Kimbrough 1999

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A Critical Assessment of Chromium in the Environment

a b c d
David Eugene Kimbrough , Yoram Cohen , Arthur M. Winer , Lynn Creelman & Clayton
e
Mabuni
a
Castaic Lake Water Agency, 27234 Bouquet Canyon Road, Santa Clarita, California, 91350
b
Department of Chemical Engineering, School of Engineering, University of California, Los
Angeles, Los Angeles, California, 90095-1590
c
Environmental Science & Engineering Program, School of Public Health, University of
California, Los Angeles, Los Angeles, California, 90095
d
Department of Environmental Health Sciences, School of Public Health, University of
e
California Department of Health Services, Food & Drug Laboratory-South, 1520 W. Pico
Blvd., Los Angeles, California, 90045
Published online: 03 Jun 2010.
To cite this article: David Eugene Kimbrough , Yoram Cohen , Arthur M. Winer , Lynn Creelman & Clayton Mabuni (1999): A
Critical Assessment of Chromium in the Environment, Critical Reviews in Environmental Science and Technology, 29:1, 1-46
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Critical Reviews in Environmental Science and Technology, 29(1):1–46 (1999)
A Critical Assessment of Chromium

in the Environment
David Eugene Kimbrough
Castaic Lake Water Agency, 27234 Bouquet Canyon Road, Santa Clarita, California, 91350
Yoram Cohen*
Department of Chemical Engineering, School of Engineering, University of California, Los
Angeles, Los Angeles, California, 90095–1590
Downloaded by [Moskow State Univ Bibliote] at 09:26 19 June 2013
Arthur M. Winer
Environmental Science & Engineering Program, School of Public Health, University of
Lynn Creelman
Department of Environmental Health Sciences, School of Public Health, University of
Clayton Mabuni
California Department of Health Services, Food & Drug Laboratory-South, 1520 W. Pico
Blvd., Los Angeles, California, 90045
* Author to whom correspondence should be addressed.
TABLE OF CONTENTS
ABSTRACT .......................................................................................................... 2
I. INTRODUCTION......................................................................................... 2
II. INDUSTRIAL USE-STREAM AND SOURCES OF CHROMIUM........... 3
III. THE CHEMISTRY OF CHROMIUM ......................................................... 5
A. General Oxidation and Reduction Reactions.......................................... 6
B. Precipitation and Dissolution Reactions................................................. 8
C. Sorption and Desorption Reactions ........................................................ 9
D. Analysis of Environmental Chromium................................................. 11
IV. FATE AND TRANSPORT OF CHROMIUM IN
ENVIRONMENTAL MEDIA .................................................................... 14
A. Chromium in the Atmosphere .............................................................. 14
B. Chromium in the Aquatic Environment ............................................... 16
C. Chromium in Soils and Sediments ....................................................... 18
Copyright© 1999, CRC Press LLC — Files may be downloaded for personal use only. Reproduction
of this material without the consent of the publisher is prohibited.
1
D. The Uptake of Chromium by the Biota .................................................20
1. Bacteria ...........................................................................................20
2. Plants...............................................................................................21
3. Aquatic Animals .............................................................................22
4. Terrestrial Animals .........................................................................23
E. Multimedia Oxidation/Reduction Cycles of Chromium .......................24
V. HEALTH EFFECTS OF CHROMIUM ......................................................26
A. Absorption, Metabolism, and Toxicology of Chromium ......................26
B. Chromium Exposures and Epidemiology .............................................31
VI. ENVIRONMENTAL RISK.........................................................................34
VII. POLICY AND REGULATION...................................................................35
ABSTRACT: This article reviews the emissions, environmental fate and transport, analytical chem-
istry, uptake and metabolism, toxicology, and human epidemiology of chromium. Chromium is
unique among regulated toxic elements in the environment in that different species of chromium, spe-
cifically chromium (III) and chromium (VI), are regulated in different ways, in contrast to other toxic
elements where the oxidation state is not distinguished. In both industrial and environmental situations
chromium (III) and chromium (VI) can inter-convert, with reduction of chromium (VI) to chromium
(III) generally being favored in most environmental situations. Chromium released into the air, water,
and soil can be transported among the various environmental media through various intermedia trans-
port processes. Once in the environment, chromium can be taken up by human and other ecological
receptors. Chromium (III) is generally absorbed through cell membranes albeit to a significantly lesser
degree than chromium (VI). Because most of the biosphere is reducing for chromium (VI) and chro-
mium (III) is relatively immobile, there is little bioconcentration or biomagnification of chromium
(VI). Chromium appears to be a nutrient for at least some plants and animals, including humans, al-
though chromium (VI) species have been reported to be toxic to bacteria, plants, and animals. Human
toxicity includes lung cancer, liver, kidney and gastric damage, and epidermal irritation and sensiti-
zation. However, it is noted that medical, toxicological, and epidemiological evidence suggests that
not all compounds containing chromium (VI) species (e.g., chromate salts) are carcinogenic.
KEY WORDS: chromium (III), chromium (VI), intermedia transport and transformations, exposure,
toxicology.
I. INTRODUCTION
Chromium is unique among regulated toxic elements in the environment in

that different species of chromium, specifically chromium (III) and chromium
(VI), are regulated in different ways based on their differing toxicities. All other
toxic elements, such as lead, cadmium, and arsenic, are regulated based on their
total concentrations, irrespective of their oxidation state. For example, the United
States Environmental Protection Agency (USEPA) classifies materials as hazard-
ous waste if they contain leachable chromium (40 CFR 261.4) but excludes those
materials from classification if it can be shown that the leachable chromium is not
chromium (VI) (40 CFR 261.94). USEPA also has proposed a “Health Based”
clean-up concentration (Preliminary Remediation Goals or “PRGs”) for chromium
Copyright© 1999, CRC Press LLC — Files may be downloaded for personal
use only. Reproduction of this material without the consent of the publisher
is prohibited.
2
(VI) in soil at much lower concentrations than chromium (III). The California EPA
has proposed a modification of the Federal PRG for chromium (VI), but not for
chromium (III), in soils at a concentration of below 1 mg/kg (Smucker, 1995). The
California EPA likewise classifies a solid as hazardous based on the total and
leachable chromium (VI) content (CCR Title 22, Section 66261.24). Many of the
Regional Water Quality Control Boards in California regulate chromium (VI) dis-
charges from waste water treatment plants. The California Air Resources Board
and local Air Quality Management Districts regulate chromium (VI) emissions. It
is worth noting that other regulations and regulatory agencies, such as the USEPA
Office of Drinking Water (Goldharber and Vogt, 1989), do not maintain a regula-
tory distinction among chromium oxidation states.
The policy decisions in some regulatory agencies to regulate the concentration
of chromium (VI) differently from chromium (III) have been based on chemical,
toxicological, and epidemiological evidence. Chromium (VI) is both a powerful

epithelial irritant and a confirmed human carcinogen (IARC Group I, 1990). Addi-
tionally, chromium (VI) is toxic to many plants, aquatic animals, and bacteria
(NAS, 1974; USEPA 1985). In contrast, chromium (III) is generally benign and
even a known micronutrient in an organic form (Anderson et al., 1977; Niebeoer
and Jusy, 1988). However, chromium (VI) and (III) can interconvert in the envi-
ronment during chemical analysis and this behavior poses problems for the existing
chromium regulatory policy.
One major problem in the regulation of chromium (VI) is the lack of reliable
analytical procedures to extract chromium (VI) quantitatively from environmental
matrices without altering its oxidation state. During sampling and extraction, chro-
mium (III) and (VI) may interconvert depending on the procedure, which chromi-
um compounds are present, and the chemistry of the matrix. This problem raises
several questions. If chromium (III) and (VI) interconvert during analysis, what is
the expected transformation in the environment? Is the analytical extraction proce-
dure representative of biological conditions and thus a reliable indicator of bio-
availability? If the different chromium (VI) compounds have different
physicochemical properties, do they have different toxicological effects? If chro-
mium (III) and (VI) inter-convert and all chromium (VI) compounds are not
equally hazardous, would the risk to the environment and human health reduced by
regulating chromium (VI)?
In order to better examine the policy implications of the above issues this
article critically reviews the environmental and analytical chemistry, intermedia
transport and transformations, toxicology, and epidemiology of chromium (VI).
II. INDUSTRIAL USE AND SOURCES OF CHROMIUM
While there are natural sources of chromium in the environment, mostly chro-
mium (III), the majority of chromium (VI) originates from industrial activities. The
is prohibited.
3
industrial use-stream of chromium begins with its mining as chromite, usually
ferrous chromite (FeO⋅Cr2O3) (Westbrook, 1983; Hartford, 1983). While there are
some direct uses of chromite ores, most notably for the production of refractory
brick (Westbrook, 1983; Hartford, 1983), the vast majority of ore is either oxidized
or reduced.
Sodium chromate (Na2CrO4) traditionally has been produced by the air roast-
ing (oxidation) of chromite with sodium carbonate and calcium oxide (lime). This
process has changed recently as no-lime and low-lime technologies replace the
older high-lime process (Langard, 1990; Gochfeld, 1991). During high-lime pro-
duction of sodium chromate (Na2CrO4), specifically calcium chromate (CaCrO4),
are produced as byproducts. It is noted that, based on the convention used in occu-
pational safety standards (NIOSH, 1975) and throughout this article, chromates
more water soluble than CaCrO4 are termed “soluble” and those of equal or lesser
water solubility are termed “insoluble.” Dichromates (Na2 or K2Cr2O7), chromic

oxide (CrO3), chromic acid (H2Cr2O7), and other oxides of chromium (e.g.,
K2CrO4), including the chromate pigments (barium, calcium, lead, strontium, and
zinc chromate; see Table 1 for solubilities), are in turn derived from Na 2CrO4.
Chromite ore can be reduced by a variety of methods using aluminum, silicon,
or carbon as reducing agents (Hathaway, 1989). These reduced materials can be
used for the production of chromium alloys and chrome alum
(NH4Cr(SO4)2⋅12H2O). Most of the chromium consumed by U.S. industry is for the
production of metal alloys (about 70% of the chromium usage) mainly wrought-
stainless and heat-resisting steels (Westbrook, 1983; Hartford, 1983). These prod-
ucts are then often welded together in their final use. In an iron alloy, chromium is
insoluble with a zero oxidation state and thus of little environmental concern. How-
ever, chromium can be oxidized and leached from stainless steel into a water-
soluble form (Merritt and Brown, 1995). Recycling of chromium is typically ac-
complished with stainless steel recycling (see NAS, 1974; Westbrook, 1983; Hart-
ford, 1983; and Stern, 1982, for descriptions of the industrial chemistry aspects of
chromium). The industrial use of chromium is summarized in Figure 1.
Chromium (VI) chemicals, which typically make up about 10 to 15% of chro-
mium usage, are principally used for metal plating (which use H 2Cr2O7), as dyes,
paint pigments, and leather tanning (e.g., Westbrook, 1983; Hartford, 1983). Chro-
mium (II) and (III) chemicals are also manufactured but in small amounts com-
pared with chromium (VI). Chromium dichloride (CrCl2) and chromium sulfate
(CrSO4) are examples of the former and chromium trifluoride (CrF3), chromium
trichloride (CrCl3), and chromium nitrate (Cr(NO3)3) are examples of the latter.
Chromium platers use heated baths of H2Cr2O7 to plate chromium onto pieces
of other metals. Under an electric current, the hydrated dichromate ions move
toward the positive electrode, which is the metal to be plated. The hydrogen and
oxygen gases formed escape the bath forming aqueous acidic chromate laden mists.
is prohibited.
4
FIGURE 1. Industrial use of chromium.
III. THE CHEMISTRY OF CHROMIUM
Although many different oxidation states of chromium exist in the environ-

ment, only chromium (III) and (VI) are the most stable (Shupak, 1991). The inter-
conversion of chromium (III) and chromium (VI) is controlled by several factors,
is prohibited.
5
including the presence and concentrations of chromium species and oxidizing or
reducing agents, the electrochemical potentials of the oxidation and reduction re-
actions, ambient temperature, light, sorbents, acid-base reactions, complexing
agents, and precipitation reactions (Saleh et al., 1989).
Chromium (VI) exists as chromate (CrO42–), dichromate (Cr2O72–), or chromi-
um trioxide (CrO3). Further, only one chromium (III) compound, (Cr2O3), is an
oxide, so the role of oxygen is central to the oxidation/reduction (redox) process
for chromium. The redox reactions between a given chromium species and other
chemical agents are governed by the agents’ capacity for donating or accepting
electrons and therefore acting as sources of or sinks for oxygen. For chromium to
be oxidized it must accept electrons from oxygen, while reduction is accomplished
by donating electrons. In a sense, the commonly used term hexavalent chromium
is a misnomer because Cr6+ does not exist as a free cation as does Cr3+. In fact, as
all chromium (VI) species are oxides, they act like a divalent anion rather than a
hexavalent cation.
The potential for an electron transfer is best measured by the redox potential
(Eh). The Eh is equivalent to the redox intensity factor (pE) (Scott and Morgan,
1990), which is the negative log of the electron activity (ae) or
pE = – log(a e ) (1)
The electron activity is the ratio of electron donors (oxidizing agents) to electron
recipients (reducing agents). The Eh is defined as
E h = E (oredoxcouple ) + 2.3RT / nF log([ox] [ red ]) (2)
or
E h = E (oredoxcouple ) + 2.3RT / nF log(a e ) (3)
where Eo is the standard electrode potential, R is the universal gas constant, T is the
absolute temperature in Kelvin, F is the Faraday constant, and n is the number elec-
trons in the half reaction. Table 1 shows a number of oxidation and reduction reac-
tions of chromium with common environmental agents.
A. General Oxidation and Reduction Reactions
There are several sources of oxygen for the oxidation of chromium. At high
temperatures molecular oxygen is both a source and sink for oxygen, such as
occurs during ore roasting. Water is the most important source of oxygen for the
is prohibited.
6
TABLE 1
Examples of Possible Oxidation/Reduction Reactionsa
E(b)
A) 2Cr+3 + 5H20 + 3O3 <=> 2CrO4–2 + 10H+ + 3O2 0.87
B) 2Cr+3 + 2H20 + 3H2O2 <=> 2CrO4–2 + 10H+ 0.58
C) 3MnO2 + 2Cr(OH)3 <=> 3Mn+2 + 2CrO4–2 + 2H2O + 2OH– 1.328
D) 2Cr+3 + 3H20 + 2MnO4– <=> Cr2O7–2 + 6H+ + 2MnO2 0.35
E) 2Cr+3 + 7H2O + 6Mn+3 <=> Cr2O7–2 + 14H+ + 6Mn+2 0.18
F) 2Cr+3 + H20 + 3PbO2 <=> Cr2O7–2 + 2H+ + Pb+2 0.13

G) HCrO4– + 3V+2 + 7H+ <=> Cr+3 + 3V+3 + 4H2O 1.45
H) HCrO4- + 3Fe+2 + 7H+ <=> Cr+3 + 3Fe+3 + 4H2O 0.56
I) 2HCrO4– + 3H2S + 8H+ <=> 2Cr+3 + 5H2O + 3S 1.18
J) 2HCrO4– + 5H+ + 3HNO2 <=> 2Cr+3 + 5H2O + 3NO3– 0.35
K) 2HCrO4– + 5H+ + 3HSO3– <=> 2Cr+3 + 5H2O + 3SO4–2 2.115
L) 2CrO4–2/Cr2O7–2 + R3CH <=> Cr+3 + R3COH

M) 2CrO4–2/Cr2O7–2 + RCH3 <=> Cr+3 + RCH2OH
N) 2CrO4–2/Cr2O7–2 + RCHO <=> Cr+3 + RCOOH
O) 2CrO4–2/Cr2O7–2 + PAH <=> Cr+3 + Quinones
P) 2CrO4–2/Cr2O7–2 + 3HCOOH <=> 2Cr+3 + 3CO2
Q) 2CrO4–2/Cr2O7–2 + 2CH3CH2OH <=> 2Cr+3 + 2CH3COOH
a Grohse et al., 1988; only reported values for E are given here.
b Volts
oxidation of chromium in the environment, as indicated in Table 1. Other sources

of oxygen include ozone, hydrogen peroxide, lead dioxide, and manganese diox-
ide. It is noted, however, that oxidation of chromium with the above agents re-
quires the presence of water and thus the interconversion of chromium oxidation
states is dominated by water chemistry.
Given the critical role of water in the redox chemistry of chromium, it is not
surprising that water pH is also very important. High values of Eh and pE in waters
correspond to strongly oxidizing conditions. Generally, there is an inverse relation
between Eh and pH for chromium, as the pH increases Eh decreases.
At lower pHs, chromates exist as chromic acid (H2CrO4) and hydrogen chro-
mate (HCrO4–). When the concentration of CrO42– is high, chromates dimerize to
form dichromate species (H2Cr2O7 or HCr2O7–). These species are strong oxidizing
is prohibited.
7
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 (see equations G-K in
Table 1). Conversely, chromium (III) is more easily oxidized at higher pH value.
The concentration level of oxidizing and reducing agents is also an important
factor affecting the oxidation/reduction of chromium. For example, while there are
many oxidizing agents capable of oxidizing chromium (III) (see Table 2), only a
few exist in environmental situations in high enough concentration to oxidize chro-
mium (III) to (VI). Conversely, there are many reducing agents for which reduction
of chromium (VI) is less favored thermodynamically, but these are typically found
at sufficiently high concentrates to play role in reducing chromium (VI) to (III).
For example, ozone can react with chromium (III) to form chromate, a reaction that
has a redox potential of 0.87 volts. However, the concentration of ozone in most
environmental media is rarely high enough to accomplish this oxidation (Groshe et

al., 1988). Conversely, the reduction of chromium (VI) by iron (II) has a low redox
potential, 0.56 volts, but the concentration of iron in many environmental media is
high enough to actually achieve this reduction (Rai et al., 1989).
B. Precipitation and Dissolution Reactions
Chromium can also undergo precipitation-dissolution reactions (Bodek et al.,

1988). These reactions are governed by the solubility of the chromium compound
and the kinetics of the dissolution. The water solubilities of both chromium (III)
and (VI) species vary over many orders of magnitude, as suggested by the equilib-
rium constants listed in Table 1. However, most of the water-soluble chromium
(III) species do not occur naturally and are unstable in the environment. The prin-
cipal chromium (III) reaction in water is the formation of chromium hydroxides of
varying water solubilities. The degree of hydroxylation is pH dependent (see
Figure 2) with the trihydroxide being the least soluble. Chromium (III) would then
tend to precipitate in neutral aqueous solutions. This tendency is enhanced by the
formation of mixed iron chromium hydroxide (Cr,Fe)(OH)3, which has an even
lower solubility than Cr(OH)3 and rapid precipitation/dissolution kinetics that
could make it an important solubility controlling compound (Sass and Rai, 1987).
In contrast, the chromate (CrO42–) and dichromate ions (Cr2O72–) are water
soluble at all pHs. However, chromate can exist as an insoluble salt of a variety of
divalent cations, such as Ba2+, Sr2+, Pb+2, Zn+2, and Cu+2 (Reactions G-I, and M-P in
Table 2), and these salts have a wide range of solubilities. The rates of precipita-
tion/dissolution reactions between chromate, dichromate anions, and these cations
vary greatly and are pH dependent. An understanding of the dissolution reactions is
particularly important for assessing the environmental effects of chromium because
Cr(VI) often enters the environment by dissolution of chromate salts. Dissolution of
is prohibited.
8
FIGURE 2. Multimedia transport and fate of chromium.
sparingly soluble chromate salts (e.g., SrCrO4) is particularly important because

they provide a continual source of chromate anions.
C. Sorption and Desorption Reactions
Sorption and desorption processes are important to understanding the fate and
transport of chromium in the environment. Sorption refers to the removal of a
solute from the aqueous phase of an environmental matrix to the surface of a solid.
Chromium ions are attracted to surfaces that have a net electric charge due to im-
is prohibited.
9
TABLE 2
Solubilization and Precipitation Reactions
Equilibrium Constant (a)

K
A) Cr(OH)3 (s) <=> Cr+3 + 3OH– 10–30 M–4

B) Cr2(SO4)3 (s) <=> 2Cr+3 + 3SO4– 1.3 × 10–7 M5
C) CrCl3 (s) <=> CrCl2+ + Cl– 1.5 × 10–3 M2
D) CrF3 (s)<=> CrF2+ + F– 0.3 × 10–2 M2
E) Cr(NO3)3 (s) <=> Cr+3 + 3(NO3)– 0.4 M4
F) CrO3 (s) <=> CrO3 (aq) 6.2 M
G) BaCrO4 <=> CrO4–2 + Ba+2 3 × 10–10 M2

H) CaCrO4 <=> CrO4–2 + Ca+2 2.3 × 10–2 M2
I) CuCrO4 <=> CrO4–2 + Cu+2 3.6 × 10–6 M2
J) K2CrO4 <=> CrO4–2 + 2K+ 0.23 M3
K) Na2CrO4 <=> CrO4–2 + 2Na+ 3.65 M3
L) (NH4)2CrO4 <=> CrO4–2 + 2NH4+ 20 M3
M) PbCrO4 <=> CrO4–2 + Pb+2 1.8 × 10–14 M2

N) ZnCrO4 <=> CrO4–2 + Zn+2 1.1 × 10–5 M2
O) ZnCrO4⋅4Zn(OH)2 <=> CrO 4
–2 +2
+ Zn + 4Zn(OH)2 5 × 10–17 M2
P) SrCrO4 <=> Sr+2 + CrO4–2 3 × 10–5 M2
Q) K2Cr2O7 <=> Cr2O7–2 + 2K+ 4.9 ×10–3 M3
R) Na2Cr2O7 <=> Cr2O7–2 + 2Na+ 5.1 × 102 M3
S) (NH4)2Cr2O7 <=> Cr2O7–2 + 2NH4+ 4.0 M3
a M denotes molarity
perfections or substitutions in the crystal lattice or due to chemical dissociation re-

actions at the solid’s surface (Freeze and Cherry, 1979). For example, chromate
ions can sorb to mineral solids that have exposed hydroxy groups on their surface
(Rai et al., 1989)
Surface − OH + H + + HCrO 4– ⇔ Surface – OH 2+ HCrO 4– (4)
is prohibited.
10
Similarly, Cr3+ can bind to solids that have exposed negatively charged silicates
and organically bound chromium will be sorbed by organic materials (Eary and
Rai, 1989).
As with redox and precipitation reactions, sorption reactions are highly influenced
by the complex environmental conditions unique to a given medium; thus, generalized
assumptions about sorption cannot be made. Such variables as pH, surface area, and
density of active sites, among others, influence sorption equilibrium.
D. Analysis of Environmental Chromium
There are two very different types of analysis that are used for the determina-
tion of chromium: (1) total chromium (i.e., with consideration as to its oxidation
state), and (2) chromium (VI) (chromium III can be inferred from the difference
between the two other analysis). The analysis for total chromium is less complex
and controversial than the analysis for chromium (VI). Although there are literally
hundreds of published methods for the determination of total chromium in a wide
variety of matrices, this focuses on the more standardized techniques.
By far the most common approach to determine the total chromium concentra-
tion is the use of hot acids that destroy chemical and physical bonds between chro-
mium and the sample matrix and convert chromium into water-soluble forms,
leaving the bulk of non-target elements as solids that can be filtered out or oxidized
to gases. USEPA SW-846 Methods 3050 and 3051 use nitric acid, mixtures of
nitric acid and hydrochloric acid, or aqua regia and are widely used and quite ade-
quate for most solid waste and soil samples (Kimbrough and Wakakuwa, 1991;
Kimbrough and Wakakuwa, 1992). Highly silicacious materials such as fly ash are
best digested using a hydrofluoric acid using a procedure such as draft method
3052. Many aqueous samples containing significant quantities of particulate must
also be digested to solubilize sorbed chromium. Standard Methods for the Analysis
of Water and Waste Water (APHA 1995) contain a number of acid digestions
(nitric acid, nitric/hydrochloric, nitric/sulfuric, nitric/perchloric and nitric/perchlo-
ric/hydrofluoric) for a range of aqueous matrices and sorbants (Methods 3030B-F,
APHA 1995). Total chromium on cellulose acetate filters is solubilized by using a
mixture of nitric acid and hydrochloric (NIOSH 7024) or a mixture of nitric acid
and perchloric acid (NIOSH 7300) depending on the instrument to be used. It has
also been shown that USEPA Method 3050B is effective on quartz-fiber filters
(Kimbrough and Suffet, 1996).
Once solubilized, chromium can be analyzed with a variety of instruments.
The most commonly used are Eletro-Thermal (or Graphite Furnace), Atomic Ab-
sorbance Spectrometry (ETAAS, GFAAS) (USEPA Methods 7191, Standard
Methods 3113/3500-CrB), Flame Atomic Absorbance Spectrometry (FAAS)
(USEPA Methods 7190, Standard Methods 3111/3500-CrB),
is prohibited.
11
Inductively Coupled Plasma Atomic (or Optical) Emission Spectroscopy
(ICP-AES or ICP-OES) (USEPA Methods 6010,200.7, Standard Methods
3120/3500-CrC), and Inductively Coupled Plasma Mass Spectroscopy (ICP-MS)
(USEPA Methods 6020A, #200.8, Standard Methods 3120/3500-CrC). The ICP-
MS and ETAAS are the most sensitive procedures but are also more susceptible to
matrix effects. ICP-AES is more robust with respect to matrix effects, but it is
subject to interelement interferences, and the sensitivity varies widely depending
on the particular instrument. FAAS is very selective and robust but has far less sen-
sitivity than the other techniques (Kimbrough and Wakakuwa, 1994). Finally, less
commonly used but increasingly popular is the use of X-ray Fluorescence (XRF),
which is a nondestructive procedure. XRF has been used in analysis with air filters
(NIOSH 7600) but has also been proposed for field screening of contaminated soils
as draft method 6200 (OSW, 1996)
Most standardized procedures for the analysis of chromium (VI) are carried
out in aqueous solutions. Measurement of chromium in water requires two steps,
sampling and analysis, while the measurement of chromium (VI) in other matrices
requires three steps: sampling, extraction of chromium (VI) into aqueous solution,
and analysis. In an aqueous solution, chromium can be separated from interfering
materials by precipitation, chelation extraction, or ion chromatography. The puri-
fied chromium can then be quantified by a variety of techniques, including colo-
rimetry, atomic emission spectroscopy, atomic absorption spectroscopy, mass
spectroscopy and polarography.
The interconversion of the oxidation states of chromium that occurs in envi-
ronmental matrices can also occur during analytical procedures. For example,
when sampling in the atmosphere, particles containing chromium are collected and
concentrated on filters or impactors over an extended period. Many of the reducing
and oxidizing agents present in the atmosphere are also collected and concentrated,
thus accelerating the reactions that might occur more slowly in the atmosphere. For
example, reductive loss of chromium (VI) has been reported when polyvinylchlo-
ride membrane filters have been used to sample chromium (VI) in air (Grohse et
al., 1988). Likewise, the sampling of water for elemental determinations usually re-
quires the preservation of the water with nitric acid, which can result in reduction
of chromium (VI), dissolution of chromium hydroxide, or the release of organical-
ly bound chromium (Beaubien et al., 1994).
Extraction of chromium (VI) from filters, impactors, tissues, or solids is also
problematic. The three general approaches are to extract either with acids, neutral
buffers, or alkaline digestions. Acids are only used for air filters when chromium (III)
is not present because chromium (VI) on the filter may be reduced to chromium (III)
by the acids (the determination is made by knowledge of chemicals in processes used
at the work site). National Institute of Occupational Safety and Health (NIOSH)
methods 7600 and 7604 (NIOSH, 1989) for the determination of chromium (VI) in
air both have an option for the determination of water soluble chromium (VI) by
soaking the filters in 0.5 N sulfuric acid solution at room temperature for 5 to 10 min.
is prohibited.
12
Neutral buffers offer little protection against interconversion of chromium ox-
idation states and are unlikely to be vigorous enough to extract chromium (VI)
from insoluble chromate salts or bound to an organic phase, such as the humic sub-
stances in soils or sediments. Alkaline digestions, such as SW-846 (USEPA,
1984a) method 3060A (James et al., 1995) and NIOSH methods 7600 and 7604
with options for total chromium (VI), extract the chromium (VI) with a heated
sodium carbonate-sodium hydroxide (pH 12) solution for 45 min. This process pre-
vents the reduction of chromium (VI) to chromium (III) but can oxidize water-
soluble chromium (III) to chromium (VI) in the presence of manganese dioxide or
oxygen (Katz, 1991). Recently, the USEPA has proposed a modified version of
method 3060A (3060B) that is intended to minimize the oxidation of chromium
(III) (James, 1996).
The extracts from soils and particles from air samplers are analyzed in the
same fashion as aqueous samples. Although there are many published analytical
methods (Beaubien et al., 1994), only a few have been given official recognition.
One of the most common methods of determining chromium (VI) is the colorimet-
ric procedure in which diphenylcarbazide is reacted with chromium (VI) to form a
red-violet complex. The extract is acidified to pH 2 and reacted with diphenylcar-
bazide, which can be done manually or in-line on an ion-chromatograph. NIOSH
method 7600, Standard Methods 3500-Cr D (APHA, 1992), and USEPA method
7196 (USEPA, 1984a) are all based on this procedure. Alternatively, aqueous chro-
mium can be analyzed FAA, GFAA, ICP-AES, ICP-MS, or polarography. USEPA
Method 218.6 (USEPA, 1979) and NIOSH Method 7604 both use ion chromatog-
raphy for separating chromium (VI) from possible interferants. USEPA methods
7195 (USEPA, 1984a) and 218.5 (USEPA, 1979) rely on precipitating chromium
(VI) as lead chromate to separate it from chromium (III) and other interferences.
There are also chelation/extractions procedures that use pyrolidine dithiocarbamic
acid to convert the chromium (VI) into a hydrophobic form that is then extracted
into an organic phase Method 7197 (USEPA, 1984a) and Method 218.4 (USEPA,
1979).
Chromium (III) (Kaczynski and Kieber, 1994) and chromium (VI) (Beaubien
et al., 1994) has been shown to bind with naturally occurring dissolved organic
carbon (DOC), although it has not been determined if chromium (VI) is reduced
during this process. In fact, hydrophobic, organically bound chromium (VI) can be
adsorbed by a reversed phase or hydrophobic guard column, such as C-18 Sep-Pak
(Waters, Inc.) or Dionex IonPak NG1 (Dionex, Inc.), that are used in ion chromato-
graphic procedures as prescribed by EPA Method 218.6. Thus, the use of ion chro-
matography as a separation technique could result in a low bias for Cr (VI).
Until recently, the sampling process for measuring Cr(VI) in stack emissions
from incinerators has also been shown to produce questionable results due to the
presence of acidic gases such as HCl and SO2 and high levels of CO2, which lead
to the reduction of Cr(VI). Steinsberger et al. (1994) have reported improved sam-
pling techniques that are not subject to these limitations.
is prohibited.
13
In summary, the fundamental redox chemistry of chromium that allows for the
interconversion of chromium (III) and (VI) in the environment is also responsible
for chromium reduction during the sampling and extraction steps in all of the most
commonly used analytical procedures. Because small sample sizes are common in
the environmental analysis for chromium (VI), the mass of chromium is generally
very low, often a few micrograms or less. Further, many of the extraction and quan-
tification processes occur under more extreme conditions of temperature and pH
than found in the environment. Thus, reaction pathways that might be trivial in the
environment take on great significance during analysis. More detailed discussions
of the analysis of chromium are provided elsewhere (Messman et al., 1986; Gut-
necht et al., 1984; Torgrimsen, 1982; James et al., 1995).
IV. FATE AND TRANSPORT OF CHROMIUM IN

ENVIRONMENTAL MEDIA
A. Chromium in the Atmosphere
Due to the extremely high boiling point of chromium (2676°C), gaseous chro-
mium is rarely encountered. The atmospheric transformation and transport of chro-
mium largely occurs in the liquid phase and solids phases (i.e., droplets and
particles) or, more generally, aerosols (Seigneur and Constantinou, 1995). Thus,
chromium emitted into the atmosphere can be particle-bound or dissolved in drop-
lets. Most aerosols generated by physical processes, such as abrasion or bubbling,
have a mass median aerodynamic diameter (MMAD) significantly larger than 10
µm. Soils are the results of abrasion that can produce particles typically no larger
than 10 µm (Hinds, 1982). However, emission factors published by the USEPA
(1995) for particulate matter less than 10 µm (PM10) suggest that mechanical
actions on road and construction sites may contribute significant PM 10 emissions.
The droplets formed during electroplating have an MMAD of around 100 µm
(Stern, 1982), while those formed from cooling towers (where chromates have
been used as antifouling and antirusting agents) are even larger (CARB, 1988).
Bonin et al. (1996) found that 90% of the mass of particles released from baths
were from 7 and 25 µm in diameter (they were unable to measure larger particles).
In contrast, aerosols generated by chemical processes, such as precipitation,
and thermal processes, such as smelting, have MMADs of 10 µm and less (Hinds,
1982). For example, the study by Cox et al. (1985) reported that 12% of the total
particle emissions from a ferrochrome smelting operation (which contained 55%
of the total particle-bound chromium) had a MMAD of <0.7 µm. In a study at a
chromate-producing factory (Bourne and Streett, 1950), “mists”, generated by
thermal heating of plating baths rather than by mechanical action, were found to
have an aerosol particle size distribution of 16% of the particles being less than 1.5
µm in diameter, 50% less than 3.8 µm, and 84% less than 9.8 µm. “Dusts” in this
is prohibited.
14
same plant had a distribution of 16% of the particles with less than 0.8 µm diame-
ter, 50% less than 1.7 µm, and 84% less than 3.7 µm. The study of Bonin et al.
(1996), regarding chromium platting operations, found that the vast majority of
particles less than 10 µm MMAD were released from platting baths as a result from
the heating of the baths and not the application of electric current. Chromium, con-
taining aerosols with an MMAD of less than 10 µm have sufficiently long atmo-
spheric half-lives, enabling them to travel significant distances from their source.
It has been suggested (USEPA, 1980b; ATSDR, 1992) that chromium-containing
particles can typically remain airborne for up to 7 to 10 days, allowing long-dis-
tance transport by the wind (Hana et al., 1982; CARB, 1988b).
Chromium entrained in aerosols may be removed from the atmosphere by both
dry deposition and wet deposition, both of which are particle size-dependent pro-
cesses. In dry deposition the particles settle and are captured by the soil or surface
waters via gravitational sedimentation, impaction, or interception. The overall dep-

osition velocity of atmospheric chromium is a function of the distribution of chro-
mium within the particle phase and the deposition velocities of chromium-
containing particles that in turn are a function of the diameter of the individual par-
ticle (Cohen, 1986).
The dry deposition velocity of aerosols can be estimated using a variety of pre-
diction methods. For example, the dry deposition of particles onto a vegetation
canopy can be estimated using the model of Slinn (1982). Also, the simple corre-
lations proposed by Whicker and Kirchner (1987), Baes et al. (1984), and Strenge
and Napier (1989) can be used to estimate the dry deposition velocity as a function
of the type and density (i.e., kg/m2) of the vegetative cover. Dry deposition onto a
water surface can be estimated using the model of Williams (1982). The applica-
tion of the above models in screening-level multimedia transport and fate models
is discussed in a number of multimedia modeling studies (Cohen and Clay, 1993,
1994; Van de Water, 1995).
Wet deposition is the process where aerosol particles are actively entrained or
scavenged by atmospheric moisture, such as rain, snow, fog, or dew. Removal of
atmospheric chromium by wet deposition is dependent on the size of the chromi-
um-containing particles and the size of the scavenging rain droplets or snowflake.
The rate of dry deposition for chromium-containing particles can be estimated fol-
lowing the approaches described by Ryan and Cohen (1986) and Tsai et al. (1991).
All of the above wet-scavenging models require knowledge of the distribution of
chromium in the particle phase as a function of particle size.
Chromium can also be introduced, or reintroduced, into the atmosphere via the
wind resuspension of chromium-containing soil particles. For particles with a di-
ameter of <50 µm, the wind-resuspension process is induced by both mechanical
and wind disturbances that provide sufficient energy to overcome gravitational
forces and allow particles to be dispersed by the wind. The rate of resuspension of
particles due to the wind’s action can be estimated by the approach described by
Cowherd et al. (1988). The procedure is based on characterizing the surfaces from
is prohibited.
15
which particles may be resuspended into two categories: (1) “limited reservoirs”
characterized by a nonhomogeneous surface (e.g., a mixture of gravel, sporadic
vegetative cover) with a threshold friction velocity; and (2) “unlimited reservoirs”
characterized by a uniform surface (e.g., agricultural soil) with a low threshold fric-
tion velocity. The application of the above approach in multimedia mass balance
studies of trace level pollutants is described in the work of Clay (1992) and Van de
Water (1995).
The reduction of chromium (VI) is far more likely than oxidation in the atmo-
sphere because of the presence and concentrations of reducing agents (such as V 2+,
Fe2+, H2S, HSO3–, NO2–, and organic materials) as well as the acidity of the atmo-
sphere. As an example of the potential atmospheric concentration of these reducing
species, a recent study by Kimbrough and Suffet (1996) found an average of
5 mg/m3 vanadium in an urban industrial setting. In both theoretical (Seigneur and
Constantinou, 1995) and experimental (Grohse et al., 1988) studies, it was found
that chromium (VI) does indeed reduce rapidly in the atmosphere. Estimates of at-
mospheric half-life for chromium (VI) reduction to chromium (III) range from 16 h
(Grohse et al., 1988) to 4.8 days (USEPA, 1984b). The few materials capable of
oxidizing chromium (III) to (VI), such as ozone, occur in concentrations too low to
produce measurable conversions in the atmosphere. Chromate may also react with
other metallic species, precipitating as lead or zinc chromate (Seigneur and Con-
stantinou, 1995). For more details of the atmospheric chemistry of chromium see
Grohse et al. (1988), Cary (1982), and Seigneur and Constantinou (1995).
B. Chromium in the Aquatic Environment
Chromium enters natural waters by weathering of chromium-containing rocks,

direct discharge from industrial operations, wet and dry deposition, and leaching
from soils. In waters, all of the transformations described earlier occur: reduction,
oxidation, sorption, desorption, dissolution, and precipitation.
Reduction of chromium (VI) can occur under a variety of conditions, even in
the presence of oxygen, if a suitable reducing agent is available (Anderson et al.,
1994). The most important naturally occurring reducing agents in waters (in order
of decreasing reducing strength) are organic substances, hydrogen sulfide, sulfur,
iron sulfide, ammonium and nitrite (excluding kinetic considerations) (Bodek et
al., 1988). Other potential reducing agents include aqueous V 2+, Fe2+, and Fe(II)-
containing minerals (e.g., glaucinite, biotite, chlorite, and magnetite) (Eary and
Rai, 1989). The reduction of chromium (VI) is favored under acidic conditions. Ex-
perimental studies have shown a wide range of reduction rates. For example,
Schroeder and Lee (1975) reported complete reduction of chromium (VI) within
1 day in the presence of dissolved sulfides, while some of the investigated reduc-
tive reactions, such as by S2– or Fe2+ ions under anaerobic conditions, were partic-
ularly instantaneous.
is prohibited.
16
In contrast to the atmosphere, many aqueous environments do contain oxidiz-
ing agents, such as MnO2 and Mn+3 (Reactions D and E, in Table 1), in sufficiently
high concentrations to produce measurable yields of chromium (VI). As with re-
duction, oxidation rates have been reported to vary greatly in experimental studies.
Dissolved oxygen by itself did not induce measurable oxidation of chromium (III),
spiked into experimental waters, even after 128 days (Saleh et al., 1989). Oxidation
of chromium (III) to chromium (VI) was only noted in one of the natural waters
and sediments studied, with half-lives ranging from 2 to 9 years. In all cases, the
extent of oxidation did not exceed 15% of the initial chromium (III) present.
Schroeder and Lee (1975) have also shown, in simulated natural water systems,
that chromium (III) can be oxidized by MnO2 and to a lesser extent, by oxygen.
However, the oxidation of chromium (III) can be inhibited by competing substanc-
es in natural water (Cary, 1982). Due to kinetic limitations, local heterogeneity,
and local catalytic effects of organisms, redox equilibrium conditions may not be
attained in many environmental systems, and reduction and oxidation can both
occur (Bodek et al., 1988). Except in estuaries, chromium concentrations in seawa-
ter are dominated by chromates, probably due to the generally oxidizing conditions
in the ocean and low suspended particulate concentration (Mayer, 1988).
As noted earlier, both Cr (III) and Cr (VI) have been shown to bind with natu-
rally occurring DOC. In a study of Lake Ontario, it was suggested that 10% of the
dissolved chromium (VI) was present in the DOC (referred to as colloidal or
organic chromium) (Kaczynski and Kieber, 1993). Organically bound chromium
(III) can stay in solution at higher pH than unbound chromium (III) (Palmer and
Wittbrodt, 1991). Organically bound chromium can also sorb to and desorb from
the organic portion of suspended and settled sediment particles. While inorganic
chromium can also sorb to and desorb from to the inorganic portions of suspended
and settled sediments. Chromium thus can move as dissolved ions or attached to
particulates, or both. Dissolved chromium (III) forms coordinate complexes with
many inorganic and organic ligands, and chromium (VI) can oxidize organic
ligands, leading to the formation of esters (Westbrook, 1983).
The oxidation and reduction of chromium are affected by sunlight (Kaczynski
and Kieber, 1994). For example, sunlight appears to degrade organically bound
chromium, releasing inorganic chromium. Further, sunlight acts indirectly by as-
sisting the reduction of iron, formation of hydrogen peroxide (Beaubien et al.,
1994; Kieber and Heiz, 1992), and the oxidation of manganese (Bartlett, 1991),
which all impact the oxidation state of chromium. Chromates have been shown to
be sensitized by DOC which increases the rate of photoreduction (Selli et al. 1996).
As noted earlier, the aqueous solubility Cr3+ is a function of the degree of hy-
droxylation of the chromium, which in turn is dependent on the pH of the water
(see Figure 2). Under neutral to basic conditions, chromium (III) will tend to pre-
cipitate out, while under acid conditions it will tend to solubilize. While chromate
and dichromate ions are extremely water soluble at all pHs, they can precipitate
with a number of divalent cations. Detailed discussions of the water chemistry of
is prohibited.
17
chromium can be found elsewhere (Rai et al., 1989; Cary, 1982; and Richard and
Bourg, 1991).
C. Chromium in Soils and Sediments
The elemental composition of soils and sediments are influenced by the com-
position of the parent rock from which they are formed. Thus, the natural concen-
trations of chromium varies greatly (Cary, 1982). As chromium is weathered from
minerals, most will initially be present in the trivalent state, which may be sorbed
on hydroxides. Naturally occurring chromates are rare and found only in highly ox-
idizing environments (Richard and Bourg, 1991). Thus, the presence of chromate
in soils and sediments is almost always the result of human activities (WHO,
1988).
Chromium input to soils and sediments from anthropogenic sources occur in-
directly due to atmospheric deposition (Rosas et al., 1989) but is more commonly
due to the dumping of chromium-bearing liquid or solid wastes from such sources
as chromate byproducts (“muds”), ferrochromium slag, or chromium plating baths.
These can be any combination of chromium (III) or (VI) of various solubilities.
Once in the soil or sediment, chromium can undergo a variety of transformations,
such as oxidation, reduction, sorption, precipitation, and dissolution.
Only a few oxidants present in soils and sediments (i.e., dissolved oxygen, and
MnO2) are capable of oxidizing chromium (III) to chromium (VI). The oxidation
of chromium (III) by MnO2 has been shown to occur in soils (Eary and Rai, 1987;
Johnson and Xyla, 1991; Fendorf and Zasoski, 1992) and oxic sediments but not
in anoxic sediments. Oxidation of chromium (III) by dissolved oxygen has been
found to be insignificant (Rai et al., 1989) when compared with MnO 2, which is the
most likely oxidant of chromium (III) in soils. Thus, if soluble chromium (III) is
added to an “average” soil, a portion of the soluble chromium (III) will become im-
mediately oxidized by MnO2 to chromium (VI) (Cary, 1982). The rest of the chro-
mium (III) may remain reduced for long periods of time, even in the presence of
electron-accepting manganese oxides, perhaps because soluble chromium (III) can
form complexes with low-molecular-weight organic molecules and then be oxi-
dized where redox conditions are optimal. It is also worth noting that the addition
of organic residues potentially as a remediation strategy for chromium (VI) con-
tamination to soils containing high levels of oxidized manganese may result in the
formation of unstable Mn (III) organic complexes that not only temporarily prevent
chromium (III) oxidation but also promote the desired reduction of chromium (VI)
(Bartlett and James, 1988).
The reduction of chromates by iron, vanadium, sulfides, and organic materials
is also well demonstrated (Cary, 1982). Losi et al. (1994) found that organic matter
content, bioactivity, and oxygen status were important factors in assessing the re-
ducing capacity of soils for Cr(VI). Iron (II) has been shown to reduce chromates
is prohibited.
18
more favorable under anoxic conditions, as oxygen can oxidize the iron (II) (Fedorf
and Li, 1996). However, high concentrations of chromium (VI) may quickly
exhaust the readily available reducing power of the soil or sediment matrices, and
excess chromium (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 (Frissel et al., 1975; Bloomfield and Pruden,
1980; Cary, 1982).
Under anaerobic conditions, the reduction of chromium (VI) was reported to be
significant when the soil contained undecomposed plant material (Bloomfield and
Pruden, 1980). The same study found that the efficiency of soils in reducing chro-
mium (VI) increased with decreasing pH. Subsoil, however, tended to reduce less
and sorb more chromium (VI) than top soil of the same pH. Under anaerobic con-
ditions, it was reported that chromium (VI) was reduced extensively at pH 6.65 in
the presence of 0.5% dried plant matter, but the soil alone was only slightly more
effective than under aerobic conditions. The reduction of chromium (VI), in the
presence of organics in sediments, is reported to depend on both the type and
amount of organic material (Saleh et al., 1989). The kinetics of chromium (VI) re-
duction has been reported to follow a simple first-order reaction kinetics (Bartlett
and James, 1988; Amacher and Baker, 1982). Amacher and Baker (1982) reported
a reduction half-life of 55 days from addition of chromium (VI) to Haegerstown
loam at 26%C and pH 5.0. They also observed that the reduction rate of chromium
(VI) by fulvic acids increased when the temperature was raised. Bloomfield and
Pruden (1980) reinvestigated earlier claims that chromium (VI) is readily reduced
to chromium (III) under normal soil conditions. They found that the analytical
methods used in previous investigations (Bartlett and Kimble, 1976) were unreli-
able because the soil extracts probably contained organic matter capable of reducing
chromium (VI). Bloomfield and Pruden (1980) found that the reduction of chromi-
um (VI) in soil of normal pH was not particularly rapid under aerobic conditions.
However, it has been suggested that light may bring about photooxidation of soil
organic matter accompanied by the reduction of chromium (VI) (Bartlett, 1991).
Chromates can be sorbed by iron, aluminum oxides, hydroxides, and other soil
components without reduction (Bartlett, 1991; Bartlett and James, 1988). Also
chromium (III) materials can be sorbed onto silicacious components. Soil pH de-
termines both the speciation of chromium (VI) and the charge characteristic of the
surface with which it reacts (James and Bartlett, 1983). Above pH 6.4, HCrO 4 – dis-
sociates to CrO4–2 as the dominant form of chromium (VI) in dilute aqueous
systems (Bartlett and James, 1988), which may in turn be sorbed in a similar
fashion as SO42– and HPO42–. Soil pH also affects the charge on soil colloids
(MacKenzie, 1977; Parfitt, 1978; Bartlett and James, 1988). Thus, binding of chro-
mium (VI) species in soils depends on soil mineralogy and soil pH (Bartlett and
James, 1988). Sorption of chromates can be a reversible process suggested by
leaching of chromium (VI) from soils (Baron et al., 1986). However, such revers-
ibility depends on the chemistry of the leachate and of the soil or sediment.
is prohibited.
19
Sorption of chromium (VI) to amorphous aluminum, iron oxides, and organic
complexes present in several northern U.S. acid soils may protect against reduction
(Bartlett and James, 1988). More highly weathered southern U.S. soils adsorbed
more chromium (VI) than the less-weathered northern soil, but the southern soils
did not bind chromium (VI) in such a way as to hinder its reduction (James and
Bartlett, 1983). As both reduction and sorption can occur simultaneously in many
soils, it is not always possible to assign the cause of chromium (VI) disappearance
as being due to reduction or sorption (Bartlett, 1991).
In the aqueous phase of soils and sediments, Cr(III) that is not sorbed by the
solid phase would generally hydrolyze to the hydroxide and precipitate. Chromates
would be far less likely to precipitate and so would be expected to be more mobile.
In this situation precipitation reactions are closely tied to oxidation and reduction
reactions. In anoxic sediments, oxidation is unlikely to take place and chromium
hydroxide could be immobilized as long as the sediments are physically stable

(Eary and Rai, 1989). However, at least one study proposed that the deeper sedi-
ments of the sea floor are richer in manganese dioxide than are the sediments near
the sea-sediment interface, so that more oxidation of chromium might occur in
these oxygen-poor sediments (Gaillard et al., 1986). More details concerning the
chemistry of chromium in soils and sediments are provided in review articles by
Cary (1982), Saleh et al. (1989), and Richard and Bourg (1991).
D. The Uptake and Transformation of Chromium by Biota
There is much evidence to show that chromium can be taken up by biota from
the air, water, and soil. Unfortunately, most of the available studies on chromium
bioaccumulation and bioconcentration report measured total chromium in the
exposed organism without distinguishing between its oxidation states. Thus, bio-
concentration factors and transfer coefficients for chromium (VI), as opposed the
total chromium, are lacking.
1. Bacteria
Microorganisms have the potential to accumulate chromium (Coleman, 1988)

and reduce chromium (VI) to chromium (III) (Shen and Wang, 1996; Wang and
Xiao, 1995; Campos et al., 1995; Deleo and Ehrlich, 1994). Although high levels
of chromium (VI) are toxic to microorganisms (Bartlett, 1991) chromium is impor-
tant to yeast metabolism (Anderson et al., 1977; Coleman, 1988) and sorption of
Cr (VI) by several species of yeast has been reported (Rapoport and Muter, 1995).
Chromium accumulation has been shown to occur in bacteria periphytic to a
crab (Helice crassa) carapace and in sewage fungus (Johnson et al., 1981; Gray and
Clarke, 1984; Coleman, 1988) and may contribute to the presence of chromium in
is prohibited.
20
the food chain. In this regard, it is noted that Coleman (1988) did not report the ox-
idation state of the chromium either found in the organisms or to which the organ-
isms were exposed. Coleman (1988) also summarized additional laboratory studies
that reflect accumulation of chromium in bacterium exposed to chromium (VI), but
the analytical techniques used in these studies mean that total chromium rather than
chromium (VI) was measured in the bacteria. The active uptake of chromate by the
sulfate transport system has been shown in the microorganism Neurospora crassa
(Roberts and Marzluf, 1971; WHO, 1988), analogous to the mechanism demon-
strated in plants (Shewry and Peterson, 1974), but there is no definitive evidence
of bioaccumulation of chromium as chromium (VI) in bacteria.
The reduction of chromium (VI) under anaerobic conditions by an Enterobac-
teria cloacae strain isolated from activated sludge was reported by Wang et al.
(1989). The rate of chromate reduction was found to depend on cell density and
chromate concentration. Earlier work suggested that indirect reduction of chromi-

um (VI) may result from microbially produced hydrogen sulfide in a seawater/sed-
iment system (Smillie et al., 1981).
2. Plants
There are conflicting views concerning the uptake and translocation of chro-
mium (VI) in plants. Ramachandran et al. (1980) suggest that CrO 42– is reduced to
chromium (III) at the surface of root cells. Other studies found chromium (VI) in
plants, which suggest that dissolved chromium (VI) may be taken up by plants
without immediate reduction (Misha et al., 1995). For instance, chromate was
found in the xylem sap of L. scoparium but not in the soluble plant fraction (Lyon
et al., 1969; Cary et al., 1977). Also, it has been shown that chromium (VI) enters
the plant through the root by active transport in barley (Hordeum vulgare L.) (Skef-
fington et al., 1976; Cary, 1982). Uptake of CrO42– by intact barley seedlings was
stimulated by Ca2+ but inhibited by SO42– and other Group VI anions (Shewry and
Peterson, 1974). Later authors (Smith et al., 1989) have interpreted the findings of
Skeffington (1976) and Shewry and Peterson (1974) to indicate that chromium
(VI) uptake is a metabolically mediated process via the sulfate pathway and thus
that chromium (VI) is readily transported through the plant. However, Cary (1982)
reports there is no evidence that chromium (VI) is translocated in the plant. It is
noted that chromate appears to be reduced during passage from culture solutions to
plant leaves, but the site of this reduction is unknown (Cary et al., 1977).
Higher concentrations of chromium have been reported in plants growing in
high chromium-containing soils (e.g., soil near ore deposits or chromium-emitting
industries and soil fertilized by sewage sludge) compared with plants growing in
normal soils (Grubinger et al., 1994). However, most of the increased uptake of
chromium results in accumulation in the roots, and only a small fraction of the total
chromium is translocated to the above-ground part of edible plants (Cary, 1982;
is prohibited.
21
WHO, 1988). Leaves usually contain higher chromium concentrations than grains
(Smith et al., 1989). In an attempt to design crop practices that might increase the
chromium in food and feed crops, Cary et al. (1977) also found that plants accu-
mulated chromium from nutrient solutions but retained most of this chromium in
the roots.
Shewry and Peterson (1974) found that plant tissues that tend to accumulate
iron also accumulate chromium. Chromium uptake was found to increase with in-
creasing chromate concentration, and most of the chromium accumulated by the
roots was present in a soluble, non-particulate form in the plant vacuoles. Although
chromium is largely retained in the roots of plants, the oxidation state of chromium,
the pH, and the presence of humic substances and plant species affect plant uptake
and transport (Smith et al., 1989). Chromium is more available to plants growing
in a neutral to basic soil than in an acidic soil probably due to the stability of chro-
mium (VI) under these conditions. However, as Smith et al. (1989) stressed, there
is a notable dearth of information pertaining to the speciation of chromium in
plants. For instance, Kwan (1988) reported a bioconcentration factor (BCF) of
1000 for an aquatic plant (Lemna minor) exposed to chromium (VI), but the infor-
mation presented was insufficient to determine the form in which chromium was
present in the plant.
The reason for the restricted chromate transport in plants has not been estab-
lished (Shewry and Peterson, 1974) but may be related to the role of chromium in
plant metabolism. Whether chromium is an essential element in plants has been
debated in the literature (Smith et al., 1989; Shewry and Peterson, 1974; Hartford,
1983). For example, the World Health Organization (WHO, 1988) reports that it is
unknown whether chromium is an essential nutrient for all plants, yet all plants
contain the element. In contrast, the subsequent study of Richard and Bourg (1991)
suggested that chromium (III) is an essential nutrient in plant metabolism (amino
and nucleic acid synthesis).
3. Aquatic Animals
A large number of bioaccumulation studies of chromium have been with

finned fish. For example, Fromm and Stokes (1962; cited by Holdway, 1988) re-
ported BCFs near unity after 10 days of exposure of rainbow trout (Salmo gaird-
neri) to chromium. The highest reported BCF for rainbow trout was about 3
(Calamari et al., 1982), and organ-specific BCFs approaching 10 have been report-
ed (Holdway, 1988). High BCFs were reported for bottom-dwelling fish (Hold-
way, 1988). In the most extreme example, brown bullhead (Ictalurus nebulosus)
concentrated chromium in liver and muscle tissue 1822 to 2622 times the river-
water concentration, but below the sediment concentration (Reisinger, 1979;
cited by Holdway, 1988). In bottom-feeder bivalves, such as the oyster (Crassos-
trea virginica), blue mussel (Mytilus edulis), and soft shell clam (Mya arenaria),
is prohibited.
22
the BCFs values for chromium (III) and chromium (VI) have reported in the range
from 86 to 192 (USEPA, 1980a; USEPA, 1984c; Fishbein, 1981; Schmidt and
Andren, 1984; ATSDR, 1992).
The assertion that chromium is ingested by fish (and perhaps bivalves) via food
uptake was proposed by Elwood et al. (1980). However, several researchers have
found that dissolved chromium passes readily through the gill membrane of fish
(Knoll and Fromm, 1960; Buhler et al., 1977) and rapidly accumulates in other
organs (Buhler et al., 1977). Other researchers (Arillo and Melodia, 1990) have
shown that fish skin mucus contains molecules (such as protein-bound sulfhydryl
groups) capable of reducing chromium (VI) nonenzymatically.
The literature on chromium bioconcentration suggests that chromium (VI) is
not expected to biomagnify in the aquatic food chain. For example, Whittle et al.
(1977) suggested that higher trophic levels contain reduced levels of chromium.
This statement has been supported by several studies which also found decreasing
concentrations of chromium along the food chain (Holdway, 1988). When chromi-
um (VI) is intracellularly sequestered and converted to chromium (III), the element
is less easily absorbed by predators and thus less likely to move through the food
chain (Arillo and Melodia, 1991) like either chromium (III) or chromium (VI).
There is some confusion in the literature regarding the BCF for chromium as
chromium (VI) in aquatic animals. In some studies fish were exposed to chromium
(VI) but the measurement in the tissue was for total chromium. A typical example
is the widely cited bioconcentration studies performed by Calamari et al. (1982;
SCAQMD, 1988) in which rainbow trout were exposed to chromium (VI) as
K2Cr2O7, but total chromium concentrations were measured in the fish. Given the
propensity of chromium (VI) to be reduced by biological systems (Arillo and
Melodia, 1991), the conservative assumption that all chromium present in the fish
is present as bioaccumulated chromate is questionable.
4. Terrestrial Animals
There is no indication of biomagnification of chromium along the terrestrial

food chain (soil-plant-animal) (Clay, 1982; ATSDR, 1992). Because it is an essen-
tial metal in animals, metabolic pathways for chromium must have evolved (Nie-
boer and Jusys, 1988). There is evidence that chromium (III) binds to the Fe(III)
transport protein transferrin (Nieboer and Jusys, 1988). Petrilli and De Flora (1978)
reported that chromate is selectively concentrated in erythrocytes (red blood cells)
where it undergoes metabolic deactivation to the trivalent form.
Chromate at physiologic pH 7.4 is capable of oxidizing both low-molecular-
weight reductants (e.g., cysteine, ascorbate, glutathione, lipoic acid) and proteins.
These reactions proceed by second-order kinetics and are dependent on the concen-
tration of both the chromate and the reductant. Using the published rate constants
and concentrations of reductants in biologic fluids ranging from 10 –1 to 10–5 M, and
is prohibited.
23
assuming similar chromate concentrations, Connet and Wetterhahn (1983) calcu-
lated reduction half-lives ranging from minutes to hours.
The metabolism studies performed by Van Brunwaene et al. (1984) showed
that radioactively labeled chromium (VI) can be absorbed orally by lactating dairy
cows. A transfer coefficient into milk of 1 × 10–5 days/l was reported. However, the
chromium in the milk was determined by radioactivity measurements of Cr 51,
which cannot distinguish chromium (VI) from other forms of chromium. Any
chromium (VI) absorbed orally by the cow could have quickly reduced to chromi-
um (III); therefore, it may be inappropriate to apply the transfer coefficient of Van
Bruwaene et al. (1984) to the secretion of chromium (VI) into milk.
E. Multimedia Oxidation/Reduction Cycles of Chromium

In some natural systems conditions exist where oxidation and reduction of

chromium can both occur (Bartlett, 1991; Bartlett and James, 1988). For example,
as noted above, in aquatic systems chromate ions may be reduced to Cr 3+. Manga-
nese dioxide can then oxidize Cr3+ back to chromate. If the water is well aerated
and sunlight can penetrate to a sufficient depth, the manganese will be reoxidized,
allowing more reduced chromium to be oxidized. A similar cycle that is dependent
on citric acid has been shown to occur in soils (Bartlett, 1991). While such a cycle
is theoretically possible in the atmosphere, it is extremely unlikely due to the far
greater preponderance of chromium (VI) reducing agents over oxidizing agents for
Cr3+ in the atmosphere (Grohse, 1988).
Just as manganese can be reoxidized by sunlight and oxygen, iron(III) can also
be reduced by sunlight to iron(II), which can then reduce chromium (VI) to (III).
Indeed, Kaczynski and Kieber (1993) and Kieber and Hetz (1992) reported a
diurnal variation in the ratio chromium (III)/(VI) in pH neutral lakes caused by in-
direct action of sunlight on chromium via iron and manganese. The ratio chromium
(III)/(VI) may also be affected by the photo disassociation of chromium from
organic materials (Kaczynski and Kieber, 1993).
The three types of chromium that take part in chromium cycles are water-
soluble chromium (III), water-insoluble chromium (III), and water-soluble chromi-
um (VI). The water-insoluble chromate pigments, specifically barium, calcium,
lead, strontium, and zinc chromate are soluble only in strong acids and are not im-
portant sources of chromate ions in water.
Figure 3 shows a generalized intermedia transport scheme for environmental
chromium. Chromium is directly emitted from industrial activity either into the air,
into water systems (e.g., streams, sewers, lakes, etc.), or to the ground. Airborne
chromium eventually settles out into soil or water. In a given parcel of soil, there
can be a mixture of chromium (VI) and chromium (III), both naturally occurring
and anthropogenic. Chromium (VI), but not chromium (III), can be leached out of
the soil and enter ground water, which in turn can become part of an aquifer and
is prohibited.
24
FIGURE 3. Human exposure routes and accumulation of chromium.
also migrate to surface waters. As chromium (VI) is leached from the soil, the re-
maining chromium (III) can slowly oxidize to chromium (VI) to reestablish the
equilibrium of the soil (Bartlett, 1991).
In aqueous environments, chromium (VI) can migrate in the dissolved form,
while both chromium (III) and (VI) can migrate bound to DOC or suspended par-
ticles. Chromium can migrate from the aqueous phase and to sediments from a dis-
solved state or with DOC or particulates. In the sediment, dissolved chromium (VI)
is prohibited.
25
can be immobilized if it enters a stable anoxic portion, but chromium (VI) in oxic
sediments can be redissolved.
V. HEALTH EFFECTS OF CHROMIUM
A. Absorption, Metabolism, and Toxicology of Chromium
There are four routes of exposure of interest for chromium, dermal absorption,
ingestion, inhalation, and ingestion secondary to inhalation (see Figure 3). Chro-
mium can act directly at the site of contact or be absorbed into, or through, human
tissues. One of the critical differences between chromium (VI) and chromium (III)
species is that the former can be a strong oxidant, while the latter is not. A second
important difference is that the chromate ion passes through cellular membranes
many orders of magnitude faster than do chromium (III) species (Levis and Bian-
chi, 1982).
Chromium (VI) can act as an oxidant directly on the skin surface or it can be
absorbed through the skin, especially if the skin surface is damaged (WHO, 1988).
In fact, irritation of the skin a most frequently reported human health effect from ex-
posure to Cr(VI), taking the form of skin ulceration (dermatosis) and allergic sensi-
tization (dermatitis) (NAS, 1974; Bagdon and Hazen, 1991; Pedersen, 1982). Skin
ulceration involves the corrosion and removal of skin, forming ulcers and subse-
quent scars by gross exposure to chromates and moisture (Johansen et al., 1994).
Indeed, dermatosis was the first observed health effect associated with chromium
(VI) exposure, although improved industrial hygiene practices have greatly reduced
its incidence. (Bagdon and Hazen, 1991; Pedersen, 1982; Pausterbach et al., 1992).
Allergic contact dermatitis is the most prominent reaction from the interaction
of chromium with skin (Nieboer and Jusys, 1988). Chromium is generally accepted
as being the second most common skin allergen in the general population, after
nickel (Polak, 1983; Haines and Nieboer, 1988); in men, it is the most frequent sen-
sitizer (Cronin, 1980; Haines and Nieboer, 1988).
Dermatitis is a sensitization to chromates creating an eczema-like condition.
Chromates absorbed into the skin create an immune response. This symptom was
reported to be the highest incidence among workers handling wet cement and other
occupation where chromium (VI) was water soluble and moisture was present. The
incidence among workers handling dry cement and other dry chromium materials
was reported to be much lower (Pedersen, 1982; Bagdon and Hazen, 1991). Further,
the addition of ferrous sulfate as a reducing agent appears to lower the incidence of
contact dermatitis among Scandinavian construction workers (Roto et al., 1995).
The absorption of chromium (VI) into the blood system through the skin has
been reported but not investigated extensively, mainly because the reported health
effects are rare. Once absorbed into the blood system there are various antioxidants
that act as reducing agents, such as glutathione and ascorbate, which rapidly reduce
is prohibited.
26
chromium (VI) to chromium (III) (Levis and Bianchi, 1982). Chromium absorbed
through the lungs into the blood system is excreted by the kidneys and the liver.
The kidney appears to absorb chromium from the blood through the venal cortex
and releases it into the urine (Wedeen and Qian, 1991). Thus, sampling of urine for
chromium can be used for biological monitoring for certain types of welding fumes
that contain water-soluble chromium (VI) (NIOSH, 1992). However, large doses
of chromium into the blood can result in acute kidney and liver damage (NIOSH,
1975; Langard, 1982; Pascale et al., 1952) with acute tubular necrosis as reported
by Weeden and Qian (1991). Chronic liver and kidney damage due to long-term
exposure of chromium (VI) has also been reported (Mutti et al., 1979). However,
chronic low-level exposure to chromium does not appear to produce measurable
renal damage (Nagaya et al., 1994). It should be noted that kidney damage has also
been observed in animal studies (NIOSH, 1975).
Chromium absorbed into the blood does not accumulate in any organs at sig-
nificant concentrations. In metabolism studies, injected and ingested chromium
was found mainly in the liver, kidneys, and blood. This is not likely to be the result
of bioaccumulation but rather that the liver and kidney are the main routes of ex-
cretion for chromium (Langard, 1982). Chromium has also been reported by Rosas
et al. (1989) to collect in the hair as a result of circulation in the blood; however,
this latter study did not appear to distinguish or establish a control for chromium
surface deposition onto the hair as opposed to actual absorption into the hair.
Animal studies suggest chromium (VI), which is absorbed into the blood
system, is reduced and excreted by either the kidneys or liver (Witmer et al., 1989).
Gargas et al. (1994) found essentially no absorption of chromium from the inges-
tion of soil contaminated with chromite ore-processing residue (COPR) among a
group of human volunteers. Controls, low-dose, and high-dose groups showed no
difference in urinary chromium concentrations. Stern et al. (1992) likewise found
no difference in chromium concentrations in urine between residents of areas with
soils with high concentrations of COPR and those from areas without COPR. This
was true even though the chromium content of household dusts was significantly
higher in the high COPR areas than the control areas. Chromium in the blood
system does not accumulate in the lungs or other internal organs except en route to
excretion. This is supported by ingestion and blood injection studies. The liver and
kidney are two organs that consistently show the highest concentration of chromi-
um. The quantities of chromium found in these organs, however, are only a small
portion of the metabolized chromium.
Chromium-containing water, soil, plant products, animal products, and parti-
cles cleared from the respiratory tract to the esophagus are possible vehicles for the
ingestion of chromium. Chromium is present in food and feed plants, but the form
is not well characterized (Cary, 1982). The likely form is soluble chromium (III)
organic compounds such as chromium (III) oxalate in plants (Lyon et al., 1969;
Smith et al., 1989) and chromium (III) amino acid complexes in food (Nieboer and
Jusys, 1988). Chromium is an important micronutrient for plants, animals, and
is prohibited.
27
humans. Humans must consume organically bound or chelated chromium as part
of the proper metabolism of Glucose Tolerance Factor (GTF).
Although chromium (VI) can be rapidly absorbed through the intestinal wall,
any ingested chromium (VI) is believed to be quickly reduced in the stomach
where the pH is around 1 and numerous organic reducing agents can be found.
Studies by Donaldson and Barreras (1966), De Flora et al. (1987), and Finley et al.
(1996) also demonstrated the reduction of chromium (VI) by acidic gastric juice.
This may explain why the absorption of orally administered chromium (VI) was
not found to exceed even 5% of the dose (Hopkins et al., 1964). Finley et al. (1996)
found similar results with three of four volunteers with one volunteer absorbing
27%. It has also been reported that less than about 3% of the dose of inorganic
chromium (III) is absorbed (Visek et al., 1953, Hopkins, et al., 1964A). On the
other hand, chromium (III) bound to polypeptides was reported to absorb through
the jejunal mucosal membranes of rats (Chen et al., 1973). Gargas et al. (1993)
found that only 2.8% (ranging from 1.5 to 5.2%) of orally ingested chromium pi-
colinate was absorbed. Any chromium (VI) that is not reduced in the stomach and
absorbed by the blood system is likely to be reduced in the stomach by the same
mechanisms already noted. It should also be noted that many common beverages
can also reduce chromate (Kerger et al., 1996).
Absorption of chromium (VI) compounds through the upper respiratory
system produces two different health effects. One is the ulceration or perforation
of the nasal septum and the second is the irritation of the upper airways. Again, it
is the oxidative power of chromates that corrodes the epithelium (NAS, 1974;
NIOSH, 1975), causing ulcers and perforations. Evidence of the above effects were
documented in early studies for chromate workers, revealing mucosal irritation and
papillomas in nasal cavity, oral cavity, and the larynx.
One of the key factors in respiratory toxicology is the penetration of particu-
lates into the lower lung airways. The largest particles that can pass the nose and
throat are about 10 µm MMAD, but generally the greatest human health risks are
posed by particles ranging from 0.2 m to 2 µm MMAD (Langard, 1982; Hinds,
1982), which can penetrate deep into the lungs. It has been suggested that half or
more of these particles may reach the gastrointestinal tract (Sheehan et al., 1991).
It is interesting to note that in a study of high chromium concentration soils in
Hudson County (New Jersey, USA), Kitsa et al. (1992) reported that only 0.26%
of the mass of soil had an MMAD of 2.5 µm or less and that only 20% of the chro-
mium was chromium (VI). Given that resuspended soil particles have a significant
size fraction above 2 µm, it is not unreasonable to expect that a sizeable fraction of
inhaled chromium-containing particles may end up in the stomach rather than the
lungs. Thus, chromium in the form of welding fumes, ore roasting fumes, and dusts
from precipitative and thermal chemical processes, all which contain mostly PM 10
particles, pose the greatest risk of inhalation into the lower lung airways. Unlike
most other toxins, absorption into the blood is not the principal health concern with
chromates. Rather, the principal concern is the effect of chromates on the bronchi
is prohibited.
28
of the lung (IARC, 1990; Cohen et al., 1993). The absorption of inhaled chromium
compounds depends on a number of factors, including physical and chemical prop-
erties of the particles (oxidation state, size, solubility) and the activity of alveolar
macrophages (ATSDR, 1992). Soluble chromium (VI) compounds are rapidly ab-
sorbed through the epithelium of the lung and cleared into the blood system where
chromates are accumulated by the red blood cells and the rest is excreted by the
kidneys (WHO, 1988; Wiegand et al., 1988). More details on the absorption and
metabolism of chromium can be found in the review by Langard (1982).
Respiratory cancer is the health effect of most concern and is the basis for the
regulation of chromium (VI). There is also some indication that chromium (VI)
may cause cancer of the upper airways and upper gastrointestinal tract, such as the
esophagus, larynx, trachea, and stomach (Alexeeff et al., 1989). Chromium (VI)
appears to be a contact carcinogen to the respiratory system. It has not been impli-
cated in skin cancer, where there is far more frequent and intense contact than for
any other part of body. Also, chromium (VI) has not been reported to be a carcin-
ogen for organs for which the only exposure to chromium (VI) is via the blood.
Autopsy studies of human lungs show that inhaled chromium builds up in the
lungs. Chromium concentration in the lungs was found to increase with age for
both occupationally and environmentally exposed individuals (Kollmeier et al.,
1987; Kollmeier et al., 1990). The upper lobes tended to have higher concentra-
tions than lower lobes and cancerous portions of lungs showed the highest chromi-
um concentrations (Alwen and Jonas, 1938; Baetjer, 1950; Hyodo et al., 1980; Kim
et al., 1985). The study of Stern et al. (1992) on environmental exposure in Hudson
County, New Jersey, showed elevated urine chromium levels among residents
living on or near landfills containing chromium; the chromium levels in urine also
correlated with chromium content of household dust, but the exposure appears to
have resulted from ingestion. Likewise, a similar study in Lecheria, Estado de
Mexico, Mexico (Rosas et al., 1989) found elevated concentrations of chromium
in the urine of residents around a chromate manufacturing plant. Respirable air-
borne particles, contaminated water, and contaminated soil were all possible expo-
sure routes.
In several epidemiological studies slightly elevated incidence of stomach
cancer were reported (Alexeeff et al., 1989). In these cases, the route of exposure
was inhalation, not ingestion. This may indicate that the chromium reaches the
stomach via clearance of the mucous membranes lining the airways. However,
these results are not definitive, and it is not widely accepted that chromium (VI) is
a carcinogen in the stomach (Lees, 1991).
Animal studies on the carcinogenicity of various chromium species have gen-
erally suggested that water-insoluble species, CaCrO4 in particular (Laskin et al.,
1970; Levy, 1975; Levy and Vennitt, 1975; Levy and Vennitt, 1986; Levy et al.,
1986), are the causative agent of respiratory cancers (NIOSH, 1975; Gad, 1989).
Laskin and co-workers (Laskin et al., 1970) implanted several species of chromium
into the lungs of rats in a metal pellet with a cholesterol vesical. Not only did
is prohibited.
29
TABLE 3
Lung Tumors After Implantationa
Induction
Number of Number of time
Treatmentb rats tumors (days)
Blank pellet 100 0

Pellet + cholesterol (vehicle) 100 0
Chromium (III) chloride hexahydrate 100 0
Sodium dichromate 100 0
Sodium chromate 100 0
Hydrogen chromate (chromic chromate)(ground) 100 1 560
Chromium trioxide (metallic) 100 0
Calcium chromate 100 8 473–734

Zinc potassium chromate 100 3 657–734
Diphenyl guanidine (DPG) 100 0
DPG + calcium chromate 100 7 502–732
Primeme 81-R benzoate 100 0
Primene + calcium chromate 100 5 440–732
Chromic chromate 100 0
Chromic chromate in silica 100 5 666–730
100% 3-Metylcolanthrene 48 34 217–730
a Source: Levy (1975).

b 2 mg 1:1 with vehicle.
calcium chromate cause tumors in the rats, but the pattern of tumors (4:1 squamous
cell carcinomas to adenocarcinomas) for the rats was the same as reported by a
USPHS (1953) study of chromate workers.
Following the work of Laskin and co-workers (1970), Levy and Vennitt (1975)
implanted pellets into the left lungs of Parton Wester rats, with the right lung acting as
a control. As can be seen in Table 3, negative controls in the form of pellets, pellets
and vehicle, and chromium (III) and water-soluble chromium (VI) produced no
tumors. The positive control, 3-methylcolanthrene, CaCrO4, H2CrO4, and ZuCrO4 all
produced tumors, mostly large keratinizing squamous cell carcinomas. Other studies
have indicated that water-soluble chromium (VI) may be carcinogenic (Cohen et al.,
1993; NIOSH, 1975; Glaser et al., 1986). Additional details of the results of animal
studies have been discussed by NIOSH (1975), Hayes (1980), and Cohen et al. (1993).
Research on the carcinogenicity of chromium (VI) has focused on that fact that
chromate ions quickly pass through cellular and nuclear membranes, while the
is prohibited.
30
trivalent species are many orders of magnitude slower (Lavelle, 1991). However,
chromium (III) binds much more readily to DNA than chromate ions, although
chromium (III) does not bind to DNA strongly. Once in the cytoplasm, chromate
ions can either pass the nuclear membrane and be reduced to chromium (III) or be
reduced in the cytoplasm (Jenette, 1979). Because neither chromium (VI) nor (III)
reacts strongly with DNA, it is thought that the reduction of chromium (VI) to (III),
either in the cytoplasm, nucleus, or the blood, produces free radicals (OH⋅, O, O2–,
RS⋅, R⋅ etc.), which in turn can bind to DNA (Wetterhahn, 1989). Indeed, the
DNA-protein crosslinks induced by chromate have been used as a biomarker for
chromium exposure (Taioli et al., 1995).
There is vast literature documenting the mutagenic and cytogenic effects of
various chromium compounds, which are reviewed in Cohen et al. (1993) and
Levis and Bianchi (1982). Various studies have shown various chromium (VI)
compounds cause many kinds of genetic damage in the laboratory. However, in a

recent field study, Gao et al. (1994) found no increased DNA damage to lympho-
cytes among exposed chromium workers when compared with an unexposed
group, even though the exposed group had elevated blood, plasma, and urine chro-
mium concentrations. On the other hand, Taioli et al. (1995) found slightly elevat-
ed numbers of chromate-specific DNA-protein crosslinks among residents of
Hudson County (New Jersey) with elevated chromium urine concentrations when
compared with a control population. Both of these studies used white blood cells
(WBCs) for DNA testing; however, because chromates are not associated with any
white blood cells or even circulatory disorders, the implication of these studies is
not clear. Another theory holds that chromium (VI)-induced damage to cells causes
the release of hydrolytic enzymes from the lyzosomes. This could yield glycidal
that might interfere with cell division (Schoental, 1975a,b).
B. Chromium Exposures and Epidemiology
Chromium is one of the most studied chemicals linked to occupational hazards,

with citations of injury dating back 150 years and the first case of occupational lung
cancer reported more than 100 years ago (Newman, 1890). The German govern-
ment recognized chromium as an occupational carcinogen in 1936, and the first ep-
idemiological studies date back almost 50 years (Machle and Gregorius, 1948).
There are four sources of occupational chromium exposure which have been stud-
ied: chromate production, pigment production, stainless steel welding, and chromi-
um plating.
Chromate production involves both ore roasting to produce sodium chromate
and the treatment of sodium chromate to produce other oxides. As shown in
Table 4, the rates of lung cancer among chromate workers was reported to be very
high in a number of studies. However, the conclusion of almost all of the studies
was that not all forms of chromium (VI) were carcinogenic, but rather that only the
is prohibited.
31
TABLE 4
Epidemiological Chromate Production Lung Cancer Studies
Estimated
Significant relative riska Ref.
Yes 29b Machle and Gregorius, 1948

Yes —d Baetjer, 1950
Yes 15b Mancuso and Hueper, 1951
Yes 14–80 USPHS, 1953
Yes — Bidstrip and Case, 1956
Yes 9b Taylor, 1966
Yes 9 Enterline, 1974
Yes —d Mancuso, 1975
Yes 0.7–3c Korallus et al., 1974

Yes 49b Ohsaki et al., 1978
Yes 2–4b Hayes et al., 1979
Yes 2b Alderson et al., 1981
Yes 3–18 Satoh et al.,1981
a The relative risk is the ratio of the observed number of cancer deaths
relative to the expected cancer mortality for the appropriate control
group.
b After Hayes (1982) calculated, based on the assumption that the ob-
served number of deaths is distributed as a Poisson random variable.
c For some groups.
d Not reported.
water-insoluble species were carcinogenic while water soluble species were not. It
should be noted that in three frequently cited papers the authors incorrectly
assumed that only chromium (III) species are water-insoluble and concluded that
chromium (III) species are at least as carcinogenic as chromium (VI) (Mancuso
and Hueper, 1951; Mancuso, 1951; and Mancuso, 1975). More recent studies have
shown lowered cancer risks at chromate production sites (see Table 4). While this
is believed to be mainly due to improved hygienic practices, some authors have
argued that this cancer risk reduction is also due to the use of low- or no-lime roast-
ing techniques which do not produce calcium chromate. Indeed, in the retrospec-
tive study of Pasides et al. (1994), five lung cancer cases were found in a new well-
designed ore roasting facility, three of which were among a cohort of workers who
had transferred from an older facility. Among workers who had only worked in the
new facility, there was no increased incidence of lung cancer compared with
several control populations (Pastides et al., 1994). This observation supports the
hypothesis that only the insoluble chromates (i.e., less soluble than CaCrO 4) are
carcinogenic (Gochfield, 1991).
is prohibited.
32
The above hypothesis is partially supported by the results of studies of chro-
mate pigment workers. In four different investigations zinc chromate was found to
be carcinogenic (Langard and Norseth, 1975; Langard and Vigander, 1984;
Dalager et al., 1980; Davies, 1984), but in another study lead chromate was found
not to be carcinogenic at exposure levels sufficient to produce clinical cases of lead
poisoning (Davies, 1984). Because lead and zinc chromates are often produced to-
gether, it is difficult to differentiate the effects of the different chromates. Results
from studies where lead and zinc chromates were both present are less definitive
(Sheffet et al., 1982; Hayes et al., 1989; Frentzel-Beyme, 1983; Haguenoer et al.,
1981). Also supportive, but even less conclusive, are the results from studies of
stainless steel welders that showed slightly elevated cancer risks (Stern, 1982). De-
pending on the type of welding that occurs, either water-soluble or -insoluble chro-
mates are generated (NIOSH, 1992). The only epidemiological study of
environmental exposures to chromium was reported by Axelsson and Rylander

(1980) for the populations around two ferrochromium plants in Sweden. In that
study, no increased risk of lung cancer was found.
Eight epidemiological studies have been reported in the literature for chromi-
um platers, where water-soluble species are used. In contrast to the epidemiologi-
cal studies for the other chromium industries, the results from chromium platers
show considerably lower cancer rates and relative risks, although some authors
considered the rates significantly higher than those for the control groups. It is im-
portant to note that in chromium plating other suspected carcinogens are present.
Metal surfaces are usually degreased prior to plating, and this is often accom-
plished with chlorinated solvents. Chromium plating is generally done after a layer
of nickel has been plated first so nickel mists are also present.
Notably, four studies of chromium platers found no increased cancer risk
(Dalager et al., 1980; Okubo, 1977; Endo, 1988; Horiguchi et al., 1987) from chro-
mium plating, while in a fifth Blair (1980) found no excess lung cancers but excess
of esophageal and liver cancers. Silverstein et al. (1981) found excess cancer and
respiratory cancers (lung and larynx) that increased with increasing years of employ-
ment. It is noted, however, that confounding carcinogens, such as PAHs, nickel, and
possibly chlorinated solvents, were present in this latter study. Further, plating scrap
was heated in a reverberatory furnace in a process called “burning off the chrome”,
which could have been a source of respirable water insoluble chromium. Royle
(1975), Waterhouse (in abstract 1975), and Sorahan (1987) reevaluated the same
group studied by (Waterhouse, 1975) and found significantly increased risk of all
cancers, mainly in the lung and stomach. The above discussion merely highlights the
issues of concern and a detailed review of the epidemiology of chromium can be
found elsewhere (Langard, 1990; Hayes, 1982; Hayes, 1980; Cohen, 1993).
The results from animal studies and human epidemiology have led some
authors to argue that water-soluble chromium (VI) should be considered as carci-
nogenic as the insoluble species (Langard, 1990; Silverstein, 1981; Alexeeff et al.,
1989). Other authors believe that the issue cannot be resolved yet.
is prohibited.
33
VI. ENVIRONMENTAL RISK
What are the risks to human health and the environment from chromium (VI)?
As has been noted, chromium (VI) is toxic to a number of organisms when it is in
the aqueous phase. However, due to the dynamic interconversion of chromium (III)
and (VI) in aqueous environments, the availability of chromium (III) may lead to
a health risk if this conversion to chromium (VI) occurs. The human health effects
are lung cancer, respiratory irritation, dermatosis, dermatitis, and kidney and liver
damage. Dermatosis, nephritis, and liver damage are the results of absorption of
very large quantities of chromium over a long period. There may be a relatively
small risk of stomach cancer associated with chromium (VI), but given the
dynamic interconversion of chromium (III) and (VI) in aqueous environments,
chromium (III) may also pose a risk. There may be also a risk for contact dermatitis
to the skin or irritation of the gastrointestinal tract from chromium (VI) in solution.
Chromium (VI) in soils may pose a risk from dermatitis and a cancer risk from
the inhalation of respirable particles. However, naturally occurring particles, such
as abraded crustal materials, are unlikely to have a MMAD of less than 10 mm, and
therefore are far too large to penetrate deeply into the lung. Further, chromium (VI)
may well be in water-soluble form, which is either entirely noncarcinogenic or only
very slightly carcinogenic. Finally, if it is determined that water-soluble chromium
attached to respirable soil particles presents a cancer risk, then, given the potential
for the oxidation of chromium (III) to (VI) in some soils, chromium (III) may also
be of concern.
Chromium (VI) contaminated soils are also thought to pose a risk of dermatitis
as it can be absorbed by the skin. The absorption of chromium (IV), from aqueous
solutions, by skin is documented in a number of studies (Walhberg, 1968; Clement,
1988; Baranowska-Dutkiewicz, 1981; Pausterbach et al., 1992). However, unlike
like aqueous solutions of chromium, soil-bound chromium is not immediately
available to be absorbed by the skin; it must first be leached from the soil. As re-
ported in the literature, only a small percentage of the chromium bound in soil is
expected to be extractable either as total chromium or as chromium (VI) (Pausten-
bach et al. 1992). Therefore, in the case of skin exposure to contaminated soils, the
degree of chromium (VI) absorption will depend on how much chromium (VI) can
leach from soil and the potential reduction of chromium (VI) to chromium (III), ox-
idation of chromium (III) to chromium (VI), or both processes.
The principal human health risk is the inhalation of water-insoluble industrial
chromium respirable particles, such as might be released into the air directly from
industrial processes or fugitive emissions from improperly stored or disposed chro-
mium materials. Aqueous mists from chromium platers and cooling towers form
droplets that are typically larger than the respirable size and also consist of water-
soluble oxides of chromium; thus, it is plausible that such mists may not pose a
direct risk.
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34
VII. POLICY AND REGULATION
The primary purpose of regulating chromium in the environment is to control

and reduce the risk of lung cancer and dermatitis to the general public associated
with the exposure to chromium (VI). Because chromium (VI) is also toxic to some
aquatic organisms and microorganisms used in waste water treatment, it is also
desired to reduce the release of chromium (VI) into these systems. The crucial
question is, Does the measurement of chromium (VI) accurately correlate with the
existing or potential environmental health risk linked to chromium exposure? The
answer must be that at the present time such a correlation cannot be scientifically
justified.
First, it is very difficult to accurately quantify chromium (VI) in most matrices,
although recent improvements have been noted for soil extractions and stack gas-
sampling techniques. Second, even if quantification were possible, it would only

be at best a “snapshot” of a dynamic condition. Third, not all species of chromium
(VI) are equally carcinogenic or allergenic. It is generally thought that only the in-
soluble species are carcinogenic to the respiratory tract, while the water-soluble
species are more allergenic to the skin.
Risk analysis based on the determination of chromium (VI), as opposed to total
chromium, probably underestimates some risks and over-estimates others. The use
of total chromium (VI) overestimates most cancer risk assessments, because it fails
to distinguish water soluble from insoluble chromium (VI) in nonaqueous matri-
ces. An analysis based on chromium (VI) determination alone does not account for
the total amount of chromium that can become water soluble; thus, such an analysis
may also underestimate the accompanying allergic or biota risk.
Finally, it must be recognized that there are many factors that affect the inter-
conversion of chromium (III) and chromium (VI). The potential health risk due to
exposure of chromium is also affected by the degree of solubility of the chromium
species. Clearly, there is a need to establish a scientifically defensible risk assess-
ment process that considers the complexity of chromium in the environment and
provides a more realistic assessment of human health risk. At present, however, it
appears that regulations that seek to reduce the risk to human health and the envi-
ronment, based on total chromium, are likely to be highly conservative.
ACKNOWLEDGMENTS
This work was supported, in part, by the California Air Resources Board and
the UC Toxic Substances Research and Teaching Program. The opinions expressed
in this article are solely of the authors and should not be interpreted as representing
the views of the sponsoring agencies.
is prohibited.
35
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Critical Reviews in Environmental Science and

A Critical Assessment of Chromium in the Environment

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A Critical Assessment of Chromium

* Author to whom correspondence should be addressed.

Chromium is unique among regulated toxic elements in the environment in

toxicological, and epidemiological evidence. Chromium (VI) is both a powerful

II. INDUSTRIAL USE AND SOURCES OF CHROMIUM

water solubility are termed “insoluble.” Dichromates (Na2 or K2Cr2O7), chromic

FIGURE 1. Industrial use of chromium.

III. THE CHEMISTRY OF CHROMIUM

Although many different oxidation states of chromium exist in the environ-

E h = E (oredoxcouple ) + 2.3RT / nF log([ox] [ red ]) (2)

E h = E (oredoxcouple ) + 2.3RT / nF log(a e ) (3)

A. General Oxidation and Reduction Reactions

A) 2Cr+3 + 5H20 + 3O3 <=> 2CrO4–2 + 10H+ + 3O2 0.87

B) 2Cr+3 + 2H20 + 3H2O2 <=> 2CrO4–2 + 10H+ 0.58

C) 3MnO2 + 2Cr(OH)3 <=> 3Mn+2 + 2CrO4–2 + 2H2O + 2OH– 1.328

D) 2Cr+3 + 3H20 + 2MnO4– <=> Cr2O7–2 + 6H+ + 2MnO2 0.35

E) 2Cr+3 + 7H2O + 6Mn+3 <=> Cr2O7–2 + 14H+ + 6Mn+2 0.18

F) 2Cr+3 + H20 + 3PbO2 <=> Cr2O7–2 + 2H+ + Pb+2 0.13

G) HCrO4– + 3V+2 + 7H+ <=> Cr+3 + 3V+3 + 4H2O 1.45

H) HCrO4- + 3Fe+2 + 7H+ <=> Cr+3 + 3Fe+3 + 4H2O 0.56

I) 2HCrO4– + 3H2S + 8H+ <=> 2Cr+3 + 5H2O + 3S 1.18

J) 2HCrO4– + 5H+ + 3HNO2 <=> 2Cr+3 + 5H2O + 3NO3– 0.35

K) 2HCrO4– + 5H+ + 3HSO3– <=> 2Cr+3 + 5H2O + 3SO4–2 2.115

L) 2CrO4–2/Cr2O7–2 + R3CH <=> Cr+3 + R3COH

oxidation of chromium in the environment, as indicated in Table 1. Other sources

environmental media is rarely high enough to accomplish this oxidation (Groshe et

B. Precipitation and Dissolution Reactions

Chromium can also undergo precipitation-dissolution reactions (Bodek et al.,

FIGURE 2. Multimedia transport and fate of chromium.

sparingly soluble chromate salts (e.g., SrCrO4) is particularly important because

C. Sorption and Desorption Reactions

Equilibrium Constant (a)

A) Cr(OH)3 (s) <=> Cr+3 + 3OH– 10–30 M–4

G) BaCrO4 <=> CrO4–2 + Ba+2 3 × 10–10 M2

K) Na2CrO4 <=> CrO4–2 + 2Na+ 3.65 M3

L) (NH4)2CrO4 <=> CrO4–2 + 2NH4+ 20 M3

M) PbCrO4 <=> CrO4–2 + Pb+2 1.8 × 10–14 M2

perfections or substitutions in the crystal lattice or due to chemical dissociation re-

Surface − OH + H + + HCrO 4– ⇔ Surface – OH 2+ HCrO 4– (4)

D. Analysis of Environmental Chromium

IV. FATE AND TRANSPORT OF CHROMIUM IN

A. Chromium in the Atmosphere

waters via gravitational sedimentation, impaction, or interception. The overall dep-

B. Chromium in the Aquatic Environment

Chromium enters natural waters by weathering of chromium-containing rocks,

C. Chromium in Soils and Sediments

hydroxide could be immobilized as long as the sediments are physically stable

D. The Uptake and Transformation of Chromium by Biota

Microorganisms have the potential to accumulate chromium (Coleman, 1988)

chromate concentration. Earlier work suggested that indirect reduction of chromi-

A large number of bioaccumulation studies of chromium have been with

There is no indication of biomagnification of chromium along the terrestrial

E. Multimedia Oxidation/Reduction Cycles of Chromium

In some natural systems conditions exist where oxidation and reduction of

FIGURE 3. Human exposure routes and accumulation of chromium.

V. HEALTH EFFECTS OF CHROMIUM