RARE METALS

Vol. 31, No. 5, Oct. 2012, p. 512

DOI: 10.1007/s12598-012-0549-9

Cloud point extraction and flame atomic absorption spectrometry analysis of

palladium, platinum, and gold ions from industrial polluted soil

LIAN Yuanpeia, ZHEN Weib, TAI Zhiganga, YANG Yalinga, SONG Juna, and LI Zonghaoa
a
Faculty of Life Science and Technology, Kunming University of Science and Technology, Kunming 650224, China;
b
Kunming Fruit Business and Economics Co., Ltd., Kunming 650106, China
Received 7 March 2012; received in revised form 12 April 2012; accepted 28 May 2012
© The Nonferrous Metals Society of China and Springer-Verlag Berlin Heidelberg 2012

Abstract

Cloud point extraction (CPE) with Tergitol TMN-6 was applied for the extraction of trace amounts of palladium (Pd(II)), platinum (Pt(IV)),
and gold (Au(III)) in the soil of industrial sewage. Ammonium pyrolysine dithiocarbamate (APDC) was adopted as the chelating agent prior
to CPE and then was detected by atomic absorption spectrometry (AAS). Different parameters such as the concentration of surfactants, che-
lating agent and salt, sample pH, equilibration temperature and time, centrifugation time and rates, and the effect of foreign ions were studied.
Under optimum conditions, the low limits of detections are 1.4, 2.8 and 1.2 ng⋅ml−1 and the enrichment factors are 21, 12, and 24 for Pd(II),
Pt(IV), and Au(III), respectively. The relative standard deviations vary from 0.6% to 1.0% (n=11). All correlation coefficients of the calibra-
tion curves are >0.9960. The proposed method was successfully applied for the determination of Pd(II), Pt(IV), and Au(III) in the real soil of
industrial sewage samples.

Keywords: cloud point extraction; ammonium pyrolysine dithiocarbamate; Tergitol TMN-6; Pd; Pt; Au; atomic absorption spectrometry

inductively coupled plasma-mass spectrometry, elements

1 Introduction
Platinum and palladium, applied in the automobile cata-
lytic converters, are ejected with the exhausted gases, due to
the abrasion of the catalytic surface, and contaminate the
roads and their surrounding area. In this way, they can be
dissolved in soil, water, and plant. Then, they can enter into
the food chain [1]. Compounds of platinum are used as cy-
totoxic drugs; however, numerous toxicities are observed,
which demonstrate that the rare metals in this form hazard
the living organisms [2−4]. Gold belongs to the group of
elements that occur on the earth in very low concentration,
which is 4 ng⋅g−1 in basic rocks and 1 ng⋅g−1 in soils. The
values of Au in sea and river are found as 0.05 and 0.2
ng⋅ml−1, respectively [5]. Its products are extensively used in
various areas such as the petrochemical industry, medicine,
electronics, and nuclear power industries. And Au in envi-
ronment can also affect living organisms and human health
[6−7]. Therefore, the determination of these metals in envi-
ronment is required.
Several analytical techniques have been reported for the
determination of trace elements in natural water such as in-
ductively coupled plasma-atomic emission spectrometry,
Corresponding author: YANG Yaling E-mail: yilyil8@163.com
electrothermal atomic absorption spectrometry (AAS),
graphite furnace AAS (GFAAS), and capillary electropho-
resis [8]. The direct determination of trace rare metal ions in
environmental samples by flame AAS (FAAS) is difficult
not only for the presence of many trace metals but also for
the interference of samples [9−10]. Therefore, a preconcen-
tration procedure is very necessary to be developed. Various
preconcentration methods prior to FAAS or GFAAS have
been developed, including ion exchange, filtration, solid-
phase extraction, cloud point extraction (CPE), and liquid-
liquid extraction (LLE) [11–14].
CPE is an alternative separation technique that is based
on the phase behavior of non-ionic and ionic surfactants in
aqueous solutions, which shows phase separation after an in-
crease of temperature or a salting-out agent [15−16]. After
the CPE procedure, the solution is separated into two phases:
a poor phase with a surfactant concentration close to the
critical micelle concentration and a rich phase containing a
high surfactant concentration in a small volume [17]. CPE
could avoid toxic organic solvents and achieve a much
higher recovery of rare metal ions than LLE, owing to the
small micellar phase volume [18].
LIAN Yuanpei, et al., Cloud point extraction and flame atomic absorption spectrometry analysis of palladium … 513

Tergitol series surfactants are polyethoxylated secondary tion is shown in Fig. 2. Following preconcentration, the metal
alcohols that are biodegradable and soluble in water and or- ions in the surfactant-rich phase were determined by FAAS.
ganic solvents [19]. The cloud point temperature of Tergitol
TMN-6 is 36 °C similar to Triton series. Therefore, it has
big potential in CPE.
In this work, ammonium pyrolysine dithiocarbamate (APDC)
was used as the chelating agent for rare metals before CPE.

2 Experimental
The chemical structure of APDC is shown in Fig. 1. Ow-
ing to the ligand possesses nitrogen and sulfur donor atoms
and a conjugated π system of APDC, it could form stable com-
plexes with Pd(II), Pt(IV), and Au(III). The complex reac- Fig. 1 Chemical structure of APDC

Fig. 2 Complex reaction of APDC with M (M standing for the Pd, Pt ,and Au)

2.1 Instruments 2.2 Reagents and solutions

A Hitachi Z2000 AAS with ethylene flame and hallow All the reagents used were analytical grade. Deionized
cathode lamps was used for the determination of metal ions. double-distilled water was used throughout. Laboratory
All instrumental settings and operating conditions are tabu- glassware was kept overnight in a 10 vol.% HNO3 solution
lated in Table 1. The instrumental parameters are adjusted and then rinsed with deionized double-distilled water.
according to the manufacturer’s recommendations. A Hi- Stock standard solutions (1000 μg⋅ml−1) of Pd, Pt, and Au
tachi 2001 spectrophotometer with 1.0 cm matched quartz were obtained from the National Institute of Standards (Bei-
cells was used for all absorbance measurements. A pH meter, jing, China). The non-ionic surfactant, TMN-6 (Aladdin,
Elico Li-129 model glass-calomel combined electrode, was China), was used without further purification, and 50
employed for measuring pH values. A centrifuge was used μg⋅ml−1 APDC (Shanghai, China) was prepared by dissolv-
to accelerate the phase separation process. ing in double-distilled water.
The buffer solution (pH 2.0) was prepared by dissolved
Table 1 Recommended procedure conditions appropriate amounts of sodium dihydrogen phosphate
Condition Numerical value (1 mol⋅L−1) and phosphoric acid solutions to reach the re-
Analytical wavelength / nm 350.4 quired pH. Acetate buffer solutions (CH3COO−/CH3COOH)
Lamp current / mV 5 were prepared by mixing appropriate volumes of acetic acid
Air flow-rate / (L⋅h−1) 480 (1 mol⋅L−1) and sodium acetate solutions (1 mol⋅L−1) at pH
Acetylene flow-rate / (L⋅h−1) 120 4.0. Phosphate buffer solutions (H2PO4−/HPO42−) were pre-
Coolant water / (L⋅min−1) 1.5 pared by mixing appropriate volumes of sodium dihydrogen
Recorder grade / mV 20 phosphate and sodium hydrogen phosphate at pH 6.0. Am-
Trap stub position — monium buffer solutions were prepared by mixing appropri-
Blow the light path / mm 5 ate amounts of ammonia and ammonium chloride solutions
Above the burner / mm 6 at pH 8.0.
514
2.3 Experimental procedure
TMN-6 (0.20 vol.%) and APDC (10 μg⋅ml−1, 1 ml) were
added in an aliquot of 10 ml aqueous solution containing 0.1
μg⋅ml−1 of metal ions. The solution was adjusted to pH 4
with phosphate buffer. Then, the mixture was shaken and
placed in a water bath at 40 °C for 20 min. The cloudy solu-
tion was separated by centrifugation at 4000 r⋅min−1 for 10
min and cooled in an ice bath for 10 min in order to increase
the viscosity of the surfactant-rich phase. After the aqueous
phase was decanted, the surfactant-rich phase was dissolved
with 0.5 ml of 1.0 mol⋅L−1 HNO3 and methanol and deter-
mined by FAAS.
2.4 Pretreatment of real samples
The samples of soil were derived from local industrial
sewage and then digested with 6 ml HCl (1.179 g⋅ml−1) and
2 ml HNO3 (1.405 g⋅ml−1) in electric hot plate digestion
system and diluted to 25 ml with deionized water. A blank
sample was treated in the same way.
3 Results and discussion
3.1 Effect of pH
pH plays an important role on metal chelate formation
and subsequent extraction. The CPE of Pd(II), Pt(IV), and
Au(III) in solutions of different pH values ranges from 2.0
to 10.0. Fig. 3 shows the effect of pH on the recoveries for
Pd(II), Pt(IV), and Au(III). It demonstrates that, when the
pH is 4.0, the highest efficiency is achieved. Therefore, pH
4.0 is selected as working pH for the subsequent work.
3.2 Effect of ligand concentration
The nature of the chelating agent and its concentration
are important factors to complexation. CPE can be used for
preconcentration of metal ions after the formation of sparing
water-soluble complexes between ions and ligands. APDC
was employed as the chelating agent for Pd(II), Pt(IV), and
Au(III). The effect of APDC concentration ranged between
0.01 and 10 μg⋅ml−1 was studied. The results are shown in
Fig. 3 Effect of pH on CPE of ions
RARE METALS, Vol. 31, No. 5, Oct. 2012
Fig. 4. When the concentration of APDC is 1.5 μg⋅ml−1, the
optimal absorbance is found. Therefore, 1.5 μg⋅ml−1 APDC
is chosen for further studies.
3.3 Effect of Tergitol TMN-6
Tergitol TMN-6 has commercial availability in forming
high homogeneous phase, environment, low cost, and high
density, which improves the extraction efficiency by cen-
trifugation. The effect of TMN-6 was studied in the range of
0.05 vol.%~0.20 vol.%. The extraction efficiency of ana-
lytes increases with the increase of TMN-6 from 0.05 vol.%
to 0.20 vol.% as shown in Fig. 5. Thus, 0.2 vol.% TMN-6 is
selected for the further studies.
3.4 Effect of NaCl concentration
The effect NaCl was investigated as electrolyte in the
concentration range of 0.005~0.500 g⋅ml−1. The highest ab-
sorbance is obtained at 0.01 g⋅ml−1 NaCl . The signal de-
creases considerably for increasing NaCl concentrations
(0.03~0.05 g⋅ml−1). Therefore, 0.01 g⋅ml−1 NaCl is used in
further experiments.
3.5 Effects of equilibration temperature and time
It is significant to use the shortest equilibration time and
the lowest temperature for the extraction and separation of
phases. The study of recovery on equilibration temperature
and time were at the range of 30~60 °C and 5~30 min. The
maximum extraction recovery is obtained at 40 °C for 20 min.
Fig. 4 Effect of ligand concentration on CPE of ions
Fig. 5 Effect of surfactant concentration on CPE of ions
LIAN Yuanpei, et al., Cloud point extraction and flame atomic absorption spectrometry analysis of palladium … 515

Therefore, 40 °C and 20 min are selected for further ex- Table 2 Effects of matrix ions on recoveries of examined metal
periments. ions
Ions Tolerance limit / (mg⋅L−1)
3.6 Effect of centrifugation − + +
Cl , K , Na 1000
It is found that centrifugation rate has no significant ef- Ca2+, Mg2+ 1000
fect on the extraction efficiency. The influence of centrifu- Cr3+, Mn2+, Zn2+, Cd2+, Ni2+, Pb2+ 800
gation time with a range of 5~30 min was studied. The Cu2+, Al3+, Fe3+, Fe2+ 750
cloudy solution is sufficiently precipitated by centrifugation NO3−, SO42−, Br−, HCO33− 750
at 4000 r⋅min−1 for 10 min. Therefore, centrifugation at
±5% of the tolerable recovery.
4000 r⋅min−1 for 10 min is selected for the following proce-
dure. 3.8 Characteristics of the method
3.7 Effect of foreign ions With the optimized condition, the method was studied
through the primary analytical characteristics shown in Ta-
To regard of the high selectivity of FAAS, the interfer-
ble 3. The preconcentration factor was figured up as the ratio
ence connected with the CPE procedure was studied. Be- between slopes of the calibration curves obtained with and
cause cations may react with APDC and lead to the decrease without the preconcentration step, and the enrichment fac-
of extraction efficiency, 10 ml of sample solution containing tors are 26, 16, and 30 for Pd(II), Pt(IV), and Au(III), re-
Pd(II), Pt(IV), and Au(III) and other ions were prepared and spectively. The low limits of detection (LODs) are 1.4, 2.8,
treated with the developed procedure. Table 2 shows the and 1.2 ng⋅ml−1 for Pd(II), Pt(IV), and Au(III), respectively,
tolerance limits of the interferential ions, and the deviation is with good relative standard deviation (RSD) of 0.6%~1.0%.

Table 3 Specification of method at optimum conditions for each element

Element Enrichment factor LOD / (μg⋅L−1) RSD / % (n=11) Linear range / (μg⋅L−1) Recovery / % (n=6) Regression equation
Pa 21 1.4 0.8 5–500 98.16 y = 0.0065x − 0.011
Pt 12 2.8 0.6 10–500 95.03 y = 0.0021x + 0.0014
Au 24 1.2 1.0 5–500 97.18 y = 0.0075x − 0.0066

3.9 Accuracy and applications ported in the study [20–24].

To evaluate the applicability of the proposed procedure, it
was applied to determine Pd(II), Pt(IV), and Au(III) in en-
vironment samples. Due to matrix effects of samples, all the
samples were spiked of three concentration levels of 0.1~1.0
μg⋅L−1. The results of determination are shown in Table 3.
The recovery is satisfactory, which indicates that the capa-
bility of the method applied in real samples is favourable.
4 Conclusion
The determination of Pd(II), Pt(IV), and Au(III) with
APDC by CPE with TMN-6 prior to FAAS was investigated.
The phase separation occurs efficiently, which results in
good enrichment factors and low LOD. In contrast with
other preconcentration techniques, any organic solvent is not
needed in CPE. TMN-6 is environmental friendly and low
cost. Owing to the physicochemical characteristics of
TMN-6 such as low cloud point and high density, phase
separation is easily obtained by centrifugation and with sta-
ble effect. The developed method shows good sensitivity
and precision, and it has advantages over other methods re-
Acknowledgements
The work was greatly supported by the National Natural
Science Foundation of China (No. 20961012), the Medical
Neurobiology Key Laboratory of Kunming University of
Science and Technology, Basic and Applied Research Pro-
ject in Yunnan Province (No. 2008ZC082M), the Analysis
and Testing Foundation of Kunming University of Science and
Technology (No. 2010121) and Innovation Fund for Small and
Medium Technology Based Firms (No. 11C26215305936),
Natural and Science Foundation of Yunnan Province (No.
2010ZC027), and Focus Fund of Department of Education
in Yunnan Province (No. 2010Z016).
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