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Talanta 74 (2008) 736740

Rapid leaching of Cr(VI) in soil with Na3PO4 in the determination of

hexavalent chromium by electrothermal atomic absorption spectrometry
Khakhathi L. Mandiwana
Department of Chemistry, Tshwane University of Technology, Private Bag X31, Rosslyn 0200, South Africa
Received 7 May 2007; received in revised form 29 June 2007; accepted 3 July 2007
Available online 7 July 2007

Abstract
A method has been developed that leaches Cr(VI) selectively from soil samples. Hexavalent chromium was leached completely from soil with
0.01 mol L1 Na3 PO4 . This was achieved by boiling the soilreagent solution mixture for a period of 5 min. The leached Cr(VI) was then quantified
by electrothermal atomic absorption spectrometry (ET-AAS) after filtration of the sample solutions through Hydrophilic Millipore PVDF 0.45 m
filter.
Statistical evaluations indicated that the new developed method is reliable since neither its comparison with the established method nor the
comparison of the sum of the concentrations of chromium species to that of the total concentration of chromium show any difference at 95% level
of confidence. The spiking of soil samples with Cr(III) standards before pretreatment show that Cr(III) was not oxidized to Cr(VI) during leaching
as the Cr(VI) content never increased. The detection limit established was 0.07 g g1 , which is an improvement to that of the US EPA method
3060A by a factor of more than 500.
The maximum concentrations of Cr(VI) found in soil samples collected around the new chromium mine was 8.0 g g1 and falls within acceptable
level of 15 g g1 in accordance with the Italian Guidelines.
2007 Elsevier B.V. All rights reserved.

Keywords: Hexavalent chromium; Soil; Leaching; Electrothermal atomic absorption spectrometry

1. Introduction Chromium exists mainly in the III and VI oxidation states

Chromium is the metallic element that exists primarily in the
mineral chromite, which is present in soils, waters, rocks, fauna
and gases. It occurs mainly as a result of human activities through
the production of waste water in metal smelting, electroplating,
tanning, metallurgy and mining. After processing, chromium
occurs in several chemical species and it is not biodegradable in
the environment [1].
The increase in demand of the industrial uses of chromium
and its unregulated application has led to the contamination of
soil, sediment, surface and ground waters thereby posing seri-
ous health problems to humans and animals [2]. Soil conditions
like electron donor availability, soil texture, competing ions,
adsorption capabilities, pH, moisture content, temperature, and
the presence of vegetation are the principal factors that govern
the mobility of chromium in soil [37].
Tel.: +27 12 382 0706; fax: +27 12 382 0820.
E-mail address: MandiwanaKL@tut.ac.za.
in soil. Hexavalent chromium, Cr(VI), is an oxyanion com-
monly occurring as relatively water-soluble chromate, CrO4 2
or dichromate, Cr2 O7 2 . In temperate region soil, where neg-
atively charged clay minerals predominate, Cr(VI) anions are
repelled by the negative charge of soil particles. Due to these
charge repulsions, hexavalent chromium is quite mobile in soil
[8]. Cr(VI) is a strong oxidizer and this makes it toxic to biologi-
cal systems [913]. Hexavalent chromiums toxicity is enhanced
by its ability to diffuse through cell membranes and oxidize
biological molecules.
Trivalent chromium, Cr(III), is relatively non-reactive and
less toxic due to its slow ligand exchange kinetics but long-
term exposures are known to cause allergic skin reactions and
cancer [14]. Cr(III) occurs as a cation in soils, forming relatively
insoluble oxide and hydroxide compounds [15]. With its large
positive charge, Cr(III) is attracted to negatively charged soil
particles, and has been found to associate with the smallest size
fractions in soils [16]. Thus, Cr(III) is less mobile in soils than
Cr(VI).

0039-9140/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.talanta.2007.07.002
 K.L. Mandiwana / Talanta 74 (2008) 736740
Although most researches have been focused on the extrac-
tion and detection of chromium species in liquid samples such
as natural and waste waters [1719], there are limited pub-
lications on the extraction of Cr(VI) from soils [20,21] and
that requires additional efforts [22]. The most recommended
method for determining Cr(VI) in solid matrices is the US
EPA method 3060A. This method is based on the reaction
of diphenylcarbazide (DPC) with Cr(VI) followed by spec-
trophotometric detection. However, under the strong alkaline
conditions of this method, humic compounds including species
that absorb at 540 nm (analytical wavelength for measuring the
absorbance of the DPC-Cr colored complex) are released from
soil. Such species interferes with the correct determination of
Cr(VI), moreover, spectrophotometric techniques suffer from
poor detection limits. This makes the US EPA method 3060A
unsuitable for determining Cr(VI) species at ultra-lower levels.
In this present research, a method has been developed to leach
Cr(VI) selectively from soil with sodium phosphate reagent
solution, followed by detection of the analyte by ET-AAS.
2. Experimental
2.1. Apparatus
A PerkinElmer Analyst 600 atomic absorption spectrom-
eter that equipped with Zeeman-effect background correction
system was used for all measurements. The chromium hollow
cathode lamp (25 mA) was operated at 357.9 nm while the spec-
tral band pass was set at 0.7 nm. Transversely heated graphite
tubes (THGA) with integrated Lvov platforms (PerkinElmer,
part N B0504033) were used as atomizers with Ar as the sheath
gas throughout.
2.2. Reagents and standard solutions
Standard stock solutions containing 1000 mg L1 Cr(VI) as
K2 CrO4 (Merck) was used for the preparation of working stan-
dards for chromium. Ultra-pure water (resistivity, 18.2 M cm),
obtained from a Milli-Q water purification system (Millipore
Corp., USA), was used for all dilutions and sample prepara-
tions. Ultra-pure HNO3 (Merck), HF (Merck) and HCl (Merck)
were used to digest samples for the total chromium determi-
nation. Hydrophilic PVDF 0.45 m filters (Millipore Millex,
USA) were employed for the filtration of all solutions. Certi-
fied Reference Material: CRM 027050 (sandy loam soil from
a moderately contaminated site located in the Western United
States) was applied as quality control sample for the evaluation
of analytical results of total Cr determination.
2.3. Samples and sample preparation
2.3.1. Samples
Samples of top sandy loam soil were taken at the site of a new
chromium mine, Thorncliff, South Africa. The soil samples that
represent 20 cm of the upper soil layer were collected into plastic
bags. They were then air-dried and ground to a particle size less
than 75 m in a tungsten carbide milling vessel.
737
2.3.2. Determination of water-soluble fraction of Cr(VI)
A nominal mass of 0.25 g sub-sample of soil was transferred
into a plastic tube in which 25.0 mL deionized water was added.
The content of the tube was shaken periodically for 24 h. The
sample solution was then filtered through Hydrophilic Millipore
PVDF 0.45 m filter [prior determination of Cr(VI) by ET-AAS]
to remove Cr(III) species that may be trapped in the colloidal
suspension.
2.3.3. Leaching of Cr(VI) with Na3 PO4
Approximately 0.25 g of soil was transferred into a 100 mL
glass beaker. Twenty-five milliliters of 0.01 mol L1 Na3 PO4
were added and the contents of the beaker were boiled on a hot-
plate for 5 min. After cooling, the sample was filtered through
Whatman No. 540 filter paper and diluted to a final volume
of 25.0 mL with deionized water. The sample solution was fil-
tered through Hydrophilic Millipore PVDF 0.45 m filter prior
determination of Cr(VI) by ET-AAS.
2.3.4. Determination of Cr(III) in soil
The precipitate that was collected on Whatman No. 540 filter
paper after the filtration was transferred into Teflon digestion
vessel (CEM type) and 5.0 mL conc. HNO3 , 3.0 mL conc. HF
and 1.0 mL conc. HCl were added. The vessel was capped and
the sample was digested in microwave at a pressure of 120 psi
for 20 min. After cooling, the cap was removed and the open
vessel was heated on a hot-plate to evaporate the excess acid.
The content was dissolved in 5.0 mL of 1% (v/v) HNO3 and
diluted to 25.0 mL with deionized water. The resulting solution
was then analyzed by ET-AAS.
2.3.5. Determination of total amount of chromium
Approximately 0.25 g of soil was accurately weighed in a
Teflon digestion vessel (CEM type) and 5.0 mL conc. HNO3 ,
3.0 mL conc. HF and 1.0 mL conc. HCl were added. The vessel
was capped and the sample was digested at a pressure of 120 psi
for 20 min. After cooling, the cap was removed and the open
vessel was heated on a hot-plate to evaporate the excess acid.
The content was dissolved in 5.0 mL of 1% (v/v) HNO3 and
diluted to 25.0 mL with deionized water. The resulting solution
was then analyzed by ET-AAS.
3. Results and discussions
3.1. Chromium determination by ET-AAS
The ET-AAS determination of chromium was achieved using
the optimized temperature program summarized in Table 1.
Table 1
Temperature program for the determination of Cr
Step Temperature ( C) Ramp (s) Hold (s) Ar (mL min1 )
1 110 1 10 250
2 250 5 20 250
3 1300 10 30 250
4 2400 0 5 0
738 K.L. Mandiwana / Talanta 74 (2008) 736740

The integrated absorption signals obtained did not differ in

their appearance time thereby signifying that the presence of
the matrix did not interfere with the correct determination
of Cr.
The calibration curve of chromium standards was linear
up to 70 g L1 and is described by the following equa-
tion: Y = 0.0061x + 0.0043, where x is the analyte concentration
(g L1 ) and Y is the integrated absorbance, with correlation
coefficients, R2 = 0.9940 (n = 5), respectively.
The limit of detection (LOD) for Cr(VI) determination has
been established using blank solutions of Na3 PO4 . The LOD,
calculated according to the equation: LOD = Xbl + 3sbl (n = 25),
was found to be 0.7 g L1 for a 10 L sample aliquot. With
respect to the soil samples, assuming that 0.25 g of soil after
digestion has been adjusted to a volume of 25.0 mL, the LOD Fig. 2. Extraction of Cr(VI) from soil with 0.01 mol L1 Na3 PO4 as a function
for Cr(VI) determination was estimated to be 0.07 g g1 . The of time: () Soil 1; () Soil 3; () water-soluble fraction in Soil 1; () water-
soluble fraction in Soil 3.
accuracy and trueness for the Cr determination was verified by
the analysis of CRM 027050 with good agreement between
certified (26.9 0.90 g g1 ) and found (26.5 0.75 g g1 ) the mixture at different time intervals. The results of this inves-
values. tigation presented in Fig. 2, show that 0.01 mol L1 Na3 PO4
leaches all Cr(VI) species within 5 min. The leaching of Cr(VI)
3.2. Optimization of the leaching of Cr(VI) from soil in soil with 0.01 mol L1 Na3 PO4 at room temperature for 48 h
did not result in quantifiable increase of the concentration of
Several concentrations of Na3 PO4 ranging from 1 104 Cr(VI).
to 0.1 mol L1 were used to leach Cr(VI) from soil to obtain Atomization profiles of chromium, which were obtained dur-
the most appropriate concentration of the reagent solution that ing the determination of Cr(VI) in the water-soluble fraction, in
can transfer the analyte completely into solution. Precautions standard solution of Cr(VI) and in soil treated with Na3 PO4
were made so as not to use extremely concentrated Na3 PO4 have the same the appearance time (Fig. 3). This suggests that
solution, thus minimizing the effects of the matrix in the graphite the presence of relatively high Na3 PO4 matrix has no influence
tube. on the release of Cr during atomization, owing to the high pyrol-
A plot of [Cr(VI)] against log [PO4 3 ] (Fig. 1) shows that ysis temperature that eliminated the majority of the matrix prior
the leaching of Cr(VI) compounds from soil is connected with to atomization.
the presence of PO4 3 ions as the level of Cr(VI) extracted
increases as the concentration of the extracting reagent solu-
tion increases. Cr(VI) was extracted completely from soil with
0.01 mol L1 Na3 PO4 . The multiple extraction of Cr(VI) by
fresh portions of 0.01 mol L1 Na3 PO4 indicated that 98% of
the analyte was extracted by a single leaching. The efficiency of
the leaching of Cr(VI) from soil was further optimized by boiling

Fig. 3. Absorbance-time signals of Cr(VI): (1) water-soluble fraction in Soil 3;

Fig. 1. Optimization of Na3 PO4 concentration during the leaching of Cr(VI) (2) Cr(VI) standard solution, 22 g g1 ; (3) total Cr(VI) concentration in Soil
from soil samples in 5 min. 3.
 K.L. Mandiwana / Talanta 74 (2008) 736740 739

Table 2
Results of Cr(III), Cr(VI) and total Cr determination in soil samples (n = 6)

Sample Water-soluble [Cr(VI)] (g g1 ) [Cr(VI)] (g g1 ) [Cr(III)] (g g1 ) {[Cr(VI)] + [Cr(III)]}a (g g1 ) {Total [Cr]}b (g g1 )

Soil 1 0.90 0.05 8.0 0.5 1005 15 1013 1015 50

Soil 2 0.75 0.03 5.8 0.3 1068 20 1074 1075 45
Soil 3 0.80 0.04 5.5 0.4 1117 30 1123 1125 30
Soil 4 0.70 0.02 5.1 0.2 1062 20 1067 1070 50
Soil 5 0.80 0.04 6.5 0.4 1341 40 1348 1350 60
a Sum of [Cr(VI)] and [Cr(III)] in each sample.
b Total chromium concentration determined by an independent method.

3.3. Mechanism for the separation of Cr(VI) from Cr(III) in
soil
The leaching of samples with Na3 PO4 transform insoluble
Cr(VI) compounds, like BaCrO4 , to soluble form according to
the equation
leaching procedure is quantitative. The leaching of soil with
Na3 PO4 results in strong alkaline solution (pH 12), which
preserved Cr(VI) for period of at least 6 months without notice-
able changes in oxidation state. It could, therefore, be concluded
that 0.01 mol L1 Na3 PO4 leaches Cr(VI) completely from soil
samples.

3BaCrO4 (s) + 2Na3 PO4 (aq)

3.5. Results of Cr(VI) determination in soil
3Na2 CrO4 (aq) + Ba3 (PO4 )2 (s)
The proposed procedure was applied in the determina-
The procedure removes all common metals, including Cr(III)
tion of Cr(VI) in soil by water (Table 2). The results show
as insoluble phosphates, oxides or hydroxides [23]. After fil-
that not all Cr(VI) complexes are soluble in water since the
tration, the solution contains only CrO4 2 anions that were
level of Cr(VI) leached was always present in relatively small
originally present in the sample in the form of insoluble salts
amount (0.90 0.05 g g1 ) (Fig. 3). The amount of Cr(VI)
of Cr(VI).
leached by 0.01 mol L1 Na3 PO4 represents the total concen-
Though chromium exists in the form of different oxidation
tration of Cr(VI) in a given soil sample. The concentration of
states ranging from 0 to +6, the oxidation states that naturally
Cr(VI) found in soil samples collected from the site of the
coexist in solids including soil are +3 and +6 [24]. Therefore,
new chromium mine, Thorncliff, South Africa, were within
after the treatment of samples with 0.01 mol L1 Na3 PO4 , all
maximum acceptable levels of 15 g g1 in accordance with
Cr(VI) species goes into solution and the remaining chromium
the Italian Guidelines [26]. Unfortunately, maximum allow-
species in the precipitates is only Cr(III) such that the diges-
able concentrations (MAC) for Cr(VI) in soils are still not well
tion of the precipitates with acids lead to the determination of
established and differ from one country to the other. The lev-
the total concentration of Cr(III) in soil samples. Cr(III) is not
els of Cr(VI) found in soil collected from the new chromium
expected to have been oxidized to Cr(VI) during leaching due
mine could be attributed to the lower period the mine had been
to unfavourable high pH (12) and moreover the concentration
operating. The total concentration of Cr in soil samples were rel-
of the probable oxidizing agent, MnO2 , was very low to have an
atively higher as compared to that of Cr(VI), the highest being
impact, viz. 3.0 g g1 [25].
1400 g g1 .

3.4. Validation of the method

The developed method was validated by comparison with

an established method and by comparison of the sum of Cr
species with total Cr concentration in the sample since solid
certified reference materials with certified values of Cr(VI) are
still lacking. A comparison of the concentration of the sum of
chromium species with the total chromium concentration indi-
cated that there is no difference between them at 95% level of
confidence (Table 2). Similarly, no difference was established
in the results of the determination of Cr(VI) by the new method
and established method [19] based on the leaching of samples
with Na2 CO3 (Fig. 4).
Soil samples were also spiked with 100500 g g1 of Cr(III)
standard solutions, to evaluate any potential conversion to Cr(VI)
during leaching. The results of the investigation showed that Fig. 4. Validation of Cr(VI) leaching by comparing the leaching efficiency of
there were no increase in Cr(VI) concentration and the mean Na3 PO4 with that of Na2 CO3 : (1) 0.01 mol L1 Na3 PO4 (5 min); (2) 0.1 mol L1
% recovery of Cr(III) was 97 3, thereby confirming that the Na2 CO3 (10 min).
740 K.L. Mandiwana / Talanta 74 (2008) 736740

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