COPPER SULFIDE

BIOLEACHING:
Process Chemistry
and Biology
Corale L. Brierley
Brierley Consultancy LLC
Objectives of presentation

 Consider microorganisms and most recent understanding

of bioleach functions and selectivity of organisms in
heap and stirred tank applications
 Examine factors affecting bioleaching & relate factors to
applications of the technology
 Discuss testwork needs and rationale
Microorganisms

 By temperature characteristics
 Mesophilic - Approx. 25-45oC (75-110oF)
 Moderately thermophilic – Approx 35-60oC (95-140oF)
 Extremely thermophilic – Approx 50-80oC (125-175oF)
 By energy source
 Iron oxidizers
 Sulfur oxidizers
 Types and numbers of microorganisms change in heap or
stirred reactors with time, temperature and chemical
conditions
 Some common microorganisms

 Mesophiles
 Acidithiobacillus ferrooxidans:
oxidize Fe, S
 Leptospirillum ferrooxidans:
oxidize Fe, predominate at high
redox/Fe3+ (e.g. stirred tank
reactor, very acidic heaps)
 Ferroplasma sp: archaea,
oxidize Fe, predominate at low
pH
 Moderate thermophiles
 Sulfobacillus sp
 Acidithiobacillus caldus
Some extremophiles

 Archaea (not bacteria)

 Sulfolobus acidocaldarius:
oxidize S, but not Fe
 Acidianus brierleyi:
oxidize S & Fe
 Extremophiles used in
aerated, stirred-tank
reactors for chalcopyrite
concentrate leaching &
sulfidic-refractory Au
heap leaching
 Bioleaching mechanism: current
thinking
 Fe oxidation by attached
(contact) & bulk leach solution
(non-contact) microbes
 Microbes produce extracellular
polymeric substances (EPS) &
attach electrostatically to
mineral
 High concentrations of
complexed Fe3+
 EPS a “reaction space” for metal
sulfide oxidation
 Fe2+ oxidation by contact
microbes occurs on microbe
membrane
From: Atomic force micrograph from
Rohwerder et al. Appl Microbiol Biotechnol
63:239-248, 2003
Model for bioleach mechanism
 Leaching pathways
Acid-nonsoluble (FeS2, MoS2) Acid soluble
(CuFeS2, ZnS)
Factors affecting
microorganisms
 Temperature  Energy source (food)
 Oxidation-reduction  Salinity
potential (redox)
 Soluble cation and anion
 pH metal/metalloid
concentrations
 Oxygen
 Process reagents
 Carbon dioxide
 Nutrients
Temperature:
generation/retention of heat
 Temperature increase result of exothermic S2- oxidation,
principally pyrite (-12,884 kJ/kg)
 Build-up of heat also dependent on reactor design
 In heaps heating dependent several factors including
height, irrigation, ambient conditions, etc.
 Stirred-tank reactors for concentrate bioleaching are water
cooled
 Temperature: heaps/dumps

 In heaps/dumps
increasing temperature
results in succession of
organisms
 ~80°C noted in Cu dumps
 Highest temperature in
sulfidic-refractory Au
heap leach was 81°C
(Tempel. 2003. SME Preprint
03-067)
Temperature: secondary
copper heaps
 Temperatures below optimum for bacteria are generally
the problem
 Why don’t secondary copper heaps heat?
 S2--S concentration (as FeS2) often sufficient (1 to 2%)
 Sulfidic-refractory Au heaps with this S2—S content do heat
(Tempel. 2003. SME Preprint 03-067)

 Could redox be the reason?

Redox: dynamics in heaps

 Redox controlled by Fe3+ : Fe2+ ratio in sulfide

leaching
 Dissolution of Cu2S occurs at a very low redox
potential (~160 mV SHE)
 Dissolution of CuS occurs at lower redox potential
(~450 mV SHE) than FeS2(650-700 mV SHE)
 In heaps Fe3+ is constantly consumed by S2- minerals
 Consumption of Fe3+ can be greater than microbial
oxidation rate of Fe2+, decreasing redox potential
 Until all (available) minerals with rest potential
lower than FeS2 are consumed, redox will not
increase high enough to oxidize FeS2
Redox: “selective leaching”

 Phenomenon of redox-controlled “selective leaching”

observed in sulfidic-refractory Au pilot test heaps
 FeAsS & ZnS leaches before FeS2 (noted by As & Zn
concentrations in effluents); redox depressed until these
minerals are depleted
 Temperature increases noted after FeAsS & ZnS depleted,
when redox increases & FeS2 begins oxidizing
Redox: high Eh scenarios

 FeS2 probably oxidizes in ROM Cu dumps because all

minerals with lower rest potential depleted
 Phenomenon best observed in column studies
 Anecdotal evidence that FeS2 will oxidize in secondary
Cu heap leach, if continue leaching after Cu minerals
depleted
 Depressed redox doesn’t occur in high performance
stirred-tank reactors
 Exception is CuFeS2
Redox: bioleaching of CuFeS2

 CuFeS2 leached at very high redox potential, but surface

passivation diminishes Cu recovery
 CuFeS2 effectively leached in 615 to 645 mV (SHE) range
at 65°+
 No surface passivation
 This is basis of BioCOP, stirred-tank bioleach
technology using extreme thermophiles
 Mintek & NICICO currently pilot testing similar
technology for heap leaching CuFeS2 ore at Sarcheshmeh
pH

 Controls Fe solubility & microbial population

 pH > 2.5 enhances Fe precipitation
 Reduce availability of Fe for microbial oxidation
 Potentially reduce heap permeability, impacting air &
solution permeability
 Can potentially coat particles, impacting leachability
 Form evaporites around air distribution system
 pH <1.2
 Increases H+ concentration, stressing microbes to
reject H+
 Reduces “diversity” of microbial population (low pH
selects for Leptospirillum & Ac. thiooxidans)
 High Fe selects for Ferroplasma
O2

 All microorganisms used in bioleaching require O2 as the

electron acceptor
4 Fe2+ + O2 + 4 H+  4 Fe3+ + 2 H2O
S° + O2 + 2 H2O  4 H+ + SO42-
 O2 utilization efficiencies in heaps around 20-30%
(higher % has been reported, but may be due to
insufficient addition)
 Can do interstitial gas measurements (20% O2 by vol is
recommended)
 DO in effluent not a good measure
 O2 utilization in stirred tanks (>40%)
 DO maintained at 2 ppm
 Aeration in high temperature, stirred tanks for CuFeS2
leaching is a challenge; use compressed O2
Nutrients: what do microbes
need?
 PO43- , NH4+, trace elements (K+ & Mg2+)
 In heaps sufficient nutrients present in solution from
mineral dissolution
 (NH4)2SO4 sometimes added to achieve 2 ppm in solution
 Excessive NH4+ and PO43- enhance Fe3+ precipitation
 Nutrients added to stirred-tank bioleach plants
 Based on chemical composition of microbes & number of
cells (109 to 1010 per ml)
 Calculated back to kg N, P & K per tonne of S2-- S oxidized
CO2: essential for microbes

 Carbon required by microorganisms for synthesis of

cellular components
 Microbes obtain carbon from CO2
 CO2 not a problem in heap/dump leaching
 CO2 evolution from acid dissolution of carbonates
 CO2 addition sometimes required in stirred tanks
 Usually limestone added in stirred tanks for acid
neutralization; CO2 evolved in this reaction
 CO2 added for CuFeS2 concentrate bioleaching when pure
O2 used
Energy source: food

 Bioleaching microorganisms require Fe2+, chemically-

reduced S compound (S°, polysulfides) as source of
energy
 Don’t gain much energy from oxidation of Fe2+ to Fe3+,
so must oxidize a lot of it to obtain sufficient energy to
“fix” CO2 from the atmosphere and synthesize complex
proteins, carbohydrates, etc.
Anion toxicity

 Single-charge anions (SCN-, NO3-, Cl- and F-) most toxic

 Microbes employ an inside-positive membrane potential
to counteract inward flux of H+ and cationic metals
(reason for tolerance to high concentrations of cations)
 Anions may cross the cell membrane
 SCN- toxic - binds to key enzymes inhibiting function
 With anion accumulation, H+ enters, acidifying
cytoplasm
 Complexation chemistry in leach solution plays a big
role in what anion concentrations are toxic
 Example: complexation of F- with Al and Fe reduces F-
toxicity
Salinity: what can microbes
tolerate?
 Bioleaching organisms relatively intolerant to Cl-
 Fe2+ oxidation significantly slowed by 4 g Cl-/L; stops
above 5 g Cl-/L
 Attempts to adapt microorganisms to Cl- unsuccessful
 Toxicity is thought to be due to unfettered transport of
Cl- across the cell membrane
Process reagents

 SX reagents, greases, oils, hydraulic fluids, and dust

suppressors can be toxic
 SX reagents generally not a problem in heap/dump
leach, because adsorb to mineral surfaces at top surface
 Some decline in microbial numbers observed as pregnant
solution passes through SX circuit
 Steps taken to treat raffinate for entrained SX reagents
before recycle to stirred-tank bioleach circuit
Microbial studies in
heaps/dumps
 Few comprehensive studies in heaps/dumps on:
 Types and numbers of microorganisms
 Microbial successions/assemblages with chemical and
physical changes
 Recent study attempts to correlate temporal
microbial community in a ROM Cu test dump with
chemical & physical factors
 Demergasso and colleagues, Universidad Catolica del
Norte, Antofagasta
 Use molecular biology tools (phylogenetic analyses of
16sRNA fragments) to determine microbial assemblages
 Work will be published in next few months
Testwork for heap leaching:
bioleach considerations
 Must use microorganisms!
 Important to evaluate effect of ore on microorganisms
 Evaluate thermophiles (moderate & extreme) for sulfidic-
refractory gold & CuFeS2 bioleaching
 Using Fe2(SO4)3 or HNO3 as an analog not acceptable
 Some column testing must include closed-cycle leaching
 Evaluate the build-up of dissolved ions on microbial viability
& performance
 Evaluate S2--S oxidation for all S2- minerals not just Cu
sulfides
 Determine Total S and S2—S before & after leaching
 Establish rates of S2—S oxidation
 Process mineralogy a useful tool
Summary

 Better understanding today of temporal changes of

microbial assemblages in bioleaching with changes in
physical & chemical conditions
 By no means a complete understanding
 Contact & non-contact microbes theory
 Contact microbes have EPS with “reaction space” for Fe3+-
mediated metal sulfide oxidation
 Microbes in solution oxidize soluble Fe2+ & polysulfides
Summary

 Factors affecting bioleaching (temperature, pH, redox,

O2, CO2 nutrients, energy sources, salinity, anions,
process reagents)
 Testwork must include
 Microorganisms
 Closed cycle leaching
 Following S2- -S during leaching