Quantitative analysis of volatile organic compounds (VOCs) in atmospheric particles

There are a number of difficulties associated with the quantitative analysis of volatile organic compounds (VOCs) in atmospheric particles. Therefore, majority of the previous studies on VOCs associated with particles have been qualitative. Air samples were collected in Izmir, Turkey to determine ambient particle and gas phase concentrations of several aromatic, oxygenated and halogenated VOCs. Samples were quantitatively analyzed using thermal desorption–gas chromatography/mass spectrometry. Gas-phase concentrations ranged between 0.02 (bromoform) and 4.65 μg m⁻³ (toluene) and were similar to those previously measured at the same site. Particle-phase concentrations ranged from 1 (1,3-dichlorobenzene) to 933 pg m⁻³ (butanol). VOCs were mostly found in gas-phase (99.9±0.25%). However, the particulate VOCs had comparable concentrations to those reported previously for semivolatile organic compounds. The distribution of particle-phase VOCs between fine (d_p<2.5 μm) and coarse (2.5 μm<d_p<10 μm) fractions was also investigated. It was found that VOCs were mostly associated with fine particles.     

Volatile organic compounds in roadside microenvironments of metropolitan Hong Kong

The characteristics and concentrations of volatile organic compounds (VOCs) in the roadside microenvironments of metropolitan Hong Kong were investigated. The VOC concentrations, especially toluene, benzene and chlorinated VOCs in Hong Kong were high when compared with those in most developed cities. The average and maximum concentration of toluene was 74.9 and 320.0 μg m⁻³, respectively. The respective values for benzene were 25.9 and 128.6 μg m⁻³. The chlorinated VOCs were dominated by trichloroethylene and tetrachloroethylene. The maximum concentrations of these two species reached 248.2 and 144.0 μg m⁻³, respectively. There were strong variations in the spatial fluctuation and characteristic of VOC concentrations. The highest VOC concentrations were found in the industrial district, which were followed by those in the commercial district, the central business district and finally the residential district. The highest concentrations of most VOC species, especially chlorinated VOC were found in the industrial and commercial districts. The average benzene/toluene ratio in Hong Kong was 0.5 suggesting that vehicular emission was the dominant VOC source in most areas of Hong Kong. There were strong deviations in benzene/toluene, benzene/ethylbenzene and benzene/(m+p-xylene) ratios in the commercial district, and highly chlorinated VOC in the industrial and commercial districts. These suggest that there were other benzene and VOC sources overlying on the high background VOC concentrations in these districts. The common usage of organic solvents in the building and construction industries, and in the small industries in the industrial and commercial districts were believed to be important sources of VOC in Hong Kong.     

Sensitivity of ozone concentrations to diurnal variations of surface emissions in Mexico City: A WRF/Chem modeling study

Sensitivity of ozone (O₃) concentrations in the Mexico City area to diurnal variations of surface air pollutant emissions is investigated using the WRF/Chem model. Our analysis shows that diurnal variations of nitrogen oxides (NO_x = NO + NO₂) and volatile organic compound (VOC) emissions play an important role in controlling the O₃ concentrations in the Mexico City area. The contributions of NO_x and VOC emissions to daytime O₃ concentrations are very sensitive to the morning emissions of NO_x and VOCs. Increase in morning NO_x emissions leads to decrease in daytime O₃ concentrations as well as the afternoon O₃ maximum, while increase in morning VOC emissions tends to increase in O₃ concentrations in late morning and early afternoon, indicating that O₃ production in Mexico City is under VOC-limited regime. It is also found that the nighttime O₃ is independent of VOCs, but is sensitive to NO_x. The emissions of VOCs during other periods (early morning, evening, and night) have only small impacts on O₃ concentrations, while the emissions of NO_x have important impacts on O₃ concentrations in the evening and the early morning.This study suggests that shifting emission pattern, while keeping the total emissions unchanged, has important impacts on air quality. For example, delaying the morning emission peak from 8 am to 10 am significantly reduced the morning peaks of NO_x and VOCs, as well as the afternoon O₃ maxima. It suggests that without reduction of total emission, the daytime O₃ concentrations can be significantly reduced by changing the diurnal variations of the emissions of O₃ precursors.     

Study of the dispersion of VOCs emitted by a municipal solid waste landfill

The dispersion of VOCs emitted by a municipal solid waste landfill was studied for a period of over one year. Sixteen VOCs were monitored: linear alkanes from C₇ to C₁₁, BTEX, trimethylbenzene, trichlorethylene, tetrachlorethylene, α and β-pinenes, limonene. The analytical procedure was first comprised of static long-term sampling of about 2 months using radial diffusion Radiello tubes containing activated carbon, followed by extraction by solvent (i.e. CS₂) and GC/MS analysis. The results were initially analysed on the basis of the total concentration of the quantified VOCs, then by examining the concentrations of certain selected compounds. The influence of different parameters such as operating conditions, meteorological conditions and site morphology was highlighted on the basis of total VOC concentrations. In order to study the VOC's dispersion more closely, 5 compounds were chosen: toluene, benzene, limonene, and the sum trichlorethylene + tetrachlorethylene, as a “marker”, to verify the origin of the VOCs emitted. The results showed that the main source of VOCs is the open cell and lead to different hypotheses on interferences from neighbouring sources and to the proposal of solutions to limit the emission of VOCs and their dispersion. To our knowledge, this type of study has not been accomplished until this day.     

Variability-lifetime relationship of VOCs observed at the Sonnblick Observatory 1999—estimation of HO-densities

An extensive dataset of VOC measurements was collected at the Sonnblick Observatory, Austria (3106 m) in Fall/Winter 1999/2000, showing high mixing ratios of anthropogenic and biogenic VOCs at this high altitude site due to upward mixing of air masses (Geophys. Res. Lett. 2F (2001) 507). Here we give an interpretation of proton-transfer-reaction (PTR-MS) mass scans obtained in November 1999 based on fragmentation data, GC-PTR-MS analysis and the variability-lifetime relationship, described by the power law, σ(ln(x))=Aτ^−b. The variability-lifetime plot of anthropogenic VOCs gave a proportionality factor A of 1.40 and a,b exponent (sink term) of 0.44 and allowed an estimate of average HO-densities on the order of (1.5±0.4)×10⁵ molecules cm⁻³. Additionally we were able to indirectly determine a diurnal HO-profile with peak values of (1.3±0.5)×10⁶ molecules cm⁻³ around midday. HO-reaction rate coefficients for higher aldehydes (heptanal to nonanal) were estimated due to photochemical losses during a stagnant air episode (27 November) and from the variability-lifetime relationship. Combining long term PTR-MS analysis of VOCs and the variability-lifetime method provides a valuable tool for assessing the dominant cause of the variability in VOC concentrations. This information is essential in understanding the sources and photochemical processing of VOCs detected in ambient air at field measurement sites.     

Ambient levels of volatile organic compounds in the atmosphere of Greater Cairo

Ambient volatile organic compounds (VOCs) samples were collected at three locations, two in urban areas in Greater Cairo (Ramsis and Haram) and background one in rural area in Menofiya province (Kafr El-Akram), during the period of June, 2004–August, 2004. The highest concentrations of VOCs were found in Ramsis, whereas the lowest concentrations were detected in Kafr El-Akram, and the difference in mean concentrations were statistically significant (p<0.001). Among all of the measured VOCs species, the contribution of individual VOC to the total VOCs concentration were very similar in Ramsis and Haram locations, toluene was the most abundant compound followed by (m, p)-xylene. This similarity implies a similar emission sources of VOCs in both urban locations, vehicle exhausts are the dominant one. Greater Cairo has high levels of volatile aromatic hydrocarbons compared with many polluted cities in the world. The BTEX (benzene: toluene: ethylbenzene: xylenes) concentration ratios were (2.01:4.94:1:4.95), (2.03:4.91:1:4.87) and (2.31:2.98:1:2.59) in Ramsis, Haram and Kafr El-Akram, respectively. The average toluene/benzene (T/B), (m, p)-xylene/benzene ((m, p)-X/B) and o-xylene/benzene (o-X/B) concentration ratios were 2.45, 1.61and 0.85, respectively in Ramsis and 2.42, 1.61 and 0.78, respectively in Haram. The ratios in both urban locations were of the same magnitude and close to those obtained from automotive exhausts, indicating that the ambient BTEX originate mainly from motor vehicle emissions. However, the (T/B), ((m, p)-X/B) and (o-X/B) concentration ratios were 1.29, 0.71 and 0.41 in Kafr El-Akram, respectively. These ratios were lower than those found in Ramsis and Haram locations and in automotive exhaust, suggesting that the BTEX in Kafr El-Akram do not come from a local source and are exclusively results from the diffusion and dispersion of VOCs produced from the traffic density in the surrounding cities. Significant positive correlation coefficients (p<0.001) were found between the concentrations of BTEX compounds at the three sampling locations. The diurnal variation of VOCs concentrations in Ramsis location showed two daily peaks linked to traffic density.     

In situ measurements of volatile aromatic hydrocarbon biodegradation rates in groundwater

Benzene and alkylbenzene biodegradation rates and patterns were measured using an in situ microcosm in a crude-oil contaminated aquifer near Bemidji, Minnesota. Benzene-D6, toluene, ethylbenzene, o-, m- and p-xylenes and four pairs of C₃- and C₄-benzenes were added to an in situ microcosm and studied over a 3-year period. The microcosm allowed for a mass-balance approach and quantification of hydrocarbon biodegradation rates within a well-defined iron-reducing zone of the anoxic plume. Among the BTEX compounds, the apparent order of persistence is ethylbenzene > benzene > m,p-xylenes > o-xylene ≥ toluene. Threshold concentrations were observed for several compounds in the in situ microcosm, below which degradation was not observed, even after hundreds of days. In addition, long lag times were observed before the onset of degradation of benzene or ethylbenzene. The isomer-specific degradation patterns were compared to observations from a multi-year study conducted using data collected from monitoring wells along a flowpath in the contaminant plume. The data were fit with both first-order and Michaelis-Menten models. First-order kinetics provided a good fit for hydrocarbons with starting concentrations below 1 mg/L and Michaelis-Menten kinetics were a better fit when starting concentrations were above 1 mg/L, as was the case for benzene. The biodegradation rate data from this study were also compared to rates from other investigations reported in the literature.     

Atmospheric BTEX-concentrations in an area with intensive street traffic

The major threat to clean air in developed and industrializing countries is now posed by traffic emissions. The effects of traffic road modifications on the air quality are, however, rarely reported in the literature. The aim of this study was to determine the influence of the modernization and renovation of a traffic artery in the region of Mortsel (Antwerp, Belgium) on the concentration of volatile organic compounds such as: benzene, toluene, ethylbenzene and m-, p-, o-xylenes (BTEX). The original goal of the reconstruction works was to reduce the traffic lanes of one of the busiest streets in Antwerp, in order to discourage the road traffic and in consequence also to improve the air quality in this region. The average concentrations of BTEX before these works in 2003 were: 1.6, 7.0, 0.9, 2.3, and 0.9 μg/m³, for benzene, toluene, ethylbenzene, m + p xylenes, and o-xylene, respectively. However, after the completion of the works, in 2005, they were slightly higher: 2.5, 9.5, 1.6, 3.4, and 1.3 μg/m³, respectively. The scatter plots of benzene against toluene, ethylbenzene and xylenes in 2003 and 2005 showed very good correlations. This fact indicated that all of the measured compounds originated from the same source, namely the road traffic. Moreover, the data obtained from an air-monitoring station at less than 6 km distance from the sampling site (operated by the Flemish Environment Agency, and located in Borgerhout, Antwerp), confirmed the lack of influence of background concentrations of BTEX. The obtained results led to the conclusion that the reduction of the number of traffic lanes had apparently increased the traffic jams and also increased the emission from cars. Therefore, these modernization works had even a negative impact on the local concentration of traffic-related pollutants as BTEX.     

Participant-based monitoring of indoor and outdoor nitrogen dioxide,volatile organic compounds,and polycyclic aromatic hydrocarbons among MICA-Air households

The Mechanistic Indicators of Childhood Asthma (MICA) study in Detroit, Michigan introduced a participant-based approach to reduce the resource burden associated with collection of indoor and outdoor residential air sampling data. A subset of participants designated as MICA-Air conducted indoor and outdoor residential sampling of nitrogen dioxide (NO₂), volatile organic compounds (VOCs), and polycyclic aromatic hydrocarbons (PAHs). This participant-based methodology was subsequently adapted for use in the Vanguard phase of the U.S. National Children’s Study. The current paper examines residential indoor and outdoor concentrations of these pollutant species among health study participants in Detroit, Michigan.Pollutants measured under MICA-Air agreed well with other studies and continuous monitoring data collected in Detroit. For example, NO₂ and BTEX concentrations reported for other Detroit area monitoring were generally within 10–15% of indoor and outdoor concentrations measured in MICA-Air households. Outdoor NO₂ concentrations were typically higher than indoor NO₂ concentration among MICA-Air homes, with a median indoor/outdoor (I/O) ratio of 0.6 in homes that were not impacted by environmental tobacco smoke (ETS) during air sampling. Indoor concentrations generally exceeded outdoor concentrations for VOC and PAH species measured among non-ETS homes in the study. I/O ratios for BTEX species (benzene, toluene, ethylbenzene, and m/p- and o-xylene) ranged from 1.2 for benzene to 3.1 for toluene. Outdoor NO₂ concentrations were approximately 4.5 ppb higher on weekdays versus weekends. As expected, I/O ratios pollutants were generally higher for homes impacted by ETS.These findings suggest that participant-based air sampling can provide a cost-effective alternative to technician-based approaches for assessing indoor and outdoor residential air pollution in community health studies. We also introduced a technique for estimating daily concentrations at each home by weighting 2- and 7-day integrated concentrations using continuous measurements from regulatory monitoring sites. This approach may be applied to estimate short-term daily or hourly pollutant concentrations in future health studies.     

Roadside BTEX and other gaseous air pollutants in relation to emission sources

Hourly concentrations of benzene, toluene, ethylbenzene, m,p-xylenes, and o-xylene (BTEX) plus CO, NO_x, SO₂ were monitored at roadsides simultaneously with the traffic volume during the dry season of 2004, in Hanoi, Vietnam. The selected three streets included Truong Chinh (TC) with high traffic volume, Dien Bien Phu (DBP) with low traffic volume, and Nguyen Trai (NT) with high traffic volume running through an industrial estate. BTEX were sampled by SKC charcoal tubes and analyzed by GC–FID. Geometric means of hourly benzene, toluene, ethylbenzene, m,p-xylenes and o-xylene are, respectively, 65, 62, 15, 43, and 22 μg m⁻³ in TC street; 30, 38, 9, 26, and 13 μg m⁻³ in DBP street; and 123, 87, 24, 56, and 30 μg m⁻³ in NT street. Levels of other gaseous pollutants including CO, NO_x, and SO₂, measured by automatic instruments, were low and not exceeding the Vietnam national ambient air quality standards. BTEX levels were comparatively analyzed for different downwind distances (3–50 m) from the street, between peak hours and off-peak hours, as well as between weekdays and weekend. Results of principal component analysis suggest that the gaseous pollutants are associated with different vehicle types.     

Compound specific carbon and hydrogen stable isotope analyses of volatile organic compounds in various emissions of combustion processes

This study presents carbon (δ¹³C) and hydrogen (δD) isotope values of volatile organic compounds (VOCs) in various emission sources using thermal desorption–gas chromatography–isotope ratio mass spectrometry (TD–GC–irMS). The investigated VOCs ranged from C6 to C10. Samples were taken from (i) car exhaust emissions as well as from plant combustion experiments of (ii) various C3 and (iii) various C4 plants. We found significant differences in δ values of analysed VOCs between these sources, e.g. δ¹³C of benzene ranged between (i) −21.7 ± 0.2‰, (ii) −27.6 ± 1.6‰ and (iii) −16.3 ± 2.2‰, respectively and δD of benzene ranged between (i) −73 ± 13‰, (ii) −111 ± 10‰ and (iii) −70 ± 24‰, respectively. Results of VOCs present in investigated emission sources were compared to values from the literature (aluminium refinery emission). All source groups could be clearly distinguished using the dual approach of δ¹³C and δD analysis. The results of this study indicate that the correlation of compound specific carbon and hydrogen isotope analysis provides the potential for future research to trace the fate and to determine the origin of VOCs in the atmosphere using thermal desorption compound specific isotope analysis.     

Biogenic VOC emissions from fresh leaf mulch and wood chips of Grevillea robusta (Australian Silky Oak)

The emissions of VOC from freshly cut and shredded Grevillea robusta (Australian Silky Oak) leaves and wood have been measured. The VOC emissions from fresh leaf mulch and wood chips lasted typically for 30 and 20 h respectively, and consisted primarily of ethanol, (E)-2-hexenal, (Z)-3-hexen-1-ol and acetaldehyde. The integrated emissions of the VOCs were 0.38±0.04 g kg⁻¹ from leaf mulch, and 0.022±0.003 g kg⁻¹ from wood chips. These emissions represent a source of VOCs in urban and rural air that has previously been unquantified and is currently unaccounted for. These VOCs from leaf mulch and wood chips will contribute to both urban photochemistry and secondary organic aerosol formation. Any CH₄ emissions from leaf mulch and wood chips were <1×10⁻¹¹ g g dry mass⁻¹ s⁻¹.     

Application of CALINE4 to roadside NO/NO2 transformations

The CALINE4 roadway dispersion model has been applied to concentrations of NO_x and NO₂ measured near Gandy Boulevard in Tampa, FL (USA) during May 2002. A NO_x emission factor of 0.86 gr mi⁻¹ was estimated by treating NO+NO₂ (NO_x) as a conserved species and minimizing the differences between measured and calculated NO_x concentrations. This emission factor was then used to calculate NO₂ concentrations using the NO/NO₂ transformation reactions built into CALINE4. A comparison of measured and calculated NO₂ concentrations indicates that for ambient O₃ concentrations less than 40 ppb the model under-predicts the chemical transformation of NO. The enhanced transformation of NO may be due to reactions of NO with oxidants such as peroxy radicals that are present either in the atmosphere or in vehicle exhaust.     

Laboratory studies on the uptake of aromatic hydrocarbons by ice crystals during vapor depositional crystal growth

Uptake of aromatic hydrocarbons (AH) by ice crystals during vapor deposit growth was investigated in a walk-in cold chamber at temperatures of 242, 251, and 260 K, respectively. Ice crystals were grown from ambient air in the presence of gaseous AH namely: benzene (C₆H₆), toluene (methylbenzene, C₇H₈), the C₈H₁₀ isomers ethylbenzene, o-, m-, p-xylene (dimethylbenzenes), the C₉H₁₂ isomers n-propylbenzene, 4-ethyltoluene, 1,3,5-trimethylbenzene (1,3,5-TMB), 1,2,4-trimethylbenzene (1,2,4-TMB), 1,2,3-trimethylbenzene (1,2,3-TMB), and the C₁₀H₁₄ compound tert.-butylbenzene. Gas-phase concentrations calculated at 295 K were 10.3–20.8 μg m⁻³. Uptake of AH was detected by analyzing vapor deposited ice with a very sensitive method composed of solid-phase micro-extraction (SPME), followed by gas chromatography/mass spectrometry (GC/MS).Ice crystal size was lower than 1 cm. At water vapor extents of 5.8, 6.0 and 8.1 g m⁻³, ice crystal shape changed with decreasing temperatures from a column at a temperature of 260 K, to a plate at 251 K, and to a dendrite at 242 K. Experimentally observed ice growth rates were between 3.3 and 13.3×10⁻³ g s⁻¹ m⁻² and decreased at lower temperatures and lower value of water vapor concentration. Predicted growth rates were mostly slightly higher.Benzene, toluene, ethylbenzene, and xylenes (BTEX) were not detected in ice above their detection limits (DLs) of 25 pg g_ice⁻¹ (toluene, ethylbenzene, xylenes) and 125 pg g_ice⁻¹ (benzene) over the entire temperature range. Median concentrations of n-propylbenzene, 4-ethyltoluene, 1,3,5-TMB, tert.-butylbenzene, 1,2,4-TMB, and 1,2,3-TMB were between 4 and 176 pg g_ice⁻¹ at gas concentrations of 10.3–10.7 μg m⁻³ calculated at 295 K. Uptake coefficients (K) defined as the product of concentration of AH in ice and density of ice related to the product of their concentration in the gas phase and ice mass varied between 0.40 and 10.23. K increased with decreasing temperatures. Values of Gibbs energy (ΔG) were between −4.5 and 2.4 kJ mol⁻¹ and decreased as temperatures were lowered. From the uptake experiments, the uptake enthalpy (ΔH) could be determined between −70.6 and −33.9 kJ mol⁻¹. The uptake entropy (ΔS) was between −281.3 and −126.8 J mol⁻¹ K⁻¹. Values of ΔH and ΔS were rather similar for 4-ethlytoluene, 1,3,5-TMB and tert.-butylbenzene, whereas 1,2,3-TMB showed much higher values.     

Use of thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS) on identification of odorant emission focus by volatile organic compounds characterisation

Volatile organic compounds (VOCs) from several different municipal solid wastes’ treatment plants in Mallorca (Spain) have been analysed by thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS). Ambient (immission) air was collected during February and March 2011 by active sampling onto sorbents Tenax™ TA and Carboxen™ 1000. The study presents the chemical characterisation of 93 volatile organic compounds (VOCs) from an overall set of 84 immission air samples. 70 VOCs were positively identified.The linear fit for all 93 external standard calibration, from 10 mg L⁻¹ to 150 mg L⁻¹ (n = 4), was within the range 0.974 < r² < 0.998. Limits of detection of the method (LOD) for all the standards were within the range 1.1–4,213 pg, as the absolute standard amount spiked into sorbent tubes in 1 μL standard mixture (dissolved in methanol).Overall results stated systematic correlation between waste’s nature and VOCs’ air composition. Organic wastes show main contribution of terpenes, waste water sludge residues’ of reduced sulphured compounds (RSCs) and municipal solid wastes show contribution of a wide sort of VOCs. The use of a chemometric approach for variable’s reduction to 12 principal components enables evaluation of similarities and dissimilarities between facilities. PCA clearly related samples to its corresponding facility on the basis of their VOCs composition and the ambient temperature.     

Aircraft measurements of O3, NOx,CO, VOCs,and SO2 in the Yangtze River Delta region

In this study, air pollutants, including ozone (O₃), nitrogen oxides (NO_x = NO + NO₂), carbon monoxides (CO), sulfur dioxide (SO₂), and volatile organic compounds (VOCs) measured in the Yangtze River Delta (YRD) region during several air flights between September/30 and October/11 are analyzed. This measurement provides horizontal and vertical distributions of air pollutants in the YRD region. The analysis of the result shows that the measured O₃ concentrations range from 20 to 60 ppbv. These values are generally below the US national standard (84 ppbv), suggesting that at the present, the O₃ pollutions are modest in this region. The NO_x concentrations have strong spatial and temporal variations, ranging from 3 to 40 ppbv. The SO₂ concentrations also have large spatial and temporal variations, ranging from 1 to 35 ppbv. The high concentrations of CO are measured with small variations, ranging from 3 to 7 ppmv. The concentrations of VOCs are relatively low, with the total VOC concentrations of less than 6 ppbv. The relative small VOC concentrations and the relative large NO_x concentrations suggest that the O₃ chemical formation is under a strong VOC-limited regime in the YRD region. The measured O₃ and NO_x concentrations are strongly anti-correlated, indicating that enhancement in NO_x concentrations leads to decrease in O₃ concentrations. Moreover, the O₃ concentrations are more sensitive to NO_x concentrations in the rural region than in the city region. The ratios of Δ[O₃]/Δ[NO_x] are ?2.3 and ?0.25 in the rural and in the city region, respectively. In addition, the measured NO_x and SO₂ concentrations are strongly correlated, highlighting that the NO_x and SO₂ are probably originated from same emission sources. Because SO₂ emissions are significantly originated from coal burnings, the strong correlation between SO₂ and NO_x concentrations suggests that the NO_x emission sources are mostly from coal burned sources. As a result, the future automobile increases could lead to rapid enhancements in O₃ concentrations in the YRD region.     

Surface ozone and NOx concentrations at a high altitude Mediterranean site,Greece

Ozone was measured in six- and NO_x in five sampling periods in 1996–97, mostly during summer, at a 1070 m altitude site in northern Peloponnese. Mean values in each sampling period ranged from 43–48 ppb exceeding the European Union 24 h plant protection standard. The background ozone concentration of 43 ppb derived from the correlation of ozone with NO^′_x also exceeded the EU plant protection standard. Ozone exhibited maxima in the afternoon and minima during the night; in certain 24–48 h periods, however, the ozone concentrations remained practically constant; in these short periods air mass back trajectories indicated air masses which originated in north Africa. NO^′_x concentrations had maximum of 24 h around noon. Their mean concentrations ranged from 0.5–0.7 ppb, smaller than respective concentrations in north-central Europe.     

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.     

Verification of diffusive and pumped samplers for volatile organic compounds using a controlled atmosphere test facility

There is a requirement to verify the performance of sorbent-based passive or active samplers and to extend their use, where possible, to monitor volatile organic compounds (VOCs) that are known to be photochemical ozone pre-cursors or are relevant to the activities of the petrochemical industry. We report measurements of the 14-day diffusive uptake rates for the VOCs: i-butane (2-methyl propane), n-butane, i-pentane (2-methyl butane), n-pentane, n-hexane, benzene, toluene, and m-xylene (at environmental level concentrations) for industry standard axial samplers (Perkin–Elmer-type samplers) containing the sorbents Carbopack-X, -Z, -B or Tenax-TA. We also present data on back-diffusion, blank levels, and storage for the above sorbents, and describe the simultaneous use of the sorbent Carbopack-X for pumped sampling of certain VOCs. The results were obtained by dosing samplers in a controlled atmosphere test facility (CATFAC) operating under well-defined conditions of concentration, nominal temperature of 20 °C, wind speed of 0.5 m s^?1, and relative humidities of 0% and 80%. Field measurements were also obtained to provide supplementary data to support the laboratory study. Results are compared to existing published data, where these are available.     

Estimation and characterization of children’s ambient generated exposure to PM2.5 using sulphate and elemental carbon as tracers

Children’s exposures to ambient and non-ambient fine particulate matter (PM_2.5) were determined using the sulphate and elemental carbon components of the PM_2.5 mixture as tracers of the ambient contribution during a 6-week winter period in Prince George, British Columbia, Canada. Personal exposures to PM_2.5 were measured in children at 5 elementary schools located throughout the city and ambient samples were collected on school rooftops. Average ambient levels and personal exposures during this time period were 13.8 μg m^?3 and 16.4 μg m^?3 respectively. From the data pooled across individuals, use of the two different tracers indicated identical estimates of median exposure to ambient PM_2.5 (7.5 μg m^?3) and similar estimates of non-ambient generated exposure (6.4 and 5.0 μg m^?3) and infiltration (0.49 and 0.52) for the sulphate and elemental carbon approach, respectively. The median fraction of the ambient concentration resulting in exposure or exposure factors were 0.54 and 0.55 respectively, however lower values of 0.46 and 0.42 were determined from regression analysis. A strong association was found between exposure to ambient PM_2.5 and measured ambient concentrations at both the closest school monitor (median r = 0.92) and a central site (median r = 0.88) demonstrating that the central site monitor was suitable for assessing longitudinal ambient generated exposure throughout the city. These results support the use of elemental carbon as a tracer of ambient generated exposure and the use of ambient data as estimates of longitudinal changes in children’s exposure in this setting. The importance of both ambient and non-ambient sources of PM_2.5 is emphasized by their almost equal contribution to total personal exposures. Comparison with other studies suggests a limited influence of climate and the cold season in Prince George on exposure levels and found similar mean non-ambient generated exposures despite large variability across and within subjects in any given location.