ISSN 1061-9348, Journal of Analytical Chemistry, 2006, Vol. 61, No. 5, pp. 416–441. © Pleiades Publishing, Inc., 2006.

Original Russian Text © L.A. Oliferova, M.A. Statkus, G.I. Tsisin, J. Wang, Yu.A. Zolotov, 2006, published in Zhurnal Analiticheskoi Khimii, 2006, Vol. 61, No. 5, pp. 454–480.

REVIEWS

On-Line Coupling of Sorption Preconcentration

to Liquid-Chromatographic Methods of Analysis
L. A. Oliferovaa, M. A. Statkusa, G. I. Tsisina, J. Wangb, and Yu. A. Zolotova
a Department of Chemistry, Moscow State University, Vorob’evy gory, Moscow, 119992 Russia
b Research Center for Analytical Sciences, Northeastern University, China

Received April 26, 2005

Abstract—Methods of analysis combining the on-line sorption preconcentration of analytes with their subse-
quent separation and determination by high-performance liquid chromatography are considered. Approaches to
the selection of sorbents, the sizes of preconcentration columns, and the sorption and desorption conditions are
discussed along with the corresponding instrumentation. Many examples of the determination of organic com-
pounds of different polarity and organic and inorganic ions are presented.
DOI: 10.1134/S1061934806050029

High-performance liquid chromatography (HPLC)
is currently one of the most popular automated and ver-
satile methods for the analysis of complex mixtures of
organic and inorganic compounds. This method is
widely used for the separation and determination of
proteins and other large molecules, narcotics, medi-
cines, pesticides, and inorganic cations and anions.
However, the possibilities of this method, even with the
use of modern detectors, are frequently limited by
insufficient sensitivity and selectivity. For example, dif-
ficult problems for HPLC are the determination of the
majority of organic and inorganic environmental toxi-
cants in natural waters at a level of maximum permissi-
ble concentrations and microcomponents in biological
fluids and other solutions of complex composition.
These problems are solved with the use of preconcen-
tration.
In combined methods of analysis, preconcentration
is performed in the off-line or on-line mode. The first
technique is technically simpler and more popular,
because the steps of preconcentration and determina-
tion are independent and separated in time. In this
mode, it is reasonable to perform preconcentration
directly during sampling in field conditions in the case
of large volumes of samples (e.g., water) to attain large
concentration coefficients of compounds and when the
macrocomposition of the concentrate must be substan-
tially changed before the chromatographic determina-
tion. Off-line preconcentration methods are hardly
automated. In spite of their laboriousness and the pos-
sibility of the contamination of the concentrate or the
loss of part of it, these methods provide the develop-
ment of unified procedures for sample preparation,
which can be performed in both stationary and field and
mobile laboratories. Off-line preconcentration is
widely used in combination with HPLC; this field is
adequately elucidated in several reviews and mono-
graphs, e.g., in [1].
In the last 20 years, flow-injection methods of anal-
ysis with the step of on-line preconcentration [2]
including sorption–HPLC methods [3] have been
intensely developed. In this case, preconcentration and
determination are successively performed in the cyclic
mode, and a concentrate is obtained under nonequilib-
rium conditions and delivered to a detector as liquid or
gas [2]. Commonly, these methods are fully automated
and exhibit high sensitivity (usually 1–2 orders of mag-
nitude higher than the same methods without precon-
centration), high performance, and reproducibility,
which is due to the use of closed systems and exact dis-
pensing of solutions [2].
The selection of a preconcentration method is gov-
erned by the properties of microcomponents (hydro-
phobicity, volatility, molecular mass, etc.), the concen-
tration coefficient necessary for attaining the given sen-
sitivity of determination, and the requirements on the
macrocomposition of the concentrate. Liquid extrac-
tion, which is widely used for the extraction of com-
pounds from solutions, has some disadvantages: the use
of toxic organic solvents, difficulties in automation, and
sometimes rather low concentration coefficients. Sorp-
tion preconcentration is more technologically conve-
nient, minimum amounts of solutions (solvents) are
required for desorption, and significantly larger con-
centration coefficients are attained in this case. A par-
ticularly promising technique is dynamic sorption,
which does not require phase separation and opens up
possibilities of the automation of the whole cycle of the
analysis including the step of sample preparation. Note
that on-line preconcentration is reasonable only in the
case when the time of preconcentration is comparable
with the time of the subsequent chromatographic deter-
mination; otherwise, unproductive expenses increase

416
 ON-LINE COUPLING OF SORPTION PRECONCENTRATION
because of the idle operation of chromatographic
instruments, which is especially important when
expensive instruments and consumable materials (elu-
ents, inert gases, etc.) are used.
This review involves the discussion of the funda-
mentals of the on-line sorption–HPLC determination of
organic and inorganic compounds in aqueous solutions,
selection of sorbents and preconcentration conditions,
and areas of the use of this method.
FUNDAMENTALS OF THE METHOD
In the simple version, the cycle of analysis includes
the preconcentration of specified compounds (micro-
components) from solutions on a minicolumn with a
sorbent, their desorption with the introduction of the
concentrate into a chromatographic column, and subse-
quent chromatographic separation and determination
[3]. More complex versions include the preconcentra-
tion of microcomponents on several columns arranged
in series with subsequent separate desorption [4], a
change in the macrocomposition of the concentrate [5,
6], or the modification of microcomponents after des-
orption before introduction into the chromatographic
column [7–9], cutting a part of the solution from the
flow for introduction into the chromatographic column
[10–13], and other procedures.
Nearly all of the proposed combined methods are
improved versions of corresponding HPLC methods
developed previously; i.e., the conditions of the chro-
matographic analysis are identical for the direct and
combined versions [14, 15]. On the one hand, this sim-
plifies the development of the combined method; how-
ever, on the other hand, this is its limitation, because the
macrocomposition of the concentrate after desorption
must be identical to the composition of the eluent for
the chromatographic separation of compounds.
In spite of the seeming simplicity of the cycle of
analysis and known conditions of the HPLC determina-
tion, to attain good performance characteristics, it is
necessary to cautiously select sorbents for preconcen-
tration and the composition of solutions for washing
and desorption and to optimize the size of the precon-
centration column and hydrodynamic modes for per-
forming all steps. Unfortunately, in the majority of pub-
lished works, this optimization was not performed;
only the particular conditions of experiments were
given, and the units of the flow systems were described.
Selection of sorbents for preconcentration. Flow
sorption–HPLC methods were proposed for the deter-
mination of hundreds of compounds. These compounds
can be arbitrarily subdivided into hydrophobic (low-
polarity), polar, and dissociating in aqueous solutions.
In the latter case, organic and inorganic ions are deter-
mined. Commonly, sorbents for preconcentration are
selected on the basis of this classification: low-polarity
compounds are extracted on low-polarity or nonpolar
sorbents (so-called reversed-phase sorbents), polar
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61
417
compounds are extracted on more polar sorbents, and
inorganic and organic ions are extracted on ion
exchangers (Table 1).
General requirements on sorbents for use in on-line
systems for analysis were previously formulated for on-
line sorption–spectrometric systems for the determina-
tion of elements in solutions [2, 78]. Evidently, the
same requirements are also valid for sorption–HPLC
systems:
the microcomponent must be quantitatively
extracted at a high flow rate of the solution; this pro-
vides the rapid accumulation of analytes on the column
in the amounts necessary for reliable detection;
the capacity of the sorbent in the column must be
sufficient for the extraction of the microcomponent
from the analyzed solution in amounts exceeding the
absolute limits of the subsequent determination;
the sorbent must be sufficiently selective for the
extraction of the given microcomponents in the pres-
ence of the other components of the analyzed solution;
to decrease the dispersion of the concentrate zone in
the flow, the size of the column with the sorbent must
be minimum;
the desorption of the microcomponent with a des-
orbing solution suitable for the subsequent determina-
tion must be performed rapidly and quantitatively;
the properties of the sorbent must remain unchanged
after many sorption–desorption cycles.
The majority of works are devoted to methods for
the determination of organic compounds (Table 1).
Chemically modified silica and organic polymer and
carbon sorbents were used for the preconcentration of
these compounds from solutions.
In many works, organic compounds were precon-
centrated on chemically modified silica in the off-line
and on-line modes. In the opinion of the authors of
review [79], this is due in part to the fact that sorbents
based on silica gel are those most frequently used for
the chromatographic separation of compounds, and
their properties and techniques for preparations are
well known. In the course of the synthesis of chemi-
cally modified silica, such important properties as
hydrophobicity, surface area, and pore diameter and
volume can be easily varied [1]. Chemically modified
silica with octadecyl [48, 80, 81], octyl [80], ethyl [82],
cyanopropyl [82], and other groups were used in on-
line sorption–HPLC systems. The presence of residual
polar silanol groups in the composition of chemically
modified silica expands the range of extracted com-
pounds; not only compounds with low polarity
( log K o/w > 3, where Ko/w is the distribution coefficient
of the compound in the octanol–water system), but also
compounds with medium polarity (3 > log K o/w > 2)
were efficiently extracted [82–85].
Polymer sorbents, which are copolymers of styrene
and divinylbenzene with different (commonly, high)
No. 5 2006
 Table 1. Sorbents and conditions of the preconcentration of compounds in flow analysis systems
418

v* in des-
Particle Column v* in preconcen- Refer-
Sorbent Preconcentrated compounds orption,
size, µm size, mm tration, mL/min ences
mL/min
Organic polymer sorbents
Highly cross-linked polystyrene sor- Phenol and its chloro and nitro derivatives; aniline and 5–120 10 × 2, 0.6–5 0.2–2 [16–38]
bents PRP-1, PLRP-s (Polymer Labs, some substituted anilines, caffeine; naphthalene monosul- 50 × 1,
Hysphere-1, Hysphere GP, Hysphere fonates and their amino and hydroxy derivatives as ion 10 × 3,
SH, Hysphere-Resin-GP, LiChrolut pairs with tetrabutylammonium; hormones: estrogen, 20 × 2,
EN, Isolute ENV+, PLRP-s membrane, progestogen; pesticides: bentazone, molinate, metolachlor, 20 × 3,
Bond Elut PPL functionalized polymer, etc.; polycyclic aromatic hydrocarbons: naphthalene, an- 4.6**
Bond-Elut Env, Cyclone) thracene, fluorene, etc.
Polymer hydrophilic–lipophilic sorbent Phenol and its chloro and nitro derivatives; hormones: es- 30–60 10 × 2, 4 0.2–2 [22, 25,
Oasis (polydivinylbenzene-N-vinylpyr- trogen, progestogen; pesticides: atrazine, simazine, terbu- 50 × 1 37]
rolidone) tylazine, etc.
Molecularly imprinted sorbent based on Ceramides Monolith- 150 × 4.6 – – [39]
styrene–divinylbenzene ic column
Carbon sorbents
Carbopak B 120/400; Hypercarb Hydroxychloroanilines, aminophenols, and cyanuric acid; 30–50 50 × 1, 4–5 0.2–1 [23, 37,
phenol; hydroxy and methoxy derivatives of benzoic acid 10 × 3 40–42]
and benzaldehyde; aminophenols and 3-aminobenzoic ac-
id; coumaric, sinapinic, and ferulic acids; polar pesticides:
oxamyl, methomyl, carbaryl, etc.
OLIFEROVA et al.

Sorbents based on silica gel

C20 Endogenous retinoids – 20 × 4 1 1 [43]
Bondapak silica gel, 37–53
C18 Chloro and nitro derivatives of phenol; caffeine, morphine, 3–70 10 × 2, 0.2–5 0.1–2 [6, 10,
Spherisorb SS, LiChrospher Si 100, and its derivatives; phthalates; hormones: estrogen, 10 × 2.1, 16, 20,
LiChrospher, LiChrospher 60, Baker, progestogen; medicines: furosemide, cortisol, prednisolo- 50 × 1, 22, 25,
Bondapak, Supelguard LC-18, Empore ne and arachidonic acid, endogenous retinoids, lesopitron 4 × 4, 30, 36,

JOURNAL OF ANALYTICAL CHEMISTRY

disk, UG 120 CAPCELL PAC, Turbo, and its derivatives, almokalant, camptothecin; natural and 20 × 2, 37, 43,
Brown Lee Labs, Pelliguard LC-18, C18 synthetic analogues of vitamin A; nerve gases: sarin, so- 20 × 2.1, 44–59]
HySpere-HD, Machery-Nagel, Zorbax man, and VX; pesticides: triazine, simazine, carbaryl, pro- 35 × 2,
SB, Hypersil, LC-18-DB, ABZ+-plus, panil, linuron, fenamiphos; polycyclic aromatic hydrocar- 10 × 4,

Vol. 61
Symmetry bons: naphthalene, anthracene, fluorene, etc. 10 × 4.3,
15 × 4,
12.5 × 4.6,

No. 5
20 × 3.9,
20 × 4,
20 × 4.6,

2006
30 × 4.6
 Table 1. (Contd.)

Particle size, Column v* during precon- v* during des- Refer-

Sorbent Preconcentrated compounds
µm size, mm centration, mL/min orption, mL/min ences

C8 Tranquilizer lesopitron and its derivatives; herbi- 5, 8, 40–70 10 × 2, 0.5–5 0.1–1.5 [30, 44,
ENVI-8 membranes, C8 with closed cides: paraquat, diquat, etc.; diuron, phenol, and oth- 4.6** 60]
rings er polar trace pollutants of natural water

C4 Aspartic acid and its derivatives 25 25 × 4 0.1 0.5 [61]

LiChrospher (with diol and C4 groups)

C2 Medicines: lesopitron and its derivatives; quetiapine; 8, 25–40 10 × 2, 0.5–5 0.1–2 [44, 50,
Analytichem, C2, Bakerbond, Bond- nifedipine; almokalant; codeine and is derivatives; 15 × 3.2, 62–67]
Elut, Perisorb, LiChroprep lamisil; retigabine, its derivatives and analogues; di- 10 × 4
uron, phenol, and other polar trace pollutants of nat-

JOURNAL OF ANALYTICAL CHEMISTRY

ural waters

Restricted-access silica gels LiChro- Natural and synthetic estrogens and progestogens; 25 25 × 4 0.9–3 0.8–1 [5, 31,
spher C18, C8, C4 pesticides: triazines and chlorotriazines 68]

Vol. 61
Silica gels with the nitrile group Aspec Diuron, phenol, and other polar trace pollutants of 5, 8 10 × 2, 1–5 1–2 [30, 69,
Xli, cyanopropylsilica gel, Stable Bond natural waters; medicines: nortriptyline, trimi- 12.5 × 4 70]

No. 5
Zorbax pramine, and maprotiline; chlorthalidone

Hisep Endogenous retinoids – 20 × 4.6 1 1 [43]

2006
Turbo phenylsilica gel Pesticides: atrazine, simazine, terbutylazine, etc. 30–50 50 × 1 5 0.2 [37]

Immunosorbents based on silica gel: sil- Phenylureas; polycyclic aromatic hydrocarbons: – 30 × 4.6 2 0.5–1 [16, 71]
ica gel with immobilized antibodies (an- naphthalene, anthracene, fluorene, etc.
ti-fluorene)

Ion exchangers
ON-LINE COUPLING OF SORPTION PRECONCENTRATION

Cation exchangers IRC-50, CBA; Aspec Low-molecular amines; biomarkers: pyridinoline 60 5.8 × 4.6, 0.45–4 0.3–2 [9, 72–
Xli and its derivatives; hallucinogens: psilocin and psilo- 10 × 4 75]
cybin; amphetamines: tetrahydrocannabinol and its
derivatives

Anion exchangers: RPR-X100; Dionex Pesticides: chlormequat, mepiquat, glyphosate, etc.; 10 20 × 2 1–5 0.5–1 [76, 77]
AG9-HC IonPac inorganic anions: nitrite, nitrate, and phosphate

* Flow rate of the solution through the preconcentration column.

** Nine PLRP-s membranes with a diameter of 4.6 mm were placed in the column.
419
420 OLIFEROVA et al.
degrees of cross-linking (PRP-1 and PLRP-s), copoly-
mers of divinylbenzene and N-vinylpyrrolidone (Oasis
HLB, which exhibits hydrophilic and lipophilic proper-
ties simultaneously), and others were also used in on-
line sorption–HPLC methods. Polymer sorbents effi-
ciently extract organic compounds of different classes
from aqueous solutions. It was noted that, in compari-
son with chemically modified silica, these sorbents
adsorb polar microcomponents much better [1, 3]. In
addition, polymer sorbents allow the preconcentration
of microcomponents in a wider range of acidity of solu-
tions than chemically modified silica [1]. Fluorocarbon
polymer sorbents were also used for recovery of hydro-
phobic compounds [86–88].
Carbon sorbents were used much less frequently.
This is primarily due to difficulties in the desorption of
compounds from these sorbents. However, the use of
carbon sorbents is necessary in the preconcentration of
the most polar compounds, e.g., cyanuric acid [41],
which is not extracted on chemically modified silica
and organic polymer sorbents.
The common feature of the majority of the above
hydrophobic sorbents in the preconcentration of com-
pounds from aqueous solutions is the necessity of their
preliminary treatment (preconditioning) with a water-
miscible polar solvent (commonly, methanol or aceto-
nitrile) to increase their wettability [1, 89]. In addition,
small amounts of the same solvents must be added to
the analyzed solution to eliminate hydrodynamic hin-
drances in the preconcentration of microcomponents
from large amounts of solutions [16]. One more charac-
teristic feature of these sorbents is the efficient, how-
ever unselective, extraction of a wide range of com-
pounds from aqueous solutions. Therefore, their use for
the extraction of microcomponents from solutions of
complex composition, such as river and waste waters
and biological fluids, is frequently complicated. In
recent years, these problems were solved using less
efficient, but more selective sorbents: restricted-access
materials, molecularly imprinted polymers, fluorocar-
bon polymer sorbents, and immunosorbents.
Different cation [9, 90] and anion [44, 73] exchang-
ers were used for the preconcentration of organic and
inorganic ions in on-line sorption–HPLC systems; ions
were also extracted on reversed-phase sorbents after the
treatment of the sorbents with reagents or as complexes
and ion pairs [19, 91] (Table 1).
Selection of conditions of preconcentration. The
main problem of the preconcentration step in on-line
systems for analysis is the quantitative and, when pos-
sible, selective extraction of microcomponents from
analyzed solutions. The successful solution of this
problem is provided by the proper selection of the sor-
bent and preliminary procedures that are performed
with the analyzed solution (transformation of micro-
and macrocomponents into the dissociated or molecu-
lar form, conduction of the reaction of derivatization of
solution components, etc.). The character of these pro-
JOURNAL OF ANALYTICAL CHEMISTRY
cedures is highly specific and is governed by the chem-
ical properties of the micro- and macrocomponents of
the solution and the sorbent. In this review, we prima-
rily consider problems of the selection of preconcentra-
tion conditions common for all on-line systems for
analysis: the particle size of the sorbent, the size of pre-
concentration columns, the flow rate of the analyzed
solution, and techniques providing an increase in the
selectivity and sensitivity of the determination of
microcomponents.
In the majority of works, conditions of preconcen-
tration were selected based on the recovery (R) of the
determined microcomponents. Commonly, experimen-
tal conditions were selected so that the microcompo-
nents were extracted quantitatively. Sometimes, at a
low value of R, the internal standard method was used
[3]. Mostly, recovery was used as the criterion for the
selection of the maximum volume of the sample: a
series of experiments was performed with a gradual
increase in the volume of the sample [4, 8, 16, 20, 22,
27–31, 34, 53, 60, 71, 76, 82, 92–102]. The total
amount of the preconcentrated compound in the sample
remained unchanged. The entire cycle of analysis was
performed in each of the experiments. Next, the depen-
dence of recovery (commonly, R was calculated as the
ratio of the areas of the chromatographic peaks of com-
pounds in the direct determination and in the determi-
nation after preconcentration at the same concentration
of the compound in the sample) on the volume of the
sample, the so-called breakthrough curve. Break-
through curves obtained under different conditions
(e.g., at different flow rates of solutions) allowed the
selection of the optimum volume of the sample and
other variable conditions of preconcentration. This
method for the selection of conditions is very time-con-
suming and requires a large number of experiments.
Another parameter which is frequently used for the
selection of conditions of preconcentration is the break-
through volume Vb [3, 103]. The fraction of the com-
pound lost in the course of the experiment is called
breakthrough bI. This value is related to recovery by the
obvious relationship bI = 1 – R. The breakthrough vol-
ume is the maximum volume of the solution of the
microcomponent of the known concentration that can
be passed through the preconcentration column under
the given conditions so that losses of the microcompo-
nent are no higher than bI. However, in the majority of
works, e.g., [104], breakthrough was defined as the
ratio of the current concentrations of the compound at
the outlet and inlet of the preconcentration column:
bD = coutlet /cinlet.
The relationship between bD and recovery is much
more intricate:
Vb
∫b D dV = 1 – R.
0
Vol. 61 No. 5 2006
 ON-LINE COUPLING OF SORPTION PRECONCENTRATION
In review [105], it was proposed to call the quantities bI
and bD the cumulative (integral) and instantaneous (dif-
ferential) breakthrough, respectively.
In several works dealing with the development of
on-line sorption–HPLC methods for the determination
of compounds, the maximum volume of a sample was
assumed equal to Vb [23, 98, 104, 106–109]. In this
case, the quantity bD was used as the breakthrough cri-
terion. The preconcentration column was attached
instead of the chromatographic column directly to the
flow detector, a solution of the microcomponent was
passed at a constant flow rate, and the dynamic elution
curve was obtained. The point corresponding to the
given breakthrough value was selected in the curve, and
the volume of the sample that could be passed through
the column at the preconcentration step was deter-
mined. It is much easier to obtain the dynamic elution
curve than to construct breakthrough curves. However,
because of the insufficient sensitivity of the detector,
the reliable determination of low breakthrough values
is sometimes impossible. In many cases, obtaining
dynamic elution curves required an increase in the con-
centration of the preconcentrated component by several
orders of magnitude in comparison with its concentra-
tion in real samples. For example, a solution of phenol
with a concentration of 10 mg/L was used for obtaining
dynamic elution curves, and the determination was per-
formed at concentrations of phenol of 4–50 µg/L [98].
It is known that the distribution coefficient (which is
directly related to the quantity Vb) depends on concen-
tration [110]. Consequently, Vb determined for high
concentrations of the macrocomponent may not coin-
cide with Vb for low concentrations. The authors of sev-
eral works noted that this approach is not rigorous [3,
107]; however, none of the known works dealing with
the on-line sorption–HPLC determination of com-
pounds presents dependences of Vb on the concentra-
tion of the microcomponent.
The value of Vb was also estimated using the data of
experiments on the chromatographic separation of
compounds [111–115]. In reversed-phase chromatog-
raphy, the use of water with small (1–3 vol %) additions
of organic solvents as the mobile phase commonly
leads to very large retention volumes. Therefore, a
series of experiments was performed varying the con-
centration of a polar organic solvent (commonly meth-
anol or acetonitrile). For example, chromatograms of
some aromatic hydrocarbons and other compounds
were obtained by this technique with the use of a col-
umn with octadecylsilica gel [111]. From the chro-
matogram, the retention volumes Vr were determined.
The value of Vr was extrapolated to the zero concentra-
tion of the polar organic solvent (disadvantages of this
approach were discussed in [103]). Next, using the rela-
tionships obtained from the plate theory for the case of
frontal chromatography [116], breakthrough volumes
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61
421
were calculated (the simplest expression for 1% instan-
taneous breakthrough):
V b = V r ⎛ 1 – --------⎞ ,
2.3
⎝ N⎠
where N is the number of theoretical plates for the pre-
concentrated column. The value of N was determined in
additional experiments or calculated by known
semiempirical relationships (e.g., by the Knox equation
[117]).
Efforts were made to model dynamic elution curves
based on the data on the chromatographic separation of
compounds [118]. The continuous flow of a solution of
a microcomponent is represented as a series of succes-
sive introductions of small volumes of the same solu-
tion into the preconcentration column. This allows the
representation of the dynamic elution curve as the sum
of separate chromatographic peaks shifted in time. The
shape and the elution time of the peak were determined
experimentally. Close agreement between the calcu-
lated and experimental dynamic elution curves was
noted. However, this approach does not differ in labori-
ousness from the calculation of Vb and Vr and provides
no additional information in comparison with this cal-
culation.
The values of Vr and Vb on reversed-phase sorbents
were estimated using correlation equations relating
these values with the logarithm of the distribution coef-
ficient of the microcomponent in the octanol–water
system log K o/w (logD, logP) [106, 112]. It was demon-
strated that the dependence of log V b on log K o/w is lin-
ear for compounds with similar properties [106].
An alternative approach was proposed in [112, 113].
It allows the prediction of retention volumes based on
the previously obtained correlation relationships of the
retention parameters on the physicochemical properties
of the microcomponent, the solvent, and the sorbent
[112, 113]. The main relationship of this model has the
form
log V r = ∑d p , i i
i
where di are the physicochemical properties of the
microcomponent (molar volume, polarizability, etc.)
known before the experiment from the literature or
other sources and pi are the parameters of the sorbent–
solvent system determined by the multiple linear
regression method. The main advantage of this
approach is that the parameters of the system pi are
independent of the nature of the microcomponent;
hence, once obtained, the set of pi (or the dependence
of pi on the composition of the mobile phase) can be
used in subsequent calculations of the retention of any
compound in this system. This allows the estimation of
not only the maximum volume of the sample but also
the volumes and compositions of solutions for washing
No. 5 2006
422 OLIFEROVA et al.
and desorption of microcomponents. However, the
wide use of this model for predicting the optimum con-
ditions of sorption preconcentration is hindered by the
small number of published pi sets and the relatively
complicated calculation of log V r .
The conditions of sorption preconcentration were
selected, and the efficiency of sorbents was compared
with the use of so-called linear models of sorption
dynamics [119]. This approach is based on the solution
of a set of differential equations of the material balance
of the microcomponent and its sorption kinetics and on
the comparison of the calculated and experimental
dynamic elution curves. The values of the main physic-
ochemical parameters characterizing sorption (distribu-
tion and external- and internal-diffusion mass transfer
coefficients), which were obtained as a result of this
comparison, allow the calculation of the optimum
amount of the sorbent, the flow rate of the sample, and
its volume (or passing time) and the correct comparison
of the efficiency of sorbents for the extraction of given
microcomponents. This approach was used to optimize
conditions of the preconcentration of phenol on poly-
mer sorbents [120]. It was demonstrated that hyper-
cross-linked polystyrenes are highly efficient in this
case. The optimum conditions of the preconcentration
of phenol in a flow system were calculated and experi-
mentally confirmed [121]. Unlike other approaches, the
use of linear models allows the simultaneous estimation
of not only thermodynamic properties of sorbents (i.e.,
retention), but also their kinetic efficiency (i.e., the
number of theoretical plates). The wide use of this
approach is hindered by difficulties in calculations.
As noted above, an increase in the efficiency of pre-
concentration was attained not only by the optimization
of general parameters of the sorption system (flow rate
of the solution, size of the preconcentration column,
etc.), but also by the use of techniques specific for the
given micro- and macrocomponents, e.g., their deriva-
tization for increasing the recovery and the removal of
the matrix by the sorption of interfering micro- and
macrocomponents. For example, for the determination
of naphthalene sulfonates in tap and river waters, these
compounds were converted into ion pairs with tetrabu-
tylammonium [8, 19]; for the determination of heavy
metal ions in potable and waste waters and methyl-,
ethyl-, and phenylmercury in model solutions, they
were converted into diethyldithiocarbamate, pyrro-
lidinedithiocarbamate, and 8-hydroxyquinolinate com-
plexes [91, 102, 122]. In the determination of bromate
in ozonized potable water, water samples before analy-
sis were passed through a column with the Guard Ag
cation exchanger for the separation of chloride and bro-
mide matrix components, which occurred in large
excess [123, 124]. On this column, chloride and bro-
mide were extracted, and bromate was not retained.
Another example of chemical processes providing an
increase in the efficiency of the on-line sorption–HPLC
determination of compounds is the neutralization of
JOURNAL OF ANALYTICAL CHEMISTRY
acidic and alkaline solutions in the determination of
anions (fluoride, chloride, bromide, nitrite, nitrate, sul-
fate, and phosphate) and cations (lithium, sodium,
potassium, and ammonium) [125]. In the determination
of anions in alkaline solutions, an ERIN column with a
cation exchanger in the ç+ form was used for neutral-
ization. An ERIN column with an anion exchanger in
the éç– form was used for the neutralization of acidic
solutions in the determination of cations.
Desorption of microcomponents and delivery of
the concentrate to the chromatographic column.
The efficiency of the on-line combination of sorption
preconcentration and HPLC determination depends not
only on the sorbent in use, but also on the condition of
the sorption of microcomponents. The subsequent des-
orption step also plays an important role. It is necessary
both to desorb extracted compounds quantitatively,
selectively, and rapidly and also to obtain the concen-
trate in a form suitable for chromatographic determina-
tion. In our opinion, it is reasonable to describe the des-
orption step using the following main parameters:
degree of desorption, the fraction of the total amount
of the adsorbed microcomponent transferred into the
solution after desorption;
minimum volume of the desorbing solution, which,
being passed, provides the given degree of desorption;
selectivity of desorption, the possibility to desorb
only the given compounds.
Only in several works was the desorption step stud-
ied separately from the determination step. Thus, after
the selection of sorbent for the preconcentration of pes-
ticides of different nature, the volume of methanol nec-
essary for the quantitative desorption of these com-
pounds was determined. For this purpose, a preconcen-
tration column was attached directly to the detector,
and the elution curve was recorded [37]. Based on these
studies, the Oasis HLB and Cyclone sorbents were
selected. With the use of these sorbents, the quantitative
desorption of pesticides required only 220 µL of meth-
anol. From the elution curve after the preconcentration
of components of blood plasma with the use of a
restricted-access cation exchanger, the minimum vol-
ume of a desorbing solution (0.2 mM LiClO4) sufficient
for the quantitative desorption of interfering macro-
components was determined [126].
In the other works, conditions of the desorption of
compounds were optimized with the use of the qualita-
tive and quantitative characteristics of chromatograms
obtained in on-line sorption–HPLC determination as
criteria and different techniques providing a decrease in
the width of peaks in chromatograms and an increase in
the selectivity and reproducibility of the determination
of compounds.
As known, the peaks in chromatograms obtained in
on-line sorption–HPLC determination are substantially
broader than in chromatograms obtained with the direct
introduction of the sample. This is due to the fact that
Vol. 61 No. 5 2006
 ON-LINE COUPLING OF SORPTION PRECONCENTRATION
the volume of the concentrate zone in the flow after the
desorption of compounds is much larger than the vol-
ume of the introduced sample in direct determination.
For example, peak widths in the determination of phe-
nols (C18 HD, Polymer Labs PLRP-s Hamilton PRP-1,
Hysphere GP, Hysphere SH, and Waters Oasis sorbents
and columns 10 × 2 mm were used for their preconcen-
tration) were 10 times larger than in the direct injection
of the sample of 10 µL [22]. Reversed-flow (backflush)
desorption is frequently used for the suppression of this
negative effect [23, 31, 60, 71, 75, 82, 99, 100, 109,
127]. However, this technique does not necessarily pro-
vide the narrowing of peaks. Evidently, in the case
when microcomponents are predominantly concen-
trated in the initial part of the preconcentration column,
desorption in the forward direction leads to additional
broadening of the concentrate zone in the flow of the
eluent, and reversed-flow desorption does not lead to
this effect. However, when microcomponents are uni-
formly distributed over the length of the column,
reversed-flow desorption does not improve the form of
the chromatogram [71, 99]. To narrow peaks, it was
proposed to introduce only a part of the concentrate into
the chromatographic column [9, 60]; however, this
technique inevitably impairs the sensitivity and repro-
ducibility of the determination.
Broadening of peaks in chromatograms due to the
sorption preconcentration of microcomponents can
also be caused by the polyfunctionality of the sorbent.
Thus, narrowing of peaks in chromatograms obtained
in the determination of retinoids was attained by the
addition of ammonium acetate into the desorbing solu-
tion for masking residual silanol groups of the ë18 sor-
bent [43].
It was demonstrated that the width of peaks in the
chromatogram is decreased by 10–15% when some
organic compounds are desorbed from reversed-phase
sorbents at a temperature increased to 75–95°C [128].
Heating of the solution is frequently favorable for the
dissolution of compounds and, correspondingly, for
rapid and quantitative desorption.
One more technique for narrowing the width of the
concentrate zone in the flow is desorption with only the
organic component of the binary aqueous–organic elu-
ent [23, 60, 99, 109]. After desorption, the concentrate
was diluted on-line with water to the composition of the
chromatographic eluent. Obviously, dilution by itself
leads to peak broadening, and, therefore, this technique
is not versatile. However, on-line dilution can be used
to focus compounds after desorption [10, 37, 50]. In
this case, the desorbing solution is diluted to attain a
composition that provides the strong retention of ana-
lytes at the beginning of the chromatographic column.
Focusing can be performed on a precolumn [127]. An
analogous effect can also be attained without the dilu-
tion of the desorbing solution: for example, atropine,
fenoterol, sotalol, and terbutaline were desorbed from a
cation-exchange column (restricted-access sorbent
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61 No. 5
423
LiChrospher 60 XDS SO3-Diol) and focused on a chro-
matographic column with the reversed-phase sorbent
LiChrospher 60 RP-Select B [126]. Compounds were
desorbed by changing the pH of the solution and adding
a small amount of an organic solvent. Because of the
different mechanisms of the retention of microcompo-
nents on the sorbents for preconcentration and separa-
tion, the analytes were retained at the initial part of the
chromatographic column.
It was noted that the nonquantitative desorption of
compounds in on-line sorption–HPLC systems leads to
a decrease not only in the sensitivity of determination
but also in its reproducibility because of the sorbent
“memory” effect. The performance characteristics of
the determination of compounds in these cases are fre-
quently improved on changing the composition of the
desorbing solution. For example, it was demonstrated
that the desorption of phenols from hyper-cross-linked
polystyrene LiChrolut EN with methanol, which is
used for the subsequent separation of these compounds,
is not quantitative; therefore, phenols were desorbed
with 1 mL of tetrahydrofuran [21]. Analogously,
300 µL of acetonitrile was used for the desorption of
substituted phenols from the PLRP-s sorbent (column
10 × 2 mm) and a methanol–water mixture was used for
separation in the gradient mode [129], because it was
previously demonstrated that the compounds are non-
quantitatively desorbed with 500 µL of methanol.
Selectivity of determination can be provided not
only by the selective extraction of analytes on the
selected preconcentration sorbent but also by the sepa-
ration of the analytes from the extracted concomitant
components at the desorption step. A popular technique
for improving selectivity is washing of the sorption col-
umn before desorption to remove the concomitant
weakly retained components [37, 59, 126]. For exam-
ple, after the preconcentration of 35 pesticides on a col-
umn with C18 silica gel from 1.3 mL of the sample, the
sorbent was washed with 4 mL of water, and the
reversed-flow desorption of compounds was performed
with a water–acetonitrile mixture [59]. Another tech-
nique for increasing selectivity consists in cutting out
the concentrate zone containing only microcomponents
from the flow of the desorbing solution. This technique
is somewhat analogous to two-dimensional chromatog-
raphy [130]; the only difference is that the separation
on preconcentration minicolumns is characterized by
low efficiency [103]. However, this cutting technique is
not always possible and requires the cautious selection
of conditions. In spite of this fact, the efficiency of this
technique was demonstrated in a large series of works
[6, 9–13, 42, 130–143], e.g., for the separation of
nitrate, nitrite, and phosphate from large amounts of
chloride [77].
A basically different approach to the optimization of
desorption consists in the selection of the sorbent and
the size of the column for the maximum efficiency of
not only the sorption step, but also the desorption step.
2006
424 OLIFEROVA et al.
Outlet CC
I ing solution into the HPLC column. This can disturb
Pump 1 Pump 2
PC
Fig. 1. Simple scheme of the connection of liquid lines and
equipment units for the sorption–chromatographic determi-
nation of compounds; PC is the preconcentration column,
CC is the chromatographic column, and I is the injector.
This approach was used by the authors of only a few
works. For example, after the detailed study of the sorp-
tion and desorption of substituted phenols with the use
of several polymer reversed-phase sorbents, a wide-
pore sorbent PLRP-s (Polymer Laboratories, Church
Stretton, Great Britain) was selected [144]; Fluorocar-
bon polymer sorbents were selected for the preconcen-
tration and desorption of polycyclic aromatic hydrocar-
bons [86–88]. Preconcentration columns of smaller
diameter than chromatographic columns were pro-
posed for decreasing the peak width in the chromato-
gram [22].
To increase the selectivity and sensitivity of sorp-
tion–HPLC determination, reactions of the derivati-
zation of desorbed compounds are also conducted
on-line before introduction into the chromatographic
column [9].
Equipment. In principle, all equipment for the
sorption–HPLC determination of compounds can be
assembled directly in a laboratory from ordinary HPLC
units: high-pressure pumps, controlled injection valves,
detectors, etc. The specialized complexes and exten-
sions for chromatographs for the same purposes PROS-
PEKT (Spark Holland, Netherlands), OSP-2 (Merck,
Germany), and ASPEC (Gilson, United States) are
commercially available [3]. Depending on the problem
at hand (necessity of the preconcentration of the micro-
components and the purification from macrocompo-
nents), the complexes include 2–4 chromatographic
high-pressure pumps, 1–3 controlled injection valves,
and different detectors [3]. Different schemes of the
connection of liquid lines were proposed for perform-
ing the cycle of analysis.
The simplest mode of linking liquid lines is when
the conditioning of the preconcentration column and
the preconcentration of components of the analyzed
solution are performed at the same position of the six-
port two-way injection valve. After switching the valve,
extracted compounds are desorbed with a mobile phase
suitable for the subsequent chromatographic separation
and transferred with the eluent flow into the chromato-
graphic column (Fig. 1). With the use of this scheme,
compounds can be desorbed both in the forward direc-
JOURNAL OF ANALYTICAL CHEMISTRY
tion and in the back-flush mode. However, in this case,
the residual part of the analyzed solution from the dead
volume of the column and from adjacent lines after pre-
concentration is transferred with the flow of the desorb-
the equilibrium in the HPLC column and impair the
form of the chromatogram [16, 145]. An advantage of
this scheme is that its implementation requires a mini-
mum equipment set: two pumps, one of which must be
a chromatographic pump and the second can be a low-
pressure pump, one two-way six-port valve, and pre-
concentration and separation columns. These schemes
are primarily used for the determination of pesticides of
different classes [96, 101]; aluminum, iron(III), and
copper(II) as their complexes with 8-hydroxyquinoline
[102]; sulfite [11], pyrocatechol, resorcinol, and hydro-
quinone [146]; mono- and dichlorophenols [147]; ethyl
methyl, isopropyl methyl, and pinacolyl methyl phos-
phonic acids (products of the hydrolysis of nerve gases:
sarin, soman, and VX) [58]; the medicine chlorthali-
done [70]; retinoids (trans- and cis-retinol) and their
derivatives [55]; and anthracene, pyrene, and other
polycyclic aromatic hydrocarbons [45] in different
samples. In the above works, the simplest scheme was
assembled for the reversed-flow desorption of com-
pounds. In the determination of triazines (atrazine,
simazine, etc.), chlorpyrifos, diazinon, and other pesti-
cides [148] and D- and L-aspartic acid [61], compounds
were desorbed in the forward direction. The simplest
scheme of linking liquid lines can be also assembled
using one four-port two-way valve [77].
As noted above, the sorption–HPLC determination
of compounds consists of several procedures: sampling
of the analyzed solution, conditioning of columns, pre-
concentration of analytes or separation of interfering
micro- and macrocomponents of the solution, derivati-
zation of components before or after preconcentration,
washing of columns, on-line dilution of solutions, “cut-
ting” of the concentrate zone from the flow, chromato-
graphic separation/determination of components, etc.
(Fig. 2).
A sample is frequently dosed using a loop. In the
determination of nitrite, nitrate, and phosphate in
highly mineralized water, this scheme was imple-
mented using four-port and six-port two-way valves
with a sample loop [77]. Analogous schemes were used
in the determination of codeine in blood plasma [63];
natural triazinone, carbamates, triazines, and organo-
phosphorus compounds in surface waters [59, 149];
and ceftazidime (antibiotic) in blood serum [150].
For conducting the derivatization reaction before or
after preconcentration, corresponding solutions are
mixed with solutions of reagents. In this case, the
equipment involves an additional pump, and solutions
are mixed with the help of a T-joint. After mixing, the
solution commonly arrives at a reactor, and in some
cases is heated in the reactor. If the processes listed
above were conducted in liquid lines at a low pressure
Vol. 61 No. 5 2006
 ON-LINE COUPLING OF SORPTION PRECONCENTRATION
Conduction
of the reaction
Column
for the extraction
of interfering
Desorbing components
solution
Preconcentration
Sample column
Sample
loop Solution
for washing
and/or gas
for drying
the sorbent
Fig. 2. Diagram of procedures in sorption–chromatographic analysis.
(in this case, the line including the chromatographic
column is linked with the previous column through an
injection valve), the reactors were made of a fluorocar-
bon polymer capillary (knotted reactors, etc.). By this
method, organic and inorganic forms of mercury(II)
were determined in fish and urine as complexes with
pyrrolidinedithiocarbamate [7]; nickel, copper(II), and
mercury(II) were determined in model aqueous solu-
tions as complexes with diethyldithiocarbamate [91];
and benzyl- and naphthalenesulfonates were deter-
mined in river water as ion pairs with trioctylamine [8].
Mixing cells of small volume with a magnetic stirrer
were used along with knotted reactors [9].
For washing the sorbent after preconcentration, the
solution, whose composition was selected previously,
was passed through the preconcentration column and
withdrawn to the outlet. Commonly, this procedure did
not require flow switching; however, an additional con-
trolled injection valve was used for the complete auto-
mation of analysis. For example, this scheme was used
in the determination of alkylphenols and hormones in
soils and bottom sediments [5], phenols in river water
[18], cortisol and prednisolone in blood plasma, and
arachidonic acid in urine [6].
The desorbing solution was heated directly before
introduction into the preconcentration column. This
technique was used in the determination of explosives
(picric acid and nitrotoluenes), triazines (cyanazine,
simazine, etc.), phenylureas (linuron, diuron, etc.), and
polycyclic aromatic hydrocarbons [128].
The composition of the desorbing solution was var-
ied on-line to the composition of the eluent using an
additional pump and a T-shaped mixer. This scheme
was used, e.g., in the determination of polar pesticides
in natural waters [129]. Extracted compounds were
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61 No. 5
425
Needle port
and sample loop
for the chromatographic
analysis
without
preconcentration
Chromatographic
column
Cutting
On-line dilution the concentrate zone
and/or conduction
of the reaction
desorbed in the gradient mode with a mixture of aceto-
nitrile and water and next mixed on-line also in the gra-
dient mode with a water–methanol solution to the com-
position required for the separation and determination.
In the determination of phenylureas (diuron, isoprotu-
ron, etc.), triazines (simazine, atrazine, etc.), and orga-
nophosphorus compounds (chlorfenvinphos and chlo-
rpyrifos), extracted compounds were desorbed with a
97% solution of methanol in water; next, the concen-
trate was mixed on-line with 3% methanol [37]. The
on-line dilution of the concentrate was also used in
other works [95, 108].
A part of a solution in the flow after desorption was
cut using additional injection valves installed in the line
preconcentration column–chromatographic column,
which were switched at the instants selected experi-
mentally [10–13, 42, 133, 135, 137-140, 142]. This
technique allowed the partial or complete separation of
concomitant components, which were eluted from the
precolumn before the elution of analytes. In some
works, in contrast, analytes were cut from the flow of
the desorbing solution into the loop of the injection
valve and next introduced into the chromatographic
column [131, 134, 143]. Sometimes analytes were
trapped after heart-cutting for the additional purifica-
tion from concomitant compounds with the use of an
additional minicolumn (trapping column) [130, 132]. A
part of the desorbing solution containing the concen-
trate can be cut from the flow by another simpler tech-
nique. Thus, for the determination of furosemide in
blood serum, a chromatographic column was attached
to a six-port two-way valve instead of the sample loop
[10]. The analyzed solution was passed through the pre-
concentration column, and simultaneously the chro-
matographic column was conditioned. Next, the des-
2006
426 OLIFEROVA et al.
orption of compounds was started in the gradient mode
increasing the concentration of acetonitrile from 0 to
18 vol %. After that, the valve was switched and the
flow was directed from the preconcentration column to
the chromatographic column increasing the concentra-
tion of acetonitrile to 35 vol %. The implementation of
this scheme required two chromatographic pumps, one
six-port two-way valve, and one valve for flow switch-
ing. A similar scheme was used in [13].
To solve some problems, it is necessary to have the
possibility of not only the on-line sorption–HPLC
determination but also the direct determination of the
same or other compounds without preconcentration
within one scheme. In this case, an additional injection
valve with a loop and a needle port was inserted into the
liquid line before the analytical column [151]. More
complex schemes of flow splitting are also used; e.g.,
the same analyzed solution is passed through several
preconcentration columns connected in series or in par-
allel, and extracted compounds are then successively
desorbed, separated, and determined using one or sev-
eral chromatographic columns. This approach substan-
tially increases the number of compounds that can be
determined within one cycle of analysis. Thus, for the
determination of phenol and its derivatives (a total of
13 compounds), river water was successively passed
through two different columns for the extraction of
hydrophilic and hydrophobic compounds, respectively
[4]. After preconcentration, the compounds were suc-
cessively desorbed from these columns into a chro-
matographic column. In the analysis of waste water,
three serially connected columns with ë18 silica gel,
hyper-cross-linked polystyrene, and a cation exchanger
were used. Extracted compounds were desorbed sepa-
rately from each column into one chromatographic col-
umn [3]. Systems with several columns were also used
for successive purification from concomitant compo-
nents. For example, in the determination of biomarkers,
metabolites of polycyclic aromatic hydrocarbons with
desoxyribonucleic acid (DNA) in model solutions
(DNA hydrolyzates), the compounds were preconcen-
trated on a restricted-access sorbent and desorbed with
methanol; the concentrate was diluted on-line, repeat-
edly preconcentrated on a column with octadecylsilica
gel, and desorbed with the mobile phase into a chro-
matographic column [127]. The first step of the analysis
of the next sample was performed simultaneously with
repeated preconcentration and separation.
To decrease the time of analysis, some steps of the
process can be performed in parallel (simultaneously
and independently of each other). In the commercial
OSP-2 system, the preconcentration and desorption
lines are not connected with each other. After precon-
centration, the cartridge (minicolumn with sorbent) is
mechanically transferred into a holder clamp for des-
orption. When the analyzed solution is passed through
one cartridge, extracted compounds are desorbed from
another cartridge [48, 51, 82]. A reasonable alternative
to the mechanical transfer of preconcentration columns
JOURNAL OF ANALYTICAL CHEMISTRY
is the use of a multiport (eight- and above) valve. Thus,
with the use of a ten-port valve and two pumps, the pre-
concentration of compounds was performed on the first
column, the desorption of compounds was performed
on the second column, and the resulting concentrate
was delivered to the chromatographic column simulta-
neously [62, 125].
A universal scheme of flow splitting that allows the
preconcentration of compounds simultaneously on two
columns connected either in series or in parallel was
proposed [152]. This scheme can be used to increase
the performance of analysis, i.e., the simultaneous pre-
concentration of compounds from several solutions, for
the separate preconcentration of components of differ-
ent classes when the solution is successively passed
through columns with different sorbents, and to solve
other problems. However, the implementation of this
scheme requires three pumps, three injection valves,
and one mixing valve.
DETERMINATION OF COMPOUNDS
IN DIFFERENT SAMPLES
The combination of sorption preconcentration and
HPLC determination in one automated cycle of analy-
sis, the possibility of varying the scheme of this combi-
nation, and the use of sorbents with different properties
for preconcentration and separation and different detec-
tors resulted in the development of a large number of
highly sensitive methods for the determination of a
wide range of compounds in samples of complex com-
position: natural and waste waters, soil, food, and bio-
logical fluids (Table 2).
Determination of hydrophobic ( log K o/w > 3)
organic compounds. Several methods were proposed
for the determination of polycyclic aromatic hydrocar-
bons in waters [16, 56, 86–88, 128, 145]. Octadecylsil-
ica gels Symmetry (5 µm) and Zorbax ODS1 (5 µm)
[56, 128], a sorbent based on hyper-cross-linked poly-
styrene PRP-1 (5–10 µm) [16], an immunosorbent [16,
145], and fluorocarbon polymer sorbents [86–88] were
used for preconcentration. Polycyclic aromatic hydro-
carbons were commonly extracted at flow rates of 1–
2 mL/min. To minimize losses of compounds at the
walls of glassware, 5 vol % acetonitrile was added to
the analyzed solution in the extraction of naphthalene
and anthracene and 10 vol % was added in the case of
the other polycyclic aromatic hydrocarbons. In the
majority of works, the desorption and separation/deter-
mination of compounds were performed in the gradient
mode. At the beginning of the process, the eluent com-
monly contained 20–50 vol % acetonitrile; its concen-
tration was then gradually increased to 100%. The iso-
cratic mode was more rarely used for desorption and
separation; the acetonitrile–water eluent (75/25) was
used in [86–88]. In all works, chromatographic col-
umns with octadecylsilica gel were used for the separa-
tion of polycyclic aromatic hydrocarbons. The detec-
Vol. 61 No. 5 2006
 Table 2. HPLC systems coupled with on-line sorption preconcentration for the analysis of particular samples
Separation Detection limit,
Analyzed samples Analytes Detector References
mode µg/L
Waters
Waste waters Cu(II), Al(III), and Fe(III) SF I 1 [102]
Waters Nitrogen-containing pesticides: oxamyl, methomyl, and 10 others The same G 0.01–0.07 [82]
Waters Phenols: phenol, 4-nitrophenol, and 9 others " The same 1 [95]
Surface waters Pesticides: atrazine, fenuron, and 26 others " " 0.1 [96]
The same Pesticides: aldicarb, methomyl, and 4 others " " 0.05–1 [99]
" Pesticides: quat, paraquat, and difenzoquat " " 0.1 [100]
River waters Phenol derivatives: 2-chlorophenol, 4-nitrophenol, and 10 others " " 0.1 [153]

JOURNAL OF ANALYTICAL CHEMISTRY

River waters Herbicides: mecoprop, silvex, and 4 others " " 1 [154]
Potable and river waters Pesticides: oxamyl, methomyl, and 11 others DA SF " 0.1 [92]
River waters Pesticides: isoproturon, fenuron, and 11 others The same " 0.05–0.5 [71]

Vol. 61
Potable waters Cd(II), Pb(II), Hg(II), Cu(II), Co(II), Ni(II), and Bi(III) " " 0.02–0.2 [122]
Natural waters Caffeine " " 0.1 [20]
Potable waters Pesticides: triazine, simazine, and 4 others " " 1.2–20.5 [47]

No. 5
Waters 16 phenol derivatives " " 0.2–0.6 [109]
Natural waters Phenols and pesticides: nitrophenol, dinitrophenol, and 7 others " " 0.03–0.17 [23]

2006
Ground waters Pesticides: chlorfenvinphos, malathion, and 18 others " " 0.01–0.5 [80]
Potable and surface waters Hormones: estrogen, progestogen, and 8 others " " 0.01–0.02 [25]
River waters Herbicides: alachlor and metolachlor " " 1.5 [26]
Surface waters Pesticides: bromophos, alachlor, and 7 others " " 0.5–7 [155]
River waters Pesticides and phenol derivatives, 10 compounds " " 0.3–1.4 [108]
Potable, ground, and sea wa- Pesticides: atrazine, simazine, and 7 others " " 0.1 [53]
ters
ON-LINE COUPLING OF SORPTION PRECONCENTRATION

Potable and river waters Pesticides: oxamyl, linuron, and 12 others " " 0.05–0.5 [94]
Estuary waters Pesticides: atrazine, simazine, and 2 others " " 0.01–5 [54]
Tap and surface waters Pesticides: aldicarb, diuron, and 15 others " " 0.1–1.1 [56]
Tap water icides: ametryne, atrazine, and 10 others " " 0.1 [34]
River waters Phenol derivatives and pesticides: phenol, methomyl, and 9 others " " 0.2–0.8 [98]
Potable and surface waters 32 pesticides and 19 explosives " " 0.1 [128]
River waters Phenol and 13 its derivatives " " 0.05–1 [4]
427
 428

Table 2. (Contd.)
Separation Detection limit,
Analyzed samples Analytes Detector References
mode µg/L
Ground waters Pesticides: oxamyl, atrazine, and 19 others " " 0.1 [101]
Natural waters 5 polar phenol derivatives " " 3 [41]
Waste waters Pnd surface waters;henols and amines, 29 compounds " " 1 [156]
Tap and river waters Naphthalenesulfonates, 12 compounds FL I 0.01–3 [19]
Surface and ground waters Herbicides: glyphosate and aminomethylphosphoric acid The same The same 0.02–0.1 [76]
River waters Naphthalenesulfonates, 7 compounds " " 0.01–3 [8]
Surface waters Polycyclic aromatic hydrocarbons: naphthalene, fluorene, and 4 others " G 0.002–0.01 [16]
Waste waters Polycyclic aromatic hydrocarbons: naphthalene, anthracene, and 4 others " The same 0.002–0.01 [145]
Potable and surface waters 16 polycyclic aromatic hydrocarbons " " <0.1 [128]
Natural waters Low-molecular amines, 10 compounds CL " 0.001 [9]
River waters Phenylureas, 9 compounds IR I 1 [81]
River waters Pesticide rotenone MS (APCI) I 0.01 [149]
Water Phenol, dimethylphenol, chlorophenols, nitrophenols, and others, the to- The same G 1 [22]
tal of 12 compounds
River waters Hormones: progestogen, estrogen, and 6 others " The same 0.001 [157]
Sea waters Pesticides: diuron, Irgarol, folpet, and dichlofluanid " " 0.005 [28]
OLIFEROVA et al.

Water 37 polar pesticides: triazines, phenylureas, and phenoxy acids " " 0.01–0.1 [129]
Drainage waters from rice Herbicides: propanil, molinate, and 10 others " " 0.1–0.02 [24]
fields
River waters Pesticides: bentazone, molinate, and 11 others " " 0.03–2.4 [29]
River waters Pesticides: simazine, diazinon, and 6 others " " 0.01–0.1 [148]
River waters Phenol and 6 its derivatives " " 0.1 [152]
Waters Phenols, 5 compounds " " 0.04–0.28 [158]

JOURNAL OF ANALYTICAL CHEMISTRY

Sea waters Pesticides: diuron, Irgarol, and 3 others " " 0.005 [36]
Potable, surface, and ground Pesticides, phenols, and phthalates, 23 compounds " " 0.1 [97]
waters
Surface waters Pesticides: simazine, alachlor, and 9 others " " 0.0004–0.013 [37]

Vol. 61
Tap water Pesticides: diuron, oxamyl, and 17 others " " 0.001–3 [38]
Natural waters Pesticides: atrazine, molinate, and 16 others " " 0.0008–0.02 [46]
MS (PB)

No. 5
Surface water Pesticides: bromophos, alachlor, and 7 others The same " 0.01–0.05 [155]

2006
 Table 2. (Contd.)
Separation Detection limit,
Analyzed samples Analytes Detector References
mode µg/L
River and potable waters Pesticides: oxamyl, linuron, and 12 others " " 0.02–0.5 [94]
River waters Pesticides: alachlor, atrazine, and 5 others " " 0.05–0.2 [159]
Waters Pesticides: fenuron, chloroxuron, and 3 others MS (ES) " 0.01 [151]
River waters Phenol and polar pesticides: diuron, oxamyl, and 11 others The same " 0.001 [30]
Potable water Quaternary ammonium herbicides, 6 compounds " " 0.006–0.085 [60]
Tap and sea waters Naphthalene monosulfonates and their derivatives, 8 compounds " " 0.05–1 [32]
Water Pesticides: atrazine, diuron, and 2 others " " 1 [33]
Natural ground and surface Pesticides: terbacil, diazinon, and 33 others " " 0.025–0.1 [59]

JOURNAL OF ANALYTICAL CHEMISTRY

waters
Potable and surface waters Herbicides: glyphosate, glyphosinate, and aminomethylphosphoric acid " " 0.03 [35]
River waters 10 organophosphorus pesticides MS (TS) " 0.01–0.1 [48]

Vol. 61
Waters containing humic Pesticides: simazine, atrazine, and 8 others MS (TS) " 0.1–10 [31]
acids
River waters Phenols, 16 compounds AM " 0.001–0.02 [18]

No. 5
River waters Aniline, phenol, caffeine, and 16 substituted anilines and phenols The same " 1 [27]
Tap water Phenols, 12 compounds " " 0.001 [104]

2006
Potable water Phenol and its derivatives: pyrocatechol, resorcinol, and 5 others " " 0.05 [40]
Highly mineralized waters Inorganic anions: nitrite, nitrate, and phosphate CDM " 100–1000 [77]
Potable ozonized water Bromate The same " 1 [123]
Surface ozonized waters Bromate " " 0.5 [124]
Water 12 polar phenol derivatives CM I 0.001 [160]
Soils and bottom sediments
Soil Herbicides and products of their degradation: 2,4,5-trichlorophenol, DA SF G 0.02–0.05 [17]
ON-LINE COUPLING OF SORPTION PRECONCENTRATION

dichlorprop, and 5 others

River silt Hormones: estradiol, estrone, and 17 others APCI MS G 0.0005–0.005 [5]
Biological materials
Serum Antidepressant nortriptyline and two its metabolites SF I 10 [69]
Plasma Codeine, norcodeine, and oxycodone The same The same 0.5 [63]
Serum Drugs: quetiapine and 3 others " " 4 [64]
429
 430

Table 2. (Contd.)
Separation Detection limit,
Analyzed samples Analytes Detector References
mode µg/L
Serum Medicine furosemide " " 5 [10]
Plasma Medicines nifedipine and nitrendipine " " 2 [65]
Serum Endogenous retinoids, 8 compounds " " 1–7 [43]
Urine Medicine chlorthalidone " " 0.1–20 [70]
Plasma Medicines: sotalol, atropine, and 4 others " " 10 [126]
Plasma and urine Medicine terbinafine and 5 its metabolites " " 20 [67]
Plasma Medicines: zidovudine and probenecid " " 1 [13]
Plasma and serum Medicine dimiracetam " " 0.03 [133]
Urine Medicine tipredane and 2 its metabolites " " 25 [134]
Serum and urine Biologically active compounds " " 0.5–2 [135]
Plasma Medicine finasteride " " – [136]
Plasma and urine Medicine efletirizine " " 10 [139]
Plasma Vitamins A, D2 , D3 , E, K1, and K3 " G 1 [131]
Plasma 4 natural and synthetic analogues of vitamin A " The same 2.5–5 [51]
Serum Antibiotic ceftazidime " " 100 [150]
Plasma, intercellular fluid, Medicine taxol " " 5 [138]
and tissues
Cells Biologically active compounds: harpagide, loganin, and 7 others DA SF I 2–5 [161]
OLIFEROVA et al.

Plasma Analogues of quinocarmycin DA SF The same 1 [12]

Plasma Tranquilizer lesopitron and 2 its derivatives FL " 1 [44]
Serum Biomarker pyridinoline and its analogue The same " 109–143* [73]
Plasma Medicine almokalant and its derivative " " 0.7 [50]
Plasma Medicine camptothecin and 3 its derivatives " " 2.5–5 [52]
Plasma Medicine citalopram and its metabolites " " 0.002 [162]

JOURNAL OF ANALYTICAL CHEMISTRY

Urine Metabolites of polycyclic aromatic hydrocarbons " " 0.0001 [142]
Plasma, intercellular fluid, Morphine and two its derivatives " G 0.85–3.4 [57]
and tissues

Vol. 61
Plasma Medicine tramadol " The same 0.1 [163]
Urine Methylmercury, ethylmercury, phenylmercury, and Hg(II) AA " 0.005–0.01 [7]
Plasma Medicine dextromethorphan and 2 its metabolites MS (APCI) " 0.5 [164]

No. 5
Plasma Medicine retigabine and 2 its derivatives The same I 0.5 [62]
Plasma and urine Cortisol, prednisolone, and arachidonic acid " I 0.002 [6]

2006
Urine Phthalic ester and 5 its derivatives " G 1 [49]
 Table 2. (Contd.)
Separation Detection limit,
Analyzed samples Analytes Detector References
mode µg/L
Cell cultures Hormones: dihydrotestosterone, testosterone, and androsterone MS (ES) G 0.05–1 [68]
Serum Sarin, soman, and VX MS (FAB) I 1–5 [58]
Plasma Hallucinogen psilocin and 6 its analogues AM G 10 [74]
Plasma and urine Medicine tetrahydrocannabinol and its metabolite AM G 5–20 [75]
Mouse embryo Endogenous retinoids, 5 compounds CM I 0.05 [55]
Food and beverages
Wine Phenol derivatives, 10 compounds DA SF G 1 [21]
Fish Methylmercury, ethylmercury, phenylmercury, and Hg(II) AA G 0.005–0.01 [7]
Potatoes, pears, and wheat Pesticides: chlormequat and mepiquat MS (ES) I 5 [72]
flour

JOURNAL OF ANALYTICAL CHEMISTRY

Dyes
Aqueous solutions of dyes Aromatic amines and phenol derivatives, 13 compounds SF The same 0.5–1.8 [165]
Model aqueous solutions

Vol. 61
Aqueous solutions Ni(II), Cu(II), and Hg(II) SF " 0.16–1.1 [91]
The same Aspartic acid and 6 its derivatives The same " 10 [61]
" Palladium(II) " " 0.3 [166]

No. 5
" Low-molecular polystyrene oligomers " " 10 [130]
" Organometallic compounds: dimethyllead, ethylmercury, and 5 others " I 0.6–3 mg/L [167]
G

2006
" Polyphenols: gallic acid, vanillin, and 36 others " G 1 [42]
" Adducts of polycyclic aromatic hydrocarbons and DNA FL I 25 [127]
" Polycyclic aromatic hydrocarbons: anthracene, pyrene, and 3 others The same The same 1 [45]
" Polycyclic aromatic hydrocarbons " " [143]
" Sulfite CDM " 1 [11]
" Inorganic anions: nitrate, chloride, sulfate The same " 50 [140]
" Inorganic anions: sulfate, sulfite, phosphate " " 10 [141]
Solutions of inorganic acids and bases
ON-LINE COUPLING OF SORPTION PRECONCENTRATION

Nitric acid Phosphate, sulfate, and chloride " " 0.1–5 [132]
Solutions of acids and bases Inorganic cations and anions: lithium, sodium, bromide, nitrate, " " 19 [125]
and 4 others
30% NH3 and 50% HF Inorganic anions: nitrate, chloride, and 5 others " G 1 [137]
Note: Separation modes: gradient (G) and isocratic (I); detectors: spectrophotometric (SF), diode array spectrophotometric (DA SF), fluorimetric (FL), atomic absorption (AA), chemiluminescence
(CL), amperometric (AM), conductometric (CDM), coulometric (CM), infrared (IR), mass-spectrometric (MS) [electrospray ionization (ES), atmospheric-pressure chemical ionization
(APCI), particle-beam interace (PB), thermospray ionization (TS), fast atom bombardment (FAB)].
* pM.
431
432 OLIFEROVA et al.
tion limits of compounds in water were 0.005–
0.040 µg/L with the use of a spectrophotometric detec-
tor [87], 0.1–1.1 µg/L with the use of a diode array
spectrophotometric detector [56], and 0.002–0.01 µg/L
with the use of a fluorimetric detector [16, 145].
Hormones (progestogens and estrogens) in the
determination in river water were preconcentrated on a
HySpher-Resin GP sorbent (column 10 × 2 mm) from
0.2–1 L of a sample at a flow rate of water of 6 mL/min
[157]. The column was washed with 4 mL of distilled
water, hormones were desorbed, and the concentrate
was delivered to a LiChrospher 100 RP-18 chromato-
graphic column 250 × 4 mm. The concentration of ace-
tonitrile in the desorbing solution, which also served as
the eluent, was linearly varied from 10 to 100 vol %
over 40 min; its flow rate was 1 mL/min. A mass-spec-
trometric detector with atmospheric-pressure chemical
ionization was used. The recovery of hormones was
96–112%; the detection limit was 1 ng/L. With the use
of an analogous procedure of sample preparation and a
spectrophotometric detector, the detection limits of the
same compounds were 10–20 ng/L [25].
The preconcentration of fat-soluble vitamins A, D2,
D3, E, K1, and K3 and some hydroxy derivatives of vita-
min D3 in their determination in blood plasma was per-
formed using silica gels with modifying aminoalkyl,
diol, cyanopropyl, phenyl, ethyl, octyl, and octadecyl
groups [131]. Aminopropylsilica gel exhibits the high-
est capacity in the extraction of the above vitamins.
After preconcentration, the sorbent was washed with
70% methanol. The compounds were desorbed with
pure methanol, and the concentrate zone was cut from
the flow using a loop with a volume of 50 µL. After the
introduction of the concentrate into a chromatographic
column (250 × 4.6 mm, ë18, 5 µm), vitamins were sep-
arated in the gradient mode. The eluent was mixture A
[acetonitrile–phosphate buffer solution with pH 6.5
(20 : 80)], mixture B [propan-2-ol–methanol (10 : 90)]
within 0–1.7 min; next, propan-2-ol–methanol (10 : 90)
within 1.7–30 min. Vitamins were detected at 270 nm.
The detection limits were 1 µg/L for recoveries of 78–
109%. Vitamin A and its synthetic analogues (retinoids)
in blood plasma and tissues were determined analo-
gously [51]. In this case, octadecylsilica gel was used
for preconcentration. The detection limits of vitamins
were 2.5–5 µg/L.
Hydrophobic pesticides (dinoseb, dinoterb,
malathion, fenitrothion, parathion-ethyl, and chloroxu-
ron) were determined in river and tap waters [19, 46].
Water was acidified to pH 3. Pesticides were precon-
centrated on LiChrospher Si100 RP-18 and ë18 Spark
columns from 200 mL of water at a flow rate of
5 mL/min [46] and on a column with polydimethylsi-
loxane from 10 mL at a flow rate of 1 mL/min [151].
The compounds were desorbed and separated with the
use of a mixture of methanol and an aqueous solution
of an ammonium salt (pH 4.5) at a flow rate of
0.8 mL/min in the gradient mode (increase in the con-
JOURNAL OF ANALYTICAL CHEMISTRY
centration of methanol from 30 to 60 vol % in 0–
20 min, from 60 to 70 vol % in 20–40 min, and from 70
to 90 vol % in 40–45 min) [46] and with an acetoni-
trile–water solution at a flow rate of 1 mL/min (5% ace-
tonitrile in 0–5 min, increase in the concentration of
acetonitrile from 5 to 100 vol % in 5–35 min, and 100%
acetonitrile in 35–40 min) [151]. In the later case, pes-
ticides were desorbed in the back-flush mode. The
detection limits were 0.8–20 ng/L with the use of a
mass-spectrometric detector with atmospheric-pressure
chemical ionization, 20–200 ng/L with a particle-beam
interface [46], and 10 ng/L with electrospraying [151].
For the determination of the solubility of polycyclic
aromatic hydrocarbons (anthracene, pyrene, m-terphe-
nyl, 9,10-dihydrophenanthrene, and guaiazulene) in
water-acetonitrile solutions at different temperatures,
the compounds were preconcentrated on a column
(20 × 2 mm) with ë18 Spherisorb SS ODS-2 (5 µm) at
a flow rate of 1 mL/min, desorbed with aqueous solu-
tions containing 80–90% acetonitrile directly into a
chromatographic column (250 × 4.6 mm) with ë18
Spherisorb SS ODS-2 (5 µm), separated in the isocratic
mode at a flow rate of the eluent of 1 mL/min, and
detected with fluorimetric and diode array spectropho-
tometric detectors [45].
Determination of polar ( log K o/w < 3) organic
compounds. Many works deal with the determination
of pesticides of different classes in waters [4, 18, 20, 22,
23, 40, 46–48, 80–82, 95, 96, 98–100, 108, 109, 129,
151, 153, etc.]. Samples of natural waters were usually
filtered directly before analysis for the separation from
suspensions. For example, natural water was filtered
through a polytetrafluoroethylene filter with a pore
diameter of 0.45 µm in the determination of atrazine,
simazine, propanil, and other compounds [47] and
through a Millipore filter with a pore diameter of
0.45 µm in the determination of atrazine, bentazone,
and malathion [46]. Pesticides were preconcentrated
using octadecylsilica gel [22, 46, 48, 80–82], octylsilica
gel [80], ethylsilica gel [82], cyanopropylsilica gel
[82], nonpolar sorbents based on the copolymer of
polystyrene and divinylbenzene [4, 18, 22, 23, 82, 98,
108, 109, 129, 160], carbon sorbents [23, 40, 82, 99,
100], immunosorbents (based on silica gel and the
copolymer of polystyrene and divinylbenzene with
immobilized antibodies) [96], and molecularly
imprinted sorbents [95, 153]. In the majority of cases,
the flow rate of the solution at the preconcentration step
was higher than at desorption; these flow rates were 5
and 0.8 [46], 5 and 0.7 [82], 4 and 1 [98], and 3 and
1 mL/min [4, 40], respectively. For the extraction of
polar pesticides with acidic properties on low-polarity
sorbents, analytes were converted into the molecular
form by acidifying the solution to pH 2–3. After pre-
concentration, the sorbent was commonly washed with
1−5 mL of distilled water; this was done, e.g., in [40,
96]. Compounds were desorbed either in the forward
direction or in the back-flush mode with a solution that
Vol. 61 No. 5 2006
 ON-LINE COUPLING OF SORPTION PRECONCENTRATION
was subsequently used as the eluent for separation [4,
40, 46, 81, 82, 96] or with an undiluted organic solvent,
which was diluted on-line after desorption [95, 99,
129]. In the majority of works, pesticides were des-
orbed and separated in the gradient mode gradually
increasing the concentration of the organic solvent in
the eluent from 20–30 vol % to 75–100 vol %. Pesti-
cides were separated using chromatographic columns
with octadecylsilica gel [4, 18, 47, 80, 81, 95, 96, 98,
99, 109, 129], octylsilica gel [48, 82], and carbon sor-
bents [40, 100]. Detectors of different types were used;
the detection limits of compounds were 0.01–0.1 µg/L
[129] and 0.0008–0.02 µg/L [46] with the use of a
mass-spectrometric detector with atmospheric-pressure
chemical ionization, 0.02–0.2 µg/L with the use of a
mass-spectrometric detector with a particle-beam inter-
face [46], 0.01–0.1 µg/L with the use of a thermospray
ionization mass spectrometer [48], 0.01–1 µg/L with
the use of a diode array spectrophotometric detector
[47, 80, 82, 96, 98], 0.001 and 0.05 µg/L with the use
of an amperometric detector [18, 40], and 1 µg/L with
the use of an IR detector [81].
Herbicides of different classes (4-(2,4-dichlorophe-
noxy)butyric acid, 2,4-dichlorophenol, 2,4,5-trichlo-
rophenol, etc.) were determined in methanol extracts
from soils [17]. Before preconcentration, the extract
was diluted to the concentration of methanol of 10 vol %.
The compounds were extracted on the Hysphere-GP
sorbent; the column was washed with water acidified to
pH 3. Compounds were desorbed in the back-flush
mode and separated on a chromatographic column
(250 × 2.4 mm) with Nucleosil 100-5 ë18. The gradient
desorption mode was used at pH 3 (4.5–18 vol % ace-
tonitrile, 0–3 min; 18–90 vol % acetonitrile, 3–35 min;
90 vol % acetonitrile, 35–40 min; 90–4.5 vol % aceto-
nitrile, 40–45 min; 4.5 vol % acetonitrile, 45–50 min).
The detection limits with the use of a diode array spec-
trophotometric detector were 0.02–0.05 µg/L; the
recovery was no lower than 80%.
In the determination of caffeine in natural water, it
was preconcentrated on the PLRP-s sorbent and deter-
mined using a chromatographic column (25 × 4 mm)
with Hypersil C18 and a diode array spectrophotometric
detector at 210 nm [20]. In preconcentration from
50 mL, a detection limit of 0.1 µg/L was attained; the
recovery of caffeine was 92–98%.
Methods were proposed for the determination of
some medicines of different classes in biological mate-
rials, such as blood, blood serum, blood plasma, urine,
and tissue samples [6, 44, 50, 63, 69, 138, 163]. Cell
cultures and biological tissues were homogenized and
then centrifuged [138]; blood plasma was also centri-
fuged [6, 50, 163]. Blood serum and urine were diluted
with water or buffer solutions [6, 69]. The relative
rather than absolute preconcentration and separation of
determined components from concomitants are com-
monly required in the determination of compounds in
biological materials. For this reason, preconcentration
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61 No. 5
433
was performed using sorbents with increased selectiv-
ity: restricted-access octadecylsilica gel [6, 163],
molecularly imprinted sorbent [163], ethylsilica gel
[44, 50, 63], and cyanopropylsilica gel [69]. After pre-
concentration, the sorbent was commonly washed with
an aqueous solution containing 1 g/L acetic acid in the
determination of arachidonic acid in urine [6], with a
10% solution of methanol in water in the determination
of cortisol and similar compounds in blood plasma,
with a 9% solution of methanol in water in the determi-
nation of nortriptyline, trimipramine, and their deriva-
tives in blood serum [6, 69], and with a 10% solution of
acetonitrile in water in the determination of lesopitron
and its derivative, 5-hydroxylesopitron in blood plasma
[44]. In the determination in blood plasma, tramadol
was first preconcentrated on a restricted-access sorbent
(LiChrospher ADS RP-18, 25 µm, 25 × 4 mm) and des-
orbed with 5% aqueous acetonitrile, and the resulting
solution was passed through the second column filled
with the molecularly imprinted sorbent. On the first
column, the molecules were separated by size differ-
ences, and on the second column, by molecular recog-
nition. From the second column, the extracted com-
pounds were desorbed directly into the chromato-
graphic column [163]. The composition of the
desorbing solution commonly coincides with the com-
position of the chromatographic eluent [6, 44, 163];
only in the determination of nortriptyline, trimi-
pramine, and their derivatives in blood serum were
these compounds desorbed with 70% aqueous acetoni-
trile and separated with the use of 34% acetonitrile
[69]. Because the number of compounds determined
simultaneously was usually small, the separation was
commonly performed in the isocratic mode. Chromato-
graphic columns with octadecylsilica gel [6, 44, 69]
and cyanopropylsilica gel [163] and spectrophotomet-
ric, fluorescence, and mass-spectrometric detectors
were used. The detection limits were 2 µg/L (com-
pounds were preconcentrated from 1 mL of the sample)
with the use of spectrophotometric detectors [69],
0.7 µg/L (500 µL of the sample) with the use of fluores-
cence detectors [50], and 1–2 µg/L (200 µL of the sam-
ple) with the use of mass-spectrometric detectors [6].
In the determination of gallic, ferulic, and other
acids in wines, samples were diluted with water two
times, the compounds were preconcentrated on the
LiChrolut EN sorbent, and the sorbent was washed with
water and dried with a helium flow [21]. The com-
pounds were desorbed with 1 mL of tetrahydrofuran
and separated on a Sentry C18 column (250 × 4 mm) in
the gradient mode at pH 2.5 (10–22 vol % methanol, 0–
30 min; 22–50 vol % methanol, 30–65 min; 50–90 vol %
methanol, 65–90 min). With the use of a diode array
spectrophotometric detector, the detection limit was
1 µg/L.
Aromatic amines and phenol derivatives were deter-
mined in aqueous solutions of dyes [165]. Aromatic
amines were preconcentrated from 5 mL of a solution
on an IEC CM-825 column (75 × 8 mm) with the car-
2006
434 OLIFEROVA et al.
boxymethylsilica gel cation exchanger and desorbed
and separated with a solution containing 40 vol % ace-
tonitrile and 60 vol % acetate buffer solution with
pH 4.6. A Nova-Pak C18 chromatographic column
(150 × 3.9 mm) and a spectrophotometric detector
(280 nm) were used. Phenol derivatives were extracted
from the same volume of the solution on a LiChrosorb
RP-18 column (25 × 4 mm). Desorption, separation,
and determination were performed using a solution
containing 17 vol % acetonitrile and 83 vol % buffer
solution and a Nova-Pak phenyl chromatographic col-
umn (75 × 3.9 mm). The flow rate of the solution was
0.9 mL/min at the preconcentration step and 1 mL/min
at desorption and separation. Detection limits of 0.5–
1.8 µg/L were attained; the recovery was 80–100%.
Determination of organic and inorganic ions. A
method was proposed for the determination of naphtha-
lenesulfonates in river water with the use of a fluorimet-
ric detector [19]. Water (20 mL) with an addition of an
ion-pair reagent (tetrabutylammonium) was passed
through a column (10 × 3 mm) with the PLRP-s sorbent
at a flow rate of 4 mL/min. Compounds were desorbed
in the back-flush mode at a flow rate of 1 mL/min. Des-
orption and separation were performed using a solution
containing 35 vol % methanol and 65 vol % phosphate
buffer solution (6.9 mM NaH2PO4–6.9 mM Na2HPO4)
with the addition of 4.6 mM tetrabutylammonium bro-
mide and a chromatographic column (150 × 4 mm) with
Kromasil 100 C18. The detection limits were 0.01–
3 µg/L. Similar results were also obtained in [8].
In the determination of pesticides exhibiting acidic
properties (chlorophenoxy acids, glyphosate and its
metabolite, aminomethylphosphoric acid, clopyralid,
dicamba, and picloram) in potable and river waters [76,
92, 154], several preconcentration techniques were
used. After the acidification of samples [92, 154], these
compounds were extracted in the molecular form on
polystyrene cross-linked with divinylbenzene. The
compounds were desorbed and introduced into a chro-
matographic column in the gradient mode with a mix-
ture of acetonitrile and a phosphate buffer solution of
pH 7 (10–15 vol % acetonitrile, 0–5 min; 15–40 vol %
acetonitrile, 5–40 min) [92]. The separation and deter-
mination of the compounds was performed on a chro-
matographic column with the Hypercarb sorbent (100 ×
4.6 mm, 5 µm). The detection limit was 0.1 µg/L with
the use of a diode array spectrophotometric detector.
For additional purification of concomitant components,
the compounds were desorbed from the polystyrene
sorbent with a 10% solution of acetonitrile in water
with the addition of alkali and next pesticides were
repeatedly extracted on an anion exchanger [154]. Des-
orption and subsequent separation were performed in
the gradient mode with a mixture of acetonitrile and
water at pH 3.8 (20–24.2 vol % acetonitrile, 0–15 min;
24.2–32 vol % acetonitrile, 15–30 min; 32–62 vol %
acetonitrile, 30–55 min). A chromatographic column
with octadecylsilica gel and a spectrophotometric
JOURNAL OF ANALYTICAL CHEMISTRY
detector were used. The detection limit was no higher
than 1 µg/L. Another approach to the determination of
acidic pesticides was proposed in [76]. In this work,
compounds were preconcentrated in the ionic form on
an anion exchanger and separated with the use of a cat-
ion exchanger. The detection limits of compounds with
the use of a fluorimetric detector were 0.02–0.1 µg/L.
A method was developed for the determination of
the herbicides chlormequat and mepiquat in pears,
fresh and canned tomatoes, and wheat flour [72]. A
sample of pears or tomatoes (10 g) was homogenized,
and deuterium-labeled chlormequat and mepiquat were
added as internal standards so that their concentrations
were 19.5 and 31.5 µg/kg, respectively. These samples
were suspended in 100 mL of a water–ethanol solution
(50 : 50) and stirred with a magnetic stirrer for 20 min,
and the resulting mixture was centrifuged. An aliquot
portion of the solution was filtered through a membrane
filter with a pore size of 0.2 mm. Wheat flour was sus-
pended in 45 mL of water adjusted to pH 4 with formic
acid, and methanol was then added to a volume of
100 mL. A portion (30 µL) of the resulting extract was
introduced into a sorption–HPLC system. Preconcen-
tration and separation were performed on columns with
ion-exchange sorbents; detection was performed with
an electrospray ionization mass-spectrometric detector.
The detection limit of the compounds was 5 µg/kg.
D- and L-aspartic acids, alanine, and their deriva-
tives were preconcentrated on the LiChrospher RO-4
ADS sorbent with the hydrophilized outer surface mod-
ified with diol compounds and the hydrophobic inner
surface with modifying C4 groups [61]. The outer sur-
face protected the sorbent from contamination with
proteins, and the inner surface adsorbed low-molecular
aminoacids as ion pairs with 1-octanesulfonate. The
compounds were separated on a Chiralpak WM chro-
matographic column (250 × 4.6 mm) with silica gel
chemically modified with chiral aminoacids. The detec-
tion limit was 10 µg/L.
A method was proposed for the determination of the
medicine psilocin and its derivatives in blood plasma
[74]. Blood plasma (410 µL) was introduced into a pre-
concentration column (10 × 4 mm) with a cation
exchanger containing carboxymethyl groups. The col-
umn was washed with 3 mL of a solution of lithium
acetate with pH 6.8. The compounds were desorbed
with methanol for 2 min at a flow rate of 2 mL/min.
Separation was performed on a LiChroCart Superspher
60 RP column (250 × 4 mm) in the isocratic mode with
the eluent containing 5.5 vol % acetonitrile and 94.5 vol %
buffer solution (pH 2.3) at a flow rate of 0.6 mL/min.
An electrochemical detector was used. The detection
limit of compounds was 10 µg/L; the recovery was
100%. Amphetamines in blood plasma and urine were
determined analogously [75]. The recovery of com-
pounds at the preconcentration step was no lower than
93%; the detection limit was 5–20 µg/L. A method was
proposed for the determination of pyridinoline and des-
Vol. 61 No. 5 2006
 ON-LINE COUPLING OF SORPTION PRECONCENTRATION
oxypyridinoline (bone tissue metabolism markers) in
blood serum. These compounds were also extracted on
a cation exchanger and separated using a reversed-
phase sorbent [73]. Detection limits of 109–143 pM
were attained with the use of a fluorimetric detector; the
recovery of the compounds was 95–100%.
Low-molecular amines (methylamine, ethylamine,
propylamine, etc.) in the protonated form were deter-
mined in tap, surface, and ground waters with the use of
a chemiluminescence detector [9]. Alkylamines were
preconcentrated from 50 mL of a sample on an IRC-50
cation-exchange column (35 µm) at a flow rate of the
solution of 2 mL/min. Sorbents were washed with 5 mL
of water and dried in an air flow. The compounds were
desorbed with a 0.16 M borate buffer solution (pH 11)
at a flow rate of 0.5 mL/min. The flow of the desorbing
solution containing the concentrate was mixed in a spe-
cial 1-mL chamber with the flow of an aqueous 2.6 ×
10–3 M solution of 5-dimethylaminonaphthalene-1-sul-
fonyl chloride. After mixing, the solution arrived at the
reactor in the form of a polytetrafluoroethylene capil-
lary (2000 × 0.8 mm) thermostated at 65°C. The flow
was stopped for 120 s; after the end of the reaction,
20 µL of the resulting solution was introduced into a
chromatographic column (150 × 3.9 mm) with Nova-
Pak C18 (4 µm). Separation was performed in the gradi-
ent mode with a mixture of acetonitrile and water at a
flow rate of 1 mL/min (25–50 vol % acetonitrile, 0–
5 min; 50 vol % acetonitrile, 5–30 min; 50–75 vol %
acetonitrile, 30–35 min; 75 vol % acetonitrile, 35–
50 min). The recovery of the compounds was above
95%; the detection limits were 0.01–0.3 µg/L.
On-line sorption–HPLC methods are used for the
determination of inorganic ions and complexes of met-
als with organic ligands. In the determination in aque-
ous solution, palladium was preconcentrated on mini-
columns (50 × 4 mm) by two techniques: as Pd2+ cat-
ions on the IonPac CG10 cation exchanger and as
2–
PdCl 4 anions on the IonPac AG4 and IonPac AG11
anion exchangers [166]. An anion-exchange chromato-
graphic column IonPac AS4 was used for the separation
of Pd from Ru, Rh, Ir, Pt, Mn, Fe, Ni, Cu, Zn, and Pb.
2–
Palladium was determined as Pd I 4 , which was
obtained in a reactor located after the column. The
highest recovery of palladium was 92% (from 0.03 M
HCl). A detection limit of palladium of 0.3 µg/L was
attained.
A method was proposed for the determination of Ni,
Cu(II), and Hg(II) in aqueous solutions [91]. The ana-
lyzed solution was mixed on-line with a solution of
sodium diethyldithiocarbamate before the preconcen-
tration column; complexes of the elements were
extracted on a column with a volume of 50 µL with the
RP-18 sorbent. The sorbent was washed with water; the
complexes were desorbed in the forward direction
directly into a YWG-C18 chromatographic column
(250 × 4.6 mm). Desorption and separation were per-
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61 No. 5
435
formed using 80% methanol; the compounds were
detected at 325 nm. It was demonstrated that Na, K, Ca,
and Mg do not interfere with the determination because
they do not form complexes with diethyldithiocarbam-
ate; zinc forms the unstable complex; and complexes
with cadmium and lead are formed but do not absorb at
325 nm. Citric acid was added to mask iron(III). Cobalt
did not interfere with the determination of nickel at the
selected conditions of chromatographic separation;
their peaks were eluted with an interval of 0.3 min. The
detection limits of the elements were 0.16–1.1 µg/L
with the use of a spectrophotometric detector. An anal-
ogous method was proposed for the determination of
Co, Ni, Cu(II), Cd, Hg(II), Pb, and Bi. Detection limits
0.02–0.2 µg/L were attained with the use of a diode
array spectrophotometric detector [122]. Al, Fe(III),
and Cu(II) ions were also preconcentrated and sepa-
rated as complexes with 8-hydroxyquinoline [102].
A method was proposed for the determination of
ionic organic compounds of mercury and lead (dimeth-
yllead, diethyllead, trimethyllead, triethyllead, meth-
ylmercury, and ethylmercury) in aqueous solutions
[167]. Before preconcentration, derivatives of organo-
metallic ions were obtained with the use of mercaptoet-
hanol and methyl thioglycolate. The obtained com-
pounds were preconcentrated on a Nucleosil ë18 col-
umn (30 × 4 mm). The compounds were separated
using two columns: Hypersil ODS (250 × 4 mm) and
Nucleosil C18 (250 × 4 mm); the process was conducted
in the gradient mode on the first column and in the iso-
cratic mode on the second column. A spectrophotomet-
ric detector (235 nm) was used. The recovery with the
use of methyl thioglycolate was 70–80%; the detection
limits were 0.6–3 mg/L.
A method was developed for the determination of
methyl-, ethyl-, and phenylmercury and inorganic mer-
cury(II) in urine and fish [7]. Analyzed solutions were
mixed on-line with a solution of ammonium pyrro-
lidinedithiocarbamate. The obtained complexes were
extracted on a minicolumn with octadecylsilica gel,
desorbed with a water–acetonitrile–ethanol mixture,
and separated on a chromatographic column with the
same sorbent. An atomic absorption spectrometer was
used for detection; determination was performed by the
cold vapor method. The detection limits of mercury
compounds were 5–10 ng/L.
A method was proposed for the determination of
phosphate, sulfate, and chloride in high-purity nitric
acid [132]. A sample (200 µL) of an analyzed solution
of acid diluted 100 times was passed through a column
(120 × 4 mm) filled with a specially synthesized high-
capacity sorbent based on the copolymer of polystyrene
and divinylbenzene with diethanolmethylamine groups
(4.5 µm). The sorbent retains nitrate more strongly than
chloride, phosphate, and sulfate. Anions were desorbed
with a 0.1 M NaOH solution at a rate of 1 mL/min. At
the desorption step, the concentrate zone containing
analyte anions was cut and directed to the next precon-
2006
436 OLIFEROVA et al.
centration column (Dionex TAC-2, 35 × 3 mm). Anions
were repeatedly desorbed with a solution containing
2.5 mM Na2CO3 and 0.5 mM NaHCO3 at a flow rate of
0.7 mL/min directly into a Metrohm Asupp 5 chro-
matographic column (100 × 4 mm). The recovery was
80–100% for chloride and 100% for sulfate and phos-
phate; the detection limits of the ions in 69% nitric acid
with the use of a coulometric detector were 0.1 (chlo-
ride), 1 (sulfate), and 5 mg/L (phosphate).
Nitrate, nitrite, and phosphate were determined in
solutions with high concentrations of chloride and sul-
fate and in sea water [77]. The anions were preconcen-
trated and separated from matrix components on a
Dionex AG9-HC column. In the course of desorption,
the first portion containing chloride was directed to the
outlet; and the injection valve was then switched and
the flow was directed into a chromatographic column.
The ions were separated on a Dionex AS9-HC column;
conductometric and spectrophotometric detectors were
used. The detection limits of nitrate, nitrite, and phos-
phate in solutions containing up to 20 g/L chloride and
up to 3 g/L sulfate were 100, 300, and 1000 µg/L,
respectively.
TRENDS
On-line sorption–HPLC methods continue develop-
ing. An evident aspect of this development is the
sophistication of chromatographic methods: the use of
new detectors, e.g., electrospray ionization mass-spec-
trometric detectors and the development of new chro-
matographic sorbents and methods for the separation of
compounds.
In our opinion, the most important trend in the
development of on-line systems is their miniaturiza-
tion. The miniaturization of practically any analytical
system substantially decreases the volume of a sample
required for analysis, which is very important, e.g., in
the analysis of blood, biological tissues, and many
other materials. Usually, the use of miniature systems
for analysis also decreases the time of the determina-
tion of compounds. A certain advantage of miniature
on-line sorption–HPLC systems is a decrease in the
consumption of solvents, which are used for washing,
desorption, separation, and determination, and, conse-
quently, a decrease in the cost of analysis.
In recent years, solid-phase microextraction was
widely used for the preconcentration of compounds
from aqueous solutions. This method allows the extrac-
tion of compounds on a very small amount of a sorbent
[168]. In this case, compounds are commonly deter-
mined by gas-chromatographic methods after ther-
modesorption. Efforts were made to adapt solid-phase
microextraction for use in on-line sorption–HPLC sys-
tems; devices for the desorption of compounds, e.g.,
needle ports of special design were proposed [169–
179]. Several works were performed with the use of
these devices and deal with the determination of
JOURNAL OF ANALYTICAL CHEMISTRY
organic pollutants in natural and waste waters [169–
172, 174, 179–181, 182–187] and medicines in urine
[175–177, 188, 189]. It was noted that a high efficiency
of the separation of compounds was attained due to the
miniaturization of the preconcentration system: e.g.,
peak broadening was not observed in chromatograms
obtained by the combined method in comparison with
chromatograms obtained by the direct introduction of
20 µL of the sample [170].
Short (50–60 cm) pieces of capillary columns for
gas chromatography were used as miniature systems
for preconcentration by the solid-phase microextrac-
tion method [190–196]; this technique allowed desorp-
tion with a small amount (30–40 µL) of a solvent. It
was noted that the variety of commercially available
stationary phases for gas chromatography allows the
selection of the most suitable phase for solving a partic-
ular analytical problem. The proposed analytical sys-
tems were used for the determination of organic pollut-
ants and medicines in waters and biological fluids
[197]. The efficiency of the extraction of compounds in
a capillary can be increased by filling the capillary with
polymer fibers [198–201]. This technique provides a
substantial increase in the surface area of the sorption
system. Thus, n-butyl phthalate was preconcentrated in
a capillary filled with poly(p-phenylene-2,6-benzo-
bisoxazole) fibers [198]. The coefficient of the increase
in the analytical signal due to the preconcentration of
compounds from 300–400 µL of a sample in the on-line
sorption–HPLC determination of phthalate was 160.
The modification of the fiber surface increased the effi-
ciency of the extraction of compounds [202–204]. For
example, after the treatment of poly(p-phenylene-2,6-
benzobisoxazole) fibers with phenylmethylpolysilox-
ane, the recovery of substituted phthalates increased
from 20 to 60–100% [202]. After decreasing the length
of the capillary filled with fibers to 5 mm, it can by
mounted directly in the rotor of the injection valve
[199, 200, 205–207]. This design allowed the minimi-
zation of the dead volume of the system to 0.3 µL and
the desorption of compounds with only 2–3 µL of a sol-
vent.
The combination of the preconcentration by solid-
phase microextraction on a capillary column for gas
chromatography with the separation of compounds by
microcolumn HPLC allowed the determination of sub-
stituted phthalates in natural and waste waters with a
low consumption of the eluent for one determination
(500–800 µL) and a low detection limit (0.10–
0.20 µg/L with the use of a UV detector) [202].
Another trend in the development of on-line sorp-
tion–HPLC methods is related to the development of
new sorbents for preconcentration. For increasing the
recovery in the dynamic mode, the surface area of sor-
bents is increased, and their structure is changed [208,
209]. For example, highly cross-linked polystyrene sor-
bents (degree of cross-linking 100% and above) with a
specific surface area of 1200 m2/g and above were syn-
Vol. 61 No. 5 2006
 ON-LINE COUPLING OF SORPTION PRECONCENTRATION
thesized. These sorbents are characterized by high
purity; their structure contains micropores with diame-
ters of 1–3 nm, which provide an increase in the contri-
bution of specific interactions necessary for the extrac-
tion of polar organic compounds from aqueous solu-
tions [208]. Another direction in the development of
sorbents for the preconcentration of poorly extractable,
commonly hydrophobic compounds is the development
of carbon sorbents with highly developed surface
(above 1000 m2/g). A modern technique for preparing
these sorbents is the pyrolysis of organic polymers.
Sorbents synthesized by this technique, e.g., Carboxen
1000, were used for the preconcentration of compounds
with solubility above 1 g/L [209].
In the preconcentration of many compounds from
aqueous solutions on hydrophobic sorbents, contact of
the sorbent with the analyzed solution is commonly
hindered. To solve this problem, polymer sorbents with
functional groups were synthesized and special poly-
mers were developed, such as LiChrospher RO-4 ADS
and Oasis HLB, which are used without precondition-
ing. These sorbents are more wettable with water, and
the recovery of analytes increases [61, 210].
Conventional sorbents for preconcentration (chemi-
cally modified silica, polymers, and carbon sorbents)
do not exhibit high selectivity; however, it is sometimes
necessary, especially in the analysis of biological mate-
rials. In this case, the volume of samples is rather small;
therefore, the requirements on the efficiency of sorbents
are not high. To solve these problems, selective sor-
bents are necessary, and approaches to their preparation
are being intensively developed. Thus, restricted-access
sorbents contain pores of a particular size, which are
formed using a special technique for their preparation
[126, 127]. In the synthesis of even more selective
molecularly imprinted sorbents, particular compounds
are introduced into the composition of the polymer
mass and removed after polymerization [153]. Both
types of sorbents are promising for the preconcentra-
tion of microcomponents from biological fluids; in this
case, large molecules (proteins, etc.) are not extracted
and microcomponents (aminoacids, medicine com-
pounds, etc.) are adsorbed [95]. There are examples of
the use of these sorbents in on-line sorption–HPLC sys-
tems [163]; however, the number of these works is
small.
Highly selective sorbents that provide the extraction
of compounds on the basis of molecular recognition
were proposed. For example, so-called immunosor-
bents were obtained by the addition of specific antibod-
ies to the sorbent matrix. The extraction of organic
compounds on these sorbents is based on the antigen–
antibody interaction. A limitation of this approach is
commonly an excessively high selectivity; the sorbents
commonly extract only one compound. Immunosor-
bents intended for the extraction of groups of structur-
ally similar compounds because of the cross reactivity
of antibodies were proposed for expanding the range of
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61
437
extracted compounds. Sorbents of this class were pri-
marily used for the preconcentration of medicines in
the analysis of biological materials [211] and in the
determination of some pesticides in waters [212, 213].
Currently, interest in the use of immunosorbents for the
selective preconcentration of compounds is very high,
which is indicated by the data presented in reviews
[214, 215].
ACKNOWLEDGMENTS
The work was supported by the Russian Foundation
for Basic Research (project no. 03-03-32702) and the
National Natural Science Foundation of China–2004
(cooperative project with the Russian Foundation for
Basic Research, no. 04-03-39002).
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