Journal of Hazardous Materials 179 (2010) 650–657

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Journal of Hazardous Materials

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Calcium polysulfide treatment of Cr(VI)-contaminated soil

Maria Chrysochoou ∗ , Daniel R. Ferreira, Chad P. Johnston
Department of Civil and Environmental Engineering, University of Connecticut, 261 Glenbrook Road, Storrs, CT 06269, United States

a r t i c l e i n f o a b s t r a c t

Article history: Batch treatability studies for a Cr(VI)-contaminated glacial soil from a Cr plating facility were conducted
Received 1 December 2009 using 1X and 2X the stoichiometric ratio of calcium polysulfide (CPS). The pH of the treated soil increased
Received in revised form 11 March 2010 from 6 to 11 upon CPS addition, but progressively returned to 8–8.5 over the course of 1 year. The 1X
Accepted 11 March 2010
dosage maintained a highly reducing environment up to 21 days of monitoring with the samples exposed
Available online 19 March 2010
to atmospheric oxygen, while 2X was reducing up to 180 days of curing. The EPA regulatory method for
solid Cr(VI) could not reliably predict Cr(VI) in the treated solid due to ongoing reduction during the test.
Keywords:
SPLP results showed that the CPS created an apparent Cr(VI) mobilization during the first 60 days of treat-
Chromium
Reduction
ment, with subsequent decrease in soluble Cr(VI) up to 1 year of monitoring. Synchrotron micro-X-ray
Calcium polysulfide analyses at 60 days curing showed that Cr(VI) was predominantly bound as highly insoluble PbCrO4 that
X-ray absorption spectroscopy precipitated in the interstitial pores of the soil, with very little to no Cr(VI) associated with the abundant
iron oxyhydroxides. Despite its spatial accessibility and due to its low solubility, PbCrO4 was recalcitrant
to treatment, which proceeded only very slowly as judged by the SPLP data. It is concluded that, while
CPS has a long residence time in the environment and is a promising reductant, in situ reduction is not an
efficient treatment method for soils with highly insoluble Cr(VI) compounds, especially in surficial layers
such as the one studied.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction ing agents such as ferrous sulfate, zero-valent iron (ZVI), and
pyrite have been previously used [5]. However, these methods
Chromium is one of the most frequently detected metal con- can have adverse effects due to the imparted acidity on the soil,
taminants in federal facilities, both in Department of Energy (DoE) are most effective under acidic conditions that are not favorable
and Department of Defense (DoD) sites. It is also frequently found for Cr(III) immobilization and are costly to apply for source treat-
in industrial facilities, such as the metallurgic, tanning and plat- ment as they are generally solid and thus not injectable. Other
ing industries. Much is known about the fate and transport of Cr in common reductants are sulfides delivered as liquid or gas and
soil and aquatic environments. Rai et al. [1] summarize the main organic materials, such as molasses and emulsified vegetable
attributes of the environmental chemistry of Cr. Toxic and car- oil. The literature on Cr treatment technologies is too extensive
cinogenic hexavalent chromium (Cr(VI)) is mobile at neutral and to effectively summarize here; a comprehensive list of relevant
alkaline pH and forms few precipitates, thus it is mobile in most documents can be found at the relevant EPA website (http://www.
soils. In oxic acidic soils it adsorbs on iron and aluminum oxyhy- clu-in.org/contaminantfocus/default.focus/sec/chromium VI/cat/
droxides and its mobility is reduced. Cr(VI) reduction to non-toxic Treatment Technologies/).
Cr(III) is facilitated by naturally occurring sulfides, ferrous iron and This study investigates the use of calcium polysulfide (CPS) as
soil organic matter. The Cr(III) precipitates as amorphous, insoluble a promising alternative that is inexpensive and can be effective
hydroxide at pH values greater than 5. under a range of pH conditions. CPS is a commercially available soil
In Cr(VI)-contaminated sites, remedial approaches have additive and has been used in field applications for contaminated
included in situ chemical reduction, monitored natural atten- soil treatment; Storch et al. [6] reported on the field application
uation under appropriate geochemical conditions [2,3] and of CPS to reduce Cr(VI) at a former chrome plating facility in Ari-
bioremediation [4]. The most common approach is the use of zona; FRTR [7] lists the use of CPS to treat chromium in an railroad
inorganic electron donors to reduce Cr(VI) and subsequently embankment with Cr-laden pigment in Morses Pond Culvert, MA;
immobilize it as insoluble chromium hydroxide. Iron-based reduc- IETEG [8] described a field application at a wood treatment facil-
ity in Ukiah, CA; Charboneau et al. [9] mentions the application of
CPS at the Hanford site. Even though these applications indicated
∗ Corresponding author. Tel.: +1 860 486 3694; fax: +1 860 486 2298. that CPS could be an effective reductant, no peer-reviewed liter-
E-mail address: maria.chrysochoou@uconn.edu (M. Chrysochoou). ature was found that methodically investigated the application of

0304-3894/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2010.03.052
 M. Chrysochoou et al. / Journal of Hazardous Materials 179 (2010) 650–657 651

CPS in soil as a function of pH, Cr speciation and other geochem-

ical parameters in bench scale studies. The only peer-reviewed
literature identified was on the use of CPS to treat chromite ore
processing residue (COPR) [10–12]. X-ray absorption near edge
structure (XANES) analyses in COPR studies showed that while dis-
solved Cr(VI) was successfully treated, solid Cr(VI) concentrations
remained high [11]. Thus, a thorough investigation on the use of
CPS in Cr(VI)-contaminated soils is warranted.
The site at the focus of this study is a chrome plating facility
in northeastern Connecticut. The history of the site is described in
detail elsewhere [3,13,14]. Briefly, drippings from the Cr plating
process and wastewater that was directly discharged into the adja-
cent wetland caused Cr contamination of the soil and groundwater. Fig. 1. Overview of treatability matrix (GW = soil under the groundwater table,
A pump-and-treat system was installed to contain the groundwa- HA = surficial soil collected with a hand auger, CPS = calcium polysulfide, L = lime,
ter contamination and prevent migration of Cr into the wetland and KC = K2 CO3 , 1X = stoichiometric dosage to reduce Cr(VI) in the soil, 2X = double the
adjacent river. However, previous studies at this site indicate that stoichiometric dosage).

99% of the chromium is tightly bound to the soil, resulting in slow

leaching rates that render the aquifer treatment inefficient over a
through a U.S. 400 sieve (38 ␮m), and contained 20 wt.% corundum
practical timescale [14]. Thus, direct treatment of the soil phase
as an internal standard. XRD data analysis was performed with the
emerged as a cost-effective alternative. The objective of this study
Jade software (Materialsdata Inc.), version 8.5, with reference to the
is to evaluate the use of CPS for Cr(VI) treatment in soil by inves-
International Center for Diffraction Data database [15].
tigating the pH and Cr(VI) speciation effects on the kinetics of the
CPS-soil reaction.
2.3. Treatment design
2. Materials and methods
The site characterization study revealed an uneven vertical dis-
tribution of chromium, with the majority of Cr(VI) contamination
2.1. Site description and sampling techniques
confined to the near-surface layer (∼5 ft depth), whereas Cr(III) was
the primary species at depths below 28 ft where the groundwa-
The facility is located on the edge of an escarpment formed by
ter table was observed (see Section 3.1). Based on these results,
glacial deposits that slopes down to a heavily vegetated wetland
the treatability study was split into two parts, addressing the soil
formed on the flood plain of the adjacent Little River. The site is
underneath the groundwater table and the near-surface soil sep-
underlain by a glaciofluvial aquifer and a well-graded silty and
arately. The notation for the two soil zones is HA (for the surficial
clayey-sand soil matrix that is typical of New England morphology.
sample collected with the hand auger) and GW for the soil col-
Soil sampling was conducted in February 2008 with a
lected from the groundwater zone. The GW soil was treated with a
GeoprobeTM drill rig at four locations within the perimeter of the
pH buffering agent (K2 CO3 ) alone, in order to investigate whether
chromium plume. Two cores were taken adjacent to the building,
Cr(III) immobilization at alkaline pH would be sufficient to reduce
where the bulk of the Cr(VI) source is. They are denoted S-1 and S-2,
Cr mobility below the CT regulatory limit of 0.11 mg/L Cr for non-
and reached depths of 40 ft and 20 ft, respectively, with the water
drinking water aquifers. The HS soil was treated with CPS with and
table at a depth of approximately 28 ft S-2 was advanced only down
without a buffering agent, to investigate whether the addition of
to 20 ft because of a large boulder encountered at that depth. Addi-
an alkaline agent would further facilitate Cr(VI) mobilization from
tionally, 4–5 kg of sample was collected with a hand auger (denoted
the soil for reductive treatment. An overview of the experimental
as HA) to a depth of roughly 4 ft in the unsaturated zone near the
matrix is given in Fig. 1.
building. The cores were separated into fractions representing 4 ft
The theoretical oxidation–reduction reaction between Cr(VI)
increments of depth and all samples were homogenized and stored
and CPS under anaerobic conditions is:
in sealed plastic bags at 4 ◦ C. Samples are denoted by core source
and depth increment in ft, e.g. S-1 (28–32).
2CrO4 2− + 3CaS5 + 10H+ ⇔ 2Cr(OH)3(s) + 15S(s) + 3Ca2+ + 2H2 O

2.2. Soil characterization Based on this reaction stoichiometry, the 29% CPS solution con-
centration, and an average HA sample Cr(VI) concentration of
Total Cr(VI) analysis was conducted according to methods EPA 7852 mg/kg, 156 mL of CPS solution were required per kg dry soil
3060A and EPA 7196. for a 1X stoichiometric relationship and 312 mL for 2X. Batch tests
SPLP analysis was conducted according to EPA method 1312. were conducted by placing 300 g of dry soil sieved through a No.
Total Cr in the SPLP leachate was analyzed by Phoenix Environ- 4 sieve (2 mm) in sealed plastic jars and the required CPS solution
mental Labs (Manchester, CT) by EPA method 6010B. Particle size and kept at a 1:1 liquid to solid (L:S) ratio. Saturated source zone
analysis was conducted according to method ASTM D422. Soil pH samples were treated with a 0.5% K2 CO3 (KC) solution and a 0.5%
analysis was conducted according to method ASTM D4980-89 and lime (L) solution for comparison. The amounts of potassium car-
water content by method ASTM 2216-98. XRF analysis of the soil bonate and lime were determined by conducting a preliminary pH
was conducted according to EPA 6200. Total metal and total organic buffering study with varying amounts of these agents. All studies
carbon analyses conducted by Phoenix Environmental Laboratories were performed in duplicate.
in Manchester, CT according to EPA methods 3015A, 6010B and The CPS product used in the study was Cascade® , a 29% CPS
9060. solution obtained from Best Sulfur Products, Inc. All other chemicals
X-ray diffraction (XRD) analysis was performed using a Bruker used are ACS certified reagents. Soil analyses were conducted at 0,
D5005 diffractometer with Bragg Brentano geometry using CuK␣ 1, 7, 28, 60, 180 and 365 days of curing. Soil pH, redox potential, total
radiation at 2Â angles between 5◦ and 65◦ , with a step size of 0.02◦ Cr(VI) and SPLP analyses were conducted according to the methods
and scanning time of 3 s per step. Samples were pulverized, passed previously described.
652 M. Chrysochoou et al. / Journal of Hazardous Materials 179 (2010) 650–657

Table 1 30 mg/kg, while Cr(total) was 380 mg/kg. Thus, Cr(VI) was only 9%
Characterization results of the control samples in the shallow HA and the ground-
of the total chromium in the groundwater zone. This is attributed to
water GW soil.
the acidic pH conditions that historically prevailed in the soil, and
Parameter CTRL – HA soil CTRL – GW soil which favored retardation of Cr(VI) in the upper zones and leaching
pH 6.3 6.0 of Cr(III) into the deeper soil. Nikolaidis et al. [13] reported a verti-
Cr(VI) (mg/kg) 7800 30 cal pH profile that ranged from 3.0 at 25 ft depth up to 5.5 close to
Cr(total) (mg/kg) 14,800 380 the ground surface. This extreme soil acidity was due to the acidic
Fe (mg/kg) 25,900 9440
solutions that leached through the facility floor, as well due to the
Al (mg/kg) 12,800 7280
Ca (mg/kg) 1000 800 discharged wastewater, both of which were the primary sources of
Mn (mg/kg) 260 140 contamination. The soil pH apparently rebounded by almost two
Pb (mg/kg)a 15,000 20 pH units over the course of the 15 years that elapsed between the
TOC (mg/kg) 12,000 260
two studies. The mechanism of pH buffering cannot be elicited from
a
Pb concentration obtained by XRF analysis. the comparison of the two studies, as soil chemistry and mineralogy
appears to be the same. Potential buffering processes are deproto-
nation of the abundant iron hydroxide surfaces, precipitation of cal-
2.4. X-ray absorption spectroscopy
cite (observed by XRD in small amounts) and microbial activity [19].
The Cr(VI) concentration was high (7800 mg/kg) in the HA
Representative samples from the 60-day cured samples of the
sample, while individual samples were found to have up to
HA soil (CTRL, 1X and 2X without KC addition) were prepared
10,000 mg/kg Cr(VI). The total Cr was at 14,800 mg/kg in the
as 30-␮m thick diamond-polished thin sections by Spectrum Pet-
HA sample, so that Cr(VI) was approximately 50% of the total
rographics (Vancouver, WA) for microprobe analyses. Micro-XRF,
chromium. The HA soil was also found to have considerably higher
␮XRD and ␮XANES measurements were performed on Beamline
Fe and TOC content compared to the saturated zone, along with a
10.3.2 at the Advanced Light Source (ALS) [16]. Micro-XRF elemen-
high Pb content of 15,000 mg/kg. The presence of Pb was a sur-
tal maps were acquired at 13.5 keV incident energy with a beam
prising finding, as it was not reported in previous studies and
size of 7 ␮m × 7 ␮m and a counting time of 50 ms/pixel. Fluores-
its source was not apparent based on the Cr plating processes.
cence counts were collected for Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn and Pb
The Pb concentration was only high at the top 5 ft and quickly
with a seven-element Ge solid-state detector. From elemental dis-
declined to background concentration of ∼20 mg/kg. The saturated
tribution maps, various spots of interest were selected for ␮XRD to
soil appeared to be closer to clean sand with lower contents of all
identify crystalline phases and for Cr K-edge ␮XANES to probe Cr
major metals. Mn concentrations were low in all zones, so that Mn-
redox state. Cr chemical mapping was performed at incident ener-
induced reoxidation of Cr(III) is not expected to be significant for
gies of 5960, 5993 and 6250 eV to obtain the background, Cr(VI)
treatment considerations.
and total Cr (Cr(total)) signals, respectively. Energy calibration was
XRD analysis showed that quartz was the predominant soil min-
performed using a Cr foil (5989.02 eV) [17]. The background map
eral, with plagioclase and potassium feldspar and some mica as
was subtracted from the two others to obtain signals attributable
secondary minerals. Traces of kaolinite clay were observed in the
to Cr only. Next, 7% of the Cr(total) signal was subtracted from that
shallow soil, along with some crystalline ferrihydrite and calcite.
of Cr(VI) to account for the finite XANES signal that Cr(III) species
typically exhibit at the Cr(VI) energy. The Cr(VI) and Cr(total) maps
3.2. pH buffering study for saturated soil
were then assembled into a composite map.
All ␮XANES spectra were collected in fluorescence mode,
Fig. 2 shows the pH and SPLP results for the buffered saturated
pre-edge background subtracted and post-edge normalized using
soil. The control sample maintained pH 6 over the course of 1 year,
custom LabView software. Three XANES standards of pure CaCrO4 ,
while the addition of potassium carbonate led to a constant pH of
PbCrO4 and BaCrO4 were obtained at the beamline; ␮XRD pat-
∼10, which is the pKa2 value for the carbonate system [20]. Lime
terns confirmed that the pure chemical corresponded to 100% pure
raised the pH to 12.4, which is the pH of lime-saturated water [21],
crystalline compound. Additional standards were provided as a
but in this case the pH decreased to 9 between 60 and 365 days of
courtesy of P. Nico and were also obtained previously at BL 10.3.2.
curing.
Microdiffraction patterns were recorded in transmission mode
The addition of 0.5% lime corresponds to the addition of
with a Bruker Smart6000 CCD camera at 17 keV for 5 min with a
0.18 equiv. OH− /kg soil, while the addition of 0.5% KC corresponds
beam size of 16 ␮m × 7 ␮m. Two-dimensional patterns were radi-
to 0.04 equiv. OH− /kg soil, assuming that the main buffering reac-
ally integrated and calibrated using the Fit2d software [18] and an
tion is CO3 2− turning into HCO3 − . However, lime was less successful
␣-alumina standard. Analysis was performed with the Jade soft-
than KC to maintain high pH in the long term.
ware v.8.5 and reference to the ICDD database.
There are two main processes that reduce pH in the amended
soil over time: CO2 sequestration and calcite formation, and release
3. Results and discussion of H+ from the protonated surfaces of iron and aluminum oxy-
hydroxides. Other processes such as deprotonation of organic
3.1. Soil characterization compounds are considered to be of less importance due to their
low content in the saturated soil. The desorption of protons from
The soil from both the HA and GW samples was well-graded iron hydroxide surfaces is thought to be a fast process [19], while
sand with a slightly higher silt and clay content (12%) in the HA CO2 sequestration is limited by the rate of diffusion of atmospheric
soil. The pH of the soil was acidic and generally decreased with CO2 into the liquid phase. The buffering capacity related to proton
depth, ranging from 6.5 to 7 close to the surface to 5.5 in the GW adsorption and desorption of Fe and Al oxyhydroxides has been
sample for the source samples close to the building and even below found to be in the range 0.04–0.4 mol/kg [22], although this referred
5 in the aquifer near the extraction well. to the pH range 3.5–8.3. Given the high Fe content of the soil in this
Table 1 shows the chemical characterization results for the com- study, pH buffering was anticipated to be substantial; however,
posite samples that were used in the treatability study. The GW it was not enough to counteract the effect of KC and lime addi-
sample was a mix from the 28–32 ft and 32–36 ft sampling depths tion. In the case of lime, CO2 sequestration was accelerated by the
and had a pH of 6. The Cr(VI) content of this composite sample was high amounts of added calcium, which produced calcite, removing
 M. Chrysochoou et al. / Journal of Hazardous Materials 179 (2010) 650–657 653

The addition of alkaline agents resulted in the mobilization

of Cr(VI) from the saturated soil, as anticipated. However, Cr(III)
immobilization under SPLP conditions was not attained. The SPLP
pH of the control sample was in the range 5.5–6, while the SPLP
pH of the KC and L samples was 9–9.5. Modeling of Cr(III) solubility
with respect to Cr(OH)3 using Visual Minteq showed that the mea-
sured concentrations were almost two orders of magnitude higher
than the predicted equilibrium concentration of 5 ␮g/L. The reason
for this behavior is unknown. It is possible that it is an artifact of
the analytical procedures, whereby Cr(III) is calculated as the dif-
ference between Cr(total) and Cr(VI). Since the largest fraction of
the mobilized Cr(total) was due to the mobilization of Cr(VI), it is
possible that the error associated with the measurement of each Cr
species caused an apparent increase in Cr(III) that was not real. In
either case, the mobilization of Cr(VI) was such that it rendered a
simple buffering treatment prohibitive. Thus, reductive treatment
of the saturated zone appeared to be necessary, despite the low
Cr(VI) concentrations in the solid.

3.3. CPS treatment of shallow soil

Fig. 3 shows the pH and redox potential over time in the CPS-
treated unsaturated soil. The pH in the control sample remained
at 6 throughout the 1-year testing period. The addition of 0.5% KC
resulted in a steady increase of soil pH to approximately 9. This is
a lower value compared to the saturated soil and the pKa2 (10.3)
of carbonate. This difference is attributed to the higher iron con-
tent of the unsaturated soil and the associated buffering capacity
of the iron oxyhydroxide surfaces. Consistently with the notion that
proton release of these surfaces occurs fast, the pH remained at 9
immediately after the addition of KC and until the end of the test-
ing period. The addition of CPS resulted in the increase of soil pH to
∼11 for the 1X dosage and 11.4 for the 2X dosage (the natural pH of
CPS is 11.5). All CPS-treated samples showed progressive decrease
in pH down to 7.2 for 1X and 7.8 for 2X, with the addition of KC not
resulting in significant change in the buffering behavior of the soil.
Fig. 2. pH (top) and SPLP Cr and Cr(VI) (bottom) in the buffered GW soil.
Again, the addition of large amounts of Ca is thought to have caused
increased sequestration of CO2 to form calcite; the buffering pH of
CO3 2− from solution. In the KC-amended soil, CO2 -imparted acid- calcite is 7.3 [19] which is consistent with the observed results. In
ity would be limited by its solubility and equilibrium concentration, terms of in situ remediation, these results indicate that the alka-
since Ca was too low for substantial calcite formation. linity imparted of CPS can be buffered over time, and that the rate
It should be noted, however, that the access to CO2 in a field of buffering will be dictated by the availability of CO2 . This process
application would be more limited compared to the batch lab con- would likely take longer than 1 year in saturated conditions, where
ditions, and thus pH decrease in the limed soil would be even CO2 diffusion into groundwater would be limited.
slower. Furthermore, carbonate advection and retardation pro- The redox potential in the control samples was oxidizing, indi-
cesses are not captured in a batch study, so that the prediction cating that in situ conditions at the site do not currently favor Cr(VI)
of equilibrium pH concentrations in a field aquifer would require reduction. The addition of CPS resulted in a sharp drop of Eh to
column studies to be more precise. −500 mV, at which Cr(VI) reduction to Cr(III) is favored. The Eh

Fig. 3. pH (left) and redox potential (right) in the CPS-treated HA soil.

654 M. Chrysochoou et al. / Journal of Hazardous Materials 179 (2010) 650–657

Fig. 4. SPLP Cr(VI) (left) and Cr(total) (right) concentrations in the CPS-treated HA soil.

remained highly reducing in the 1X samples until 21 days, after mobilization in the CTRL-KC0.5 and the CPS-treated samples com-
which it increased sharply to −70 mV and progressively to a mildly pared to the control was also observed in the HA soil, as was the case
oxidizing environment. This signaled a consumption of sulfide that in the GW soil. The SPLP pH could again not account for this obser-
could be due to oxidation by chromate, by diffusing oxygen or by vation, as the SPLP pH of the control sample was approximately
the natural oxidizing capacity of the solid. The 2X sample main- 7, while the SPLP pH of all other samples was in the range 8–9, in
tained a reducing environment for longer, with the Eh increasing which Cr(III) is theoretically more insoluble. Since Cr(III) was found
at some point between 60 and 180 days of curing. It is recognized to be associated with amorphous and crystalline hydroxide by X-
that subsurface conditions would not expose sulfide to as much ray absorption spectroscopy, it is not apparent why the addition of
oxygen as the batch study did and that sulfide would likely have KC or CPS would cause a mobilization of Cr(III) from the soil. The
a longer staying power. Even so, sulfide oxidation appeared to be only plausible hypotheses at this time are (a) analytical artifacts;
slower compared to ferrous iron, which can be quickly oxidized in and (b) increased mobilization caused by physical dissolution of
the presence of oxygen [23]. Cr(VI)–Cr(III) mixed grains under alkaline conditions. Overall, SPLP
The success of the reductive treatment could not be evalu- is not the best test to assess the mobility of metal species under in
ated using the EPA regulatory method for Cr(VI) measurement
in the solid. While the control samples yielded constant Cr(VI)
concentrations and spike recoveries over the entire curing
period, CPS-treated samples consistently yielded non-detectable
(<5 mg/kg) Cr(VI) concentrations, and spiked samples had recover-
ies of 0%. Clearly, unreacted sulfide in the samples reacted with the
released Cr(VI) during the test, resulting in artificially low concen-
trations. Similar observations have been reported for chromite ore
processing residue [24]. Thus, alkaline digestion cannot be used to
assess the effectiveness of reductive treatment when the reductant
has not been exhausted.
The SPLP results (Fig. 4) confirmed that the alkaline digestion
results were an artifact of the test, since there was substantial leach-
ing of Cr(VI) up to 60 days curing. Cr(VI) leaching then declined
substantially in both the 1X and 2X treatments, reaching non-
detectable values (<10 ␮g/L) at 365 days of curing. Cr(VI) leaching
was below the control sample only at the 1-year point. However,
it should be stressed that the creation of alkaline conditions in the
CPS samples renders them comparable to the CTRL-KC0.5 sample,
in which substantial mobilization of Cr(VI) was observed due to
the alkaline pH. It is therefore concluded that Cr(VI) reduction did
take place, with the decreasing trend commencing after 28 days
of curing in the 1X sample and after 60 days of curing in the 2X
sample. These curing times coincide with the increase of the redox
potential in these samples (Fig. 3), confirming that sulfide oxida-
tion took place around that time and that chromate reduction was
at least partially responsible for sulfide consumption. Thus, chro-
mate reduction by CPS in the soil appeared to be a very slow process.
Ongoing studies show that once Cr(VI) is in solution, reduction by
CPS occurs very rapidly (unpublished data), so that the limiting step
for Cr(VI) reduction is considered to be its release from the solid.
Evidence to this end will be presented in Section 3.4.
The SPLP Cr(total) leaching levels in the CPS-treated soil also
declined with time and were below the CT regulatory limit of Fig. 5. Tricolor XRF maps of untreated HA sample (top) and 1X-treated HA sample
0.5 mg/L by 365 days of curing. However, the same surprising Cr(III) at 60 days (bottom).
 M. Chrysochoou et al. / Journal of Hazardous Materials 179 (2010) 650–657 655

Fig. 6. Inverse grayscale Cr(VI) micro-XRF maps of the control HA sample and the samples treated with 1X and 2X CPS.

situ conditions in the soil, as both the TCLP and SPLP tests have been intensity was not possible, as differences were attributed to sample
previously found to change metal speciation during the test in ways variability rather than redox reactions.
that were not consistent with field conditions [25,26]. However, the The ratio of Cr(VI) to Cr(total) was considered a more suitable
regulation of the site by the CT Department of Environmental Pro- indicator of reduction processes in the treated soil, as the total Cr
tection and the Environmental Protection Agency dictated that this presence would be normalized across different samples. Table 2
test had to be conducted for regulatory purposes. shows that the average counts of Cr(VI) were 37% of the Cr(total)
in the untreated sample after 60 days of curing in aqueous solu-
tion; this value dropped to 19% in the 1X-treated and to 17% in the
3.4. Micro-X-ray absorption spectroscopy 2X-treated sample. Chemical analyses yielded a Cr(VI)-to-Cr(total)
ratio of 50% in the control sample. The difference between this value
Micro-XRF, -XAS and -XRD analyses were conducted on samples and the 37% observed by ␮XRF may be either due to sample vari-
cured for 60 days. Fig. 5 shows the distribution of Cr, Fe and K in ability or due to the natural reducing capacity of the control soil; the
two of three samples (untreated and 1X-treated). Fe and K were the high TOC content in the surficial soil renders organically-induced
most abundant elements and thus representative of the presence Cr(VI) reduction a viable possibility. Both treated samples appeared
of solid grains in the sample. Cr was found to be primarily associ- to have a similar level of success in reducing Cr(VI), as the differ-
ated with finer grains, either as distinct particles, or as distinct halo ence between 17% and 19% is not considered statistically significant
on the rim of larger particles. Some Cr was found diffuse within without looking at more samples. Even though the differences in
larger grains (e.g. in the large grain of the untreated sample), but its Cr(total) concentrations make it difficult to draw definitive con-
concentration was significantly lower, so that the faint red color is clusions as to how much Cr(VI) was reduced, the reduction in the
difficult to see. Since thin sections yield two-dimensional images, it Cr(VI)/Cr(total) ratio suggested that reduction did occur and that it
is difficult to say whether the diffuse Cr was located within the inte- could be up to 50% of the original Cr(VI) content.
rior of the larger particle or if it was found adsorbed on its surface. In The distribution of counts between the pixels was very sim-
either case, it appears that the majority of the Cr mass was located ilar for the two treated samples, but had differences with the
on the rims of larger particles and in the finer grained fraction of untreated sample: as an indication, 50% of the pixels accounted
the soil. Cr-rich particles with diameter ranging from 20 to 100 ␮m for 9% of the Cr counts in the treated samples and 24% of the Cr
were observed in all three maps, with the largest ones found in the counts in the untreated sample. In other words, the distribution
untreated sample. The Cr species associated with each type of par- of pixel intensity was biased towards pixels with higher counts
ticles was further investigated with the use of the chemical maps in the treated samples. This suggests that reduction preferentially
and XANES. targeted areas of low Cr(VI) concentration, while high-Cr(VI) areas
Fig. 6 shows the Cr(VI) maps for the control and the treated remained largely intact. This suggests that high-Cr(VI) compounds
samples, with the intensities drawn to scale, i.e. the intensity of the were not amenable to treatment after 60 days of curing time. The
color corresponds to magnitude of concentration. Table 2 shows comparison of the ␮XRF Cr(VI) maps (Fig. 6) confirms that dark
the average pixel intensity over these three maps, as well as the spots persisted in the treated samples, whereby the 2X sample had
corresponding Cr(total) maps of the three samples. There was vari- reduced intensity and smaller dark spots. Interestingly, this is the
ability in the average Cr(total) intensity in the three maps, which opposite phenomenon of Cr(VI) reductive treatment of chromite
suggests that there is variability in the Cr distribution within the ore processing residue, in which high-Cr(VI) compounds were more
soil. The area captured in the control sample consisted of fewer
larger grains, which tended to have less Cr, whereby the areas in
the treated samples appeared to be more fine-grained and have Table 2
Average pixel intensity over the XRF-mapped regions for Cr(VI) and Cr(total) in the
higher Cr concentrations. One of the shortcomings of micro-X-ray untreated vs. the treated samples of the HA soil.
analyses is that the time required to collect the ␮XRF maps limits
the size of the areas and the number of samples that can be analyzed Cr(VI) Cr(total) Cr(VI)/Cr(total) (%)

within the available beam time, so that sample variability becomes Control – 60 days 6,700 18,000 37
an issue when comparing the untreated and the treated samples. 1X-treated – 60 days 9,600 50,000 19
2X-treated – 60 days 4,600 27,300 17
Thus, judging the success of treatment based on the average Cr(VI)
656 M. Chrysochoou et al. / Journal of Hazardous Materials 179 (2010) 650–657

Fig. 8. XANES point of control HA sample and Cr(VI) sorbed on goethite (spectrum
courtesy of Rick Wilkin, USEPA).

PbCrO4 , while Cr was present in excess and in the trivalent form,

which was more mobile in the acidic soil conditions and leached to
the saturated zone.
The prevalence of PbCrO4 as the main form of Cr(VI) in the
soil also explains the difficulty to treat the HA sample. Disso-
lution of this highly insoluble Cr(VI) compound could proceed
only extremely slowly, kinetically inhibiting the reduction pro-
cess. Additionally, galena (PbS) was observed in a few of the ␮XRD
patterns, scavenging part of the added sulfide.
The speciation of the remaining Cr(VI) points was a mixture
of Cr(OH)3 and PbCrO4 according to linear combination fitting.
This agrees with the assumption that increased Cr(III) mobiliza-
tion could be attributed to the physical dissolution of mixed
Cr(III)–Cr(VI) grains. Only one point could not be fitted with the
Fig. 7. XANES spectra of selected points as compared to pure Cr(OH)3 (a) and PbCrO4 available spectra and it resembled more Cr(VI) sorbed to goethite
(b) (spectra offset for clarity). (Fig. 8). This was the only point that was taken within the inte-
rior of one large grain, while other points were located in the more
amenable to treatment [27]. Thus, different mechanisms of Cr(VI) fine-grained areas surrounding the large grains.
release take place in different geochemical systems. Given the bias introduced in the statistical analysis of Cr(VI)
The speciation of Cr(VI) was also investigated by point ␮XANES speciation by the choice of a few selected points, it was thought
and ␮XRD in order to further elucidate the reduction mechanisms. that the association of Cr with Fe may have been underestimated
Twenty points were analyzed in the control sample and ten points through this process, both in terms of Cr(VI) sorption as well
in each of the treated samples; points were chosen to represent a as Cr(III) co-precipitation with Fe(III) hydroxides. The association
variety of Cr(VI) intensities in the Cr(total) ␮XRF map. of the two elements was further investigated by examining the
Fig. 7 shows the XANES spectra of points that resembled pure correlation between the pixel values of these elements over the
Cr(OH)3 : 8 points belonged to the control sample, 3 to the 1X- entire obtained maps, using the custom XRF map analysis software
treated and 5 to the 2X-treated sample. Additionally, seven points that was developed at BL 10.3.2. Cr(total) and Cr(VI) correlation
(2 CTRL, 2 1X and 3 2X) resembled Cr(OH)3 in the post-edge region, with Fe were investigated independently. The analysis showed
but still had a discernable Cr(VI) peak at 5993 eV. Based on the that Cr was not associated with Fe in the majority of the pixels.
␮XRF maps these points were obtained from areas with high vari- The Pearson correlation coefficient between the Fe and Cr pixel
ability in the element distribution; Cr is associated with either intensity was 0.33 in the 1X map, 0.32 in the 2X map and 0.11
Pb, Fe or no other element in adjacent pixels with a resolution in the control HA sample. The analysis further showed that the
of 10 ␮m × 10 ␮m; thus, it is concluded that a physical mixture of pixels with high correlation between the Cr and Fe values corre-
Cr(III) and Cr(VI) compounds is responsible for the observed XANES sponded to a single isolated particle in the HA and the 1X maps,
spectra. with a diameter of 50 and 80 ␮m, respectively. One large (50 ␮m)
The majority (8 out of 13) of high-Cr(VI)-bearing points were and several smaller (20 ␮m) particles with high Fe–Cr correla-
found to very closely resemble PbCrO4 (Fig. 7(b)). This was fur- tion were observed in the 2X map. Thus, co-precipitation of Cr
ther confirmed by ␮XRD, which showed crystalline crocoite as with Fe was not observed to be a dominant mechanism in this
the only mineral found in these points. The Pb content of the soil soil.
could account for approximately half of the Cr(VI) being present Similar observations were made for the Cr(VI)–Fe correlation.
as PbCrO4 (Table 1) at the top 5 ft of the unsaturated zone, while The Pearson coefficient was 0.07 in the control sample, 0.17 in 1X
deeper layers contained no appreciable Pb levels (<20 mg/kg). and 0.07 in 2X. A visual inspection of the ␮XRF maps confirmed
While the Pb source is not known (it is assumed that it is also the that the physical locations of Fe and Cr(VI) did not coincide for the
discharged wastewater and drippings), it appears that Pb migration most part. The reason for this appears to be that Fe was mostly con-
into the deeper layers was inhibited by the formation of insoluble tained within the larger soil grains, while Cr(VI) was preferentially
 M. Chrysochoou et al. / Journal of Hazardous Materials 179 (2010) 650–657 657

located within the finer grained regions (see Fig. 5). Thus, Cr(VI) References
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the financial support of the investigation. Luke Hellerich of AECOM [25] D. Dermatas, G. Shen, M. Chrysochoou, D.G. Grubb, N. Menounou, P. Dutko, Pb
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[27] M. Chrysochoou, S. Fakra, M.A. Marcus, D.H. Moon, D. Dermatas, Microstruc-
Matthew A. Marcus of LBNL provided continuous support for the tural analyses of Cr(VI) speciation in chromite ore processing residue (COPR),
␮XAS data acquisition, analysis and interpretation. ALS-LBNL oper- Environ. Sci. Technol. 43 (14) (2009) 5461–5466.
ations are supported by the Director, Office of Science, Office of
Basic Energy Sciences, US Department of Energy under contract
number DE-AC02-05CH11231.