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European Journal of Applied Sciences – Vol. 10, No. 4

Publication Date: August 25, 2022

DOI:10.14738/aivp.104.12661. Anikwe, U. F., Okenwa, E. J., Ona, J. S. E., Anikwe, C. H., & Oparaji, E. H. (2022). Risk Assessment of Heavy Metal Toxicity and Stress

Marker Enzyme in Waste Water from Municipal Dam Site around Enugu Metropolis, Enugu State. European Journal of Applied

Sciences, 10(4). 716-725.

Services for Science and Education – United Kingdom

Risk Assessment of Heavy Metal Toxicity and Stress Marker

Enzyme in Waste Water from Municipal Dam Site around Enugu

Metropolis, Enugu State

Anikwe, Uchenna, Fredrick

Department of Applied Biology and Biotechnology

Enugu State University of Science and Technology

Okenwa, Ezinne Jennifer

Department of Applied Biology and Biotechnology

Enugu State University of Science and Technology

Ona, Jekwu, S. E.

CSDP, Enugu state

Anikwe, Chidera, Henry

Department of Civil Engineering, Institute of Management and

Technology, Enugu state

Oparaji, Emeka H.

Department of Biochemistry, University of Nigeria

Nsukka, Enugu state

ABSTRACT

Impact of waste water toxicity from collection ditches within Enugu metropolis,

Enugu state was assessed in the present study. Risk impact of heavy metal

recalcitrant was also determined in the present study as the waste water from the

ditch were used by subsistence farmers around for irrigation purposes.

Physicochemical analysis of the soil irrigation with the domestic waste water was

carried and revealed the following: pH 6.65, conductivity 792 respectively.

Dissolved mineral contents were found in the following order:

Cl>Ca>Fe>SO4>Mg>Cu>K>Pb>PO3 while heavy metals of Hg, As and Cd were found

at below detectable limit range (BDL). Total organic carbon (TOC) and total organic

matter (TOM) contents were found at 179.93 and 221 mg/kg in the various

treatments. These varied significantly from the control treatment. Physicochemical

properties of the domestic waste water were equally analyzed. Soil enzymes

showed the activity of the lipase, urease, peroxidase and catalase with an increased

of lipase, urease and peroxidase after the irrigation with OD of 0.610, 0.677 and

0.712 respectively catalase activity was reduced downwardly. Health risks to

human through utilization of the waste water by human were assessed by:

estimated dietary intake (EDI), estimated weekly intake (EWI) and Target hazard

quotient (THQ). EDI for the heavy metals of Pb, Cu and Fe were 3.98 x 10-3, 1.22 x 10-

2 and 1.2 x 10-2 mg/g, respectively estimated while EDI of 1.36 x 10-3, 8.33 x 10-3 and

9.52 x 10-3 mg/g were obtained for Pb, Cu and Fe from the control experiments. EWI

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Anikwe, U. F., Okenwa, E. J., Ona, J. S. E., Anikwe, C. H., & Oparaji, E. H. (2022). Risk Assessment of Heavy Metal Toxicity and Stress Marker Enzyme

in Waste Water from Municipal Dam Site around Enugu Metropolis, Enugu State. European Journal of Applied Sciences, 10(4). 716-725.

URL: http://dx.doi.org/10.14738/aivp.104.12661

for heavy metals of Pb, Cu and Fe were 9.52 x 10-3, 583 x 10-2 and 6.7 x 10-2 mg/g,

respectively. The results showed that the THQ for Fe and Cu were less than 1 while

that of Pb was greater than 1. THQ were less than 1in all the analysed metals from

the control experiment. The findings from this study show that there is a

considerable health risks connected with utilization of waste water from our study

locale and these waste water bioaccumulate heavy metal levels which are

potentially poisonous to humans who consume them.

Key words: waste water, heavy metals, enzymes, risk-assessment.

INTRODUCTION

The use of municipal waste water and effluent of domestic constituents on agricultural soil have

provided a salvage pathway for waste disposal through utilization of the recyclable constituents

in the waste water for optimized agricultural produce (Khalid et al., 2017).

Wastewater production sources include different human activities, such as: Industrial,

commercial, and domestic activities (Alobaidy et al., 2010). Municipal wastewater is also

sometimes distinguished into urban, rural, and agricultural areas and sources. With the rapid

expansion of human population, cities, industries, and the domestic water supply, the quantity

of wastewater production is increasing at the same proportion (Khalid et al., 2017). The average

volume of wastewater generated daily by human activities depends on the availability of the

water quantity in the house, the cultural level and type, the cost of the water, and the economic

conditions (Alobaidy et al., 2010).

Agriculture is the most common area in which untreated wastewater is reused. According to an

estimate in 2004, approximately 20 million ha is irrigated with wastewater in fifty countries

worldwide (Chen et al., 2013). The use of wastewater for crop irrigation has further increased

in recent years. The municipal wastewater demand corresponds to 11% of the water

withdrawal globally (Thebo et al., 2017). About 3% of the municipal wastewater demand is

consumed and the remaining 8% is being discharged as wastewater; that is, 330 km3 of

wastewater per year, which is potentially irrigating almost 40 million ha (approximately 8000

m3 per ha) or 15% of all irrigated lands (Chen et al., 2013).

Wastewater usage for crop irrigation has certain advantages such as providing the essential

nutrients and organic matter, saving water and nutrients, and reducing water contamination

(Huibers et al., 2005). It has been reported that quite sufficient quantities of macronutrients (N,

P, and K) are supplied to soil and plants via wastewater application (Huibers et al., 2005).

Therefore, it is a great temptation for poor farmers to irrigate crops with wastewater as it can

reduce the crop production cost, with the cost of crop production decreasing by 10%–20%

when irrigated using wastewater (WHO, 2006).

The fundamental problem facing our country Nigeria is inadequate machinery in waste

management. This is to an extent due to the bridge of policies, inadequate infrastructure and

economic challenges. This has hampered the nation’s economic developments in agriculture,

industrial and other otherwise (Emeka, 2008). Agriculture still stands out as a major fulcrum

in our country’s major developmental stride for the achievements of her dream 2020. Over the

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European Journal of Applied Sciences (EJAS) Vol. 10, Issue 4, August-2022

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years, records from ecological impact assessments have shown how various wastes from

different sources have impacted on the various ecological niches/properties of our biosphere.

These records have kept mouth shattering of the sustainability our environment (soil) which is

the centre for various earthly activities (Ajanaku, 2007). Sustainability of the agricultural sector

in our developing country Nigeria cannot be over emphasized; assessment of quality markers

of soil for efficient agricultural practices give a view of the level of recalcitrant present in the

soil. Agricultural practices and its bountifulness can only improve when the integrity of the

surrounding soil is not compromised. The present study provides information on the impact of

domestic waste water from a cafeteria irrigated on agricultural soil on soil physicochemical

properties and soil quality marker enzymes.

MATERIALS AND METHODS

Materials

All the reagents, equipment used in the present study were of analytical grade and products of

BDh, May and Baker, Sigma Aldrich. The equipments are calibrated at each use.

Collection of the Experimental Samples

Samples Collection

Arable soil sediments and waste water were collected from four municipal dam for domestic

waste collection located within Enugu metropolis, Enugu state (Long.140N, SE 4) as described

by Ezenwelu et al. (2022). The samples were collected in clean sterile sample containers and

was taken to the lab for further experiments

Determination of physicochemical properties of the soil and waste water

Soil and waste water physicochemical properties were determined as described in the journal

of ATSDR, 2009. Physicochemical properties: pH, conductivity, dissolved minerals (Cl, Mg, Ca,

K, PO3, TS, TDS, TSS, DO, BOD, heavy metals (As, Cd, Cr, Hg, Pb, Cu) were assessed.

Health Risk Assessment of Heavy Metals

The health risks connected with the association of the waste water analyzed in this study were

assessed based on the Target hazard quotient (THQ), estimated daily intake (EDI), estimated

weekly intake (EWI) and carcinogenic risk (CR) of the heavy metals.

Estimated Daily Intake (EDI)

Estimated Daily Intake (EDI) of heavy metals depend both on waste water concentration of the

particular metals and average consumption of the water samples.

EDI is calculated using the equation below:

EDI = Concentration of metals × Daily water intake

Average Body weight ................................. eqn 1

Where: EDI is Estimated Daily Intake

Estimated Weekly Intake (EWI)

The chronic toxicity of the metals was calculated as the Estimated Weekly Intake (EWI).

Tolerable intakes are expressed on a weekly basis because the contaminants given this

designation may accumulate within the body over a period of time (Herrman and Younes, 1999)

The EWI (μg/kg bw) was determined using the following equation as reported by (Copat et al.,

2012).

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Anikwe, U. F., Okenwa, E. J., Ona, J. S. E., Anikwe, C. H., & Oparaji, E. H. (2022). Risk Assessment of Heavy Metal Toxicity and Stress Marker Enzyme

in Waste Water from Municipal Dam Site around Enugu Metropolis, Enugu State. European Journal of Applied Sciences, 10(4). 716-725.

URL: http://dx.doi.org/10.14738/aivp.104.12661

EWI= Cm X IRw

BW ..............................................................................eqn 2

Where: EWI is Estimated Weekly Intake

Cm: the metal concentration in plantain

IRw: is the weekly ingestion rate (seven times the daily ingestion rate) (Renieri et al., 2014).

BW: Body weight.

Target Hazard Quotient

Target Hazard Quotient (THQ) is the ratio between exposure and reference oral dose (RfDing)

and it is normally used to express the risk of non-carcinogenic effects. According to this ratio,

exposed populations are prone to experience health risks if the value is equal to or greater than

1. Values less than 1 consequently indicate no health risk for those metals for the exposed

population.

THQ was calculated based on the equation below:

THQ = Concentration of metals × Daily water intake

RfD × Average Body weight ..................................eqn3

Where: THQ is target hazard quotient

RfD is reference oral dose

Soil Enzyme Assessment

Soil quality marker enzymes were determined using standard assay protocols, enzyme such as:

Lipase, catalase, urease and peroxidase were assayed as described by Ezenwelu et al. (2022),

Latha (2013), Douglas and Bremner (1971) respectively.

Statistical Analysis

One way analysis of variance (ANOVA) and statistical micro word excel was used in the analysis

of the data. T-student test was used in comparism of the data significances

RESULTS

Table one shows the physicochemical properties of the waste water from municipal ditch

characterized with cafeteria effluent. The results showed very much in contrast the properties

of the waste water from the control experiment.

Table two shows the physicochemical properties of the waste water from municipal ditch

characterized with cafeteria effluent. The results showed very much in contrast the properties

of the waste water from the control experiment.

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Table 1: Physicochemical Properties of the Waste Water

Physiochemical Parameters Control Water

Sample

Waste Water Sample

pH 7.20 5.30

Water Conductivity (Ω-1cm-1) 782 913

Chloride ion (Mg/L) 7123 1203.42

Dissolved oxygen (Mg/L) 7.02 5.76

Magnesium (Mg/L) 16.24 24.21

Potassium (Mg/L) 1.02 8.18

Calcium (Mg/L) 32.33 39.76

B0D5 0.93 4.02

Total Organic Carbon (TOC)

(mg/L)

38.40 184.41

Total Organic Matter (mg/L) 46.74 226.82

N=2

Table 2: Heavy Metal Profile of the Municipal Ditch within Enugu Metropolis

Heavy metals control sample waste water

Iron (Mg/L) 1.25 22.29

Cadmium (Mg/L) BDL BDL

Mercury (Mg/L) BDL BDL

Arsenic (Mg/L) BDL BDL

Lead (Mg/L) BDL 10.32

Copper (Mg/L) 1.14 17.22

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Anikwe, U. F., Okenwa, E. J., Ona, J. S. E., Anikwe, C. H., & Oparaji, E. H. (2022). Risk Assessment of Heavy Metal Toxicity and Stress Marker Enzyme

in Waste Water from Municipal Dam Site around Enugu Metropolis, Enugu State. European Journal of Applied Sciences, 10(4). 716-725.

URL: http://dx.doi.org/10.14738/aivp.104.12661

Table 3: Physicochemical Properties of the Soil Sediments

Physiochemical parameters Control experiment Soil sample

pH 7.6 4.24

Soil Conductance 610 433

Chloride ion (Mg/g) 433 1151.614

Phosphorus (Mg/g) 1.78 1.23

Magnesium (Mg/g) 6.27 11.27

Potassium (Mg/g) 7.22 11.52

Calcium (Mg/g) 18.23 19.34

Total petroleum hydrocarbon

(TPH)(Mg/g)

0.34 1014.93

Total Organic Carbon (TOC)

(Mg/g)

10.45 78.64

Total Organic Matter (TOM)

(mg/g)

12.85 196.73

Table 4: Heavy metal concentrations in the soil sediments from the municipal ditch

Heavy metals Control experiment Test sample

Iron(Mg/g) 3.52 38.7

Cadmium(Mg/g) BDL 0.015

Mercury(Mg/g) BDL BDL

Arsenic(Mg/g) BDL BDL

Lead(Mg/g) BDL 1.73

Copper(Mg/g) 1.08 25.49

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Table 2 Estimated Dietary Intake (EDI) OF Heavy Metals

Heavy metals (mg/g) Control experiment Bodoh sample

Lead 1.36 x 10-3 3.98 x 10-3

Iron 9.5 x 10-3 1.2 x 10-2

Arsenic BDL BDL

Copper 8.33 x 10-3 1.22 x 10-2

Cadmium BDL BDL

Mercury BDL BDL

N=2 * BDL= Below detectable limits

Table 3 Estimated Weekly Intake (EWI) OF Heavy Metals

Heavy metals (mg/g) Control experiment Bodoh sample

Lead 9.52 x 10-3 2.8 x 10-2

Iron 6.0 x 10-2 8.0 x 10-2

Arsenic BDL BDL

Copper 5.83 x 10-2 8.6 x 10-2

Cadmium BDL BDL

Mercury BDL BDL

N=2 * BDL= Below detectable limits

Table 3 Estimated Weekly Intake (EWI) OF Heavy Metals

Heavy metals (mg/g) Control experiment Bodoh sample

Lead 9.52 x 10-3 2.8 x 10-2

Iron 6.0 x 10-2 8.0 x 10-2

Arsenic BDL BDL

Copper 5.83 x 10-2 8.6 x 10-2

Cadmium BDL BDL

Mercury BDL BDL

N=2 * BDL= Below detectable limits

Table 4 Target Hazard Quotient of Heavy Metals.

Heavy metals (mg/g) Control experiment Bodoh sample

Lead 3.4 x 10-3 1.01

Iron 5.3 x 10-3 4.03 x 10-2

Arsenic BDL BDL

Copper 2.3 x 10-4 3.9 x 10-3

Cadmium BDL BDL

Mercury BDL BDL

N=2 * BDL= Below detectable limits

Fig one shows the activity of the identified soil quality marker enzymes from the agricultural

soil contaminated with the municipal waste water and the control experiment.

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Anikwe, U. F., Okenwa, E. J., Ona, J. S. E., Anikwe, C. H., & Oparaji, E. H. (2022). Risk Assessment of Heavy Metal Toxicity and Stress Marker Enzyme

in Waste Water from Municipal Dam Site around Enugu Metropolis, Enugu State. European Journal of Applied Sciences, 10(4). 716-725.

URL: http://dx.doi.org/10.14738/aivp.104.12661

Fig. 1. Activity of soil enzymes from the waste water polluted soil.

DISCUSSION

The use of municipal waste water and effluent of domestic constituents on agricultural soil have

provided a salvage pathway for waste disposal through utilization of the recyclable constituents

in the waste water for optimized agricultural produce. Besides these benefits, a number of

drawbacks are associated with the use of wastewater for crop irrigation (WHO, 2006).

Wastewater contains potentially toxic elements (PTEs) such as zinc, chromium, copper,

cadmium, nickel, lead, mercury, and parasitic worms, which can induce severe risks to the

human health and the environment.

This study looked at assessing the health risk factor associated with heavy metal toxicity in a

municipal ditch within Enugu metropolis on soil physicochemical properties and quality

marker enzyme activity. Physicochemical analysis of the soil showed the presence of the

following: pH 7.4 and 6.65, conductivity 488 and 792 respectively. This can be attributed to the

nature of the contaminant in the soil such as oil and other kitchen condiments which can

contain higher acidic contents (oleic, benzoic acids) as stated in the proceedings of the ASTDR,

2009. Dissolved mineral contents were found in the following order:

Cl>Ca>Fe>SO4>Mg>Cu>K>Pb>PO3 while heavy metals of Hg, As and Cd were found at below

detectable limit range (BDL) in both the soil samples. Total organic matter (TOM) and total

organic carbon (TOC) contents were found at 91.66, 22.05 and 76.85, 179.93 in the various

treatments. Chikere et al., 2006 in their study at Eleme petrochemical jetting port site reported

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

LIPASE UREASE PEROXIDASE CATALASE

OD nM

Soil Enzymes

control

Test sample

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a similar correlation of ions concentrations in the contaminated Eleme port soil. They revealed

a higher concentration of the mineral ions in the following order 2.28, 1.84, 5.22 and 1789.22

mg/g respectively for K, nitrate, magnesium and chloride ions. Khalid et al., 2017 in their

assessment study on soil pollution and Lead (Pb) accumulation revealed higher quotients of

heavy metals like Fe, Pb and Cu in the soil while heavy metals of Hg, As, Cd were found below

detectable limits in the soil. The same trend was found in the waste water as the BOD5 quotients

was found at 5.2mg/ml with initial dissolved oxygen concentrations at 6.2 mg/ml. Vallero 2010

stated that dissolved oxygen concentration (DO) is said to have reciprocal relationship with the

biochemical oxygen demand (BOD) in water, he went on to state that the presence of organic

matter in water bodies increases biochemical activities of aquatic flora and fauna and such

leads to their exponential multiplications (Bloom) and demand for oxygen for biochemical

activities (oxidation, respiration etc). Dissolved mineral concentrations such as Cl, Ca, Mg, PO3,

Cu, Fe and SO4 were found richly in abundance. Heavy metals such as Pb was found in trace

quantity were as Cd, As and Hg were found in non detectable range. TDS, TSS and TS were

recorded at 23036, 396.5 and 23433.

This as reported in the proceedings of ASTDR, 2009 that every exposed water body are

characterized by the presence of solid particles which may be suspended within the costal

water axis or dissolved in the olefiers of the water bed.

The proceedings went further to state that these solid particles constituents of the water can

be as a result of rock weathering, human activities such as querrying, volcanic eruption in the

water bed and water bodies eutrophications.

Analysis of soil enzymes showed the activity of the lipase, urease, peroxidase and catalase with

corresponding OD reading of 0.403, 0.611, 0.652 and 0.817 respectively. There was an increase

of lipase, urease and peroxidase after the irrigation with the waste with OD of 0.610, 0.677 and

0.712 respectively while catalase activity was reduced. Vallero 2010 reported the activities of

quality marker soil enzymes in the presence of recalcitrants; most constitutive enzymes are

said to be mark qualities of soil otherwise House-keeping enzymes whose activities are

activated in the presence/influx of recalcitrants to a particular ecological nich(es). Lipases are

activated in the presence of triacylglyceride while peroxidase and catalse activity is stimulated

in the presence of peroxide and other superoxides; urease activity is activated in the presence

of organic matter urea.

CONCLUSION

The results from the present study have shown the vulnerability of agricultural soil to effluent

from domestic sources used for irrigation and its impact on agricultural productivity. Despite

the agronomical potentials of the waste water in composite such as abundant dissolved mineral

contents (Cl, Ca, Mg, Cu, Fe), high conductivity among other benefits, there exist a reasonable

amount of potential toxic element (PTE) they contain such as Pb.

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Anikwe, U. F., Okenwa, E. J., Ona, J. S. E., Anikwe, C. H., & Oparaji, E. H. (2022). Risk Assessment of Heavy Metal Toxicity and Stress Marker Enzyme

in Waste Water from Municipal Dam Site around Enugu Metropolis, Enugu State. European Journal of Applied Sciences, 10(4). 716-725.

URL: http://dx.doi.org/10.14738/aivp.104.12661

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