Professional Documents
Culture Documents
5
The Transport and Fate of Cr(VI)
in the Environment
CONTENTS
5.1 The Presence of Chromium in the Environment .................................163
5.1.1 Antropogenic Sources...................................................................164
5.1.2 Natural Sources .............................................................................165
5.2 Geochemistry of Chromium ....................................................................165
5.2.1 Cr(III)...............................................................................................166
5.2.2 Cr(VI)...............................................................................................167
5.3 Oxidation-Reduction of Chromium........................................................168
5.3.1 Review of Oxidation-Reduction Reactions ...............................168
5.3.2 General Redox Behavior of Chromium
in the Environment .......................................................................169
5.3.3 Oxidation of Chromium...............................................................170
5.3.3.1 Oxidation of Cr(III) to Cr(VI) by Dissolved
Oxygen and Manganese Dioxides ...............................171
5.3.3.2 Oxidation of Cr(III) to Cr(VI) by H2O2 .......................172
5.3.4 Reduction of Cr(VI) to Cr(III) .....................................................172
5.3.4.1 General..............................................................................172
5.3.4.2 Fe(II) (Dissolved Fe(II) and Fe(II)-Containing
Minerals)...........................................................................173
5.3.4.3 Sulfides .............................................................................175
5.3.4.4 Organic Matter ................................................................175
5.3.4.5 Cu(I) ..................................................................................176
5.3.4.6 Hydrogen Peroxide(H2O2).............................................176
5.4 Precipitation/Dissolution Reactions of Chromium .............................176
5.5 Sorption and Desorption Reactions of Chromium ..............................177
5.5.1 General Discussion of Sorption ..................................................177
5.5.2 Sorption of Chromium .................................................................178
5.5.2.1 Sorption of Cr(III) ...........................................................178
5.5.2.2 Sorption of Cr(VI) ...........................................................179
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treatment, etc.), but also its natural presence in rocks enriched in chromium
(i.e., ultramafic rocks such as serpentinite). Compared to the results of con-
tamination of soil and groundwater by industrial practices, the naturally-
occurring concentrations of chromium in soil and groundwater are relatively
low. However, relatively high concentrations of naturally-occurring dis-
solved chromium have been observed, usually associated with the very
soluble chromate species (Robertson, 1975). Thus, both anthropogenic (man-
made) and natural sources of chromium can lead to locally elevated levels
in soils and waters.
The presence of chromium in the environment is discussed by several
authors (Davis and Olsen, 1995; Kimbrough et al., 1999; Richard and Bourg,
1991; Kotas and Stasicka, 2000). Their presentations are briefly summarized
below. Chapter 4 gives additional information on naturally-occurring Cr(VI)
in groundwater.
5.2.1 Cr(III)
In aqueous systems, Cr(III) can be present as Cr3+, Cr(OH)2+, Cr(OH)2+, and
Cr(OH)4. Additionally, the precipitated phase Cr(OH)3 predominates
between pH 6 and pH 12 (Rai et al., 1987). Under slightly acidic to alkaline
conditions, and if Fe(III) is present, Cr(III) can precipitate as an amorphous
mixed hydroxide CrxFe1x(OH)3 (Eary and Rai, 1988). Amorphous Cr(OH)3
can crystallize as Cr(OH)3 3H2O or Cr2O3 (eskolaite) under different condi-
tions (Palmer and Puls, 1994). With high redox potential, Cr(VI) predomi-
nates with a much higher solubility (Loyaux-Lawniczak et al., 2001). In a
reducing environment, and in the absence of Fe, Cr(III) precipitates readily
to form Cr(OH)3 (Rai et al., 1987).
In relatively low Eh environments, the main aqueous Cr(III) species are
Cr3+, Cr(OH)2+, Cr(OH)30 and Cr(OH)4 (Rai et al., 1986, 1987). The Cr3+ species
is prevalent only at pH lower than about 4. With increasing pH, hydrolysis
of Cr3+ yields Cr(OH)2+ (generally present in groundwater at a pH of 6 to 8
but also in some acidic waters), and Cr(OH)30 and Cr(OH)4 (generally in
alkaline groundwater) (Rai et al., 1987). Polymeric species such as Cr2(OH)24+,
Cr3(OH)45+ and Cr4(OH)66+ are never significant in natural systems (Rai et al.,
1986, 1987). Cr(III) readily forms complexes with a variety of ligands:
hydroxyl, sulfate, ammonium (NH4), cyanide and sulphocyanide, fluoride
and chloride (to a lesser extent), and natural and synthetic organic ligands
(Richard and Bourg, 1991). Only one Cr(III) compound, Cr2O3, is an oxide,
so the role of oxygen is central to the oxidation/reduction (redox) process
for chromium (Kimbrough et al., 1999).
Solubility can significantly limit the concentration of Cr(III) in groundwa-
ter at a pH above 4. The low solubility of the Cr(III) solid phases, Cr2O3 and
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Cr(OH)3 (Hem, 1977), is likely the major reason why Cr(III) generally makes
up a small percentage of the total chromium concentration in natural or
contaminated groundwaters. Cr(III) tends to be essentially immobile in most
groundwaters because of its low solubility (Calder, 1988).
5.2.2 Cr(VI)
Chromium(VI) exists in the environment as part of several compounds, Cr(VI)
is present in solution as monomeric forms: H2CrO40, HCrO4 (bichromate),
CrO42 (chromate), and CrO3 (chromium(III) oxide), or as the dimeric ion
Cr2O72 (dichromate) (Palmer and Puls, 1994). Under oxidizing conditions,
aqueous chromium is present in a Cr(VI) anionic form, HCrO4 or CrO42,
depending on the pH (CrO42 at a higher pH) (Richard and Bourg, 1991).
Within the normal pH range in natural waters (i.e., 6 to 8), the CrO42, HCrO4
and Cr2O72 ions are the forms expected. At relatively high Cr(VI) concentra-
tions, the Cr2O72 ion predominates in acidic environments (Richard and
Bourg, 1991).
It should be noted here that the term Cr(VI) is somewhat of a misnomer.
This is because Cr(VI) is not present in the environment as a free cation
(whereas Cr(III) does exist in the environment as previously mentioned). In
fact, as all Cr(VI) species are oxides, they act like a 2 anion (ion2) rather
than a Cr(VI) cation (Kimbrough et al., 1999).
The relative concentration of the various Cr(VI) species depends on the
pH and the total Cr(VI) concentration (Palmer and Puls, 1994). For example,
significant concentrations of H2CrO40 only occur under the extreme condition
of pH around 1. Above a pH of about 6, CrO42 generally dominates (Davis
and Olsen, 1995). Below pH of about 6, HCrO4 dominates when the Cr(VI)
concentrations are relatively low, but Cr2O72 becomes more significant as
Cr(VI) concentrations increase, or it may even dominate when the total
Cr(VI) concentrations are relatively high (Palmer and Puls, 1994). These
species constitute many of Cr(VI) compounds which are quite soluble and
thus mobile in the environment (Kotas and Stasicka, 2000). These species
differ in their solubility and in their tendency to be sorbed by soil or aquifer
materials (Calder, 1988).
There are no significant solubility constraints on the concentrations of
Cr(VI) in groundwater. The chromate (CrO42) and dichromate ions
(Cr2O72) are water soluble at all pH. However, chromate can exist as an
insoluble salt of a variety of divalent cations, such as Ba2+, Sr2+, Pb2+, Zn2+,
and Cu2+, and these salts have a wide range of solubilities. The rates of
precipitation/dissolution reactions between chromate, dichromate
anions, and these cations vary greatly and are pH dependent. An under-
standing of the dissolution reactions is particularly important for assess-
ing the environmental effects of chromium because Cr(VI) often enters
the environment by dissolution of chromate salts (e.g., SrCrO4) (Rai et al.,
1987).
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pe = log(ae) (5.1)
Also,
Eh = (pe)(2.3RT/F)
= 0.059 pe
where
R = gas constant
T = temperature
F = Faraday constant
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H2O/O2 (aq)
Mn(II)/Mn(IV)
NO2/NO3
Fe(II)/Fe(III)
S2/SO42
CH4/CO2
Cr(III) Cr(VI)
The concentration of these oxidizing and reducing agents affects the oxi-
dation-reduction of chromium. Many oxidizing agents are known to oxidize
Cr(III) to Cr(VI), but only a few of them are found in the environment (i.e.,
groundwater) in sufficient concentration to do so. On the other hand, the
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many reducing agents for Cr(VI) reduction to Cr(III) are typically found at
sufficient levels. For example, ozone (O3) can theoretically oxidize Cr(III) to
chromate (a reaction with Eh = 0.87 volts), but the concentration of ozone in
the environment is usually insufficient (it is relatively unstable) to accom-
plish this oxidation (Grohse et al., 1988). However, the reduction of Cr(VI)
by Fe(II), even though less favored thermodynamically (a reaction with Eh
only 0.56 volts) is feasible because iron concentrations are generally sufficient
in the environment (Rai et al., 1989).
At lower pHs, chromates exist as chromic acid (H2CrO4) and hydrogen
chromate (HCrO4). When the concentration of CrO42 is high, chromates are
transformed to dichromate (H2Cr2O7 or HCr2O7), which are strong oxidizing
agents and are thus rapidly reduced in the presence of reducing agents at
low pH or high Eh. At high pH, chromates exist in the form of CrO42, which
is a poor oxidizing agent and hence, with lower Eh values, are more stable.
Cr(VI) can be transported great distances in groundwater due in part to
its high solubility, whence it may be transformed by reduction to, and pre-
cipitated as, Cr(III) if the transported Cr(VI) enters an area with relatively
low Eh. Cr(VI) can be reduced readily to Cr(III) in the presence of organic
matter, especially where pH is low (Bartlett and Kimble, 1976; Bloomfield
and Pruden, 1980). Cr(VI) can also be reduced by Fe(II) and dissolved sul-
fides (Schroeder and Lee, 1975).
Cr(III) generally is not transported great distances by groundwater because
of its low solubility. However, Cr(III) can be transformed to the more soluble
Cr(VI) if the redox conditions along the transport pathway change from
reducing to oxidizing. Under natural conditions, Cr(III) has been found to
be oxidized to Cr(VI) by manganese (Schroeder and Lee, 1975; Bartlett and
James, 1979). In the laboratory, Cr(III) can exist as highly soluble organic
complexes, particularly under low pH conditions (Bartlett and Kimble, 1976;
James and Bartlett, 1983). Therefore, if Cr(III) is in a complexed form, it could
be present at much higher concentrations in groundwater than if it is uncom-
plexed. However, the existence of Cr(III) complexes has not been docu-
mented under field conditions.
Amacher and Baker, 1982). First, the Cr(III) would be sorbed onto MnO2
surface sites. Then, the Cr(III) would be oxidized to Cr(VI) by Mn(IV) on the
surface sites, however, all the Mn(IV) reaction sites are probably not acces-
sible to Cr(III) (Rai et al., 1986; Amacher and Baker, 1982). Finally, the reaction
products, Cr(VI) and Mn(II), would be desorbed. Richard and Bourg (1991)
give theoretical stoichiometries that have been suggested for this oxidation:
and
This is described by Palmer and Puls (1994) as a rather complex process. The
presence of Fe3+ increases the reduction rate, and the Fe3+ is reduced at the
mineral surface. The iron in the crystal structure is oxidized, K+ is released
to solution, and Cr(VI) in solution is then reduced by the Fe2+. The Fe3+
resulting from this reduction reaction is then sorbed to the surface of the
biotite where it is again reduced to Fe2+.
Palmer and Puls (1994) state that Cr(VI) reduction in the presence of iron
oxides has been observed in several experiments (Eary and Rai, 1989; White
and Hochella, 1989). In the case of hematite, the reduction is suggested to
occur in solution after the FeO component has dissolved. The reduction of
Cr(VI) via Fe(II) in pyrite is described in work by Lancy (1966), who sug-
gested that pyrite could be used for treating spent cooling waters that contain
Cr(VI) as a corrosion inhibitor, because reduction of Cr(VI) occurs at the
pyrite surface rather than in solution. This reduction was described as occur-
ring even in slightly alkaline solutions; however, the pyrite had to be con-
tinuously abraded to remove surface coatings. Batch testing reported by
Blowes and Ptacek (1992) involving pyrite both in the presence and in the
absence of calcite showed faster removal of Cr(VI) with no calcite. Also,
Loyaux-Lawniczak, et al. (2001) demonstrated that Fe(II)-Fe(III) hydroxysalt
green rusts can reduce Cr(VI); ferrihydrite is the Cr(III)-bearing solid phase
that is formed from this reduction.
Under neutral to alkaline pH conditions, Fe(II) controls the reduction of
Cr(VI) in natural anaerobic systems (Pettine et al., 1998), while at acidic pH
levels, other reductants may be more efficient than Fe(II). The involvement
of Fe(II) in Cr(VI) reduction, where the Fe(II) (as FeO) comes from hematite
or biotite, can be expressed as follows (Richard and Bourg, 1991):
[3FeO] + 6H+ + Cr(VI) (aq) = Cr(III) (aq) + 3Fe(III) (aq) + 3H2O (5.5)
5.3.4.3 Sulfides
Sulfides (reduced sulfur) can be a major factor in the reduction of Cr(VI) to
Cr(III). Although most sulfides are not soluble, some dissolved sulfides can
be present in the environment due to processes including the discharge of
industrial wastes, the decomposition of organic matter, and sulfate reduction
(a common process in the biodegradation of chlorinated solvent chemicals).
Laboratory studies have reported that the reduction of Cr(VI) involving
sulfides is initially rapid, slows down in a few minutes, but reaches comple-
tion after one day (Schroeder and Lee, 1975). The rates of reduction of Cr(VI)
with H2S have been studied by Pettine et al. (1994) and Pettine et al. (1998).
5.3.4.5 Cu(I)
Reduced copper [Cu(I)] may also play a role in the reduction of Cr(VI) to
Cr(III), discussed by Pettine et al. (2002) especially in atmospheric and sur-
face waters with low pH and low ionic strength (Abu-Saba et al., 2000). The
reduction of Cr(VI) with Cu(I) has been produced in the laboratory by
radiolysis experiments in dilute solutions in the presence of Cr(II).
Partitioning ratios (Kd) for Cr(III) have been estimated to be very high.
Cr(III) sorption is nonlinear, however, so the Kd sorption model cannot be
used for assessing retardation except for a particular concentration. If these
partitioning ratios were equivalent to Kds, retardation factors of 500 to 6100
could be estimated, indicating the relative immobility of Cr(III) due to sorption
at a pH of around 4. Above this pH, Cr(III) would also be relatively immobile
because of its low solubility. It is probable that Cr(III) mobility would be
enhanced by the formation of complexes due to their decreased sorption or
increased solubility compared with the uncomplexed form of Cr(III).
would correspond to retardation factors of 2.5 to 329 (much lower than those
calculated for Cr(III)), indicating that Cr(VI) mobility at pH 7 could range
from high to lowlower below a pH of 7 and higher above a pH of 7 (and
above a pH of 8.5, Cr(VI) would be entirely unretarded).
Competing anions have a drastic effect on Cr(VI) sorption, with the effect
being variable, depending on dissolved concentrations of the competing
anion and CrO42, on their relative affinities for the solid surface, and on
surface site concentration (Rai et al., 1986). The competitive sorption of
Cr(VI) with cations and anions has been investigated by much research (Rai
et al., 1986; Stollenwerk and Grove, 1985; Rai et al., 1988; Rai et al., 1984;
Music et al., 1986; Zachara et al., 1987; Benjamin and Bloom, 1981). The
electrostatic sorption of anions is enhanced by cation sorption (due to
enhanced positive surface charge). Also, chromates either increase or have
no effect on the sorption of heavy metals (Cd2+, Co2+, Zn2+); competition for
surface sites is relatively minor (Benjamin and Bloom, 1981). Additionally,
sorption of chromates in the presence of a mixture of ions is lower than in
two-solution systems, particularly when H2SiO42 is present. The effect
appears to be additive (Rai et al., 1986; Zachara et al., 1987).
Richard and Bourg (1991) note that the kinetics of Cr(VI) sorption are not
well documented. The sorption of chromates on soils apparently follows a
two-step reaction rate (Amacher et al., 1988). Also, sorption of Cr(VI) does
not seem totally reversible. Amacher et al. (1986) attributed this lack of
reversibility to reduction of Cr(VI) to Cr(III), possibly by organic matter from
the soil they studied.
The two stable oxidation states of chromium in the atmosphere are Cr(III)
and Cr(VI). Atmospheric particles do not contribute to the chemical reactions
that control the occurrence and ratio between Cr(III) and Cr(VI). Instead,
precipitation, complex formation, and oxidation reactions influence the
abundance and ratio of Cr(III) and Cr(VI).
Computer simulations by Seigneur and Constantinou (1995) have led to
the conclusion that typical atmospheric conditions favor the Cr(VI) reduction
to Cr(III). This is the likely case because of the presence and concentrations
of reducing agents in the air (i.e., V2+, Fe2+, H2S, HSO3, NO2, and organic
materials) as well as the acidity of the atmosphere. Cr(VI) can be reduced
rapidly in the atmosphere based on theoretical (Seigneur and Constantinou,
1995) and experimental (Grohse et al., 1988) studies. Estimates of atmo-
spheric half-life for Cr(VI) reduction to Cr(III) range from 16 h (Grohse et al.,
1988) to 4.8 days. The few materials capable of oxidizing Cr(III) to Cr(VI) in
the atmosphere, such as ozone, occur in concentrations too low to produce
measurable conversions in the atmosphere.
activity and thermal stratification. Therefore, depth and season heavily influ-
ence the concentration and speciation of chromium. Dissolved chromium
usually decreases in the summer months, and the areas dominated by Cr(VI)
versus Cr(III) become more segregated to surface and deep layers, respec-
tively. This distribution of chromium species is consistent with what would
be expected from seasonal increases in temperature, a decrease in pH, and
the oxygen content in the basinal water. The aerobic regime favors Cr(VI),
and Cr(III) is favored in anaerobic areas.
Chromium generally enters oceans via rivers and from atmospheric fall-
out. Atmospheric inputs result in more homogeneous distribution of chro-
mium in the ocean water compared with river inputs; the latter are the
subject of eustarine removal processes and ocean circulation patterns Spokes
and Jickells, 1995). It has been proposed that chromium sources to the oceans
are mostly as particles (suspended solids from river and aerosols). In ocean
waters, dissolved and precipitated chromium exist together in equilibrium.
Dissolved chromium is generally removed from the aqueous phase and
incorporated into biologic material (i.e., siliceous and carbonaceous skele-
tons) and by adsorption onto sediment particles. This removal occurs both
in the water column and at the sedimentwater interface, resulting in deep
and bottomwater enrichment of dissolved chromium.
Except in estuaries, chromium concentrations in seawater are dominated
by chromates, probably due to the generally oxidizing conditions in the ocean
and low suspended concentration of particles. Reduction of Cr(VI) occurs in
anaerobic basins and the oxygen-free zones, where increased Cr removal
may be due to Cr(III) adsorption onto bottom sediments (Smith et al., 1995).
Chromium cycling in the water column occurs in response to nutrient bio-
geochemistry. When Cr scavenged by particles is deposited on the ocean
floor, diagenetic processes can lead to remobilization of Cr either as chromate
or as organic Cr(III) complexes. The remobilization of Cr(III) from sediment
can also occur by its oxidation, carried out mostly by manganese dioxide.
5.6.2.2 Groundwater
Richard and Bourg (1991) and Calder (1988) give detailed discussions of the
behavior of chromium in groundwater environments, and their work is
summarized here. The mobility of chromium in groundwater depends on
its solubility and its tendency to be sorbed by soil or aquifer materials. These
factors, in turn, depend on the groundwater chemistry and the characteristics
of soil or aquifer material in contact with the chromium-containing ground-
water. Otherwise, much of the basic considerations discussed for surface
waters also apply for the understanding of the transport and fate of chro-
mium in groundwater.
Large plumes of chromium-contaminated groundwater in shallow aqui-
fers have been well documented (Stollenwerk and Grove, 1985; Deutsch,
1972; French et al., 1985; Perlmutter and Lieber, 1970; Wiley, 1983). Sources
of this contamination can be the same as those listed for surface waters. Such
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plumes in sand and gravel aquifers have been reported to reach lengths of
up to 1300 m (Perlmutter and Lieber, 1970). Impacts of many of the plumes
have been serious enough to necessitate the abandonment of local ground-
water supplies.
Groundwater contamination by chromium can be extensive in permeable
aquifers (i.e., sand and gravel and fractured rock aquifers) because ground-
water velocities in these materials are relatively high (i.e., about 0.1 and 5 m
per day, respectively). On the other hand, groundwater velocities in aquifers
of much lower permeability (i.e., clayey materials) tend to be low, perhaps
on the order of a few centimeters or less per year. Thus, chromium-contam-
inated groundwater in these settings cannot extend far from the source of
the chromium.
Cr(III) tends to be relatively immobile in most groundwater because of the
precipitation of Cr(III) compounds of low-solubility (e.g., Cr(OH)3(s),
FeCr2O4(s), (Fe1x, Crx)(OH)3(ss)) in neutral to alkaline pH range (i.e., above
pH 4). This results in low Cr(III) dissolved concentrations. Also, in neutral
to slightly acidic conditions (i.e., especially below pH 4), Cr(III) is removed
from solution by sorption. Calder (1988) reported that sorption of Cr(III)
increases with increasing pH. Furthermore, it has been speculated that Cr(III)
may be mobile in groundwater if it is in a complexed form, although this
has not been documented in the field. Precipitation and sorption can be
inhibited by complex formation with dissolved ligands such as natural
organic matter (Gerritsee et al., 1982).
Cr(VI) tends to be moderately to highly mobile in most shallow ground-
water aquifers. This tends to be due to two major factors: (1) the lack of
solubility constraints; and, (2) the low to moderate sorption of Cr(VI)
anionic form in neutral to alkaline waters. In soils or sediments with high
content of Fe and Mn oxides conditions, Cr(VI) should be removed by
sorption processes (Rai et al., 1986; Eary and Rai, 1987; Stollenwerk and
Grove, 1985; Rai et al., 1988; Cary et al., 1977). But sorption is significantly
depressed by competing background anions (Rai et al., 1988) so that Cr(VI)
can expected to be highly mobile. In alkaline environments, sorption is not
strong enough to keep Cr(VI) from migrating through soil or sediments.
Cr(VI) sorption generally increases with decreasing pH, so sorption of
Cr(VI) can be very significant in neutral to acidic groundwater. As previ-
ously discussed, Cr(VI) sorption can be strongly nonlinear, such that sorp-
tion decreases with increasing Cr(VI) concentration. Also, sorption also
appears to be rate-dependent, so the kinetics of the sorption process would
very important, especially in high-velocity groundwater regimes. Also,
Cr(VI) reduced to Cr(III) with subsequent precipitation and sorption is
believed to control the mobility of Cr(VI) (Rai et al., 1988): Cr(VI) reduction
to Cr(III), which is afterwards rapidly precipitated or sorbed. In Fe(II)-rich
and dissolved organic matter-rich environments, the reduction of Cr(VI) is
more likely to occur and the resulting aqueous Cr(III) concentration will be
controlled by the solubility of Cr(III). In such cases, Cr(VI) should not migrate
significantly.
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Metals exist in soil solution as either free (uncomplexed) metal ions (e.g.,
Cr3+), or in soluble complexes with inorganic or organic ligands, or associated
with mobile inorganic and organic colloidal material. A complex is a molec-
ular unit where a central metal ion is bonded by a number of associated
atoms or molecules ( e.g., Cr(OH)4), and these associated atoms or molecules
are termed ligands (i.e., OH is a ligand). Metals will form soluble complexes
with inorganic ligands such as SO42, Cl, OH, PO43, NO3, and CO32.
Soluble complexes with organic ligands are not as well defined. The free
metal ion is generally the most bioavailable and toxic form of the metal.
With complex formation, the resulting metal species may be positively or
negatively charged or be electrically neutral. The presence of a complex
species of a metal in the soil solution can significantly affect the migration
of metals through the soil relative to the free metal ion. In addition to
dissolved metal complexes, metals also may associate with mobile colloidal
particles (size of 0.01 to 10 m). Colloidal particles include iron and manga-
nese oxides, clay minerals, and organic matter. These surfaces have a high
capacity for metal sorption.
The extent of migration of metals from the ground surface into and through
the subsurface depends on the retention capacity of the soil is exceeded, and
it is directly related to the solution and surface chemistry of the soil and to
the specific properties of the metal and associated waste matrix. The mech-
anisms for retention of metals in soil include sorption and precipitation.
Retention of cationic metals is related to soil properties such as pH, redox
potential, surface area, cation exchange capacity, organic matter content, clay
content, iron and manganese oxide content, and carbonate content. Anionic
metal retention has been correlated with pH, iron and manganese oxide
content, and redox potential. Consideration must also be given to the type
of metal, its concentration, the presence of competing ions and complexing
ligands, and the pH and redox potential of the soil-waste matrix. Also, the
migration of metals can depend on the type of wastes that may be associated
with the metal. Therefore, because of the differing varieties of soils, and the
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many different forms of metals themselves and the wastes containing them,
evaluating the extent of metal retention by a soil is site specific, soil specific,
and waste specific.
Precipitation and sorption are the main metal retention mechanisms in
soil. Precipitation is where metals precipitate to form a solid (three-dimen-
sional) phase in soils, which might be a pure solid or a mixed solid (e.g.,
(FexCr1x)(OH)3); the latter forms when various elements co-precipitate. Sorp-
tion of metals is the accumulation of ions at the solid phaseaqueous phase
interface. Sorption of metals in the soil matrix often involves organic matter,
clay minerals, iron and manganese oxides and hydroxides, carbonates, and
amorphous aluminosilicates. Binding of metals to organic matter ranges
from weak forces of attraction to formation of strong chemical bonds. Soil
organic matter can be the main source of soil cation exchange capacity.
Organic matter content generally decreases with depth in soil, so that the
mineral (inorganic) constituents of soil will become a more important surface
for sorption with increasing depth. There have been numerous studies of
the adsorptive properties of clay minerals, in particular montmorillonite and
kaolinite, and iron and manganese oxides. Griffin and Shimp (1978) found
the relative mobility of 9 metals through montmorillonite and kaolinite to
be: Cr(VI) > Se > As(III) > As(V) > Cd > Zn > Pb > Cu > Cr(III). Also, Jenne
(1968) concluded that Fe and Mn oxides are the principal soil surface that
control the mobility of metals in soils and water. In arid soils, carbonate
minerals may immobilize metals by providing sorbing and nucleating sur-
face (Santillan-Medrano and Jurinak, 1975; Cavallaro and McBride, 1978;
McBride, 1980; Jurinak and Bauer, 1956; McBride and Bouldin, 1984; Dudley
et al., 1988, 1991).
Generally, the sorption capacity for anions (some metals form anionic
contaminants) is lower than the cation sorption capacity of soils. The sorption
capacity (both exchange and specific sorption) of a soil is determined by the
number and kind of sites available. Sorption process are affected by various
soil factors (i.e., pH, redox potential, clay, soil organic matter, oxides, and
calcium carbonate content), by the form of the metal added to the soil, and
by the solvent introduced along with the metal. Therefore, interactions of
these influences on sorption may increase or decrease the migration of metals
in soil.
Although the principles affecting sorption and precipitation are similar for
cationic and anionic metals, the following is a list with a brief description
of factors affecting the behavior of cationic metals in soils.
Competing cations: Trace cationic and anionic metals are preferentially
sorbed over the major cations (Na+, Ca2+, Mg2+) and major anions (SO42,
NO3). However, when the specific sorption sites become saturated, exchange
reactions dominate and competition for these sites with soil major ions
becomes important.
Complex formation: Metal cations form complexes with inorganic and
organic ligands, whereby the ligand forms a coordinate bond with the metal
atom. The resulting association has a lower positive charge than the free
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metal ion (and might even be uncharged or negatively charged). The effect
of complex formation on sorption is dependent on the type and amount of
metal present, and type and amount of ligands present, soil surface proper-
ties, soil solution composition, pH, and redox. The presence of complexing
ligands may either increase metal retention or greatly increase metal mobil-
ity. Data from the literature that do not consider the presence of complexing
ligands at the site, both organic and inorganic, may lead to significant error
in estimating metal mobility.
pH: The pH of the soil system is a very important parameter, directly
influencing sorption/desorption, precipitation/dissolution, complex forma-
tion, and oxidationreduction reactions. The pH affects several mechanisms
of metal retention of soils both directly and indirectly. Sorption increases
with pH for all cationic metals, but retention does not significantly increase
until the pH gets above 7. As true for all oxyanions (i.e., Cr(VI)), sorption
decreases with pH. The pH dependence of sorption reactions of cationic
metals is due in part to the preferential sorption of the hydrolyzed metal
species in comparison to the free metal ion. Many sorption sites in soils are
pH dependent (i.e., Fe and Mn oxides, organic matter, carbonates, and the
edges of clay minerals). As the pH decreases, the number of negative sites
for cation sorption diminishes while the number of sites for anion sorption
increases. Also, as the pH becomes more acidic, metal cations also face com-
petition for available permanent charged sites by Al3+ and H+. Jenne (1968)
stated that hydrous oxides of Fe and Mn play a principle role in the retention
of metals in soils. Solubility of Fe and Mn oxides is also pH-related. Below
pH 6, the oxides of Fe and Mn dissolve, releasing sorbed metal ions to
solution (Essen and El Bassam, 1981). In soils with significant levels of
dissolved organic matter, increasing soil pH may actually mobilize metal
due to complex formation. A word of caution is warranted here, however.
The complexity of the soil-waste system (several types of surfaces and solu-
tion compositions) may render generalizations just given to be not true. For
example, cationic metal mobility can actually increase with increasing pH
due to the formation of metal complexes with dissolved organic matter.
Oxidation-Reduction: Many metals have more than one oxidation state, and
are directly affected by changes in the oxidation-reduction (redox) potential
of the soil. Redox reactions can greatly affect contaminant transport, in
slightly acidic to alkaline environments. In general, oxidizing conditions
favor retention of metals in soils, while reducing conditions contribute to
accelerated migration.
It has been thought that Cr(VI) can be reduced to Cr(III) under normal
soil pH and redox conditions. However, Bloomfield and Pruden (1980) rein-
vestigated earlier claims that Cr(VI) is readily reduced to Cr(III) under such
normal soil conditions, and they found that the analytical methods used in
previous investigations (Bartlett and Kimble, 1976) were unreliable because
the soil extracts probably contained organic matter capable of reducing
Cr(VI). They also found that the reduction of Cr(VI) in soil of normal pH
was not particularly rapid under aerobic conditions.
The reduction of chromates by Fe, V2+, sulfides, and organic materials is
well demonstrated (Cary, 1982), and the kinetics of Cr(VI) reduction has
been reported to follow a simple first-order reaction kinetics (Amacher and
Baker, 1982; Bartlett and James, 1988). Soil organic matter has been identified
as the important electron donor (i.e., the principal reducing agent) in this
reaction (Bartlett and Kimble, 1976; Bloomfield and Pruden, 1980), and the
reduction of Cr(VI) in the presence of organic matter proceeds at a slow rate
at normal levels of pH and temperatures found in the environment (Bartlett
and Kimble, 1976; James and Bartlett, 1983). This relatively slow rate of
Cr(VI) reduction increases with decreasing soil pH (Bloomfield and Pruden,
1980; Cary et al., 1977). In the absence of soil organic matter, Fe(II)-containing
minerals reduce Cr(VI), however, tests have shown that this reduction occurs
in subsurface soil with a low pH (<5) (Eary and Rai, 1991). Reduction by
Fe(II) is more favorable under anaerobic conditions since oxygen can oxidize
the iron (II) (Fendorf and Li, 1996). However, high concentrations of Cr(VI)
may quickly exhaust the available reducing capacity of the soil, and excess
Cr(VI) may persist for years in soils (Baron et al., 1996). In general, it has
been noted that chromates are relatively stable and mobile in soils that are
sandy or have low organic content (Cary, 1982; Bloomfield and Pruden, 1980;
Frissel et al., 1975).
Under conditions prevalent in some soils, Cr(III) can be oxidized (Bartlett
and James, 1979). Only a few oxidants present in soils and sediments (i.e.,
dissolved oxygen and MnO2) are capable of oxidizing Cr(III) to Cr(IV). The
oxidation of Cr(III) by MnO2 (which serves as an electron acceptor) has been
shown to occur in soils (Eary and Rai, 1987; Johnson and Xyla, 1991; Fendorf
and Zasoski, 1992), and aerobic sediments, but not in anaerobic sediments.
Oxidation of Cr(III) by dissolved oxygen has been found to be insignificant
(Rai et al., 1989) when compared with MnO2, which is the most likely oxidant
of Cr(III) in soils. Thus, if soluble Cr(III) is added to an average soil, a
portion of the soluble Cr(III) will become immediately oxidized by MnO2 to
Cr(VI) (Cary, 1982). The rest of the Cr(III) may remain reduced for long
periods of time, even in the presence of electron-accepting manganese
oxides, perhaps because soluble Cr(III) can form complexes with low-molec-
ular mass organic molecules and then be oxidized where redox conditions
are optimal. Added organic matter also may facilitate oxidation of Cr(III) to
Cr(VI). This has implications to remediation strategies. The addition of
organic residues potentially as a remediation strategy for Cr(VI)-contami-
nated soils containing high levels of oxidized manganese may result in the
L1608_C05.fm Page 195 Friday, July 23, 2004 5:44 PM
Some of these criteria are relatively simple while others require additional
tests and interpretation. Each are discussed below.
Aqueous species
Sorbed ions
Mineral constituents
Organic matter
The presence of Cr(III) may indicate either active reduction in the soil or
neutralization of acidic waters containing Cr(III) with subsequent precipita-
tion of chromium hydroxides. Therefore, specific reductants in the aquifer
should be identified, and this can be fairly straightforward. Reductants (such
as pyrite, FeS2) can be readily identifiable by visual characteristics or by
L1608_C05.fm Page 198 Friday, July 23, 2004 5:44 PM
and Puls (1994) report that at many sites, the total Cr(VI) associated with the
soil matrix is the sum of BaCrO4 and the phosphate-extractable Cr(VI). This
sum is then added to the aqueous Cr(VI) to get the total concentration of
Cr(VI) in the soil (Cr(VI)tot).
As the distance XC increases, the mass of Cr(VI) that can be reduced also
increases. A key difficulty in applying this criterion is in providing a reason-
able estimate of the total mass of Cr(VI) in the source area (MO).
The total Cr(VI) reducing capacity can be obtained using the classical
Walkley-Black method for determining soil organic carbon (Bartlett and
James, 1988; Walkley and Black, 1934). Although this method has its limita-
tions (Nelson and Sommers, 1982), it is a direct measure of how much Cr(VI)
can be reduced by a soil at extreme acid conditions. Variations on this method
have been described (Barcelona and Helm, 1991; Nelson and Sommers, 1982).
The extreme conditions of pH and temperature used in the total Cr(VI)
reducing capacity test may yield a greater reducing capacity than would be
available under most environmental conditions. The available reducing
capacity test of Bartlett and James (1988) is designed to determine the
reducing capacity at pH values more likely to be encountered in the field.
However in long-term reduction tests at near neutral pH, reduction has been
observed to be occurring after 250 days. Such long-term reduction tests are
not practical at most waste sites.
L1608_C05.fm Page 200 Friday, July 23, 2004 5:44 PM
about these rate processes under a wider range of conditions with respect
to pH, the use of the natural attenuation option for contaminated soils will
continue to be a highly debated issue.
Maq = v CV (5.9)
the soil matrix (Mads) can be computed from an sorption isotherm. There
is no unique amount of Cr(VI) precipitate for a given Cr(VI) concentration.
Therefore it is impossible to estimate mass of this fraction of Cr(VI) in the
subsurface using only the measured concentrations in monitoring wells.
Thus, natural attenuation of Cr(VI) from mass balances using monitoring
well data can only be used when it can be reasonably demonstrated the
Cr(VI) precipitates cannot form within the aquifer. Even when it is dem-
onstrated that the formation of precipitates within the aquifer is unlikely,
there are inherent problems with any monitoring system, creating uncer-
tainties in the estimated mass of Cr(VI) during a sampling round.
remediation, which have been developed for site where natural attenuation
is insufficient to prevent chromate migration (i.e., permeable reactive barri-
ers, injection of chemical reactants to reduce chromate, and injection of a
reductant to react with the aquifer materials to form reduced minerals in the
aquifer). The new finding by Ellis et al. (2002) that 53Cr/52Cr ratios reveal
the extent of abiotic reduction suggests that 53Cr/52Cr measurements can
assist in the evaluation of the effectiveness of all these approaches to chro-
mate reduction in groundwater.
Chromium has four stable isotopes of masses 50 (4.35%), 52 (83.8%),
53 (9.50%), and 54 (2.37%) (Rotaru and Birck, 1992; Handbook of Chemistry
L1608_C05.fm Page 203 Friday, July 23, 2004 5:44 PM
and Physics, 1996). Ellis et al. (2002) measured chromium isotope fraction-
ation during reduction of Cr(VI) by slurries of magnetite and two sediment
samples. Because magnetite is a likely reducing agent in some aquifer sed-
iments (Anderson et al., 1994), the magnetite experiment provided a simple
analog for a natural aquifer. (In these experiments) at pH 6 to 7, sorption of
Cr(VI) was negligible. As reduction proceeded and the Cr(VI) concentrations
decreased, 53 Cr (defined in Chapter 2) values of the remaining unreduced
Cr(VI) increased, indicating preferential reduction of the lighter isotopes.
These experiments showed that reduction of Cr(VI) results in Cr stable-
isotope fractionation.
To estimate initial isotopic compositions of the contaminants, Ellis et al.
(2002) measured 53Cr values in samples of plating baths in active use at
different sites, the chromic acid supply used to make up plating baths,
laboratory chromium reagents, and basaltic rock standards. All of these
samples yielded 53Cr values close to 0%. Therefore, Ellis et al. (2002)
suggested that Cr released as plating waste generally has an initial 53Cr
value slightly greater than zero. If so, detection of Cr(VI) reduction in
groundwater systems would be relatively simple, as the initial 53Cr value
would be known and groundwater values greater than that would directly
indicate the extent of reduction. If, on the other hand, plating wastes have
variable 53Cr values, then it may be possible to distinguish different
contamination sources via their 53Cr values. In studies of groundwater
contamination sites, Ellis et al. (2002) showed that all of the groundwater
Cr(VI) analyses indicated enrichment in the heavy isotope relative to the
plating baths, and Cr(VI) reduction had preferentially removed lighter
isotopes from the groundwater. The variation in 53Cr values at each of
the sites suggested that reduction of Cr(VI) was occurring and had pro-
gressed to different degrees in different parts of the contaminant plumes.
The highest 53Cr values were found in samples with lowest Cr(VI) con-
centration at (the sites studied). This result was to be expected because
the fringe areas of the contaminant plumes likely would have greater
degrees of reduction than the plume cores, where chromium concentra-
tions are high and the reducing power of the aquifer materials had been
depleted.
Stable Cr isotope ratios can thus serve as indicators of the extent of Cr(VI)
reduction in groundwater. Cr(VI) reduction by bacteria or reducing agents
other than those studied by Ellis et al. (2002) could induce greater or lesser
isotopic fractionation than (they) observed. And, processes other than reduc-
tion (i.e., sorption, precipitation, and uptake by plants and algae) could also
be responsible for removing chromium from solution (James and Bartlett,
1983, 1984, and 1988). If such processes and/or Cr(III) oxidation also induce
isotopic fractionation, this could complicate the interpretation of 53Cr mea-
surements. However, as with S and Se isotopes (Johnson et al., 1999) it could
be expected that the dominant cause of chromium isotope fractionation is
reduction.
L1608_C05.fm Page 204 Friday, July 23, 2004 5:44 PM
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