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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
626
Duran et al.
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
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Duran et al.
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.
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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Duran et al.
Chromium(VI)
1
7.4
8.0
5.0
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).
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
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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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 (%)
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
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.
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
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.
15
15
10
Methanol
65
3000
225 mg
0.02
17
7.0
1.0
25
75
4.40
0.90
1.28
1.0
19
32
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
25
720 mg
37
2.0
30
15 Cr(VI),
20 Cr(III)
3.4
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
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.
REFERENCES
1. White, M. A.; Sabbioni, E. Sci. Tot. Environ. 1998, 216, 253.
2. Barkay, T.; Pritchard, H. Microbiol. Sci. 1988, 5, 165.
3. Hadjiliadis, N. D. Cytotoxic, Mutagenic and Carcinogenic
Potential of Heavy Metals Related to Human Environmen;
Kluwer Academic Publishers, Dordrecht: The Netherlands,
1996.
4. Nriagu, J. O.; Nieboer, E. Chromium in the Natural and Human Environment; Wiley: New York, 1988.
5. Tao, H. Bunseki Kagaku 1997, 46, 239.
6. Barnowski, C.; Jakubowski, N.; Stuewer, D. J. Anal. At.
Spectrom. 1997, 12, 1155.
7. Gwizdala, A. B.; Johnson, S. K.; Mollah, S.; Houk, R. S. J.
Anal. At. Spectrom. 1997, 12, 503.
8. Gjerde, D. T.; Wiederin, D. R.; Smith, F. G.; Mattson, B. M.
J. Chromatogr. A 1993, 640, 73.
Duran et al.