Coordenao de Anlises Minerais COAM

Setor de Caracterizao Tecnolgica - SCT

SIMULTANEOUS SPECIATION OF
CHROMIUM BY SPECYTOPHOTOMETRY
AND MULTICOMPONENT ANALYSIS

Maria Ins Couto Monteiro

Manuel Castro Carneiro
Arnaldo Alcover Neto
Ricardo Soares
Srgio de Souza Henrique Junior
Fernanda Veronesi Marinho Pontes
Llian Irene Dias da Silva
Ricardo Erthal Santelli

Setembro/2009
CT2009-034-00 Comunicao Tcnica publicada na revista Chemical Speciation
and Bioavailability, pg.153-160-2009.

Chemical Speciation and Bioavailability (2009), 21(3)

153

Simultaneous speciation of chromium by

spectrophotometry and multicomponent analysis
Ricardo Soaresa, Manuel Castro Carneiroa, Maria Ines Couto Monteiroa*,
Sergio de Souza Henrique Juniora, Fernanda Veronesi Marinho Pontesa,
Llian Irene Dias da Silvaa, Arnaldo Alcover Netoa and Ricardo Erthal Santellib
a

Setor de Caracterizacao Qumica, COAM, Centro de Tecnologia Mineral, Av. Pedro Calmon, 900,
Ilha da Cidade Universitaria, Rio de Janeiro - RJ, 21941-908, Brazil
b
Departamento de Geoqumica, Universidade Federal Fluminense, NiteroIyRJ, Brazil
*E-mail: mmonteiro@cetem.gov.br

ABSTRACT
A simple, fast and sensitive spectrophotometric method for the simultaneous determination of Cr(III)
and Cr(VI) in effluents and contaminated waters using a UV-visible spectrophotometer, which operates
with an advanced software for multicomponent analysis, is proposed. The method consists in the
complexation of Cr (III) with EDTA and reaction of Cr(VI) with diphenylcarbazide (DPC). Variables, such
as pH and colour stability time, were studied. The effect of concomitant ions on the simultaneous Cr(III)
and Cr(VI) determination was also investigated. The sums of the chromium species concentrations
obtained by the proposed method were compared with the total chromium concentrations found by
electrothermal atomic absorption spectrometry. Recoveries of the chromium species between 75 and
136% were obtained for spiked samples. The linear working range for Cr(III) was 0.5 30 mg L
1, while
for Cr(VI) was 0.005 0.30 mg L
1. The detection limits were 0.3 mg L
1 for Cr(III) and 0.003 mg L
1 for
Cr(VI) while the quantification limits were 1.0 mg L
1 for Cr(III) and 0.01 mg L
1 for Cr(VI).
Keywords: chromium speciation, multicomponent analysis, spectrophotometry, tannery effluent,
contaminated water

INTRODUCTION
Chromium is used in several industries such as
metallurgical (steel, ferrous- and nonferrous alloys),
refractory (chrome and chrome-magnesite) and
chemical engineering (pigments, dyes, electroplating,
tanning, cooling water, leather and wood preservation
and cement manufacturing). As a consequence of
these industrial activities, chromium compounds
enter the environment causing pollution (Han et al.,
2007; Hagendorfer et al., 2008).
The two main oxidation states of chromium, Cr(III)
and Cr(VI), present in natural waters, significantly
differ in biological, geochemical and toxicological
properties. Over a narrow concentration range, trivalent chromium is considered essential for mammals
for the maintenance of glucose, lipid and protein

metabolism, whereas Cr(VI) is reported to have a

toxic effect on humans (Lin et al., 2001; Monteiro
et al., 2002).The high toxicity of Cr(VI) is related to
its ability to cross the cell membrane and its strong
oxidation properties (Girard et al., 1996). Hexavalent
chromium is readily soluble in water and can be
accumulated in soil and plants (Kumar et al., 1997),
while Cr(III) probably exists in environmental waters
in the form of many different species: hydrolysed,
complexed and adsorbed on colloidal matter. Also,
Cr(III) can undergo speciation changes from inorganic form to organic complex by plants, being
transported as carboxylate complex (Juneva and
Prakash, 2008). Fortunately, not all of the chromium
released by industrial plants is Cr(VI). In many cases,
waste solutions are subjected to reduction, releasing
Cr(III) to the environment (Pankow et al., 1974).
doi: 10.3184/095422909X466095

www.scilet.com

154

Simultaneous speciation of chromium by spectrophotometry and multicomponent analysis

However, in natural environmental compartments

like soil and water, the interconversion of Cr
species takes place readily, depending on pH, redox
potential and ligands available (Kumar et al., 1996).
In Great Britain, the allowable concentration of
chromium is limited to 15 mg L
1 for surface waters
(Chwastowska et al., 2005). The Brazilian environmental legislation (CONAMA, 2008) states that
Cr(III) and Cr(VI) in final effluents should not
exceed 1.0 mg L
1 and 0.1 mg L
1, respectively.
There are several methods for the determination of
Cr(III) and Cr(VI) in aqueous solutions. One option
consists in the complexation and selective extraction
of both Cr(III) and Cr(VI) before instrumental
analysis, which involves laborious and timeconsuming steps. Another alternative is to determine
Cr(VI) and total chromium, after Cr(III) oxidation,
and then calculate the Cr(III) concentration by
subtraction (Gomez et al., 2006). However, the
conversion of metal species from one form to
another can cause serious problems including incomplete conversions (particularly at low concentrations),
introduction of contamination by the oxidationyreduction agents and interferences from other
metals. In addition, these procedures are generally
time-consuming (Sperling et al., 1992).
One of the most used colorimetric methods for the
Cr(VI) andyor total chromium determination is
based on the reaction of Cr(VI) with diphenylcarbazide (DPC) (Lynch et al., 1984; Andrade et al.,
1985; Milacic et al., 1992; Sule et al., 1996;
Clesceri et al., 2002; Mulaudzi et al., 2002; Giusti
et al., 2005). The absorbance of the red violet
complex of unknown composition, formed at the
pH range of 1.6 2.2, is read at 540 nm (Clesceri
et al., 2002). Chromium (III) does not react with the
DPC reagent (Pflaum et al., 1956). The sample
acidification carried out before the DPC addition
prevents the solubilization of Cr(III) species, the
releasing of Cr(III) from complexes or colloidal
particles, or even the increase of Cr(VI) reduction
by organic compounds in the sample (Sule et al.,
1996). Studies showed that interferences from organically complexed Cr(III) species were almost negligible in soil extracts when non-acidified DPC was
used, and more significant with acidified DPC
(Milacic et al., 1992). Elemental interference
studies revealed that concentrations as high as
200 mg L
1 Mo or Hg could be tolerated.
Vanadium concentrations up to 10 times higher
than Cr concentrations did not cause any trouble.
Iron concentrations greater than 1 mg L
1 produced

a yellow colour, but the Fe(III) colour was not

strong and no interference was found. Alternative
procedures such as the use of chloroform to remove
interfering amounts of Mo, V, Fe and Cu by the
extraction of the metals cupferrates (Clesceri et al.,
1998), as well as the removal of organic compounds
from the samples (Mulaudzi et al., 2002), have been
proposed.
Very few methods for Cr determination are based
on the formation of Cr(III) complexes in aqueous
solution, and this is probably due to the slow
reaction rate of the strongly hydrated Cr(III) ions.
Even so, methods based on the formation of an
extremely stable complex of Cr(III) with ethylenediamintetraacetic acid (EDTA) have been used (Den
Boef et al., 1960; Costa et al., 1999; Gomez et al.,
2006). Optimum pH values for the Cr(III)-EDTA
complex formation were lower than 5 (from 2.5 to
4.0 or pH 4.75) (Costa et al., 1999; Gomez et al.,
2006), since the Cr(III) solubility decreases at pH
values higher than approximately 5 (Sule et al.,
1996; Fendorf, 1995). Studies revealed that
Cr : EDTA molar ratios from 1 : 3 to 1 : 18 could
be used (Costa et al., 1999). Reaction times of 5 min
at 90 C, using a heating plate (Gomez et al., 2006),
and of 3 min with microwave oven irradiation
(92 C) (Costa et al., 1999) have been reported.
The complex was stable for at least 30 days
(Gomez et al., 2006). The wavelengths for the
maximum absorbance of Cr(III)-EDTA complex
were 540 nm (Gomez et al., 2006), 542 nm (Costa
et al., 1999) and 545 nm (Den Boef et al., 1960).
Interference studies showed that 2 g L
1 of Al, Ba,
Bi, Cd, Ca, Pb, Sr, La, Mn, Hg, Mo, W, Ti, U, V
and Zn, as well as 0.5 g L
1 of Cu, Co, Ni and Fe,
did not cause any interference on 0.1 g L
1 Cr(III)
absorbance signal (Costa et al., 1999). The alkaline
and alkaline earth metals and the more common
anions, such as Cl
, NO3
, CH3COO
and
SO42
, did not interfere on the Cr(III)-EDTA
absorbance signal (Den Boef et al., 1960).
Simultaneous spectrophotometric determination of
several components is a very complex problem in
analytical chemistry due to spectral interferences,
which results in widely overlapped absorption
bands. In these cases, the conventional univariate
calibration method is impracticable due to contribution of one species on the absorption signals of
others and vice versa. Then, other methods have
been used, such as multicomponent analysis
program. It is based on an extension of Beers law
to various components. The multicomponent cali-

Maria Ines Couto Monteiro et al.

bration uses the analytical function concept of

combining absorbance and derivative data to give
function results. This technique usually improves
the resolution bands, eliminates the influence of
background or matrix and provides more defined
fingerprints than traditional ordinary or direct absorbance spectra, since it enhances the detectability of
minor spectral features. Derivative transformation
permits discrimination against broad band interferents, arising from turbidity or non-specific matrix
absorption, and it tends to emphasize subtle spectra
features, allowing the enhancement of the sensitivity
and specificity in mixtures analysis (Rojas and
Ojeda, 2009).
The multivariate curve resolution method has been
recently used for chromium speciation in tanning and
environmental samples (Gomez et al., 2006). In a
first step, Cr(III) was determined as the Cr(III)
EDTA complex, while in a second step, Cr(VI) was
determined by the addition of a NaOH solution that
converted the dichromate to chromate, in the
presence of the Cr(III) EDTA complex. Limits of
detection of 8 mg L
1 for Cr(III) and 2 mg L
1 for
Cr(VI) were obtained. Methods for simultaneous
spectrophotometric determinations of Cr(III) and
Cr(VI) have not been found.
This paper describes a simple, fast and sensitive
spectrophotometric method for the simultaneous
determination of Cr(III) and Cr(VI) in effluents
and contaminated waters with the aid of a UV-vis
spectrophotometer equipped with a computer with
advanced software for multicomponent analysis.

EXPERIMENTAL
Equipment
The chromium concentration measurements were
performed on a spectroscopy system based on an
Agilent 8453 spectrophotometer and an Agilent
ChemStation advanced software for multicomponent
analysis (MCA) on a Hewlett-Packard 7540
computer (Waldbronn, Germany). The system was
equipped with an automatic pumping sampler model
1FS. The chromium species spectra were recorded
from 300 to 900 nm. The data analysis parameters for
spectral processing were: first-order derivative, filter
length of 5; polynomial degree of 4; wavelength
range of 450 680 nm; reference wavelength range
of 820 850 nm and maximum likelihood calculation
method. A continuous flow quartz cuvette with a
1 cm optical path and 62 mL was used. The pumping

155

and washing times were 30 and 15 s, respectively.

The solution heating was performed on a heating
plate from Mistura Equipamentos para Laboratorio
model MA 085 (Piracicaba, SP, Brazil). All pH
measurements were carried out with a pH meter
with a combined glass electrode from Thermo
Electron Corporation, model Orion (Beverly, MA,
USA). The samples preliminary analyses were carried
out by using an inductively coupled plasma optical
emission spectrometer (ICP-OES) from Horiba Jobin
Yvon, model Ultima 2 (Longjumeau, France) and a
modular ion chromatograph (IC) from Metrohm
(Herisau, Switzerland). The determination of total
chromium was performed on an electrothermal
atomic absorption spectrometer (ET AAS) Varian
model AA-240 Z (Victoria, Australia) equipped
with Zeeman-effect background corrector. All
measurements were made at 357.9 nm, by using a
Cr hollow-cathode lamp (Varian) with a current of
6 mA and a bandwidth of 0.2 nm. The temperature
program was the same employed by Monteiro et al.
(2002) for atomization on a pyrolytic graphite platform. The analyte addition method was used.

Reagents, standards and samples

All solutions were prepared with analytical grade
reagents and ultra-pure water, obtained from a
Milli-Q water purification system (Millipore Corp.,
Millford, MA, USA). All glassware vessels were
soaked in 12% (vyv) HNO3 for 24 h and rinsed
thoroughly with distilled water and, finally, rinsed
for the last time with ultra-pure water.
Standard stock solutions containing 1000 mg L
1
Cr (III) and 1000 mg L
1 Cr (VI), as CrCl3 and
K2CrO4, were prepared from Titrisol concentrate
(Merck, Darmstadt, Germany) and Fixanal concentrate (Riedel-de-Haen, Seelze, Germany), respectively. Intermediate low concentration solutions of
Cr(III) and Cr(VI) were prepared daily by dilution of
the corresponding stock solution with water. Sulfuric
acid, EDTA, DPC and acetone were supplied from
Vetec Qumica Fina Ltda (RJ, Brazil). A 0.45 mol
L
1 sulfuric acid solution was prepared. A DPC
solution was prepared by dissolving 250 mg of the
reagent in 50 mL of acetone. In the interference
study, NaCl, Na2SO4 (both from Vetec Qumica
Fina Ltda, RJ, Brazil) and NaNO3 (from Merck,
Darmstadt, Germany) were used to prepare the
stock solutions of 1000 mg L
1 Cl
, SO42
and
NO3
. Also, standard stock monoelemental solutions containing 1000 mg L
1 of Al, Mn, Fe, Ni,

156

Simultaneous speciation of chromium by spectrophotometry and multicomponent analysis

Figure. 1 Cr(III) EDTA and Cr(VI) DPC spectra produced by 50 mg L
1 Cr(III) and 0.05 mg L
1 Cr(VI) in the wavelength range of
300 to 900 nm. (2
2) Cr(III) EDTA and (- - -) Cr(VI) DPC.

Zn and Cu were used. These solutions were prepared

from AlCl3, Mn(NO3)2 (Merck, Darmstadt,
Germany), Fe(NO3)3, Ni(NO3)2, Zn(NO3)2 and
Cu(NO3)2 (VHG Labs, Manchester, NH, USA).
Three tanning and beamhouse effluent samples
from the same tannery, collected at time intervals of
5 min, and one water sample from Paraibuna River,
collected close to the tannery and other industrial
areas, were analysed. The certified reference materials SRM 1643d trace elements in water, SRM
1640 trace elements in natural water, both from
NIST, USA and SLRS-3 riverine water, from
National Research Council Canada, containing
38.6+ 1.6 mg
kg
1
18.53+ 0.20 mg
L
1,

3

(density 1.0015 g
cm
at
22 C)
and
0.30 + 0.04 mg L
1 of total chromium, respectively,
were analysed and also used for recovery experiments.

cold water was used to avoid evaporation. After

cooling at room temperature, 1 mL of DPC solution
(5 mg) was added to react with Cr(VI). The solution
was transferred to a 50 mL volumetric flask, and the
volume was completed with purified water. The
solution was let stand for 5 10 min for full colour
development. Then, it was pumped to the 62 mL
cuvette for spectrophotometric analysis. Blank and
mixed standard solutions had the same treatment. The
mixed standard solutions used in the analytical work
were: 0.005 mg L
1 Cr(VI)y0.5 mg L
1 Cr(III),
0.01 mg L
1 Cr(VI)y1.0 mg L
1 Cr(III), 0.05 mg
L
1 Cr(VI)y5.0 mg L
1 Cr(III), 0.10 mg L
1
Cr(VI)y10 mg
L
1
Cr(III),
0.20 mg
L
1

1
Cr(VI)y20 mg L
Cr(III) and 0.30 mg L
1

1
Cr(VI)y30 mg L
Cr(III).

Procedure
A sample aliquot, previously filtered on a 0.45 mm
membrane, containing about 0.025 2.5 mg of Cr(III)
and 2.5 15 mg of Cr(VI) was transferred to a 125 mL
Erlenmeyer flask. In this work, aliquots of 25 mL
were taken from the samples. Only the tanning and
beamhouse effluents were previously diluted 10 and
50 times, respectively. Then, an excess of EDTA
(65 mg) was added for Cr(III) complexation. A
0.45 mol L
1 sulfuric acid solution (about 500 mL)
was added until pH 4.5. The solution was heated at
90 C for 5 min. A cold finger condenser containing

Influence of the pH on the absorbance signals of

Cr(III) and Cr(VI)

RESULTS AND DISCUSSION

The effect of pH (2.5, 3.5 and 4.5) on the absorbance

signals of 50 mg L
1 Cr(III) and 0.05 mg L
1
Cr(VI) solutions was investigated. The experiment
was performed in triplicate. The highest absorbance
signals for Cr(III) and Cr(VI) at 544 nm were
obtained at pH 4.5 and, therefore, it was selected.
The Cr(III)-EDTA and Cr(VI)-DPC spectra produced
by the analyses of 50 mg L
1 Cr(III) and 0.05 mg
L
1 Cr(VI) solutions, in the wavelength range of 300
to 900 nm, are depicted in Figure 1.

Maria Ines Couto Monteiro et al.

157

Figure 2 Average recoveries of chromium species at different elapsed times (n 3).

Stability study
Mixed standard solutions containing 0.003 mg L
1
Cr(III)y0.3 mg L
1 Cr(VI), 0.005 mg L
1 Cr(III)y
0.5 mg L
1 Cr(VI), 0.05 mg L
1 Cr(III)y5.0 mg
L
1 Cr(VI) and 0.30 mg L
1 Cr(III)y30 mg L
1
Cr(VI) were analysed by the proposed procedure.
The chromium species concentrations were measured
at the elapsed times of 0 (after 5 10 min for the
colour development), 1, 2, 3, 12, 24 and 40 h. The
glass flasks containing the coloured solutions were
covered with aluminium foil to avoid exposure to
light, and the flasks used for the times 12, 24 and 40 h
were also kept in a refrigerator, and brought up to
room temperature before beginning the proposed
procedure. The experiment was carried out in triplicate. Negative concentrations were found for the
mixed standard solutions containing 0.003 mg L
1
Cr(III)y0.3 mg L
1 Cr(VI) at elapsed time zero and
therefore, they were eliminated. The relative standard
deviations of the chromium species concentrations
for the remainder mixed standard solutions were
lower than 8%. The average recoveries of the chromium species in these solutions at different elapsed
times are present in Figure 2. The recoveries at time
zero have been put to 100%. All the solutions

remained stable up to at least 24 h, when the

Students t-test at 95% of confidence level was
used for comparison of the average concentrations
with those obtained at time zero. Also, good agreement was obtained between the found and theoretical
chromium species concentrations up to 24 h, when
regression lines were applied. Slopes from 1.0049 to
1.0784 and from 0.9811 to 1.1058; intercepts from
0.2701 to 0.4897 and from 0.00001 to 0.0049;
product moment correlation coefficients from
0.9987 to 0.9998 and from 0.9993 to 0.9998 were
obtained for Cr(III) and Cr(VI), respectively. These
results indicate good linearity in the ranges of 0.005
0.30 mg L
1 for Cr(VI) and 0.5 30 mg L
1 for
Cr(III) up to 24 h.

Interference study
The sample preliminary results obtained by ICP-OES
and IC and the sample final dilution factors for the
proposed method were used to select the ion concentration ranges for the interference study on the
determination of the chromium species. A solution
containing 20 mg L
1 Cr(III) and 0.2 mg L
1 Cr(VI)
was used (Table 1). The experiment was carried out
in triplicate. Tolerance limits of interfering ions were

158

Simultaneous speciation of chromium by spectrophotometry and multicomponent analysis

Table 1 Effect of potential coexisting ions on the simultaneous

determination of 20 mg L
1 Cr(III) and 0.2 mg L
1 Cr(VI)
(n 3)
Ion

Al

Cu2

Fe3

Concentration
(mg L
1)
0.1
0.5
0.7
1.0
5.0
10
0.005
0.01
0.02
0.05
0.1
0.2
0.5
1.0
3.0
5.0
10
30

Recovery (%)
Cr(VI)

Cr(III)

97 + 1
97 + 1
94 + 4
98 + 4
99 + 4
99 + 6

102+ 8
98 + 2
102+ 1
101+ 2
100+ 1
103+ 2

103 + 5
96 + 3
102 + 6
90 + 4
94 + 5
100 + 14

99 + 1
106+ 5
103+ 3
115+ 2
121+ 4
120+ 3

96 + 5
98 + 10
100 + 5
90 + 3
94 + 7
101 + 6

102+ 2
103+ 2
98 + 2
99 + 1
101+ 4
104+ 12

Mn2

0.05
0.1
0.2
0.5
1.0
5.0

94 + 5
95 + 6
96 + 9
90 + 7
90 + 3
98 + 11

104+ 1
102+ 3
99 + 1
102+ 1
94 + 10
99 + 4

Ni2

0.001
0.02
0.01
0.05
0.1
0.2

94 + 3
96 + 10
90 + 2
102 + 3
91 + 3
93 + 1

104+ 2
106+ 3
113+ 1
104+ 1
113+ 1
121+ 1

Zn2

0.05
0.1
0.2
0.5
1.0
2.0

95 + 3
95 + 4
96 + 4
100 + 7
98 + 3
92 + 5

106+ 4
103+ 2
100+ 6
107+ 2
107+ 1
113+ 5

93 + 8
95 + 4
100 + 9
90 + 5
107 + 4
90 + 17

93 + 4
101+ 2
110+ 1
98 + 3
113+ 7
113+ 9

103 + 10
102 + 16
105 + 9
94 + 7
100 + 7
83 + 3

97 + 3
108+ 2
110+ 5
110+ 7
109+ 4
110+ 6

95 + 4
94 + 10
93 + 11
100 + 12
90 + 5
98 + 4

103+ 7
96 + 2
96 + 3
102+ 22
121+ 3
122+ 8

Cl

NO3

SO42

10
50
100
250
1000
2500
0.2
1.0
1.5
2.0
10
15
50
100
300
500
1000
3000

established at those concentrations that did not cause

recoveries lower than 90% and higher than 115%.
The results indicated that Cu2 (from 0.1 to 0.2 mg
L
1), Ni2 (0.2 mg L
1) and SO42
(from 1000 to
3000 mg L
1) caused slightly higher Cr(III) recoveries (from 120 to 122%). Interferences of the
potential coexisting ions on the Cr(VI) recoveries
were not observed.

Analytical results
The detection limit (LOD) was defined as three times
the standard deviation (3s) of three consecutive
measurements of the lowest concentration, and the
quantification limit (LOQ) was defined as 10s,
considering in both cases the two-fold dilution of
the sample in the analytical procedure. The LODs
were 0.3 mg L
1 for Cr(III) and 0.003 mg L
1for
Cr(VI). The LOQs were 1.0 mg L
1 for Cr(III) and
0.01 mg L
1 for Cr(VI). The relative standard deviations were lower than 11%. The LOQs meet the
limits of the Brazilian regulation of 1.0 mg L
1 for
Cr(III) and 0.1 mg L
1 for Cr(VI) in final effluents
(CONAMA, 2008).
Table 2 shows the results for the chromium
species in spiked samples. The experiment was
carried out in triplicate, and all relative standard
deviations were lower than 17%. The initial concentrations of Cr(III) and Cr(VI) in the certified water
samples SLRS-3, NIST 1640 and NIST 1643b were
not detected by the proposed method, which can be
explained only for SLRS-3: total chromium
(0.30 + 0.04 mg L
1) was lower than the LOQs of
chromium species found by the proposed method.
For NIST 1643b, the non detection of Cr(VI) is in
agreement with the result obtained by Sperling et al.
(1992), who attributed this fact to a probable result
of the sample conservation used by NIST.
According to the certificate, the sample was
conserved in 0.5 mol L
1 nitric acid. In this condition, Cr(III) is the predominant species (Brookins,
1988). Chromium species recoveries between 75
and 136% were obtained for the spiked samples.
Table 3 shows the sums of the concentrations of
chromium species determined by the proposed
method and the total chromium concentrations
obtained by the ET AAS method. The chromium
species sums for the tanning effluents B and C and
the beamhouse effluent A were in good agreement
with the total chromium concentrations obtained by
the comparative method, when the Students t-test,
at 95% confidence level was applied (n 3). The

Maria Ines Couto Monteiro et al.

159

Table 2 Analytical results of Cr(III) and Cr(VI) in spiked samples (n 3)

Chromium concentration (mg L
1)

Sample
Cr(III)
initial

Cr(VI)
initial

Cr(III)
added

Cr(VI)
added

Cr(III)
found

Cr(VI)
found

Water SLRS-3

ND

ND

5.0
10
20
30

0.05
0.10
0.20
0.30

5.2 + 0.1
9.80 + 0.01
20.2 + 0.2
30.3 + 0.3

0.052 + 0.001
0.097 + 0.001
0.203 + 0.002
0,302 + 0.003

Water NIST 1640

ND

ND

10
30
50

0.10
0.30
0.50

12.1 + 0.2
27.3 + 0.5
44.0 + 0.2

0.14 + 0.02
0.300 + 0.006
0.485 + 0.005

Water NIST 1643d

ND

ND

10
30
50

0.10
0.30
0.50

9.20 + 0.02
29.7 + 0.4
51 + 1

0.089 + 0.002
0.276 + 0.003
0.460 + 0.005

Water from the

Paraibuna River

ND

ND

5.0
10
20
30

0.05
0.10
0.20
0.30

5.9 + 0.1
12 + 2
27 + 2
35 + 5

0.0445 + 0.0005
0.117 + 0.014
0.186 + 0.007
0.279 + 0.008

Tanning effluent

143 + 1

1.2+ 0.1

5.0
10
20

0.05
0.10
0.20

148.6 + 0.2
153.7 + 0.1
169 + 1

1.26 + 0.05
1.38 + 0.02
1.40 + 0.02

Beamhouse
effluent

764 + 10

6.7+ 1.0

5.0
10
20
30

0.05
0.10
0.20
0.30

769.9 + 0.3
774.0 + 0.3
783 + 1
796 + 2

6.8 + 0.1
6.9 + 0.3
6.9 + 0.2
7.1 + 0.1

ND, Not detected.

Table 3 Comparison of the total chromium concentrations (mg L
1) obtained by the

proposed and ET AAS methods (n 3)
Sample

Proposed method

ET AAS method

139 + 4
137 + 2
141 + 34
752 + 23
734 + 11
748 + 19

152+ 2
140+ 3
151+ 4
836+ 23
823+ 17
859+ 26

Tanning effluent A
Tanning effluent B
Tanning effluent C
Beamhouse effluent A
Beamhouse effluent B
Beamhouse effluent C

results obtained for the tanning effluent sample A

and beamhouse effluents B and C were slightly
lower (9 13%) but acceptable, when the regression
line was applied for all effluent samples
(slope 0.8751;
intercept 9.984;
product
moment correlation coefficient 0.9997).

L
1. The detection limits were 0.3 mg L
1 for

Cr(III) and 0.003 mg L
1 for Cr(VI) while the
quantification limits were 1.0 mg L
1 for Cr(III)
and 0.01 mg L
1 for Cr(VI). Better limits could be
obtained by using lower dilution factor of the sample
in the analytical procedure.

CONCLUSIONS

ACKNOWLEDGEMENTS

The proposed method for Cr(III) and Cr(VI) simultaneous spectrophotometric determination in effluents
and contaminated waters is simple and fast. The
linear working range for Cr(VI) was 0.005
0.30 mg L
1, while for Cr(III) was 0.5 30 mg

The authors thank the Conselho Nacional de

Pesquisas e Desenvolvimento Tecnologico (CNPq)
for financial support. We also thank Amanda
Gerhardt de Oliveira and Fernanda Nunes Ferreira
for the analytical support.

160

Simultaneous speciation of chromium by spectrophotometry and multicomponent analysis

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