Determination of airborne polycyclic aromatic hydrocarbons at an airport by gas chromatography–mass spectrometry and evaluation of occupational exposure

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Abstract

The aim of this study was to determine airborne polycyclic aromatic hydrocarbons (PAHs) and biphenyl at an airport by gas chromatography–mass spectrometry and to evaluate occupational exposure by environmental monitoring. A total of 12 samplings were carried out in three areas: (1) a handling area where baggage was unloaded manually from vehicles onto conveyor belts (n = 5); (2) the runway with plane and motor vehicle traffic (n = 5) and (3) a departure lounge (n = 2). PAHs levels were in most cases low. The higher levels found refer to naphthalene (130–13,050 ng/m3) and to its methyl-substitutes 2-methylnaphthalene (64–28,500 ng/m3) and 1-methylnaphtalene (24–35,300 ng/m3), and biphenyl (24–1610 ng/m3). A method was used to quantify twenty-four airborne PAHs, and biphenyl, and to detect a variety of other chemical compounds by means of the deconvolution program AMDIS. After sampling air on quartz filter and PUF and XAD-2 sorbents; extraction with dichloromethane, and concentration and purification on silica cartridges, analyses were carried out by gas chromatography–ion trap mass spectrometry. We used 20 deuterated PAHs to quantify both the 24 native PAHs and biphenyl. The native substances had been subdivided into small groups and in this way, their volatility was adequately reflected by the D-PAH present in each group. The limit of detection was 0.1 ng/m3 for all the PAHs, and a linear range of at least about three-fold the maximum level studied (naphthalene) was obtained both for D-PAHs and the native PAHs. A good recovery pattern was obtained for D-PAHs on quartz filters, PUF and XAD-2.

Introduction

Polycyclic aromatic hydrocarbons (PAHs) usually occur as complex mixtures made up of two or more condensed benzene rings, and the resulting molecules contain only carbon and hydrogen atoms.

Thermodynamically stable PAHs are formed during pyrolysis and the incomplete combustion of organic materials in a variety of occupational and environmental settings [1], [2]. Several routes of absorption are known both for the general population and exposed workers. They include inhalation of environmental air, ingestion of contaminated foods and drinks and cutaneous absorption [3], [4], [5], [6], [7], [8], [9].

Industries where occupational exposure to PAHs is likely to occur include coke ovens and coal tar use, iron and steel works, aluminium mechanism, foundries, carbon electrode and carbon black manufacture, asphalt manufacture and use, and many others [2]. The tertiary sector also contributes to PAH pollution due to road traffic [10], [11], [12], [13], [14].

Epidemiological studies have revealed an increased incidence of cancer, especially of the lung and bladder, among workers occupationally exposed to PAHs [15], [16], [17], [18].

Sampling of airborne PAHs requires special equipment since PAHs with a lower molecular weight are found mainly as vapour, while those with a higher molecular weight are to be found in the condensed phase. Consequently, an adequate sampling method must combine a filter for the collection of particulate, and one or more sorbents such as XAD-2 and/or polyurethane foam [19], [20], [21].

At present the most widespread method used for extracting PAHs from the filter is extraction by sonication, while Soxhlet solvent and the supercritical CO2 extraction techniques are used for extracting these substances from sorbents.

After extraction and concentration, the purification of PAHs can be performed by chromatography on various sorbents such as silica or alumina.

Analysis is carried out by gas chromatography (GC) coupled with mass spectrometry, and high performance liquid chromatography (HPLC) [22], [23], [24] coupled with fluorimetry [25], [26], respectively.

To date the literature provides no information concerning airborne PAHs at an airport environment where airborne PAHs may be associated with emissions from motor vehicles and from aircraft exhausts.

The aim of our study was to test a method of quantifying 24 airborne PAHs and biphenyl at an airport in order to evaluate the occupational exposure of workers. An additional aim was to identify tentatively other chemical compounds by using the deconvolution program AMDIS.

Section snippets

Materials and reagents

Air was sampled with an ECHO PUF (TCRTECORA, Corsico, Italy) area sampler equipped with a 103 mm diameter quartz micro-fibre filter (Munktell Filter AB, Grycksbo, Sweden), a 50 mm × 60 mm (thickness × diameter) polyurethane foam (Tisch Environmental INC., Villane of Cleves, OH, US) and a 30 mm layer (30 g) of 20–60 mesh XAD-2 resin (Supelco, Bellafonte, PA, US). The polyurethane foam (PUF) was separated from the XAD-2 resin by a fine-mesh stainless steel gauze. The XAD-2 layer was held on another gauze

Results and discussion

As can be seen from Table 2, a maximum of three native PAHs were quantified by 1 deuterated analogue (generally there were only two). Recoveries of deuterated congeners were satisfactory, and, as the standard deviations suggest, there was an acceptable spread of results.

Table 3, Table 4, Table 5 show the levels of each PAH found on the three sampling media on the different sampling days. The PAH levels refer to the sum of particulate and/or vapour fractions. Note that, for each compound, the

Conclusions

In the occupational environment we investigated, selective sampling on quartz fibre, PUF and XAD-2 resin filter coupled with gas chromatography–ion trap mass spectrometry proved to be a valid instrument for evalutating the risk of exposure to PAHs in a work environment such as the airport we investigated for the first time for this type of risk. We found that airborne PAHs were basically low in all the sampling locations. Few regulatory institutions such as OSHA, ACGIH, NIOSH and the Deutsche

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