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.     

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.     

Vertical fluxes of aromatic and aliphatic hydrocarbons in the Northwestern Mediterranean Sea

Aliphatic and aromatic hydrocarbon fluxes were measured in time series sediment trap samples at 200 m and at 1000 m depths in the open Northwestern Mediterranean Sea, from December 2000 to July 2002. Averaged fluxes of n-alkanes, UCM and T-PAH₃₅ were 2.96 ± 2.60 μg m⁻² d⁻¹, 64 ± 60 μg m⁻² d⁻¹ and 0.68 ± 0.59 μg m⁻² d⁻¹, respectively. Molecular compositions of both hydrocarbon classes showed a contamination in petrogenic hydrocarbons well above the background levels of such an open site, whereas pyrolytic hydrocarbons stand in the range of other open Mediterranean locations. Fluxes displayed ample interannual and seasonal variabilities, mainly related to mass flux variation while concentration evolutions trigger secondary changes in pollutant fluxes. High lithogenic flux events exported particles with a larger pollutant load than biogenic particles formed during the spring bloom and during the summer. Sinking hydrocarbons were efficiently transported from 200 m to 1000 m.     

Determination of polycyclic aromatic hydrocarbons and substitutes (Nitro-, Oxy-PAHs) in urban soil and airborne particulate by GC-MS and NCI-MS/MS

A method involving high resolution gas chromatography combined with ion trap (HRGC-MS/MS) and negative chemical ionisation (NCI) was developed for the determination of nitrated or oxygenated polycyclic aromatic hydrocarbons (nitro-PAHs, oxy-PAHs) and other electrophilic substitutes in soil samples. Efficient clean-up was achieved by a combination of methods for the determination of PAHs in soil and nitro-PAHs in aerosol using solid phase extraction (SPE) and semipreparative high performance liquid chromatography (HPLC). In samples of surface soil from the city of Basle (Switzerland), nitro-PAHs (mainly 3-nitrofluoranthene and 1-nitropyrene) were found in concentrations between 30 and 800 ng/kg dry weight. Oxy-PAHs and parent PAHs revealed 10²-10⁴-fold higher levels. Nitro-PAHs which are up to 10⁵ times more mutagenic seem to be less persistent in soil than the parent forms, although their entire mutagenic potential has to be estimated as being on the same order of magnitude. In urban air particulate matter, the amounts of nitro-PAHs (2–62 pg/m³) were 10–100 times lower than oxyPAHs and parent PAHs which were both found in a similar range. 3-nitrobenzanthrone, a recently described suspected human carcinogen has not yet been detected. Using multivariate statistical analysis, it was possible to elucidate similarities or special characteristics of substances in a given matrix reflecting their chemical properties or specific emission sources.