Chem. Anal.

(Warsaw), 51, 339 (2006)

REVIEW

Selected Problems in Speciation Analysis of Vanadium

in Water Samples**
by Krystyna Pyrzyska
Department of Chemistry, Warsaw University,
ul. Pasteura 1, 02-093 Warsaw, Poland
Keywords:

Vanadium; Speciation analysis; Separation

Two most commonly vanadium forms, V(IV) and V(V), have different toxicity and nutritious properties. Speciation of vanadium is necessary in environmental samples. The
objective of this paper is to highlight some aspects of vanadium speciation analysis, such
as stability of species and possibility of their redistribution, as well as separation techniques
and analytical methods.
Biologiczna rola wanadu i jego toksyczno zale gwnie od formy chemicznej, w jakiej
wystpuje w analizowanych prbkach. W pracy przedstawiono gwne problemy zwizane
z analiz specjacyjn wanadu, gwnie V(IV) i V(V), takie jak trwao form specjacyjnych
w roztworach, przygotowanie roztworw wzorcowych o zdefiniowanej formie chemicznej
oraz metody rozdzielania i oznaczania wanadu.

* Corresponding author. E-mail: kryspyrz@chem.uw.edu.pl

** Presented at the 7th Polish Conference on the Analytical Chemistry, Toru 37 July 2006.

340

K. Pyrzyska

The growing awareness of the strong dependence of the toxicity of elements upon
their chemical forms has led to an increasing interest in their qualitative and quantitative
determination. Speciation analysis is carried out for a number of reasons, including
characterization and evaluation of systems in environmental science, medicine, monitoring of biological processes, nutrition, and industry. Biochemical and toxicological investigations have shown that chemical forms of particular elements or oxidation states in
which they are introduced into the environment is crucial for living organisms.
Vanadium is one of the essential trace metal elements. It plays an important role in
environmental and biological systems. In geological and geochemical studies the content of vanadium in rocks, soils, and water provide information on the origin and/or
history of the sample. Vanadium is widely used in industrial processes and its compounds are released to the environment in large quantities. It can serve as a useful marker of potential release of toxic trace metals from fossil fuels, particularly oils, as it is
always present in these materials [1]. Vanadium precipitated in soil can be easily leached
by rainwater. Despite low concentration in seawater, ranging from 0.3 to 3.2 mg L1,
vanadium is accumulated at relatively high levels (0.21 mg g1) in some ascidians,
particularly belonging to the suborder of Phlebobranchia [2]. Vanadium is also accumulated, though to much lesser extent, by Amanita mushrooms and this process is unrelated to the metal content in soil [3]. Vanadium and its compounds have gained
an interest in medical and biological sciences after their biochemical activity was discovered. Biochemical activity of vanadium is based on chemical similarity of vanadate to
phosphate, which makes the former interact with numerous enzymes by either inhibiting or activating them [4, 5]. Particular case of these interactions is when vanadium
interferes with the glucose uptake processes by mimicking insulin. For some time
vanadium compounds have been considered as ideal candidates for oral anti-diabetes
drugs. Recently, however, their medical applications have become doubtful due to the
possible toxicity of prolonged administration [6]. Vanadyl ion VO2+ can be used as
a physicochemical marker of metal binding sites in proteins [7].
Despite its toxicity at higher concentration, vanadium is assumed to be an essential
element for living organisms, although its biological role is still not clear [8]. Determination of vanadium has received much attention due to its increasing importance in environmental and biological studies [911]. Moreover, speciation analysis allows one to
determine vanadium compounds, in which it appears at various oxidation states, as well
as to study different interactions of vanadium species in living organisms. The procedures used for determination of vanadium species are limited by several problems, such
as: (i) stability and possibility of redistribution, (ii) low content of several species, and
(iii) necessity of use of preconcentration and separation methods. The objective of this
paper is to highlight the above aspects of vanadium speciation analysis, performed
particularly in water samples. Vanadium is incorporated into the human body mainly

Selected problems in speciation analysis of vanadium

341

from water. For this reason determination of vanadium species in water samples is
crucial in biochemical, geochemical, and environmental studies.
Vanadium species in aqueous solution
Distribution of vanadium between different oxidation states plays an important role
in its environmental chemistry. In aqueous solutions vanadium appears at various oxidation states and ionic forms, the most common in natural waters are V(IV) and V(V).
V(V) occurs as VO2+ in acidic media and as VO43 in alkaline media. It is expected to be
the predominant form in water exposed to the atmospheric oxygen. Speciation of V(V)
is very complex as different oligomeric (n = 110) vanadate anionic species might
occur simultaneously in equilibrium (Fig. 1). In the whole pH range, several species
may coexist, however more than 90% of total vanadium consists of either 2 or 3
species [12]. Turner et al. [13] have determined distribution of vanadium in seawater
(pH ~8.2) and obtained the following results: 38% HVO42, 19% H2VO4, 43% NaHVO4, and
1% KHVO4. V(V) can be reduced to V(IV) by a number of biologically active reducing
agents, such as ascorbate, cysteine, and glutathione [4]. V(IV) in the form of vanadyl
cation (VO2+) is stable in acidic solution, but it is oxidized to the pentavalent state by
atmospheric oxygen at higher pH.
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1 mmol L1, ionic strength 1 mol L1). (Reprinted with permission from [12]. Copyright
American Chemical Society)

342

K. Pyrzyska

Solubility of vanadium species decreases when they are moved from the oxidizing
to the reducing environment. Thus, concentration of dissolved vanadium might be
an indicator of its input from reducing sources within river drainage [14]. In oceanic
sediments and its components vanadium has been examined as a possible indicator of
the redox history of specific areas [15, 16].
Both vanadium species have different nutritious and toxic properties, with V(V)
being more toxic than V(IV). Patel et al. [17] have investigated toxicological effect of
vanadium by exposing yeast cells to two stable species of this element. Yeast cells
dosed with concentrations above 200 mg L1 of toxic V(V) did not grow, whereas
those exposed to less toxic V(IV) tolerated its higher concentration. Under physical
conditions vanadium exists predominantly as either H2VO4 or VO2+. Anionic form resembles phosphate to some extent, while vanadyl cation behaves as typical transition metal
ion, which competes with others ions for coordination sites in biogenic ligands and
compounds.
Stability of species
Stability of compounds at particular oxidation states is essential for the accurate
speciation analysis of vanadium. pH, redox potential, and possibility of complexation
are important factors determining relative stabilities of V(IV) and V(V) in aqueous systems. V(IV) is stable only in acidic medium. At pH 5.6 it is gradually oxidized in deionized water and fully transformed into V(V) at pH 9 within 3 min [18]. Oxidation rates of
vanadium (IV) added to natural lake water (pH 7.7) and seawater (pH 7.9) were faster.
Solution of V(V) in deionized water was stable in the pH range of 29 [18].
In order to determine the total metal content, liquid samples are usually acidified to
dissolve large particles, to prevent hydrolysis, and to minimize the analyte loss due to its
adsorption onto the container walls. However, acidification might modify chemical
forms of the analyte or disturb the equilibrium between various species. Nukatsuka
et al. [19] have observed rapid oxidation of V(IV) spiked into artificial seawater at
pH 7.8, while V(V) was stable for several days (Fig. 2A). Oxidation proceeded slower
in artificial seawater acidified to pH 2.0. At this pH, redox potential of V(V)/V(IV)
couple was estimated as 0.76 V and oxidation of V(IV) was still possible (E of O2/H2O
couple at pH 2 is 1.1 V). It has been found that oxidation was slower in 0.01 mol L1
HCl solution [19]. On the other hand, slight reduction of V(V) was also observed under
these conditions. However, in deionized water of the same pH V(V) was hardly reduced
(Fig. 2B). In this case reduction was probably caused by the presence of natural organic matter, e.g. humic substances. The rate of this reaction might depend on the amount
of organic substances as well as on their chemical form [18]. In natural seawater
sample (acidified to pH 2.0), half-life of V(V) species was about 3 h [19]. For this
reason sample solutions should be acidified directly before the analysis and analyzed as
quickly as possible in order to correctly perform speciation of vanadium.

Selected problems in speciation analysis of vanadium

V(IV or V) found, ng mL1

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Figure 2. Oxidation state of vanadium in artificial seawater: (A) at natural pH 7.8, (B) after acidification
to pH 2.0; the samples were spiked with (a) V(IV) and (b) V(V) up to 2.0 ng mL1 [19].
(Reprinted with permission from Japan Society of Analytical Chemistry)

Distribution of vanadium species might depend also on the presence of dissolved

gases. The changes in V(IV) and V(V) concentrations after addition of both species
(up to 80 mg L1 of each) to the lake water sample (at natural pH 7.1) during its storage
are shown in Figure 3. Oxidation rate of V(IV) was slower when the sample was
degassed before determination [10].

344

K. Pyrzyska

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Figure 3. The changes in V(IV) and V(V) concentrations after addition to the lake water sample (natural
pH 7.1) stored in PTFE container; (A) before degassing, (B) degassed sample (20 min at 20C);
(Based on Ref.10, with permission from Elsevier Science)

In speciation analysis, it is important to use stock solution of the known chemical

composition and containing a given metal at the known oxidation state. For this purpose either commercially available metal standard solutions are used, or they are prepared by dissolving appropriate solid salts or pure metal in concentrated acids. We have
investigated the changes that VOSO4 undergoes in Merck standard solution (in 0.5 mol
L1 H2SO4) during storage. After 6 months of storage, blue solution became green and
about 30% decrease in the maximum absorbance of V(IV) was observed. Dark green
colour of the solution was ascribed to the presence of the mixed valence V(IV)V(V)
complex [20]. Thus, it is recommended to prepare fresh V(IV) solution every day by
dissolving vanadyl sulfate in the presence of reductant. Otherwise, the analyte is easily
oxidized by atmospheric oxygen [18, 20, 21]. Soldi et al. [22] have proposed to store
V(IV) solution under nitrogen to prevent chemical changes. Oxidation rate of V(IV)
increases with the increasing pH and temperature. Pure V(V) solution can be prepared
only by dissolving the metal in HNO3. Small amount of hydrogen peroxide (12 mL)
decreases the content of V(IV) to 1020% [23].
Separation and determination of vanadium species
It is obvious that the use of combined systems consisting of separation modules
and element-selective detections, such as liquid chromatography (LC) or capillary electrophoresis (CE), in speciation analysis is extremely advantageous. One of the most
important advantages of LC is the extended range of available separation mechanisms
using different mobile and stationary phases. However, preservation of original species
is at least as necessary as their good separation. Thus, the choice of separation mecha-

Selected problems in speciation analysis of vanadium

345

nism and reagents must not be accidental. For vanadium speciation mostly ion
exchange chromatography [2426] and reversed-phase HPLC [23, 25, 2731] have
been applied.
For successive chromatographic separation of vanadium species in natural samples
sensitive detector is required. Hyphenated techniques of liquid chromatography coupled
with AAS [17, 23], ICPOES [18, 25, 26], ICPMS [27, 28, 30, 32, 33] and spectrophotometric detection after appropriate derivatization [24, 29, 31] have been reported.
Wann and Jiang [27] have determined the content of both vanadium species in certified
water reference materials from NRCC using HPLCICPMS method. In these materials only the total vanadium content is certified. Concentrations of V(IV) and V(V) in the
open ocean seawater reference material NAAS4 was (0.61 0.06) and (0.86 0.08)
mg L1, respectively. In the near-shore seawater reference material CASS3 the ratio of
V(IV) to V(V) was 9/5 with the total vanadium concentration of (1.50 0.15) mg L1.
In the river water reference sample SLRS3 only V(IV) was found at the concentration
of (0.38 0.05) mg L1.
Examples of chromatographic determinations of vanadium species in some natural
samples are presented in Table 1.
Table 1. Exemplary results of determination of vanadium species in natural samples using chromatographic methods. TBAP tetrabutylammonium phosphate, TBABr tetrabutylammonium
bromide, TBAOH tetrabutylammonium hydroxide, g-ABHX g-aminobutylohydroxamate
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346

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Capillary electrophoresis (CE) is an alternative method to liquid chromatography in

metal speciation studies due to its high efficiency and rapid separation [34]. The possibility of modification of metal ion mobility by complexation with aminopolycarboxylic
acids has attracted much attention since these acids or their salts exhibit good solubility
in water. Formation of complexes as well as their charge can be controlled by varying
the pH. Vanadium species were chelated with EDTA, DTPA, NTA, and HEDTA to form
anionic complexes, which were separated by CE with UV detection [3537]. Chen and
Naidu [36] have examined several aminopolycarboxylic acids as derivatizing ligands
and supporting electrolytes for the on-column separation of V(IV) and V(V). Two
distinct peaks were formed in chromatograms; they were attributed to vanadium complexes with EDTA and DTPA. The complex with EDTA exhibited higher UV absorptivity and its signal was positioned at 185 nm (Fig. 4). In contrast, anionic complexes of
V(V) and V(IV) were formed only when NTA and HEDTA were used, respectively.
Presumably, these ligands were selective for specific oxidation states of vanadium.
Coupling of CE with ICPMS for vanadium speciation has been demonstrated by Yeh
and Jiang [38]. They achieved detection limit in the range of 0.10.5 mg L1. Also 4-(2pyridylazo) resorcinol has been applied in CE separation to obtain stable complexes
with both vanadium species [39, 40].
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Figure 4. Electropherograms for V(IV) and V(V) complexes with EDTA, NTA, DTPA, and HEDTA
ligands. Electrolyte: 10 mmol L1 ligand at pH 4, applied potential 20 kV, UV detection at
185 nm, concentration of each vanadium species: 0.2 mmol L1 [36]. (Reprinted with permission of Springer Science)

Selected problems in speciation analysis of vanadium

347

For vanadium speciation analysis also simple non-chromatographic separation methods can be applied. They utilise packed microcolumns to achieve maximum preconcentration capacity and flexibility. Retained species can be afterwards eluted from the
column with an appropriate reagent. Two different separation/preconcentration strategies have been employed. In the first strategy only one species: either V(IV) or V(V) is
sorbed, while the other one is either complexed or directly determined [19, 4146] after
its conversion (reduction or oxidation) and by calculating the difference after total
vanadium determination. In the second approach both vanadium species are sorbed and
then sequentially eluted [22, 42, 45, 47, 48]. Vanadium species can be also sorbed on
two different microcolumns for selective preconcentration and separation [18, 49].
The GibbsDonnan model was used to predict conditions for the separation of vanadium species applying very popular Chelex 100 chelating resin with iminodiacetate
groups [22]. The method includes sorption of both species at pH ~ 4.5 and stripping
V(V) under alkaline conditions (pH 10) and V(IV) at acidic pH (pH 0.8). The equilibrium time was 2 h. It has been observed that the oxidation state of V(IV) is highly
stable after sorption on Chelex 100, so that after sorption the procedure could be carried out in air.
The content of vanadium in natural samples is very low. Hence, sensitive methods
are required for its determination. Most of the spectrophotometric methods based on
the formation of coloured vanadium complexes are not sensitive enough without sample
pretreatment. Kinetic methods based on vanadium-catalyzed redox reactions are more
sensitive [50, 51] and the application of flow injection approach with a strict control of
reaction time improves their accuracy [52]. Electrothermal atomic absorption spectrometry (ETAAS) has been applied as a routine approach to the determination of trace
vanadium. However, some problems concerning mainly tailing of the absorbance
signal, carbide formation, and acid interferences have been encountered [5355]. Several matrix modifiers have been testing for vanadium determination by ETAAS in different kinds of samples [5658].
ICPMS offers better sensitivity for determination of vanadium than ETAAS
[5964]. The signals of diatomic 35Cl 16O+ and 34S 16OH+ ions (from the sample matrix)
overlap at m/z = 51 with the signal of the most abundant isotope of vanadium. The best
solution to the isobaric interference problem is to analyse the samples under high mass
spectral resolution ICPMS [59, 60]. At the resolution of m/Dm = 3000, the signal of
ClO+ is easily resolved from that of 51V+, even if only trace amount of this analyte is to
be determined. Dynamic reaction cell with NH3 has been also proved to be an effective
method for the elimination of spectroscopic interferences [60, 61]. A new on-line
method for removal of ClO+ mass spectral interference in vanadium determination by
quadrupole ICPMS has been proposed by Garcia-Sanchez et al. [64]. In the sample
introduction system fused silica capillary was connected with a direct injection nebulizer and treated with a strong anion exchanger containing 3-aminopropyltrimethoxy

348

K. Pyrzyska

silane functional groups. Chloride anions were retained in the capillary and interferences from ClO+ were reduced. Moreover, separation between both vanadium species
was possible in the pH range 24. V(V) was quantitatively retained as H2VO4 anion by
protonated amine groups. In the applied pH range V(IV) existed as VO2+ cation and thus
was eluted from the capillary and directly determined by ICPMS. Detection limit of
12 ng L1 was achieved, which corresponds to the absolute value of 60 pg.

CONCLUSION
Speciation analysis of vanadium is a great of importance due to the extensive
occurrence of this element and properties of its compounds. Prolonged sample manipulation may significantly affect distribution of vanadium species, particularly when
acidity, salinity, or redox potential of the sample are changing. Since sample pre-treatment should be reduced to minimum, it is preferred to use separation/preconcentration
procedures allowing determination of individual species. Application of hyphenated systems comprising separation modules (LC or EC) and element-selective detection is
obvious. However, such factors as separation mechanisms, mobile phase, pH, and the
steps of sample preparation must be carefully considered to prevent interconversion of
species and to ensure correct sample characterization.
It is crucial to assure satisfactory quality of the analytical procedure. For this purpose representative reference materials (RM), certified for the relevant species, are
used. Although several certified reference materials for vanadium containing different
matrices are available, they are only certified for the total metal content. Preparation of
certified RM for V(IV) and V(V) in water matrix is complex due to the insufficient
long-term stability of the species, as it has been already observed for inorganic selenium [65]. More research is still needed to prepare stable solution of vanadium species.

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Received August 2005

Accepted January 2006