Chemical Engineering Science 55 (2000) 783}795

Bioleaching of a pyrrhotite ore by a sulfooxidans strain:

kinetic analysis
F. Vegliò!,*, F. Beolchini!, A. Nardini!, L. Toro"
!Dipartimento di Chimica, Ingegneria Chimica e Materiali, Facolta+ di Ingegneria, Universita+ degli Studi dell'Aquila,
67040 Monteluco di Roio, L+Aquila, Italy
"Istituto di Chimica Industriale, Universita+ **La Sapienza++ di Roma, Italy
Received 29 March 1998; accepted 24 February 1999

Abstract

A kinetic study of the batch leaching of a pyrrhotite ore by a sulfooxidans strain is reported in this work. A mathematical model
consistent with experimental data is developed, which takes into account both direct and indirect mechanism. The development has
been performed from a separate study of microorganisms' adsorption on the solid surface and of chemical leaching of pyrrhotite by
ferric iron. The representative equations of these phenomena (Langmuir equation and a kinetic model with variable activation energy,
respectively) have been combined with material balances of total iron, ferric iron and biomass. The "nal model consists of a system of
three ordinary di!erential equations, where the independent variable is time and dependent variables are total iron, ferric iron and
biomass concentrations in solution. The key parameters of the model were: the speci"c growth rate, k , the growth yield, >@ of
A A
adsorbed bacteria, and the reaction rate constant of ferrous iron oxidation, k. These parameters were estimated by curve "tting using
experimental data and estimated values (k "1.34$0.02 d~1, >@ "3.6$0.3]1013 cells/mol, k"0.229$0.004 d~1) are in agree-
A A
ment with values found in the literature. ( 1999 Elsevier Science Ltd. All rights reserved.

Keywords: Pyrrhotite; Bioleaching; Kinetic modeling; Thiobacillus thiooxidans; Direct and indirect mechanisms

1. Introduction of the two leaching mechanisms depend on the types of

Important reserves of gold associated to pyrrhotite
occur in the world (Veglio', Nardini, Toro, Ubaldini
& Abbruzzese, 1995) and bioleaching has been demon-
strated to be e!ective as a pretreatment to enhance gold
recovery from pyrrhotite in a conventional cyanidation
process (Ubaldini, Veglio', Toro & Abbruzzese, 1995).
The mechanism of bioleaching is usually discussed in
terms of a direct bacterial attack on sul"de minerals and
an indirect attack via ferric iron (Konishi, Kubo & Asai,
1992). In the direct mechanism, bacteria act as the pri-
mary oxidant, necessitating a direct contact between the
bacteria and the sul"de mineral (Murthy & Natarajan,
1992). In the indirect mechanism, microorganisms act
indirectly, since they regenerate ferric iron through the
oxidation of ferrous iron in solution. The contributions
* Corresponding author. Tel.: #39-862-434223; fax: #39-862-
434203.
E-mail address: veglio@ing.univaq.it (F. Veglio)
sul"de mineral and on the operating conditions (Konishi
et al., 1992). The kinetics of bioleaching due to direct and
indirect mechanism have been under investigation by
many researchers. The most studied minerals were pyrite
(Konishi, Asai & Katoh, 1990; Asai, Konishi & Yoshida,
1992; Konishi, Yoshida & Asai, 1995; Chang & Myerson,
1982; Shrirari, Modak, Kumar & Gandhi, 1995; Kargi
& Weissman, 1983, Nagpal, Dahlstrom & Oolman,
1994), chalcopyrite (Escobar, Jedlicki, Wiertz & Vargas,
1996; Boon & Heijnen, 1993) and zinc sul"de (Konishi et
al., 1992; Sanmugasunderam et al., 1985; Gormely, Dun-
can, Branion & Pinder, 1975). Although its interest, few
information is available in the literature on pyrrhotite
bioleaching (Bhatti, Bigham, Carlson & Touvinen, 1993).
The aim of this work is to study the kinetics of the
batch leaching of a pyrrhotite ore by a sulfooxidans
strain collected in natural waters. A mathematical model
consistent with experimental data is developed, which
takes into account both direct and indirect mechanism.
The development has been performed considering as
a reference the Konishi et al. (1992) model. In this case

0009-2509/00/$ - see front matter ( 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 9 9 ) 0 0 3 5 4 - 1
784 F. Vegliò et al. / Chemical Engineering Science 55 (2000) 783}795
Nomenclature
A surface area of solid particles, (m2)
A initial surface area of solid particles, (m2)
0
C0 3` initial ferric iron concentration in solution,
F%
(mol/m3, mM)
C0 pyrrhotite concentration in the solid}liquid
F%S
mixture at the beginning of the process,
(mol/m3)
C 2` ferrous iron concentration in the liquid phase,
F%
(mol/m3)
C 3` ferric iron concentration in solution, (mol/m3,
F%
mM)
C pyrrhotite concentration in the solid}liquid
F%S
mixture during the process, (mol/m3)
C 505 total iron concentration in the liquid phase,
F%
(mol/m3)
k "rst-order rate constant, (d~1)
K adsorption equilibrium constant, (m3/cell)
A T
R universal gas constant, (J/mol/K)
R growth rate of adsorbed bacteria, (cell/d/m3)
A A
r leaching rate of pyrrhotite by direct bacterial
B
action, (mol FeS/d/m3)
r leaching rate of pyrrhotite by ferric iron, (mol
C A
FeS/d/m3)
r 3` ferric iron consumption rate, due to chemical
F% ,#0/4
leaching of pyrrhotite, (mol/d/m3)
the model is valid for sulfooxidans microorganisms, and
this aspect represents the novelty of the mathematical
approach.
2. Materials and methods
2.1. Ore
The pyrrhotite ore comes from Atoroma mine, in
Bolivia. The ore characterization has been performed at
the Istituto Trattamento Minerali (ITM) of CNR, Rome.
Table 1 shows the chemical composition of the pyrrhotite
ore. Before experiments it was ground and sieved at
(74 lm. The speci"c surface area of the solid particles
was determined as 3.8 ($0.3) m2/g using a nitrogen
porosimeter Micromeritics Asap 2000.
2.2. Microorganisms
Thiobacillus thiooxidans was isolated from sulfur
waters in Cotilia (Rieti, Italy). The strain was routinely
cultivated in 9 K liquid medium (Cote, 1996) with pyr-
rhotite 10 per cent (w/v) as energy source, using 300 ml
Erlenmeyer #asks containing 100 ml of the medium.
r 3` ferric iron generation rate, due to chemical
F% ,'%/
oxidation of ferrous iron, (mol/d/m3)
t time, (d)
¹ temperature, (K)
< volume of solid}liquid mixture, (m3)
X number of adsorbed bacteria per unit
A
weight of mineral ore, (cell/g)
X concentration of the adsorbed bacteria
a
per unit surface area of solid particles,
(cell/m2)
X maximum adsorption capacity per unit
Am
weight of solid particles, (cell/kg)
X maximum adsorption capacity per unit sur-
am
face area of solid particles, (cell/m2)
X concentration of the free bacteria in the
L
liquid phase, (cell/ml)
X total concentration of bacteria in the
solid}liquid mixture, (cell/m3)
>@ growth yield of bacteria on pyrrhotite ore,
(cell/mol)
a pyrrhotite conversion
k speci"c growth rate of bacteria on solid sur-
face, (d~1)
h fraction of adsorption sites unoccupied by
v
cells, (dimensionless)
Flasks were incubated at 303C on a rotary shaker (New
Brunswick mod. G25) at 200 rpm. An inoculum age of
about 6 d was used in the experimental trials.
2.3. Analytical determinations
Ferric iron concentration was determined spectro-
photometrically by the colorimetric thiocyanate method
(Welcher & Hahn, 1955).
Total iron concentration (ferrous plus ferric iron) was
determined by atomic absorption spectrophotometry.
Ferrous iron was determined as the di!erence between
the Fe and Fe3` analyses. Sulfate determination was
505
performed spectrophotometrically by the turbidimetric
barium sulfate method (Welcher & Hahn, 1955).
The number of cells in the liquid phase was counted
with Thoma's Hematometer (Imai, Sugio & Tano, 1970;
Duarte, Estrada, Pereira & Beaumont, 1993) in an op-
tical microscope (NIKON OPTIPHOT 2-POL) at ]400
magni"cation connected with a monitor (SONY KX-
14CP1). Samples (1 ml) were collected after sedimenta-
tion of solids in the #asks. The experimental procedure
is described in details elsewhere (Beolchini et al.,
submitted).
 F. Vegliò et al. / Chemical Engineering Science 55 (2000) 783}795
Table 1
Chemical composition of the pyrrhotite ore
Compound
FeS
SiO
2
Al O
2 3
MgO
K O
2 (Bhatti et al., 1993).
TiO
2
MnO
CaO
Other sulphides
Sn
As
Cu
Pb
Sb
Cr
Zn
Au
Ag
2.4. Adsorption experiments
In the adsorption experiments, a known amount of
pyrrhotite ore was mixed with 100 ml of 9 K liquid me-
dium previously inoculated. Volumes inoculated were
di!erent in order to investigate di!erent values of cell
concentrations. Flasks were kept at room temperature
and vigorously stirred. pH was initially set at 2 and it
did not change signi"cantly during the adsorption
experiments. Samples were collected periodically for de-
termination of cells in solution. The number of cells
adsorbed on the mineral surface was determined from the
di!erence of the number of cells in the liquid phase before
and after adsorption, since the adsorption of cells onto
the #ask wall was found to be negligible.
2.5. Chemical leaching with ferric iron
The chemical leaching of pyrrhotite ore was examined
as follows: 250 ml shake #asks were "lled with 100 ml of
a solution of Fe (SO ) at di!erent concentrations of
2 43
ferric iron. The reaction was started by adding a known
amount of ore (according to experimental conditions).
Periodically 1 ml samples were collected for ferric iron,
total iron and sulfate determinations.
2.6. Bioleaching experiments
Bioleaching experiments were performed in 300 ml
shake #asks "lled with 100 ml of 9 K liquid medium
(Atlas, 1993) with pyrrhotite 3 per cent (w/v) as energy
source. Initial pH was 2. Fe (SO ) was added according
2 43
to experimental conditions (initial ferric iron concentra-
tion: 0, 100 and 200 mM). A bioleaching run was started
by inoculating 10 ml of an active culture of the microbial
785
strain. Flasks were incubated at 303C on a rotary shaker
(New Brunswick mod. G25) at 200 rpm. Periodically
1.5 ml samples were collected for ferric iron, total iron,
%
sulfate and determination of cells. Many #asks were
46.25 inoculated at the same time and they were removed after
19.72 di!erent periods of treatment in order to recover the solid
4.57 residue. The solid residue was treated with HCl 5 M for
0.68 the dissolution of eventual precipitate compounds
0.44
0.37
0.09
0.01
3.58 3. Experimental results
1.35
0.85
0.18 In addition to the bioleaching runs, experiments for
0.10 the investigation of microorganisms adsorption and kin-
0.03 etic leaching with ferric iron have been performed, in
0.02 order to separately investigate the main phenomena
0.02
10 g/t
which take place during the process. Just in this way
9 g/t a kinetic model able to simulate the overall bioleaching
process can be developed.
3.1. Adsorption of bacteria
A detailed investigation of microorganisms adsorption
on pyrrhotite ore is reported elsewhere (Beolchini et al.,
submitted). The process was demonstrated to be very
fast, since it reaches equilibrium within the "rst 15 min of
exposure to the solid particles. An isotherm for the
microorganisms adsorption on pyrrhotite ore particles is
presented in Fig. 1.
It is evident that the equilibrium isotherm data are
characterized by a monotonic approach to a limiting
adsorption concentration. This indicates that data can
be modeled by the Langmuir isotherm (Konishi et al.,
1992):
K X X
X " A Am L , (1)
A 1#K X
A L
where X (cell/g) is the number of adsorbed bacteria per
A
unit weight of mineral ore, X (cell/ml) is the concentra-
L
tion of free bacteria in the liquid phase, X (cell/g) is the
Am
maximum adsorption capacity and K (ml/cell) is the
A
adsorption equilibrium constant. Parameters of Eq. (1)
were estimated by "tting the model to experimental
data, according to the Mezaki's least-squares method
(Himmelblau, 1970). Estimated values were: X "
Am
3.5$0.7]1012 cell/kg (X "9.2]108 cell/m2), K "
am A
4$2]10~15 m3/cell. Fig. 1 shows that there is a good
agreement between experimental and calculated data by
Eq. (1).
3.2. Chemical leaching with ferric iron
The chemical leaching of pyrrhotite with ferric iron in
the absence of microorganisms represents the indirect
786 F. Vegliò et al. / Chemical Engineering Science 55 (2000) 783}795

Fig. 1. Equilibrium adsorption isotherm for bacteria adsorption on pyrrhotite ore particles. Solid line represents calculated values by the Langmuir
equation (temperature 303C; pyrrhotite concentration: 3}5 per cent).

mechanism of bioleaching. A kinetic model for this chem-
ical reaction has been developed and the detailed analysis
reported elsewhere (Beolchini & Veglio', submitted). The
study performed has demonstrated that:
f the sulfur moiety of pyrrhotite is oxidised incompletely
by ferric iron to elemental sulfur as shown by Eq. (2):
FeS#2Fe3`H3Fe2`#S".
f the process kinetics is controlled by the chemical reac-
tion, as con"rmed by an activation energy of the pro-
cess equal to about 100 kJ/mol.
f the mathematical model able to predict the process
kinetics is the following:
energy on the pyrrhotite conversion (Brittan, 1975). Fig. 2
shows experimental and calculated pyrrhotite conversions
vs. time pro"les, at di!erent experimental conditions.
3.3. Bioleaching
Typical bioleaching behavior of the pyrrhotite ore is
shown in Figs. 3 and 4, where pH, total iron, ferric iron,
(2)
sulphate and cell concentration are reported as a func-
tion of time. Experimental trials have been performed in
duplicate, in order to have an indication of the process
reproducibility.
Fig. 3 shows that the e!ect of microorganisms on
pyrrhotite oxidation is remarkable. In fact, in the absence
of biomass, no increase in the iron dissolution was ob-

C A B D
da 99]103 1 1 27]103a served after the "rst two days of treatment.
"1440.8]10~4e ! ! ! ,
dt R ¹ 298 R¹ Data reported in Figs. 3 and 4 have been used in order
to represent the relative increase of total iron as a func-
A B
C 3` 0.47
] F% (1!a)2@3, (3) tion of the relative increase of sulfate (Fig. 5). Considering
1000
that the slope of the regression line is equal to 1, the
where a is the pyrrhotite conversion, t the time (d), bacterial leaching seems to proceed stoichiometrically,
C 3` the ferric iron concentration in solution (mol/m3), according to the following reaction:
F%
R the universal gas constant (J/mol/K), and ¹ the tem-
FeS#2O PFe2`#SO2~. (4)
perature (K). 2 4
The model has been developed from the unreacted No precipitation takes place in the tested experimental
core model, considering a dependence of the activation conditions. In fact, the ratio between relative increases of
 F. Vegliò et al. / Chemical Engineering Science 55 (2000) 783}795 787

Fig. 2. Experimental (points) and calculated by the unreacted core model with variable activation energy (lines) values of pyrrhotite conversion during
chemical leaching with ferric iron.

Fig. 3. Total and ferric iron vs. time pro"les during pyrrhotite bioleaching (initial ferric iron 0; mineral concentration 3 per cent w/v; temperature
303C). Solid lines represent calculated values by the developed mathematical model. Dotted lines are related to trials with no microorganisms.
788 F. Vegliò et al. / Chemical Engineering Science 55 (2000) 783}795
Fig. 4. pH, sulfate and cell concentration vs. time pro"les during pyrrhotite bioleaching (initial ferric iron 0; mineral concentration 3 per cent w/v;
temperature 303C).
iron and sulfate was constant and equal to 1 during the
whole trial. A con"rmation was given by the treatment of
solid residues with HCl 5 M (Bhatti et al., 1993). Neither
iron, nor sulfate were found in solution after the acid
treatment. Consequently, precipitate compounds such as
ferric hydroxide or jarosites (Bhatti et al., 1993) were
demonstrated not to be formed on the mineral surface.
Furthermore, the bioleaching process was not limited by
mass transfer rates of gaseous solutes, such as oxygen and
carbon dioxide. In fact, the shaking rate had no signi"-
cant e!ect on the oxidation rate of pyrrhotite, with
a 3 per cent (w/v) solid concentration.
The ferrous iron formed after pyrrhotite bioleaching is
consequently oxidised according to the reaction
4Fe2`#O #4H`P4Fe3`#2H O. (5)
2 2
If microorganisms use the ferrous iron oxidation as
energy source, i.e. they are ferrooxidans, this is a biolo-
gical reaction and it is very fast (Konishi et al., 1992).
Otherwise the ferrous iron oxidation proceeds more
slowly, and it is due just to the oxygen chemical action.
Fig. 3 shows that in the absence of microorganisms no
signi"cant ferric iron concentrations are determined in
the solution. This is due to a very fast indirect mechanism
with respect to the chemical oxidation of ferrous iron. In
fact, the ferric iron formed after chemical oxidation of
ferrous iron (Eq. (5)) is immediately involved in the in-
direct mechanism and it is reduced according to Eq. (2).
These results evidence that the presence of both pyrrho-
tite and microorganisms have a positive e!ect on the
ferrous iron oxidation, even if the bacterial strain is not
a ferrooxidans one. Some tests were performed in order
to verify if the selected microorganisms were really
sulfooxidans. From an inoculated #ask containing
pyrrhotite 3 per cent (w/v) an inoculum was performed
into a #ask containing 9 K medium and ferrous sulfate
as energy source (no mineral). The cell concentration
was monitored during time and the obtained results are
shown in Fig. 6. It is evident that no cell growth
took place, not even after an initial lag phase for cell
adaptation. Optical microscope observation and some
growth tests on selective solid media for T. thiooxidans
and T. ferrooxidans (Visca, Bianchi, Polidoro, Buon"glio,
Valenti & Orsi, 1989; Atlas, 1993) were also performed.
 F. Vegliò et al. / Chemical Engineering Science 55 (2000) 783}795 789

Fig. 5. Relative increase of iron and sulfate during pyrrhotite bioleaching (initial ferric iron 0; mineral concentration 3 per cent w/v; temperature 303C).
The solid line represents the stoichiometric increase (slope"1).

Fig. 6. Cell concentration vs. time pro"le during growth in 9 K medium with FeSO as energetic source (no mineral; temperature 303C; inoculum from
4
pyrrhotite 3 per cent).
790 F. Vegliò et al. / Chemical Engineering Science 55 (2000) 783}795

A very remarkable growth was observed just in the (Eq. (2)), as follows:
T. thiooxidans selective solid medium. Furthermore, the
dC 3`
results shown in Fig. 4 also evidence that microorgan- F% "r 3` #r 3` (7)
dt F% ,'%/ F% ,#0/
isms were sulfooxidans. In fact, sulfate and cell concen-
tration vs. time pro"les proceed in the same way. The ferric iron consumption rate can be related to the
chemical leaching rate considering the stoichiometry of
Eq. (2):
4. Mathematical model for pyrrhotite bioleaching r 3` "!2 ) r (8)
F% ,#0/4 C
The theoretical approach reported here has been de- where r (mol FeS/d/m3), the chemical leaching rate, is
C
veloped considering as a reference the model of Konishi linked to Eq. (3) according to the following expression:
et al. (1992) for batch zinc sul"de leaching by T. fer- dC
rooxidans. As for pyrrhotite, zinc sul"de bioleaching is r "! F%S
C dt
due to a direct and indirect bacterial action. In the direct

C A B
99]103 1 1
action, bacteria multiply on the sul"de mineral that acts "C0 1440.8]10~4e ! !
F%S R ¹ 298
as a solid substrate; parts of the cells are released from the

DA B
solid surface into the liquid medium. In the presence of 27]103a C 3` 0.47
ferric iron, chemical leaching occurs, with formation of ! F% (1!a)h (9)
R¹ 1000 v
ferrous iron. In the Konishi et al. (1992) model, the
ferrous iron formed is readily oxidized by T. ferrooxidans, where C and C0 (mol/m3) are pyrrhotite concentra-
F%S F%S
so that the concentration of ferric iron is practically tion in the solid}liquid mixture during the process and at
maintained at the initial concentration. Besides, accord- the beginning, respectively, and the term h takes into
v
ing to this leaching scheme, bacterial growth occurs not account the mineral fraction not available for reaction
only on the sul"de mineral as a solid substrate, but also with ferric iron since it is occupied by adsorbed cells.
in the liquid medium containing soluble iron. In the As concerns the ferric iron generation rate, r 3` ,
F% ,'%/
model developed here, for sulfooxidans microorganisms, due to chemical oxidation, a "rst-order kinetics is as-
the oxidation of ferrous iron is not as fast as with fer- sumed as follows:
rooxidans microorganisms. Consequently, the hypothe- r 3` "k ) C 2`"k(C 505!C 3`) (10)
sis of a constant ferric iron concentration cannot be F% ,'%/ F% F% F%
assumed and an equation for the ferrous iron chemical where k (d~1) is the "rst-order rate constant,
oxidation has to be considered. Furthermore, microor- C 2` (mol/m3) and C 505 (mol/m3) are the ferrous iron
F% F%
ganisms are assumed as not grown in solution, since they and the total iron concentrations in the liquid phase,
use as energetic substrate just the sulphide mineral and respectively.
the elemental sulfur that is formed on the mineral surface As in the Konishi et al. (1992) model, the total leaching
as a consequence of ferric iron leaching (Eq. (2)) (Boon rate of iron from pyrrhotite is comprised of the leaching
& Heijnen, 1993). Other hypotheses are the following: no rate r due to the direct bacterial action and the rate of
B
precipitate formation during bioleaching and no limita- ferric iron leaching, r :
C
tion by mass transfer rates of gaseous solutes such as dC 505
oxygen and carbon dioxide. F% "r #r (11)
dt B C
Considering these assumptions, the total growth rate
is equal to the growth rate of adsorbed bacteria, The bioleaching rate r can be related to the growth
B
R (cell/s/m3) as follows: rate R of the adsorbed bacteria, as follows:
A A
R
dX
T"R. r " A (12)
(6) B >@
dt A
where >@ (cell/mol) is the growth yield of adsorbed bac-
According to Konishi et al. (1992) model, the growth A
teria, de"ned as the ratio of the total number of cells
rate of bacteria adsorbed on the mineral surface, R , is
A formed by the bacterial growth on the solid surface to the
proportional to the product of the concentration X
a moles of solid substrate utilized.
(cell/m2) of adsorbed cells, the fraction h of adsorption
v The total concentration X of bacteria per unit volume
T
sites unoccupied by cells and the speci"c growth rate of solid}liquid mixture can be expressed in terms of the
k (d~1) (details can be found in Konishi et al., 1992).
A concentration X of cells suspended in the liquid medium
L
Furthermore, the change in ferric iron concentration (see Konishi et al., 1992 for details):
can be expressed as the sum of a generation rate, r 3` ,
F% ,'%/ K X X A
due to chemical oxidation and a consumption rate, X " A am L ) #X (13)
r 3` , due to the chemical leaching of pyrrhotite T 1#K X < L
F% ,#0/4 A L
 F. Vegliò et al. / Chemical Engineering Science 55 (2000) 783}795 791

By di!erentiating, the following expression is achieved: f also the parameters of chemical leaching of pyrrhotite
with ferric iron, which appear in Eq. (3), were measured

C D
A 1!a X 1
dX "K X 0 ! L dC 505 in separate leaching experiments, in the absence of
T A am < (1#K X )2 1#K X C0 F% biomass;
A L A L F%S
#dX (14) f the surface area of solid particles at the beginning
L of the process, A , was estimated as 11400 m2, from
0
Substituting Eqs. (1) and (14) in Eq. (6), Eqs. (3), (8)}(10) the speci"c surface area experimentally determined
in Eq. (7), and Eqs. (1), (3), (8), (9) and (12) in Eq. (11), the (3800 m2/kg), the solid concentration in the system
following system of three "rst-order ordinary di!erential (3%, w/v) and the reaction volume (100 ml);
equations is achieved: f the initial concentration of pyrrhotite in solution, C0 ,
F%S
was determined as 0.157 M, from the pyrrhotite con-
dX
L"f (X ,C 3`, C ) tent in the mineral ore (46%, w/w), the ore concentra-
dt 1 L F% F%505 tion (3%, w/v) and molecular weight of pyrrhotite
dC 3` (88 g/mol).
F% "f (X , C 3`, C )
dt 2 L F% F%505
Three parameters: the speci"c growth rate k , the
A
dC 505 growth yield >@ and the rate constant of ferrous iron
F% "f (X , C 3`, C ) (15) A
dt 3 L F% F%505 chemical oxidation, k, were unknown and estimated as
adjustable parameters during numerical resolution of
By integration of this system with a numerical method, system (15) by using the Runge}Kutta method. The
cell concentration, ferric iron and total iron pro"les vs. estimated values, which agreed well with the experi-
time can be determined. mental data, are the following: k "1.34$0.02 d~1,
A
>@ "3.6$0.3]1013 cells/mol, k"0.229$0.004 d~1.
A
Figs. 3 and 7 compare the experimental data with the
5. Application of the mathematical model to the predicted curves using the developed model with esti-
experimental data mated parameters. It is evident a good agreement be-
tween the experimental and the calculated values.
Parameters included in system (15) were "xed as Table 2 shows a comparison between k and >@ values
A A
follows: estimated in this work with other values found in the
literature. A value for parameter k was not found in
f K and X were measured in separate adsorption the literature, since most models have been developed
A am
experiments; for ferrooxidans microorganisms and, as a consequence,

Fig. 7. Model simulation of cell concentration in the liquid phase and adsorbed on the mineral surface. Points represent experimental cell
concentration in solution (initial ferric iron 0; mineral concentration 3 percent w/v; temperature 303C).
792 F. Vegliò et al. / Chemical Engineering Science 55 (2000) 783}795

Table 2
Comparison between parameters estimated in this work and values found in the literature

k [d~1] > ]10~13 [cells/mol] Mineral Microorganism Ref.

A A
1.34$0.02 3.6$0.3 Pyrrhotite ¹hiobacillus thiooxidans This work
1.8 2.7 Zinc sul"de ¹hiobacillus ferrooxidans Konishi et al., 1992
2.5 4.0}4.6 Pyrite ¹hiobacillus ferrooxidans Asai et al., 1992
9.0 3.1 Pyrite Acidianus brierleyi Konishi et al., 1995
1.6 2 Elemental sulfur ¹hiobacillus ferrooxidans Konishi et al., 1994
2.5 0.6 Pyrite ¹hiobacillus ferrooxidans Shrirari et al., 1995

ferrous iron oxidation is considered very fast with respect
to the bioleaching process. Table 2 shows that there is
a good agreement in general between values estimated in
this work and other values found in the literature. In
particular, parameter k is in agreement with other
A A A
values, except the one obtained with A. brierley, a ter-
mophile microorganism which was demonstrated to be
very e!ective in pyrite bioleaching (Konishi et al., 1995).
The con"dence helixes of parameters were estimated
according to Himmelblau (1970), in order to have more
information on the parameters' estimation error. Fig. 8
shows, as example, the con"dence helixe for pair k !k.
A
The dotted lines delimitate the variability region that is
achieved considering just single parameters con"dence
limits. It is evident that a satisfactory variability has
been achieved. A further information on the estimated
values was achieved by performing a sensitive analysis
(Himmelblau, 1970). A 10 per cent variation imposed
singularly to experimental data determined a maximum
variation of 0.8, 1.1 and 0.34 per cent in the estimates of
k , >@ and k, respectively.
Considering that the chemical leaching with ferric iron
is very important in pyrrhotite bioleaching, some experi-
mental tests were performed adding ferric iron at the
beginning of the process (C0 3`"100 mM and 200 mM).
F%
Fig. 9 shows experimental iron extraction yields (points)
and predicted values by the developed model (solid lines).
It is evident, as expected, the positive e!ect of ferric
iron. In fact, the bioleaching rate increases as the initial
ferric iron concentration increases. Furthermore, the
iron extraction yields achieved at the end of the process
are higher in the presence of an higher ferric iron

Fig. 8. Con"dence helixe at 95 per cent for pair mA-k.

 F. Vegliò et al. / Chemical Engineering Science 55 (2000) 783}795 793

Fig. 9. E!ect of initial ferric iron concentration on the iron extraction yields vs. time pro"le. Solid lines were calculated with the mathematical model
developed in the text. Broken lines represent data points when insoluble product was deposited on the mineral surface. Points represent experimental
data (mineral concentration 3 per cent w/v; temperature 303C).

Fig. 10. Direct and indirect mechanisms contributions in the investigated experimental conditions (see text for details).

concentration. Fig. 9 also evidences that after some presence of high ferric iron concentration (Bhatti et al.,
days of treatment experimental data signi"cantly di!er 1992).
from predicted values. This aspect might be connected Fig. 10 shows direct and indirect mechanisms contri-
to precipitation phenomena, that are favoured in the butions as calculated by the developed model, in the
794 F. Vegliò et al. / Chemical Engineering Science 55 (2000) 783}795
Fig. 11. Flow diagram of a possible con"guration for pyrrhotite oxidation pretreatment.
investigated experimental conditions. The solid lines rep-
resent the indirect mechanism's rate vs. time pro"les and
they are associated to the y-axis on the left. The dotted
lines are the biological leaching rate vs. time pro"les
and are associated to the y-axis on the right. It is evident
that in all cases the indirect mechanism is signi"cantly
dominant.
6. Conclusions
A kinetic study of the batch leaching of a pyrrhotite
ore by a sulfooxidans strain is reported in this work.
A mathematical model consistent with experimental data
is developed, which takes into account both direct and
indirect mechanism. The development has been per-
formed from a separate study of microorganism's adsorp-
tion on the solid surface and of chemical leaching of
pyrrhotite by ferric iron. The representative equations of
these phenomena (Langmuir equation and a kinetic
model with variable activation energy, respectively) have
been combined with material balances of total iron, ferric
iron and biomass. The "nal model consists of a system of
three ordinary di!erential equations, where the indepen-
dent variable is time and dependent variables are total
iron, ferric iron and biomass concentrations in solution.
The key parameters of the model were: the speci"c
growth rate, k , and the growth yield, >@ , of adsorbed
A A
bacteria, and the reaction rate constant of ferrous iron
oxidation, k. These parameters were estimated by regres-
sion analysis using a least-square algorithm during nu-
merical resolution of the di!erential equations. The
development has been performed considering as a refer-
ence the Konishi et al. (1992) model. In this case the
model is valid for sulfooxidans microorganisms, and
this aspect represents the novelty of the mathematical
approach.
The indirect mechanism, that is the chemical leaching
of pyrrhotite by ferric iron, was demonstrated to be very
important during pyrrhotite bioleaching. It was evid-
enced both by experimental results increasing the initial
ferric iron concentration in solution (Fig. 9) and by nu-
merical resolution of the developed model (Fig. 10). This
aspect suggests a possible con"guration for pyrrhotite
oxidation pretreatment prior to cyanidation for gold
extraction, which might be more e!ective with respect to
the bioleaching process. A #ow diagram of the proposed
con"guration is shown in Fig. 11. The pyrrhotite oxida-
tion takes place just through the chemical action of ferric
iron and ferrous iron is subsequently oxidized to ferric
iron in a separate biological reactor where Thiobacillus
ferrooxidans has previously been inoculated. Further
study will be performed in this direction.
Acknowledgements
This research has been carried out with the "nancial
support of CNR. Authors are grateful to Mr. Marcello
Centofanti and Dott. Silvia Di Pietro for their helpful
collaboration in the experimental work.
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