K.Kodometal 2012 BSSC A 712073 O
K.Kodometal 2012 BSSC A 712073 O
K.Kodometal 2012 BSSC A 712073 O
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Knowledge of soil heavy metal concentration is very important for assessing the purity
and quality of the soil in an environment. The concentrations of nine heavy metals
(NHM), Zn, Pb, Cr, Cu, Co, Ni, Cd, Hg, and As, from the near-surface soils (∼ 0–15 cm)
from an industrial cluster in Kumasi, Ghana, were qualitatively and quantitatively
measured and analyzed using X-ray fluorescence (XRF) spectroscopy analysis. The
sources of these NHM were mainly anthropogenic as a result of the indiscriminate
industrial waste disposal. In all, a total of about 100 soil samples were taken from six
sampling sites, four of which were industrial and the remaining two residential. Forty
soil samples out of the total number were carefully selected for elemental analyses
and the mean heavy metal concentrations were calculated using statistical methods.
The results from locations of high industrial impact showed that the mean concentra-
tions of the NHM present in the soil were in the order of Zn (189.2−908.6 mgkg−1),
Pb (133.7−571.3 mgkg−1), Cr (91.3−545.8 mgkg−1), Cu (62.9−334.6 mgkg−1), Co
(38.6−81.9 mgkg−1), Ni (12.4−30.9 mgkg−1), Cd (6.9−13.2 mgkg−1), Hg (5.5−10.4 mg
kg−1), and As (2.3−18.6 mgkg−1). Apart from Ni and As, all the heavy metals recorded
concentrations that ranged from 10−900% higher than their respective threshold limit
values (TLVs). Heavy metal concentrations from the residential sites were compara-
tively far lower with only Cr, Cd, and Hg registering concentrations between 65−250%
above their TLVs. The cluster with its residential communities is at a serious risk of soil
heavy metal toxicity and awareness to this needs to be created as such.
Keywords Heavy metals, X-ray fluorescence (XRF), soil pollution, soil sample, thresh-
old limit values (TLVs)
1. Introduction
Most environmental scientists are now of the view that industry is largely to blame for some
of the major soil heavy metal pollution in the environment, since pollution due to heavy
or toxic metals has generated much concern in most metropolitan and urban complexes. It
is believed that the concentrations of these metals released into the ecosystem may lead to
1006
XRF Analysis of Heavy Metal Pollution 1007
Figure 1. Portion of the Kumasi city center showing the study area. Inset: Map of Ghana showing
the Ashanti region (bold outline) and the Kumasi city center.
XRF Analysis of Heavy Metal Pollution 1009
Figure 2. Experimental sampling: (A) Field procedures showing specific transect of 2 m Interval;
(B) core-sampling showing selected depth of soil (0–15 cm).
Figure 3. Map of the study area showing soil sampling locations (Not drawn to scale).
In order to reduce soil matrix effects, the soil samples were thoroughly homogenized
and sieved to fine particle sizes of about 75 μm with Retsch aluminium test-sieves with
vibratory electronic sieve shaker. Generally, XRF probes better only at a depth of 100 μm
or less for most sample matrices (Guthrie, 2007). Therefore, the fine powdery particles
that passed through the 75 μm sieve were re-packaged and carefully stored for further
investigation.
As described by Kodom et al. (2010), pulverization of the soil samples in general
includes grinding, mixing, or milling into a finer loose powder state. Since XRF spectrom-
eters only analyze a sample’s surface layer, which must be representative of the whole
sample, each sample was carefully and homogeneously prepared into pellets with smooth
surfaces of equal density. This was achieved by milling or pulverizing the loose powdered
samples (75 μm) to further reduce the particle size to about 60 μm and below.
Before the milling or mixing procedure, 0.9 g of a powdery binder (Hoechst wax)
containing cellulose, starch, polyvinyl alcohol, or other organics (Buhrke et al., 1998) was
weighed into 4 g of each sample using an electronic balance. The resulting mixture (sample
and binding material), having a total mass of 4.9 g, was put into deformable aluminium
cups (screw-top grinding jars) for the process of thorough milling and homogenization
using the RETSCH Mixer Mills (MM 301), which also aided the further pulverization of
the sample. By using a SPECAC hydraulic press with a maximum pressure limit of 15
tons (or 15000 kg), each pulverized sample was manually pressed into pellets with uniform
diameter (32 mm) and thickness (3 mm), as discussed by Kodom et al. (2010).
2.3.1 XRF Instrumentation and Elemental Analyses. The concentrations of the heavy
metals were determined using a polarized energy dispersive X-ray fluorescence (PED-XRF)
XRF Analysis of Heavy Metal Pollution 1011
spectrometer. Specifically, the Spectro X-LAB 2000 PED-XRF spectrometer equipped with
a Rh anode X-ray tube, and a 0.5 mm Be side window was employed. This Spectro X-Lab
2000 XRF equipment has a carousel (circular rotating position sample changer) placed
inside a sample chamber that has the capacity to hold a maximum of 20 sample holder
disks of 32 mm diameter for sequential sample analyses. The XRF is a very sensitive
technique, hence great caution was taken to avoid contamination of the pellets ahead of the
analysis. Poor handling of the samples could seriously affect the results of the analysis due
to high sensitivity of the spectrometer, which was sensitive enough to detect fingerprints on
the pellet’s surface layer (Kodom et al., 2010; Brouwer, 2006). Taking into consideration
these cautious measures, the 20 sample holder disks (sample cups) were all filled with the
pellets by holding the sample pellets by the edges (not the surface layer). In the sample
chamber, the 20 samples were characterized by allocating them with sample numbers for
easy identification.
A computer-based multi-channel analyzer, which contained menu-based SPECTRO
X-LAB Pro. Software Package (Turboquant), was set for controlling the spectrometer
functions, spectral analysis, collecting and storage of data, as well as data evaluation. The
samples were therefore analyzed using a pre-set method, made up of a series of tasks,
which acquires several spectra for each sample, one spectrum per target (Guthrie, 2007).
The instrumentation used was a SPECTRO X-LAB 2000 equipped with a 400 W Rh end
window tube and a Si(Li) detector with a resolution of 148 eV (1000 cps Mn Kα). The
available targets were A12 03 and B4C used as a BARKLA polarizer, an HOPG (High
Oriented Pyrolitic Graphite) - crystal used as a BRAGG polarizer, and Al, MO, and Co
used as secondary targets. The irradiation chamber could be operated under vacuum or by
using a gas purge either with nitrogen or helium. The automatic sample changer could be
equipped with 20 samples maximum (Schramm et al., 1999).
Inside the spectrometer, the method selected the first task and all sample spectra were
acquired one after the other. By rotating the target carousel and adjusting other parameters,
the system moved on to the next task and acquired the next set of spectra lines. The net top
positions of the spectra generally represented the various elements present, and the areas
of the line spectra represented the intensity. Qualitatively, the top positions of the spectra
characterized the various elements in the sample, while quantitatively the net intensity
of the peaks of the spectra were converted into concentrations (Brouwer, 2006). The
EDXRF systems depend on semiconductor-type detectors, which receive the entire emitted
spectrum from the sample and decode it into a histogram of number of counts versus
photon energy. The peak height for any element is directly related to the concentration of
that element within the sampling volume (HORIBA, 2009). To identify the net intensity of
the peaks of the spectra and convert them into concentrations, calibration standards with
accurately known element concentrations are used to generate calibration curves (XRF
peak intensity versus concentration). These curves are then used to calculate concentrations
from observed spectra. The method works extremely well, and is recommended for best
accuracy (HORIBA, 2009), since a good relationship exists between the peak height and the
recorded concentrations. Peaks in the energy spectrum, once acquired, are subject to a large
degree of massaging by the software in the connected computer. Sophisticated algorithms
sense and quantitatively correct for high backgrounds due to Compton scattering from
low atomic number matrices (Metz et al., 1994; Guthrie, 2007). Due to the secondary
targets used by the spectrometer, several energy spectra for each sample were acquired,
one from each target. Since each target yields better sensitivity in one part of the spectrum,
the information from the energy spectra is combined to quantitate each element being
analyzed.
1012
Table 1
Mean heavy metal concentrations ± SD [mg kg–1] for all sampled locations (n = 40)
For the Spectro X-Lab 2000, the software handles all spectral deconvolution and
elemental quantitation. The analyses do not even require the user to inspect the acquired
energy spectra frequently. The results are, however, automatically calculated and reported
as a mass fraction, which is simply recorded in parts-per-million (ppm). Detection in this
instrument is accomplished with a Si(Li) detector with an active surface of 10–30 mm2 and
an effective thickness of 3–4 mm. The maximum energy resolution of the detection system,
which includes the preamplifier, is 150 eV at 5.9 keV and a count rate of 1000 cps. The
output is fed to a main amplifier and then to an analog-to-digital converter (ADC). The
ADC is interfaced with a PC, which runs the Spectro X-Lab Pro software. The specified
detection limits in an organic matrix for the X-Lab 2000 vary from 0.3 ppm by weight for
Cd to 2000 ppm for Na. These detection limits fluctuate depending on the matrix type and
are calculated by the system software based on the measured background noise (Jenkins
et al., 1995; Guthrie, 2007; Spectro, 2011). The total analysis time varies from 15 minutes
to several hours, depending on the number of tasks or targets in the method (Brouwer, 2006;
Guthrie, 2007).
Table 2
Summary results of descriptive statistical analysis of selected heavy metal concentrations,
compared with their TLV for Zone 4, along a 38 m transect [n = 20]
The graphical results reported (Figures 4–5) show the variations of the measured heavy
metal concentration along the 38 m transect for top-soils (0–15 cm depth) of Zone 4. In
Figure 5, heavy metals with concentrations lower than 50 mg kg–1 are plotted separately
for clarity.
3.1.2. HM Accumulation. The summarized results obtained from the trace analysis pre-
sented in Table 1 depict that the heavy metal (HM) levels in the surface soils (∼ 0–15 cm),
Figure 4. Variation of NHM concentration along the 38 m transect. Measured NHM concentrations
along a 38 m transect of Zone 4 for; 4a: Arsenic (As); 4b: Lead (Pb); 4c: Mercury (Hg); 4d: Cadmium
(Cd); 4e: Chromium (Cr); 4f: Cobalt (Co); 4g: Nickel (Ni); 4h: Zinc (Zn); and 4i: Copper (Cu).:
Reference (0,0): 06.43 16.8 .
XRF Analysis of Heavy Metal Pollution 1015
Figure 4. (Continued).
according to Figure 5 (“a” and “b”), showed varying concentrations along the specified
transect. With the exception of As and Ni, which recorded concentrations within their
threshold levels, Zone 4, in particular, showed a remarkable heavy metal accumulation
(according to Table 2 and Figure 6a). Moreover, the concentrations of Zn, Pb, Cu, Cr, Co,
Cd, and Hg showed far higher values above their various threshold limits. These escalated
levels can therefore be attributed to the heavy metallurgical and industrial impacts at the
study area.
Considering Figure 6b, with the exception of the residential communities (Kwantwima
and Abusuakrowa), all the zones recorded escalated levels of Pb with Zone 12 and Zone
7 recording the maximum and the minimum, respectively. However, according to Figure
6c, all the measured zones (including the residential communities) recorded concentrations
of Zn below the TLV, with the exception of Zone 4 and Zone 12, which recorded highly
dominant values of Zn. Concentrations of Cu, Cr, Co, Cd, and Hg were highly dominant as
well.
The high content of Pb and Zn at Zone 4 and 12 (Figures 6b and 6c) illustrate the
impact of the industrial activity on the surface soils of those areas. This is because, when
comparing the concentration of the heavy metals at the industrial zones to the two residential
communities (Fig. 6f), the distribution showed wide variations with all the measured heavy
metal concentrations at industrial areas recording highly dominant values as compared
to the residential areas. The total mean heavy metal concentration at the industrial zones
showed a relative dominant pattern in the order of As< Hg< Cd< Ni< Co< Cu< Cr<
1016 K. Kodom et al.
Figure 6. a. Heavy metal accumulation in soils of all sampled zones at the study area. b Measured
mean Pb concentration at each sampled location compared with the TLV. c. Measured mean Zn
concentration at each sampled location compared with the TLV.
1018 K. Kodom et al.
Figure 6. d. Mean heavy metal concentration and distribution of sampled soils in communities with
high industrial impact. e. Mean HM concentration and distribution of sampled soils in communities
with less industrial impact. f. Total heavy metal accumulation in the sampled soils at locations of
high industrial activity compared to that of a residential community.
XRF Analysis of Heavy Metal Pollution 1019
Pb< Zn (as shown in Fig. 6f). However, the residential zones showed a similar pattern of
As< Hg< Cd< Ni< Cu< Co< Pb< Cr< Zn, with a slight change in the positions of Pb
and Cr, as well as Cu and Co.
Considering all the NHM analyzed from the entire study area (Figs. 6a–d), Zones 4
and 12 generally recorded the highest heavy metal concentrations in the sampled soils.
Therefore, for all the analyzed heavy metals investigated in this study, the most polluted
zone is in the order of Zone 4 >Zone 12 >Anomanye Junction >Zone 7 >Abusuakrowa
>Kwantwima (Figure 6a).
4. Conclusions
The soils in the near surface (∼ 0–15 cm) of the Suame industrial cluster in Kumasi showed
accumulated concentrations of the nine heavy metals Zn, Pb, Cr, Cu, Co, Ni, Cd, As,
and Hg from 10–900% above their threshold values. The residential zone surrounding this
cluster showed relatively lower concentrations, but still these were about 65–650% higher
than their threshold values. These anomalous concentrations are a result of anthropogenic
activities, including smelting procedures, chemical and metallurgical processes, and the
indiscriminate industrial waste disposal on the unprotected soil. The associated high heavy
metal pollution from the residential sites (which are within a 5 km radius from the industrial
sites) might be partly due to atmospheric fallout from the industrial sites. In addition, there
is a high possibility of pollutant transport and surfacial mobility due to occasional flooding
and run-offs resulting from precipitation. Solute transport to the residential sites is facilitated
by the streams (Figure 3).
Soil heavy metal pollution in the Suame cluster and environs is astronomically high. It
is recommended that river channels and gutters should be regularly desilted and furthermore
indicators like pH, salinity, moisture content, temperature, and redox potential that influence
heavy metal speciation, mobility, and retention in soils (Ogundare, 1998; Kadem et al., 2004;
Oguntimehin and Ipinmoroti, 2008) should be regularly monitored to protect human and
animal life.
Acknowledgement
The research was partly supported by the Geochemistry and Laboratories at Geological
Survey Department, Accra, Ghana. The authors wish to acknowledge the invaluable help
rendered by Mr. Edwin Bawa (Physics Department Laboratory, KNUST), Mr. Emmanuel
Afum (Geochemistry and Laboratory, Geological Survey Department., Accra), and Mr.
Gilbert (Geotechnical Laboratory, Civil Engineering Department., KNUST) for assisting
in the laboratory work.
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