TABLE OF CONTENT DECLARATION ii
CERTIFICATION……………………………………………………………………………………….. iii
DEDICATION……………………………………………………………………………………………… iv
ACKNOWLEDGEMENTS…………………………………………………………………………… v
LIST OF FIGURES……………………………………………………………………………………. viii
LIST OF PLATES………………………………………………………………………………………… ix
ABSTRACT…………………………………………………………………………………………………. xi
CHAPTER ONE……………………………………………………………………………………………. 1
INTRODUCTION…………………………………………………………………………………………. 1
- Background of Study……………………………………………………………………….. 1
CHAPTER TWO…………………………………………………………………………………………… 7
LITERATURE REVIEW……………………………………………………………………………… 7
- Polycyclic Aromatic Hydrocarbons (PAHs)……………………………………….. 7
CHAPTER THREE…………………………………………………………………………………….. 30
RESEARCH METHODOLOGY…………………………………………………………………. 30
CHAPTER FOUR……………………………………………………………………………………….. 39
RESULTS AND DISCUSSION……………………………………………………………………. 39
- Result…………………………………………………………………………………………….. 39
CHAPTER FIVE…………………………………………………………………………………………. 43
CONCLUSION AND RECOMMENDATION……………………………………………… 43
REFERENCES……………………………………………………………………………………………. 45
APPENDIX………………………………………………………….. Error! Bookmark not defined.
LIST OF FIGURES
Figure 2.1: Molecular arrangement of the polycyclic aromatic hydrocarbons……… 9 Figure 2.2: The most commonly analyzed polycyclic aromatic hydrocarbons (PAHs)…………………. 10
Figure 2.3: Natural and anthropogenic sources of PAHs……………………………………. 14
Figure 2.4: PAHs dispersion through air, terrestrial and aquatic environments………. 16
Figure 2.5: Removal of PAHs from atmosphere by either dry deposition or wet deposition 29
LIST OF PLATES
Plate 3.1: Soil Samples……………………………………………………………………………………. 31
Plate 3.2: Soxhlet Apparatus extracting POPs from soil sample………………………….. 33
Plate 3.3: Silica Column…………………………………………………………………………………. 34
Plate 3.4: Concentration of PAHs by evaporation……………………………………………… 37
Plate 3.5 GC- MS machine used for the analysis……………………………………………… 38
LIST OF TABLES
Table 4.1: Concentration of PAHs in Sample 1………………………………………….. 40
Table 4.2 Concentration of PAHs in Sample 2………………………………………….. 40
Table 4.3: Total concentration of PAHs in sample 3…………………………………… 41
Table 4.4: Total concentration of PAHs in sample 2…………………………………… 41
ABSTRACT
This work covers the determination of PAHs in soil samples around selected ABUAD power generators. The PAHs in the soil samples where extracted in the laboratory using Soxhlet extraction method. Samples where finally concentrated and analyzed using Gas Chromatography and Mass Spectrometry (GC-MS).
The total concentration of PAHs in sample one was 10.6186mg/g and in sample 2 was 18.9826mg/g. Naphthalene had the highest concentration in sample 1, it was 2.1016mg/g. Naphthalene, -methyl had the highest concentration in sample 2, it was 7.9991mg/g
Indene, octahydro had the lowest concentration in sample 1, it was 8.8861mg/g. Indene,
-dihydro- -dimethyl had the lowest concentration in sample 2, it was 0.366mg/g.
It could be assumed that the main source of PAHs in these soil samples analysed are were processes related to fossil fuel combustion.
CHAPTER ONE INTRODUCTION
Background of Study
Polycyclic Aromatic Hydrocarbons refers to a large class of organic compounds which contains two or more fused aromatic rings made up of carbon and hydrogen atoms. PAHs have the following general characteristics common to them; high melting and boiling points, low vapour pressure and very low water solubility which tends to decrease with increasing molecular mass (Ahland and Mertens, 1980). Most of the PAHs with low vapour pressure in the air are adsorbed on particles. When dissolved in water or adsorbed on particulate matter, PAHs can undergo photodecomposition when exposed to ultraviolet light from solar radiation. In the atmosphere, PAHs can react with pollutants such as ozone, nitrogen oxides and sulfur dioxide, yielding diones, nitro- and dinitro-PAHs, and sulfonic acids, respectively. PAHs may also be degraded by some microorganisms in the soil (WHO, 1987; USDHHS, 1994).
PAHs are important priority organic pollutants. They may be released during incomplete combustion or pyrolysis of organic matter. This is a major source of human exposure. PAHs emanate primarily as combustion products from vehicle and generator emissions, coal and oil burning plants. They are conveyed by rainfall into the aquatic environment after being absorbed onto smoke particles settling in all kinds of surfaces. (Brookes and Lawley, 1964).
Toxicological studies have shown that some of these PAHs have the potential for tetratogenesis or carcinogenesis in human beings. As a result of their highly hazardous nature, they are monitored in waste waters, soils and atmosphere. Sensitive
detection and accurate reproducible quantification of organics is very important in minimizing the health risks of PAHs. (Larsson, 1982).
PAHs are formed mainly as a result of pyrolytic processes, especially the incomplete combustion of organic materials during industrial and other human activities, such as processing of coal and crude oil, combustion of natural gas, including for heating, combustion of refuse, vehicle traffic, cooking and tobacco smoking, as well as in natural processes such as carbonization. There are several hundred PAHs; the best known is benzo[a]pyrene (BaP). In addition a number of heterocyclic aromatic compounds (e.g. carbazole and acridine), as well as nitro-PAHs, can be generated by incomplete combustion (WHO, 1987).
The emissions of BaP into the air from several sources in the Federal Republic of Germany in 1981 were estimated to amount to 18 tonnes: about 30% was caused by coke production, 56% by heating with coal, 13% by motor vehicles and less than 0.5% by the combustion of heating oil and coal-fired power generation. Other BaP sources were not taken into consideration (WHO, 1987). However, the present contributions from the different important sources, such as residential heating (coal, wood, oil), vehicle exhausts, industrial power generation, incinerators, the production of coal tar, coke and asphalt, and petroleum catalytic cracking, are very difficult to estimate. These figures may also vary considerably from country to country. In the USA, the residential burning of wood is now regarded as the largest source of PAHs (USDHHS, 1994). Stationary sources account for a high percentage of total annual PAH emissions. However, in urban or suburban areas, mobile sources are additional major contributors to PAH release to the atmosphere (Baek et al., 1991).
Atmospheric PAHs are continuously deposited to the earth by dry or wet deposition processes. Some of these PAHs are from nearby sources, such as automotive
or generators exhaust. Other PAHs are from more distant sources and have been carried various distances through the air. About 500 PAHs and related compounds have been detected in the air, but most measurements have been made on BaP. Data obtained prior to the mid-1970s may not be comparable with later data because of different sampling and analytical procedures (WHO, 1987). The natural background level of BaP may be nearly zero. In the USA in the 1970s, the annual average value of BaP in urban areas without coke ovens was less than 1 ng/m3 and in other cities between 1 and 5 ng/m3. In several European cities in the 1960s, the annual average concentration of BaP was higher than 100 ng/m3 (WHO, 1987). In most developed countries BaP concentrations have decreased substantially in the last 30 years. Thus PAH levels lower by a factor of 5 to 10 than those in 1976 were reported for a traffic tunnel in Baltimore and for ambient air in London in the second half of the 1980s (Baek et al., 1991). The declines were attributed to the increased use of catalytic converters in motor vehicles, a reduction in coal and open burning with a movement to oil and natural gas as energy sources, and improved combustion technology. PAH emissions from open burning, especially coal, have been declining in many developed countries as a result of efforts to control smoke emissions (Baek et al., 1991). In 1990, a German study found BaP concentrations of below 1 ng/m3 at monitoring stations not affected by emission sources, from 1.77–3.15 ng/m3 at stations close to traffic, and 2.88–4.19 ng/m3 at stations with traffic and additional industrial emission sources. The annual (1989-1990) average concentration of BaP close to traffic in the Rhine-Ruhr area was reported to be 3–6 ng/m3 (Pfeffer, 1994). In Copenhagen, the mean BaP concentration (January to March 1992) at a station in a busy street was found to be 4.4 ng/m3 (Nielsen et al., 1995).
Additional contributions from tobacco smoking and the use of unvented heating sources can increase PAH concentrations in indoor air and, in certain cases, PAHs can
increase to very high levels indoors (Mumford et al., 1991 and Maroni et al., 1995). BaP levels of 14.7 μg/m3 were found in Chinese (Xuan Wei) homes burning smoky coal (Mumford et al., 1987). In India, the BaP concentration was reported to average about 4 μg/m3 during cooking with biomass fuel (WHO, 1987). Very high concentrations of BaP can occur in workplaces. Measurements using stationary samplers or personal samplers over an 8-hour period showed average BaP concentrations of between 22 and 37 μg/m3 on the topside of older coke oven batteries and between 1 and 5 μg/m3 at several other worksites in the same plants. High values have also been reported in the retort-houses of coal-gas works in the United Kingdom, ranging from 3 μg/m3 in mask samples to more than 2 mg/m3 in peak emissions from the retorts. In the aluminum-smelting industry, concentrations much higher than 10 μg/m3 were found at some workplaces (WHO, 1987).
Statement of Problem
Atmospheric PAHs are continuously deposited to the soil by dry or wet deposition processes. Some of these PAHs are from nearby sources, such as generator exhaust. The atmosphere is the most important means of PAH dispersal, it receives the bulk of the PAHs environmental load resulting in PAHs being ubiquitous in the environment. PAHs are emitted to the atmosphere primarily from the incomplete combustion of organic matter. The combustion sources can be either natural or anthropogenic. The natural sources include volcanoes and forest fires. While the anthropogenic sources are vehicle exhaust, agricultural fires, power plants, coke plants, steel plants, foundries and other industrial sources. PAHs tend to be found in greater concentrations in urban environments than in rural environments because most PAH sources are located in or near urban centers. Once released to the atmosphere, PAHs are found in two separate phases, a vapor phase and a solid phase in which the PAHs
are sorbet onto particulate matter (Ravindra et al., 2008; Wang et al., 2013; Zhang and Tao, 2009). Hydrophobic organic chemicals with low vapor pressures, such as PAHs, are sorbet to atmospheric particulates more readily than chemicals with higher vapor of different PAH compounds cause the individual PAHs to distribute in different concentrations in the vapor (Kameda, 2011) and other sorbet phases (Kuo et al., 2012).
PAHs can be added to soils if fill materials contain PAHs. When PAHs are deposited onto the earth’s surface, they can become mobile. Since the majority of PAHs in the soil will be bound to soil particles (Masih and Teneja, 2006; Cachada et al., 2012), the most important factors influencing PAH mobility of particulates in the subsurface will be sorbent particle size and the pore throat size of the soils. Such pore throat can be defined as the smallest opening found between individual grains of soil (Riccardi et al., 2013). If particles to which PAHs are sorbet cannot move through the soil then the movement of PAHs will be limited because they tend to remain sorbet to particles.
17 PAHs have been identified as being of greatest concern with regard to potential exposure and adverse health effects on humans and are thus considered as a group. The International Agency for Research on Cancer (IARC, 2010) classifies some PAHs as known, possibly, or probably carcinogenic to humans (Group 1, 2A or 2B). Among these are benzo[a]pyrene (Group 1), naphthalene, chrysene, benz[a] anthracene, benzo[k]fluoranthene and benzo[b]fluoranthene (Group 2B) (IARC, 2010). Some PAHs are well known as carcinogens, mutagens, and teratogens and therefore pose a serious threat to the health and the well-being of humans. The most significant health effect to be expected from inhalation exposure to PAHs is an excess risk of lung cancer (Kim et al., 2013).
Aim and Objectives
The research aim and objectives are:
Aim
The aim of this study is to quantify the concentrations of Polycyclic Aromatic Hydrocarbons (PAHs) in soil samples collected around selected ABUAD power generators.
Objectives
The specific objectives are to:
- extract PAHs from soil samples collected around selected ABUAD generators using Soxhlet extraction method.
- determine the concentration of PAHs from (i)
- identify control measures for PAHs deposition in soil
Scope of study
This work covers the determination of PAHs in soil samples around selected ABUAD power generators. The PAHs in the soil samples where extracted in the laboratory using Soxhlet extraction method. Samples where finally concentrated and analyzed using Gas Chromatography and Mass Spectrometry (GC-MS).
CHAPTER TWO LITERATURE REVIEW
Polycyclic Aromatic Hydrocarbons (PAHs)
Polycyclic aromatic hydrocarbons (PAHs) are organic compounds that are mostly colorless, white, or pale yellow solids. They are a ubiquitous group of several hundred chemically related compounds, environmentally persistent with various structures and varied toxicity. They have toxic effects on organisms through various actions. Generally, PAHs enter the environment through various routes and are usually found as a mixture containing two or more of these compounds, e.g. soot. Some PAHs are manufactured in the industry. The mechanism of toxicity is considered to be interference with the function of cellular membranes as well as with enzyme systems which are associated with the membrane. It has been proved that PAHs can cause carcinogenic and mutagenic effects and are potent immune- suppressants. Effects have been documented on immune system development, humoral immunity and on host resistance (Armstrong et al., 2004; CCME, 2010). PAHs can be formed both during biological processes and as products of incomplete combustion from either natural combustion sources (forest and bush fires) or man-made combustion sources (automobile emissions and cigarette smoke). Thus, PAHs are commonly detected in air, soil, and water. Therefore, PAHs are considered ubiquitous in the environment (Baklanov et al., 2007; Latimer and Zheng, 2001. The ubiquitous nature of PAHs in the environment has been well summarized by Menzie et al. (Menzie et al., 1992).
The term ‘‘PAH” refers to compounds consisting of only carbon and hydrogen atoms. Chemically the PAHs are comprised of two or more benzene rings bonded in linear, cluster, or angular arrangements (Arey and Atkinson, 2003; Di-Toro et al 2000).
Such molecular arrangements are illustrated in Figure 2.1. Although there are many PAHs, most regulations, analyses, and data reporting focus on only a limited number of PAHs, typically between 14 and 20 individual PAH compounds.
Polycyclic aromatic hydrocarbons have two or more single or fused aromatic rings with a pair of carbon atoms shared between rings in their molecules. PAHs containing up to six fused aromatic rings are often known as ‘‘small” PAHs, and those containing more than six aromatic rings are called ‘‘large” PAHs. The majority of research on PAHs has been conducted on small PAHs due to the availability of samples of various small PAHs. The simplest PAHs, as defined by the International Agency for Research on Cancer (IARC, 2010), are phenanthrene and anthracene, which both contain three fused aromatic rings. On the other hand, smaller molecules, such as benzene, are not PAHs. Naphthalene, which consists of two coplanar six-membered rings sharing an edge, is another aromatic hydrocarbon. Therefore, it is not a true PAH, though is referred to as a bicyclic aromatic hydrocarbon. The most extensively studied PAHs are 7, 12-dimethylbenzoanthracene (DMBA) and benzo(a)pyrene (BaP) (CCME, 2010). The most commonly analyzed PAHs are given in Figure 2.2. The general characteristics of PAHs are high melting and boiling points (therefore they are solid), low vapor pressure, and very low aqueous solubility (Masih et al., 2012). The latter two characteristics tend to decrease with increasing molecular weight, on the contrary, resistance to oxidation and reduction increases (Masih et al., 2010). Aqueous solubility of PAHs decreases for each additional ring (Masih et al., 2010). Meanwhile, PAHs are very soluble in organic solvents because they are highly lipophilic. PAHs also manifest various functions such as light sensitivity, heat resistance, conductivity; emit ability, corrosion resistance, and physiological action (Akyuz and Cabuk, 2010).
