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Effervescence-assisted dispersive micro-solid phase extraction

Guillermo Lasarte-Aragons, Rafael Lucena, Soledad Crdenas and Miguel Valcrcel

Department of Analytical Chemistry. Institute of Fine Chemistry and Nanochemistry.
Marie Curie Building (Annex). Campus de Rabanales. University of Crdoba.14071 Crdoba

Extraction techniques plays a key role in the majority of analytical methodologies,
allowing isolation and/or pre-concentration of the target analytes from the sample
matrix, which considering their (usually) low concentration led to an improvement in the
sensitivity and selectivity of the determination. The efficiency of these techniques may
be defined by thermodynamic (as measure of the potential transfer of target analytes
from donor phase to aceptor phase) and kinetic aspects (as measure of the velocity of
the cited transfer), both of relevance. Solid phase extraction (SPE) is a surfacedependent process whichis controlled by the available active surface and particle size
of the sorbent [1]. In fact, most of the situations do not take advantage of the extractive
potential of the technique, due to the aggregation tendency of the sorbent, which
reduces dramatically the available surface area [2]. This behaviour is specially
significant in the case of nanostructured sorbents, such as carbon nanotubes [3] or
magnetic nanoparticles [4]. In fact, aggregation tendency is a critical aspect when the
sorbent amount employed in the microextraction technique is reduced to few milligrams
or even micrograms, due to the limited extractive capacity.
Anastassiades et al. proposed the dispersive solid phase extraction technique (D-SPE)
in 2003 [5], which main objective is the selectivity enhancement. The DSPE
procedures are based on two key aspect, namely: (i) the effective dispersion of the
sorbent or active material on the sampleand, (ii) the quantitative phase separation. The
dispersion process takes place usually by application of external energy viz. of
mechanical agitation or ultrasound irradiation.
On the other hand, in micro solid-phase extraction (D-SPE), small amounts of sorbent
are added to the liquid extract or sample for the isolation of analytes and further eluted
in a few microliters of organic solvent, after eliminating the liquid phase and drying.
Generally, the dispersed phase includes organic solvents such as methanol or
acetonitrile as dispersant agents, but in most of the cases they interfere with the

extraction process increasing the analytes solubility on water samples, with the
consequent reduction of the extraction efficiency [6,7].
With the aim of reducing the use of organic solvents and enhancing the dispersability
of the sorbent in the sample matrix new dispersion alternatives are desirable. Our
research group recently developed a new dispersion approach namely "Effervescenceassisted micro solid phase dispersion", based on in situ generation of CO2 within the
aqueous sample to disperse a polymeric [8] or nanostructured [9] sorbent. The
suitability of the alternatives have been demonstrated out by the determination of
organic contaminants in water samples such as nitroaromatic compounds in the case
of polymeric sorbent and triazine herbicides in the case of carbon nanotubes.
However, the dispersability of extractants is a critical aspect not only in solid phase
extraction but also in liquid phase modes. In this sense, we recently develop a new
modality of co-dispersion of organic solvent at the low microliter level and magnetic
nanoparticles in effervescent mode by using a dispersion of 1-Octanol/magnetic
nanoparticles in acetic acid in order to extract and preconcentrate triazine herbicides in
water sample containing a CO2 precursor such as sodium carbonate. Phase separation
was rapid and affective by the synergist effect of dispersion forces and magnetic
In view of the obtained results, the effervescent-assisted alternative is a suitable mode
of dispersion of the extractant in solid or liquid extraction approaches within the
aqueous sample. The proposed alternatives present favorable analytical features for
the model analytical problems selected.
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5. M. Anastassiades, S.J. Lehotay, D. Stajnbaher, F.J. Schenck, J. AOAC Int. 86
(2003) 412
6. F.Galn-Cano, R.Lucena, S.Crdenas, M.Valcrcel, Anal.Methods 3 (2011) 991

7. S. Crdenas, Enc. of Anal. Chem John Wiley & Sons Ltd (2010)
8. G. Lasarte-Aragons, R.Lucena, S.Crdenas, M.Valcrcel, J. Chromatogr. A (2011)
9. G. Lasarte-Aragons, R.Lucena, S.Crdenas, M.Valcrcel, Anal. Bioanal. Chem 405
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