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TABLE 2.8.1 Priority PAH as food toxicants: evidence for carcinogenicity and relative potencies. Evidence for carcinogenicitya Compound Naphthalene Acenaphthylene Acenaphthene Fluorene Anthracene Phenanthrene Fluoranthene Pyrene Chrysene Benz[a]anthracene Benzo[b] uoranthene Benzo[k] uoranthene Benzo[a]pyrene Indeno[1,2,3-cd]pyrene Benzo[g,h,i]perylene Dibenz[a,h]anthracene
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Group 1, the compound is carcinogenic in human; Group 2A, the compound is probably carcinogenic in humans; Group 2B, the compound is possibly carcinogenic in humans; Group 3, the compound is not classi able as to its carcinogenicity in humans. TEF = toxicity equivalency factors; ND = no adequate data; I, inadequate evidence; L = limited evidence; S = suf cient evidence.
probable human carcinogen (Group 2A) has been recently reclassi ed by the WHO International Agency for Research on Cancer (IARC) as a human carcinogen (Group 1 carcinogen; Table 2.8.1) (1,3). Thus, exposure to PAHs is a signi cant public health problem. Over 100 different PAHs have been identi ed and they often occur as complex mixtures as a result of the pyrolytic process. Of these, the US Environmental Protection Agency (EPA) has listed 16 PAHs as priority pollutants (4). These priority pollutants include naphthalene, acenaphthylene, acenaphthene, uorene, anthracene, phenanthrene, uoranthene, pyrene, chrysene, benz[a]anthracene, benzo[b] uoranthene, benzo[k] uoranthene, B[a]P, indeno[1,2,3-cd]pyrene, benzo[g,h,i]perylene, and dibenz[a,h]anthracene (Fig. 2.8.1). This chapter will discuss the occurrence of these PAHs in food, methods of detection and analysis, mechanism of formation in the processing and cooking of food, mitigation, biomonitoring and biomarkers of exposure, health risks, and risk management.
POLYAROMATIC HYDROCARBONS
Figure 2.8.1 The 16 PAHs that are priority pollutants listed by the US EPA. The curved arrow shows the presence of a bay region in carcinogenic PAH.
OCCURRENCE
There are numerous reports of detection of the 16 PAH priority pollutants in almost all food sources (5 7). The presence of PAHs in food appears to be from several major routes, including the growth of fruit and vegetables in contaminated soils, the ingestion of seafood from oceans contaminated with crude oil, and man-made food preparation techniques such as smoking, grilling, broiling, and roasting, which can contaminate food unnecessarily. The introduction of PAHs into food by food-processing methods cannot be considered without the recognition that the food itself may already be contaminated with these toxicants prior to processing. To conduct meaningful risk assessment, cross-comparison between food groups and across studies would be ideal. However, this is made almost impossible due to the different analytical protocols that have been applied, and in some instances, stateof-the-art methods (e.g., gas chromatography-mass spectrometry [GC-MS]) have not been used routinely, raising concerns about the robustness of these data. Nevertheless, there appears to be agreement in the trends observed.
OCCURRENCE
PAHs in the Food Chain
The natural and anthropogenic sources of PAHs in foods are numerous. PAHs are produced and released into the atmosphere during incomplete combustion or pyrolysis of organic substances by industrial process and human activity. They are emitted into the environment as the result of burning coal, wood, petroleum, and petroleum products, and from coke production, refuse burning, and motor vehicle exhaust fumes (8, 9). They are also formed in coal gasi cation plants, municipal incinerators, and in aluminum production facilities (10 12), and are thus released as emissions from these plants. Most PAHs have a low volatility and poor water solubility. Thus, PAHs have a high tendency to absorb onto small organic particulate matter (<2.5 m) like y ash and soot. Particles containing PAHs fall from the atmosphere as a primary source of contamination of the soil, a problem that is exacerbated when it rains. Consequently, cereals, grain, and vegetables grown in contaminated soil will absorb the PAHs due to their lipophilic properties. Unfortunately, PAHs in the soil build up in a cumulative fashion. Soil samples collected in Rothamsted Experimental Station in S.E. England over a period of 140 years (1846 1980) were analyzed for PAHs. In the upper 3.0 cm of soil, B[a]P concentrations had increased from 18 to 130 g/kg over this time period (13). As a result of soil contamination in some parts of the world, concentrations as high as 590 2301 g B[a]P/kg can be observed in the peelings of vegetables. Grazing herds that feed in contaminated areas can also have PAHs enter into their milk supply and dairy products can thus become contaminated (14). Particles containing PAH also fall into surface water; they can enter the nearshore marine environment as a result of urban water drain runoffs, water runoff from highways, ef uent from industrial and sewage outlets (15, 16), and from creosote-treated wharfs and pilings (17). They accumulate in river or marine sediments to which they are strongly bound, and these sediments act as a pollution reservoir from which PAHs may be constantly released. Oceans and waterways contaminated with crude oil or engine oil due to either oil tanker disasters or industrial waste will create sediments more heavily contaminated with PAHs. It is estimated that PAHs constitute about 20% of the total hydrocarbon content of crude oil (18). Filter-feeding bivalves such as mussels, clams, and oysters are the rst invertebrate targets for exposure to PAHs since they lter large amounts of water and have a very poor metabolic clearance for PAHs. They thus play an important role in the transfer of PAHs to seafood and sh, and to higher animals through the food chain (19, 20). 2.8.2.2 PAH Contamination in Food Preparation and Processing
Food preparation and processing techniques can unavoidably increase the content of PAHs in foods that may or may not be already contaminated. 2.8.2.2.1 Smoking Smoking of food is one of the oldest methods to preserve and avor food, e.g., meat, sh, and cheese. Smoke is generated in the