Speciation of Cr(III) and Cr(VI) in geological and water samples by ytterbium(III) hydroxide coprecipitation system and atomic absorption spectrometry.

Abstract

A novel coprecipitation method with ytterbium(III) hydroxide has been established for speciation of Cr(III) and Cr(VI) in geological and water samples. At pH 10, while Cr(III) was quantitatively recovered, Cr(VI) was recovered under 10% levels. Total chromium was determined reducing of Cr(VI) to Cr(III) in acidic media with KI reagent. The concentration of Cr(VI) was calculated by the concentration difference between the total chromium and Cr(III). For the quantitative recovery of Cr(III), parameters such as pH, amount of ytterbium, centrifugation time and speed, matrix effect, KI amount, and sample volume were investigated. The preconcentration factor was 30. The limit of detection was obtained as 1.1 μg/L for Cr(III). The accuracy was checked by analyte addition and analyses of standard reference materials (TMDA-54.4 Certified Reference Water, NIST 2710 Montana Soil). Method has been successfully applied to the chromium speciation for industrial waste water of leather factories located in Bor-Nigde, and also for mine and soil samples.

Full text

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Speciation of Cr(III) and Cr(VI) in geological and water samples
by ytterbium(III) hydroxide coprecipitation system and atomic
absorption spectrometry
Ali Durana, Mustafa Tuzena, Mustafa Soylakb,⇑
aGaziosmanpasa University, Faculty of Science and Arts, Chemistry Department, 60250 Tokat, Turkey
bErciyes University, Faculty of Science, Department of Chemistry, 38039 Kayseri, Turkey
a r t i c l ei n f o
Article history:
Received 17 March 2011
Accepted 12 April 2011
Available online 16 April 2011
Keywords:
Coprecipitation
Chromium speciation
Ytterbium(III) hydroxide
Flame atomic absorption spectrometry
a b s t r a c t
A novel coprecipitation method with ytterbium(III) hydroxide has been established for speciation of
Cr(III) and Cr(VI) in geological and water samples. At pH 10, while Cr(III) was quantitatively recovered,
Cr(VI) was recovered under 10% levels. Total chromium was determined reducing of Cr(VI) to Cr(III) in
acidic media with KI reagent. The concentration of Cr(VI) was calculated by the concentration difference
between the total chromium and Cr(III). For the quantitative recovery of Cr(III), parameters such as pH,
amount of ytterbium, centrifugation time and speed, matrix effect, KI amount, and sample volume were
investigated. The preconcentration factor was 30. The limit of detection was obtained as 1.1 lg/L for
Cr(III). The accuracy was checked by analyte addition and analyses of standard reference materials
(TMDA-54.4 Certified Reference Water, NIST 2710 Montana Soil). Method has been successfully applied
to the chromium speciation for industrial waste water of leather factories located in Bor-Nigde, and also
for mine and soil samples.
? 2011 Elsevier Ltd. All rights reserved.
1. Introduction
Today, the importance of speciation studies in controlling the
environmental fatal, toxicity and bioavailability of trace elements
is now well established (Soylak et al., 1993; Soylak and Turkoglu,
1999). Chromium is one of the regulated toxic metals in the envi-
ronment (Narin et al., 2002; Pagana et al., 2011; Bayramoglu and
Arica, 2011). Naturally, this element exists mainly in two oxidation
states, as Cr(III) and Cr(VI). If they are compared, Cr(VI) is more
toxic than Cr(III) and it is carcinogenic and mutagenic to living
organisms. On the other hand, Cr(III) is only toxic to plants at high
concentrations and less toxic or non toxic to animals, while in trace
amounts it influences sugar and lipid metabolism in humans.
Although Cr(III) is considerably less toxic than Cr(VI), it may be
accumulated in high amounts in the environment as a result of
the discharge of untreated or partially treated industrial wastewa-
ter or the disposal of chromium containing sludge; then it is oxi-
dized to the toxic Cr(VI) in the environment (Kanojia et al., 1996;
Voutsa et al., 1996; Kimbrough et al., 1999; Dantas et al., 2001;
Kocaoba and Akcin, 2002; Costa, 2003; Farag et al., 2006; Ezoddin
et al., 2010; Wu et al., 2010). Chromium species are major environ-
ment pollutants due to its widely usage in various industrial appli-
cationsincludingmetal, textile,wood,leathertanning,
electroplating, paint, battery industries and etc. The World Health
Organization recommended that the maximum allowable concen-
tration in drinking water for total Cr should be 0.05 mg/L.
The speciation procedures for chromium are generally based on
thepreconcentrationandseparationofoneofthechromiumspecies.
Total chromium was determined after the reduction of Cr(VI) or by
the oxidation of Cr(III) in so many reported studies (Ghaedi et al.,
2006; Bantrjee and Das, 2006; Eid et al., 2002; Pazos-Capeans
et al., 2006; Mehra and Guimond, 1999; Aparna et al., 2006;
Moghdam and Dadfarnia, 2010; El-Shahawi et al., 2011). Most
preconcentration methods for separating the two chromium oxida-
tionstatesinvolveion-exchange,solid-phaseextraction,cloudpoint
extraction and liquid–liquid extraction have also been used (Mehra
and Guimond, 1999; Demirata, 2001; Eid et al., 2002; Liang and Li,
2005; Aparna et al., 2006; Pazos-Capeans et al., 2006; Tuzen et al.,
2007a; Sahana et al., 2011).
Coprecipitation with metal hydroxides has been widely used for
preconcentration and separation of trace metal ions (Saracoglu
et al., 2001; Aydin and Soylak, 2007). This method is simple, rapid
and efficient with high preconcentration factor. Over the past few
years, different carrier elements such as magnesium (Elci and
Saracoglu, 1998; Tuzen et al., 2007b), ytterbium (Atsumi et al.,
2005; Kagaya et al., 2006), europium (Soylak and Onal, 2006), in-
dium (Hiraide et al., 1991), lanthanum (Kujirai and Yamada,
1996), samarium (Saracoglu et al., 2003), terbium (Minami et al.,
2005), erbium (Soylak et al., 2005), gallium (Akagi and Horaguci,
0278-6915/$ - see front matter ? 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fct.2011.04.016
⇑Corresponding author. Fax: +90 352 4374933.
E-mail addresses: soylak@erciyes.edu.tr, msoylak@gmail.com (M. Soylak).
Food and Chemical Toxicology 49 (2011) 1633–1637
Contents lists available at ScienceDirect
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Page 2

1990), hafnium (Ueda et al., 1997), dysprosium (Peker et al., 2007;
Karatepe et al., 2010), thulium (Aydin and Soylak, 2009), gadolin-
ium (Soylak and Balgunes, 2008), cerium (Divrikli et al., 2008)
and neodymium (Soylak and Kizil, in press) have been reported
for coprecipitation by hydroxide of various metal ions.
The value of solubility product constant of ytterbium hydroxide
is reported as 2.5 ? 10?24(Dean, 1999). Chromium speciation by
ytterbium(III) hydroxide coprecipitation system is a novel study.
The goal of the study is to explore the preconcentration perfor-
mance of a coprecipitation system prior to atomic absorption spec-
trometric determination by carrying out speciation of Cr(III) and
Cr(VI) in real samples with ytterbium(III) hydroxide. The proposed
procedure was applied to geological and water samples.
2. Experimental
2.1. Instrumentation
The analysis was carried out using a Perkin–Elmer Model 3110
(Norwalk, CT, USA) atomic absorption spectrometer, equipped with
a flame burner. Air-acetylene flame was used for measurements.
Other instrumental parameters for chromium were adjusted
according to the recommendations of manufacturer (wavelength:
357.9 nm, slit width: 0.7 nm, lamp current: 10 mA, air flow rate:
5 L/min, acetylene flow rate: 3 L/min).
The pH values in the aqueous phase were measured with a Sar-
torius PT-10 model (Gottingen, Germany) pH meter. ALC PK 120
model centrifuge was used during centrifugation processes.
2.2. Reagents and solutions
Distilled water was used throughout the work. All chemicals
were of analytical reagent grade unless otherwise stated. All the
plastic and glassware were cleaned by soaking in 10% HNO3solu-
tion and then rinsed with distilled water prior to use. Stock solu-
tions of analyte ions, 1000 mg/L, were diluted daily for obtaining
reference and working solutions. About 0.1% (m/v) ytterbium(III)
solutionwasprepared freshly
1124100005, Merck, Darmstadt, Germany) in small amounts of
1 mol/L HNO3and diluting to 100 mL with distilled water. Cr(VI)
and Cr(III) stock solutions (1000 mg/L) were prepared from
K2Cr2O7and Cr(NO3)3?9H2O (Merck, Darmstadt, Germany). Stock
solutions of diverse elements were prepared from the high purity
compounds (99.9%) (St. Louis, MO, USA).
bydissolving Yb2O3
(No:
2.3. Preconcentration procedure
In order to optimize the preconcentration system, 25 mL of
model solutions containing 25 lg of Cr(III) and 0.1% Yb(III) (m/v)
solutions were used. Then the pH of the solutions was adjusted
to related pH by the addition of 1 mol/L NaOH solution. The solu-
tions were centrifuged for a while at a constant speed. The precip-
itate was collected through a cellulose nitrate membrane filter of
0.45 lm size and 47 mm diameter. The precipitates together with
the membrane were dissolved in 0.5 mL of concentrate nitric acid,
and then the solution was diluted to 10 mL with water. The metal
contents of the final solution were determined by flame AAS. 3
runs were carried out for the replicates.
Reduction of Cr(VI) to Cr(III) has been performed by using the
procedure given in literature (Yalçin and Apak, 2004; Aydin and
Soylak, 2009; Karatepe et al., 2010). pH values were adjusted to
1.0 using 2.0 M H2SO4. 10 mL of 0.5% KI (m/v) solution was added
and the solution was boiled for 30 min. After cooling the solution
to the room temperature, test procedure given above was applied.
Chromium was determined by flame AAS. After reduction of Cr(VI)
to Cr(III), the method was applied to the determination of the total
chromium. The level of Cr(VI) was calculated by difference of total
chromium and Cr(III) concentrations.
2.4. Application to real samples
Certified reference materials (TMDA-54.4 fortified lake water
and NIST SRM 2710 Montana soil) were used for validation.
Montana soil weighed 0.3 g was digested with 12 mL aqua regia
and heated to dryness. The digested sample was dissolved in
1 mol/L HNO3and 10 mL of distilled water was added to the resi-
due. The suspension was filtered through a blue band filter paper,
and the insoluble part was washed with distilled water.
TMDA-54.4 fortified lake water was used directly and the pre-
concentration procedure given above was applied to the final solu-
tions after adjusting the pH to 10 by using 1 mol/L NaOH solution.
The proposed method was applied to different geological and
water samples including tap water, industrial waste water of
leather factories located in Bor-Nigde organized industrial zone,
mine and soil samples. For the solid samples, 1 g sample was di-
gested with 16 mL aqua regia and heating to dryness. For the wet
residue, this process was repeated twice with 12 mL aqua regia
and the same procedure above was applied. The water samples
analyzed were collected in pre-washed polyethylene bottles. The
samples were filtered through a Millipore cellulose membrane of
pore size 0.45 lm. The samples were stored in 1 L polyethylene
bottles and acidified to 1% with nitric acid and were subsequently
stored at 4 ?C in a refrigerator. Before the analysis, the pHs of the
samples were adjusted to 10 by using 1 M NaOH solution. The pre-
concentration procedure given above was applied to the final solu-
tions. All determinations were carried out by flame atomic
absorption spectrometry (FAAS).
3. Results and discussion
3.1. Effect of pH
Sample pH plays an important role for the quantitative recover-
ies. Reported studies about the effect of pH on the quantitative
recovery of chromium(III) and chromium(VI) species give a pH
range of 8.0–12.0 (Ueda et al., 1997; Aydin and Soylak, 2009;
Karatepe et al., 2010; Hosseini-Bandegharaei et al., 2010). For the
reason, effect of pH on the recoveries of Cr(III) and Cr(VI) species
was investigated in the pH range of 7.0–13.0. As shown in Fig. 1,
quantitative recoveries (>95%) were obtained for Cr(III) in the pH
range of 8.0–13.0. The recoveries of Cr(VI) were not quantitative
at the all working pH ranges. These results show that quantitative
and selective separation of Cr(III) and Cr(VI) is possible at the pH
0
20
40
60
80
100
78910
pH
111213
Recovery, %
Cr(III)
Cr(VI)
Fig. 1. Effect of pH on the recoveries of Cr(III) and Cr(VI), N = 3.
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A. Duran et al./Food and Chemical Toxicology 49 (2011) 1633–1637

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range of 8.0–13.0. Therefore, the pH was adjusted to about 10.0 for
the quantitative speciation of chromium(III) and chromium(VI) in
subsequent experiments.
3.2. Effect of ytterbium(III) amount
The effect of ytterbium(III) amount as carrier element on the
recovery of Cr(III) were also investigated in the range of 0–4.0 mg.
The results are shown in Fig. 2. The recovery of chromium(III) was
about 20% without ytterbium(III). The recovery values increased
with the increasing amount of ytterbium(III) due to the formation
ofytterbium(III)hydroxide.After0.5 mgofytterbium(III),thequan-
titative recovery values were achieved in the range of 0.5–4.0 mg.
3.3. Effect of sample volume
In order to investigate the possibility of enrichment low con-
centrations of analyte from large volume, the effect of sample vol-
ume on the recovery of Cr(III) was also studied between the range
of 25–400 mL. The precipitate including analyte ions was success-
fully dissolved in 1 mL of 1 mol/L HNO3. The recoveries decreased
with increasing sample volume after 300 mL. The final volume of
the presented study was 10.0 mL. The preconcentration factor for
simultaneous preconcentration and extraction is calculated by
the ratio of the highest sample volume for analyte (300 mL) and
the lowest final eluent volume (10.0 mL). In present study the pos-
sible preconcentration factor was 30.
3.4. Effect of centrifugation time and speed
The effect of the centrifugation time and speed on the recover-
ies of chromium(III) on the presented coprecipitation system were
investigated in the time range of 0–60 min, and centrifugation
speed range of 1500–4000 rpm. The quantitative recoveries were
obtained after 20 min and in the range of 2000–4000 rpm. So,
20 min and 3000 rpm were chosen for the further works.
3.5. Effect of matrix ions
Interference effect of the matrix is a main problem on the flame
atomic absorption spectrometric determination of metal ions
(Narin et al., 2000; Ndungu et al., 2003; Ahmadi et al., 2009; Li
et al., 2009; Martendal et al., 2009; Vieira et al., 2009; Zhao et al.,
2009). Effect of the matrix ions on the recovery of chromium(III)
was also investigated. Various amounts of metal ions were added
to a solution containing fixed amounts of chromium(III) ions and
the present procedure was followed. The experimental results are
summarized in Table 1. It is seen that the presence of major cations
and anions has no significant influence on the adsorption of chro-
mium(III) ions under the selected conditions.
0
20
40
60
80
100
01234
Amount of ytterbium, mg
Recovery, %
Cr(III)
Fig. 2. Effect of ytterbium(III) amount on the recovery of chromium(III), N = 3.
Table 1
Effects of matrix ions on the recovery of chromium(III), N = 3, pH 10.
Concentration (mg/L) Added asRecovery (%)
Cd2+
Zn2+
NO?
Na+
K+
Mg2+
Ca2+
SO2?
I?
Cu2+
Co2+
Ni2+
Pb2+
PO3?
Fe3+
Cr6+
HPO2?
Al3+
CO2?
3
20
10
Cd(NO3)2?4H2O
Zn(NO3)2?6H2O
KNO3
NaCl
KCl
MgCl2?6H2O
CaCI2
Na2SO4
NaI
Cu(NO3)2?3H2O
Co(NO3)2?6H2O
Ni(NO3)2?6H2O
Pb(NO3)2
Na3PO4
Fe(NO3)3?9H2O
K2CrO4
Na2HPO4?7H2O
Al(NO3)3?9H20
Na2CO3
95 ± 1a
95 ± 1
98 ± 1
100 ± 1
100 ± 1
100 ± 1
100 ± 1
95 ± 1
94 ± 2
99 ± 1
94 ± 1
95 ± 1
95 ± 1
97 ± 2
100 ± 2
102 ± 2
95 ± 2
98 ± 1
100 ± 1
3
2500
10000
2500
1000
2500
2500
10000
4
10
10
10
20
4
2500
10
5
4
2500
20
2500
aMean ± standard deviation.
Table 2
Total chromium determinations in spiked tap water solutions, N = 3, Vsample: 300 mL.
Added (lg)Found (lg)Calculated (lg)
Cr(III) Cr(VI)Cr(III)Cr(III) + Cr(VI)Cr(VI)
0
5
12.5
20
25
25
20
12.5
5
0
–
4.50 ± 0.6
11.9 ± 0.6
18.9 ± 0.6
24.4 ± 0.6
24.1 ± 0.8a
24.6 ± 0.8
24.6 ± 0.8
24.6 ± 0.8
24.4 ± 0.8
–
20.1 ± 0.5
12.7 ± 0.5
5.70 ± 0.5
–
aMean ± standard deviation.
Table 3
Total chromium determinations in certified reference material samples.
Certified reference materialsCertified value Found value
NIST SRM 2710 Montana soil, N = 5
TMDA-54.4 fortified lake water, N = 3
39 lg/g
438 lg/L
39 ± 3alg/g
443 ± 19 lg/L
aMean ± standard deviation.
Table 4
Determination of chromium(III) and chromium(VI) in industrial waste water of
leather factories located in Bor-Nigde organized industrial zone, N = 3.
SampleCr(III) (lg/L)Cr(VI) (lg/L)
1
2
3
4
5
6
7
184 ± 16a
989 ± 41
302 ± 27
853 ± 31
374 ± 16
492 ± 47
410 ± 27
BDL
253 ± 25
181 ± 11
127 ± 4
181 ± 15
BDL
BDL
aMean ± standard deviation; BDL: below detection limit.
Table 5
Application of presented procedure for the determi-
nation of total chromium in solid samples, N = 3.
SamplesTotal chromium (lg/g)
Develi mine
Yahyalı mine
Runway soil
309 ± 19a
177 ± 14
79 ± 4
aMean ± standard deviation.
A. Duran et al./Food and Chemical Toxicology 49 (2011) 1633–1637
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3.6. Determination of total chromium
In order to determine the total chromium, model solutions that
contain different amounts of Cr(VI) and Cr(III) were prepared. Then
Cr(VI) ions in the model solutions were reduced to Cr(III) by using
KI in acidic media (Yalçin and Apak, 2004; Aydin and Soylak, 2009;
Karatepe et al., 2010). Quantitative recoveries for reduction of
chromium(VI) to chromium(III) was obtained by using 0.5% KI.
After reduction process, the pH of the solutions was adjusted to
pH 10.0 by the addition of 1 mol/L NaOH. Then the preconcentra-
tion procedure given in Section 2 was applied to these solutions.
The results are given in Table 2. The results show that the proposed
method could be applied for the determination of total chromium.
3.7. Limit of detection
Limit of detection (LOD) of the presented coprecipitation
method for the determination of chromium(III) was studied under
optimal experimental conditions after application of the precon-
centration procedure to blank solutions. The detection limit for
Cr(III) was found to be 1.1 lg/L.
3.8. Applications
For the validation of the proposed coprecipitation method, the
method was applied to NIST SRM 2710 Montana soil and TMDA-
54.4 fortified lake water certified reference material. The results
are presented in Table 3. The results are in good agreement with
the certified values for chromium. Also the application of the pro-
posed procedure for determination of chromium(III) and chro-
mium(VI) in industrial waste water of leather factories located in
Bor-Nigde organized industrial zone and for determination of total
chromium in wet digested geographical samples was performed
given in Tables 4 and 5, respectively.
4. Conclusion
This is the first time for ytterbium hydroxide precipitate, using
for the coprecipitation of chromium species in geological and
water samples, and the method was successfully applied. The
coprecipitation procedure presented for Cr(III) and Cr(VI) is simple
and economic for the speciation and preconcentration. No interfer-
ences of various matrix components of the natural water samples
were observed. The comparison of the results found in the present
study and some recent studies on chromium speciation by copre-
cipitation system was given in Table 6 (Ueda et al., 1997; Wang
et al., 2002; Krishna et al., 2004; Tuzen et al., 2008; Aydin and Soy-
lak, 2009; Bulut et al., 2009; Uluozlu et al., 2009a,b; Karatepe et al.,
2010). The detection limits of analytes are superior to those of pre-
concentration and speciation techniques for analyses.
Conflict of Interest
The authors declare that there are no conflicts of interest.
Acknowledgments
The authors are grateful for the financial support of the Units of
the Scientific Research Project of Gaziosmanpasa University and
Erciyes University.
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System pHPFLOD (lg/L) References
Hafnium hydroxide
Pb(PDC)2
Ethyl xanthate complex onto naphthalene
5-Chloro-2-hydroxyaniline–copper(II)
Thulium hydroxide
Ni2+/2-nitroso-1-naphthol-4-sulfonic acid
3-ethyl-4-(p-chlorobenzylidenamino-4,5-dihydro-1H-1,2,4-triazol-5-one (EPHBAT)
5-Chloro-3-[4-(trifluoromethoxy)phenylimino] indolin-2-one (CFEMEPI)
Dysprosium hydroxide
Ytterbium hydroxide
11.0
9.0
2.5
8.0
12.0
8.0
8.0
8.0
12.0
10.0
– 0.02
0.02
0.5
1.2
0.87
1.33
1.0
0.7
0.65
1.1
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Uluozlu et al. (2009b)
Bulut et al. (2009)
Karatepe et al. (2010)
This study
15
100
50
200
50
50
40
100
30
LOD: limit of detection; PF: preconcentration factor.
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