring relationships between outdoor air particulate-associated polycyclic aromatic hydrocarbon and PM2.5: A case study of benzo(a)pyrene in California metropolitan regions

Polycyclic aromatic hydrocarbons (PAHs) and particulate matter (PM) are co-pollutants emitted as by-products of combustion processes. Convincing evidence exists for PAHs as a primary toxic component of fine PM (PM_2.5). Because PM_2.5 is listed by the US EPA as a “Criteria Pollutant”, it is monitored regularly at sites nationwide. In contrast, very limited data is available on measured ambient air concentrations of PAHs. However, between 1999 and 2001, ambient air concentrations of PM_2.5 and benzo(a)pyrene (BaP) are available for California locations. We use multivariate linear regression models (MLRMs) to predict ambient air levels of BaP in four air basins based on reported PM_2.5 concentrations and spatial, temporal and meteorological variables as variates. We obtain an R² ranging from 0.57 to 0.72 among these basins. Significant variables (p<0.05) include the average daily PM_2.5 concentration, wind speed, temperature and relative humidity, and the coastal distance as well as season, and holiday or weekend. Combining the data from all sites and using only these variables to estimate ambient BaP levels, we obtain an R² of 0.55. These R²-values, combined with analysis of the residual error and cross validation using the PRESS-statistic, demonstrate the potential of our method to estimate reported outdoor air PAH exposure levels in metropolitan regions. These MLRMs provide a first step towards relating outdoor ambient PM_2.5 and PAH concentrations for epidemiological studies when PAH measurements are unavailable, or limited in spatial coverage, based on publicly available meteorological and PM_2.5 data.     

Polycyclic aromatic hydrocarbons in ambient air in the Philippines derived from passive sampler with polyurethane foam disk

Passive samplers with polyurethane disks (PUF) were applied in the determination of the concentration of polycyclic aromatic hydrocarbons (PAHs) in ambient air in six residential areas in the Philippines during four simultaneous sampling periods. The uptake profiles of PAHs were determined at one site during one sampling period. Most of the PAHs that were detected in air at concentrations that were significantly higher than their analytical detection limits exhibited a linear uptake trend on the PUF disk. The linear uptake profiles of some high molecular weight (HMW) PAHs were not established and this is attributed to the low concentration of the compounds in air in the gaseous phase. The retention concentrations of phenanthrene-d-10 were determined after depuration in four sampling sites during two sampling periods. The sampling rate for phenanthrene-d-10 was calculated at the linear phase of the uptake using the k_A derived from depuration experiments and the relationship of k_A and sampling rate which was established in a previous passive sampling study. The average sampling rate obtained for phenanthrene d-10 (2.94±0.69 m³ d⁻¹) was applied for derivation of the concentrations of the PAHs in the field samples.The passive sampler with PUF disk and short integration time of 42–56 days is applicable for the derivation of the concentrations of PAHs in ambient air in the Philippines. The concentrations of the organic pollutants derived from the passive sampler showed variability for the six residential areas; reflecting the influence of possible sources of emission of the pollutants at the sites at the different sampling periods. The weather conditions, including the occurrence of a tropical cyclone, increased rainfall and high-relative humidity during the rainy season, had an influence on the concentrations of PAHs derived by the passive sampler.     

Migration of polycyclic aromatic hydrocarbons (PAHs) in urban treatment sludge to the air during PAH removal applications

In the present study, the amounts of polycylic aromatic hydrocarbons (PAHs) penetrating into air during PAH removal applications from the urban treatment sludge were investigated. The effects of the temperature, photocatalyst type, and dose on the PAH removal efficiencies and PAH evaporation were explained. The sludge samples were taken from an urban wastewater treatment plant located in the city of Bursa, with 585,000 equivalent population. The ultraviolet C (UV-C) light of 254 nm wavelength was used within the UV applications performed on a specially designed setup. Internal air of the setup was vacuumed through polyurethane foam (PUF) columns in order to collect the evaporated PAHs from the sludge during the PAH removal applications. All experiments were performed with three repetitions. The PAH concentrations were measured by gas chromatography–mass spectrometry (GC-MS). It was observed that the amounts of PAHs penetrating into the air were increased with increase of temperature, and more than 80% of PAHs migrated to the air consisted of 3-ring compounds during the UV and UV-diethylamine (DEA) experiments at 38 and 53 °C. It was determined that 40% decrease was ensured in Σ₁₂ (total of 12) PAH amounts with UV application and 13% of PAHs in sludge penetrated into the air. In the UV-TiO₂ applications, a maximum 80% of Σ₁₂ PAH removal was obtained by adding 0.5% TiO₂ of dry weight of sludge. The quantity of PAH penetrating into air did not exceed 15%. UV-TiO₂ applications ensured high levels of PAH removal in the sludge and also reduced the quantity of PAH penetrating into the air. Within the scope of the samples added with DEA, there was no increase in PAH removal efficiencies and the penetration of PAHs into air was not decreased. In light of these data, it was concluded that UV-TiO₂ application is the most suitable PAH removal alternative that restricts the convection of PAH pollution.

Implications: Polycyclic aromatic hydrocarbon (PAH) evaporation rates from sludge samples obtained from an urban wastewater treatment plant were investigated here for the first time by employing removal applications. TiO₂ and diethylamine were used as photocatalysts in this study. A special device was designed and successfully used in this study. Treatment sludge can be a significant source of PAHs for the atmosphere. The data highlight the need for removal of PAHs in treatment sludge via methods limiting their evaporation to the air. It was observed that UV-TiO₂ application was the most suitable PAH removal alternative that restricts the convection of PAH pollution.     

Wood smoke as a source of particle-phase organic compounds in residential areas

The objective of this study was to investigate the organic composition of wood smoke emissions and ambient air samples in order to determine the wood smoke contribution to the ambient air pollution in the residential areas. From November 2005 to March 2006 particle-phase PM₁₀ samples were collected in the residential town Dettenhausen surrounded by forests near Stuttgart in southern Germany. Samples collected on pre-baked glass fibre filters were extracted using toluene with ultrasonic bath and analysed by gas chromatography mass spectrometry (GC-MS). 21 polycyclic aromatic hydrocarbons (PAH) including 16 USEPA priority pollutants, different organic wood smoke tracers, primarily 21 species of syringol and guaiacol derivatives, levoglucosan and its isomers mannosan, galactosan and dehydroabietic acid were detected and quantified in this study. The concentrations of these compounds were compared with the fingerprints of emissions from hardwood and softwood combustion carried out in test facilities at Universitaet Stuttgart and field investigations at a wood stove during real operation in Dettenhausen. It was observed that the combustion derived PAH was detected in higher concentrations than other PAH in the ambient air PM₁₀ samples. Syringol and its derivatives were found in large amounts in hardwood burning but were not detected in softwood burning emissions. On the other hand, guaiacol and its derivatives were found in both softwood and hardwood burning emissions, but the concentrations were higher in the softwood smoke compared to hardwood smoke. So, these compounds can be used as typical tracer compounds for the different types of wood burning emissions. In ambient air samples both syringol and guaiacol derivatives were found which indicates the wood combustion contribution to the PM load in such residential areas. Levoglucosan was detected in high concentrations in all ambient PM₁₀ samples. A source apportionment modelling, Positive Matrix Factorization (PMF) was implemented to quantify the wood smoke contribution to the ambient PM₁₀ bound organic compounds in the residential area.     

Compositional fractionation of polycyclic aromatic hydrocarbons (PAHs) in mosses (Hypnum plumaeformae WILS.) from the northern slope of Nanling Mountains,South China

High mountains may serve both as condenser for vapor phase persistent organic pollutants (POPs) and as barrier/sink for particulate associated less volatile POPs. The fractionation of POPs along altitudinal profiles is of interest in understanding the role of high mountains in the atmospheric transport of POPs. In the present study, polycyclic aromatic hydrocarbons (PAHs) in a selected moss species, Hypnum plumaeformae WILS, from two altitudinal profiles on the northern slope of Nanling mountains in Southern China were analyzed and compared with those in air samples. The total PAH concentration in the mosses was 310–1340 ng g⁻¹ dry weight, with phenanthrene being the most abundant. The distribution patterns of PAHs in the moss samples matched well with those in bulk atmosphere deposition in the adjacent source areas. The PAH distribution pattern in the mosses was a composite of both particle-associated and vapor phase PAHs, with heavy PAHs are susceptible to uptake/retention by mosses than light PAHs. A plot of log (C_moss/C_air) against log K_oa gave a good linear relationship in the log K_ao range of 6.7–10.2. It is suggested that the widely spread moss, H. plumaeformae WILS, can be used as an effective tool in the biomonitoring of atmospheric PAHs pollution in East Asia. The concentrations of most PAHs in the mosses generally declined with increasing altitude. In addition, there was a shift in compound pattern with an increase in the proportion of light PAHs (2–3 rings), a decrease in heavy PAHs (5–6 rings) and a relatively stable content of 4-ring PAHs. A combination of particulate scavenging and cold condensation are proposed as the major mechanisms for the compositional fractionation of PAHs along the altitudinal profile.     

Characterisation of volatile organic compounds and polycyclic aromatic hydrocarbons in the ambient air of steelworks

Investigations have been undertaken at two integrated steelworks in the UK to characterise airborne organic micro-pollutants and to assess the contribution of iron ore sintering and coke making operations on the air quality. Concentrations of volatile organic compounds (VOCs), namely benzene, toluene and p-xylene, were measured continuously within the boundary of a coking plant using for the first time differential optical absorption spectrometry (DOAS) between 2004 and 2006. Concentrations were obtained along two monitoring paths surrounding the coke plant and the average benzene concentration measured along both paths over the campaign was 28 μg m^?3. Highest benzene concentrations were associated with winds downwind of the coke oven batteries. Concentrations of polycyclic aromatic hydrocarbons (PAHs) in ambient air were measured during 27 consecutive days in 2005 at three different locations on an integrated steelworks. PAH profiles were determined for each sampling point and compared to coke oven and sinter plant emission profiles showing an impact from the steelworks. The mean benzo [a] pyrene concentration determined in the immediate vicinity of the coke ovens downwind from the battery was 19 ng m^?3, whereas for the two other sites average benzo [a] pyrene concentrations were much lower (around 1 ng m^?3). Data were analysed using principal components analysis (PCA) and results showed that coke making and iron ore sintering were responsible for most of the variation in the PAH concentrations in the vicinity of the investigated plant.     

Modeling PAH uptake by vegetation from the air using field measurements

We examined PAH uptake by Norway spruce needles following the emergence of new buds in spring 2004–June 2005. Atmospheric PAH concentrations (gaseous phase and particle-bound) were monitored during this period, and PAH concentrations from these three environmental media were then used to calculate deposition and transfer velocities. Benzo(a)pyrene was found almost exclusively associated to particles and thus was used to determine a particle-bound deposition velocity of 10.8 m h^?1. PAHs present in both compartments had net gaseous transfer velocities ranging from negligible values to 75.6 m h^?1 and correlated significantly with log K_OA. The loss velocities thereafter calculated were found to be higher for more volatile PAHs. Using the calculated average atmospheric PAH concentrations and deposition velocities, it was thus possible to model PAH uptake by vegetation through time. We demonstrate that this approach can be used to determine deposition velocities without the use of a surrogate surface. In considering both particulate-bound and gaseous deposition processes this model can be used not only to study air–foliage exchange of semi-volatile organic compounds, but also to illustrate the relative contribution of gaseous deposition and particulate-bound deposition in the overall atmospheric vegetation uptake of semi-volatile organic compounds.     

Chemical characteristics of organic aerosols in Algiers city area: influence of a fat manufacture plant

Total concentrations and homologue distributions of organic fraction constituents have been determined in particulate matter emitted from different units of a fat manufacturer (i.e. oils refining and conditioning plants, and production and conditioning units of a soap industry) located in Algiers area, as well as in atmospheric aerosols. In particular n-alkanes, n-alkanoic and n-alkenoic acids, n-alkan-2-ones and polycyclic aromatic hydrocarbons (PAH) were investigated. Organic aerosol contents varied broadly among the plant units, depending upon nature of the manufactured products. The percent composition of all classes of compounds investigated in ambient atmosphere was similar to those observed indoor at industrial plant units. Organic acids, n-alkanoic as well as n-alkenoic, appeared by far the most abundant organic constituents of aerosols, both indoor and outdoor, ranging from 7.7 to 19.8 and from 12.7 to 17.1 μg m⁻³, respectively. The huge occurrence of acids and n-alkanes in ambient aerosols was consistent with their high levels present in oil and fat materials. Among minor components of aerosols, n-alkan-2-ones and PAH, seemed to be related to thermally induced ageing and direct combustion of raw organic material used for oil and soap production.     

C2–C10 nonmethane hydrocarbons measured in Dallas,USA—Seasonal trends and diurnal characteristics

Nonmethane hydrocarbons (NMHCs) are important precursors of ozone and other photo oxidants. We presented continuous hourly average concentrations of 45 C₂–C₁₀ NMHCs measured in urban area of Dallas, USA from 1996 to 2004. Most of the selected compounds are good variables with less noise. The top 10 species with high ozone-generating potential were identified according to their concentrations and reactivities. The ambient concentrations of abundant anthropogenic emission hydrocarbons measured in Dallas were about 2–4 times of the background values measured in the remote areas with adjacent latitude. The time series for anthropogenic emission hydrocarbons showed an obvious seasonal cycle with relatively high concentration in winter and low concentration in summer. The sinusoidal function with a linearly decreasing factor could well fit the time series of NMHCs. The phase of seasonal cycle for the aromatic hydrocarbons of toluene, m/p xylene and o-xylene that might come from both vehicle emission and solvent utilities evaporation was about 1 month earlier than that for alkanes and alkenes that mainly came from vehicle emission. Ambient NMHCs in Dallas decreased with a stable rate during 1996–2004. For most of compounds with high ozone-generating potential, the rate of ambient concentration decrease was higher or much higher than the rate of volatile organic compounds (VOCs) source emission reduction estimated by EPA's National Emission Inventory. On weekdays, the morning hydrocarbon concentration peak was coincident with morning traffic rush time in Dallas. Another concentration peak was delayed to afternoon traffic rush time. The characteristics of VOCs sources, photochemical removal processes and atmospheric dilution could be interpreted by the diurnal variations of benzene/ethylbenzene (B/E), toluene/ethylbenzene (T/E) and xylene/ethylbenzene (X/E). The ratio of VOC/NO_x measured in Dallas was substantially smaller than that calculated for USA cities. Ozone formation in Dallas was VOC sensitive.     

Polycyclic aromatic hydrocarbons in sediments,pore water and the amphipod Pontoporeia hoyi from Lake Michigan

Polycyclic aromatic hydrocarbon (PAH) concentrations were measured in Pontoporeia hoyi, the most abundant benthic organism in Lake Michigan, and in its associated sediment/pore water matrix. Individual PAH concentrations ranged from 10 ppb to 1 ppm in three sedimentary environments having different levels of organic carbon. Pore water concentrations appeared to be independent of sediment concentrations. P. hoyi bioconcentration factors ranged from approximately 10⁴ to 10⁵ for seven analyzed PAHs. A major fraction of the phenanthrene, fluoranthene and pyrene in P. hoyi appears to come from sediments and pore water, while chrysene and BaP are primarily obtained from water.     

PAH air pollution at a Portuguese urban area: carcinogenic risks and sources identification

This study aimed to characterize air pollution and the associated carcinogenic risks of polycyclic aromatic hydrocarbon (PAHs) at an urban site, to identify possible emission sources of PAHs using several statistical methodologies, and to analyze the influence of other air pollutants and meteorological variables on PAH concentrations.The air quality and meteorological data were collected in Oporto, the second largest city of Portugal. Eighteen PAHs (the 16 PAHs considered by United States Environment Protection Agency (USEPA) as priority pollutants, dibenzo[a,l]pyrene, and benzo[j]fluoranthene) were collected daily for 24 h in air (gas phase and in particles) during 40 consecutive days in November and December 2008 by constant low-flow samplers and using polytetrafluoroethylene (PTFE) membrane filters for particulate (PM₁₀ and PM_2.5 bound) PAHs and pre-cleaned polyurethane foam plugs for gaseous compounds. The other monitored air pollutants were SO₂, PM₁₀, NO₂, CO, and O₃; the meteorological variables were temperature, relative humidity, wind speed, total precipitation, and solar radiation. Benzo[a]pyrene reached a mean concentration of 2.02 ng?m^?3, surpassing the EU annual limit value. The target carcinogenic risks were equal than the health-based guideline level set by USEPA (10^?6) at the studied site, with the cancer risks of eight PAHs reaching senior levels of 9.98?×?10^?7 in PM₁₀ and 1.06?×?10^?6 in air. The applied statistical methods, correlation matrix, cluster analysis, and principal component analysis, were in agreement in the grouping of the PAHs. The groups were formed according to their chemical structure (number of rings), phase distribution, and emission sources. PAH diagnostic ratios were also calculated to evaluate the main emission sources. Diesel vehicular emissions were the major source of PAHs at the studied site. Besides that source, emissions from residential heating and oil refinery were identified to contribute to PAH levels at the respective area. Additionally, principal component regression indicated that SO₂, NO₂, PM₁₀, CO, and solar radiation had positive correlation with PAHs concentrations, while O₃, temperature, relative humidity, and wind speed were negatively correlated.     

Oxidant denuder sampling for analysis of polycyclic aromatic hydrocarbons and their oxygenated derivates in ambient aerosol: evaluation of sampling artefact

The concentrations of some polycyclic aromatic hydrocarbons (PAH) and oxygenated PAH (O-PAH) can be changed by oxidation reactions during sampling. This can lead to an over- or underestimation of the corresponding adverse health effects. The aim of this study was the evaluation of these sampling artefacts. The potential of using an oxidant denuder was shown by parallel low-volume sampling with and without MnO₂ ozone denuder. Twenty-three PAH and 11 O-PAH in ambient air were analysed, both in the vapour and particulate phase. The denuder was proven to be highly efficient for stripping ozone from air while causing no significant particle losses. In general, the concentrations of 5- to 7-ring PAH, which are predominantly associated with particles, were underestimated in non-denuded samples. The highest losses due to reaction with ozone and other atmospheric oxidants were observed for benzo[a]pyrene and perylene. Concurrently, the concentrations of most of the mainly particle-associated 4- to 5-ring O-PAH were higher in the non-denuded samples. The denuder did not only remove ozone, moreover other gaseous species such as more volatile PAH and O-PAH were partially oxidized on the catalytic surface, too. Degradation of PAH and concurrent degradation/formation reactions of O-PAH occurred. The corresponding reactivities of selected PAH and O-PAH are discussed.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta

Twenty-four hour PM_2.5 samples from a rural site, an urban site, and a suburban site (next to a major highway) in the metropolitan Atlanta area in December 2003 and June 2004 were analyzed for 19 polycyclic aromatic hydrocarbons (PAH). Extraction of the air samples was conducted using an accelerated solvent extraction method followed by isotope dilution gas chromatography/mass spectrometry determination. Distinct seasonal variations were observed in total PAH concentration (i.e. significantly higher concentrations in December than in June). Mean concentrations for total particulate PAHs in December were 3.16, 4.13, and 3.40 ng m^?3 for the urban, suburban and rural sites, respectively, compared with 0.60, 0.74, and 0.24 ng m^?3 in June. Overall, the suburban site, which is impacted by a nearby major highway, had higher PAH concentration than did the urban site. Total PAH concentrations were found to be well correlated with PM_2.5, organic carbon (OC), and elemental carbon (EC) in both months (r² = 0.36–0.78, p < 0.05), although the slopes from the two months were different. PAHs represented on average 0.006% of total PM_2.5 mass and 0.017% of OC in June, compared with 0.033% of total PM_2.5 and 0.14% of OC in December. Total PAH concentrations were also correlated with potassium ion (r² = 0.39, p = 0.014) in December, but not in June, suggesting that in winter biomass burning can potentially be an important source for particulate PAH. Retene was found at a higher median air concentration at the rural site than at the urban and suburban sites—unlike the rest of the PAHs, which were found at lower levels at the rural site. Retene also had a larger seasonal difference and had the weakest correlation with the rest of the PAHs measured, suggesting that retene, in particular, might be associated with biomass burning.     

Identification and source apportionment of polycyclic aromatic hydrocarbons in ambient air particulate matter of Riyadh, Saudi Arabia

In an effort to assess the occurrence and sources of polycyclic aromatic hydrocarbons (PAHs) in the ambient air of Riyadh, Saudi Arabia, PM₁₀ samples were collected during December 2010. Diagnostic PAH concentration ratios were used as a tool to identify and characterize the PAH sources. The results reflect high PM₁₀ and PAH concentrations (particulate matter (PM)?=?270–1,270 μg/m³). The corresponding average PAH concentrations were in the range of 18?±?8 to 1,003?±?597 ng/m³ and the total concentrations (total PAHs (TPAHs) of 17 compounds) varied from 1,383 to 13,470 ng/m³ with an average of 5,871?±?2,830 ng/m³. The detection and quantification limits were 1–3 and 1–10 ng/ml, respectively, with a recovery range of 42–80 %. The ratio of the sum of the concentrations of the nine major non-alkylated compounds to the total (CPAHs/TPAHs) was 0.87?±?0.10, and other ratios were determined to apportion the PM sources. The PAHs found are characteristic for emissions from traffic with diesel being a predominant source.     

Gas- and particle-phase distribution of polycyclic aromatic hydrocarbons in two-stroke, 50-cm3 moped emissions

Gas- and particle-phase polycyclic aromatic hydrocarbons (PAHs) concentrations evaluated in the exhaust of 10 two-stroke, 50-cm³ mopeds belonging to three different levels of emission legislation (EURO-0, EURO-1 and EURO-2) were used to assess the prevalent mechanism driving the gas/particle partitioning of PAHs in moped exhaust. Sampling was performed on a dynamometer bench both during the “cold-start” and the “hot” phases of the ECE-47 driving cycle. Gas and particulate phase PAHs were collected on polyurethane foam (PUF) plugs and 47-mm Pallflex T60A20 filters, respectively, under isokinetic conditions by using sampling probes inserted into the dilution tunnel of a Constant Volume Sampling – Critical Flow Venturi (CVS–CFV) system.The results show that semi-volatile PAHs were predominantly partitioned to the particle phase. The soluble organic fraction (SOF) of the collected particulates ranged between 72 and 98%. Measured total suspended particulate matter normalized partition coefficients (K_p) were predicted within a factor of 3–5 by assuming absorption into the organic fraction according to a model developed by Harner and Bidleman [Harner, T., Bidleman, T.F., 1998. Octanol–air partition coefficient for describing particle/gas partitioning of aromatic compounds in urban air. Environmental Science & Technology 32, 1494–1502.]. This suggests that the gas/particle partitioning in moped exhaust is mainly driven by the high fraction of organic matter of the emitted particles and that absorption could be the main partitioning mechanism of PAHs.     

A comparative evaluation of passive and active samplers for measurements of gaseous semi-volatile organic compounds in the tropical atmosphere

The polyurethane foam (PUF) disk-based passive air samplers (PAS), mounted inside two aluminium bowls to buffer the air flow to the disk and to shield it from precipitation and sunlight, were used for the collection of atmospheric SVOCs in Singapore during April 2008–June 2008. Data obtained from PAS measurements are compared to those from active high-volume air sampling (AAS). Single factor ANOVA tests show that there were no significant differences in chemical distribution profiles between actively and passively collected samples (PAHs, F = 3.38 × 10^?8 < F_critical = 4.17 with p > 0.05; OCPs, F = 2.71 × 10^?8 < F_critical = 4.75 with p > 0.05). The average air-side mass transfer coefficient (k_A) for PAS, determined from the loss of depuration compounds such as 13C₆ – HCB (1000 ng), 13C₁₂ – 4,4′ DDT (1000 ng) and 13C₁₂ – PCB 101 (1000 ng)spiked on the disks prior to deployment, was 0.12 ± 0.04 m s^?1. These values are comparable to those reported previously in the literature. The average sampling rate was 3.78 ± 1.83 m³ d^?1 for the 365 cm² PUF disk. Throughout the entire sampling period (～68 d), most of the PAHs and all OCPs exhibited a linear uptake trend on PAS, while naphthalene, acenaphthylene, acenaphthene and fluorene reached the curvilinear phase after the first ～30 d exposure. Theoretically estimated times to equilibrium (t_eq) ranged from around one month for Acy to hundreds of years for DB(ah)A. Sampling rates, based on the time integrated active sampling-derived concentrations and masses collected by PUF disks during the linear uptake phase, were determined for all target compounds with the average values of 2.50 m³ d^?1 and 3.43 m³ d^?1 for PAHs and OCPs, respectively. More variations were observed as compared to those from the depuration study. These variation were most likely due to the difference of physicochemical properties of individual species. Lastly, multiple linear regression models were developed to estimate the log-transformed gaseous concentration of an individual compound in air based on the mass collection rate of the gaseous SVOCs measured using the PAS and the molecular weight (MW) of the particular compound for both PAHs and OCPs, respectively.     

Phase distribution and artifact formation in ambient air sampling for polynuclear aromatic hydrocarbons

Laboratory and field sampling experiments were conducted to determine the phase-distribution of polynuclear aromatic hydrocarbons (PAH) in the ambient atmosphere and to determine the potential for artifact formation due to volatilization and ozone (O₃) reaction during normal sampling conditions. The study was conducted in two segments to investigate both summer and winter ambient temperature effects. The winter measurements reflect stronger association of PAH with the particulate phase than the summer data, but data from both seasons show appreciable filter losses due to volatilization of phenanthrene, anthracene, fluoranthene, benz(a)anthracene and chrysene. No evidence was found for volatilization of the heavier PAH, including benzo(e)pyrene, benzo(a)pyrene, indeno(l,2,3-c,d)pyrene, benzo(g,h,i)perylene and coronene. Although O₃ reacted readily with particulate matter that was freshly spiked with PAH in the laboratory experiments, no evidence was found for reaction of O₃ with particulate matter during the field sampling experiments.     

Quality control for sampling of PCDD/PCDF emissions from open combustion sources

Both long duration (>6 h) and high temperature (up to 139 °C) sampling efforts were conducted using ambient air sampling methods to determine if either high volume throughput or higher than ambient air sampling temperatures resulted in loss of target polychlorinated dibenzodioxins/dibenzofurans (PCDDs/PCDFs) from a polyurethane foam (PUF) sorbent. Emissions from open burning of simulated military forward operating base waste were sampled using EPA Method TO-9A for 185 min duration using a filter/PUF/PUF in series combination. After a 54 m³ sample was collected, the sampler was removed from the combustion source and the second PUF was replaced with a fresh, clean PUF. An additional 6 h of ambient air sampling (171 m³) was conducted and the second PUF was analyzed to determine if the PCDD/PCDF transferred from the filter and the first PUF. Less than 4.4% of the initial PCDD/PCDF was lost to the second PUF. To assess the potential for blow off of PCDD/PCDF analytes during open air sampling, the mobility of spiked mono- to hepta-PCDD/PCDF standards across a PUF sorbent was evaluated from ambient air temperatures to 145 °C with total volumes between 600 L and 2400 L. Lower molecular weight compounds and higher flow amounts increased release of the spiked standards consistent with vapor pressure values. At 600 L total sampled volume, the release temperature for 1% of the tetra-CDD (the lowest chlorinated homologue with a toxic compound) was 87 °C; increasing the volume fourfold reduced this temperature to 73 °C.     

Spatial and temporal variations and mobile source emissions of polycyclic aromatic hydrocarbons in Quito, Ecuador

Motor vehicles are a major source of air pollution in Quito, Ecuador; however, little work has been done to characterize spatial and temporal variations in traffic-related pollutants, or to measure pollutants in vehicle emissions. We measured PAH continuously for one year at two residential sites in Quito, and PAH and traffic patterns for one week near a busy roadway. Morning rush-hour traffic and temperature inversions caused daily PAH maxima between 06:00 and 08:00. SO₂, NO_x, CO, and PM_2.5 behaved similarly. At the residential sites PAH levels during inversions were 2-3-fold higher than during the afternoon, and 10-16-fold higher than 02:00-03:00 when levels were lowest. In contrast, at the near-roadway site, PAH concentrations were 3-6-fold higher than at the residential sites, and the effects of inversions were less pronounced. Cars and buses accounted for >95% of PAH at the near-roadway site. Near-roadway PAH concentrations were comparable to other polluted cities.     

Size distribution of polycyclic aromatic hydrocarbons in a roadway tunnel in Lisbon, Portugal

Atmospheric aerosols of four aerodynamic size ranges were collected using high volume cascade impactors in an extremely busy roadway tunnel in Lisbon (Portugal). Dust deposited on the tunnel walls and guardrails was also collected. Average particle mass concentrations in the tunnel atmosphere were more than 30 times higher than in the outside urban background air, revealing its origins almost exclusively from fresh vehicle emissions. Most of the aerosol mass was concentrated in submicrometer fractions (65%), and polycyclic aromatic hydrocarbons (PAH) were even more concentrated in the finer particles with an average of 84% of total PAH present in sizes smaller than 0.49 μm. The most abundant PAH were methylated phenanthrenes, fluoranthene and pyrene. About 46% of the total PAH mass was attributed to lower molecular weight compounds (two and three rings), suggesting a strong influence of diesel vehicle emissions on the production of local particulate PAH. The application of diagnostic ratios confirmed the relevance of this source of PAH in the tunnel ambient air. Deposited dust presented PAH profiles similar to the coarser aerosol size range, in agreement with the predominant origin of coarser aerosol particles from soil dust resuspension and vehicle wear products.