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Heavy Metal Pollution
Heavy Metal Pollution
Michael Kwame Vowotor, M.Phil1; Background. Elevated concentrations of heavy metals in soil have detrimental consequences on
Christiana Odumah Hood, M. Phil1; the environment, which translates into damaging effects on humans.
Samuel Sonko Sackey, PhD1; Alfred Objective. An evaluation was carried out to determine the concentrations of seven heavy metals
Owusu, PhD1; Ebenezer Tatchie, (As, Cd, Cr, Cu, Hg, Pb, Zn) in soil sediments collected from 12 different stations within the
M.Phil1; Savanna Nyarko, B.Sc1; Benya Lagoon in Komenda Edina Eguafo Abrem Municipality (KEEA) in Ghana.
Daniel Manu Osei, B. Sc1; Kwadwo Methods. The calibration and concentration measurements of the elements were carried out
Kesse Mireku, M.Phil2; Crystal using a fast sequential hydride generation atomic absorption spectrophotometer.
Bubune Letsa, B.Sc3; Sampson M. Results. An assessment according to metal concentration in terms of abundance found that
Atieomo, M.Phil4 Pb registered the highest, while a comparison with standard sediment criteria by USEPA and
CBSQG indicated heavy pollution levels of As, Cd, Hg, and Pb. Using Pearson's coefficient
1 Department of Physics, University of matrix, As-Cd had a correlation of 1.000, while Zn-Pb registered 0.858, indicating the same or
Cape Coast, Cape Coast, Ghana similar source input for each pair. Both the geo-accumulation index (Igeo) and the contamination
2 Department of Fisheries & Aquatic factor (CF) gave the extent of contamination in the order Cd > Pb > As > Hg > Cu > Cr > Zn,
Science, University of Cape Coast, Cape while the degree of contamination Cd at the stations was in the order 1 > 3 > 4 > 5 > 6 > 2 > 7 > 8
Coast, Ghana > 9 > 10 > 12 > 11, indicating Station 1 as the most polluted. The Hakanson index established the
3 Department of Mathematics & Statistics, order of decreasing threat of a potential ecological risk as Cd > Hg > As > Pb > Cu > Cr > Zn.
University of Cape Coast, Cape Coast, Discussion. The high sums of the individual potential risks values obtained at the sampling
Ghana stations point to a possible detrimental effect on the health of inhabitants that use resources
4 Ghana Atomic Energy Commission, directly from the lagoon without treatment, and therefore the need for education to curtail
Accra, Ghana any unanticipated disasters.
Competing Interests. The authors declare no competing financial interests.
Keywords. Benya Lagoon; heavy metal pollution; Pearson's coefficient matrix correlation;
Corresponding Authors: geo-accumulation index; degree of contamination; Hakanson index/potential ecological risk
Michael Kwame Vowotor assessment
delavowotor@yahoo.com J Health Pollution 6: 26-39 (2014)
polluted water. For this study, the heavy threatens the livelihood of the fishermen
metals investigated were arsenic (As), living in the KEEA municipality. The
cadmium (Cd), chromium (Cr), copper seriousness of this pollution has long
Introduction (Cu), mercury (Hg), lead (Pb), and been identified, but so far no actions
zinc (Zn). have been taken to rectify and reverse
High concentrations of heavy metals in this trend.1 Despite the EPA’s report
soils are a grave health concern as they The Benya Lagoon is located along the on the heavy pollution in the lagoon,
have adverse effects on the environment Gulf of Guinea within the Komenda commercial activities around it, which
and all living things therein. Such Edina Eguafo Abrem (KEEA) include fishing and mining of salt, still
health risks occur as living organisms, municipality, in the Central Region thrive and are on the increase.
including humans, breathe in dust of Ghana (Figure 1). This lagoon has
coming from soils laden with heavy been reported by the Environmental The lagoon is principally fed from
metals or eat plants tainted with them. Protection Agency (EPA) to be one the Gulf of Guinea and then runs
The plants may be contaminated of the most polluted lagoons in the through the community in various
through normal uptake when cultivated country and is drying up as a result of directions, as depicted in Figure 1. The
on affected soils or when irrigated with its heavy pollution. This development water on its northern side is pumped
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Journal of Health & Pollution Vol. 4, No. 6 — March 2014 Vowotor et al
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Vowotor et al Journal of Health & Pollution Vol. 4, No. 6 — March 2014
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Methods
Figure 4 — Market and repair shops at the background. Figure 5 — Dumping ground for unused fishing items.
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Journal of Health & Pollution Vol. 4, No. 6 — March 2014 Vowotor et al
Research An Assessment of Heavy Metal Pollution in Sediments of a Tropical Lagoon
sampling, was employed in the Heavy Metal Composition concentrations and converting them
selection of the sample spots. The Calibration and concentration into the final concentrations using
spots numbered on the lagoon map are measurements of elements in the Equation 1.
the stations where the samples were samples were carried out using a PC–
collected for analysis and are relatively based Varian AA240 fast sequential Nominal volume was given as 20 ml
easily accessible places on the lagoon. hydride generation atomic absorption and the sample weight for soil was
spectrophotometer (AAS). AAS was the 1.5 grams.
Sampling and Sample Collection preferred choice due to its simplicity
All sampling equipment and new in sample preparation and handling, Determination of Hg using cold-vapor
containers were pre-cleaned with high sensitivity, detection limit, degree AAS and As were also measured using
heavy metal grade acetone before of accuracy and reproducibility and Varian AA 240 fast sequential hydride
and after use. Heavy metal grade its general advantage over flame generation AAS.8 The instrument was
hydrochloric acid (HCl) was also used photometry and colorimetry methods.7 set up according to the manufacturer’s
to rinse all containers before placing Each prepared solution was taken to specifications. It was equipped with
the samples in them. For quality the AAS instrument for readings with argon to drive the hydride system.
control, blank determinations were standards from Fluka Analytical (Sigma HCl (6 M) and sodium borohydride
carried out. –Aldrich Chemie GmbH, Switzerland), (NaBH4) (0.6%) generated the hydride.
to serve as internal positive controls.
The services of professional fishermen Working standard solutions of Cd, Cr, Results
were employed during the sampling Cu, Pb, and Zn were prepared from the
period as their boats and skills aided stock standard solutions. A. Assessment According to
in reaching some of the not easily Heavy Metal Concentrations
accessible stations earmarked for About 1.0 g of the soil sample was The concentration of each metal
investigation. weighed and quantitatively transferred investigated in the composite sediment
into a 10 mL test-tube. It was wet ashed from each sampling station is shown in
Superficial (upper 10 cm) sediment with 3 mL aqua regia and placed on Table 2. Metal concentrations ranged
samples were randomly collected using a hot plate (95oC) to heat for an hour within the following intervals: As:
a sediment coring device at a speed of or until all brown fumes ceased. The 14.4-105.6 mg/kg; Cd: 3.6-26.4 mg/kg;
not more than 0.3 m/s near the banks solution was cooled, filtered and topped Cr: 30.8-100.8 mg/kg; Cu: 4.8-217.6
of the lagoon at all of the sampling to the 10 mL mark with deionised water. mg/kg; Hg: 0.4-8.8 mg/kg; Pb: 40.8-
stations. The upper and middle 5 cm It was then sent for hydride generation 309.2 mg/kg; and Zn: 2.0-177.2 mg/kg,
of sediment samples were removed AAS analysis. and their mean concentrations were:
with a pre-cleaned spoon and placed As: 61.9 mg/kg; Cd: 15.5 mg/kg; Cr:
in a sampling bowl. The process was The calibration curves were prepared for 62.6 mg/kg; Cu: 56.2 mg/kg; Hg: 1.3
repeated for three (3) different areas each element individually by applying a mg/kg; Pb: 109.4 mg/kg; and Zn: 45.4
within each sample station and placed linear correlation least square method. mg/kg. Arranging the metals in terms
in the same bowl to form a composite A blank reading was taken and the of abundance in the sampling sites
sample. The composite sediment necessary correction made during the yielded the order Pb > Cr > As > Cu
samples were then mixed until a determination of the concentrations of > Zn > Cd > Hg. The high standard
uniform colour and consistency was the various elements. deviation (SD) values obtained
achieved. This was repeated at every indicate that the spatial distribution
sample station, yielding a total of 12 The quantitative analysis involved the of the individual metal contamination
composite samples. The composite calculation of the final concentrations at the various sampling sites was not
sediment sample from each station from the identified elements’ initial uniform.
was then placed in a plastic container,
coded with indelible pen, and placed
in a labelled Ziploc bag to avoid cross
contamination. They were then stored
Initial Concentration x Normal Value
in a refrigerator and transported to the Final Concentration =
Ghana Atomic Energy Commission Sample Weight in Grams
(GAEC) Preparation Laboratory for
digestion and analyses. Equation 1
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Vowotor et al Journal of Health & Pollution Vol. 4, No. 6 — March 2014
Research
Stations As Cd Cr Cu Hg Pb Zn
The high levels of heavy metals mine"), and the surrounding area well Nets used for fishing have lead
registered in the sediments of the noted for trade activities involving ingots attached to their ends to act as
Benya Lagoon could possibly be gold.9 Due to these past activities weights to help sink the nets to the
attributed to the following activities along the banks of the lagoon, there is bottom of the lagoon. These ingots
that took place in and around the a slow transfer through the dynamic are prepared along the banks of
KEEA in the past. From 1482 to equilibrium process of erosion and the lagoon. These past and present
1486, the Portuguese built Elmina accretion of heavy metals. In the activities may explain why the lagoon
Castle on a strategically narrow strip 1980’s, Ghana sold petroleum fuel is so heavily contaminated by Pb, As
of land bounded by the ocean (Gulf laced with Pb, and more recently in and Hg, with Pb registering the highest
of Guinea) and the Benya River. 2012, activity involving the mining concentration of 309.2 mg/kg at
The river provides a natural shelter of gold around the lagoon was sampling site 3.
harbour and feeds the lagoon with stopped by the government, although
water. The castle was built to protect some inhabitants claimed they had The presence of Cu and Cd in the
the gold rich land of 'El Mina' ("the discovered gold in the area. lagoon may be attributed to spillages
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Journal of Health & Pollution Vol. 4, No. 6 — March 2014 Vowotor et al
Research An Assessment of Heavy Metal Pollution in Sediments of a Tropical Lagoon
from products such as Cd batteries, B. Assessment According to the agricultural runoff and atmospheric
detergents, paints, inks used for Correlation between the Elements fallouts.12
printing, boating activities, domestic To determine the correlation, if any,
garbage dumps and sewage treatment between the heavy metal sediment C. Assessment According to the
plants, urban wastewater runoffs samples studied, Pearson's correlation United States Environmental
and industrial effluents, phosphate coefficient matrix was used and the Protection Agency (USEPA) and
fertilizers in agricultural runoff, findings are presented in Table 3. Consensus–Based Sediment Quality
mining activities, impurities from The correlation coefficients between Guidelines (CBSQG) SQG (2003)
electroplating steel, and the remixing elements give information about their The concentrations of metals
of petroleum products. Cr is used in possible sources.11 investigated were compared with
the manufacture of cements, pigments sediment criteria proposed by the
for paints, paper, rubber and metal The significant correlation between USEPA and CBSQG.13,14 The findings
alloys. Some activities around the the contaminants of As and Cd (r are shown in Table 4. The average
lagoon make use of cement, paints and = 1.000) and Zn and Pb (r = 0.858) concentration of As, Cd, Hg, and Pb
paper products, which eventually end could indicate the same or similar according to the CBSQG scale indicated
up being washed into the lagoon.10 source inputs. Elmina is an old town a heavy pollution level, with Pb and Cd
with very old buildings roofed using also registering a heavy pollution level
The highest metal concentration zinc sheets with lead paints. Therefore, according to the USEPA standard.
values for As, Cd and Hg were the high correlation between Zn and
recorded at Station 1, while Station Pb in sediment could be attributable The mean concentration of 56.2 mg/
2 and 3, respectively, registered the to roofing sheets and paints from the kg registered for Cu indicates a ‘heavy
highest concentrations for Cu and homes located along the banks of the pollution level’ according to the
Pb. This was to be expected, as the lagoon. USEPA standard and a ‘slight pollution
fish market, repair and fabrication level’ according to the CBSQG scale.
shops for lead ingots and fuel Cd is a soft metal which can form Cr, according to both the USEPA and
dispensing points are all concentrated complex compounds, usually hydrated, CBSQG scale, registered an average
at these sample stations. Zn and with carbonated, arsenate, phosphate, of a ‘slight pollution level’, but some
Cr had the highest concentration or oxalate ions. The presence of As-Cd of the sampling stations registered
values registered at Station 6 and 7, at a location has been attributed to the concentration values way above the
respectively, which are residential inappropriate disposal of radioactive ‘heavily polluted levels’ according
areas and therefore have homes and waste, soil parent materials, sludge, to both the USEPA and CBSQG
settlements around them. industrial effluents, fertilizers in standards.
As Cd Cr Cu Hg Pb Zn
As 1
Cd 1.000 1
Cr 0.029 0.029 1
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Vowotor et al Journal of Health & Pollution Vol. 4, No. 6 — March 2014
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As ---- ---- ---- < 9.8 9.8 – 21.4 > 21.4 14.4 – 105.6 61.9
Cd ---- ---- >6 < 0.99 0.99 – 3 >3 3.6 – 26.4 15.5
Hg ---- ---- ---- < 0.18 0.18 – 0.64 > 0.64 0.4 – 8.8 1.3
Zu < 90 90 – 200 > 200 < 90 90 – 200 > 200 2.0 – 177.2 45.4
D. Assessment According to
Geo-accumulation Index (Igeo)
Igeo= log2[Cn ⁄(1.5Bn)] The degree of pollution in sediments
can also be assessed by determining
Equation 2
the geo-accumulation index Igeo, a
criterion able to evaluate the heavy
metal pollution in sediments as
originally defined by Muller.15 It is
mathematically expressed in
Equation 2, where Cn is the
Igeo Class Igeo Class Sediment Quality
concentration of element ‘n’ and
Bn is the geochemical background
0 Igeo ≤0 Uncontaminated
value [world surface rock average
1 0 < Igeo ≤ 1 Uncontaminated to moderately contaminated given by Martin and Meybeck].16
The factor ‘1.5’ is incorporated
2 1 < Igeo ≤ 2 Moderately contaminated in the relationship to account for
possible variation in background data
3 2 < Igeo ≤ 3 Moderately to heavily contaminated due to lithogenic effect. See Table
2 for a listing of the geochemical
4 3 < Igeo ≤ 4 Heavily contaminated
background values (Bn) for each
5 4 < Igeo ≤ 5 Heavily to extremely contaminated metal tested. The geo-accumulation
index scale consists of seven grades
6 5 < Igeo Extremely contaminated (0–6) defining pollution levels
ranging from unpolluted to highly
Table 5 — Pollution Grades of Geo-Accumulation polluted, as given in Table 5.16 Table
Index of Metals Igeo class (Muller Scale) 6 gives the calculated Igeo values for
the metals investigated and the class
in which they fall.
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As Cd Cr Cu
Table 6 — Igeo Values and Class for the Metals Investigated in Soil Sediments of Benya
Lagoon by Sampling Station
It can be deduced from Table 6 that 4 ranged from uncontaminated to heavily contaminated’, 33.3%
with reference to the Muller scale, to moderately contaminated for were ‘moderately contaminated’
none of the stations showed signs Cu, while the remaining stations while the remaining 16.7% were
of sediment contamination for Cr indicated no contamination (Igeo ≤ 0). divided into the ‘uncontaminated’
and Zn. For Pb, the sediments were Cd registered the highest Igeo values and ‘uncontaminated to moderately
moderately contaminated (1 < Igeo for all of the stations (‘extremely contaminated’ categories. Using
≤ 2) for Station 2, 7, 8, 9 and 12, but contaminated’), except for Station the mean values of Igeo, the
were heavily contaminated for Station 11, which recorded a sediment sediments studied may be said to
3 and 6. Sediments in Station 1 were quality of ‘heavily contaminated’. be contaminated with metals in the
heavily contaminated with Hg, while From Table 6, it can be deduced order Cd > Pb > As > Hg > Cu > Cr
Station 7 showed signs of moderate that 50% of the samples studied > Zn.
contamination. Station 2, 3 and 11 fell within the range ‘moderately
showed no signs of contamination
to moderate contamination and the
rest of the stations showed no sign
of contamination. Stations 10 and 2 Measured Concentration
CF =
were moderately contaminated and Background Concentration
moderately to heavily contaminated
for Cu, respectively. Stations 6 and Equation 3
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Vowotor et al Journal of Health & Pollution Vol. 4, No. 6 — March 2014
Research
Hg Pb Zn Cd = Σ CiF
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Journal of Health & Pollution Vol. 4, No. 6 — March 2014 Vowotor et al
Research An Assessment of Heavy Metal Pollution in Sediments of a Tropical Lagoon
F. Assessment According to Potential Multiple metals increase the PER. As, where Tri is the metal toxic response
Ecological Risk (PER) Cr, Cd, Cu, Hg, Pb and Zn are prior factor for a given substance.21
The Hakanson index is a diagnostic considered objects;
tool used to assess the Potential (3) toxicresponse—heavy biological The values for each element
Ecological Risk (PER) for water toxicity metals have more evidence investigated are in the order:
pollution control purposes and helps for potential risks and magnitude for Zn = 1 < Cr = 2 < Cu = Pb = 5 < As =
determine which water bodies and abundance correction; 10 < Cd = 30 < Hg = 40.
substances need to be given special (4) sensitivity—based on the biological
attention.18 The methodology is based production index (BPI); sensitivity CiF is the contamination factor (a ratio
on the assumption that the sensitivity differs in different water quality between reference records, CiD and
of the aquatic system depends on its systems.19, 20 measured concentration values in
productivity. The PER assessment sediments, CiR).
system, defined in Dumcius et al., Mathematically the PER is expressed
is based on element abundance and as in Equation 5 as: The potential ecological risk of a given
several preconditions: contaminant is defined in Table 9 and 10.
(1) concentration—aggravated The sum of the individual potential risks
metal pollution degree in sediments Eir = Tri x CiF (RI) is the potential risk for that
increases the PER; particular water body.19 The risk
(2) species number—the metals in Equation 5 assessment findings are given in Table 11.
sediment express the additive effect.
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Vowotor et al Journal of Health & Pollution Vol. 4, No. 6 — March 2014
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Journal of Health & Pollution Vol. 4, No. 6 — March 2014 Vowotor et al
Research An Assessment of Heavy Metal Pollution in Sediments of a Tropical Lagoon
Stations As Cd Cr Cu Hg Pb Zn RI
ER Grade Moderate Very high Low Low Considerable Low Low All Σ RI = Very high
Table 11 — Potential Ecological Risk Assessment for Soil Sediments of Benya Lagoon
attributed to the use of lead-painted above the heavily polluted levels at is employed to evaluate possible
zinc roofing sheets used along the some individual sampling stations. The anthropogenic input of metals to
banks of the lagoon. degree of pollution in the sediments observed sediment, and degree of
was assessed by determining the geo- contamination (Cd), used to assess the
The metal concentrations obtained accumulation index Igeo, a decisive excessive values of monitored elements
were compared with standard factor capable of evaluating heavy in soil sediment samples, were also
sediment criteria recommended by metal pollution in sediments. The used as indicators of the extent of
the United States Environmental findings indicated that the sediments environmental contamination. The
Protection Agency (USEPA) and showed a moderate contamination highest CF value was obtained for
consensus–based sediment quality level for Pb and no contamination for Cd, which registered a very high
guidelines (CBSQG). Using these Cr and Zn. Using the mean values of contamination factor, with low
guidelines, the average concentrations Igeo, the sediments studied may be said contamination factors being registered
of As, Cd, Hg, and Pb indicated heavy to be contaminated with the metals in for Cr and Zn. On the basis of the
pollution levels, while Cr, according the order Cd > Pb > As > Hg > Cu > mean CF values, the sediments may
to both standards, registered a Cr > Zn. be considered to be polluted by the
slight pollution level on average, but metals investigated in the order Cd
registered concentration values way The contamination factor (CF), which > Pb > As > Hg > Cu > Cr > Zn.
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Vowotor et al Journal of Health & Pollution Vol. 4, No. 6 — March 2014
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Considering the cumulative effect of Research Writing (Environmental) 8. Ritsema R, Donard OFX. On-Line speciation of
all of the individual metals present organized by AuthorAID and the mercury and methylmercury in aqueous samples by
at the stations, Station 1 registered knowledge acquired was applied chromatography-atomic fluorescence spectrometry
the highest degree of contamination, during the write-up of this paper. We after hydride generation. Appl Organometallic Chem.
while Station 11 registered the lowest. also wish to thank the technicians 1994;8(7-8):571-5.
In decreasing order, the degree of and staff of the Ghana Atomic Energy 9. Medit: Elmina Castle [Internet]. Accra, Ghana:
contamination among the stations can Commission at Kwabenya-Accra for BeautifulGhana; c2007 [cited 2013 Aug 8]. [about 2
be expressed as: 1 > 3 > 4 > 5 > 6 > 2 > their kind assistance in the analysis of screens]. Available from: http://www.beautifulghana.
7 > 8 > 9 > 10 > 12 > 11. the samples. com/content/view/76/135/lang,en/
10. Luoma SN. Processes affecting metal
The Potential Ecological Risk (PER) for concentrations in estuarine and coastal marine
the water from which the sediments sediments. In: Furness RW, Rainbow PS, editors.
were harvested was determined using Heavy metals in the marine environment. Boca Raton
the Hakanson index. The findings References (FL): CRC Press; 1990. p. 51 – 66.
indicated that Cd and Hg need to be 11. LA Currie. The importance of chemometrics
watched closely as they registered high 1. F. Schmermer. Silt and dirt chokes Fosu Lagoon in biomedical measurements. In: Subramamanian
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