CHAPTER ONE

1.1 INTRODUCTION

Polycyclic aromatic hydrocarbons (PAHs) are a group of organic compounds consisting of two or more fused benzene rings (linear, cluster or angular arrangement), or compounds made up of carbon and hydrogen atoms grouped into rings containing five or six carbon atoms. They are called ?PAH derivatives? when an alkyl or other radical is introduced to the ring, and heterocyclic aromatic compounds (HACs) when one carbon atom in a ring is replaced by a nitrogen, oxygen or sulphur atoms. PAHs originate mainly from anthropogenic processes particularly from incomplete combustion of organic fuels. PAHs are distributed widely in the atmosphere. Natural processes, such as volcanic eruptions and forest fires, also contribute to an ambient existence of PAHs (Suchanova et al., 2008). PAHs can be present in both particulate and gaseous phases, depending on their volatility. Low molecular weight PAHs (LMW PAHs) that have two or three aromatic rings (molecular weight from 152 to 178g/mol) are emitted in the gaseous phase, while high molecular weight PAHs (HMW PAHs), molecular weight ranging from 228 to 278g/mol, with five or more rings, are emitted in the particulate phase, (ATSDR, 1995) . In the atmosphere, PAHs can undergo photo-degradation and react with other pollutants, such as sulfur dioxide, nitrogen oxides, and ozone. Due to widespread sources and persistent characteristics, PAHs disperse through atmospheric transport and exist almost everywhere. There are hundreds of PAH compounds in the environment but in practice PAH analysis is restricted to the determination of six (6) to sixteen (16) compounds. Human beings are exposed to PAH mixtures in gaseous or particulate phases in ambient air. Long term exposure to high concentration of PAHs is associated with adverse health problems. Since some PAHs are

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considered carcinogens, inhalation of PAHs in particulates is a potentially serious health risk linked to lung cancer (Philips, 1999).

1.2. Physical and Chemical Characteristics of PAHs.

PAHs are a group of several hundred individual organic compounds which contain two or more aromatic rings and generally occur as complex mixtures rather than single compounds. PAHs are classified by their melting and boiling points, vapour pressure, and water solubility, depending on their structure. Pure PAHs are usually coloured, crystalline solids at ambient temperature. The physical properties of PAHs vary with their molecular weight and structure (Table1). Except for naphthalene, they have very low to low water solubilities, and low to moderately high vapour pressures. Their octanol-water partition coefficients (Kow) are relatively high, indicating a relatively high potential for adsorption to suspended particles in the air and in water, and for bioconcentration in organisms (Sloof et al., 1989). Table 1 shows physical and chemical characteristics of few selected PAHs from the sixteen (16) priority PAHs, listed by the US EPA. (see appendix). Most PAHs, especially as molecular weight increases, are soluble in non-polar organic solvents and are barely soluble in water (ATSDR, 1995).

Most PAHs are persistent organic pollutants (POPs) in the environment. Many of them are chemically inert. However, PAHs can be photochemically decomposed under strong ultraviolet light or sunlight, and thus some PAHs can be lost during atmospheric sampling. Also, PAHs can react with ozone, hydroxyl radicals, nitrogen and sulfur oxides, and nitric and sulfuric acids which affect the environmental fate or conditions of PAHs (Dennis et al., 1984; Simko, 1991).

PAHs possess very characteristic UV absorbance spectra. Each ring structure has a unique UV spectrum, thus each isomer has a different UV absorbance spectrum. This is especially useful in

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the identification of PAHs. Most PAHs are also fluorescent, emitting characteristic wavelengths of light when they are excited (when the molecules absorb light). Generally, PAHs only weakly absorb light of infrared wavelengths between 7 and 14‘m, the wavelength usually absorbed by chemical involved in global warning (Ramanathan, 1985).

Polycyclic aromatic hydrocarbons are present in the environment as complex mixtures that are difficult to characterize and measure. They are generally analyzed using gas chromatography coupled with mass spectrometry (GC-MS) or by using high pressure liquid chromatography (HPLC) with ultraviolet (UV) and fluorescence dectetors (Slooff et al., 1989)