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DOI 10.1007/s10653-007-9097-x
ORIGINAL PAPER
Abstract Several million tons of Chromite Ore Scanning electron microscopy analyses revealed
Processing Residue (COPR) were deposited at two well-crystallized ettringite needles exceeding 40 mm
sites in New Jersey and Maryland, USA, and over in length for this sample, while ettringite crystals less
time they exhibited extensive heaving phenomena. than 15 mm in length formed in the sample tested at
Ettringite, a needle-shaped mineral and an expansive 258C. Therefore, the results suggest that the quantity
mineral commonly recognized in the literature con- of ettringite and the extent of crystallization play a
cerning cement- and soil, has been identified exten- key role in the heave of COPR.
sively in numerous COPR samples collected from
these sites. It was therefore believed that ettringite Keywords Confined swell tests COPR
formation and its crystal growth are strongly associ- Ettringite SEM Temperature XRPD
ated with COPR heaving. We investigated the
correlation between ettringite and the heaving phe-
nomena in COPR materials that contained no initial Introduction
ettringite. Two identical COPR samples were ex-
posed to a 4% w/w sulfate solution (258C, 508C) in a Chromite Ore Processing Residue (COPR), the solid
confined swell test apparatus. Both swell test samples residue generated as a by-product of chromite ore
were analyzed by means of X-ray powder diffraction. processing to extract chromate and dichromates, has
The peak intensities of newly formed ettringite were been discussed extensively in the literature (Burke
more pronounced in the sample tested at 508C, and et al. 1991; James 1996; Farmer et al. 1999; Darrie
swell development was only observed in this sample. 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
D. H. Moon (&) D. Dermatas M. Wazne the USA (Mckee 1988). COPR material, which
A. M. Sanchez M. Chrysochoou D. G. Grubb contains both Cr(III) and Cr(VI), was discovered to
W.M. Keck Geoenvironmental Laboratory,
be very problematic; a yellow chromate solution is
Center for Environmental Systems,
Stevens Institute of Technology, often observed to leach from locations where COPR
Hoboken, NJ 07030, USA has been deposited, and elevated hexavalent chro-
e-mail: dmoon@stevens.edu mium concentrations have been measured in ground
water and water bodies proximate to these sites
D. G. Grubb
Schnabel Engineering North, LLC, 510 East Gay Street, (Geelhoed et al. 2002). Consequently, COPR has
West Chester, PA 19380, USA become a major contamination source of the highly
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initial height. The swell test devices were operated in Scanning electron microscopy analyses
a temperature-controlled chamber.
Prior to scanning electron microscopy (SEM) anal-
Testing conditions ysis, all samples were dried for 3 days in a nitrogen-
purged chamber and prepared using double-sided
The confined swell test was performed under alter- carbon tape. SEM analyses were conducted using a
nating wet and dry cycles to facilitate the establish- LEO-810 Zeiss microscope equipped with an
ment of a lithified sample state. During wet cycles the ISIS-LINK system.
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 Results and discussion
liquid level above the top of the sample. A fan was
used to assist in the drying of the sample during the Swell behavior
test conducted at 258C; the sample that was tested at
508C was allowed to dry at the testing temperature. No significant swell development was observed in S1
Samples 1 and 2 (S1, S2) were tested at 258C and at 258C after 10–24 h (Fig. 2) so the experiment was
508C, respectively. Bulk samples were gently com- terminated. However, S2 at 508C showed significant
pacted at *0.8 cm per layer using a rubber pestle swell development during the same time interval
(diameter 3.2 cm) inside the chamber until each (Fig. 2). Specifically, about 2.5% swelling was
compacted sample reached its field density. An initial observed during the third wet cycle and this was
sample height of 4.2 cm was achieved in each case. attributed to ettringite formation, on the basis of the
The testing conditions were switched from wet to dry XRPD and SEM analyses (next two sections). Each
cycles and vice versa when the height change became wetting cycle began with a consolidation step, which
negligible. Similarly, the tests were terminated when may have resulted from dissolution of cementation
the systems reached apparent equilibrium, i.e., no bonds, lubrication or effective stress increases in the
additional height changes were observed. sample associated with drying. Then, as the sulfate
solution permeated the macropores, crystal formation
X-ray powder diffraction analyses within likely corresponded to swell and initiation of
new micropores due to sample expansion and crack-
After each test, each sample was subdivided into ing. Drying cycles corresponded to positive swell.
three layers (top, middle and bottom) and sub- This trend continued for the first two cycles as the
samples collected from each layer were analyzed pores presumably filled with new ettringite crystals
using X-ray powder diffraction (XRPD). Prior to which first reduced, then eliminated, consolidation
this analysis, all samples were dried for 3 days in a while producing a net increase in positive swell over
nitrogen-purged chamber to mitigate the potential the long term.
for carbonation reactions and then pulverized to pass
a U.S. standard #400 sieve (38 mm). Step-scanned 3.0 2nd 3r d c ycle 4th cy cle
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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
CAC3 o
CAC3 S1 (25 C)
Untreated
5 10 15 20 25 30 35 40 45 50 55 60 65
2 theta
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Environ Geochem Health
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