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Int.J.Curr.Microbiol.App.Sci (2014) 3(7) 277-293

ISSN: 2319-7706 Volume 3 Number 7 (2014) pp. 277-293 http://www.ijcmas.com

Original Research Article Levels of polycyclic aromatic hydrocarbons (PAHS) in some Egyptian and fruits and their influences by some treatments

Abou-Arab, A.A.K.1*, Abou-Donia, M. A. M.1, El-Dars, F. M. S. E.2, Ali, O. I. M.2 and Hossam A. Goda3

1Food Toxicology and Contaminants, National Research Center, Egypt 2Chemistry Department, Faculty of Science, Helwan University, Cairo Governorate, Egypt 3Quality Control Manager, Luna for Perfumes and Cosmetics (Lunapac), Egypt *Corresponding author

A B S T R A C T

The levels of PAHs in some Egyptian vegetables (potatoes and spinach) and fruits (apple and guava) that collected from different regions in Cairo were investigated. The PAHs in samples were determined using gas chromatography- . Data indicated that the highest of total PAHs was K e y w o r d s detected in Spinach (8.977 µg/kg), followed by potatoes (6.196 µg/kg), apple (2.867 µg/kg) and guava (2.334 µg/kg). Washing with tap and acetic PAHs, solutions at 1% and 2% showed reduction of PAHs levels in investigated vegetables, vegetables. Washing with tap water, 1% and 2% solution reduced the fruits, amount of total and carcinogenic PAHs in spinach by 4.23 and 5.73%, 54.02 and washing, 66.03% and 74.36 and 79.62%, respectively. The corresponding reduction in case peeling. of potatoes was 17.52 and 11.69%, 72.93 and 90.84% and 87.6 and 98.71%, respectively. Peeling of potatoes reduced the amount of total and carcinogenic PAHs by 93.85 and 93.18%, respectively, while boiling of peeled potatoes reduced total and carcinogenic PAHs by 98.39 and 97.19%, respectively. It could be recommended that careful washing of foodstuffs especially by acidic detergents, peeling process and boiling may be effective in reducing the daily intake of PAHs containing .

Introduction

Polycyclic aromatic hydrocarbons (PAHs) Over 100 PAHs have been identified and are a group of chemicals composed of two occur as complex mixtures, never as or more fused aromatic rings that are formed individual component (ATSDR, 1995). during the incomplete combustion or high- However, only 16 compounds were selected of , oil, gas, as priority pollutants by the wood, fossil fuels, garbage, or other Environmental Protection Agency (USEPA) substances, such as tobacco and charbroiled (Simko, 1991). (Grimmer and Boehnke, 1975).

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USEPA has classified benzo[a], chrysene, dibenz[a,h]anthracene, and benzo[a], benzo[a]fluoranthene, indeno [1,2,3-c,d] pyrene have induced benzo[k]fluoranthene, chrysene, tumors in laboratory animals when they dibenzo[a,h]anthracene, and indeno[1,2,3- breathed these substances in the air, when c,d]pyrene as probable carcinogens they ate them, or when they had long (group B2). The International Agency for periods of skin contact with them. Studies of Research on Cancer (IARC) established that people show that individuals exposed to benzo[a]anthracene and benzo[a]pyrene are PAHs in mixtures through breathing or skin probable human carcinogens, whereas contact for long periods and other benzo[b]fluoranthene, benzo-[j] compounds can also develop cancer fluoranthene, benzo [k] fluoranthene, and (ATSDR, 1995). indenol[1,2,3-c,d] pyrene are possible human carcinogens (Llobet et al., 2006). During the last decades, increasing demand PAHs have been detected in many of food safety has stimulated research products including , potatoes, grain, regarding the risk associated with flour, bread, vegetables, fruits, oils, and consumption of contaminated foods smoked or broiled meat and (Tuteja et (D Mello, 2003). High-performance al., 2011; Zohair, 2006; Bulder et al., 2006). chromatography with fluorescence detection (HPLC-FLD), gas chromatography with Seventy percentages of individuals are mass spectrometry (GC MS), gas exposed to PAHs predominantly from chromatography with flame ionization dietary sources. PAHs are found in detector (GC-FID) and solid phase substantial quantities in some foods, microextraction (SPME) followed by GC depending on the mode of cooking, MS are the most commonly techniques for preservation, and storage (Purcaro et. al, PAHs determination (Kishikawa et al., 2006). Concentration of PAHs in uncooked 2003; Vigeas et al., 2012; Jira, 2004; food may vary from region to another Olatunji et al., 2014; Aguinaga et al., 2007). according to the type of the product and the type and concentration of pollution in this The aim of the present work is to study the region. Vegetables and fruits obtained from levels of polycyclic aromatic hydrocarbons a polluted environment may contain higher (PAHs) in some Egyptian edible vegetables PAHs concentrations than those obtained and fruits from different localities and their from non- polluted environment. Wang and influences by some treatments as washing, Meresz (1982) reported that peeling and boiling. Benzo[a]pyrene, dibenz[a,h]anthracene, and chrysene were detected in vegetables grown Materials and Methods near heavily travelled road. Thus, food may be contaminated by environmental PAHs Chemicals and that are present or during processing as drying, and cooking like grilling, A mixture of 15 polyaromatic reference roasting and frying (Bulder et al., 2006). standards containing acenaphtene, acenaphthylene, anthracene, benzo(a) PAHs can be harmful to human health under anthracene, benzo(a)pyrene, benzo(k) some circumstances. Several of the PAHs, fluoranthene, benzo (ghi) perylene, including benzo [a] anthracene, benzo[a] chrysene, dibenzo (a,h) anthracene, pyrene, benzo [b] fluoranthene, benzo[j fluoranthene, fluorene, indeno (1,2,3,-cd) ]fluoranthene, benzo[k] fluoranthene, pyrene, , pyrene and 2-

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Int.J.Curr.Microbiol.App.Sci (2014) 3(7) 277-293 bromonaphthalene were purchased from sodium sulphate and eluted by Supleco Inc., USA., PAHs working chloride and n-. The eluate was solutions (10 µg/mL) was prepared from a collected and evaporated to dryness by stock solution of PAHs containing 200 rotary evaporator at room temperature. µg/mL. Dichloromethane, n-hexane, , acetonirile (Pestiscan Instrumentation and analysis conditions Chromatography grade), sodium sulphate, (BDH chemicals), florisil The dry eluate sample was dissolved in 1 ( silicate) was obtained from mL n-hexane and injected into a Hewlett Merck, , Acetic acid. Packered Gas Chromatograph 5890 fitted with HP-5 fused silica capillary column (50 Food Samples m x 0.2 mm i.d. x 0.3 µm film thickness) and connected to Hewlett Packered 5970 A total of 78 vegetables samples belonging series mass selective detector. The carrier to two different species (potatoes and gas was helium at a flow rate of 1.0 mL/min. spinach) and 18 fruit samples belonging to The injection port temperature was 275 C two different species (apple and guava) were with electron energy of 70 eV. The randomly collected during the period of quadruple temperature was 280 C. The January 2012 up to March 2012 to instrument was tunned on determine the concentrations of PAHs. The perflorotributylamine (PFTBA). The oven samples were quite representative since they programme was as follows; initial collected from districts where foodstuffs temperature 70 C, continued for 5 min, were scattered throughout the different followed by an increase to 290 C at 3 regions in Cairo. All of the samples were C/min, then finally hold for 30 min. kept in a freezer at 4°C until analysis. Calibration was done using external standards (mixture of 15 compounds). The Quality assurance procedures and mass spectrometer was operated in selective precautions were carried out to ensure monitoring mode using separate to reliability of the results, all materials used identify and confirm compounds. for processing were screened by dilute nitric acid, hot water, chromic acid, acetone and Experimental of PAHs detoxification distilled water for possible removal of PAHs contamination according to the method of PAHs detoxification by washing Tuteja et al. (2011). Samples of vegetables (spinach and Sample preparation, extraction and clean potatoes) were separately washed with tap up water or acetic acid solutions (1% and 2%). The washing procedure was carried out on The different weights of samples were naturally contaminated samples by high homogenized separately and 30 g of the levels of PAHs. fresh homogenate was mixed with 90 g of anhydrous sodium sulphate for extraction PAHs detoxification by peeling according to the method of Zohair (2006) using quick fit soxhelt unit for 24 h with 300 Samples of potatoes were peeled as applied ml hexane: acetone (1:1, v/v) mixture. The at home. The peeling procedure was carried samples were cleaned up using activated out on naturally contaminated samples by florisil (60/100 mesh) and anhydrous high levels of PAHs.

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PAHs detoxification by boiling observed among the different samples collection. Data proved also that 2- Samples of (spinach and potatoes) bromonaphthalene, acenaphthylene, were boiled for 10 min at 100°C on open , fluorene and anthracene were flame. The boiling procedure was carried not detected in spinach or guava samples. In out on naturally contaminated samples by contrast, samples contained high levels of PAHs. acenaphthene, fluorene and anthracene at mean levels of 0.510, 0.271 and 1.470 Recovery µg/kg, respectively. However, acenaphthylene and fluorene were only Recovery results of PAHs from vegetables found in the collected apple samples at mean and fruits samples under investigation values of 0.026 and 0.012 µg/kg, were studied according to the method of respectively. On the other hand, pyrene was Chantara and Sangchan, (2009). The results not detected in spinach samples, but it was showed that the recovery was ranged found in potato, guava and apple samples at between 95 -97%. The average of mean concentration of 0.788, 0.565 and triplicate analysis was calculated for each 0.138 µg/kg, respectively. Regarding to PAHs fluoranthene, it was not detected in potato or guava samples; however, it recorded mean Statistical analysis values of 2.785 and 0.193 µg/kg in spinach and apple samples, respectively. With The data obtained from this study was respect to benzo(k)fluorancene and statistically subjected to analysis of variance benzo(ghi)perylene, data revealed that they (ANOVA) and means separation was by were detected in spinach, guava and apple Snedecor and Cochran (1980). The least samples, while they not detected in potato significant difference (L.S.D) value was (Table 1). The Table 1 shows also that used to determine significant difference indeno(1,2,3-cd)pyrene was not detected in between means and to separate means at (P the samples of potato, guava and apple, 0.05) using SPSS package version 15.0. while it detected in spinach at mean level of 1.129µg/kg. The collected data indicated Results and Discussion that the highest concentration of total PAHs was detected in spinach, while the highest PAHs in some Egyptian vegetables and concentration of total carcinogenic PAHs fruits was detected in spinach. It was noticed from the results that the 3-4 rings PAHs were Concentrations of PAHs in different types of predominates in all samples collection. vegetables (potato and spinach) and fruits (guava and apple) which collected from The most important source of the different locations in Greater Cairo Urban contamination by PAHs is atmospheric Region (GCUR) were determined and data pollution from industrial or motor vehicle presented in Table 1 and illustrated in Fig 1. emission. The mean concentrations of PAHs Data shows that PAHs levels in the samples in different vegetables and fruits under collection are quite variable among the investigation are quite variable. Total and vegetables and fruits samples. Analysis of carcinogenic PAHs in spinach are more than variance revealed that highly significant that present in potato, guava and apple, this differences (P 0.005) of PAHs levels were explained by its greater surface contact to

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Int.J.Curr.Microbiol.App.Sci (2014) 3(7) 277-293 the ambient air during growth. These results be more contaminated than cores. For leafy agree with those reported by Lin and Zhu vegetables, cabbage showed maximum (2005) who showed that PAHs accumulated PAHs (11.6 µg/kg) as compared to the cores from air due to high surface area of tea of fruit vegetables (Ashraf et al., 2013). leaves. Besides, Tuteja et al. (2011) and Bishnoi et al. (2006) reported that leafy In the present study, the ratio of vegetables are found to be more fluoranthene to pyrene in apple shows that contaminated with higher concentration of the incomplete combustion products via PAHs as compared to underground pyrolytic process and this in agreement with vegetables due to their greater surface area the results of Zohair (2006). which is responsible to trap higher concentration of PAHs. Tuteja et al. (2011) Detoxification of PAHs from some showed also that the concentration of lower vegetables by washing molecular weight PAHs compounds was found to be greater than higher molecular In plants and at home, vegetables are weight PAHs in all types of vegetables. conveyed to the water flumes and washing with high sprays. The effect of In the present study the mean total PAHs in washing with tap water and acetic acid vegetable and fruit samples collected from solutions at 1% and 2% on PAHs contents in different locations ranged from 2.334 to contaminated spinach and potatoes were 8.977 µg/kg. Similar results reported by studied and data presented in Table 2 and Zohir (2006) who showed that total PAHs in illustrated in Fig. 2. The results indicated Egyptian vegetables was ranged from 1.22 that washing of spinach generally caused to 12.63 ppb. This indicates that PAHs reduction in total PAHs under investigation levels in uncooked food largely depend on and carcinogenic PAHs compounds. In the origin of the food and can be subjected addition, the results revealed the efficient to regional variations. Ashraf and Salam role of washing with acetic acid solutions at (2012) reported that in the fruit vegetables, 1% and 2% in reduction of PAHs and all the peels were found to be more carcinogenic compounds. Statistical analysis contaminated than cores. However, in leafy proved that significant differences (P 0.05) vegetables, maximum PAHs level was were detected between the different washing shown by cabbage (8.34 µg/kg), which solutions. turned out to be more than any of the cores of fruit vegetables. The results demonstrated that a variation in reduction of PAHs was observed with the Additionally, Greenberg et al., (1990) different washing solutions. These proved that the level of benzo(a)pyrene in differences increased as the levels of acetic kale was in a range of 12.6-48.1 ng/g. acid increased. It was noticed that washing While, Kazerouni et al., (2001) revealed that with 2% acetic acid decreased the levels of the highest level of benzo(a)pyrene was phenanthrene, fluoranthene, chrysene, found in collards and kale with levels of benzo(a)anthracene, benzo(k)fluoranthene, 0.48 and 0.47 ng/g, respectively. These benzo(a)pyrene, dibenz(a,h)anthracene, levels were higher than those detected in the benzo(ghi)perylene and indeno(1,2,3- present investigation. While for the fruit cd)pyrene more efficiently than 1% acetic vegetables (like tomato, cucumber, eggplant, acid and more than with tap water. and bitter gourd) all the peels were found to

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PAHs contents of potatoes as affected by Some crops as potatoes can be peeled with washing (tap water and acetic acid solutions different methods as the lye, mechanically 1% and 2%) were studied (Table 3 and Fig. and by hands. Thus, it could be reasonable 3). Data demonstrated that the different to expect that such operations may cause procedures of washing led to reduction in some reduction of PAHs content in total and carcinogenic PAHs levels. The contaminated samples. The roles of peeling results showed that washing with tap water on PAHs with or without washing were only caused a reduction in total PAHs under investigated and the results are presented in investigation and carcinogenic PAHs Table 4 and illustrated in Fig. 4. The results compounds by 17.52% and 11.69%, demonstrated the efficient role of peeling respectively. process in reduction of PAHs from contaminated samples. The percentage of In addition, the results revealed the efficient total and carcinogenic PAHs removed from role of washing with acetic acid solutions at potatoes was 93.85 and 93.18%, 1% and 2% in reduction of PAHs and respectively. These percentages were carcinogenic compounds whichwere 72.93% increased to 96.44 and 98.82%, respectively and 90.84%, in this order at 1% acetic acid when peeling process was followed by solution. The corresponding values with 2% washing with tap water. Peeling of potatoes acetic acid solution were 87.6% and followed by washing with tap water 98.71%, respectively. Statistical analysis decreased the levels of acenaphthene, proved that significant differences (P fluorene, anthracene, phenanthrene, pyrene, 0.005) were detected between the different chrysene, benzo(a)anthracene, washing solutions. These differences benzo(a)pyrene and dibenz(a,h)anthracene increased as the levels of acetic acid more efficiently than peeling alone. The increased. Otherwise, the results results proved that most PAHs contaminants demonstrated that, reduction of PAHs was were concentrated on the surface of the food observed with the different compounds due and not completely penetrated inside the to the different washing treatments. Washing food. Therefore, peeling and washing reduce with tap water reduced the levels of the values of PAHs in vegetables and fruits. acenaphthene, fluorene, anthracene, Wang and Meresz (1981) analyzed onions, phenanthrene, pyrene, chrysene, beets, tomatoes, and for 17 PAHs, and benzo(a)anthracene, benzo(a)pyrene and found also that most of the PAHs dibenz(a,h)anthracene less than washing contamination was in the peels. In addition, with 1% and 2% acetic acid solutions. Vega et al. (2012) reported that in crops (apple and cactus stem), the values of PAHs It could be observed that washing with were high over the surfaces for high and acetic acid is more efficient than tap water in intermediate molecular weights, but the removal PAHs and washing with 2% was values declines with adequate washing or more efficient than 1% acetic acid which peeling. The waxy surface of vegetables and means that decreasing pH led to more fruits can concentrate low molecular mass reduction in PAHs levels. These results were PAHs mainly through surface adsorption. in agreement with Pawar et al. (2013) study The concentrations of PAHs are generally who reported that the second greatest rate of greater on plant surface (peel, outer leaves) PAHs reduction was found at pH 6.0. than on internal tissue. Consequently, washing or peeling may remove a significant Detoxification of PAHs from some proportion of the total PAHs. vegetables by Peeling 282

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Table.1 Levels of PAHs in some Egyptian vegetable and fruit samples collected from Greater Cairo Urban Region (GCUR) Mean concentration (µg/kg) ± SD PAHs Compounds Potato spinach Guava Apple 2-Bromonaphthalene ND ND ND ND Acenaphthylene ND ND ND 0.026± 0.01 0.510 ± Acenaphthene ND ND ND 0.03 0.271 ± Fluorene ND ND 0.012±0.01 0.02 1.470 ± Anthracene ND ND ND 0.18 2.326±0.1 0.337±0.0 Phenanthrene 0.800±0.06 0.475±0.05 7 2 0.565±0.0 Pyrene 0.788±0.08 ND 0.138±0.01 4 2.785±0.2 Fluoranthene ND ND 0.193±0.02 1 0.197±0.0 0.230±0.0 Chrysene** 0.525±0.04 0.250±0.01 2 2 0.599±0.0 0.631±0.0 Benzo(a)anthracene* 1.337±0.09 0.705±0.08 4 3 Benzo(k)fluorancene* 0.602±0.0 0.139±0.0 ND 0.594±0.03 * 3 1 0.245±0.0 0.193±0.0 Benzo(a)pyrene* 0.174±0.02 0.093±0.01 1 2 Dibenz(a,h)anthracene 0.810±0.0 0.321±0.01 ND ND * 7 0.284±0.0 0.239±0.0 Benzo(ghi)perylene ND 0.381±0.01 1 1 Indeno(1,2,3,- 1.129±0.0 ND ND ND cd)pyrene** 9 Total PAHs 6.196 8.977 2.334 2.867 Total Carcinogenic 2.357 3.582 1.193 1.642 PAHs ND: Not detectable. SD: Standard Deviation * IARC Group 2a: Probably carcinogenic to human according to IARC. ** IARC group 2b: Possibly carcinogenic to according to IARC. * & ** classified as carcinogenic to human by US EPA and WHO/IPCS.

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Fig.1. Levels of PAHs in some Egyptian vegetable and fruit samples

Fig.2 Mean levels (µg/kg) of PAHs and reduction percentage in spinach as affected by washing using tap water and acetic acid solutions (1 and 2%).

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Table.2 Mean levels (µg/kg) of PAHs and reduction percentages in spinach as affected by washing using tap water and acetic acid solutions (1% and 2%).

Mean concentration (µg/kg) ± SD PAHs Compounds washing with washing with washing with 2% Control tap water 1% acetic acid acetic acid 2-Bromonaphthalene ND ND ND ND Acenaphthylene ND ND ND ND Acenaphthene ND ND ND ND Fluorene ND ND ND ND Anthracene ND ND ND ND 3.071 ± 2.956 ± 0.18 1.918 ± 0.15 1.055 ± 0.09 Phenanthrene 0.23 (3.74%)*** (37.54%) (65.65%) Pyrene ND ND ND ND 3.872 ± 3.780 ± 0.25 2.013 ± 0.18 1.060 ± 0.11 Fluoranthene 0.32 (2.38%) (48.01%) (72.62%) 0.192 ± 0.171 ± 0.02 0.094 ± 0.01 ND Chrysene** 0.01 (10.94%) (51.04%) (100%) 0.804 ± 0.724 ± 0.05 0.075 ± 0.01 0.039 ± 0.01 Benzo(a)anthracene* 0.06 (9.95%) (90.67%) (95.05%) 0.837 ± 0.798 ± 0.07 ND ND Benzo(k)fluorancene** 0.07 (4.66%) (100%) (100%) 0.368 ± 0.280 ± 0.01 0.113 ± 0.01 0.039 ± 0.01 Benzo(a)pyrene* 0.02 (23.91%) (69.29%) (89.40%) Dibenz(a,h)anthracene 0.803 ± 0.761 ± 0.05 0.321 ± 0.02 0.090 ± 0.01 * 0.06 (5.23%) (60.02%) (88.79%) 0.321 ± 0.293 ± 0.03 ND ND Benzo(ghi)perylene 0.29 (8.72%) (100%) (100%) Indeno(1,2,3,- 1.809 ± 1.803 ± 0.15 1.019 ± 0.09 0.813 ± 0.07 cd)pyrene** 0.21 (0.33%) (43.67%) (55.06%) 11.566 5.553 3.096 Total PAHs 12.077 (4.23%) (54.02%) (74.36%) Total carcinogenic 4.537 1.622 0.981 4.813 PAHs (5.73%) (66.30%) (79.62%) ND: Not detectable. SD: Standard Deviation ***: Reduction percentage * IARC Group 2a: Probably carcinogenic to human according to IARC. ** IARC group 2b: Possibly carcinogenic to humans according to IARC. * & ** classified as carcinogenic to human by US EPA and WHO/IPCS.

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Table.3 Mean levels (µg/kg) of PAHs and their reduction percentage in potatoes as affected by washing using tap water and acetic acid solutions (1% and 2%).

Mean concentration (µg/kg) ± SD PAHs compounds washing with washing with washing with Control tap water 1% acetic acid 2% acetic acid 2-Bromonaphthalene ND ND ND ND Acenaphthylene ND ND ND ND 0.960 ± 0.05 0.610 ± 0.02 0.190 ± 0.02 Acenaphthene 1.091 ± 0.09 (12.01%) (44.09%) (82.58%) 0.405 ± 0.03 ND ND Fluorene 0.895 ± 0.07 (54.75%) (100%) (100%) 1.860 ± 0.17 1.010 ± 0.15 0.690 ± 0.07 Anthracene 2.091 ± 0.21 (11.05%)*** (51.7%) (67%) 1.027 ± 0.09 0.813 ± 0.08 0.314 ± 0.04 Phenanthrene 1.189 ± 0.13 (13.62%) (31.62%) (73.59%) 0.968 ± 0.08 ND ND Pyrene 1.320 ± 0.09 (26.67%) (100%) (100%) Fluoranthene ND ND ND ND 0.581 ± 0.06 0.031 ± 0.01 0.022 ± 0.01 Chrysene** 0.769 ± 0.06 (24.45%) (95.97%) (97.14%) 1.604 ± 0.13 0.029 ± 0.01 ND Benzo(a)anthracene* 1.697 ± 0.16 (5.48%) (98.24%) (100%) Benzo(k)fluorancene** ND ND ND ND 0.397 ± 0.04 0.046 ± 0.01 0.025 ± 0.01 Benzo(a)pyrene* 0.473 ± 0.05 (16.07%) (90.27%) (94.71%) 0.627 ± 0.05 0.227 ± 0.03 ND Dibenz(a,h)anthracene* 0.695 ± 0.07 (9.78%) (67.34%) (100%) Benzo(ghi)perylene ND ND ND ND Indeno(1,2,3,-cd)pyrene** ND ND ND ND 8.429 2.766 1.241 Total PAHs 10.220 (17.52%) (72.93%) (87.6%) 3.209 0.333 0.047 Total carcinogenic PAHs 3.634 (11.69%) (90.84%) (98.71%) ND: Not detectable. SD: Standard Deviation *** Reduction percentage * IARC Group 2a: Probably carcinogenic to human according to IARC. ** IARC group 2b: Possibly carcinogenic to humans according to IARC. * & ** classified as carcinogenic to human by US EPA and WHO/IPCS.

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Table.4 Mean levels (µg/kg) of PAHs and reduction percentage in potatoes as affected by peeling and washing with tap water

Mean concentration (µg/kg) ± SD PAHs compounds Washing of peeled Control Peeled potatoes potatoes by tap water 2-Bromonaphthalene ND ND ND Acenaphthylene ND ND ND Acenaphthene 0.030 ± 0.01 0.019 ± 0.01 1.091 ± 0.09 (97.25%) (98.26%) Fluorene ND ND 0.895 ± 0.07 (100%) *** (100%) Anthracene 0.210 ± 0.03 0.190 ± 0.03 2.091 ± 0.22 (89.96%) (90.91%) Phenanthrene 0.065 ± 0.008 0.048 ± 0.01 1.189 ± 0.13 (94.53%) (95.96%) Pyrene 0.076 ± 0.009 0.064 ± 0.02 1.320 ± 0.09 (94.24%) (95.15%) Fluoranthene ND ND ND Chrysene** 0.057 ± 0.006 ND 0.769 ± 0.06 (92.59%) (100%) Benzo(a)anthracene* 0.075 ± 0.009 ND 1.697 ± 0.16 (95.58%) (100%) Benzo(k)fluorancene** ND ND ND Benzo(a)pyrene* 0.017 ± 0.02 0.013 ± 0.01 0.473 ± 0.05 (96.41%) (97.25%) Dibenz(a,h)anthracene* 0.099 ± 0.01 0.030 ± 0.01 0.695 ± 0.07 (85.76%) (95.68%) Benzo(ghi)perylene ND ND ND Indeno(1,2,3,- ND ND ND cd)pyrene** Total PAHs 0.629 0.364 10.220 (93.85%) (96.44%) Total carcinogenic 0.248 0.043 3.634 PAHs (93.18%) (98.82%) ND: Not detectable. SD: Standard Deviation ***: Reduction percentage * IARC Group 2a: Probably carcinogenic to human according to IARC. ** IARC group 2b: Possibly carcinogenic to humans according to IARC. * & ** classified as carcinogenic to human by US EPA and WHO/IPCS.

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Fig.3 Mean levels (µg/kg) of PAHs and their reduction percentage in potatoes as affected by washing using tap water and acetic acid solutions (1% and 2%)

Total PAHs 12 Total carcinogenic PAHs

10

n 8 o i t a r t ) n g 6 e k c / g n µ o ( C

s 4 H A P 2

0 Washing control tap water1%a cetic aci2d% a cetic acid

Fig.4 Mean levels (µg/kg) of PAHs and reduction percentage in potatoes as affected by peeling and washing with tap water

Total PAHs 12 Total carcinogenic 10 PAHs n

o 8 i t a r t ) n 6g e k c / g n µ o (

C 4 s H A

P 2

0 Peelin control peeled potato washing of peeled potato

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Table.5 Mean levels (µg/kg) of PAHs and reduction percentage in spinach as affected by boiling

Mean concentration (µg/kg) ± SD PAHs Compounds Control Boiling 2-Bromonaphthalene ND ND Acenaphthylene ND ND Acenaphthene ND ND Fluorene ND ND Anthracene ND ND 0.809 ± 0.09 Phenanthrene 3.071 ± 0.23 (73.66%)*** Pyrene ND ND 0.690 ± 0.05 Fluoranthene 3.872 ± 0.32 (82.18%) 0.018 ± 0.01 Chrysene** 0.192 ± 0.02 (90.63%) ND Benzo(a)anthracene* 0.804 ± 0.06 (100%) 0.399 ± 0.04 Benzo(k)fluorancene** 0.837 ± 0.07 (52.33%) 0.243 ± 0.03 Benzo(a)pyrene* 0.368 ± 0.04 (33.97%) 0.006 ± 0.01 Dibenz(a,h)anthracene* 0.803 ± 0.06 (99.25%) 0.127 ± 0.02 Benzo(ghi)perylene 0.321 ± 0.29 (60.44%) Indeno(1,2,3,- ND 1.809 ± 0.21 cd)pyrene** (100%) 2.292 Total PAHs 12.077 (81.02%) 0.666 Total carcinogenic PAHs 4.813 (86.16%) ND: Not detectable. SD: Standard Deviation *** Reduction percentage * IARC Group 2a: Probably carcinogenic to human according to IARC. ** IARC group 2b: Possibly carcinogenic to humans according to IARC. * & ** classified as carcinogenic to human by US EPA and WHO/IPCS.

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Table.6 Mean levels (µg/kg) of PAHs and reduction percentage in potatoes as affected by boiling

Mean concentration (µg/kg) ± SD Extract of boiling Boiled Extract of PAHs compounds Boiled of Control water of shelled peeled boiling water of shelled potato potato potato peeled potato 2-Bromonaphthalene ND ND ND ND ND Acenaphthylene ND ND ND ND ND 1.091 ± 0.300 ± 0.05 0.419 ± 0.03 ND ND Acenaphthene 0.09 (72.50%) (91.59%)*** (100%) (100%) 0.895 ± ND ND ND ND Fluorene 0.07 (100%) (100%) (100%) (100%) 0.030 ± 2.091 ± 0.400 ± 0.03 0.890 ± 0.09 ND Anthracene 0.01 0.21 (80.87%) (57.44%) (100%) (98.57%) 0.033 ± 1.189 ± 0.102 ± 0.01 0.591 ± 0.06 ND Phenanthrene 0.01 0.13 (91.42%) (50.29%) (100%) (97.22%) 1.320 ± 0.022 ± 0.01 ND ND ND Pyrene 0.09 (98.33%) (100%) (100%) (100%) Fluoranthene ND ND ND ND ND 0.102 ± 0.769 ± 0.279 ± 0.03 ND ND Chrysene** 0.02 0.06 (63.72%) (100%) (100%) (86.74%) 1.697 ± ND ND ND ND Benzo(a)anthracene* 0.16 (100%) (100%) (100%) (100%) Benzo(k)fluorancene** ND ND ND ND ND 0.473 ± 0.017 ± 0.01 0.018 ± 0.01 ND ND Benzo(a)pyrene* 0.05 (96.41%) (96.19%) (100%) (100%) Dibenz(a,h)anthrac- 0.695 ± 0.130 ± 0.02 ND ND ND ene* 0.07 (81.29%) (100%) (100%) (100%) Benzo(ghi)perylene ND ND ND ND ND Indeno(1,2,3,- ND ND ND ND ND cd)pyrene** 1.250 1.918 0.165 ND Total 10.220 (87.77%) (81.23%) (98.39%) (100%) Total carcinogenic 0.426 0.018 0.102 ND 3.634 PAHs (88.28%) (99.50%) (97.19%) (100%) ND: Not detectable. SD: Standard Deviation ***: Reduction percentage * IARC Group 2a: Probably carcinogenic to human according to IARC. ** IARC group 2b: Possibly carcinogenic to humans according to IARC. * & ** classified as carcinogenic to human by US EPA and WHO/IPCS

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Particle bound high molecular mass PAHs phenanthrene, pyrene, chrysene, which remain on the surface are easily benzo(a)anthracene, benzo(a)pyrene and washed off whereas low molecular mass dibenz(a,h)anthracene. compounds which are in the vapour phase can penetrate the waxy layer of fruits and The present investigation proved that vegetables and are less efficiently removed PAHs levels in street vended foodstuffs by washing (European Commission, were quite variable; hence, there is a need 2002). for concerted efforts to improve the safety of street vended foods. The results showed Detoxification of PAHs from some the efficient role of washing with tap water vegetables by Boiling in the reduction of PAHs from investigated foodstuffs. This reduction Some Foods like vegetables may be increased with acetic acid solutions at cooked with different methods at home or different levels. Also, peeling process was plants. Each method has an important an efficient role for reducing PAHs effect on PAHs levels in food. Boiling is a content from the contaminated vegetables. major method of home cooking which is This reduction is due to that, peeling very important for vegetables which helps process removed the adhered PAHs with to remove PAHs from leafy or ground the skin. Boiling process proved an vegetables. The role of boiling cooking important role on reducing PAHs levels process of spinach for 10 min at 100 °C from the contaminated vegetables. It could was investigated and data are presented in be recommended that careful washing of Table 5. The results demonstrated the vegetables especially by acidic detergents efficient role of boiling process in and peeling process could be effective in reduction percentage of PAHs from reducing the daily intake of PAHs contaminated samples. containing foods. The percentage of total and carcinogenic References PAHs removed from spinach was 81.02 and 86.16%, respectively. Boiling Aguinaga N., Campillo, N., Vinas, P., decreased the levels of phenanthrene, Hernandez-Cordoba, M., 2007. fluoranthene, chrysene, Determination of 16 polycyclic benzo(a)anthracene, benzo aromatic hydrocarbons in milk and (k)fluoranthene, benzo(a)pyrene, dibenz related products using solid-phase (a,h)anthracene benzo(ghi)perylene and microextraction coupled to gas indeno(1,2,3-cd)pyrene. Also, the results chromatography mass spectrometry, in Table 6 proved the efficient role of Anal. Chem. Acta 596, 285 290. boiling process on PAHs of shelled or Ashraf, M. W. and Salam, A. 2012. peeled potatoes. The comparative Polycyclic Aromatic Hydrocarbons percentages of total and carcinogenic (PAHs) in Vegetables and Fruits PAHs removed from shelled potatoes were Produced in Saudi Arabia. Bull 87.77 and 88.28%, respectively. These Environ Contam. Toxicol. 88: 543 percentages were increased to 98.39 and 547. 97.19%, respectively when peeling Ashraf, M. W.; Iqleem, S. H.; Amber R. process followed by boiling. Boiling of Solangi, R. A. and Qureshi, U. A. potatoes decreased the levels of 2013. Distribution and Risk acenaphthene, fluorene, anthracene, Assessment of Polycyclic Aromatic

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