Analytica Chimica Acta 540 (2005) 231–238

Review

Digestion treatments and risks of Cr(III)–Cr(VI) interconversions

during Cr(VI) determination in soils and sediments—a review
Maurizio Pettine ∗ , Silvio Capri
Water Research Institute, National Research Council, via Reno 1, 00198 Rome, Italy

Received 18 November 2004; received in revised form 8 March 2005; accepted 15 March 2005
Available online 8 April 2005

Abstract

Threshold values for Cr(VI) in various types of solid matrices have been set up to protect human health and biota. To ascertain the
compliance of solids with these limits different types of extractants and different conditions of pH and temperature have been proposed in the
literature. These extraction procedures are reviewed and their potentialities in quantitatively extracting Cr(VI) from solids without inducing
undesired Cr(VI)–Cr(III) interconversions during the extraction are carefully evaluated. This evaluation takes into account the knowledge
of the kinetics of most important redox reactions of chromium gathered in recent years. Among possible Cr(VI) reductants made available
during the digestion, a number of species including Fe(II), sulphide, sulfite and humic matter were considered, while oxidants included
hydrogen peroxide, dissolved oxygen, manganese oxides. Theoretical calculations suggest that pH higher than 10, high temperature and
high concentrations of carbonate and magnesium ions minimize Cr(III)–Cr(VI) interconversions. The EPA Method 3060A meets these basic
requirements. However, the applicability of this method to the analysis of Cr(VI) in soil and sediment samples, whose extracts may suffer
from the interference by humic matter, is questionable.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Solid matrices; Chromium extraction; Kinetics of chromium reactions; Chromium analysis

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
2. Summary of literature methods for Cr(VI) determinations in solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
3. Theoretical kinetic background for Cr(III)–Cr(VI) interconversions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
3.1. Cr(VI) reduction processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
3.2. Cr(III) oxidation processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
4. Weakness of the standard DPC method applied to Cr(VI) determination in soil and sediment extracts . . . . . . . . . . . . . . . . . . . . . . . . 237
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238

1. Introduction
given rise to specific concentration limits for Cr(VI) in var-
The higher toxicity of Cr(VI) with respect to Cr(III) along ious types of solid matrices, including atmospheric partic-
with its proved mutagenic and carcinogenic properties have ulate, solid wastes, compost and soil. Permissible exposure
limits proposed by US Occupational Safety & Health Ad-
DOI of original article:10.1016/j.aca.2005.03.041.
ministration (OSHA) [1] in workplace atmospheres are 0.50
∗ Corresponding author. Tel.: +39 06 8841451; fax: +39 06 8417861. and 0.25 ␮g/m3 , as time weighted average (TWA) and action
E-mail address: [email protected] (M. Pettine). level (AL), respectively. The Swedish Guideline values [2]

0003-2670/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.aca.2005.03.040
232 M. Pettine, S. Capri / Analytica Chimica Acta 540 (2005) 231–238

suggest maximum concentrations for the most sensitive type netics of redox chromium reactions. Literature information
of land use of 5 and 120 mg/kg dry substance for Cr(VI) and on the kinetics of Cr redox reactions with the most proba-
Cr(III). Canadian Guidelines [3] give Cr(VI) values (mg/kg ble reductants and oxidants occurring during the digestion of
dry substance) of 0.4 for soil exploited for agricultural, res- solids is reviewed with the aim of giving theoretical support to
idential and parkland uses and 1.4 for commercial and in- the choice of extraction conditions that minimise the risks of
dustrial land uses. In USA Cr limits may differ among dif- Cr(III)–Cr(VI) interconversions. This revisitation has pointed
ferent states. The cleanup standards proposed by the State out that the interference by humic substances that are an im-
of Maryland for residential and non-residential soil, for ex- portant component in soil and sediments, has not received
ample, are 23 and 610 mg/kg, respectively [4]. In Italy, the till now adequate attention, while that by Fe(II) and Fe(III)
recommended maximum concentration for Cr(VI) in com- deserves a better focusing of critical involved aspects.
post material is 10 mg/kg [5] and the highest permissible Experimental conditions adopted by the US EPA Method
Cr(VI) concentrations in soil are 2 and 15 mg/kg, depend- 3060A appear to be suitable to prevent Cr(III)–Cr(VI) inter-
ing on whether they are exploited for parkland or industrial conversions during the extraction. However, under the strong
uses [6]. alkaline conditions of this method humic compounds are re-
Experimental procedures for determining Cr(VI) in solid leased from soil and sediment making the subsequent analysis
matrices have been significantly improved in recent years. of Cr(VI) by the DPC method questionable.
The more recent methods keep interferences at a minimum,
although they have not yet completely solved this complex
problem. The report Soil Guideline values for chromium con- 2. Summary of literature methods for Cr(VI)
tamination [7] underlines that many analytical procedures for determinations in solids
determining Cr(VI) in soil allow interconversion of Cr(III)
and Cr(VI) forms making accurate determinations of Cr(III) The first efforts to set up an analytical protocol for de-
and Cr(VI) a considerable challenge. termining Cr(VI) in solid material date back to the end of
To quantify Cr(VI) concentrations in a solid matrix and seventies. Since then, many studies and new analytical proto-
verify their compliance with maximum contaminant limits, cols for Cr(VI) analysis and, more in general, Cr speciation in
a preliminary extraction of chromium(VI) from the solid is solid matrices have been proposed [10]. Some of these works
necessary. Extractants should be able to solubilize all forms giving an idea of the historical evolution in the protocols for
of Cr(VI) without inducing changes in the speciation of the analysis of Cr(VI) in solids are later on briefly described.
chromium. The extraction procedure is not required to be se- The attention was initially given to Cr(VI) levels in work-
lective for Cr(VI) since the differentiation between oxidised place atmospheres: in 1977, the National Institute for Oc-
and reduced Cr species may be obtained by using specific cupational Safety and Health (NIOSH) proposed a method
analytical methods. for the determination of total Cr(VI) in atmospheric particu-
The most common method for determining Cr(VI) in late. This consisted of spectrophotometric analysis of Cr(VI)
aqueous solutions is that based on the reaction of dyphenyl- with the DPC reagent after its acid extraction from air-filtered
carbazide (DPC) with Cr(VI) at pH of 1.0 ± 0.3 [8]. However, particles [11,12].
this spectrophotometric method suffers from the presence of In aqueous media, the first efforts were devoted to sol-
interfering compounds, which may be solubilized during the ubilize exchangeable Cr(VI) by shaking 2.5 g soil in 25 mL
extraction of Cr(VI). These include: (a) potentially reduc- K-phosphate buffer adjusted at pH 7.2; Cr(VI) was then deter-
ing compounds that react rapidly with Cr(VI) under the very mined by the standard DPC method [13]. In 1984, the USEPA
acid conditions of the standard DPC method, and (b) species proposed a protocol, known as Method 3060 [14], which con-
that absorb at 540 nm, which is the wavelength for measur- sisted of digesting 100 g solid sample in 400 mL hot, alkaline
ing the absorbance of the DPC–Cr colored complex. Another solution 0.28 M Na2 CO3 and 0.5 M NaOH (pH about 12) for
possible method for determining Cr(VI) is the ion chromato- 30–45 min. The filtered digestate was diluted to 1000 mL and
graphic analysis with post-column derivatization of Cr(VI) adjusted to pH 7–8 with nitric acid before being analysed for
with DPC [9]. The application of this method to digestates has Cr(VI) with DPC under standard pH conditions. In the ap-
the advantage that some of possible interfering compounds plication of this method it was also suggested to subtract the
are removed before of Cr(VI) derivatization. The digestate is absorbance before the DPC addition from that after the DPC
in fact adjusted to pH 9.0–9.5 with (NH4 )2 SO4 /NaOH buffer addition. This extraction protocol was not proved to give re-
solution and introduced into the ion chromatograph provided liable results [15], particularly in reducing sediments, and
with a guard column, which removes most of the organic it was removed from the following third edition of USEPA
compounds before Cr(VI) as CrO4 2− is separated on an an- methods [16].
ion exchange column and derivatized. IRSA-CNR [17] has proposed that total Cr(VI) in sludge
The growing interest for the determination of Cr(VI) in samples was determined by the DPC method, following solid
solid matrices has stimulated a critical revisitation of the pro- extraction under very acid conditions. According to this pro-
cedures proposed for extracting Cr(VI) from solids, in the cedure, 5 g dried, powdered and homogenised sample were
light of the knowledge gathered in recent years on the ki- suspended in 500 mL 0.18 M H2 SO4 and the suspension was
 M. Pettine, S. Capri / Analytica Chimica Acta 540 (2005) 231–238 233

stirred at room temperature for 10 min. Users of this method In 1996, Bartlett and James [23] proposed that readily
were warned against possible Cr(VI) underestimates in the soluble Cr(VI) was determined after soil extraction with
presence of reductants. deionised water. To this end, 2 g air or oven (40 ◦ C) dried and
These experimental efforts pointed out that Cr(VI) alka- powdered sample were suspended in 25 mL deionised water
line extraction has to be preferred to acid extraction because it and the suspension was maintained for 2 h under stirring.
ensures a better solubility of chromate compounds [18], some Methods for Cr(VI) quantitative extraction were also par-
of them insoluble under acid conditions, and also helps re- alleled by less aggressive attacks able to solubilize specific
ducing interferences by undesired Cr redox transformations Cr(VI) fractions and also give prompt response. A screen-
as well as by other common metals. The lowering of pH to ing method (DIN 19730) has been proposed for testing the
7–8 after alkaline digestion favour the formation of insolu- presence of Cr(VI) in soil consisting of 20 g soil shaken with
ble metal species (carbonate, oxides and hydroxocarbonates) 50 mL 1 M NH4 NO3 solution for 2 h [24].
which are removed by filtering the solution after digestion More recently, the Piemonte Region in Italy [25] has pro-
[19]. posed that Cr(VI) in composts is extracted with phosphate
Vitale et al. [20] tested the accuracy of the hot alkaline buffer solutions, following a method similar to that previ-
digestion of soil samples and investigated the reasons for oc- ously proposed for exchangeable Cr(VI) [13]. To this end, 2 g
casionally poor Cr(VI) spike recoveries. In their study they dried and powdered sample are suspended in 100 mL deaer-
confirmed the ability of the method to extract soluble and in- ated 0.1 M K2 HPO4 solutions buffered to pH 8.0 ± 0.1. Af-
soluble Cr(VI) forms and concluded that poor or 0% Cr(VI) ter 3 h stirring at room temperature, the suspension is filtered
spike recovery were observed only in strongly reducing sam- through 0.45 ␮m membrane filters.
ples. They proved that method-induced oxidation of Cr(III) The US Occupational Safety & Health Administration
might occur with freshly precipitated Cr(OH)3 , although they (OSHA) [1] has proposed that particulate Cr(VI) from work-
also noted that fresh Cr(OH)3 s is not likely to be present in place atmospheres is determined, after an alkaline digestion
real environmental samples. To help interpret recovery data, (10% Na2 CO3 /2% NaHCO3 in the presence of phosphate
they suggested the use of ancillary soil chemical parameters, and magnesium), by ion chromatography provided with an
including redox potential, pH, S2− and total organic carbon UV–vis detector.
concentrations as indicators of the redox state of samples. In Rüdel and Terytze [26] have proposed a laborious pro-
the case of samples characterised by strong reducing condi- tocol able to extract soluble Cr(VI) minimising possible in-
tions, poor Cr(VI) recovery would not be indicative of method terferences. To this end, 10.0 g soil were treated with 45 mL
deficiency; according to Vitale et al. [20], this should simply 0.1 M phosphate buffer adjusted to pH 8.0 and 1 mL 0.37 M
indicate the potential of samples to reduce Cr(VI) spike or Al2 (SO4 )3 was added. 1 mL 0.93 M Na2 SO3 was added to
not sustain the existence of Cr(VI) in the original sample. this suspension to reduce possible oxidising compounds other
James et al. [18] compared five different extractants than Cr(VI) that should not react with sulfite under these
for Cr(VI) from soil: distilled water (pH 5.7), phosphate conditions. More sulfite was in case added in order to as-
buffer (5 mM K2 HPO4 /5 mM KH2 PO4 , pH 7.0), carbonate- sure the presence of free sulfite that was checked by using
hydroxide solutions (0.28 M Na2 CO3 /0.5 M NaOH, pH 11.8) a sulfite-testing strip. If necessary, the suspension was ad-
with and without heating, and hydroxide solutions (0.1 M justed to pH 8, shaken for 30 min on a horizontal shaker and
NaOH, pH 13) with sonication. Their findings suggested that separated by centrifugation and filtration. Afterwards, 1 mL
a carbonate-hydroxide solution heated at 85 ◦ C was the most NaOCl (about 10 g/L Cl2 ) was added to the filtrate along
effective extractant for operationally defining total Cr(VI) in with 1 mL M H3 PO4 and 5 g NaCl to oxidise reducing com-
soil. This same comparative scheme was then adopted [21] pounds, included residual sulfite; the hypochlorite surplus is
to test the ability of the hot carbonate-hydroxide solution to converted to chlorine under these conditions and removed by
dissolve the less soluble Cr(VI) compound (BaCrO4 ). sparging air through the solution. This method was then stan-
In 1996 USEPA [22] revised the Method 3060 for extract- dardised and published by DIN [27] for the determination of
ing Cr(VI) from soil, sludges, sediments and solid wastes. Cr(VI) in phosphate buffer extracts.
This new method (3060A) was based on the findings by Finally, 0.1 M Na2 CO3 has been recently used to release
James et al. [18] and consisted of alkaline digestion at total Cr(VI) from soil [19]: subsamples of 0.25 g of soil were
90–95 ◦ C for 60 min. According to this method, 2.5 g of added to 25 mL 0.1 M Na2 CO3 , the mixture was boiled for
a field-moist and homogenised sample were placed into a 10 min, filtered trough Whatman no. 540 filter paper; then,
250 mL digestion vessel; 50 mL of digestion solution (0.28 M the soil was washed with other 0.1 M Na2 CO3 aliquots that
Na2 CO3 /0.5 M NaOH) followed by 400 mg of MgCl2 and were added to the previous filtrate. The latter was adjusted
0.5 mL of 1.0 M phosphate buffer (0.5 M K2 HPO4 /0.5 M to 25 mL volume with distilled water. Panichev et al. [19]
KH2 PO4 ) were added to the solid sample. The addition of also reported a protocol for determining Cr(VI) which can
Mg2+ in a phosphate buffer to the alkaline extraction solu- be “naturally” leached from soil. This method consists of pe-
tion prevented risks of Cr(III) oxidation, which may lead riodically shaking 0.25 g soil with 25.0 mL deionized water
to Cr(VI) overestimate, particularly in samples with high for 24 h and bubbling CO2 through the suspension for at least
Cr(III)/Cr(VI) ratios. 30 min. The Authors proved that the amount of Cr(VI) ex-
234 M. Pettine, S. Capri / Analytica Chimica Acta 540 (2005) 231–238

tracted did not change when the bubbling time was extended Table 1
from 30 min to more than 10 h. Redox half reactions relevant for chromium speciation and related equilib-
rium constants estimated at 95 ◦ C and 1.3 M ionic strength, unless otherwise
indicated
Reaction log K
3. Theoretical kinetic background for Cr(III)–Cr(VI)
interconversions O2 (g) + 4H+ + 4e → 2H2 O 64.6
O2 (g) + 2H+ + 2e− → H2 O2 17.4
CrO4 2− + 5H+ + 3e− → Cr(OH)3 + H2 O 46.2
The experimental conditions adopted for the extraction CrO4 2− + 4H+ + 3e− → Cr(OH)4 − 37.7
of Cr(VI) from solid matrices significantly influence the ␥-MnOOH + 3H+ + e− → Mn2+ + 2H2 O 17.8a
reliability of the final results owing to possible undesired ␥-MnOOH + 2H2 O + e− → Mn(OH)4 2− + H+ −21.7b
Cr(VI)–Cr(III) interconversions. Fe(OH)3 (s) + 3H+ + e− → Fe2+ + 3H2 O 12.7
Fe(OH)3 (s) + e− → Fe(OH)3 − −14.2
The thermodynamic values of pE, which expresses the po- SO4 2− + 9H+ + 8e− → HS− + 4H2 O 25.4
tentiality of a redox couple to accept or donate electrons, are 2CO2 (aq) + 2e− → C2 O4 2− −15.6
shown in Fig. 1 as a function of pH for redox couples of envi- C6 H5 COO− + 3H+ + 2e− → C6 H5 CHO + H2 O −2.8
ronmental relevance for chromium speciation. The pE values CH3 COCH3 + 2H+ + 2e− → CH3 CHOHCH3 2.3
were calculated at 95 ◦ C and 1.3 M ionic strength, which are γ = 1 for uncharged species; γ = 0.40 for Cr(OH)4 − , Fe(OH)3 − , HS− ,
the experimental conditions adopted by the US EPA method C6 H5 COO− ; γ = 0.30 for Fe2+ , Mn2+ ; γ = 0.05 for CrO4 2− , SO4 2− ,
3060A for the extraction of chromium. Equilibrium constants Mn(OH)4 2− , C2 O4 2− ; γ = 1.3 for H+ .
a The enthalpy of formation for ␥-MnOOH was estimated from that of
at 95 ◦ C were calculated with the van’t Hoff equation, start- MnO2 and ␥-Fe(OOH).
ing from thermodynamic values obtained from the literature b log K is at 25 ◦ C due to the uncertainty on the standard enthalpy of

or calculated from changes in standard Gibbs free energy. In formation of Mn(OH)4 2− that prevented the calculation at 95 ◦ C.
these calculations, it was assumed that changes in the stan-
dard enthalpy for the redox half reactions were independent at 1.5 M NaCl [28] and were supposed not to be significantly
of temperature in the range 25–95 ◦ C and ionic strength in the affected by temperature up to 95 ◦ C. Relevant redox couples
range 0–1.3 M. The activity coefficients (γ) were estimated in the pH range 7.5–13 are listed in Table 1 together with
by analogy with those of similar charged species calculated the equilibrium constants estimated at 95 ◦ C and 1.3 M ionic
strength. For Fe(II), Mn(II) and Cr(III), in addition to Fe2+ ,
Mn2+ and Cr(OH)3 that are dominant in the lower part of
the pH range 7.5–13, we considered the species Fe(OH)3 − ,
Mn(OH)4 2− and Cr(OH)4 − as possible products of the re-
duction of Fe(OH)3 (s), ␥-MnOOH and CrO4 2− under strong
alkaline conditions (pH >10–11).
It is clear from Fig. 1 that Cr(VI) may react with many
inorganic reductants such as Fe(II) and sulfide; a number
of organic compounds including carboxylic and hydroxo-
carboxylic acids, aldehydes, phenols, humic acid (HU), etc.
are also able to reduce chromium(VI). Humic matter and Fe
are common components in soil and sediments and can be
easily released from these solids under strong alkaline solu-
tions. The attack of solid material with 0.5 M NaOH solution
is in fact suggested to solubilize humic substances [29]. Fur-
thermore, the solubility of Fe(III) is markedly increased in
strongly alkaline solutions (pH >10) because of the forma-
tion of Fe(OH4 − ) species [30].
Thermodynamic calculations also suggest that a number
of chemicals including molecular oxygen and Mn(IV) oxides
are potential oxidants for Cr(III) under acid and alkaline con-
ditions, while hydrogen peroxide and Mn(III) oxides may be
an oxidant or a reductant depending on pH [31,32].
Fig. 1. Values of pE for redox couples of environmental relevance
for chromium speciation as a function of pH. A: O2 /H2 O; B:
Cr(III)–Cr(VI) interconversions may take place when re-
O2 /H2 O2 ; C: CrO4 2− /Cr(OH)4 − ; D: CrO4 2− /Cr(OH)3 ; E: SO4 2− /HS− ; actants, which are able to reduce Cr(VI) or oxidise Cr(III),
F: Fe(OH)3 s/Fe(OH)3 − ; G: Fe(OH)3 s/Fe2+ ; H: MnOOHs/Mn2+ ; I: are present and the operational conditions are suitable for
MnOOHs/Mn(OH)4 2− ; L: C2 O4 2− /CO2 aq; M: C6 H5 CHO/C6 H5 COO− ; N: these redox reactions to occur. Therefore, the kinetic charac-
CH3 CHOCH3 /CH3 COCH3 . Calculations were performed with the equilib- teristics of the redox reactions, which on a thermodynamic
rium constants given in Table 1 and assuming: [Mn(II)] = [Fe(II)] = 10−6 M;
O2 = 0.2 atm; [H2 O2 ] = 10−7 M; concentration ratio of 1:1 for oxidized and
basis may be responsible for Cr(VI)–Cr(III) interconversions
reduced species. during the digestion, need to be carefully evaluated.
 M. Pettine, S. Capri / Analytica Chimica Acta 540 (2005) 231–238 235

constants for the reaction of Cr(VI) with Fe(II) as a function

of pH. Rates for this reaction are very fast under both very
acid and very alkaline pH while show a minimum at pH of
about 5.
Under acid solutions, the oxidation of Fe(II) with O2 is
very slow with a half-life of days to weeks [35]; therefore,
free hydrated Fe(II) is quite stable in the presence of oxygen
and is available to react with Cr(VI) during acid extraction.
This reaction leads to Cr(VI) underestimates in the solid.
According to the stoichiometry and kinetics of this reaction
[33,34], Cr(VI) may react completely with Fe(II) giving a
Cr(VI) loss that amounts to 1/3 of the molar concentration of
Fe(II). Therefore, when the Fe(II) molar concentration in the
solid is higher than a factor of 3 with respect to that of Cr(VI),
the latter may not be revealed at all. In this case, the method
may be insensitive or respond only partially to Cr(VI) spikes
to the solid sample.
The extraction of Cr(VI) under strong alkaline conditions
prevents the interference by Fe(II). Under these conditions,
the reaction of Cr(VI) with Fe(II) is still theoretically possible
and the rates are as fast as those under strong acid conditions
Fig. 2. Logarithmic values of the overall kinetic constant for the reduction
(Fig. 2). However, under strong alkaline conditions, Fe(II) is
of 0.95 ␮m Cr(VI) with 39.2 (䊉) and 9.8 () ␮m Fe(II) as a function of pH
in 0.1 M NaCl at 10 ◦ C, Pettine et al. [34]. rapidly oxidised by dissolved oxygen and made unavailable
to interact with Cr(VI). The kinetics of the reaction of Fe(II)
3.1. Cr(VI) reduction processes with O2 increase with increasing pH and in the pH range 6–9
the rates are second order in [OH] [36,37]. Table 2 compares
Fe(II) is a common component in solid matrices and its the rates (M min−1 ) for the oxidation of Fe(II) with Cr(VI)
reaction with Cr(VI) during the extraction treatment leads to (Rate A) and O2 (Rate B) at various pH (6; 8; 10; 12). Rate A
Cr(VI) concentrations, which are lower than the real ones. were calculated according to the Eq. (3) by considering that
Although the reaction of Cr(VI) with Fe(II) is thermody- d[Fe(II)]/dt = 3(d[Cr(VI)]/dt), while rates B were calculated
namically possible over the entire pH field [33,34], its ac- by using the rate law reported by Millero [37]
tual occurrence during the digestion depends on the kinetic
−d[Fe(II)]/dt = kFe(II) [Fe(II)][OH]2 [O2 ] (4)
characteristics of the reaction. Pettine et al. [34] obtained the
following rate expression for this reaction where kFe(II) may be expressed as a function of temperature
−d[Cr(VI)]/dt = kCr(VI) [Cr(VI)][Fe(II)] (1) and ionic strength (I) by
1545
where k (M−1 min−1 ) is given by the equations log kFe(II) = 21.56 − + 0.47 I 0.5
T
188.5
log kCr(VI) = 6.74 − 1.01pH − (2) 646 I 0.5
T − + 0.72 I (5)
T
4260
log kCr(VI) = 11.93 + 0.95pH − − 1.06I 0.5 (3)
T In these calculations it was assumed that both the ki-
that are valid in the pH ranges 1.5–4.5 (σ = ±0.2) and 5–8.7 netic Eqs. (3) and (5), fitted to rate data in the range of pH
(σ = ±0.2), respectively, from 5 to 40 ◦ C and 0.01 to 2 M ionic from 5 to about 9, might be extended to slightly higher pH
strength. Fig. 2 shows the logarithmic values of the kinetic values. Cr(VI) and Fe(II) concentrations used in these cal-

Table 2
Comparison of rates (M min−1 ) calculated at various pH for the oxidation of Fe(II) with Cr(VI) (Rate A) and O2 (Rate B) under two different conditions: (a)
0.01 M NaCl, 25 ◦ C, [O2 ] = 2.5 × 10−4 M; (b) 50 ◦ C, 1 M NaCl, [O2 ] = 1.4 × 10−3 M
pH Rate A, 0.01 M; 25 ◦ C Rate B, 0.01 M; 25 ◦ C; Rate A, 1 M; 50 ◦ C Rate B, 1 M; 50 ◦ C;
[O2 ] = 2.5 × 10−4 M [O2 ] = 1.4 × 10−3 M
6 1.9 × 10−7 1.8 × 10−10 2.7 × 10−7 5.0 × 10−9
8 1.5 × 10−5 1.8 × 10−6 2.2 × 10−5 5.0 × 10−5
10 1.2 × 10−3 1.8 × 10−2 1.7 × 10−3 5.0 × 10−1
12 9.6 × 10−2 1.8 × 102 1.4 × 10−1 5.0 × 103
In both (a) and (b) cases [Cr(VI)] = 0.95 ␮M and [Fe(II)] = 39.2 ␮M.
236 M. Pettine, S. Capri / Analytica Chimica Acta 540 (2005) 231–238

culations were 0.95 and 39.2 ␮M and two different experi- Sulfite is another possible reductant of Cr(VI). The rates
mental conditions were considered: (1) 25 ◦ C, 0.01 M ionic of the reaction also in this case are fast under acid conditions
strength and 2.5 × 10−4 M O2 ; (2) 50 ◦ C, 1 M ionic strength while become very slow under alkaline conditions [41–43].
and 1.4 × 10−4 M O2 . Eckert et al. [44] and Wittbrodt and Palmer [45] have in-
Table 2 clearly shows that under strong alkaline conditions vestigated the rates of the reaction of Cr(VI) with humic acids
the rates of the oxidation of Fe(II) with dissolved oxygen be- and found that this reductant is efficient at very acid pH. A
come faster than those for the oxidation of Fe(II) with Cr(VI). half-life for Cr(VI) reduction of a few minutes was obtained
It also results from Table 2 that temperature increases have a at pH 1, in the presence of 100 mg/L HU, while the reduc-
higher influence on the rates of the oxidation of Fe(II) with O2 tion takes place on a kinetic scale of hours at pH 3, and of
with respect to those for the oxidation of Fe(II) with Cr(VI). days and weeks in the pH range 4–7 at 20–800 ␮M Cr(VI)
The actual difference between the rates of these two com- and 25 ◦ C [45]. Fukushima et al. [46] calculated pseudo first
petitive redox processes under high alkaline conditions can- order rate constants for the reduction of Cr(VI) with 40 mg/L
not be strictly evaluated since the above rate expressions are HU of 2.71 × 10−3 and 1.99 × 10−3 h−1 at pH 3.2 and 5.1,
accurate up to pH 9–10 and temperatures of 40–50 ◦ C. How- respectively. Wittbrodt and Palmer [47] and Zhilin et al. [48]
ever, the rate difference resulting from Table 2 is a conser- also reported a catalytic effect of Fe(III) on the reduction
vative estimate. In high alkaline, carbonate-rich solutions, of Cr(VI) in the presence of humic and fulvic acids. Many
rates for the oxidation of Fe(II) with O2 are in fact strongly other organic reductants have a similar behaviour as sul-
increased by the species Fe(CO3 )2 2− that reacts faster than phide, sulfite and HU with high and negligible rates under
Fe(OH)2 [35], while oxidation rates of Fe(II) with Cr(VI) are strongly acid and alkaline conditions, respectively. A neg-
not affected by carbonate species [34]. The positive effect of ative influence of increasing pH has also been proved for
carbonates on the rates of oxidation of Fe(II) with O2 should surface-catalysed Cr(VI) reduction by low molecular weight
widely balance the diminished concentration of O2 with in- organic compounds [49].
creasing temperature up to 80–90 ◦ C. On the contrary, under Kinetic and thermodynamic characteristics of the reac-
acid conditions the oxidation of Fe(II) with Cr(VI) becomes tions for Cr(VI) reduction and increased competition by
dominant with respect to the parallel oxidation of Fe(II) with molecular oxygen reacting faster than Cr(VI) with possible
molecular oxygen. The effect of phosphate on the rates of reductants contribute to lower the risk of reduction of Cr(VI)
oxidation of Fe(II) with Cr(VI) in the pH range 7–8 has also at pH higher than 10.
been investigated in two previous investigations [33,34]. Re-
sults were contrasting with an increase in the rates in the 3.2. Cr(III) oxidation processes
former case and a lowering of a factor 2–10 in the latter.
However, even in the more propitious case of a lowering in Contrary to the diminished risk of reduction of Cr(VI)
the rates, risks for the reduction of Cr(VI) by Fe(II) at pH with increasing pH, the risk of oxidative processes converting
7–8 are present (see Table 2), discouraging the digestion in Cr(III) to Cr(VI) tends to increase with increasing pH. The
the presence of phosphate buffer. oxidation of Cr(III) with H2 O2 was found to be first order with
The above considerations suggest that a value of pH ≥10 respect to OH− [31,50]. The proposed rate expression was
along with high carbonate concentration and high tempera-
d[Cr(III)]/dt = −kCr(III) [Cr(III)][H2 O2 ] (6)
tures would be able to prevent interference by Fe(II) since
they favour its oxidation by dissolved oxygen. where kCr(III) (M−1 min−1 ) = k1 /[H2 O2 ] (k1 is the pseudo
The alkaline digestion also minimises other possible re- first order kinetic constant) is given by
actions leading to the reduction of Cr(VI) by sulfide, sulfite,
5.13
humic matter and other organic compounds. log kCr(III) = −4.60 − + 0.87pH (7)
Pettine et al. [38,39] have investigated the rates of the re- T
duction of Cr(VI) with sulfide in the pH range 7.6–9.5 at from 5 to 40 ◦ C, pH 7–9 and I = 0–1 M (S.D. = ±0.06 in
Cr(VI) concentrations of 1.9 ␮M and sulfide concentrations log k). In these studies it was proved that oxidation rates are
in the range 400–1400 ␮M. They found that Cr(VI) half lives strongly influenced by Cr(III) aging at pH >9. In the absence
lowered from about 2 h at pH 7.6 to more than 160 h at pH of significant aging, Eq. (7) gives a half-life for the oxidation
9.5. Similar findings were obtained at much higher Cr(VI) of Cr(III) with 10−6 M H2 O2 at 40 ◦ C of about 423 min at
concentrations and about 800 mM sulfide [40]. According to pH 9. At pH >9 aging processes make Cr(III) less prone to
these previous findings, rates are expected to continue low- be oxidised. Once results are corrected for aging, the above
ering at pH >9.5 because the free H2 S fraction, that was rate expression holds up to pH higher than 10; its application
supposed to control the kinetics through its interaction with to 40 ◦ C, 10−6 M H2 O2 , pH 10 and 12 gives half-lives of
CrO4 2− , diminishes with increased pH. Such low rates of 57 and 1 min, respectively. These calculated rates would
reduction of Cr(VI) with sulfide at high pH, along with the make the alkaline digestion unsuitable for the determination
competitive oxidation of sulfide by oxygen, make this re- of Cr(VI). However, Cr(III) aging is also strongly and
ductant unable to interact with Cr(VI) in strongly alkaline positively affected by increase in pH and temperatures, thus
digestion. reducing as matter of fact the potential oxidation of Cr(III).
 M. Pettine, S. Capri / Analytica Chimica Acta 540 (2005) 231–238 237

H2 O2 occurs in surface waters, atmosphere and soil material. 4. Weakness of the standard DPC method applied to
Recently, the large amount of H2 O2 that are introduced Cr(VI) determination in soil and sediment extracts
to soil through wet and dry depositions and its role as an
oxidant have been stressed [51]. In addition to Cr(III)–Cr(VI) interconversions that may
Molecular oxygen and manganese oxides are, probably, occur during the extraction of chromium from soil and sed-
more important oxidants with respect to H2 O2 during the iment, the subsequent DPC determination of Cr(VI) in the
digestion of solids. The kinetics of the oxidation of Cr(III) extract may be biased by the presence of extractable reducing
to Cr(VI) with O2 is known to be slow with half lives in the compounds. This is the case for soils and sediments that re-
order of 1–20 months [52–57]. Van Der Weijden and Reith lease humic compounds under the strong alkaline conditions
[56], in particular, did not observe any oxidation of Cr(III) of the US EPA method 3060A. The organic matter content
by O2 after 6 weeks at 320 K. varies widely from arid to peat soil and a conservative aver-
Mn oxides were found to be faster oxidants for Cr(III) than age estimate for the HU content in most soils is in the range
O2 . The 1 ␮M Cr(III) in seawater at pH 8.1 and 25 ◦ C was 0.5–2% [61]. If 1 g soil material with 1% HU is digested
oxidised by 30 mg/L ␥-MnOOH in 100 h, giving an overall according to the US EPA method 3060A [22], the HU con-
constant k ≈ 0.0008 M−1 s−1 [58]. According to the equilib- centration in the 50 mL extract may be as high as 100 mg/L
rium constants estimated at 95 ◦ C and 1.3 M ionic strength assuming that only 50% of the total HU is released during
(Fig. 1), ␥-MnOOH should not be an oxidant of Cr(III) at the extraction of chromium.
pH 8.1. A rate constant of 0.0063 M−1 s−1 for the oxidation Under these conditions, the standard pH of the DPC
of 100 mg/L Cr(III) at pH about 6 with 100 mg/L MnO2 in method of 1.0 ± 0.3 [8] is very critical, since Cr(VI) half
both freshwater and seawater was also reported [55]. Rates lives were reported in the order of minutes in the presence
of oxidation have been found to be strongly related to the of 100 mg/L humic compounds [45]. The inversion in the
amount and surface area of Mn oxides. Different theoretical order of the reagents (DPC followed by acid) or the simul-
stoichiometry and rates have been suggested for different Mn taneous addition of acid and DPC to the sample is recom-
oxides [57,59]. Eary and Rai [57] have reported that Cr(III) is mended in this case for reducing possible interferences. Un-
readily oxidised to Cr(VI) by ␤-MnO2 (s) over the pH range fortunately, the strong influence pH plays on the rates of the
3.0–10.1 and calculated a half-life of 95 days for the oxida- reaction of Cr(VI) with HU, makes the latter able to com-
tion of a 10−5 M Cr(III) solution for 1 kg of a 20% porosity pete with DPC for Cr(VI) at pH 1. Although it is not possi-
soil containing 0.05 wt% ␤-MnO2 (s) with a surface area of ble a priori to evaluate the actual weight of this interference
5.0 m2 g−1 . Other forms of soil manganese oxides such as since it depends on the concentration of HU in the extract
birnessite (␦-MnO2 ) and cryptomalene (␣-MnO2 ), that are and also on the type of humic material and its functional
likely to have higher surface energies than ␤-MnO2 (s), may groups and the presence of possible catalysts, it is doubt-
cause a more rapid oxidation of Cr(III) than ␤-MnO2 (s). ful that the above changes of the method may prevent this
The USEPA method 3060A [22] took into account the interference.
possibility that native Cr(III) in solid matrices could be Furthermore, HU solutions absorb at 540 nm, which is the
oxidised under alkaline conditions and suggested that, in the wavelength for the measurement of the Cr–DPC product. A
case the oxidation was suspected, Mg2+ was added to the concentration of 5 mg/L HU, which is much lower than that
alkaline extracting solution to suppress the oxidation. It was expected in the extract, gives an absorbance of 0.075 U using
hypothesised that the suppression was due to Cr(III) copre- 5 cm pathlength. This value corresponds to the absorbance
cipitation with Mg2+ or to sorption of Mg2+ on Mn oxides given by 20 ␮g/L Cr(VI). The subtraction of the absorbance
rendering them less prone to oxidise Cr(III) [20]. Mg2+ was given by a sample aliquot spiked with acid at pH 1 in the
also proved to play a strong negative effect on the rates of absence of the DPC reagent may partially help measure the
oxidation of Cr(III) with H2 O2 because of its influence on the actual absorbance given by the Cr–DPC product. However,
aging of Cr(III) [50]. This effect was supposed to be due to the the higher is the ratio between the absorbances of the blank
formation of a solid phase of the type Crx Mg(1 − x)1.5 (OH)3 and the Cr–DPC product the lower becomes the significance
that, similarly to the mixed solid phase Crx Fe(1 − x)1.5 (OH)3 of the measurement.
[60], controls the solubility of chromium(III). This effect of The combination of these two types of interference caused
Mg2+ is probably observed also in the case of the oxidation by HU may seriously bias the DPC determination of Cr(VI)
of Cr(III) with O2 and MnO2 and substantiates the USEPA in soils and sediments, also in the case the extraction is car-
choice of adding this metal to suppress the oxidation of Cr(III) ried out without producing any change in the speciation of
during the alkaline digestion of solids. A similar influence on chromium. Zhilin et al. [48] stressed that the applicability
Cr(III) aging was also proved in the case of carbonate [50]. of the spectrophotometric DPC method requires a complete
Based on these considerations concerning the kinetics of removal of humic substances prior to analysis and for this
Cr(III) oxidation, a value of pH around 10, high temperature purpose used capillary zone electrophoresis.
and high concentrations of Mg2+ and carbonate ions would These considerations have stimulated our interest in de-
minimise risks of Cr(III) conversion to Cr(VI) during the veloping a modified DPC protocol for the analysis of Cr(VI)
digestion of solid samples. in the presence of humic compounds [62].
238 M. Pettine, S. Capri / Analytica Chimica Acta 540 (2005) 231–238

5. Conclusions [21] R.J. Vitale, G.R. Mussoline, K.A. Rinehimer, J.C. Petura, B.R.
James, Environ. Sci. Technol. 31 (1997) 390.
The comparative analysis of variables affecting either the [22] United States Environmental Protection Agency, Method 3060A, in:
Test Methods for Evaluating Solid Wastes, Physical/Chemical Meth-
kinetics of Cr(VI) reduction or the kinetics of Cr(III) oxida-
ods, SW-846, Update, Office of Solid Waste and Emergency Re-
tion highlights that a pH higher than 10, high temperature sponse, Washington, DC, 1996.
along with the presence of high concentrations of carbonate [23] R.J. Bartlett, B.R. James, Chromium, in: D.L. Sparks (Ed.), Methods
and magnesium ions are necessary conditions for minimising of Soil Analysis. Part 3—Chemical Methods, SSSA, Madison, WI,
Cr(III)–Cr(VI) interconversions during the digestion of solid 1996.
[24] DIN 19730, Berlin, 1997.
samples. These theoretical considerations support the ability
[25] Regione Piemonte—Assessorato all’Ambiente, Metodi di analisi dei
of the Method 3060A for extracting Cr(VI) from solids; how- compost, 1998.
ever, the applicability of the DPC method to the analysis of [26] H. Rüdel, K. Terytze, Chemosphere 39 (1990) 697.
Cr(VI) in alkaline extract from soil and sediment samples is [27] DIN 19734, Berlin, 1999.
questionable because of the complex interfering role played [28] F.J. Millero, D.R. Schreiber, Am. J. Sci. 282 (1982) 1508.
[29] M.H.B. Hayes, R.S. Swift, R.E. Wardle, J.K. Brown, Geoderma 13
by humic matter.
(1975) 231.
[30] F.J. Millero, W. Yao, J. Aicher, Mar. Chem. 50 (1995) 21.
[31] M. Pettine, F.J. Millero, Limnol. Oceanogr. 35 (1990) 730.
[32] M. Pettine, L. Campanella, F.J. Millero, Environ. Sci. Technol. 36
(2002) 901.
References [33] D.L. Sedlak, P.G. Chan, Geochim. Cosmochim. Acta 61 (1997) 2185.
[34] M. Pettine, L. D’Ottone, L. Campanella, F.J. Millero, R. Passino,
[1] United States Occupational Safety & Health Administration, OSHA Geochim. Cosmochim. Acta 62 (1998) 1509.
Analytical Methods Manual, second ed., Method ID-215, 1998. [35] D.W. King, Environ. Sci. Technol. 32 (1998) 2997.
[2] Swedish Environmental Protection Agency, Guidelines for polluted [36] F.J. Millero, S. Sotolongo, M. Izaguirre, Geochim. Cosmochim. Acta
soils, 2002 (Chapter 2). 51 (1987) 793.
[3] Canadian Council of Ministers of the Environment, Canadian Envi- [37] F.J. Millero, Mar. Chem. 28 (1989) 1.
ronmental Quality Guidelines, Winnipeg, 2001. [38] M. Pettine, F.J. Millero, R. Passino, Mar. Chem. 46 (1994) 335.
[4] State of Maryland, Department of the Environment, Interim Final [39] M. Pettine, I. Barra, L. Campanella, F.J. Millero, Water Res. 32
Guidance, 2001. (1998) 2807.
[5] Comitato Interministeriale n. 915, Gazzetta Ufficiale Supplemento [40] C. Kim, Q. Zhou, B. Deng, E.C. Thornton, H. Xu, Environ. Sci.
Ordinario N. 253, 1984. Technol. 35 (2001) 2219.
[6] Decreto Ministeriale n. 471, Gazzetta Ufficiale Supplemento Ordi- [41] J.P. Beukes, J.J. Pienaar, G. Lachmann, E.W. Giesekke, Water SA
nario N. 293, 1999. 25 (1999) 363.
[7] Environment Agency R&D Dissemination Centre, Swindon, 2002. [42] C.R. Martins, C.A. Cabral Neto, J.J.F. Alves, J.B. de Andrade, J.
[8] APHA, AWWA, WEF 20th ed., APHA, Washington, DC, 1998. Braz. Che. Soc. 10 (1999) 453.
[9] United States Environmental Protection Agency, Method 7199, Of- [43] L. Che-Jen, Water Air Soil Pollut. 139 (2002) 137.
fice of Solid Waste and Emergency Response, Washington, DC, [44] J.M. Eckert, J.J. Stewart, T.D. Waite, R. Szymczak, K.L. Williams,
1996. Anal. Chim. Acta 236 (1990) 357.
[10] M.J. Marqués, A. Salvador, A.E. Morales-Rubio, M. de la Guardia, [45] P.R. Wittbrodt, C.D. Palmer, Environ. Sci. Technol. 29 (1995)
Fresenius J. Anal. Chem. 362 (1998) 239. 255.
[11] National Institute for Occupational Safety and Health, Method No. [46] M. Fukushima, K. Nakayasu, Sh. Tanaka, H. Nakamara, Toxicol.
P&CAM 169, in: NIOSH Manual of Analytical Methods, vol. 1, Environ. Chem. 62 (1997) 207.
second ed., Cincinnati, OH, NIOSH, 1977 (DHEV/NIOSH Pub. No. [47] P.R. Wittbrodt, C.D. Palmer, Environ. Sci. Technol. 30 (1996)
77-157-A). 2470.
[12] National Institute for Occupational Safety and Health, Method No. [48] D.M. Zhilin, P. Schmitt-Koplin, I.V. Perminova, Environ. Chem. Lett.
S317, in: NIOSH Manual of Analytical Methods, vol. 3, second ed., 2 (2004) 141.
Cincinnati, OH, NIOSH, 1977 (DHEV/NIOSH Pub. No. 77-157C). [49] B. Deng, A.J. Stone, Environ. Sci. Technol. 30 (1996) 2484.
[13] B.R. James, R.J. Bartlett, J. Environ. Qual. 12 (1983) 177. [50] M. Pettine, F.J. Millero, T. La Noce, Mar. Chem. 34 (1991) 29.
[14] United States Environmental Protection Agency, Method 3060, in: [51] B.R. Petigara, N.V. Blough, A.C. Mignerey, Environ. Sci. Technol.
Test Methods for Evaluating solid wastes, physical/chemical meth- 36 (2002) 639.
ods, second ed., SW-846. Office of Solid Waste and Emergency [52] R.E. Cranston, J.M. Murray, Anal. Chim. Acta 99 (1978) 275.
Response, Washington, DC, 1984. [53] R.M. Fukai, D. Vas, J. Oceanogr. Soc. Jpn. 25 (1969) 47.
[15] United States Environmental Protection Agency, USEPA Rep. 600/4- [54] D.C. Schroeder, G.F. Lee, Water Air Soil Pollut. 4 (1975) 355.
86/039, Cincinnati, OH, 1986. [55] S. Emerson, R.E. Cranston, P.S. Liss, Deep-Sea Res. 26 (1979) 859.
[16] United States Environmental Protection Agency, in: Test Methods for [56] C.H. Van der Weijden, M. Reith, Mar. Chem. 11 (1982) 565.
Evaluating Solid Wastes, Physical/Chemical Methods, third ed., SW- [57] L.E. Eary, D. Rai, Environ. Sci. Technol. 21 (1987) 1187.
846. Office of Solid Waste and Emergency Response, Washington, [58] E. Nakayama, S. Tsurubo, T. Fujinaga, Anal. Chim. Acta 130 (1981)
DC, 1990. 401.
[17] IRSA-CNR, Quad. Ist. Ric. Acque 64 (1986) 1. [59] F.C. Richard, A.C.M. Bourg, Water Res. 25 (1991) 807.
[18] B.R. James, R.J. Vitale, G.R. Mussoline, J.C. Petura, Environ. Sci. [60] B.M. Sass, D. Rai, Inorg. Chem. 26 (1987) 2228.
Technol. 29 (1995) 2377. [61] E. Myslinska, Geolog. Quart. 47 (2003) 39.
[19] N. Panichev, K. Mandiwana, G. Foukaridis, Anal. Chim. Acta 491 [62] M. Pettine, S. Capri, Anal. Chim. Acta (in press).
(2003) 81.
[20] R.J. Vitale, G.R. Mussoline, J.C. Petura, B.R. James, J. Environ.
Qual. 23 (1994) 1249.