Particle Size Effects in the Microbiological
f eaching of Sulfide Concentrates by
Thiobacillus Ferrooxidans
M. A. Blancarte-Zurita and R. M. R. Branion
Department of Chemical Engineering, University of British Columbia,
Vancouver, British Columbia, Canada V6T 1W5
R. W. Lawrence
B. C. Research, 3650 Wesbrook Mall, Vancouver, British Columbia,
Canada V6S 2L2
Accepted for publication July 9, 1985
INTRODUCTION
The microbiological leaching of metals from sulfide
minerals has attracted much attention from researchers
and metal producers. An excellent critical review of
this topic has been published by Brierley.' One of the
foci of such research is the leaching of sulfide mineral
concentrates, which is the concern of the present work.
Specifically, this communication deals with the effects
of leaching on particle size when Cu and Fe are leached
from a chalcopyrite concentrate and Zn is leached from
a ZnS concentrate by Thiobucillus ferrooxiduns.
MATERIALS AND METHODS
Microorganism
The microorganism used in this study was originally
isolated by Razzell and Trussel12 from a copper mine
located at Britannia, B.C. It has been routinely main-
tained on copper concentrate suspended in the 9 K
medium, but without the iron described by Silverman
and L ~ n d g r e n . ~
It was determined4 that to minimize the time taken
to reach maximum copper concentration and to max-
imize the rate of copper extraction an inoculum age of
8 days was optimal. Thus transfers to new media were
made every 8 days.
Substrate
The chalcopyrite concentrate used in this study was
a commercial flotation concentrate supplied by New-
mont Mines Ltd., Similkameen Div., Princeton, B.C.
This concentrate was wet ball milled at 55% solids
Biotechnology a n d Bioengineering, Vol. XXVI11, Pp. 751-755 (1986)
0 1986 J o h n Wiley & Sons, Inc.
for 1 h to give 91.8% smaller than 400 Tyler mesh. It
was then recovered by filtration and dried at 60°C. The
elemental analysis of the concentrate was 27.8% cop-
per, 28.0% iron, 31.1% sulfur, and 5.5% insoluble.
Culture Technique
All experiments were carried out in 250-mL bottom-
baffled Erlenmeyer flasks containing 7.5 g of concen-
trate and 70 mL of the iron-free 9 K medium of Sil-
verman and L ~ n d g r e n The
. ~ pH was adjusted to 2.0
with IN HZS04.The flasks were loosely stoppered with
a cotton plug and mounted on a gyratory shaker. The
shaker was located in a dark room, maintained at 35°C
with a C0,-enriched atmosphere.
Before inoculation, but after the adjustment of pH
to 2, the flasks were held for 24 h to allow for acid
consumption by alkaline gangue present in the con-
centrate. After this the pH was readjusted to 2.0 and
the flasks inoculated with 5 mL of T . ferrooxiduns
suspension.
Evaporative water losses were made up periodically
by adding distilled water. In the sterile control flasks
1 mL of 1 :70 v/v phenol solution was added instead
of inoculum.
Analyses
The copper and iron contents of the medium were
determined at various times by stopping the shaker,
allowing the solids to settle for 10-15 min, then with-
drawing a 1-mL sample of the supernatant. The metal
analyses were done using an atomic absorption
spectrophotometer.
CCC 0006-3592/86/050751-05$04.00
Concentrate Size Fractionation
In some of our studies we wanted to follow the ef-
fects of leaching on particle size and vice versa; thus
we needed to get fractions of chalcopyrite having dif-
ferent particle sizes. The beaker decantation method5
is a simple way of doing this. Concentrate is added to
water in a large beaker or any other suitable container.
The slurry is stirred to mix it well then allowed to settle
for a predetermined time. The larger particles settle
while the smaller ones remain in suspension. The su-
pernatant suspension is carefully poured off into an-
other beaker and the process repeated using a longer
settling time, etc.
This fractionation procedure requires the use of a
deffoculatingagent to obtain uniform dispersions. Tween
40 (polyoxyethylene sorbitan monopalmitate) was used.
It was subsequently removed from the fractionated
particles by solvent extraction with isopropanol in the
presence of K2C03.6Tween 40 inhibited leaching but
after removal by the solvent extraction technique no
such inhibition was observed. 99% removal of the dis-
persant could be a ~ h i e v e d . ~
Particle Size Analysis
Dilute suspensions of the various fractions were made
in 10 mL of ethanol using 0.1% aerosol GPG (sodium
dioctyl sulfosuccinate in ethanol and water) as a dis-
persant in an ultrasonic bath. Microscope slides were
prepared from these suspensions and size distributions
were measured using an eyepiece micrometer in a mi-
croscope to measure the Martin's diameters of 100
particles~
assuming that the particle shape factor is constant gives
for the change in particle mass
dN -
-- d dP
- - 3 p a dp2 __ (3)
dt dt
The rate of appearance of Cu in solution can be
measured; call this rate r which is expressed in terms
of mass x volume-' x time-'. To convert the rate
of Cu dissolution to a rate of particle dissolution we
must divide r by the weight fraction f of Cu in the
concentrate. Thus the rate of particle dissolution is r/f.
The term - 3a dp2 (d dpldt) represents the dissolution
rate of a single particle. The measurement of r is made
in a suspension containing many particles per unit vol-
ume. Let n be the number of particles per unit volume.
Assume that no particles disappear during leaching;
then n is a constant and is equal to Cdpa dpO3,where
C, is the initial mass of concentrate per unit volume
in the leach system and dpo is the initial particle diameter.
Then
which reduces to
-3C0 dp2 -d = dp- r
(5)
dpO3 dt f
r, f , and dp, can be measured, and C, can be set by
the experimenter; thus eq. ( 5 ) can be integrated to give
particle diameter as a function of time.
If necessary the assumption of no total disappear-
ance of particles during leaching can be relaxed but
then the integration must be done numerically; r is a

function of the amount of mineral surface per unit vol-

After the leaching phase of this study was completed ume available to the organism and thus a function of
use of a Leitz image analyzer became possible so the dp since surface area is proportional to dp2. For batch
unleached fractions were reanalyzed using this instru- leaches r is also a function of time.
ment counting at least 1000 particles.
RESULTS AND DISCUSSION
THEORETICAL
Table I provides data about the initial sizes of the
The following shrinking particle model is proposed various fractions used in the leaching experiments as
to describe the leaching behavior. Since material is well as the mean size of the unfractionated concentrate.
being solubilized from the particles the particle mass
decreases and it is assumed that as leaching occurs the
particles get smaller. The rate of particle size decrease Table I. Properties of particle size fractions.
is given by - dN/dt, where N is the particle mass and Mean particle diameter (pm)
t is time. Assuming that the particles have a constant
density p, we have Fraction Image
number Microscope analyzer
dN -
-- dV
- -P-& (1) 1 0.38 0.20
dt
2 1.81 2.68
where V is particle volume, which can be represented 3 1.67 2.76
by 4 3.10 3.53
5 5.64 5.98
V = a dp3 (2) 6 6.74 6.45
Unfractionated 1.86 2.86
where dp is the particle diameter and a the particle concentrate
shape factor. Now substituting eq. (2) into eq. ( 1 ) and

752 BIOTECHNOLOGY AND BIOENGINEERING, VOL. 28, MAY 1986

 ,
I
O h 181urn 72h 184um 24h 228um

7 -1 -1
240h 141um 10
330 h 1.42 urn

E I0

Lnr ' m

6 0

0 0
0 00 I I6 I 20 I 30 4 8
SIZE i m c ~ w l o f ~ l

Figure 1. Particle size distribution as a function of leach time for fraction 2.

>-
0
11 -
r.
6 1
10- ,--A
&fraction 1
v

z 9- / nfraction 2
x fraction 3
fraction 4
p: 7- Xfraction 5 0 I

0
b
z; 6-
I LEGEND I
z 5-

"p:
0
4-

w 3-
a
3
" 2-

1-

0 50 100 150 200 250 300
TIME (h)
Figure 2. Copper concentration solution as a function of leach time
for various particle sizes.
Figure 1 shows a typical size distribution as a func-
tion of leach time (for fraction 2 ) , indicating that par-
ticle size does decrease with time but not, for this
particular concentrate, by very much.
Figure 2 plots copper concentration as a function of
leach time for the various concentrate fractions. Figure
2 shows that the rate of Cu dissolution r is a function
of dp and of time. However, since this concentrate did
not leach very well, i.e., the Cu extraction was typi-
cally of the order of 26%, we assumed the r would not
change much as a result of particle size changes during
leaching; however, r was treated as a function of leach
time t. Curves of the form
[CU]
atb = (6)
where a and b are constants and [Cu] is copper con-
centration were fitted to the data of Figure 2 for each
particle size fraction. From (6)
350 400 450 0 50 100 I50 200 250 300 350 400 450
TIME (hours)
Figure 3. Particle size vs leach time for fractions 2, 3, and 5. The
lines are calculated using eq. (9). The points are experimental mea-
surements using a microscope.
Figure 3 and 4 show that the predictions of the model
are not in disagreement with the measured data and
thus the model has some credibility. On the other hand,
there is a great deal of scatter in the measured data.
Moreover, the concentrate used did not leach very well
and thus did not provide an ideal test of the model for
particle shrinkage.
Torma et a].' measured particle size distributions
initially and at various intervals during the leaching of
a ZnS concentrate. They and Sanmugasunderam8 also
published data from which the rate of Zn dissolution
can be calculated. In these ZnS leaching studies much
higher levels of Zn extraction were observed (80 + %);
thus the particles would become much smaller or, in
the case of the smaller ones, disappear.

Introducing (7) into ( 5 ) leads to

(7)

h
m
6u
5-

- dp2 d dp = -
ab
f
I: tb-' dt (8)
I.
u
c

i
2
4-

4
which integrates to .I

1/3
9 3-

(9)
dP0
Plots of dp vs. c for fractions 2 , 3, and 5 of Table I
as calculated by eq. (9) are shown in Figure 3. Also
shown are the measured values taken from Figure 1
and others like it (not shown). These values are those
ol
measured using the microscope. 0 50 100 150 200 250
Later a test was run using the unfractionated con- TIME (hours)
centrate and analyzing particle size distribution with Figure 4. Particle size vs. leach time for the unfractionated con-
the image analyzer. These results are presented in Fig- centrate. The line is calculated using eq. (9). The points are exper-
ure 4. imental measurements using an image analyzer.

754 BJOTECHNOLOGY AND BIOENGINEERING, VOL. 28, MAY 1986

 and Engineering Research Council of Canada, and El Consejo Na-
; o o * l 90
cional d e Ciencia y Tecnologia (MCxico).

“ T - - i - -
7 7- 1
0 5 10 15 10 25 30 35 40
PARTICLE DIAMETER (urn)
Figure 5. Cumulative particle size (mass basis) distribution of a
ZnS concentrate after 212 h of leaching. The line is calculated using
a program based on eq. (5). The points represent the experimental
data of Torma et a].’
A computer program based on the model presented
in this work was written to predict the size distributions
measured by Torma et al.’ A more detailed description
is given in ref. 9. This program integrated eq. ( 5 ) using
equations fitted to Torma’s and Sanmugasunderam’s
data to give r as a function of dp. It also allowed for
the disappearance of particles before completion of the
leach. Figure 5 plots the cumulative mass-based par-
ticle size distributions as calculated by the program
and as measured by Torma et al.’ Agreement is good,
thus lending further credibility to this model.
Financial assistance for this project has been provided by B.C. Re-
search, The University of British Columbia, The Natural Sciences
NOMENCLATURE
Constants
Initial mass of concentrate per unit volume (g/L)
Particle diameter (cm)
Initial particle diameter (cm)
Weight fraction of copper in concentrate
Particle mass (g)
Number of particles per unit volume (L-’)
Time (h)
Leaching rate (g/L h)
Particle volume (cm’)
Particle shape factor
Density of concentrate (g/cm3)
References
1. C. L. Bnerly, “Bacterial leaching,” CRC Crir. Rev. Microbiol.,
207 (1978).
2. W. E. Razzel and P. C. Trussel, J. Bacteriol., 85, 595 (1963).
3. M. P. Silverman and D. G. Lundgren, J. Bacteriol., 77,642 (1959).
4. M. A. Blancarte-Zurita, “Effect of particle size on the kinetics
of microbiological leaching of chalcopyrite,” M.A.Sc. Thesis,
University of British Columbia, (1983).
5. E. J. Pryor, Mineraf Processing (Elsevier, Amsterdam, 1965).
6. Organization for Economic Co-operation and Development
(OECD), Proposed method for the determination of the biode-
gradability of surfactants used in synthetic detergents, Paris, 1974.
7. A. E. Torma, C. C. Walden, and R. M. R. Branion, Biorechnoi.
Bioeng., 12, 500 (1970).
8. V. Sanmugasunderam, “Kinetic studies on the biological leaching
of ZnS concentrate in 2 stage, continuous, stirred tank reactors,”
Ph.D. Thesis, University of British Columbia (1981).
9. M. A. Blancarte-Zunta, R. M. R. Branion, and R. W. Lawrence,
Preprints, International Symposium on Biohydrometallurgy,
Vancouver, 1985.

COMMUNICATION TO THE EDITOR 755