Talanta 63 (2004) 201223

Review
Application of flowing stream techniques to water analysis
Part III. Metal ions: alkaline and alkaline-earth metals, elemental and
harmful transition metals, and multielemental analysis
Manuel Mir , Jos Manuel Estela, Vctor Cerd
Department of Chemistry, Faculty of Sciences, University of the Balearic Islands, Carretera de Valldemossa, Km. 7.5, E-07122 Palma de Mallorca, Spain

Received 16 August 2003; received in revised form 20 October 2003; accepted 31 October 2003

Abstract

In the earlier parts of this series of reviews [1,2], the most relevant flowing stream techniques (namely, segmented flow analysis, continuous
flow analysis, flow injection (FI) analysis, sequential injection (SI) analysis, multicommuted flow injection analysis and multisyringe flow
injection analysis) applied to the determination of several core inorganic parameters for water quality assessment, such as nutrients and anionic
species including nitrogen, sulfur and halogen compounds, were described.
In the present paper, flow techniques are presented as powerful analytical tools for the environmental monitoring of metal ions (alkaline and
alkaline-earth metals, and elemental and harmful transition metals) as well as to perform both multielemental and speciation analysis in water
samples. The potentials of flow techniques for automated sample treatment involving on-line analyte separation and/or pre-concentration
are also discussed in the body of the text, and demonstrated for each individual ion with a variety of strategies successfully applied to
trace analysis. In this context, the coupling of flow methodologies with atomic spectrometric techniques such as flame atomic absorption
spectrometry (FAAS), electrothermal atomic absorption spectrometry (ETAAS), inductively coupled plasma mass spectrometry (ICPMS) or
hydride-generation (HG)/cold-vapor (CV) approaches, launching the so-called hyphenated techniques, is specially worth mentioning.
2003 Elsevier B.V. All rights reserved.

Keywords: Flowing techniques; Metal ion; Multielemental analysis; Speciation; Water

1. Introduction The hyphenation of flow injection (FI) with atomic spec-

Large amounts of toxic elements such as metal ions
have been and are nowadays discharged into the environ-
ment as a consequence of human activities. Exposure to
these compounds is of great concern as it poses not only
severe carcinogenic risks to humans, but also potentially
unacceptable ecological risks to plants, animals and mi-
croorganisms. Therefore, it is necessary to ensure a timely
warning for possible accumulation of polluting trace metal
in natural waters in order to protect public health. The
accurate determination of trace metals in a variety of envi-
ronmental samples at the low ng ml1 levels according to
the tolerable levels imposed by European directives is thus
required, along with the development of speciation schemes
to discriminate between different chemical forms.
Corresponding author.
E-mail addresses: mmirollado@hotmail.com, manuel@p01.uib.es
(M. Miro).
trometric techniques, such as flame emission spectroscopy
(FES), inductively coupled plasma mass spectrometry
(ICPMS), hydride-generation (HG) or cold vapor (CV)
atomic absorption spectrometry, flame atomic absorption
spectrometry (FAAS) or electrothermal atomic absorption
spectrometry (ETAAS) has proven to be a powerful analyt-
ical tool for the determination of ultratrace levels of metals
without risk of sample contamination, since an entirely
enclosed environment is guaranteed [3,4]. An additional
noteworthy feature of ICPMS is the ability of perform-
ing simultaneous multielemental analysis, which are of
particular importance for fast screening of metal profiles
in environmental waters [5]. Yet, the foregoing detection
techniques, mainly ICPMS, inherently show relatively low
tolerance to sample constituents present in environmental
matrices, including high concentrations of easily ionized
elements, salts and mineral acids (after sample treatment),
which might cause severe matrix effects and spectral inter-
ferences. In this respect, the isolation of the metal of interest

0039-9140/$ see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.talanta.2003.10.047
202 M. Miro et al. / Talanta 63 (2004) 201223
from the matrix components using on-line separation tech-
niques readily adaptable to flowing stream methods are
called for [35] Among them, solvent extraction/stripping
procedures, (co)precipitation schemes, adsorption on knot-
ted reactors, gas-diffusion protocols, cold vapor generation
techniques and microcolumn extraction approaches, which
concomitantly entail analyte preconcentration, are espe-
cially remarkable.
Sequential injection (SI), multicommuted flow injection
(MCFI) and multisyringe flow injection (MSFI) systems are
currently raised as competitive methodologies of the parent
flow injection technique in terms of reagent consumption,
robustness, simplicity of sample and reagent manipulation,
manifold versatility, and system automation. Of special in-
terest is also the straightforward interfacing with the discon-
tinuous, non-flow nature of the ETAAS detector as well as
their potentials to implement on-line sample pre-treatment
strategies, as demonstrated and exemplified in the bulk of
the text.
2. Multielemental analysis
Flow injection analysis can be regarded as a simple and
versatile tool to determine metal cations in water matrices
(e.g. estuarine, river, ground, coastal or ocean seawater) as
stated in several extensive reviews [6,7]. The combination
of flowing stream systems with robust detection techniques
such as inductively coupled plasma (time-of-flight)-mass
spectrometry enabled the multielement analysis [8,9] of
numerous transition metal ions (namely, Cd, Co, Cu, Mn,
Cr, Fe, Mo, Ni, Ag, Tl, V and Zn), and even the deter-
mination of their respective isotopes. The potentialities
of coupling FI with capillary electrophoresis for sample
preparation, analyte separation and automated on-line mul-
tiparametric monitoring of cationic species [10] together
with the ability to implement the so-called hydrodynamic
injection [11], which enables repeated sample injections
in one electrophoretic run, were also assessed. Besides,
the on-line sample preconcentration [12,13], clean-up steps
[14,15], matrix modification [16], on-line dilution by the
zone sampling technique [17] or isotope selection [18]
have recently attracted considerable research effort in both
atomic absorption and emission spectrometric techniques
in attempts to control interference effects and enable multi-
elemental analysis of cationic species at sub ng ml1 levels.
The most common active agents used for solid-phase ex-
traction of several species in the conventional packed-bead
reactor or disk-type membrane fashions [19] are two types
of chelators, namely 8-hydroxyquinoline [20] and iminodi-
acetate [15] attached to a variety of supports, such as silica
gel, controlled-pore glass, or silicone tubing, although por-
phyrin species were also used as a precolumn filling. One
exception is the use of reversed-phase sorbents [21] (viz.
octadecyl or phenyl functional groups bonded to silicagel,
activated carbon fiber or acetylated cellulose) to collect
dithiocarbamate-metal [22] or dithiophosphate-metal com-
plexes [23]. Alternative approaches, including sorption of
metal species on metal oxides (viz. ZrO2 ) [24] with high
specific surface area or on algae-silica preparations [25]
with high binding capacity as well as preconcentration us-
ing cloud point extraction of metaldithiophosphate chelates
in a non-ionic surfactant medium [26] were described. The
properties of controlled-pore glass and sand were compared
for their effectiveness in the immobilization of the fungus
Penicillium notatum using normal and ultrasonic tech-
niques and its use for preconcentration of different heavy
metals (viz. Cu, Zn, Cd, Pb and Fe) was assessed [27].
Coprecipitation of metal ions with Cu, Ni or Co chelates,
such as cobalt-pyrrolidinedithiocarbamate [28] and copper
[29]/nickel [30]-diethyldithiocarbamates (DDTC), or pre-
cipitation of metal-diethyldithiocarbamates [31] onto the
inner walls of a knotted reactor are also worth mentioning.
Heavy metal derivatization-solvent extraction procedures
prior to delivering the extractant phase to a cycling nebulizer
system of an ICP-spectrometer were easily implemented in
flow injection manifolds. A significant improvement of the
analytical throughput for multielemental analysis (viz. Cd,
Ni and Pb) was attained using a flow network based on the
multicommutation concept that allowed cation-exchange
and elution steps to be simultaneously performed in several
columns in parallel [32]. The sandwich-type SI-wetting film
strategy based on the differential flow velocities of aque-
ous and organic phases was applied to the simultaneous
determination of cadmium and mercury ions capitalized
on the formation of dithizonates at different pH extraction
conditions [33].
Chemometric multivariate methods (e.g. partial least-
squares, unfold partial least-squares and n-way partial least
squares) coupled with diode array spectrophotometry en-
abled simultaneous monitoring of Cu, Zn and Mn in the
presence of concomitant interfering ions [34]. Spectropho-
tometric determination of Cd, Cu and Pb using sulfarsazene
as chromogenic reagent and partial least-squares calibra-
tion was carried out preceded by both selective removal
of metal interferences and on-line preconcentration by sor-
bent extraction [35]. The same multivariate mathematical
algorithm was selected for the on-line simultaneous de-
termination of Fe, Co and Ni with 2,2 -dipyridyl ketone
picolinohydrazone using flow injection analysis [36]. The
different reaction and retention rates of Fe, Ni and Zn
onto 1-(2-thiazolylazo)-2-naphthol containing C18 -bonded
silicagel support combined with multivariate calibration
was the scheme of a solid-phase spectrophotometric pro-
cedure for the simultaneous determination of the above
metals [37]. A full factorial experimental design was ap-
plied to the optimization of the pre-electrolysis poten-
tial, supporting electrolyte concentration, metal deposition
time and thickness of the Hg-film in the simultaneous
flow injection square-wave anodic stripping voltammet-
ric determination of Cu, Zn, Pb and Cd in freshwaters
[38].
 M. Miro et al. / Talanta 63 (2004) 201223
3. Alkaline metal ions
Rapid and direct determination of alkaline metals in
natural waters was successfully achieved by flow injec-
tion coupled to either flame atomic absorption (FAA) or
flame emission spectrometry (FES). Flow systems were
suitable tools to perform on-line dilution procedures prior
to atomic absorption or emission detection using a dilution
chamber [39], splitting zones or zone sampling methods
[17].
Dicyclohexano or benzo-18-crown-6-based methodolo-
gies gained special interest in this field. Thus, ion associ-
ations formed between the K or Na-crown-ether inclusion
complex and an azo dye counter anion enabled sequential
spectrophotometric determination of alkaline ions following
flow injection solvent extraction and chromatographic sepa-
rations [40]. Moreover, a flow-through sensor for Na, K and
Rb comprising a crown-ether based ion-selective electrode
and a hydrophilic membrane was developed and compared
with voltammetric methods [41]. The K-crown-ether com-
plexation also improved the turbidimetric determination
of the alkaline metal with the tetraphenylborate counter
ion [42]. The application of an ISE-array modeled via the
NikolskiiEisenmann equation using simplex optimization
for the simultaneous determination of Na and K in flow
systems was reported [43]. The outstanding features of the
designed multi-sensor approach over existing single elec-
trode measurements are the better precision and reliability,
the diagnosis of electrode performance without recalibra-
tion and the accurate characterization of the array response
with simple models. The same authors raise the possibil-
ity of using both an enhanced kinetic-based selectivity for
analytical measurements and a multiple ionophore sensor
to improve the electrode array performance [44]. Potentio-
metric detection of Na and K with two ISEs arranged in
parallel without coupling a conventional reference electrode
was also evaluated [45].
The selectivity of the bis(tert-butylbenzo)-21-crown-7-
ionophore for cesium over the other alkaline metals was thor-
oughly investigated by coating a PVC membrane containing
the macrocyclic ligand on the tip of a silver wire incorpo-
rated into the flow set-up [46]. In the context of radioisotope
analysis, a rapid, safe and cost effective radiometric 137 Cs
determination in radioactive wastewaters was achieved by
coupling flow injection analysis with a solid semiconductor
-ray counting detector (viz. NaI (Tl) scintillator) [47].
4. Alkaline-earth metal ions
In this section, the most remarkable parameter for water
characterization is the total hardness determination (viz. the
sum of Ca and Mg concentrations). To this aim, researchers
proposed flow injection photometric procedures or poten-
tiometric titrations using the conventional eriochrome black
T-EDTA chemical system or a gradient mixing tube-based
203
hardness ISE, respectively [48]. Metalligand buffer so-
lutions used in sequestration reactions coupled to both
spectrophotometric or potentiometric detection are com-
mon FIA reagents [49]. Another strategy for water hardness
measurement involves complexation of both Ca and Mg
with chromogenic agents; e.g. acid alizarin violet-N or
chlorophosphonazo III.
Chemometric multivariate approaches such as multilin-
ear regression [50], partial least squares calibration [51],
counter-propagation neural networks [52] and H-point
standard addition methods [53] applied to both flow and
sequential injection systems allowed the simultaneous spec-
trophotometric determination of Ca and Mg in environmen-
tal water samples at a wide range of concentrations using
moderately or scarcely selective chromogenic reagents; e.g.
4-(2-pyridylazo)resorcinol [54] or arsenazo III [55].The
dependence of calcium concentration on the yield of the
arsenazoMg complex was demonstrated with such multi-
variate calibration procedures [56], and various side effects
like overlapping of reagent spectrum with those of its com-
plexes, blank bias error, matrix effects and faulty signals
were accounted for. A sandwich-based FIA technique in-
volving the injection of a masking solution between two
sample slugs was also described for metal discrimination
[57]. High levels of alkaline-earth metal ions in natural
waters were easily determined without previous sample
treatment using FIA/SIA analyzers hyphenated with ICP
[58]or FAA [59] spectrometry.
The underlying chemistry for the individual determina-
tion of calcium ion in rain, snow, boiler feed, borehole,
natural and paper machine white waters is the selec-
tive complexation with chromogenic ligands [60] (viz.
o-cresolphthalein complexon, chlorophosphonazo III or
m-chloroantipyrylazo) at a suitable pH using 8-hydroxy-
quinoline (8-HQ) as a masking agent for Mg [61]. Imple-
mentation of different sample processing conditions to attain
limited, medium, and large dispersion degree for the afore-
mentioned determination without manifold re-configuration
was permitted through the multicommutation concept [62],
also applied to potentiometric titrations [63]. The abil-
ity of alkaline-earth metals to displace Cu(II) ions in the
CuEDTAPAR system was successfully exploited for indi-
rect Ca monitoring [64]. Flow injection potentiometry with
photo-cured membrane-based coated-wire Ca ISE sensors
[65] should be also highlighted in this context. The effect
of the ionic strength adjustment on the response of the elec-
trode and on the magnitude of additive interferences was
thoroughly investigated [66]. The concept of pulsed flow
chemistry characterized by turbulent mixing and low axial
dispersion was introduced and exemplified with the on-line
potentiometric titration of calcium [67]. The response of a
cobalt wire electrode to phosphate ions was used for indi-
rect flow injection potentiometric detection of Ca (or Mg)
based on the reduction of the phosphate activity as a con-
sequence of precipitate formation with the target species
[68].
204 M. Miro et al. / Talanta 63 (2004) 201223
Fig. 1. Manifold devised for the sequential injection spectrofluorimetric determination of magnesium using 8-hydroxyquinoline-5-sulfonic acid as a
derivatization reagent. HTAC: hexadecyltrimethylammonium chloride; HQS: 8-hydroxyquinoline-5-sulfonic acid; EGTA: ethylene glycol-bis(-aminoethyl
ether)-N,N,N ,N -tetraacetic acid; C: mixing coil.
Selective spectrophotometric methods for Mg monitoring
in natural waters containing macroamounts of Ca were de-
scribed using the Xylylazo Violet chelating reagent in mi-
cellar medium [69], or the inhibitory effect of the analyte
on the succinimide dioxime oxidation catalyzed by Mn(II)
in the presence of nitrilotriacetic acid [70]. The indirect am-
perometric determination of Mg based upon the formation
of the MgEriochrome Black T complex and measurement
of the excess of ligand on a glassy carbon electrode [71]
is also worthmentioning. Fig. 1 depicts a typical sequen-
tial injection spectrofluorimetric set-up for the determina-
tion of magnesium in various environmental waters based
on the formation of the Mg8-HQ complex in the presence
of masking agents [72].
Sequential injection has been presented as a powerful
automated technique to perform radiochemical isolations/
determinations as demonstrated with 90 Sr and 226 Ra assays.
The former radioisotope was rapidly determined in high
activity residues using either a renewable bead-suspension
entrapped into a specially designed microcolumn [73]
or a functionalized macrocyclic ligand-based extraction
chromatographic column [74], both on-line coupled to
liquid-scintillation spectrometry. Renewable wetting-film
extraction by ionophore immobilization onto the inner walls
of a PTFE reactor enabled 90 Sr detection at environmental
activity levels [75]. Both 90 Sr and 226 Ra radionuclides were
isolated in a sequential injection method following sorption
onto a MnO2 -impregnated cotton filter and further elution
with a hydroxylamine solution [76].
Though the determination of trace amounts of beryllium
in natural waters is of increasing interest as it can indi-
cate environmental pollution and could provide information
of the metal uptake through these sources, scarce applica-
tions of flowing stream methods in water matrices are found
in literature. Recently, determination of beryllium in natu-
ral and wastewaters at the low g l1 level has been suc-
cessfully performed through ETAAS using lutetium as a
semi-permanent modifier. The developed multicommutated
system included quantitative on-line precipitation of beryl-
lium with ammonia, collection in a Tygon tube and disso-
lution in acidic medium prior to eluate injection into the
electrothermal atomizer [77].
5. Aluminum
Although aluminum is the third most abundant element
in the Earsths crust, its concentration in neutral waters is
low because of the relatively low solubility of aluminum
minerals (viz. feldspars). In spite of this fact, the possible
relationship between environmental aluminum exposure
and Alzheimers disease prompted an increased awareness
of aluminum levels in the environment and forced the de-
velopment of analytical methodology suitable for ultratrace
detection of the target element. The determination of alu-
minum at endogenous levels (>1 g l1 ) in water samples
requires the development of sorbent extraction methodolo-
gies based on the temporal immobilization of the metal
 M. Miro et al. / Talanta 63 (2004) 201223
ion onto cation exchangers [78] or 8-HQ functionalized
resins [79] or an analyte derivative onto copolymeric (viz.
XAD-2) [80], polyethylene powder [81] or C18 -bonded sil-
ica gel [82] microcolumns implemented into flow devices.
The on-line preconcentrated analyte is further eluted and
measured by spectrophotometry [83], ICPAES [84], FAAS
[78] or ETAAS [85]. Among chromogenic reagents, the Py-
rocatechol Violet [86], Chrome Azurol S [87], compounds
of triphenylmethane series and Eriochrome Cyanine R [88],
also used as an immobilized reagent phase in diffuse re-
flectance optrodes [89], are the best suited for photometric
flow procedures. Salicylaldehyde-based fluorimetric pro-
cedures [90], also adapted to flow-through sorbent-based
sensors [82], attracted the attention of many analysts owing
to its excellent selectivity. Other simple approach for the de-
termination of trace levels of Al using fluorescent detection,
requiring neither masking agents nor micelle forming com-
pounds to improve both selectivity and sensitivity, involved
lumogallion complexation [91]. 8-HQ or Eriochrome Red
B sensitized by traces of fluoride [92] were also selected
as fluorogenic ingredients in multisyringe/multicommuted
procedures [93] or in flow injection methods implementing
different solvent extraction modalities [94].
Aluminum chemistry in acid impacted aquatic systems is
receiving nowadays increasing attention owing to the toxic
effects of this element on the environment. The dependence
of aluminum toxicity on its speciation chemistry forested
the development of fractionation methods [95], wherein a
precise control of reaction time is required. Kinetic discrim-
ination protocols [96] based on the Al species reaction with
8-hydroxyquinoline at different rates were implemented in
both solvent [97] and sorbent [98] extraction flow systems
for determination of the fast reactive aluminum fraction at
different levels [99]. The applicability of such protocols for
complexation studies of aluminum with fulvic and humic
acids has been demonstrated [100]. The speciation of total
reactive aluminum in the labile or exchangeable fraction
(i.e. free aluminum, monomeric aluminum sulfate, fluo-
ride, hydroxide and other weak complexes), the non-labile
monomeric fraction (i.e. monomeric alumino-organic com-
plexes) [101] and the acid soluble fraction (i.e. colloidal
polymeric aluminum) has been reported using Pyrocatechol
Violet [102] or 8-HQ [103] chelation/ion-exchange flow
methodologies. Kinetic and thermodynamic considerations
for time-based fractional partition methods have been de-
scribed attending the strong influence of competing ligands
on the chelating reaction rate [104].
6. Transition metal ions
In this section, the most common transition elements
present in water matrices are itemized in two groups accord-
ing their source. One group includes some micronutrients or
natural trace elements such as molybdenum, cobalt, iron and
manganese. In the second group, anthropogenic or environ-
205
mental harmful elements such as mercury, chromium(VI),
lead, zinc, nickel, cadmium and copper will be thoroughly
reviewed.
6.1. Essential elements
6.1.1. Molybdenum
The simple, rapid and accurate determination of molyb-
denum at nanogram levels is of great interest because plants
and animals require small quantities of this element.
Numerous segmented and unsegmented continuous-flow
methods have been proposed for the determination of trace
amounts of molybdenum in natural fresh (viz. river, lake,
sea) and tap water samples. In these flowing systems, the
chemiluminescence reaction between luminol or lucigenin
and Mo(III) produced by a Jones reductor enabled metal
determination over the wide linear range 0.11000 g l1
Mo. A sensitive flow injection spectrophotometric method
for the determination of the analyte at low g l1 lev-
els was developed using the Mo-catalyzed oxidation of
ascorbic acid with hydrogen peroxide and the succes-
sive condensation of the generated dehydroascorbic acid
with o-phenylendiamine to produce quinoxaline deriva-
tives [105]. As nearly all of the catalymetric procedures
for molybdenum suffer from strong interferences, requiring
the use of chelating agents [105], flow/sequential injection
methods coupled with ETAAS or ICPAES detection are
commonly explored owing to their high sensitivity and
selectivity. The performance of on-line preconcentration
strategies prior to the detection step involving molybdenum
co-precipitation with Fe(II)-pyrrolidinedithiocarbamate on
the walls of a PTFE tubing [106], analyte enrichment on
iminodiacetate polymeric resins [107] or activated alumina
[108] as well as chelation with diethyldithiocarbamate
or oxine [109] ligands and further complex sorption on
C18 -sorbent packed reactors were exhaustively assessed.
Sequential injection-wetting film extraction combining an-
alyte complexation with thiocyanate and extraction as an
ion paired complex into a coated toluene phase containing
a counter ion was exploited to exclude interference from
more than 40 metal species and anions tested, while as-
suring high sampling rate [110]. A selective flow injection
ion-exchange absorptiometric method using Tiron as a color
forming reagent including a pre-column for molybdenum
isolation/pre-concentration was proposed for the determi-
nation of the analyte at the g l1 level in various natural
waters [111].
6.1.2. Cobalt
The concentration of cobalt in aquatic environments is
extremely low and it has been suggested that this element
may act as a limiting nutrient for marine phytoplankton. It
is only toxic to plant and mammals at relatively high con-
centrations (>1 mg l1 ), which are rarely observed in en-
vironmental waters. Cobalt demonstrates a scavenged-type
vertical distribution in the open ocean, it has a maximum of
206 M. Miro et al. / Talanta 63 (2004) 201223
about 1020 ng l1 in surface water and is depleted to less
than 1 ng l1 at depths below 1000 m. It has been found a
cobalt enrichment in hydrothermal fluids on the sea-floor
has been found, and hence, this metal is interesting from
the geochemical point of view as a chemical indicator of
hydrothermal activity.
Commonly used laboratory techniques for sub-ng l1
cobalt determination in tap, mineral, river, estuarine and
oceanwater samples include flow injectionelectrothermal
atomic absorption spectrometry following on-line precon-
centration steps. In this context, physical adsorption of the
Co-nitroso-R-salt-tetrabutyl ammonium ion-pair [112] or
the ammonium pyrrolidine dithiocarbamate complex [113]
on the inner walls of PTFE knotted tubing, the on-tube for-
mation of a metal chelate into a knotted reactor precoated
with the 1-phenyl-3-methyl-benzoylpyrazol-5-one chelat-
ing reagent [114] and the reversed-phase sorbent extraction
of a low-polar analyte derivative onto a modified silicagel
packed microcolumn using sodium diethyldithiocarbamate
as the complexing agent [115] are worthmentioning. In the
latter procedure, enrichment factors as high as 210-fold were
achieved with high loading times. In solid-phase extraction
approaches prior to atomic spectrometric detection, the
air-segmented eluate modality is widely adopted in order to
reduce the eluent volume and minimize analyte dispersion
when delivering to either the graphite electrothermal atom-
izer [113] or the laser-excited atomic fluorescence detector
[116]. The generation of volatile diethyldithiocarbamate
and acetylacetonate cobalt chelates and the implementation
of a thermospray device into the flow injection set-up en-
abled the direct preconcentration of the target analyte on
the surface of the graphite tube platform [117].
The ability of impregnated polyurethane foam (PUF)
microcolumns to tackle real environmental problems was
assessed and demonstrated with the development of a
fast and sensitive flow injectionflame atomic absorption
method for monitoring cobalt at the g l1 level using
a PUF-2-(2-thiazolylazo)-p-cresol-based column [118].
Direct on-line precipitation of the target species with
1-nitroso-2-naphthol as well as deposition of cobalt as its
cyano complex onto activated acidic alumina [119] were
useful trace enrichment strategies performed prior to flame
atomic absorption analysis.
Significant progress has been recently made in the devel-
opment of continuous flow and flow injection spectropho-
tometric catalytic methods for determining trace levels of
dissolved cobalt in water matrices. These approaches were
proven extremely suitable for marine chemical research
on-board a ship [120], especially when in-line tangential
filtration units were assembled into the flow manifolds for
the removal of suspended particulate matter [121]. Such
automated systems were generally based upon catalytic ox-
idation reactions of o-dihydroxybenzene derivatives [122],
such as protocatechuic acid or Tiron or p-diaminobenzene
compounds [123] in strong alkaline medium. The direct
determination of low amounts of cobalt in seawater without
any preliminary steps and at a pH range close to that of
the sample medium was performed exploiting the oxidation
reaction of N,N -diethyl-p-phenylenediamine catalyzed by
the target species and activated by Tiron [120]. Flow injec-
tion systems with chemiluminescence detection based on
the catalytic effect of cobalt on the oxidation of quercetin,
luminol, gallic acid or pyrogallol by hydrogen peroxide
were also reported [124,121]. The lack of selectivity over
alkaline-earth ions is usually overcome by implementation
of 8-HQ containing strong chelating resins in the flow
assembly as a matrix removal step [124,121]. In some in-
stances, masking strategies were adopted in flow injection
procedures aiming to minimize heavy metal interferences
[125].
Flow injection with spectrophotometric detection also ap-
pears to hold considerably promise for trace level deter-
minations of cobalt. Hence, both the cadmiumporphyrin
complex [126] and the 4-benzylpiperidinedithiocarbamate
in a tertiary solvent system [127] were used as color de-
veloping reagents to determine the target species at low
g l1 levels. The inherent disadvantage of porphyrins re-
lated to the large overlap of the absorption spectra of the free
reagent and the Co-complex was solved with photochemical
decomposition of the excess of reagent using only visible
light irradiation [126]. A flow-through optrode containing
1-(2-pyridylazo)-2-naphthol immobilized on phosphorilated
cellulose disks was also designed as a highly sensitive alter-
native for ultratrace determinations of the heavy metal [128].
The interaction of nitroso-R-salt with cobalt in the presence
of water-soluble polymers, its kinetic role for flow injection
spectrophotometric procedures and the likelihood of cobalt
membrane concentration were carefully investigated [129].
Finally, in the scope of electrochemical methodologies, a
miniaturized sequential flow analyzer coupled with adsorp-
tive cathodic stripping voltammetry was described for per-
forming on-line measurements of cobalt in the marine en-
vironment with controlled perturbation of natural equilibria
of the element [130].
6.1.3. Iron
The hypothesis that iron limits primary production in the
oceans and acid rain problems stimulates its research in
water samples. As a result, methods for total iron determi-
nation in a gas-segmented continuous flow, flow injection or
sequential injection fashion have been developed with high
sensitivities. A great number of chelating resins containing
various functional groups such as 8-HQ [131,132], iminodi-
acetic acid [133], N-hydroxyethylethylenediamine [134] or
2-mercaptobenzimidazole [135], or reversed-phase sorbents
following iron chelation [136138] are proven suitable for
flowing stream preconcentration methodologies interfaced
with both ICP [139] and FAA [140] spectrometry and
also with spectrophotometric [141] detection. In the latter
case, typical analytical procedures involve Fe(III) reaction
with thiocyanate exploited in modelation and optimization
computational techniques [142] or in ion-exchange-based
 M. Miro et al. / Talanta 63 (2004) 201223
flow-through optrodes [143,144]; and Fe(II) complexation
with ferrozine [145] or 1,10-phenanthroline [146] em-
ployed for ultratrace determinations of the target analyte
using bead injection [147] or solid-phase spectrophotomet-
ric/photoacoustic strategies [146,148,149]. Furthermore,
new sampling modalities adapted to sequential injection
analysis such as monosegmented [150] or reversed-flow
[151] approaches and novel flow-through cells such as long
liquid waveguide capillary cells [152] were characterized
using the aforementioned chemistries. The catalytic ac-
tion of iron species on the oxidation of phenylenediamine
compounds was also intensively investigated [153,154].
A plethora of highly sensitive chemiluminogenic pro-
cedures for determination of iron species in seawater at
subnanomolar levels was reported [155,156]. In this con-
text, the catalytic effect of Fe(II) or Fe(II)oxine complexes
on the oxidation reaction of luminol by hydrogen peroxide,
dissolved oxygen [157] or potassium periodate [158], in
the presence of citric acid and cationic surfactants [159],
was considered. Enhanced chemiluminescence emission
of the brilliant sulfoflavinH2 O2 [160,134], diaryl oxalate
estersO2 [161] and gallocyaninH2 O2 systems with traces
of Fe(II) were also described.
Discrimination between the different oxidation states (viz.
Fe(II) and Fe(III)) in natural waters is relevant since iron
is one of the few elements that is an active participant
in aquatic redox processes at pH < 6 and at oxic-anoxic
boundaries. Many speciation methods deal with chelating
agents or reagent phases with a strong affinity for a par-
ticular redox state of the metal [162,163]. In this context,
the Fe(III)Chrome Azurol S, Fe(III)semi-xylenol orange,
Fe(III)iron and Fe(II)Ferene S systems should be un-
derlined [164166]. The catalytic actions of the Fe(III) or
Fe(III)EDTA species on the oxidation of hydroxylamine
[167], p-phenetidine [168], or tetramethylbenzidine [169],
using 1,10-phenanthroline as an effective activator estab-
lished the basis of alternative proposals. A flow injection
manifold for spectrophotometric monitoring of trace levels
of iron exploring Shinn reaction as a detection scheme is
shown in Fig. 2. The sequential determination of Fe(II) and
Fe(III) taking advantage of the different reaction kinetics
with Tiron, and the acceleration action of Cu(II) on the ox-
Fig. 2. Flow injection set-up for the catalymetric determination of traces of Fe(III) exploiting the metal-catalysed oxidation of hydroxylamine prior to
nitrite monitoring via Shinn reaction. SAM: sulphanilamide; NED: N-(1-naphthyl)ethylenediamine; EDTA: ethylenediaminetetraacetic acid; IV: injection
valve; S: sample; PP: peristaltic pump; SP: spectrophotometer; TB: thermostatic bath; RC: reaction coil; W: waste.
207
idation of ferrous ion in the presence of the chromogenic
reagent was reported [170]. Anodic stripping voltammetric
methods have been also developed for receiving information
relating to speciation and organic complexation of the metal
[171].
Off-line or on-line redox reactions in solution for iron
discrimination were performed by the addition of ascorbic
acid [172], sulfite [131], hydroxylamine [134] or hydrogen
peroxide [135]. On-line Fe(III) reduction or Fe(II) oxi-
dation in heterogeneous phase was successfully achieved
using amalgamated [173] or copperized zinc [157], or
Folin-Ciocalteu-based [143] regenerable micro-columns,
respectively, and thus the analyte is obtained in a suitable
oxidation state to undergo the derivatization reaction. Fi-
nally, multivariate methods such as partial least-squares
calibration [174] enabled the simultaneous determination
of various iron species without requiring the foregoing
additional reagents.
Table 1 summarizes the analytical figures of merit of the
aforementioned flowing stream methods for the determi-
nation and/or speciation of iron species. Trace concentra-
tions are frequently determined following sorbent extrac-
tion schemes using ion exchangers, iminodiacetic-based
resins, 8-hydroxyquinoline microcolumns or newly de-
veloped chelating materials with chemically immobilized
mercapto or hydroxyethylenamine moieties. Packed-bead
microcolumns are currently implemented in both flow and
sequential injection manifolds interfaced mainly with spec-
trophotometric or atomic absorption detection, although
flow-through optosensors based upon solid-phase absorp-
tiometry or bead-injection are proven excellent alternatives
to avoid the undesirable post-column analyte dilution, and
hence, higher enrichment factors are attained.
6.1.4. Manganese
The determination of manganese in public and industrial
waters is important because manganese may cause stain-
ing of clothes and reduction of pipeline carrying capacities
due to encrustation. The most important source of man-
ganese found in ground and natural waters is the chemi-
cal erosion of the earths crust. In the last years, a host
of flow injection catalymetric methods has been reported
 208
Table 1
Analytical features of relevant flowing stream methods applied to the determination and/or speciation of iron in water samples
Flow Detection Reagent/characteristics Linear range R.S.D. (%) DL Water sample Sampling Reference
method technique rate (h1 )
FIA SPS DPPS/PC-AE 0.012 g l1 1.3 (0.5 g l1 ) 0.01 g l1 Highly purified 4 [146]
water
FIA Spec DPD-CR/PC-CHRC (8-HQ) Up to 1.6 nM 1.5 (0.71 nM) 0.016 nM Sea 56 [132]
FIA Spec/AAS SCN/PC-MBI-SG/SP Up to 1.0 mg l1 <5 150 ng l1 Mineral, well, () [135]
(0.15 g l1 -1.0 mg l1 ) drinking
SIA Spec TIRON/SP 0.15100.0 mg l1 Fe(III), <1.3 Fe(III), <0.8 Fe(II) 0.10 mg l1 Fe(III), Effluent streams 30 [166]
0.3080.0 mg l1 Fe(II) 0.15 mg l1 Fe(II)
SIA Spec TIRON/SP 0.0020.026 M 0.4 (0.013 M) 0.002 Industrial 17 [165]
FIA CL BSF/PC-AMB-HEEED/SP 0.8200 nM 4 (2 nM) 0.36 nM FeTotal 0.80 nM Rain, tap, river, 10 [134]
Fe(II) coastal sea
FIA Spec PHEN/PC-FOAM 5100 g l1 1.5 (20 g l1 ) 0.45 g l1 Well, river, lake 15 [138]
and sea

M. Miro et al. / Talanta 63 (2004) 201223

FIA Spec DPD-CR/PC-CHRC (8HQ) Up to 9 nM 2.5 (0.35 nM) 0.025 nM Sea 30 [153]
FIA CL LUM/PC-CHRC (8HQ)/SP 0.0410 nM 3.2 (1.0 nM) 40 pM (Fe(II) + Fe(III)) Estuarine, coastal 20 [131]
FIA Spec PSPmH Up to 210 g l1 0.69 (106 g l1 ) 10 g l1 River 70 [163]
FIA Spec FERR/SP Up to 300 M 0.65 (1 M) 10 nM Lake, river 45 (FeTotal ), [141]
60 (Fe(II))
FIA CL AE-LUM/SP 11000 g l1 for Fe(II) and 3.5 and 4.5 (10 g l1 0.4 g l1 Ground, rain, river, 40 [157]
Fe(III) Fe(II) and Fe(III)) lake
FIA-SF CL LUM 0.25200 nmol Fe(II) kg1 38 (<4 nmol 0.06 nmolFe(II) kg1 , Ocean, coastal () [155]
Fe(II) kg1 ), 25 0.15 nmol Fe(II) kg1
(>4 nmol Fe(II) kg1 )
FIA and Spec FERR 0.56 mg l1 (FIA), 0.3 (FIA), 0.28 (rFIA) 0.012 mg l1 (FIA), Waste 90 (FIA), 50 [145]
rFIA 0.15 mg l1 (rFIA) 0.010 mg l1 (rFIA) (rFIA)
SIA Spec SCN/PC-CHRC-CH100 0.050.6 mg l1 3.0 (0.1 mg l1 ) 0.02 mg l1 Tap, well, sea 20 [133]
FIA AAS FERR/PC-C18 /SP 0.0050.5 mg Fe(II) l1 <5.0 (0.0050.5 mg 0.005 mg Fe(II) l1 Environmental 30 [136]
Fe(II) l1 )
FIA Spec FERR/PC-CHRC/SP 075 nM Fe(II), 0200 nM 3 (0.175 nM) nM Fe(II), 0.3 nM (Fe(III) Sea () [137]
Fe(III)
FIA ICPMS APDC/PC-PTFE KR/SP 4 104 to 0.12 mg l1 2.9 (0.01 mg l1 ) 8 105 mg l1 Tap, river, ground 21 [139]
SIA AAS CHRC-CH100 0.051.2 mg l1 4.0 (1.0 mg l1 ) 0.012 mg l1 Natural () [140]
FIA BI PHEN/PC-CHRC-CH100/SP Up to 3.90 mol Fe(II) l1 4.0 (3.90 mol Fe(II) l1 ) 0.45 mol Fe(II) l1 Tap, pond, drinking () [147]
FIA SPS SCN/AE-SP 80500 g l1 for total iron 3.4 (80500 g l1 ) 80 g l1 River () [143]
SIA Spec SCN 520 mg l1 1 (10.4 mg l1 ) 5 mg l1 Natural 110 [142]
FIA SPS SCN/AE 10200 g l1 2.5 (10200 g l1 ) 10 g l1 Natural 30 [144]
SIA-MSFA Spec PHEN 0.58.0 mg Fe(II) l1 1.1 (1.0 mg Fe(II) l1 ) 0.5 mg Fe(II) l1 Natural () [150]
FIA CL LUM/CITR-TTAB/SP 5 109 1 106 mol l1 3 (4 108 mol l1 2 109 mol l1 Fe(II), 1 River 36 [159]
(Fe(II) and total iron) Fe(II)), 1.5 (1 109 mol l1 total iron
107 mol l1 total iron)
SIA Spec TIRON 0200 mg l1 0.41 (50 mg l1 ) 0.03 mg l1 Mine 24 [164]
FIA DPASV PYP/PC-SP 106 104 M for Fe(II) and 3.7 Fe(III) (1 106 M), 2.4 108 M Fe(III), 2.7 Tap 12 [171]
Fe(III) 2.3 Fe(II) (1 106 M) 108 M Fe(II)
SIA Spec PHEN 0.16.0 mg l1 1.5 (2.6 mg l1 ) 0.1 mg l1 Waste 40 [172]
FIA Spec TIRON-Cu(II)/SP 1.8 105 1.8 104 mol l1 0.2 (Fe(III), 9 1.8 105 mol l1 Synthetic 30 [170]
105 mol l1 ) 0.7 (Total
iron, 9 105 mol l1 )
GSCFA Spec FERR/LLWCFC-TAF2400/SP Up to 50 nM Fe(II), Up to 7 (0.6 nM Fe(II)) 0.1 nM Fe(II) Natural () [152]
60 nM total iron
SIA Spec PHEN/SP 0.050.8 mg l1 5.77.8 (0.050.8 mg l1 ) 0.02 mg l1 Fe(II), Natural, waste 20 [173]
0.03 mg l1 total iron
FIA Spec 8-HQ/PHEN-MVM/SP 0.062.0 mg l1 512 (0.15 mg l1 ) 0.06 mg l1 Fe(II) and Fe(III) Lake, ground 85 [174]
FIA SPPA DPPS/AE 2.515.0 g l1 9 (3.34 g l1 ) 0.33 g l1 River 6 [149]
FIA Spec PH-PH/TWEEN 0.530 g l1 Fe(II) and Fe(III) 2.6(5 g l1 Fe(III)) 0.2 g l1 River, lake, sea 30 [154]
rFIA CL LUM/PHEN 1.0 104 0.6 mg l1 Fe(II) 0.9 (5.0 103 mg l1 3 106 mg l1 Fe(II) Underground () [158]
Fe(II))
FIA Spec 5-Br-PSAA 3-10 g l1 Fe(II) 0.6 (10 g l1 Fe(II)) 1 g l1 Fe(II) Ground 12 [162]
FIA Spec TMB/CR/SP 0.2200 g l1 for Fe(II) and 1 (5 g l1 Fe(III)) 0.05 g l1 River, lake 12 [169]
Fe(III)
rSIA Spec PHEN 0.256 mg l1 Fe(II) 1.7 (2.3 mg l1 Fe(II)) 0.06 mg l1 Fe(II) Natural 22 [151]
FIA Spec EDTA-HYDR/CR-Shinn 3.5150 g l1 6.7 (5 g l1 ) 2 g l1 Natural 60 [167]
FIA SPS FERR/AE 5500 g l1 13 (5500 g l1 ) 4.3 g l1 Tap, river 50 [148]
0.412 g l1 4.7 (8.5 g l1 ) 0.05 g l1

M. Miro et al. / Talanta 63 (2004) 201223

FIA Spec PHENE/PC-CR Sea 40 [168]
CFA CL LUM/PC-CHRC(8HQ) 0.091.8 nM 1.2 (0.91 nM Fe(III)) 0.05nM Fe(III) Oceanic, () [156]
hydrothermal
FIA CL BSF/PC-CHRC (8HQ) 0.25100 nM Fe(III) 25 (>2.5 nM) 0.25 nM Sea 7 [160]
R.S.D: relative standard deviation; LD: detection limit; FIA: flow injection analysis; CFA: continuous flow analysis; SIA: sequential injection analysis; SPS: solid-phase spectrophotometry; BI:
bead-injection; rFIA: reversed flow injection analysis; MCFIA: multicommuted flow injection analysis; GSCFA: gas segmented continuous flow analysis; MSFA: monosegmented flow analysis;
rSIA: reversed sequential injection analysis; SP: speciation between Fe(II) and Fe(III); SF: stopped flow; Spec: spectrophotometry; AAS: atomic absorption spectrometry; CL: chemilumines-
cence; ICPMS: inductively coupled plasma-mass spectrometry; DPASV: differential pulse anodic stripping voltammetry; SPPA: solid phase-photoacoustic spectroscopy; LLWCFC: long liquid waveg-
uide capillary flow cell; TAF2400: Teflon AF-2400; MVM: multivariate method; CR: catalysed reaction; PC: preconcentration; AE: anion exchanger; CHRC: chelating resin column; FOAM:
polyurethane foam; AMB: amberlite XAD-4; CH100: Chelex-100; C18 : octadecyl-chemically modified silica gel; PTFE: polytetrafluoroethylene. KR: knotted reactor; MBI: 2-mercaptobenzimidazole;
HEEED: N-hydroxyethylethylenediamine; 8-HQ: 8-hydroxyquinoline; DPPS: 4,7-diphenyl-1,10-phenanthrolinedisulfonate; SCN: thiocyanate; TIRON: 4,5-dihidroxy-1,3-benzenedisulfonic acid; BSF:
brilliant sulfoflavine; PHEN: 1,10-phenanthroline; DPD: N,N-dimethyl-p-phenylenediamine; LUM: luminol; PSPmH: 2-pyridyl-3 -sulfophenylmethanone 2-pyrimidylhydrazone; FERR: ferrozine
(3-(2-pyridyl)-5,6-bis(4-phenylsulfonic acid)-1,2,4-triazine; APDC: ammonium pyrrolidinedithiocarbamate; PYP: pyrophosphate; PH-PH: N-phenyl-p-phenylenediamine with m-phenylenediamine;
5-Br-PSAA: 2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino)aniline; TMB: 3,3 ,5,5 -tetramethylbenzidine; EDTA: ethylenediaminetetraacetic acid; HYDR: hydroxylamine; PHENE: phenetidine;
CITR: citric acid; TTAB: tetradecyltrimethylammonium bromide; TWEEN: surfactant Tween 80.

209
210 M. Miro et al. / Talanta 63 (2004) 201223
to determine spectrophotometrically the typical concentra-
tion levels of manganese found in waters, ranging from
ca. 0.01 to 10 g l1 . They are based on the catalytic ef-
fect of the analyte on the oxidation reaction of organic
compounds such as N,N-diethylaniline [175], Tiron [176],
benzothiazoline derivatives [177], leucomalachite green
[178] and phenylenediamine species [179] with oxidizing
agents (viz. periodate, hydrogen peroxide, Cr(VI) or V(V)).
Heterogeneous reactions relying upon the temporal entrap-
ment of the target analyte as a PAN-chelate in an optrode
membrane [180] as well as oxidation of Mn2+ to perman-
ganate by sodium bismuthate [181] or lead(IV)oxide [182]
containing solid-phase reactors enabled spectrophotometric
assays in waters and effluent streams at the mg l1 level.
Substitution reactions in homogeneous phase comprising
the Cd(II)-imidazole-functionalized porphyrin system were
also reported [183].
Chemiluminescence procedures involving measurement
of light emission from either tetracyanoquinodimethane
[184] or luminol [125] oxidation catalyzed by traces of
Mn(II) are shown excellent strategies for the quality control
of underground drinking water during water treatment [185],
albeit they usually require sample pretreatment (e.g. addi-
tion of masking agents [125], oxidation to permanganate
[186] or metal isolation onto an ion exchanger or chelator
[187]) to remove potential metal interfering species [188].
The former approaches compete in terms of sensitivity and
selectivity with flame or electrothermal atomic absorption
spectrometry combined with on-line preconcentration of the
pyrrolidinedithiocarbamate [189], dialkyldithiophosphate
[190] or Eriochrome Black T [191] derivatives, and with
clean-up steps for removal of spectral interferences from
sulfide ion [192].
6.2. Harmful metals
6.2.1. Mercury
The accurate determination of mercury in environmental
samples is recognized as a relevant issue for water quality
assessment as a consequence of the toxicity of this element
and its ability to bioacumulate in living beings such as ma-
rine organisms, which become a biological path of Hg to
humans. Studies of mercury mobility in estuaries and oceans
that play a predominant role in the global Hg cycle were
recently performed for a long-time distribution control.
In recent years, continuous-flow/flow injection/sequential
injection-cold vapor generation techniques for determina-
tion of mercury at the low ng l1 level by atomic absorption
spectrometry in seawater, wastewater, drinking and natural
water samples have enjoyed increasing popularity owing
to their outstanding performance as opposed to the earlier
batch-wise operated systems. A fully automated CVAAS
analyzer involves the preliminary on-line sample reaction
with a reducing agent, mainly stannous chloride [193]
or potassium tetrahydroborate [194], in order to generate
elemental mercury from inorganic mercury. Aqueous chro-
mous solution was also recommended as a reducing reagent
owing to its ability to decompose mercury-iodide complexes
as opposed to tin(II) chloride [195]. The mercury vapor
is then stripped from the solution by an argon carrier into
the quartz absorption cell of the detector using dedicated
flow-through gasliquid separators. A 20-fold improve-
ment in the detection limit was reported using a dedicated
CV-system consisting of a flow injection unit equipped
with an Hg lamp, quartz cell and Hg detector [196]. A
gold trap for mercury amalgamation/preconcentration based
on an Au-Pt gauze and a controlled heating system for
metal release, integrated in the flow manifold prior to the
detection step, is a currently used strategy for ultratrace
determination of Hg [197]. Reduced mercury was also
detected as an amalgam by using a gold-coated piezo-
electric crystal coupled to an automatic microgravimetric
screening system [198]. Different minicolumn designs and
packing materials involving 8-hydroxyquinoline and imin-
odiacetate groups were evaluated in terms of sensitivity
for on-line enrichment of inorganic mercury followed by
CVAAS detection [199]. Solid-phase extraction onto ion
exchangers with mercapto groups attached to co-polymeric
matrices was exploited using an on-line reductive elu-
tion procedure [200]. In-line adsorption/preconcentration
of the Hg-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol
complex on the inner walls of a knotted reactor coupled
to CVAAS was proven useful for monitoring the target
species in unpolluted waters at ultratrace levels (>5 ng l1 )
[201]. Iridium, tungstate and zirconium coated graphite
tubes were thoroughly evaluated as effective traps for Hg
vapor before ETAAS analysis [202].
Continuous flow, flow injection and multisyringe flow
injection-CV generation approaches were also efficiently
coupled to either atomic fluorescence [203] or ICP-
optical emission [204]/mass spectrometry with isotopic
dilution for Hg detection. These hyphenated techniques
require preconcentration strategies to determine the metal
analyte at sub-ng l1 levels. In this context, sorption of
mercury species onto sulphydryl cotton [205] or silicagel
functionalized with chelating groups such as 2-merca-
ptobenzimidazole [206], methylthiosalicylate [207] or
1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide [208],
reversed-phase sorption of Hg-dithiophosphate chelates
[209], and cloud point extraction of a Hg derivative me-
diated by micelles of a non-ionic surfactant [204] are
worthmentioning.
Determination of organic mercury (viz. methyl-, ethyl-,
amido-, and phenyl-mercury amongst other Hg-bonded con-
taining species) can be performed with the aforementioned
procedures, the only requirement is that mercury should be
present in inorganic form. Selective reduction of inorganic
mercury and selected organomercurials to Hg0 was de-
scribed using SnCl2 in acidic medium and a more energic
reducing agent such as NaBH4 , respectively [202]. Meth-
ods available for oxidation of mercury compounds that are
easily adapted to flow and sequential injection techniques
 M. Miro et al. / Talanta 63 (2004) 201223
usually include chemical digestion under temperature con-
trol [210] using strong acids and chemical oxidants such
as electrogenerated cobalt(III) [211] or potassium perox-
odisulfate in sulfuric acid medium [212] with the addition
of iron(III) acting as a catalyst [213], microwave-assisted
oxidation with high temperature and pressure [214] and
UV-irradiation [215] using Br /BrO3 as oxidation mix-
ture [216]. The catalytic effect of copper(II) on the chemical
decomposition of organomercury employing tin(II) chlo-
ride in alkaline solution was also exploited. Best results
in terms of recovery rates under dynamic regime were
reported with UV digestion when applied to a governmen-
tal monitoring station at the River Elbe [217]. The need
for chemical oxidants, high pressure and temperature for
degradation of organomercurials was eliminated exploring a
room temperature ultrasonic irradiation-based advanced ox-
idation process [218]. Speciation of mercury species at sub
ng l1 levels following preconcentration using a dithiocar-
bamate resin microcolumn was accomplished by butylation
with a Grignard reagent, isolation in a gas chromatograph
furnished with a non-polar analytical column and further
detection with a microwave-induced plasma emission de-
tector [219]. Improvement in analytical throughput, signal
stability, memory effects and environmental friendliness for
a similar detection limit was attained with a flow injection
liquid chromatography cold vapor atomic absorption tech-
nique [220]. Selective continuous liquidliquid extraction
of mercury compounds into a xylene phase as bromide
species, cold Hg vapor generation directly from the organic
phase and final ICP-atomic emission spectrometry detection
was also proposed as a speciation strategy [221].
Construction of very efficient flow-through cells for Hg
detection by potentiometric stripping analysis [222] using
either the thin gold layer of recordable compact disks [223]
or platinum foils [224] as working electrodes was of intense
interest. Both chalcogenide glass ion-selective electrodes
[225] and substituted diazacrown ionophore containing
membrane-based sensors [226] were prepared, character-
ized and adapted to rapid continuous flow determination
of mercury at different pHg levels. A tetraiodomercuriate
liquid electrode was proven highly selective for mercury
iodide species and inorganic mercury after on-line transfor-
mation into analytical active species [227]. The inhibition
of the enzymatic conversion of urea to carbon dioxide and
ammonia by mercury traces in a gas-diffusion flow injection
system equipped with a urease reactor was also evaluated
and potentiometrically monitored with a pH electrode [228].
Displacement reactions were useful approaches for the
indirect determination of inorganic mercury by both lumi-
nescence and spectrophotometric flow injection procedures.
Thus, the replacement of iron(II) from the iron(II)EDTA
complex by inorganic mercury was coupled to the chemilu-
minogenic reaction of luminol with dissolved oxygen. The
catalytic effect of the target analyte on the ligand substitution
reaction rate between hexacyanoferrate and , -bipyridyl
was also thoroughly investigated [229]. The accelerating
211
effect of mercury(II) on the decomposition of hexacyano-
ferrate was also used as the basis of straightforward and
moderately selective chemiluminescence and photometric
methodologies [230]. Improved selectivity is gained by the
addition of chelating masking agents in the carrier stream,
so that interferences caused by heavy metals are greatly
minimized. Similar strategies were adopted in both the spec-
trophotometric determination of mercury by water-soluble
chlorinated porphyrins [231] and the fluorometric detection
of the Hg-calcein complex in alkaline medium [232].
6.2.2. Chromium
The interest in understanding the chemical behavior of
chromium in natural aquatic systems and the requirement of
analytical techniques able to determine trace levels in envi-
ronmental samples is governed by the fact that its toxicity
depends critically on its oxidation state. Chromium(III) is
considered an essential trace element as it is able to coordi-
nate several amino acid ligands in the human body and it is
frequently supplied as a dietary complement. On the other
hand, chromium(VI) is known to be toxic to humans, capa-
ble of permeating cell membranes, thus, being a powerful
mutagen and a potential carcinogen. Both oxidation states
enter the environment as a result of effluent discharge from
steel, electroplating and tanning industries, oxidative dyeing
or cooling water towers. Chromium may also enter drinking
water supply systems from the corrosion inhibitors used in
water pipes or by contamination of the underground water
from sanitary landfill leaching.
There are few flow analytical techniques available that
have enough sensitivity and selectivity for the direct de-
termination of ultra-trace levels of Cr(VI) in water matri-
ces. Sample pre-treatment methodologies which include
analyte isolation and preconcentration are required in or-
der to determine the low levels of hexavalent chromium,
even with highly sensitive techniques such as ETAAS. In
this context, the development of rapid, robust and selec-
tive time-based FI-ETAAS methods using the ammonium
pyrrolidinedithiocarbamate-iso butylmethylketone extrac-
tion procedure [233] or chelate adsorption on the inner
walls of a knotted reactor [234] as well as sorbent extrac-
tion approaches after chromium derivatization [235] are
especially worthwhile for Cr(VI) determination within the
5500 ng l1 range. FI-FAAS technique, which can tolerate
considerable salt amounts, is ideally suited for hexavalent
chromium determination in seawater, although measure-
ments at the g l1 level require pre-concentration strategies
involving either retention of suitable complexes on silanised
C18 column reactors or direct chelation of the target species
onto a cellulose support functionalized with quaternary
amine groups [236]. The above hyphenated technique was
also useful for determining both the soluble chromium
fraction in industrial effluents after on-line filtration and
the total chromium content following microwave-assisted
sample digestion [237]. Recently, ICPAES and ICPMS cou-
pled to microcolumn separation have been established as
212 M. Miro et al. / Talanta 63 (2004) 201223
powerful tools for the sensitive determination of the ana-
lyte, although in the latter case matrix effects by molecular
ion peaks are observed. In the field of electrochemistry and
taking advantage of the electrocatalytic effect of polyani-
line, a polyaniline/polystyrene composite electrode was
characterized and used as a sensitive flow injection detector
for assays at the sub-g l1 -level of Cr(VI) [238].
As stated above, in view of the different toxicity of both
oxidation states, and in order to follow the pathways for in-
terconversion in the environment, it is increasingly important
to monitor the concentration of individual species as well as
the total concentration of chromium in environmental wa-
ters. The most widely accepted spectrophotometric method-
ology for chromium speciation in flow injection/sequential
injection assemblies is undoubtedly the selective com-
plexation of Cr(VI) with 1,5-diphenylcarbazide (DPC) in
acidic medium [172], which has been used for develop-
ing flow-through ion-exchange solid-phase spectrophoto-
metric sensors [239]. Incorporation of cation-exchange
pre-columns for removal of polyvalent cations [239]
and quantitative sorption of Cr(VI) onto activated alu-
mina [240] or zirconium(IV) oxide modified silica gel
[241] as well as on nanometer-size titanium(IV) oxide
(anatase) powers [242] are frequently recommended prior
complex formation to attain both selective and sensitive
spectrophotometric determinations. Sensitivity enhance-
ment is also provided by a recently developed wetting
film-sequential injection system based on the formation of
an ion-pair between the reaction product of Cr(VI) with
DPC and perchlorate, and further extraction into an or-
ganic film coating the inner walls of PTFE tubing [243].
Diantipyryl-(p-N,N-dimethylamino)phenylmethane was
also investigated as a chromogenic reagent for the flow
injection determination of hexavalent chromium in the pres-
ence of Mn(II), employing an on-line microwave-irradiation
method to accelerate the color forming reaction [244].
Industrial samples from electroplating baths and residual
washing waters containing Cr(VI) concentrations rang-
ing from 0.2 to 2 mg l1 were analyzed by monitoring
an aminochrome intermediate compound resulting from
oxidation of the alkaloid brucine [245]. Furthermore, to-
tal chromium determination was accomplished following
sample pre-oxidation with oxidizing agents [239] such as
potassium peroxodisulfate, potassium periodate, and acidic
cerium(IV), or heterogeneous oxidation using a lead(IV)
oxide column at high temperature. Speciative determination
of Cr(VI) and Cr(III) was also performed by formation of
the Cr(VI)-4-(2-thiazolylazo)resorcinol complex at pH 5.0
in the presence of 1,2-cyclohexanediaminetetracetic acid as
a masking agent for Cr(III) [246].
Selective determination of trivalent chromium with FAAS
detection was carried out using on-line coprecipitation
strategies based on collection of the precipitate formed
with lanthanum hydroxide in a knotted reactor without
filtration [247]. The chemical inertness of Cr(III), which
hinders the efficient complexation with dithiocarbamate
ligands, resulting in poor sensitivity, low sample through-
put and incomplete recovery was circumvented by using
Mn(II)-diethyldithiocarbamate as a chelate carrier during
the FI-FAAS determination [248]. The selective sorption
of Cr(III) ions on poly(aminophosphonic acid) [236] or
poly(hydroxamic acid) [249] chelating resins was also ex-
ploited as a pre-concentration approach prior to FAAS
detection. In addition to the most widely used chemical
reduction, total chromium concentration was determined
after electrochemical reduction of chromate ions to Cr(III)
at a porous gold-coated glassy carbon electrode [250].
The selective sorption of Cr(III) and Cr(VI) on activated
alumina microcolumns at pH 7 and 2, respectively, and
further elution of preconcentrated species directly to the
nebulizer burner of a FAA spectrometer using acidic and
alkaline conditions for trivalent and hexavalent chromium,
respectively, was successfully used as a speciation scheme
in flow injection [251] and sequential injection systems
[252]. An alternative procedure capitalized on the cloud
point extraction of the Cr(III)-8-hydroxyquinoline hy-
drophobic complex combined with fluorimetric detection
allowed the reliable determination of Cr(III) (and Cr(VI)
following reduction by sulfite) at levels as low as 0.2 g l1
in complex water matrices [253]. The usefulness of cation
and anion-exchange microcolumns assembled in series for
automatic and rapid preconcentration and speciation fol-
lowed by atomic absorption measurements was assessed by
several researchers [254].
Flow injection chemiluminescence methods have been
proposed as low-expensive and sensitive alternatives for
chromium speciation in tap and wastewater [255]. Thus,
Cr(III) and Cr(VI) ions were determined, respectively, by
measuring the light emitted as a result of the catalyzed oxi-
dation reaction of luminol or N-ethylphthalyhydrazide with
oxidant species, and quercetin with hydrogen peroxide in al-
kaline medium. Indirect chemiluminescence determination
of chromate ions was proposed by on-line generation of the
oxidizing agent (viz. hexacyanoferrate(III)) through the fast
oxidation reaction between hexavalent chromium and hexa-
cyanoferrate(II) [256]. Increase in sensitivity of the Cr(III)
determination was achieved by introducing bromide in the
reaction mixture while the selectivity of the assays was
improved by addition of EDTA [257] or the incorporation
of packed-bead cation exchangers [256]. In this context, a
new bundle flow-cell design for chemiluminescence assays
that provide a 50% improvement in sensitivity respect to
the most used spiral cell has been recently characterized
and evaluated for monitoring traces of Cr(III) [258].
6.2.3. Nickel
Interest in the determination of nickel has increased over
the last few years because of the influence of this metal on
humans. Adverse effects of inorganic, water soluble nickel
species occur after contact with the skin, causing nickel
dermatitis. After inhalation, respiratory tract irritation and
asthma can also result. Besides, carcinogenesis bioassays in
 M. Miro et al. / Talanta 63 (2004) 201223
animals showed that certain nickel compounds are potent
carcinogens when administered via parenteral routes. Thus,
accurate, reliable and sensitive methodologies for nickel de-
termination are called for. Both flame and electrothermal
atomic absorption spectrometric detectors hyphenated with
flow or sequential injection systems are the most appro-
priate instrumental techniques for measurement of the low
nickel content in river, seawater and industrial wastewater
samples. Nevertheless, analytical protocols with enrichment
stages prior to analysis by atomic absorption are frequently
necessary. In this context, on-line reversed-phase sorbent
extraction of Ni-dimethylglyoxime (DMG) or diethyldithio-
carbamate complexes onto chemically modified silica gel
[259] or fullerene C60 [260] was of great interest. Precon-
centration approaches using the cloud point phenomenon
based on entrapping chelates of the metallic species into
micelles upon increasing the temperature [261], the ana-
lyte co-precipitation with Cu(II)-diethyldithiocarbamate in a
knotted reactor [262] and the generation of volatile products
(viz. nickel tetracarbonyl) and its trapping into a graphite
tube [263] are also worthmentioning. The performance of
eluting renewable loaded beds or transporting them directly
from the sequential injection-lab-on-valve (LOV) assembly
to the atomizer was thoroughly examined [264]. A square
wave adsorptive stripping voltammetric method involving
a mass-transport controlled preconcentration step, during
which the Ni-dimethylglyoxime complex is retained onto an
in-situ film of a flow-through electrode, followed by a re-
ductive stripping scan was applied for the continuous online
monitoring of trace levels of Ni(II) [265].
Straightforward spectrophotometric procedures relying
on Ni(DMG)2 formation in solution or integration of an-
alyte derivatization with PAN, retention and detection in
a solid-phase flow-through optrode [266] were described.
Fig. 3 illustrates a multisyringe flow injection set-up de-
signed for the spectrophotometric determination of Ni(II) in
metallurgical liquors using a multichannel system in which
the sample zone reacts consecutively with oxidizing and
choromogenic reagents [267]. The rate of the pseudo-first
order dissociation of the citrate complex of Ni(II) in alka-
line medium was used as an SIA discriminatory tool for the
kinetic determination of the target species at trace levels in
the presence of Co(II) [268]. Nickel was also reported to
act as a catalyst in the anthracene green-peroxide hydrogen
chemiluminescence system for the determination of the
metal ion at low g l1 levels.
6.2.4. Lead
Adverse health effects from exposure to lead are nowa-
days recognized to be one of the most significant health
problems in industrialized societies. Drinking water is the
major source of the heavy metal exposure for the general
population. Lead enters drinking waters primarily as a re-
sult of corrosion, or wearing away of materials containing
lead in the water distribution system and household plumb-
ing. EPA has set strict regulations on lead concentrations in
213
Fig. 3. Multisyringe flow injection assembly with an ancillary multipo-
sition valve for the spectrophotometric determination of Ni(II) using a
multichannel configuration. SV: solenoid valve; MV: multiposition valve;
S: syringe pumps; SA: sample; C: carrier (diammonium citrate solution);
R1: oxidising reagent (saturated iodine solution); R2: chromogenic reagent
(dimethylglyoxime in alkaline medium); HC: holding coil; RC: reaction
coil; D: detector; W: waste.
drinking water, requiring lead action if the concentration
of heavy metal exceeds 15 g l1 in more than 10% of tap
water samples collected during a preset monitoring period.
The most attractive modes for determination of lead
traces in aqueous solutions with reported detection limits
from 0.01 to 8 g l1 are both flame atomic absorption
spectrometry (FAAS) and flame laser-enhanced ionization
technique integrated with on-line continuous flow/flow in-
jection/sequential injection microcolumn preconcentration
[269]. With regard to solid-phase extraction of lead species
in flow systems prior to atomic absorption, interactions
based on chelate formation are generally utilized. The com-
mercially available chelating resin Chelex 100 with iminodi-
acetate groups was the earliest material used for that purpose
[270], although as a consequence of its swelling/shrinking
effects it has been progressively replaced by mechanically
resistant sorbents containing either 8-hydroxyquinoline or
Pyrocatechol Violet [271] as well as nitroso R-salt/aliquat
336 [272] immobilized on controlled-pore glass or
chemically-modified silica gel. The selectivity of immobi-
lized hydroxyquinoline for trace amounts of lead over other
heavy metals such as Fe, Cu and Zn was improved by in-
cluding different complexing agents in the buffered carrier
stream [273]. Preconcentration of Pb(II) on ion exchangers
(viz. activated fibrous alumina or hydroxyapatite) [274] in
flow injection-AAS was also described. Sequential injection
lead preconcentration exploiting the sorption characteristics
of the poly(vinylpyrrolidone) co-polymer in a thin filtering
layer was recently proposed [275]. Furthermore, several
researchers recommended functionalized cellulose sorbents
with carboxymethyl or phosphonic acid groups [276] as a
consequence of their excellent dynamic properties of reten-
tion as well as the ability to differentiate between inorganic
214 M. Miro et al. / Talanta 63 (2004) 201223
and organic lead species using different eluent phases
[271].
Sorption of both oxine and dithiocarbamate chelates
[277] as well as ammoniacal [278] and 1-nitroso-2-naphthol
[279] complexes formed in the solution on non-polar poly-
meric resins, C18 -bonded silica columns or onto the inner
walls of a knotted reactor using an on-line multiplexed pre-
concentration procedure [280] with repetitive sample injec-
tions to improve retention efficiency were reported prior to
FAAS analysis. Coprecipitation methods using either zinc
diethyldithiocarbamate or Co-pyrrolidinedithiocarbamate
[281] as carriers and elution of the collected precipitate
onto a PTFE membrane or on the walls of a knotted reactor
directly to the atomic absorption spectrometer were also
presented. Classical flow injection liquidliquid extraction-
FAAS procedures with on-line sample/solvent segmentation
and analyte derivatization provided determination limits at
the g l1 level. A dual stage extraction-FAAS system in-
volving lead retention onto a cation exchanger followed by
solvent preconcentration as the ion-pair formed between the
iodo plumbate anion and the tetrabutylammonium cation
was efficiently coupled to a flow injection assembly [282].
Flow injection [283] and multicommuted flow networks
[260] with sorbent extraction after dithiocarbamate [284]
or Tiron [285] complex formation were also success-
fully interfaced with ETAAS, achieving detection limits
of 39 ng l1 Pb in saline waters without deterioration of
the sample throughput [283]. The retention of Pb chelates
on the inner walls of PTFE reactors is usually joined with
air-segmented ethanolic elution strategies aiming to reduce
the eluate volume and minimize the dispersion effect dur-
ing analyte transportation into the graphite tube atomizer
[286]. On-line electrochemical preconcentration in tungsten
coil electrothermal AAS using a Pt flow-through anode
and the atomizer itself as the cathode was designed for
the determination of the target analyte in natural waters
at low g l1 levels [287]. The attractiveness of coupling
flow injection with hydride-generation-AAS based on an-
alyte pre-oxidation in acidic oxidant media [288] (viz.
hexacyanoferrate-hydrochloric acid, peroxodisulphate-nitric
acid, dichromate-acid lactic and hydrogen peroxide-nitric
acid) to Pb(IV) before generation of volatile species by
sodium tetrahydroborate or sodium tetraethylborate [289]
was evaluated in terms of selectivity and sensitivity of
analysis [288].
Both extraction chromatographic procedures relying upon
the formation of an inclusion complex using functionalized
macrocyclic 18-crown-6 ethers [290] and PTFE adsorp-
tion [291]/microcolumn [292] preconcentration approaches
were efficiently coupled to ICPMS detection with reported
detection limits below 0.2 g l1 . The incorporation of
an ultrasonic nebulizer-membrane dryer prior to the ICP
torch allowed implementation of sorbent extraction-elution
procedures using organic solvents such as methanol and
ethanol since solvent vapors were significantly prevented
from entering the detector [293].
In the field of electrochemical techniques, flow injec-
tion stripping analysis using cellulose triacetate [294] or
Nafion [295]-modified mercury film electrodes was de-
scribed for the determination of lead in environmental sam-
ples. Automated Osteryoung square-wave anodic stripping
voltammetry and potentiometric stripping analysis were
demonstrated to be effective alternatives for monitoring
low g l1 levels of lead in tap, river and seawater [294].
Besides, poly(vinylchloride) membranes containing sub-
stituted diazacyclooctadecane species were prepared and
evaluated for flow injection potentiometric determination of
lead within the linear interval of concentrations (expressed
as pPb) ranging from 6.0 to 2.0 [226].
Classical photometric methods with selectivity improve-
ment via solvent extraction [270] or micro-column precon-
centration [296] using dithizone, 4-(2-pyridylazo)resorcinol,
sulfarsazen, 2,2 -dipyridyl-2-pyridylhydrazone or tirodin as
chromogenic agents [270,296] were readily implemented
in flowing stream systems. The color-forming reaction of
lead with functionalized porphyrins at different pH con-
ditions was also studied, heavy metal interferences being
minimized by addition of acetylacetone to the reagent mix-
ture [297]. A simple and reliable spectrophotometric flow
injection method based on the lead-catalyzed reduction of
resazurin to resorufin by sulfide was presented for lead de-
termination in tap waters with a detection limit of 1 g l1
without requiring preliminary preconcentration steps [298].
Other reported alternatives for the determination of trace
amounts of the target species involved the chemiluminogenic
lucigenin-hydroxide peroxide-lead(II) system and the re-
placement reaction of Fe(II) by Pb(II) from the Fe(II)EDTA
complex prior to luminol oxidation. In the scope of environ-
mental optical sensors, novel flow-through optical sensing
systems for trace lead monitoring (>0.1 g l1 ) based on the
formation of quinoline sulphonate chelates and further im-
mobilization onto the surface of anion-exchange resin beads
prior to room temperature phosphorescence measurements
were recently devised [299].
6.2.5. Copper
Copper is an essential trace element, a component of crus-
tacean respiratory pigments like hemocyanin, and is com-
monly present in the coastal marine environment, where it
may reach level toxics to both animals and plants. Increases
in copper concentration in coastal areas have resulted from
industrial and domestic waste discharge, disposal of mining
washings, refineries and the use of the heavy metal as a
base compound for antifouling paints. Thus, the monitor-
ing of extremely low levels of copper in natural waters has
received special attention as a way to assess the early im-
pact of human sources and detect potential health hazards.
Hyphenation of flow injection sample processing with de-
tection by electrothermal or flame atomic absorption spec-
trometry is a widely accepted methodology for trace copper
determination, with reported detection limits below 0.06
g l1 Cu. Several flow injection and sequential injection
 M. Miro et al. / Talanta 63 (2004) 201223
preconcentration/matrix removal methods well suited to
in-field sampling techniques [300] were based on the use
of reactors loaded with reversed-phase materials, poly-
meric sorbents, classical ion exchangers or chelating resins
containing pyrocatechol violet [301], Eriochrome Blue
Black R [301] or heterocyclic azo compounds [302] such
as calmagite [303] or 1-(2-pyridylazo)-2-naphthol [300].
Optimization of preconcentration-based flow analyzers us-
ing multiple-factor experimental designs was successfully
performed [302]. Ligands such as sodium/ammonium di-
ethyldithiocarbamate [304] and 1-nitroso-2-naphthol [305]
may be also dissolved in the carrier or reagent solution, and
procedures relying upon sorption of Cu-chelates formed in
homogeneous phase on non-polar silica-gel based sorbents
[305], activated carbon [306] or on PTFE knotted reactor
[307]/filter systems [304] were commonly reported for trace
analysis. Both segmented liquidliquid extraction [308]
and wetting-film methodology [309] with chelating agents
(namely, 8-HQ [309] or an halogen derivative [308,310]
dissolved in isobutyl methyl ketone [309] or in a mixed
solvent solution [310]) as well as coprecipitation techniques
using Ni(II)-diethyldithiocarbamate as a coprecipiting car-
rier were also interfaced with flow injection-FAAS detection
for copper monitoring at low g l1 levels. The combina-
tion of a multipurpose sandwich-type dialyzer employed
for automated dilution with flow injection-AAS was proven
suitable to handle environmental samples (e.g. industrial
effluent samples) where there is a great variation in Cu(II)
concentration levels [311].
Spectrophotometric methods for monitoring traces of
copper in environmental and wastewater waters are ad-
vantageous because they are easily operated and inexpen-
sive when compared to atomic absorption spectrometry.
N,N-substituted derivatives of dithiocarbamic acid such as
diethyldithiocarbamate are often used as color develop-
ing reagents for the determination of the heavy metal in
aqueous phase or following solvent extraction [312], since
the Cu(II)DDTC stability constant is more than one or-
der of magnitude higher than that of other DDTC-metal
chelates. A new type of dithiocarbamate derivative, i.e.
4-benzylpiperidinedithiocarbamate [313] was recently syn-
thesized and proposed as a chromogenic reagent for the de-
termination of Cu(II) at the low g l1 range (25 g l1 )
using flow injection analyzers furnished with strong
cation-exchange containing stationary phases [314]. The
flow injection photometric determination of Cu with het-
erocyclic complexing agents such as nitroso-R salt [315]
and 4-(2-pyridylazo)-resorcinol (PAR) was also exploited
in weak acidic medium in order to promote the selective
reaction with the target analyte [316]. Nevertheless, most of
the analytical methods, as for example the CuPAR system
under acidic conditions, require additional procedures for
increasing selectivity, imposing the resorting to masking
agents (viz. EDTA, citrate, tartrate, hydroxylamine or hexa-
cyanoferrate), differential kinetic methods using pyridylazo
compounds [162], and selective resin preconcentration
215
strategies involving the use of polymeric sorbents such as
poly(ethylenimine) [316] or immobilized chelating species
[317]. A continuous liquidliquid extraction procedure us-
ing a dedicated hollow fiber membrane separator was suc-
cessfully applied to the spectrophotometric determination of
the target species at concentrations above 15 g l1 follow-
ing on-line formation of the Cu-bathocuproine-perchlorate
ternary complex [318]. The on-line segmented solvent ex-
traction of the ion associate of dibromocuprate(I) with a
sort of cationic azo dyes was thoroughly examined in a
spectrophotometric flow injection set-up. The use of mi-
croemulsions as a medium for liquidliquid extraction
was also investigated, attaining particular benefits for the
Cu(II)/neocuproine complex [319].
Much attention has been recently focused on flow-injection
kinetic methods of analysis based on catalytic reactions,
since trace or ultratrace amounts of copper are read-
ily monitored. For example, an oxidative coupling of
N-phenyl-p-phenylenediamine with m-phenylenediamine
in the presence of hydrogen peroxide as oxidant species
and pyridine and ammonia as activators was used as an
indicator reaction for the photometric catalytic determi-
nation of Cu(II) at the low g l1 level (0.1 g l1 )
[320]. As an alternative, the Cu-catalyzed coupling of
p-anisidine with N,N-dimethylaniline with different hete-
rocyclic activators was proposed. The redox reactions of
both 2,6-dichlorophenolindophenol with hydrogen perox-
ide [321] and cysteine with iron(III) in the presence of
1,10-phenanthroline [322] catalyzed by traces of Cu(II)
were exploited for the development of photometric flow-
ing stream procedures for the determination of the heavy
metal from 5.0 to 70 g l1 and 0.110 g l1 , respectively.
On-line monitoring of copper traces in steam condensate
and boiler feed-water was successfully carried out us-
ing the catalytic effect of the metal ion on the oxidation
of hidroquinone by hydrogen peroxide, the quinone pro-
duced was detected by absorptiometry at 490 nm [323].
A rapid flow injection method for the determination
of copper, based on the catalytic action on the decol-
oration reaction of iron(III) with thiosulphate was also
devised. Catalymetric procedures involving the chemilu-
minogenic luminoloxidantCu(II) system, the enhance-
ment of the Co(II)-catalyzed chemiluminescence oxidation
reaction of 1,10-phenanthroline by Cu(II) traces and the
fluorescein-sensitized -nitrostyrene-based chemilumines-
cence reaction in the presence of micelles should be also
highlighted [324].
Flow injection analysis with chemiluminescence detection
relying upon the reaction of copper with 1,10-phenanthroline,
and further oxidation of the complex formed by hydrogen
peroxide was used for the determination of dissolved cop-
per in seawater after on-line matrix removal [325] as well
as for speciation and complexation studies [326], which
are crucial to understand the ecological role of copper in
marine ecosystems. Since more than 95% of dissolved
copper occurs in strong organic complexes in seawater,
216 M. Miro et al. / Talanta 63 (2004) 201223
a contamination-free approach such as UV-digestion is
usually explored for the breakdown of copper complexing
organic ligands prior to total dissolved Cu determination by
the aforementioned chemiluminescence reaction [327]. The
effect of photolysis on the uptake of the heavy metal from
three model ligands, i.e. glycine, nitrilotriacetic acid and
EDTA was investigated using a chelating column linked
to an AA spectrometer [328]. A two-column ion-exchange
method for copper differentiation between a labile fraction
and a negatively charged organic-bound fraction was also
integrated in flow injection-flame AAS systems [329].
The partitioning of dissolved copper between labile in-
organic species and non-labile organically bound species is
frequently detected through electroanalytical methods in-
volving a stripping cycle, such as differential pulse anodic
stripping voltammetry [330]. Sequential injection analysis
was demonstrated to be a practical tool for anodic stripping
voltammetry in terms of sensitivity using flow reversals,
selectivity exploiting its inherent ability for performing
medium exchange procedures, and reduction of mercury
containing waste since the mercury film is on-line plated
[331]. Accurate analytical data for the labile fraction of cop-
per was also obtained by oscillating flow injection stripping
potentiometry, which appears to be a versatile technique
with respect to the sample matrix as demonstrated via
standard addition and direct calibration approaches [332].
Continuous flow methods for evaluating the response of a
copper ion-selective electrode to total and free copper con-
centrations were recently assessed using an extrapolation
method based on the fitting of an empirical mathematical
equation to the electrode timeresponse curve [333]. A
dedicated coated tubular solid-state copper(II)-sensor con-
structed from a copper tube and Tygon tubing, treated with
ammonium sulfide to provide the copper/copper sulfide
electrode was specially designed to be assembled into the
conduits of a flow injection set-up [334].
The analytical application of a simple polarographic
flow-through cell containing a conventional dropping mer-
cury electrode, a mercury pool and a platinum wire as the
working, reference and counter electrodes, respectively,
was proposed for the continuous determination of copper in
diluted water samples following a preliminary analyte en-
richment step onto a Chelex-100 containing microcolumn
[335]. A flow injection amperometric method based on the
oxidation of the CuDDTC complex at a Pt microelectrode
fitted to a conventional wall-jet flow cell was also described
using a high resistance toluene carrier stream [336]. The re-
producible preconcentration and subsequent determination
of the accumulated Cu(II) (>90 g l1 ) using chemically
modified carbon paste electrodes was accomplished exploit-
ing differential pulse polarographic techniques [337].
6.2.6. Cadmium
Cadmium is known to be a highly toxic trace metal which
plays important roles in biological metabolism. Numerous
spectral and electrochemical flow methods have been devel-
oped for cadmium monitoring but undoubtedly the predom-
inating methodologies in routine laboratories are nowadays
AAS with flame [338] or electrothermal atomization [339]
and ICPAES [340] or vapor generation-ICPMS with isotope
dilution [341]. Nevertheless, direct instrumental analysis of
complex water samples as seawater is difficult because of
the large salt content and the minute concentration of the
analyte. Preconcentration techniques can solve the above
problems and lead to a more straightforward determination.
Several methods such as coprecipitation with a Cu-chelate,
solvent extraction using dithizone as extractant, knotted
reactor sorption and microcolumn extraction were devel-
oped for this purpose [29,342]. The column extraction
method in flow assemblies was widely used as a conse-
quence of the relatively high concentration factors attained.
Flow injection/sequential injection systems furnished with
resin columns of immobilized 2-mercaptobenzothiazole,
dithiocarbamate species [343] or phosphonic acid [344]
for direct analyte retention and octadecyl-modified sil-
icagel [345] and polymeric Amberlite-type [346] sorbents
for the temporal sorption of metal chelates were applied
to cadmium determination in seawater, river and drink-
ing water samples at trace levels (>0.5 ng l1 ). Among
the most commonly employed chelating agents, sodium
diethyldithiocarbamate [342], iminodiacetic acid [339]
(Chelex 100), 1-(2-pyridylazo)-2-naphthol [347] and hete-
rocyclic azo compounds such as 4-(2-pyridylazo)resorcinol
[348] and 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol
[346] should be highlighted. New silica-based sor-
bents with organic ligands such as 1,5-bis(di-2-pyridyl)
methylene thiocarbohydrazide and methylthiosalicylate
[340] and reversed-phase copolymeric materials such as
poly(octadecyl diitaconate) [338] were synthesized, and the
efficiency for cadmium preconcentration in flowing stream
systems was thoroughly studied. The third generation of
flow injection, so-called sequential injection lab-on-valve,
handling renewable hydrophobic bead surfaces (namely,
PTFE or octadecyl-modified copolymeric bead materials)
was exploited for the ETAAS determination of cadmium (>
5 ng l1 ) [349] in environmental waters as shown in Fig. 4.
Numerous schemes were developed for cadmium spe-
ciation in water samples involving various separation and
detection techniques. Two operational fractions with en-
vironmental meaning (i.e. available and non-available
for aquatic organism bioaccumulation) were determined
through kinetic discrimination using the aforementioned
sorbents: a Chelex 100 labile fraction consisting of Cd(II)
ions and weak cadmium complexes, and an octadecyl-silica
gel hydrophobic fraction involving stable cadmiumorganic
complexes [350]. Speciation of dissolved cadmium in
fresh waters was also reported using differential-pulse an-
odic stripping voltammetric measurements in a flow sys-
tem composed of a filtration module and an enrichment
unit [351]. The same detection principle was employed
in flow-injection systems furnished with Donnan dialy-
sis units containing strong cation-exchange sulphonated
 M. Miro et al. / Talanta 63 (2004) 201223
Fig. 4. Schematic representation of the bead injection SI-LOV system for the ETAAS determination of trace levels of cadmium using PTFE beads.
LOV: lab-on-valve microconduit; ETAAS: electrothermal atomic absorption spectrometer; SP1 and SP2: syringe pumps; C1 and C2 : microcolumns; PP:
peristaltic pump; T: T-connector; HC: holding coil.
fluorocarbon membranes for the determination of free cad-
mium concentrations in solutions containing organically
complexed cadmium [352]. Three different fractions of
complexed Cd-species were discriminated by interfacing
two microcolumns packed with Chelex-100 and a strong
anion-exchange resin with AAS [353].
Flow injection-vapor generation coupled to atomic ab-
sorption spectrometry was evaluated as a rapid and straight-
forward method for ultratrace determination of Cd in
wastewater and natural waters [354], without requiring the
presence of cationic surfactants [355]. Elimination of in-
terfering metals such as Cu, Pb, Ni and Zn was readily
accomplished by addition of cyanide to the tetrahydrob-
orate reductant solution [356]. Iridium-, tungsten- and
zirconium-coated graphite tubes were evaluated for the
in-situ trapping of volatile cadmium species at the low
ng l1 level prior to atomization in a graphite furnace [357].
Flow-through potentiometric detectors with homogeneous
crystalline double membrane tubular electrodes for sensi-
tivity improvement [358] and commercial solid-state cad-
mium ISEs [359] were adapted to flow injection systems for
the determination of either free cadmium in the presence of
ligands [359], or halogen complexes of the target species
[360]. As a consequence of the limited selectivity of the po-
tentiometric sensors, quantitative retention of the cadmium
chloro-complex onto a strong basic anion-exchange resin
microcolumn is recommended to alleviate interferences from
other metallic cations and inert components present in en-
vironmental matrices [358]. In the scope of optical sensors,
a flow-through diffuse reflectance bulk optrode membrane
that incorporates a pyridylazo chromogenic compound was
characterized for the determination of cadmium at the mg l1
level using different kinetic methods based on continuous
flow, flow injection and stopped-flow analysis [361].
217
6.2.7. Zinc
Interest in zinc concentrations in environmental waters
from its dual role as a required nanonutrient and potential
toxicant due to its widespread industrial (viz. metallurgy,
galvanizing and alloy manufacturing) and marine usage is
recently shown. In the case of surface seawater the major
Zn inputs include atmospheric deposition (both natural and
anthropogenic origin), fluvial, runoff and upwelled waters.
It is known from vertical profiles in the marine environment
that zinc is actively incorporated into phytoplankton in sur-
face waters and transported to depth in association with par-
ticulate matter or passively adsorbed onto particles. Recent
studies indicate that the majority of dissolved zinc in sea-
water is organically complexed but the origin and behavior
of the Zn-binding ligands is still under investigation.
Dissolved zinc concentrations ranging from 0.1 to
500 g l1 in drinking, river, estuarine, open-ocean
and nearshore seawater samples were determined by
flow-injection solid-phase preconcentration using unload
polyurethane foam for Zn-isocyanate complex retention
[362], chelating resins such as silicagel functionalized with
a thiocarbohydrazide derivative [363] or carboxymethyl-
cellulose with 8-HQ or thiocyanate groups [364] as
well as the temporal immobilization of the Zn-8-HQ
chelate on activated carbon [365] and adsorption of a
Zn-pyridylazoaminophenol complex onto a PTFE tubing
[366], followed by graphite furnace/flame AAS or isotope
dilution ICPMS. In the latter case, interactions between an-
alytical variables and their optimal levels were thoroughly
explored using two level factorial and Doehlert matrix
designs [363].
Highly sensitive spectrofluorimetric determinations in
natural waters with reported detection limits of ca. 3 g l1
Zn were performed by either the selective complexation of
218 M. Miro et al. / Talanta 63 (2004) 201223
the metal with salicylaldehyde thiocarbohydrazone [367]
or the chelating reaction with a functionalized quinoline
indicator ligand (viz. p-tosyl-8-aminoquinoline [368] or
5,7-dichloro-2-methylquinolin-8 ol [369]) in a non-ionic
micellar medium. A cation-exchange column was required
in the latter case to separate zinc from interfering alkaline
and alkaline-earth ions when high saline content samples
were analyzed. Flow-injection kinetic methods based on
the formation of metalloporphyrin chelates of Zn in the
presence of imidazole acting as a catalyst were exploited
for the photometric determination of trace levels of zinc
[370]. Substituted policyclic diazo-compounds were also
reported as efficient chromogenic reagents for monitoring
the target species at the low g l1 range. An automated
flow injection system based on the zincon method with
differential demasking of the cyanide metal complexes
with cyclohexanone was described. Under the optimum
experimental conditions, zinc is rapidly liberated to form a
1:1 complex with zincon, which is monitored spectropho-
tometrically [371]. Enzymic methods with immobilized
bovine carbonic anhydrase relying on the measurement of
recovered esterase activity of the metal-free apoenzyme
after taking up the metal from the sample solution were
presented as an alternative for the determination of low
amounts of Zn [372]. In the field of optical sensors, a
flow-through solid-phase spectrophotometric sensing device
with an extended dynamic range was recently devised. The
integration of metal sorption, matrix removal and detection
steps was carried out in a Helma-type flow cell contain-
ing 1-(2-pyridylazo)-2-naphthol immobilized on a cation
exchanger [373].
7. Concluding remarks
In the three parts of this series of papers, several meth-
ods applied to the determination of core inorganic param-
eters for water surveillance were reviewed in the field of
flowing stream techniques. Though the implementation of
environmental analysis in automatic devices is not always a
straightforward task, water samples are readily analysed by
flow techniques as demonstrated in the bulk of the text.
Direct flow injection spectrophotometric procedures us-
ing moderately or highly selective chromogenic reagents
are frequently devised aiming to determine both nutrients
and anionic species. These approaches are easily adaptable
to in-situ and real time monitoring of water parameters,
as well as to multiparametric assays. Thus, shipboard an-
alyzers have been designed and successfully deployed for
vertical distribution surveys in marine ecosystems and
monitoring of key analytes in coastal and estuarine wa-
ters during various tidal cycles. The adaptation of classical
methods to the recently developed SIA, MCFIA, MSFIA
and LOV-SIA techniques together with the variety of ex-
isting injection modalities have been also reviewed. The
versatility of the above automated systems for monitoring
programs and their inherent flexibility for the implementa-
tion of separation modules (viz. dialysis, pervaporation and
gas-diffusion units), sorbent extraction procedures, in-line
dilution strategies as well as solid-phase reactors used for
redox and displacement reactions were emphasized in the
body of the text. As shown along the three parts of the re-
view, different schemes to determine N-total, P-total, C-total
and total metal concentration such as chemical digestion,
microwave-assisted oxidation, UV-irradiation and ultra-
sonic extraction were successfully coupled to flow injection
assemblies, minimizing both the analyst manipulation and
laboratory contamination while assuring better analytical
performance in terms of sampling frequency, accuracy, pre-
cision and reliability than that provided by batch methods.
Moreover, important efforts have been carried out to
adapt electrochemical techniques such as potentiometry
with conventional electrodes or dedicated tubular ISEs, or
those requiring stripping cycles (viz. anodic/cathodic strip-
ping voltammetry and potentiometric stripping analysis) to
continuous flow/flow injection/sequential injection systems
for monitoring trace levels of relevant parameters in water
samples.
In recent years, for accurate and selective determination
of extremely low levels of heavy metals, atomic absorp-
tion spectrometry and inductively coupled plasma mass
spectrometry coupled to flowing stream methods appear
to be the most attractive detection options. In this context,
a plethora of on-line preconcentration methods have been
devised to achieve the desirable sensitivity. Among the dif-
ferent reported schemes, those based on incorporation of
column reactors packed with a sort of chelating sorbents or
non-polar materials such as copolymeric resins or octade-
cyl chemically-modified silicagel are specially worthmen-
tioning. (Co)-precipitation/adsorption procedures involving
entrapment of the precipitate/chelate on the inner walls of
a knotted PTFE reactor, sorption of volatile species onto
coated-graphite tubes of an electrothermal atomizer and sol-
vent extraction methods including both phase-segmentation
or wetting-film modalities should be also featured as worth-
while strategies for on-line analyte enrichment with con-
comitant matrix removal. Hydride-generation schemes are
presented as promising alternatives for the determination
of ultratrace levels of metalloid species and performance of
speciation approaches.
Significant progress has been also made in applying con-
tinuous flow and flow injection spectrophotometric catalytic
methods for trace metal determinations as this approach is
proven extremely suitable for implementation in portable
devices and hence, for on-site and real-time analysis. Most
of such systems are based on well-known catalytic oxida-
tion reactions of phenol or aniline derivatives as well as on
the oxidative coupling of amines. Flow injection with in-line
matrix removal coupled to chemiluminescence detection is
a noteworthy option owing to the high sensitivity and se-
lectivity, wide dynamic ranges, rapid analysis (seconds), ro-
bustness, portability and low costs.
 M. Miro et al. / Talanta 63 (2004) 201223
Acknowledgements
Manuel Mir expresses his appreciation to the Spanish
Ministry of Science, Culture and Sports for financial support
(ref. EX2002-0982). The authors are also grateful to the
MCyT (Ministerio de Ciencia y Tecnologa) for supporting
the project PPQ2001-0474.
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