Health Risk Measurement of Polycyclic Aromatic Hydrocarbons (Pahs) In Barbecue Food “Nile Tilapia” (Oreochromis Niloticus)

PAH and classified as carcinogenic by the International Agency for Research on Cancer and regulated by the European Food Safety Authority. Estimated daily intake: mg/kg (bw)/ day , using the median and maximum; worst-case scenario. C = concentration (mg/kg) of PAHs (EFSA indicators). Fish ingestion rate (IR) = 68.5 g/day = 0.0685 kg/day, and Body weight (BW) = 70 kg . The Chronic Daily Intake , which refers to the increased likelihood of an individual developing cancer over their lifetime due to exposure to a possible carcinogen, was determined using the following Eq. (2): CDI = C×IR×EF×ED BW×AT (2) C = concentration (mg/kg). Fish ingestion rate (IR) = 68.5 g/day = 0.0685 kg/day. Body weight (BW) = 70 kg . Exposure frequency (EF) = 365 days/year. Exposure duration (ED) = 70 years. Averaging time (AT) = 70 × 365 = 25,550 days. Oral cancer slope factor for BaP = 7.3 (mg/kg/day)−1. BMDL10 for BaP = 0.07 mg/kg/day. MOE and ILCR (excess lifetime cancer risk) were calculated as shown in the equations (3, 4): MOE = BMDL10 EDI (3) ILCR=CDI×CSF (4) Table 1: Estimated Daily Intake of PAHs on Barbecued fish Sample BaP (mg/kg) Fresh Tilapia 0.26 Wrapped & Roasted 3.79 Roasted 0.64 Table 2: Chronic Daily Intake of PAHs on Barbecued fish Sample CDI (mg/kg/day) Fresh 2.54 × 10−4 Wrapped & Roasted 3.71 × 10−3 Roasted 6.26 × 10−4 Table 3: Margin of Exposure of PAHs on Barbecued fish Parameter Fresh Wrapped & Roasted Roasted EDI (mg/kg/day) 2.54×10−4 3.71×10−3 6.26×10−4 CDI (mg/kg/day) 2.54×10−4 3.71×10−3 6.26×10−4 ILCR 1.85×10−3 1.85×10−3 2.71×10−2 4.57×10−3 MOE 276 276 19 112 All calculated ILCR values exceed 10−4, indicating potential carcinogenic risk, especially for wrapped & roasted fish. The wrapped and roasted tilapia exhibited the highest carcinogenic risk indices, followed by roasted fish, while fresh fish showed comparatively lower but still elevated risk levels. The calculated MOE values were significantly below the safety benchmark of 10,000 established by EFSA, suggesting potential long-term carcinogenic risk associated with frequent consumption. Table 4: Summary of the concentrations (mg/kg) of PAHs in the different types of barbecued fish PAHs Solvent Blank Fresh Tilapia Fish Rapped & Roasted Tilapia fish Roasted Tilapia Fish Naphthalene N.D. N.D. 0.28 0.18 Acenaphthylene N.D. 0.12 1.10 0.87 Acenaphthene N.D. 0.74 0.75 1.98 Fluorene N.D. 0.10 0.94 1.36 Phenanthrene N.D. 0.61 0.43 0.54 Anthracene N.D. 0.53 0.16 2.62 Fluoranthene N.D. 0.27 1.39 3.17 Pyrene N.D. 0.31 0.93 4.24 Benz[a]anthracene N.D. 0.15 0.19 3.19 Chrysene N.D. 0.76 3.71 9.56 Benzo[b]fluoranthene N.D. 1.22 1.56 2.42 Benzo[k]fluoranthene N.D. 0.07 0.87 2.40 Benzo[a]pyrene N.D. 0.26 3.79 0.64 Indeno[1,2,3- c,d]pyrene N.D. 0.09 1.53 2.49 Dibenz[a,h]anthracene N.D. 0.14 1.18 1.03 Benzo-[g,h,i]perylene N.D. 1.37 0.04 3.11 ND - not detected. Numbers reduced to significant digits. Fig. 3. Concentrations of PAHs in different barbecued fish; (A) Fresh Tilapia Fish (B) Rapped & Roasted Tilapia fish of PAH-26 in barbecued fish (C) Roasted Tilapia Fish of PAH-26 in barbecued fish. Barbecue Geometry The analytical results demonstrate clear variations in polycyclic aromatic hydrocarbon concentrations across fresh, wrapped & roasted, and directly roasted tilapia samples. The solvent blank showed no detectable (N.D.) PAHs, confirming the reliability of the analytical procedure and absence of laboratory contamination. Baseline Contamination in Fresh Tilapia Fresh tilapia contained detectable but generally low concentrations of several PAHs. Notably higher levels were observed for benzo[g,h,i]perylene (1.37 mg/kg), benzo[b]fluoranthene (1.22 mg/kg), chrysene (0.76 mg/kg), and acenaphthene (0.74 mg/kg). The presence of these compounds in unprocessed fish suggests environmental exposure, likely arising from: Petroleum contamination of aquatic ecosystems, Atmospheric deposition of combustion by-products, Bioaccumulation in sediments. High-molecular-weight PAHs such as benzo[g,h,i]perylene and benzo[b]fluoranthene are typically associated with pyrogenic sources, indicating that the aquatic environment may already be impacted by combustion-related pollution. Effect of Wrapped & Roasted Processing Wrapped and roasted tilapia showed a noticeable increase in several PAHs compared to fresh samples. Particularly elevated compounds included: Benzo[a]pyrene (3.79 mg/kg), Chrysene (3.71 mg/kg), Indeno[1,2,3-c,d]pyrene (1.53 mg/kg), Fluoranthene (1.39 mg/kg), Benzo[b]fluoranthene (1.56 mg/kg). Although foil wrapping reduces direct contact with flames and smoke particulates, the data indicate that thermal degradation of lipids and organic matter still promotes PAH formation. Lipid pyrolysis and dripping fats interacting with heat sources can 0 2 4 6 8 10 12 Acenaphthylene Fluorene Anthracene Pyrene Chrysene Benzo[k]fluoranthene Indeno[1,2,3-c,d]pyrene 0 2 4 6 8 10 12 Naphthalene Acenaphthene Phenanthrene Fluoranthene Benz[a]anthracene Benzo[b]fluoranthene Benzo[a]pyrene Dibenz[a,h]anthracene generate PAH-rich smoke that penetrates the wrapping material. Interestingly, some low- molecular-weight PAHs (e.g., anthracene, phenanthrene) decreased compared to fresh samples, likely due to volatilization at elevated temperatures. Impact of Direct Roasting Directly roasted tilapia exhibited the highest PAH concentrations overall, clearly demonstrating the strong influence of direct exposure to combustion gases and smoke. The most abundant compounds were:, Chrysene (9.56 mg/kg), Pyrene (4.24 mg/kg), Fluoranthene (3.17 mg/kg), Benz[a]anthracene (3.19 mg/kg), Benzo[g,h,i]perylene (3.11 mg/kg), Anthracene (2.62 mg/kg).mThese compounds are predominantly high-molecular-weight PAHs, which are more stable, lipophilic, and carcinogenic. Their formation is strongly linked to: Incomplete combustion of wood fuel, pyrolysis of fish lipids, and direct deposition of smoke particulates. The extremely high concentration of chrysene (9.56 mg/kg) indicates intense pyrogenic activity. The elevated levels of benz[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, and indeno[1,2,3- c,d]pyrene further confirm that direct roasting enhances carcinogenic PAH generation. Behavior of Benzo[A]Pyrene Benzo[a]pyrene , a recognized marker for carcinogenic PAHs, showed: 0.26 mg/kg in fresh fish, 3.79 mg/kg in wrapped & roasted fish, and 0.64 mg/kg in directly roasted fish. The unexpectedly higher BaP level in wrapped samples compared to directly roasted samples may reflect: Differences in combustion intensity, Variable smoke circulation. Possible shielding effects that altered temperature distribution However, even 0.64 mg/kg in directly roasted fish remains concerning due to BaP’s potent carcinogenicity. Overall Trend and Toxicological Implications The general trend observed was: Fresh < Wrapped & Roasted < Directly Roasted This pattern confirms that thermal processing significantly increases PAH formation, particularly under direct flame exposure. Key toxicological concerns include: Increased concentration of high-molecular-weight PAHs Enhanced formation of carcinogenic congeners. Potential dietary exposure above recommended safety limits. High levels of chrysene, benz[a]anthracene, benzo[b]fluoranthene, indeno[1,2,3-c,d]pyrene, and benzo[g,h,i]perylene suggest substantial carcinogenic risk if such products are consumed frequently. Public Health Significance The results highlight that: Environmental contamination contributes to baseline PAH levels in fresh fish. Thermal processing, especially direct roasting, dramatically elevates PAH concentrations. High-temperature cooking methods are critical determinants of consumer exposure (Torgerson et al., 2015). Frequent consumption of directly roasted fish may increase long-term cancer risk due to cumulative exposure to carcinogenic PAHs. This study clearly demonstrates that processing method strongly influences PAH accumulation in tilapia and other grilled food. Direct roasting promotes the highest formation of carcinogenic PAHs, while foil wrapping offers partial but incomplete protection. These findings underscore the need for: Improved roasting techniques to reduce smoke deposition, temperature control during processing, public health awareness regarding safer cooking practices, regulatory monitoring of PAH levels in smoked and barbecued foods. Overall, the data provide strong evidence that cooking method is a major determinant of PAH contamination and associated health risk in barbecued fish. Results and Discussion All PAH26 analyzed were detected in every barbecued fish sample collected in Yenagoa. According to the European Food Safety Authority and joint FAO/WHO Expert committee on food Additives as being harmful to health. The combined concentration of benzo[a]anthracene , chrysene , benzo[a]pyrene , and benzo[b]fluoranthene , collectively referred to as PAH4, serves as a reliable indicator of carcinogenic PAHs in food products. Method validation results are presented in Table 4. For chromatographic analysis and recovery assessment, the AJTB-005 certified reference material from Gas Chromatography–Mass Spectrometry system comprising an Agilent 6890N Gas Chromatograph coupled with an Agilent 5973 Mass Selective Detector (Agilent Technologies, Santa Clara, USA). Was used, containing PAH congeners dissolved in acetonitrile. Individual PAH concentrations and total PAH levels (mg/kg) for Wrapped and Directly Roasted barbecued fish are presented in Figures 3 and 4. The limits of detection and quantification ranged from 0.01–0.06 μg/kg and 0.03–0.16 μg/kg, respectively. PAH concentrations ranged from 0.10 to 1.37 mg/kg in fresh tilapia fish, 0.04 to 3.79 mg/kg foiled wrapped & barbecued fish and from 0.18 to 9.56 mg/kg in direct barbecued fish. All measured values were detected some below the maximum limits established whereas, other above the permissible limits set by European Union regulations (2 mg/kg for BAP and 12 mg/kg for PAH4). Furthermore, these levels were lower than those reported in several previous studies. For comparison, a study conducted by (Martin et al., 2015). Reported an observed value of PAH concentration of 5.16 to 31.1 μg/kg in Beef and Beef burgers. In contrast, smoked fish from Ghana showed considerably higher PAH levels (3.1 to 65 μg/kg in wild samples). Likewise, 10 PAH congeners within 1.9 to 35 μg/kg. The lowest and highest individual PAH concentrations observed in this study were chrysene (0.18 to 9.56 mg/kg in direct-barbecued fish), Benzo[a]pyrene (0.04 to 3.79 mg/kg in wrapped & barbecued fish) and Benzo-[g,h,i]perylene (0.10 to 1.37 mg/kg in fresh Tilapia fish respectively). The observed BAP concentrations (0.26, 0.64 and 3.79 mg/kg in fresh, wrapped and direct barbecued fish) two of the sample analyzed were substantially lower than the regulatory maximum of 2 mg/kg, suggesting minimal immediate health risk whereas, one far was higher than the recommended limits suggesting public risk. Despite the relatively low and high concentrations observed in the current study, the carcinogenic potential of BAP residues in food remains a significant public health concern. Among the detected compounds, except naphthalene for the fresh tilapia fish samples, all the others 15 PAH26 were frequently occurring PAHs in barbecued fish. Although NAP is classified as a low-molecular-weight PAH, its toxicity depends on the route and duration of exposure. The presence of these compounds may reflect both environmental background contamination and formation during the barbecuing process. Prolonged barbecuing and thermal degradation likely contribute to PAH formation, particularly since vendors often extend barbecuing duration to preserve fish and reduce spoilage prior to sale. Conclusion This investigation assessed the occurrence of polycyclic aromatic hydrocarbons and the related health implications in barbecued Nile tilapia sourced from Swali Market, Yenagoa, Bayelsa State, Nigeria. Higher PAH burdens were recorded in hot-barbecued samples processed via direct flame exposure and foil-assisted grilling. Of the PAH-26 examined, fluoranthene was the most abundant congener, with pyrene occurring at the next highest frequency. Measured benzo[a]pyrene levels in both hot- and cold-treated fish remained below the maximum residue limits set by the European Union. Non-carcinogenic risk assessment showed Hazard Quotient (HQ) values within permissible safety margins. Similarly, the estimated Incremental Lifetime Cancer Risk values for hot- and cold-smoked products (3.69 × 10−7 and 5.41 × 10−7, respectively) were far below the acceptable risk benchmark of 1 × 10−4, indicating minimal carcinogenic concern associated with consumption. Despite the low estimated health risk, proactive control measures are advisable. Implementation of improved processing practices— including indirect smoking techniques, appropriate fuelwood selection, and optimized temperature–time control—can substantially limit PAH generation. Strengthening public health outreach and consumer awareness programs will further help reduce dietary exposure to PAHs within the Nigerian population. 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