Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 173 (2017) 532–536

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Spectrochimica Acta Part A: Molecular and Biomolecular

Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Simultaneous spectrophotometric determination of trace copper, nickel,

and cobalt ions in water samples using solid phase extraction coupled
with partial least squares approaches
Yugao Guo a,b,⁎, He Zhao a,b, Yelin Han b, Xia Liu b, Shan Guan a,b, Qingyin Zhang a,b, Xihui Bian a,b
a
State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin Polytechnic University, Tianjin 300387, China
b
School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, China

a r t i c l e i n f o a b s t r a c t

Article history: A simultaneous spectrophotometric determination method for trace heavy metal ions based on solid-phase ex-
Received 22 May 2016 traction coupled with partial least squares approaches was developed. In the proposed method, trace metal ions
Received in revised form 28 September 2016 in aqueous samples were adsorbed by cation exchange fibers and desorbed by acidic solution from the fibers.
Accepted 5 October 2016
After the ion preconcentration process, the enriched solution was detected by ultraviolet and visible spectropho-
Available online 06 October 2016
tometer (UV–Vis). Then, the concentration of heavy metal ions were quantified by analyzing ultraviolet and vis-
Keywords:
ible spectrum with the help of partial least squares (PLS) approaches. Under the optimal conditions of operation
Cation exchange fiber time, flow rate and detection parameters, the overlapped absorption peaks of mixed ions were obtained. The ex-
Ultraviolet and visible spectrophotometer perimental data showed that the concentration, which can be calculated through chemometrics method, of each
Solid phase extraction metal ion increased significantly. The heavy metal ions can be enriched more than 80-fold. The limits of detection
Partial least squares (LOD) for the target analytes of copper ions (Cu2+), cobalt ions (Co2+) and nickel ions (Ni2+) mixture was
Heavy metal ions 0.10 μg L−1, 0.15 μg L−1 and 0.13 μg L−1, respectively. The relative standard deviations (RSD) were less than
5%. The performance of the solid-phase extraction can enrich the ions efficiently and the combined method of
spectrophotometric detection and PLS can evaluate the ions concentration accurately. The work proposed here
is an interesting and promising attempt for the trace ions determination in water samples and will have much
more applied field.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Heavy metal ions such as Cu2+, Co2+ and Ni2+, through their inher-
ent toxicity, have been an increasing serious problem as the develop-
ment of industries [1]. Many physical health problems were caused by
them even microscale more than body needs [2]. Therefore, developing
smart detection methods for the heavy metal ions in water environment
became special issues that we need to deal with.
Various analytical techniques such as atomic absorption spectrome-
try (AAS) [3,4], cold vapour atomic fluorescence spectrophotometry
(CVAFS) [5], inductively coupled plasma mass spectrometry (ICP-MS)
[6], liquid chromatography (LC) [7], ultraviolet-visible spectrophotome-
try (UV–Vis) [8] electrochemical method [9], capillary electrophoresis
(CE) [10], enzyme analysis method [11] and sensor [12], have been de-
veloped for the determination of heavy metal ions. AAS, which can
⁎ Corresponding author at: State Key Laboratory of Separation Membranes and
Membrane Processes, School of Environmental and Chemical Engineering, Tianjin
Polytechnic University, Tianjin 300387, China.
E-mail address: guoyugao@tjpu.edu.cn (Y. Guo).
detect only one single element each run and require a long measure-
ment period, was an expensive and destructive method, but it managed
to determine heavy metal ions at a low concentration in range of micro-
gram-perpliter [13]. A precise detection and multielement simulta-
neous determination can be implemented in AFS simultaneously but,
because its specificity for metal ions, it is astricted by the lower limit
of detection [14]. ICP-MS, which can detect up to 10 elements at one
time in both solid and liquid samples, was developed based on their
mass to charge ratios for the multielement analysis. Though high detec-
tion sensitivity obtained, it was limited by the operating environment,
which made ICP-MS to be a destructive and very high cost technique
[13]. Some shortcomings also came forth in the accurate determination
of trace heavy metal ions [15]. CE has become established as a powerful
technique for metal ion separation with the unique problem of changing
the selectivity of the separation system [10]. Many advantages such as
rapid detection, wide detection range, simple to operate and low cost
showed in UV–Vis and thus, it was selected for heavy metal ions detec-
tion [16,17]. However, there were many difficulties in determining trace
amounts of heavy metals in environmental samples due to lower sensi-
tivity and overlapped peaks [18–20]. Therefore, it is necessary to

http://dx.doi.org/10.1016/j.saa.2016.10.003
1386-1425/© 2016 Elsevier B.V. All rights reserved.
 Y. Guo et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 173 (2017) 532–536
developed some supplementary means to make UV–Vis suit for the
trace detection of heavy metal ions mixture.
In order to solve the above-mentioned problems in UV–Vis,
preconcentration and chemometrics method were adopted [21]. Vari-
ous preconcentration methods such as cloud point extraction [22],
solid phase extraction [23,24], membrane filtration [25], liquid–liquid
extraction [26], chemical precipitation [27] and biosorption [28,29]
have been developed for the enrichment of trace heavy metal ions.
Among these techniques, solid phase extraction become one of the
most widely developed technique because it is a rapid and selective ex-
traction [30]. In these research, cation exchange fiber have been pro-
posed preferentially as one of the solid phase extraction for multi-
metal adsorption at trace level because of its excellent performance
such as large superficial area, mass transfer rate, high chemical resis-
tance, good mechanical strength and great recycling nature. With cation
exchange fiber employed in preconcentration of various metal ions,
rapid process for both adsorption and desorption were realized [31].
On the other hand, in order to solve the problem of overlapped peaks
in UV–Vis spectra for mixed heavy metal ions, PLS was selected to
make UV–Vis spectra relate to the concentrations of the metal ions
through model established with the given concentration information
and relative matrix factorization [18].
In this paper, simultaneous spectrophotometric determination
method for trace heavy metal ions by cation exchange fiber extraction
coupled with partial least squares approaches was proposed. All of the
influence factors for preconcentration such as pH values, time and
flow rate were studied and optimized. The enrichment performance of
various heavy metal ions was validated by the comparison of the pro-
posed method and ICP-MS. The detection above-mentioned method
was demonstrated to be rapid, inexpensive, useful and convenient in
preconcentration and quantitative approach to various heavy metal
ions.
2. Experimental
2.1. Reagents and Samples
Cation exchange fibers were purchased from Sigma-Aldrich. All
chemicals were analytical reagents (AR) without further purification
Fig. 1. Schematic diagram for preconcentration and determination of metal ions.
533
and purchased from Tianjin Kermel Co., Ltd., China. Deionized water
was used for all the dissolution and dilution in the experiments. All
the glassware were carefully cleaned by immersing in specific HNO3 so-
lution and rinsed with distilled water before use.
Buffer of acetic acid-sodium acetate (CH3COOH/CH3COONa) was
prepared by mixing of appropriate volumes of pure acetic and sodium
acetate for pH 5–6. As chromogenic reagent, 2% xylenol orange (XO)
was prepared by dissolving appropriate XO in deionized water. 0.05
mg L−1 solution of Cu2+, Co2+ and Ni2+ were used for adsorption.
2.2. Instruments
The procedure of preconcentration was implemented by using 2PB-
1005 constant flow pump with flow rate ranged 0.1–99.9 mL min−1 ob-
tained from Beijing Xingda Science and Technology Development Co.,
Ltd., China. The EVOLUTION 300 UV–Vis spectrometer, which was se-
lected as the detection tools for all the samples, was purchased from
Thermo Fisher Scientific Co., Ltd., USA. The UV–Vis spectra range from
200 to 800 nm were obtained at room temperature. Agilent 7900 ICP-
MS from Agilent Technologies was used for validating the proposed de-
tection method in the paper. Solid phase extraction was carried out in a
self-made extractor with fiber filled.
2.3. Procedures
The cation exchange fiber, filled in extractor, was activated by dip-
ping in 2.0 mol L−1 H2SO4 for 30 min at room temperature before ad-
sorption. After that, the fiber should be kept in pure water to remain
its excellent performance. At the beginning of the experiment, 100 mL
samples were pushed through the extractor and recirculated for some
time by pump. Then, the raffinate was removed from the extractor
and the adsorption procedure completed. After that, the mixed ions
were eluted, with the same procedure as adsorption, by 1.0 mL of 0.5
mol L− 1 H2SO4 solution flowed through the cation exchange fiber.
After the desorption process, 2.5 mL buffer solution (pH = 6) with
color developing agent were added into the eluent to make UV–Vis de-
tection sensitive. Finally, the UV–Vis spectra data, which obtained from
EVOLUTION 300 UV–Vis spectrometer, were disintegrated into individ-
ual of each ion with the help of PLS. Upon the Matlab calculation, certain
534 Y. Guo et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 173 (2017) 532–536

concentrations of each ion in samples were acquired. The operation pro-

cess can be illustrated in Fig. 1 briefly.

3. Results and Discussion

In order to obtain an effective and sensitive detection method for the

mixed heavy metal ions in aqueous sample, conditions of enrichment
and detection such as cycle time, flow rate, pH and quantity of XO
were optimized. The enrichment factor (EF) of heavy metal ions was
calculated from the initial concentration (Cinitial) of sample solution
and the final concentration (Cfianl) of ions in elution (EF = Cfianl / Cinitial).

3.1. Effect of Flow Rate and Operation Time for Adsorption

From theoretical point of view, high flow rate was preferred in ad-
sorption procedure by enhancing mass transfer rate. However, the
higher the flow rate is, the greater the pressure will be, which will
have negative effect on the microextractor and the tubing coupling.
Therefore, the maximum safety flow speed of 30 mL min−1 were cho-
sen as the optimal conditions of the microextraction process.
Under this flow rate, the effect of adsorption time on the enrichment
of 0.05 mg L−1 Cu2 +, Co2 + and Ni2 + sample solution was examined
ranged 0–16 min. The relationship of enrichment factor data and oper-
ation time were showed in Fig. 2. According to the time profile, 10 min
was chosen as the optimal adsorption time because the adsorption equi-
librium reached at that time.
3.2. Effect of Desorption Time
After considering the elution efficiency of methanoic acid, acetic
acid, citric acid and sulfuric acid to the microextractor, 0.5 mol L− 1
H2SO4 solution was selected as the elution because weak acid cannot
desorb the heavy metal ions from cation exchange fiber effectively
and 0.5 mol L−1 is the lowest concentration for desorbing ions thor-
oughly. Then, the elution was processed under the flow speed of 30
mL min−1, as mentioned in Section 3.1, with 1.0 mL H2SO4 solution in
order to suit for the traditional UV–Vis detection.
Under these operation conditions, the effect of desorption time on
the enrichment was examined from 0 to 8 min. The relationship of en-
richment factor data and desorption time were showed in Fig. 3. Accord-
ing to the time profile, 3 min was chosen as the optimal adsorption time.
3.3. Effect of pH for Measured Sample
The pH of sample to be tested is a very important factor for the
UV–Vis detection. Absorbance of eluant with Cu2 +, Co2 + and Ni2 +
Fig. 3. Effect of desorption time on the enrichment factor.
were detected by UV–Vis spectrometer at the pH of 4–9. The rela-
tionship between absorbance and pH data were displayed in Fig. 4.
It was showed that the absorbance data had the highest-level at
the pH in vicinity of 6. Therefore, pH = 6 was chosen as the detection
pH value for all the experiments.
3.4. Effect of Quantity of 2% XO Solution for Detection
XO was used as coordination agent for metal ions in these experi-
ments. Then, the mixture of Cu2+-XO, Co2+-XO, Ni2+-XO in eluant so-
lution were detected by UV–Vis spectrometer. The absorbance data of
intense UV–Vis spectra peaks of different quantity of 2% XO solution
were illustrated in Fig. 5. It was illustrated that there was no significant
difference in the absorbance data when the quantity of 2% XO solution
added more than 1.0 mL. Therefore, 1.0 mL 2% XO solution was chosen
for the further experiments.
3.5. Method Evaluation
The method was validated by comparing the real value with calcu-
lated value of sample concentrations [32]. The model built for PLS
was from UV–Vis spectra of mixed heavy metal ions samples and the
UV–Vis spectra was prepared according to 80 random number series,
which ranged from 0.1 mg L− 1 to 8 mg L−1. The root-mean-square
error of cross-validation (RMSECV), which was an important index for
predictive value through using the optimal factor number (LV), were
calculated. On the basis of the computed result, RMSECV were

Fig. 2. Effect of adsorption time on the enrichment factor. Fig. 4. Effect of detection pH for measured sample.
 Y. Guo et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 173 (2017) 532–536
Fig. 5. Effect of quantity of 2% XO solution for detection.
0.31186, 0.14459 and 0.23197, when the LV for Cu2+, Co2+ and Ni2+ in
sample solutions was confirmed at 5, 12 and 5, respectively. The rela-
tionships between predictive values and truth values of each ion were
all higher than 0.99.
3.6. Analytical Performance
Under the optimal experimental conditions, heavy metal ions solu-
tions with different concentration in the linear range from 1.0 μg L−1
to 50 mg L−1 were investigated. With the S/N = 3 (the signal-to-
noise ratio), the LOD for Cu2 +, Co2 + and Ni2 + was 0.10 μg L− 1,
0.15 μg L−1 and 0.13 μg L−1, respectively. In order to estimate the reli-
ability of the proposed method, the calculation results for the enriched
sample from 0.05 mg L−1 solution for each ion were compared with
the determination values of ICP-MS. The comparison data were shown
in Table 1 with RSD (n = 6) lower than 5% and recovery values in the
range of 95–106%.
4. Conclusion
Simultaneous spectrophotometric quantization method for trace
heavy metal ions in water samples using solid phase extraction coupled
with PLS approaches was proposed here. This presented work showed
that the solid phase extractor filled with fiber can enriched trace ions
in water sample effectively and the PLS approaches can calculate the
concentration of mixed heavy metal ions by analyzing UV-Vis spectrum
efficiently. After studying the optimal operation conditions, the LOD of
Cu2 +, Co2+ and Ni2+ was determined to be 0.10 μg L−1, 0.15 μg L−1
and 0.13 μg L−1, respectively. The reliability of the proposed method,
with the ion concentration of 0.05 mg L−1 for each ion, was confirmed
by the RSD lower than 5% and the recovery of 95–106%. All the data
showed that the proposed system was accuracy and feasible. There is
a great potential for applications in detecting trace metal ions samples
with the help of preconcentration and chemometrics calculation.
Acknowledgments
This work was supported by the Project of Innovation and Entrepre-
neurship Training for College Students of China (no. 201410058050),
Table 1
Comparison of the proposed method with the ICP-MS data.
Detection method Cu2+ Co2+
UV-Vis 4.43 4.14
ICP-MS 4.46 4.23
535
the National Natural Science Foundation of China (no. 21405110) and
the National Natural Science Foundation of China (no. 21476172).
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