Hydrometallurgy 157 (2015) 292–297

Contents lists available at ScienceDirect

Hydrometallurgy

journal homepage: www.elsevier.com/locate/hydromet

Reductive dissolution of magnetite and jarosite by Acidiphilium

cryptum JF-5
Ernesto González a,⁎, Amalia Espada b, Jesús Ángel Muñoz b, María Luisa Blázquez b,
Felisa González b, Antonio Ballester b
a
School of Biochemical Engineering, Pontificia Universidad Católica de Valparaíso, Avenida Brasil 2085, Valparaíso, Chile
b
Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica, Facultad de Ciencias Químicas, Universidad Complutense, Av. Complutense s/n, 28040 Madrid, Spain

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

Article history: Nowadays there is an increasing interest for applying iron reducing bacteria to hydrometallurgical processes.
Received 13 February 2015 Although most isolated bacteria grow at circumneutral pH, Acidiphilium cryptum is able to reduce iron oxides
Received in revised form 27 July 2015 in acidic environments and promote its dissolution.
Accepted 2 August 2015
In this study, the reductive dissolution of magnetite and jarosite by A. cryptum JF-5 was tested in two culture
Available online 11 August 2015
media, over a period of 38 days with 1% pulp density. In a medium without oxalic acid, bacteria were crucial to
Keywords:
increase the magnetite and jarosite dissolution from 0.2 and 0.3% to 20.4 and 2.5%, respectively. In a medium
Acidiphilium cryptum containing oxalic acid, the abiotic dissolution of magnetite and jarosite (1.6 and 2.0%, respectively) was clearly
Reductive dissolution surpassed in the inoculated tests (to 26.9 and 10.4%, respectively).
Jarosite The pH control was essential to attain a significant degree of magnetite dissolution. A stoichiometric ratio
Magnetite between sulfuric acid consumed and iron dissolved was obtained for both solids tested. Finally, magnetic stirring
Oxalate tests pointed out that the dissolution process was kinetically controlled by the solid surface.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
Currently, iron is the largest metal produced in the world, account-
ing almost for 109 Mg/year (Gerst and Graedel, 2008), mainly obtained
from hematite (Fe2O3) and magnetite (Fe3O4) through pyrometallurgy.
This process consumes 21.9 GJ/t of extracted iron (Norgate and
Jahanshahi, 2010), with coal as the main energy source. Hence, the
steel industry is responsible for the highest share of CO2-emissions
from the manufacturing sector, about 27% (IEA, 2007). Other mining
industries, among them copper (Dresher, 2001) and gold (Xie et al.,
2009), have successfully implemented hydrometallurgical processes,
which are generally recognized to produce less environmental impact
and be able to beneficiate low grade ores.
Hematite is the preferred raw material in iron pyrometallurgy, as it
is easily excavated and separated from gangue, and because it provides
a significantly more efficient mining and beneficiation procedure, while
magnetite and taconite need previous stages: crushing, screening,
grinding, magnetic separation, filtering and drying (Duade, 2011).
The know-how of the copper hydrometallurgy could be used as a
starting point to develop a hydrometallurgical route for benefiting
iron ores, which may involve the iron leaching from their ores, followed
by the recovery of dissolved iron through electrowinning (Cardarelli,
⁎ Corresponding author at: Escuela de Ingeniería Bioquímica, P. Universidad Católica de
Valparaíso, Av. Brasil 2085, Valparaíso, Chile.
E-mail address: ernesto.gonzalez@ucv.cl (E. González).
2008, 2011; Eisele, 2005). According to the characteristic of the preg-
nant leach solution, an intermediate stage of solvent extraction could
be also needed to remove impurities or increase iron concentration
(Dresher, 2001).
Since iron is commonly found in nature as Fe(III), the ability of some
microorganism to reduce these compounds could be the key to achieve
their dissolution (Eisele and Gabby, 2014; Lovley et al., 2004). Being
most of these microorganisms chemoorganoheterotroph (Heijnen,
1999), organic matter can be used as a source of carbon, energy and
electrons for their metabolism and the Fe(III) reduction.
Jarosite is a family of iron rich compounds with the chemical formula
MFe3(SO4)2(OH)6, where M represents: monovalent cations (e.g. Na+,
K+, Rb+, H3O+, NH+ + +
4 , Ag , Tl ), 0.5Pb
2+
or 0.5Hg2+ (Dutrizac, 1999).
Despite the fact that this mineral is naturally present in acidic soils
and mine waste formed by oxidation of sulfide minerals (Swayze
et al., 2008), the roast/leach/electrowin process for zinc production
generates high amounts of jarosite waste.
There is an increasing interest to recover metals such as Zn, Ag, Pb,
Cu, Cd and Fe (Ahern and Schaekers, 2004; Castro et al., 2013; Ju et al.,
2011; Nheta and Makhatha, 2013; Peters et al., 1992) from this kind of
residues, which usually are stored in lined ponds to avoid environmen-
tal hazards (Vyas, 2011).
Among the iron reducing bacteria, Shewanella spp. and Geobacter
spp. have been widely studied (Bingjie et al., 2014; Bonneville et al.,
2006; Lovley et al., 2011). In contrast, there are fewer works on
Acidiphilium cryptum (Bridge and Johnson, 2000; Küsel et al., 1999), an

http://dx.doi.org/10.1016/j.hydromet.2015.08.003
0304-386X/© 2015 Elsevier B.V. All rights reserved.
 E. González et al. / Hydrometallurgy 157 (2015) 292–297 293

acidophilic bacterium able to reduce Fe(III) even in the presence of ox-
ygen. Early studies performed with Acidiphilium sp. focused on variables
such as: mineral phases, direct contact, pH and ligands (Bridge and
Johnson, 2000).
In this work the dissolution of magnetite and jarosite was tested
under abiotic and biotic (A. cryptum JF-5) conditions, using two culture
media and different stirring modes. Thereby, these solids could be used
as starting materials for a hydrometallurgical route of iron extraction, as
was previously proposed by Laguna et al. (2011).
2. Materials and methods
2.1. Bacterial strain and culture media
Unless otherwise mentioned, the pH was controlled off-line adding
to the vials different portions of 0.5 mol/L H2SO4. The amount of acid
added was calculated from the pH measurement and titration curves
previously obtained for both media.
2.4. Different shake modes
The solid dissolution was also assayed in E/Ox medium at room tem-
perature both statically and under different shake modes: an orbital
shaker (150 RPM), magnetic stir bars (triangular section bar and
250–350 RPM) and a homemade stirring “Ferris” wheel (40 RPM),
where the vials fit parallel and perpendicular to the shaft, similar to a
shaking hybridization incubator (supplementary data).

A. cryptum JF-5, kindly supplied by Prof. W. Sand (University of
Duisburg-Essen), was grown in E medium, containing per liter: 2.0 g
(NH4)2SO4, 0.1 g KCl, 0.5 g K2HPO4, 0.5 g MgSO4·7H2O, 0.3 g yeast
extract and 3.0 g glucose. The pH was adjusted to 2.4 with H2SO4, and
later the medium was autoclaved at 121 °C for 15 min. Bacterial cells
used as inocula in dissolution experiments were pre-grown aerobically
in cotton plugged flasks containing E medium, using an orbital incuba-
tor at 150 RPM and 35 °C. The E/Ox medium, with a similar composition
to E medium but containing 2 mmol/L of oxalic acid, was sterilized by
filtration, adjusting previously its pH to 2.4 by H2SO4.
2.5. Ore and solid residue analysis
The total extractable iron was determined in triplicate by complete
digestion of both solids in warm nitro-hydrochloric acid, followed by
AAS analysis. Untreated solids and residues were analyzed by X-ray
diffraction (XRD) and scanning electron microscopy (SEM) to deter-
mine crystalline phases and morphology. The particle-size distribution
was measured using the Malvern Mastersizer 2000 equipment.
3. Results

2.2. Preparation and disinfection of ferric solids 3.1. Magnetite dissolution in orbital shaker

Museum grade magnetite was kindly provided by Dr. Joan Viñals The iron extraction, pH and pE + pH (pE: the negative logarithm of
(University of Barcelona). Its chemical and mineralogical composi- the electron activity) profiles for experiments carried out with magne-
tions were determined by X-Ray Fluorescence (XRF) and X-ray dif- tite in E and E/Ox media are shown in Fig. 1; while total dissolved iron
fraction (XRD), respectively. The ore was ground, sieved (particle
size b 0.090 mm) and stored in capped bottles at room temperature.
Jarosite was synthesized in a bioreactor in the presence of a culture
of Sulfolobus metallicus, grown at 65 °C in 9K medium (Silverman and
Lundgren, 1959); with stirring and aeration rates of 700 RPM and 0.5–
0.8 vvm (air volume flow per unit of liquid volume per minute), respec-
tively. The pH was periodically adjusted to 1.8–2.0 adding NH4OH (30%,
w/v). The jarosite was collected, washed (using distilled water), dried
(at 105 °C overnight), sieved (particle size b 0.090 mm) and stored in
capped bottles at room temperature.
Empty vials (100 mL useful volume) were capped with aluminum
foil and autoclaved (121 °C and 15 min). Then, 0.60 g of ore was trans-
ferred to sterile vials and covered with ethanol (96%, v/v) for three days.
Finally, the capped vials containing the solids were placed on a drying
oven (90–100 °C over night) to evaporate the ethanol.

2.3. Culture conditions and sampling

All experiments were carried out in duplicate at 1% pulp density,

adding 60 mL of medium to the vials containing ore. Once vials were
capped with butyl rubber stoppers and sealed with crimp-caps, the
experiments were performed in an orbital incubator at 35 °C and
150 RPM, except when different shake modes were studied. The initial
bacterial population for inoculated vials was 1 · 108 cell/mL, determined
through a Neubauer improved counting chamber (depth 0.01 mm).
Before sampling, vials were shaken and the ore was allowed to
settle, while rubber stoppers were disinfected externally with ethanol
(96%, v/v). The supernatant was sampled using previously deoxygenat-
ed sterile syringes, ensuring the replacement of the volume of sample
(2 mL) with a N2:CO2 gas mixture (80:20, v/v). An aliquot was immedi-
ately diluted (1:10, 1 mol/L HCl) to measure Fe(II) and total dissolved
iron by the ferrozine method (Stookey, 1970) and atomic absorption Fig. 1. Extracted iron (A), pE + pH (B) and pH (C) profiles for magnetite dissolution in E
(□,■,▲) and E/Ox (○,●) media. Solid and hollow symbols represent A. cryptum JF-5
spectroscopy (AAS), respectively. The redox potential (combined gold inoculated vials and abiotic controls, respectively. Results obtained when pH was not
electrode — Ag/AgCl, KCl 3 mol/L) and pH were measured in the remain- controlled (▲) are also included. The pH 2.4 after each H2SO4 addition (arrow) was
ing sample. estimated.
294 E. González et al. / Hydrometallurgy 157 (2015) 292–297

(FeTotal) and Fe(II) profiles are displayed in the supplementary data

(Fig. S1). According to Fig. 1, the presence of A. cryptum and a systematic
pH control was essential to achieve a high yield of iron dissolution.
The addition of oxalic acid to the medium caused a slight chemical
dissolution of magnetite (abiotic tests) and the disappearance of the
plateau observed in inoculated vials containing E medium between
days 10 and 20.
Magnetite characterization by XRF and acid digestion showed a
similar iron content (68.8 and 71.7 ± 2.1% w/w Fe, respectively). Iron
extraction in Fig. 1 is referred to the iron content determined by acid
digestion. The XRD analysis revealed the presence of magnetite with
low amounts of hematite and wüstite (supplementary data Fig. S2).
SEM micrographs of magnetite residues (supplementary data Fig. S3)
showed that particles obtained from the experiment where pH was
not controlled were partially covered by a new solid phase, identified
by XRD as siderite (supplementary data Fig. S2). Finally, Fig. 2 shows
the theoretical and experimental relationships between extracted iron
and consumed H2SO4.

3.2. Jarosite dissolution in orbital shaker

Fig. 3 depicts extracted iron, pH and pE + pH profiles for those

experiments performed with jarosite in both media; while FeTotal and
Fe(II) profiles are presented in the supplementary data (Fig. S4). The
presence of A. cryptum also had a positive effect in this experiment,
increasing the jarosite dissolution in both media (Fig. 3). However, a
significant iron dissolution yield was obtained only in the presence of
oxalic acid. As for magnetite, iron extraction in Fig. 3 is referred to the
iron content in jarosite (33.8 ± 0.6% (w/w)) determined by acid
digestion. Fig. 3. Extracted iron (A), pE + pH (B) and pH (C) profiles for jarosite dissolution in E
(□,■) and E/Ox (○,●) media. Solid and hollow symbols represent A. cryptum JF-5 inocu-
lated vials and abiotic controls, respectively. The pH 2.4 after the H2SO4 addition
3.3. Jarosite dissolution under different shake modes (arrow) was estimated.

A stirring “ferris” wheel, similar to the rotor of a hybridization incu-

bator, was made of PVC. This device was able to maintain the jarosite
completely suspended when its rotation speed was faster than
~ 35 RPM. Unlikely, both solids remained significantly suspended for
less than 10 min in those experiments performed in the orbital shaker
(at 150 RPM).
Fig. 4 shows the extracted iron profiles for the jarosite dissolution by
A. cryptum under different shake conditions, while FeTotal and Fe(II)
measurements are shown in the supplementary data (Fig. S5). The tem-
perature difference between environment (27–32 °C) and incubator
(3 ± 1 °C warmer) was considered negligible. Finally, Fig. 5 displays
the relation between H2SO4 consumed and extracted iron in those
vials stirred with magnetic bars.
Considering that jarosite under magnetic stirring turned pale yellow
and settled more slowly (supplementary data Fig. S7), residues
obtained from abiotic controls (supplementary data Fig. S6) were char-
acterized by SEM and a laser diffraction technique (Fig. 6).
4. Discussion
The term pE + pH, proposed by Cornell and Schwertmann (2003b),
will be used to describe the redox systems. Unlike rH (the negative log-
arithm of the hydrogen partial pressure), this term can be easily read
from currently available Pourbaix diagrams (Keene et al., 2010), Fig. 7.
The iron extraction profiles in Figs. 1 and 3 show an initial iron dis-
solution in all cases where A. cryptum was present. However, only
when pH was periodically corrected (adding H2SO4) the dissolution
process was supported, as shown in reaction (1) (Mulder and Cresser,

Fig. 4. Extracted iron profiles for jarosite dissolution assayed in E/Ox medium, in the
Fig. 2. Relationship between extracted iron and H2SO4 consumed in the reductive dissolu- presence of Acidiphilium cryptum JF-5, under different stirring conditions: static vials
tion of magnetite in E/Ox (■; 2 mmol/L oxalate) and E media (●). The straight line has a (○), orbital shaker at 150 RPM (●), stirring bar at 250–350 RPM (►), and the homemade
slope equal to 1. rotor at 40 RPM, where the vials were placed in radial (□) and axial (■) positions.
 E. González et al. / Hydrometallurgy 157 (2015) 292–297 295

Fig. 5. Relationship between extracted iron and consumed H2SO4 in the reductive dissolu-
tion of jarosite in E/Ox medium (►; 2 mmol/L oxalate) inoculated with Acidiphilium
cryptum. The straight line has a slope equal to 0.5.

1994). Blebs formed by A. cryptum JF-5 (Küsel et al., 1999) could be in-
volved in the dissolution of ferric solids, despite the fact that Fig. 7. Pourbaix diagram of Fe–NH+4 –S–O2–CO2–H2O system. aFe = 10
−2
, 10−3, 10−4 and
Acidiphilium SJH uses an indirect mechanism (Bridge and Johnson, 10−5; P CO2 = 10−1 bar,aNHþ = aSO2− = 10−2. The standard Gibbs free energy formation for
4 4

2000). Fig. 7 shows that the formation of Fe(II) solid phases, as siderite, ammoniojarosite was obtained from Gaboreau and Vieillard (2004), while all other ther-
can also occur under circumneutral pH (Roh et al., 2003), as can be modynamic data were obtained from Langmuir (1997).

Fig. 6. SEM micrographs of abiotical jarosite residues under different stirring conditions (A–G) and their particle-size distribution (H). Static vials (A), orbital shaker at 150 RPM (B), stirring
bar at 250–350 RPM (C ×250 and G ×3000), and the homemade rotor at 40 RPM, where the vials were placed in radial (D) and axial (E) positions; compared to the starting material (F).
296 E. González et al. / Hydrometallurgy 157 (2015) 292–297
observed in the magnetite test without pH control (Fig. S2).
n=2 M 2=n O þ nHþ →Mnþ þ n=2H 2 O
The slowdown in magnetite dissolution, observed between 10 and
20 days in E medium, coincides with a sudden increase in pE + pH
(Fig. 1). Since A. cryptum is only able to grow in a pH range 2.1–5.8
(Küsel et al., 1999), the pH close to 6.0 achieved on day 3 (Fig. 1C) prob-
ably affected negatively the bacterial population, which could not
maintain the reducing environment. This did not occur in E/Ox medium,
where oxalate possibly buffered pH oscillations and kept this variable in
the range where A. cryptum JF-5 could grow.
In abiotic tests with E/Ox medium, the dissolution of both solids
(Figs. 1 and 3) and the occurrence of Fe(II) in solution (Figs. S1 and
S4) could be explained by the presence of oxalic acid and its reducing
power (Eisele and Gabby, 2014; Sulzberger et al., 1989). However, the
good results achieved for jarosite in the presence of A. cryptum and
oxalate could be attributed to a ligand-promoted dissolution under re-
ducing conditions (Zinder et al., 1986) or to the fact that oxalate can
also facilitate the electron transfer from a dissolved reduced ion to the
solid surface (Blesa et al., 1987; Panias et al., 1996; Sulzberger et al.,
1989; Suter et al., 1988).
In a heterogeneous system, the reaction rate is coupled to one or
more transfer processes, where the slowest process will be the limiting
step. Fig. 4 shows that poor mixing in the orbital shaker led to a better
performance than static condition, as reported by Royer et al. (2003).
The fact that a better stirring performance in the homemade rotor did
not improve the results obtained in the orbital shaker supports the
idea that jarosite dissolution was not under mass transport control.
Fig. 4 also shows that the jarosite dissolution rate in magnetically
stirred vials was significantly greater than in other cases. The mechani-
cal action of the stirring bar had a disaggregating and grounding effect
on solid particles that increased its exposed surface area (Fig. 6). The
linear increase of iron in solution observed in Figs. 1 and 3 would sug-
gest that the dissolution process was controlled by the solid surface
(Cornell and Schwertmann, 2003a; Furrer and Stumm, 1986; Hering
and Stumm, 1990; Stumm and Wollast, 1990; Zinder et al., 1986). This
assumption was later confirmed by the results obtained in magnetically
stirred vials.
Considering that iron concentration is significantly greater than the
concentration of added oxalate, and taking into account that new
mineral phases were not found in residues, magnetite and jarosite
dissolution could be described through reactions (2) and (3), respec-
tively. Iron release and H2SO4 consumed for both solids (Figs. 2 and 5)
practically follow the straight lines representing 1:1 and 1:2 ratios
predicted by reactions (2) and (3), respectively. Discrepancies observed
at high values of H2SO4 consumed could be related to the pH-adjusting
procedure.
12Fe3 O4 þ 36H2 SO4 þ C 6 H12 O6 →36Fe2þ þ 36SO2−
4 þ 42H 2 O þ 6CO2
24NH 4 Fe3 ðSO4 Þ2 ðOH Þ6 þ 3C 6 H 12 O6 þ 36H 2 SO4 →24NH4 þ
þ84SO4 2− þ 72Fe2þ þ 18CO2 þ 126H 2 O
Nowadays, the hydrometallurgical extraction of iron would have
prohibitive costs considering the time and reactants required. However,
this technology could be useful for other purposes, among them the
production of non-ferrous metals (Hallberg et al., 2011) or the
upgrading of products (as kaolin, silica or bauxite) by removal of iron
impurities (Eisele and Gabby, 2014). Eventually, the depletion of iron
deposits and the tightening of environmental regulations could turn
the hydrometallurgy of iron oxides into a viable option.
5. Conclusions
The identification of main variables is one of the first steps for study-
ð1Þ
ing a chemical process. In the present work the dissolution of magnetite
and jarosite was assayed, both abiotically and in the presence of
A. cryptum, in two culture media. It was confirmed that A. cryptum
generated a reducing environment responsible for the magnetite disso-
lution. In turn, the pH rose and the consumption of protons had to be
controlled in order to keep the reaction progress. The addition
of oxalate to the medium did not increase the magnetite but jarosite
dissolution rate.
The jarosite dissolution under poor and good mixing conditions was
similar, which provides additional evidence that the dissolution process
is controlled by the solid surface. For both solids, the acid consumption
was successfully correlated to the reaction stoichiometry. These find-
ings confirm the feasibility of using iron reducing bacteria in hydromet-
allurgical processes.
Acknowledgments
The authors wish to express their gratitude to the Spanish Ministry
of Economy and Competitiveness for funding this work (project
MAT2011-24186).
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.hydromet.2015.08.003.
References
Ahern, N. and Schaekers, J.M., 2004. Recovery of metals from jarosite-containing
materials. Patent: 7037357, USPTO, May 2nd, 2006, 10/654635.
Bingjie, O., Xiancai, L., Huan, L., Juan, L., Tingting, Z., Xiangyu, Z., Jianjun, L., Rucheng, W.,
2014. Reduction of jarosite by Shewanella oneidensis MR-1 and secondary mineraliza-
tion. Geochim. Cosmochim. Acta 124, 54–71. http://dx.doi.org/10.1016/j.gca.2013.09.
020.
Blesa, M.A., Marinovich, H.A., Baumgartner, E.C., Maroto, A.J.G., 1987. Mechanism of
dissolution of magnetite by oxalic acid–ferrous ion solutions. Inorg. Chem. 26 (22),
3713–3717. http://dx.doi.org/10.1021/ic00269a019.
Bonneville, S., Behrends, T., Cappellen, P.V., Hyacinthe, C., Röling, W.F.M., 2006. Reduction
of Fe(III) colloids by Shewanella putrefaciens: a kinetic model. Geochim. Cosmochim.
Acta 70 (23), 5842–5854. http://dx.doi.org/10.1016/j.gca.2006.04.029.
Bridge, T.A.M., Johnson, D.B., 2000. Reductive dissolution of ferric iron minerals by
Acidiphilium SJH. Geomicrobiol J. 17 (3), 193–206. http://dx.doi.org/10.1080/
01490450050121161.
Cardarelli, F., 2008. Electrochemical process for the recovery of metallic iron and chlorine
values from iron-rich metal chloride wastes. Patent: WO 2008/034212, WIPO, March
27th, 2008, PCT/CA2007/000026.
Cardarelli, F., 2011. Electrochemical process for the recovery of metallic iron and sulfuric
acid values from iron-rich sulfate wastes, mining residues and pickling liquors.
Patent: WO 2009/124393 A1, WIPO, October 15th, 2009, PCT/CA2009/000471.
Castro, L., García-Balboa, C., González, F., Ballester, A., Blázquez, M.L., Muñoz, J.A., 2013.
Effectiveness of anaerobic iron bio-reduction of jarosite and the influence of
humic substances. Hydrometallurgy 131–132, 29–33. http://dx.doi.org/10.1016/j.
hydromet.2012.10.005.
Cornell, R.M., Schwertmann, U., 2003a. Dissolution. In: Cornell, R.M., Schwertmann, U.
ð2Þ (Eds.), The Iron Oxides. Structure, Properties, Reactions, Occurrences and Uses.
Wiley-VCH, pp. 297–344.
Cornell, R.M., Schwertmann, U., 2003b. Solubility. In: Cornell, R.M., Schwertmann, U.
(Eds.), The Iron Oxides. Structure, Properties, Reactions, Occurrences and Uses.
ð3Þ Wiley-VCH, pp. 201–220.
Dresher, W.H., 2001. How Hydrometallurgy and the SX/EW Process Made Copper the
“Green” Metal URL:, http://www.copper.org/publications/newsletters/innovations/
2001/08/hydrometallurgy.html (Last accessed: January 16th, 2015).
Duade, J., 2011. The Important Factors to Consider When Investing in Iron Ore URL:,
http://seekingalpha.com/article/262764-the-important-factors-to-consider-when-
investing-in-iron-ore (Last accessed: January 19th, 2015).
Dutrizac, J.E., 1999. The effectiveness of jarosite species for precipitating sodium jarosite.
JOM 51 (12), 30–32. http://dx.doi.org/10.1007/s11837-999-0168-6.
Eisele, T.C., 2005. Direct Biohydrometallurgical Extraction of Iron from Ore. Michigan
Technological University.
Eisele, T.C., Gabby, K.L., 2014. Review of reductive leaching of iron by anaerobic bacteria.
Miner. Process. Extr. Metall. Rev. 35 (2), 75–105. http://dx.doi.org/10.1080/
08827508.2012.703627.
 E. González et al. / Hydrometallurgy 157 (2015) 292–297
Furrer, G., Stumm, W., 1986. The coordination chemistry of weathering: I. Dissolution
kinetics of δ-Al2O3 and BeO. Geochim. Cosmochim. Acta 50 (9), 1847–1860. http://
dx.doi.org/10.1016/0016-7037(86)90243-7.
Gaboreau, S., Vieillard, P., 2004. Prediction of Gibbs free energies of formation of minerals
of the alunite supergroup. Geochim. Cosmochim. Acta 68 (16), 3307–3316. http://dx.
doi.org/10.1016/j.gca.2003.10.040.
Gerst, M.D., Graedel, T.E., 2008. In-use stocks of metals: status and implications. Environ.
Sci. Technol. 42 (19), 7038–7045. http://dx.doi.org/10.1021/es800420p.
Hallberg, K.B., Grail, B.M., Plessis, C.A.D., Johnson, D.B., 2011. Reductive dissolution of ferric
iron minerals: a new approach for bio-processing nickel laterites. Miner. Eng. 24 (7),
620–624. http://dx.doi.org/10.1016/j.mineng.2010.09.005.
Heijnen, J.J., 1999. Bioenergetics of microbial growth. In: Flickinger, M.C., Drew, S.W.
(Eds.), Encyclopedia of Bioprocess Technology: Fermentation, Biocatalysis and
Bioseparation. John Wiley & Sons, Inc., pp. 267–291.
Hering, J.G., Stumm, W., 1990. Oxidative and reductive dissolution of minerals. In:
Hochella, M.F.J., White, A.F. (Eds.), Mineral–Water Interface Geochemistry. Mineral-
ogical Society of America, Chelsea, Michigan, pp. 427–465.
IEA, 2007. Tracking Industrial Energy Efficiency and CO2 Emissions. URL: http://www.iea.
org/publications/freepublications/publication/tracking_emissions.pdf (Last accessed:
January 16th, 2015).
Ju, S.H., Zhang, Y.F., Zhang, Y., Xue, P.Y., Wang, Y.H., 2011. Clean hydrometallurgical route
to recover zinc, silver, lead, copper, cadmium and iron from hazardous jarosite
residues produced during zinc hydrometallurgy. J. Hazard. Mater. 192 (2), 554–558.
http://dx.doi.org/10.1016/j.jhazmat.2011.05.049.
Keene, A.F., Johnston, S.G., Bush, R.T., Sullivan, L.A., Burton, E.D., 2010. Reductive dissolu-
tion of natural jarosite in a tidally inundated acid sulfate soil: geochemical implica-
tions. 19th World Congress of Soil Science, Soil Solution for a Changing World,
Brisbane, Australia, pp. 100–103.
Küsel, K., Dorsch, T., Acker, G., Stackebrandt, E., 1999. Microbial reduction of Fe(III) in
acidic sediments: isolation of Acidiphilium cryptum JF-5 capable of coupling the
reduction of Fe(III) to the oxidation of glucose. Appl. Environ. Microbiol. 65 (8),
3633–3640.
Laguna, C., González, F., García-Balboa, C., Ballester, A., Blázquez, M.L., Muñoz, J.A., 2011.
Bioreduction of iron compounds as a possible clean environmental alternative for
metal recovery. Miner. Eng. 24 (1), 10–18. http://dx.doi.org/10.1016/j.mineng.2010.
08.026.
Langmuir, D., 1997. Aqueous Environmental Geochemistry. Prentice Hall, New Jersey
(600 pp.).
Lovley, D.R., Holmes, D.E., Nevin, K.P., 2004. Dissimilatory Fe(III) and Mn(IV) reduction.
Advances in Microbial Physiology. Academic Press, pp. 219–286.
Lovley, D.R., Ueki, T., Zhang, T., Malvankar, N.S., Shrestha, P.M., Flanagan, K.A., Aklujkar, M.,
Butler, J.E., Giloteaux, L., Rotaru, A.E., Holmes, D.E., Franks, A.E., Orellana, R., Risso, C.,
Nevin, K.P., 2011. Geobacter: the microbe electric's physiology, ecology, and practical
applications. In: Poole, R.K. (Ed.), Advances in Microbial PhysiologyAdvances in
Microbial Physiology vol. 59. Academic Press Ltd-Elsevier Science Ltd, London,
pp. 1–100. http://dx.doi.org/10.1016/b978-0-12-387661-4.00004-5.
Mulder, J., Cresser, M.S., 1994. Soil and soil solution chemistry. In: Moldan, B., Černý, J.
(Eds.), Biochemistry of Small Catchments: A Tool for Environmental Research.
Wiley & Sons, pp. 107–131.
297
Nheta, W., Makhatha, M.E., 2013. Leaching of nickel from a jarosite precipitate with
hydrochloric acid. International Conference on Chemical and Environmental Engi-
neering, Johannesburg, South Africa, pp. 18–21.
Norgate, T., Jahanshahi, S., 2010. Low grade ores — smelt, leach or concentrate? Miner.
Eng. 23 (2), 65–73. http://dx.doi.org/10.1016/j.mineng.2009.10.002.
Panias, D., Taxiarchou, M., Paspaliaris, I., Kontopoulos, A., 1996. Mechanisms of dissolution
of iron oxides in aqueous oxalic acid solutions. Hydrometallurgy 42 (2), 257–265.
http://dx.doi.org/10.1016/0304-386X(95)00104-O.
Peters, M.A., Hazen, W.W. and Reynolds, J.E., 1992. Process for recovering metal values
from jarosite solids. Patent: 5078786, USPTO, January 7th, 1992, 07/438502.
Roh, Y., Zhang, C.-L., Vali, H., Lauf, R.J., Zhou, J., Phelps, T.J., 2003. Biogeochemical and
environmental factors in Fe biomineralization: magnetite and siderite formation.
Clay Clay Miner. 51 (1), 83–95. http://dx.doi.org/10.1346/ccmn.2003.510110.
Royer, R.A., Dempsey, B.A., Jeon, B.-H., Burgos, W.D., 2003. Inhibition of biological reduc-
tive dissolution of hematite by ferrous iron. Environ. Sci. Technol. 38 (1), 187–193.
http://dx.doi.org/10.1021/es026466u.
Silverman, M.P., Lundgren, D.G., 1959. Studies on the chemoautotrophic iron bacterium
Ferrobacillus ferrooxidans. J. Bacteriol. 77 (5), 642–647.
Stookey, L.L., 1970. Ferrozine — a new spectrophotometric reagent for iron. Anal. Chem.
42 (7), 779–781. http://dx.doi.org/10.1021/ac60289a016.
Stumm, W., Wollast, R., 1990. Coordination chemistry of weathering: kinetics of the
surface-controlled dissolution of oxide minerals. Rev. Geophys. 28 (1), 53–69.
http://dx.doi.org/10.1029/RG028i001p00053.
Sulzberger, B., Suter, D., Siffert, C., Banwart, S., Stumm, W., 1989. Dissolution of
Fe(III)(hydr)oxides in natural waters; laboratory assessment on the kinetics
controlled by surface coordination. Mar. Chem. 28 (1–3), 127–144. http://dx.doi.
org/10.1016/0304-4203(89)90191-6.
Suter, D., Siffert, C., Sulzberger, B., Stumm, W., 1988. Catalytic dissolution of
iron(III)(hydr)oxides by oxalic acid in the presence of Fe(II). Naturwissenschaften
75 (11), 571–573. http://dx.doi.org/10.1007/bf00377723.
Swayze, G.A., Desborough, G.A., Smith, K.S., Lowers, H.A., Hammarstrom, J.M., Diehl, S.F.,
Leinz, R.W., Driscoll, R.L., 2008. Understanding jarosite — from mine waste to Mars.
In: Verplanck, P.L. (Ed.), Understanding Contaminants Associated with Mineral
Deposits. U.S. Geological Survey, Reston, Virginia, pp. 8–13.
Vyas, A.K., 2011. Solidification–stabilization technique for metal bearing solid waste from
zinc industry — a case study. International Conference on Environmental and
Computer Science. IPCBEE, Singapore, pp. 151–155.
Xie, X.H., Xiao, S.M., Wang, H.T., Liu, J.S., 2009. Biooxidation of refractory gold ores by
mixed moderate thermophiles in airlift bioreactor. In: Donati, E.R., et al. (Eds.),
Biohydrometallurgy: A Meeting Point Between Microbial Ecology, Metal Recovery
Processes and Environmental Remediation. Advanced Materials Research. Trans
Tech Publications Ltd, Stafa-Zurich, pp. 469–472.
Zinder, B., Furrer, G., Stumm, W., 1986. The coordination chemistry of weathering: II.
Dissolution of Fe(III) oxides. Geochim. Cosmochim. Acta 50 (9), 1861–1869. http://
dx.doi.org/10.1016/0016-7037(86)90244-9.