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Journal of the Chinese Chemical Society, 2007, 54, 625-634

625

Speciation of Cr(III) and Cr(VI) in Environmental Samples after Solid Phase


Extraction on Amberlite XAD-2000
Celal Duran,a Mustafa Soylak,b* Volkan Numan Bulut,c Ali Gundogdu,a Mehmet Tufekci,a
Latif Elcid and Hasan Basri Senturka
a

Department of Chemistry, Faculty of Art and Science, Karadeniz Technical University,


61080 Trabzon-Turkey
b
Department of Chemistry, Faculty of Art and Science, Erciyes University, 38039 Kayseri-Turkey
c
Department of Chemistry, Giresun Faculty of Art and Science, Karadeniz Technical University,
28049 Giresun-Turkey
d
Department of Chemistry, Faculty of Art and Science, Pamukkale University, 20020 Denizli-Turkey

A method for speciation of Cr(III) and Cr(VI) in real samples has been developed. Cr(VI) has been
separated from Cr(III) and preconcentrated as its pyrrolidinedithiocarbamate (APDC) complex by using a
column containing Amberlite XAD-2000 resin and determined by FAAS. Total chromium has also been
determined by FAAS after conversion of Cr(III) to Cr(VI) by oxidation with KMnO4. Cr(III) has been calculated by subtracting Cr(VI) from the total. The effect of pH, flow-rate, adsorption and batch capacity
and effect of various metal cations and salt anions on the sorption onto the resin were investigated. The adsorption is quantitative in the pH range of 1.5-2.5, and Cr(VI) ion was desorbed by using H2SO4 in acetone.
The recovery of Cr(VI) was 97 4 at a 95% confidence level. The highest preconcentration factor was 80
for a 200 mL sample volume. The adsorption and batch capacity of sorbent were 7.4 and 8.0 mg g 1
Cr(VI), respectively, and loading half time was 5.0 min. The detection limit of Cr(VI) is 0.6 mg/L. The procedure has been applied to the determination and speciation of chromium in stream water, tap water, mineral spring water and spring water. Also, the proposed method was applied to total chromium preconcentration in microwave digested moss and rock samples with satisfactory results. The developed method
was validated with CRM-TMDW-500 (Certified Reference Material Trace Metals in Drinking Water) and
BCR-CRM 144R s (Certified Reference Material Sewage Sludge, Domestic Origin) and the results obtained were in good agreement with the certified values. The relative standard deviations were below 6%.
Keywords: Chromium speciation; Preconcentration; APDC; Amberlite XAD-2000; FAAS.

INTRODUCTION
The large amount of waste disposal has resulted in
serious environmental pollution over the last decades.
Among various pollution sources, heavy metals tend to
cause a series of risks, including carcinogenic effects to human health, ecological threats and extinction of species.1-3
Studies have shown that the carcinogenesis induced by certain toxic metals could be further enhanced or inhibited
through their interactions with other metals, which processes depend strongly on the chemical forms of the metals.3 Nowadays, the growing awareness of the strong dependence of the toxicity of heavy metals upon their chemical forms has led to an increasing interest in metal specia-

tion analysis.
Toxicological studies have shown that the degree of
toxicity of some elements depends on the chemical form
in which the element is present. Chromium(III), for example, is considered an essential micronutrient for humans,
whereas chromium(VI) is a potentially carcinogenic agent.4
It is therefore necessary to control the level of chromium in
wastewater, natural water and drinking water. Many countries have developed laws along this line, but since the legislation permits a larger content of Cr(III) than Cr(VI),
speciation of chromium in environmental samples is very
important.5 Therefore, the knowledge on the speciation of
chromium is of particular necessity.
Chromium is widely used in various industries, such

* Corresponding author. Tel/Fax: +90-352-4374933; E-mail: soylak@erciyes.edu.tr, msoylak@gmail.com

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J. Chin. Chem. Soc., Vol. 54, No. 3, 2007

as plating, tanning, paint and pigment production, and


metallurgy, which possibly contaminate the environment.
Chromium(III) compounds are one of the essential trace
nutrients in human bodies, and play an important role in the
metabolism of glucose and certain lipids, whereas chromium(VI) compounds are toxic and carcinogenic.6-8 The
United States Environmental Protection Agency (USEPA)
has regulated the permissible limit of 0.1 mg L1 of total
chromium in drinking water. In Japan, the maximum tolerable concentration of chromium in wastewater is 0.5 and
0.05 mg L1 for total chromium and chromium(VI), respectively. However, the World Health Organization (WHO)
thinks that the guideline value of 0.05 mg L1 of chromium(VI) is too high, compared with its high risk of carcinogenicity. Consequently, the development of a sensitive
method, as well as the speciation method of chromium in
environmental sample is absolutely essential.
Various analytical techniques have been used for determination of chromium including spectrophotometry,
atomic absorption spectrometry (AAS), inductively coupled plasma mass spectrometry (ICP-MS), etc.9-14 Due to
the levels of chromium species in the natural water samples
being generally at mg L1 and the high matrix contents of
the samples, separation/preconcentration techniques (solvent extrtaction,15 coprecipitation,16 solid phase extraction17-19) are necessary, prior to determination of chromium
by an instrumental technique.20
Solid phase extraction is one of the well-known preconcentration/separation techniques for trace metals, and
various supports are used in this technique.21-27 Amberlite
XAD-2000, which is a polystyrene-divinylbenzene copolymer, is one of the Amberlite XAD adsorption resins, and
the studies related to this resin are seldom encountered in
the literature.28,29 It has a high adsorption capacity like
other members of the Amberlite XAD resin family.30 It has
been used for the solid phase extraction of biomolecules
and pharmaceuticals.30,31 Because Amberlite XAD-2000 is
not used for the speciation of Cr(III) and Cr(VI) according
to our literature survey and due to its good adsorption properties, it was selected as an adsorbent for the present work.
In this work, we combined this well known procedure
with the column preconcentration procedure. As the APDC
is very selective for Cr(VI), Cr(VI) has been preconcentrated as its pyrrolidinedithiocarbamate complex onto a
column containing Amberlite XAD-2000 and determined
by flame atomic absorption spectrometry. Total chromium
has been determined similarly after oxidizing the Cr(III) to

Duran et al.

Cr(VI). The concentration of Cr(III) was obtained by difference.

EXPERIMENTAL
Instrumentation
A Unicam AA-929 atomic absorption spectrophotometer equipped with single element hollow cathode lamps
and an air/acetylene burner (10 cm) was used for the determination of chromium. The instrumental parameters were
those recommended by the manufacturer. The wavelength
(nm) selected for the determination of chromium was 357.9
nm. A Hanna 211 pH meter with glass electrode was used
for the pH adjustments. A mechanical shaker Nuve SL 350
having speed control was used for batch experiments. A
Milestone Ethos D microwave oven was used for digestion
of certified reference materials (sewage sludge), lichen and
rock samples. A glass mini-column (10 cm length and 1.0
cm diameter), having a porous disk and a stopcock, was
used for preconcentration of the metals.
Reagents
All solutions were prepared using analytical reagent
grade chemicals purchased from Merck and Fluka, unless
otherwise specified, and doubly distilled-deionized water.
Stock solutions of studied metals (Cr(III) prepared Cr(NO3)3
in 0.5 mol L1 HNO3 and Cr(VI) prepared K2CrO4 in water)
with a concentration of 1000 mg L1 were used. The model
and standard solutions of the metals were prepared by appropriately diluting the stock solutions. H2SO4 (Merck) and
KOH (Sigma) were used for pH adjustments. Amberlite
XAD-2000 resin (particle size of 20-60 mesh and surface
area of 600 m2g1) and ammonium pyrrolidinedithiocarbamate (APDC) was purchased from Sigma Chem. Co., St.
Louis. 0.1% (w/v) solution of APDC in ethanol was used as
a chelating agent. Trace metal in drinking water standard
(CRM-TMDW-500) from High-Purity Standards, Inc and
Certified Reference Material Sewage Sludge, Domestic
Origin (BCR-CRM 144R s) from the Institute for Reference Materials and Measurements (IRMM) were used as
standard reference materials.
Sampling
Water samples were taken from the tap, which provides drinking water for Karadeniz Technical University,
from the stream of Degirmendere River, which supplies

Speciation of Cr(III) and Cr(VI)

drinking water to Trabzon city, from the stream of the Solakli


River (Trabzon/Of), from mineral spring water (Trabzon/
Bengisu district) and from spring water (Trabzon/OfTashanpazari district). Polyethylene bottles were used for
sample storage and were thoroughly washed with detergent, tap water, 1 mol L-1 HNO3, and distilled-deionised
water, respectively, prior to collection of the water samples. Finally, the water samples were acidified with conc.
HNO3 in order to adjust pH to ~ 2 and filtered through a
nitrocellulose membrane with a 0.45 mm pore size.
A plant sample (moss), collected from Cayeli (Rize)
in Turkey, and a rock sample (analyzed by ACME Analytical Lab. (ISO 9002 Accredited Co.) in CANADA) collected from Kumbet Plateau (Giresun) in Turkey were
dried in an oven for 20 hours at 105 C and finely powdered.
Column Preparation
A glass column (10 cm length and 1.0 cm diameter)
containing 0.3 g of Amberlite XAD-2000 resin (~1.5 cm
bed height) was used for preconcentration of chromium.
XAD-2000 (ground and sieved to 150-200 mm) resin was
washed successively with 1 mol L1 NaOH, water, 1 mol
L1 HNO3, water, acetone and water. A glass-wool plug was
rested on the stopcock of the column and another plug of
glass-wool was placed on top of the resin to avoid the distribution of resin during sample passage. The sorbent was
washed with ethanol and 1 mol L-1 HNO3 and was thoroughly washed with H2O until the effluents were neutral.
After each use, the resin in the column was washed thoroughly with water and sulphuric acid (0.05 mol L-1) in order to condition and clean it, and then it was stored in water
for further applications.
Determination of Cr(VI)
The method was tested with model solutions before
its application to environmental samples. For the optimization of column separation and preconcentration method,
100 mL of spiked sample solutions containing 10 mg of
Cr(VI) and 5 mg of Cr(III) were used. pH of the spiked sample solution was adjusted to the desired value (pH 2) at
which the recovery of Cr(VI) is the highest (Cr(III) < 3%)
with sulphuric acid and then 5 mL 0.1% (w/v) APDC was
added into the model solution. Cr(VI)-APDC solution was
passed through the column at a flow rate of 10 mL min1.
The retained species (Cr-APDC) on the column was eluted
with 7.5 mL of 0.05 mol L-1 H2SO4 solution in acetone. The

J. Chin. Chem. Soc., Vol. 54, No. 3, 2007

627

eluent was evaporated over a hot plate to near dryness. The


residue was diluted to 2.5 mL with 1 M HNO3. Chromium
content in the eluate was determined by FAAS.
Determination of Total Chromium
Total chromium was determined as Cr(VI) by the
method described above after oxidizing Cr(III) to Cr(VI)
by the addition of KMnO4 in acid medium. For this purpose, 4 or 5 drops of KMnO4 (0.02 mol L-1) solution and 0.5
mL of concentrated H2SO4 were added into a 250 mL
beaker containing 100 mL of the spiked solution, 0.1 mg
L-1 Cr(VI) and 0.05 mg L-1 Cr(III). The beaker was covered
with a watch glass and heated without boiling (~45 C) for
about 15 min to complete oxidation. The solution was
cooled and sodium azide solution (2.5%, w/v) was added
dropwise to reduce the excess of KMnO4 (decolorizing the
pink solution), waiting a few seconds after the addition of
each drop. Then, the solution was transfered to a 100 mL
volumetric flask. APDC solution (5 mL 0.1%) was added
and the solution was diluted with water to the mark and
mixed thoroughly. pH of the solution was controlled with a
pH meter and adjusted to the desired value (pH 2). After
oxidation of Cr(III) to Cr(VI) by using KMnO4 in acidic
media, the method was applied to the determination of the
total chromium. The level of Cr(III) is calculated by subtracting Cr(VI) from total chromium.
Analysis of the Real Samples
The water samples (tap water, river waters, mineral
spring water, spring water and CRM-TMDW-500 trace
metal in drinking water certified reference material) analyzed were collected in pre-washed polyethylene bottles.
The samples, except for certified reference material, were
filtered through a Millipore cellulose membrane of pore
size 0.45 mm, 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 (200 mL for tap water, river waters, mineral spring
water, spring water and 50 mL for certified reference material, CRM-TMDW 500) were adjusted to 2.0. Then 0.1%
APDC solution was added. The sample was passed through
the column. The APDC chelates adsorbed on the column
were eluted with 0.05 mol L-1 H2SO4 in acetone. The effluent was evaporated to near dryness and made up to 2.5 mL
with 1 mol L1 HNO3. The level of chromium was determined by FAAS.
Prior to the preconcentration step for standard refer-

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J. Chin. Chem. Soc., Vol. 54, No. 3, 2007

ence material and solid samples analyzed, sewage sludge of


domestic origin (BCR-CRM 144R s), plant sample (moss),
and rock sample were also microwave digested. Digestion
conditions for a microwave system for the samples were
applied as (35 bar) 1 min for 250 W, 1 min for 0 W, 10 min
for 650 W, 5 min for 250 W, vent: 3 min, respectively.
BCR-CRM 144R s (0.15 g) were digested with 6.0
mL of HCl (37%), 2.0 mL HNO3 (65%) and 0.5 mL HF
(39%) in a microwave digestion system. Plant samples
(moss) (1.00 g) were digested with 6 mL of HNO3 (65%), 2
mL of H2O2 (30%) in a microwave digestion system. Rock
samples (0.5 g) were digested with 4.5 mL of HCl (37%),
1.5 mL HNO3 (65%) and 2 mL HF (39%) in a microwave
digestion system.
After microwave digestion, the suspension was filtered through a blue band filter paper, and the insoluble part
was washed with distilled water. And then the volume of
the sample was made up to 50.0 mL with distilled water.
Blanks were prepared in the same way as the sample, but
omitting the sample. The preconcentration procedure given
above was applied to the samples. The final volume was 2.5
mL.
Batch Capacity of the Resin
100 mL of working solution containing 1 mg Cr(VI)
chelated with APDC was brought to pH 2 and transferred to
a polyethylene bottle and then to which was added 0.1 g of
XAD-2000. After shaking for 1, 3, 5, 10, 30, 60 and 120
min at room temperature separately, the metal-loaded sorbent was filtered off, and the metal remaining in the filtrate
was measured by FAAS.
Adsorption Capacity of the Resin
The adsorption capacity is the maximum metal quantity taken up by 1 gram of resin and given by mg metal g1
resin or meg (miliequivalent gram). In order to determine
this, test solutions of Cr(VI) weighing in the range of 10010000 mg were loaded to the column containing 300 mg of
resin and recoveries were investigated. Langmuir isotherms were plotted in order to determine the resin capacity. According to the Langmuir isotherm, a plot of Ce/qe
versus Ce shows linearity, hence Langmuir constants qmax
and aL can be calculated from the slope and intercept of the
plot where q e is the amount of metal adsorbed per unit
weight of the resin (mg g1) at equilibrium, Ce the final concentration in the solution (mg L1), qmax the maximum adsorption at monolayer coverage (mg g1), and aL the ad-

Duran et al.

sorption equilibrium constant which is related to energy of


adsorption (L mg1). The amount of maximum total chromium (qmax) adsorbed on 1.0 g resin is calculated from the
slope of the plot obtained for chromium.

RESULTS AND DISCUSSION


To determine for quantitative recoveries of chromium
on XAD-2000, the separation/preconcentration procedure
was optimized for various parameters such as pH, sample
volume and eluent type. The percentage of chromium(VI)
adsorbed was calculated from the amounts of chromium(VI)
in the starting sample and the amounts of chromium(VI)
eluted.
Effect of pH
The efficiency of recoveries of Cr(III) and Cr(VI)
were investigated in the pH range 1-12. pH of the solution
was adjusted in a range of 1-12 by using H2SO4 and KOH
and passed through the column (containing 0.3 g of XAD2000). According to the recovery results (Cr(VI) 97.0%,
Cr(III) 2.0%) the optimum pH was determined as 2. In addition, it was revealed that the H2SO4 used for pH 2 did not
have a negative effect, hence the following optimization
work was carried out at pH 2. The change of recovery of
Cr(VI) and Cr(III) with pH is shown in Fig. 1. As can be

Fig. 1. Effect of the pH on the recoveries of chromium


species on XAD-2000 (Ligand amount: 5 mg,
amount of adsorbent: 300 mg, sample flow rate:
10.0 mL min1, Eluent type and volume: 7.5 mL
of 0.05 mol L-1 H2SO4 solution in acetone, sample volume: 50 mL, N = 3).

Speciation of Cr(III) and Cr(VI)

seen in Fig. 1 quantitative recovery (97%) was found at the


pH 1.5-2.5 with Cr(VI) while the recovery of Cr(III) is
rather low (2%). This could make it possible to separate
Cr(VI) from Cr(III). According to the recovery results the
optimum pH was determined as 2.0 for Cr(VI).
Effect of ligand amount
The effects of the APDC amounts on the adsorption
of Cr(VI) on the resin was investigated. The recoveries of
Cr(VI) were < 8%, when APDC was not added to the solution. The recovery values increased with the addition of
APDC. The quantitative values were obtained after 3.0 mg
(0.1% (w/v) in ethanol 3 mL) of APDC. After this point the
recoveries were quantitative in all working ranges of
APDC. In all further studies, 5 mg (0.1%, w/v in ethanol 5
mL) of APDC was used.
Effect of amount of adsorbent (bed height)
The influences of amounts of XAD-2000 on the retention of Cr(VI) were investigated. The results are given
in Fig. 2. The recovery values for chromium were not quantitative till 250 mg of XAD-2000. Quantitative recovery
values were obtained in the 250-600 mg range of XAD2000. All experiments were performed with 300 mg of
XAD-2000.
Influence of flow rate of sample
The rate of the flow of model solutions through the

J. Chin. Chem. Soc., Vol. 54, No. 3, 2007

629

column is one of the factors affecting the duration of the determination. The rate of the flow through the column is directly related to the contact of the Cr(VI)-APDC complex
with the resin. Hence, model solutions of 50 mL were
passed through the column with rates in the range of 1-23
mL min1. It was observed that the recovery values were
quantitative in the flow rate range of 1-12 mL min1. Thus,
the flow rate 10.0 mL min1 was chosen for all the subsequent experiments.
Eluent type and volume
For the elution of Cr(VI) complex, sulphuric acid, hydrochloric acid, nitric acid, acetone, ethanol, methanol and
their combinations have been tested as eluent. As can be
seen in Table 1 the best elution (97% recovery) was obtained by using 7.5 mL of 0.05 mol L-1 H2SO4 solution in
acetone. The volume of 0.05 mol L-1 H2SO4 solution in acetone as eluent was also tested. The recoveries of chromium(VI) were quantitative (> 96%) 7.5-15.0 mL of 0.05
mol L-1 H2SO4 solution in acetone. In all further works, 7.5
mL 0.05 mol L-1 H2SO4 solution in acetone was used.
Effect of sample volume
As the concentrations of chromium in real samples
are too low, by using samples with large volumes, chromium in these volumes should be taken into smaller volumes for determination of these metals with high accuracy.

Table 1. Effect of the type of elution solution on the recovery of


Cr(VI)-APDC complex (pH: 2.0, ligand amount: 5 mg,
amount of adsorbent: 300 mg, sample flow rate: 10.0
mL min1, Eluent volume: 7.5 mL, sample volume: 50
mL, N = 3)
Type of elution solution

Fig. 2. Effect of resin amount on the recovery of


Cr(VI) (pH: 2.0, ligand amount: 5 mg, sample
flow rate: 10.0 mL min1, Eluent type and volume: 7.5 mL of 0.05 mol L-1 H2SO4 solution in
acetone, sample volume: 50 mL, N = 3).

HCl in acetone
HCl in methanol
HNO3 in acetone
HNO3 in methanol
H2SO4 in acetone
H2SO4 in acetone
H2SO4 in acetone
H2SO4 in methanol
H2SO4 in water
HCl in water
HNO3 in water
Acetone
Ethanol
Methanol

Concentration
(mol L1)

Recovery
(%)

1.0
1.0
1.0
1.0
000.025
00.05
0.1
00.05
00.05
1.0
1.0

80 3
45 1
91 2
36 1
89 2
97 3
92 2
36 2
<5
<5
<5
35 3
28 2
12 1

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J. Chin. Chem. Soc., Vol. 54, No. 3, 2007

Hence, the maximum sample volume was optimized by the


investigation of the recovery of trace metal (10 mg for Cr(VI),
5 mg for Cr(III)) in various sample volumes in the range of
50-300 mL by using the proposed separation and preconcentration procedure described above. Consequently, the
recovery was found to be stable until 200 mL for Cr(VI)
(97%). The results are depicted in Fig. 3. Above 200 mL,
the recovery decreased with increasing volume of sample
(93% for 225 mL, 84% for 250 mL and 65% for 300 mL). In
this work, because the elution volume was 2.5 mL, the
highest preconcentration factor was 80 for a 200 mL sample volume, theoretically.
Adsorption and batch capacity of the resin and
loading half-time
The amount of maximum metal (qmax) adsorbed on
1.0 g resin was calculated as 7.4 mg g1 from Langmuir isotherms (Figs. 4 and 5). The result is given in Table 2. The
sorption percentage of the Cr(VI) is recorded as a function
of time in Fig. 6. Batch capacity of the Amberlite XAD2000 resin was obtained as 8.0 mg g-1 for Cr(VI). Sorption
was complete within 10 min. for chromium (Fig. 6). The
sorption half-times were 5.0 min. Both half-time and batch
capacity are tabulated in Table 2. As seen from the data in
Table 2, the proposed method developed using Amberlite
XAD-2000 resin has a high sorption capacity, and it is very
fast with a loading half-time, t1/2 of 5.0 min.

Duran et al.

Table 2. Adsorption and batch capacities and loading half-time


(N = 3)
Parameters

Chromium(VI)
1

Adsorption Capacity (mg g )


Batch Capacity (mg g1)
Loading Half-Time (min)

7.4
8.0
5.0

Amberlite XAD-2000 is a styrene-divinylbenzene


copolymer. The adsorption of Cr(VI)-APDC chelates on
Amberlite XAD-2000 is based on molecular adsorption.
The desorption of the metal chelates are performed by using 0.05 mol L-1 H2SO4 in acetone to break down the physical interactions between resin and metal chelates.

Fig. 4. Adsorption capacity of the resin for Cr(VI): Ce


vs qe graph (pH: 2.0, N = 3).

Fig. 3. Influences of sample volume on Cr(VI) retentions (pH: 2.0, ligand amount: 5 mg, amount of
adsorbent: 300 mg, sample flow rate: 10.0 mL
min1, Eluent type and volume: 7.5 mL of 0.05
mol L-1 H2SO4 solution in acetone, N = 3).

Fig. 5. Adsorption capacity of the resin for Cr(VI): Ce


vs Ce/qe graph (pH: 2, N = 3).

Speciation of Cr(III) and Cr(VI)

J. Chin. Chem. Soc., Vol. 54, No. 3, 2007

Effect of diverse ions


Na+, K+, Ca2+, Mg2+, Cl-, NO3-, PO43- and SO42- ions
with various concentrations were added to the preconcentration medium in order to identify the effects of these ions
on trace metal recovery. The efficiency of the recovery was
not affected by whether these ions exist individually or altogether, defined as mixed containing 10000 mg L1 Na+,
1000 mg L1 K+, 1000 mg L1 Ca 2+, 1000 mg L1 Mg2+,
12500 mg L1 Cl, 1000 mg L1 PO43-, 10000 mg L1 NO3,
500 mg L1 SO42, Cu2+, Ni2+, Cd2+, Co2+, Pb2+, Zn2+ (10 mg
L1) and Fe3+, Mn2+ (20 mg L1) ions (Table 3). Hence, this
method can be applied to sea water since it was not affected
by high concentrations of Na+ and Mg2+ and environmental
samples.

Fig. 6. The rate of Cr(VI) sorption on XAD-2000 resin


(pH: 2.0, N = 3).

Detection limit for Cr(VI)


The detection limit (n = 20, blank + 3s, where s is
standard deviation of blank estimation) was found to be
0.6 mg L1. The precision of the determination of chromium(VI) was evaluated under the optimum conditions
mentioned above. For this purpose, the procedure was repeated ten times for chromium(VI). It was found that the
recovery of Cr(VI) was 97 4 at the 95% confidence level.
Determination of total chromium
In order to determine total chromium, firstly model
solutions that contain different amounts of Cr(VI) and
Cr(III) were prepared. Then Cr(III) ions in the model solutions were oxidized to Cr(VI) by using KMnO4 in acidic
media. The pH of the solution was adjusted to 2.0 by the addition of 0.05 mol L1 H2SO4 carefully. Then the procedure
presented was applied to these solutions. The results are
given in Table 4. The results show that the proposed method
could be applied for the determination of total chromium.
Applications
The proposed method was applied to the speciation of
Cr(VI) and Cr(III) in tap water, river water samples, mineral spring water and spring water collected from Trabzon.
The samples were filtered through MFS membrane filters
(pore size 0.45 mm). The Cr(VI) and total chromium were
determined in unspiked and spiked original water samples.
For this purpose, Cr(VI) and Cr(III) were added to all samples in different amounts and the proposed method was applied. The obtained results are given in Table 5. As can be

Table 3. Influences of some ions on the recovery of chromium(VI) on the XAD-2000 (pH:
2.0, ligand amount: 5 mg, amount of adsorbent: 300 mg, sample flow rate: 10.0 mL
min1, Eluent type and volume: 7.5 mL of 0.05 mol L- 1 H2SO4 solution in acetone,
sample volume: 50 mL, N = 3)
Ions

631

Concentration (mg L1)

Recovery (%)

100000
1000
1000
1000
125000
1000
0500
100000
0010
0020

94 2
96 3
97 2
93 4
95 4
98 5
93 3
95 2
97 2
93 3
95 4

Na
K+
Ca2+
Mg2+
ClPO43SO42NO3Cu2+, Ni2+, Cd2+, Co2+, Pb2+, Zn2+
Fe3+, Mn2+
Mixed*
* The solution containing ions in Table 3 combined.

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J. Chin. Chem. Soc., Vol. 54, No. 3, 2007

Duran et al.

Table 4. Determination of total chromium in spiked test solutions (pH: 2.0, ligand amount: 5
mg, amount of adsorbent: 300 mg, sample flow rate: 10.0 mL min1, Eluent type and
volume: 7.5 mL of 0.05 mol L- 1 H2SO4 solution in acetone, sample volume: 50 mL,
N = 3)
Added (mg)
Cr(VI)
0
5
7.5
10
15

Found (mg)

Cr(III)

Total Chromium

Total Chromium

Recovery (%)

15
10
7.5
5
0

15
15
15
15
15

14.4 0.2
14.1 0.3
14.2 0.3
14.7 0.5
14.5 0.4

96
94
95
98
97

Table 5. Determination of Cr(III), Cr(VI) and total chromium in tap water and river water (pH: 2.0, ligand amount: 5
mg, amount of adsorbent: 300 mg, sample flow rate: 10.0 mL min1, Eluent type and volume: 7.5 mL of
0.05 mol L- 1 H2SO4 solution in acetone, sample volume: 200 mL, N = 3)
Added (mg)
Samples

Found (mg)
Cr(III)

Cr(VI)

Total
Chromium

Cr(III)

Cr(VI)

Total
Chromium

0.76 0.04
5.4 0.2
10.6 0.40
4.5 0.1
9.3 0.3
14.2 0.40
1.10 0.03
5.9 0.1
10.8 0.30
0.45 0.02
5.6 0.2
10.5 0.40
0.56 0.05
5.4 0.3
10.5 0.50

BDL*
10.1 0.30
4.9 0.2
BDL
9.3 0.3
4.7 0.2
BDL
9.9 0.4
4.8 0.2
BDL
9.7 0.5
5.1 0.2
BDL
9.4 0.2
4.6 0.3

0.76 0.04
15.5 0.40
15.5 0.50
4.5 0.1
18.6 0.40
18.9 0.50
1.10 0.03
15.8 0.40
15.6 0.30
0.45 0.02
15.3 0.60
15.6 0.40
0.56 0.05
14.8 0.40
15.1 0.60

94
99

98
98

97
97

1030
1010

97
99

1010
98

93
94

99
96

97
1020

94
92

98
98

95
97

98
97

99
1010

95
97

Cr(III) Cr(VI)

KT Tap Water

Degirmendere
River
Solakli River

Mineral Spring
Water
Spring Water

05
10

05
10

05
10

05
10

05
10

10
05

10
05

10
05

10
05

10
05

Recovery (%)

* Below detection limit.

Table 6. The level of total chromium in the standard reference materials after application of
the presented procedure (pH: 2.0, ligand amount: 5 mg, amount of adsorbent: 300
mg, sample flow rate: 10.0 mL min1, Eluent type and volume: 7.5 mL of 0.05 mol
L- 1 H2SO4 solution in acetone, sample volume: 50 mL, N = 3)
Sample
1

CRM-TMDW-500* (mg L )
BCR-CRM 144R s (mg g1)**

Found value

Certified value

Recovery (%)

19.6 0.2
87.0 5.1

20.0 0.1
90.0 6.3

98
97

* Certified reference material trace metals in drinking water.


** Certified reference material sewage sludge, domestic origin.

seen from Table 5, the method could be applied successfully for the separation, preconcentration and speciation of
trace amounts of chromium in original water samples. The

accuracy of the results was quite satisfactory. Relative error was lower than 6% for both Cr(VI), Cr(III) and total
chromium.

Speciation of Cr(III) and Cr(VI)

J. Chin. Chem. Soc., Vol. 54, No. 3, 2007

The accuracy of the proposed separation/preconcentration method was examined by determination of total
chromium in certified reference drinking water materials
(CRM-TMDW-500) from High-Purity Standards, Inc. and
certified reference sewage sludge, domestic origin (BCRCRM 144R s) from the Institute for Reference Materials

633

and Measurements (IRMM). The results are given in Table


6. The results show that this system provided analytical
data within the ranges of the certified values.
The proposed preconcentration method was applied
to the determination of chromium in environmental samples. Environmental samples, except for the water sample,

Table 7. The level of chromium species in environmental sample from Trabzon, Giresun and
Rize after application of the presented procedure (pH: 2.0, ligand amount: 5 mg,
amount of adsorbent: 300 mg, sample flow rate: 10.0 mL min1, Eluent type and
volume: 7.5 mL of 0.05 mol L- 1 H2SO4 solution in acetone, sample volume: 50 mL,
N = 3)
Concentration (mg L1)

Sample
Tap water
Degirmendere River
Solakli River
Mineral Spring Water
Spring Water

Chromium(III)

Chromium(VI)

3.8 0.2
22.5 0.50
5.5 0.1
2.3 0.1
2.8 0.3
Total Chromium (mg g-1)

BDL
BDL
BDL
BDL
BDL

1.01 0.05
10.1 0.40

Moss
Rock*

* Rock sample was determined as 10.7 mg/g (RSD: < 5%) by ACME Analytical Laboratory
(ISO 9002 Accredited Co.) in CANADA.

Table 8. Comparative data from some recent studies for preconcentration and speciation of chromium using SPE methods and detection
by FAAS
System

Flow rate,
mL min1

PF

Resin capacity,
mg g1

LOD,
mg L1

Ref.

0.2 mol L1 NaOH

15

15

10

Methanol

65

3000

225 mg

0.02

17

1 mol L1 HNO3 in acetone


0.05 mol L1 HCl

7.0
1.0

25
75

4.40
0.90

1.28
1.0

19
32

2 mol L1 HNO3 in acetone


1 mol L1 HCl in acetone
0.05 mol L- 1 H2SO4 in
methanol
2 mol L1 HCl

5.0
5.0
1.5

71
1250
25

4.50
4.76
0.40

0.75
2.70
45

33
34
35

5.0

58

36

1 mol L1 HNO3 + 0.1%


methanol (v/v)
Acetone

25

720 mg

37

2.0

30

15 Cr(VI),
20 Cr(III)
3.4

0.05 mol L- 1 H2SO4

10.0

80

Column 7.4
Batch 8.0

pH

Melamine-urea-formaldehyde
2.0
resin
C-18 octadecyl silica disks/
4.0
TEBD
Amberlite XAD-2010/DDTC
2.5
Amberlite XAD-16/shellac
4.5
sorbent
Chromosorb 108/dithizone
8.0
Ambesorb 563/APDC
2.5
Amberlite XAD-16/1,51.0
diphenylcarbazide
Amberlite XAD-2/5-palmitoyl4.5
8-hydroxyquinoline
C-18 bonded silica disks/cetyl
7.0-8.0
trimethyl ammonium bromide
Ambersorb 563/1,50.05 mol L- 1
diphenylcarbazide
H2SO4
Amberlite XAD-2000/APDC
2.0

Eluent

0.6

LOD: Limit of detection, PF: Preconcentration factor, SPE: Solid-phase extraction, TEBD: (E)-N1-((1-thiophen-2-yl)ethylidene)benzene-1,2-diamine, APDC: Ammonium pirrolidinedithiocarbamate, DDTC: Diethyldithiocarbamate.

38
This
work

634

J. Chin. Chem. Soc., Vol. 54, No. 3, 2007

were digested in a microwave digestion system. The results


are given in Table 7.

CONCLUSION
The proposed separation and preconcentration method
using XAD-2000 as a sorbent material for FAAS has been
evaluated and demonstrated to be promising for routine
speciation and determination of chromium at low levels in
environmental samples. A 80-fold enrichment factor was
obtained. The methodology proposed has shown adequate
accuracy and selectivity, besides being simple and economical.
The method was also compared with other preconcentration/speciation procedures for chromium in the literature. The suggested procedure has a relatively high preconcentration factor, flow rate and resin capacity, and low
LOD when compared to similar methods given in Table 8.

ACKNOWLEDGEMENTS
Authors thank the Unit of the Scientific Research
Projects of Karadeniz Technical University for financial
support.

Received October 30, 2006.

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