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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-


trometric techniques, such as flame emission spectroscopy
Large amounts of toxic elements such as metal ions (FES), inductively coupled plasma mass spectrometry
have been and are nowadays discharged into the environ- (ICPMS), hydride-generation (HG) or cold vapor (CV)
ment as a consequence of human activities. Exposure to atomic absorption spectrometry, flame atomic absorption
these compounds is of great concern as it poses not only spectrometry (FAAS) or electrothermal atomic absorption
severe carcinogenic risks to humans, but also potentially spectrometry (ETAAS) has proven to be a powerful analyt-
unacceptable ecological risks to plants, animals and mi- ical tool for the determination of ultratrace levels of metals
croorganisms. Therefore, it is necessary to ensure a timely without risk of sample contamination, since an entirely
warning for possible accumulation of polluting trace metal enclosed environment is guaranteed [3,4]. An additional
in natural waters in order to protect public health. The noteworthy feature of ICPMS is the ability of perform-
accurate determination of trace metals in a variety of envi- ing simultaneous multielemental analysis, which are of
ronmental samples at the low ng ml1 levels according to particular importance for fast screening of metal profiles
the tolerable levels imposed by European directives is thus in environmental waters [5]. Yet, the foregoing detection
required, along with the development of speciation schemes techniques, mainly ICPMS, inherently show relatively low
to discriminate between different chemical forms. tolerance to sample constituents present in environmental
matrices, including high concentrations of easily ionized
Corresponding author.
elements, salts and mineral acids (after sample treatment),
E-mail addresses: mmirollado@hotmail.com, manuel@p01.uib.es which might cause severe matrix effects and spectral inter-
(M. Miro). 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- dithiocarbamate-metal [22] or dithiophosphate-metal com-
niques readily adaptable to flowing stream methods are plexes [23]. Alternative approaches, including sorption of
called for [35] Among them, solvent extraction/stripping metal species on metal oxides (viz. ZrO2 ) [24] with high
procedures, (co)precipitation schemes, adsorption on knot- specific surface area or on algae-silica preparations [25]
ted reactors, gas-diffusion protocols, cold vapor generation with high binding capacity as well as preconcentration us-
techniques and microcolumn extraction approaches, which ing cloud point extraction of metaldithiophosphate chelates
concomitantly entail analyte preconcentration, are espe- in a non-ionic surfactant medium [26] were described. The
cially remarkable. properties of controlled-pore glass and sand were compared
Sequential injection (SI), multicommuted flow injection for their effectiveness in the immobilization of the fungus
(MCFI) and multisyringe flow injection (MSFI) systems are Penicillium notatum using normal and ultrasonic tech-
currently raised as competitive methodologies of the parent niques and its use for preconcentration of different heavy
flow injection technique in terms of reagent consumption, metals (viz. Cu, Zn, Cd, Pb and Fe) was assessed [27].
robustness, simplicity of sample and reagent manipulation, Coprecipitation of metal ions with Cu, Ni or Co chelates,
manifold versatility, and system automation. Of special in- such as cobalt-pyrrolidinedithiocarbamate [28] and copper
terest is also the straightforward interfacing with the discon- [29]/nickel [30]-diethyldithiocarbamates (DDTC), or pre-
tinuous, non-flow nature of the ETAAS detector as well as cipitation of metal-diethyldithiocarbamates [31] onto the
their potentials to implement on-line sample pre-treatment inner walls of a knotted reactor are also worth mentioning.
strategies, as demonstrated and exemplified in the bulk of Heavy metal derivatization-solvent extraction procedures
the text. 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
2. Multielemental analysis analytical throughput for multielemental analysis (viz. Cd,
Ni and Pb) was attained using a flow network based on the
Flow injection analysis can be regarded as a simple and multicommutation concept that allowed cation-exchange
versatile tool to determine metal cations in water matrices and elution steps to be simultaneously performed in several
(e.g. estuarine, river, ground, coastal or ocean seawater) as columns in parallel [32]. The sandwich-type SI-wetting film
stated in several extensive reviews [6,7]. The combination strategy based on the differential flow velocities of aque-
of flowing stream systems with robust detection techniques ous and organic phases was applied to the simultaneous
such as inductively coupled plasma (time-of-flight)-mass determination of cadmium and mercury ions capitalized
spectrometry enabled the multielement analysis [8,9] of on the formation of dithizonates at different pH extraction
numerous transition metal ions (namely, Cd, Co, Cu, Mn, conditions [33].
Cr, Fe, Mo, Ni, Ag, Tl, V and Zn), and even the deter- Chemometric multivariate methods (e.g. partial least-
mination of their respective isotopes. The potentialities squares, unfold partial least-squares and n-way partial least
of coupling FI with capillary electrophoresis for sample squares) coupled with diode array spectrophotometry en-
preparation, analyte separation and automated on-line mul- abled simultaneous monitoring of Cu, Zn and Mn in the
tiparametric monitoring of cationic species [10] together presence of concomitant interfering ions [34]. Spectropho-
with the ability to implement the so-called hydrodynamic tometric determination of Cd, Cu and Pb using sulfarsazene
injection [11], which enables repeated sample injections as chromogenic reagent and partial least-squares calibra-
in one electrophoretic run, were also assessed. Besides, tion was carried out preceded by both selective removal
the on-line sample preconcentration [12,13], clean-up steps of metal interferences and on-line preconcentration by sor-
[14,15], matrix modification [16], on-line dilution by the bent extraction [35]. The same multivariate mathematical
zone sampling technique [17] or isotope selection [18] algorithm was selected for the on-line simultaneous de-
have recently attracted considerable research effort in both termination of Fe, Co and Ni with 2,2 -dipyridyl ketone
atomic absorption and emission spectrometric techniques picolinohydrazone using flow injection analysis [36]. The
in attempts to control interference effects and enable multi- different reaction and retention rates of Fe, Ni and Zn
elemental analysis of cationic species at sub ng ml1 levels. onto 1-(2-thiazolylazo)-2-naphthol containing C18 -bonded
The most common active agents used for solid-phase ex- silicagel support combined with multivariate calibration
traction of several species in the conventional packed-bead was the scheme of a solid-phase spectrophotometric pro-
reactor or disk-type membrane fashions [19] are two types cedure for the simultaneous determination of the above
of chelators, namely 8-hydroxyquinoline [20] and iminodi- metals [37]. A full factorial experimental design was ap-
acetate [15] attached to a variety of supports, such as silica plied to the optimization of the pre-electrolysis poten-
gel, controlled-pore glass, or silicone tubing, although por- tial, supporting electrolyte concentration, metal deposition
phyrin species were also used as a precolumn filling. One time and thickness of the Hg-film in the simultaneous
exception is the use of reversed-phase sorbents [21] (viz. flow injection square-wave anodic stripping voltammet-
octadecyl or phenyl functional groups bonded to silicagel, ric determination of Cu, Zn, Pb and Cd in freshwaters
activated carbon fiber or acetylated cellulose) to collect [38].
M. Miro et al. / Talanta 63 (2004) 201223 203

3. Alkaline metal ions hardness ISE, respectively [48]. Metalligand buffer so-
lutions used in sequestration reactions coupled to both
Rapid and direct determination of alkaline metals in spectrophotometric or potentiometric detection are com-
natural waters was successfully achieved by flow injec- mon FIA reagents [49]. Another strategy for water hardness
tion coupled to either flame atomic absorption (FAA) or measurement involves complexation of both Ca and Mg
flame emission spectrometry (FES). Flow systems were with chromogenic agents; e.g. acid alizarin violet-N or
suitable tools to perform on-line dilution procedures prior chlorophosphonazo III.
to atomic absorption or emission detection using a dilution Chemometric multivariate approaches such as multilin-
chamber [39], splitting zones or zone sampling methods ear regression [50], partial least squares calibration [51],
[17]. counter-propagation neural networks [52] and H-point
Dicyclohexano or benzo-18-crown-6-based methodolo- standard addition methods [53] applied to both flow and
gies gained special interest in this field. Thus, ion associ- sequential injection systems allowed the simultaneous spec-
ations formed between the K or Na-crown-ether inclusion trophotometric determination of Ca and Mg in environmen-
complex and an azo dye counter anion enabled sequential tal water samples at a wide range of concentrations using
spectrophotometric determination of alkaline ions following moderately or scarcely selective chromogenic reagents; e.g.
flow injection solvent extraction and chromatographic sepa- 4-(2-pyridylazo)resorcinol [54] or arsenazo III [55].The
rations [40]. Moreover, a flow-through sensor for Na, K and dependence of calcium concentration on the yield of the
Rb comprising a crown-ether based ion-selective electrode arsenazoMg complex was demonstrated with such multi-
and a hydrophilic membrane was developed and compared variate calibration procedures [56], and various side effects
with voltammetric methods [41]. The K-crown-ether com- like overlapping of reagent spectrum with those of its com-
plexation also improved the turbidimetric determination plexes, blank bias error, matrix effects and faulty signals
of the alkaline metal with the tetraphenylborate counter were accounted for. A sandwich-based FIA technique in-
ion [42]. The application of an ISE-array modeled via the volving the injection of a masking solution between two
NikolskiiEisenmann equation using simplex optimization sample slugs was also described for metal discrimination
for the simultaneous determination of Na and K in flow [57]. High levels of alkaline-earth metal ions in natural
systems was reported [43]. The outstanding features of the waters were easily determined without previous sample
designed multi-sensor approach over existing single elec- treatment using FIA/SIA analyzers hyphenated with ICP
trode measurements are the better precision and reliability, [58]or FAA [59] spectrometry.
the diagnosis of electrode performance without recalibra- The underlying chemistry for the individual determina-
tion and the accurate characterization of the array response tion of calcium ion in rain, snow, boiler feed, borehole,
with simple models. The same authors raise the possibil- natural and paper machine white waters is the selec-
ity of using both an enhanced kinetic-based selectivity for tive complexation with chromogenic ligands [60] (viz.
analytical measurements and a multiple ionophore sensor o-cresolphthalein complexon, chlorophosphonazo III or
to improve the electrode array performance [44]. Potentio- m-chloroantipyrylazo) at a suitable pH using 8-hydroxy-
metric detection of Na and K with two ISEs arranged in quinoline (8-HQ) as a masking agent for Mg [61]. Imple-
parallel without coupling a conventional reference electrode mentation of different sample processing conditions to attain
was also evaluated [45]. limited, medium, and large dispersion degree for the afore-
The selectivity of the bis(tert-butylbenzo)-21-crown-7- mentioned determination without manifold re-configuration
ionophore for cesium over the other alkaline metals was thor- was permitted through the multicommutation concept [62],
oughly investigated by coating a PVC membrane containing also applied to potentiometric titrations [63]. The abil-
the macrocyclic ligand on the tip of a silver wire incorpo- ity of alkaline-earth metals to displace Cu(II) ions in the
rated into the flow set-up [46]. In the context of radioisotope CuEDTAPAR system was successfully exploited for indi-
analysis, a rapid, safe and cost effective radiometric 137 Cs rect Ca monitoring [64]. Flow injection potentiometry with
determination in radioactive wastewaters was achieved by photo-cured membrane-based coated-wire Ca ISE sensors
coupling flow injection analysis with a solid semiconductor [65] should be also highlighted in this context. The effect
-ray counting detector (viz. NaI (Tl) scintillator) [47]. 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
4. Alkaline-earth metal ions chemistry characterized by turbulent mixing and low axial
dispersion was introduced and exemplified with the on-line
In this section, the most remarkable parameter for water potentiometric titration of calcium [67]. The response of a
characterization is the total hardness determination (viz. the cobalt wire electrode to phosphate ions was used for indi-
sum of Ca and Mg concentrations). To this aim, researchers rect flow injection potentiometric detection of Ca (or Mg)
proposed flow injection photometric procedures or poten- based on the reduction of the phosphate activity as a con-
tiometric titrations using the conventional eriochrome black sequence of precipitate formation with the target species
T-EDTA chemical system or a gradient mixing tube-based [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 Though the determination of trace amounts of beryllium
in natural waters containing macroamounts of Ca were de- in natural waters is of increasing interest as it can indi-
scribed using the Xylylazo Violet chelating reagent in mi- cate environmental pollution and could provide information
cellar medium [69], or the inhibitory effect of the analyte of the metal uptake through these sources, scarce applica-
on the succinimide dioxime oxidation catalyzed by Mn(II) tions of flowing stream methods in water matrices are found
in the presence of nitrilotriacetic acid [70]. The indirect am- in literature. Recently, determination of beryllium in natu-
perometric determination of Mg based upon the formation ral and wastewaters at the low g l1 level has been suc-
of the MgEriochrome Black T complex and measurement cessfully performed through ETAAS using lutetium as a
of the excess of ligand on a glassy carbon electrode [71] semi-permanent modifier. The developed multicommutated
is also worthmentioning. Fig. 1 depicts a typical sequen- system included quantitative on-line precipitation of beryl-
tial injection spectrofluorimetric set-up for the determina- lium with ammonia, collection in a Tygon tube and disso-
tion of magnesium in various environmental waters based lution in acidic medium prior to eluate injection into the
on the formation of the Mg8-HQ complex in the presence electrothermal atomizer [77].
of masking agents [72].
Sequential injection has been presented as a powerful
automated technique to perform radiochemical isolations/ 5. Aluminum
determinations as demonstrated with 90 Sr and 226 Ra assays.
The former radioisotope was rapidly determined in high Although aluminum is the third most abundant element
activity residues using either a renewable bead-suspension in the Earsths crust, its concentration in neutral waters is
entrapped into a specially designed microcolumn [73] low because of the relatively low solubility of aluminum
or a functionalized macrocyclic ligand-based extraction minerals (viz. feldspars). In spite of this fact, the possible
chromatographic column [74], both on-line coupled to relationship between environmental aluminum exposure
liquid-scintillation spectrometry. Renewable wetting-film and Alzheimers disease prompted an increased awareness
extraction by ionophore immobilization onto the inner walls of aluminum levels in the environment and forced the de-
of a PTFE reactor enabled 90 Sr detection at environmental velopment of analytical methodology suitable for ultratrace
activity levels [75]. Both 90 Sr and 226 Ra radionuclides were detection of the target element. The determination of alu-
isolated in a sequential injection method following sorption minum at endogenous levels (>1 g l1 ) in water samples
onto a MnO2 -impregnated cotton filter and further elution requires the development of sorbent extraction methodolo-
with a hydroxylamine solution [76]. gies based on the temporal immobilization of the metal
M. Miro et al. / Talanta 63 (2004) 201223 205

ion onto cation exchangers [78] or 8-HQ functionalized mental harmful elements such as mercury, chromium(VI),
resins [79] or an analyte derivative onto copolymeric (viz. lead, zinc, nickel, cadmium and copper will be thoroughly
XAD-2) [80], polyethylene powder [81] or C18 -bonded sil- reviewed.
ica gel [82] microcolumns implemented into flow devices.
The on-line preconcentrated analyte is further eluted and 6.1. Essential elements
measured by spectrophotometry [83], ICPAES [84], FAAS
[78] or ETAAS [85]. Among chromogenic reagents, the Py- 6.1.1. Molybdenum
rocatechol Violet [86], Chrome Azurol S [87], compounds The simple, rapid and accurate determination of molyb-
of triphenylmethane series and Eriochrome Cyanine R [88], denum at nanogram levels is of great interest because plants
also used as an immobilized reagent phase in diffuse re- and animals require small quantities of this element.
flectance optrodes [89], are the best suited for photometric Numerous segmented and unsegmented continuous-flow
flow procedures. Salicylaldehyde-based fluorimetric pro- methods have been proposed for the determination of trace
cedures [90], also adapted to flow-through sorbent-based amounts of molybdenum in natural fresh (viz. river, lake,
sensors [82], attracted the attention of many analysts owing sea) and tap water samples. In these flowing systems, the
to its excellent selectivity. Other simple approach for the de- chemiluminescence reaction between luminol or lucigenin
termination of trace levels of Al using fluorescent detection, and Mo(III) produced by a Jones reductor enabled metal
requiring neither masking agents nor micelle forming com- determination over the wide linear range 0.11000 g l1
pounds to improve both selectivity and sensitivity, involved Mo. A sensitive flow injection spectrophotometric method
lumogallion complexation [91]. 8-HQ or Eriochrome Red for the determination of the analyte at low g l1 lev-
B sensitized by traces of fluoride [92] were also selected els was developed using the Mo-catalyzed oxidation of
as fluorogenic ingredients in multisyringe/multicommuted ascorbic acid with hydrogen peroxide and the succes-
procedures [93] or in flow injection methods implementing sive condensation of the generated dehydroascorbic acid
different solvent extraction modalities [94]. with o-phenylendiamine to produce quinoxaline deriva-
Aluminum chemistry in acid impacted aquatic systems is tives [105]. As nearly all of the catalymetric procedures
receiving nowadays increasing attention owing to the toxic for molybdenum suffer from strong interferences, requiring
effects of this element on the environment. The dependence the use of chelating agents [105], flow/sequential injection
of aluminum toxicity on its speciation chemistry forested methods coupled with ETAAS or ICPAES detection are
the development of fractionation methods [95], wherein a commonly explored owing to their high sensitivity and
precise control of reaction time is required. Kinetic discrim- selectivity. The performance of on-line preconcentration
ination protocols [96] based on the Al species reaction with strategies prior to the detection step involving molybdenum
8-hydroxyquinoline at different rates were implemented in co-precipitation with Fe(II)-pyrrolidinedithiocarbamate on
both solvent [97] and sorbent [98] extraction flow systems the walls of a PTFE tubing [106], analyte enrichment on
for determination of the fast reactive aluminum fraction at iminodiacetate polymeric resins [107] or activated alumina
different levels [99]. The applicability of such protocols for [108] as well as chelation with diethyldithiocarbamate
complexation studies of aluminum with fulvic and humic or oxine [109] ligands and further complex sorption on
acids has been demonstrated [100]. The speciation of total C18 -sorbent packed reactors were exhaustively assessed.
reactive aluminum in the labile or exchangeable fraction Sequential injection-wetting film extraction combining an-
(i.e. free aluminum, monomeric aluminum sulfate, fluo- alyte complexation with thiocyanate and extraction as an
ride, hydroxide and other weak complexes), the non-labile ion paired complex into a coated toluene phase containing
monomeric fraction (i.e. monomeric alumino-organic com- a counter ion was exploited to exclude interference from
plexes) [101] and the acid soluble fraction (i.e. colloidal more than 40 metal species and anions tested, while as-
polymeric aluminum) has been reported using Pyrocatechol suring high sampling rate [110]. A selective flow injection
Violet [102] or 8-HQ [103] chelation/ion-exchange flow ion-exchange absorptiometric method using Tiron as a color
methodologies. Kinetic and thermodynamic considerations forming reagent including a pre-column for molybdenum
for time-based fractional partition methods have been de- isolation/pre-concentration was proposed for the determi-
scribed attending the strong influence of competing ligands nation of the analyte at the g l1 level in various natural
on the chelating reaction rate [104]. waters [111].

6.1.2. Cobalt
6. Transition metal ions The concentration of cobalt in aquatic environments is
extremely low and it has been suggested that this element
In this section, the most common transition elements may act as a limiting nutrient for marine phytoplankton. It
present in water matrices are itemized in two groups accord- is only toxic to plant and mammals at relatively high con-
ing their source. One group includes some micronutrients or centrations (>1 mg l1 ), which are rarely observed in en-
natural trace elements such as molybdenum, cobalt, iron and vironmental waters. Cobalt demonstrates a scavenged-type
manganese. In the second group, anthropogenic or environ- 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 any preliminary steps and at a pH range close to that of
than 1 ng l1 at depths below 1000 m. It has been found a the sample medium was performed exploiting the oxidation
cobalt enrichment in hydrothermal fluids on the sea-floor reaction of N,N -diethyl-p-phenylenediamine catalyzed by
has been found, and hence, this metal is interesting from the target species and activated by Tiron [120]. Flow injec-
the geochemical point of view as a chemical indicator of tion systems with chemiluminescence detection based on
hydrothermal activity. the catalytic effect of cobalt on the oxidation of quercetin,
Commonly used laboratory techniques for sub-ng l1 luminol, gallic acid or pyrogallol by hydrogen peroxide
cobalt determination in tap, mineral, river, estuarine and were also reported [124,121]. The lack of selectivity over
oceanwater samples include flow injectionelectrothermal alkaline-earth ions is usually overcome by implementation
atomic absorption spectrometry following on-line precon- of 8-HQ containing strong chelating resins in the flow
centration steps. In this context, physical adsorption of the assembly as a matrix removal step [124,121]. In some in-
Co-nitroso-R-salt-tetrabutyl ammonium ion-pair [112] or stances, masking strategies were adopted in flow injection
the ammonium pyrrolidine dithiocarbamate complex [113] procedures aiming to minimize heavy metal interferences
on the inner walls of PTFE knotted tubing, the on-tube for- [125].
mation of a metal chelate into a knotted reactor precoated Flow injection with spectrophotometric detection also ap-
with the 1-phenyl-3-methyl-benzoylpyrazol-5-one chelat- pears to hold considerably promise for trace level deter-
ing reagent [114] and the reversed-phase sorbent extraction minations of cobalt. Hence, both the cadmiumporphyrin
of a low-polar analyte derivative onto a modified silicagel complex [126] and the 4-benzylpiperidinedithiocarbamate
packed microcolumn using sodium diethyldithiocarbamate in a tertiary solvent system [127] were used as color de-
as the complexing agent [115] are worthmentioning. In the veloping reagents to determine the target species at low
latter procedure, enrichment factors as high as 210-fold were g l1 levels. The inherent disadvantage of porphyrins re-
achieved with high loading times. In solid-phase extraction lated to the large overlap of the absorption spectra of the free
approaches prior to atomic spectrometric detection, the reagent and the Co-complex was solved with photochemical
air-segmented eluate modality is widely adopted in order to decomposition of the excess of reagent using only visible
reduce the eluent volume and minimize analyte dispersion light irradiation [126]. A flow-through optrode containing
when delivering to either the graphite electrothermal atom- 1-(2-pyridylazo)-2-naphthol immobilized on phosphorilated
izer [113] or the laser-excited atomic fluorescence detector cellulose disks was also designed as a highly sensitive alter-
[116]. The generation of volatile diethyldithiocarbamate native for ultratrace determinations of the heavy metal [128].
and acetylacetonate cobalt chelates and the implementation The interaction of nitroso-R-salt with cobalt in the presence
of a thermospray device into the flow injection set-up en- of water-soluble polymers, its kinetic role for flow injection
abled the direct preconcentration of the target analyte on spectrophotometric procedures and the likelihood of cobalt
the surface of the graphite tube platform [117]. membrane concentration were carefully investigated [129].
The ability of impregnated polyurethane foam (PUF) Finally, in the scope of electrochemical methodologies, a
microcolumns to tackle real environmental problems was miniaturized sequential flow analyzer coupled with adsorp-
assessed and demonstrated with the development of a tive cathodic stripping voltammetry was described for per-
fast and sensitive flow injectionflame atomic absorption forming on-line measurements of cobalt in the marine en-
method for monitoring cobalt at the g l1 level using vironment with controlled perturbation of natural equilibria
a PUF-2-(2-thiazolylazo)-p-cresol-based column [118]. of the element [130].
Direct on-line precipitation of the target species with
1-nitroso-2-naphthol as well as deposition of cobalt as its 6.1.3. Iron
cyano complex onto activated acidic alumina [119] were The hypothesis that iron limits primary production in the
useful trace enrichment strategies performed prior to flame oceans and acid rain problems stimulates its research in
atomic absorption analysis. water samples. As a result, methods for total iron determi-
Significant progress has been recently made in the devel- nation in a gas-segmented continuous flow, flow injection or
opment of continuous flow and flow injection spectropho- sequential injection fashion have been developed with high
tometric catalytic methods for determining trace levels of sensitivities. A great number of chelating resins containing
dissolved cobalt in water matrices. These approaches were various functional groups such as 8-HQ [131,132], iminodi-
proven extremely suitable for marine chemical research acetic acid [133], N-hydroxyethylethylenediamine [134] or
on-board a ship [120], especially when in-line tangential 2-mercaptobenzimidazole [135], or reversed-phase sorbents
filtration units were assembled into the flow manifolds for following iron chelation [136138] are proven suitable for
the removal of suspended particulate matter [121]. Such flowing stream preconcentration methodologies interfaced
automated systems were generally based upon catalytic ox- with both ICP [139] and FAA [140] spectrometry and
idation reactions of o-dihydroxybenzene derivatives [122], also with spectrophotometric [141] detection. In the latter
such as protocatechuic acid or Tiron or p-diaminobenzene case, typical analytical procedures involve Fe(III) reaction
compounds [123] in strong alkaline medium. The direct with thiocyanate exploited in modelation and optimization
determination of low amounts of cobalt in seawater without computational techniques [142] or in ion-exchange-based
M. Miro et al. / Talanta 63 (2004) 201223 207

flow-through optrodes [143,144]; and Fe(II) complexation idation of ferrous ion in the presence of the chromogenic
with ferrozine [145] or 1,10-phenanthroline [146] em- reagent was reported [170]. Anodic stripping voltammetric
ployed for ultratrace determinations of the target analyte methods have been also developed for receiving information
using bead injection [147] or solid-phase spectrophotomet- relating to speciation and organic complexation of the metal
ric/photoacoustic strategies [146,148,149]. Furthermore, [171].
new sampling modalities adapted to sequential injection Off-line or on-line redox reactions in solution for iron
analysis such as monosegmented [150] or reversed-flow discrimination were performed by the addition of ascorbic
[151] approaches and novel flow-through cells such as long acid [172], sulfite [131], hydroxylamine [134] or hydrogen
liquid waveguide capillary cells [152] were characterized peroxide [135]. On-line Fe(III) reduction or Fe(II) oxi-
using the aforementioned chemistries. The catalytic ac- dation in heterogeneous phase was successfully achieved
tion of iron species on the oxidation of phenylenediamine using amalgamated [173] or copperized zinc [157], or
compounds was also intensively investigated [153,154]. Folin-Ciocalteu-based [143] regenerable micro-columns,
A plethora of highly sensitive chemiluminogenic pro- respectively, and thus the analyte is obtained in a suitable
cedures for determination of iron species in seawater at oxidation state to undergo the derivatization reaction. Fi-
subnanomolar levels was reported [155,156]. In this con- nally, multivariate methods such as partial least-squares
text, the catalytic effect of Fe(II) or Fe(II)oxine complexes calibration [174] enabled the simultaneous determination
on the oxidation reaction of luminol by hydrogen peroxide, of various iron species without requiring the foregoing
dissolved oxygen [157] or potassium periodate [158], in additional reagents.
the presence of citric acid and cationic surfactants [159], Table 1 summarizes the analytical figures of merit of the
was considered. Enhanced chemiluminescence emission aforementioned flowing stream methods for the determi-
of the brilliant sulfoflavinH2 O2 [160,134], diaryl oxalate nation and/or speciation of iron species. Trace concentra-
estersO2 [161] and gallocyaninH2 O2 systems with traces tions are frequently determined following sorbent extrac-
of Fe(II) were also described. tion schemes using ion exchangers, iminodiacetic-based
Discrimination between the different oxidation states (viz. resins, 8-hydroxyquinoline microcolumns or newly de-
Fe(II) and Fe(III)) in natural waters is relevant since iron veloped chelating materials with chemically immobilized
is one of the few elements that is an active participant mercapto or hydroxyethylenamine moieties. Packed-bead
in aquatic redox processes at pH < 6 and at oxic-anoxic microcolumns are currently implemented in both flow and
boundaries. Many speciation methods deal with chelating sequential injection manifolds interfaced mainly with spec-
agents or reagent phases with a strong affinity for a par- trophotometric or atomic absorption detection, although
ticular redox state of the metal [162,163]. In this context, flow-through optosensors based upon solid-phase absorp-
the Fe(III)Chrome Azurol S, Fe(III)semi-xylenol orange, tiometry or bead-injection are proven excellent alternatives
Fe(III)iron and Fe(II)Ferene S systems should be un- to avoid the undesirable post-column analyte dilution, and
derlined [164166]. The catalytic actions of the Fe(III) or hence, higher enrichment factors are attained.
Fe(III)EDTA species on the oxidation of hydroxylamine
[167], p-phenetidine [168], or tetramethylbenzidine [169], 6.1.4. Manganese
using 1,10-phenanthroline as an effective activator estab- The determination of manganese in public and industrial
lished the basis of alternative proposals. A flow injection waters is important because manganese may cause stain-
manifold for spectrophotometric monitoring of trace levels ing of clothes and reduction of pipeline carrying capacities
of iron exploring Shinn reaction as a detection scheme is due to encrustation. The most important source of man-
shown in Fig. 2. The sequential determination of Fe(II) and ganese found in ground and natural waters is the chemi-
Fe(III) taking advantage of the different reaction kinetics cal erosion of the earths crust. In the last years, a host
with Tiron, and the acceleration action of Cu(II) on the ox- of flow injection catalymetric methods has been reported

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.
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- mous solution was also recommended as a reducing reagent
tion levels of manganese found in waters, ranging from owing to its ability to decompose mercury-iodide complexes
ca. 0.01 to 10 g l1 . They are based on the catalytic ef- as opposed to tin(II) chloride [195]. The mercury vapor
fect of the analyte on the oxidation reaction of organic is then stripped from the solution by an argon carrier into
compounds such as N,N-diethylaniline [175], Tiron [176], the quartz absorption cell of the detector using dedicated
benzothiazoline derivatives [177], leucomalachite green flow-through gasliquid separators. A 20-fold improve-
[178] and phenylenediamine species [179] with oxidizing ment in the detection limit was reported using a dedicated
agents (viz. periodate, hydrogen peroxide, Cr(VI) or V(V)). CV-system consisting of a flow injection unit equipped
Heterogeneous reactions relying upon the temporal entrap- with an Hg lamp, quartz cell and Hg detector [196]. A
ment of the target analyte as a PAN-chelate in an optrode gold trap for mercury amalgamation/preconcentration based
membrane [180] as well as oxidation of Mn2+ to perman- on an Au-Pt gauze and a controlled heating system for
ganate by sodium bismuthate [181] or lead(IV)oxide [182] metal release, integrated in the flow manifold prior to the
containing solid-phase reactors enabled spectrophotometric detection step, is a currently used strategy for ultratrace
assays in waters and effluent streams at the mg l1 level. determination of Hg [197]. Reduced mercury was also
Substitution reactions in homogeneous phase comprising detected as an amalgam by using a gold-coated piezo-
the Cd(II)-imidazole-functionalized porphyrin system were electric crystal coupled to an automatic microgravimetric
also reported [183]. screening system [198]. Different minicolumn designs and
Chemiluminescence procedures involving measurement packing materials involving 8-hydroxyquinoline and imin-
of light emission from either tetracyanoquinodimethane odiacetate groups were evaluated in terms of sensitivity
[184] or luminol [125] oxidation catalyzed by traces of for on-line enrichment of inorganic mercury followed by
Mn(II) are shown excellent strategies for the quality control CVAAS detection [199]. Solid-phase extraction onto ion
of underground drinking water during water treatment [185], exchangers with mercapto groups attached to co-polymeric
albeit they usually require sample pretreatment (e.g. addi- matrices was exploited using an on-line reductive elu-
tion of masking agents [125], oxidation to permanganate tion procedure [200]. In-line adsorption/preconcentration
[186] or metal isolation onto an ion exchanger or chelator of the Hg-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol
[187]) to remove potential metal interfering species [188]. complex on the inner walls of a knotted reactor coupled
The former approaches compete in terms of sensitivity and to CVAAS was proven useful for monitoring the target
selectivity with flame or electrothermal atomic absorption species in unpolluted waters at ultratrace levels (>5 ng l1 )
spectrometry combined with on-line preconcentration of the [201]. Iridium, tungstate and zirconium coated graphite
pyrrolidinedithiocarbamate [189], dialkyldithiophosphate tubes were thoroughly evaluated as effective traps for Hg
[190] or Eriochrome Black T [191] derivatives, and with vapor before ETAAS analysis [202].
clean-up steps for removal of spectral interferences from Continuous flow, flow injection and multisyringe flow
sulfide ion [192]. injection-CV generation approaches were also efficiently
coupled to either atomic fluorescence [203] or ICP-
6.2. Harmful metals optical emission [204]/mass spectrometry with isotopic
dilution for Hg detection. These hyphenated techniques
6.2.1. Mercury require preconcentration strategies to determine the metal
The accurate determination of mercury in environmental analyte at sub-ng l1 levels. In this context, sorption of
samples is recognized as a relevant issue for water quality mercury species onto sulphydryl cotton [205] or silicagel
assessment as a consequence of the toxicity of this element functionalized with chelating groups such as 2-merca-
and its ability to bioacumulate in living beings such as ma- ptobenzimidazole [206], methylthiosalicylate [207] or
rine organisms, which become a biological path of Hg to 1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide [208],
humans. Studies of mercury mobility in estuaries and oceans reversed-phase sorption of Hg-dithiophosphate chelates
that play a predominant role in the global Hg cycle were [209], and cloud point extraction of a Hg derivative me-
recently performed for a long-time distribution control. diated by micelles of a non-ionic surfactant [204] are
In recent years, continuous-flow/flow injection/sequential worthmentioning.
injection-cold vapor generation techniques for determina- Determination of organic mercury (viz. methyl-, ethyl-,
tion of mercury at the low ng l1 level by atomic absorption amido-, and phenyl-mercury amongst other Hg-bonded con-
spectrometry in seawater, wastewater, drinking and natural taining species) can be performed with the aforementioned
water samples have enjoyed increasing popularity owing procedures, the only requirement is that mercury should be
to their outstanding performance as opposed to the earlier present in inorganic form. Selective reduction of inorganic
batch-wise operated systems. A fully automated CVAAS mercury and selected organomercurials to Hg0 was de-
analyzer involves the preliminary on-line sample reaction scribed using SnCl2 in acidic medium and a more energic
with a reducing agent, mainly stannous chloride [193] reducing agent such as NaBH4 , respectively [202]. Meth-
or potassium tetrahydroborate [194], in order to generate ods available for oxidation of mercury compounds that are
elemental mercury from inorganic mercury. Aqueous chro- easily adapted to flow and sequential injection techniques
M. Miro et al. / Talanta 63 (2004) 201223 211

usually include chemical digestion under temperature con- effect of mercury(II) on the decomposition of hexacyano-
trol [210] using strong acids and chemical oxidants such ferrate was also used as the basis of straightforward and
as electrogenerated cobalt(III) [211] or potassium perox- moderately selective chemiluminescence and photometric
odisulfate in sulfuric acid medium [212] with the addition methodologies [230]. Improved selectivity is gained by the
of iron(III) acting as a catalyst [213], microwave-assisted addition of chelating masking agents in the carrier stream,
oxidation with high temperature and pressure [214] and so that interferences caused by heavy metals are greatly
UV-irradiation [215] using Br /BrO3 as oxidation mix- minimized. Similar strategies were adopted in both the spec-
ture [216]. The catalytic effect of copper(II) on the chemical trophotometric determination of mercury by water-soluble
decomposition of organomercury employing tin(II) chlo- chlorinated porphyrins [231] and the fluorometric detection
ride in alkaline solution was also exploited. Best results of the Hg-calcein complex in alkaline medium [232].
in terms of recovery rates under dynamic regime were
reported with UV digestion when applied to a governmen- 6.2.2. Chromium
tal monitoring station at the River Elbe [217]. The need The interest in understanding the chemical behavior of
for chemical oxidants, high pressure and temperature for chromium in natural aquatic systems and the requirement of
degradation of organomercurials was eliminated exploring a analytical techniques able to determine trace levels in envi-
room temperature ultrasonic irradiation-based advanced ox- ronmental samples is governed by the fact that its toxicity
idation process [218]. Speciation of mercury species at sub depends critically on its oxidation state. Chromium(III) is
ng l1 levels following preconcentration using a dithiocar- considered an essential trace element as it is able to coordi-
bamate resin microcolumn was accomplished by butylation nate several amino acid ligands in the human body and it is
with a Grignard reagent, isolation in a gas chromatograph frequently supplied as a dietary complement. On the other
furnished with a non-polar analytical column and further hand, chromium(VI) is known to be toxic to humans, capa-
detection with a microwave-induced plasma emission de- ble of permeating cell membranes, thus, being a powerful
tector [219]. Improvement in analytical throughput, signal mutagen and a potential carcinogen. Both oxidation states
stability, memory effects and environmental friendliness for enter the environment as a result of effluent discharge from
a similar detection limit was attained with a flow injection steel, electroplating and tanning industries, oxidative dyeing
liquid chromatography cold vapor atomic absorption tech- or cooling water towers. Chromium may also enter drinking
nique [220]. Selective continuous liquidliquid extraction water supply systems from the corrosion inhibitors used in
of mercury compounds into a xylene phase as bromide water pipes or by contamination of the underground water
species, cold Hg vapor generation directly from the organic from sanitary landfill leaching.
phase and final ICP-atomic emission spectrometry detection There are few flow analytical techniques available that
was also proposed as a speciation strategy [221]. have enough sensitivity and selectivity for the direct de-
Construction of very efficient flow-through cells for Hg termination of ultra-trace levels of Cr(VI) in water matri-
detection by potentiometric stripping analysis [222] using ces. Sample pre-treatment methodologies which include
either the thin gold layer of recordable compact disks [223] analyte isolation and preconcentration are required in or-
or platinum foils [224] as working electrodes was of intense der to determine the low levels of hexavalent chromium,
interest. Both chalcogenide glass ion-selective electrodes even with highly sensitive techniques such as ETAAS. In
[225] and substituted diazacrown ionophore containing this context, the development of rapid, robust and selec-
membrane-based sensors [226] were prepared, character- tive time-based FI-ETAAS methods using the ammonium
ized and adapted to rapid continuous flow determination pyrrolidinedithiocarbamate-iso butylmethylketone extrac-
of mercury at different pHg levels. A tetraiodomercuriate tion procedure [233] or chelate adsorption on the inner
liquid electrode was proven highly selective for mercury walls of a knotted reactor [234] as well as sorbent extrac-
iodide species and inorganic mercury after on-line transfor- tion approaches after chromium derivatization [235] are
mation into analytical active species [227]. The inhibition especially worthwhile for Cr(VI) determination within the
of the enzymatic conversion of urea to carbon dioxide and 5500 ng l1 range. FI-FAAS technique, which can tolerate
ammonia by mercury traces in a gas-diffusion flow injection considerable salt amounts, is ideally suited for hexavalent
system equipped with a urease reactor was also evaluated chromium determination in seawater, although measure-
and potentiometrically monitored with a pH electrode [228]. ments at the g l1 level require pre-concentration strategies
Displacement reactions were useful approaches for the involving either retention of suitable complexes on silanised
indirect determination of inorganic mercury by both lumi- C18 column reactors or direct chelation of the target species
nescence and spectrophotometric flow injection procedures. onto a cellulose support functionalized with quaternary
Thus, the replacement of iron(II) from the iron(II)EDTA amine groups [236]. The above hyphenated technique was
complex by inorganic mercury was coupled to the chemilu- also useful for determining both the soluble chromium
minogenic reaction of luminol with dissolved oxygen. The fraction in industrial effluents after on-line filtration and
catalytic effect of the target analyte on the ligand substitution the total chromium content following microwave-assisted
reaction rate between hexacyanoferrate and , -bipyridyl sample digestion [237]. Recently, ICPAES and ICPMS cou-
was also thoroughly investigated [229]. The accelerating 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- ligands, resulting in poor sensitivity, low sample through-
lyte, although in the latter case matrix effects by molecular put and incomplete recovery was circumvented by using
ion peaks are observed. In the field of electrochemistry and Mn(II)-diethyldithiocarbamate as a chelate carrier during
taking advantage of the electrocatalytic effect of polyani- the FI-FAAS determination [248]. The selective sorption
line, a polyaniline/polystyrene composite electrode was of Cr(III) ions on poly(aminophosphonic acid) [236] or
characterized and used as a sensitive flow injection detector poly(hydroxamic acid) [249] chelating resins was also ex-
for assays at the sub-g l1 -level of Cr(VI) [238]. ploited as a pre-concentration approach prior to FAAS
As stated above, in view of the different toxicity of both detection. In addition to the most widely used chemical
oxidation states, and in order to follow the pathways for in- reduction, total chromium concentration was determined
terconversion in the environment, it is increasingly important after electrochemical reduction of chromate ions to Cr(III)
to monitor the concentration of individual species as well as at a porous gold-coated glassy carbon electrode [250].
the total concentration of chromium in environmental wa- The selective sorption of Cr(III) and Cr(VI) on activated
ters. The most widely accepted spectrophotometric method- alumina microcolumns at pH 7 and 2, respectively, and
ology for chromium speciation in flow injection/sequential further elution of preconcentrated species directly to the
injection assemblies is undoubtedly the selective com- nebulizer burner of a FAA spectrometer using acidic and
plexation of Cr(VI) with 1,5-diphenylcarbazide (DPC) in alkaline conditions for trivalent and hexavalent chromium,
acidic medium [172], which has been used for develop- respectively, was successfully used as a speciation scheme
ing flow-through ion-exchange solid-phase spectrophoto- in flow injection [251] and sequential injection systems
metric sensors [239]. Incorporation of cation-exchange [252]. An alternative procedure capitalized on the cloud
pre-columns for removal of polyvalent cations [239] point extraction of the Cr(III)-8-hydroxyquinoline hy-
and quantitative sorption of Cr(VI) onto activated alu- drophobic complex combined with fluorimetric detection
mina [240] or zirconium(IV) oxide modified silica gel allowed the reliable determination of Cr(III) (and Cr(VI)
[241] as well as on nanometer-size titanium(IV) oxide following reduction by sulfite) at levels as low as 0.2 g l1
(anatase) powers [242] are frequently recommended prior in complex water matrices [253]. The usefulness of cation
complex formation to attain both selective and sensitive and anion-exchange microcolumns assembled in series for
spectrophotometric determinations. Sensitivity enhance- automatic and rapid preconcentration and speciation fol-
ment is also provided by a recently developed wetting lowed by atomic absorption measurements was assessed by
film-sequential injection system based on the formation of several researchers [254].
an ion-pair between the reaction product of Cr(VI) with Flow injection chemiluminescence methods have been
DPC and perchlorate, and further extraction into an or- proposed as low-expensive and sensitive alternatives for
ganic film coating the inner walls of PTFE tubing [243]. chromium speciation in tap and wastewater [255]. Thus,
Diantipyryl-(p-N,N-dimethylamino)phenylmethane was Cr(III) and Cr(VI) ions were determined, respectively, by
also investigated as a chromogenic reagent for the flow measuring the light emitted as a result of the catalyzed oxi-
injection determination of hexavalent chromium in the pres- dation reaction of luminol or N-ethylphthalyhydrazide with
ence of Mn(II), employing an on-line microwave-irradiation oxidant species, and quercetin with hydrogen peroxide in al-
method to accelerate the color forming reaction [244]. kaline medium. Indirect chemiluminescence determination
Industrial samples from electroplating baths and residual of chromate ions was proposed by on-line generation of the
washing waters containing Cr(VI) concentrations rang- oxidizing agent (viz. hexacyanoferrate(III)) through the fast
ing from 0.2 to 2 mg l1 were analyzed by monitoring oxidation reaction between hexavalent chromium and hexa-
an aminochrome intermediate compound resulting from cyanoferrate(II) [256]. Increase in sensitivity of the Cr(III)
oxidation of the alkaloid brucine [245]. Furthermore, to- determination was achieved by introducing bromide in the
tal chromium determination was accomplished following reaction mixture while the selectivity of the assays was
sample pre-oxidation with oxidizing agents [239] such as improved by addition of EDTA [257] or the incorporation
potassium peroxodisulfate, potassium periodate, and acidic of packed-bead cation exchangers [256]. In this context, a
cerium(IV), or heterogeneous oxidation using a lead(IV) new bundle flow-cell design for chemiluminescence assays
oxide column at high temperature. Speciative determination that provide a 50% improvement in sensitivity respect to
of Cr(VI) and Cr(III) was also performed by formation of the most used spiral cell has been recently characterized
the Cr(VI)-4-(2-thiazolylazo)resorcinol complex at pH 5.0 and evaluated for monitoring traces of Cr(III) [258].
in the presence of 1,2-cyclohexanediaminetetracetic acid as
a masking agent for Cr(III) [246]. 6.2.3. Nickel
Selective determination of trivalent chromium with FAAS Interest in the determination of nickel has increased over
detection was carried out using on-line coprecipitation the last few years because of the influence of this metal on
strategies based on collection of the precipitate formed humans. Adverse effects of inorganic, water soluble nickel
with lanthanum hydroxide in a knotted reactor without species occur after contact with the skin, causing nickel
filtration [247]. The chemical inertness of Cr(III), which dermatitis. After inhalation, respiratory tract irritation and
hinders the efficient complexation with dithiocarbamate asthma can also result. Besides, carcinogenesis bioassays in
M. Miro et al. / Talanta 63 (2004) 201223 213

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 Fig. 3. Multisyringe flow injection assembly with an ancillary multipo-
micelles upon increasing the temperature [261], the ana- sition valve for the spectrophotometric determination of Ni(II) using a
lyte co-precipitation with Cu(II)-diethyldithiocarbamate in a multichannel configuration. SV: solenoid valve; MV: multiposition valve;
S: syringe pumps; SA: sample; C: carrier (diammonium citrate solution);
knotted reactor [262] and the generation of volatile products
R1: oxidising reagent (saturated iodine solution); R2: chromogenic reagent
(viz. nickel tetracarbonyl) and its trapping into a graphite (dimethylglyoxime in alkaline medium); HC: holding coil; RC: reaction
tube [263] are also worthmentioning. The performance of coil; D: detector; W: waste.
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 drinking water, requiring lead action if the concentration
wave adsorptive stripping voltammetric method involving of heavy metal exceeds 15 g l1 in more than 10% of tap
a mass-transport controlled preconcentration step, during water samples collected during a preset monitoring period.
which the Ni-dimethylglyoxime complex is retained onto an The most attractive modes for determination of lead
in-situ film of a flow-through electrode, followed by a re- traces in aqueous solutions with reported detection limits
ductive stripping scan was applied for the continuous online from 0.01 to 8 g l1 are both flame atomic absorption
monitoring of trace levels of Ni(II) [265]. spectrometry (FAAS) and flame laser-enhanced ionization
Straightforward spectrophotometric procedures relying technique integrated with on-line continuous flow/flow in-
on Ni(DMG)2 formation in solution or integration of an- jection/sequential injection microcolumn preconcentration
alyte derivatization with PAN, retention and detection in [269]. With regard to solid-phase extraction of lead species
a solid-phase flow-through optrode [266] were described. in flow systems prior to atomic absorption, interactions
Fig. 3 illustrates a multisyringe flow injection set-up de- based on chelate formation are generally utilized. The com-
signed for the spectrophotometric determination of Ni(II) in mercially available chelating resin Chelex 100 with iminodi-
metallurgical liquors using a multichannel system in which acetate groups was the earliest material used for that purpose
the sample zone reacts consecutively with oxidizing and [270], although as a consequence of its swelling/shrinking
choromogenic reagents [267]. The rate of the pseudo-first effects it has been progressively replaced by mechanically
order dissociation of the citrate complex of Ni(II) in alka- resistant sorbents containing either 8-hydroxyquinoline or
line medium was used as an SIA discriminatory tool for the Pyrocatechol Violet [271] as well as nitroso R-salt/aliquat
kinetic determination of the target species at trace levels in 336 [272] immobilized on controlled-pore glass or
the presence of Co(II) [268]. Nickel was also reported to chemically-modified silica gel. The selectivity of immobi-
act as a catalyst in the anthracene green-peroxide hydrogen lized hydroxyquinoline for trace amounts of lead over other
chemiluminescence system for the determination of the heavy metals such as Fe, Cu and Zn was improved by in-
metal ion at low g l1 levels. cluding different complexing agents in the buffered carrier
stream [273]. Preconcentration of Pb(II) on ion exchangers
6.2.4. Lead (viz. activated fibrous alumina or hydroxyapatite) [274] in
Adverse health effects from exposure to lead are nowa- flow injection-AAS was also described. Sequential injection
days recognized to be one of the most significant health lead preconcentration exploiting the sorption characteristics
problems in industrialized societies. Drinking water is the of the poly(vinylpyrrolidone) co-polymer in a thin filtering
major source of the heavy metal exposure for the general layer was recently proposed [275]. Furthermore, several
population. Lead enters drinking waters primarily as a re- researchers recommended functionalized cellulose sorbents
sult of corrosion, or wearing away of materials containing with carboxymethyl or phosphonic acid groups [276] as a
lead in the water distribution system and household plumb- consequence of their excellent dynamic properties of reten-
ing. EPA has set strict regulations on lead concentrations in 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 In the field of electrochemical techniques, flow injec-
[271]. tion stripping analysis using cellulose triacetate [294] or
Sorption of both oxine and dithiocarbamate chelates Nafion [295]-modified mercury film electrodes was de-
[277] as well as ammoniacal [278] and 1-nitroso-2-naphthol scribed for the determination of lead in environmental sam-
[279] complexes formed in the solution on non-polar poly- ples. Automated Osteryoung square-wave anodic stripping
meric resins, C18 -bonded silica columns or onto the inner voltammetry and potentiometric stripping analysis were
walls of a knotted reactor using an on-line multiplexed pre- demonstrated to be effective alternatives for monitoring
concentration procedure [280] with repetitive sample injec- low g l1 levels of lead in tap, river and seawater [294].
tions to improve retention efficiency were reported prior to Besides, poly(vinylchloride) membranes containing sub-
FAAS analysis. Coprecipitation methods using either zinc stituted diazacyclooctadecane species were prepared and
diethyldithiocarbamate or Co-pyrrolidinedithiocarbamate evaluated for flow injection potentiometric determination of
[281] as carriers and elution of the collected precipitate lead within the linear interval of concentrations (expressed
onto a PTFE membrane or on the walls of a knotted reactor as pPb) ranging from 6.0 to 2.0 [226].
directly to the atomic absorption spectrometer were also Classical photometric methods with selectivity improve-
presented. Classical flow injection liquidliquid extraction- ment via solvent extraction [270] or micro-column precon-
FAAS procedures with on-line sample/solvent segmentation centration [296] using dithizone, 4-(2-pyridylazo)resorcinol,
and analyte derivatization provided determination limits at sulfarsazen, 2,2 -dipyridyl-2-pyridylhydrazone or tirodin as
the g l1 level. A dual stage extraction-FAAS system in- chromogenic agents [270,296] were readily implemented
volving lead retention onto a cation exchanger followed by in flowing stream systems. The color-forming reaction of
solvent preconcentration as the ion-pair formed between the lead with functionalized porphyrins at different pH con-
iodo plumbate anion and the tetrabutylammonium cation ditions was also studied, heavy metal interferences being
was efficiently coupled to a flow injection assembly [282]. minimized by addition of acetylacetone to the reagent mix-
Flow injection [283] and multicommuted flow networks ture [297]. A simple and reliable spectrophotometric flow
[260] with sorbent extraction after dithiocarbamate [284] injection method based on the lead-catalyzed reduction of
or Tiron [285] complex formation were also success- resazurin to resorufin by sulfide was presented for lead de-
fully interfaced with ETAAS, achieving detection limits termination in tap waters with a detection limit of 1 g l1
of 39 ng l1 Pb in saline waters without deterioration of without requiring preliminary preconcentration steps [298].
the sample throughput [283]. The retention of Pb chelates Other reported alternatives for the determination of trace
on the inner walls of PTFE reactors is usually joined with amounts of the target species involved the chemiluminogenic
air-segmented ethanolic elution strategies aiming to reduce lucigenin-hydroxide peroxide-lead(II) system and the re-
the eluate volume and minimize the dispersion effect dur- placement reaction of Fe(II) by Pb(II) from the Fe(II)EDTA
ing analyte transportation into the graphite tube atomizer complex prior to luminol oxidation. In the scope of environ-
[286]. On-line electrochemical preconcentration in tungsten mental optical sensors, novel flow-through optical sensing
coil electrothermal AAS using a Pt flow-through anode systems for trace lead monitoring (>0.1 g l1 ) based on the
and the atomizer itself as the cathode was designed for formation of quinoline sulphonate chelates and further im-
the determination of the target analyte in natural waters mobilization onto the surface of anion-exchange resin beads
at low g l1 levels [287]. The attractiveness of coupling prior to room temperature phosphorescence measurements
flow injection with hydride-generation-AAS based on an- were recently devised [299].
alyte pre-oxidation in acidic oxidant media [288] (viz.
hexacyanoferrate-hydrochloric acid, peroxodisulphate-nitric 6.2.5. Copper
acid, dichromate-acid lactic and hydrogen peroxide-nitric Copper is an essential trace element, a component of crus-
acid) to Pb(IV) before generation of volatile species by tacean respiratory pigments like hemocyanin, and is com-
sodium tetrahydroborate or sodium tetraethylborate [289] monly present in the coastal marine environment, where it
was evaluated in terms of selectivity and sensitivity of may reach level toxics to both animals and plants. Increases
analysis [288]. in copper concentration in coastal areas have resulted from
Both extraction chromatographic procedures relying upon industrial and domestic waste discharge, disposal of mining
the formation of an inclusion complex using functionalized washings, refineries and the use of the heavy metal as a
macrocyclic 18-crown-6 ethers [290] and PTFE adsorp- base compound for antifouling paints. Thus, the monitor-
tion [291]/microcolumn [292] preconcentration approaches ing of extremely low levels of copper in natural waters has
were efficiently coupled to ICPMS detection with reported received special attention as a way to assess the early im-
detection limits below 0.2 g l1 . The incorporation of pact of human sources and detect potential health hazards.
an ultrasonic nebulizer-membrane dryer prior to the ICP Hyphenation of flow injection sample processing with de-
torch allowed implementation of sorbent extraction-elution tection by electrothermal or flame atomic absorption spec-
procedures using organic solvents such as methanol and trometry is a widely accepted methodology for trace copper
ethanol since solvent vapors were significantly prevented determination, with reported detection limits below 0.06
from entering the detector [293]. g l1 Cu. Several flow injection and sequential injection
M. Miro et al. / Talanta 63 (2004) 201223 215

preconcentration/matrix removal methods well suited to strategies involving the use of polymeric sorbents such as
in-field sampling techniques [300] were based on the use poly(ethylenimine) [316] or immobilized chelating species
of reactors loaded with reversed-phase materials, poly- [317]. A continuous liquidliquid extraction procedure us-
meric sorbents, classical ion exchangers or chelating resins ing a dedicated hollow fiber membrane separator was suc-
containing pyrocatechol violet [301], Eriochrome Blue cessfully applied to the spectrophotometric determination of
Black R [301] or heterocyclic azo compounds [302] such the target species at concentrations above 15 g l1 follow-
as calmagite [303] or 1-(2-pyridylazo)-2-naphthol [300]. ing on-line formation of the Cu-bathocuproine-perchlorate
Optimization of preconcentration-based flow analyzers us- ternary complex [318]. The on-line segmented solvent ex-
ing multiple-factor experimental designs was successfully traction of the ion associate of dibromocuprate(I) with a
performed [302]. Ligands such as sodium/ammonium di- sort of cationic azo dyes was thoroughly examined in a
ethyldithiocarbamate [304] and 1-nitroso-2-naphthol [305] spectrophotometric flow injection set-up. The use of mi-
may be also dissolved in the carrier or reagent solution, and croemulsions as a medium for liquidliquid extraction
procedures relying upon sorption of Cu-chelates formed in was also investigated, attaining particular benefits for the
homogeneous phase on non-polar silica-gel based sorbents Cu(II)/neocuproine complex [319].
[305], activated carbon [306] or on PTFE knotted reactor Much attention has been recently focused on flow-injection
[307]/filter systems [304] were commonly reported for trace kinetic methods of analysis based on catalytic reactions,
analysis. Both segmented liquidliquid extraction [308] since trace or ultratrace amounts of copper are read-
and wetting-film methodology [309] with chelating agents ily monitored. For example, an oxidative coupling of
(namely, 8-HQ [309] or an halogen derivative [308,310] N-phenyl-p-phenylenediamine with m-phenylenediamine
dissolved in isobutyl methyl ketone [309] or in a mixed in the presence of hydrogen peroxide as oxidant species
solvent solution [310]) as well as coprecipitation techniques and pyridine and ammonia as activators was used as an
using Ni(II)-diethyldithiocarbamate as a coprecipiting car- indicator reaction for the photometric catalytic determi-
rier were also interfaced with flow injection-FAAS detection nation of Cu(II) at the low g l1 level (0.1 g l1 )
for copper monitoring at low g l1 levels. The combina- [320]. As an alternative, the Cu-catalyzed coupling of
tion of a multipurpose sandwich-type dialyzer employed p-anisidine with N,N-dimethylaniline with different hete-
for automated dilution with flow injection-AAS was proven rocyclic activators was proposed. The redox reactions of
suitable to handle environmental samples (e.g. industrial both 2,6-dichlorophenolindophenol with hydrogen perox-
effluent samples) where there is a great variation in Cu(II) ide [321] and cysteine with iron(III) in the presence of
concentration levels [311]. 1,10-phenanthroline [322] catalyzed by traces of Cu(II)
Spectrophotometric methods for monitoring traces of were exploited for the development of photometric flow-
copper in environmental and wastewater waters are ad- ing stream procedures for the determination of the heavy
vantageous because they are easily operated and inexpen- metal from 5.0 to 70 g l1 and 0.110 g l1 , respectively.
sive when compared to atomic absorption spectrometry. On-line monitoring of copper traces in steam condensate
N,N-substituted derivatives of dithiocarbamic acid such as and boiler feed-water was successfully carried out us-
diethyldithiocarbamate are often used as color develop- ing the catalytic effect of the metal ion on the oxidation
ing reagents for the determination of the heavy metal in of hidroquinone by hydrogen peroxide, the quinone pro-
aqueous phase or following solvent extraction [312], since duced was detected by absorptiometry at 490 nm [323].
the Cu(II)DDTC stability constant is more than one or- A rapid flow injection method for the determination
der of magnitude higher than that of other DDTC-metal of copper, based on the catalytic action on the decol-
chelates. A new type of dithiocarbamate derivative, i.e. oration reaction of iron(III) with thiosulphate was also
4-benzylpiperidinedithiocarbamate [313] was recently syn- devised. Catalymetric procedures involving the chemilu-
thesized and proposed as a chromogenic reagent for the de- minogenic luminoloxidantCu(II) system, the enhance-
termination of Cu(II) at the low g l1 range (25 g l1 ) ment of the Co(II)-catalyzed chemiluminescence oxidation
using flow injection analyzers furnished with strong reaction of 1,10-phenanthroline by Cu(II) traces and the
cation-exchange containing stationary phases [314]. The fluorescein-sensitized -nitrostyrene-based chemilumines-
flow injection photometric determination of Cu with het- cence reaction in the presence of micelles should be also
erocyclic complexing agents such as nitroso-R salt [315] highlighted [324].
and 4-(2-pyridylazo)-resorcinol (PAR) was also exploited Flow injection analysis with chemiluminescence detection
in weak acidic medium in order to promote the selective relying upon the reaction of copper with 1,10-phenanthroline,
reaction with the target analyte [316]. Nevertheless, most of and further oxidation of the complex formed by hydrogen
the analytical methods, as for example the CuPAR system peroxide was used for the determination of dissolved cop-
under acidic conditions, require additional procedures for per in seawater after on-line matrix removal [325] as well
increasing selectivity, imposing the resorting to masking as for speciation and complexation studies [326], which
agents (viz. EDTA, citrate, tartrate, hydroxylamine or hexa- are crucial to understand the ecological role of copper in
cyanoferrate), differential kinetic methods using pyridylazo marine ecosystems. Since more than 95% of dissolved
compounds [162], and selective resin preconcentration 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 oped for cadmium monitoring but undoubtedly the predom-
usually explored for the breakdown of copper complexing inating methodologies in routine laboratories are nowadays
organic ligands prior to total dissolved Cu determination by AAS with flame [338] or electrothermal atomization [339]
the aforementioned chemiluminescence reaction [327]. The and ICPAES [340] or vapor generation-ICPMS with isotope
effect of photolysis on the uptake of the heavy metal from dilution [341]. Nevertheless, direct instrumental analysis of
three model ligands, i.e. glycine, nitrilotriacetic acid and complex water samples as seawater is difficult because of
EDTA was investigated using a chelating column linked the large salt content and the minute concentration of the
to an AA spectrometer [328]. A two-column ion-exchange analyte. Preconcentration techniques can solve the above
method for copper differentiation between a labile fraction problems and lead to a more straightforward determination.
and a negatively charged organic-bound fraction was also Several methods such as coprecipitation with a Cu-chelate,
integrated in flow injection-flame AAS systems [329]. solvent extraction using dithizone as extractant, knotted
The partitioning of dissolved copper between labile in- reactor sorption and microcolumn extraction were devel-
organic species and non-labile organically bound species is oped for this purpose [29,342]. The column extraction
frequently detected through electroanalytical methods in- method in flow assemblies was widely used as a conse-
volving a stripping cycle, such as differential pulse anodic quence of the relatively high concentration factors attained.
stripping voltammetry [330]. Sequential injection analysis Flow injection/sequential injection systems furnished with
was demonstrated to be a practical tool for anodic stripping resin columns of immobilized 2-mercaptobenzothiazole,
voltammetry in terms of sensitivity using flow reversals, dithiocarbamate species [343] or phosphonic acid [344]
selectivity exploiting its inherent ability for performing for direct analyte retention and octadecyl-modified sil-
medium exchange procedures, and reduction of mercury icagel [345] and polymeric Amberlite-type [346] sorbents
containing waste since the mercury film is on-line plated for the temporal sorption of metal chelates were applied
[331]. Accurate analytical data for the labile fraction of cop- to cadmium determination in seawater, river and drink-
per was also obtained by oscillating flow injection stripping ing water samples at trace levels (>0.5 ng l1 ). Among
potentiometry, which appears to be a versatile technique the most commonly employed chelating agents, sodium
with respect to the sample matrix as demonstrated via diethyldithiocarbamate [342], iminodiacetic acid [339]
standard addition and direct calibration approaches [332]. (Chelex 100), 1-(2-pyridylazo)-2-naphthol [347] and hete-
Continuous flow methods for evaluating the response of a rocyclic azo compounds such as 4-(2-pyridylazo)resorcinol
copper ion-selective electrode to total and free copper con- [348] and 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol
centrations were recently assessed using an extrapolation [346] should be highlighted. New silica-based sor-
method based on the fitting of an empirical mathematical bents with organic ligands such as 1,5-bis(di-2-pyridyl)
equation to the electrode timeresponse curve [333]. A methylene thiocarbohydrazide and methylthiosalicylate
dedicated coated tubular solid-state copper(II)-sensor con- [340] and reversed-phase copolymeric materials such as
structed from a copper tube and Tygon tubing, treated with poly(octadecyl diitaconate) [338] were synthesized, and the
ammonium sulfide to provide the copper/copper sulfide efficiency for cadmium preconcentration in flowing stream
electrode was specially designed to be assembled into the systems was thoroughly studied. The third generation of
conduits of a flow injection set-up [334]. flow injection, so-called sequential injection lab-on-valve,
The analytical application of a simple polarographic handling renewable hydrophobic bead surfaces (namely,
flow-through cell containing a conventional dropping mer- PTFE or octadecyl-modified copolymeric bead materials)
cury electrode, a mercury pool and a platinum wire as the was exploited for the ETAAS determination of cadmium (>
working, reference and counter electrodes, respectively, 5 ng l1 ) [349] in environmental waters as shown in Fig. 4.
was proposed for the continuous determination of copper in Numerous schemes were developed for cadmium spe-
diluted water samples following a preliminary analyte en- ciation in water samples involving various separation and
richment step onto a Chelex-100 containing microcolumn detection techniques. Two operational fractions with en-
[335]. A flow injection amperometric method based on the vironmental meaning (i.e. available and non-available
oxidation of the CuDDTC complex at a Pt microelectrode for aquatic organism bioaccumulation) were determined
fitted to a conventional wall-jet flow cell was also described through kinetic discrimination using the aforementioned
using a high resistance toluene carrier stream [336]. The re- sorbents: a Chelex 100 labile fraction consisting of Cd(II)
producible preconcentration and subsequent determination ions and weak cadmium complexes, and an octadecyl-silica
of the accumulated Cu(II) (>90 g l1 ) using chemically gel hydrophobic fraction involving stable cadmiumorganic
modified carbon paste electrodes was accomplished exploit- complexes [350]. Speciation of dissolved cadmium in
ing differential pulse polarographic techniques [337]. fresh waters was also reported using differential-pulse an-
odic stripping voltammetric measurements in a flow sys-
6.2.6. Cadmium tem composed of a filtration module and an enrichment
Cadmium is known to be a highly toxic trace metal which unit [351]. The same detection principle was employed
plays important roles in biological metabolism. Numerous in flow-injection systems furnished with Donnan dialy-
spectral and electrochemical flow methods have been devel- sis units containing strong cation-exchange sulphonated
M. Miro et al. / Talanta 63 (2004) 201223 217

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- 6.2.7. Zinc


mium concentrations in solutions containing organically Interest in zinc concentrations in environmental waters
complexed cadmium [352]. Three different fractions of from its dual role as a required nanonutrient and potential
complexed Cd-species were discriminated by interfacing toxicant due to its widespread industrial (viz. metallurgy,
two microcolumns packed with Chelex-100 and a strong galvanizing and alloy manufacturing) and marine usage is
anion-exchange resin with AAS [353]. recently shown. In the case of surface seawater the major
Flow injection-vapor generation coupled to atomic ab- Zn inputs include atmospheric deposition (both natural and
sorption spectrometry was evaluated as a rapid and straight- anthropogenic origin), fluvial, runoff and upwelled waters.
forward method for ultratrace determination of Cd in It is known from vertical profiles in the marine environment
wastewater and natural waters [354], without requiring the that zinc is actively incorporated into phytoplankton in sur-
presence of cationic surfactants [355]. Elimination of in- face waters and transported to depth in association with par-
terfering metals such as Cu, Pb, Ni and Zn was readily ticulate matter or passively adsorbed onto particles. Recent
accomplished by addition of cyanide to the tetrahydrob- studies indicate that the majority of dissolved zinc in sea-
orate reductant solution [356]. Iridium-, tungsten- and water is organically complexed but the origin and behavior
zirconium-coated graphite tubes were evaluated for the of the Zn-binding ligands is still under investigation.
in-situ trapping of volatile cadmium species at the low Dissolved zinc concentrations ranging from 0.1 to
ng l1 level prior to atomization in a graphite furnace [357]. 500 g l1 in drinking, river, estuarine, open-ocean
Flow-through potentiometric detectors with homogeneous and nearshore seawater samples were determined by
crystalline double membrane tubular electrodes for sensi- flow-injection solid-phase preconcentration using unload
tivity improvement [358] and commercial solid-state cad- polyurethane foam for Zn-isocyanate complex retention
mium ISEs [359] were adapted to flow injection systems for [362], chelating resins such as silicagel functionalized with
the determination of either free cadmium in the presence of a thiocarbohydrazide derivative [363] or carboxymethyl-
ligands [359], or halogen complexes of the target species cellulose with 8-HQ or thiocyanate groups [364] as
[360]. As a consequence of the limited selectivity of the po- well as the temporal immobilization of the Zn-8-HQ
tentiometric sensors, quantitative retention of the cadmium chelate on activated carbon [365] and adsorption of a
chloro-complex onto a strong basic anion-exchange resin Zn-pyridylazoaminophenol complex onto a PTFE tubing
microcolumn is recommended to alleviate interferences from [366], followed by graphite furnace/flame AAS or isotope
other metallic cations and inert components present in en- dilution ICPMS. In the latter case, interactions between an-
vironmental matrices [358]. In the scope of optical sensors, alytical variables and their optimal levels were thoroughly
a flow-through diffuse reflectance bulk optrode membrane explored using two level factorial and Doehlert matrix
that incorporates a pyridylazo chromogenic compound was designs [363].
characterized for the determination of cadmium at the mg l1 Highly sensitive spectrofluorimetric determinations in
level using different kinetic methods based on continuous natural waters with reported detection limits of ca. 3 g l1
flow, flow injection and stopped-flow analysis [361]. Zn were performed by either the selective complexation of
218 M. Miro et al. / Talanta 63 (2004) 201223

the metal with salicylaldehyde thiocarbohydrazone [367] programs and their inherent flexibility for the implementa-
or the chelating reaction with a functionalized quinoline tion of separation modules (viz. dialysis, pervaporation and
indicator ligand (viz. p-tosyl-8-aminoquinoline [368] or gas-diffusion units), sorbent extraction procedures, in-line
5,7-dichloro-2-methylquinolin-8 ol [369]) in a non-ionic dilution strategies as well as solid-phase reactors used for
micellar medium. A cation-exchange column was required redox and displacement reactions were emphasized in the
in the latter case to separate zinc from interfering alkaline body of the text. As shown along the three parts of the re-
and alkaline-earth ions when high saline content samples view, different schemes to determine N-total, P-total, C-total
were analyzed. Flow-injection kinetic methods based on and total metal concentration such as chemical digestion,
the formation of metalloporphyrin chelates of Zn in the microwave-assisted oxidation, UV-irradiation and ultra-
presence of imidazole acting as a catalyst were exploited sonic extraction were successfully coupled to flow injection
for the photometric determination of trace levels of zinc assemblies, minimizing both the analyst manipulation and
[370]. Substituted policyclic diazo-compounds were also laboratory contamination while assuring better analytical
reported as efficient chromogenic reagents for monitoring performance in terms of sampling frequency, accuracy, pre-
the target species at the low g l1 range. An automated cision and reliability than that provided by batch methods.
flow injection system based on the zincon method with Moreover, important efforts have been carried out to
differential demasking of the cyanide metal complexes adapt electrochemical techniques such as potentiometry
with cyclohexanone was described. Under the optimum with conventional electrodes or dedicated tubular ISEs, or
experimental conditions, zinc is rapidly liberated to form a those requiring stripping cycles (viz. anodic/cathodic strip-
1:1 complex with zincon, which is monitored spectropho- ping voltammetry and potentiometric stripping analysis) to
tometrically [371]. Enzymic methods with immobilized continuous flow/flow injection/sequential injection systems
bovine carbonic anhydrase relying on the measurement of for monitoring trace levels of relevant parameters in water
recovered esterase activity of the metal-free apoenzyme samples.
after taking up the metal from the sample solution were In recent years, for accurate and selective determination
presented as an alternative for the determination of low of extremely low levels of heavy metals, atomic absorp-
amounts of Zn [372]. In the field of optical sensors, a tion spectrometry and inductively coupled plasma mass
flow-through solid-phase spectrophotometric sensing device spectrometry coupled to flowing stream methods appear
with an extended dynamic range was recently devised. The to be the most attractive detection options. In this context,
integration of metal sorption, matrix removal and detection a plethora of on-line preconcentration methods have been
steps was carried out in a Helma-type flow cell contain- devised to achieve the desirable sensitivity. Among the dif-
ing 1-(2-pyridylazo)-2-naphthol immobilized on a cation ferent reported schemes, those based on incorporation of
exchanger [373]. 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-
7. Concluding remarks tioning. (Co)-precipitation/adsorption procedures involving
entrapment of the precipitate/chelate on the inner walls of
In the three parts of this series of papers, several meth- a knotted PTFE reactor, sorption of volatile species onto
ods applied to the determination of core inorganic param- coated-graphite tubes of an electrothermal atomizer and sol-
eters for water surveillance were reviewed in the field of vent extraction methods including both phase-segmentation
flowing stream techniques. Though the implementation of or wetting-film modalities should be also featured as worth-
environmental analysis in automatic devices is not always a while strategies for on-line analyte enrichment with con-
straightforward task, water samples are readily analysed by comitant matrix removal. Hydride-generation schemes are
flow techniques as demonstrated in the bulk of the text. presented as promising alternatives for the determination
Direct flow injection spectrophotometric procedures us- of ultratrace levels of metalloid species and performance of
ing moderately or highly selective chromogenic reagents speciation approaches.
are frequently devised aiming to determine both nutrients Significant progress has been also made in applying con-
and anionic species. These approaches are easily adaptable tinuous flow and flow injection spectrophotometric catalytic
to in-situ and real time monitoring of water parameters, methods for trace metal determinations as this approach is
as well as to multiparametric assays. Thus, shipboard an- proven extremely suitable for implementation in portable
alyzers have been designed and successfully deployed for devices and hence, for on-site and real-time analysis. Most
vertical distribution surveys in marine ecosystems and of such systems are based on well-known catalytic oxida-
monitoring of key analytes in coastal and estuarine wa- tion reactions of phenol or aniline derivatives as well as on
ters during various tidal cycles. The adaptation of classical the oxidative coupling of amines. Flow injection with in-line
methods to the recently developed SIA, MCFIA, MSFIA matrix removal coupled to chemiluminescence detection is
and LOV-SIA techniques together with the variety of ex- a noteworthy option owing to the high sensitivity and se-
isting injection modalities have been also reviewed. The lectivity, wide dynamic ranges, rapid analysis (seconds), ro-
versatility of the above automated systems for monitoring bustness, portability and low costs.
M. Miro et al. / Talanta 63 (2004) 201223 219

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