Christopher Stark

Carcinogenic potential, levels and sources of polycyclic aromatic hydrocarbon mixtures in indoor and outdoor environments and their implications for air quality standards

Both the World Health Organization and the UK Expert Panel on Air Quality Standards (EPAQS) have considered benzo(a)pyrene (BaP) as a marker of the carcinogenic potency of the polycyclic aromatic hydrocarbons (PAH) mixture, when recommending their respective guidelines for PAHs in outdoor air. The aim of this research is to compare the concentrations and relative abundance of individual PAH and their contribution to the overall carcinogenic potential of the PAH mixture in indoor and outdoor environments to assess the suitability of the UK air quality standard derived for outdoor air for use as a guideline for indoor environments. Samples were collected onto filters using active sampling in different indoor and outdoor microenvironments. The ratio of individual compounds to BaP, the BaP equivalent concentrations and the percentage contribution of each individual compound to the total carcinogenic potential of the PAH mixture were calculated. Mean concentrations were generally lower indoors (BaP=0.10 ng/m(3)) than outdoors (BaP=0.19 ng/m(3)), with the exception of indoor environments with wood burners (BaP=2.4 ng/m(3)) or ETS (BaP=0.6 ng/m(3)). The ratio of individual PAHs to BaP showed no significant differences between indoors (e.g. DahA/BaP=0.27) and outdoors (DahA/BaP=0.31). The relative contribution of BaP to the PAH overall carcinogenic potency is similar indoors (49%), outdoors (54%) and in the smelter environment (48%) used by EPAQS to derive the UK Air Quality Standard for ambient air. These results suggest the suitability of BaP as a marker for the carcinogenic potential of the PAH mixture irrespective of the environment. Despite small differences in PAH mixture composition indoors and outdoors, the level of protection afforded by the present EPAQS standard is likely to be similar whether it is applied to indoor or outdoor air.

Use of a versatile high efficiency multiparallel denuder for the sampling of PAHs in ambient air: gas and particle phase concentrations, particle size distribution and artifact formation.

The design and performance of a multiparallel plate denuder able to operate at low and high-flow (3-30 L/min) for the collection of polycyclic aromatic hydrocarbon (PAH) vapor is described. The denuder, in combination with a micro orifice uniform deposit impactor (MOUDI) was used to assess processes of artifact formation in MOUDIs used with and without an upstream denuder. Duplicate sampling trains with an upstream denuder showed good repeatability of the measured gas and particle-phase concentrations and low breakthrough in the denuder (3.5-15%). The PAH size distributions within undenuded and denuded MOUDIs were studied. Use of the denuder altered the measured size distribution of PAHs toward smaller sizes, but both denuded and undenuded systems are subject to sampling artifacts.

Receptor modelling study of polycyclic aromatic hydrocarbons in Jeddah, Saudi Arabia

Measurements of 14 polycyclic aromatic hydrocarbons (PAH) have been made in Jeddah, Saudi Arabia, with a view to establishing the concentrations in this major city, and quantifying the contributions of major sources. Particulate and vapour forms have been sampled and analysed separately. The concentrations are compared to measurements from other sites in the Middle Eastern region and are towards the lower end of the range, being far lower than concentrations reported from Riyadh (Saudi Arabia), Assiut (Egypt) and Tehran (Iran) but broadly similar to those measured in Damascus (Syria) and higher than those measured in Kuwait. The partitioning between vapour and particle phases is similar to that in data from Egypt and China, but with many compounds showing a higher particle-associated percentage than in Birmingham (UK) possibly reflecting a higher concentration of airborne particulate matter in the former countries. Concentrations in Jeddah were significantly higher at a site close to the oil refinery and a site close to a major ring road than at a suburban site to the north of the city. Application of positive matrix factorisation to the pooled data elicited three factors accounting respectively for 17%, 33% and 50% of the measured sum of PAH and these are interpreted as arising from gasoline vehicles, industrial sources, particularly the oil refinery, and to diesel/fuel oil combustion.

Using Variable Ionization Energy Time-of-Flight Mass Spectrometry with Comprehensive GC×GC To Identify Isomeric Species

Although GC×GC-ToF-MS allows the separation of thousands of peaks, many of these peaks are not positively identified owing to the lack of mass spectral library data and/or standard materials, leading to a substantial amount of information being inaccessible. The fragmentation patterns of molecules in mass spectrometers using electron impact ionization at 70 eV can be useful for molecule identification, provided a match is available in a published EI MS library, but are indistinguishable for many isomeric organic compounds (for example, linear and branched alkanes). Lower ionization energies have been exploited leading to organic compounds being ionized with lower excess internal energy and less fragmentation, retaining the molecular ion and maximizing its relative signal. This has enabled the identification of a large number of isomeric organic compounds, both aliphatic and aromatic, between C12-C36, in the previously unresolved complex mixture (UCM) of two motor oil samples. This technique also demonstrates problems associated with separation of coeluting isomers, particularly for the n-alkanes, which are routinely measured by 1D GC/MS and may be overestimated, due to coelution. As a consequence retention times in 2 dimensions and mass spectra at variable ionization energies are shown to give unparalleled power to identify specific isomers.

Urinary metabolites of polycyclic aromatic hydrocarbons in Saudi Arabian schoolchildren in relation to sources of exposure

Polycyclic aromatic hydrocarbons contain a number of known carcinogenic compounds, and urinary biomarkers have been widely used as a measure of exposure but quantitative relationships with exposure variables have proved elusive. This study aimed to quantify the relationship between exposures to phenanthrene and pyrene from atmospheric and dietary sources with the excretion of 1-hydroxypyrene and hydroxyphenanthrenes in urine as biomarkers of exposure. The study population consisted of 204 male schoolchildren attending three schools in different parts of Jeddah, Saudi Arabia who provided urine samples on each of three consecutive days. Outdoor air measurements of polycyclic aromatic hydrocarbons were made at the schools and the children provided information on diet, exposure to environmental tobacco smoke and incense, and various lifestyle factors through a questionnaire. Mixed models with random effects for subjects nested within site were fitted in order to examine the relationship between exposure variables and urinary PAH metabolites. A unit increase (1 ng m(-3)) in ambient pyrene (particulate plus gaseous phase) was associated with a 3.5% (95% CI: 1.01%, 5.13%) increase in urinary 1-hydroxypyrene concentration. A unit increase in ambient phenanthrene was associated with a 1.01% (95% CI: 0.03%, 2.02%) increase in total hydroxyphenanthrene concentrations. Consumption of chargrilled food increased the 1-hydroxypyrene and hydroxyphenanthrene concentrations by 24% (95% CI: 11%, 37%) and 17% (95% CI: 8%, 26%) respectively. We did not find evidence of association for environmental tobacco smoke exposure or incense burning. It is concluded that both respiratory exposure and consumption of chargrilled food are considerable sources of PAH exposure in this population as reflected by concentrations of urinary biomarkers.