Daytime resolved analysis of polycyclic aromatic hydrocarbons in urban aerosol samples - impact of sources and meteorological conditions

Urban aerosol was collected in a summer and a winter campaign for 7 and 3 days, respectively. Low volume samples were taken with a time resolution of 160 min using a filter/sorption cartridge system extended by an ozone scrubber. Concentrations of mainly particle associated polycyclic aromatic hydrocarbons (PAH) and oxidised PAH (O-PAH) were determined by gas chromatography/high resolution mass spectrometry. The sampling site was located in the city centre of Augsburg, Germany, near major roads with high traffic volume. The daily concentrations and profiles were mainly governed by local emissions from traffic and domestic heating, as well as by the meteorological conditions. During the winter campaign, concentrations were more than 10 fold higher than during the summer campaign. Highest concentrations were found concurrent with low boundary layer heights and low wind speeds. Significant diurnal variation of the PAH profiles was observed. Enhanced influences of traffic related PAH on the PAH profiles were evident during daytime in summer, whereas emissions from hot water generation and domestic heating were obvious during the night time of both seasons. A general idea about the global meteorological situation was acquired using back trajectory calculations (NOAA ARL HYSPLIT4). Due to high local emissions in combination with low air exchange during the two sampling campaigns, effects of mesoscale transport were not clearly observable.     

Analysis of particle-associated semi-volatile aromatic and aliphatic hydrocarbons in urban particulate matter on a daily basis

PM_2.5 Particle-associated semi-volatile organic compounds (SVOC) were determined in the city of Augsburg, Germany. Daily samples were collected at a central monitoring station from late summer to late autumn 2002. The concentrations of polycyclic aromatic hydrocarbons (PAH), oxidized PAH (O-PAH), n-alkanes, hopanes and long chain linear alkylbenzenes were determined by direct thermal desorption-gas chromatography-time of flight mass spectrometry (DTD-GC-TOFMS). Additionally, PM_2.5 particle mass and number concentrations were measured. The sampling campaign can be divided into two parts, distinguished by a lower temperature level in the second part of the campaign. The particulate mass concentration showed no significant changes, whereas most of the SVOC had significant higher mean and peak concentrations in the colder period. The analysis of the data showed an increased influence of non-traffic sources in the colder period, reflected by a weak shift in the PAH profile and a significant shift in the hopane pattern. Statistical analysis of the inter-group correlations was carried out. Eight clusters partly representing different sources of the aerosol have been identified.     

An experimental set up of a PAH vapour generator and its use to test an annular denuder

The aim of this work is to develop and test a dynamic gas generator for semi-volatile organic compounds (SVOC). A single compound, naphthalene, is used as a surrogate PAH to test the system. The dynamic generation of PAH is based on the permeation technique [Analyst 106 (1981) 817; Am. Ind. Hyg. Assoc. J. 38 (1977) 712]. Monitoring the temperature and measuring the mass of PAH present in the permeation chamber every 48 h gives a direct measurement of the sublimation rate of the PAH. Knowing the flow rate, gives an accurate value of the concentration of PAH from the generator. It was found stable over a period of time under constant operating conditions. This concentration is diluted down to between 0.3 and 30 ppbv by a controlled flow of pure air. The diluting airflow is a mixture of dry and wet air, making it possible to control the relative humidity of the flow from the generator as well as its concentration in PAH. We used this generator to calibrate an annular denuder tube, based on the study by Gundel et al. [Atmos. Environ. 29 (1995) 1719]. Although this technique has been shown to be artefact-free for sampling gaseous PAH [Polycyclic Aromatic Compounds 9 (1996) 67; Atmos. Environ. 28 (1994) 3083], its trapping efficiency still depends on environmental parameters (temperature, relative humidity and sampling duration). Accordingly, we used our generator to calibrate a single annular denuder under controlled conditions (T degrees C, HR%, CPAH, sampling duration). The trapping efficiency of the denuder was calculated by two independent methods. Firstly, by comparing the amount trapped on a denuder with the measured mass sublimated in the generator. Secondly, by putting two denuders in series and comparing the mass collected on the first and the second tube. These two methods gave similar results, within the 10% relative uncertainties of both methods. The first results obtained show that, in environmental conditions, the efficiency ranges between 90 and 100%.     

Polycyclic aromatic hydrocarbon emissions from clinical waste incineration

Since the introduction of the Environmental Protection Act in the UK, there are few reports of PAH emissions from clinical waste incinerators (CWIs) operating to improved performance standards. The main aim of this study is to determine PAH emissions from a state-of-the-art CWI focusing on the effects of reactive gases and operating variables on emissions. This was carried out by collection of stack samples over three phases of operation.

At stack conditions, most PAHs are predicted to be in the vapour phase. Reactive losses of PAHs were closely correlated by rank with expected reactivities from laboratory studies. Estimates of emissions incorporating sampling losses were derived, although no correlation was found between PAH losses and the modest levels of reactive stack gases. PAH concentrations were one to two orders of magnitude lower than earlier reports from incinerators without effective air pollution control equipment (APCE). The low levels of carbon monoxide recorded were not correlated with any PAHs.

This study demonstrates the impact of efficient combustion conditions and APCE on PAH emissions from a CWI.     

A fabric denuder for sampling semi-volatile species

A new style of diffusion denuder has been evaluated specifically for sampling HNO3. A coated fabric is used as the denuder substrate, which can be loaded directly into a standard filter holder. This approach allows direct denuder sampling with no additional capital costs over filter sampling and simplifies the coating and extraction process. Potential denuder materials and coatings were evaluated in the laboratory to test the removal efficiency. NaCl coatings were used to assess more than 20 materials for HNO3 collection efficiency. Particle retention, which would cause a denuder to have a positive bias for gas concentration measurements, was evaluated by ambient air sampling using particulate sulfate as the reference aerosol. Particle retention varied from 0 to 15%, depending on the denuder material tested. The best performing material showed an average particle retention of less than 3%. Denuder efficiency of four fabric materials was tested under ambient conditions to determine removal efficiency. The fabric denuder method was compared with a long path-length Fourier transform infrared (FTIR) spectrometer, a tunable diode laser absorption spectrometer (TDLAS), and a denuder difference sampler to independently measure HNO3. HNO3 collection efficiency was typically 90% for the denuders, whether coated with NaCl or not. For 10-L/min sampling rates with the fabric denuder, the square of the correlation coefficient with the FTIR spectrometer was 0.73, compared to 0.24 with the TDLAS.     

The effect of EURO-0 vehicle substitution on polycyclic aromatic hydrocarbon and carbon monoxide concentrations in an urban area

From 1994 to 2003, daily air concentrations of particle-bound polycyclic aromatic hydrocarbons (PAHs) and carbon monoxide (CO) were regularly monitored at two traffic-oriented sampling sites (A and B) in urban Genoa, Italy. The data were used to estimate effects on air quality in real situations due to progressive substitution of EURO-0 vehicles, started in 1993, with less-polluting vehicles (EURO-1, EURO-2), mainly gasoline vehicles with a catalyst. PAH profile classification and diagnostic PAH ratios were used to identify 345 samples of predominantly traffic origin. At both sites, CO and PAH daily concentrations decreased exponentially with time and the apparent half-life values calculated were 6.3 and 5.5 for CO and 3.7 and 3.5 years for PAHs at sites A and B, respectively. At site A, monitored for traffic intensity, multiple regression analyses confirmed that daily PAH and CO concentrations were positively correlated with the number of non-catalytic vehicles estimated to cross this site during sampling and negatively correlated with seasonal variables (air temperature, ozone concentration, relative air humidity). The reduction in air pollution estimated for complete substitution of non-catalytic gasoline vehicles was 89% for BaP, 85% for total PAHs and 69% for CO.     

Effects of Heating Season on Residential Indoor and Outdoor Polycyclic Aromatic Hydrocarbons, Black Carbon, and Particulate Matter in an Urban Birth Cohort

Exposure to air pollutants has been associated with adverse health effects. However, analyses of the effects of season and ambient parameters such as ozone have not been fully conducted. Residential indoor and outdoor air levels of polycyclic aromatic hydrocarbons (PAH), black carbon (measured as absorption coefficient [Abs]), and fine particulate matter <2.5 μm (PM)(2.5) were measured over two-weeks in a cohort of 5-6 year old children (n=334) living in New York City's Northern Manhattan and the Bronx between October 2005 and April 2010. The objectives were to: 1) characterize seasonal changes in indoor and outdoor levels and indoor/outdoor (I/O) ratios of PAH (gas + particulate phase; dichotomized into Σ(8)PAH(semivolatile) (MW 178-206), and Σ(8)PAH(nonvolatile) (MW 228-278)), Abs, and PM(2.5); and 2) assess the relationship between PAH and ozone. Results showed that heating compared to nonheating season was associated with greater Σ(8)PAH(nonvolatile) (p<0.001) and Abs (p<0.05), and lower levels of Σ(8)PAH(semivolatile) (p<0.001). In addition, the heating season was associated with lower I/O ratios of Σ(8)PAH(nonvolatile) and higher I/O ratios of Σ(8)PAH(semivolatile) (p<0.001) compared to the nonheating season. In outdoor air, Σ(8)PAH(nonvolatile) was correlated negatively with community-wide ozone concentration (p<0.001). Seasonal changes in emission sources, air exchanges, meteorological conditions and photochemical/chemical degradation reactions are discussed in relationship to the observed seasonal trends.     

Estimation of PAHs dry deposition and BaP toxic equivalency factors (TEFs) study at Urban, Industry Park and rural sampling sites in central Taiwan, Taichung

The concentrations of polycyclic aromatic hydrocarbons (PAHs) in gas phase and particle bound were measured simultaneously at industrial (INDUSTRY), urban (URBAN), and rural areas (RURAL) in Taichung, Taiwan. And the PAH concentrations, size distributions, estimated PAHs dry deposition fluxes and health risk study of PAHs in the ambient air of central Taiwan were discussed in this study. Total PAH concentrations at INDUSTRY, URBAN, and RURAL sampling sites were found to be 1650 +/- 1240, 1220 +/- 520, and 831 +/- 427 ng/m3, respectively. The results indicated that PAH concentrations were higher at INDUSTRY and URBAN sampling sites than the RURAL sampling sites because of the more industrial processes, traffic exhausts and human activities. The estimation dry deposition and size distribution of PAHs were also studied. The results indicated that the estimated dry deposition fluxes of total PAHs were 58.5, 48.8, and 38.6 microg/m2/day at INDUSTRY, URBAN, and RURAL, respectively. The BaP equivalency results indicated that the health risk of gas phase PAHs were higher than the particle phase at three sampling sites of central Taiwan. However, compared with the BaP equivalency results to other studies conducted in factory, this study indicated the health risk of PAHs was acceptable in the ambient air of central Taiwan.     

Optimized method for dissolved hydrogen sampling in groundwater

Dissolved hydrogen concentrations are used to characterize redox conditions of contaminated aquifers. The currently accepted and recommended bubble strip method for hydrogen sampling (Wiedemeier et al., 1998) requires relatively long sampling times and immediate field analysis. In this study we present methods for optimized sampling and for sample storage. The bubble strip sampling method was examined for various flow rates, bubble sizes (headspace volume in the sampling bulb) and two different H2 concentrations. The results were compared to a theoretical equilibration model. Turbulent flow in the sampling bulb was optimized for gas transfer by reducing the inlet diameter. Extraction with a 5 mL headspace volume and flow rates higher than 100 mL/min resulted in 95-100% equilibrium within 10-15 min. In order to investigate the storage of samples from the gas sampling bulb gas samples were kept in headspace vials for varying periods. Hydrogen samples (4.5 ppmv, corresponding to 3.5 nM in liquid phase) could be stored up to 48 h and 72 h with a recovery rate of 100.1+/-2.6% and 94.6+/-3.2%, respectively. These results are promising and prove the possibility of storage for 2-3 days before laboratory analysis. The optimized method was tested at a field site contaminated with chlorinated solvents. Duplicate gas samples were stored in headspace vials and analyzed after 24 h. Concentrations were measured in the range of 2.5-8.0 nM corresponding to known concentrations in reduced aquifers.     

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.     

PAH deposition to snow surface

The urban snowpack effectively acts as a collection device for atmospheric-deposited PAHs. When these PAHs are flushed out in a short time interval along with springtime snowmelt, these cause shockloading to receiving waters. In order to assess the PAH deposition and accumulation in urban snowpacks, a deposition survey of PAH for the winter months of 1991-92 from the city of Sault Ste. Marie, Ontario, Canada was undertaken. The results of the survey are interpreted in view of prevailing meteorology and various emission sources in the study area. The relative PAH deposition levels (to BaP) are compared with relative source emission fingerprints to examine consistency in sampling and analysis. While analyzing the PAH samples using the ASTM (1987) method, the problem of concentration levels being below the detection level was encountered. The ASTM method for PAH analysis was modified to enhance the detection limit of the PAHs by concentrating the PAH extract to very low volumes, on the order of 200-300 microL.     

Dicarboxylic acid concentration trends and sampling artifacts

Dicarboxylic acids associated with airborne particulate matter were measured during a summer period in Philadelphia that included multiple air pollution episodes. Samples were collected for two 10 h periods each day using a high-volume sampler with two quartz fiber filters in series, and analyzed by gas chromatography mass spectrometry (GCMS) with diazomethane derivatization. Among the dicarboxylic acids investigated, phthalic acid and adipic acid exhibited the greatest diurnal variations and the strongest linear relationship with maximum daily ozone concentration. Dicarboxylic acids and ozone concentration exhibited a poor linear relationship with organic to elemental carbon ratio. All species investigated were affected by significant sampling artifact errors at low concentrations, but sampling errors were negligible at high concentrations observed during ozone episodes.     

An automated systems for air sampling with annular denuder systems at a remote site

An automated air sampling system has been designed for use with the annular denuder system (ADS). The automated air sampling system allows for accurate measurements of air volume and day-night sampling while preventing the accumulation of moisture within the ADS caused by condensation or cloud events. The sampling system consists of air flow, monitoring and control subsystems. Calibration of the sampling system against a Hoffer turbine flow meter indicated accurate measurement of air flow volumes. Field testing and preliminary data have shown that the sampling system functions well in a remote mountain forest site, and was relatively unaffected by condensation, fog, or cloud events.     

Carbonyl atmospheric reaction products of aromatic hydrocarbons in ambient air

To convert gaseous carbonyls to oximes during sampling, an XAD-4 resin denuder system pre-coated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine and followed by analysis with methane positive chemical ionization gas chromatography/mass spectrometry was used to measure carbonyls in ambient air samples in Riverside, CA. In conjunction with similar analyses of environmental chamber OH radical-initiated reactions of o- and p-xylene, 1,2,4-trimethylbenzene, ethylbenzene, 4-hydroxy-2-butanone and 1,4-butanediol, we identified benzaldehyde, o-, m- and p-tolualdehyde and acetophenone and the dicarbonyls glyoxal, methylglyoxal, biacetyl, ethylglyoxal, 1,4-butenedial, 3-hexene-2,5-dione, 3-oxo-butanal, 1,4-butanedial and malonaldehyde in the ambient air samples. As discussed, these carbonyls and dicarbonyls can be formed from the OH radical-initiated reactions of aromatic hydrocarbons and other volatile organic compounds emitted into the atmosphere, and we conclude that in situ atmospheric formation is a major source of these carbonyls in our Riverside, CA, ambient air samples.     

Simultaneous sampling of NH3, HNO3, HC1, SO2 and H2O2 in ambient air by a wet annular denuder system

A new sampling device is described for the simultaneous collection of NH₃, HNO₃, HCl, SO₂ and H₂O₂ in ambient air. The apparatus is based on air sampling by two parallel annular denuder tubes. The gases are collected by absorption in solutions present in the annulus of the denuder tubes. After a sampling time of 30 min at flow rate of 32 ℓ min⁻¹ the solutions are extracted from the denuders and analyzed off-line. The detection limits of NH₃, HNO₃, HCL and SO₂ are in the order of 0.1–0.5 μm⁻³. For H₂O₂ the detection limit is 0.01 μm⁻³. The reproducibility is 5–10% at the level of ambient air concentrations. Comparison of this novel technique with existing methods gives satisfactory results. The compact set-up offers the possibility of field experiments without the need of extensive equipment.     

The gas/particle partitioning of polycyclic aromatic hydrocarbons collected at a sub-Arctic site in Canada

Polycyclic aromatic hydrocarbons (PAH) were measured in air samples at a remote air monitoring site established in the Yukon Territory, Canada as part of a global project (International Polar Year; IPY) to study the potential for atmospheric long-range transport of anthropogenic pollutants to the Arctic. Gas- and particle-phase PAH were collected in polyurethane foam plugs and on glass fibre filters respectively from August 2007 to October 2009. PAH concentrations were found to be highest in the winter months and lowest in summer. The gas/particle partitioning coefficients of 3–5 ringed PAH were computed and seasonal averages were compared. In the summer time, lower molecular mass PAH exhibited relatively higher partitioning into the particle-phase. This particle-phase partitioning led to the shallowest slopes being recorded during summer for the log–log correlation plots between the PAH partition coefficients and their sub-cooled vapour pressures. Air mass back trajectories suggest that local impacts may be more important during the summer time which is marked by increased camping activities at camping sites in the proximity of the sampling station. In conclusion, both summer and wintertime variations in PAH concentrations and gas/particle partitioning are considered to be source- and phototransformation-dependent rather than dependent on temperature-driven shifts in equilibrium partitioning.     

Simultaneous sampling of gas- and aerosol-phase TDI with a triple filter system

A new triple filter system sampler/model is proposed for the precise and accurate simultaneous sampling and determination of gas- and aerosol-phase 2,4-toluene diisocyanate (TDI). The system consists of two front Teflon filters for sampling aerosol-phase TDI and a final coated glass fiber filter to collect gas-phase TDI. The aerosol-phase TDI is collected on the first Teflon filter, while the second Teflon filter is used to estimate gaseous TDI adsorbed by the first. According to the gas adsorption test of two Teflon filters in series, the TDI gas adsorption fraction of the two filters is almost the same. Results of the evaporation test using pure TDI aerosols collected on the Teflon filter show that significant evaporation of the compound does not occur during sampling. These two findings allow the use of a model to estimate accurate gas- and aerosol-phase TDI concentrations. The comparison test with an annular denuder shows that the triple filter system can minimize the TDI sampling bias between the dual filter and the annular denuder systems.     

Diffusion scrubber technique used for measurements of atmospheric ammonia

A diffusion scrubber (DS) was developed to measure trace levels of gaseous ammonia in ambient air. The sampling resolution time for this method is 10 min and the detection limit is estimated to be 0.01 ppbv. The response to the NI-I₃ concentrations is found to be dependent on the relative humidity in the ambient air and the temperature. The method is calibrated by using a diluted NH₃ cylinder gas, and the concentrations of the calibration gas were in the range 0.02–2 ppbv during the test. Sampling performed with the DS-method is compared to sampling performed by a filter pack and a continuous flow denuder (AMANDA). The DS-method shows good agreement with the continuous flow denuder and the filter pack.     

Comparing field performances of denuder techniques in the high Arctic

A field evaluation between two annular denuder configurations was conducted during the spring of 2003 in the marine Arctic at Ny-Ålesund, Svalbard. The IIA annular denuder system (ADS) employed a series of five single-channel annular denuders, a cyclone and a filter pack to discriminate between gas and aerosol species, while the EPA-Versatile Air Pollution Sampler (VAPS) configuration used a single multi-channel annular denuder to protect the integrity of PM_2.5 sample filters by collecting acidic gases. We compared the concentrations of gaseous nitric acid (HNO₃), nitrous acid (HONO), sulfur dioxide (SO₂) and hydrochloric acid (HCl) measured by the two systems. Results for HNO₃ and SO₂ suggested losses of gas phase species within the EPA-VAPS inlet surfaces due to low temperatures, high relative humidities, and coarse particle sea-salt deposition to the VAPS inlet during sampling. The difference in HNO₃ concentrations (55%) between the two data sets might also be due to the reaction between HNO₃ and NaCl on inlet surfaces within the EPA-VAPS system. Furthermore, we detected the release of HCl from marine aerosol particles in the EPA-VAPS inlet during sampling contributing to higher observed concentrations. Based on this work we present recommendations on the application of denuder sampling techniques for low-concentration gaseous species in Arctic and remote marine locations to minimize sampling biases. We suggest an annular denuder technique without a large surface area inlet device in order to minimize retention and/or production of gaseous atmospheric pollutants during sampling.     

Assessment of bioavailable PAH, PCB and OCP concentrations in water, using semipermeable membrane devices (SPMDs), sediments and caged carp

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed at several freshwater sites in and around the city of Amsterdam. Carp (Cyprinus carpio) were caged for 4 weeks at 10 sites, together with semipermeable membrane devices (SPMDs). In addition, sediment samples were taken at each site. SPMDs and sediments were analysed for PAHs, PCBs and OCPs. Carp muscle tissues were analysed for PCBs and OCP, while PAH metabolites were assessed in fish bile. Contaminant concentrations in the water phase were estimated using three different methods: 1. Using fish tissue concentrations and literature bioconcentration factors (BCFs), 2. Using SPMD levels and a kinetic SPMD uptake model, and 3. Using sediment levels and literature sorption coefficients (K_ocs). Since PAH accumulation in fish is not considered an accurate indicator of PAH exposure, calculated aqueous PAH concentrations from SPMD data were compared with semiquantitatively determined biliary PAH metabolite levels. Contaminant concentrations in the water phase estimated with fish data (Cw_fish) and SPMD data (Cw_spmd) were more in line for compounds with lower K_ow than for compounds with higher K_ow values. This indicates that the assumption of fish–water sorption equilibrium was not valid. At most sites, sediment-based water levels (Cw_sed) were comparable with the Cw_spmd, although large differences were observed at certain sites. A significant correlation was observed between biliary PAH metabolite levels in fish and aqueous PAH concentrations estimated with SPMD data, suggesting that both methods may be accurate indicators of PAH exposure in aquatic ecosystems.