See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/358694926

Determination and human health risk assessment of polycyclic aromatic

hydrocarbons (PAHs) in surface and ground waters from Ifite Ogwari,
Anambra State, Nigeria

Article in International Journal of Environmental Analytical Chemistry · February 2022

DOI: 10.1080/03067319.2022.2038587

CITATIONS READS

14 1,774

5 authors, including:

Vincent Okafor Daniel O. Omokpariola

Nnamdi Azikiwe University, Awka Nnamdi Azikiwe University, Awka
21 PUBLICATIONS 74 CITATIONS 52 PUBLICATIONS 216 CITATIONS

SEE PROFILE SEE PROFILE

All content following this page was uploaded by Daniel O. Omokpariola on 18 February 2022.

The user has requested enhancement of the downloaded file.

 International Journal of Environmental Analytical
Chemistry

ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/geac20

Determination and human health risk assessment

of polycyclic aromatic hydrocarbons (PAHs) in
surface and ground waters from Ifite Ogwari,
Anambra State, Nigeria

Vincent N. Okafor, Daniel O. Omokpariola, Eucharia C. Igbokwe, Chidera M.

Theodore & Nwaamaka G. Chukwu

To cite this article: Vincent N. Okafor, Daniel O. Omokpariola, Eucharia C. Igbokwe, Chidera M.
Theodore & Nwaamaka G. Chukwu (2022): Determination and human health risk assessment
of polycyclic aromatic hydrocarbons (PAHs) in surface and ground waters from Ifite Ogwari,
Anambra State, Nigeria, International Journal of Environmental Analytical Chemistry, DOI:
10.1080/03067319.2022.2038587

To link to this article: https://doi.org/10.1080/03067319.2022.2038587

Published online: 18 Feb 2022.

Submit your article to this journal

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

https://www.tandfonline.com/action/journalInformation?journalCode=geac20
INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY
https://doi.org/10.1080/03067319.2022.2038587

Determination and human health risk assessment of

polycyclic aromatic hydrocarbons (PAHs) in surface and
ground waters from Ifite Ogwari, Anambra State, Nigeria
Vincent N. Okafor , Daniel O. Omokpariola, Eucharia C. Igbokwe,
Chidera M. Theodore and Nwaamaka G. Chukwu
Department of Pure and Industrial Chemistry, Nnamdi Azikiwe University, Awka, Nigeria

ABSTRACT ARTICLE HISTORY

Levels of Polycyclic Aromatic Hydrocarbons in surface and under­ Received 7 November 2021
ground water sources from Ifite Ogwari, Ayamelum Local Accepted 29 January 2022
Government Area of Anambra State were investigated. Ecological KEYWORDS
and human health exposure risks were assessed following US EPA PAHs; GC-FID; human health;
methods. The surface water sources are Isiachala, Iyiutu, Ube, Ahala risk assessment; water; Ifite
Tabasi, Nabaloku, Atammele, Ogbu streams, and Omambala river. Ogwari
Underground water sources include Igbazine, Double, Ogba,
Onowulugbe, Orator, and Commodore hand-dug wells. The water
samples were collected using precleaned 500 cm3 glass bottles and
were analysed for the presence of 16 US EPAPAHs using Gas
Chromatography – Flame Ionisation Detector (GC- FID). The vali­
dated method showed that regression (R2) for all the PAHs ranged
between 0.9622 and 0.9983. Limits of detection (LOD) ranged from
0.0033 to 0.1236 µg L−1 and limits of quantification (LOQ) from
0.0109 to 0.4115 µg L−1. Precision CV values ranged from 5.12 to
18.24%, and recovery values of the analytes in water varied
between 83.94 and 99.99%. Naphthalene and chrysene were pre­
sent in all the water samples while pyrene was absent in all except
in Iyiutu. All the PAHs analysed were detected in Isiachala and Iyiutu
except pyrene which was absent in Isiachala. All the samples con­
tained at least three PAHs with concentrations ranging from 1.003
ng/µl of benzo[a] pyrene in Tabasi to 128.652 ng/µl of chrysene in
Iyiutu. Ecological risk shows that the value was above US EPA back­
ground value. Human health risk assessment depicts that hazard
index and total cancer risk ranges from 9.63E-05 to 1.93E-02. This
study has shown that the inhabitants of Ifite Ogwari will experience
adverse health and cancer illnesses over some time and therefore,
a holistic approach by researchers and government agencies is
needed to mitigate the ecological and health risk effects.

1. Introduction
Water occurs in several phases across various environmental media (atmosphere, hydro­
sphere, and lithosphere) and so becomes entangled with various components, affecting
its beauty and quality through time [1,2]. Water quality is influenced by both natural and

CONTACT Vincent N. Okafor vnw.okafor@unizik.edu.ng

© 2022 Informa UK Limited, trading as Taylor & Francis Group
2 V. N. OKAFOR ET AL.

artificial activity over time, as water dissolves a large amount of toxins due to its polar
nature. Water contamination has an impact on human health as well as the health of
plants and animals [3].
Water contamination is frequently caused by human activities such as agriculture,
mining, manufacturing, garbage generation and disposal, and so on. These activities
result in the deposition of toxic substances and persistent organic pollutants on the
microscale and nanoscale as a result of contamination by heavy metals, agrochemicals,
and polycyclic aromatic hydrocarbons (PAHs), which are transported as effluent into water
sources through direct dissolution and leaching mode, rendering them unfit for human
consumption [4–7].
Ifite Ogwari is a community in Nigeria’s Anambra State that relies on surface and
groundwater bodies for existence. Water is life, and every community relies on it for
survival. Surface and groundwater bodies in Ifite Ogwari include streams, rivers, and hand-
dug wells. Figure 1 depicts a few of them.
Food processing mills such as rice mills, cassava mills, and maize mills for rice, cassava,
and maize processing are among the major industrial equipment working in Ifite Ogwari.
In the community, road construction companies (Nigercat and RCC) are also active. These
industries’ activities have resulted in several garbage dump sites and car emissions in and
around the neighbourhood. Artisans such as roadside mechanics and welders, among
others, are among the community’s residents, each doing their own thing. The town is
traversed by major state and federal roadways connecting Anambra State to Adani town
in Enugu State. The use of agrochemicals, indiscriminate waste disposal, automobile
emissions, sewage water irrigation, and indiscriminate trash disposal are all on the rise
in the community [8] and can introduce toxins into the town’s water bodies, including
polycyclic aromatic hydrocarbons (PAHs).

Figure 1. (a). Lady fetching water from Ube stream (b). Man drinking from Iyiutu stream (c). A view of
Nabaloku stream (d). Woman already fetched water from Isiachala stream (e). Fisherman doing his job
at Omambala river f. Onowulugbe hand dug well.
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 3

PAHs are produced by the thermal breakdown of organic molecules with hydrogen and
carbon as their major constituents, which can come from both natural and man-made
sources [9]. They are a class of compounds that contain two or more aromatic rings and
are produced via the pyrolysis and pyrosynthesis processes [10]. Natural sources such as
bushfires, forest fires, and volcanoes are modest contributors when compared to artificial
ones such as automotive emissions, sanitary waste dumps, and chemical companies [11].
These pollutants can occur from both natural and manmade sources as a result of incom­
plete combustion of organic matter. As PAHs are discharged into a variety of environmental
matrices (water, air and soil), humans are exposed in a variety of ways, including water
ingestion (oral intake of water) and dermal (skin contact), both of which constitute health
concerns over time [2]. Reproductive and developmental effects, skin cancer, pulmonary and
respiratory problems, and genetic concerns are all linked to PAH exposure [12]. Research
shows that PAHs are highly dangerous to human health, genotoxic, neurotoxic, and cause
behavioural alterations in both adults and children, according to several studies [13–15].
The amount and composition of PAHs generated vary greatly depending on the
reaction conditions, temperature and amount of air present. Lower temperatures (400
to 500°C) result in lower molecular mass compounds (128 to 202 gmol−1) and higher
temperatures (600 to 650 oC) result in higher molecular mass compounds (228 to 278 g
mol−1) [16–18]. There are over 100 PAHs known, many of which are present in complex
mixtures rather than single components [18].
PAHs are one of the most common groups of contaminants that have caused concern
among scientists and the food industry due to their carcinogenic and mutagenic proper­
ties. They’ve been added to priority pollutant lists by the International Agency for
Research on Cancer (IARC), the Environmental Protection Agency (EPA), and the
European Union (EU) [19].
Furthermore,, IARC has classified benzo[a]pyrene as a compound that is demonstrably
carcinogenic to humans, while naphthalene, chrysene, benzo[a]anthracene, and benzo[k]
fluoranthene, benzo[b]fluoranthene have been classified as possible human carcinogens.
PAH contamination has been found in a variety of foods, primarily smoked or heat-treated
foods [16,17].
Polycyclic aromatic hydrocarbon pollution of waterways, drinks, and foods has
been the subject of numerous investigations [20–29]. However, no published paper
has studied surface and groundwater sources in the Ifite Ogwari community using all
of the pollution risk assessment models. As a result, it is worthwhile to investigate
the dangers associated with the use of surface and groundwater sources in Ifite
Ogwari, Anambra State, Nigeria.

2. Materials and methods

2.1. Study area
Ifite Ogwari town, located 45 kilometres from Awka, Anambra State’s capital [30] is
located between latitude 6.6041° North and longitude 6.9507° East, at an elevation of
91 metres above sea level [31]. Figure 2 illustrates the research area. Ifite Ogwari is located
4 V. N. OKAFOR ET AL.

Figure 2. (a) Map of Anambra State, Nigeria showing Ifite Ogwari, (b) Map of Ifite Ogwari showing
sample collection points.

on the banks of the Omambala river and boasts lush foliage and fertile fields suitable for
the growth of food crops such as rice, maize, yam, cassava, okro, and plantain, making it
an ideal location for the Faculty of Agriculture, Nnamdi Azikiwe University.
The annual and monthly total rainfall averages are 5798.78 mm and 1739.62 mm,
respectively [32]. The minimum and maximum temperatures are 25.4°C and 30.6°C,
respectively, and the vegetation is tropical forest [33,34].

2.1.1. Sampling
Fifteen water samples [9 surface: Isiachala (SA), Iyiutu (SB), Ube (SC), Ahala (SD), Tabasi
(SE), Nabaloku (SF), Atammele (SG), Ogbu (SH), and Omambala (RA) and 6 hand dug
wells: Igbazine (WA), Double (WB), Ogba (WC), Onowulugbe (WD), Orator (WE) and
Commodore (WF)] were collected from Ifite Ogwari, Anambra State, Nigeria. Water
sources were selected for study on the basis that they serve the community in all
seasons throughout the year. The sampling sites information were depicted in Table 1
and Figure 2.
Sampling was done on 20 February 2020using previously cleaned glass bottles. At each
point of the collection, the bottle was rinsed twice with the water sample to be collected.
They were labelled SA–SH for stream, RA for river and WA-WF for hand dug well. The
water sample points were geo-referenced using the Garmin GPS map. The samples were
packaged and transported to Central Laboratory, Nigerian Institute for Oceanography and
Marine Research, Victoria Island, Lagos for analysis.
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 5

2.1.2. Quality control

Reagents used for the analyses were of high-quality analytical grade, which were pur­
chased from BDH Chemical Ltd, UK, and Sigma- Aldrich Chemie GmbH, Germany. The
glassware and sample bottles were washed with detergents and deionised water. They
were immersed overnight in a 10% HNO3 in 1% HCl solution before being rinsed with
deionised water. A PAH mix containing naphthalene, acenaphthylene, acenaphthene,
fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chry­
sene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-c,d]pyr­
ene, dibenzo[a,h]anthracene, and benzo[g,h,i] perylene at 2000.0 mg L−1 in methanol:
methylene chloride (1:1) purchased from Supelco (Bellefonte, USA) was used as standard.

2.2. Extraction and analysis

2.2.1. Extraction of PAHs from the samples
A separating funnel was used for the extraction of PAHs from the water samples and their
spiked duplicates for PAHs followed a common procedure. The 250 cm3 separating funnel
contains 100 cm3 of an equal mixture of chromatographic grade dichloromethane (DCM)
and n-hexane. The samples were extracted for 2 hours under reflux; the crude extracts
were concentrated to a volume of nearly 2 cm3 using a rotary vacuum evaporator. The
concentrates were purified by short-column silica gel chromatography using DCM as the
eluting solvent, the eluates were further reduced to a final volume of 2 cm3 using nitrogen
gas and reconstitute with 2 cm3 of chromatographic grade iso-octane. The purified
extracts (in sealed vials) were kept in the refrigerator for analysis with Gas chromatogra­
phy/ flame ionisation detector (GC-FID).

2.2.2. Chromatographic analysis

Chromatographic analyses were performed with 7890A Agilent gas chromatograph coupled
to a flame ionisation detector, Polaris Q, manufactured by Thermo Scientific. A HP-5 capillary
column (30 m × 320 µm × 0.25 µm) from Agilent Technology Inc. (Santa Clara, USA) was
used with an oven temperature program, starting at 60°C followed by heating at a rate of
30°C min−1 to 150°C, an increase to 210°C at a rate of 12°C min−1 held for 4 min, an increase
to 240°C at a rate of 15°C min−1, an increase to 320°C at a rate of 8°C min−1 held for 5 min.
The carrier gas was helium (99.999%) at a flow rate of 1.2 mL min−1 with a make-up gas:
nitrogen. Ignition gases were hydrogen and compressed air. The injector was operated at
270°C in splitless mode for 3 min. The ion trap was operated in the electronic impact mode
(EI) with 70 eV energy and positive mode. The temperature of the ion source was 250°C and
the interface temperature was 300°C. The analysis was performed in segment scan mode
(m/z 50–300). Total run time and detector temperature were 32.25 min and 325°C respec­
tively. The concentration of the analytes was determined by the peak area of the sample
against those of the standard with which the equipment was calibrated.

2.2.3. Method validation

Performance parameters such as limit of detection (LOD), limit of quantification (LOQ),
precision, and recovery were evaluated according to the recommendations of the
Eurachem Guide [35]. We adopted the recommendation which was previously used by
dos Santos et al. (2021) [10] with modifications. The calibration curves for the analytes were
6 V. N. OKAFOR ET AL.

made, in triplicate, at 7 concentration levels using deionised water spiked with PAH solu­
tions. Concentration levels were 0.5, 1.0, 2.0, 4.0, 8.0, 16.0 and 32.0 µg L−1. LODs and LOQs
were obtained by analysing10 blanks.. Multiplying the LOD by 3.33, the LOQ was calculated.
Intra-day precision was evaluated at concentrations of 2.0 and 8.0 µg L−1, and 3 replicates
were performed at each concentration. Inter-day precision was assessed on 2 consecutive
days. Recovery was evaluated at a concentration of 4.0 µg L−1 through 5 replicates.

2.3. Statistical analysis

The measured GC-FID data were analysed using the Microsoft Excel 2019 software to
determine Pareto chart, Pearson correlation and other statistical tools [36].

2.4. Ecological risk assessment

It was analysed according to United States Environmental Protection Agency (US EPA)
guidelines [37].

2.4.1. Contamination factor (CF)

This is the concentration of PAHs of interest against the background value according to
US EPA [36].

PAHsofinterest
CF ¼ (1)
USEPAbackgroundvalue

US EPA background values for some PAHs used in the present work were adapted from
Verbruggen (2012) [36]

2.4.2. Degree of contamination (Cdeg)

This is the summation of contamination factor of all PAHs in different water samples
X
Cdeg ¼ ðCFPAHs Þ ¼ CF1 þ CF2 þ CF3 þ � � � þ CFn (2)

where CF is contamination factor of PAHs of interest and n is total number of PAHs

present

2.4.3. Pollution load index (PLI)

This is the product of contamination factor of all PAHs in different water samples

PLI ¼ ðCF1 � CF2 � CF3 � � � � � CFn Þ1=n (3)

where CF is contamination factor of PAHs of interest and n is total number of PAHs

present [36].
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 7

2.5. Human health risk assessment (HHRA)

It involves the possible adverse health effects due to PAH exposure on a population
matrix. It is divided into carcinogenic and non-carcinogenic risk assessments, which were
first conducted by the US EPA. HHRA was calculated for the fifteen studied water samples
by the equations Chronic Daily Intake by Dermal (CDIder, 4) and Chronic Daily Intake by
Ingestion (CDIing, 5) respectively, as shown below.
�
CDIder ¼ CS�SAxAFxABS�ETEF�ED�CF
BW�AT (4) [37]
CS�IR�EF�ED�CF
�
CDIing ¼ BW�AT (5) [37]
where: CS is concentration of PAHs of interest
SA is skin area (Adults and children: 19652cm2 and 6365 cm2) [37]
AF is water adherence (Adults and children: 0.2mgcm−2) [37]
ABS is fraction of PAHs absorbed through the skin (0.13) [37]
ET is exposure time (Adult during bathing, cooking, washing and other domestic activ­
ities: 3 h/event, children during bathing, playing and other domestic activities, 2 h/event) [37]
EF is exposure frequency (350 days) [37]
ED is exposure duration (Adults and children: 30 years and 6 years) [37]
CF is conversion factor (1.00E-06) [37]
BW is body weight (Adults and children: 80 kg and 15 kg) [37].
AT is average time (non-carcinogen: ED×365; carcinogen: 70 × 365) [37]
IR is ingestion rate (Adult and children: 2.5 L/day and 0.78 L/day) [37]
The carcinogenic risk assessment is given in Equation 6:
Risktotal ¼ Riskder þ Risking ¼ ðCDIder þ CDIingÞxCSF (6) [37]
where: Risk is unitless probability of individual development cancer over a lifetime.
CSF is cancer slope factor (mg/kg/day).
The non-carcinogenic risk � assessment
� �CDIingis
�� given in Equation 7:
HI ¼ HQder þ HQing ¼ CDIder RfD þ RfD (7) [37]
where: HI is hazard index, which is the probability to experience health effect.
HQ is Hazard quotient.
RfD is reference dose (mg/kg/day).

3. Results and discussions

3.1 Method validation For each analyte, the coefficients of determination (R2), LODs, and
LOQs are listed in Table 2. The R2 values demonstrate that the linear models proposed are
well adjusted. R2 values greater than 0.995, according to Christian (2003) [38] and
Eurachem (1998) [39], are acceptable. The R2 for all PAHs was between 0.9622 and
0.9983, showing acceptable regression line linearity as well as good correlation and
hence good instrument calibration. The LODs and LOQs obtained in this investigation
were significantly lower than those by Coelho et al. [40], with the exception of BghiP,
where the authors reported LOD and LOQ of 0.10 and 0.32, respectively, which are slightly
lower than those obtained in this study. However, the LODs and LOQs obtained in this
study are consistent with those reported by dos Santos et al. (2021) [10]. All these facts
demonstrate that the approach had good sensitivity.
8 V. N. OKAFOR ET AL.

Table 1. Selected points for water sampling in Ifite Ogwari, Anambra State.
No Sampling point Sample Code Coordinates
1 Isiachala stream SA 06°34.589′ N, 06°57.083′ E
2 Iyiutu stream SB 06°14.816′ N, 07°07.287′ E
3 Ube stream SC 06°36.702′ N, 06°56.478′ E
4 Ahala stream SD 06°36.289′ N, 06°56.666′ E
5 Tabasi stream SE 06°36.015′ N, 06°56.581′ E
6 Nabaloku stream SF 06°36.195′ N, 06°56.383′ E
7 Atammele stream SG 06°36.509′ N, 06°57.185′ E
8 Ogbu stream SH 06°36.067′ N, 06°57.082′ E
9 Omambala river RA 06°36.737′ N, 06°56.074′ E
10 Igbazine hand dug well WA 06°36.221′ N, 06°56.527′ E
11 Double hand dug well WB 06°36.434′ N, 06°57.139′ E
12 Ogba hand dug well WC 06°36.274′ N, 06°57.198′ E
13 Onowulugbe hand dug well WD 06°36.154′ N, 06°57.176′ E
14 Orator hand dug well WE 06°36.174′ N, 06°57.085′ E
15 Commodore hand dug well WF 06°36.041′ N, 06°57.024′ E

Table 2. Coefficient of determination (R2), limit of determination (LOD) and limit of quantification
(LOQ) of the GC-FID method of PAHs analysis.
LOD (µg L−1) LOQ (µg L−1)
2 −1 −1
PAH Analyte Abbreviation R LOD (µg L ) LOQ (µg L ) [40] [40]
Naphthalene Nap 0.9891 0.0157 0.0522 0.27 0.91
Acenaphthylene Ace 0.9919 0.0083 0.0278 0.06 0.21
Acenaphthene Acn 0.9983 0.0204 0.0680 0.08 0.28
Fluorene Flu 0.9725 0.0211 0.0703 0.11 0.38
Phenanthrene Phe 0.9967 0.0038 0.0125 0.12 0.38
Anthracene Ant 0.9980 0.0056 0.0186 0.09 0.31
Fluoranthene Flt 0.9860 0.0060 0.0201 0.07 0.25
Pyrene Pyr 0.9758 0.0130 0.0434 0.19 0.63
Benzo[a]anthracene BaA 0.9916 0.0044 0.0147 0.50 1.67
Chrysene Cry 0.9641 0.0033 0.0109 0.44 1.48
Benzo[b]fluoranthene BbF 0.9935 0.0178 0.0592 0.09 0.29
Benzo[k]fluoranthene BkF 0.9904 0.0244 0.0814 0.08 0.27
Benzo[a]pyrene BaP 0.9957 0.0127 0.0423 0.12 0.41
Indeno[123-c,d]pyrene I123cdP 0.9622 0.0608 0.2025 0.10 0.34
Dibenzo[a,h]anthracene DBA 0.9871 0.1236 0.4115 0.23 0.77
Benzo[g,h,i]perylene BghiP 0.9833 0.1131 0.3767 0.10 0.32

Table 3 shows the CV results for intra-day and inter-day accuracy evaluation for
concentration levels 2.0 and 8.0 g L−1, as well as the % recovery for level 4.0 g L−1.
Precision CV values ranged from 5.12 to 18.24%, showing that the approach was accurate.
The analyte recovery values in water samples ranged from 83.94 to 99.99%, which is
consistent with earlier research findings of 83.6 to 98.5% [40], 80 to 111% [41], and 80.1 to
100.3% [10].

3.1. Composition of PAHs in different water sources

Table 4 gives the concentration of 16 priority PAHs assessed from selected water samples
collected from Ifite Ogwari, Anambra State. From the Table extracted from GC-FID
chromatograms of the water bodies, streams (SA – SH), river (RA) and wells (WA – WF)
had presence of Nap (5.07–5.76 ng/μl) and Cry (49.68–128.65 ng/μl) across all samples. As
regards other PAHs components, BkF was present in all samples except SE, RA, WC, WD,
WE and WF, as the highest concentration was WB (24.53 ng/μl) and least for SA (5.26 ng/
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 9

Table 3. Precision and recovery of GC-FID method for PAH analysis in water samples from Ifite Ogwari,
Anambra State.
PAH Analyte Intra-assay Inter-assay Recovery (%)
PAHs 2.00 µg L−1. 8.00 µg L−1. 2.00 µg L−1. 8.00 µg L−1. 4.00 µg L−1.
Nap 7.92 9.99 15.37 12.33 96.52
Ace 8.33 10.01 16.41 12.34 91.47
Can 9.20 10.20 13.23 11.00 86.02
Flu 12.52 9.12 14.66 9.70 99.99
Phe 7.81 5.45 17.70 13.28 87.34
Ant 8.00 5,12 16.15 17.17 97.12
Flt 11.56 9.41 17.90 10.11 99.20
Pyr 11.56 10.40 17.90 10.11 97.56
BaA 12.80 13.11 13.36 13.00 98.50
Cry 14.73 10.10 12.58 8.67 88.99
BbF 10.81 9.26 18.24 16.25 95.96
BkF 13.47 11.00 12.50 11.20 87.91
BaP 10.70 7.98 15.12 15.00 91.92
I123cdP 10.40 6.96 15.00 12.49 94.59
DBA 9.77 8.22 13.79 12.00 83.94
BghiP 8.11 5.72 12.51 10.00 98.23

μl) accordingly. BbF was present in SA (21.13 ng/μl), SB (28.92 ng/μl), SD (20.25 ng/μl), SE
(11.93 ng/μl), RA (13.90 ng/μl), WC (11.68 ng/μl), WD (12.14 ng/μl), WE (16.33 ng/μl), WF
(17.25 ng/μl).
The GC-FID chromatogram for SA is shown in Figure 3. The chromatograms for the
other water bodies are presented in appendix 1. BaP is used as a reference PAHs
component as stated by WHO (2017) and US EPA (2017) for conducting evaluation of
other priority PAHs components as depicted in Table 5. As such, we can see that BaP was
present in 8 sampling points (SA, SB, SC, SD, SE, RA, WB and WE), which had lower
concentration as regards other PAHs components assessed. Pyr was present in SB (3.58
ng/μl) only with Flt and DBA present in SA and SB respectively. Figure 3 gives the
percentage stark column of detected PAHs components across different sample locations
in Ifite Ogwari. A cursory review shows that Cry was predominantly present with percen­
tage concentration ranging from 60–87% across all samples. Nap ranged between 4 and
8%, with other PAHs having percentage concentration between 25 and 45%.
As regards the sampling points (Table 4), we can see that SB had the highest number of
PAHs components (Nap, Flt, Pyr, BaA, Cry, BkF, BbF, BaP, DBA and BghiP) which was
represented in the pareto chart as shown in Figure 4. In decreasing order, the cumulative
PAHs are SB (194.68 ng/μl) > SA (161.00 ng/μl) > SD (157.96 ng/μl) > WB (153.41 ng/μl) >
WF (144.90 ng/μl) > SG (115 ng/μl) > RA (114.33 ng/μl) > WE (112.04 ng/μl) > SC (105.60
ng/μl) > WD (90.97 ng/μl) > SH (77.17 ng/μl) > SF (70.41 ng/μl) > WC (69.09 > SE (68.74 ng/
μl) > WA (67.61 ng/μl). In addition, from the pareto chart (Figure 4), we can see that there
is steady increase from 10% pareto line towards 105%. This is due to the relative closeness
of variable PAHs components assessed in tandem to different sampling points.

3.2. Correlation matrix of different water sources

Table 5 gives the correlation matrices of assessed PAHs components which evaluated the
strength and direction of a linear relation (PAHs variables of interest). In order to derive
salient information, the correlation was conducted at significance p ≤ 0.05 having
 10
V. N. OKAFOR ET AL.

Table 4. Concentration of the 16 priority PAHs (ng/µl) in the water samples.

PAHs SA SB SC SD SE SF SG SH RA WA WB WC WD WE WF [36]
Nap 5.297 5.157 5.226 5.207 5.080 5.074 5.086 5.098 5.545 5.167 5.581 5.263 5.241 5.760 5.193 0.04
Flt 4.036 3.953 BDL BDL BDL BDL BDL BDL BDL BDL 5.467 BDL BDL BDL BDL 0.05
Pyr BDL 3.582 BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL 0.5
BaA 4.070 4.781 4.154 4.321 BDL BDL BDL BDL 4.228 BDL 5.347 BDL BDL BDL BDL 0.005
Cry 82.408 128.652 69.314 101.476 50.729 51.651 89.216 57.780 89.314 49.680 107.479 52.151 73.589 71.549 100.889 0.05
BkF 5.264 7.604 17.874 5.371 BDL 13.685 21.026 14.293 BDL 12.760 24.531 BDL BDL BDL BDL 0.005
BbF 21.134 28.915 BDL 20.248 11.931 BDL BDL BDL 13.896 BDL BDL 11.682 12.136 16.327 17.246 0.005
BaP 3.467 5.136 1.762 2.281 1.003 BDL BDL BDL 1.349 BDL 5.002 BDL BDL 2.078 BDL 0.0005
DBA 23.505 4.003 BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL BDL 0.0005
BghiP 11.819 2.893 7.273 19.071 BDL BDL BDL BDL BDL BDL BDL BDL BDL 16.331 21.575 0.03
Total PAHs 161.00 194.676 105.603 157.975 68.743 70.41 115.328 77.171 114.332 67.607 153.407 69.096 90.966 112.045 144.903
BDL = < 0.001
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 11

Figure 3. GC-FID Chromatogram of SA (Stream A – Isiachala satrem).

Table 5. Correlation matrix of PAHs component in relation to sampling points.

PAHs Nap Flt Pyr BaA Cry BkF BbF BaP DBA BghiP
Nap 1
Flt 0.265 1
All Pyr −0.146 0.449 1
Samples BaA 0.316 0.668 0.361 1
(Streams, Cry 0.225 0.584 0.573 0.669 1
River and BkF −0.159 0.334 −0.018 0.243 0.096 1
Wells) BbF 0.166 0.243 0.535 0.307 0.530 −0.700 1
BaP 0.413 0.871 0.557 0.834 0.691 0.199 0.434 1
DBA 0.018 0.536 0.099 0.335 0.143 −0.096 0.403 0.397 1
BghiP 0.229 −0.056 −0.083 0.129 0.349 −0.343 0.513 0.148 0.214 1
Nap 1
Flt 0.556 1
Streams Pyr 0.019 0.646 1
(SA – SH) BaA 0.845 0.599 0.455 1
Cry 0.374 0.599 0.739 0.700 1
BkF −0.217 −0.360 −0.171 −0.249 −0.080 1
BbF 0.489 0.763 0.633 0.691 0.722 −0.727 1
BaP 0.643 0.855 0.742 0.865 0.770 −0.470 0.898 1
DBA 0.712 0.781 0.028 0.412 0.180 −0.334 0.481 0.512 1
BghiP 0.792 0.197 −0.127 0.740 0.403 −0.336 0.503 0.453 0.362 1
Nap 1
Flt 0.429 1
Pyr 0.000 0.000 1
BaA 0.429 1.000 0.000 1
Well Cry 0.297 0.643 0.000 0.643 1
(WA – WF) BkF 0.213 0.869 0.000 0.869 0.355 1
BbF 0.068 −0.610 0.000 −0.606 0.059 −0.894 1
BaP 0.754 0.914 0.000 0.914 0.604 0.744 −0.427 1
DBA 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 1
BghiP 0.219 −0.310 0.000 −0.312 0.392 −0.460 0.720 −0.110 0.000 1
Significance p ≤ 0.05

predominantly positive correlation than negative using correlation level of: strong (≥ 0.70
PC ≤ 1.00), medium (≥ 0.30 PC ≤ 0.69) and weak (≥ 0.00 PC ≤ 0.29) correlations [42].
Therefore, correlation conducted on all samples (surface and underground waters) gave
a mix of weak and medium correlation which entails that the PAHs component were from
similar source but its interactions were not strong due to varying biochemical and leaching
12 V. N. OKAFOR ET AL.

Figure 4. Pareto chart of cumulative PAHs in the 15 sampling points of Ifite Ogwari.

process from either the surface water (stream and river) or underground water (well)
sources [43,44]. BaP produced strong correlation with Flt (0.87) and BaA (0.83) respectively.
For stream correlation matrices, we can see that there was presence of strong, medium and
weak medium correlations, which entails that there were strong interactions of all stream
sources to give such regression. As such, correlation of BaP produced strong correlation
with Flt (0.855), Pyr (0.742), BaA (0.865), Cry (0.770) and BbF (0.898). Nap correlated strongly
with BaA (0.845), DBA (0.712) and BghiP (0.792). Flt correlated with BbF (0.763) and DBA
(0.781). Cry correlated with Pyr (0.739). For Wells (WA – WF), we can see that there was
strong correlation of BaP with Nap (0.754), Flt – BaA (0.914) and BkF (0.744), BkF correlated
strongly with Flt and BaA (0.869), which entails that there was strong indication that BaA,
BkF and Flt contaminants were predominant across all well sources. Having assessed the
aforementioned, we can therefore state that across all three assessed correlations, BbF and
BkF correlated negatively (– 0.700, – 0.727 and – 0.894), which means that there was
different biochemical interaction taking places in all sample sources [45]. For positive
correlations, we can postulate that all assessed PAHs components were from similar
pollution source and migratory behaviour that can in-turn speciate with diverse organ­
isms (flora and faunas) in relation to human exposure [46,47].
PAHs from petrogenic sources are defined by the predominance of Low Molecular
Weight (2 or 3-rings) (LMW PAHs), whereas PAHs from pyrogenic sources are characterised
by High Molecular Weight (4–6-rings) (HMW PAHs), according to Bucheli et al., (2014) [48]
and Shamilishvily et al., (2018) [49]. This is due to the fact that LMW PAHs are produced at
low to moderate temperatures, such as during biomass burning, whereas HMW PAHs are
produced at high temperatures, such as during automobile emissions [50]. In comparison
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 13

to heavy PAHs, Nap and other light PAHs found in the groundwater of the study area are
less harmful and carcinogenic. The ability of more of the lower molecular weight PAHs to
leach easily through the soil to the groundwater as a result of rainfall in stream samples
compared to well samples could be attributed to the fact that wells are not covered,
allowing more of the lower molecular weight PAHs to leach easily through the soil to the
groundwater as a result of rainfall [51]. Similarly, run-off from various locations near the
sampling site carries some dissolved PAHs with it, polluting the subsurface water with this
type of trace organics more [52,53]. Similarly, an increase in the volume of water in the
ground during the wet season may facilitate the breakdown of additional PAHs, particularly
low molecular weight PAHs, resulting in higher concentrations during the wet season
[54,55]. The presence of PAHs in the stream investigated could be ascribed to anthropo­
genic activity including forest and firewood burning for cooking, which is typical in the
area. Another source could be the eroding of the asphalt layer on the area’s major high­
ways, automotive emissions, the burning of carbon-containing garbage in mechanic shops
in nearby cities, and other human activities [56]. The discharged PAHs settle in soils and
surface water before being washed into groundwater after heavy rains or runoff.
PAHs have been found to produce biological alterations in organisms as a result of
biochemical transformations and chemical interactions in both water and sediment in
a variety of water sources [57,58]. PAHs are generally teratogenic, carcinogenic, and
mutagenic, and may cause lung, bladder, and skin cancer [59], since high levels of PAHs
have been proven to have immunosuppressive effects and to cause oxidative stress
during metabolism [60].
According to Santucci and Shah (2000) [61], Nap in high concentrations has a negative
impact on red blood cell synthesis in the bones and can cause hereditary disorders such as
glucose-6-phosphate dehydrogenase deficiency (G6PD), which affects 400 million people
worldwide. It can cause haemolytic anaemia in children, resulting in high fatigue, low
appetite, restlessness, pale skin, and jaundice, as well as nausea, vomiting, diarrhoea, blood
in the urine, and jaundice [62]. Because Cry is estimated to have 1% biological toxicity with
BaP [63–65], BaP has been used as a reference PAHs compound to assess the carcinogenesis
of other PAHs components. Furthermore, BaP has been proven to induce both short-term
(anaemia and red blood cell damage) and long-term (nervous and reproductive system
disruption, immune suppression) health problems over time [12,66–69]. BbF and BkF are
recognised carcinogens that are present in pyrogenic emissions and bioaccumulate in
organisms before being deposited in sediment and infiltrating subsurface water sources
[70]. The carcinogenic ingredient BaA has been linked to organ tumours [71,72]. BghiP is
formed through incomplete burning of petroleum and coal and has no known cancer risks;
nevertheless, when combined with BaP, it has the potential to produce skin tumours and
organ failure over time [73,74].

3.3. Ecological risk assessment

Ecological risk assessment was conducted in using the US EPA model adopted by
Verbruggen (2012) [36] to determine the potential impact of PAHs to the aquatic ecosys­
tem of Ifite Ogwari. Instrumental data presented in ng/µl was converted to mg/l as shown
in Equation 8, to enable ecological statistical assessment [75].
14 V. N. OKAFOR ET AL.

ng 109 g 109 6 g 103 g 1mg

¼ ¼ ¼ ¼ (8)
μl 10 6 l l l l

Table 6 depicts ecological calculations conducted for Ifite Ogwari using US EPA background
standards as utilised by Verbruggen (2012) [36]. The contamination factor (CF) of various
water samples revealed that Nap ranged from 126.85 to 144.00, BaA from 814 to 1069.4, Cry
from 993.6 to 2573.04, BkF from 1052.8 to 4906.2, and BaP from 2006 to 10,272. After
accessing the CF, the degree of contamination, which is a cumulative sum of CF, ranged from
(WC) 3511 to (SA) 62,293 for all samples, indicating a moderate level of contamination across
various water samples. As a result, the PLI was calculated in tandem with the number of
variables examined and was greater than one (1), indicating PAH pollution in all samples [43].
The result of ecological risk showed that these detected PAHs contaminants pose
a high ecological risk to flora and fauna in relation to humans who consume them as
food, as the release of these PAHs contaminants could be transboundary [46], which could
exacerbate the problem in Ifite Ogwari, which is an agrarian community involved in
farming and rearing of animals. In addition, other PAH contributors could be from
automobiles, burning of sanitary landfills, and bush burning can lead to ground water
infiltration over a long period [44,76].

3.4. Health and exposure risk assessment

The rational in conducting risk assessment is to evaluate the extent of chronic daily intake
(CDI) across different exposure medium (ingestion and dermal contact) of PAHs in streams
(SA – SH), river (RA) and wells (WA – WF) that are connected via the biochemical
interaction with diverse organisms (flora and faunas). Human health and exposure risk
assessment was conducted on PAHs concentration in water sources using US EPA risk
assessment models that gives the exposure proportion with regards to the health impli­
cation (carcinogenesis and non-carcinogenesis) for adults and children [77].
Table 7 gives the result of cancer risk evaluated from cumulative sum of CDI – ingestion
and CDI – dermal contact of PAHs concentration in water samples. The sum total of each
of both adults and children ranged from 9.20E – 05 to 4.38E–02 and 1.43E–04 to 6.81E – 02
respectively. Using USEPA reference standards (1 × 10E–06 – 1 × 10E–04), we can state
that for Adults: SF, SG, SH WA and WB were within the reference range, while others (SA,
SB, SC, SD, SE, RA, WC, WD, WE and WF) were above the set standard (<10E–04). As regards
children, we can suggest that SG, SH and WA were within the reference range and vice
versa for other PAHs components [78–80].
Figure 5 gives the sum-total of cancer risk evaluated from different exposure mediums,
as preliminary review shows that the cancer risk values of children were predominantly
higher than adults. Therefore, values below 1 × 10E – 4 will experience carcinogenic
influence over a period of time [70].
The hazard index of the PAHs component assessed was evaluated for the exposure
population (adults and children) as shown in Table 8. Figure 6 also depicts the hazard
index of the detected PAHs for the exposure population. As such, we can see that all the
evaluated samples were above 1 as stipulated by US EPA, which implies that both adults
and children will experience health-related issues over a period of time.
Table 6. Contamination factor (CF), degree of contamination (Cdeg) and pollution load index (PLI) value of water samples.
PAHs SA SB SC SD SE SF SG SH RA WA WB WC WD WE WF
Nap 132.43 128.93 130.65 130.18 127.00 126.85 127.15 127.45 138.63 129.18 139.53 131.58 131.025 144.00 129.83
Flt 80.72 79.06 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 109.34 0.00 0.00 0.00 0.00
Pyr 0.00 7.16 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BaA 814.00 956.2. 830.80 864.20 0.00 0.00 0.00 0.00 845.60 1069.40 0.00 0.00 0.00 0.00
Cry 1648.16 2573.04 1386.28 2029.52 1014.58 1033.02 1784.32 1155.60 1786.28 993.60 2149.58 1043.02 1471.78 1430.98 2017.78
BkF 1052.80 1520.8. 3574.80 1074.20 0.00 2737.00 4205.20 2858.60 0.00 2552.00 4906.20 0.00 0.00 0.00 0.00
BbF 4226.80 5783.00 0.00 4049.60 2386.20 0.00 0.00 0.00 2779.20 0.00 0.00 2336.40 2427.2 3265.40 3449.20
BaP 6934.00 10272.00 3524.00 4562.00 2006.00 0.00 0.00 0.00 2698.00 0.00 10004.00 0.00 0.00 4156.00 0.00
DBA 47010.00 8006.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BghiP 393.97 96.43 242.43 635.70 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 544.37 719.17
Cdeg 62292.87 29422.62 9688.963 13345.4 5533.78 3896.87 6116.67 4141.65 8247.705 3674.775 18378.05 3510.995 4030.005 9540.747 6315.972
N* 9 10 6 7 4 3 3 3 5 3 6 3 3 5 4
PLI 1263.302 645.3522 878.4617 1163.146 886.2004 710.49 984.4461 749.4919 1094.419 689.3243 1094.731 684.4437 776.4274 1087.677 897.8319
N* is number of PAH used in calculating Cdeg and PLI.
INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY
15
 16

Table 7. Cancer risk of PAHs exposure matrix in adults and children.

ADULT SA SB SC SD SE SF SG SH RA WA WB WC WD WE WF
V. N. OKAFOR ET AL.

Nap 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Flt 5.95E-05 5.83E-05 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 8.06E-05 0.00 0.00 0.00 0.00
Pyr 0.00 5.28E-04 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BaA 6.00E-04 7.05E-04 6.12E-04 6.37E-04 0.00 0.00 0.00 0.00 6.23E-04 0.00 7.88E-04 0.00 0.00 0.00 0.00
Cry 1.21E-04 1.90E-04 1.02E-04 1.50E-04 7.48E-05 7.61E-05 1.32E-04 8.52E-05 1.32E-04 7.32E-05 1.58E-04 7.69E-05 1.08E-04 1.05E-04 1.49E-04
BkF 7.76E-06 1.12E-05 2.63E-05 7.92E-06 0.00 2.02E-05 3.10E-05 2.11E-05 0.00 1.88E-05 3.62E-05 0.00 0.00 0.00 0.00
BbF 3.12E-03 4.26E-04 0.00 2.99E-03 1.76E-03 0.00 0.00 0.00 2.05E-03 0.00 0.00 1.72E-03 1.79E-03 2.41E-03 2.54E-03
Bap 5.11E-03 7.57E-03 2.60E-03 3.36E-03 1.48E-03 0.00 0.00 0.00 1.99E-03 0.00 7.37E-03 0.00 0.00 3.06E-03 0.00
DBA 3.46E-02 5.90E-03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BghiP 1.74E-03 4.26E-05 1.07E-04 2.81E-04 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 2.41E-04 3.18E-04
TOTAL 4.38E-02 1.93E-02 3.45E-03 7.42E-03 3.31E-03 9.63E-05 1.62E-04 1.06E-04 4.79E-03 9.20E-05 8.44E-04 1.79E-03 1.89E-03 5.82E-03 3.01E-03
CHILDREN SA SB SC SD SE SF SG SH RA WA WB WC WD WE WF
Nap 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Flt 9.25E-05 9.06E-05 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.25E-04 0.00 0.00 0.00 0.00
Pyr 0.00 8.21E-04 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BaA 9.33E-04 1.09E-03 9.52E-04 9.90E-04 0.00 0.00 0.00 0.00 9.69E-04 0.00 1.23E-03 0.00 0.00 0.00 0.00
Cry 1.89E-04 2.95E-04 1.59E-04 2.33E-04 1.16E-04 1.18E-04 2.04E-04 1.32E-04 2.05E-04 1.14E-04 2.46E-04 1.20E-04 1.69E-04 1.64E-04 2.31E-04
BkF 1.21E-05 1.74E-05 4.10E-05 1.23E-05 0.00 3.14E-05 4.82E-05 3.28E-05 0.00 2.92E-05 5.62E-05 0.00 0.00 0.00 0.00
BbF 4.84E-03 6.63E-03 0.00 4.64E-03 2.73E-03 0.00 0.00 0.00 3.18E-03 0.00 0.00 2.68E-03 2.78E-03 3.74E-03 3.95E-03
Bap 7.95E-03 1.18E-02 4.04E-03 5.23E-03 2.30E-03 0.00 0.00 0.00 3.09E-03 0.00 1.14E-02 0.00 0.00 4.76E-03 0.00
DBA 5.39E-02 9.17E-03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BghiP 2.71E-04 6.63E-05 1.67E-04 4.37E-04 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 3.74E-04 4.94E-04
TOTAL 6.81E-02 2.99E-02 5.36E-03 1.15E-02 5.15E-03 1.50E-04 2.53E-04 1.65E-04 7.45E-03 1.43E-04 1.31E-02 2.80E-03 2.95E-03 9.04E-03 4.68E-03
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 17

Figure 5. Cancer risk total of PAHs across different water samples.

A human health risk assessment conducted showed varying chronic daily intake for
ingestion and dermal contact. The cancer risk showed that some water sources were
within and vice versa for other water sources, which implies that cancer related illness is
presumed to manifest in the exposed population (adults and children) over a period of
time depending on age, sex, body weight, exposure period, and location and proximity to
exposure points. All water sources had a hazard index (HI) greater than one (1), implying
that the entire population is at risk of adverse health illness via dermal rather than oral
ingestion exposure route. New studies by WHO and UE EPA have shown that the human
body excretes PAHs via sweat or urination [36]. (VerBruggen, 2012). Children are prone to
health risks and related complications compared to adults, and therefore they are at risk
compared to adults, which implies that the study location is unfit for recreational and
domestic utilisation, as in the case of stream water. This observation is in agreement with
that of Chen et al. (2004) [57].
This study is likely the first of its sort in terms of evaluating PAHs in a rural community
in Ifite Ogwari and its environs. Human health risk evaluation of water samples from the
town reveals that those exposed in the community may develop cancer at some point in
their lives. As a result of this research, people in rural Anambra communities are more
aware of the poor water supply and the need for the government to provide alternate
sources of potable water.

4. Conclusions
This investigation identified naphthalene, fluoranthene, pyrene, benzo [a] anthracene,
chrysene, benzo[k]fluoranthene, benzo[b]fluoranthene, benzo[a]pyrene, dibenzo[a,h]
anthracene, and benzo[ghi]perylene, all of which were above the specified drinking
water criteria of 0.005 The accumulation of PAHs can be harmful to human health
and, in some situations, can lead to life-threatening disorders such as cancer of the
organs. According to the Pareto chart, the high cumulative variance peaked at 105%
when compared to other PAHs discovered. Ecological risk indicates that the result
was higher than the US EPA background value, implying that it may have an
influence on the ecosystem and natural balance of plants and animals. The hazard
 18

Table 8. Hazard index of PAHs exposure matrix in adults and children.

ADULT SA SB SC SD SE SF SG SH RA WA WB WC WD WE WF
V. N. OKAFOR ET AL.

Nap 1.87E-01 1.82E-01 1.85E-01 1.84E-01 1.79E-01 1.79E-01 1.79E-01 1.80E-01 1.96E-01 1.83E-01 1.97E-01 1.86E-01 1.85E-01 2.04E-01 1.83E-01
Flt 7.13E-02 6.98E-02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 9.66E-02 0.00 0.00 0.00 0.00
Pyr 0.00 8.44E-02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BaA 9.59E-02 1.13E-01 9.79E-02 1.02E-01 0.00 0.00 0.00 0.00 9.96E-02 0.00 1.26E-01 0.00 0.00 0.00 0.00
Cry 1.94E+00 3.03E+00 1.63E+00 2.39E+00 1.19E+00 1.22E+00 2.10E+00 1.36E+00 2.10E+00 1.17E+00 2.53E+00 1.23E+00 1.73E+00 1.69E+00 2.38E+00
BkF 1.24E-01 1.79E-01 4.21E-01 1.27E-01 0 3.22E-01 4.95E-01 3.37E-01 0.00 3.01E-01 5.78E-01 0.00 0.00 0.00 0.00
BbF 4.98E-01 6.81E-01 0 4.77E-01 2.81E-01 0.00 0.00 0.00 3.27E-01 0.00 0.00 2.75E-01 2.86E-01 3.85E-01 4.06E-01
Bap 8.17E-02 1.21E-01 4.15E-02 5.37E-02 2.36E-02 0.00 0.00 0.00 3.18E-02 0.00 1.18E-01 0.00 0.00 4.89E-02 0.00
DBA 5.54E-01 9.43E-02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BghiP 2.78E-01 6.81E-02 1.71E-01 4.49E-01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 3.85E-01 5.08E-01
TOTAL 3.83E+00 4.62E+00 2.55E+00 3.78E+00 1.68E+00 1.72E+00 2.78E+00 1.88E+00 2.76E+00 1.65E+00 3.65E+00 1.69E+00 2.20E+00 2.71E+00 3.47E+00
CHILDREN SA SB SC SD SE SF SG SH RA WA WB WC WD WE WF
Nap 2.69E-01 2.62E-01 2.66E-01 2.67E-01 2.58E-01 2.58E-01 2.57E-01 2.59E-01 2.82E-01 2.63E-01 2.84E-01 2.68E-01 2.67E-01 2.93E-01 2.64E-01
Flt 1.03E-01 1.01E-01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.39E-01 0.00 0.00 0.00 0.00
Pyr 0.00 1.21E-01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BaA 1.38E-01 1.62E-01 1.41E-01 1.47E-01 0.00 0.00 0.00 0.00 1.43E-01 0.00 1.81E-01 0.00 0.00 0.00 0.00
Cry 2.79E+00 4.36E+00 2.35E+00 3.44E+00 1.72E+00 1.75E+00 3.03E+00 1.96E+00 3.03E+00 1.68E+00 3.65E+00 1.77E+00 2.49E+00 2.43E+00 3.42E+00
BkF 1.79E-01 2.58E-01 6.06E-01 1.82E-01 0.00 4.64E-01 7.13E-01 4.85E-01 0.00 4.30E-01 8.32E-01 0.00 0.00 0.00 0.00
BbF 7.17E-01 9.80E-01 0.00 6.87E-01 4.05E-01 0.00 0.00 0.00 4.71E-01 0.00 0.00 3.96E-01 4.12E-01 5.54E-01 585E-01
Bap 1.18E-01 1.74E-01 5.97E-02 7.73E-02 3.40E-02 0.00 0.00 0.00 4.57E-02 0.00 1.70E-01 0.00 0.00 7.05E-02 0.00
DBA 7.97E-01 1.36E-01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BghiP 4.01E-01 9.81E-02 2.47E-01 6.47E-01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 5.55E-01 7.32E-01
TOTAL 5.52E+00 6.66E+00 3.67E+00 5.45E+00 2.42E+00 2.47E+00 3.99E+00 2.70E+00 3.97E+00 2.38E+00 5.25E+00 2.43E+00 3.17E+00 3.89E+00 5.00E+00
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 19

Figure 6. Hazard Index of PAHs across different water samples.

index and total cancer risk were found to be below the US EPA recommended value
(1) and ranges (1.0E-06 – 1.0E-04) in a human health risk assessment. This means that
youngsters will suffer from a variety of health problems, including cancer, over time.
As a result, researchers and government agencies must take a holistic strategy to
address the negative ecological and health risks faced by residents of Ifite Ogwari in
Anambra State.

Acknowledgments
The authors would like to thank Nnamdi Azikiwe University for supporting the work and technical
staff of Central Laboratory, Nigerian Institute for Oceanography and Marine Research, Victoria
Island, Lagos for technical assistance.

Disclosure statement
No potential conflict of interest was reported by the author(s).

Funding
This work was unfunded.

ORCID
Vincent N. Okafor http://orcid.org/0000-0002-3838-9635
20 V. N. OKAFOR ET AL.

Authorship contribution statement

Project conceptualization, investigation, methodology, and the first draft of the manuscript [Vincent
N. Okafor]. The final text of the manuscript, as well as literature searches and data curation [Vincent
N. Okafor, Daniel O. Omokpariola, Eucharia C. Igbokwe, Chidera M. Theodore, and Nwaamaka
G. Chukwu]. All of the authors read and approved the final manuscript.

Data availability statement

All data and materials are available.

References
[1] American Conference of Governmental Industrial Hygienists (ACGIH), Polycyclic Aromatic
Hydrocarbons (Pahs) Biologic Exposure Indices (BEI) Cincinnati, OH: American Conference
of Governmental Industrial Hygienists, (2005).
[2] A.T. Lawal, Cogent Environ. Sci. 3, Article 1339841 (2017). doi:10.1080/
23311843.2017.1339841.
[3] E. Boelee, G. Geerling, B. van der Zaan, A. Blauw and A.D. Vethaak, Acta Trop. 193, 217 (2019).
doi:10.1016/j.actatropica.2019.03.011.
[4] C.N. Obi and C.O. Okocha, J. Eng. Appl. Sci. 2, 920 (2007). http://docsdrive.com/pdfs/medwell
journals/jeasci/2007/920-929.pdf. https://medwelljournals.com/abstract/?doi=jeasci.2007.
920.929
[5] C.M.A. Ademorati, Environ. Chem. Toxicol. Foludex Press Ltd Ibadan, Nigeria. 218, (1996).
[6] C.E. Enyoh and B.O. Isiuku, Chem. Afr. 3, 1059 (2020). doi:10.1007/s42250-020-00171-2.
[7] F.C. Ibe, A.I. Opara, C.E. Amaobi and B.O. Ibe, Appl. Water Sci. 11, Article 24 (2021).
doi:10.1007/s13201-020-01355-4.
[8] J.N. Ihedioha, H.O. Abugu, O.T. Ujam and N.R. Ekere, Environ. Monit. Assess. 193, Article 620
(2021). doi:10.1007/s10661-021-09386-3.
[9] S.S. Saini, A. Kabir, A.L.J. Rao, A.K. Malik and K.G. Furton, Separations 4, 22 (2017). doi:10.3390/
separations4020022.
[10] R.R. Dos Santos, M. Orlando, Z. Cardeal and H.C. Menezes, Food Control. 126, 108104 (2021).
doi:10.1016/j.foodcont.2021.108104.
[11] J.O. Omokpariola, D.O. Omokpariola and E.C.E. Omokpariola, Adv. J. Chem. Section B. 3, 68
(2021). doi:10.22034/ajcb.2021.121909.
[12] World Health Organization (WHO), Guidelines for Drinking-water Quality: Fourth Edition
Incorporating the First Addendum (WHO, Geneva, 2017). 978-92-4-154995-0. License: CC BY-
NC-SA 3.0 IGO. https://creativecommons.org/licenses/by-nc-sa/3.0/igo
[13] M.P. Seopela, R.I. McCrindle, S. Combrinck and T.J.C. Regnier, J. Soil Sediments. 16, 2740
(2016). doi:10.1007/s11368-016-1499-x.
[14] T. Sharma, J. Chem. Pharm. Res. 6, 873 (2014). https://www.jocpr.com/articles/in-silico-
investigation-of-polycyclic-aromatic-hydrocarbons-against-bacterial-12-dioxygenase.pdf .
[15] T.C. Nugyen, P. Loganathan, T.V. Nugyen, S. Vigneswaran, J. Kandasame, D. Sly, G. Stevenson
and R. Naidu, Ecotoxicol. Environ. Saf. 104, 339 (2014). doi:10.1016/j.ecoenv.2014.03.010.
[16] L.P. Garcia, B.L. Gonçalves, G. Panho and V.M. Scussel, PUBVET 19, Article 1788 (2014).
doi:10.22256/pubvet.v8n19.1788.
[17] H.I. Abdel-Shafy and M.S.M. Mansour, Egypt. J. Pet. 25, 107 (2016). http://dx.doi.org/10.1016/j.
ejpe.2015.03.011 .
[18] T.E. McGrath, W.G. Chan and M.R. Hajaligol, J. Anal. Appl. Pyrolysis. 66, 51 (2003). doi:10.1016/
S0165-2370(02)00105-5.
[19] A.J. Rascón, A. Azzouz and E. Ballesteros, J. Sci. Food Agric. 99, 1117 (2019). doi:10.1002/
jsfa.9279.
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 21

[20] A. Ishizaki, K. Saito, N. Hanioka, S. Narimatsu and H. Kataoka, J. Chromatogr. A. 1217, 5555
(2020). doi:10.1016/j.chroma.2010.06.068.
[21] A.L.V. Escarrone, S.S. Caldas, E.B. Furlong, V.L. Meneghetti, C.A.A. Fagundes, J.L.O. Arias and
E.G. Primel, Food Chem. 146, 597 (2014). doi:10.1016/j.foodchem.2013.09.006.
[22] L. Singh, J.G. Varshney and T. Agarwal, Food Chem. 199, 768 (2016). doi:10.1016/j.
foodchem.2015.12.074.
[23] R.F. Lima, R.G. Dionello, M.C.R. Peralba, S. Barrionuevo, L.L. Radünz and F.W. Reichert-Júnior,
Food Chem. 215, 165 (2017). doi:10.1016/j.foodchem.2016.07.164.
[24] I.A. Bertinetti, C.D. Ferreira, J.L.F. Monks, P.J. Sanches-Filho and M.C. Elias, J. Food Compos.
Anal. 66, 109 (2018). doi:10.1016/j.jfca.2017.12.009.
[25] R.R. Dos Santos, L.D. Vidotti-Leal, Z. de Lourdes-cardeal and H.C. Menezes, J. Chromatogr. A.
1584, 64 (2019). doi:10.1016/j.chroma.2018.11.046.
[26] V.N. Okafor, U.B. Uche and R.C. Abailim, Chem. Sci. Int. J. 29, 47 (2020). doi:10.9734/CSJI/2020/
v29i130157.
[27] S.A.O. Adeyeye, Curr Nutr Food Sci 16, 866 (2020). doi:10.2174/
1573401315666190215112216.
[28] J. Zhang, G. Liu, R. Wang and J. Liu, Anal. Lett. 47, 2294 (2014). doi:10.1080/
00032719.2014.902464.
[29] V.N. Okafor, P.U. Umennadi, C.C. Odidika and D.C. Vinna, J. Chem. Soc. Niger. 46, 0688 (2021).
doi:10.46602/jcsn.v46i4.646.
[30] S.C. Ewuim, G.O. Ogbuozobe, D.C. Ezeonyejiaku and T.C. Mogbo, Anim. Res. Int. 15, 3065
(2018).
[31] Wikipedia, Orthetrum icteromeles, (2018). http://en.m.wikipedia.org (accessed. Aug 8, 2021).
[32] A. Ifeka, Akinbobola Atmos. Clim. Sci. 5, (2015). DOI:10.4236/acs.2015.51001.
[33] O.R. Iheke and J.C. Nwaru, Niger. J. Rural Sociol. 9, 69 (2009).
[34] NIMET, 2014 Seasonal Rainfall Prediction (SRP). S and E Consulting, Scottsdale, 9 (2014).
[35] Eurachem, Eurachem Guide of 2014, (2014). https://www.eurachem.org/index.php/publica
tions/guides/mv (accessed Jan 15, 2020).
[36] E.M.J. Verbruggen, National Institute for Public Health and the Environment, Ministry of
Health, Welfare and Sport, (2012). https://www.rivm.nl/bibliotheek/rapporten/607711007.
pdf .
[37] Health Canada (HC), Selection of Body Weights Values for Use in Human Health Risk
Assessment (HHRA), Government of Canada, Canada.ca, (2016). assessed July 17, 2021.
[38] G.D. Christian, Analytical Chemistry, 6th ed. (Wiley & Sons, New York, 2004), p. 128.
[39] Eurachem, The Fitness for Purpose of Analytical Methods: A Laboratory Guide to Method
Validation and Related Topics, (1998). https://www.eurachem.org/guides/pdf/valid.pdf
(accessed July 27, 2020).
[40] E. Coelho, C. Ferreira and C.M.M. Almeida, J. Braz. Chem. Soc. 19, 1084 (2008). doi:10.1590/
S0103-50532008000600006.
[41] T. Yoshioka, Y. Nagatomi, K. Harayama and T. Bamba, J. Biosci. Bioeng. 126, 126 (2018).
doi:10.1016/j.jbiosc.2018.01.014.
[42] Z.Y. Zhang and J. Pawliszyn, Chemistry 67, 34 (1995). doi:10.1021/ac00097a007.
[43] O.F. Ojaniyi, P.A.C. Okoye and D.O. Omokpariola, Asian J. Appl. Chem. Res. 9, 64 (2021).
doi:10.9734/AJACR/2021/v9i130205.
[44] T.E. Olagunju, A.O. Olagunju, I.H. Akawu and C.U. Ugokwe, J. Toxicol. Risk Assess. 6, 1 (2020).
doi:10.23937/2572-4061.1510033.
[45] H. Zhi, Z. Zhao and L. Zhang, Chemosphere 119, 1134 (2015). doi:10.1016/j.
chemosphere.2014.09.054.
[46] X. Zheng, B. Han, P. Thavamani, L. Duan and L.R. Naidu, Environ. Earth Sci. 74, 2669 (2015).
doi:10.1007/s12665-015-4287-9.
[47] H.Y. Chen, Y.G. Teng, J.S. Wang, L.T. Song and R. Zuo, Sci. Total Environ. 444, 401 (2013).
doi:10.1016/j.scitotenv.2012.11.108.
[48] T.D. Bucheli, F. Blum, A. Desaules and Ö. Gustafsson, Chemosphere 56, 1061 (2004).
doi:10.1016/j.chemosphere.2004.06.002.
22 V. N. OKAFOR ET AL.

[49] G. Shamilishvily, E. Abakumov and D. Gabov, Solid Earth. 9, 669 (2018). doi:10.5194/se-9-669-
2018.
[50] T.A. Adedosu, O.K. Adeniyi and H.O. Adedosu, Malaysian J. Anal. Sci. 19, 636 (2015). http://
mjas.analis.com.my/wpcontent/uploads/2018/11/Adedosu_19_3_20.pdf .
[51] O.A. Ekpete, O.S. Edori and W.A. Iyama, Int. J. Environ. Sci. Nat. Resour. 21, 556066 (2019).
doi:10.19080/IJESNR.2019.21.556066.
[52] V. Tornero and M. Ribera d’Alcalà, Sci. Total Environ. 466-477, 820 (2014). doi:10.1016/j.
scitotenv.2013.06.106.
[53] United States Environmental Protection Agency (US EPA), (2008). Polycyclic Aromatic
Hydrocarbons (Pahs) — EPA Fact Sheet. Washington (DC): National Center for
Environmental Assessment, Office of Research and Development.
[54] United State Environmental Protection Agency (US EPA) (2009). Provisional Peer-Reviewed
Toxicity Values for Complex Mixtures of Aliphatic and Aromatic Hydrocarbons. (EPA/690/
R-09/012F). Office of Research and Development, National Center for Environmental
Assessment, Superfund Health Risk Technical Support Center. Cincinnati, OH 45268.
[55] United States Environmental Protection Agency (US EPA) (1993). Provisional Guidance for
Quantitative Risk Assessment of Polycyclic Aromatic Hydrocarbons, EPA/600/R-93/089. Office
of Research and Development Washington, DC 20460.
[56] D.O. Omokpariola, E.C.O. Omokpariola and V.U. Okechukwu, Bull. Chem. Soc. Ethiopia. 35, 461
(2021). doi:10.4314/bcse.v35i2.18.
[57] B. Chen, X. Xuan, L. Zhu, J. Wang, Y. Gao, K. Yang, X. Shen and B. Lou, Water Res. 38, 3558
(2004). doi:10.1016/j.watres.2004.05.013.
[58] C.C. Aralu, P.A.C. Okoye and K.G. Akpomie, Int. J. Environ. Anal. Chem. 2021. doi:10.1080/
03067319.2021.1949587
[59] J.C. Fetzer, Polycycl. Aromat. Compd. 27, 143 (2010). doi:10.1080/10406630701268255.
[60] R. Hoover, NASA, (2014). https://www.nasa.gov/ames/need-to-track-organic-nano-particles-
across-the-universe-nasas-got-an-app-for-that
[61] K. Santucci and B. Shah, Acad. Emergency Med. 7, 42 (2000). doi:10.1111/j.1553-2712.2000.
tb01889.x.
[62] S. Sanches, C. Leitão, A. Penetra, V.V. Cardoso, E. Ferreira, M.J. Benoliel, M.T. Barreto Crespo
and V.J. Pereira, J. Hazard. Mater. 192, 1458 (2011). doi:10.1016/j.jhazmat.2011.06.065.
[63] C.A. Menzie, B.B. Potocki and J. Santodonato, Environ. Sci. Technol. 26, 1278 (1992).
doi:10.1021/es00031a002.
[64] D. Mukhopadhyay, P. Nandi, A.C. Varghese, R. Gutgutia, S. Banerjee and A.K. Bhattacharyya,
Fertil. Steril. 94, 595 (2010). doi:10.1016/j.fertnstert.2009.02.031.
[65] Q. Niu, H. Zhang and X. Li, Occup Environ Med 67, 444 (2010). doi:10.1136/oem.2009.047969.
[66] K. Dutta, D. Ghosh, A. Nazmi, K.L. Kumawat and A. Basu, PLoS One 5, 9984 (2010). doi:10.1371/
journal.pone.0009984.
[67] J. Bouayed, F. Desor, H. Rammal, A.K. Kiemer, E. Tybl, H. Schroeder, G. Rychen and
R. Soulimani, Toxicology 259, 97 (2009). doi:10.1016/j.tox.2009.02.0100.
[68] M.M. McCallister, M. Maguire, A. Ramesh, Q. Aimin, S. Liu, H. Khoshbouei, M. Aschner, F.
F. Ebner and D.B. Hood, Neurotoxicology 29, 846 (2008). doi:10.1016/j.neuro.2008.07.008.
[69] F. Sanchez, J.A. Garbarino and A. Vanella, Life Sci. 78, 1401 (2006). doi:10.1016/j.
lfs.2004.10.085.
[70] Agency for Toxic Substances and Drug Registry (ATSDR), Agency for Toxic Substances and Drug
Registry (ATSDR) (Washington, DC, USA: U.S. Department of Health & Human Services, 1995).
[71] Y. Li and X. Duan, Environ. Sci. Pollut. Res. 22, 15432 (2015). doi:10.1007/s11356-015-5333-6.
[72] R. Talhout, T. Schulz, E. Florek, J. van Benthem, P. Wester and A. Opperhuizen, Int. J. Environ.
Res. Public Health. 8, 613 (2011). doi:10.3390/ijerph8020613.
[73] B. Yang, Q.M. Wang, C. Yang, Y.J. Jiang, S.E. Jorgensen, F.L. Xu and X.L. Zhao, Sci. Total Environ.
496, 414 (2014). doi:10.1016/j.scitotenv.2014.07.045.
[74] F. Beltrán, F.J. Rivas, F. Carvalho, B. Acedo and O. Gimeno, J. Hazard. Mater. 116, 95 (2004).
doi:10.1016/j.jhazmat.2004.07.022.
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 23

[75] NZ-EPWP, Data Handling, Monitoring and Sampling Manual, New Zealand Environmental
Protection and Water Policy (2018). http://data-handling-units-and-concentrations.pdf
(assessed Dec 23, 2020).
[76] A.M. Odukoya, S.B. Olobaniyi, T.O. Oluseyi and U.A. Adeyeye, Environ. Nanotechnol. Monit.
Manage. 8, 290 (2017). doi:10.1016/j.enmm.2017.10.005.
[77] United States Environmental Protection Agency (US EPA), (2021). Regional Screening Levels
(Rsls) - Generic Tables. Tables as of: November 2021. https://www.epa.gov/risk/regional-
screening-levels-rsls-generic-tables .
[78] United States Environmental Protection Agency (US EPA) (2005). Guidelines for Carcinogen
Risk Assessment. Report EPA/630/P-03/001F, March 2005. US EPA Risk Assessment Forum,
Washington, DC. https://www.epa.gov/risk/guidelines-carcinogen-risk-assessment
[79] United States Environmental Protection Agency (US EPA), (2005). Supplemental Guidance for
Assessing Susceptibility from Early-life Exposure to Carcinogens. Report EPA/630/R-03/003F,
March 2005. US EPA Risk Assessment Forum, Washington DC. https://www3.epa.gov/air
toxics/childrens_supplement_final.pdf .
[80] United States Environmental Protection Agency (US EPA), (2017). Toxicological Review of
Benzo[a]pyrene [CASRN 50-32-8], Report EPA/635/R-17/003Fa, January 2017. US EPA
Integrated Risk Information System. National Center for Environmental Assessment. Office
of Research and Development. Washington, DC. https://cfpub.epa.gov/ncea/iris/iris_docu
ments/documents/toxreviews/0136tr.pdf.

View publication stats