Solid Phase Extraction of Trace Elements: Review

Spectrochimica Acta Part B 58 (2003) 1177–1233
Review
Solid phase extraction of trace elements
´ Camel*
Valerie
Institut National Agronomique Paris-Grignon, Analytical Chemistry Laboratory, 16 Rue Claude Bernard,
Paris Cedex 05 75231, France
Received 2 December 2002; accepted 26 March 2003
Abbreviations: AAS, Atomic absorption spectrometry; ACN, Acetonitrile; AES, Atomic emission spectrometry; APDC,
Ammonium pyrrolidine dithiocarbamate; BAS, Biswl-hydroxy-9,10-anthraquinone-2-methylxsulfide; 5-BrPADAP 2-(5-bromo-2-
pyridylazo)-5-diethylaminophenol; BSQ, 8-(Benzenesulfonamido)quinoline; 18C6, 18-Crown-6; CA, Chromotropic acid; CTA,
Cetyltrimethylammonium; CV-AAS, Cold vapour atomic absorption spectrometry; DAD, Diode array detector; DDQ, 7-Dodecenyl-
8-quinolinol; DDTC, Diethyldithiocarbamate; DDTP, 0,0-Diethyl-dithiophosphate; DEBT, N,N9-Diethyl-N9-benzoylthiourea; DESe,
Diethyl selenide; DMBS, Dimethylglyoxal bis(4-phenyl-3-thiosemicarbazone); DMDSe, Dimethyl diselenide; DMG, Dimethylglyox-
ime; DMSe, Dimethyl selenide; DPC, Diphenylcarbazide; DPCO, Diphenylcarbazone; DPD, N,N-Dimethyl-p-phenylenediamine;
DPTH, l,5-bis(di-2-pyridyl) methylene dithiocarbohydrazide; DVB-VP, Divinylbenzene-vinylpyrrolidone; DZ, Dithizone; DzS,
Dithizone sulfonic acid; ECD, Electron capture detection; EDTA, Ethylene diamine tetraacetic acid; ERT, Eriochrome black-T; ET-
AAS, Electrothermal atomic absorption spectrometry; Et, Ethyl; EtOH, Ethanol; F-AAS, Flame atomic absorption spectrometry;
FI, Flow injection; FPD, Flame photometric detection; FZ, Ferrozine; GC, Gas chromatography; GCB, Graphitized carbon black;
HDEHP, Bis(2-ethylhexyl) hydrogen phosphate; HMDC, Hexamethylenedithiocarbamate; H2 MEHP, 2-Ethylhexyl dihydrogen
phosphate; 8-HQ, 8-Hydroxyquinoline; 8-HQ-5-SA, 8-Hydroxyquinoline-5-sulfonic acid; HT18C6, Hexathia-18-crown-6;
HT18C6TO, Hexathia-18-crown-6-tetraone; IBMK, Isobutyl methyl ketone; ICP, Inductively coupled plasma; IDA, Iminodiacetate;
IP, Ion-pair; KR, Knotted reactor; LC, Liquid chromatography; LLE, Liquid–liquid extraction; LOD, Limit of detection; MBT, 2-
Mercaptobenzothiazole; Me, Methyl; MeOH, Methanol; MPSP, 3-Methyl-l-phenyl-4-stearoyl-5-pyrazolone; MPT, Microwave plasma
torch; MS, Mass spectrometry; NCH, Neocuproine; NDSA, 2-Naphthol-3,6-disulfonic acid; NN, 1-Nitroso-2-naphthol; ODETA, 4-
(N-octyl)diethylenetriamine; PA, Polyacrylate; PAA, Piconilic acid amide; PADMAP 2-(2-pyridylazo)-5-dimethylaminophenol;
PAN, 1-(2-pyridylazo)2-naphthol; PaPhA, Poly(aminophosphonic acid); PAR, 4-(2-pyridylazo)resorcinol; PC, Pyrocatechol;
PDATA, Propylenediaminetetraacetic acid; PDT, 3-(2-Pyridyl)-5,6-diphenyl-l,2,4-triazine; PDTC, Poly(dithiocarbamate); PE,
Polyethylene; PGC, Porous graphitized carbon; Ph, Phenyl; PipDTC, Piperidine dithiocarbamate; PS-DVB, Polystyrene-divinylben-
zene; PTFE, Polytetrafluoroethylene; PUF, Polyurethane foam; PV, Pyrocatechol violet; ROMP, Ring-opening metathesis polymer-
isation; SA, Salicylic acid; SDS, Sodium dodecylsulfate; SFE, Supercritical fluid extraction; SGBM, Silica gel bound macrocycles;
SPE, Solid phase extraction; SPS, Solid-phase spectrophotometry; TAN, 1-(2-tiazolylazo)-2-naphthol; TBP, Tri-n-butyl phosphate;
T4BPP, Tetra-(4-bromophenyl)-porphyrin; TBT, Tributyltin; TCPP, Carboxyphenylporphyrin; THF, Tetrahydrofuran; TOPO, Tri-n-
octylphosphine oxide; TPhT, Triphenyltin; TS, Methylthiosalicylate; TSA, Thiosalicylic acid; TTA, 2-Thenoyltrifluoroacetone; UV,
Ultraviolet; XO, Xylenol orange.
*Corresponding author. Tel.: q33-1-44-08-17-25; fax: q33-1-44-08-16-53.
E-mail address: camel@inapg.fr (V. Camel).
0584-8547/03/$ - see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0584-8547Ž03.00072-7
1178 V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233
1. Introduction tants, especially pesticides, in water samples w3x.

However, numerous studies have also shown the
Despite the selectivity and sensitivity of analyt- great potential of this technique for speciation
ical techniques such as atomic absorption spec- studies.
trometry, there is a crucial need for the
preconcentration of trace elements before their 2.1. Presentation of the technique
analysis due to their frequent low concentrations
in numerous samples (especially water samples). 2.1.1. Basic principles
Additionally, since high levels of non-toxic com- An SPE method always consists of three to four
ponents usually accompany analytes, a clean-up successive steps, as illustrated in Fig. 1. First, the
step is often required. Liquid–liquid extraction is solid sorbent should be conditioned using an
a classical method for preconcentrating metal ions appropriate solvent, followed by the same solvent
andyor matrix removal. Solid phase extraction as the sample solvent. This step is crucial, as it
(SPE) is another approach that offers a number of enables the wetting of the packing material and
important benefits. It reduces solvent usage and the solvation of the functional groups. In addition,
exposure, disposal costs and extraction time for it removes possible impurities initially contained
sample preparation. Consequently, in recent years in the sorbent or the packaging. Also, this step
SPE has been successfully used for the separation removes the air present in the column and fills the
and sensitive determination of metal ions, mainly void volume with solvent. The nature of the
in water samples. After outlining the theory of this conditioning solvent depends on the nature of the
technique, guidelines are given for the develop- solid sorbent. Typically, for reversed phase sorbent
ment of SPE-based methods for preconcentration (such as octadecyl-bonded
{ silica), methanol is
of many trace elements. Finally, examples of appli- frequently used, followed with water or aqueous
cations are presented. buffer whose pH and ionic strength are similar to
that of the sample. Care must be taken not to
2. Theory allow the solid sorbent to dry between the condi-
tioning and the sample treatment steps, otherwise
The principle of SPE is similar to that of liquid– the analytes will not be efficiently retained and
liquid extraction (LLE), involving a partitioning poor recoveries will be obtained. If the sorbent
of solutes between two phases. However, instead dries for more than several minutes, it must be
of two immiscible liquid phases, as in LLE, SPE reconditioned.
involves partitioning between a liquid (sample The second step is the percolation of the sample
matrix) and a solid (sorbent) phase. This sample through the solid sorbent. Depending on the system
treatment technique enables the concentration and used, volumes can range from 1 ml to 1 l. The
purification of analytes from solution by sorption sample may be applied to the column by gravity,
on a solid sorbent. The basic approach involves pumping, aspirated by vacuum or by an automated
passing the liquid sample through a column, a system. The sample flow-rate through the sorbent
cartridge, a tube or a disk containing an adsorbent should be low enough to enable efficient retention
that retains the analytes. After all of the sample of the analytes, and high enough to avoid excessive
has been passed through the sorbent, retained duration. During this step, the analytes are concen-
analytes are subsequently recovered upon elution trated on the sorbent. Even though matrix com-
with an appropriate solvent. The first experimental ponents may also be retained by the solid sorbent,
applications of SPE started fifty years ago w1,2x. some of them pass through, thus enabling some
However, its growing development as an alterna- purification (matrix separation) of the sample.
tive approach to liquid–liquid extraction for sam- The third step (which is optional) may be the
ple preparation started only in the mid-1970s. It washing of the solid sorbent with an appropriate
has been extensively used in the past fifteen years solvent, having a low elution strength, to eliminate
for the preconcentration of organic micropollu- matrix components that have been retained by the
V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233 1179
Fig. 1. SPE operation steps.
solid sorbent, without displacing the analytes. A 2.1.2.1. Adsorption. Trace elements are usually
drying step may also be advisable, especially for adsorbed on solid phases through van der Waals
aqueous matrices, to remove traces of water from forces or hydrophobic interaction. Hydrophobic
the solid sorbent. This will eliminate the presence interaction occurs when the solid sorbent is highly
of water in the final extract, which, in some cases, non-polar (reversed phase). The most common
may hinder the subsequent concentration of the sorbent of this type is octadecyl-bonded silica
extract andyor the analysis. (C18-silica). More recently, reversed polymeric
The final step consists in the elution of the phases have appeared, especially the styrene-divi-
analytes of interest by an appropriate solvent, nylbenzene copolymer that provides additional p-
without removing retained matrix components. The p interaction when p-electrons are present in the
solvent volume should be adjusted so that quanti- analyte w4x. Elution is usually performed with
tative recovery of the analytes is achieved with organic solvents, such as methanol or acetonitrile.
subsequent low dilution. In addition, the flow-rate Such interactions are usually preferred with on-
should be correctly adjusted to ensure efficient line systems, as they are not too strong and thus
elution. It is often recommended that the solvent they can be rapidly disrupted. However, because
volume be fractionated into two aliquots, and most trace element species are ionic, they will not
before the elution to let the solvent soak the solid be retained by such sorbents.
sorbent.
2.1.2.2. Chelation. Several functional group atoms
are capable of chelating trace elements. The atoms
2.1.2. Retention of trace elements on the sorbent most frequently used are nitrogen (e.g. N present
Adsorption of trace elements on the solid sor- in amines, azo groups, amides, nitriles), oxygen
bent is required for preconcentration (see Fig. 2). (e.g. O present in carboxylic, hydroxyl, phenolic,
The mechanism of retention depends on the nature ether, carbonyl, phosphoryl groups) and sulfur
of the sorbent, and may include simple adsorption, (e.g. S present in thiols, thiocarbamates, thioeth-
chelation or ion-exchange. Also, for trace elemen- ers). The nature of the functional group will give
ts, ion-pair solid phase extraction may be used. an idea of the selectivity of the ligand towards
trace elements. In practice, inorganic cations may

be divided into 3 groups:
– group I-‘hard’ cations: these preferentially react

via electrostatic interactions (due to a gain in
entropy caused by changes in orientation of
hydration water molecules); this group includes
alkaline and alkaline-earth metals (Ca2q,
Mg2q, Na2q) that form rather weak outer-sphere
complexes with only hard oxygen ligands.
– group II-‘borderline’ cations: these have an
intermediate character; this group contains
Fe2q, Co2q Ni2q Cu2q Zn2q Pb2q Mn2q. They
possess affinity for both hard and soft ligands.
– group III-‘soft’ cations: these tend to form
covalent bonds. Hence, Cd2qand Hg2q possess
strong affinity for intermediate (N) and soft (S)
ligands.
For soft metals, the following order of donor

atom affinity is observed: 0-N-S. A reversed
order is observed for hard cations. For a bidentate
ligand, affinity for a soft metal increases with the
overall softness of the donor atoms: (0, 0)-(0,
N)-(N, N)-(N, S). The order is reversed for
hard metals. In general, the competition for a given
ligand essentially involves Group I and Group II
metals for O sites, and metals of Group II and
Group III for N and S sites. The competition
between metals of Group I and Group III is weak.
Chelating agents may be directly added to the
sample for chelating trace elements, the chelates
being further retained on an appropriate sorbent.
An alternative is to introduce the functional che-
lating group into the sorbent. For that purpose,
three different means are available: (1) the synthe-
sis of new sorbents containing such groups (new
sorbents); (2) the chemical bonding of such
groups on existing sorbents (functionalized sor-
bents); and (3) the physical binding of the groups
on the sorbent by impregnating the solid matrix
with a solution containing the chelating ligand
(impregnated, coated or loaded sorbents). The
latter remains the most simple to be used in
practice. Its main drawback is the possible flush
Fig. 2. Interactions occurring at the surface of the solid sorbent. of the chelating agent out of the solid sorbent
F, functional group; TE, trace element; MS, matrix solvent; MI, during sample percolation or elution that reduces
matrix ions; ES, elution solvent. the lifetime of the impregnated sorbent.
Different ligands immobilized on a variety of 2.1.2.4. Ion exchange. Ion-exchange sorbents usu-
solid matrices have been successfully used for the ally contain cationic or anionic functional groups
preconcentration, separation and determination of that can exchange the associated couter-ion. Strong
trace metal ions. Chelating agents with an hydro- and weak sites refer to the fact that strong sites
phobic group are retained on hydrophobic sorbents are always present as ion-exchange sites at any
(such as C18-silica). Similarly, ion-exchange resins pH, while weak sites are only ion-exchange sites
are treated with chelating agents containing an ion- at pH values greater or less than the pKa. Strong
exchange group, such as a sulfonic acid derivative sites are sulfonic acid groups (cation-exchange)
of dithizone (i.e. diphenylthiocarbazone) (DzS), and quaternary amines (anion-exchange), while
5-sulfo-8-quinolinol, 5-sulfosalicylic acid, thiosal- weak sites consist of carboxylic acid groups (cat-
icylic acid, chromotropic acid, or carboxyphenyl- ion-exchange) or primary, secondary and tertiary
porphyrin (TCPP) w5–8x. amines (anion-exchange). These groups can be
Binding of metal ions to the chelate functionality chemically bound to silica gel or polymers (usually
is dependent on several factors: (1) nature, charge a styrene-divinylbenzene copolymer), the latter
and size of the metal ion; (2) nature of the donor allowing a wider pH range.
atoms present in the ligand; (3) buffering condi- An ion-exchanger may be characterized by its
tions which favor certain metal extraction and capacity, resulting from the effective number of
binding to active donor or groups; and (4) nature functional active groups per unit of mass of the
of the solid support (e.g. degree of cross-linkage material. The theoretical value depends upon the
for a polymer). In some cases, the behavior of nature of the material and the form of the resin.
immobilized chelating sorbents towards metal pre- However, in the column operation mode, the oper-
concentration may be predicted using the known ational capacity is usually lower than the theoret-
values of the formation constants of the metals ical one, as it depends on several experimental
with the investigated chelating agent w9x. However, factors, such as flow-rate, temperature, particle
the presence of the solid sorbent may also have an size and concentration of the feed solution. As a
effect and lead to the formation of a complex with matter of fact, retention on ion-exchangers depends
a different stoichiometry than the one observed in on the distribution ratio of the ion on the resin,
a homogeneous reaction w10,11x. In fact, several the stability constants of the complexes in solution,
characteristics of the sorbent should be taken into the exchange kinetics and the presence of other
account, namely the number of active groups competing ions. Even though ion-exchangers
available in the resin phase w7,10x, the length of recover hydrated ions, charged complexes and ions
the spacer arm between the resin and the bound complexed by labile ligands, they are of limited
ligand w12x, and the pore dimensions of the resin use in practice for preconcentration of trace ele-
w13x. ments due to their lack of selectivity and their
retention of major ions w17x. Yet, for some partic-
2.1.2.3. Ion-pairing. When a non-polar sorbent is ular applications they may be a valuable tool.
to be used, an ion-pair reagent (IP) can be added Hence, iron speciation was possible through selec-
to the sorbent w14x. Such reagents contain a non- tive retention of the negative Fe(III)-ferron com-
polar portion (such as a long aliphatic hydrocar- plex on an anion-exchanger w18x. Selenium
bonated chain) and a polar portion (such as an speciation was also feasible by selectively eluting
acid or a base). Typical ion-pair reagents are Se(IV) and Se(VI) retained on a anion-exchanger
quaternary ammonium salts and sodium dodecyl- w19x.
sulfate (SDS) w15,16x. The non-polar portion inter-
acts with the reversed-phase non-polar sorbent, 2.1.3. Elution of trace elements from the sorbent
while the polar portion forms an ion-pair with the The same kind of interactions usually occur
ionic species present in the matrix (that could be during the elution step. This time, the type of
either free metallic species in solution or solvent must be correctly chosen to ensure stronger
complexes). affinity of the trace element for the solvent, to
containers is available. In addition, the size of the

column (i.e. the sorbent weight) may be adapted
to the sample volume. In particular, it allows larger
sample volumes, thus enabling the preconcentra-
tion of metal ions at very low concentration levels.
However, such columns must be reused, so that
careful blank washings should be conducted to
avoid cross-contamination. In addition, columns
with a narrow internal diameter limit usable flow-
rates to a range 1–10 mlymin that necessitates
long trace-enrichment times for large sample vol-
umes w22x.
As will be discussed later, micro-columns are
frequently used in systems affording the on-line
coupling of SPE to analytical techniques. However,
in that case, the size of the column is limited to
Fig. 3. Disposable sorbent containers.
achieve acceptable analytical performance.
ensure disruption of its interaction with the sorbent 2.2.2. Disposable cartridges and syringe barrels
(as illustrated in Fig. 2). Thus, if retention on the Nowadays, the most frequently used design in
sorbent is due to chelation, the solvent could off-line SPE is the cartridge or the syringe barrel.
contain a chelating reagent that rapidly forms a They are usually made of polypropylene or poly-
stronger complex with the trace metal. Elution ethylene and filled with packing material having
may also be achieved using an acid that will different functional groups. The solid sorbent is
disrupt the chelate and displace the free trace contained between two 20 mm polypropylene frits
element. Similarly, if retention is due to ion (in some cases they may be made of glass). They
exchange, its pH dependence enables the use of afford great selectivity due to the broad types of
eluents with different pH to be used, such as acids. sorbents contained in commercially available sys-
Of prime importance is to selectively elute only tems with different column volume available. In
the target species. So, if they are more strongly addition, their disposable character prevents pos-
retained on the sorbent than the interferent com- sible cross contamination.
pounds, a washing step with a solvent of moderate Cartridges vary from as little as 100 mg to 1 g
elution strength is highly advisable before elution or more. Syringe barrels range in size from 1 to
of the target species with the appropriate solvent. 25 ml and packing weights from 50 mg to 10 g.
Solvent reservoirs may be used at the top of the
2.2. Operation syringe barrels to increase the total volume (50–
100 ml). The barrel of the syringe terminates in a
The sorbent may be packaged in different for- male Luer tip, which is the standard fitting to be
mats: filled micro-columns, cartridges, syringe bar- used with various SPE vacuum manifolds availa-
rels and discs w2,20,21x. The disposable sorbent ble. For cartridges, both a female and male Luer
containers are illustrated in Fig. 3. tips are present, to enable use of either a positive
or negative pressure.
2.2.1. Micro-columns The major disadvantages of cartridges and
The use of a micro-column is a common pro- syringe barrels are slow sample-processing rates
cedure for extraction of trace elements from vari- and a low tolerance to blockage by particles and
ous samples. It affords the opportunity of packing adsorbed matrix components, due to their small
the column with the desired sorbent, so that a cross-sectional area. Channeling reduces the capac-
broader choice than the commercially disposable ity of the cartridge to retain analytes and results
in contamination of the isolated analytes with cartridges, so that for real samples (e.g. high
impurities originating from the manufacturing and content of natural organic matter in river water)
packing process. Such contaminants were evident incomplete retention of the target metal species
for C18-silica cartridges, while less contaminants may result w27x. As a consequence, disks are
were observed with C18-silica disks w23,24x. recommended when there is a strong interaction
between the analyte and the sorbent.
2.2.3. Disks
The use of flat disks with a high cross-sectional 2.3. Advantages of the technique
area may largely prevent all the problems encoun-
Classical liquid–liquid extractions of trace ele-
tered with columns, cartridges and tubes w21x. The
ments are usually time-consuming and labor-inten-
packing material is usually embedded in an inert
sive. In addition, they require strict control of
matrix of polytetrafluoroethylene (PTFE) microfi-
extraction conditions, such as temperature, pH and
brils, with a typical composition of 90% wyw
ionic strength. For all these reasons, several pro-
sorbent and 10% wyw PTFE fibers w25x. Other
cedures tend to be replaced by SPE methods. This
types of disks use a glass-fibre matrix to hold the
technique is attractive as it reduces consumption
sorbent particles, in order to enable a higher flow-
of and exposure to solvents, their disposal costs
rate. The disks are available in different diameters
and extraction time w28x. It also allows the achieve-
from 4 to 90 mm, the size most frequently used
ment of high recoveries w29x, along with possible
being 47 mm. They are designed to be used in
elevated enrichment factors. However, as different
conjunction with a filtration apparatus connected
results between synthetic and real samples may be
to a water aspirator w25x. In order to remove
observed w30x, recoveries should be estimated in
potential interferences and to ensure optimal
both cases as far as possible. In addition, SPE can
extraction of the analyte of interest, disk cleaning
be interfaced on-line with analytical techniques,
and conditioning should be done before its use.
such as liquid chromatography (LC) or atomic
Due to a lower void volume and a higher surface
absorption spectrometry (AAS). Its application for
area associated with small particles as compared
preconcentration of trace metals from different
to cartridges, partitioning of the analytes is
samples is also very convenient due to sorption of
favored. Hence, a smaller mass of sorbent is
target species on the solid surface in a more stable
required to process a similar volume of sample.
chemical form than in solution. Finally, SPE
Disks thus present the advantage of reducing sol-
affords a broader range of applications than LLE
vent volumes for both the conditioning and elution
due to the large choice of solid sorbents.
steps. Additionally, the decreased back-pressure
encountered with these devices enables the use of 2.3.1. Preconcentration
high flow-rates, and their wide bed minimizes the LLE requires the use of large volumes of high-
chance of plugging. In addition, new technology purity solvent, thereby affording limited precon-
for embedding the stationary phase prevents chan- centration factors. The use of SPE enables the
neling and improves mass transfer. As classical simultaneous preconcentration of trace elements
disks are dedicated to the SPE of large-volume and removal of interferences, and reduces the
samples, new systems have very recently emerged usage of organic solvents that are often toxic and
that enable the use of disks for small-volume may cause contamination. Upon elution of the
samples: the extraction disk cartridge (the disk is retained compounds by a volume smaller than the
placed in a syringe-barrel format), and the 96-well sample volume, concentration of the extract can
microtiter plate configuration w20,21,26x. Such sys- be easily achieved. Hence, concentration factors
tems are primarily dedicated to biological samples. of up to 1000 may be attained.
One of the drawbacks of using disks is the
decrease in the breakthrough volume (which is the 2.3.2. Preservation and storage of the species
volume that can be percolated without analyte SPE allows on-site pre-treatment, followed by
losses). In addition, disks have lower capacity than simple storage and transportation of the pre-treated
samples with stability of the retained metallic 2.3.4.1. On-line coupling to liquid chromatogra-
species for several days w21,24,31,32x. This point phy. On-line systems mainly use a micro-column.
is crucial for the determination of trace elements, The sorbent is chosen not only for its efficiency
as the transport of the sample to the laboratory in trapping analytes, but also for its compatibility
and its storage until analysis may induce problems, with the stationary phase packed into the chromat-
especially changes in the speciation. In addition, ographic column. Indeed, it is highly recommend-
the space occupied by the solid sorbents is minimal ed to use the same packing in the precolumn and
and avoids storage of bulky containers and the the chromatographic column to prevent losses in
manpower required to handle them. efficacy upon analysis. For the case of two differ-
ent sorbents being used, the retention of the anal-
2.3.3. High selectivity ytes in the precolumn should be lower than in the
SPE offers the opportunity of selectively extract- analytical column to ensure band refocusing at the
ing and preconcentrating only the trace elements head of the chromatographic column. On-line sys-
of interest, thereby avoiding the presence of major tems with several detectors have been reported,
ions. This is crucial in some cases, such as with such as ultraviolet (UV) detector w39x or induc-
spectrophotometric detection, since the determina- tively coupled plasma mass spectrometer (ICP–
tion of heavy metals in surface waters may neces- MS) w40x, with detection limits in the 0.05–50
sitate the removal of non-toxic metals, such as Fe mgyl range. Detection limits as low as 0.5 ngyl
could even be achieved by detection at the maxi-
or Zn, when they occur at high concentrations
w33x. It may also be possible to selectively retain mum absorption wavelength using a photodiode
array UV detector w41x. Additional coupling may
some particular species of a metal, thereby ena-
be feasible, such as the on-line coupling of super-
bling speciation. For example, salen I modified
critical fluid extraction (SFE) with an on-line
C18-silica is quite selective towards Cu(II) w34x,
SPE–LC system w42x. The coupling of SPE to LC
while chemical binding of formylsalicylic acid on
via flow injection has also been reported using
amino-silica gel affords selectivity towards Fe(III)
w35x. This high selectivity may also be used to cold vapour AAS (CV-AAS) as the detection,
enabling enrichment factors approximately 850
remove substances present in the sample that may w43x.
hinder metal determination, such as lipid sub-
stances in the case of biological samples w36x.
2.3.4.2. On-line coupling to atomic absorption
spectrometry. Olsen et al. w44x and Fang et al.
2.3.4. Automation and possible on-line coupling to w45,46x were the first to describe an on-line flow-
analysis techniques injection (FI) sorbent extraction preconcentration
SPE can be easily automated, and several com- system for flame AAS (F-AAS) using micro-
mercially available systems have been recently columns packed with a cation-exchanger. Later,
reviewed w26x. Home-made systems have also been they also proposed a system for on-line flow-
reported w37x. In addition, SPE can be coupled on- injection sorbent extraction preconcentration with
line to analysis techniques. On-line procedures electrothermal vaporization AAS (ET-AAS) using
avoid sample manipulation between preconcentra- lead as a model trace element w47x. Since then,
tion and analysis steps, so that analyte losses and numerous papers reported FI with on-line precon-
risk of contamination are minimized, allowing centration followed by AAS, as exemplified by
higher reproducibility w38x. In addition, all the determination of Cu, Cr(VI) or Pb w48–50x.
sample volume is further analyzed, which enables Selected applications are reported in Table 1. The
smaller sample volume to be used. However, in sorbent should provide for rapid sorption and
the case of complex samples, off-line SPE should desorption of the analytes to be used in FI systems
be preferred due to its greater flexibility, and the w65x. In addition, it should be provided for a high
opportunity to analyze the same extract using selectivity. In practice, C18-silica is very frequently
various techniques. used as organic solvents (such as methanol) can
Table 1
Applications of SPE to FI on-line preconcentration systems
Matrix Trace Chelating Sorbent Eluent Analysis method Recovery Loading Preconcentration LOD Sampling Ref.
elements agent (%) time factor (ngyl) frequency
added (volume) (hy1)
Inorganic sorbents
Sea and waste Cd None DPTH- HNO3 – ICP–AES 97.5–104 1 min 86 1100 40 w51x
waters functionalized- HCl
SiO2
Sea and waste Cd None TS- Thiourea ICP–AES 95.2– 2 min 62 4300 24 w51x
V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

waters functionalized- 2.5% in 103.3
SiO2 HNO3
Sea waters Fe None 8-HQ- HCl Spectro- 106.3 2 min — 0.016 nM — w52x
functionalized- photometry
SiO2
Geological Ag None MBT- Thiourea F-AAS 93.5–101 1 min — 660 60 w53x
sample, Cu functionalized-
metal, Pb SiO2
nitrate
Certified ore Ag, Au, None Amidino- Thiourea F-AAS 98.7–101.4 1 min — 1100–17 000 — w54x
samples, Pd thioureido- (4.5 ml)
Ni alloy, SiO2
anode slime,
electrolytic
solution
Fish, human MeHg, APDC C18-silica MeOH- LC–CV-AAS 92–106 20 min 750–950 5.5–10.4 2.3 w43x
urine EtHg, ACN- (58.5 ml)
PhHg, water
Hg(II)
Sea water MeHg, DDTC C18-silica EtOH CV-AAS 85–107.5 (25 ml) 500 16 — w55x
Hg(II)
Certified sea Cu, Cd APDC C18-silica MeOH ET-AAS 86.7– 104 s 25–100 6.5–1.26 — w56x
waters 106.5 (0.5 ml)
Certified sea Cu, Cd, Co 1,10- C18-silica EtOH F-AAS 88.9– 30 s 22–32 300–6000 90 w57x
water, Phenan- 100.5
mussel, throline
geological
samples
Certified Cd PAR or C18-silica MeOH ET-AAS 82.5– 110 s 25–50 1.7–4 9–12 w58x
sea waters PADMAP 111.2 (0.5 ml)
1185
1186
Table 1 (Continued)
Sea water, Cr(III), DDTC C18-silica MeOH F-AAS 95–105 60–300 s 90–500 20 30 w59x
industrial Cr(VI),
effluents Cr(total)
Sea, river Cr(VI), DDTC C18-silica EtOH ET-AAS 101–105 1 min 12 1600– 22 w60x
waters Cr(total) (3 ml) 1800
Certified low Co NN C18-silica Acidified F-AAS 98–102 30 s 17.2 3200 90 w61x

alloy steel, EtOH (3.25 ml)
mussel,
tomatoe leaves
Certified Pb DDTC C18-silica IBMK F-AAS 99.2– 2–10 min 60–189 3000 24 w62x
biological, 137.9
vegetable
samples
Standard Pb DDTP C18-silica EtOH F-AAS — 2.5–75 14–1000 300–3000 — w63x

solutions min
(10–150
ml)
Certified citrus MeHg, DDTP C18-silica EtOH CV-AAS 99.6– 4.5 min 20 10 12 w64x
leaves, Hg(II) 112.5 (23.85 ml)
marine
sediment
Standard Cu, Pb DDTC, 8- C18-silica MeOH F-AAS — 80 s 14–60 4000– — w65x
solutions quinolinol (4 ml) 10 000
or PAR
Sea water Cu None TAN-loaded- HCl ET-AAS 93.2–99.6 1 min 33 5 35 w66x
C18-silica (3 ml)
Pharmaceutical Zn None TAN-loaded- HCl Spectro- 89.8–107.8 — — 10 000 45 w67x
preparations C18-silica photometry
Sea water Fe(II), None FZ-loaded- MeOH Spectro- — 2–20 min 6–60 0.1– — w68x
Fe(III) C18-silica photometry (4–40 ml) 0.3 nM
River, tap, rain Al, Bi, None ZrO2 HNO3 ICP–AES 95.4–99 33 min 100 6–90 — w69x
waters Cd, Co, (100 ml)
Cr, Cu,
Fe, Ga,
In, Mn,
Mo, Ni,
Table 1 (Continued)
Pb, Tl,
V, Sb,
Sn, Zn
Waters Cr(VI) None Acidic Al2O3 NHq
4 ICP–AES — (2 ml) 10 200 — w70x
Lake, river, Cr(III), None Acidic Al2O3 HNO3 or F-AAS 90–106 35 s 25 800–1000 55 w71x
tap waters Cr(VI) NHq
4
Sewage waters Cr(III), None Al2O3 HNO3 or F-AAS 86–117 — — 42 000– — w72x

Cr(VI) NHq
4 81 000
Urine Cr(III) None Basic Al2O3 HNO3 ICP–AES )93 (10 ml) 50 50 — w73x
Organic sorbents
Tap, river, Cu APDC PTFE turnings IBMK F-AAS 94–102 1 min 340 50 40 w48x
coastal waters (12 ml)
Tap, river, Cr(VI) APDC PTFE turnings IBMK F-AAS 95.5– 3 min 80 800 18 w49x
coastal, 100.5 (37.8 ml)
industrial
waste waters
Tap, river and Pb APDC PTFE turnings IBMK F-AAS 95–102 3 min 330 800 15 w50x
coastal (39 ml)
waters,
marine
sediment,
fish and
mussel tissues
Drinking, sea Cr(VI) APDC PTFE (KR) EtOH ET-AAS 105 1 min 19 4.2 21.2 w74x
waters (5 ml)
Certified natural Cr(VI) APDC PTFE (KR) EtOH ET-AAS — 1 min 16.3 16 16.7 w75x
water, sea (5 ml)
water
Certified Cd, Co, Cu, Dithizone PTFE (KR) IBMK F-AAS 95.3– 1 min 23.4–69.3 1060– 18 w76x
human air, pig Zn 108.4 (5 ml) 2560
liver, sea
prawn
Certified Cd DDTC PTFE (KR) IBMK F-AAS 97.9–110 50 s 30 100 55 w77x
humain hair (4.2 ml)
and rice
powder
Certified natural Cr(VI) APDC PTFE beads EtOH ET-AAS 104–108 1 min 30.1 8.8 16.7 w75x
water, sea (5 ml)
1187
water
1188
Table 1 (Continued)
Standard Pb DDTP PUF EtOH F-AAS — 2.5–75 14–1000 300–3000 — w63x
solutions min
(10–150
ml)
Certified Cu None PAN-coated- HCl- F-AAS 99.6–103 (2.5– 29.1–296.1 60–600 — w32x
seawaters XAD-4 EtOH 25 ml)
Standard Cd, Zn None BSQ-loaded- HCl Fluorimetry — 20 s 10 1600– — w78x

samples XAD-7 (0.1 ml) 1900
Alloys, ores Pd, Pt, Rh ODETA Highly cross- HCl- F-AAS 77.8–103.6 1 min — 3000– 30 w79x
linked EtOH 8000
polystyrene
Tap water Cu, Cd, — IDA-Novarose HCl ICP–AES — 10 min 500–1000 — — w80x
Ni
River, ground Cu, Cd, Sulfa- Lewatit HCl Spectro- 80–120 50 min 50 2000– — w33x
waters Pb sarzene TP807’84 photometry (100 ml) 5500
River, mineral Cr(III) None PAPhA HCl F-AAS 97–01 90 s 35 200 30 w81x
and tap (6.6 ml)
waters
Estuarine Cu, Cd, None Toyopearl AF- HNO3 ICP–MS 87–10 1 min — 1.4–86 — w82x
waters Ni, Chelate 650 (1 ml)
Zn, Mn M
Synthetic sea Cd, Cu, None Cation HNO3 F-AAS — — 50–105 30–200 60 w45x
water Pb, Zn exchanger
Natural waters Cr(VI), DPC Cation HNO3- Spectro- 93–08 — — 8.9–15.2 — w83x
Cr(total) exchanger acetone photometry
Certified pig Cd, Ni, Pb None Cation HCl ICP–MS 96.7–03.7 2 min 10 1000–4000 90 w84x
kidney, rye exchanger (7.8 ml)
grass, rice
flour, tomato
leaves
Ground Cu Batho- Anion HNO3 Spectro- — 10 min — 80 — w85x
water cuproine exchanger photometry (8.3 ml)
Water, vegeta- Cd None Anion HNO3 Spectro- 94–104 90 s — 230 20 w86x
ble samples exchanger photometry (5 ml)
Standard Pb DDTP Activated EtOH F-AAS — 2.5–75 14–1000 300–3000 — w63x
solutions carbon min
(10–150
ml)
Table 1 (Continued)
Steels, Al solutions Bi DDTP Activated EtOH ET-AAS 87–104.3 4 min 14 48 7 w87x
carbon (10 ml)
Tap, mineral, Cu APDC Activated IBMK F-AAS 88–113 2 min 100 600 17 w88x
well, river, carbon (4.5 ml)
swimming
pool waters
Silicon, tap Fe None Activated HCl MPT–AES 97.4–105 1 min 4.3–6.4 1000–36 000 — w89x

water carbon (1.2 ml)
Rock, copper Pd None Activated Thiourea F-AAS 103–107 3 min 145 300 15–20 w90x
ore carbon (15.6 ml)
1189
be used as eluting solvents leading to a high alized silica gel for example w51,69x. Similarly,
sensitivity in flame AAS. Complexing reagents numerous studies have reported on-line coupling
are, therefore, added for efficient retention of trace to ICP–MS, as noted earlier w95x. A few examples
metals. Their choice is based on their fast reaction are given in Table 1 w82,84x.
with metals, such as diethyldithiocarbamate
(DDTC) and ammonium pyrrolidine dithiocarba- 2.3.4.4. On-line coupling to spectrophotometry.
mate (APDC) w56,59,60,62,91x. In addition, both Spectrophotometry offers the advantage of requir-
reagents are water soluble and do not adsorb on ing inexpensive and very common instrumentation.
C18-silica so that it does not overload with the In addition, by choosing a non-selective chromo-
reagent itself. However, these reagents lack selec- genic reagent, multi-metal determinations may be
tivity, so that other reagents have been used for possible w33x. Its coupling to FI analysis is well
particular applications, like 1-10-phenanthroline suited for monitoring purposes and a few studies
w57x, 4-(2-pyridylazo)resorcinol (PAR) or 2-(2- present such systems as indicated in Table 1
pyridylazo)-5-dimethylaminophenol (PADMAP) w33,52,68,86x. Solid-phase spectrophotometry
w58x, 0,0-diethyl-dithiophosphate (DDTP) w63x, l- (SPS) has also been reported with FI systems due
nitroso-2-naphthol (NN) w61x. l-(2-tiazolylazo)-2- to its simplicity and low detection limits. The solid
naphthol (TAN) w66x. The microcolumn can be sorbent is packed in either commercially available
inserted into the tip of the PTFE capillary in the or customized flow cells. With such systems the
autosampler arm of a graphite furnace atomic retained analytes are periodically removed from
absorption spectrometer w56x. the flow cell using an acid or a complexing
Even though C18-silica has been the most fre- solution w67,83,85x.
quently used sorbent for FI preconcentration, other On-line FI sorbent extraction procedures have
sorbents were found satisfactory for some appli- several advantages over the corresponding off-line
cations as shown in Table 1, such as functionalized methods: higher sample throughput (increased by
silica w51–53x, alumina w70–73x, activated carbon 1 to 2 orders of magnitude), lower consumption
w63,87–90x, polyurethane foam (PUF) w63,92x, or of sample and reagent (also reduced by 1 to 2
PTFE turnings w48–50x. A particular knotted reac- orders of magnitude), better precision (with rela-
tor (KR) has been recently developed, which tive standard deviations approx. 1–2%), lower risk
consists of a long tube properly knotted usually of loss or contamination and easy automation.
made of PTFE. The trace element species are However, the FI method by using column extrac-
adsorbed on the inner wall of the tubing as tion has some disadvantages. In particular, it may
indicated by scanning electron microscopy w77x. suffer from insufficient adsorption on the resin and
This reactor allows higher sample loading volumes clogging of the column when insoluble ligands are
than micro-columns due to its lower back-pressure. used w96x.
In addition, the inner wall may be precoated with
a hydrophobic ligand for subsequent retention of 3. Step-by-step method development guide
trace elements w93x. However, on the other hand,
lower enrichment factors are attained as compared Development of an SPE method can be consid-
to micro-columns w75x. For that reason, in case of ered as a two-step procedure. First, the most
trace metals, micro-columns are usually preferred appropriate sorbent for the application should be
for the achievement of low levels of determination. chosen (the following is intended to help the reader
in choosing a solid sorbent for trace element
2.3.4.3. On-line coupling to ICP–AES or ICP– determination). Optimization of the most influen-
MS. The first report of FI on-line preconcentration tial parameters should then be undertaken. Obvi-
coupled to ICP-atomic emission spectrometry ously, optimization should initially be performed
(AES) appeared nearly twenty years ago w94x. using spiked synthetic solutions, but it must be
Since then, several studies have used this coupling followed by the use of certified reference materials
with different sorbents such as ZrO2 or function- or spiked real samples, as matrix components
(such as ligands or other ions) may change the as organic based ones (natural polymers, as well
trace element retention on the sorbent, thereby as synthetic polymers) and inorganic based ones
decreasing recoveries of the target species. (silica gel SiO2, alumina A12O3, magnesia MgO
and other oxide species). Immobilization of organ-
3.1. Selection of solid sorbent ic compounds on the surface of the solid support
is usually aimed at modifying the surface with
Solid sorbents may be hydrophobic or polar. It certain target functional groups for a higher selec-
is common to call reversed-phase sorbents the tivity of the extraction. The selectivity of the
packing materials that are more hydrophobic than modified solid phases towards certain metal ions
the sample, which are frequently used with aque- is attributed to several well-known factors, such as
ous samples. On the other hand, normal-phase the size of the organic compound used to modify
sorbents refer to materials more polar than the the sorbent, the activity of the loaded surface
sample and they are used when the sample is an groups, and the type of the interacting functional
organic solvent containing the target compounds. group. However, the selective extraction of a single
When hydrophobic supports are used, retention of trace element from other interfering ion(s) repre-
ionic metal species will require the formation of sents a direct challenge for finding a suitable phase
hydrophobic complexes. This can be achieved capable of exhibiting a sufficient affinity to selec-
through addition of the proper reagent to the tively bind that metal ion. For particular applica-
sample or thorough immobilization of the reagent tions, the combination of two sorbents may thus
on the hydrophobic solid sorbent. Addition of be advisable. As an example, the passage of water
reagent to the sample is appropriate for the fixation samples through two successive chelating resins
of unstable metal species (such as Cu(I) and enabled the determination of trace and major
Fe(II)) to maintain speciation, while immobiliza- elements w98x. Similarly, the combination of an
tion offers the convenience of having a prepared anion and a cation-exchange resin enabled the
cartridge or disk before analysis. Immobilization speciation of Cu and Mn in milk samples w99x.
may also provide a significant development in
speciation analysis, because metal equilibrium in 3.1.1. Inorganic based sorbents
the sample may not be affected by reaction on the Inorganic based sorbents are mainly made of
cartridge. silica gel even though other inorganic oxides may
The nature and properties of the sorbent are of be used, as discussed later (cf. Fig. 4). Silica gel
prime importance for effective retention of metallic based sorbents present the advantages of mechan-
species. Careful choice of the sorbent is thus ical, thermal and chemical stability under various
crucial to the development of SPE methodology. conditions. They frequently offer a high selectivity
In practice, the main requirements for a solid towards a given metal ion. However, all silica-
sorbent are: (1) the possibility to extract a large based sorbents suffer from different chemical lim-
number of trace elements over a wide pH range itations, namely the presence of residual surface
(along with selectivity towards major ions); (2) silanol groups (even after an end-capping treat-
the fast and quantitative sorption and elution; (3) ment) and a narrow pH stability range. Applica-
a high capacity; (4) regenerability; and (5) acces- tions of such sorbents to off-line SPE are presented
sibility. In particular, sorbents that allow fast reac- in Tables 2 and 3.
tion rates are preferred to achieve faster extraction
as well as higher loading capacities. Hence, sor- 3.1.1.1. Silica gel. Silica gel can be used as a very
bents based on hydrophilic macroporous polymers successful adsorbing agent, as it does not swell or
and cellulose or on fibrous materials provide excel- strain, has good mechanical strength and can
lent kinetic properties w97x. undergo heat treatment. In addition, chelating
The broad variety of sorbents available explains agents can be easily loaded on silica gel with high
one of the most powerful aspects of SPE, which stability, or be bound chemically to the support,
is selectivity. Sorbents can be mainly categorized affording a higher stability.
Fig. 4. Sorbents based on inorganic supports.
The surface of silica gel is characterized by the bent, or by soaking the adsorbent in the reagent
presence of silanol groups, which are known to be solution.
weak ion-exchangers, causing low interaction, Impregnating reagents are ion-exchangers or
binding and extraction of ionic species w131x. In chelating compounds. Numerous reagents have
particular, silica gel presents high sorption capacity been investigated for impregnation of silica gel as
for metal ions, such as Cu, Ni, Co, Zn or Fe w132x. a means of increasing retention capacity and selec-
Retention is highly dependent on sample pH with tivity of the sorbent for trace elements, namely
quantitative retention requiring pH values over thionalide (2-mercapto-N-2-naphthylacetamide)
7.5–8, as under acidic conditions silanol groups w101,102x, 2-mercaptobenzothiazole (MBT)
are protonated and the ion-exchange capacity of w133x, NN w103x, 8-hydroxyquinoline (8-HQ)
the silica gel is greatly reduced or even reduced w134,135x, 3-methyl-l-phenyl-4-stearoyl-5-pyrazo-
to zero at low pHs. In addition, this sorbent has a lone (MPSP) w100x, salicylaldoxime w132x, dime-
very low selectivity, and is prone to hydrolysis at thylglyoxime (DMG) w13x, Aliquat 336 (methyl-
basic pH. Consequently, modification of the silica tricaprylammonium chloride) and Calcon (hydro-
gel surface has been performed to obtain solid phobic sodium sulfonate) w136x. Examples of
sorbents with greater selectivity. Two approaches applications are given in Table 2. Increased stabil-
are used for loading the surface with specific ity of the sorbent is obtained by the chemical
organic compounds, chemical immobilization and binding of chelating functional groups on silica
physical adsorption. In the first case, a chemical gel w104x. Applications to the determination of
bond is formed between the silica gel surface trace elements have been reported for more than
groups and those of the organic compound (func- twenty years with several functional groups, such
tionalized sorbent). In the second approach, the as amines, dithiocarbamates, iminodithiocarba-
organic compound is directly adsorbed on the mates or dithioacetals w13,105,106,137,138x. Care-
silanol groups of the silica gel surface (impregnat- ful choice of the bound chelating groups enables
ed or loaded sorbent), either by passing the reagent speciation studies. Hence, dithizone-functionalized
solution through a column packed with the adsor- silica gel was reported selective towards Hg(II)
Table 2
Applications of off-line SPE to water samples using inorganic supports
Matrix Trace Sorbent Operation Experimental Analysis Recovery Adsorptive Preconcentration LOD Ref.
elements conditions method (%) capacity factor (mgyl)
Silica
Tap water CuyCoyNi MPSP-loaded- Glass Sample F-AAS 94.6–101 43y45y49 40 60y40y70 w100x
SiO2 column pH: 4.5 mmolyg
Elution:
HCl 1 M
Sea water Pd Thionalide- Glass Sample pH: 4 F-AAS 83–99 0.8 mgyg 3200 0.03 w101x

loaded-SiO2 column Washing
(1 cm elution:
i.d) thiourea 0.2
MqHCl 0.1 M
Sea water As(III) Thionalide- Glass Sample pH: 7 Spectro- 92–95 5.6 mmolyg — 0.12 w102x
loaded-SiO2 column Washing photometry
(1 cm elution:
i.d) NaBoratey
NaOHy
Iodine
(pH 10)
River and sea Co NN-loaded- Glass Sample pH: 3.5 g-Emission 96–98 0.03 10–100 — w103x
water SiO2 column Washing mmolyg
elution:
acetic
acid
Spiked tap Hg(II) Dithizone- Column Elution: CV-AAS 99–99.5 300 mmolyg 200 3.96 w104x
water functionalized- HCl 10 M
SiO2
Tap and sea Hg(II) Dithioacetals- Column Elution: water CV-AAS 91–100 917–1100 5 — w105x
waters functionalized- mmolyg
SiO2
Spiked tap Hg(II) Dithiocarbamates- Glass Elution: water CV-AAS 88–100 0.6–0.983 — — w106x
and sea functionalized- column mmolyg
waters SiO2
1193
1194
Table 2 (Continued)
Sea water VyCoyNiy 8-HQ- Column Washing ICP–MS 85–116 — 10 0.00037– w107x
GayYyMoy functionalized- (6 mm i.d, sample 2200 ngyl
CdyCryPry fluorinated 30 mm pH: 5 Washing
NdySmyEu metal bed elution: HNO3
yGdyTbyDy alkoxide height) 0.5 M
yMoyEry glass backflush
TmyYbyLuy
WyU

Other oxides
Rain, river, Cr(III)yCr TiO2 Glass Sample pH: ET-AAS 78.4–99.2 8125y6983 100 0.030y0.024 w108x
sea, tap (VI) column 2 or 8 Elution: mgyg
waters (1 cm HNO3 0.5
i.d) or 1 M
Natural, waste, CdyCoyCu TiO2 Glass Sample pH: 8 F-AAS 89–100 5000 300 0.01– w109x
sea waters yFeyMnyNi column Elution: mgyg 0.04
yPb (1 cm HNO3 1 M
i.d) andyor EDTA
0.1 M
Tap, ground Cr(III)y Neutral Column Sample pH: ET-AAS 99–100 — 25 0.01 w110x
waters Cr(VI) Al2O3 (1 cm 6.5–7 Elution:
i.d) NH3 1 Mq
HNO3 4 M
Tap, ground Se(IV)y Acidic Teflon Sample pH: ET-AAS 90–98 23.2y2.0 16y100 0.049y w111x
waters Se(VI) Al2O3 column 2–8 Elution: mgyg 0.80
(1 cm NH3 0.1
i.d) M and 4 M
Table 3
Applications of off-line SPE to water samples using C18-silica based supports
Matrix Trace Reagent Operation Experimental Analysis Recovery Adsorptive Preconcentration LOD Ref.
No reagent
Sea water TBT None Cartridge Conditioning GC–ECD 93.5– — 1000 — w24x
or sample drying 111.5
Empore elution:
disk acidified
(25 mm) ethyl acetate
Spiked sea TPhT None Bond Elut Conditioning: Fluorimetry 81–89 — 100 — w112x

waters cartridge MeOHqNaCl
Sample
Washing
Air drying
Elution:
10y4 M FlOH
in MeOH
backflush
Sea water TPhT None Bond-Elut Washing Fluorescence — — 250 — w113x
cartridge sample (after addition
(40 mm) Washing air of flavonol
drying elution: to the eluate)
MeOH
Addition of the reagent to the sample
Sea water SeySb APDC Glass Sample ET-AAS 94–97 — 40–75 0.007y0.05 w114x
column pH: 1.2
(1.4 cm Washing
i.d) elution:
MeOH
Sea water CdyZnyCuy 8-HQ Glass Sample ET-AAS 67–108 — 50–100 — w115x
MnyFeyNiy column pH: 8.9
Co (1.4 cm Washing
i.d) (waterq
oxine)
elution:
MeOH
1195
1196
Table 3 (Continued)
Loaded reagent onto the sorbent
River water Cu Neocuproine Empore Washing Spectro- 99.7– 940 mg 50–100 0.12 w116x
disks conditioning: photometry 102.6 Cu2q
(47 mm) MeOH Sample (454 nm)
pH: 5.0 Drying
Elution:
isopentyl

alcohol
CRM water Cu(I) Bathocuproine Bond Elut Conditioning: Spectro- — — 20–40 0.40–3.8 w27x
(SLRS-3), cartridge MeOHqwater photometry
lake, Empore Sample pH: 4.3 (484 nm)
river, disk Elution:
drinking MeOH-
waters water 90:10
(vyv)
Tap waters, Fe Bathophenan- Empore Washing Spectro- — — 0.080 w117x
well water throline disks activation: photometry
(47 mm) MeOHqwater (533 nm)
Sample
pH: 4–7
Elution:
EtOHq
NaClO4
Synthetic MeHgy Dithizone Sep Pak Sample pH: LC–DAD 95–104 200 0.14y w31x
seawaters PhHgy cartridge 4qEDTA 0.16y
Hg(II) 0.001 0.14
M Washing
Elution: MeOH
Rain, lake, MonoBTy Tropolone Sep-Pak Conditioning: Ethylation-GC– — — — — w118x
river DiBTyTBT cartridge MeOH sample FPD
waters yMonoPhT pH: 2–3 Air
yDiPhTyTP drying Elution:
hT diethyl ether
Tap, well and Cu Quinone Empore Washing F-AAS 98.4–102 360 mg 400 0.2 w119x
river waters derivative disks Conditioning: Cu2q
(47 mm) buffer sample
pH: 7.0
Drying
Elution: HNO3
0.1 M
Table 3 (Continued)
Tap, rain, Cu(II) Schiff’s base Empore Washing AAS — 396 mg )500 0.004 w34x
snow and (salen I) disk sample Cu2q
sea waters (47 mm) pH: 5.5–6
Air drying
elution: HNO3
0.1 M
Synthetic and Pb(II) Schiff’s base Empore Washing F-AAS 97.1– 700 50 16.7 w120x
spring waters disk sample 100.2 mgydisk

pH: 2–8 Air
drying Elution:
HNO3 O.5 M
River water Pb(II) BAS Empore Washing F-AAS — 476 mg G300 0.050 w121x
disk sample Pb2q
(47 mm) pH: 2–7 Air
drying elution:
acetic acid 1 M
Sea waters Fe(II) Ferrozine Sep Pak Conditioning: Spectro- 91 — 40 0.6 w122x
cartridge MeOHqwater photometry nmolyl
sample pH: (562 nm)
6.8–8.3
Washing
Elution: MeOH
Rain, sea Fe(II) Ferrozine Sep Pak Conditioning: LC–UV 92–99 — 100–500 0.1 nmolyl w123x
waters cartridge MeOHqwater (254 nm)
Sample
Washing
Elution: MeOH
Certified sea CuyCd APDC Teflon Conditioning: ET-AAS 95.8– — 25–50 0.0024y w124x
waters cartridge MeOHqwater 103.3 0.00018
(NASS-2 and (0.94 mm Sample: 6–8
SLEW-1) i.d) Air drying
Elution:
MeOH
Tap and U(IV) TOPO Empore Washing Spectro- 85 4033 8 0.1 w125x
Spring disk conditioning photometry mgydisk
waters (47 mm sample elution:
i.d) MeOH
1197
1198
Table 3 (Continued)
Sea waters LayCeyPry HDEHPy Sep Pak Sample ICP–MS 88.8–99.8 — 200–1000 — w126x
NdySmyEuy H2ME cartridge pH:3–3.5
GdyTby HP Washing
DyyHoy elution:
EryTmy HCl 6 M
YbyLu
Spiked natural Bi Cyanex 301 Cartridge Conditioning: ET-AAS 98.5–100 — 10–100 105 w127x
waters (0.5 g) HCl 0.1 M

Sample
pH: 1
Air drying
Elution:
HNO3 3 M
Sea, well Be Quinalizarin Sep pak Washing F-AAS 98–101 200 mg 200 0.2 w128x
and tap cartridge conditioning
waters sample
pH: 6–6.6
Elution:
HNO3 0.5 M
Tap, spring Agq HT18C6 Empore Conditioning: AAS 996– 210 mg 200 0.050 w129x
waters disk MeOHqwater 100.3 Agydisk
Sample elution:
Na2S2O3 0.1 M
Tap, river, Hg(II) HT18C6TO Empore Washing CV-AAS 97.1– 241 mg 50 0.006 w130x
well and disk sample 101.3 Hg2q
spring waters (47 mm pH:-7 Air
i.d) drying
Elution:
HBr 1 M
w104x, even though dithizone was reported to react An alternative approach is to form the complex
with many trace elements w139x. Similarly, purpu- by passing the sample through a C18-silica con-
rogallin-bound silica gel enabled selective extrac- taining the immobilized reagent. Octadecyl bonded
tion of Fe(III) w140x. Simultaneous retention of silica, modified by suitable ligands has been suc-
trace elements is possible by choosing a non- cessfully used for the separation and sensitive
selective chelating group, such as N-propylsalicy- determination of metal ions. Examples are given
laldimine w141x or Bismuthol I (2,5-dimercapto- in Table 3. The careful choice of the ligand may
l,3,4-thiadiazole) w142x. Acidic groups can also be add selectivity to the extraction step, favoring
used for further chelation of trace elements, such speciation. For example, salen I-modified C18-
as phosphonic acid w143x and calixarene tetrahy- silica was found selective for Cu(II) w34x, while
droxamic acid w144x. Alternatively, macrocycles impregnation of C18-silica with neocuproine was
may be bound to silica (SGBM) w145x, such as suitable for Cu(I) w116x. C18-silica
{ coated with bis
18-crown-6 (18C6) w146x. wl-hydroxy-9,10-anthraquinone-2-methylxsulfide
It must be kept in mind that despite chemical (BAS) was preferred for Pb(II) retention w121x,
bonding of functional groups on the silica gel while coating with N,N9-diethyl-N9-benzoylthiourea
surface, free silanol groups still remain w143x. (DEBT) was recommended for Pd w147x. Macro-
Their number can be minimised by end-capping cycles may also be loaded on C18-silica and effi-
the sorbent, but some will still be present. As a ciently used for the retention of trace metals, such
consequence, they will participate in the retention as hexathia-18-crown-6 (HT18C6) w129x or calix-
of trace elements somewhat, especially at pHs arene hydroxamate w144x.
above their pKa (ionized form). For some particular applications, mixed ligand
complexes may be used to ensure synergistic
adsorption of the metal complex on the solid
3.1.1.2. C18-bonded silica gel. Despite the large sorbent. Thus, while Cu(II) ions cannot complex
variety of bonded phases available, octadecyl- with neutral tri-n-butyl phosphate (TBP) mole-
bonded silica has currently become the most pop- cules adsorbed on C18-silica, the form of Cu(TTA)
ular phase used. Numerous applications report the complex (TTA being 2-thenoyltrifluoroacetone)
use of C18-silica, as indicated by the studies was retained at approximately 80% w148x. Alter-
reported for water samples in Table 3. In particular, natively, in some cases, loading the chelating agent
organometallic compounds (e.g. tributyltin (TBT), on C8-silica instead of C18-silica may give better
triphenyltin (TPhT), alkylselenides) can be results as observed for the retention of bismuth on
retained on this sorbent due to possible hydropho- oxinate-loaded reversed phase w149x.
bic interaction w19,24,112,113x. Bare C18-silica can Despite their broad application to trace element
also retain a fraction of inorganic trace elements, preconcentration, bonded silica phases (either C18-
probably due to the presence of silanol groups on silica or functionalized-silica gel) present the
its surface w34x. However, in practice, due to its drawback of a limited range of pH that can be
hydrophobic character, C18-silica is not well suited used, as in acidic (below 2 to 4) and basic (above
for retention of trace element species, as the latter 8) pHs hydrolysis may occur, which changes the
are often polar or ionic. Retention on C18-silica interactions that occur between the sorbent and the
may be improved by addition of a ligand reagent trace elements. As a consequence, polymeric sor-
to the sample before its percolation through the bents may be preferred.
sorbent. The hydrophobic part of the ligand will
thus have hydrophobic interaction with the C18- 3.1.1.3. Other inorganic oxides. Apart from silica
silica and be retained on the sorbent, while the other inorganic oxides have been tested for the
functional group of the ligand will ensure chelation adsorption of trace elements as shown in Tables 1
of the trace element. Among reagents, one can cite and 2. Whereas SiO2, due to its acidic properties,
8-HQ w115x, APDC w114x, 1,10-phenanthroline is expected to adsorb only cations, basic oxides
w18x, or bathocuproine w27x. (such as magnesia MgO) should adsorb only
Fig. 5. Sorbents based on organic supports.
anions. As a matter of fact adsorption of ions on studies. With regards to chromium speciation, neu-
oxide surfaces is believed to proceed with partici- tral alumina has been used for that purpose
pation of hydroxyl groups. These groups are neg- w110,150x.
atively charged (deprotonated) under basic The preparation technique is of prime impor-
conditions, thereby retaining cations and positively tance w109x, as the adsorption properties of many
charged (protonated) under acidic conditions, oxides strongly depend on the characteristics of
thereby retaining anions. Consequently, on ampho- the solid, namely crystal structure, morphology,
teric oxides (namely titania TiO2, alumina Al2O3, defects, specific surface area, hydroxyl coverage,
zirconia ZrO2), cations are adsorbed under basic surface impurities and modifiers. Thus, the coating
conditions (pH above the isoelectric point of the of acidic alumina with an anionic surfactant
oxide which was reported to be 6.2 for TiO2 allowed the selective retention of Cr(VI) in very
w109x) while anions are adsorbed under acidic acidic solutions w151x. Adsorption on inorganic
conditions (pH below the isoelectric point of the oxides may also be influenced by the presence of
oxide). For example, chromium speciation may be salts in the matrix. In particular, high concentra-
achieved by careful adjustment of the sample pH: tions of phosphates and sulfates may decrease
pH 2 and 7 for retention of Cr(VI) (anionic) and trace element retention on titania w152x. On the
Cr(III) (cationic), respectively, on acidic alumina opposite, major cations (Naq, Kq, Ca2q, Mg2q)
w70,71x; pH 2 and 8 for retention of Cr(VI) and are weakly adsorbed on titania w152,153x.
Cr(III) on titania, respectively w108x. The concur-
rent adsorption of Hq is responsible for the 3.1.2. Organic based sorbents
absence of retention of cationic species at very Organic based sorbents may be divided into
low pHs. However, changing the sample pH may polymeric and non-polymeric sorbents, as shown
affect speciation and should be avoided as far as in Fig. 5. Polymeric sorbents have been, by far,
possible. So it may be preferred to find a suitable the most used for trace element preconcentration
sorbent for retaining the targeted species with having the advantage over bonded silica in that
subsequent selective elution for further speciation they can be used over the entire pH range. Their
disadvantage is that the conditioning step is more 8-quinolinol) w166x, APDC w167x or 5-BrPA-DAP
time consuming as they require extensive cleaning (2-(5-bromo-2-pyridylazo)-5-(diethylamino) phe-
before use. Comprehensive reviews on polymeric nol) w168x. Macrocycles can also be adsorbed,
phases have been published w97,154x. Masque´ et such as calixarene hydroxamate w144x. However,
al. published an extensive review on sorbents used in practice, the resins prepared by impregnation of
for the SPE of polar organic micropollutants from the ligand are difficult to reuse, due to partial
natural waters w155x. The purpose of this section leaching of the ligand (thus resulting in poor
is to summarize the most frequently used organic repeatability). To overcome this problem, the resin
based sorbents for trace elements, as well as the may be chemically functionalized. Several chemi-
more recently reported ones. cal modifications of PS-DVB have recently been
In most applications, new sorbents have been reviewed w169x, but only a few are commercially
synthesized by chemically bonding chelating available. The ligands are generally coupled to a
groups to polymeric cross-linked chains and char- methylene or an azo spacer on the matrix. Among
acterizing their ability to selectively adsorb trace {ligands, one can cite Alizarin Red-S w170x, sali-
elements. Most of the chelating groups reported cylic acid (SA) w171x, thiosalicylic acid (TSA)
have low water solubility to avoid their leaching w172x, pyrocatechol violet (PV) w173x, chromo-
from the sorbent, as most applications deal with tropic acid (CA) w174x, pyrocatechol (PC)
aqueous samples. At the same time, a too hydro- w175,176x, Tiron (disodium salt of l,2-dihydroxy-
phobic group will hinder wettability of the sorbent benzene-3,5-disulfonic acid) w177x, quinalizarin
by the aqueous sample, resulting in poor retention (1,2,5,8-tetrahydroxy-anthraquinone) w22x, bicine
efficiency. A compromise is thus necessary. In wN,N-bis (2-hydroxy-ethyl) glycinex w178x, and
addition to the functional group, the efficiency of poly(dithiocarbamate) (PDTC) w179x.
polymeric sorbents depends on various physico- Of great interest are also the sulfonated PS-
chemical parameters, such as particle size, surface
DVB resins, as they show excellent hydrophilicity
area, pore diameter, pore volume, degree of cross-
and high extraction efficiencies for polar organic
linking and particle size distribution.
compounds w154,155x. In the case of rapid sulfo-
nation under mild conditions, a mixed-mode reten-
3.1.2.1. Polystyrene-divinylbenzcne based sor-
tion can be observed: adsorption of neutral
bents. Macroporous hydrophobic resins of the
Amberlite XAD series are good supports for devel- compounds on the polymeric resin, and cation
oping chelating matrices. Amberlite XAD-1, exchange of ionic species on sulfonate groups
w180x. The use of a particular sulfonated PS-DVB
XAD-2, XAD-4 and XAD-16 are polystyrene-
divinylbenzene (PS-DVB) resins with a high resin has been recently reported to enable chro-
hydrophobic character and no ion-exchange capac- mium speciation w181x. 2-Naphthol-3,6-disulfonic
ity. In addition to the hydrophobic interaction that acid (NDSA) has been coupled to the PS-DVB
also occurs with C18-silica, such sorbents allow through an azo function. In that way, the formation
p–p interactions with aromatic analytes. of an azo cation at very low pHs enabled retention
Due to the hydrophobic character of PS-DVB, of the anionic Cr(VI), whereas the sulfonate group
retention of trace elements on such sorbents enabled retention of Cr(III) in neutral and basic
requires the addition of a ligand to the sample. media w181x. For particular applications, trimethy-
Inorganic ligands may be used w156x, but organic lammonium functionalized PS-DVB may also be
ligands are preferred, such as APDC w157,158x, 8- used with anion-exchange properties.
HQ w159,160x, or diphenylcarbazide (DPC) w161x. As summarized in Table 4, which presents
Alternatively, ligands may be attached to the PS- selected applications of polymeric sorbents for the
DVB by physical adsorption such as dithizone preconcentration of trace elements from water
w162x, PDT (3-(2-pyridyl)-5,6-diphenyl-l,2,4-tria- samples, even though PS-DVB has been probably
zine) w4x, tropolone w163,164x, l-(2-pyridylazo)2- the most widely used of polymers, others also
naphthol (PAN) w32,165x, DDQ (7-dodecenyl- have been successfully used as detailed below.
1202
Table 4
Applications of off-line SPE using polymeric sorbents to water samples
Adsorptive resins
Tap water CdyCuy XAD-2 Polypropylene Conditioning ICP–AES 82.3– — 100 — w160x
MnyNiy column sample 97.2
PbyZnq pH: 8–9
8-HQ Elution:
HCl 2 M
Tap water Cr(VI), XAD-16 Glass column Washing F-AAS 97.3–99.0 0.4 5.25 45 w161x

total (1 cm i.d) sample mgyg
CrqDPC pH: 1
Elution:
H2SO4 0.05
MyMeOH
Drinking and BiyCdyCoy Chromosorb- Glass column Washing F-AAS 95–110 — 300 0.10–11 w158x
sea waters CuyFeyNiy 102 (0.9 cm i.d) conditioning
PbqAPD sample pH: 6
C Elution:
acetone
Tap, mineral, Coq8-HQ Chromosorb- Column Washing ET-AAS 95.2–99.2 — 80 0.0134 w182x
river 105 (4 mm i.d) sample
waters pH: 8
Elution:
EtOHy
HNO3 2 M
Tape, lake, Cr(III) Cellulose Syringe barrel Purification ET-AAS 98–99.3 — 100 0.0018 w183x
waste sample
waters pH: 11
Elution:
HCl 2 M
Chelating resins
Waters TBT Tropolone- Glass column Sampleq ET-AAS 104 — 80 0.0144 w164x
loaded- (1.5 cm i.d) 0.8%
XAD-2 H2SO4
Washing
Elution:
IBMK
Table 4 (Continued)
Sea water CoyCuy PDT-loaded- Column Washing F-AAS 96.3– — — — w4x
FeyNiy XAD-2 (0.9 cm i.d) elution: 103.5
Zn MeOH in
Soxhlet
apparatus
Well water, CuyCdy Quinalizarin- Glass column Washing F-AAS 91–98 3.15y 100y50y40y50y 2.0y1.3y5.0y w22x
river water CoyPby functionalized- (1 cm i.d) sample 1.70y 100y65y65 15.0y1.0y1.6
ZnyMn XAD-2 pH: 5–7 1.62y

Elution: 5.28y
HNO3 4 M 1.42y
0.94y
2.19 mgyg
Well waters ZnyCdy PV- Glass column Washing F-AAS 98 1410y 60y50y — w173x
PbyNi functionalized- (1 cm i.d) sample 1270y 23y18
XAD-2 pH: 3–7 620y
Elution: 1360
HNO3 4 M mgyg
Well waters ZnyPb Salicylic acid- Glass column Washing F-AAS 98–100 1146y461 180y140 — w171x
functionalized- (1 cm i.d) sample mgyg
XAD-2 pH: 5.0
Elution:
HCl 1
M-2–4 M
Well waters ZnyCdy Alizarin Red-S- Glass column Washing F-AAS 95–100 511y124y 40 10 w170x
PbyNi functionalized- (1 cm i.d) sample 306y124
XAD-2 pH: 4–6 mgyg
Elution:
HNO3
1–4 M or
HCl 4 M
River waters CuyCdyCo Tiron- Glass column Washing F-AAS 91–99 — 25–200 0.5–24 w177x
yNiyPbyZny functionalized- (1 cm i.d) sample
MnyFe XAD-2 pH: 4–7.5
Elution:
HNO3 4 M
1203
1204
Table 4 (Continued)
River waters CdyCoyCu CA- Glass column Washing F-AAS 95–100 9.35y 100–200 — w174x
yNiyFeyZn functionalized- (1 cm i.d) sample 3.84y
XAD-2 pH: 4–7 8.50y
Elution: 3.24y
HNO3 or 6.07y
HCl 2 M 9.65
mgyg
River and tap Pb CA- Glass column Washing F-AAS 97 186.3 200 4.06 w176x

waters functionalized- (1 cm i.d) sample mmolyg
XAD-2 pH: 3–8
Elution:
HNO3
2–10 M
River and tap CdyCoyCu PC- Glass column Washing F-AAS — 0.023– 80–200 — w175x
waters yFeyNiyZn functionalized- (1 cm i.d) sample 0.092
XAD-2 pH: 3–6.5 mmolyg
Elution:
HNO3 2 M
River and tap Pb PC- Glass column Washing F-AAS 94 104.7 100 3.80 w176x
XAD-2 pH: 5–7.5
Elution:
HNO3 1 M
River and tap Pb TSA- Glass column Washing F-AAS 93 89.3 100 4.87 w176x
XAD-2 pH: 4
Elution:
HNO3
0.5–2 M
Tap, river CdyCoyCuy TSA- Glass column Washing F-AAS 92–98 197.5y 180–400 0.48y0.20y w172x
waters FeyNiyZn functionalized- (1 cm i.d) sample 106.9y 4.05y0.98y
XAD-2 pH: 3.5–7 214.0y 1.28y3.94
Washing 66.2y
elution: 309.9y
HNO3 2 M 47.4
mmolyg
Table 4 (Continued)
Artificial sea CdyCuyMny APDC-loaded- Glass column Sample ICP–AES 98.2–99.6 9.47y 180y230y120y 0.1y0.4y0.3y w167x
water, NiyPbyZn XAD-4 (0.9 cm i.d) pH: 5.0 11.08y 130y160y215 0.4y0.6y0.5
natural Washing 8.62y
waters elution: 7.21y
HNO3 4 M 10.25y
10.62
mgyg
Artificial sea CdyCuy pipDTC-loaded- Glass column Sample ICP–AES 97.6–99.1 9.18y 150y200y140y 0.7y1.0y0.8y w167x

water, MnyNiy XAD-4 (0.9 cm i.d) pH: 5.0 10.76y 120y150y200 0.9y1.7y1.2
natural PbyZn Washing 8.17y
waters elution: 7.46y
HNO3 4 M 9.86y
10.28
mgyg
Sea water AgyAly DDQ-loaded- Teflon column Washing F-AAS or ET- 73–107 0.55 62.5 0.00016–0.3 w166x
BiyCdy XAD-4 (8 mm i.d) sample AAS mmolyg
CuyFey pH: 8
GayMny Washing
NiyPbyTi elution:
HCl 2 M
Backflush
Tap water CuyMnyZn Calixarene Plastic Sample F-AAS — — 25 — w144x
Tetrahydroxa- cartridge pH: 8.5
mate- (0.9 cm i.d) Elution:
loaded- acidified
XAD-4 water
(pH 2.0)
Tap and Mn PDTC- Glass column Conditioning F-AAS 97.2 9.1 20 0.5 w179x
mineral functionalized- (1 cm i.d) sample mmolyg
waters XAD-4 pH: 10
Elution:
HNO3 8 M
Spiked CoyCuy Bicine- Glass column Conditioning ET-AAS 97.6–99.1 0.32–0.44 40–50 — w178x
solutions FeyHgy functionalized- sample mmolyg
NiyPbyZn XAD-4 pH: 5.5–7
Elution:
HCl 1 M
1205
1206
Table 4 (Continued)
Waste waters Cr(III)yCr NDSA- Glass column Sample pH: F-AAS 85.9–96.1 0.40y1.18 20 — w181x
(VI) functionalized- (1 cm i.d) 1.5 or 6 mmolyg
PS-DVB Elution:
HCl 4 M
River water Hg(II) PAA- Glass column Conditioning Spectro- 96 0.6 30 — w184x
functionalized- (1 cm i.d) sample photometry mmolyg
PS-DVB pH: 5.4
Elution:

H2SO4 2 M
River and Pb XO-loaded- Glass column Washing F-AAS 91 16.9 100 2.44 w176x
tap XAD-7 (1 cm i.d) Sample mmolyg
waters pH: 5
Elution:
HNO3 1 M
River waters CdyCoyCu XO-loaded- Glass column Sample F-AAS 96–100 1.6–2.6 10–200 9y24y6y w185x
yFeyNiyZn XAD-7 pH: 4–5 mgyg 6y3y21
Elution:
HCl 1 or 2 M
River and Cr(III) 8-HQ- Glass column Washing ICP–MS 98–105 41.7 5 0.06 w186x
reservoir functionalized- (4 mm i.d) sample mmolyg
waters polyacrylonitrile pH: 6
Washing
Elution:
HCl 2 My
HNO3 0.1 M
Aqueous AuyPty Aminothiourea- Glass column Washing ICP–AES 97–99 2.80y 6–65 — w187x
sample PdyIr functionalized- (0.5 cm i.d) sample 1.75y
from a non- polyacrylonitrile pH: 2 1.56y
ferrous metal Washing 1.15
smelter elution: mmolyg
HCl 4 My
CS(NH2)2 3%
Sea water BeyBiy Aminophosphonic- Glass column Sample ICP–MS 93–104 0.83–74.1 200 0.002–0.601 w188x
CoyGay dithiocarbamate- (4 mm i.d) pH: 6 mmolyg ngyl
AgyPby functionalized- Washing
CdyCuy polyacrylonitrile elution:
MnyIn HCl 2 M
Table 4 (Continued)
River, lake Hg(II)y Dithiocarbamate- Column Washing CV-AAS 91–95 — 667 0.0002 w189x
and rain MeHg functionalized- (1.5 cm i.d) Sample
waters polyvinyle pH: 1–11
Elution:
thiourea
5% in HCl
Sea water CdyCuy Chelamine Column Washing ET-AAS 91–102 1 200 0.0023– w190x
MnyNiy sample mmolyg 0.033

PbyZn pH: 6.5
Washing
elution:
HNO3 2 M
Sea water CdyCoy Chelex-100 Column Sample ET-AAS or )98 — 50 0.001–0.1 w191x
CuyMny pH: 6.5 F-AAS
NiyPbyZn Washing
elution:
HNO3 2 M
River water, CdyPbyZn Amberlite Glass column Washing F-AAS 63–104 1.06y 10 — w192x
seawater IRC-718 (0.5 cm i.d) conditioning 0.096y
sample 1.77
washing mmolyg
elution:
HNO3
Ground and Se(IV)ySe Amberlite Glass column Washing LC–ICP– 93–97 — 55 0.010 w193x
fresh (VI)y IRA-743 (1 cm i.d) conditioning MS
waters SeCyst sample
elution:
HClO4 1
Mqwater
Ion exchangers
Waste water Cr Anion Cartridge Activation: Spectro- 80–98.8 — — 8 w194x
exchanger (0.5 g) MeOHq photometry
(SAX) buffer (544 nm) after
Sample reaction DPC
pH: 4.5
Elution:
Na2SO4
0.5 M
1207
1208
Table 4 (Continued)
Sea, river, Se(IV)y Anion Cartridge Conditioning GC–MS 91–99 — 40–500 1600y w19x
tap Se(VI) exchanger Sample 1400
waters (SAX) pH: 7
Elution:
HCOOH 1
MqHCl 3 M
River, spring, Be Anion Column Conditioning: F-AAS 95–102.5 — 125 0.045 w195x
waste exchanger (1 cm i.d) HClqH2Oq

waters NaOH
Sample
pH: 6–8
Elution:
HCl 1.5 M
3.1.2.2. Divinylbenzene-vinylpyrrolidone copoly- poly(ethylene glycol dimethacrylate-hydroxyethyl-

mers. Sorbents made of divinylbenzene-vinylpyr- methacrylate) microbeads w197x.
rolidone (DVB-VP) copolymers have recently
been developed, such as Oasis HLB w154x. The 3.1.2.4. Polyurethane polymers. Due to its sorption
hydrophilic N-vinylpyrrolidone
{ affords good wett- capacity for several trace elements polyurethane
ability of the resin, while the hydrophobic divinyl- foam has been tested for use in SPE. Most of the
benzene provides reversed-phase retention of time complexing reagents are added to enhance
analytes. This sorbent has been successfully the sorption capacity. Hence, PUF coated with
applied to the determination of polar organic com- DMG, NN, DDTC or hexamethylenedithiocarba-
pounds in water samples. It is more convenient to mate (HMDC) was found efficient in retaining
use, compared to classical sorbents, as it can dry trace elements w198–200x. The chelating reagent
out during the extraction procedure without reduc- can also be directly added to the sample, and the
ing its ability to retain analytes. In addition, it is metal chelates further retained on PUF, as observed
stable over the entire pH range. However, until with thiocyanate complexes w92,201,202x and
now, no application related to the preconcentration DDTP complexes w63x. Very recently, the immo-
of trace elements has been reported. Similarly, the bilization of an enzyme (alkaline phosphatase) has
use of Oasis MCX, a sulfonated divinylbenzene- been reported on PUF with further application as
vinylpyrrolidone copolymer w154x, may be useful an enzymatic procedure for Pb(II) determination
for the retention of trace element species, as this w203x.
sorbent combines the properties of the previous
sorbent with those of a strong cation-exchanger. 3.1.2.5. Polyethylene polymers. Polyethylene is
Application to the preconcentration of triphenyltin also attractive for SPE of trace elements as this
has been reported w36x. support adsorbs several metal complexed with
hydrophobic ligands. Additionally, the adsorbed
3.1.2.3. Polyacrylate polymers. Amberlite XAD-7 complexes can be eluted with a small volume of
and XAD-8 are ethylene-dimethacrylate resins. organic solvents permitting high enrichment fac-
They are non-aromatic in character and possess tors. Polyethylene can also be used in strongly
very low ion-exchange capacity. Due to the polar- acidic and basic media and for that reason, it has
ity of acrylates, such resins enable the recovery of been used as a sorbent for the retention of chro-
polar compounds. However, this polarity is quite mium in an acidic medium after the addition of
moderate so that most of the time reagents are DPC w204x.
added to increase retention. Direct addition to the
sample is sometimes performed. As an example, 3.1.2.6. Polytetrafluoroethylene polymers. PTFE
Cu(II) forms a complex with 8-hydroxyquinoline- can retain trace elements after addition of a che-
5-sulfonic acid (8-HQ-5-SA), which can be further lating reagent to the sample such as APDC, DDTC
retained on Amberlite XAD-8 as an ion-pair with or dithizone (DZ) w48–50,74,76x. PTFE may also
cetyltrimethylammonium (CTA) w15x. Yet, most of be precoated with a suitable ligand, like 2-methyl-
the time chelating reagents have been loaded on 8-hydroxyquinoline w93x. The sorbent can be used
such resins, mainly Amberlite XAD-7, to increase as PTFE turnings w48–50x, PTFE beads w75x, or
their retention capacity for trace elements andyor as a PTFE tubing in a knotted reactor w74,76x.
their selectivity such as 8-(benzenesulfonami-
do)quinoline (BSQ) w78x, xylenol orange (XO) 3.1.2.7. Polystyrene polymers. Polystyrene poly-
w176,185x, 5-BrPADAP w168x, or dimethylgly- mers may be an interesting alternative to common
oxal bis(4-phenyl-3-thiosemicarbazone) (DMBS) sorbents (namely Amberlites XAD-2 and XAD-8,
w196x. Such loaded sorbents are stable for several C18-silica) when they have a hyper cross-link
months and can be reused. For a higher stability, structure. The addition of a reagent to the sample
chemical binding of the chelating group may be is required to form complexes that are further
performed, as reported for dithizone on retained on the hydrophobic sorbent w79x.
3.1.2.8. Polyamide polymers. Polyamide polymers ion-exchange chelating sorbents with aminophos-
have been used for the retention of rare earth phonic, dithiocarbamate or aminothiourea groups
elements w205x. A chelating reagent was added to w187,188x. However, as such synthesis are time-
the sample for complexing the trace elements. This consuming an alternative is to coat the polyacry-
reagent Thorin (o-w3,6-disulfo-2-hydroxy-l- lonitrile fiber with a proper reagent for further
naphthylazoxbenzenearsonic acid) was chosen to trace element retention such as 8-HQ w186,212x.
enable interaction with the sorbent through electro-
static forces and non-hydrophobic interaction. 3.1.2.12. Ring-opening metathesis polymerisation-
based polymers. A high-capacity carboxylic acid-
3.1.2.9. Iminodiacetate-type chelating resins. Pol- functionalized resin has been prepared using
ymeric resins containing iminodiacetate groups ring-opening metathesis polymerisation (ROMP)
w–CH2–N(CH2COOy)2 x as active sites (IDA res- w213x. Electron microscopy revealed that the
ins) have been widely used for the retention of obtained material consists of irregularly shaped,
trace elements. They have been synthesized by agglomerated particles having a non-porous struc-
bonding the iminodiacetate functional groups to ture with diameter and specific surface area
several polymeric sorbents, such as polystyrene dependent on the polymerisation sequence and the
(Chelex-100) w10,29,30,191,206–209x or a highly stoichiometries. This material was pH stable and
crosslinked agarose gel (IDA-Novarose) w80x. The could be reused. The presence of the carboxylic
spacer arm length was found to have an effect on groups confers an excellent hydrophilic character
the formation of metal complex species in the to the sorbent (ensuring a high wettability of the
chelating resin w12x. sorbent by water), while the polyunsaturation of
A major drawback of such sorbents is that, due the carrier chain, as well as the entire backbone
to the weak acid character of the functional group, provides for a significant reversed-phase character.
the degree of protonation will critically affect the The carboxylic acid groups provide weak coordi-
ability of the resin to retain metal cations. Hence, nation sites enabling the retention of rare earth
for Chelex-100, protonation of the carboxylates elements. Similarly, dipyridyl amide-functionalized
and the donor N atom are reported to be complete resins have been reported to allow the extraction
at pH 2.21, while a completely deprotonated form of ‘soft’ metals such as Pd(II) and Hg(II) w214x.
is reached at pH 12.30. Also, such sorbents are
non-selective, so that trace element retention may 3.1.2.13. Carbon sorbents. Activated carbon is
be reduced due to retention of major ions (namely prepared by low-temperature oxidation of vegeta-
Ca(II) and Mg(II)) w99,191x. Besides, the presence ble charcoals. Due to their large surface areas
of ligands in the sample may prevent trace element (300–1000 m2 yg), these sorbents are well-recog-
retention on the sorbent due to their complexation nized for their very strong sorption both for trace
as observed in real waters due to the presence of organic compounds and trace elements. There is
organic matter w80,210x. evidence of two types of adsorption sites on
activated carbons: (1) graphite-like basal planes
3.1.2.10. Propylenediaminetetraacetate-type che- that enable adsorption through van der Waals
lating resins. The synthesis of a fine-particle forces, especially p-electron interactions, and (2)
macroporous polymer-based propylenediaminete- polar groups like carbonyls, hydroxyls and carbox-
traacetic acid (PDATA) type resin has been recent- yls, that may interact via ionic interaction of
ly reported w211x. The structure of this sorbent is hydrogen bonding w215x. Consequently, trace ele-
very similar to that of ethylene diamine tetraacetic ments may be directly adsorbed on activated car-
acid (EDTA) with a spacer arm enabling the bon w19,216x. Metal chelates may also be retained
retention of several trace elements upon chelation. on this sorbent after addition of a proper chelating
agent to the sample w17x such as amino acids
3.1.2.11. Polyacrylonitrile based resins. Polyacry- w217x, dithizone w218x, APDC w88,219x, PAN
lonitrile fibers have been functionalized to obtain w220x, 8-HQ w221x, cupferron w221x, Bismuthiol II
(3-phenyl-5-mercapto-l,3,4-thiadiazole-2(3H)-thi- retained Se(IV) and Se(VI) species using nitric

one) w222x, or DDTP w63,87x. The ligand should acid at two different concentrations w225x.
be chosen to avoid a strong interaction with the
activated carbon otherwise complete dissociation 3.1.2.15. Naphthalene based sorbents. Retention
of the metal chelate would be observed w215x. of trace elements on microcrystalline naphthalene
The main drawback when using activated car- is also feasible, either after addition of a ligand to
bons is their heterogeneous surface with active the sample w226x, or after functionalization of the
functional groups that often lead to low reproduc- solid to ensure better adsorption characteristics
ibility. In addition, these sorbents are very reactive towards trace elements w227,228x. However, the
and can act as catalysts for oxidation and other use of this solid support is rather uncommon. In
chemical reactions. Fortunately, along with the addition, until now it has been reserved to batch
development of polymer materials and bonded experiments.
phases, a new generation of carbon sorbents
appeared in the 1970s and 1980s with a more 3.2. Influential parameters
homogeneous structure and more reproducible
properties. Graphitized carbon blacks (GCB) are The main experimental variables that affect
obtained from heating carbon blacks at 2700–3000 analyte recovery by SPE have been extensively
8C in an inert atmosphere w155x. They are non- reported by Poole et al. w2,229x. They are briefly
specific and non-porous sorbents (surface area discussed below and illustrated with reported
approx. 100 m2 yg), and are considered to be both applications.
reversed-phase sorbents and anion-exchangers due
to the presence of positively charged chemical 3.2.1. Conditioning parameters
heterogeneities on their surface. Such sorbents
have been extensively used in the past few years
3.2.1.1. Washing step. A washing step is highly
for the SPE of polar organic pollutants from water
recommended, especially when ultratraces of ele-
samples w155x, but their use for trace elements is
ments are to be determined. Thus, blank extracts
still rare w223x. Their main drawbacks are possible containing trace levels of Zn, Cu and Fe were
irreversible retention of analytes, which may be suspected to be due to contaminants from C18-
overcome by elution in the backflush mode, and silica w115x.
poor mechanical stability. Porous graphitized car-
bon (PGC) is a more stable carbon based sorbent
3.2.1.2. Conditioning solvent. Even though some
than GCB as the graphite is immobilized on a
sorbents have been used without a conditioning
silica substrate. So this sorbent should be suitable
step this is not recommended. This step will at
for trace element retention even though until now
least remove possible remaining contaminants and
its applications have been limited to trace organic
air from the sorbent bed. Additionally, in some
compounds.
cases, this step is crucial for successful retention
of the analytes. The nature of the conditioning
3.1.2.14. Cellulose. Cellulose was found effective solvent must be appropriate to the nature of the
in retaining trace elements present in water sam- solid sorbent to ensure good wettability of the
ples either directly or upon addition of a chelating functional groups. As an example with hydropho-
agent to the sample w183,224x. In particular, the bic supports such as C18-silica or PS-DVB, quite
selective retention of Cr(III) was reported thereby polar organic solvents such as methanol should be
enabling chromium speciation w183x. This sorbent used. The sorbent should further be conditioned
may also be functionalized to increase the SPE by a solvent whose nature is similar to that of the
selectivity. Thus, selenium speciation has been sample. Thus, for aqueous samples, the solvent
reported on cellulose functionalized with quater- will be water with a pH and ionic strength similar
nary amine due to the selective elution of the to that of the sample.
require lower maximum flow-rates than disks rang-

ing typically from 0.5 to 5 mlymin. This value
may be increased by a factor of 10 using disks.
3.2.2.3. Sample pH. Sample pH is of prime impor-

tance for efficient retention of the trace elements
on the sorbent. Its influence strongly depends on
the nature of the sorbent used. Careful optimization
of this parameter is thus crucial to ensure quanti-
tative retention of the trace elements and in some
Fig. 6. Typical representation of the breakthrough curve (i.e.
cases selective retention. In particular with ion-
concentration of the analyte at the outlet of the SPE system vs. exchangers, correct adjustment of sample pH is
sample volume percolated through the system). VB is the break- required to ensure preconcentration. Thus, in the
through volume, VR the chromatographic elution volume and case of cationic-exchangers, low pH usually results
VC the sample volume corresponding to the retention of the in poor extraction due to competition between
maximum amount of analyte, C0 is the initial analyte concen-
tration in the sample.
protons and cationic species for retention on the
sorbent.
When retention of trace elements is based on
3.2.2. Loading parameters chelation (either in the sample or on the solid
sorbent), the sample pH is also a very important
3.2.2.1. Sample volume to be percolated. An factor as most chelating ligands are conjugated
important parameter to control in SPE is the bases of weak acid groups and accordingly, they
breakthrough volume, which is the maximum sam- have a very strong affinity for hydrogen ions. The
ple volume that should be percolated through a pH will determine the values of the conditional
given mass of sorbent after which analytes start to stability constants of the metal complexes. By
elute from the sorbent resulting in non-quantitative contrast, pH may have no influence with some
recoveries (Fig. 6). The breakthrough volume is non-ionizable organic ligands w130x.
strongly correlated to the chromatographic reten- For inorganic oxides, pH is also of prime impor-
tion of the analyte on the same sorbent and tance. In particular, on amphoteric oxides such as
depends on the nature of both the sorbent and the TiO2 or Al2O3, cations are adsorbed at elevated
trace element, as well as on the mass of sorbent pHs due to the deprotonation of functional groups,
considered and the analyte concentration in the whereas anion retention requires acidic conditions
sample w3x. In addition, it depends on the sorbent for the protonation of functional groups.
containers, as disks usually offer higher break-
through volumes than cartridges. This volume may 3.2.2.4. Sample matrix. The presence of ligands in
be determined experimentally or estimated using the sample matrix may affect trace element reten-
several methods w229x. For that purpose the nature tion when stable complexes are formed in the
of the sample has to be taken into account, as the sample with these ligands, as trace elements are
possible presence of ligands may dramatically less available for further retention. Thus, if metals
reduce the breakthrough volume w230x. are present in the sample as strong complexes,
they may not dissociate resulting in no retention
3.2.2.2. Sample flow-rate. The sample flow-rate of the free metal on the sorbent. As an example,
should be optimized to ensure quantitative reten- reduction in the retention of Cu(II) on Amberlite
tion along with minimization of the time required CG50 occurs in the presence of ligands such as
for sample processing. This parameter may have a glycine w230x. In the case of real samples, the
direct effect on the breakthrough volume, and presence of natural organic matter is of great
elevated flow-rates may reduce the breakthrough concern as it may complex trace elements as
volume w4,229x. As a rule, cartridges and columns observed for Cu(II) w231,232x. Yet, in some cases
the presence of ligands may be a valuable tool for power, the less retained analytes can be recovered
adding selectivity to the SPE step. This requires without eluting the strongly retained compounds.
that the added ligands be correctly chosen to Thus, if the elements of interest are those that
complex only the elements that are not of interest, remain on the sorbent another elution step with a
so that they are not retained on the sorbent w31x. more eluent solvent will ensure their quantitative
The presence of ions other than the target ones recovery. In that way interferent analytes were
in the sample may also cause problems during the removed during the first eluting step (also called
SPE step. In particular, due to their usually high washing step). On the opposite, if the compounds
levels (e.g. Ca(II)), they may hinder the precon- of interest are the less retained on the sorbent their
centration step by overloading the sorbent or cause elution with a low or moderate eluting solvent
interferences during spectrophotometric analysis. ensures their selective recovery, as the interferent
Therefore, their influence should be studied before compounds will remain on the sorbent due to
validating a SPE method. Sometimes the addition stronger interactions with the solid support. In
of a proper masking agent (such as EDTA, thiourea some cases, this selectivity may authorized speci-
or ethanolamine for example) may prevent the ation. For example, 1 M HCOOH removed only
formation of interferences due to ions present in Se(IV) from an anion-exchange resin, leaving
the sample w128x. Se(VI) retained on the sorbent, which was further
Finally, the ionic strength of the sample is eluted using 2 M HCl w19x.
another parameter to control for an efficient SPE, Finally, the elution solvent should be compatible
as it may influence the retention of trace elements, with the analysis technique. In particular, when
and thus the value of the breakthrough volume for using both flame and electrothermal AAS, HNO3
a given sorbent w122,195x. should be preferred to other acids (namely
H2SO4, HCl), as nitrate ion is a more acceptable
3.2.3. Elution parameters matrix w128x.
3.2.3.1. Nature of the solvent. The nature of the 3.2.3.2. Solvent pH. As retention of trace elements
elution solvent is of prime importance and should on solid sorbents is usually pH-dependent, careful
optimally meet three criteria: efficiency, selectivity choice of the elution solvent pH may enhance
and compatibility, as discussed below. In addition, selectivity in the SPE procedure. As an example,
it may be desirable to recover the analytes in a once retained on eriochrome black-T (ERT)-func-
small volume of solvent to ensure a significant tionalized-silica gel, Mg(II) could be eluted first
enrichment factor. The eluent may be an organic at a pH approximately 4, while increasing the pH
solvent (when reversed-phase sorbents are used), to 5–6 was required for eluting Zn(II) w9x.
an acid (usually with ion-exchangers), or a com-
plexing agent. 3.2.3.3. Elution mode. Most of the time, for prac-
Firstly, the eluting solvent should be carefully tical reasons, sample loading and elution steps are
chosen to ensure efficient recovery of the retained performed in a similar manner. However, to avoid
target species and quantitative recovery as far as irreversible adsorption and ensure quantitative
possible. As an example among several solvents recoveries, elution in the backflush mode is rec-
tested for the elution of TPhT from C18-silica ommended in some cases. This means that the
(namely a Triton X-100 surfactant aqueous solu- eluent is pumped through the sorbent in the oppo-
tion, acetonitrile, tetrahydrofuran (THF), metha- site direction to that of the sample during the
nol–water 80:20, methanol), only methanol preconcentration step. This is especially crucial
enabled the achievement of acceptable recoveries when carbon-based sorbents have to be used due
(approx. 85%) w112x. to possible irreversible adsorption of the analytes.
A further characteristic of the elution solvent
arises with the possibility of introducing selectivity. 3.2.3.4. Solvent flow-rate. The flow-rate of the
Using a solvent with a low or moderate eluting elution solvent should be high enough to avoid
excessive duration, and low enough to ensure Hence, a FI preconcentration on-line with F-AAS
quantitative recovery of the target species. Typical has been reported for the determination of Cd(II)
flow-rates are in the range of 0.5 to 5 mlymin for w77x. Cadmium complexed with DDTC was sorbed
cartridges and of 1 to 20 mlymin for disks w34x. on the inner walls of a PTFE knotted reactor, and
As a rule, the higher the flow-rate, the larger the further on-line eluted with isobutyl methyl ketone
solvent volume required for complete elution (IBMK) giving a detection limit of 0.1 mgyl.
w119,121,129,130x. However, very acidic pHs (lower than 2) were
required for optimum sensitivity and collection
3.2.3.5. Solvent volume. Similar to the break- efficiency. In addition, DDTC is rather non-selec-
through volume, the elution volume may be deter- tive, so that retention of other trace elements may
mined either experimentally or estimated occur. This drawback maybe overcome by adding
theoretically w229x. Minimum elution volume for masking agents, such as thiourea and ascorbic
a cartridge is defined as 2 bed volumes of elution acidyphenanthroline for copper and iron, respec-
solvent. Bed volume is typically 120 mly100 mg tively, or by choosing a more selective reagent,
of sorbent. For classical disks, the minimum sol- such as DDTP w233x. Still very acidic pHs were
vent volume required is approximately 10 mlymg required for optimum sensitivity and collection
of sorbent w20x. Consequently, larger elution vol- efficiency. APDC offers the advantage of a broader
umes would be required for disks. The elution pH range without decomposition. Hence, Cd(II)
volume can usually be reduced by increasing the complexed with APDC was stable for pHs between
concentration of the eluting solvent (e.g. acid). 4 and 8, and could be efficiently retained on C18-
However, in this case, problems with subsequent silica w56,124x. Further elution with methanol and
analysis may be encountered (e.g. F-AAS). Alter- FI on-line ET-AAS analysis enabled detection
natively, the use of micro-sized disks may allow limits of 0.178 ngyl or 1.26 ngyl depending on
reduced solvent volume w20x. the system used. Other chelating reagents may be
The elution step should enable sufficient time used, such as PAR or PADMAP w58x, or tetra-(4-
and elution volume to permit the metallic species bromophenyl)-porphyrin (T4BPP)w41x.
to diffuse out of the solid sorbent pores. As a rule, Impregnation of the sorbent with a chelating
2 elution cycles are usually recommended as com- reagent has been reported for the preconcentration
pared to a single step (e.g. 2=5 ml elution should of Cd(II). In that case, the choice of a chelatant
be preferred to a single 10 ml elution). Soaking that have a high affinity for cadmium is preferred
time is also critical and 2 to 5 min soak is most to ensure high selectivity. For example, BSQ has
of the time allowed before each elution. been immobilized on Amberlite XAD-7 and used
in a FI system giving a detection limit of 1.9 mgy
4. Applications of SPE to the determination of l w78x. However, Zn(II) was also retained, while
selected trace elements other ions were found to interfere (namely Mg(II),
Cu(II), Fe(III)). Amberlite XAD-7 coated with
4.1. Cadmium DMBS also enabled the retention of Cd(II) from
neutral medium with simultaneous retention of
Cadmium is known to be a highly toxic trace Pb(II) w196x.
metal. Owing to its very low concentrations in the When ICP–AES is used as the analysis tech-
environment, a preconcentration is usually required nique, the use of organic solvents should be
for its determination. This can be performed on an avoided as they may generate strong turbulence in
anion-exchange resin, after reaction of Cd(II) with the ICP. So, new chelating resins were developed
chloride and the formation of the anionic CdCl2y 4 for the Cd(II) preconcentation in a FI–ICP–AES
complex w86x. Yet, Cd(II) retention generally system, such as l,5-bis(di-2-pyridyl) methylene
occurs through chelation, either by adding a che- dithiocarbohydrazide (DPTH)- or methylthiosali-
lating agent to the sample, by impregnation of the cylate (TS)-functionalized silica gel leading to
sorbent, or by the synthesis of new chelating resins. detection limits of 1.1 and 4.3 mgyl, respectively
w51x. They offer the advantage of having no is very selective for Cr(VI) so it can be performed
affinity for sodium, potassium, calcium and mag- directly without a separation step. The chromate
nesium, enabling the Cd(II) analysis in real water oxidizes DPC to diphenylcarbazone (DPCO) to
samples. However, other trace elements reduced form a soluble strongly red–violet compound with
Cd(II) retention on both resins, such as Zn(II) or Cr(III) (Cr(III)-DPCO(3yn)q ). A large excess of
Cu(II). In some cases, the interfering effect of DPC is essential as compounds present in the
Zn(II) can be avoided by careful adjustment of sample may consume the reagent. The Cr(III)-
the sample pH, as observed on the Lewatit DPCO complex can be retained on polyethylene
TP807’84 resin that contains a phosphonic deriv- packed in a column and subsequently eluted with
ative as extractant w33x. Nevertheless, other ions methanol before being analyzed by LC w204x. This
were still co-extracted with Cd(II), namely Cu(II) procedure was applied to the determination of
and Pb(II). chromium in geological samples. The determina-
tion of total chromium may also be achieved after
4.2. Chromium preliminary oxidation of Cr(III). Elements posing
interference with this method are mainly Mo(VI),
Chromium species enter the environment as a Fe(III) and V(V), and their separation using SPE
result of effluent discharge from steel industries, with an anionic-exchanger (SAX) has been per-
electroplating, tanning industries, oxidative dyeing, formed for the subsequent spectrophotometric
chemical industries and cooling water towers. They determination of chromium w194x. The Cr(III)-
may also enter drinking water supply systems from DPCO complex was also found to be retained on
the corrosion inhibitors used in water pipes and cation-exchange (SCX) membrane disks w234x.
containers or by contamination of the underground The color intensity of the membrane was then
water from sanitary landfill leaching. Therefore, it correlated to the Cr(VI) concentrations by visual
is of major concern to study the characteristics of analysis. This simple procedure was found to
chromium in aquatic systems. Chromium occurs provide a highly sensitive semi-quantitative field
mainly in (III) and (VI) oxidation states. While test for the determination of Cr(VI) in aqueous
Cr(III) is an essential trace element, Cr(VI) is samples. A cation-exchange resin was also used
highly carcinogenic and mutagenic due to its high for the FI on-line preconcentration of the Cr(III)-
oxidative character. So, it is important to develop DPCO complex w83x, which can be retained at pH
analytical methods that enable analysis of chro- 1 on Amberlite XAD-16 resin and then eluted
mium in its different oxidation states. However, using 0.05 M H2SO4 solution in methanol w161x.
sampling and preconcentration steps might disturb In this way, Cr(VI) can be determined in tap water
the redox equilibrium between Cr(III) and Cr(VI), samples, as total chromium after oxidation of
thereby affecting the original speciation state of Cr(III) into Cr(VI) using potassium permanganate.
the sample. Cr(VI) may also be chelated by DDTC, and
Most SPE methods are based on the high reac- subsequently retained on C18-silica w60x. Total
tivity of Cr(VI), due to the relatively inert nature chromium may be estimated using the same pro-
of Cr(III). Many methods are thus based on the cedure with prior oxidation of Cr(III) to Cr(VI).
determination of Cr(VI) and total chromium. FI The FI on-line preconcentration systems enabled
on-line preconcentration procedures reported for detection limits of 16 ngyl for Cr(VI) and 18 ngy
chromium species were exhaustively reviewed up l for total Cr. Very recently, selective retention of
to 1992 by Sperling et al. w71x, and later (until Cr(VI), compared to Cr(III) was obtained using
1998) by Prasada Rao et al. w59x. PTFE turnings packed in the micro-column of a
FI manifold. APDC was used for complexation of
4.2.1. Cr(VI) Cr(VI) in the samples before preconcentration,
The determination of chromium is frequently and elution was achieved with IBMK before anal-
achieved by spectrophotometry after derivatisation ysis using F-AAS w49x. Similarly, after reaction
with a reagent such as DPC. The reaction of DPC with APDC, the Cr(VI) complex could be retained
on the PTFE inner wall of a knotted reactor or on achieved on a chelating ion-exchange column
PTFE beads packed into a column, and subse- packed with poly(aminophosphonic acid) (PaPhA)
quently eluted with ethanol w74,75x. Also, acidic resin w81x. By using on-line FI preconcentration
alumina enables selective retention of Cr(VI) w70x coupled to F-AAS, a detection limit of 0.2 mgyl
and a micro-column was used in a FI manifold to could be obtained with a sample throughput of 30
separate and preconcentrate Cr(VI) from Cr(III) hy1.
in water samples. However, it was later reported
that between pH 3 and 6 Cr(III) could also be 4.2.3. Cr(VI)yCr(III)
retained on that sorbent w235x. A procedure based on the reaction of chromium
species with APDC and subsequent retention of
4.2.2. Cr(III) the complexes on SPE permitted a subsequent on-
Very recently, selective preconcentration of line LC–UV analysis w39x. The Cr(III) reacts with
Cr(III) on a cellulose micro-column has been the chelating agent under relatively mild conditions
reported to be highly dependent on sample pH to give only one product, i.e. triswpyrrolidine-l-
w183x. Below pH 8, very low retention occurred, dithioato-S,S9xchromium(III), whereas Cr(VI)
while at pH 11 almost quantitative adsorption reacts to give two products, one being the former
could be achieved. Elution of the retained Cr(III) complex. Thus, the concentration of Cr(VI) needs
species with 5 ml of HCl (2 M) enabled its to be corrected for the Cr(III) complex. The
subsequent determination by ET-AAS with a 1.8 automated SPE system was optimized to yield
ngyl limit of detection. This method also enabled detection limits of 0.2 mgyl for Cr(III) and 0.06
the determination of total chromium following mgyl for Cr(VI). A FI on-line preconcentrarion
initial reduction of Cr(VI) to Cr(III) with procedure followed by F-AAS detection has been
hydroxylamine. reported to allow determination of both chromium
The coating of the positively charged acidic species in water samples based on selective for-
alumina with an anionic surfactant, SDS, has been mation of DDTC complexes of Cr(VI) in the pH
reported to enable selective retention of Cr(VI) in range of 1–2, and of Cr(III) in the 4–9 pH range
strongly acidic solution, while the cationic Cr(III) w59x. A detection limit of 0.02 mgyl could thus be
remains unabsorbed w151x. Separation of the two achieved. Cr(III) could also be retained in the
species could thus be obtained and Cr(III) deter- presence of Mn(II), which enhances the Cr(III)
mined by ET-AAS. However, this method presents signal w59x.
two major limitations; no analyte enrichment and TiO2 has been recently reported to be very
the need to adjust sample pH to 0.6, which may promising for chromium speciation w108x. Indeed,
affect chromium speciation. In another study, basic this sorbent can selectively adsorb Cr(III) or
alumina has been shown to selectively retain Cr(VI) depending on the pH of the sample. At pH
Cr(III) at pH 2–7 w73x, permitting elution with 2, Cr(VI) is the sole chromium species retained,
nitric acid. while at pH 8 it is Cr(III). Nitric acid (0.5 or 1
Selective retention of Cr(III) was also reported M) allows quantitative elution of the retained
with a macroporous PS-DVB resin (CHP-20P) species. Acidic alumina has also been reported to
after complexation in solution with 8-HQ at 85 8C retain both Cr(III) and Cr(VI) w235x. However,
w159x. The use of hydroxylamine as a reductant careful adjustment of the pH was of prime impor-
was found efficient for the reduction of Cr(VI) to tance as below pH 3 and above pH 6 retention of
Cr(III) without affecting Cr(III) retention as it Cr(III) and Cr(VI), respectively, decreased w235x.
does not complex this species. 8-HQ-immobilized- Hence, a FI on-line preconcentration method has
polyacrylonitrile fiber has been recently reported been reported on activated acidic alumina with
to selectively retain Cr(III) at pH 6, enabling its buffering of the sample before retention either at
preconcentration from river and reservoir water pH 7 (for Cr(III)) or pH 2 (for Cr(VI)) w71x.
samples, while Cr(VI) was unretained w186x. Cr(III) exhibited a typical cationic sorption (it
Selective retention of Cr(III) (cationic) was also increased with pH and decreased when competing
cations are present), whereas Cr(VI) exhibited a no-silica gel enabled the preconcentration of
typical anionic sorption (it decreased with increas- Fe(III) from a mixture containing other trace
ing pH and in the presence of competing dissolved elements in batch experiments w35x. The capacity
anions). Thus, the use of neutral alumina seems of this sorbent for Fe(III) was 0.95 mmolyg. This
more appropriate for chromium speciation since it high selectivity was attributed to the presence of
offers the advantage of requiring no adjustment of two chelating oxygen atoms. The selective SPE of
the water sample pH. Hence, both Cr(III) and Fe(III) on purpurogallin chemically immobilized
Cr(VI) can be quantitatively retained on neutral on silica gel has also been reported w140x. Once
alumina with speciation being achieved using eluted from the sorbent the iron species were
selective elution of the species, i.e. 1 M ammonia analyzed using AAS. Due to strong affinity of
solution for Cr(VI) followed by 4 M HNO3 for Fe(III) to the bound organic compound, as com-
Cr(III) w110x. This method affords a 25-fold prepared to Fe(II) (the distribution coefficient, Kd,
concentration factor with a limit of detection of was found to be 120 500 for Fe(III) and 12 700
10 ngyl. A similar preconcentration on alumina for Fe(II)), speciation of iron could be achieved
followed by selective elution for separation of the using this procedure. Only minor Fe(III) (2.1%)
two chromium species has been reported w72x. was found to be reduced to Fe(II) upon interaction
A new resin that consists of PS-DVB function- with the sorbent. Using batch experiments, Fe(III)
alized with NDSA enabled the retention of Cr(VI) could be selectively extracted from tap water as
at sample pH of 1.5, and of Cr(III) at pH 6.5 well as from a soft drink sample (7-Up).
w181x. Thus, speciation of chromium was accom- Yamini and Amiri w117x developed an efficient
plished by adjustment of the pH along with the method for the selective extraction, concentration
percolation of two sub-samples at the desired pH. and determination of trace amounts of Fe(III) in
The selective retention of both chromium species aqueous media, enabling determination of iron in
could also be achieved on a polymeric sorbent a 500 ml water sample in less than 30 min with a
containing aminocarboxylic groups at pH 3 and 7, reproducibility better than 3%. Iron(III) was ini-
for Cr(VI) and Cr(III), respectively w236x. Micro- tially reduced to Fe(II) by addition of hydroxyla-
wave heating was found to promote the sorption. mine (NH2OH) and the bathophenanthroline
Chromium species may also be retained on an complex Fe(bathophenanthroline)2q 3 was analyzed
anionic-exchanger (SAX) after their complexation by the use of C18-silica membrane disks and
with EDTA w237x. Controlled elution of the anal- spectrophotometry. The ligand was added to the
ytes with 0.5 M NaCl enables their speciation. In sample before SPE, and the solution heated to
this manner, detection limits of 0.4 and 1.1 mgyl enhance formation of the complex. By comparison
were obtained for Cr(III) and Cr(VI), respectively. with AAS and ICP emission spectrometry, this
method offers simplicity and applicability to field
4.3. Iron determination of iron. However, pure solvents
eluted only a fraction of the complex and addition
Iron is widely distributed in nature and is one of NaClO4 to the elution solvent was required for
of the most important elements in biological sys- complete removal of the retained complex, indi-
tems. Its biological effectiveness is influenced by cating that interactions between the complex and
its chemical properties, such as valence, solubility the C18-silica are dispersive or ionic. At sample
and the degree of chelation or complex formation. pH below 2.5 recovery decreased probably due to
Several methods have been proposed for the deter- competition of Hq with Fe(II) for reaction with
mination of Fe(III) and Fe(II) species. bathophenanthroline. The influence of several ions
was investigated, most were tolerated at high levels
4.3.1. Fe(III) without interfering with the determination of iron.
Some solid phases have been synthesized to However, some species such as Co2q, Ni2q,
2q
enable high selectivity towards Fe(III). Thus, the VOy 3 and especially Cu , interfered. The inter-
2q
chemical bonding of formylsalicylic acid on ami- ference effect of Cu is due to the preferential
formation of a very stable, almost colorless, com- avoiding the presence of the Cu(FZ)2 complex.
plex between Cu(I) and bathophenanthroline. Its However, in this method both the Fe(FZ)3 complex
effect was eliminated by the addition of excess and the excess FZ were eluted and contributed to
amounts of thiourea, as a masking agent, while the absorbance measurement, which may result in
the effect of the other ions was eliminated by use unreliable determination of low Fe(II) concentra-
of excess amounts of bathophenanthroline. A FI tions. Therefore, this procedure was further
catalytic spectrophotometric method has also been improved by performing a chromatographic sepa-
developed for the shipboard determination of iron ration of the two species after the SPE step. In
in sea water samples w52x. Retention was achieved addition, 254 nm was found more suitable for
using 8-HQ-functionalized silica gel. After elution detection than 562 nm. In this way, ultratrace
with HCl mixing with the reagents (H2O2 and amounts of Fe(II) could be determined in several
N,N-dimethyl-p-phenylenediamine (DPD)) was samples (aerosols, rainwater and sea water) w123x.
performed to ensure the formation of the color. A A procedure, similar to that reported by King et
detection limit of 0.016 nM could thus be al. w122x has been used for the on-line FI precon-
achieved.
centration of Fe(II) from sea water samples w68x.
It could be extended to Fe(III) determination based
4.3.2. Fe(II)
on its initial reduction by addition of ascorbic acid
Iron(II) is thermodynamically unstable in sea
water containing dissolved oxygen due to its rapid to the sample. Copper interference could be sup-
oxidation to Fe(III) (half-life being approx. 4–10 pressed by loading the C18-silica with a mixture
min depending on the pH). Yet, the determination of FZ and NCH, but at the same time the column
of Fe(II) in sea water is important because of its capacity was lower than when loaded with FZ
role in the solubility, speciation and biological alone.
utilization of iron in oceanic surface waters; in
addition Fe(II) may reduce oxygen, thereby pro- 4.3.3. Fe(III)yFe(II)
ducing radicals in the water. Most of the methods report the determination of
The colorimetric reagent ferrozine (FZ) w3- only one of the two iron species mainly by
(2-pyridyl)-5,6-bis(4-phenylsulfonic acid)l,2,4-tri-
selective complexation. However, this can cause a
azinex forms a stable, colored complex with Fe(II)
shift in the Fe(II)yFe(III) equilibrium in the solu-
in a pH range of 4–10, but not with Fe(III) w238x.
tion as a result of redox reactions. To prevent such
Interferences are also possible due to complexation
of Cu(I), and to a lesser extent of Co(II) and problems, a procedure has been reported that
Ni(II) by FZ. Thus, a procedure has been devel- enables the simultaneous complexation of both
oped enabling the preconcentration of Fe(II) from Fe(II) and Fe(III) in the sample followed by
sea water, thanks to its retention as the Fe(FZ)3 retention of the complexes on selective solid sor-
complex on a C18-silica cartridge and subsequent bents w18x. Fe(II) was complexed by addition of
elution with methanol w122x. Iron was then ana- 1,10-phenanthroline, while Fe(III) formed a com-
lyzed directly by spectrophotometry (562 nm). plex with ferron (8-hydroxy-7-iodoquinoline-5-sul-
C18-silica was loaded with FZ by passing a FZ fonic acid). The solution was thus passed
solution through the cartridge (the retention capac- successively to an anion-exchange resin and a
ity of the cartridge for FZ increased with increasing reversed-phase sorbent. Since the Fe(III)-ferron
ionic strength of the solution). Once the sea water complex is negatively charged, it was retained by
has been passed through the cartridge, washing the first solid phase (for sample pH 3–6), while
was performed with 5 ml of 0.1 M NaCl–0.005 the Fe(II)-phenanthroline was passed through due
M NaHCO3 to remove sea salts and prevent to its non-polar character. This complex was then
precipitation of Mg2qand Ca2q in methanol upon retained by the second solid sorbent (C18-silica).
elution. Cu(I) interference was minimised by add- This method enabled the determination of both
ing neocuproine (NCH) to the methanol extract labile Fe(II) and Fe(III) species in wine samples.
4.4. Lead with a limit of detection of 16.7 myl. Retention of

lead was quite selective even in the presence of
Lead is a toxic metal, which accumulates in the other ions. The addition to the sample of ammonia
vital organs of man and animals. Its cumulative as a masking agent was recommended to suppress
poisoning effects are serious haematological dam- the interfering effect of some cations, namely
age, anemia, kidney malfunctioning, brain damage, Cu(II), Zn(II) and Hg(II). Similarly, the coating
etc. Lead is still emitted into the biosphere in of C18-silica with BAS was found highly selective
considerable amounts owing to its application as a in retaining Pb(II) with subsequent elution using
fuel additive, mainly as tetraethyllead and tetraacetic acid and F-AAS analysis leading to 50 ngy
methyllead. It is also present in many industrial l as a limit of detection w121x. Pb(II) could also
streams. Due to the presence of lead in environ- be retained on Amberlite XAD-7 coated with
mental samples at low levels, its separation from DMBS w196x or XO w176x, Amberlite IRA-904
other elements present and the use of a preconcen- impregnated with TCPP w8x, or PUF coated with
tration step prior to lead determination are usually 2-(2-benzothiazolylazo)-2-p-cresol w240x.
necessary. All the studies reported until now Chelating resins have also been synthetized for
focused on the preconcentration of inorganic lead the selective preconcentration of Pb(II). For exam-
Pb(II). The performances of Pb determination ple, Amberlite XAD-2 was functionalized through
using different sorbent materials have been an azo spacer by several chelating agents, such as
reviewed recently w50,176x. Some examples are CA, PC and TSA, and used for the retention of
given below. Firstly, as a cationic species, Pb(II) Pb(II) from water samples w176x. Similarly, this
can be retained on cation-exchangers, such as basic sorbent functionalized with SA also enabled the
alumina w239x. However, such sorbents are rather retention of Pb(II), along with Zn(II) w171x. In
non-selective. So, other strategies have been used each case nitric acid enabled lead desorption.
that are the retention of Pb complexes on hydro- Limits of detection in the 2.4–4.9 mgyl range were
phobic sorbents, the retention of Pb(II) on sorbents obtained. Amberlite XAD-7 functionalized with a
coated with a chelating reagent and the synthesis crown ether was also found suitable for the pre-
of new chelating resins. concentration of Pb(II) w241x.
Lead complexed with DDTP could be retained Very recently, an attractive test procedure has
on C18-silica, activated carbon and PUF w63x. In been reported that enables the determination of as
that way analysis through a FI system coupled to low as 20 ngyl of Pb(II) w203x. It is based on the
F-AAS was performed with limits of detection of immobilization of an enzyme, alkaline phosphatase
0.3, 1.2 and 3 mgyl for C18-silica, PUF and on PUF.
activated carbon, respectively. In another FI system
Pb(II) was complexed with APDC retained on 4.5. Mercury
PTFE turnings and further eluted with IBMK
leading to 0.8 mgyl as a limit of detection w50x. The presence of mercury species in aquatic food
This method enabled the determination of Pb(II) chain is of great concern as it is well-known that
in various environmental and biological samples. inorganic mercury (Hg2q) is converted into highly
Complexes can be formed with DDTC in acidic toxic methylmercury (MeHgq) by aquatic organ-
medium, further retained on C18-silica and eluted isms. Due to the presence of mercury in environ-
with IBMK or methanol before F-AAS, enabling mental samples at low levels, its separation from
the detection of 3 to 10 mgyl w62,233x. Alterna- other elements present and the use of a pre-
tively, the sorbent can be impregnated with the concentration step prior to the determination is
chelating reagent. Hence, the SPE of lead on C18- usually necessary.
silica disks has been reported after impregnation
of the sorbent with a S-containing Schiff’s base to 4.5.1. Hg(II)
enable Pb(II) chelation w120x. After elution with Mercury can be preconcentrated from aqueous
nitric acid lead was further analyzed by F-AAS samples using a chelating ion-exchange resin con-
taining histidine covalently bound to its carboxyl Complexation of mercuric species with APDC,
group w242x. A chelating PS-DVB-based resin with FI on-line preconcentration on C18-silica, further
picolinic acid amide (PAA) as the functional group separation with LC, and analysis by CV-AAS has
was also found efficient for Hg(II) retention from been reported w43x. In this manner, Hg species
water samples w184x. Several functional groups (methylmercury, ethylmercury, phenylmercury and
chemically bound to silica gel have also been Hg(II)) in fish and human urine could be analyzed
reported to afford selective sorbents for preconcen- at the ngyl level. Chelation with DDTP and pre-
tration of Hg(II) during adsorption. This was the concentration on C18-silica in a FI–CV-AAS sys-
case with DZ w104x and dithioacetal derivatives tem resulted in detection limits of 10 ngyl for
w105x. Another procedure involving the use of methylmercury and Hg(II) with an enrichment
C18-silica disks impregnated with hexathia-18- factor of 20 w64x. Several ligands were tested:
crown-6-tetraone (HT18C6TO), was shown to DDTC, APDC and DZ (or diphenylthiocarbamate)
quantitatively extract Hg(II) from natural waters w55x. Results showed the superiority of carbamate
in less than 15 min w130x. Recovery was nearly type reagents for the preconcentration of Hg(II)
independent of pH (in the range of 1 to 7) as and methylmercury using this system. With
already reported for the solvent extraction of met- DDTC, detection limits of 16 ngyl of Hg could be
als with crown ethers. Before eluting Hg2q with 1 obtained.
M HBr, a washing step with 1 M HNO3 was
recommended to remove small amounts of retained 4.6. Selenium
Cu2q, Zn2q, Pb2q and Cd2q.
Selenium is present in the environment from
4.5.2. Hg(II)yorganic Hg both natural and anthropogenic inputs. This ele-
A chelating resin based on vinyl polymer and ment has been recognized as an essential nutrient.
containing dithiocarbamate groups was found effi- However, at concentrations higher than 130 mgyl
cient for retention of inorganic and organic mer- it becomes toxic. Se(IV) and Se(VI) are the
cury from water samples over a broad range of predominant species in natural waters. Biomethy-
pHs (1 to 11) w189x. The species were eluted lation may also occur, leading to the formation of
using an acidic aqueous solution of 5% (wyv) organic species such as dimethyl selenide (DMSe),
thiourea, enabling a preconcentration factor of 666 dimethyl diselenide (DMDSe) and diethyl selenide
and the determination of mercuric species with a (DESe), and detoxification. Therefore, a reliable
limit of detection of 0.2 ngyl. The use of another speciation procedure is required to evaluate toxic-
chelating resin containing dithiocarbamate groups ity of samples. An overview of SPE procedures
was also found effective in retaining inorganic as developed for selenium has been recently given
well as organic mercury in the pH range 1–4 w193x and some are detailed below. It appears that
resulting in limit of detection of 0.5 ngyl w243x. most methods were dedicated to the determination
The on-line FI preconcentration of mercury species of inorganic selenium.
(Hg(II), methylmercury, ethylmercury) on a
dithiocarbamate resin has also been reported w244x. 4.6.1. Se(IV)
Detection limits of 0.05 ngyl and 0.15 ngyl for APDC has been loaded on C18-silica and used
organic and inorganic mercury, respectively, could for the preconcentration of Se from sea water prior
be obtained. However, this method involved man- to ET-AAS w114x. Speciation of inorganic Se(IV)
ual steps once the species were eluted with thio- and Se(VI) was possible since APDC selectively
urea, extraction into toluene as the diethyl chelates Se(IV). A reduction of Se(VI) to Se(IV)
dithiocarbamate complexes, butylation with a Gri- prior to chelation is required for the determination
gnard reagent and subsequent gas chromatography of total inorganic Se. However, this method was
(GC) analysis. In addition, preconcentration failed not selective as other trace elements were retained
in the presence of high amounts of humic sub- on the sorbent (such as Bi, Pb, Zn, As, Sn, V).
stances in the water samples. Complexation of Se(IV) could also be obtained
with 3-phenyl-5-mercapto-1,3,4-thiadiazole-2- 4.6.3. Organic Se

(3H)-thione (Bismuthiol II), which was then Tanzer and Heumann w248x developed a method
retained on activated carbon in batch experiments for the selective determination of acidicyneutral
w222x. Se(IV) could also be retained on Chelex- and basic organoselenium species in water samples
100 (in the iron form) over a wide pH range (up based on the selective retention of the species on
to 10) w245x. Amberlite XAD-2 at different sample pHs (3 and
8, respectively). However, this method was found
questionable by other authors who noted partial
4.6.2. Se(IV)ySe(VI) retention of Se(IV) on that sorbent w225x.
Both forms of inorganic selenium can be
retained on acidic alumina and extracted from
natural waters without any pH adjustment w111x. 4.6.4. Se(IV)ySe(VI)yorganic Se
Selective elution is achieved using ammonia at Simultaneous preconcentration of inorganic and
different concentrations for eluting Se(VI) and organic selenium species is a more difficult task.
then Se(IV) enabling speciation of inorganic sele- A combined SPE method has been reported to
nium in natural waters. Quantitative recoveries enable preconcentration of both inorganic and
from spiked tap water and ground water were organic species of selenium w19x. An anion-
obtained except for one tap water, where 42 and exchanger cartridge was placed on the top of a
154% of Se(IV) and Se(VI), respectively, were C18-silica cartridge so that inorganic selenium was
recovered possibly due to oxidation of Se(IV) by retained on the first cartridge, while organic spe-
residual chlorine. Similar observations were made cies were retained on the reversed-phase sorbent.
in another study w40x. The cartridges were then separated and the species
eluted: 1 M HCOOH for Se(IV), 3 M HCl for
Dowex-lX8 ion-exchanger enabled preconcen-
Se(VI), CS2 for organic compounds. In another
tration of both Se(IV) and Se(VI) w246x. The
recent procedure, simultaneous determination of
species were then separated during elution with
organic (selenocystine) and inorganic selenium
two different concentrations of HCl. Inorganic
(Se(IV) and Se(VI)) species was achieved using
selenium species were also retained on several
off-line preconcentration on Amberlite IRA-743
anion-exchange resins based on either cellulose or
followed by separation of the species and analysis
PS-DVB copolymer w225x. Despite a lower affinity,
using LC–ICP–MS w193x. No adjustment of the
the functionalized cellulose sorbent was preferred,
sample pH was required. However, the sorbent
as it enabled a better separation of Se(IV) and
was not selenium selective, and selenomethionine
Se(VI) during elution with different concentrations
could not be retained under the conditions devel-
of nitric acid. Traces of Se(IV) and Se(VI) could
oped due to strong competition with hydrogen
also be retained on a molybdate-form anion- carbonate.
exchange resin in batch experiments w247x, per-
mitting speciation of inorganic selenium in natural
waters except sea water (where foreign ions 4.7. Tin
interfered).
The coupling of SPE to LC–ICP–MS enabled Organotin compounds have found widespread
the speciation of inorganic selenium in natural industrial applications as biocides, antifouling
water samples by ion-pairing (with tetrabutylam- paints, catalysts and polyvinyl chloride stabilizers.
monium phosphate as the reagent) and sorption on So, there are a variety of pathways for their entry
C18-silica, subsequent elution and separation in the into the environment. Whereas inorganic tin is
chromatographic column by anion-exchange w40x. basically harmless, some organotin compounds are
However, sample volumes were limited to 10 ml highly toxic, especially tri-substituted organotin
due to the limited capacity of the preconcentration species. Therefore, there is a need for sensitive
column. methods that enable the determination and speci-
ation of these compounds. Several studies report species (monobutyltin, monophenyltin, dibutyltin,
the use of SPE for organotin determination w249– diphenyltin, TBT and TPhT) was achieved using
251x. methanol and their separation and analysis was
performed using GC–AES. In this manner, with
4.7.1. Butyltins rather small sample volumes (10–50 ml) detection
Tributyltins have been used as insecticides, fun- limits in the range of 0.10–0.17 ngyl could be
gicides, acaricides and preservatives for many obtained. Application of the method was tested
different types of materials. In particular, they have with real river water samples, and results were
been used as antifouling paints (as biocides) on consistent with those obtained using classical liq-
ships, boats and dock resulting in release of TBTs uid–liquid extraction. Similarly, in an off-line sys-
directly into the aquatic environment where they tem, organotins derivatised by sodium
are non-specific and extremely toxic to non-target
tetraethylborate could be retained on C18-silica
animal and plants species. C18-silica, either in
disks, and further eluted with supercritical CO2
cartridges or in PTFE disks, has been found
w252x.
effective in preconcentrating TBTs from aqueous
solutions w24x. Enrichment factors up to 1000 can The use of tropolone-loaded C18-silica has also
be obtained enabling the quantification of TBTs at been used for the retention of several butyltins and
the 0.1 mgyl level. In addition, TBTs can be stored phenyltins (mono-, di-, tri- and some tetra-substi-
on such solid supports at room temperature for at tuted compounds) w118x. However, selectivity
least 1 month. Amberlite XAD-2 impregnated with could not be achieved using SPE only. Organotins
tropolone has also been reported to retain TBT were separated by subsequent GC analysis after
and dibutyltin, while monobutyltin was not their ethylation with Grignard reagent. This meth-
retained w164x. The addition of 0.8% sulfuric acid od affords a sensitivity of low ngyl in surface
to the water sample enabled the selective retention waters and mgykg in sewage sludges.
of only TBT on the resin. This species was Speciation of tin has also been reported using
subsequently eluted with IBMK and analyzed by both graphitized carbon black and silica gel as
ET-AAS enabling quantitative determination of sorbents w223x. Water samples were first passed
TBT in water samples with a limit of detection of through GCB, allowing the retention of TBT and
14.4 ngyl and a preconcentration factor of 80. TPhT, while inorganic tin passed unimpeded and
was analyzed directly. The organic species were
4.7.2. Phenyltins subsequently eluted with a mixture of methanoly
Triphenyltin is retained on C18-silica cartridges, dichloromethane (4:1), and separated on silica gel.
even though a fraction of the compound cannot be
The overall method provided an enrichment factor
recovered w112x. Hence, best recoveries (between
of up to 80 000, but required the complete evapo-
81 and 89%) were obtained by elution in the
ration of the organotin fraction eluted from GCB,
backflush mode with 10y4 M 3-hydroxyflavone in
methanol. Retention of TPhT on other silica-based and the dissolution of the solid residue in hexane
sorbents (octyl, phenyl and cyanopropyl) has also before separation on silica gel.
been reported w112x. Finally, organotins can be efficiently retained on
strong cation-exchange silica-based bonded phases
4.7.3. Butyltinsyphenyltins (Bond-Elut SCX) and strong cation-exchange
A semi-automated system was reported that polymeric-based phase (Oasis-MCX). The pres-
enabled organotin speciation w251x, wherein pre- ence of NHq 4 was essential for elution of the
concentration was performed using a microcolumn compounds. Recoveries were lower with the pol-
of C18-silica placed in a FI manifold. Percolation ymeric phase particularly for TPhT, probably
of a derivatising reagent (sodium tetraethylborate) because of strong interaction of the aromatic rings
through the column enabled derivatisation of the with the N-vinylpyrrolidone-divinylbenzene sup-
organotin compounds. Elution of the derivatised port w36x.
5. Conclusion References
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Solid Phase Extraction of Trace Elements: Review

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Spectrochimica Acta Part B 58 (2003) 1177–1233

Received 2 December 2002; accepted 26 March 2003

1. Introduction tants, especially pesticides, in water samples w3x.

Fig. 1. SPE operation steps.

trace elements. In practice, inorganic cations may

– group I-‘hard’ cations: these preferentially react

For soft metals, the following order of donor

containers is available. In addition, the size of the

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

Standard Pb DDTP C18-silica EtOH F-AAS — 2.5–75 14–1000 300–3000 — w63x

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

Fig. 4. Sorbents based on inorganic supports.

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

Fig. 5. Sorbents based on organic supports.

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

V. Camel / Spectrochimica Acta Part B 58 (2003) 1177–1233

3.1.2.2. Divinylbenzene-vinylpyrrolidone copoly- poly(ethylene glycol dimethacrylate-hydroxyethyl-

(3-phenyl-5-mercapto-l,3,4-thiadiazole-2(3H)-thi- retained Se(IV) and Se(VI) species using nitric

require lower maximum flow-rates than disks rang-

3.2.2.3. Sample pH. Sample pH is of prime impor-

4.4. Lead with a limit of detection of 16.7 myl. Retention of

with 3-phenyl-5-mercapto-1,3,4-thiadiazole-2- 4.6.3. Organic Se

by graphite furnace-atomic absorption spectroscopy sorption preconcentration in a microwave field, Analyst

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