Chemosphere 73 (2008) 572–579

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Speciation of scandium and gallium in soil

Justyna Połedniok *
Department of Analytical Chemistry, University of Silesia, 9 Szkolna Street, 40-006 Katowice, Poland

a r t i c l e i n f o a b s t r a c t

Article history: A method for the speciation of scandium and gallium in soil has been developed. The sequential extrac-
Received 27 February 2008 tion scheme of Tessier et al. for heavy metals was examined for the scandium and gallium separation. The
Received in revised form 19 May 2008 regents proposed by Tessier were used for the extraction, and only for the residual fraction the HClO4 was
Accepted 5 June 2008
replaced with H2SO4. The optimum conditions for leaching scandium and gallium from the soil were cho-
Available online 23 July 2008
sen for each fraction. Very sensitive, spectrophotometric methods based on the mixed complexes of
Sc(III) and Ga(III) with Chrome Azurol S and benzyldodecyldimethylammonium bromide were applied
Keywords:
for the scandium and gallium determination after their separation by solvent extraction. 100% mesityl
Gallium
Scandium
oxide and a 0.5 M solution of 2-thenoyltrifluoroacetone in xylene were chosen for the extraction of scan-
Soil dium and butyl acetate was selected for gallium. Soil samples from two different regions of Poland were
Speciation the object of this research. The content of scandium and gallium found in the individual fractions of
Sequential extraction Upper Silesia soil (industrial region) was [in lg g 1] Sc: I, 1.52; II, 0.53; III, 7.78; IV, 1.79; V, 0.20; Ga:
Spectrophotometry I, 24.7; III, 29.2; IV, 35.4; V, 6.9. In Podlasie soil (agricultural region), the content of both elements was
clearly lower. The total content of scandium and gallium in the five soil fractions was in good correlation
with the total content of these elements in the soils found after HF–H2SO4 digestion. Analysis using the
ICP-OES method gave comparable results.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction
Among the many chemical constituents, trace elements play an
important role in the biological environment, showing a positive or
toxic impact on the natural environment depending on their con-
centration. As a result of human economic and technological activ-
ity, particularly in industrialised areas, the natural circulation of
trace elements in the environment has been subject to interfer-
ence. Each change in the chemical balance causes not only distur-
bances in the plant or animal world, but may also have an adverse
influence on human health. One of the environmental components
from which trace elements transfer to living organisms is soil: the
principal place of accumulation of many chemical substances, pol-
luted by atmospheric dusts, solid waste dumps, plant protection
agents, mineral fertilisers and others (Kabata-Pendias and Pendias,
1992, 1999).
Gallium is a very widespread trace element. Its content in the
lithosphere amounts to 10 g/t. Gallium is a cryptomorphic element
whose average clarkes (geochemical density indicators) in the lith-
osphere are relatively high, but due to the practical inability to
form its own minerals in natural conditions, it is considered quite
rare. The gallium content in soil varies between 5 and 300 ppm
(usually 5–70 ppm). The lowest gallium concentration can be
* Tel.: +48 32 3591642; fax: +48 32 2599978.
E-mail address: justyna.poledniok@us.edu.pl
observed in light sandy and limestone soils. The presence of gal-
lium in the soil is connected with the occurrence of silty minerals.
Moreover, it is sorbed by Fe(III) and Mn(III) oxides and by an or-
ganic substance. Despite quite a large clarke (11 ppm), scandium
is also considered a rare element, hard to concentrate or separate,
which is connected with a lack of specific reagents reacting with
this element. Similar to gallium, scandium is accumulated in soil
in silty minerals and accompanies iron and magnesium minerals.
The average scandium content in soil amounts to 2–12 ppm. The
smallest content of scandium can be observed in podzols whereas
in brown soil and black-earth it is the greatest. The soil around
industrial plants exploiting the natural energy resources contains
an increased amount of the element (Kabata-Pendias and Pendias,
1999).
Scandium and gallium are the components of almost all plants.
The average scandium content is between 0.008 and several tenths
of a ppm, whereas the gallium content varies between 0.05 and
5 ppm. The biological role of Sc and Ga in the development and
functioning of plants has not been specifically defined so far. No
information on their toxicity has been reported, either. However,
there are hardly any publications concerning this question. The to-
pic still remains open, up-to-date and raised by researchers in var-
ious parts of the globe. The latest studies have proven that some
plants (lichen, the phylum Bryophyta, and also papilionaceous
plants) show the ability to accumulate gallium, even at the
60 ppm concentration level, and the larger values of Ga/Al ratio

0045-6535/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2008.06.012
 J. Połedniok / Chemosphere 73 (2008) 572–579
in land plants confirm the selective absorption of gallium. More-
over, it has been proven that Sc absorbed by plants is accumulated
in the roots, seeds and old leaves, while the accumulation is scarce
in the young leaf explants (Shtangeeva, 2005). The scandium con-
tent in the leaves of various plants and in the soil of the Brazilian
forests was compared, and a distinct correlation was observed be-
tween the amount of contaminants present and the content of
scandium in the soil. It was found that the scandium content
growth in the soil could affect its concentration in the roots of
plants and the absorbability of other significant nutrients (Ferrari
et al., 2006). The effect of scandium accumulation in the wheat
seeds on the absorbability of the macro- and micro-components
from the soils was examined, and it was found that the bioaccumu-
lation of scandium had significantly affected the changes in the
concentration of the elements that are important for the plants
(Na, K, Zn) (Shtangeeva et al., 2004). In view of the above, consid-
ering the growing pollution of soils with trace elements, including
Sc and Ga, the determination of the functional speciation of the ele-
ments in the soil seems to be advisable and helpful for further
studies on the correlations between the soil and the plant, partic-
ularly in areas subjected to various anthropogenic influences.
In the last 15 years there have been few publications concerning
scandium and gallium determination in soils. Certified materials
and real samples were analysed and the total content or concentra-
tion of these elements in soil profiles was determined. Scandium
was determined using the following analytical methods: NAA
(Schulze et al., 1997; Minowa and Ebihara, 2003; Riberio et al.,
2005), ICP-MS (Tyler, 2004), ICP-OES (Buhl and Połedniok, 1999,
2000; Tyler, 2004) and spectrophotometry (Buhl and Połedniok,
1999, 2000). As far as gallium is concerned, the most frequently
used techniques were: AAS (Langodegard and Wibetoe, 2002;
Lopez-Garcia et al., 2004) and XRF (Saini et al., 2002; Zambello
and Enzweiler, 2002; Liang et al., 2004; Yu et al., 2006), but also
AES (Sun et al., 2004), NAA (El-Ghawi et al., 2005), ICP-MS (Chan-
drajith et al., 2005) and spectrophotometry (Buhl and Połedniok,
1999, 2000). Currently, speciation is the approach more and more
frequently mentioned in scientific publications. An increased inter-
est in speciation results from the fact that the total content of a gi-
ven element does not provide satisfactory information to describe
its environmental behaviour (e.g. toxicity, bioavailability, migra-
tion, and accumulation). Most publications on speciation are de-
voted to heavy metals due to their impact on human health
(Solecki and Chibowski, 2000; Sobczyński and Siepak, 2001; Jarosz
and Mirzyńska, 2006). Research so far has been carried out for Cr,
Cd, Co, Cu, Fe, Pb, Ni, As, U, Hg, Sn, Sb, Zn, Mn and V. Various instru-
mental methods have been used, e.g. ICP-OES, ICP-MS, AAS, FIA,
HPLC, XRF and spectrophotometry. The research covered: brown
coal (Vogt, 1994), marine sediment (Marin et al., 1997), soil
(Arunachalam et al., 1996; Połedniok and Buhl, 2003) and water
(Plessow and Heinrichs, 2000; Hirose, 2006). Gallium speciation
has not been analysed so far but an article on scandium speciation
was published (Marin et al., 1997), covering the determination of
scandium in a marine sediment (Standard Reference Material
SRM 1646a) using a sequential extraction scheme recommended
by BCR and the ICP-MS technique.
The purpose of the study was to determine the speciation of
scandium and gallium in real soil samples from two different
regions of Poland: Upper Silesia (an industrial region) and Podlasie
(an agricultural region) based on the sequential extraction scheme
developed by Tessier et al. (1979) for heavy metals (Cd, Co, Cu, Ni,
Pb, Zn, Fe and Mn). For the determination of scandium and gallium,
very sensitive, spectrophotometric methods developed in the
Department of Analytical Chemistry of the University of Silesia
were used. The methods are based on the mixed complexes Sc(III)
and Ga(III) with Chrome Azurol S (CAS) and benzyldodecyldime-
thylammonium bromide (ST) (eSc = 1.37  105 and eGa =
573
1.10  105 L mol 1 cm 1) (Kwapulińska et al., 1993; Kwapulińska,
1995). The scandium determination was preceded by Sc(III) extrac-
tion with 100% mesityl oxide (TM) from an ammonium thiocyanate
solution (Kwapulińska et al., 1993) or a 0.5 M solution of
2-thenoyltrifluoroacetone (TTA) in xylene (Buhl and Połedniok,
1999). The gallium determination was preceded by Ga(III) extrac-
tion with butyl acetate (Buhl and Połedniok, 1999).
2. Experimental
2.1. Apparatus
A DR/2010 (Hach, USA) VIS spectrophotometer was used for the
research.
The spectrometric measurements were carried out in a Spectro-
flame-ICP type M (Spectro Analytical Instruments, Germany) spec-
trometer. The operating conditions were as follows: power 1.1 kW,
frequency 27.12 MHz, nebuliser gas Ar 1.0 L min 1, coolant gas
14.0 L min 1, auxiliary gas 0.5 L min 1, amount of dosed sample
1 mL min 1, viewing height over induction coil 11 mm, dispersion
of grating in 1st reciprocal order 0.55 nm mm 1.
pH-meter type N-517 (Mera Elwro, Poland). Universal Shaker
type 327 (Premed, Poland).
2.2. Reagents and standard solutions
All reagents used in the study were analytically pure
reagents. Doubly distilled water obtained from an ELIX3 (Millipore,
Molsheim, France) was used during the experiments.
Scandium(III) standard solution: 1 mg mL 1 (Promochem,
Poland). The working solutions were prepared by the appropriate
dilution of the scandium(III) standard solution with the 1 
10 2 M HCl. Gallium(III) standard solution: 1 mg mL 1 (Wzormat,
Warsaw, Poland). The working solutions were prepared by the
dilution of the gallium (III) standard solution with 1  10 3 M
HCl. Chrome Azurol S (CAS) was purchased from Fluka (Buchs,
Switzerland): 1.43  10 3 M and 5  10 4 M aqueous solutions
were used for the research. Benzyldodecyldimethylammonium
bromide: 10% commercial product Sterinol (ST) was from Polfa
(Cracow, Poland): 1.43  10 2 M and 5  10 2 M aqueous
solutions were used in the studies. TM: 100% mesityl oxide (Fluka,
Buchs, Switzerland). TTA: a 0.5 M solution in xylene was made
from 2-thenoyltrifluoroacetone (Fluka, Buchs, Switzerland). Xylene
(POCh Gliwice, Poland). Butyl acetate (POCh Gliwice, Poland). AA: a
50% solution in chloroform was made from acetylacetone
(Ubichem, Hampshire, England). Chloroform (POCh Gliwice,
Poland). Ascorbic acid (Polfa, Cracow, Poland): aqueous solutions
were prepared directly before using. Magnesium chloride
(MgCl2
6H2O), sodium acetate and ammonium thiocyanate were
from (POCh Gliwice, Poland). Hydroxylamine hydrochloride and
ammonium acetate (POCh Gliwice, Poland): a 0.04 M solution in
25% CH3COOH and a 3.2 M solution in 20% HNO3, respectively,
were used for the research. Hydrogen peroxide: 30% (POCh
Gliwice, Poland). Hydrochloric acid (POCh Gliwice, Poland): 35–
38%. Hydrofluoric acid (POCh Gliwice, Poland): 40%. Nitric acid
(Fluka, Buchs, Switzerland): 65%. Sulfuric acid (Hetalab, USA):
96%. Acetic acid (POCh Gliwice, Poland): 99.5%.
2.3. Sampling and sample preparation
Soil samples were collected from the arable layer (0–20 cm) of
two Polish fields located in Upper Silesia (Da˛brówka Wielka) and
Podlasie (Biała Podlaska) and prepared according to the procedure
described in Polish Standard PN-R-04031 (1997). Next, the samples
were dried at room temperature for 7 days and after division by
574 J. Połedniok / Chemosphere 73 (2008) 572–579
the coning and quartering method the samples were ground in an
agate mortar. The grain size was less than 200 lm.
Soil from Upper Silesia is brown soil developed in weakly struc-
tured clayey sands and loams. Soil from Podlasie is white soil.
Brown soils in most cases originate from rocks abundant with
plant nutrition components and calcium. They are characterised
by a well-formed accumulation level, gray or brown coloured,
gradually turning into an intensive weathering, gray-brown col-
oured strata (Bac et al., 1999). The reaction of the soils is slightly
acid or neutral, i.e. the best for crop growth. The intensive biolog-
ical circulation of the mineral components prevents their washing
into the depth of the soil and facilitates their accumulation on the
upper levels. The fast mineralisation of the forest rainfall and
favourable direction of its humification prevent the accumulation
of acid overlay humus and production of more fulvic acids that
would enable the movement of soil mineral weathering product
into the depth of the soil (Bednarek and Prusinkiewicz, 1997).
White soils are formed from vernacular formations with low nutri-
ent content. The soils have an acid or slightly acid reaction, high
hydrolytic and exchangeable acidity and a very low basic cation
saturation ratio, which makes some of the nutrients unavailable
to the plants. The moving humus acids, washed from the overlay
humus, with their complexation abilities, play the most important
role in the genesis of white soils. The humus acids (mainly the ful-
vic acid fraction) create easily soluble complex connections with
iron and aluminium ions in the upper part of the profile (Bednarek
and Prusinkiewicz, 1997).
2.4. Leaching procedure
Fraction 1: The soil sample (scandium: 2 g; gallium: 1 g for
Upper Silesia soil and 2 g for Podlasie soil) was extracted at room
temperature with, respectively, Sc: 10 mL and Ga: 8 mL of 1 M
MgCl2 (pH 7) with continuous agitation. Next, the mixture was fil-
tered using a filter with medium wide pores (Spezialpapierfabrik
Niederschlag, Germany; yellow label filter no. 389) and the filtrate
was diluted to 50 mL with water.
Fraction 2: The solid residue from fraction 1 was leached at
room temperature with continuous agitation with 1 M sodium ace-
tate adjusted to pH 5 with acetic acid. The 8 mL of CH3COONa was
used in the case of gallium and 10 mL was applied in the case of
scandium. After that, the mixture was filtered according to the pro-
cedure described above.
Fraction 3: The solid residue from fraction 2 was extracted with
20 mL of 0.04 M NH2OH
HCl in 25% acetic acid at 96 ± 3 °C with
occasional agitation. Next, the mixture was filtered and the filtrate
was evaporated to dryness. The dry residue was dissolved and di-
luted to 50 mL with 0.1 M HCl.
Fraction 4: The following solutions were added to the solid res-
idue from fraction 3: 3 mL of 0.02 M HNO3 and 5 mL of 30% H2O2
adjusted to pH 2 with HNO3, and the mixture was heated to
85 ± 2 °C with occasional agitation (time 1). Next, 3 mL of 30%
H2O2 (pH 2 with HNO3) was added and the sample was heated
again to 85 ± 2 °C with occasional agitation (time 2). After cooling,
2 mL of 3.2 M ammonium acetate in 20% HNO3 was added, and the
sample was diluted to 20 mL with water and agitated continuously
for 30 min. The mixture was filtered and the filtrate was evapo-
rated to dryness. The dry residue was dissolved and diluted to
50 mL with 0.1 M HCl.
Fraction 5: The residue from fraction 4 was digested in a plati-
num crucible with conc. HF–H2SO4 mixture. For 1 g of the sample,
1 mL of H2SO4 and 10 mL of HF were used for the first time and
7 mL of HF was used for the second time. The obtained solution
was evaporated to dryness and the residue was dissolved and
diluted to 25 mL with 0.5 M HCl.
2.5. Scandium separation and determination
Fractions 1, 2, 4 or 5. The following solutions were placed in
25 mL beakers: 5 mL of the solution obtained after the leaching
of fractions: 1, 2 or 4; 2 mL of the solution obtained after the diges-
tion of fraction 5 and 5 mL of ammonium thiocyanate solution con-
taining 1.425 g NH4SCN. Next, the pH was adjusted to 1 with HCl
using a pH-meter and water was added to make the volume of
the solutions about 12.5 mL. The samples were then transferred
into 50 mL separatory funnels and scandium was extracted with
5 mL of 100% mesityl oxide for 2 min. The water phase was re-
jected and Sc was reextracted twice from the organic phase with
10 mL and 5 mL of 0.2 M HCl for 2 min. The reextracts (15 mL)
were place in a 100 mL beaker and evaporated to dryness. The res-
idue was dissolved in water and transferred quantitatively into a
measuring flask. Then 1 mL of a pH 5 acetate buffer solution,
4 mL of 5  10 4 M CAS and 0.66 mL of 5  10 2 M ST were added
subsequently to the flask and the mixture was diluted to 25 mL
with water. The absorbance was measured in 1 cm long glass cells
at k = 610 nm against a reagent blank.
Fraction 3: The following were placed in a 50 mL separatory fun-
nel: 3 mL of the solution obtained after the leaching of fraction 3,
0.5 mL of 0.5 M HCl and 7 mL of water. Scandium was extracted
twice with 5 mL of a TTA solution in xylene for 5 min. The water
phase was rejected and the both organic phases were washed with
5 mL of 0.03 M HCl (10 s). After that, the scandium was reextracted
with 10 mL of 2 M HCl for 5 min. The reextract was washed with
5 mL of xylene (10 s), transferred into a 100 mL beaker and evapo-
rated to dryness. Next, 1 mL of conc. HNO3 was added to the beaker
and the sample was evaporated to dryness again. Finally, the resi-
due was dissolved in water and transferred into a 25 mL measuring
flask. Then the colour reaction with CAS and ST was developed and
the measurements were carried out according to the procedure
described above.
The scandium concentration was found from the calibration
graphs (obtained after extraction) in the range: 0.04–0.50 lg mL 1
(a = 0.0898, b = 0.0298, r = 0.9996) for 100% TM and 0.04–
0.40 lg mL 1 (a = 0.117, b = 0.044, r = 0.9998) for a TTA solution
in xylene.
2.6. Gallium separation and determination
Fractions 1, 2, 3, 4 or 5. The following solutions were placed in
25 mL beakers: 3 mL of the solution obtained after the leaching of
fractions 1 or 4; 5 mL of the solution obtained after the leaching
of fractions 2 or 3; 5 mL of the solution obtained after the digestion
of fraction 5. Next, the pH was adjusted to about 1.5–2.0 with HCl
using a pH-meter. The samples were then transferred into 100 mL
separatory funnels and ascorbic acid was added: 2 mL of a 1%
ascorbic acid solution was used for the reduction of Fe(III)
contained in fractions 1 and 2, 2 mL of a 5% solution was used
for fractions 3 and 4, whereas 5 mL of a 25% solution was used
for fraction 5.
After 10 min., the solutions were diluted to 10 mL with water.
Next, 10 mL of conc. HCl and 20 mL of butyl acetate were added
and gallium was extracted for 1 min. Then the water phase was re-
jected and the organic phase was washed twice with 2.5 mL of a
6 M HCl solution. After that, gallium was reextracted twice for
1 min. with 10 mL of water. The reextracts (20 mL) were
evaporated in 100 mL beakers until the solutions reached a pH of
3.7–4.0. Then the solutions were quantitatively carried to 25 mL
measuring flasks and 1 mL of a pH 4.5 acetate buffer solution,
2 mL of 1.43  10 3 M CAS and 2 mL of 1.43  10 2 M ST were
added. Finally, the mixtures were diluted with water up to the
mark. The absorbance was measured in 1 cm long glass cells at
k = 620 nm against a reagent blank. The content of gallium was

found from the calibration graph obtained after extraction in the
range: 0.12–0.40 lg mL 1. The linear regression coefficients were:
a = 0.049, b = 0.011, r = 0.9995.
3. Results and discussion
3.1. Optimisation of scandium and gallium leaching
Weight of samples. Preliminary studies showed that the total
content of gallium and scandium obtained after digestion of the
samples with the HF–H2SO4 mixture was, respectively [in
lg g 1] – Upper Silesia soil: 94.7 and 11.1; Podlasie soil: 41.6
and 2.2. Therefore, the weight of soil samples chosen for the
research was: scandium: 2 g; gallium: 1 g for Upper Silesia soil
and 2 g for Podlasie soil.
Effect of extractants: The reagents proposed by Tessier et al.
(1979) were applied for the partitioning of scandium and gallium
into the five soil fractions. The NH2OH
HCl solution was chosen
for the leaching of fraction 3. Other extractants used by Tessier
et al. for this fraction interfered in the CAS-ST determination. In or-
der to improve the safety of work, conc. HClO4 was replaced with
conc. H2SO4 and the residual fraction was digested using the HF–
H2SO4 mixture. The maximum concentration of gallium in all soil
extracts and scandium in fractions 3–5 were obtained following
the Tessier method. In the case of fractions 1 and 2, the optimum
volume of reagents for scandium extraction was, respectively:
10 mL of 1 M MgCl2 and 10 mL of 1 M CH3COONa.
Effect of temperature: The temperatures of extraction suggested
by Tessier et al. (1979) were optimum for scandium and gallium
leaching from the soil: room temperature for fractions 1 and 2,
96 ± 3 °C for fraction 3 and 85 ± 2 °C for fraction 4.
Effect of time: Figs. 1–3 show the influence of time on the effi-
ciency of scandium and gallium extraction from the soil. The con-
centration of Sc(III) and Ga(III) in the MgCl2 (pH 7) leaching
solution (fraction 1) reached the maximum value after 0.5 h of
extraction and it was stable for the next 1 h (Fig. 1). The concentra-
tion of Sc(III) in the CH3COONa (pH 5) leaching solution used for
the separation of fraction 2 reached the maximum value after 1 h
and then slowly reduced with time, whereas the concentration of
Ga(III) – for both examined soils – was less than the detection limit
of the applied method even after 5 h of extraction. It means that
1000
Concentration of scandium and gallium [ μg L-1]
900
800
700
600
500
400
300
200
100
0
0.5
Fig. 1. Effect of leaching time on scandium and gallium concentration in the MgCl2 extracting solution (pH 7); error bars (±SD).
J. Połedniok / Chemosphere 73 (2008) 572–579 575
gallium does not form compounds with carbonates in soil. Fig. 2
indicates that content of scandium and gallium in NH2OH
HCl
solution applied for the isolation of fraction 3 was at the maximum
level after 0.5 h of extraction and it was stable for 1 h and 1.5 h,
respectively. Next, the maximum value was clearly decreasing
with time. Probably the elements from the leaching solution were
adsorbed on the surface of the soil. Fig. 3 shows that the optimum
time for scandium and gallium leaching from the fraction 4 was the
combination: 1.5 h + 1.5 h (Sc) and 2 h + 2 h (Ga). Gallium concen-
tration in the HNO3–H2O2 mixture was comparable for all times
that were examined, whereas scandium concentration after the
optimum time was clearly lower. Fraction 5 (residual) was
digested with conc. HF and conc. H2SO4 until the white fumes of
SO3 appeared. Next, the second part of HF was added, then the
mixture was evaporated to dryness and the solid residue was dis-
solved in the HCl solution. The suitable time of dissolving was
40 min.
The optimum time of soil leaching chosen for further research
was the following, scandium: 1 h for fractions: 1, 2, 3 and combi-
nation (1.5 + 1.5) h for fraction 4; gallium: 1 h for fractions: 1, 3
and a combination (2 + 2) h for fraction 4.
The optimum time of dissolving of fraction 5 for both elements
was 40 min.
3.2. Selectivity of separation
The methods of scandium and gallium separation by the solvent
extraction were elaborated using model solutions containing
macro- and micro-components of soil and reagents proposed by
Tessier for the leaching. The criterion for interference was the con-
tent of scandium and gallium varying by more than 5% from the
expected value for these elements alone.
Scandium. It was shown that 100% mesityl oxide separated 5 lg
Sc(III) from 100 mg Ca(II), 30 mg Mg(II), 5 mg Mn(II) and Cr(III),
2 mg Al(III), 0.5 mg Zn(II) and In(III), 150 lg Fe(III), 50 lg Ga(III),
Cu(II) and Mo(VI), and 500 mg acetate (Table 1). NH2OH
HCl inter-
fered in the CAS-ST scandium determination after extraction with
mesityl oxide: absorbance of the complex was clearly lower. The
solution of TTA in xylene separated 5 lg Sc(III) from 100 mg Mg(II),
75 mg Ca(II), 5 mg Cr(III) and Zn(II), 0.5 mg Mo(VI), 100 lg Al(III),
50 lg V(V), 50 lg Ga(III), 10 lg In(III), 5 lg Fe(III) and 5.5 mg
Gallium in Upper Silesia soil
Scandium in Upper Silesia soil
Gallium in Podlasie soil
1 1.5 2 3 5
Time [h]
576 J. Połedniok / Chemosphere 73 (2008) 572–579

800

Concentration of scandium and gallium [μg L-1]

700 Gallium in Upper Silesia soil
Scandium in Upper Silesia soil
Gallium in Podlasie soil
600

500

400

300

200

100

0
0.5 1 1.5 2 3 5
Time [h]

Fig. 2. Effect of leaching time on scandium and gallium concentration in the NH2OH
HCl extracting solution (pH 2); error bars (±SD).

1400
Concentration of scandium and gallium [µg L-1]

Scandium in Upper Silesia soil

1200
Gallium in Upper Silesia soil
Gallium in Podlasie soil

1000

800

600

400

200

0
(1+1) (1.5+1.5) (2+2) (2+3)

Time [h]

Fig. 3. Effect of leaching time on scandium and gallium concentration in the HNO3 + H2O2 extracting solution (pH 2).

NH2OH
HCl (Table 1). Therefore, 100% mesityl oxide was chosen from Ga(III) using butyl acetate. The concentration and volume of
for the scandium separation from fractions: 1, 2, 4 and 5, and the ascorbic acid was chosen experimentally for each fraction and it
solution of TTA in xylene was applied for scandium separation is presented in Section 2.6.
from fraction 3 instead. Before scandium extraction using TTA
and mesityl oxide (from fractions: 3, 4 and 5) Fe(III) was previously 3.3. Determination of scandium and gallium in synthetic mixture
separated by solvent extraction with 20 mL of a 50% solution of
acetylacetone in CHCl3 at pH 1. The optimum time of extraction Scandium and gallium were found in a synthetic mixture using
was 5 min. The number of extractions was chosen experimentally the CAS-ST method after extraction with mesityl oxide, TTA and
for each fraction and it was: 5 for fractions 3 and 5; 3 for fraction 4. butyl acetate, respectively.
Ions of Al(III) were separated simultaneously with Fe(III). The synthetic mixture shows the average composition of the
Gallium. It was pointed out that butyl acetate separated 10 lg soil (in a sample with the mass of m = 0.1 g), i.e. the content of
Ga(III) from 60 mg Al(III), 22 mg Ca(II), 13 mg Mg(II), 100 lg In(III), macro- and micro-elements: 1 mg Ca(II), 0.5 mg Mg(II), 2 mg
Cu(II), Zn(II) and Mo(VI), 75 lg Mn(II), 50 lg Cr(III), 10 lg Sc(III), Al(III), 2 mg Fe(III), 10 lg Cu(II), 60 lg Mn(II), 5.5 lg Cr(III),
57 mg acetate and 5.5 mg NH2OH
HCl (Table 2). The coextraction 0.25 lg Mo(VI), 15 lg Zn(II), 10 lg Pb, 10 lg V(V) and 1 lg In(III)
of Ga(III) and Fe(III) was observed: the absorbance was clearly (Wa˛chalewski, 1997). Before the analysis, 5 lg of Sc(III) and
above normal. Therefore, Fe(III) was reduced to Fe(II) with ascorbic 10 lg of Ga(III) were added to each sample. The results obtained
acid (t = 10 min) before the gallium extraction. Fe(II) is separated are shown in Tables 1 and 2. The extraction with mesityl oxide,
 J. Połedniok / Chemosphere 73 (2008) 572–579 577

Table 1
Recovery of scandium in presence of various soil compounds and reagents applying TM and TTA solvent extraction

Extractant Foreign ions, reagents Sc added (lg) Sc founda (lg) RSD (%) Recovery (%)
TM Ca(II) 100 mg 5 4.78 ± 0.24 2.0 95.6
Mg(II) 30 mg 5 4.79 ± 0.44 3.7 95.8
Mn(II) 5 mg 5 5.00 ± 0.59 4.8 100.0
Cr(III) 5 mg 5 5.14 ± 0.42 3.3 102.8
Al(III) 2 mg 5 4.83 ± 0.36 3.0 96.6
Zn(II) 0.5 mg 5 5.18 ± 0.21 1.6 103.6
In(III) 0.5 mg 5 5.20 ± 0.65 5.1 104.0
Fe(III) 150 lg 5 4.98 ± 0.31 2.5 99.6
Cu(II) 50 lg 5 5.00 ± 0.43 3.5 100.0
Mo(VI) 50 lg 5 5.10 ± 0.38 3.1 102.0
Ga(III) 50 lg 5 5.14 ± 0.67 5.3 102.8
Acetate 500 mg 5 4.80 ± 0.32 2.7 96.0
Synthetic mixtureb 5 5.08 ± 0.43 3.4 101.6
TTA Mg(II) 100 mg 5 5.25 ± 0.51 3.9 105.0
Ca(II) 75 mg 5 5.00 ± 0.47 3.8 100.0
Zn(II) 5 mg 5 4.83 ± 0.32 2.7 96.6
Cr(III) 5 mg 5 5.11 ± 0.28 2.2 102.2
Mo(VI) 0.5 mg 5 5.09 ± 0.24 1.9 101.8
Al(III) 100 lg 5 5.15 ± 0.51 4.0 103.0
V(V) 50 lg 5 4.90 ± 0.39 3.2 98.0
Ga(III) 50 lg 5 5.10 ± 0.44 3.5 102.0
In(III) 10 lg 5 4.85 ± 0.48 4.0 97.0
Fe(III) 5 lg 5 5.15 ± 0.34 2.7 103.0
NH2OH
HCl 5.5 mg 5 4.87 ± 0.26 2.3 97.4
Synthetic mixtureb 5 4.79 ± 0.43 3.6 95.8
a
Average of three replicates of each sample: x3 ± t0.95 SD – confidence interval at a probability level of 95%; t0.95 – student’s coefficient.
b
Synthetic mixture with average content of macro- and micro-components of soil in a sample with the mass of 0.1 g.

Table 2
Recovery of gallium in presence of various soil compounds and reagents applying butyl acetate solvent extraction

Extractant Foreign ions, reagents Ga added (lg) Ga founda (lg) RSD (%) Recovery (%)
Butyl acetate Al(III) 60 mg 10 10.30 ± 0.73 2.8 103.0
Ca(II) 22 mg 10 9.96 ± 0.30 1.2 99.6
Mg(II) 13 mg 10 10.00 ± 0.35 1.4 100.0
In(III) 100 lg 10 10.10 ± 0.85 3.4 101.0
Cu(II) 100 lg 10 9.86 ± 0.86 3.3 98.6
Zn(II) 100 lg 10 9.65 ± 0.98 4.1 96.5
Mo(VI) 100 lg 10 9.70 ± 0.65 2.7 97.0
Mn(II) 75 lg 10 10.10 ± 0.86 3.5 101.0
Cr(III) 50 lg 10 10.40 ± 0.82 3.2 104.0
Sc(III) 10 lg 10 10.10 ± 0.73 3.0 101.0
Acetate 57 mg 10 10.00 ± 1.24 5.0 100.0
NH2OH
HCl 5.5 mg 10 10.10 ± 0.39 1.6 101.0
Synthetic mixtureb 10 10.20 ± 0.77 3.1 102.0
a
Average of three replicates of each sample: x3 ± t0.95 SD – confidence interval at a probability level of 95%; t0.95 – student’s coefficient.
b
Synthetic mixture with average content of macro- and micro-components of soil in a sample with the mass of 0.1 g.

TTA and butyl acetate makes it possible to separate 5 lg of Sc(III)
and 10 lg of Ga(III) from the elements present in 0.1 g of soil, as
well as to determine scandium and gallium in a reliable way. It
points to the possibility of using the extractants in the analysis
of real samples.
3.4. Speciation of scandium and gallium in soil
The content of gallium in individual fractions of soil from Upper
Silesia was [in lg g 1]: fraction 1, 24.7; fraction 3, 29.2; fraction 4,
35.4; fraction 5, 6.9 and it was the highest in the organic fraction,
indicating of input by anthropogenic activities (due to the complex-
ation properties of natural organic matter and the accumulation of
trace metals in living organisms (Tessier et al. (1979)). The organic
fraction constitutes an important source of the potentially available
gallium and the information to estimate the pollution of the region.
While evaluating the anthropogenic activity, the properties of the
soil in question must certainly be considered (including the mineral
content in the soil, pH, organic matter type or rather the quantitative
share of its various forms), which also affect the metal content in this
fraction. The content of scandium in Upper Silesia soil was following
[in lg g 1]: fraction 1, 1.52; fraction 2, 0.53; fraction 3, 7.78; fraction
4, 1.79; fraction 5, 0.20. The highest concentration of scandium was
found in fraction Fe–Mn oxides. In Podlasie soil, the content of gal-
lium was clearly lower than in Upper Silesia soil and it was [in
lg g 1]: fraction 1, 20.0; fraction 3, 10.3; fraction 4, 12.0. The concen-
tration of scandium in all fractions and gallium (fraction 2 and 5) was
less than detection limit of the applied method. The precision of the
results was satisfactory. The relative standard deviation (RSD, n = 6)
for scandium determination was in the range from 4.3% to 11.4% and
it depended on scandium content in the fraction. In the case of gal-
lium, the RSD was higher; between 7.8% and 15% (Table 3). In order
to assess the reliability of the results obtained and the accuracy of the
methods developed, the total content of Sc and Ga was determined in
both soils examined, following the procedure given for fraction 5.
The recovery of the Sc and Ga standards (introduced in the samples
of the soils at the beginning of the analysis) was examined, following
the same way as in the determination of the total content of the ele-
578 J. Połedniok / Chemosphere 73 (2008) 572–579

Table 3
Content of scandium and gallium in particular fractions of Upper Silesia and Podlasie soils determined by spectrophotometric and ICP-OES methods

Region Fraction Spectrophotometry CAS-ST method ICP-OES method

x6 ± t0.95 SD, lg g 1; RSD (%) x6 ± t0.95 SD, lg g 1
; RSD (%)
Ga Sc Ga Sc
Upper Silesia 1 24.7 ± 2.33 (9.0) 1.52 ± 0.14 (8.6) 20.1 ± 0.95 (4.5) 1.63 ± 0.18 (10.5)
2 – 0.53 ± 0.06 (11.4) – 0.42 ± 0.06 (12.7)
3 29.2 ± 3.06 (10.0) 7.78 ± 0.35 (4.3) 29.7 ± 1.88 (6.0) 7.04 ± 0.16 (2.5)
4 35.4 ± 4.08 (11.0) 1.79 ± 0.10 (5.5) 34.6 ± 2.62 (7.2) 1.95 ± 0.16 (7.6)
5 6.9 ± 1.08 (15.0) 0.20 ± 0.02 (11.2) 6.7 ± 0.58 (8.3) 0.23 ± 0.33 (13.5)
P
96.2 11.82 90.1 11.27
Totala 94.7 ± 3.58 (3.6) 11.10 ± 0.46 (4.0) 93.2 ± 7.14 (7.3) 12.70 ± 0.11 (0.8)
Podlasie 1 20.0 ± 1.60 (7.8) – 19.6 ± 1.29 (6.2) –
2 – – – –
3 10.3 ± 0.97 (9.0) – 10.8 ± 0.96 (8.5) –
4 12.0 ± 1.37 (10.9) – 11.6 ± 1.22 (10.0) –
5 – – – –
P
42.3 – 42.0 –
Totala 41.6 ± 3.19 (7.3) 2.2 ± 0.18 (7.8) 38.3 ± 3.75 (9.3) 2.0 ± 0.20 (9.2)

All numbers in this table are mean values. Standard deviation (SD) and relative standard deviation (RSD) based on six replicate analysis; x6 ± t0.95 SD – confidence interval at a
P
probability level of 95%; t0.95 – student’s coefficient; – summary content (1–5).
a
Total content found after digestion of soil with concentrated HF–H2SO4 mixture.

ments in the soil and in fraction 5. Simultaneously, the parallel anal-
ysis of the samples was carried out by another analytical method –
the ICP-OES technique. The samples for the analysis were prepared
in the same way as for the spectrophotometric methods, only the
Fe(III) reduction, Fe(III) extraction and colour reaction steps were
omitted. Measurements were carried out at the wavelength
k = 294.364 nm in the case of gallium and k = 361.384 nm in the case
of scandium. The content of the elements was found from the cali-
bration graphs in the range: 0.12–2.0 lg mL 1 for gallium and
0.05–2.0 lg mL 1 for scandium. The results obtained are presented
in Tables 3 and 4. The comparison of the total content to the sum-
P
mary content of Sc and Ga in the particular fractions ( ) reaching
the probability level of 95% confirms the reliability of the results.
The recovery of the Sc and Ga standards (Table 4) is satisfactory,
being at the level of 92–95%, which suggests good accuracy for both
methods. The sample analysis with the use of the ICP-OES technique
gave comparable results, which also indicates the good accuracy of
the said methods and the possibility to use them for the analysis of
soils in terms of functional speciation.
3.5. Comparison of spectrophotometric methods with the ICP-OES
technique
The limit of quantification (LOQ = 3 LOD; limit of detection)
indicated for the determination of Sc with the use of the spectro-
photometric method and the ICP-OES technique is comparable
and amounts to [lg mL 1]: 0.0195 and 0.0200, respectively. For
gallium, however, the LOQ of the spectrophotometric method is
significantly lower (0.0232) than the ICP-OES techniques
(0.0500), which indicates its higher sensitivity and predisposes it
for determination of lower concentrations of this element in soils.
The linear working range is more extensive in the case of the ICP-
OES technique; however, when determining Sc and Ga in soils, due
to their low concentration level, it is practically insignificant. The
precision of both methods depends on the concentration of the ele-
ments. The precision of the ICP-OES is better (Table 3) for deter-
mining Sc occurring in higher concentrations (total content,
fraction 3 of Upper Silesia soil). While determining very low Sc
concentrations (fractions 1, 2, 4 and 5 of Upper Silesia soils) the
RSD values calculated for the spectrophotometric method are sig-
nificantly lower (Table 3), which indicates the better precision of
this particular method. Due to the low contents of scandium in
the soils, spectrophotometry seems to be a more suitable method
of analysing this material than the ICP-OES technique. In the case
of gallium, spectrophotometry is more precise for the determina-
tion of higher concentrations, while the ICP-OES technique is more
suitable for the lower concentrations of this element (Table 3).
Considering the economic aspect (the cost and availability of appa-
ratus) the spectrophotometric methods presented can be recom-
mended for the determination of the Sc and Ga content in soils
for practically any laboratory with basic analytical equipment.

Table 4
Determination of the total content of scandium and gallium in soil: checking the 4. Conclusions
standard recovery

Region Element Addeda Foundb x3 ± t0.95 SD Average standard The sequential extraction procedure developed by Tessier et al.
(lg) (lg) recovery (%) (1979) for heavy metals was examined for the speciation of scan-
Upper Ga – 3.79 ± 0.17 93.5 dium and gallium in soil. The soil from industrial and agricultural
Silesia 4.8 8.28 ± 0.35 regions of Poland was the object of this research.
Sc – 2.76 ± 0.14 92.3 The results obtained indicate that gallium content in the indi-
2.6 5.16 ± 0.25
vidual fractions of both soils clearly depends on the region (except
Podlasie Ga – 1.67 ± 0.17 93.8 exchangeable and carbonate fractions) and the total concentration
3.2 4.67 ± 0.47
Sc – 0.55 ± 0.05 95.0
of gallium. The content of gallium was the highest in the organic
1.0 1.50 ± 0.13 fraction of Upper Silesia soil (industrial region). In Podlasie soil
a
(agricultural region) the content of gallium was clearly lower.
Per analysed sample: 0.5 g of soil was digested with conc. HF–H2SO4 mixture
and diluted to 25 mL (Ga) or 10 mL (Sc) with HCl; 2 or 5 mL of the solutions,
The absence of gallium in fraction 2 of Upper Silesia and Podlasie
respectively, were taken to the analysis. soils shows that gallium does not form compounds with carbon-
b
Average of three replicates of each sample: x 3 ± t0.95 SD – confidence interval at ates. The content of gallium found in the exchangeable fraction
a probability level of 95%; t0.95 – student’s coefficient. was similar for both soils. It indicates the constant amount of Ga
 J. Połedniok / Chemosphere 73 (2008) 572–579
accessible for plants, which does not depend on the total concen-
tration of this element in the soil.
The speciation of scandium was determined only in Upper Sile-
sia soil. The concentration of Sc in individual fractions of Podlasie
soil was less than the detection limit of the applied methods. The
content of scandium in Upper Silesia soil was the highest in Fe–
Mn oxides fraction. It was in good correlation with literature data
concerning the occurrence of scandium in soils (Kabata-Pendias
and Pendias, 1999). The content of scandium found in the organic
fraction of the soil was considerably lower than in the case of gal-
lium and near to the content of Sc in the exchangeable fraction.
The low content of scandium and gallium in fraction 5 confirms
the inability of these elements to form their own minerals.
The sequential extraction scheme of Tessier et al. and spectro-
photometric methods based on the mixed complexes Sc(III) and
Ga(III) with Chrome Azurol S and benzyldodecyldimethylammoni-
um bromide can be recommended for gallium speciation in soils
from industrial and agricultural areas and for scandium speciation
in soils with high content of this element.
References
Arunachalam, J., Emons, H., Krasnodebska, B., Mohl, C., 1996. Sequential
extraction studies on homogenized forest soil samples. Sci. Total Environ.
181, 147–159.
Bac, S., Gonel, Z., Krymuski, J., 1999. Foundations of Crop Production. Państwowe
Wydawnictwo Rolnicze i Leśne, Warsaw.
Bednarek, R., Prusinkiewicz, Z., 1997. Geography of Soils. PWN, Warsaw.
Buhl, F., Połedniok, J., 1999. Content of scandium, gallium and vanadium in Upper
Silesia soil. Arch. Environ. Prot. 25, 117–123.
Buhl, F., Połedniok, J., 2000. The comparison of gallium, vanadium and scandium
content in soil from industrial and agricultural regions. Roczniki gleboznawcze
51, 67–75.
Chandrajith, R., Dissanayake, C.B., Tobschall, H.J., 2005. The abundances of rare trace
elements in paddy (rice) soils of Sri Lanka. Chemosphere 58, 1415–1420.
El-Ghawi, U.M., Bejey, M.M., Al-Fakhri, S.M., Al-Sadeq, A.A., Doubali, K.K., 2005.
Analysis of Libyan arable soils by means of thermal and epithermal NAA. Arab. J.
Sci. Eng. 30, 147–163.
Ferrari, A.A., Franca, E.J., Fernandes, E.A.N., Bacchi, M.A., 2006. Surface
contamination effects on leaf chemical composition in the Atlantic Forest. J.
Radioanal. Nucl. Chem. 270, 69–73.
Hirose, K., 2006. Chemical speciation of trace metals in seawater: a review. Anal. Sci.
22, 1055–1063.
Jarosz, M., Mirzyńska, B., 2006. Some Problems of Environmental Speciation
Analysis of Heavy Metals. Publishing House of Warsaw Technical University,
Warsaw.
Kabata-Pendias, A., Pendias, H., 1992. Trace Elements in Soil and Plants. CRC Press,
Boca Raton.
Kabata-Pendias, A., Pendias, H., 1999. Biogeochemistry of Trace Elements. PWN,
Warsaw.
Kwapulińska, G., 1995. A sensitive spectrophotometric method of determination of
gallium(III) using Chrome Azurol S and benzyldimethyllaurylammonium
bromide. Chem. Anal. Warsaw 40, 783–789.
579
Kwapulińska, G., Buhl, F., Połedniok, J., 1993. Spectrophotomertic studies on the
system Sc – Chrome Azurol S – benzyldimethyllaurylammonium bromide (ST)
and its application in chemical analysis. Chem. Anal. Warsaw 38, 201–210.
Langodegard, M., Wibetoe, G., 2002. Determination of gallium in soil by slurry
sampling GFAAS. Anal. Bioanal. Chem. 373, 820–826.
Liang, S., Liu, Y., Hu, H., 2004. Determination of C, N and other 36 elements in soil
samples by XRF. Yankuang Ceshi 23, 102–108.
Lopez-Garcia, I., Campillo, N., Arnau-Jerez, I., Hernadez-Cordoba, M., 2004. ETAAS
determination of gallium in soils using slurry sampling. J. Anal. Atom. Spectrom.
19, 935–937.
Marin, B., Valladon, M., Polve, M., Monaco, A., 1997. Reproducibility testing of a
sequential extraction scheme for the determination of trace metal speciation in
a marine reference sediment by inductively coupled plasma-mass
spectrometry. Anal. Chim. Acta 342, 91–112.
Minowa, H., Ebihara, M., 2003. Separation of rare earth elements from scandium by
extraction chromatography. Application to radiochemical neutron activation
analysis for trace rare earth elements in geological samples. Anal. Chim. Acta
489, 25–37.
Plessow, A., Heinrichs, H., 2000. Speciation of trace elements in acidic pore waters
from waste rock dumps by ultrafiltration and ion exchange combined with ICP-
MS and ICP-OES. Aquat. Geochem. 6, 347–366.
Połedniok, J., Buhl, F., 2003. Speciation of vanadium in soil. Talanta 59, 1–8.
Polish Standard PN-R-04031, 1997. Chemical and Agricultural Analysis of the Soil.
Sampling.
Riberio, A.P., Fiqueiredo, A.M.G., Sigolo, J.B., 2005. Determination of heavy metals
and other trace elements in lake sediments from a sewage treatment plant by
neutron activation analysis. J. Radioanal. Nucl. Chem. 263, 645–651.
Saini, N.K., Mukherjee, P.K., Rathi, M.S., Khanna, P.P., Purohit, K.K.J., 2002. Trace
element estimation in soils: an appraisal of ED-XRF technique using group
analysis scheme. J. Trace Microprobe Tech. 20, 539–551.
Schulze, D., Krüger, A., Kupsch, H., Segebade, C., Gawlik, D., 1997. Enrichment and
distribution of elements in flood-plain soils of the Bitterfeld industrial area
studied by neutron activation analysis. Sci. Total Environ. 206, 227–248.
Shtangeeva, I., 2005. Trace and Ultratrace Elements in Plants and Soil. WIT Press,
Southampton.
Shtangeeva, I., Ayrault, S., Jain, J., 2004. Scandium bioaccumulation and its effect on
uptake of macro- and trace elements during initial phases of plant growth. Soil
Sci. Plant Nutr. 50, 877–883.
Sobczyński, T., Siepak, J., 2001. Speciation of heavy metals in bottom sediments of
lakes in the area of Wielkopolski National Park. Pol. J. Environ. Stud. 10, 463–
474.
Solecki, J., Chibowski, S., 2000. Examination of trace amounts of some heavy metals
in bottom sediments of selected lakes of South-Eastern Poland. Pol. J. Environ.
Stud. 9, 203–308.
Sun, Z., Zhang, Z., Mao, Y., Chen, Z., 2004. Determination of trace amount of silver,
tin, lead, boron and gallium in geochemical exploration samples by electric arc
distillation- emission spectrometry. Yankuang Ceshi 23, 153–156.
Tessier, A., Campbell, P.G.C., Bisson, M., 1979. Sequential extraction procedure for
the speciation of particulate trace metals. Anal. Chem. 51, 844–851.
Tyler, G., 2004. Vertical distribution of major, minor and rare elements in a Haplic
Podzol. Geoderma 119, 277–290.
Vogt, C., 1994. Speciation of the inorganic components in brown coal. Fresen. J. Anal.
Chem. 350, 89–92.
Wa˛chalewski, T., 1997. Items of Environmental Chemistry. AGH Publishers, Cracow.
Yu, B., Yan, Z., Yang, L., Wang, R., Li, X., 2006. Determination of 36 major, minor and
trace elements in soil and stream sediment samples by X-ray florescence
spectrometry. Yankuang Ceshi 25, 74–78.
Zambello, F.R., Enzweiler, J., 2002. Multi-element analysis of soils and sediments by
wavelength-dispersive X-ray fluorescence spectrometry. J. Soils Sediments 2,
29–36.