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Determination of Polycyclic Aromatic Hydrocarbons and Total
Petroleum Hydrocarbons in Crude Polluted Soil from Esaba, Ughelli
South, Delta Nigeria
Ogana, Joy, Nworji, Ogechukwu Frances, Orji, Celestine Ejike, Ogbodo, Uchechukwu Chibuzo, Ngwu,
Ogochukwu Rita and Iloanya, Ebele lauretta
Nnamdi Azikiwe University, Awka, Anambra State, Nigeria
DOI: https://doi.org/10.51584/IJRIAS.2025.1010000046
Received: 26 Sep 2025; Accepted: 03 Oct 2025; Published: 03 November 2025
ABSTRACT
The current research examined the levels and composition of Polycyclic Aromatic Hydrocarbons (PAHs) and
Total Petroleum Hydrocarbon (TPH) at six locations affected by crude oil spills (E1, E2, E3, E4, E5, and E6)
within the Esaba community in the Niger Delta region, which is notable for petroleum exploration. The
samples were assessed for the 16 priority PAHs recognized by the USEPA utilizing GC/FID analysis. The
concentrations of Σ16 PAHs and TPH in the soil ranged from 19.322 to 83.542mg/kg with (average of
45.562mg/kg) and 890.908 to 4393.094mg/kg (average of 2622.097mg/kg) respectively. The concentrations of
Σ16PAHs US-EPA and TPH in all the studied locations far exceeded the safety value of 10mg/kg and
100mg/kg respectively, set by the soil quality guidelines of Switzerland and above which is regarded as being
highly contaminated for Agricultural soils of Poland. The mean PAHs concentrations recorded in E1, E2 and
E3 studied locations were significantly greater that the permissible limit of 40mg/kg set by Department of
Petroleum Resources (DPR) for oil spill sites. The result from this study showed higher distribution of low
Molecular Weight (LMW) PAHs than high Molecular Weight (HMW) PAHs indicating possible petrogenic
source. The research found that Site E2 had highest level of PAHs than the other sampled locations. It is
recommended that immediate intervention not only at studied locations of E1, E2 E3 but also E4 be carried out
given that all individual PAHs in E4 are known carcinogens.
Keywords: Polycycic Aromatic Hydrocarbon, Total Petroluem Hydrocarbon, Aliphatic Esaba, soil
INTRODUCTION
In Nigeria, the Niger Delta is well-known for its severe environmental pollution resulting from crude oil
exploration and production operations. The extensive processes of extraction, transportation, and utilization of
crude oil have increased the likelihood of unintentional oil spills, which damage both terrestrial and aquatic
ecosystems and present significant risks to the health of humans and animals (Saadoun, 2015). Between 2008
and 2018, a total of 7,581 oil spill incidents were documented on the Nigerian Oil Spill Monitor (NOSDRA)
website, all occurring within the Niger Delta region. According to the data from the NOSDRA online oil spill
monitor, approximately 418,414.57 barrels of crude oil were spilled during the 2008 to 2018-time frame,
although 31.66% of the total incidents (2,400 incidents) had unavailable information on the volume of oil
spilled.
The natural environment affected by oil spills is extremely challenging to clean up, particularly in marshes and
mangroves (Wali et al., 2019). Oil spills that lead to contamination of environmental elements such as soil,
water, and air have been associated with various health issues for local residents, including respiratory
problems like cancer, skin conditions, and digestive disorders (Kuppusamy et al., 2020; Onyena and Sam,
2020). If the spill contains a significant quantity of light aromatic hydrocarbons, it can cause toxic effects such
as plant asphyxiation and organism fatalities (Linden and Jonas, 2013).
The primary constituents of crude oil are hydrocarbons, which are categorized into saturated, unsaturated, and
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polycyclic aromatic hydrocarbons; derivatives of petroleum products fall into two major classifications:
aliphatics and aromatics (Mostert et al., 2010). The aliphatic compounds found in petroleum hydrocarbons are
predominantly alkanes that can be either straight-chain or branched (Militon et al., 2010; Khan et al., 2018).
Aromatic compounds vary from those containing a single benzene ring to complex substances formed by
several fused rings, including polycyclic aromatic hydrocarbons (PAHs) (Khan et al., 2018), which are
recognized as significant hazardous environmental pollutants resulting from oil spills (Dudhagara et al., 2016).
Total Petroleum Hydrocarbons (TPHs) primarily consist of both aliphatic and aromatic components (Khan et
al., 2018). They are frequently introduced into the environment through unintentional spills and leaks during
their transportation or storage. When such leaks happen, TPHs typically accumulate in the top layers of the soil
(Varjani, 2017), where they impact physical characteristics like pH, nutrient bioavailability, and biodiversity
(Varjani, 2017; Devatha et al., 2019).
Total petroleum hydrocarbons (TPH) are the primary components of crude oil, making them one of the most
prevalent pollutants in soils contaminated by oil. When hydrocarbon pollution persists over an extended period,
the compounds become tightly bound, resulting in the predominance of a recalcitrant fraction of hydrocarbons
that are not easily bioavailable (Semple et al., 2007). While it may be seen as less toxic than an area that has
been recently contaminated, the impact of lasting compounds in a chronically contaminated location is
significant (Jonker et al., 2006). As different petroleum components diminish due to weathering, polycyclic
aromatic hydrocarbons (PAHs) remain trapped within the soil matrix, posing substantial health risks to both
humans and the environment.
Polycyclic aromatic hydrocarbons (PAHs) comprise a group of thousands of hazardous and widespread
organic pollutants present in the environment. These compounds are naturally occurring, unsubstituted organic
molecules made up of two or more fused benzene rings arranged in linear, angular, or clustered formations,
typically found as complex mixtures instead of isolated substances (Lee and Vu, 2010). They pose health risks
to humans (Fetzer, 2000; Tiwari et al., 2015, 2017). PAHs are recognized as persistent organic pollutants,
categorized as organic micro-pollutants that are notably resistant to biodegradation and have detrimental
effects on the environment (Boisa et al., 2019; Gao et al., 2019). Monitoring of these substances in the
environment began over four decades ago, highlighted by a list released by the U.S. Environmental Protection
Agency (EPA) in 1976 (Keith and Telliard, 1979; Keith, 2015).
Physically, polycyclic aromatic hydrocarbons are primarily characterized as colorless, white, or pale-yellow
solids, exhibiting a range of boiling and melting points (Abdel-Shafy and Mansour, 2015). They are typically
categorized based on their melting and boiling points, vapor pressure, and solubility, which are influenced by
their structural composition. PAHs possess low vapor pressure, minimal solubility in water, sensitivity to light,
resistance to heat, thermal conductivity, emission capabilities, and corrosion resistance. They are also highly
lipophilic and exhibit physiological effects (Akyuz and Cabuk, 2010). In aquatic environments or when
adsorbed onto particulate matter, PAHs may undergo photodecomposition when exposed to ultraviolet light
from solar radiation. In the atmosphere, PAHs can react with ozone, nitrogen oxides, and sulfur dioxide,
resulting in the formation of diones, nitro- and dinitro-PAHs, and sulfonic acids, respectively (WHO, 1987;
ATSDR, 1994).
The existence of polycyclic aromatic hydrocarbons (PAHs) in crude oil is well documented. As noted by Gao
et al. (2019), these compounds are regarded as the primary toxic constituents of crude oil, with many identified
as carcinogenic or mutagenic. They have been classified as priority pollutants by both the European Union and
the United States Environmental Protection Agency (US EPA). PAHs can be categorized into two principal
groups: Light Molecular Weight PAHs (LMW), which consist of two or three aromatic rings and include
compounds such as naphthalene, anthracene, fluorene, acenaphthene, and phenanthrene, are recognized for
their acute toxicity. In contrast, High Molecular Weight PAHs (HMW), characterized by four or more rings
and comprising substances like chrysene, pyrene, benzo(a)pyrene, and fluoranthene, are predominantly viewed
as genotoxic (ATSDR, 1995; Ghosal et al., 2016). Boisa et al. (2019) highlighted that HMW are particularly
concerning due to their stability, high toxicity, and lipophilic nature, which facilitates their bioaccumulation in
biological tissues. Furthermore, according to the Comprehensive Environmental Response, Compensation and
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Liability Act (CERCLA), PAHs were ranked 7th in 2005 in the biennial assessment of hazardous substances
that pose the most significant risk to human health (Christopher, 2008).
Low-molecular-weight (LMW) polycyclic aromatic hydrocarbons present in contaminated soils exhibit a half-
life ranging from 5 to 7 years, whereas high-molecular-weight (HMW) PAHs have a half-life of 9 to 10 years
(Wild et al., 1991). The removal of PAHs from contaminated soils is essential due to the negative health
impacts on humans linked to their ingestion (Haritash and Kaushik, 2009).
Polycyclic aromatic hydrocarbons (PAHs) in soil can become encapsulated within minerals and exist in non-
aqueous liquids, which may pose a risk of human exposure (Tarafdar et al., 2018). These compounds can
adversely affect soil functions and disrupt the soil microbiome due to their persistence and resistance to natural
degradation processes (Zhao et al., 2021; Roslund et al., 2018). The ubiquitous presence of PAHs has sparked
research into various remediation methods (Gan et al., 2009). Therefore, there is an immediate necessity for
effective and environmentally friendly strategies to alleviate the detrimental effects of oil spills on the
ecosystem. This study focused on assessing the concentration and distribution of total petroleum hydrocarbons
(TPH) and PAHs in contaminated soil samples from the Esaba community in Delta State.
MATERIALS AND METHODS
Description of the Study Area
The host communities are located in the Ughelli south local government of Delta state. Esaba is located in the
west of the region of Ughelli South, its situated near to Otutuama village as well as Okwagbe town. It has a
tropical monsoon climate It is located on the Bight of Benin, with a shoreline spanning about 60 km with
latitudes of 5° 24′ 52′′ N and 5° 46′ 49′′ E. The residents of Esaba primarily engage in farming and fishing, and
the community is home to a Shell flow station. Unfortunately, the agricultural lands in this area have been
adversely affected by crude oil pollution resulting from years of oil bunkering, illegal refineries activities, and
environmental contamination.
Sampling collection
Six soil samples were collected from each sub-area of Esaba (E1, E2, E3, E4, E5 and E6) and homogenized
into a composite sample. The samples were collected with an improvised soil augur (nitric acid sterilized PVC
pipes) A total of eighteen batch soil samples made into six different composite samples were collected at depth
of 0-15 cm, after the removal of the exposed surface.
A thin layer of the composite samples was sieved (212-μm) to remove fragments of plants debris and stone.
The screened samples were thereafter air-dried in the dark. The dry soil samples were then ground into powder
in a ceramic mortar and demagnetized with a magnetic rod and kept in sealed vials labeled. Soil samples were
taken to the laboratory for analysis
Methods Soil Extraction
A solvent mixture consisting of acetone and methylene chloride in a 50:50 ratio was prepared. A 10g aliquot of
the thoroughly mixed sample was transferred into a beaker that had been rinsed with solvent, followed by the
addition of 50ml of the solvent mixture to the sample. Subsequently, 1ml of the surrogate mixture was
introduced. The sample was then placed in a sonicator and subjected to sonication for approximately 10 to 15
minutes at around 70°C. Anhydrous sodium sulfate, weighing 10g, was added to the sample until a clear
extract was obtained. The extract solvent was then transferred into a round-bottom flask. This process was
repeated with an additional 50ml of the solvent mixture, and the beaker was allowed to settle before decanting
into the same round-bottom flask. Finally, the solvent was concentrated to a volume of approximately 1 to 3ml.
The sample was subsequently prepared for purification utilizing a silica gel column. The columns were filled
with 10 grams of 100-200 mesh silica gel, which had been pre-conditioned by baking at 105°C overnight. The
silica was combined with dichloromethane to create a slurry. Column chromatography was performed to
separate the aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) fractions through successive
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elution with 20 mL of n-hexane followed by 70 mL of a n-hexane/dichloromethane (7:3 v/v) mixture. The
PAH fraction was then concentrated using a rotary evaporator at 30°C to approximately 1 mL, transferred to a
1.5 mL vial, and reduced to 0.5 mL under a gentle nitrogen stream. The analysis was conducted using gas
chromatography with a Flame Ionization Detector (GC/FID).
Statistical Analysis
Descriptive (mean and standard deviation) statistical analysis was used to present data in numerical forms
RESULTS
Table 1: Polyclclic Aromatic hydrocarbon concentration of the different sampled sites
PAHs component
(mg/kg)
E1
E2
E3
E4
E5
E6
Mean of the
∑PAH
component
Naphthalene
10.094
14.098
-
-
-
0.605
8.265
Acanaphthalene
13.358
22.826
-
-
2.323
0.861
9.842
Acenaphthene
-
9.525
-
-
-
-
9.525
Florene
17.602
9.147
6.021
-
18.777
1.193
10.548
Phenathrene
5.351
14.119
42.547
-
2.632
0.957
13.121
Anthracene
8.311
2.745
-
-
13.889
2.957
6.727
Fluoranthene
-
-
4.112
-
-
1.667
2.888
Pyrene
-
-
-
-
-
17.248
17.248
Benzo(a) anthracene
-
5.895
-
2.203
-
-
4.049
Crysene
-
5.182
-
3.860
-
-
4.526
Benzo(b)
fluoranthrene
-
-
-
4.762
-
-
4.762
Benzo(a) pyrene
-
-
-
4.553
-
-
4,553
Benzo(k)
fluoranthracene
-
-
-
3.944
-
-
3.944
Indeno(123)perylene
-
-
-
-
-
-
Mean of the
∑PAH
component
Dibenzo(a,h)
anthracene
-
-
-
-
-
-
Benzo (g,h,i)
perylene
-
-
-
-
-
-
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Total (mg/kg)
54.716
83.542
52.680
19.322
37.620
25.491
E1, E2, E3, E4, E5 and E6 are the different sampled locations at Esaba,
(- ) = below detectable limit
E1, E2, E3, E4, E5 and E6 are the different sampled locations at Esaba
Figure 1: % of Polycyclic Aromatic Hydrocarbon in the different sampled sites
E1, E2, E3, E4, E5 and E6 are the different sample locations at Esaba
Figure 2: Mean Total Polycylic Aromatic Hydrocarbon Concentrations of the different sampled sites
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E1, E2, E3, E4, E5 and E6 are the different sampled locations at Esaba
Figure: 3 Total Aliphatic Hydrocarbon of the different sampled sites
E1, E2, E3, E4, E5 and E6 are the different sampled locations at Esaba
Figure 4: Total Petroleum Hydrocarbon concentration of the different sampled sites
PAHs contamination of Agricultural soil by the exploration of crude oil and oil spill in Niger Delta region has
been reported by many researchers, but study on PAHs contamination in Esaba crude oil community of
Ughelli South Local Government of Delta State remain unavailable and that brought about this study. The
analysis of the PAHs content and TPH on crude oil contaminated soil from Esaba at different sampled
locations showed various contamination level and distribution of PAHs component and TPHs. From our result
the concentrations of the sixteen PAHs identified by the United State Environmental Protection Agency
(USEPA) as priority pollutants investigated in our study as shown in table1, indicated the presence of thirteen
PAHs in all the sampled locations expect for indeno (123) pyrene, dibenzo (h g), anthracene and benzo (ghi)
perylene that were below detection limit of the analytical equipment used in all the sampled points. The order
of increase of total individual PAHs concentration is as follows: phenathrene ˃ florene ˃ acenaphthalene ˃
anthracene > naphthalene > pyrene > acenaphthene > chrysene > benz (a) anthracene > fluoranthene > benzo
(b) fluoranthen > benzo (a) pyrene ˃ Benzo (k) fluoranthene with respective concentrations in mg/kg as
(65.606, 52.740, 39.368, 26.908, 24.797, 17.248, 9.525, 9.052, 8.098, 5.776, 4.762, 4.553 and 3.944).
For the source identification and distribution of the PAHs, our result showed that both petrogenic and
pyrogenic (that is the LMW and the HMW PAHs) sources were identified in all sampled locations studied.
Soil that are polluted by petrogenic (oil spillage contamination) sources tends to have higher percentage of
LMW PAHs in their PAHs composition while soil polluted by pyrogenic (coal and fossil fuel combustion)
sources tend to have higher percentage of HMW PAHs in their PAHs composition (Wang et al., 1999: Moore
et al.,2015). The result from this study showed that all the study sampled locations had higher concentration of
LMW PAHs indicating the possible contaminants of the surface soil sampled originated from petrogenic
sources expect for E4 that only showed HMW PHAs concentrations. The LMW PAHs are very unstable and
tends to evaporate in the soil when in contact or exposed to sunlight over time, and are highly violate (Sanches
et al., 2011; Ukiwe et al., 2013). The evidence for the LMW PAHs in most of the sampled is due to the fact
that there are ongoing crude oil activities on these sites resulting in continuous oil spillage.
The PAHs mean concentrations for surface soil exceeded the DPR Intervention limit of 40mg/kg for some of
the sampled locations (E1, E2 and E3) while the other sampled locations (E4, E5 and E6) were below DPR
intervention. In our study E2 sample location had the highest total PAHs concentration, while E4 had the
lowest as shown in figure 2.
However the total PAH concentrations in all the sampled locations (54.716, 83.542, 52.680, 19.322, 37.062
and 25.491mg/kg for E1, E2, E3, E4, E5 and E6 respectively) were far higher than when compared with the
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maximum background limits of 15mg/kg for polluted soils set by Dutch Environment Ministries and E1, E2
E3 sampled points were higher than 50mg/kg set by Polish Environment Ministries in polluted soil , (Polish
Environment Ministry, 2002). Also, the concentrations of Σ16PAHs in all sampled locations exceeded the
precautionary value of 1000 ng/g 10mg/kg set by the soil quality guidelines of Switzerland (Dasaules et al.,
2008. Based on these classifications, sampled soil from Esaba could be classified as heavily contaminated with
PAHs
Naphthalene concentration in the soil ranged from 10.094 to 0.603mg/kg with an average value of 8.266
mg/kg. A lower naphthalene concentration was reported by (Ayedun et al., 2024) in a crude oil contaminated
soil. Also, Al-Sad et al. (2019) reported a higher naphthalene concentration. Acenaphthylene ranged from
22.86 to 0.861 mg/kg with an average value of 39.368 mg/kg. Acenaphthene was only detected in E2 soil
sample. Fluorene ranged from 18.777 to 1.193 mg/kg with an average value of 10. 548mg/kg. Phenanthrene
ranged from 42.547 to 0.957 mg/kg with an average value of 13.121 mg/kg. Anthracene ranged from 13.889 to
2.748 mg/kg with an average value of 6,727 mg/kg. Floranthene was detected in E3 and E6 with the value of
4.112 and 1.6657 mg/kg respectively. Pyrene was only detected in E6 with the value of 17.248 mg/kg.
Chrysene and Benz(a)anthracene was detected only in E2 and E4 with 5.895 and 5.182 for Chrysene and 2.203
and 3.860mg/kg for Benzo(a) anthracene respectively.
PAH components detected in E2 and E4 falls within the category of PAHs with the highest health risk
especially at prolonged exposure (ATSDR, 1999). Although E4 having the lowest total PAHs concentration of
19.322 mg/kg when compared to other sampled locations, but had five PAHs that are described as carcinogens
according to the USEPA (California Environmental Protection Agency, 1994) namely benzo(a)anthracene,
chrysene, benzo(b)fluoranthrene, benzo(a) pyrene and benzo (k) fluoranthrene. These PAHs pose a major
threat in terms of its mutagenic and carcinogenic effects. Some studies have also shown that some of these
PAHs can induce dioxin-like activity and weakened estrogenic responses (Villeneuve et al., 2002).
Dudrikova et al. (2023) reported presence of naphthalene, floranthene, pyrene, chrysene, and
benz(a)anthracene in natural and anthropogenically transformed coastal soils of Southern Russia. Lower than
our present study is the report of Barrán-Berdón at al. (2012) who reported a total PAHs concentrations range
of 0.0007mg/kg to 1.384 mg / kg with an average PAHs concentration of 0.22 mg/Kg in soil samples. They
also noted that Naphthalene is more abundant followed by Fluorene, Chrysene, Benzo [a] Anthracene and
Dibenzo [a, h] Anthracene in their study. Also, when compared to this present study, Ayedun et al. (2024)
reported lower concentration of PAHs in crude oil contaminated soil. Aoeed et al. (2023) reported a higher
total PAHs concentration of 609.77 ug/kg in soil from oil company visinity, with naphthalene Fluorene and
Acenaphthylene showing high concentrations in all the seasoned. Abundant value of fluorene, followed by
acenaphthylene and naphthlene was reported by Abed et al., 2015 at North Biji City in Iraq, the total
concentration of 16 polycyclic aromatic hydrocarbons ranged from 49.9 to 986.4 μg / kg and average of 587.2
μg / kg, which is also lower than our present study
Comparing our present result with other study from Niger Delta region, Faboya et al. (2023) reported a total
PAHs range of 24330.68 - 40845.32 with average of 299523.47ng/g and 7361.66 -14141.49ng/g with average
of 9819.96 ng/g. Also, Aedosu et al. (2013) have previously reported PAHs concentrations ranged of 23.8 to
120 and 7.40–78.3 ng/g, respectively in polluted soil from Niger Delta region. All this reports from Niger
Delta regions where all below the concentration revealed in our present study, as such DPR has to intervene,
and help reduce the level and future occurrence.
Total Petroleum Hydrocarbons (TPHs) are mainly composed by aliphatic and aromatic fractions (Khan et al.,
2018). The concentrations of aliphatic hydrocarbons present in crude oil contaminated soil is presented in
figure 3, the aliphatic hydrocarbons ranging from C8 to C40 range were detected in sampled locations as
872.969, 4309.574, 1907.506, 3194.193 and 865.417mg/kg for E1, E2, E3, E4, E5 and E6 respectively. Similar
to our study is Martinez-Cuesta et al. (2023), that reported aliphatic value of 3944.4 at the initial concentration
in polluted soil before ecopilcs remediation. The TPH concentration present in the contaminated soil samples
were 927.685mg/kg for location E1, 4393.094 mg/kg for location E2, 4362.254mg/kg for location E3,
1926.828 mg/kg for location E4, 3231.813 mg/kg for location E5 and 890.908 mg/kg for location E6 as shown
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in Figure 4. The total petroleum hydrocarbons obtained at the six sampled locations in this study were all
below the Department of Petroleum Resources (DPR) limit of 5000 mg/L.
Concentration of TPH higher than 10–100 mg/kg, indicates pollution (Adeniyi and Afolabi 2002), from above
it can be said that all the soil samples collected at the polluted sites are polluted with THP. Akagbue et al.,
(2024) reported a high TPH concentration of 7829.23ppm in crude oil polluted soil from Souther Ijaw. Their
concentration is far higher when compared with our present study and it could attribute to higher crude oil
contamination level.
CONCLUSION
The high concentration and abundance of LMW PAHs gave evidence that the nature of the contamination was
mainly from crude oil. The results obtained from this study reveals that the level of total petroleum
hydrocarbons (TPH) obtained from all the samples were lower than the maximum recommended levels by the
Department of Petroleum Resources (DPR). while the concentration of total PAHs in most of the sampled
locations were higher than the maximum recommended level for DPR. Even at low concentration of PAHs it
can exert some harmful effect on human, as such this study recommends remediation measures by the
government given that PAHs in some of sampled locations were above the DPR limit for intervention. Though
some of the PAHs and TPH level were below intervention limit.
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