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Analytical note
Department of Analytical Chemistry, Faculty of Chemistry, Biochemistry and Pharmacy, National University of San Luis,
Chacabuco and Pedernera, P.O. Box 375, 5700 San Luis, Argentina
b
Consejo Nacional de Investigaciones Cientficas y Tecnicas (CONICET), Rivadavia 1917, CP C1033 AAJ, Ciudad de Buenos Aires, Argentina
Received 1 December 2004; accepted 15 February 2005
Available online 2 April 2005
Abstract
A method for the preconcentration and speciation of chromium was developed. On-line preconcentration and determination were
obtained using inductively coupled plasma optical emission spectrometry (ICP-OES) coupled with flow injection. To determinate the
chromium (III) present in parenteral solutions, chromium was retained on activated carbon at pH 5.0. On the other hand, a step of reduction
was necessary in order to determine total chromium content. The Cr(VI) concentration was then determined by difference between the total
chromium concentration and that of Cr(III). A sensitivity enrichment factor of 70-fold was obtained with respect to the chromium
determination by ICP-OES without preconcentration. The detection limit for the preconcentration of 25 ml of sample was 29 ng l 1. The
precision for the 10 replicate determinations at the 5 Ag l 1 Cr level was 2.3% relative standard deviation, calculated with the peak heights.
The calibration graph using the preconcentration method for chromium species was linear with a correlation coefficient of 0.9995 at levels
near the detection limits up to at least 60 Ag l 1. The method can be applied to the determination and speciation of chromium in parenteral
solutions.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Chromium speciation; On-line preconcentration; Activated carbon; ICP-OES; Parenteral solutions
1. Introduction
Total parenteral nutrition (TPN) can be defined as the
procedure by which all required nutrients are administered
intravenously [1].
Parenteral solutions have been identified as chromium
sources. The importance of trace elements in the nutritional management of patients receiving total parenteral
nutrition is now widely recognized. Long-term TPN
patients can inadvertently receive significant amounts of
chromium present as contaminant in TPN. Many of the
solutions for parenteral nutritional support could have a
T Corresponding author. Department of Analytical Chemistry, Faculty of
Chemistry, Biochemistry and Pharmacy, National University of San Luis,
Chacabuco and Pedernera, P.O. Box 375, 5700 San Luis, Argentina.
Fax: +54 2652 430224.
E-mail address: ldm@unsl.edu.ar (L.D. Martinez).
0584-8547/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2005.02.008
532
Table 1
Procedures for preconcentration and determination of chromium
Sampling
frequency (h 1)
Detection limit
Cr(III) (Ag l 1)
Relative standard
deviation (%)
Enrichment
factor
Sample
volume (ml)
Retention
(%)
Technique
References
25
7.5
10
10
0.029
0.02
0.14
400
0.02
0.02
2.3
b5.0
b4.0
3.8
2.9
70
10
7.4
50
50
50
25.0
5.0
50
50
50
80
5464
15
80
80
ICP-OES
ICP-OES
ETAAS
EDXRF
FAAS
FAAS
This work
[6]
[7]
[9]
[10]
[14]
2. Experimental
2.1. Reagents
The activated carbon (Merck, Darmstadt, Germany, 50
70 mesh) was used after pretreatment with acid [activated
Table 2
ICP-OES instrumental parameters employed for chromium determination
Forward power
RF generator
Nebulizer
Coolant gas flow rate
Auxiliary gas flow rate
Carrier gas flow rate
Solution uptake rate
Observation height (above load coil)
1.0 kW
40.68 MHz
Glass, Meinhard
8.5 l min 1
1.0 l min 1
0.5 l min 1
1.5 ml min 1
15 mm
533
2.3. Samples
Samples analyzed were collected from the Argentinean
market. The samples under study were: Ringer Physiological Solution (100 ml: 0.86 g NaCl, 0.03 g KCl, 0.03 g
CaCl.2H2O, H2O); KCl Parenteral Solution (100 ml: 7.45 g
KCl, H2O); NaHCO3 Parenteral Solution (100 ml: 8.4 g
NaHCO3, H2O) and Isotonic dextrose 5% Physiological
Solution (100 ml: 5 g d-glucose monohydrate, H2O).
2.4. Column preparation
The conical minicolumn was prepared by replacing 100
mg of AC into an empty conical tip using the dry packing
method. To avoid loss of AC when the sample solution
passed through the conical minicolumn, a small amount of
quartz wool was placed a both sides of conical minicolumn.
The column was then connected to a peristaltic pump with
PTFE tubing to form the preconcentration system.
V2
P
(a)
V1
B
E
(b)
To Nebulizer
M
To Nebulizer
Pneumatic
Nebulizer
Plasma
Torch
Fig. 1. Schematic diagram of the instrumental setup. S, sample; B, buffer diluted; E, eluent; W, waste; P1 and P2, peristaltic pumps; M, minicolumn; V1, two
way valve, V2, load injection valve ((a) load position; (b) injection position).
534
80
60
40
20
0
0
10 11
pH
Fig. 2. Dependence of retention of Cr(III) on pH of loading solutions
(95% confidence interval, n = 6). Preconcentration of 25 ml of Cr(III)
solutions; chromium concentration was 50 Ag l 1; nitric acid concentration was 10% (v/v).
Table 3
Recovery study (95% confidence interval, n = 6)
Aliquots
Base value
(Ag l 1)
Quantity of Cr
added (Ag l 1)
Quantity of Cr
found (Ag l 1)
Recovery
(%)a
1b
2b
3b
4b
5b
6c
7c
8c
9c
10c
0.60
0.60
0.60
0.60
0.00
0.00
0.00
0.00
0.00
0.50
1.00
2.00
3.00
0.00
0.30
0.50
1.00
1.50
0.60 F 0.05
1.11 F 0.04
1.58 F 0.04
2.60 F 0.03
3.54 F 0.05
NDd
0.29 F 0.03
0.49 F 0.04
1.01 F 0.04
1.49 F 0.03
102.0
98.0
100.0
98.0
96.6
98.0
101.0
99.3
The detection limit was calculated such as was defined in the Analytical
Performance section.
a
100 [(found base) / added].
b
Recuperation for Cr(III).
c
Recuperation study for Cr(VI) (The concentration of Cr(VI) found was
obtained such as is mentioned in Introduction section).
d
ND: not detected.
4. Conclusions
The work described in this paper has shown that
adequate sensitivity and accuracy can be attained using an
on-line preconcentration/speciation system with a FIICPOES method. The coupling of an on-line system with FI
ICP-OES increases the speed of the of the preconcentration
and analysis process, and reduces sample consumption and
contamination risks. The manifold presented provided a
recovery of 80% of the Cr(III) from the minicolumn. The
proposed system of preconcentration and speciation associated with ICP-OES allowed the Cr(III) and Cr(VI) (which
was spiked) determination in parenteral solutions at
concentrations as low as Ag l 1.
Acknowledgements
This work was supported by Consejo Nacional de
Investigaciones Cientficas y Tecnicas (CONICET); Agencia Nacional de Promocio n Cientfica y Tecnolo gica
(FONCyT) (PICT-BID); Programa FOMEC and Universidad Nacional de San Luis (Argentina).
References
[1] Environmental Protection Agency, Toxicological review of trivalent
chromium (CAS No.16065-83-1), Support of Summary Information
on the Integrated Risk Information System (IRIS), U.S. Environmental Protection Agency, Washington DC, 1998.
[2] M.M. Pluhator-Murton, R.N. Fedorak, R.J. Audette, B.J. Marriage,
R.W. Yatscoff, L.M. Gramlich, Trace element contamination of total
parenteral nutrition, Jpen-Parenter. Enter. 23 (1999) 222 227.
[3] Environmental Protection Agency, Toxicological review of hexavalent
chromium (CAS No.18540-29-9), Support of Summary Information
on the Integrated Risk Information System (IRIS), U.S. Environmental Protection Agency, Washington DC, 1998.
[4] F.Y. Leung, Trace elements in parenteral micronutrition, Clin.
Biochem. 28 (1995) 561 566.
535