CHAPTER ONE 1.

1 INTRODUCTION Soil is the term used to describe the geologic mantle that covers most of the terrestrial earths surface. Soils vary in development from old, strongly weathered types to young types that have only recently been exposed to weathering as they were deposited from active geological processes such as volcanism or floods and erosional processes. Except where bare stone or water forms the earths surface, we all live on top of a soil layer.This situation results in soil contributing to beneficial activities of humans, such as growing row and horticultural crops. On the other hand, soil is subjected to deleterious activities such as disposing of waste, spilling of petroleum products and discharging of air contaminants that fall to the ground, and subsistence farming that drains the soil of nutrients. Organic compounds can be a major pollution problem in soil. Their presence in soil and ground water can create a hazard to public health and the environment. This research focuses on BTEX (Benzene, Toluene, Ethyl benzene and Xylene) and PAHs (Polycyclic aromatic hydrocarbons) which make up the main groups of organic compounds that find their way into our soils whether clay loam or sand. Though the areas contaminated are relatively small in size, the contaminant concentration at these sites is often high and associated with co-contaminants such benzene, toluene, ethylene and xylene (BTEX) compounds, heavy metals and aliphatic hydrocarbons, which can hinder remediation efforts. Soils can be contaminated with between 1 g kg and 300 g kg PAHs,[15 ] depending on the source of contamination (eg.old coal gasification sites have the higher level stated). Atmospheric levels of PAHs resulting from the incomplete combustion of materials such as coal and wood have been found to be between 60 gm and 3mgm air.[3] PAHs occur in oil, coal, and tar deposits, and are produced as byproducts of fuel burning (whether fossil fuel or biomass). As a pollutant, they are of concern because some compounds have been identified as carcinogenic, mutagenic, and teratogenic. PAHs are also found in cooked foods. Studies have shown that high levels of PAHs are found, for example, in meat cooked at high temperatures such as grilling or barbecuing, and in smoked fish one of the most common sources of BTEX
1 1 3 3

contamination of soil are spills involving the release of petroleum products such as gasoline, diesel fuel, lubrication oil and heating oil from oil tank leaks. Due to the polarity and soluble characteristics of the organic chemicals of petroleum products the find their way into the soil. Contaminant desorption is one of the most important processes affecting site remediation but often receives little attention in remedial design.

1.1.1AIM OF STUDY This study was carried out to analyze the desorption of PAHs and BTEX from clay, loamy and sand soils. 1.1.2SCOPE OF STUDY This study entails collection of soil various soil samples- clay from Egbema West, Imo State; Loamy soil from a waste site in Benin, Edo State and sand from a tarred road in Benin then, using soxhlet extraction to desorb PAHs and BTEX from the collected soil samples in the laboratory. 1.1.3 RELEVANCE OF STUDY The amount of 'Total BTEX' and PAHs, the sum of the concentrations of each of the constituents of BTEX and PAHs, is sometimes used to aid in assessing the relative risk or seriousness at contaminated locations and the need of remediation of such sites.

CHAPTER TWO 2.1 POLYCYCLIC AROMATIC HYDROCARBNONS (PAHs) The simplest PAHs, as defined by the International Union of Pure and Applied Chemistry (IUPAC) (G.P Moss, IUPAC nomenclature for fused-ring systems), are phenanthrene and anthracene, which both contain three fused aromatic rings. Smaller molecules, such as benzene, are not PAHs. PAHs may contain four-, five-, six- or seven-member rings, but those with five or six are most common. PAHs composed only of six-membered rings are called alternant PAHs. Certain alternant PAHs are called benzenoid PAHs. The name comes from benzene, an aromatic hydrocarbon with a single, sixmembered ring. These can be benzene rings interconnected with each other by single carbon-carbon bonds and with no rings remaining that do not contain a complete benzene ring.

Figure 2.2.1 Clockwise from top left: benz(e)acephenanthrylene, pyrene and dibenz(ah)anthracene The set of alternant PAHs is closely related to a set of mathematical entities called polyhexes, which are planar figures composed by conjoining regular hexagons of identical size. 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. Due to the availability of samples of the various small PAHs, the bulk of research on PAHs has been of those of up to six rings. The biological activity and occurrence of the large PAHs does appear to be a continuation of the small PAHs. They are found as combustion products, but at lower levels than the small PAHs due to the kinetic limitation of their production through addition of successive rings. In addition, with many more isomers possible for larger PAHs, the occurrence of specific structures is much smaller. Polycyclic aromatic hydrocarbons are lipophilic, meaning they mix more easily with oil than water. The larger compounds are less water-soluble and less volatile (i.e., less prone to evaporate). Because of these properties, PAHs in the environment are found primarily in soil, sediment and oily substances, as opposed to in water or air. However, they are also a component of concern in particulate matter suspended in air. Natural crude oil and coal deposits contain significant amounts of PAHs, arising from chemical conversion of natural product molecules, such as steroids, to aromatic hydrocarbons. They are also found in processed fossil fuels, tar and various edible oils.[7] PAHs are one of the most widespread organic pollutants. In addition to their presence in fossil fuels they are also formed by incomplete combustion of carbon-containing fuels such as wood, coal, diesel, fat, tobacco, and incense.[8] Different types of combustion yield different distributions of PAHs in both relative amounts of individual PAHs and in which isomers are produced. Thus, coal burning produces a different mixture than motor-fuel combustion or a forest fire, making the compounds potentially useful as indicators of the burning history. Hydrocarbon emissions from fossil fuel-burning engines are regulated in developed countries.[9]

Although the health effects of individual PAHs are not exactly alike, the following seventeen (17) PAHs are considered as a group in this profile issued by the Agency for Toxic Substances and Disease Registry (ATSDR):[10] acenaphthene, acenaphthylene, anthracene, benz[a]anthracene, benzo[a]pyrene, benzo[e]pyrene, benzo[b]fluoranthene, benzo[ghi]perylene, benzo[j]fluoranthene, benzo[k]fluoranthene, chrysene, coronene, dibenz(a,h)anthracene, fluoranthene, fluorene, indeno(1,2,3cd)pyrene, phenanthrene, pyrene. PAHs toxicity is very structurally dependent, with isomers (PAHs with the same formula and number of rings) varying from being nontoxic to being extremely toxic. Thus, highly carcinogenic PAHs may be small or large. One PAH compound, benzo[a]pyrene, is notable for being the first chemical carcinogen to be discovered (and is one of many carcinogens found in cigarette smoke). The EPA has classified seven PAH compounds as probable human carcinogens: benz[a]anthracene, benzo[a]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, chrysene, dibenz(a,h)anthracene, and indeno(1,2,3-cd)pyrene. PAHs known for their carcinogenic, mutagenic and teratogenic properties are benz[a]anthracene and chrysene, benzo[b]fluoranthene, benzo[j]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene, coronene, dibenz(a,h)anthracene (C20H14), indeno(1,2,3cd)pyrene (C22H12) and ovalene.[11] High prenatal exposure to PAH is associated with lower IQ and childhood asthma.[12] The Center for Children's Environmental Health reports studies that demonstrate that exposure to PAH pollution during pregnancy is related to adverse birth outcomes including low birth weight, premature delivery, and heart malformations. Cord blood of exposed babies shows DNA damage that has been linked to cancer. Follow-up studies show a higher level of developmental delays at age three, lower scores on IQ tests and increased behaviorial problems at ages six and eight.[13] 2.2 BTEX BTEX is an acronym that stands for benzene, toluene, ethylbenzene, and xylenes. These compounds are some of the volatile organic compounds (VOCs) found in petroleum derivatives such as petrol (gasoline). Toluene, ethylbenzene,

and xylenes have harmful effects on the central nervous system. These four chemicals are often found together at contaminated sites. BTEX are found naturally in such petroleum products as crude oil, diesel fuel and gasoline, and ethyl benzene which is a gasoline and aviation fuel additive and used extensively in manufacturing processes. Benzene is used in the production of synthetic materials and consumer products, such as synthetic rubber, plastics, nylon, insecticides and paints. Toluene is used as a solvent for paints, coatings, gums, oils, and resins. Ethylbenzene may be present in consumer products such as paints, inks, plastics, and pesticides. Xylenes are used as a solvent in printing, rubber, and leather industries. Once released to the environment, BTEX can volatilize (evaporate),dissolve,attach to soil particles or degrade biologically. Volatilization occurs when chemicals evaporate,allowing them to move from a liquid into the air. Volatilization of the BTEX components of gasoline commonly occurs when you pump gasoline into your car, and is responsible for the characteristic odor.This phenomenon can also occur within the air pockets present in soils, maintained underground storage tanks.Other sources of BTEX contamination are releases from large bulk facilities, surface spills, and pipeline leaks. BTEX Components of Gasoline (% weight) Benzene 11% Toluene 26% Ethyl benzene 11% Xylene BTEX can also dissolve into water, allowing it to move in the groundwater.Since BTEX can stick to soil particles, these chemicals move slower than the groundwater. If oxygen is present in sufficient quantities, BTEX can also degrade biologically, albeit slowly. 2.3 DESORPTION Desorption is a phenomenon whereby a substance is released from or through a surface. The process is the opposite of sorption (that is, either adsorption and absorption). This occurs in a system being in the state of sorption equilibrium between bulk phase (fluid, i.e. gas or liquid solution) and an adsorbing surface (solid or boundary separating two fluids). When the

concentration (or pressure) of substance in the bulk phase is lowered, some of the sorbed substance changes to the bulk state. All the currently adopted desorption models greatly simplify desorption by assuming that desorption is the simple reverse of adsorption and that the partition coefficients determined through sorption experiments are also applicable to desorption. The desorption of contaminants from soils/sediments is one of the most important processes controlling contaminant transport and environmental risks. None of the currently adopted desorption models can accurately quantify desorption at relatively low concentrations; these models often overestimate the desorption and thus the risks of hydrophobic organic chemicals, such as benzene and chlorinated solvents. In reality, desorption is generally found to be biphasic, with two soil-phase compartments. A new dual-equilibrium desorption (DED) model has been developed to account for the biphasic desorption. However, numerous studies have shown that desorption is indeed bi-phasic (Figure 1) at high concentrations, desorption is rapid, but at low concentrations, desorption is very difficult and contaminants in this region persist much longer than would be expected from conventional physical-chemical and microbial parameters (Linz, D.G. & Nakles, D.V., 1997). Such bi-phasic desorption may greatly reduce the availability of contaminants in subsurface and therefore may significantly hinder soil and groundwater remediation, assuming that the current cleanup standards have to be met. Thus, using the conventional desorption models in remediation design, one could greatly underestimate the costs and time associated with site remediation. A dual-equilibrium desorption (DED) model has been developed to quantitatively describe this bi-phasic desorption phenomenon. In the DED model, sorption is assumed to be a linear combination of the first and second compartments: q=q +q (1) where q (mg/kg-soil) represents total sorption; and q and q (mg/kg-soil) represent sorption to the 1st and 2nd compartments. Sorption to the 1st compartment follows the linear isotherm while sorption to the 2ndcompartment can be described with a Langmuir-type isotherm (Kan, A.T., et al, 1998):
1st 2nd 1st 2nd

q = k .f .c q = (Koc2nd.f .f.q
1st oc oc 2nd oc

max

2nd.

c)/(f.q

max

2nd

+ Koc

2nd

.f .c )
oc

(2) (3)

where: C (mg/L) is the aqueous concentration of the contaminant; Koc1st and Koc2nd (L/kg-OC) are the organic carbon normalized partition coefficients for the 1st and 2nd compartments, respectively; q is the maximum sorption capacity of the 2nd compartment (mg/kg-soil); f is the fractional organic carbon; and f is the fraction of the 2nd compartment that is saturated upon exposure. It has been shown for field systems that assigning a value of f equal to one is reasonable (Kan, A.T., et al, 1998) and will always yield a conservative estimate of q. Combining Equations 1, 2, and 3 and assuming f = 1, the general DED isotherm model can be expressed as (Kan, A.T., et al, 1998)
max 2nd OC

q = Koc1st.f c + (k
oc.

oc

2nd

.f .q .c)/(q
oc max

max

2nd

+ Koc2nd.f .c)
oc

(4)

An important aspect that is not presently available for any other bi-phasic desorption theory is that all of the necessary parameters in Equation 4 can be readily obtained. The value of Koc1st can be obtained from numerous tabulations, specific correlations and explicit measurement. The value of k has been found to be a single constant for all hydrophobic compounds tested, to date: log K = 5.92 0.16, n = 41 (5)
t oc 2nd oc 2nd

q =f (k C ) (6) where K (L-water/L-octanol) is the octanol-water partition coefficient; and C (mg/L) is the aqueous solubility (Chen, W., et al, 2002). Note: The bi-phasic effect is more significant for organic chemicals with low hydrophobicity (e.g., benzene and dichloroethene) because the difference between Koc1st and koc2nd is more profound for such compounds. For highly hydrophobic chemicals (e.g.,hexachlorobenzene and DDT), since Koc1st and Koc2nd are very close, the DED model and the conventional linear model are very similar (refer to Figure 2). While Equations 1 and 4 are probably the most widely applicable, there are situations wherein Equations 1 and 4 need to be modified to quantify the presence of other specific processes, such as free phase contaminant, colloid, surfactant,
max 2nd oc ow sat 0.534 OW sat

co-solvent, total petroleum hydrocarbon (TPH), and other types of non-aqueous phase liquids (NAPL). These are discussed in detail in Chen et al. (Chen, W., et al, 2002). The DED model is based on extensive laboratory experiments using a number of chemicals and many different soils and sediments (Kan, A.T., Fu, G. & Tomson, M.B., 1994;Kan, A.T., et al, 1998;Chen, W., Kan, A.T. & Tomson, M.B., 2000). It has been tested using a wide range of laboratory and field data from other scientists ((Readman, J.W. & Mantoura, R.F.C., 1987;Pereira, W.E., et al,1988;McGroddy, S.E. & Farrington, J.W., 1995). The model has also been used to explain key observations related to underground storage tank sites (Chen, W., et al, 2002). Overall, it has been foundthat the DED model is much more accurate than conventional desorption models. Detailed comparisons between the DED model predictions and field observations are included in Chen et al. (Chen, W., et al, 2002).