Environ Geochem Health
DOI 10.1007/s10653-007-9097-x
ORIGINAL PAPER
Swelling related to ettringite crystal formation in chromite
ore processing residue
Deok Hyun Moon Æ Dimitris Dermatas Æ
Mahmoud Wazne Æ Adriana M. Sanchez Æ
Maria Chrysochoou Æ Dennis G. Grubb

Springer Science+Business Media B.V. 2007
Abstract Several million tons of Chromite Ore
Processing Residue (COPR) were deposited at two
sites in New Jersey and Maryland, USA, and over
time they exhibited extensive heaving phenomena.
Ettringite, a needle-shaped mineral and an expansive
mineral commonly recognized in the literature con-
cerning cement- and soil, has been identified exten-
sively in numerous COPR samples collected from
these sites. It was therefore believed that ettringite
formation and its crystal growth are strongly associ-
ated with COPR heaving. We investigated the
correlation between ettringite and the heaving phe-
nomena in COPR materials that contained no initial
ettringite. Two identical COPR samples were ex-
posed to a 4% w/w sulfate solution (258C, 508C) in a
confined swell test apparatus. Both swell test samples
were analyzed by means of X-ray powder diffraction.
The peak intensities of newly formed ettringite were
more pronounced in the sample tested at 508C, and
swell development was only observed in this sample.
D. H. Moon (&)
D. Dermatas
M. Wazne

A. M. Sanchez
M. Chrysochoou
D. G. Grubb
W.M. Keck Geoenvironmental Laboratory,
Center for Environmental Systems,
Stevens Institute of Technology,
Hoboken, NJ 07030, USA
e-mail: dmoon@stevens.edu
D. G. Grubb
Schnabel Engineering North, LLC, 510 East Gay Street,
West Chester, PA 19380, USA
Scanning electron microscopy analyses revealed
well-crystallized ettringite needles exceeding 40 mm
in length for this sample, while ettringite crystals less
than 15 mm in length formed in the sample tested at
258C. Therefore, the results suggest that the quantity
of ettringite and the extent of crystallization play a
key role in the heave of COPR.
Keywords Confined swell tests
COPR

Ettringite
SEM
Temperature
XRPD
Introduction
Chromite Ore Processing Residue (COPR), the solid
residue generated as a by-product of chromite ore
processing to extract chromate and dichromates, has
been discussed extensively in the literature (Burke
et al. 1991; James 1996; Farmer et al. 1999; Darrie
2001; Deakin et al. 2001; Geelhoed et al. 2003;
Chrysochoou et al. 2006). COPR was widely used as
structural fill in England, Japan, West Germany and
the USA (Mckee 1988). COPR material, which
contains both Cr(III) and Cr(VI), was discovered to
be very problematic; a yellow chromate solution is
often observed to leach from locations where COPR
has been deposited, and elevated hexavalent chro-
mium concentrations have been measured in ground
water and water bodies proximate to these sites
(Geelhoed et al. 2002). Consequently, COPR has
become a major contamination source of the highly
123

mobile and toxic hexavalent chromium in many
urban areas.
The major COPR deposition sites in the USA are
located in Maryland, New Jersey, Ohio and New
York (Public Health Service 1953). About 1 million
tons of COPR have been deposited over an 85-acre
area at Dundalk Marine Terminal, Baltimore, Mary-
land, and this COPR deposition site has exhibited
extensive heaving over time, severely limiting site
use (Moon et al. 2006).
The major mineral phases identified in COPR
materials are brownmillerite [Ca2(Fe, Al)O5], peri-
clase (MgO) and quicklime (CaO). The main
pozzolanic reaction products derived from brown-
millerite are hydrogarnets [katoite (CaO)3Al2O3
(H2O)6 being the main phase] and hydrotalcites
[Al2Mg4(OH)12(CO3)(H2O)3 is a representative com-
pound]. Calcium aluminum chromium oxide hydrates
[CACs-Ca 4 Al 2 O 6 (CrO 4 )
nH 2 O], ettringite
[Ca6Al2(SO4)3(OH)12
26H2O] and calcite (CaCO3)
will form when chromate, sulfate and carbonate are
respectively introduced into the system. Brucite
[Mg(OH)2] is the main periclase hydration product
and hydrated lime [Ca(OH)2] the product of quick-
lime hydration.
The heaving related to brownmillerite hydration
and carbonation reactions was investigated, and no
significant correlation between hydrogarnet and cal-
cite formation with vertical swell development was
determined (Moon et al. 2006). Since ettringite is
commonly recognized as an expansive mineral in the
in the literature concerning cement and soil, heaving
related to ettringite formation in COPR materials was
specifically evaluated by exposing COPR materials to
sodium sulfate solutions in a confined swell test
apparatus. The transformation of brownmillerite to
ettringite upon exposure to sulfate can be written as:
3ðCa2 ðFe; AlÞO5 Þ þ 6Hþ þ 3SO2 4 þ 35H2 O !
Ca6 Al2 ðSO4 Þ3 ðOHÞ12
26H2 O
þ AlðOHÞ3 þ 3FeðOHÞ3 ð1Þ
Temperature effects on swell development were
also investigated at 258C and 508C, where the latter
temperature approaches the upper stability limit of
ettringite. However, ettringite was found to be stable
in solution up to 608C at a pH of about 11 (Ghorab
and Kishar 1985).
123
Environ Geochem Health
Experimental methodology
COPR samples and reagent
Two identical COPR samples collected from the
Dundalk Marine Terminal (DMT) were tested in this
study. The COPR samples were grey black granular
sand-size materials (designated as GB). These COPR
samples contained high amounts of brownmillerite
(initial reaction stage) and low amounts of transfor-
mation products, such as hydrotalcite, hydrogarnets
and CACs (Dermatas et al. 2006). Sodium sulfate
(Na2SO4) (Fisher Scientific, Suwanee, GA) dissolved
in DI water (4% w/w) was used as the sulfate source
to form ettringite.
Test apparatus
Figure 1 illustrates the one dimensional (1D) confined
swell test device (GeoSyntec, Kennesaw, GA) used in
this study. The COPR sample was placed in a
stainless-steel chamber with an effective diameter of
7.24 cm and a height of 7.62 cm. Filter paper covered
both the top and the bottom of the sample, followed
by a pair of porous stones. A steel frame was used to
apply the confining pressure using a dead load of
2.27 kg. Sample height change was measured by the
linear vertical displacement transducer (LVDT) every
10 s. All the readings were automatically recorded
using a Geolog Box and computer. The swell index
was estimated by dividing the change in height by the
Porous
Stone Top ring
Sample Chamber
Bottom
Support
LVDT
Dead load
5 lb
Fig. 1 1D confined swell test apparatus
Environ Geochem Health

initial height. The swell test devices were operated in
a temperature-controlled chamber.
Testing conditions
The confined swell test was performed under alter-
nating wet and dry cycles to facilitate the establish-
ment of a lithified sample state. During wet cycles the
sodium sulfate solution (4% w/w) was introduced
manually from the top of the sample, and the samples
were maintained in a wet state by maintaining the
liquid level above the top of the sample. A fan was
used to assist in the drying of the sample during the
test conducted at 258C; the sample that was tested at
508C was allowed to dry at the testing temperature.
Samples 1 and 2 (S1, S2) were tested at 258C and
508C, respectively. Bulk samples were gently com-
pacted at *0.8 cm per layer using a rubber pestle
(diameter 3.2 cm) inside the chamber until each
compacted sample reached its field density. An initial
sample height of 4.2 cm was achieved in each case.
The testing conditions were switched from wet to dry
cycles and vice versa when the height change became
negligible. Similarly, the tests were terminated when
the systems reached apparent equilibrium, i.e., no
additional height changes were observed.
X-ray powder diffraction analyses
After each test, each sample was subdivided into
three layers (top, middle and bottom) and sub-
samples collected from each layer were analyzed
using X-ray powder diffraction (XRPD). Prior to
this analysis, all samples were dried for 3 days in a
nitrogen-purged chamber to mitigate the potential
for carbonation reactions and then pulverized to pass
a U.S. standard #400 sieve (38 mm). Step-scanned
Scanning electron microscopy analyses
Prior to scanning electron microscopy (SEM) anal-
ysis, all samples were dried for 3 days in a nitrogen-
purged chamber and prepared using double-sided
carbon tape. SEM analyses were conducted using a
LEO-810 Zeiss microscope equipped with an
ISIS-LINK system.
Results and discussion
Swell behavior
No significant swell development was observed in S1
at 258C after 10–24 h (Fig. 2) so the experiment was
terminated. However, S2 at 508C showed significant
swell development during the same time interval
(Fig. 2). Specifically, about 2.5% swelling was
observed during the third wet cycle and this was
attributed to ettringite formation, on the basis of the
XRPD and SEM analyses (next two sections). Each
wetting cycle began with a consolidation step, which
may have resulted from dissolution of cementation
bonds, lubrication or effective stress increases in the
sample associated with drying. Then, as the sulfate
solution permeated the macropores, crystal formation
within likely corresponded to swell and initiation of
new micropores due to sample expansion and crack-
ing. Drying cycles corresponded to positive swell.
This trend continued for the first two cycles as the
pores presumably filled with new ettringite crystals
which first reduced, then eliminated, consolidation
while producing a net increase in positive swell over
the long term.
3.0 2nd 3r d c ycle 4th cy cle

X-ray patterns were collected by means of a Rigaku 2.5

DXR-3000 computer-automated diffractometer using 2.0 S2

%Swell

Bragg-Brentano geometry. XRPD analyses were 1.5

1.0
conducted at 40 kV and 40 mA using a diffracted
0.5
beam graphite-monochromator with Cu radiation.
0.0 S1
XRPD data were collected in a range of 58 to 658 2h -0.5 1s t W C 1s t D C
2nd W C 2nd D C
with a step size of 0.028 and a count time of 3 s per -1.0 3r d W C 3r d D C
4t h WC 4th D C
step. Qualitative analyses of XRPD patterns were -1.5
0 500 1000 1500 2000 2500 3000 3500
performed using the JADE software version 7.1
Times (hrs)
(MDI 2004) and the International Centre for
Diffraction Data database (ICDD 1998) reference Fig. 2 Swell behavior of chromite ore processing residue
patterns. samples (258C and 508C) as a function of time and wetting

123
 Environ Geochem Health

Fig. 3 X-ray patterns for CAC3: Calcium aluminum chromium oxide hydrate-
untreated and Na2SO4- 14H2O, B: Brownmillerite, P:Periclase, Br: Brucite, C:
Calcite, E: Ettringite, S: Stichtite, Qu: Quintinite, K:
treated DMT chromite ore
Katoite, H: Hydroandradite
processing residue samples E
B

R ela tiv e in ten sity (%)

B
B B B
E o
Qu, S B BC C, B P B C, B S2 (50 C)
Br H, K E E B B B B
Br B B

CAC3 o
CAC3 S1 (25 C)

Untreated

5 10 15 20 25 30 35 40 45 50 55 60 65
2 theta

XRPD analyses role in the capacity of the pores to accommodate their

X-ray diffraction patterns were obtained from top,
middle and lower regions of each sample, as previ-
ously described. The XRPD patterns obtained from
the middle layer of each sample after the fourth cycle
are presented in Fig. 3. The reduction in peak
intensities of brownmillerite was not clearly pro-
nounced. This may be due to its predominance (60%
w/w on average) (Dermatas et al. 2006) and the
incongruent dissolution of only a relatively small
fraction. We also noticed that the calcite peak
increased after swell tests when compared with the
untreated sample. However, calcite formation has
been reported not to be related to heaving in COPR
(Moon et al. 2006). Ettringite was clearly identified in
each region in both samples, based on its 2h values
(9.18, 15.88).
The peak intensities of ettringite were more
pronounced in S2, indicating a potentially larger
quantity of ettringite. Even though ettringite was
formed in both samples upon exposure to sulfate,
significant swell was observed only in S2. This
suggests that swell development in COPR materials
may be influenced by the quantity of ettringite and
the capacity of the pore structure to accommodate its
needle-like structure. Initially, the pore structure will
accommodate the small quantity of ettringite; how-
ever, once a threshold value is reached (e.g., after 2
cycles), net positive expansion is maintained there-
after. Also, the crystal size of ettringite may play a
size, i.e., the larger needles are less likely to be
accommodated, thus requiring expansion. Crystal
size between two samples was therefore evaluated
using SEM analyses.
SEM analyses
Following the swell tests, S1 and S2 were examined
using the SEM to evaluate the degree of crystalliza-
tion of ettringite. Figures 4 and 5 show the ettringite
needles occurring in both samples, consistent with the
XRPD data. In S2, ettringite needles were well
crystallized with a length typically exceeding 40 mm
(Fig. 5). However, in S1, ettringite needles were
smaller in length (<15 mm) than those in S2 (Fig. 4).
This suggested that the elevated temperature in S2
provided a rapid rate of ettringite formation in terms
of both quantity and size. While the XRPD and SEM
data for S1 clearly show ettringite formation, the lack
of swell for S1 (Fig. 2) clearly indicates that COPR
can tolerate some ettringite development in the short
term. The swell observed at the DMT site may have
been caused by the exposure of sufficient amounts of
COPR to sulfate at ambient temperatures (20–258C)
over many decades, which have led ultimately to the
production of swell on the order of inches to feet.
Accordingly, as a practical matter, ettringite forma-
tion in COPR at deposition sites is inevitable. Since
COPR sites often occur in urban areas, the results for
S2 also suggest that waste heat from local sources

123
Environ Geochem Health
Fig. 4 SEM images showing ettringite needles from S1
Fig. 5 SEM images showing ettringite needles from S2
(cooling water from buildings, power plants, refiner-
ies, etc.), if amended with sulfate, could be used to
accelerate brownmillerite conversion to ettringite to
exhaust the swell potential of COPR (Eq. 1). This
may be potentially accomplished via a site/cell
flooding program or soil mixing processes.
Conclusions
Confined swell tests were conducted using COPR
materials, which initially did not contain quantifiable
amounts of ettringite. Two identical COPR samples
were tested at 258C and 508C to evaluate the
relationship between ettringite formation and swelling
with respect to temperature. A sodium sulfate (4% w/
w) solution was added as a soluble sulfate source to
COPR samples. Overall, swell test results showed that
significant swell development (2.5%) was observed
only in the sample tested at 508C (S2). Crystallization
and the quantity of ettringite formed were found to be
mainly responsible for swelling. The specific findings
are summarized as follows:
• Ettringite formation was thermodynamically
favored when sulfate was introduced into the
COPR system. This was confirmed based on the
presence of ettringite peaks in XRPD results for
both samples.
• The ettringite peaks were more pronounced in the
sample tested at 508C (S2) than in a sample tested
at 258C (S1). About 2.5% swelling was observed
in S2; no swelling was observed in S1.
• SEM analyses indicated that larger crystals of
ettringite were present in S2 than in S1. This
indicated that smaller crystals of ettringite formed
in S1 were accommodated in voids within the
experimental time frame, while larger crystals
formed in S2 created adequate swell pressure.
• Crystallization (quantity, size) of ettringite was
mainly responsible for swelling in the COPR
material.
Acknowledgment This study was supported by Honeywell
International Inc.
References
Burke, T., Fagliano, J., Goldoft, M., Hazen, R. E., Iglewicz, R.,
& Mckee, T. (1991). Chromite ore processing residue in
Hudson County, New Jersey. Environ Health Perspect,
92, 131–137.
Chrysochoou, M., Dermatas, D., Moon, D. H., French, C.,
Morris, J. & Kaouris, M. (2006). Investigation of barium
treatment of chromite ore processing residue (COPR).
Journal of ASTM International, 3(6), doi: 10.1520/
JAI13314.
Darrie, R. G. (2001). Commercial extraction technology and
process waste disposal in the manufacture of chromium
chemicals from ore. Environ Geochem Health, 23, 187–
193.
Deakin, D., West, L. J., Stewart, D. I., & Yardley, B. W. D.
(2001). Leaching behavior of a chromium smelter waste
heap. Waste Management, 21, 265–270.
Dermatas, D., Chrysochoou, M., Moon, D. H. & Christodou-
latos C. (2006). Mineralogical characterization of chro-
mite ore processing residue at Dundalk Marine Terminal
area 1800. In B.C. Alleman & M.E. Kelley (Eds.), Pro-
123

ceedings of the 8th International In Situ and On-Site
Bioremediation Symposium, Battelle, Columbus, Ohio,
2005.
Farmer, J. G., Graham, M. C., Thomas, R. P., Licona-Manzur,
C., Parterson, E., & Campbell, C. D. (1999). Assessment
and modeling of the environmental chemistry and poten-
tial for remediative treatment of chromium-contaminated
land. Environ Geochem Health, 21, 331–337.
Geelhoed, J. S., Meeussen, J. C. L., Hillier, S., Lumsdon, D. G.,
Thomas, R. P. (2002). Identification and geochemical
modeling of processes controlling leaching of Cr(VI) and
other major elements from chromite ore processing resi-
due. Geochimica Cosomchimica Acta, 66, 3927–3942.
Geelhoed, J. S., Meeussen, J. C. L., Roe, M. J., Hillier, S.,
Thomas, R. P., Farmer, J. G., & Paterson, E. (2003).
Chromium remediation or release? Effect of iron(II) sul-
fate addition on chromium(VI) leaching from columns of
chromite ore processing residue. Environmental Science
& Technology, 37, 3206–3213.
Ghorab, H. Y., & Kishar, E. A. (1985). Studies on the stability
of calcium sulfoaluminate hydrates. Part 1: Effects of
123
Environ Geochem Health
temperature on the stability of ettringite in pure water.
Cement and Concrete Research, 15, 93–99.
International Centre for Diffraction Data (1998). Powder Dif-
fraction File, PDF-2 Database Release.
James, B. R. (1996). The challenge of remediating chromium-
contaminated soil. Environmental Science & Technology,
30, 248A–51A.
Materials Data Inc. (2004). Jade Version 7.1. California, USA.
McKee, T. (1988). Chromate chemical production industry:
waste treatment past and Present. Report to the New
Jersey Department of Environmental Protection, Trenton,
NJ.
Moon, D.H., Dermatas, D., Chrysochoou, M., & Gang, S.
(2006). An investigation of the heaving mechanism re-
lated to chromite ore processing residue. Journal of ASTM
International, 3(6), doi: 10.1520/JAI13309.
Public Health Service (1953). The chromate-producing indus-
try. In: Health of workers in chromate producing industry-
a study. Federal Security Agency, Public Health Service,
Publication No. 192.