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4, 2003
Trends
Jianhua Wang,
Elo Harald Hansen*
Department of Chemistry,
Technical University of
Denmark, Building 207,
Kemitorvet, DK-2800
Kgs. Lyngby, Denmark
*Corresponding author.
Tel.:+45-4525-2346;
Fax:+45-4588-3136;
E-mail: ehh@kemi.dtu.dk
1. Introduction
Appropriate sample pre-treatment prior
to analysis remains inevitably the bottleneck of the entire analytical procedure
with modern instrumentation [1,2].
Flow-injection analysis (FIA) has led to
signicant progress in this eld, not only
in terms of eciency, but also in reliability, rapidity and robustness. Since its
introduction in 1975 [3], this technique,
or rather analytical concept, has grown
into a discipline covered by a series of
monographs and more than 12,500 scientic publications [4]. All this clearly
shows that in the past 27 years FIA has
grown almost exponentially. In fact, it
has been characterized as having gone
0165-9936/03/$ - see front matter # 2003 Published by Elsevier Science B.V. doi:10.1016/S0165-9936(03)00401-1
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Table 1. The applications of mSI-LOV system for micro-miniaturized in-valve uid and microcarrier bead handling as well as appropriate in-valve
interactions followed by real-time monitoring and/or as a front end to CE
LOV system
Applications
Detection
Ref.
mSI-LOV
Phosphate assay
Enzymatic activity assay of protein
Savinase
Fermentation monitoring of ammonia,
glycerol, glucose and free iron
Absorbance
[8,12]
Fluorescence
[8]
Absorbance
[11]
mSI-LOV with
reduction column
Absorbance
[12]
mSI-BI-LOV
(jet-ring-cell)
Fluorescence
Absorbance
[8]
[8]
mSI-LOV-CE
Absorbance
[13]
4. Solving a dilemma
Column-based SPE is among the most ecient and
widely employed on-line separation/pre-concentration
techniques [6,14,15], and the interfacing of SPE with
detection by ETAAS and ICP-MS has received extensive
attention.
In conventional FI, on-line column, pre-concentration systems, the column is used as a permanent
component. For reliable application, the break-through
capacity of the column, the extent of interfering eects
and the particle size of the sorbent material must be
carefully balanced. Although smaller particle sizes
result in higher break-through capacities, ner particles tend to cause progressively tighter packing and
hence create ow resistance in the column. Moreover,
some sorbent materials undergo volume changes, i.e.,
swelling or shrinking, at dierent experimental conditions, which make the situation even worse, not to
mention complicated [16].
Although some approaches to alleviate the ow resistance have been quite successful, such as use of bidirectional ows during loading and elution sequences
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6. Trace-metal examples
In the experiments described below, an aqueous suspension of SP Sephadex C-25 cation-exchange resin (drybead size 40^125 mm; H+- or K+-form) was employed [22].
When using ETAAS as the detection device, two different schemes for dealing with the analyte loaded
beads can be exploited (Fig. 3) [22^24]:
1. after the resin beads have been exposed to a certain amount of sample solution, the loaded beads
are eluted with a small, well-dened volume of
an appropriate eluent, which is ultimately
transported into the graphite tube for quantication, whereupon the used beads are discarded.
New beads are aspirated and fresh columns are
generated for the ensuing sample cycles.
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Figure 3. Illustration of the two possible schemes for dealing with analyte-loaded beads in the renewable micro-column approach. (a) The
analyte-loaded beads are eluted and the eluate is exploited for quantication by ETAAS and/or ICP-MS. (b) The analyte-loaded beads are
transported directly into the graphite tube of the ETAAS, where, following pyrolysis of the beads, the analyte is quantied.
air segmentation, the eluate is transported into the graphite tube [23].
In the second approach (Fig. 5), the separation/preconcentration is carried out in column position C2, and,
on completion, the analyte-retaining beads are, along
with a certain amount of carrier solution, usually
30^40 ml, transferred back to column position C1. (This
is necessary because all external communication is
eected via syringe pump SP). Afterwards, via air segmentation and through port 4, the beads and the carrier zone are transported to the graphite tube of the
ETAAS instrument, where the beads are pyrolyzed and
the analytes quantied [22]. The validity of both
schemes has been demonstrated by the determination
of Ni in biological and environmental samples.
It should be emphasized that, in the bead-pyrolysis
scheme, a temperature of more than 1000 C and a
holding time of ca. 40 s is required to pyrolyze the
beads. These conditions are obviously not applicable for
the determination of metals with a low atomization
temperature, particularly Cd, Bi and Pb. In such cases,
it is necessary to make use of the rst approach comprising an elution step, since the eluate can be pyrolyzed at
substantially lower temperatures as compared to the
beads themselves, which helps to avoid analyte loss
before atomization. This was demonstrated by the
determination of trace levels of Bi in biological and
environmental samples [24].
Table 2 clearly shows that the procedures based on
the employment of renewable columns give much
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Table 2. Comparisons of the performance data for the pre-concentration of Ni and Bi in the SI-BI-LOV system using a renewable column or a permanent
column with uni-directional and bi-directional repetitive operation
With detection by ETAAS
Conventional
Bead pyrolysis
Elution
Ni
Ni
1.5
1.7
10.2, 11.4c
71.1
3.4
9c
72.1
uni-direct.
bi-direct.
Bi
2.3b
Ni
5.8
Ni
4.9
27.0
33.4
42.0
24.0
Ni
2.9
15.0
35.2
Bi
1.7
4.0
28.4 (1.63.2 mg/l)
9.1 (0.041.6 mg/l)
detection by ETAAS, might help to minimize the dispersion [25^27]. Yet, in the experience of the present
authors, with interfacing FI/SI on-line sample pretreatment systems with an ELAN 5000 ICP-MS
[28,29], the use of air segments tend to extinguish the
plasma.
However, dispersion is particularly critical when
using a conventional nebulization system. The low
sample transport eciency of a cross ow nebulizer,
typically 1^2%, might cause an unduly large dispersion of the eluate zone. Therefore, it is clearly not
appropriate for delivering such a small volume of
eluate.
To overcome these drawbacks, a direct-injection,
high-eciency nebulizer (DIHEN) was found to be eective [30]. The eluate zone was sandwiched between
carrier segments, and transport was eected by a continuous infusion pump (IP). Under such conditions, no
signicant dispersion was encountered.
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References
[1] J. Ruzicka, E.H. Hansen, Flow Injection Analysis, 2nd Edn,
John Wiley & Sons, Chichester, Sussex, UK, 1988.
[2] Z. Fang, Flow Injection Separation and Pre-concentration,
VCH Publishers Inc., New York, USA, 1993.
[3] J. Ruzicka, E.H. Hansen, Anal. Chim. Acta 78 (1975) 145.
[4] E.H. Hansen, Flow injection bibliography, http://www.
owinjection.com/
[5] J. Ruzicka, J. Flow Inject. Anal. 15 (1998) 151.
[6] E.H. Hansen, J.-H. Wang, Anal. Chim. Acta 467 (2002) 3.
[7] J. Ruzicka, G.D. Marshall, Anal. Chim. Acta 237 (1990) 329.
[8] J. Ruzicka, Analyst (Cambridge, UK) 125 (2000) 1053.
[9] E.H. Hansen, Anal. Chim. Acta 308 (1995) 3.
[10] J. Ruzicka, in: A. van den Berg, W. Olthuis, P. Bergveld,
(Editors), Micro Total Analysis Systems 2000, Kluwer
Academic Publishers, Dodrecht, The Netherlands, 2000, pp.1^10.
[11] C.-H. Wu, L. Scampavia, J. Ruzicka, B. Zamost, Analyst
(Cambridge, UK) 126 (2001) 291.
[12] C.-H. Wu, J. Ruzicka, Analyst (Cambridge, UK) 126 (2001)
1947.
[13] C.-H. Wu, L. Scampavia, J. Ruzicka, Analyst (Cambridge, UK)
127 (2002) 898.
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[14] E.V. Alonso, A.G. Torres, J.M.C. Pavon, Talanta 55 (2001) 219.
[15] J.L. Burguera, M. Burguera, Spectrochim. Acta Part B 56
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[17] Z.-R. Xu, S.-K. Xu, Z.-L. Fang, Atom. Spectrosc. 21 (2000) 17.
[18] Z.-R. Xu, H.-Y. Pan, S.-K. Xu, Z.-L. Fang, Spectrochim. Acta
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[20] J. Ruzicka, L. Scampavia, Anal. Chem. 71 (1999) 257, A.
[21] J. Ruzicka, Analyst (Cambridge, UK) 123 (1998) 1617.
[22] J.-H. Wang, E.H. Hansen, Anal. Chim. Acta 424 (2000) 223.
[23] J.-H. Wang, E.H. Hansen, Anal. Chim. Acta 435 (2001) 331.
[24] J.-H. Wang, E.H. Hansen, Atom. Spectrosc. 22 (2001) 312.
[25] K. Benkhedda, H.G. Infante, E. Ivanova, F. Adams, J. Anal. At.
Spectrom. 15 (2000) 1349.
[26] K. Benkhedda, H.G. Infante, E. Ivanova, F. Adams, J. Anal. At.
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[27] V. Stefanova, V. Kmetov, L. Futekov, J. Anal. At. Spectrom. 12
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[28] J.-H. Wang, E.H. Hansen, J. Anal. At. Spectrom. 17 (2002)
1284.
[29] J.-H. Wang, E.H. Hansen, J. Anal. At. Spectrom. 17 (2002)
1278.
[30] J.-H. Wang, E.H. Hansen, J. Anal. At. Spectrom. 16 (2001)
1349.
[31] B. Willumsen, G.D. Christian, J. Ruzicka, Anal. Chem. 69
(1997) 3482.
[32] J. Ruzicka, A. Ivaska, Anal. Chem. 69 (1997) 5024.
[33] I. Lahdesmaki, L.D. Scampavia, C. Beeson, J. Ruzicka, Anal.
Chem. 71 (1999) 5248.
Elo Harald Hansen, who is one of the two inventors of FI, is Professor of Analytical Chemistry at the Department of Chemistry, Technical University of Denmark. His research interests are instrumental
and automated analysis with special emphasis on the development
and application of procedures based on FI/SI. In recent years, he has
focused particularly on developing FI/SI schemes for the determination of trace levels of metals in complex matrices by hyphenation with
atomic spectrometric techniques and ICP-MS.
Jianhua Wang obtained his MSc from Nankai University, China.
After employment at Yantai Normal University, he spent one year at
the University of Delaware, USA, before commencing his PhD studies
at the Technical University of Denmark in 1999. He was awarded the
PhD degree in 2002. He is currently pursuing his interests in the
development and use of FI/SI procedures at Northern University,
Shenyang, China, where he has joined Professor Zhaolien Fangs
research group.
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