TRAVELS THROUGH BIOLEACHING

Geoffrey Hansford
Professor Emeritus Department of Chemical Engineering, University of Cape Town, Rondebosch 7701,
South Africa. gsh@chemeng.uct.ac.za

ABSTRACT
This paper will cover the progress of research into the mechanism and kinetics of bioleaching of
sulfide minerals. It will cover the early work on the bioleaching of pyrite and the recognition that
bioleaching produced holes in the pyrite particles and that the rate of leaching was linearly dependent
on the surface area of the particles. The elucidation of the mechanism of leaching, consisting of three
sub-processes will be described as well as the two pathways followed by the sulfur moiety. Identification
of the predominant microorganisms in mesophilic bioleaching of pyrite and arsenopyrite/pyrite will be
discussed. Recent work on the investigation of the microbial oxidation of ferrous iron by mesophiles
and thermophiles will be presented.

INTRODUCTION
The plenary lectures at previous International Biohydrometallurgy Symposia have detailed the
fundamental and industrial development of the bioleaching of sulfide minerals. I do not presume to
attempt a repeat of those excellent presentations. Rather I plan to detail my personal travels in the field
of bioleaching. This will include my introduction to bioleaching and the work of my students and post-
doctoral fellows and how my understanding and interest in bioleaching has grown through the people I
have met along the way, and the many good friends that I have made. Needless to say that in pursuit of
knowledge about bioleaching I have been able to visit many exciting places around the world.

THE JOURNEY
In the mid 1970’s I was carrying out research on the use of biofilm reactors for the bio-treatment of
industrial wastewaters. A colleague introduced me to Eric Goldblatt who was developing the BACFOX
process at GENCOR for the microbial oxidation of iron to the ferric form for use as a lixiviant for
uranium extraction at gold mines on the West Rand. When I visited Goldblatt at the GENCOR
Research Laboratories in Krugersdorp west of Johannesburg he showed me the reactors in which iron-
oxidizing bacteria were bacteria attached to a film of jarosite on plastic packing. He also showed me the
pilot plant work he was pioneering on the development of bioleaching to remove arsenic from refractory
gold concentrate as an alternative to roasting for use on the Fairview Gold Mine in Barberton. At the
time the fact that microorganisms could flourish in an environment of pH less than 2.0 and devoid of
organic substrate was amazing. And yet I have spent the remainder of my career investigating the
behaviour of these remarkable creatures.
My early work, sadly never published, was done by Candice Polson and Kim Clarke who ran biofilm
reactors oxidizing ferrous iron medium with what we believed were Thiobacillus ferrooxidans but
noticed that we had characteristic spirillum-shaped bacteria in our system. Candy and Kim compiled an
excellent comprehensive survey of the bioleaching literature of that time.
Some years later, Ian Corrans [1] and Rob Dunne, who were then at MINTEK, supported a master’s
student, Marianna Drossou, who measured the rate of bioleaching of pyrite concentrate using five
different size fractions. From her work we concluded that the rate was linearly related to the surface
area of the pyrite. Further work using a narrow size fraction at several concentrations confirmed these
observations. It was at about this time that Angela and Malcolm Southwood found from polished
sections of bioleached pyrite that pores developed along crystallographic axes. Using bioleached pyrite
from the investigations of Drossou and Chapman we found similar leach patterns [2]. These were
similar to the leach patterns reported by Tributsch and Rojas-Chapana [3].

Proceedings of the 16th International Biohydrometallurgy Symposium 25 – 29 September 2005

Editors: STL Harrison, DE Rawlings and J Petersen Cape Town, South Africa
ISBN: 1-920051-17-1 Produced by Compress www.compress.co.za
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Figure 1. Scanning electronmicrograph of euhedral pyrite bioleached for four dyas at 30oC and pH1.8 with
Acidithiobacillus ferrooxidans [2]

Just prior to this I had been sponsored by the South African Chamber of Mines to attend the 1985
IBS in Vancouver. Having read much of the literature, I was familiar with the names of many of the
people in bioleaching, but had not met them. Imagine my surprise at the opening function when
standing at the back next to a rather quiet man he turned and remarked that I must be a new and
introduced himself as Jim Brierley. There started a firm friendship that has lasted twenty years with
much advice and guidance on my research. After the conference I had my first introduction to heap
bioleaching in a visit to the Brierley’s and Arpad Torma in Socorro NM and the heap bioleach facility
[4]. I still use this Murr paper as a means of introducing new students to bioleaching.
During a year of sabbatical leave spent at MINTEK with Tony Pinches, he introduced me to many
aspects of bioleaching including the logistic equation as a means of correlating bioleach data. This was
used successfully by Deborah Miller to correlate BIOX pilot plant data [5,6].
The tank bioleaching processes were being limited to below 20% solids and the reasons for this were
unclear although it was generally accepted that gas-liquid mass transfer limitation might be the most
probable reason. Andrew Bailey reviewed the literature on this and showed experimentally that for the
mesophilic bioleaching of pyrite, oxygen transfer was indeed limiting above 20% solids. He determined
oxygen demand and compared this with oxygen supply derived from correlations for kLa [7,8]. This
important aspect of bioleaching has received minimal attention by researchers.
With the implementation of the BIOX and BacTech-Mintek tank bioleaching processes for leaching
arsenic from refractory gold concentrates, and the growing interest in a more engineering approach to
heap bioleaching, research in bioleaching in general grew.
During the early 1990’s several factors strongly influenced the progress of my research in bioleaching.
The first was the support from Billiton for a continuous mini-plant for the investigation of unsteady
state phenomena and arsenic toxicity in their BIOX process, support from MINTEK and also from
Gold Fields of South Africa and O’okiep Copper for investigations of the bioleaching of copper and
zinc. It was this latter that showed me that ‘wild’ cultures were very effective at bioleaching. Secondly I
had the privilege of spending a year working with Prof Sef Heijnen and his doctoral student Mieke
Boon at TUDelft. Prof Heijnen approached bioleaching from the point of view of thermodynamics and
with a background in wastewater treatment used off-gas analysis and oxygen utilization to investigate
bioleach kinetics. This was to prove a turning point in my approach to bioleaching research. The third
was generous grants from the Gold Fields Foundation facilitated by Richard Beck and THRIP by
Andre van der Westhuizen that enabled Chemical Engineering at UCT to equip the minerals

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bioprocessing laboratory with a series of stirred and air-lift bioreactors linked to off-gas analyzers and
oxygen utilization instruments. These are still in constant use.
Prior to this the importance ‘direct’ versus ‘indirect’ mechanism was debated at biohydrometallurgy
symposia and other conferences on minerals bioprocessing. In her doctoral on the bioleaching of pyrite
and the microbial oxidation of ferrous iron, Mieke Boon showed very elegantly that the microbial
activity of Leptospirillum-like bacteria was the same at equal redox potentials for growth on either
pyrite or ferrous iron [9,10]. From this it was concluded that bioleaching involved the sub-processes of
microbial iron oxidation and acid-ferric leaching of the pyrite. Shortly thereafter, Schippers and Sand
[11] showed that the sulfur moiety of sulfide minerals could follow one of two paths of further oxidation
viz., the hyposulfite route in which little if any sulfur substrate was available to support the growth of
sulfur oxidizing microorganisms, and the other which occurs with most sulfide minerals where the sulfur
passes via a polysulfide pathway to elemental and permits the growth of microbial sulfur oxidizers.
These findings then lead to the formulation of the following, most likely mechanism for the
bioleaching. This is that the sulfide mineral is leached by an acid, ferric reaction that leads to the
dissolution of metal ions, the iron is reduced to the ferrous form and in most cases with the exception of
pyrite, and polysulfide decomposes to elemental sulfur. The ferrous provides the substrate for iron-
oxidizing microorganisms which produce the ferric lixiviant and the sulfur-oxidizing microorganisms
oxidize the sulfur to sulfate and in the process generate protons to maintain the low pH necessary for
mineral leaching. The work of Rawlings has found that in the bioleaching of an arsenopyrite-pyrite
concentrate, a sulfur-oxidizer, Acidithiobacillus caldus and an iron oxidizer Leptospirillum ferriphilum
co-exist and predominate. Reasons for this have been suggested and are in agreement with the
mechanism proposed [12]. These concepts have guided my research approach. Although to my
knowledge no direct enzymatic mechanism of bioleaching has been demonstrated, there are credible
reports of bioleaching taking place in the absence of iron, which suggest that some direct mechanism is
involved [13]. It has also been demonstrated that the bioleaching microorganisms attach to the sulfide
minerals by means of a layer of extracellular polymeric substance, EPS, and that in this EPS layer, the
concentrations of ferric ions and protons are greater than in the bulk solution, [14]. In the absence of a
build up of a sulfur layer on the mineral surface, a balance between the acid-ferric leach kinetics and the
microbial ferrous-iron oxidation rate determines the rate of bioleaching. In a continuous system
bioleach system the operating condition will then be defined by the intersection of the two kinetic curves
[10].

Figure 2. The rates of ferrous iron oxidation by Acidithiobacillus ferrooxidans and Leptospirillum
ferrooxidans and the rate of ferric oxidation of pyrite.

This has been used to explain why Leptospirillum ferriphilum is found to be the predominant Fe-
oxidizer rather than Acidithiobacillus ferrooxidans in the bioleaching of pyrite and arsenopyrite. On the
other hand for copper sulfides such as chalcocite which leach at lower solution potentials [15]

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Acidithiobacillus ferrooxidans maybe the predominant iron-oxidizer. This however, has not been
demonstrated experimentally.
Further evidence in favour of the indirect or contact mechanism was provided by May et al., [16] who
compared microbial and bioleach rates of pyrite over the same range of redox potentials.

Figure 3. The rates of pyrite leaching by Leptospirillum ferrooxidans and the rate of abiotic ferric leaching
of pyrite.

Using the initial rates of isopotential ferric leaching of chalcopyrite [17], it has also been suggested
that this is the reason for the successful bioleaching of chalcopyrite by thermophiles that have iron-
oxidation kinetics which decrease at the higher potentials where chalcopyrite has decrease leach rates
[18,19].
Using this approach it is also possible to develop a model for continuous tank bioleaching. Some
attempts have been published and undoubtedly comprehensive models are available within industrial
organizations.
The group at the University of Cape Town has investigated the ferrous iron oxidation kinetics by
Leptospirillum ferriphilum over a narrow range of temperature and pH [20,21,22]. Recently Searby [23]
has completed an investigation of the iron-oxidation kinetics by a thermophilic culture, the results show
a similar trend to the mesophiles with the onset of ferric inhibition at lower potentials than
Leptospirillum ferriphilum. Interestingly the biomass yield decreases steady with increasing temperature,
contrary to theoretical predictions using Gibbs free energy of formation. These results will be published
shortly.
Ojumu, Searby and Petersen [17] have reviewed all the data and rate equations for microbial ferrous
iron oxidation. These have been investigated under mesophilic conditions and have concentrated mainly
on Acidithiobacillus ferrooxidans with a few studies on Leptospirillum ferriphilum and none on
thermophilic cultures. Several methods have been used to study the kinetics; initial rate, batch culture,
continuous culture and iso-potential culture. It was concluded that only the last two gave results that
were of use in predicting the performance of bioleach systems according to the sub-process mechanism.
Furthermore despite many published rate equations proposed to include a range of phenomena, it was
found that the majority of the continuous culture data could be fitted with a simple model of the form
proposed by Boon et al., [9].

Where:
qFe2+ is the specific rate of iron oxidation (moleFe).(moleC)-1h-1
qFe2+max the maximum specific rate (moleFe).(moleC)-1h-1
K the inhibition constant

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 All the studies investigated were carried out at near optimum conditions, and yet many bioleach
systems in particular heaps have conditions such as temperature, pH and dissolved ion concentrations
that may be far away from optimal. Although Franzmann et al., [24] have studied the effect of
temperature in batch culture, and Vargas and co-workers [25] have studied kinetics at higher pH, there
is need for a more comprehensive investigation of the kinetics of microbial iron and sulfur oxidation by
the most common microorganisms found in industrial process and also the shifts in microbial
population under changing conditions in tank and heap bioleaching. It is in this area where our current
studies are focussed.

REFERENCES
1. Corrans, I.J. (1974) Kinetic and Mechanistic Studies on the Biological and Chemical Leaching of
Nickel from Sulphide Ores. PhD Thesis University of Natal, Durban, South Africa.
2. Hansford, G.S. and M.Drossou (1988) in Norris, P.R. and D.P. Kelly (Eds) Biohydrometallurgy
Proceedings of the International Symposium, Warwick (July 1987).
3. Tributsch, H. and J. Rojas-Chapana (2004) in Tzesos, M., A. Hatzikioseyian and E. Remoundaki,
15th International Biohydrometallurgy Symposium (IBS2003) September 2003 Athens, Greece.
1047-1055.
4. Murr, L.E.(1980) Minerals Sci.Engng. 12, 121-189.
5. Miller, D.M. and G.S. Hansford, (1992) Minerals Engineering, 5, 737-750.
6. Dew, D.W., E.N. Lawson and J.L. Broadhurst (1997) in Rawlings, D.E.(ed.) Biomining: Theory,
Microbes and Industrial Processes, Springer-Verlag, 45-80.
7. Bailey, A.D. and G.S. Hansford, (1993) Biotechnol. Bioeng. 42, 1164-1174.
8. Hansford, G.S. and A.D. Bailey (1993), in Biohydrometallurgical Technologies Vol. I, 469-478, A.E.
Torma, J.E. Wey and V.L. Lakshmanan (Eds.) The Minerals, Metals and Materials Society,
Warrendale, PA.
9. Boon, M., G.S. Hansford and J.J. Heijnen (1995) in Biohydrometallurgical Processing, Vol. I,
Proceedings of International Biohydrometallurgy Symposium, Via del Mar, Chile (November
1995) T. Vargas, C.A. Jerez, J.V. Wiertz and H. Toledo (Eds.), University of Chile, Santiago, 153-
163.
10. Boon, M (1996), Theoretical and Experimental Methods in the Modelling of Bio-oxidation Kinetics
of Sulfide Minerals. PhD Thesis, TUDelft, The Netherlands.
11. Schippers, A. and W. Sand (1999), Appl.Environ.Microbiol. 62, 319-321.
12. Rawlings, D.E., H. Tributsch and G.S. Hansford (1999) Microbiology 145, 5-13.
13. Pisotrio, M., G. Curuchet, E. Donati and P. Tedesco (1994) Biotechnol. Lett. 16, 419.
14. Kinzler, K., W. Sand, J. Telegdi and E. Kalman (2004) in Tzesos, M., A. Hatzikioseyian and E.
Remoundaki, 15th International Biohydrometallurgy Symposium (IBS2003) September 2003
Athens, Greece. 1003-1009.
15. Hansford, G.S. (1997) in Rawlings, D.E.(ed.) Biomining: Theory, Microbes and Industrial
Processes, Springer-Verlag, 154-175.
16. May, N., D.E. Ralph and G.S. Hansford (1997) Minerals Engineering, 10, 1279-1290.
17. Kametani, H. and A. Aoki (1985) Metall. Trans.B, 16B, 695-705.
18. Hansford, G.S. (1988) Proc.Randol Copper Hydromet. Round Table, Vancouver, Canada (Nov.
1998) Randol International Ltd, Golden, CO. 229-234.
19. Hansford, G.S., T.A. Furamera, M.A. Jaffer and G.E. Searby (1999) Alta Copper Conference,
Gold Coast, Australia (Sept.!999).
20. Breed, A.W., C.J.N. Dempers, G.E. Searby, M.N. Gardner, D.E. Rawlings and G.S. Hansford
(1999) Biotechnol.Bioeng. 65, 44-53.
21. Breed, A.W. and G.S. Hansford (1999) Biochem.Eng.Jour., 3, 193-201.
22. van Scherpenzeel, D.A., M. Boon, C. Ras, G.S. Hansford and J.J. Heijnen (1998) Biotechnol.Prog.
14, 425-433.
23. Searby, G.E. and G.S. Hansford (2004) in Tzesos,M., A. Hatzikioseyian and E. Remoundaki, 15th
International Biohydrometallurgy Symposium (IBS2003) September 2003 Athens, Greece. 1227-
1235.
24. Ojumu, T.V., Petersen, J., Searby, G. and Hansford, G.S. (2005): A Review Of Rate Equations
Proposed For Microbial Ferrous-Iron Oxidation With A View To Application To Heap

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 Bioleaching in S.T.L. Harrison, D.E. Rawlings and J. Petersen (eds.): IBS2005 - Proceedings of the
16th International Hydrometallurgy Symposium; in press
25. Franzmann, P.D., Haddad, C.M., Hawkes, R.B., Robertson, W.J and Plumb, J.J. (2005): Effects of
temperature on the rates of iron and sulfur oxidation by selected bioleaching Bacteria and
Archaea: Application of the Ratkowsky equation; Minerals Engineering; in press.
26. Meruane, G., C. Sahle, J. Wiertz and T.Vargas (2002) Biotechnol. Bioeng., 80, 280.

ACKNOWLEDGEMENTS
I wish to thank all the students, post-doctoral fellows and friends who have taught me so much
bioleaching, and who have shared an exciting and rewarding journey. I am particularly grateful for the
opportunities I have had to visit many parts of the world and of the hospitality and healthy discussion I
have enjoyed.
I also wish to acknowledge the financial support I have received from the South African FRD and
THRIP, the Chamber of Mines, Gold Fields of South Africa, the Gold Fields Foundation, BHP-
Billiton, MINTEK, CONYCIT(Chile), CONICET(Argentina) the University of Cape Town, the
University of Hamburg, The Parker Centre, Perth and the Ian Wark Centre, Adelaide (Australia), Rio
Tinto, AMIRA, USHEPiA BioMinE(FP6) and BioPaD. This has enabled me to support research
students, equip my laboratories and to visit research centres and universities.

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