V-/EPA
                           United States
                           Environmental Protection
                           Agency
                          Water Engineering
                          Research Laboratory
                          Cincinnati OH 45268
                           Research and Development
                          EPA/600/M-86/015  June 1986
ENVIRONMENTAL
RESEARCH   BRIEF
           Effect of Chlorine on Chromium Speciation in Tap Water
                                       Nancy Sue Ulmer*
Abstract
The 24-hr oxidation of trivalent chromium to hexavalent
chromium is reported in pH 5, 6, 7, and 8 chlorinated tap
water with low levels of alkalinity, chloride, sulfate, and
total organic carbon (TOC). The applicability and use of
analytical  methods for hexavalent chromium in the pre-
sence of chlorine are discussed.

Introduction

Chromium may occur in various forms in natural waters as
a result of the weathering of bedrock and soils or the
discharge of chromium-bearing wastes from sources such
as tanneries, cooling towers, animal glue manufacturers,
metal dipping, pickling and electroplating industries, and
sewage treatment plants. The origin, occurrence, and fate
of chromium in water and the oxidation-reduction proc-
esses  controlling  its speciation during transport and
storage have been the topic of many investigations during
the last decade.

In nature, chromium generally occurs as the stable mineral
chromite (FeO-Cr2Oa);  it is usually  immobilized  in the
trivalent form in bedrock and  most soils (1).  However,
Bartlett and James (2) have  reported the  oxidation of
trivalent chromium [Cr(lll)] to hexavalent chromium [Cr(VI)]
in many soils containing manganese. Robertson (3) cited
the occurrence of Cr(VI) at levels exceeding 0.05 mg/L in
ground water in Paradise Valley, Maricopa County, Arizona.
Osaki et al. (4) investigated the speciation of chromium in
the Muromi River of Japan and reported high concentra-
tions of Cr(VI) in  the spring and streams  of the river's
headwaters as a result of oxidation in the groundwater
sources. Downstream and in the reservoir, the Cr(lll) level
*Drmkmg Water Research Division, Water Engineering Research Laboratory,
 Cincinnati, OH 45268
                      increased because the rate of reduction of Cr(VI) by humic
                      substances was faster than the rate of oxidation of Cr(lll) by
                      dissolved oxygen. While studying the Columbia River,
                      Cranston and Murray (5) observed that 98 percent of the
                      chromium was in the  hexavalent form. An interesting
                      transport study by Canter and Gloyna (6) revealed that
                      hexavalent chromium predominated in the  non-polluted
                      river but was reduced to the trivalent form when exposed to
                      organic pollution.  Schroeder and Lee (7) studied chromium
                      speciation in simulated  natural waters and reported that
                      Cr(VI)  was reduced  by divalent  iron [Fe(ll)], dissolved
                      sulfides, and certain organic compounds with sulfhydryl
                      groups. They also noted  that Cr(lll) was oxidized by a large
                      excess of manganese dioxide (MnOa) at a slower rate by
                      oxygen under conditions approximating those in natural
                      waters. The factors controlling chromium speciation in
                      natural waters were summarized by Florence and Batley (1)
                      as follows:

                      1.  oxygen content and  redox potential of the water,
                      2.  presence of dissolved or paniculate organic matter,
                         and
                      3.  presence of suspended inorganic matter.

                      Chromium speciation m biological systems has also been
                      investigated during the  last decade. Trivalent chromium
                      appears to be  the predominant species in cells, and  its
                      essential role in  maintaining glucose, lipid, and protein
                      metabolism in mam ma Man systems has been reported (1, 8,
                      9).  Hexavalent chromium, however,  appears to diffuse
                      through cell membranes, oxidize, and then bind with other
                      biochemical molecules to produce carcinogenic and muta-
                      genic effects (1, 9).

                      Cognizant of these of these previous studies, reporting the
                      toxicity of hexavalent  chromium and the  conversion
                      potential of trivalent chromium in nature, the U.S. Envi-
                      ronmental Protection Agency (EPA) has been reviewing the

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applicability of the current drinking water regulation for
chromium. The advisability of changing the regulation from
a single maximum contaminant level (MCL) basis (total
chromium concentration) to a dual  MCL  basis (separate
MCL for each of the two valence states) is being considered
(10). To provide  a fuller  understanding  of the potential
trivalent chromium  conversion  to hexavalent chromium
during and after drinking water treatment, two research
investigations of the effects of chlormation on chromium
speciation in water were conducted. One study, performed
extramurally by Clifford and Chau (11),  investigated the
effects of chlorination on chromium speciation in natural
waters and other matrices containing sodium  chloride
(NaCI), ammonia (NH3) and humics. A report of this study is
in preparation. Another study was conducted mhouse to
determine the effects  of 2 mg/L free residual chlorine on
the speciation of 0.5 mg/L Cr(lll) added to Cincinnati tap
water at initial pH levels  of 5, 6, 7, and 8. The approach,
observations, conclusions, and recommendations of the
latter study are reported here

Approach

General Study Design

A large aliquot of Cincinnati tap water was collected, and its
free residual chlorine (FRC) concentration  was adjusted to
approximately 2  mg/L. Two 1 -L aliquots of this chlorine-
adjusted tap water were transferred to 1 -L cubitamers and
forwarded  to the laboratory  for physical and chemical
characterization  (alkalinity,  arsenic, barium, cadmium,
calcium, chloride, total chromium, color, specific conduc-
tance, copper, fluoride, iron, lead, magnesium, manganese,
mercury, pH, total filterable residue or total dissolved solids,
selenium, silver,  sodium,  sulfate, turbidity and zinc).

Four  exposure  study test solutions were prepared by
transferring 2-L aliquots of chlorine-adjusted tap water to
individual containers,  adjusting the pH levels to pH 5, 6, 7,
and 8, respectively, adding sufficient Cr(lll) to achieve an
approximate concentration of 0.5-mg/L and then quickly
readjusting the pH levels as necessary. Each of the four test
solutions was then divided into two portions. The first liter
was labeled "initial sample" and immediately subjected to
analysis for alkalinity, total and hexavalent chromium, FRC,
pH, and  TOC. The  second portion of  each of  the test
solutions was transferred to  an individual 1-L, ground-
glass-stoppered  bottle, labeled "final sample," and set
aside in the dark at room temperature for about 24 hr before
analyses were initiated  for  dissolved oxygen  and the
aforementioned  six characteristics.  The details  of the
sample collection and  preservation,  reagent and test
solution  preparation, and  analytical methodology are
presented in the following section.

Analytical Approach

The study of the effect of chlorine on the speciation of
chromium in Cincinnati tap water was conducted us ing the
facilities, materials, and equipment of the Inorganics and
Paniculate  Control Branch,  Drinking Water  Research
Division, Water Engineering Research Laboratory.

Reagents, Equipment, and Analytical  Methods-
were first cleaned using 1.1 nitric acid (HNOa) and then
rinsed  liberally with deionized distilled  water   All test
solutions  and analytical reagents were  prepared  using
A C.S.  reagent grade chemicals  and deionized  distilled
water unless otherwise specified All samples were col-
lected, preserved, and analyzed according to the specifica-
tions in the analytical methods cited in Table 1.
Preparation of Test Solutions—

The preparation of the special test solutions for the exposure
study was initiated  by filling a 5-gal Nalgene®* jug with
Cincinnati tap  water (pH  ~8 05).  Sufficient  saturated
chlorine solution, freshly prepared by bubbling gaseous
chlorine into  deionized distilled water, was immediately
added to the jug contents to raise the FRC concentration
from 1.37 to 2.04 mg/L. Both FRC levels were determined
amperometrically using the Penwalt Wallace & Tiernan
Series A790 Titrator Four  2-L  aliquots  of this chlorine-
adjusted Cincinnati  tap water were transferred from the
5-gal jug to individual 3-L beakers, and the pH levels were
quickly adjusted to pH 5,  6, 7, and 8,  respectively, using
either 1 N sulfunc acid (H2SO.t) or  1 N sodium  hydroxide
(NaOH) All pH measurements were performed using an
Orion Model 801 Research lonalyzer pH Meter equipped
with a Metrohm Model AG91 00 combination pH electrode
and calibrated using fresh prepared Beckman Altex pH 4
and  6.86  buffers. Then  20  mL of  a freshly prepared
chromium chloride  (CrCI3)  solution  containing 50 mg/L
Cr(lll) was added to each 2-L aliquot, and any additional pH
adjustment required to maintain the pH 5, 6, 7, or 8 levels
was quickly made using  1  N H2S04 or 1  N NaOH.  The
increase in  each solution  volume with the addition of
chromium solution and pH adjustment solution was < 1.05
percent and neglected in subsequent calculations.
Total Chromium Analyses—

All analyses  for  total  chromium  were  performed  by
flameless atomic absorption  technology using a Perkm
Elmer Model  4000 Atomic  Absorption Spectrometer,
equipped with a Perkm  Elmer Model 400 HGA Furnace,
AS-40 Autosampler, background corrector, chromium
hollow cathode lamp, nonpyrolyzed graphite tubes, argon
gas, a 357 9-nm  wavelength, and  a  0.7-nm  slit. The
procedural steps and operating conditions are presented in
Table 2. The instrument  was calibrated using six standard
solutions containing 0, 5, 25, 50, 75, and 1 00 /ug/L Cr(VI)
These were prepai ed by appropriate dilution of aliquots of a
stock Cr(VI) solution (0.1414 g K2Cr2O7/L) and preserved
with 1.5 mL concentrated HNOa/L. After electrothermal
atomization, the absorption response of a 20-fjL aliquot of
each of the six solutions was observed,  and a calibration
plot relating absorption response and Cr(VI)  concentration
was prepared. The total chromium concentration of each
initial and final test solution sample was then determined
by electrothermally  atomizing  20 fj\- of a 1.5  dilution
thereof, observing the absorption response, deriving the
corresponding chromium concentration from the calibration
plot, and multiplying by the appropriate dilution factor.
During the exposure study of the four test solutions and all
the related analyses, the laboratory glass and plastic wares
 *Mention of trade names or commercial products does not constitute
 endorsement or recommendation for use

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Table 1.    Analytical Methods Used in Sample Analysis





Characteristic             Method
Reference
                  Comments
Alkalinity
Arsenic
Barium
Cadmium
Calcium
Carbon, total organic
Chloride
Chlorine, free residua/
Chromium, total
Chromium, hexavalent
Chromium, tnvalent
Color
Conductance, specific
Copper
Fluoride
Iron
Lead
Magnesium
Manganese
Mercury
Oxygen, dissolved
pH
Residue, total filterable
(total dissolved solids)
Selenium
Silver
Sodium
Potentiometnc
Flame/ess atomic absorption
Atomic absorption, direct asp/rat/on
Flameless atomic absorption
Atomic absorption, direct aspiration
UV promoted, persulfate oxidation
Potentiometnc, modified
Amperometnc tit ration
Flameless atomic absorption
Revised diphenylcarbazide
color/metric
Calculation
Visual comparison
Wheatstone bridge
Atomic absorption, direct aspiration
Complexone
Atomic absorption, direct aspiration
F/ameless atomic absorption
Atomic absorption, direct aspiration
Atomic absorption, direct aspiration
Manual cold vapor
Membrane electrode
Electrometr/c
Gravimetric
Flameless atomic absorption
Atomic absorption, direct aspiration
Atomic absorption, direct aspiration
SM 403* Automatic titration to carbonate equivalence
point
EPA 2062**
EPA 208 1 NaCI substituted for KCI in reagents
EPA 21 3 2 Instrumental parameters modified
EPA 215 1
SM(1 6) 505B\ With DC 54 Xertex Dohrmann instrument
SM407C Automatic titration using silver, specific ion
electrode
SM 408C
EPA 218 2
SW7196U With standard additions^
Difference between total and hexavalent
chromium
SM 204A With Hellige glass reference discs
EPA 120 1
EPA 220 1
SM413E
EPA 236 1
EPA 239 2
EPA 242 1
EPA 243 1
EPA 245 1
EPA 360 1
EPA 1 50 1
SM 209C
EPA 2702
EPA 272 1
EPA 273 1
SM 325B
Sulfate
                         Turbidimetnc
                                                             EPA 3754

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Table 1.    (Continued)

Characteristic            Method
                                                        Reference
                                                                        Comments
 Turbidity
Zinc
Nephelometric
                                                        EPA 180 1
                       Atomic absorption, direct aspiration    EPA 289 1
 *SM refers to American Public Health Association, American Water Works A ssociation, and Water Pollution Control Federation Standard
  Methods for the Examination of Water and Wastewater 15th edition, unless otherwise specified American Public Health Association,
  Washington, DC 1981
**EPA refers to Environmental Monitoring and Support Laboratory Methods for Chemical Analysis of Water and Wastes EPA/600/4-
  79/020  US Environmental Protection Agency, Cincinnati, OH March 1983
 \SM(16) refers to previously cited SM reference, but 16th ed, 1985
 ttSW refers to Office of Solid Waste and Environmental Response  Test Methods for Evaluating Solid Waste Physical/Chemical Methods
  SW-846  2nd ed US Environmental Protection Agency, Washington, DC July 1982
 §See discussion in Trace Analysis, Spectroscopic Methods for Elements J W Wmefordner, ed Vol 46 of Chemical Analysis JohnWiley
  & Sons, New York, NY 1946 pp 41-42.
Table 2.
           Conditions for Electrothermal Atomization of
           Chromium

Step
No
1
2
3
4

Temp
1C)
100
130
WOO
2700

Ramp Time
(sec)
10
2
10
1
Holding
Time
(sec)
10
20
30
6

Argon Flow
Setting
Regular
Regular
Mm if low
Miniflow
Hexavalent Chromium Analyses—

The hexavalent chromium content of each initial and final
test solution was  determined by applying  the standard
additions technique  to the  revised  diphenylcarbazide
color!metric procedure (see Table 1). Three 100-mL aliquots
of each initial sample and three 50-mL aliquots of each final
sample were processed. To the second and third aliquots in
each set of three were added 0.5 and 1.0 mL, respectively,
of a 4-/jg/mL hexavalent chromium (K2Cr207) solution. The
effective Cr(VI) levels in the second and third aliquots of the
initial and final samples were consequently 0.02 and 0.04
mg/L and 0.04 and 0.08 mg/L, respectively. All aliquots
were then diluted to 101 mL, 2 mLof color reagent (250 mg
1,5-diphenylcarbazide  in 50 mL A.C.S. reagent  grade
acetone) was added, and the pH was adjusted to 2 0 with
50% sulfunc  acid (required  volume  < 0.5  mL). The
absorbance of each processed aliquot was determined after
1 5 min against that of a reagent  blank at 540 nm using a
Beckman B Spectrophotometer equipped with a matched
set of 5-cm cells. The absorbances of each set of three
aliquots  were  then plotted  versus  the corresponding
amounts of added Cr(VI) and the linearity of the plot
checked. The Cr(VI) concentration of each test sample was
then calculated by a linear regression analysis of the data
and checked by graphical extrapolation.

Quality Assurance

All laboratory analyses were conducted  using the control
measures recommended  in the  EPA's analytical quality
control manual (12). Accuracy was periodically evaluated
by determining  the percent recovery  of  analyte  from
                                  reference samples or from test samples spiked with known
                                  quantities of analyte. Precision was similarly determined
                                  periodically by replicate determinations of analyte, sample
                                  volume  permitting. Appropriate Shewhart control charts
                                  and limits were established and maintained
                                  Results and Discussion

                                  Total and Hexavalent Chromium Method
                                  Evaluation and Quality Control

                                  Before initiating the study of the effect of chlorine on the
                                  speciation  of  chromium in  Cincinnati tap  water,  the
                                  applicability of the methods for determining hexavalent and
                                  total chromium was evaluated  First applied was  EPA
                                  method 218.5 (13), a flameless atomic absorption technique
                                  for  determining  dissolved  hexavalent  chromium after
                                  coprecipitation. Unfortunately,  the  time this approach
                                  required to  isolate  and wash the coprecipitate of  lead
                                  chromate/lead sulfate exceeded 1 hr. Consequently, the
                                  chlorine action on the trivalent chromium  could  not be
                                  stopped with sufficient speed  or control. The timing of the
                                  diphenylcarbazide  colonmetric method  for  hexavalent
                                  chromium (14), however, proved to be satisfactory, since
                                  only 1 5 to 30 mm elapsed between sample aliquotmg and
                                  initiation of color development.  The absorbance  of  the
                                  developed color, however, was dependent on the concen-
                                  tration  of free residual chlorine. A  study of samples
                                  containing 0.05 mg/L Cr(VI) in the presence of 0, 0.5, 1.0,
                                  and 2.1 mg/L FRC revealed a 5% color depression with  1
                                  mg/L chlorine and a significant 15% color depression with
                                  2 1  mg/L chlorine. Since the 2-mg/L FRC contents of the
                                  proposed study test solutions might decrease variably with
                                  the  degree of reaction with  the trivalent chromium, the
                                  method of standard additions, as outlined previously, was
                                  applied to the colorimetric procedure to ensure accurate
                                  hexavalent chromium observations.  Solutions containing
                                  0.05 mg/L Cr(VI) in the presence of 0, 0 5,  1.0, and 2.1
                                  mg/L FRC were analyzed to verify the applicability of this
                                  approach  The chromium additions to the second and third
                                  sample aliquots in each analysis set were equivalent to
                                  0 10 and 0.20 mg/L, respectively. In each case the observed
                                  hexavalent chromium concentration  was 0.05 mg/L. The
                                  accuracy of  the approach was thus  validated. A solution
                                  containing 0 5 mg/LCr(lll)was also subjected to hexavalent

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chromium analysis using the standard additions approach
with the colorimetric procedure. The Cr(VI) additions to the
second and third sample aliquots in this analysis set were
equivalent  to  0.02 and 0.04 mg/L,  respectively.  The
observed hexavalent chromium concentration was 0.0008
mg/L, and confirmed both the specificity of the hexavalent
chromium method and the trivalent chromium speciation in
the CrCh used in preparing the study test solutions.

A  flameless atomic absorption technique,  EPA  method
218.2 (12), was used for determining total chromium. Two
reference solutions were analyzed—EPA No. WS12-1 and
U.S. Geological Survey No. 77 with theoretical chromium
concentrations of 14.3 and 20.3 jug/L, respectively. The
total chromium observations were 15.1 and 20.6 ug/L,
respectively, while the corresponding percent recoveries
were 105.6 and 101.5. The precision of the test solution
preparation [Cr(lll) addition] and the total chromium anal-
yses were  evaluated together by determining the total
chromium in the initial and final aliquots of each of the four
study test solutions The mean (M) total chromium concen-
tration was 0.464 mg/L with a standard deviation (s) of ±
0.01 2 mg/L and a coefficient of variation (s/M) of 0.0259.

Influence of Chlorine on Chromium Speciation

The character of the chlorine-adjusted Cincinnati tap water
used in preparing the four test solutions in this study is
presented in Table 3. The analyses revealed that the tap
water had a low alkalinity, chloride, and sulfate, and a pH
above  neutral. The primary and secondary  inorganic
constituent levels were below the  maxim limits specified in
the drinking water regulations.

Table 3.    Characterization of Chlorine-Adjusted Cincinnati
           Tap Water
Characteristic*
Alkalinity (as CaCOJ
Arsenic
Barium
Cadmium
Chloride
Chlorine, free residual
Chromium, total
Color, c.u.
Conductance, specific.
umhos/cm at 25°C
Copper
Fluoride
Iron
Lead
Magnesium
Manganese
Mercury
pH, units
Residue, total filterable
(total dissolved solids)
Selenium
Silver
Sodium
Sulfate
Turbidity, n t u
Zinc
Observation
36.0
< 0 0005
0.25
< 0002
20 1
204
< OOO5
2

290
< 0.02
0.9
< 0.1
< 0005
7 11
< 003
< 0 0005
a. 05

175
< 0.05
< 0.03
11.
58.
0.08
< 0.02
 The character of the four initial and final test solutions is
 presented in Table 4. The analyses revealed that the 36.0
 mg/L alkalinity level of the chlorine-adjusted tap water was
 altered by the final pH adjustment after the Cr(lll) addition
 The alkalinity levels of the four initial test solutions with pH
 levels adjusted to 5, 6, 7, and 8 were 0,13.6, 30 4, and 36.5
 mg/L, respectively. During the subsequent 24-hr exposure
 study, these alkalinity levels were not altered significantly,
 however. The  mean TOC  level of the four initial test
 solutions was 1.57 ±002 mg/L; it increased slightly to
 1.70 ± 0.07 mg/L during the test. This 8-percent increase
 probably reflects sampling and  analytical  variation. The
 dissolved oxygen (DO) analyses were performed only on the
 final four test solutions because of  instrumental  mal-
 function. In each case, the observed final  DO approximated
 the aqueous saturation level for the test temperature and
 pressure. Thus little, if any, oxygen consumption appears to
 have occurred during the test.

 FRC, however, declined in each of the four test solutions
 during the 24-hr exposure The  concentration decreases
 ranged from 0.44 to 0.79 mg/L, with changes > 0.65 mg/L
 in those solutions with initial  pH  levels < 6.0

 The chromium analyses revealed that  the  oxidation of
 trivalent chromium  to  hexavalent  chromium  definitely
 occurred in the test solutions  prepared from Cincinnati tap
 water containing 2 04 mg/L FRC and 0.464 ± 0.01 2 mg/L
 Cr(lll) with initial pH  levels of  approximately 5, 6, 7, and 8.
 Because of the time  elapsed between initiation of the test
 solution exposures and color development in the hexavalent
 chromium analyses,  the initial and final hexavalent obser-
 vations actually represent the 1/2-  and  24-hr levels. The
 Cr(VI) concentrations in the four initial  test solutions were
 all low, ranging from 0.007 to 0 019 mg/L. In the 24-hr test
 solutions, however, the Cr(VI) levels were more significant
 and ranged from 0.094 to 0 1  99  mg/L. The percent Cr(lll)
 conversion to Cr(VI) appeared to vary with the initial pH of
 the solution (Figure 1) In the 24-hr test solutions with the
 initial pH levels of 6 and 8, the  observed  maximum and
 minimum conversions were 43.4 and 20  9%, respectively

 Chromium oxidation  by chlorine has also been observed by
 other investigators. In 1978,  Toyama et al. (15) reported
 observing the formation of  hexavalent chromium in solu-
 tions initially containing 10  mg/L Cr(lll)  and 20  mg/L

Figure 1.    Percent Cr(lll) conversion to Cr(VI) in Cincinnati
           tap water containing 0 5  mg/L Cr(lll) and 2.04
           mg/L FRC.
"Unit is mg/L unless otherwise noted.
                5678

              Test Solution Number (Initial solution pH)

                          5

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Table 4.    Periodic Characterization of Test Solutions
Test
Solution
No.
5
6
7
8
Sampling Period
Initial
X
X
X
X
Final
X
X
X
X
pH
499
4.15
603
595
699
6.39
804
7.30
Free Residual
Chlorine
Img/L)
204
1 25
2.05
1.40
2.04
1 60
204
1 59
Total
Cr
0482
0.476
0470
0459
0464
0466
0.447
0.450
Cr(VI)
Img/L)
0007
0126
0.019
0 199
0017
0 139
0012
0094
Alkalinity
fmg CaCOa/L)
0
0
136
132
30.4
29.6
365
36.4
Total
Organic Carbon
Img/L)
1.56
1.65
1.61
1 65
1.56
1.70
1.54
1.80
Dissolved
Oxygen
Img/L)
9.4
9.4
96
95
'Each test solution was originally spiked with 0.5 mg/L Cr(lll)
chlorine (added as sodium hypochlorite) and having  pH
levels ranging from < 1 to 1 3 After 2.5 hr, the Cr(VI) levels
varied  from 01  to  1.35  mg/L, the highest level being
observed in the solution with an initial pH of 7. Clifford and
Chau (11) have just completed an extensive study of the fate
of chromium in chlorinated water and will soon be reporting
the conversion of Cr(lll)  and Cr(VI) in  various aqueous
solutions with  pH levels ranging from 5 to 10.3.

Although  the  effects of  chlorine  on the speciation of
chromium  in aqueous solutions  have been observed by
several investigators, chlorine apparently  has not  been
included as a factor in the various diagrams or models of
chromium speciation. In a recent summary  of the thermo-
dynamic properties and environmental chemistry of chro-
mium, Schmidt (16) presented a number of  illustrations of
the distribution of chromium species at various pH and
redox potential (pE) levels  He indicated that the pE/pH
diagram, reproduced here as Figure 2, predicts many,  but
not all, of the previously reported chromium speciation
observations in natural waters. He emphasized that some
of the occurrences of chromium species  resulted from
chromium complexation and reduction by organic matter,
adsorption and oxidation by  manganese oxides  in sus-
pended matter, and reduction by hydrogen sulfide (H2S)
Consequently, Schmidt introduced a modified model (Figure
3) to  demonstrate the  influence of these  factors on
chromium speciation in  the  environment.  He  further
reported the i ncorporat ion of the chromium thermodynamic
data  into  the geochemical  computer model MINTEQ,
currently  being  developed  by  his  colleagues at Battelle
Pacific Northwest Laboratory. Perhaps a  model for  the
speciation of chromium in chlorinated drinking water could
possibly be derived  by  incorporating the appropriate
chlorine thermodynamic data into this program.
Conclusions and Recommendations

This investigation has demonstrated that trivalent chro-
mium can  be oxidized to hexavalent chromium in a tap
water with a low alkalinity,  chloride,  sulfate, and  TOC
content In  test solutions with initial pH levels rang ing from
5 to 8, the quantity of Cr(VI) formed from 0 464 mg/L Cr(lll)
Figure 2.   pE-pH diagram of aqueous inorganic Crspeciesat
           total Cr concentrations of 1 0 8 M (reprinted with
           permission, see reference 16).
    15
    10
    10
                                       (Cr)T= 1Cr8M
                                             Cr202(c)
                                        10
                                                12
                             pH
in 24 hr ranged from 0.094 to 0.199 mg/L (20.9 to 43.4
percent conversion).

Our knowledge and understanding of the conditions under
which trivalent chromium oxidizes to hexavalent chromium
in aqueous solutions containing  free  residual  chlorine
might  be  enhanced by the incorporation of appropriate
chlorine thermodynamic data into the  MINTEQ  program
and the development of a model for chromium speciation in
the presence of FRC.

Acknowledgments

Gratitude  is expressed to Tom Sorg, Chief, Inorganic and
Paniculate Control  Branch, for his  encouragement and

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Figure 3.   Model of processes controlling the distribution of
           Cr in the environment (reprinted with permission,
           see references 16 and 17).
                      Organisms,
                    Organic Matter
////////////////////////////////T////
                    Sediment (Soil)
technical suggestions. The author also greatly appreciates
the analytical assistance of Jim Caldwell, William Chaney,
Carl Shadix, and Lou Trombly, all of the aforementioned
Branch. Thanks are also expressed to Brad Smith, Organics
Control Branch, for conducting the TOC determinations.

References

  1.  Florence, T. M., and Batley, G. E  Chemical Speci-
     ations in  Natural Waters. CRC Critical Reviews in
     Analytical Chemistry. 9(3)'262-263, 1980.
  2   Bartlett, R , and James, B  Behavior of Chromium in
     Soils- III  Oxidation. J.  Environ. Qua/.  8(1}:31-35,
     1979
  3.  Robertson, F. N. Hexavalent Chromium m the Ground
     Water in  Paradise Valley, Arizona. Ground Water
     13(6)-51 6-527, Nov./Dec. 1975.
  4.  Osaki, S., Osaki, T., and Takashima, Y. Distribution of
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