The Science of the Total Environment, 86 (1989) 25-41 25

Elsevier Science Publishers B.V., Amsterdam - - Printed in The Netherlands

KINETICS OF CHROMIUM T R A N S F O R M A T I O N S IN THE

ENVIRONMENT

FARIDA Y. SALEH, THOMAS F. PARKERTON, RICHARD V. LEWIS, JULIE H. HUANG

and KENNETH L. DICKSON
Institute of Applied Sciences, University of North Texas, Denton, TX 76203 (U.S.A.)

ABSTRACT

Kinetics of chromium transformations under typical environmental conditions were systemat-

ically investigated using batch, microcosm and column experiments. Oxidation and reduction rates
were evaluated in single phase water systems and in two phase water-solid systems. Natural and
reference waters, sediments and soils representing a broad range of characteristics were used.
Some of the investigated reactions, such as the reduction of Cr(VI) by S~- or Fez+ ions under
anaerobic conditions, were instantaneous and the experimental results exactly followed the
stoichiometric and equilibrium calculations. Other reactions, such as the reduction of Cr(VI) by
organics in sediments and soils, or the oxidation of Cr(III) by MnO2, were much slower and clearly
exhibited kinetic controls. Reduction of Cr(VI) by organics was dependent on both the type and
amount of organic material. Dissolved oxygen by itself did not induce measurable oxidation of
Cr(III), spiked to the experimental waters, after 128 days. Slow Cr(III) oxidation to Cr(VI) was only
noted in one of the natural waters and sediments with half-lives ranging from 2 to 9 years. In all
cases the extent of Cr(III) oxidation did not exceed 15% of the initial Cr(III) present. The overall
results indicate that the transport and transformation of chromium can be predicted using kinetics
data derived from a simplified laboratory experiment, the Eh-pH data and the aquatic system
characteristics. Results of the microcosm and laboratory experiments were in good agreement with
the predicted concentrations.

INTRODUCTION

P r e d i c t i n g t h e f a t e of c h e m i c a l s i n t h e e n v i r o n m e n t is l a r g e l y d e p e n d e n t o n
the major equilibrium and kinetic reactions controlling their behavior. Until
r e c e n t l y , g e o c h e m i c a l a n d e n v i r o n m e n t a l m o d e l s h a v e c o n s i d e r e d t h e f a t e of
m e t a l s i n t h e e n v i r o n m e n t as e q u i l i b r i u m p r o c e s s e s o n l y , w h i l e i n f a c t t h e y
m a y n o t be i n e q u i l i b r i u m ( F e l m y et al., 1983; M o r g a n a n d S t o n e , 1985).
I n r e c e n t years, it has become obvious t h a t k i n e t i c r e a c t i o n s play a n
i m p o r t a n t role in the fate of m e t a l s in the e n v i r o n m e n t , but e n v i r o n m e n t a l
m e t a l s k i n e t i c s is s t i l l a l a r g e l y u n d e r d e v e l o p e d d i s c i p l i n e . A d e q u a t e e x p e r i -
mental data on metals kinetics, including chromium, are very scarce (Stumm
a n d M o r g a n , 1981).
C h r o m i u m is o n e o f t h e t r a n s i t i o n e l e m e n t s a n d m a y e x i s t i n v a l e n c e s t a t e s
v a r y i n g f r o m - 2 to + 6. T h e t r i v a l e n t a n d h e x a v a l e n t s t a t e s a r e t h e m o s t s t a b l e

0048-9697/89/$03.50 © 1989 Elsevier Science Publishers B.V.

26

forms. Under redox conditions normally found in natural waters and

sediments, Cr(III) is the most stable form. Chromium(III) is a hard acid which
exhibits a strong tendency to form hexacoordinate octahedral complexes with
a variety of ligands, such as water, ammonia, urea, halides, sulfates, ethyldi-
amine, and organic ligands containing oxygen, nitrogen or sulfur donor atoms.
It is reported that ~ 50% of soluble Cr(III) in sea water is organically bound
(Nakayama et al., 1981).
In neutral and basic solutions, Cr(III) may form polynuclear compounds in
which adjacent chromium atoms are linked through OH or O bridges. These
compounds eventually precipitate as chromic hydroxide, Cr(OH)3nH20 (Faust
et al., 1981; Spiccia and Marty, 1986). Conflicting reports have appeared in the
literature on the presence and importance of polynuclear complexes under
normal environmental conditions (Stunsi and Marty, 1983; Rai and Zachara,
1986). The solubility of aqueous Cr(III) is limited by the formation of several
insoluble oxides or hydroxides. Chromium(III) hydroxo complexes are reported
to be dominant species of Cr(III) in natural waters. However, the thermochemi-
cal data for the dominant species are still not precisely known; Chromite,
Cr203, is the thermodynamically favored species of Cr(III) and should
ultimately be formed, given sufficient time.
Chromium(III) solubility may be limited by co-precipitation with Fe(OH)3
due to the formation of CrxFel_x(OH)3, where x is the mole fraction of
chromium. Kinetics of such reaction are reported to be fast. A recent study (Rai
and Zachara, 1986) has shown that typical anions present in surface and
groundwater, such as CI-, SO~ and NO~, do not form dominant aqueous
complexes with Cr(III).
Hexavalent chromium forms a number of oxyacids or anions. The dissolved
species of Cr(VI) are the hydrochromate (HCrO~), dichromate (Cr20~-) and
chromate (CrO42- ). All the anionic forms are quite soluble and thus quite mobile
in the environment.
The three important reactions controlling the distribution of chromium in
environmental systems are oxidation-reduction, precipitation~lissolution and
sorption-desorption. The thermodynamic properties of chromium have
recently been reviewed (Schmidt, 1984; Rai and Zachara, 1986).
This paper presents the results of 2 years research conducted to evaluate the
kinetics of chromium transformations in the aquatic and terrestrial environ-
ments. The approach used was to utilize the best available thermodynamics
data to predict chromium distribution and equilibrium concentrations.
Kinetics data were derived from experimental batch experiments. Simplified
microcosm and column experiments were used to evaluate the predicted data.

EXPERIMENTAL

Samples
Five experimental waters representing a broad range of characteristics
were used. Solid samples included two reference materials, three sediments and
three soils. Water and solids characteristics are summarized in Table 1.
 27

e~

~ v vv~ v ~0
e.,

VV OO
.--.

19 eg~
~.~¢ ~~ O O O O O O O O O O
e~ ,
. - ~
~ ~
.o~, V V ~

~o~

+1 +1 +1

"~ ).5
v ~

g
N
r.,p~

e~
119
O

•~ ~ o

r.p
m
~ ~ z ~
28
Reagents

Sodium bichromate, Na2Cr207. 2H20 (CAS Reg. 7789-12-0), and chromium

chloride, CrC13"6H2 O (CAS Reg. 10060-12-5), were used as sources of Cr(VI) and
Cr(III), respectively. Chromium hydroxide was precipitated and aged for 24 h
before use. Natural and synthetic water matrices included MilliQ water (MQ),
rainwater (RW), hardwater (HW), Cross Lake water (CLW), MilliQ-fulvic acid
(MQ-FA) and secondary effluent (WW). Synthetic waters were prepared
according to published procedures (Black et al., 1965; Seward, 1985). Eight
different types of solid phases were used in the liquid-solid phases experiments.
These included two reference solids, mortmorillonite clay (MMC) and
reference soil (RS); three natural sediments, Cross Lake sediment (CLS),
Mississippi River sediment (MRS) and Trinity River sediment (TRS); and three
soils, natural soil (NS), garden soil (GS) and potting soil (PS).

Procedures

Liquid-phase batch experiments included spiking the experimental waters

with 10 mg l- 1 Cr(VI) or Cr(III) hydroxide (24 h precipitated). The samples were
well mixed under air or nitrogen and were monitored for pH, E h and dissolved
oxygen. At time intervals, subsamples were taken for analysis of total filtrable
(0.45 #m) and hexavalent chromium. Selected samples .were analyzed for total
organic carbon (TOC) and soluble Fe 2+ and Mn 4÷ .
Liquid- and solid-phase batch experiments were similar to the previous
experiments except that variable amounts of solids were added. Microcosm
experiments were performed in 601 glass aquaria. Each aquarium was filled
with 581 of experimental water. The outflow was received in a purging flask and
re-introduced into the aquarium. Calculated (% solids) amounts of sediment
were introduced into several petri dishes and were placed in the bottom of the
aquarium. This design allowed complete mixing of the test solution without
sediment resuspension. Two types of columns were used, one was packed with
natural soil and the second was packed with a blend of 30% garden soil and
70% sand. Both columns were eluted with rainwater.

Instrumentation and analysis

Total and filtrable chromium were analyzed by atomic absorption spec-

trometry (AAS) (Perkin Elmer Model 2380). Samples were filtered and digested
according to standard methods (APHA, 1985). Hexavalent chromium was
analyzed by the modified colorimetric method (Bartlett and James, 1979).
Selected samples were analyzed for Cr(III) and Cr(VI) by the ion chromato-
graphy procedures developed in our laboratory (Saleh et al., 1988).
 29

THERMODYNAMICS AND KINETICS

This section includes a s u m m a r y of the r e l e v a n t e q u a t i o n s and d a t a used to

e v a l u a t e the e x p e r i m e n t a l results based on a r e v i e w of the r e c e n t l i t e r a t u r e
(Martell and Smith, 1974; Baes and Mesmer, 1976; Stunsi and M a r t y , 1983;
Schmidt, 1984; Rai and Z a c h a r a , 1986). The r e l e v a n t h a l f r e a c t i o n s are shown
in Table 2.

Reaction with dihydroxyphenols

Combining h a l f r e a c t i o n (a) as a r e d u c t i o n a n d h a l f r e a c t i o n (b) as an

o x i d a t i o n (in this case d i h y d r o x y p h e n o l is used to r e p r e s e n t the o r g a n i c
compounds) gives the following ionic reaction:
Cr20~- + 8H ÷ + 3C6H4(OH)2 ~ 2Cr 3÷ + 3C6H402 + 7H20 (1)
Log K ~ = 64
As in o t h e r equilibria the v a l u e of K ~ is a m e a s u r e of the completeness of the
reaction. It should be n o t e d h o w e v e r t h a t the high v a l u e of the c o n s t a n t
indicates the f a v o r a b l e conditions of the r e a c t i o n , but provides no i n f o r m a t i o n
on the r e a c t i o n rate.

Reaction with sulfides

Combining h a l f r e a c t i o n (a) as a r e d u c t i o n and h a l f r e a c t i o n (c) as an

o x i d a t i o n gives the ionic reaction:
Cr20~- + 3S 2- + 14H ÷ = 3S + 2Cr 3÷ + 7H20 (2)
Log K ~ = 187
These r e a c t i o n conditions c o r r e s p o n d to E x p e r i m e n t 2 w h e r e 0.2 × 10 -3 M S 2-
was added to 1.9 × 10 -4 M Cr(VI) in r a i n w a t e r at pH 3.75 and h a r d w a t e r at
pH7.9. The r e a c t i o n between the d i c h r o m a t e a n i o n and the sulfide ion is

TABLE 2

Relevant half reactions

E~ (V)
(a) Cr2072- + 14H + + 6 e - ~- 2Cr 3+ + 7 H 2 0 + 1.33
(b) C6H402 ( q u i n o n e ) + 2H+ + 2e- ~ C6H4(OH)2 + 0.699
(c) S + 2e- ~ S 2 - 0.51
(d) Fe 3÷ + e - ¢- Fe 2÷ + 0.77
(e) M n 0 2 + 4H + + 2 e - ~-- M n 2+ + 2 H 2 0 + 1.23
(f) H2SO 3 ÷ 4H ÷ + 4 e - ~- S + 3 H 2 0 - 0.45
(g) SO42- + 4H ÷ + 2e- ~ H2SO 3 + H 2 0 - 0.17
(h) ~O2 + 2H ÷ + 2e- ~ H 2 0 + 0.85
3o
further complicated by other sulfide ion reactions such as:
HS- ~ S(s) + H* + 2e- LogK = 2.2 (3)
and
SO~- + 8H ÷ + 6e- ~ S(s) + 4H20 LogK = 36.2 (4)
SO~- + 3H2S(aq) + 2H ÷ ~ 4S(s) + 4H20 Log K = 21.8 (5)

Reaction with ferrous iron

Combining half reaction (a) as reduction and half reaction (d) as oxidation
gives the following ionic reaction:
Cr20~- + 14H + + 6Fe 2+ ~ 2Cr 3+ + 6Fe 3÷ + 7H20 (6)
Log Keq = 57
This represents the reaction conditions in Experiment 3, where 2 × 10 -3 M
FeSO4 was added to 1.9 x 10 -4 M Cr(VI) in rai nw at er and hardwater.

Reaction with manganese dioxide

Combining half reaction (e) as reduction and half reaction (a) as oxidation
gives the following ionic reaction:
3MnO2 + H20 + 2Cr 3+ ~ 3Mn 2÷ Cr20~- + 2H + (7)
Log K~ - 10.16
This r eact i on corresponds to Experiment 7 where 5.75 × 10 _4 M MnO2 was
used to oxidize 1.9 × 10 -4 M Cr(III) in r a i n w a t e r and hardwater.
The redox reaction mechanism is often much more complicated t h a n the
simple stoichiometric equation would indicate (Laitinen and Harris, 1975). For
example, r e a c t i on (6) is t hought to proceed t h r o u g h a series of one or two
electron-transfer steps involving Cr(IV) and Cr(V) as intermediates. Thus, Eqn
(6) represents only the sum of the intermediate reactions. It is worth noting
th at there are some uncertainties in calculations involving E ° of half reaction
(a). Although E ° is given as 1.33, the practical formal potential in 1 M HC1 is
only 1.09V. Also, half reaction (a) is a typical example of an irreversible
reaction. Thus the Nernst equation cannot be used to calculate the variation
of potential with either changes in the ratio of oxidized to reduced forms or
with changes in pH. Understanding these limitations is very useful in
evaluation of the experimental data.
Figure 1 shows the Eh-pH diagram of chromium species based on the ther-
mochemical data shown in Table 3 and the experimental c o n c e n t r a t i o n of
chromium which corresponds to 1.92 × 10-4M. The figure also shows the
initial and final Eh-pH data points of Microcosm Experiment 2.
 31

2.0
Microcosm 2 ®--- Wafer,Start O-'---Woler,End
DataPoints Sedlmenf,StartA----Sediment,End
18t
&--

1.6

1.4
Cr2072-

I0

-0,4- H2 " ~

-I.0 o ~; ,~ ~ ~ ,~, ,~, ,4

pH

Fig. 1. E h - p H d i a g r a m b a s e d on e x p e r i m e n t a l c h r o m i u m c o n c e n t r a t i o n . D a s h e d l i n e is b a s e d on E q n
[(C) (c)] (see T a b l e 3).

TABLE 3

E q u a t i o n s u s e d to c o n s t r u c t t h e E h - p H d i a g r a m

(A) E h - i n d e p e n d e n t e q u a t i o n s
(a) H C r 0 4 ~ CrO 2- + H + pk = 6.51
(b) Cr z÷ + 2 H 2 0 ~-~ Cr(OH)~ + 2H + pk = 10.20
(c) Cr(OH)~ + H 2 0 ~-~ Cr(OH)3 + H + pk = 7.79
(d) Cr(OH)~ ~-- Cr(OH)~ + 2 O H - pk = 10.8
(e) CrO 2 + 2H20 ~ Cr(OH)2 + 2 O H - pk = 10.24
(f) ½Na2Cr207 + ½H20 ~ CrO 2- + N a + + H + pka = 4.95
(g) Cr20~- + H 2 0 ~ 2HCrO~ pk = 2.20
(h) C r O H 2+ + H 2 0 ~ Cr(OH)~ + H + pk = 6.28
(i) Cr 3+ + H 2 0 ~ Cr(OH) 2+ + H + AG ° = 5.35 k c a l m o l - ' pk = 3.92

[ o b t a i n e d by s u b t r a c t i n g E q n (h) from E q n (b)]

(B) p H - i n d e p e n d e n t e q u a t i o n s
(a) Cr 3+ + e - ~ Cr 2+ ~ = - 0.41V, E = - 0.41 V
(b) Cr 3+ + 3e- ~ Cr ~ = - 0.74V , E = - 0.81 V
(c) Cr 2+ + 2e- ~ Cr E° = - 0.86V , E = - 0.97 V

(C) E h- a n d p H - d e p e n d e n t e q u a t i o n s
(a) C r 2 0 ~- + 14H + + 6 e - ~ 2Cr ~+ + 7H 20 E° = 1.33
(b) CrO42- + 6H ÷ + 3e- ~ C r ( O H ) / + 2H 20 E° = 1.32
(c) HCrO~ + 7H ÷ + 3e- ~ Cr 3+ + 4H~O E° = 1.20
(d) HCrO~ + 5H + + 3 e - ~ Cr(OH)~ E° = 1.20
32

Solubility of Cr(III) in aquatic systems

F i g u r e 2 s h o w s a s u m m a r y of t h e a q u e o u s solubilities of Cr(OH)3 as a
f u n c t i o n of p H as d e r i v e d f r o m t h e studies of B a e s a n d M e s m e r (1976), F e l m y
et al. (1983) a n d R a i a n d Z a c h a r a (1986). T h e figure also includes t h e d a t a p o i n t s
f r o m E x p e r i m e n t 6.
. \

) ~ \ ~ Sae$ and Mesmer,1976#

r3(O H)54+ Cr(OH - )$(S

', k\ \ ~ \ / / ~ (Minteq)
\ ~ Felmy et QI,19B3~

log [Cr [ ] ] ], r(O Cr(OH)

=,or ,, ', ,,\\ Cr<O > //

.--------~\ % 0.46~ R / (Mintecl)
X= 0 I 0.15 .

-9 (Crx FeI_x)(OH)3
'Roi and ZQchara,1986
T I I ' I i I ' I
3 5 7 9 II 13
pH
Fig. 2. Aqueous solubilities of Cr(OH)3 as a function of pH. (x) Mole fraction of chromium; (®)
Experiment 6 data points. From Baes and Mesmer (1976), Felmy et al. (1983) and Rai and Zachara
(1986).

Kinetic calculations

I n e n v i r o n m e n t a l f a t e m o d e l i n g (Burns et al., 1981), all d a t a on t r a n s p o r t a n d

t r a n s f o r m a t i o n p r o c e s s e s a r e p u t in t h e f o r m of first-order r e l a t i o n s in w h i c h
o n l y t h e c o n c e n t r a t i o n of t h e p o l l u t a n t is a v a r i a b l e . R a t e c o n s t a n t s a n d
r e a c t i v e e n v i r o n m e n t a l i n t e r m e d i a t e s a r e g r o u p e d t o g e t h e r as c o n s t a n t s
t y p i c a l of a specific site. I n t h e case of m e t a l s kinetics, t h e r e a c t i o n s m a y be
m o r e c o m p l e x a n d h e t e r o g e n e o u s . H o w e v e r , this a p p r o a c h w a s f o u n d useful in
e v a l u a t i n g t h e r e l a t i v e i m p o r t a n c e of different t r a n s f o r m a t i o n a n d t r a n s p o r t
processes.
W e h a v e selected to use t h e s a m e a p p r o a c h for e v a l u a t i n g t h e k i n e t i c s d a t a
f r o m this r e s e a r c h . T h e r a t e c o n s t a n t s a n d half-lives a r e c a l c u l a t e d b a s e d on
first-order k i n e t i c s w i t h r e s p e c t to Cr(IV) r e d u c t i o n or Cr(IH) o x i d a t i o n . F o r
example, in t h e r e a c t i o n :
Cr20~- + 6Fe 2÷ + 14H ÷ --* 2Cr 3÷ + 6Fe 8+ + 7H20 (8)
- dC/dt = KC
 33

where C is the concentration of Cr(VI) at time t, the first-order rate constant

is given by:
k = 2.303/t log (Co/Ct) (9)
and the half-life by:
t1/2 = In 2/k (10)

Ideal first-order calculations would correspond to 20-80% change in the

reactant concentration during time t. Several, but not all, of the reactions
studied in this research followed typical first-order behavior. A few, especially
those on oxidation of Cr(III), were very slow and the extent of the reaction was
< 20% within the time of the experiment. In such cases the kinetics data should
be considered only as estimates.

RESULTS AND DISCUSSIONS

Table 4 shows a summary of all the experiments, which includes 16 batch

experiments, four microcosm experiments and two column experiments. Initial
spiking concentrations of Cr(VI) or Cr(III) were 10mg 1-1, except in
Experiment 5.

Batch experiments

The batch experiments evaluated the kinetics of Cr(VI) reduction and Cr(III)
oxidation. Both reactions were investigated in the water phase only or in the
water-solid phases.

Water-phase reduction of Cr(VI)

Four experiments were performed to study Cr(VI) reduction in the experi-
mental waters and in the presence of typical reducing agents. The reducing
agents included S 2- and Fe ~÷, and the organic matrix usually present in
secondary wastewater effluent. The results indicate that Cr(VI) dissolved in the
experimental waters at levels of 10mg 1-1 or 1.9 × 10-4M, exhibits ther-
m o d y n a m i c stability under aerobic conditions. Even secondary wastewater
effluent did not induce measurable reduction of Cr(VI) in 41 days under
anaerobic conditions.
In Experiments 2 and 3, the results show that Cr(VI) dissolved in RW or HW
can be reduced by addition of S 2- or Fe 2÷ ions. The reactions generally followed
,the stoichiometry, except in the case of competing reactions such as S 2- under
aerobic conditions. Reduction half-lives ranged from instantaneous to a few
days, depending on the reaction conditions. Changing the reaction conditions
from anaerobic to aerobic after the reduction had occurred resulted in much
slower oxidation rates (Fig. 3). Chromium(VI) reduction rates were at least 10
times faster than the re-oxidation rates. In the case of rain water, soluble
Cr(III) compounds were detected as intermediates.
34

TABLE 4

Summary of all experiments ~

Experiment No. Important results

Batch, water-phase kinetic experiments

Water-phase-reduction of Cr(VI)
1 Cr(VI) spiked to five No measurable reduction
waters; aerobic, 41 Mass balance 97-112%
days
2 Cr(VI) + 6.4mg 1-~ S2- Reactions instantaneous and
in rainwater and follow stoichiometry under
hardwater; aerobic, N2. Air interfereswith the S 2-
21 days; anaerobic, 78 oxidation. Cr(VI) reduction
days irreversible
3 Cr(VI) + 16rag 1-1 Fe 2+ Reactions instantaneous and
in rainwater and follow stoichiometry under N 2.
hardwater; aerobic, Re-oxidation slow with tl/2from
13 days; anaerobic, 99 to 173 days. Coefficientof
23 days variation, 5.7-5.9%
4 Cr(VI) spiked N o detectable change under
to secondary aerobic or anaerobic conditions
municipal effluent;
aerobic, 41
days
Water-phase-oxidation of Cr(III)
5 Cr(III) spiked to Percent soluble Cr(IH) ranged
five waters; aerobic, from 0.58 to 3.16%
42 days
6 Cr(III) spiked to Percent soluble Cr(III) ranged
five waters; aerobic, from 1.53 to 13.9%
128 days Cr(VI) detected in CLW,
oxidation tl/2 = 9 years
Chemical changes occur upon
aging of Cr(OH)~
7 Cr(III) oxidation by RW oxidation tl/2 = 3.48 years;
50 mg 1-1 ~-MnO2 % soluble Cr(III), 45%
in rainwater and HW oxidation tl/2= 1.95 years
hardwater; aerobic, 28 No measurable soluble Cr(III)
days
Water-solid-phases-reduction of Cr(VI)
8 Cr(VI) in 10% No measurable reduction and/or
montmorillonite clay adsorption
or natural soil, in
Cross Lake, rain and
hard water; aerobic
14 days; anaerobic,
14 days
 35

TABLE 4 (continued)

Experiment No. Important results

9 Cr(VI) in 10% Cross Aerobic reduction t~/2 = 15 min

Lake sediment in Anaerobic reduction tl/2
Cross Lake water; instantaneous
aerobic, 7 days;
anaerobic, 7 days
10 Cr(VI) in 1% Cross Aerobic reduction ti/2(1) = 35
Lake sediment in days; ti/2(2) = 231 days
Cross Lake water; Equilibrium concentration = 6.60
anaerobic, 71 days; mg 1-1
aerobic 71 days Anaerobic: instantaneous
Aerobic oxidation tl/2 = 2.63
years
11 Cr(VI) in Cross Lake No measurable reduction and/or
water + 1% n a t u r a l adsorption
soil; aerobic, 24
days; anaerobic, 24
days
12 Cr(VI) in Cross Lake Aerobic reduction t~/2 ~ 11.2
water + 1% days
potting soil; aerobic, Anaerobic reduction tl/~ = 21.5
10 days; anaerobic, days
10 days
13 Cr(VI) in Cross Lake Aerobic, no change
water + 1% Anaerobic, reduction
garden soil or GS ti/2 = 4 days
Trinity River TR tl/~ = 6 days
sediment or MR t~/2 = 53 days
Mississippi River
sediment; aerobic, 10
days; anaerobic, 10
days
14 Rain water + 1% GS, reduction t~/2 = 2.2 days
garden soil or NS, no change
natural soil;
anaerobic, 14 days
Water-solid-phases-oxidation of Cr(III)
15 Cross Lake water + 1% Day 44, Cr(VI) ranged
n a t u r a l soil, from 2.0 to 2.5%
reference soil and Oxidation tl/~ ranged from 3.2
potting soil; to 37 years
aerobic, 44 days
16 Cross Lake water and Day 37, Cr(VI) ranged
1% Trinity River from 0.12 to 11.48%. Oxida-
sediment or tion t~/2 ranged from 0.58
Mississippi River to 37.2 years
sediment or Cross
Lake sediment;
aerobic, 37 days (continued)
36

TABLE 4 (continued)

Experiment No. Important results

Microcosm experiments
M1 Cross Lake water Apparent equilibrium in 20 days
and 1% sediment; Water column equilibrium
aerobic, 47 days; Cr(VI) = 7mg 1-1
uncovered Reduction tl/~ = 33 days
M2 Cross Lake water Apparent equilibrium in 52 days
and 1.2% sediment; Water column equilibrium Cr(VI)
anaerobic, 95 days; = 3.6mg 1-1
covered Reduction tl/2 = 31.5 days
M3 Hardwater + 2% Apparent equilibrium in 55 days
Mississippi River Water column equilibrium Cr(VI)
sediment; .aerobic, = 3.5mg 1-1
81 days; covered Reduction t~/~ = 34.7 days
M4 Hardwater + 3% Apparent equilibrium in 45 days
Trinity River Water column equilibrium Cr(VI)
sediment; aerobic, = 8.3mg 1-I
84 days; covered Reduction tl/~ = 140 days
Column experiments
C1 Cr(VI) reduction; natural Predicted < 10% Cr(VI) reduction
soil column; 30 cm x 10 Experimental results showed
cm i.d.; eluent: rainwater; reduction ranging from 0.4 to
flow, 1 ml min- ~; anaerobic, 5.7%
3 days
C2 Cr(VI) reduction; blend of Predicted 82% Cr(VI) reduction
30% GS and 70% sand in 10 Experimental results showed
cm 1-1 x 1 cm i.d. glass reduction ranging from 76 to
column; eluent: rainwater; 78%.
gravity flow, 15ml day-l;
anaerobic, 12 days

aIn all experiments, except for Experiment 5, the spiking concentration of Cr(III) or Cr(VI) was
10mg 1-1.

Water-solid phases oxidation of Cr(III)

I n E x p e r i m e n t s 5, 6 a n d 7, C r ( I I I ) o x i d a t i o n i n t h e e x p e r i m e n t a l w a t e r s a n d
i n t h e p r e s e n c e of 50 m g 1-1 fl-MnO2 w a s e v a l u a t e d . R e s u l t s s h o w e d t h a t C r ( I I I )
s p i k e d t o t h e e x p e r i m e n t a l w a t e r , as 24-h-aged Cr(OH)3, a t c o n c e n t r a t i o n s of
10 m g 1-1, w a s f a i r l y s t a b l e u n d e r a e r o b i c c o n d i t i o n s . O n l y i n t h e c a s e of C L W
w a s s l o w o x i d a t i o n n o t e d a n d m e a s u r a b l e a m o u n t s of Cr(VI) w e r e d e t e c t e d
a f t e r 38 d a y s . T h e e s t i m a t e d o x i d a t i o n r a t e c o n s t a n t s c o r r e s p o n d e d t o
2.1 × 10 _4 d a y -1 a n d t1/2 c o r r e s p o n d e d to 9 y e a r s . T h e o x i d a t i o n of C r ( I I I )
r e q u i r e d t h e p r e s e n c e o f a n o x i d a n t s u c h as MnO2 i n C L W . S o l u b l e i n o r g a n i c
 37

CR(VI) SPIKED TO RAIN AND HARD WATER UNDER N2 WITH FE+2

WATER,RWN2
PLOT OF XTOTCR'TIME SYMBOLUSED IS T
PLOT OF XTFCR*TIME SYMBOLUSED IS F
PLOT OF XFHEX'TIME SYMBOLUSED IS H

I®
t
II ÷

®
'
10

T
P
I
e I ~ @

7 ÷ \
i \

E
i \ []
~ N
C ! x
(9 6
; N'" E

~'-.&
÷
i

-; ....... ; ...... [~...... ~ ...... ~ ...... ~ ...... ~ ...... ~---

Time, days

Fig. 3. Experiment 3; plot of total, total filtered and filtered Cr(VI) concentration in rainwater
under anaerobic conditions. Q Total; [] filtered; ~ hexavalent.

and organic Cr(III) complexes were detected in HW, CLW, and MQ-FA at
ranges of 0.58 to 11.51%.
In the presence of 50 mg l- 1 MnO2, the half-lives for Cr(III) oxidation in RW
and HW are 3.48 and 1.95 years, respectively. The percent soluble Cr(III) was
45.5% in the case of RW, while 1.78% soluble Cr(III) was detected in HW.
Chemical changes seemed to occur upon aging of Cr(OH)3 in the experimental
water matrices. An ion chromatography study provided initial data on the
recoveries of Cr(III) from aged samples. The overall results indicate that Cr(III)
compounds exhibit very wide solubility ranges that are influenced by pH,
constituents in the water matrix, and time (Saleh et al., 1988).

Water-solid phases reduction of Cr(VI)

In Experiments 8-14, reduction of Cr(VI) in the presence of liquid and solid
phases was evaluated. In Experiment 8, the results indicated that mont-
morillonite clay or natural soil in CLW did not influence measurable
adsorption and/or reduction of Cr(VI) under anaerobic conditions for 14 days.
In Experiment 9, Cr(VI) was instantaneously reduced by 10% CLS in CLW
under both aerobic and anaerobic conditions. Using 1% sediment or soil in
experimental water, in Experiments 10-14, Cr(VI) at the same concentration
38
was reduced at a measurable rate. The reduction seemed to have occurred in
two steps resulting in two rate constants. Fast reactions would occur in
minutes to hours, and slower reactions would occur in several days. Generally,
the reduction rates were much faster under anaerobic conditions t h a n under
aerobic conditions.
Each sediment or soil had a characteristic reducing capacity that could be
related to the amounts of reducing agents present in the sample. In most, but
not all, cases, the solids' reducing capacities were related to the organic carbon
content of the solid. Reversing the reaction conditions from anaerobic to
aerobic resulted in a much slower oxidation rate.

Water-solid phases oxidation of Cr(III)

In Experiment 15, Cr(III) oxidation by NS, RS, and MRS in CLW was
evaluated. The results indicated slow formation of Cr(VI) in 44 days. The extent
of Cr(III) oxidation ranged from 0.20 to 2.5%, and thus the kinetics data on
these experiments are only estimates. In Experiment 16, where 1% CLS in CLW
was used, the extent of Cr(III) oxidation was the highest and corresponded to
2.7% in 25 days. The results are supportive of Experiment 6 where CLW was the
only water that induced oxidation of Cr(III).

Microcosm experiments

A very good chromium mass balance was maintained in all, and for the
duration of all, experiments. The recovered total chromium ranged from 95 to
114%. Sediments were found to play an important role in reducing Cr(VI) to
Cr(III) and subsequent precipitation. Each sediment seemed to have its own
reducing capacity which could be related to the percent organic carbon, the
amount of Fe 2÷ or S2- , or any other reducing agent.
The Eh values of the sediments were very useful probes to indicate the
reducing capacities of the sediments. In all experiments, as the Eh of the
sediments approached that of the water column apparent equilibrium
conditions were established and no further Cr(VI) reduction occurred.
The Eh of the water column showed slight variation throughout the
experiments and corresponded to the Cr(VI) species, as shown in the pH-Eh
diagram. Figure 1 shows the initial and final data points of Microcosm
Experiment 2 (M2). Figure 4 shows the variation of chromium distribution with
time in Experiment M2.
The stoichiometry of the reaction between Cr(VI) in the water and the
reducing compounds in the sediment controls the extent of chromium
reduction. The Cr(VI) concentration in the water compartment, at apparent
equilibrium conditions, was specific for each microcosm and could be related
to the amount of sediment used and the percent organic carbon in the sediment.
Under aerobic conditions, the rates of reduction were a function of percent
organic carbon in the sediment, but not the total amount of sediment used.
 39

I0

6 6 Total Cr
Total Cr (fO+Zmg/kg)
(mg/L) 5 5 B
@

4 4

3 3

2 2

I I

Water Column 0 o Sediment Phase

I0 2'0 3' 0 4 0' 5 0" 6 0' 70' 8 '0 90
~. : Total
Time ( d a y s )
O: Water
0 : Sediment

Fig. 4. Microcosm Experiment 2: CLW and 1.2% sediment; anaerobic. Variation of total chromium
in the water and sediment phases.

TABLE 5

Column Experiment 1. Physical properties and data on Cr(VI) reduction

Column A Column B

Bulk density (g cm 3) 0.97 1.01

Porosity (%) 0.63 0.62
Flow rate (ml rain -1) 0.93 0.95
Hydraulic conductivity (m day ~) 0.022 0.094
Eluent total volume (ml) 1083.2 916.5
Soil total dry mass (g) 1052.6 928.9
Ranges of:
DO (mg 1-~ at 25°C) 7.20-7.20 8.1~1.7
E h at 25°C 0.43-0.50 0.47-0.46
Corresponding pH 6.90-6.56 5.19~.14
Total amount of Cr(VI)
added (mg) 141 55.68
Total amount of Cr(VI)
in the eluent (mg) 133 55.48
Recovery (%) 94.33 99.64

Natural soil column eluted with rainwater.

40

M o n i t o r i n g t h e w a t e r a n d s e d i m e n t E h - p H v a l u e s c a n be u s e d to p r e d i c t t h e
b e h a v i o r of a q u a t i c s y s t e m s u n d e r specific m i x i n g c o n d i t i o n s .
In s u m m a r y , t h e f o u r m i c r o c o s m e x p e r i m e n t s i n d i c a t e t h a t m i c r o c o s m s
p r o v i d e v e r y u s e f u l t o o l s for e s t i m a t i n g t h e d i s t r i b u t i o n a n d r a t e s of c h r o m i u m
t r a n s f o r m a t i o n r e a c t i o n s u n d e r q u i e s c e n t c o n d i t i o n s r e p r e s e n t a t i v e of s e v e r a l
surface water t r a n s p o r t processes.

Column experiments

T a b l e 5 i n c l u d e s a s u m m a r y of C o l u m n E x p e r i m e n t 1 w i t h NS. The
p r e d i c t i o n s i n d i c a t e t h a t < 10% of Cr(VI) w o u l d be r e d u c e d . T h e e x p e r i m e n t a l
r e s u l t s s h o w d d r e d u c t i o n s r a n g i n g from 0.4 to 5.7%. T h e r e s u l t s of C o l u m n
E x p e r i m e n t 2 a r e s h o w n in T a b l e 6 w i t h GS. I t is p r e d i c t e d t h a t > 82% of Cr(VI)
w o u l d be r e d u c e d . T h e e x p e r i m e n t a l r e s u l t s s h o w e d 76 a n d 78% r e c o v e r i e s in
d u p l i c a t e c o l u m n s . T h e t w o c o l u m n e x p e r i m e n t s i l l u s t r a t e d t h e f e a s i b i l i t y of
u s i n g s u c h e x p e r i m e n t s for p r e d i c t i n g t h e p o s s i b l e t r a n s f o r m a t i o n s of
c h r o m i u m c o m p o u n d s in a specific g r o u n d w a t e r site.

TABLE 6

Column Experiment 2: Physical properties and Cr(VI) reduction data

Column A Column B

Glass column dimensions 67cm × 1.3cmo.d. 67cm × 1.3cmo.d.

Solids column dimensions 10cm × lcmi.d. 10cm × lcmi.d.
Porosity (%) 21.37 21.17
Flow rate (ml day -1) 13.4 ± 5.2 15.3 ± 6.6
Total weight of blend (g) 10 10.0
Amount of Cr(VI) added (mg) 0.10 0.10
Amount of Cr(VI) recovered in
11 days (rag) 22.13 x 10_3 24.21 × 10_3
Total volume of eluent in
11 days (ml) 166 215
Percent reduction of Cr(VI)
from the first aliquot (%) 78 75.5
Total amount of Cr(VI)
added in 47 days (mg) 1.05 1.25
Total amount of Cr(VI)
in the eluent (rag) 0.4470 0.3362
Total amount of Cr(VI) in
the blend, Day 47 (mg) 0.4350 0.7350
Total percent recovery (%)) 84 86.4
Blend of 30% GS and 70% sand eluted with rainwater.

ACKNOWLEDGMENT

T h i s r e s e a r c h w a s s u p p o r t e d by t h e I n d u s t r i a l H e a l t h F o u n d a t i o n u n d e r
c o n t r a c t w i t h t h e U n i v e r s i t y of N o r t h T e x a s .
 41

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