67 © Adama Science & Technology University https://ejssd.astu.edu.et Ethiopian Journal of Science and Sustainable Development (EJSSD) p-ISSN 1998-0531 Volume 5 (2), 2018 Engineering and Chemical Characterisation of Natural Bitumen Resources from Nigeria Ademila O.* and Ojo F. G. Department of Earth Sciences, Adekunle Ajasin University, Akungba-Akoko, Nigeria, *corresponding author, e-mail: omowumi.ademila@aaua.edu.ng Abstract Engineering and chemical properties of bitumen in Agbabu were evaluated for their suitability in road pavement construction. Raw samples of natural bitumen were collected in Agbagbu, Mile 2 and Mulekangbo, Ondo State, Nigeria. The engineering properties analysis involves bitumen penetration, flash and fire points, water content, loss on heating and specific gravity. Chemical evaluation includes analysis of heavy metals by the use of Atomic Absorption Spectroscopy (AAS) and analysis of Poly Aromatic Hydrocarbons (PAHs) using Gas Chromatography/Mass Spectrometer (GCMS). Agbabu and Mulekangbo bitumen samples fall within 200/300 penetration grade, classified as temperature susceptible bitumen, while samples of Mile 2 fall within 100/150 penetration grade, classified as conventional paving bitumen. Thus, Agbabu and Mulekangbo bitumen can be used in temperate regions of the world, while Mile 2 bitumen can best be applied in tropics, after upgrading by modifiers. The results of AAS indicate a high concentration of iron in the samples in the decreasing order of Fe Zn > Cu >Mn>Pb. The concentration of iron is the highest (8905 mg/kg) while Pb is the lowest (1.00 mg/kg). The concentration of heavy metals in the samples shows slight similarities with the work obtained by Bakare et al. (2015). The exceptional high concentration of iron for sample collected from Mile 2 (Sample A) may be as a result of the presence of the sample in waterlogged area. The regular occurrences of the high rainfall and flooding have contributed to the leaching of most trace elements and this has contributed to the increased level of these metals. The relatively high levels of Fe, Pb and Ni observed in the result of some of the samples may be associated with the bitumen sample obtained from the marine environment. The presence of Manganese (Mn) and Lead (Pb) in sample from Mile 2 and Mulekangbo, may pose environmental hazard and catalytic poisons during the refining of the bitumen. The differences that occur with other studies may be due to the fact that previous studies of Ipinmoroti and Aiyesanmi (2001) and Adebiyi and Omole (2007) were conducted on bituminous sand while the present study used flow bitumen obtained from Ademila O. & Ojo F.G. EJSSD, V 5 (2), 2018 77 © Adama Science & Technology University https://ejssd.astu.edu.et observatory wells. During the process of extraction of bitumen from bituminous sand, some of the metal contents might have been leached out from the sample, hence, the relatively lower concentrations of some metals reported. It is observed that work has not been carried on Mulekangbo observatory well. The result of Mulekangbo bitumen sample indicates high concentration of Fe, Mn, Pb, and Zn. These heavy metals when present in high quantity cause environmental hazards. The exceptionally high concentration of heavy metals may be due to contaminations during collection of the sample, because the sample was found in contact with biogenic materials and with water emanated from the well beneath. Table 3: Concentrations of trace metals (ppm) in bitumen samples Sample locations Heavy metals (mg/kg) Agbabu Mile 2 Mulekangbo Zn 16.00 48.00 36.00 Cu 14.00 39.00 35.00 Pb 1.00 7.00 5.00 Ni ND 1.01 ND Cd ND ND ND Mn ND 37.00 27.00 Fe 509.00 8905.00 8605.00 ND: not detected 5.3. Polycyclic Aromatic Hydrocarbons The asphalt binders (or bitumen) release fumes which have PAHs. The PAHs belong to a class of complex chemical compound whose structure is in the form of linked benzene rings, and is widely distributed in the atmosphere. However, some PAHs are considered to have carcinogenic and/or mutagenic potential. Bitumen emissions, generated upon heating, may contain two-ring to seven-ring PAHs, several of which are mutagenic and carcinogenic (IARC, 2011). In mammalian cells, exposure to bitumen emissions or their condensates produced mutagenic intermediates and DNA adducts. Analysis of the sample from Mile 2 contains wide spectrum of PAHs (Figure 3). In the sample, 37 PAHs have been found, with Hexadecane showing a higher percentage of 6.56%, others like Phenanthrene, Naphthalene and its derivatives show lower percentage. The United States Environmental Protection Agency (USEPA, 2000), ranked sixteen PAHs as priority in relation to health and the environment: Naphthalene (Na), Acenaphthalene (Ac), Acenaphthene (Ace), Fluorene (Flu), Phenanthrene (Ph), Anthracene (An), Pyrene (Py), Chrysene (Ch), Fluoranthene (FL), Benzo [a] anthracene (BaA), Benzo [b] fluoranthene (BbF), Benzo [k] fluoranthene (BKF), Benzo [a] pyrene (BaP), Dibenzo [a, h] anthracene (DA), Benzo Ademila O. & Ojo F.G. EJSSD, V 5 (2), 2018 78 © Adama Science & Technology University https://ejssd.astu.edu.et [g, h, i] perylene (BPE) and Indeno [1,2,3-c, d] pyrene (IP). Possible long-term damage caused by chronic health hazard has diverted more attention to PAHs. According to WHO (1998), apart from PAHs, several other substances potentially harmful to health are asphaltenes, straight and branched aliphatic hydrocarbons, naphthene aromatics and resins. From the analysis of Agbabu bitumen sample, Duodecane, ethyl ester shows a wide spectrum (Fig. 4) and the presence of benzene (target) ranged from 1.16 to 2.57%. Spectrum of PAHs values of bitumen sample collected at Mulekangbo is shown in Fig. 5. The result of PAHs from bitumen sample collected at Mulekangbo indicates higher amount of Pyrene, and a considerable high amount of the entire target PAHs like Chrysene, Fluorene, Anthracene, Phenanthrene, Triphenylene and Fluoranthrene, but Triphenylene, Benz [a] anthracene, and Cyclohexane are negligible. The effects of PAHs present in Mulekangbo bitumen sample are considered to have carcinogenic and/or mutagenic potential. Exposure to these compounds through inhalation or even absorption through the skin during application to streets and roads can cause skin cancer (Gasthauer et al., 2007). The emissions generated during the production and application of the bitumen from this location would pose health and environmental risk to those involved. Also, these PAHs can leach into the environment through the degradation of the road surface and contaminate water bodies. When bitumen is applied during mixing in asphalt binders, it is usually handled at elevated temperatures, so trace amounts of PAHs may occur in the hot bitumen fume and cause cancers risk to the workers handling the mixing. Figure 3. Spectrum of PAHs values of bitumen sample collected at Mile 2. Ademila O. & Ojo F.G. EJSSD, V 5 (2), 2018 79 © Adama Science & Technology University https://ejssd.astu.edu.et Figure 4. Spectrum of PAHs values of bitumen sample collected at Agbabu. Figure 5. Spectrum of PAHs values of bitumen sample collected at Mulekangbo 6. Conclusion The engineering and chemical properties of natural bitumen samples collected from Agbabu and its environs have been determined using standard methods. The water content of bitumen Ademila O. & Ojo F.G. EJSSD, V 5 (2), 2018 80 © Adama Science & Technology University https://ejssd.astu.edu.et and loss on heating of the samples in the locations are greater than the recommended values of 0.2% and 1 max respectively. The specific gravity of the samples is below the standard value of 1.01 for bitumen of good grade. From the penetration values, the bitumen are classified into two grades. Agbabu and Mulekangbo bitumen samples are classified as temperature susceptible bitumen while, Mile 2 (sample A and B) are classified as conventional paving bitumen. Mile 2 bitumen can be applied successfully in road construction in the tropics, but this can only be achieved after they must have been upgraded. The AAS test carried out showed that Agbabu, Mile 2 and Mulekangbo have a low concentration of heavy metals except for the high concentration of iron. However, low concentrations of lead and nickel in all the samples may pose environmental hazard and catalytic poisons during the refining of the bitumen. The GCMS revealed high percentage of PAHs in the bitumen sample collected from Mulekangbo and the targets PAHs like Pyrene, Anthracene, Fluorene, etc. are carcinogenic and mutagenic in nature. Exposure to these target PAHs during application to streets and roads through inhalation and absorption through the skin tend to pose health hazards. Therefore, exploitation of Mulekangbo bitumen must undergo the primary bitumen refining process “distillation” in order to remove the PAHs from the bitumen. The percentage of targets PAHs like Naphthalene in the samples collected from Agbabu and Mile 2 are low with no Pyrene, Anthracene and Fluorene. 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