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dier in terms of leaching behavior and mineralogy due to variations in chromite ore composition, extraction process, and deposition practices. Some ores could be rich in silica, iron, aluminum,
or impurities which cause the resulting mineralogy to vary. For
example, the COPR at Glasgow has twice the amount of silicon as
the COPR at New Jersey. This may have very strong implication
on the mineralogy of COPR as it may favor the formation of cementitious silicious phases. Similarly, inecient extraction of sulfates during the sodium sulfate operation during processing or the
intrusion of sulfate due the oxidation of sulfur in certain kiln fuel
oil (Allied Signal) may change the resulting mineralogy of COPR.
The introduction of sulfates to COPR may cause the formation of
ettringite, a swell causing mineral in cement chemistry. Reports of
catastrophic heave and swell are abound at the Jersey site, however,
no heave was reported at Glasgow (Geelhoed et al., 2002; Dermatas et al., 2006a). Moreover, often times COPR is mixed with
indigenous soils at some deposition sites whereas at other sites it
is deposited as pure COPR. Even at pure COPR sites, the manner of deposition may have implications on COPR behavior. For
example, if COPR is deposited in homogenous layers, its behavior
may dier had it been deposited through conduits where the ner
material is expected to settle to the bottom of the heap and the
coarser material will collect on top similar to alluvial depositions at
deltas. The mineralogical composition of the ne and coarse materials is expected to be dierent (Dermatas et al., 2006b). Moreover,
due to its high alkalinity, COPR absorbs signicant amounts of
atmospheric CO2 where it combines with COPR constituents to
form various carbonate phases. The degree of atmospheric exposure
and manner of CO2 exposure may determine the amount of CO2
absorbed. For example, CO32 constitutes approximately 11.5% of
total mass of COPR at the Jersey site (total carbonate at Glasgow
is not reported). In addition, hydrotalcites were clearly identied
at the Jersey site but are not reported at Glasgow. This has implications on COPR mineralogy and leaching behavior, because hydrotalcites, which are magnesium aluminum carbonate hydrates, are
reported to sequester chromates through anionic exchange (Alvarez-Ayuso and Nugteren, 2005). Consequently, the leaching behavior and the resultant mineralogy will dier signicantly depending
on the parent ore, extraction process, and deposition practices.
Moreover, modeling techniques may dier in terms of scope
and methodology. For example, Yalin and nl (2006) reported
on a mechanistic model to simulate Cr(VI) leaching from COPR
obtained at an industrial plant in Turkey. The model incorporates
a sequence of batch (dissolution) and ushing (leaching) operations. It uses Runge Kutta method to solve the resultant coupled
dierential equations and determine the parameters of the leaching
reactor. The study does not address the geochemistry of COPR
leaching or mineralogy. Conversely, Geelhoed et al. (2002) reports
on the leaching of Cr(VI) in COPR originating from a Glasgow
site. The authors use leaching tests, XRPD, and equilibrium based
geochemical modeling to describe the leaching behavior of COPR.
The concentration of leached Ca, Al, Si, Mg, and Cr(VI) are used
to calibrate for the solubility constants of some solid phases that
were used in the model calculations. The mineral phases identied in the residues of the leaching tests and other phases that may
be present in COPR are used in their model. Even though the
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Sample Characterization
The elemental composition of the COPR samples was determined by digesting the COPR material using USEPA Method
3051A (USEPA, 1996a) followed by USEPA Method 6010B
(USEPA, 1996b). Hexavalent chromium concentration was
obtained using USEPA Method 3060 (USEPA, 1996c) and
USEPA Method 7196A (USEPA, 1992). Total carbon was
measured using ASTM D5291 (ASTM, 2001) and it was as-
The pulverized COPR samples were added to a beaker with liquidto-solid ratio of 20. After a predetermined HCl acid dosage was
added to the samples, the beakers were capped with a plastic covers
and the contents were mixed with magnetic stirrers. Periodically
homogenous subsamples were withdrawn by a plastic syringe and
ltered using 0.45 m syringe lter. The ltrates were analyzed for
Cr(VI) and pH. Two sets of experiments were performed at acid
dosages of 5.5 and 9.2 [H+] eq/Kg COPR.
Geochemical Modeling
Leaching Tests
The objective of these experiments was to study the quantities
of soluble chromium species ultimately released in COPR leachates
at various pH values for a mixing time of 1 wk. Representative
air-dried samples COPR were pulverized to ner than 150 m
(mesh-100). The pulverized COPR samples were mixed with DI
water using a liquid-to-solid ratio of 20. Incremental amounts of
concentrated HCl were added to cover a wide range of pH values.
The mixtures were left on an end-over-end mixer for 1 wk before
the pH values of the mixtures were recorded. The leachates were
analyzed for total Cr and Cr(VI). The residues were submitted for
XRPD analyses. Upon sample acidication, part of the carbonate
species degassed as CO2. The samples were allowed to degas before
they were capped. Duplicate samples were prepared with the same
acid dosage. The duplicate samples were air-dried and the total
carbonate contents were determined using ASTM D5291 (ASTM,
2001). The measured total carbonate concentrations at various pH
values were used in the model calculations.
Another set of leaching tests was conducted to study the release
and exchange of soluble chromium species in COPR leachate for
shorter time scale (minutes). The time scale of these experiments
varied in the range of 0 to 80 h. Representative COPR samples
were air-dried then pulverized to ner than 150 m (mesh-100).
Wazne et al.: Leaching Mechanisms of Cr(VI) from Chromite Ore Processing Residue
2127
Leaching Tests
Chemical formula
Log K
Ca3Si2O4(OH)6
64.92a (1)
Ca4Al2Fe2O10
139.13a (2)
Ca2Al2(OH)10.3H2O
58.19b (3)
CaAl2(OH)8.6H2O
37.99b (4)
Ca4Al2(OH)14.6H2O
107.25b (5)
Ca4Al2(OH)14.12H2O
103.68b (6)
Ca2Al2(OH)6SiO8H8.H2O 49.16c (7)
Ca3Al2(H4O4)3
78.27d (8)
4MgOAl2O310H2O
73.78c (9)
Ca4Al2(OH)12SO4.6H2O 71.97e (10)
CaAl2SiO10.(OH)4
18.07b (11)
7.29f (12)
8.93f (13)
3.9f (14)
10.85f (15)
12.78f (16)
20.37f (17)
11.69f (18)
3.22f (19)
4.28f (20)
Parameters used in the model: Best fit active adsorbent sites = 10.95 mmol/L.
gSurface site (SOH) density = 11 sites/nm2. gSpecific surface area = 600 m2/g.
Source(s): a: Common Thermodynamic Database Project (2004); b: EQ3/6
(Lawrence Livermore National Laboratory [1994]); c: Bennet et al. (1992); d:
Reardon (1992); e: Phreeqc Database, Parkhurst and Appelo (1999); f: David and
Allison (1999); g: Dzombak and Morel (1990).
The results of the short time scale leaching tests are shown in
Fig. 1. For both acid dosages, immediately after acidication the
pH dropped to approximately 3 for the sample with the high
acid dosage and 5 for the sample with the lower acid dosage.
However, the pH values started to increase as the acid is neutralized by the alkalinity of the COPR matrix. It appears that the
pH values stabilized at approximately 8 and 9 for the higher and
lower acid dosages respectively, after approximately 20 h.
The measured Cr(VI) concentrations in the leachates
15 min after the addition of acid were approximately 125 mg/L
and 200 mg/L for the high and low acid dosages, respectively.
Cr(VI) concentrations for both samples reached maximum
values after approximately 2 h. The Cr(VI) concentration of
the COPR sample with the smaller acid dosage (pH 9), peaked
at approximately 240 mg/L and then it decreased to approximately 200 mg/L after 76 h. Conversely, the Cr(VI) concentration in the COPR sample with the higher acid dosage (pH 8)
peaked at approximately 270 mg/L and then it decreased to
approximately 250 mg/L. The moderate decrease in Cr(VI)
concentration of approximately 17% for the lower acid dosage
(pH 9) could be attributed to incorporation of chromate in
stable COPR minerals at that pH. Adsorption is not expected
to play a signicant role at this pH range (Zachara et al., 1987).
In addition, had this decrease been due to adsorption, higher
removal rates would have been expected at the high rather than
the low acid dosage since the rate of adsorption of anions is
known to be greater at lower pH values. This information is
signicant for any remediation scheme incorporating leaching
techniques to solubilize Cr(VI) since no solid phase is reported
to control the solubility of Cr(VI) at pH <10.5.
The results of the long-term leaching tests (1 wk) are presented in Fig. 2 where the concentration of total and hexavalent
chromium (left ordinate) and amount of acid in [H+] eq/Kg
COPR (right ordinate) are plotted vs. pH. Concentration levels
for total Cr and Cr(VI) in the leachate are virtually identical at
pH greater than approximately 5. This indicates that all leached
total Cr in this pH region is in the hexavalent state. At pH values <5, Cr concentration is greater than Cr(VI) concentration.
The dierence between total Cr and Cr(VI) concentrations at
pH values less than approximately 5 is attributed to Cr(III).
Figure 2 indicates that almost all of the chromium was released
when the pH was below 1.5. Approximately 32 equivalents of
acid [H+] per 1 kg of dry COPR were needed to attain pH 1.5.
In addition, the majority of Cr(VI), quantied by alkaline digestion, was leached at pH 8. For example, Cr(VI) concentration
in the leachate was approximately 260 mg/L at pH of 8, with
a liquid-to-solid ratio of 20, meaning that 5200 mg/Kg Cr(VI)
was leached from the COPR sample; constituting approximately
93% of the total leachable Cr(VI). However, the entire Cr concentration was leached at pH < 1.5. The measured Cr concentration was 1100 mg/L which is equivalent to 22,000 mg/Kg.
Table 2. Elemental composition of composite chromite ore processing residue sample B1B2.
Element
Al
Ca
CO32
Cr(VI)
Cr
Fe
Mg
Mn
Na
Si
SO42
4.6
23.9
11.5
0.56
2.1
11.8
0.03
6.1
0.12
0.37
1.98
0.34
2128
Fig. 1. Plot of Cr(VI) concentration and pH as a function of time due to the additions of 5.5 and 9.2 eq/Kg [H+].
Fig. 2. Concentration of Cr and Cr(VI) in the leachates vs. pH after 1 wk of mixing with liquid-to-solid ratio of 20 for composite sample B1B2.
Wazne et al.: Leaching Mechanisms of Cr(VI) from Chromite Ore Processing Residue
2129
Fig. 3. The x-ray diffraction patterns of the residues of the leaching tests at various pH values.
drotalcites through anionic substitution. Even though Cr(VI)ettringite is reported to control the solubility of chromate at
pH >10.4 (David and Allison, 1999; Jing et al., 2006; USEPA,
2006) it was not identied in any of the COPR samples. Conversely, hydrotalcite phases such as quintinite and sjogrenite were
identied in many COPR samples as evidenced by XRPD in Fig.
3 and Table 3, and also by SEM as shown in Fig. 4.
The SEM images indicated the presence of hydrotalcite
phases with extensive chloride substitution in the interlayers
probably due to the use of HCl in the ANC tests. However, the
chromium peak at approximately 5.4 keV could be due to the
substitution of CrO42, Cr3+ or both in the crystal structure.
Hydrotalicte has platy like hexagonal structure as shown clearly
in Fig. 4. The crystals were clearly identied at pH 10.9, but as pH
decreased it seems that the crystal size decreased and there appears
to be some disorder in addition to some coating. In general, hydrotalcite crystals were more dicult to identify at lower pH values.
Modeling
The diuse double layer surface complexation model (Dzombak and Morel, 1990; USEPA, 2006) is used to describe Cr(VI)
adsorption data. Carbonate adsorption is incorporated into the
model since carbonate is reported to adsorb onto iron hydroxides (Zachara et al., 1987; Van Geen et al., 1994; Wijnja and
Schulthess, 2001). Silicate has also been reported to adsorb onto
iron hydroxides (Meng et al., 2000) and therefore it is included
in the model. The total concentration of iron and aluminum in
the leaching solution are 98.21 and 87.03 mM, respectively.
The calculated best t for the active adsorbent concentration is 10.95 mM, which indicates that the molar ratio of the
active sites to the total iron and aluminum concentration is
<6% It is worth noting that the adsorption sites are not assumed to associate with any specic solid phase.
Brownmillerite was the major mineral phase observed in the
residues of the leaching tests. However, brownmillerite is not
2130
Table 3. Rietveld quantification of minerals and phases in the residues of the leaching tests.
pH
Mineral phases
Calcium aluminum oxide chromium hydrate
Brownmillerite
Brucite
Calcite
Hydroandradite
Katoite
Periclase
Quartz
Quinitinite-2H
Sjoegrenite
Albite
Gibbsite
Percent crystalline phases
Noncrystalline phase
Percent total
12.03
11.04
10.58
9.35
8.30
7.76
6.42
5.24
%
0.87
26.82
2.84
8.53
3.19
2.61
2.21
3.19
1.22
1.45
5.17
0.69
33.84
3.64
6.04
3.98
3.77
2.40
3.64
1.65
1.85
7.00
28.47
2.14
6.38
2.31
2.09
2.09
2.73
1.66
1.23
4.50
29.66
1.87
6.84
1.62
0.69
37.16
1.41
7.18
1.59
0.47
37.94
0.74
6.84
33.99
0.81
5.01
20.57
3.15
0.64
4.72
4.72
3.95
4.27
4.42
4.41
1.47
5.59
1.14
6.04
0.86
8.78
58.11
41.94
100.06
68.50
31.37
99.86
53.62
46.38
100.00
49.18
50.82
100.00
58.83
41.11
99.94
56.97
43.03
100.00
53.86
46.14
100.00
0.60
7.11
1.67
35.53
64.47
100.00
1.17
Fig. 4. Scanning electron microscopy (SEM) images of the leaching residue at pH 10.9 and pH 9.4.
Wazne et al.: Leaching Mechanisms of Cr(VI) from Chromite Ore Processing Residue
2131
Fig. 5. Model prediction of Cr(VI) concentration as function of pH for the leaching tests.
2132
Fig. 6. Model prediction of mineral phases, present in the residues of the leaching tests for composite sample B1B2, at various equilibrium pHs.
Conclusions
The leaching mechanism of Cr(VI) from COPR was investigated using the XRPD analyses and geochemical modeling.
The model was able to simulate the adsorption edge at approximately pH 5 and the precipitation edge at approximately
pH 11. The experimental and modeling results suggested the
presence of a mineral phase controlling the solubility of Cr(VI)
in the pH region 8 < pH < 11. Experimental results indicated
that hydrotalcite may be controlling the solubility of chromate
though anionic exchange in that pH region. The COPR, at the
deposition sites, is expected to continuously leach Cr(VI) at a
concentration equivalent to the solubility of Cr(VI) with respect Cr(VI)-hydrocalumite. If pH were to drop below pH 11,
signicant increase in Cr(VI) leaching will ensue; however, this
seems unlikely due to the high buering capacity of COPR.
Finally, all chromium was released when 32[H+] eq/Kg of acid
was added to the COPR matrix. This information is very useful
for stabilization or recovery of chromium in COPR matrices.
Acknowledgments
The authors wish to thank Honeywell International Inc.
for the nancial support of this study.
Wazne et al.: Leaching Mechanisms of Cr(VI) from Chromite Ore Processing Residue
2133
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