Ecological Risk Profiles of Heavy Metals and Polycyclic Aromatic Hydrocarbon in Soil Around Industries in Ilorin, Nigeria

doi:10.21203/rs.3.rs-3335229/v1

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Ecological Risk Profiles of Heavy Metals and Polycyclic Aromatic Hydrocarbon in Soil Around Industries in Ilorin, Nigeria

https://doi.org/10.21203/rs.3.rs-3335229/v1

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Ecological risk profiles of heavy metals and Polycyclic Aromatic Hydrocarbons were assessed in soil from selected occupational workplaces in Ilorin, Nigeria. Soil samples from nine (9) occupational workplaces, - automobile workshops, wood and furniture, and metal & steel industries sites were collected randomly, composited and digested. Cadmium, Copper, Chromium, Iron and Lead were analyzed using Atomic Absorption Spectrometer. The pollution status and ecological risk parameters were determined using standard models (Contamination Factor, Enrichment Factor, Geo-accumulation Index, Ecological Risk Factor and Potential Ecological Risk Index). For the determination of PAHs, soil samples were extracted using QUECHERS method. The cleaned extracts were analyzed for the presence of 16 EPA priority PAHs using Gas chromatography-mass spectrometer (GC-MS). The results showed that Iron concentration ranged between (4807.20 ± 23.15 mg/kg -12031. ± 40.25 mg/kg) in soil samples from the nine (9) selected study areas which were higher than the World Health Permissible limit of (445 mg/kg). The concentration range of the other heavy metals from the nine (9) selected study areas are, Cadmium (1.15 ± 0.40 mg/kg − 1.98 ± 0.46 mg/kg), chromium (15.0 ± 1.52 mg/kg − 142.30 ± 50.55 mg/kg), Copper (17.85 ± 4.60 mg/kg – 85.20 ± 13.80mg/kg) and Lead (5.8 ± 4.20mg/kg – 27.0 ± 10.24 mg/kg) accordingly. The standard models revealed the study area to be moderately contaminated with heavy metals. The GC-MS result revealed that (0.53%) anthracene was detected in Egbejila automobile workshop. Aliphatic chain compounds such as (Dibutylpthalate, Di-n-octylpthalate and Bis (2-ethyl hexylpthalate) which could be traced to plastic products and automobile upholstery were also detected.

Heavy metals

Polycyclic Aromatic Hydrocarbons

Wood & Furniture industries

Automobile Workshop

Metal & Steel industries

Heavy metals and polycyclic aromatic hydrocarbons (PAHs) are undisputed environmental pollutants due to their toxicity and resistance to chemical and microbiological breakdown. These ever-present toxins are rightfully recognized as major environmental concerns (Mojiri et al., 2019). Significant amount of heavy metals and PAHs contributions to environmental and health concerns could largely be attributed to anthropogenic waste (Adeniji et al., 2019). Carcinogenic nature of these compounds is a major concern because many of these pollutants have resulted in critical health challenges (Wang et al., 2017; Hiller et al., 2015).

Heavy metals constitute a serious threat to human health, animals, plants, and whole ecosystems (Malvandi, 2017; Liu et al., 2016; Suresh et al., 2012) since they are vast, ominous invaders of our natural environment. Their toxic nature, incessant persistence, resilience to degradation, and ability to accumulate inside living creatures (Wu et al., 2018) amplify the severity of their effects on the environment (Alahabadi and Malvandi, 2018)

Most metals are generally located deep inside the earth (Ajah et al., 2015) but naturally present at low concentrations in the earth’s crust (Orellana-Mendoza et al., 2022). Toxic metals have accumulated in the environment due to the widespread use of natural resources for industrial purposes (Ajah et al., 2015). These harmful substances are released into our environment through mining, industrial, and agricultural processes, the sputtering emissions of numerous automobiles, oil spills, and wastelands of landfills (Tanee and Albert, 2013).

The proliferation of heavy metal concentrations in soil are largely due to industrial activities, oil extraction, agricultural practices employing fertilizers and pesticides, the disposal of sewage sludge, and unregulated waste disposal methods (Ohiagu et al., 2020). These human activities have played a pivotal role in elevating the presence of heavy metals within the soil, posing a concerning threat to environmental and human health alike (Ekiyor et al., 2019; Rai et al. 2019).

Non-degradability of toxic metals within the soil presents a persistent challenge, rendering soil pollution a pervasive and global concern (Essien et al., 2019; Hu et al., 2017). Damage to ecosystems and human health may ensue when toxic metals leach into the soil and disrupt its natural functions and composition (Agbeshie et al., 2020; Yu et al., 2020).

Soil contamination with heavy metals may be evaluated accurately with the use of contamination indices (Orellana-Mendoza et al., 2022). This is crucial for soil quality and sustainability monitoring (Kowalska et al., 2018). To underscore the necessity for effective mitigation measures, contamination indices serve as essential tools for assessing the pollution status and ecological risks associated with heavy metal presence in soil (Chandrasekaran and Ravisankar, 2019; Huang et al., 2019; Keshavarzi and Kumar, 2019; Kumar et al., 2019).

This study therefore aimed at determining the ecological risk of heavy metals (Fe, Cu, Cr, Cd and Pb) on soils around medium and small-scale industries (Automobile, Metal & Steel and Wood & Furniture) in Ilorin metropolis.

Study Area

This study was carried out in the vibrant city of Ilorin, the capital city of Kwara State, Nigeria. Situated at a latitude of 83⁰N and a longitude of 435E, within its boundaries lie three distinct local district councils: Ilorin East, West, and South. The UN World Urbanization Prospects revealed the city's bustling population reaching an impressive 1,030,498 individuals in 2023. Merging tradition with modernity, Ilorin's unique charm presents a harmonious blend of a traditional town and a thriving urban center. In the metropolis, there are large, medium, and small industrial companies. This research was conducted in areas housing medium to small scale industries. Soil samples were collected from 9 locations around the industries (Table 1). Coordinates of each sample location were obtained using GPS (geographical positioning system) and used to generate study area map (Figure 1).

Table 1: Location and the type of industries

Location	Type of Industry	Symbol
Yeregi	Wood and Furniture	W1
Sawmill	Wood and Furniture	W2
Ojagboro	Wood and Furniture	W3
Osere	Automotive	A1
Ipata Oloje	Automotive	A2
Egbejila	Automotive	A3
Jimba Oja	Metal and Steel	M1
Eruda	Metal and Steel	M2
Sango	Metal and Steel	M3

Samples Collection

The soil auger was pre-cleaned with concentrated nitric acid before sampling. At each location, samples were taken and composited at depths that varied from 0 to 20 cm. Substances including stones, pebbles, and organic and inorganic detritus were taken out of the soil before samples were taken. The samples were sealed in plastic bags, labelled, and sent off to a laboratory for heavy metal analysis.

Sample Preparation and Digestion

After 48 hours of air drying, soil samples were crushed and sieved through a 0.5mm mesh size. 10 mL of HNO₃ was added to a digestion flask containing 0.5 g of the soil sample. This was then heated on a hot plate till near dryness. Afterwards, 10 mL HCl was added and heated until near dryness. We added 10 mL of perchloric acid and heated. Once again, 10 mL of HCl was added and evaporated nearly entirely by heating. The sample was cooled after 10 mL of distilled water was added. An Erlenmeyer flask was then used to filter the material. A 50 mL volumetric flask was used to add distilled water to the digestate. Atomic absorption spectrophotometer (AA320N) readings for Fe, Cu, Pb, Cd, and Cr were taken from the digestate.

Extraction of Soil for PAHs determination

QUECHERs method of extraction was employed for the sample extraction and preparations. 3g soil sample was weighed into a centrifuge tube, 3mL distilled water added and vigorously shaken. 10mL acetonitrile was added and then shaken vigorously. 4g of Magnesium Sulphate was added followed by 0.5 g Sodium Chloride and then shaken vigorously. The sample mixture was inserted into a centrifuge machine for 5 min at 4000 rpm (to separate into two phases). The upper layer which is liquid contains the acetonitrile and the analytes of interest. 6 mL of the extracted liquid was transferred into a clean-up kit containing primary-secondary amine and Magnesium Sulphate. The clean- up kit containing the analytes of interest was shaken vigorously and kept in a centrifuge machine for 5 min at 4000 rpm. The supernatant which contains the analytes of interest was transferred into a GCMS glass for analysis.

Data Analyses

Statistical analysis was conducted on laboratory results to enhance data interpretation. With precision, the study harnessed the power of statistical tool by calculating the mean and standard deviation. To comprehensively assess ecological risks, the research employed well-established indices, including the contamination factor, pollution load index, enrichment factor, geoaccumulation index, ecological risk factor, and potential ecological risk index.

Contamination Factor (CF)

CF measures the level of contamination in relation to the average measured background values of a certain heavy metal in a geologically comparable and uncontaminated location (Hakanson, 1980). The soil's heavy metal concentration and its correlation to the earth's overall geochemical value are assessed. The CF may be determined using the formula:

CF = Concentration of the metal in soil

Background value

The global average elemental concentrations of heavy metal in the earth crust as reported by Turekian and Wedepohl, 1961 were used as reference background values in this study due to unavailability of regional values of the metals (Ihedioha, 2017). Turekian and Wedepohl, 1961 gave world average values of heavy metals in mg/kg as: “0.30 for Cd, 95 for Zn, 68 for Ni, 45 for Cu, 20 for Pb, 90 for Cr, 850 for Mn and 47,200 for Fe”.

According to Hakanson, 1980, there are four classes of contamination: “CF<1 (low contamination), 1<CF<3 (moderate contamination), 3<CF<6 (considerable contamination) and CF>6 (very high contamination)”.

Pollution Load Index (PLI)

Contamination factor indicates the site’s pollution status in terms of individual metal whereas the pollution load index gives overall pollution state of the site. PLI can be calculated by:

PLI = (CF1 X CF2 X CF3 X CF4 ……X CF_N)^1/N (Tomlinson et al., 1980)

N is the number of metals studied in the site and CF is the contamination factor for each metal.

The PLI indicates pollution status of the site with respect to heavy metals and the necessary action that needed to be taken.

A PLI<1 indicates an unpolluted site; PLI = 1 represents moderate pollution, and PLI>1 site is polluted (Tomlinson et al., 1980).

Geo-accumulation Index (Igeo)

The geo-accumulation index assesses the level of heavy metal pollution in soil from anthropogenic or geogenic inputs and was developed by Muller, 1969 as:

Igeo = log₂(𝐶/1.5𝐵)

where: Soil heavy metal concentration is denoted by C, whereas the metal's background geochemical value is denoted by B. Due to environmental metal changes, the correction constant is 1.5 (Kamani et al., 2017).

Igeo is categorized into seven: “Igeo≤0 - unpolluted, 0<Igeo≤1 - unpolluted to moderately polluted, 1<Igeo≤2 – moderately polluted, 2<Igeo≤3 – moderately to heavily polluted, 3<Igeo≤4 - heavily polluted, 4<Igeo≤ 5 - heavily to extremely polluted extremely, and Igeo>5 – extremely polluted” (Muller, 1979).

Enrichment Factor (EF)

EF is used to measure how much of heavy metal in soil has increased due to anthropogenic activities compared to the average natural abundance. It is calculated as:

EF = (Metal) Sample

(Metal) Background

(Turekian and Wedepohl, 1961).

EF has 5 classes, these are “(EF<2) no enrichment, (2<EF<5) moderate enrichment, (5< EF< 20) significant enrichment, (20<EF<40) very high enrichment, and (EF>40) extremely high enrichment” (Reimann and De Caritat, 2000).

Ecological Risk Factor (E)

The Ecological risk factor quantitatively expresses the potential ecological risk associated with specific individual metal (Hakanson, 1980). It can be calculated as follows:

E = T X CF

where T = toxic response factor of a specific heavy metal (Iron = 1, Copper = 5, lead = 5, Cadmium = 30, and Chromium = 2) (Orellana-Mendoza et al., 2022; Hakanson, 1980) and CF = contamination factor.

Ecological risk factors are classified as follows: “(E<40) low ecological risk, (40 ≤E<80) moderate ecological risk, (80≤ E<160) considerable ecological risk, (160≤E<320) high ecological risk, and (E≥320) very high ecological risk” (Hakanson, 1980).

Potential Ecological Risk Index (RI)

RI presents the total ecological risk associated with various heavy metals in soil (Orellana-Mendoza et al., 2022; Hakanson, 1980). RI estimates the harmful effect of metals in soils.

RI = ∑E

The followings represent the different classes of RI: “(RI<150) Low risk, (150≤RI<300) moderate risk, (300≤RI<600) high risk, and (RI≥600) very high risk” (Hakanson, 1980).

Table 2: Concentration of Heavy Metal in Soil Samples

Sampling Location	Descriptive Statistics	Heavy Metal Concentration (mg/kg)
		Fe	Cu	Pb	Cd	Cr
A1	Mean	4807.20	56.80	13.40	1.15	107.90
A1	SD	23.15	10.20	6.40	0.40	60.25
A2	Mean	10521.60	58.23	22.30	1.76	99.20
A2	SD	20.50	12.00	4.00	0.45	14.62
A3	Mean	7851.60	40.50	5.80	1.26	21.70
A3	SD	16.20	16.80	4.20	0.30	13.25
W1	Mean	7814.80	17.85	8.00	1.25	18.80
W1	SD	17.65	4.60	3.15	0.04	10.51
W2	Mean	9081.10	31.10	12.30	1.37	74.00
W2	SD	18.25	11.15	3.50	0.42	13.63
W3	Mean	8318.10	22.2	9.30	1.32	15.00
W3	SD	13.00	9.21	4.62	0.54	1.52
M1	Mean	12031.90	55.82	27.00	1.82	142.30
M1	SD	40.25	14.35	10.24	0.34	50.55
M2	Mean	9064.60	73.90	12.20	1.88	86.60
M2	SD	18.35	14.45	3.80	0.52	19.62
M3	Mean	8724.70	85.20	11.50	1.93	94.10
M3	SD	19.65	13.80	2.65	0.46	18.00

*SD = Standard Deviation

The results of heavy metal concentration in soil sampled from nine (9) locations in Ilorin metropolis are presented in table 2. The minimum and maximum mean concentration of heavy metals in the samples are Cr (15.0±1.52 – 142.30±50.55), Cd (1.15±0.4 – 1.93±0.46), Pb (5.80±4.20 – 27.0±10.24), Cu (17.85±4.60 – 85.20±13.80) and Fe (4807.20±23.15 – 12,031±40.25). The results showed that the concentrations of Fe in all samples analyzed were below the natural background value, an indication that the sites are not contaminated with Fe. The results of this research however show higher concentration of Fe when compared with the work of Enete et al., 2022, Agbesie et al., 2020 and Sharma and Raju, 2013. Pb content in all locations falls below the background concentration except for site A2 and M1. Values of Cr in the soil sampled from wood and furniture industry were below the background concentration while those from Automotive and metal & steel industries were higher - an indication of anthropogenic contamination of the sites. For Cu, samples from wood and furniture industry show lower concentrations while other industries show higher concentrations when compared with geochemical reference value. All soil samples show high Cd content when compared with background concentration and exceeded the concentration presented by Enete et al., 2022 and Agbeshie et al., 2020. The high Cd concentration in the soil is suspected to be caused by human activities across all the locations (Alloway and Steinnes, 1999).

Sites A1, A3, M1, and W3 showed mean concentration of heavy metals in the following order: Fe> Cu> Cr> Pb> Cd while soil from A1, W1, W2, M2 and M3 has heavy metal concentration in the order Fe> Cr> Cu> Pb> Cd. Soil sampled in M1 shows the highest values of heavy metal while soil taken from W1 has the lowest heavy metal concentrations.

The GCMS results revealed that there was limited presence of PAHs in studied samples. Anthracene was detected (0.53%) in Egbejila mechanic workshop, which may be toxic on long term exposure. The samples contain majorly aliphatic chain compounds and also organic compounds such as (Dibutylpthalate, Di-n-octylpthalate and Bis (2-ethyl hexylpthalate), which are products from plastic consumer products and automobile upholstery which can affect the liver and reproductive system of individuals exposed to it.

CF evaluates soil contamination from anthropogenic inputs from a single heavy metal (Hakanson, 1980). Figure 2 shows the CF of the five (5) heavy metals investigated in soil of all the sites. The results of the CF showed low contamination at sites W1, W2 W3 (wood and furniture industry) while the remaining sites showed moderate contamination. Fe indicated low CF at all locations, Cu, Cr and Pb showed low to moderate contamination at all sites while Cd showed very high contamination in all the sites. The high Cd contamination of all the study sites can be a result of the use of Cd-containing materials by all the industries in these areas (Alloway and Steinnes, 1999).

Figure 3 shows the PLI values for all the locations studied. The PLI ranges from 0.47 to 2.94 with sites A3, W1 and W3 having less than 1 and thus uncontaminated while sites M1, M2, M3 (metal & steel industry), W1, A1 and A2 values are greater than 1, this therefore shows heavy metal contamination in the sites.

The Igeo values as shown in figure 4 had all element studied to be below 1 across all sites except for Cd, the sites are thus considered uncontaminated with these metals. This result is similar to the work of Alahabadi and Malvandi, 2018.

The values of EF are presented in figure 5. There were heterogeneous EF values across all sites. Cadmium had the highest and was interpreted as been very highly enriched. Other elements showed EF values between 1 and 1.39 and are classified as no, moderate, and significantly enriched. Generally, the EF values follow the trend Cd > Cu > Cr > Pb > Fe.

Indicator E was used to evaluate the risk associated with each metal (figure 6). From the results, all elements studied presents low ecological risk (E < 40) in all locations except Cd with considerable and high ecological risk classifications across all sampling sites.

Figure 7 shows E values in all locations of the study. All soil samples around wood & furniture industries and automobile industries show low potential ecological risk except site A2 with moderate potential ecological risk. Soil from metal & steel industries presents moderate potential ecological risk from heavy metals across all sites.

This research presents useful information on the concentration, pollution and ecological risk of heavy metals (Fe, Cu, Pb, Cd and Cr) in soil collected around some industries in Ilorin Metropolis. Findings show all sites investigated have low degree of contamination with all metals investigated except Cd. Results of this research also show varied ecological risks associated with heavy metals in different sites.

“All authors have read, understood, and have complied as applicable with the statement on "Ethical responsibilities of Authors" as found in the Instructions for Authors.

Ethical approval: This is an observational study for which no ethical approval is required.

Conflict of Interest: The authors declared that there is no conflict of interest.

Funding: No funding was received for conducting this study

Authors Contributions: DTO conceptualization, investigation, methodology, YAI data curator, draft preparation and editing. AAB experimental, writing review. EOO review, proofread, editing, resources. All authors approved the manuscript in the present state and approved for submission.

Availability of data and materials: The datasets/information used for this study are available within the manuscript.

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No competing interests reported.

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Ecological Risk Profiles of Heavy Metals and Polycyclic Aromatic Hydrocarbon in Soil Around Industries in Ilorin, Nigeria

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