Preconcentration of trace multi-elements in water samples using Dowex

50W-x8 and Chelex-100 resins prior to their determination using

inductively coupled plasma atomic emission spectrometry (ICP-OES)
Philiswa N. Nomngongo
a
, J. Catherine Ngila
a,
, Titus A.M. Msagati
a
, Brenda Moodley
b
a
Department of Applied Chemistry, University of Johannesburg, Doornfontein 2028, Johannesburg, South Africa
b
School of Chemistry and Physics, University of KwaZulu Natal, P/Bag X54001, Westville, Durban, 4000, South Africa
a r t i c l e i n f o
Article history:
Available online 28 August 2013
Keywords:
Trace multi-element
Simultaneous preconcentration
Ion exchange resins
Chelex-100
Dowex 50W-x8
Drinking water
a b s t r a c t
This work presents a solid phase extraction (SPE) method for simultaneous preconcentration of trace ele-
ments in water samples prior to their ICP-OES determination. Dowex 50W-x8 and Chelex-100 resins
were used as SPE sorbent materials for preconcentration of trace Cd, Co, Cr, Cu, Fe, Ni, Pb and Zn. The opti-
mum sample pH, eluent concentration and sample ow rates were found to 6, 3.0 mol L
1
and
3.0 mL min
1
, respectively. In terms of multi-element preconcentration capabilities, Dowex 50W-x8
appeared to be a better sorbent. The recoveries for all the tested analytes were >95%. However,
Chelex-100 showed a better performance in terms of recovery (>95%) towards Cu, Fe and Zn. Under opti-
mized conditions using Dowex 50W-x8, the relative standard deviations for different metals were <3%.
The limits of detection and limits of quantication ranged from 0.010.39 lg L
1
and 0.050.1.3 lg L
1
,
respectively. The accuracy of the preconcentration method was conrmed by spike recovery test and
the analysis of certied reference materials. The SPE method was applied for preconcentration of the ana-
lyte ions in tap water, bottled water and wastewater samples.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
Monitoring of trace metals in environmental samples is crucial
since most of these metals have negative or positive effects on
human health even at very low concentrations not easily detect-
able with standard techniques (Tufekci et al., 2012; Kazi et al.,
2009). Even though some of the metals such as Co, Cr, Cu, Fe, Ni
and Zn have a range of biochemical functions in living organisms,
they still can be toxic when taken in excess (Tufekci et al., 2012).
In contrast, the presence of non-essential metals such as lead and
cadmium, even in trace levels, damages central nervous functions,
lowers energy levels, damages the blood composition, lung, kid-
neys, liver, and other vital organs (Tufekci et al., 2012; Afridi
et al., 2006). Therefore, monitoring of trace elements in the envi-
ronment is extremely important because it helps to control expo-
sure of humans and animals to these substances (dos Santos
Silva et al., 2012).
Due to the high toxicity of heavy metals, it is crucial to detect
ultra-low levels especially in drinking water. The determination
of metal ions in water samples has been successfully carried out
with different analytical techniques (Soylak, 2004; Tuzen et al.,
2005). These include ame atomic absorption spectrometry
(FAAS), graphite furnace atomic absorption spectrometry (GFAAS),
inductively coupled plasma optical emission spectrometry
(ICP-OES) and inductively coupled plasma-mass spectrometry
(ICP-MS) (Soylak, 2004; Komjarova and Blust, 2006; Bezerra
et al., 2007). Among the above mentioned analytical techniques,
ICP-OES is extensively used for the determination of metal ions.
This is because ICP-OES displays attractive features such as mul-
ti-element detection capacity, wide linear range, low limits of
detection and high sample throughput (Xiong et al., 2010). How-
ever, ICP-OES is not suitable for direct analysis of extremely low
metal levels. In addition, it suffers from matrix interferences.
Therefore, prior to detection with ICP-OES an effective pre-concen-
tration step such as solid phase extraction (SPE) is required. The
latter is a widely applied and powerful pre-treatment approach
prior to analysis (Hennion, 1999). Among other advantages, SPE
is commonly used because a variety of extraction materials (sor-
bents) are available, and the extraction can be tuned depending
on how these sorbents interact with the analytes. As a result, var-
ious adsorbents such as Amberlite XAD resins (Ramesh et al., 2002;
Elci et al., 2000; Narin et al., 2003; Malla et al., 2002), Chelex-100
(Soylak, 2004), Chemisorb 108 (Tuzen et al., 2005) and Dowex
50W-x4 (Pohl and Prusisz, 2004), among others, have been used
for the separation/pre-concentration of trace elements in various
complex samples.
1474-7065/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.pce.2013.08.007

Corresponding author. Tel.: +27 115596196; fax: +27 115596154.

E-mail address: jcngila@uj.ac.za (J. Catherine Ngila).
Physics and Chemistry of the Earth 66 (2013) 8388
Contents lists available at ScienceDirect
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j our nal homepage: www. el sevi er . com/ l ocat e/ pce
The present study seeks to determine the most suitable cation
exchange resin that will have high metal retention efciency over
a wide operating pH range. Therefore, performance of Chelex-100
and Dowex 50W-x8 sorbents for simultaneous pre-concentration
of cadmium, cobalt, chromium, copper, iron, nickel, lead and zinc
in aqueous solutions was investigated. Various factors affecting
the cation exchange process, such as sample volume, concentration
of the eluent, sample and eluent ow rates as well as the accuracy
of the method, were investigated.
2. Experimental
2.1. Instrumentation
Analyte metal ions were determined using Spetro Arcos ICP-OES
equipped with Cetac ASX-520 autosampler. Solid phase extraction
was carried out in a VacMaster-24 sample SPE station (Supelco, PA,
USA). The latter was used to control the sample loading and elution
ow rate to 3.0 mL min
1
.
2.2. Reagents and solutions
All reagents were of analytical reagent grade unless otherwise
stated and Millipore water was used throughout the experiments.
Spectrascan stock solutions (1000 mg L
1
) of Cd, Co, Cr, Cu, Fe, Ni,
Pb and Zn (Teknolab A/S, Drbak, Norway) were used to prepare
the working solutions for SPE at concentrations of 6 lg L
1
(Cr,
Co, Ni), 10 lg L
1
(Cd), 12 lg L
1
(Pb), 30 lg L
1
(Cu, Fe and Zn).
Working solutions, as per the experimental requirements, were
freshly prepared from the stock solution for each experimental
run. A Spectrascan multi-element standard solution at concentra-
tion of 100 mg L
1
was used to prepare working standard solutions
at concentrations of 1070 lg L
1
for Cd, Co, Cr, Fe, Ni and Pb; and
30180 lg L
1
for Cu and Zn in measurements of concentrations of
analytes in all model and sample solutions. Solutions of nitric acid
at concentrations of 0.5, 1.0, 2.0, 3.0 and 4.0 mol L
1
used for the
elution of the analytes from the column were prepared from ultra-
pure concentrated acid (65%, SigmaAldrich, St. Loius, MO, USA).
The pH adjustments were performed with 1.0 M HNO
3
and NaOH
solutions. The cation exchangers used in this study as packing
materials were Chelex-100 and Dowex 50W-x8 (sodium forms)
purchased from Sigma Aldrich (St. Loius, MO, USA).
2.3. Water samples and preparation
Tap water samples were obtained from University of Johannes-
burg (Doornfotein and Kingsway campuses). Efuent wastewater
samples were collected from Johannesburg Water. The wastewater
samples were ltered through a 0.45 lm pore-size Millipore
cellulose nitrate membrane to remove any ne particulate matter
present. Bottled water samples were obtained from a local
supermarket.
2.4. Column preparation
Supelco polyethylene columns (1.35 cm in diameter and 6.5 cm
in length) with frits were employed for SPE. The columns were
soaked in 5% HNO
3
solution and then rinsed successively with
Millipore water. Afterwards, slurries of 1.5 g of Chelex-100 or Dow-
ex 50W-x8 resin in Millipore water were loaded into the columns.
A porous frit was placed at the bottom of the column and at the top
of the packing material to hold and conne the adsorbent within
the designated capacity/volume. The resin columns were washed
using triple distilled water followed by conditioning with 10 mL
ammonium acetate buffer (1.0 mol L
1
, pH 9.0). After each use,
the resin in the column was washed with 20 mL of water followed
by 10 mL of 1.0 mol L
1
NaOH. This was done in order to keep the
resin in sodium form.
2.5. Preconcentration procedure
The pH values of the model solutions of Cd, Co, Cr, Cu, Fe, Ni, Pb
and Zn were adjusted to 6. The solutions were then each passed
through a SPE column packed with either Chelex-100 or Dowex
50W-x8 at a ow rate of 2.0 and 3.0 mL min
1
, respectively. Metal
ions retained on the resins were eluted with 5.0 mL of HNO
3
at a
ow rate of 3.0 mL min
1
. The metal concentrations in the nal
solution were determined using ICP-OES. The same procedure
was applied to the blank solutions. After each run, the columns
were conditioned as per Section 2.3.
2.6. Optimization of preconcentration parameters
The SPE system was optimized in order to determine the best
retention/ elution conditions for trace metal ion determinationwith
good sensitivity and precision (Soylak, 2004). Several experimental
variables affecting the pre-concentrationsystemsuchas eluent con-
centrations, sample and eluent owrates, among other parameters,
were evaluatedandoptimized. To obtainthese conditions, prelimin-
ary tests were performed to investigate factors that exert signicant
inuence on the retention of the analytes by cation exchange resin.
The factors selectedinclude eluent concentration, sample volume as
well as sample ow rate. In previous study (Soylak, 2004), the max-
imum retention of the analytes onto the cation exchange resin was
observed at pH 6. We decided to use the same pH value at 6 in the
present study, for all the experiments.
The optimization of the sample ow rate was carried out to en-
sure the quantitative retention of the analytes of interest. The ef-
fect of ow rate of the sample solution on the retention of the
studied metal ions on the Chelex-100 and Dowex 50W-x8 resins
was carried out with a column packed with 1.5 g of resin. Sample
solutions were passed through the column at various ow rates
(1.05.0 mL min
1
). The ow rates less than 1.0 mL min
1
were
not studied to avoid long analysis time.
3. Results and discussion
The SPE system was optimized in order to determine the best
retention/elution conditions for trace metal ion determination
with good sensitivity and precision (Soylak, 2004). Several experi-
mental variables affecting the pre-concentration system, such as
eluent concentrations, sample and eluent ow rates, among other
parameters, were evaluated and optimized. The percentage recov-
eries were calculated by relating the nal obtained concentration
(C
f
) of the analyte to the original concentration (C
i
) of the metal
ion in the model solution.
3.1. Effect of pH
The sample pHfor quantitative preconcentrationof Cd, Co, Cr, Cu,
Fe, Ni, Pb and Zn in the Dowex 50W-x8 and Chelex 100 columns is
one of the most important factors (Jimnez et al., 2002). This is
because, highly acidic solutions may lead to protonation of resins
functional group while highly alkaline solution may result in the
precipitation of metal ions as hydroxides. This may results in the
underestimation of metal ion concentrations in drinking water
samples. Therefore, the effect of sample pH on the retention of the
analytes onto Dowex 50W-x8 and Chelex 100 resins was carried
out between pH 4 and 10. The inuence of the sample pH on the
pre-concentration of Cd, Co, Cr, Cu, Fe, Ni, Pb and Zn is presented
in Fig. 1. It was observed that for both resins, lower recoveries
84 P.N. Nomngongo et al. / Physics and Chemistry of the Earth 66 (2013) 8388
(<95%) were obtainedfor all metal ions at pH4andthis canbe attrib-
utedto competitionbetweenthe metal ions andthe hydroniumions
for the active sites on the adsorbent surface. However, quantitative
recoveries were obtainedfor all analytes at pHrange 67and57for
Dowex 50W-x8 and Chelex 100 resins, respectively. Therefore, pH6
was chosen for subsequent investigations.
Fig. 2. Inuences of the eluent concentration on the recoveries of the analytes on (A) Dowex 50W-x8 and (B) Chelex-100 columns. Experimental conditions: sample pH 6.0;
sample volume 20 mL; amount of resin 1.5 g, ow rates of sample and eluent 3.0 mL min
1
, respectively n = 3.
Fig. 3. Effect of sample volume on the recoveries of metal ions: (A) Dowex 50W-8, (B) Chelex-100. Experimental conditions: pH 6.0; analyte concentration 10 lg L
1
; amount
of sorbent 1.5 g; ow rates of sample and eluent 3.0 mL min
1
; eluent volume 5 mL; replicates n = 3.
Fig. 1. The effect of pH on the recoveries of 20 lg L
1
metal ion solution: (A) Dowex 50W-8, (B) Chelex-100. Experimental conditions: sample volume 20 mL; amount of resin
1.5 g, ow rates of sample and eluent 3.0 mL min
1
, respectively n = 3.
P.N. Nomngongo et al. / Physics and Chemistry of the Earth 66 (2013) 8388 85
3.2. Effect of eluent concentration
The desorption/elution of metal ions from Dowex 50W-x8 and
Chelex-100 using various nitric acid concentrations (0.5
4.0 mol L
1
) has been investigated. From the results in Fig. 2, it
was observed that in order to desorb the metal ions from Dowex
50W-x8, a higher concentration of nitric acid as compared to Che-
lex-100 was used. This implied that Dowex 50W-x8 strongly binds
the metal ions compared to Chelex-100. The results indicated that
metal ions were quantitavely recovered from Chelex-100 when the
concentration of HNO
3
was between 1.0 and 2.0 mol L
1
while in
the case of Dowex 50W-x8 3.0 mol L
1
HNO
3
was used. This should
be expected because Chelex-100 (iminodiacetic acid functional
group) is a weakly acidic cation exchanger whereas Dowex 50W-
x8 (sulfonic acid functional group) is a strongly acidic cation
exchanger.
3.3. Effect of ow rate
The optimization of the sample ow rate was carried out to
ensure the quantitative retention of the analytes of interest. The
effect of ow rate of the sample solution on the retention of the
studied metal ions on the Dowex 50W-x8 resin was carried out
with a column packed with 1.5 g of resin. Sample solutions were
passed through the column at various ow rates (1.0
5.0 mL min
1
). The ow rates less than 1.0 mL min
1
were not
studied to avoid long analysis time. The optimum ow rate for this
work was dened as the rate of ow of the sample solution
through the column at which more than 95% retention of metal
ions takes place. The results (Fig. 3) showed that the optimum ow
rate for quantitative sorption of metal ions onto the resin was
between 1.0 and 3.0 mL min
1
. The increase of ow rate more than
3.0 mL min
1
caused a gradual decrease in sorption due to insuf-
cient contact time between the resin and the metal ions; hence, 2.0
and 3.0 mL min
1
ow rates were chosen as the optimum ow rate
for sample loading onto Chelex-100 and Dowex 50W-x8 resins,
respectively.
3.4. Preconcentration of multi-element
The efciency of studied cation exchange resins for pre-concen-
tration of multi-elements (concentration of each analyte equal to
10 lg L
1
) in aqueous solution was investigated under optimum
conditions. The results indicated that the highest retention of the
analytes from aqueous model solutions was observed on Dowex
50W-x8 resin (Table 1). This might be due to the larger exchange
capacity (1.7 meq mL
1
) and its functional groups (sulfonic acid).
The recoveries of metal ions from Dowex 50W-x8 ranged from
95% to 101%. It can be concluded that the afnity of studied ana-
lytes towards Dowex 50W-x8 was very similar. Therefore, they
could be pre-concentrated with the same efciency (Pyrzyska
and Joca, 2000). The results in Table 1 indicated that Chelex-
100 was only suitable for the removal of Cu, Fe and Zn at an opti-
mum ow rate of 2.0 mL min
1
. The rest of the metals were not
quantitatively recovered at this optimum ow rate. It was then
concluded that Chelex-100 was not suitable for pre-concentration
of multi-element in aqueous matrices. Therefore, Dowex 50W-x8
at an optimum ow rate of 3.0 mL min
1
was used for further
analysis.
Table 1
Recovery (%) of multi-element in aqueous solution using Dowex 50W-x8 and Chelex-100 SPE methods.
Resins Recovery (%)
Cd Co Cr Cu Fe Ni Pb Zn
Dowex 99.2 1.4 97.4 1.3 96.3 1.2 101 1.2 99.3 4.2 96.4 1.4 95.1 1.2 97.9 2.1
Chelex 88.9 1.2 80.6 3.8 85.3.1 4.0 95.8 2.4 97.5 2.4 78.1 1.2 91.0 1.2 96.5 3.8
Experimental conditions: sample volume = 20 mL; amount of resin = 1.5 g; ow rates = 2.0 and 3.0 mL min
1
for Chelex-100 and Dowex 50W-x8, respectively; eluent
volume = 5 mL; replicates = 3.
Fig. 4. Effect of sample volume on the recoveries of metal ions. Experimental
conditions: pH 6.0; analyte concentration 10 lg L
1
; amount of sorbent 1.5 g; ow
rates of sample and eluent 3.0 mL min
1
; eluent volume 5 mL; replicates n = 3.
Table 2
Analysis of certied reference materials (mean of 3 replicates; concentration in lg L
1
).
Cations BCR-713 Efuent wastewater CRM TMDW-500 drinking water
Certied Obtained Recovery Certied Obtained Recovery
Cd 5.1 0.6 5.0 0.8 97.5 1.1 10.0 0.05 9.7 0.7 97.0 2.1
Co NC
a
15.3 1.3 25.0 0.1 24.3 0.6 97.2 1.4
Cr 21.9 2.4 22.1 0.7 100.9 0.5 20.0 0.1 19.6 0.3 98.0 1.1
Cu 68.4 3.3 66.8 1.3 97.7 2.4 20.0 0.1 20.1 0.2 100.5 0.9
Fe 398.3 32.0 383.5 3.5 96.3 1.4 100.0 0.5 97.8 0.6 97.8 1.7
Ni 30.6 4.6 29.7 2.1 97.1 1.3 60.0 0.3 57.9 0.9 96.5 1.3
Pb 47.0 4 48.3 1.3 102.8 0.8 40.0 0.2 38.7 0.4 96.8 2.4
Zn 216.2 32.13 213.5 1.8 98.8 3.1 70.0 0.4 70.3 0.1 100.4 0.5
Experimental conditions: sample volume = 100 mL; amount of resin = 1.5 g; ow rates = 3.0 mL min
1
; eluent volume = 5 mL.
a
NC = not certied.
86 P.N. Nomngongo et al. / Physics and Chemistry of the Earth 66 (2013) 8388
3.5. Effect of sample volume
The inuence of sample volume on the recoveries of analyte
ions on the solid phase was studied in order to obtain high precon-
centration factor (Shishehbore et al., 2011; Aydin and Soylak,
2010). Therefore, the effect of sample volume on the retention of
Cd, Co, Cr, Cu, Fe, Ni, Pb and Zn onto Dowex 50W-x8 resin was
investigated in the range of 501000 mL, while keeping the metal
ion concentration xed at 10 lg L
1
. It is seen from the Fig. 4 that
the retention of metal ions can be achieved quantitatively (P95%)
by sample volume up to 700 mL. Therefore, the highest preconcen-
tration factor was found to be 140 when the adsorbed metal ions
were eluted with 5 mL of 3 mol L
1
HNO
3
. At volumes higher than
700 mL, a decrease in quantitative recoveries of metal ions was ob-
served. This might be due to the saturation of the active sites of the
adsorbent. For further investigations, 100 mL was used.
3.6. Column regeneration
In order to investigate the recyclability of Dowex 50W-x8 col-
umn, successive retention and elution cycles were performed by
passing 20 mL of copper, iron and zinc solutions through the col-
umn. The regeneration of Dowex 50W-x8 column were evaluated
by monitoring the changes in the recoveries of copper, iron and
zinc through 200 retentionelution cycles. The Dowex 50W-x8 col-
umn was reused after regeneration with 20 mL Millipore water and
10 mL of 1.0 mol L
1
NaOH, respectively. It was found to be stable
up to 150 retention/elution cycles without observable decrease in
the recoveries of copper, iron and zinc (>95%).
3.7. Analytical performances
The analytical performance of the SPE-Dowex 50W-x8 method
under optimum conditions for pre-concentration of metal ions
was evaluated. The dynamic linear range of the method was eval-
uated and obtained as 1070 lg L
1
for Cd, Cr, Co, Ni and Pb; 30
160 lg L
1
for Cu, Fe and Zn. The correlation coefcients (R
2
) of
the calibration curves were in the range 0.99910.9997. The IUPAC
limit of detection (LOD) and limit of quantication (LOQ) for the
SPE method under optimized conditions were obtained from the
signals of 20 successive measurements of the blank and the slope
(m) of the calibration curve. The LOD of Cd, Co, Cr, Cu, Fe, Ni, Pb,
and Zn were found to be 0.06, 0.08, 0.05, 0.02, 0.01, 0.39 and
0.02 lg L
1
, respectively; and LOQ were 0.19, 0.26, 0.11, 0.08,
0.05, 1.3 and 0.08 lg L
1
for Cd, Co, Cr, Cu, Fe, Ni, Pb, and Zn,
respectively. The LOD and LOQ values obtained in this study can
be improved by increasing the volume of the sample.
The precision (reproducibility) of the SPE method was studied
by performing 15 successive measurements at a concentration le-
vel of 10 lg L
1
of multi-element aqueous solution (containing Cd,
Co, Cr, Cu, Fe, Ni, Pb and Zn). The overall reproducibility of pre-con-
centration procedure expressed in terms of relative standard devi-
ation (%RSD) was reasonably good (<3%).
The analytical procedure was validated by analysis of certied
reference materials, BCR-713 (Efuent wastewater) and CRM
TMDW-500 drinking water. The results in Table 2 displayed a good
agreement between the obtained values and certied values with
satisfactory recoveries ranging 97103%. These results conrmed
the validity of the Dowex 50W-x8 SPE method for the preconcen-
tration of the metal ions from aqueous matrices. In addition, they
conrm that SPE-Dowex 50W-x8 is a suitable sample preparation
method that can be applied an a last step in drinking water puri-
cation plants to check the quality of drinking water before it is dis-
tributed for human consumption.
3.8. Application
Water quality is one of the important aspects in human and
environmental health. This is because majority of diseases that
cause morbidity and mortality in population are water related
(El-Harouny et al., 2008). For this reason, different organisations
such as USEPA, WHO and South African National Standards (SANS)
have set some guidelines for the concentration limits of heavy met-
als in drinking water (WHO, 2008; USEPA, 2011; SANS, 2005).
The Dowex 50W-x8 SPE method was applied for the determina-
tion of trace Cd, Co, Cr, Cu, Fe, Ni, Pb, and Zn in tap water, bottled
water and wastewater (efuent) samples. For analysis, 100 mL of
water samples were studied by the Dowex 50W-x8 SPE method.
The results of analysis are given in Table 3. Copper, Fe, Ni and Zn
were present in all water samples investigated. In the case of
drinking water, the highest concentrations of Zn, Cu, Fe and Ni
were found in TW 1, TW 3 and TW 5 samples, respectively. The le-
vel of the cadmium was found to be below the detection limit in
TW 1, TW 2, TW 3 and BW 1 samples whereas Pb was not detected
in TW 1, TW 2, BW 1 and BW 2. Chromium on the other hand was
found to be below the detection limit in TW 2 and BW2 samples
whereas TW 4 and TW 5 were found to contain highest Cr concen-
tration compared to other water samples. Generally, bottled water
samples were found to contain lower metal ion content compared
to tap water samples. The differences in metal levels between tap
and bottled water samples might be attributed to different types of
Table 3
Concentration (lg L
1
) of Cd, Co, Cr, Cu, Fe, Ni, Pb, and Zn in water samples.
Samples Cd Co Cr Cu Fe Ni Pb Zn
TW
a
1 ND ND 0.36 0.01 60.20 0.94 59.91 0.38 6.12 0.16 ND 480.89 2.15
TW 2 ND ND ND 125.05 0.31 10.11 0.19 9.37 0.21 ND 54.57 0.75
TW 3 ND 0.80 0.02 2.78 0.05 277.49 1.86 16.15 0.95 4.70 0.27 0.62 0.11 167.53 0.13
TW 4 9.21 0.74 12.44 0.23 23.53 0.85 22.53 0.33 93.71 1.10 27.36 0.63 1.82 0.05 78.65 0.69
TW 5 9.83 0.21 11.32 0.11 26.31 0.87 20.84 0.73 103.21 1.12 26.42 0.56 2.12 0.44 76.45 0.77
BW
b
1 ND ND 1.16 0.01 34.38 0.53 8.25 0.24 8.95 0.14 ND 21.76 0.11
BW 2 1.22 0.32 2.10 0.03 ND 12.32 0.12 19.75 0.23 3.48 0.22 ND 23.38 0.45
WWE
c
40.32 0.23 2.91 0.59 5.48 0.11 22.19 0.24 265.27 2.98 3.54 0.33 9.15 0.42 91.50 0.18
ND = not detectable; Experimental conditions: sample volume = 100 mL; amount of resin = 1.5 g; ow rates = 3.0 mL min
1
; eluent volume = 5 mL; replicates n = 5.
a
TW = tap water.
b
BW = bottled water.
c
WWE = wastewater Efuent.
Table 4
Guidelines for the presence of heavy metals in drinking water; concentration in lg
L
1
.
Organizations Cd Co Cr Cu Fe Ni Pb Zn
SANS <5.0 <500 <100 <1000 <200 <150 <20 <5000
USEPA 5.0 100 1000
1300
300 15.0 5000
WHO 3.0 50.0 5.0 2000 300 70 10 3000
P.N. Nomngongo et al. / Physics and Chemistry of the Earth 66 (2013) 8388 87
lters or/and adsorbents used and to how often these lters or/and
adsorbents are changed or cleaned. As expected, wastewater con-
tained all the studied metal ions with highest Fe content, followed
by Zn and Cd.
The metal ion concentrations obtained were compared against
the allowed maximum contamination levels (MCLs) by USEPA
(2011), WHO (2008) and SANS 241 (2005) in drinking water. The
MCL values for the analytes of interest are given in Table 4. Based
on the drinking water samples analysed, all samples investigated
in this study showed no pollution Co, Cr, Cu, Fe, Ni, Pb, and Zn
except for TW 4 and TW 5 samples which showed pollution of Cd.
4. Conclusions
In this study, the efciency of Chelex-100 and Dowex 50W-x8
cation exchange resins for the separation and pre-concentration
of multi-element in aqueous solutions was investigated and the re-
sults demonstrated that Dowex 50W-x8 resin has good capability
and efciency for the simultaneous preconcentration of metal ions.
In comparison, Chelex-100 showed limited performance (precon-
centration with percentage recovery P95%) to only few metals
namely Cu, Fe and Zn whereas Dowex 50W-x8 had the best overall
performance for a wider range of metals.
The limits of detection (0.010.39 lg L
1
) and quantication
(0.051.3 lg L
1
) were relatively low, suggesting that the method
may be applied for trace analysis of these analytes in drinking
water and wastewater samples. The accuracy (% recovery) and
precision (% RSD) of the Dowex 50W-x8 SPE method ranged from
95105% and 1.22.2%, respectively. The proposed procedure was
applied to the determination of trace metals in CRMs drinking
water and wastewater samples. The results revealed that the
method can be used for routine monitoring or spot analysis of
metal ion contaminants in the drinking water supplies. In addition,
the results indicated that all except for TW 4 and TW 5 passed the
drinking water standards (guidelines) for the studied trace metals
set by WHO, USEPA and SANS.
Acknowledgements
Ms P.N. Nomngongo wishes to thank Sasol and NRF for nancial
assistance. University of Johannesburg (Spectrau) is acknowledged
for providing ICP-OES facilities.
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