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Environ Monit Assess (2008) 138:167172

DOI 10.1007/s10661-007-9754-7

Determination of total chromium by flame atomic


absorption spectrometry after coprecipitation
by cerium (IV) hydroxide
Umit Divrikli & Mustafa Soylak & Latif Elci

Received: 7 August 2006 / Accepted: 11 April 2007 / Published online: 12 June 2007
# Springer Science + Business Media B.V. 2007

Abstract A method for the preconcentration of the Keywords Cerium (IV) hydroxide . Coprecipitation .
total chromium based on coprecipitation with cerium Flame atomic absorption spectrometry .
(IV) hydroxide is proposed for determination of Total chromium . Wastewater
chromium by flame atomic absorption spectrometry.
Different factors including carrier element amount,
pH, sample volume and matrix ion effects for the
precipitation were examined. The detection limit of Introduction
the total chromium (k=3, N=15) was 0.18 g l1. The
presented method was applied for the determination Chromium is widely used in various industries, such
of chromium in the wastewater samples from Kayseri as steel, electroplating, tanning, paint and pigment
and Nigde Organized Industrial Region-Turkey and in production, and metallurgy, which possibly contami-
drinking water from our laboratory, Kayseri with nate the environment. The contamination of chromi-
satisfactory results (relative standard deviations below um is mostly observed in wastewater. Chromium at
8%, recoveries 95%). The analytical results obtained trace levels may also enter in drinking water supply
by the proposed method for certified copper sample systems. Chromium exists in the contaminated water
was in good agreement with the certified value. samples as chromium (III) and chromium (VI)
oxidation states having different chemical and bio-
logical properties. Chromium (III) is essential for the
organism, but chromium(VI) has toxic and carcinogenic
effects (Berman 1980; Florence 1982; Zhitkovich 2005;
Hosseini and Sarab 2007).
The allowable concentration of chromium by the
U. Divrikli (*) : L. Elci United State Environmental Protection Agency (US-
Fen Edebiyat Fakultesi, Pamukkale Universitesi, EPA) is limited to 100 g l1 in drinking water. In
Kimya Bolumu,
Japan, the maximum tolerable concentration of chro-
20020 Denizli, Turkey
e-mail: undivrikli@pamukkale.edu.tr mium in wastewater is 500 g l1 and 50 g l1 for
total chromium and chromium(VI), respectively. The
European Community Directive for drinking water
M. Soylak
standards has put the limit of total chromium not
Fen Edebiyat Fakultesi, Erciyes Universitesi,
Kimya Bolumu, exceeding 50 g l1 (Narin et al. 2006). Therefore, the
38039 Kayseri, Turkey total chromium content is not an important criterion
168 Environ Monit Assess (2008) 138:167172

only for the control of industrial wastewaters, but also Table 1 FAAS analytical conditions for chromium
for the evaluating of pollution level of natural waters Absorption Lamp Slit Burner Air C2H2
such as drinking, sea and river waters (Barrera et al. line (nm) current (nm) height (l min1) (l min1)
1998; Boughriet et al. 1994; Marques et al. 2000; (mA) (mm)
Gardner and Ravencscroft 1996; Wattoo et al. 2006).
357.9 15 0.7 7.5 9.5 2.3
The low level of chromium given above is under the
detection limit of flame atomic absorption spectrome-
try (FAAS). Thus, preconcentration-separation is fre-
quently required in order to improve the detection
capability of preconcentration technique. double distilled water was used in all experiments. A
The preconcentration and separation methods stock standard solution of 1,000 mg l1 Cr (III) was
including solvent extraction, solid phase extraction, prepared from 7.6960 g chromium nitrate (Cr(NO3)3.
electrophoresis and coprecipitation have been used 9 H2O, Merck, Darmstadt, Germany) dissolved in
prior to instrumental determination of heavy metal double distilled water and diluted to a final volume of
ions (Efendioglu et al. 2007; Suleiman et al. 2007; 1,000 ml. A stock standard solution of 1,000 mg l1
Dogru et al. 2007; Li et al. 2007). Among these Cr (VI) was prepared from 2.8290 g potassium
preconcentration methods, coprecipitation of chromi- dichromate (K2Cr2O7, Merck, Darmstadt, Germany)
um species with metal hydroxides such as gallium dissolved in double distilled water and diluted to a
(Boughriet et al. 1994); ferric (Nakayama et al. 1981); final volume of 1,000 ml.
hafnium (Ueda et al. 1997); indium (Hiraide et al. A cerium (IV) solution (1 mg ml1) was freshly
1997); samarium (Saracoglu et al. 2003); cerium prepared by dissolving the requisite amounts of Ce
(Divrikli and Elci 2002) and erbium (Soylak et al. (SO4)4.4 H2O (E.Merck, Darmstadt, No: T61454) in
2005) hydroxides is often chosen because of mini- small amounts of nitric acid and diluting to 100 ml
mum contamination risk and relatively easy. with double distilled water. Ammonia solution (6 mol l1)
The aim of the present work is to show the was prepared in water from ammonia (E.Merck,
performance of the cerium (IV) hydroxide coprecipi- Darmstadt) and used for pH adjustment. The cellulose
tation procedure for preconcentration and separation nitrate membrane filters were purchased from Sartarious
of total chromium as chromium (III) plus chromium (0.45 m pore size, 47 mm diameter). The standard
(VI) from natural water samples, without the use of reference materials used in experimental studies were
any reduction or complexing reagent. certified copper sample (CRM Cu 1/3 alloy China).

Sampling
Experimental
The wastewater samples were collected in pre-
Instruments washed-cleaned polyethylene bottles from Kayseri
and Nigde Organized Industrial Regions-Turkey. The
A Perkin Elmer Model 3110 atomic absorption collected water samples were filtered through
spectrometer was used for the absorbance measure- 0.45 m pore size cellulose nitrate membrane filters
ments. The enstrument settings were shown in Table 1. immediately after sampling. The samples were stored
The sample solutions as 100 l were introduced into in a polyethylene (PE) bottle at 4C in a refrigerator,
the nebulizer using an injection technique (Berndt and prior to use.
Jackwerth 1975). Nel 900 model pH-meter in combi-
nation with a glass-electrode was employed to adjust Preconcentration procedure
the pH of the model solution and the water samples.
A 50 ml of model solution containing 10 g Cr (III)
Reagents and solutions and/or 10 g Cr (VI) was prepared. 9 mg of cerium
(IV) as cerium (IV) sulfate was added to this solution
Analytical reagent grade chemicals were employed and the pH of solution was adjusted to desirable pH
for the preparation of all solutions. Freshly prepared over the range of 211, using 6 mol l1 ammonia
Environ Monit Assess (2008) 138:167172 169

110
as accurately weighed into a 50 ml beaker and 0.5 ml
of concentrated nitric acid was added to the sample.
90 The beaker was covered with a watch-glass and the
mixture was evaporated on a hot plate about 95C
almost to dryness. Then the solution was cooled and
Recovery, %

70
diluted to 10 ml with distilled water. Finally, the
preconcentration procedure given above was applied
50
to the final diluted solution. The same procedure was
applied to the blank solution.
30

Analysis of water samples


10
2 3 4 5 6 7 8 9 10 11 To apply the examined method, 9 mg of Ce (IV)
pH
Fig. 1 Dependence of Cr(III) ( ) and Cr(VI) ( ) carrier element was added to 400 ml portion of
coprecipitations on pH of solutions (Amount of cerium (IV) : wastewater or drinking water samples and pH of the
9 mg, N:3) solution was adjusted to about 6 for coprecipitation of
Cr (III) and Cr (VI). Then the procedure given above
solution. The formed precipitate, Ce(OH)4, was was followed. The total chromium in the final
settled for 20 min then, it was filtered by suction solutions was determined by flame atomic absorption
using a cellulose nitrate membrane filter from spectrometry.
Sartarious, 0.45 m pore size, 47 mm diameter. The
membrane loaded with the precipitate was dissolved
with 1 ml of concentrated HNO3 and the solution was Results and discussion
diluted to 2 ml with 1 mol l1 HNO3. Then, to
determine the chromium in the concentrated solutions Effect of pH
for the samples, an aliquot 100 l of the solution was
introduced to the nebulizer of the flame atomic The most important parameter is pH to obtain the
absorption spectrometer by micro injection method. quantitative recoveries in the preconcentration with
coprecipitation. Because, the chemical forms of
Procedure for the certified copper CRM sample analyte and the quality of coprecipitation depend on
pH of sample solution. Therefore, pH was firstly
For copper analysis, a portion (0.04 g) of the certified optimized. The coprecipitation of chromium (III) and
copper sample (CRM Cu 1/3 Cu alloy from China) chromium (VI) with cerium (IV) hydroxide was
w-
Table 2 Tolerable levels of
some ions on proposed Ions Added as Tolerable concentration, mg l1 Concentration in the effluent, mg l1
coprecipitation procedure
(Sample volume: 50 ml, to- Na+ NaCl 50,000 118
tal chromium: 10 g, N=3) Cl NaCl 50,000 BDL
K+ KCl 2,500 919
Ca2+ CaCl2 1,000 95
Mg2+ MgCl2 2,500 342
SO24 Na2SO4 320 BDL
Cu2+ Cu(NO3)2 800 50
Ni2+ Ni(NO3)2 250 24
Co2+ Co(NO3)2 250 44
Pb2+ Pb(NO3)2 250 17
Zn2+ Zn(NO3)2 250 44
Fe3+ Fe(NO3)3 200 169
BDL Below the detection Fe2+ FeSO4 250 98
limit
170 Environ Monit Assess (2008) 138:167172

Table 3 Analysis of drink-


ing water samples spiked Sample Added (g) Found (g) Recovery (%)
total chromium (Sample
volume: 50 ml, Final vol- Drinking water 0 BDL
ume: 2 ml, N:3) 3 2.85 952
6 5.89 982
12 11.60 971
Waste water 0 0.24
3 3.39 1053
6 5.96 952
BDL Below the detection 12 12.00 981
limit

investigated in the pH range of 211. Figure 1 shows Until 9 mg of Ce (IV), the recoveries were under 95%.
that chromium (III) and chromium (VI) were copre- The quantitative recoveries, 95% for Cr (III) and Cr
cipitated quantitatively in the pH range of 410 and in (VI) ions were obtained in the range of 912 mg
the range pH 47, respectively. Considering these cerium. Therefore, in the following works, 9 mg of
results, the selected pH was 6.0 for the total cerium was used for the coprecipitation.
chromium in all further experiments.
Effect of sample volume on recovery of chromium
Adsorption mechanism
The influences of the sample volume were examined
In the pH range that chromium (VI) is quantitatively to obtain high preconcentration factor, as a function of
coprecipitated; pH 47, there is equilibrium between the volume of sample solution containing chromium
H2CrO4 and HCrO4 as dominant species in aqueous species at constant amount such as 5 g for each of
solutions (Kotas and Stasicka 2000). For this reason, Cr (III) and Cr (VI) in the range of 50800 ml. The
probably, Cr (VI) as H2CrO4 and/or HCrO4 forms results indicated that recoveries of chromium were
may be coprecipitated by cerium (IV) hydroxide. Cr quantitative up to 400 ml of sample volume. After
(III) in the presence of Ce (IV) can be oxidized to Cr 400 ml, the coprecipitation for chromium was not
(VI) as depending on their redox potentials (Skoog et quantitative. Highest preconcentration factor was 200,
al. 1996). However, Cr (III) ions are strongly hydrated when the final volume was 2 mL.
and most stable in range of pH 49 (Kotas and
Stasicka 2000). Moreover, aqua/hydroxo Cr (III) Effect of amount of chromium on recovery
complexes have a strong tendency to be adsorbed by of chromium
solids. On the other hand, it is known that both Cr
(III) and Cr(VI) can strongly sorb to iron hydroxide The influence of the amounts of the chromium species
solids from water samples (Parks et al. 2004). On for the quantitative recoveries was also investigated.
basing these knowledges, it may be concluded that Cr For this purpose, the proposed procedure was applied
(III) as Cr (VI) and/or hydratized Cr (III) species may to 50 ml solution containing equal amounts of the
be also coprecipitated by cerium (IV) hydroxide
under the experimental conditions. Yet, these ideas
have been not investigated as experimental in detail. Table 4 Concentrations of total chromium in water samples
(Sample volume: 400 ml, Final volume: 2 ml, N: 5)
Effect of cerium (IV) amounts on recovery Samples Chromium concentration (g
of chromium l1)

The amount of cerium (IV) as sulfate was examined for Drinking water (Erciyes BDL
the quantitative coprecipitation of the chromium ions Uni.)
Waste water (Kayseri) 4.900.49
with cerium (IV) hydroxide in the range of 012 mg
Waste water (Nigde) 3.530.07
cerium (IV). Without any cerium (III), the recovery of
chromium was 43% under the working conditions. Mean expressed as 95% tolerance limit
Environ Monit Assess (2008) 138:167172 171

both chromium species at various levels. Quantitative confirm the accuracy of the procedure and the absence
recoveries were obtained from 2 to 400 g of total of matrix effects. The preconcentration factor was 200.
chromium, with equal amounts of Cr (III) and Cr The precision of the coprecipitation procedure was
(VI). After 400 g of total chromium, the coprecipi- evaluated as the relative standard deviation (RSD)
tation efficiency was not quantitative. obtained after replicate analyses of wastewater sam-
ples. The relative standard deviation was between 1.6
Effect of matrix ions and 8.0% (Table 4). The analytical figures given
above for the proposed coprecipitation of chromium
To assess the possible analytical applications of the are better or comparable with the data from some
proposed procedure, the effect of some foreign ions recent studies on determination of chromium species
which interfere with the determination of metal ions given in the literature (Narin et al. 2006).
by flame atomic absorption spectrometry or/and often
accompany analyte ions in various water real samples Application to the real samples
was examined. The results were given in Table 2. The
tolerance limit of foreign ions was considered as the The method with the characteristic performance data
ion concentration causing a relative error smaller than given above was successfully applied to the determi-
5% related to the preconcentration and determina- nation of total chromium in two industrial wastewater
tion of the chromium ion. As it is seen, large numbers samples from the metal plants in the industrial
of ions used have no considerable effect on the organized region of Kayseri and Nigde-Turkey. The
determination of total chromium. The concentrations presented method was also applied to a drinking water
of these ions in the analysed water samples were samples taken from Erciyes University. The results
found lower than that of their tolerance limits on the are given in Table 4.
recovery of chromium. The accuracy of the proposed cerium (IV) hydroxide
with coprecipitation method was examined by determi-
Figure of merits nation of total chromium in certified copper sample
from China. The results are given in Table 5. The
The limit of detection (LOD) of the proposed method relative error for the recommended procedure is
was studied by applying the procedure for blank 7.7%. The relative standard deviation was 2.8% for
solutions. The detection limit based on three times the the analysis of the certified sample. These analytical
standard deviations of the blank for flame atomic parameters are satisfactory for many purposes.
absorption spectrometric measurements for total chro-
mium was found as 0.18 g l1.
Conclusion
The analytical performance of coprecipitation with
cerium (IV) hydroxide-flame atomic absorption spec-
The combination of coprecipitation with cerium (IV)
trometry system was also considered. To validate the
hydroxide and FAAS has been evaluated and demon-
present method, the recovery of chromium spiked into
strated to be a promising for determination of total
analyzing wastewater and drinking water from Kayseri
chromium at low levels in wastewater, drinking water
was studied, satisfactory results were obtained as
and certified samples. The procedure is easy and fast.
shown in Table 3. The quantitative recovery values
The proposed coprecipitation has shown adequate
accuracy and precision, besides being simple and
economical for preconcentration of total chromium
Table 5 Results of the analysis of standard reference materials without to use a complexing reagent.
(CRM Cu I/III), (N: 7)
Acknowledgements The authors wish to express thanks to
Element Concentration (w/w) %
the Unit of the Scientific Research Project of Erciyes University
Certified value Observed value (Kayseri-Turkey) for the financial support for this study. Also,
the authors would like to thank the Scientific and Technological
Cr 2.20102 (2.030.01)102 Research Council of Turkey (TUBITAK) for providing Perkin-
Elmer 3110 atomic absorption spectrometer used in the present
Mean expressed as 95% tolerance limit study.
172 Environ Monit Assess (2008) 138:167172

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