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Spectrochimica Acta Part B 60 (2005) 531 535

www.elsevier.com/locate/sab

Analytical note

On-line preconcentration and determination of chromium in parenteral


solutions by inductively coupled plasma optical emission spectrometry
R.A. Gila, S. Ceruttia,b, J.A. Gasqueza, R.A. Olsinaa,b, L.D. Martineza,b,T
a

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

chromium content which exceeds, in part considerably the


suggested threshold concentration of 5Ag l 1 [1,2].
Several studies indicate that TPN solutions should not
be further supplemented with Cr. The manufacturers of
amino acid, dextrose, lipid, and salt additives used in TPN
solutions need to carefully monitor, and reduce as
necessary, its Cr concentrations to avoid an increase in
the bodys burden of Cr, even during short-term parenteral
infusion. [35].
There are several techniques which have been used for
determination and speciation of chromium at low concentrations, such as inductively coupled plasma optical
emission spectrometry (ICP-OES) [6], electrothermal
atomic absorption spectrometry (ETAAS) [7,8], energy
dispersive X-ray fluorescence (EDXRF) [9], flame atomic
absorption spectrometry (FAAS) [10,11], inductively
coupled plasma-mass spectrometry (ICP-MS) [12], spectrophotometric determinations [13], among others.

532

R.A. Gil et al. / Spectrochimica Acta Part B 60 (2005) 531535

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]

Although the ICP-OES or ETAAS are the most used


techniques in the determination of traces of chromium, the
low level of chromium concentration in parenteral solutions
is not compatible with the detection limits of these
techniques. In order to achieve accurate, reliable and
sensitive results, preconcentration is needed when the
concentration of the elements in the sample are too low to
be determined directly by the analytical technique.
Various preconcentration techniques for the determination
of chromium have been proposed, including chelation,
sorption on any sorbent and ion-exchange resins [6
11,13,14]. Table 1 shows a comparison among preconcentration procedures developed for chromium determination.
Since its introduction in analytical chemistry, activated
carbon (AC) has been used as a collector, permitting the
preconcentration and separation of low levels of analytes in
several matrices [1517]. The mechanism of sorption on AC
is still under investigation. The most common models used
for heavy metals adsorption are the classic empirical
adsorption (e.g. Langmuir and Frendlich equations). The
major advantage of these models is their simplicity; however,
the models fail to describe accurately the sorption equilibrium
under varying conditions, such as pH and ionic strength. The
adsorption equilibrium studies have revealed that pH is the
dominant parameter controlling the adsorption [18].
In the present work, a method for on-line preconcentration and speciation of chromium coupled to ICP-OES
determination is proposed. 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). Chromium was retained by sorption on the minicolumn packed with activated carbon in the absence of a
complexing reagent, under the form of Cr(III), the pH
values adjustment of the solution suffices to retain
chromium (III) ion. The determination was performed by
ICP-OES associated with a flow injection (FI) methodology.

2. Experimental
2.1. Reagents
The activated carbon (Merck, Darmstadt, Germany, 50
70 mesh) was used after pretreatment with acid [activated

carbon was heated with 10% (v/v) hydrochloric acid for 30


min and then with 10% (v/v) nitric acid for 20 min and
finally washed with deionized water at neutral pH was
reached].
A stock standard solution of 1000 mg l 1 Cr(III) was
prepared from 7.6960 g chromium nitrate (Cr(NO3)3 9H2O,
Merck) dissolved in ultrapure water and diluted to a final
volume of 1000 ml. A stock standard solution of 1000 mg
l 1 Cr(VI) was prepared from 2.8290 g potassium dichromate (K2Cr2O7, Merck) dissolved in ultrapure water and
diluted to a final volume of 1000 ml.
A buffer solution was prepared by diluting a 2.0 mol l 1
acetic acid solution adjusted to pH 5.0 with sodium
hydroxide.
Ultrapure water (18 MV cm) was obtained from EASY
pure RF (Barnsted, Iowa, USA). All the reagents were of
analytical-reagent grade and the presence of chromium was
not detected within the working range.
2.2. Instrumental
The measurements were performed with a ICP-OES
[BAIRD (Bedford, MA, USA) ICP 2070]. The 1 m-Czerny
Turner monochromator had an holographic grating with
1800 grooves mm 1. The ICP operating conditions are
listed in Table 2. A minipulse peristaltic pump [Gilson
(Villiers, Le-Bell, France)] was used. Sample injection was
achieved using a Rheodine Model 50 4-way (Cotati, CA,
USA). A conical minicolumn (40 mm length, 4.5 mm
internal upper-diameter and 1.5 mm internal lower-diameter) was used as the AC holder. Pump tubesTygon type
(Ismatec, Cole-Parmer Instrument, Niles, IL, USA) were
employed to propel the sample and eluent. The 283.653 nm
emission line was used and measurements of the FI system

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

R.A. Gil et al. / Spectrochimica Acta Part B 60 (2005) 531535

were expressed as peak height, which was corrected against


the reagents blank.

533

2.6. Preconcentration procedure and determination


Before loading, the column was conditioned for preconcentration at the correct pH with the buffer diluted (1 : 10)
solution, valve V1 in position B (Fig. 1). The sample (25 ml)
was then loaded on the AC at flow rate of 15 ml min 1 with
valve V1 in position S and valve V2 in load position (a).
Finally, valve V2 was switched to the injection position (b)
and the retained metal was eluted with 10% (v/v) nitric acid
directly in pneumatic nebulizer and subsequently to the ICPOES. The operating conditions were established and the
determination was carried out. Due to the characteristics of
the proposed system, the standard solutions were also passed
through the minicolumn.

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.

3. Results and discussion


3.1. Parameters controlling the preconcentration
In order to optimize the sorption conditions for the
retention of the chromium on AC, the chromium signal was
monitored by measuring it with ICP-OES while changing
the pH of the solution that passes through the conical
minicolumn packed with AC. Fig. 2 shows that the optimal
pH values for Cr(III) retention were in the range of 4.55.5.
Accordingly, the selected pH was 5.0. On the other hand,
Cr(VI) was not retained on the activated carbon at any pH
value.
The sample flow rate through the column packed with
AC is a very important parameter, since this is one of the
steps that controls the time of analysis [19]. We could

2.5. Reduction of Cr(VI) to Cr(III) prior total chromium


determination
In order to determine total chromium, it is necessary to
reduce Cr(VI) to Cr(III) prior to sorption on AC. This was
made by heating solutions in HCl 0.1 mol l 1 at 50 8C using
1ml of 99.8% (v/v) ethanol as reductant reagent and then,
the solution was diluted up to 50 ml. After that, Cr(VI) is
completely reduced in an hour.

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

R.A. Gil et al. / Spectrochimica Acta Part B 60 (2005) 531535

3.3. Validation study


100

Due to the method of standard addition is considered as a


validation method [20]; we used it in order to demonstrate
the validity of this method. Then, 500 ml of parenteral
solution were collected and divided into twenty portions of
25 ml each. The proposed method was applied to ten
portions (five for Cr(III) and five for Cr(VI)) and the
average quantity of each specie was taken as a base value.
Then increasing quantities of Cr(III) and Cr(VI) were added
to the other aliquots of sample and the analyte was
determined by the same method. As shown in Table 3 as
an example, the recovery values are between 98.0102.0%
for Cr(III) and 96.6101.0% for Cr(VI). The results were
compared with the t-test and no significant differences were
observed at 95% confidence level [21,22]. The recovery
studies for the other samples showed similar recovery
percentages.

Relative response (%)

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).

verify that with flow rates up to 15 ml min 1 there are


no effect on the analyte recovery which in optimum
conditions is 80%; at higher flow rates the recovery
decreases.
In order to elute the analyte sorbed on AC, nitric acid
was chosen as eluent. The chromium signal was monitored
by measuring it with ICP-OES while changing the nitric
acid concentration. We could verify that with nitric acid
concentrations between 1015% (v/v) there is no effect on
the analyte recovery.
3.2. Interferences
The effects of representative potential interference
species (at the concentration levels at which they may
occur in the studied sample) were tested. Cu2+, Zn2+,
Pb2+, Cd2+, Ni2+, Co2+, Mn2+, and Fe3+ could be
tolerated up to at least 500 Ag l 1 . Commonly
encountered such alkali and alkaline elements are not
retained on the AC under working conditions. On the
other hand, anions such as CO32 , F , SO42 , Cl , PO43 ,
malonate and ascorbate could be tolerated up to at least
1000 Ag l 1.
The recoveries are not influenced by these ions because
they are not retained on the AC at pH 5.0 prior to the elution
of chromium and can be easily washed out through the AC
allowing for highly selective determination of chromium in
the presence of other ions. The value of blank signal was not
modified by the presence of potentially interfering ions
assayed.

3.4. Analytical performance


The overall time required for preconcentration of 25 ml
of sample (1.67 min, at a flow rate of 15 ml min 1), elution
(0.4 min, at a flow rate of 2 ml min 1), and washing and
conditioning (0.4 min) was about 2.47 min; hence,
throughput was approximately 25 samples h 1. An enrichment factor of 70 was obtained with respect to the
chromium determination in parenteral solutions by ICPOES without preconcentration.
The reproducibility of the preconcentration method was
evaluated by passing 25 ml of standard solution of
chromium (5 Ag l 1) through the minicolumn and
repeating this procedure ten times. The relative standard
deviation (RSD) was 2.3%, calculated from the peak
heights obtained. The calibration graph using the precon-

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.

R.A. Gil et al. / Spectrochimica Acta Part B 60 (2005) 531535

centration system for chromium was linear with a


correlation coefficient of 0.9995 at levels close to the
detection limit up to at least 60 Ag l 1. The detection limit
(DL) was calculated as the amount of chromium required
to yield a net peak that was equal to three times the
standard deviation of the background signal (3r). The
value of DL obtained for the preconcentration of 25 ml of
aqueous solutions of Cr was 29 ng l 1.
Finally, the method was applied to the chromium
determination in parenteral solutions. The concentrations
were in the range 0.33.4 Ag l 1 of chromium (III). On the
other hand, Cr(VI) was not detected on any sample. The
results obtained are in good agreement with those of PluhatorMurton et al. [2]. The maximum concentration of chromium
in parenteral solutions reported by these authors is 5 Ag l 1.

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).

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