Mineralogy
Overview
Jarofix: Addressing Iron Disposal in
the Zinc Industry
Sylvain Seyer, Tzong T. Chen, and John E. Dutrizac
In the Jarofix process, jarosite precipitates
made during the leaching of zinc ferrites are
mixed with preset ratios of Portland cement,
lime, and water. The reaction generates a
chemically and physically stable material,
reducing the long-term liability associated
with iron residue disposal while offering
concomitant processing advantages. Sup-
porting mineralogical studies of aged Jarofix
products indicate that jarosite reacts with
the alkaline constituents of the cement to
form various stable phases that incorporate
zinc and other soluble metals. The persis-
tence of alkaline phases in the Jarofix product
helps to ensure its long-term environmental
stability.
INTRODUCTION
More than 80% of the world’s annual
zinc output of approximately 8 million
tonnes is made using the roast-leach-
electrolysis process. In the roasting part
of the process, combustion of the sulfur
contained in the concentrates with air at
temperatures >900∞C allows its conver-
sion to SO2 and, subsequently, to sulfu-
ric acid. Much of the zinc is converted to
ZnO in the roasting operation, but a
significant percentage reacts with the
inevitable iron impurity to form zinc
ferrite, ZnFe2O4. Although the ZnO dis-
solves readily in dilute H2SO4 media, the
ZnFe2O4 requires hot concentrated acid
to effect its dissolution. These aggres-
sive conditions also result in the dissolu-
Figure 1. Jarofix process block diagram.
32
Figure 2. The block diagram for the fixation of
jarosite residues.
tion of the associated iron, which must
be eliminated from the solution to pre-
vent its persistent accumulation. Over
the years, the zinc industry has devel-
oped a number of technologies, such as
the jarosite process, to precipitate the
dissolved iron in a readily filterable
form.1 However, the jarosite precipitate,
as formed, is not physically stable, and it
entrains soluble salts of zinc, cadmium,
and lead. Consequently, it must be stored
in specially constructed ponds with on-
going monitoring and
maintenance.
Canadian Electrolytic
Zinc (Noranda, CEZinc)
is one of the largest zinc
producers in the world.
The refinery, situated in
Valleyfield, Quebec, has
an annual capacity of
260,000 tonnes of zinc,
500,000 tonnes of sulfu-
ric acid, 500 tonnes of cad-
mium, and 5,000 tonnes
of copper residue. The
iron contained in the zinc
concentrates is elimi-
nated in the conversion
circuit as sodium jarosite,
at a rate of 160,000 t/y.
Studies undertaken in
1993 to identify a long-
term solution for residue
disposal led to the selec-
tion of the Jarofix process.2 This stabili-
zation/solidification process was suc-
cessfully integrated into the existing op-
erations in 1998. Characterization results
on fresh Jarofix, as well as on cured
Jarofix stored in a disposal area near the
plant site, have confirmed the chemical
and physical stability of the Jarofix prod-
uct, as detailed below.
THE PROCESS
Leaching Circuit
Noranda, CEZinc employs a three-
stage counter-current leaching process.
Zinc oxide contained in the calcine is
recovered in the first two stages, which
consist of a neutral leach and a low-acid
leach. The zinc ferrites are leached in the
third, or conversion, stage, where iron is
simultaneously precipitated with so-
dium carbonate as sodium jarosite. The
jarosite residue is separated from the
solution in a series of thickeners to re-
cover most of the soluble zinc sulfate.
The final thickener underflow is the feed
to the residue filtration circuit, wherein
the jarosite residue, together with the
residue from the basic zinc sulfate cir-
cuit, is de-watered and washed on three
64.5 m2 vacuum belt filters. The filtrates
from the filters are recycled to the leach-
ing circuit to recover their zinc units. A
partial filtrate bleed maintains the plant
inert and volume balances. The well-
washed residue is then transferred to the
Jarofix circuit for stabilization/solidifi-
cation, as is illustrated in Figure 1.
Residue Fixation, Transportation
and Disposal
The residue from the filtration opera-
tion is sequentially re-slurried, and then
mixed with lime and Portland cement in
Table I. Average Compositions of the
Unreacted and Reacted Sodium Jarosite
(wt.%)*
Unreacted Reacted
Element Na-Jarosite** Na-Jarosite***
Fe 30.95 33.86
Na 2.51 2.76
SO4 35.85 24.36
Ca <0.01 1.96
Si 0.11 0.88
Al 0.11 0.11
Zn 0.66 1.02
* Electron-microprobe-determined
** Jarosite Residue
*** Jarofix Product
JOM • December 2001
preset ratios; Figure 2 illustrates the mix-
ing sequence used. The partial decom-
position of the jarosite residue by reac-
tion with the Portland cement guaran-
tees the long-term chemical and physi-
cal stability of the Jarofix product.
The residue leaving the Jarofix mixing
circuit is transferred to trucks for trans-
portation to the disposal area, which is
shown in Figure 3. The paste is unloaded
from the trucks and is stockpiled on
Noranda, CEZinc property near the plant
site, where curing of the Jarofix product
occurs over several months.
Proper washing and adequate mixing
of the washed jarosite residue with Port-
land cement and lime give the resulting
Jarofix product good mechanical
strength, low hydraulic conductivity,
high neutralizing capability and long-
term chemical stability. Jarofix is consid-
ered an inert solid waste and does not
require the high security cell that a
jarosite residue would necessitate. Rain-
fall contacting the Jarofix stockpile is
collected and analyzed to confirm envi-
ronmental compliance of the disposal-
area effluent.
CHARACTERIZATION OF
THE JAROFIX PRODUCTS
Mineralogical Characterization
Detailed mineralogical studies of the
Jarofix products have been reported pre-
viously.3,4 After three months of curing,
Jarofix products still contain small
amounts of moisture; however, they al-
ready have developed a good compres-
sive strength and low permeability.
The products consist of major amounts of
partly reacted sodium jarosite and
gypsum, together with minor amounts
of Ca-Al-Fe silicate-sulfate-hydrate,
Ca6Fe2(SO4)3(OH)12.nH2O (sturmanite, an
ettringite-type compound), and traces of
ZnFe2O4, Ca-Al-Fe oxide, Fe2O3, Ca-Fe
sulfate, quartz, ferric oxyhydroxide,
Ca(OH)2, calcite, and unreacted cement.
Figure 4 shows the Jarofix product after
three months of curing. The smaller
(1–6 mm) particles are partly reacted so-
dium jarosite; the large, lath-like crystals
are gypsum, which were added to the
mixture during Jarofix preparation; and
Figure 3. The Jarofix disposal area as it existed in August 2000.
2001 December • JOM
Table II. Average Compositions of the
Calcium-Silicate Phase in Portland
Cement and the Ca-Al-Fe Silicate-
Sulfate-Hydrate Cement Reaction
Product (wt.%)*
Portland Cement
Element Cement Reaction Product**
Ca 49.96 10.64
Si 11.70 8.26
Fe 0.66 4.83
SO4 0.12 9.81
Na 0.08 0.78
Zn 0.04 1.53
Mg 0.90 1.76
Al 0.73 1.31
* Electron-microprobe-determined
** Jarofix Product
the large, dark grains are various Ca-Al-
Fe silicate-sulfate-hydrate cement reac-
tion products. The rare, tiny, bright par-
ticles are zinc ferrite or hematite. Most of
the cement particles have reacted, and
nearly all the sodium jarosite particles
have partly reacted, despite the fact that
only approximately 30% of the original
mass of sodium jarosite has been con-
verted to other species. Generally, the
cement has completely reacted with wa-
ter and sodium jarosite to form Ca-Al-Fe
oxide and various Ca-Al-Fe silicate-sul-
fate-hydrate phases. The initial large frag-
ments of cement have disintegrated into
smaller particles of new compounds,
which are dispersed among the reacted
sodium-jarosite particles. These fine-
grained new compounds, together with
newly formed gypsum and Ca-Fe sul-
fate, constitute the interstitial material
between the partly reacted jarosite par-
ticles. The fine-grained interstitial phases
bond the various particles and give the
Jarofix product its mechanical strength
and low permeability. Figure 5 shows the
morphology of the reacted sodium-
jarosite particles. Although the external
morphology of the particles seems to re-
main unchanged during the cement-
jarosite reaction, the sodium jarosite
has undergone a significant chemical al-
teration. The slightly darker phase
(matrix) is mainly residual sodium
jarosite, whereas the brighter phase is
an iron-oxide-rich phase mixed with
Ca6Fe2(SO4)3(OH)12.nH2O (dark). The
reaction has taken place
throughout the mass of
the jarosite, and the reac-
tion sites appear to be ran-
domly distributed. By
contrast, the unreacted
sodium jaro-site before
Jarofix formation is both
chemically and morpho-
logically uniform.
Table I presents the
average bulk composi-
tion of the reacted so-
dium-jarosite particles as
well as the initial compo-
sition of the sodium
jarosite before Jarofix for-
mation; the iron content of the reacted
sodium-jarosite particles increases
slightly and the sulfate content decreases
significantly, relative to the unreacted
jarosite. The reaction products are en-
riched in calcium and silicon, and this
indicates that soluble silicate species from
the cement diffuse into the jarosite par-
ticles and react therein. Significantly,
the sodium in the original sodium
jarosite remains in the reaction product,
likely occurring as Na2SO4 or substituting
for calcium in the Ca6Fe2(SO4)3(OH)12
.nH O phase.
2
Sodium jarosite and Portland cement
react in the presence of water. The so-
dium jarosite reacts with the alkaline con-
stituents of the cement to form ferric
oxyhydroxide, the Ca6Fe2(SO4)3(OH)12
.nH O phase, and Na SO , which further
2 2 4
reacts to form gypsum:
2NaFe3(SO4)2(OH)6 + 6 Ca(OH)2
+ nH2O Æ
Na2SO4 + Ca6Fe2(SO4)3(OH)12.nH2O
+ 4Fe(OH)3 (1)
Na2SO4 + Ca(OH)2 + 2H2O Æ
CaSO4.2H2O + 2Na(OH) (2)
2Fe(OH)3 Æ Fe2O3.3H2O (3)
2➔
➔
5
➔
4
➔
3 6
2
➔
1
100 mm
Figure 4. The general morphology of the
commercial Jarofix product after three months
of curing (polished section). 1—ZnFe2O4, 2—
Ca-Al-Fe silicate-sulfate-hydrate cement re-
action product, 3—reacted sodium jarosite,
4—gypsum, 5—Ca-Al-Fe oxide, 6—Fe2O3.
1
2
➔
3
10 mm
Figure 5. The detailed morphology of reacted
sodium-jarosite particles in the commercial
Jarofix product after three months of curing
(polished section). 1—sodium jarosite, 2—Na-
Ca-Fe-Si-SO4 reaction product, 3—iron-ox-
ide-rich phase.
33

Table III. Average Compositions of the Cement Reaction Products in the Laboratory
Jarofix Products Relative to the Composition of the Calcium-Silicate Phase in Portland
Cement (wt.%)*
Portland Cement
Element Type-X
Fe 0.49
Ca 47.65
SO4 0.24
Na 0.11
Si 11.66
Al 1.30
Zn <0.01
Mg 0.92
* Electron-microprobe-determined
Fe(OH)3 + Si(OH)4 Æ FeSi(OH)7 (4)
The Ca6Fe2(SO4)3(OH)12.nH2O phase is
stable only in the “wet” Jarofix products,
which still contain small amounts of
moisture. An amorphous iron-oxide spe-
cies, such as Fe(OH)3, is produced, but
this species likely reacts further to form
amorphous iron oxides or complex sili-
cate species as suggested by Equations 3
and 4. Portland cement also reacts with
sodium jarosite, in the presence of water,
to form various Ca-Al-Fe silicate-hy-
drate-hydrate phases and Ca-Al-Fe ox-
ide. Table II presents the composition of
the Ca-Al-Fe silicate-sulfate-hydrate
phase and the initial composition of the
Portland cement. The cement reaction
product (i.e., the Ca-Al-Fe silicate-sul-
fate-hydrate phase) shows a marked in-
crease in its SO4, Fe and Na contents, but
indicates a major reduction in the cal-
cium and silicon contents, in compari-
son to the initial cement composition.
The implication is that the iron, SO4 and
sodium from the decomposed sodium
jarosite diffuse into, and react with, the
cement particles to form various Ca-Al-
Fe silicate-sulfate-hydrate phases and/
or gypsum. Water-soluble ZnSO4 and
water-soluble magnesium are stabilized
in the cement reaction products. The
greater the amount of water-soluble zinc
in the jarosite residue, the higher are the
zinc and SO4 contents of the cement reac-
tion products. The implication is that
zinc is structurally incorporated in the
Ca-Al-Fe silicate-sulfate-hydrate phase,
and hence, that the zinc is immobilized.
A trace amount of unreacted cement is
present, and this provides residual neu-
tralization capacity for any acid species
remaining in the Jarofix product.
To evaluate the long-term stability of
the Jarofix products, aged material was
studied that was prepared previously in
the laboratory, cast into cylindrical molds,
cured under ambient conditions for >56
days, and then stored for various periods
after curing. In comparison to the freshly
cured products, the aged products are
compact, dry and harder; however, they
exhibit similar micro-textures to those of
the freshly cured products. Figure 6 shows
the general morphology of a Jarofix prod-
uct after more than six years of storage.
34
Cured for Stored for
~ 3 Months ~ 6 Years
2.38 2.37
11.02 4.19
2.67 3.81
0.83 0.59
11.95 13.02
0.97 1.29
1.96 2.33
1.12 2.34
The product is compact, exhibits few frac-
tures and is uniform in micro-texture.
Although more than six years old, the
product consists of essentially the same
species as those present in the freshly
cured products, except for the absence of
the Ca6Fe2(SO4)3(OH)12.nH2O phase and
residual cement; however, it contains
more gypsum, calcite, cement reaction
products (Ca-Al-Fe silicate-sulfate-hy-
drate phase), and Ca-Fe sulfate. The re-
sidual cement particles have been con-
verted to various Ca-Al-Fe silicate-sul-
fate-hydrate phases; the original large
particles have disintegrated into smaller
grains, which are dispersed among the
interstices of the reacted sodium-jarosite
particles. Figure 7 shows the morphol-
ogy of the reacted sodium-jarosite par-
ticles after approximately six years of
storage. The gross outlines of the reacted
sodium-jarosite particles remain essen-
tially unchanged from those of the freshly
cured product. However, the reacted
sodium-jarosite particles have lower
iron, calcium and SO4 contents than those
of the freshly cured product, and the
reacted particles are depleted in the
Ca6Fe2(SO4)3(OH)12.nH2O phase. They
appear to contain only residual sodium
jarosite and an iron-oxide-rich phase.
This phase assemblage becomes more
apparent in Jarofix products stored for
more than six years, in which the reacted
sodium-jarosite particles consist pre-
➔
➔ 9 ➔
8
7
6
➔ 4
➔
5
3 1,2➔
➔
➔
4 7
➔
2 1
➔
8
1 1
➔
11 10
100 mm
Figure 6. The general morphology of the labo-
ratory Jarofix product after more than six years
of storage (polished section). 1—reacted so-
dium jarosite, 2—gypsum, 3—Fe2O3, 4—
quartz, 5—ZnFe2O4, 6—SnO2, 7—sphalerite,
8—reacted cement compound, 9—Ca-Al-Fe
oxide, 10—CaCO3, 11—basic iron sulfate.
dominantly of residual sodium jarosite
and an iron-oxide-rich phase. Long-term
storage not only reduces the amount of
the Ca6Fe2(SO4)3(OH)12.nH2O phase, but
it also improves the stability of the iron
species by the formation of an iron ox-
ide-rich phase. Figure 7 also shows that
more gypsum is produced during stor-
age. Table III presents the compositions
of the cement reaction products after
various periods of storage. The cement
reaction products in the freshly cured
(three months) Jarofix product show a
major decrease in calcium, but exhibit a
significant enrichment in their Fe, SO4,
Na, Zn, and Mg contents in comparison
to the initial Portland cement composi-
tion. After approximately six years of
storage, the cement reaction products
show a further reduction in calcium, and
a further increase in their zinc and mag-
nesium contents, implying that more
water-soluble zinc and magnesium are
stabilized in the cement reaction prod-
ucts and that more gypsum is formed.
Occasionally, trace amounts of calcite
are present in the freshly cured Jarofix
products. Calcite forms from the air-car-
bonation of Ca(OH)2, which is a common
hydration product of Portland cement.
Aged Jarofix products contain relatively
greater amounts of calcite. Figure 8 shows
6
➔
5
➔
4 1
➔
2
4
3
10 mm
Figure 7. The detailed morphology of the labo-
ratory Jarofix product after approximately six
years of storage (polished section). 1—re-
sidual sodium-jarosite, 2—iron oxide-rich
phase, 3—Ca-Fe sulfate, 4—gypsum, 5—
ZnFe2O4, 6—reacted cement compound.
6
➔
4 3
5
➔
➔
➔
➔
3 2 5
10 mm
Figure 8. The detailed morphology of the labo-
ratory Jarofix product after approximately six
years of storage (polished section). 1—CaCO3,
2—(Mg,Ca)CO3, 3—gypsum, 4—reacted so-
dium jarosite, 5—reacted cement compound,
6—ZnFe2O4, 7—Fe2O3.
JOM • December 2001
 the zinc industry for the treatment of
Table IV. Leachate Results for Samples Collected from the Jarofix Stockpile leachable iron residues. Its chemical and
in 2000 and 2001 (mg/L)
physical stability significantly reduce the
TCLP 1311 Test TCLP 1312 Test long-term liability associated with wa-
Element 2000 2001 2000 2001 ter infiltration, underground water and
Al <0.1–0.2 <0.1–0.2 0.1–0.3 0.2–0.3 soil contamination, and wind erosion.
As 0.02–0.06 0.03–0.04 <0.01–0.03 0.01–0.03 Furthermore, the technology offers con-
Be <0.01 <0.01 <0.01 <0.01 comitant process advantages, such as in-
Cd <0.005 <0.005–0.006 <0.005 <0.005 creased zinc recoveries, improved plant
Co 0.09 0.09–0.10 <0.02–0.04 0.03–0.04 volume and inert balances, enhanced
Mn 0.02–0.03 0.05–0.20 <0.01–0.02 0.01 impoundment management, and the
Ni <0.01 <0.01 <0.01 <0.01
Pb <0.05 <0.05 <0.05 <0.05
production of a stabilized residue.
Zn 0.01–0.03 <0.01–0.12 0.01–0.03 <0.01 ACKNOWLEDGEMENTS
several calcite particles present in a Jarofix stockpiled is still inert chemically, as The study was part of a joint project among
product after approximately six years of indicated in Table IV, which presents the CANMET, Noranda, CEZinc and the
storage. The calcite occurs as approxi- results for the leachates from the TCLP Noranda Technology Centre. The authors
mately 20 mm particles and cements the 1311 and TCLP 1312 leaching tests for thank Noranda Inc., CEZinc for encourag-
reacted jarosite particles. The morphol- samples collected from the Jarofix stock- ing the publication of this work, and M.J.
ogy implies that the calcite formed dur- pile in 2000 and 2001. The stockpiled Agnew and L.I. Rosato of Noranda Inc.,
ing the storage of the Jarofix product. Jarofix product is also subjected to peri- CEZinc for their technical advice.
Also shown in Figure 8 are several calcite odic physical characterization tests
References
particles, containing cores of (Mg,Ca)CO3, (uunconfined compressive strength, hy-
1. J.E. Dutrizac, “The Iron Control Problem in Zinc Hydro-
that are associated with the reacted ce- draulic conductivity). After three years, metallurgy, and Possible Solutions,” Acta Metallurgica Slovaca.,
ment compounds. The presence of a mag- the Jarofix stockpiled at the disposal site 2 (2) (1996), pp. 88–102.
2. L.I. Rosato and M.J. Agnew, “Iron Disposal Options at
nesium-rich core in the calcite implies has not shown any sign of physical deg- Canadian Electrolytic Zinc,” In Iron Control and Disposal, eds.
that water-soluble magnesium is stabi- radation despite the extreme Canadian J.E. Dutrizac and G.B. Harris (Montreal, Canada: The Cana-
dian Institute of Mining, Metallurgy and Petroleum, 1996),
lized, at least in part, as a carbonate in the weather conditions prevalent in the re- pp. 77–89.
Jarofix products. The presence of calcite gion. Because the physical characteriza- 3. T.T. Chen and J.E. Dutrizac, “Mineralogical Study of
Jarofix Products for the Stabilization of Zinc Industry Jarosite
and magnesium-bearing carbonate re- tion of the Jarofix stockpile is a reliable Residues,” Second Int. Symp. Extraction and Processing for the
flects the alkaline environment of the indication of the ability of the stabilized Treatment and Minimization of Wastes, eds. V. Ramachandran
and C.C. Nesbitt (Warrendale, PA: TMS, 1996), pp. 659–672.
Jarofix products, and suggests that the residue to resist chemical attack, the con- 4. T.T. Chen and J.E. Dutrizac, “A Mineralogical Study of
stored Jarofix retains the ability to neu- sistency of the results from the annual Jarofix Products for the Stabilization of Jarosite Residues for
Disposal,” Lead-Zinc 2000, eds. J.E. Dutrizac et al. (Warrendale,
tralize residual acid species. campaigns is promising for the long- PA: TMS, 2000), pp. 917–933.
term behavior of Jarofix. Tzong Chen and John Dutrizac are research scientists in
Chemical and Physical
the Mining and Mineral Sciences Laboratories of
Characterization CONCLUSIONS CANMET; they specialize in mineralogical characteriza-
The Jarofix product stockpiled in the By the end of 2001, the Jarofix process tion and metallurgical processing. Sylvain Seyer is a
senior process metallurgist at Noranda, CEZinc special-
disposal area is subjected to various will have undergone five years of labo- izing in operations support and project management.
chemical-leaching tests (Water Leach- ratory and pilot testing, followed by three
For more information, contact T.T. Chen,
ing Test, TCLP 1311, Method 1312, BC years of successful operation and envi- CANMET, 555 Booth Street, Ottawa, Ontario,
Initial Test, Dynamic Leach Test) on a ronmental compliance. The Jarofix pro- Canada K1A OG1: (613) 995-9490; e–mail
regular basis. After three years, the Jarofix cess represents a major breakthrough in tchen@nrcan.gc.ca.

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2001 December • JOM 35