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Sulphide mineral leaching
chemistry of sulphide
oxidation of bacteria
Content
● Introduction
● Microorganisms
● Bioleaching processes
● Conclusion
● Bibliography
Introduction
1. Metals as minerals are present as oxides, carbonates or sulphides in
the earth’s crust
2. Minerals in which metals are concentrated are called ‘ores’
3. Conventional methods for metal recovery - pyrometallurgy,
hydrometallurgy and pyrohydrometallurgy
4. Mine wastes - pyrite - common sulphide ore - oxidation - Acid Mine
Drainage (AMD) - serious problem
166 AD
First time in copper
mine at Cyprus -
copper recovery
Commercial
scale
Rio Tinto mine at
Spain Copper heap
leaching
Colmer
and Hinkle
First to demonstrate
bacterial catalysis of
iron oxidation
Isolated the bacterial
strain T. ferrooxidans
1920
Reported the oxidation
of Zinc sulphide by
Sulphur oxidisers
Not confirmed till 1947
Then came
Biometallurgy
Biohydrometallurgy
Bioleachinig
Bioleaching
Water insoluble metal sulphide Water soluble metal sulphates
A branch of biohydrometallurgy
Ability of microorganisms or their metabolites to attack or dissolve metals
Microorganisms
● Backbone of biomining activity
● Isolated from industrial
leaching operations
● Includes bacteria, fungi,
archaea, alage, and some
yeast
● Rio tinto – ‘copper mine’ - first
large scale operation to isolate
organisms for leaching
● Colmer and Hinkle isolated the
strain - Thiobacillus
Diverse group of
bacteria
Chemolithotrophs - use ferrous ions and
reduced sulphur compounds for energy
source
Important mesophiles are:
Acidothiobacillus ferrooxidans
Acidothiobacillus thiooxidans
Leptospirillum ferrooxidans,
Chromebacterium violaceum, Micrococcus
lactilytious, Methallogenium spp.,
Hyphomicrobium spp., Desulfovibrio spp.
Desulfotomaculum spp
Moderate and extreme thermophiles
Sulfolobus spp. TH-1, Acidinus spp.,
Acidiphilum spp, Acidimicrobium
ferrooxidans, Thiobacillus caldus ,
Galolieria sulphararia , Sulfobacillus
thermosulfidooxidans, Ferromicrobium
spp., Metallosphera and Sulfurisphaera
Microorganisms involved in bioleaching and
their preferred energy source
Energy source used by the organism
Ferrous iron
Elemental sulphur
Microorganism
Acidithiobacillus ferrooxidans
Leptospirillum spp.
Ferroplasma acidarmanus
Acidimicrobium ferrooxidans
Ferromicrobium acidophilus
Alicydobacillus tolerans
Sulfolobus metallicus
Metallosphaera spp.
Acidianus spp.
Sulfobacillus acidophilus
Acidithiobacillus thiooxidans
Acidithiobacillus caldus
Mechanisms
Mechanisms of bioleaching
Metal extraction from the sulphidic ores,
concentrate and tailing was initially
described by two mechanisms
1. Direct leaching or enzymatic
oxidation
2. Indirect leaching or non -
enzymatic oxidation
3. Galvanic conversion
 Ferric ion - Oxidising agent
 Ferric ion and proton (+) ion is
responsible for mineral solubilization
 Microorganisms - produce chemical
agents - ‘LIXIVIENT’ - and produce
space for leaching reaction to take
place - ‘EXOPOLYSACCHARIDE’ serves
as space
The mineral dissolution reaction
is not identical for all metal
sulphides as it varies depending
on the nature of the sulphides.
The oxidation of different metal
sulphides proceeds by means of
one of the two main pathways
via different intermediates.
Pathways
1. Direct
2. Indirect
3. Thiosulphate pathway
4. Polysulfide mechanism
Direct/contact
Bacteria in physical
contact with the
mineral surface and
resulting in the
oxidation of iron
sulfides
Indirect mechanism
No physical contact is here necessary
Bacteria lixiviant
Acid and/or iron(III) - oxidizing agents
Bacteria - catalyst of the mineral dissolution,
concentrating the attacking agents (i.e., protons
and/or iron(III) ions) at the interface of the minerals
and thus enhancing the degradation process
Iron(II), elemental sulphur, sulphates, thiosulphates,
and hydrogen sulphide are produced
Recent studies - redefined pathways
Acid solubility of the minerals
Thiosulphate pathway
Occurs when the acid insoluble metal sulphides
such as pyrite (FeS2) and molybdenite (MoS2) are
oxidized
Solubilisation - ferric iron attack on the acid-
insoluble metal sulphides where thiosulfate is the
main or first intermediate and sulphate is the main
end product
Polysulfide mechanism
Takes place when the acid soluble metal sulphides such as sphalerite (ZnS),
chalcopyrite (CuFeS2) or galena (PbS) are solubilised
In this case, solubilisation - combined attack by ferric iron and protons, with
elemental sulphur as the main intermediate
Elemental sulphur is relatively stable but may be oxidized to sulphate by the
sulphur-oxidizing microbes present in the system
In both the pathways, the ferrous iron
produced gets re-oxidized to ferric iron
by the iron-oxidizing microorganisms
EPS layers, which provides a zone of high oxidation activity
Factors
Nutrients
O2 and CO2
pH
Temperature
Mineral substrate
Heavy metals
Surfactants and organic extractants
Redox potential
Influencing bioleaching
Conclusion
Further scope
● Low cost carriers - Organic
carriers can be used for
immobilization
● Designing a well controlled
reactor system – to minimize the
release of GMM in environment
● Prolong the life of immobilized
carriers and increase the biomass
concentration
Thank you

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Sulphide mineral leaching and chemistry of sulphide oxidation by bacteria

  • 1. Sulphide mineral leaching chemistry of sulphide oxidation of bacteria
  • 2. Content ● Introduction ● Microorganisms ● Bioleaching processes ● Conclusion ● Bibliography
  • 3. Introduction 1. Metals as minerals are present as oxides, carbonates or sulphides in the earth’s crust 2. Minerals in which metals are concentrated are called ‘ores’ 3. Conventional methods for metal recovery - pyrometallurgy, hydrometallurgy and pyrohydrometallurgy 4. Mine wastes - pyrite - common sulphide ore - oxidation - Acid Mine Drainage (AMD) - serious problem
  • 4. 166 AD First time in copper mine at Cyprus - copper recovery Commercial scale Rio Tinto mine at Spain Copper heap leaching Colmer and Hinkle First to demonstrate bacterial catalysis of iron oxidation Isolated the bacterial strain T. ferrooxidans 1920 Reported the oxidation of Zinc sulphide by Sulphur oxidisers Not confirmed till 1947 Then came Biometallurgy Biohydrometallurgy Bioleachinig
  • 5. Bioleaching Water insoluble metal sulphide Water soluble metal sulphates A branch of biohydrometallurgy Ability of microorganisms or their metabolites to attack or dissolve metals
  • 6. Microorganisms ● Backbone of biomining activity ● Isolated from industrial leaching operations ● Includes bacteria, fungi, archaea, alage, and some yeast ● Rio tinto – ‘copper mine’ - first large scale operation to isolate organisms for leaching ● Colmer and Hinkle isolated the strain - Thiobacillus
  • 7. Diverse group of bacteria Chemolithotrophs - use ferrous ions and reduced sulphur compounds for energy source Important mesophiles are: Acidothiobacillus ferrooxidans Acidothiobacillus thiooxidans Leptospirillum ferrooxidans, Chromebacterium violaceum, Micrococcus lactilytious, Methallogenium spp., Hyphomicrobium spp., Desulfovibrio spp. Desulfotomaculum spp Moderate and extreme thermophiles Sulfolobus spp. TH-1, Acidinus spp., Acidiphilum spp, Acidimicrobium ferrooxidans, Thiobacillus caldus , Galolieria sulphararia , Sulfobacillus thermosulfidooxidans, Ferromicrobium spp., Metallosphera and Sulfurisphaera
  • 8. Microorganisms involved in bioleaching and their preferred energy source Energy source used by the organism Ferrous iron Elemental sulphur Microorganism Acidithiobacillus ferrooxidans Leptospirillum spp. Ferroplasma acidarmanus Acidimicrobium ferrooxidans Ferromicrobium acidophilus Alicydobacillus tolerans Sulfolobus metallicus Metallosphaera spp. Acidianus spp. Sulfobacillus acidophilus Acidithiobacillus thiooxidans Acidithiobacillus caldus
  • 10. Mechanisms of bioleaching Metal extraction from the sulphidic ores, concentrate and tailing was initially described by two mechanisms 1. Direct leaching or enzymatic oxidation 2. Indirect leaching or non - enzymatic oxidation 3. Galvanic conversion  Ferric ion - Oxidising agent  Ferric ion and proton (+) ion is responsible for mineral solubilization  Microorganisms - produce chemical agents - ‘LIXIVIENT’ - and produce space for leaching reaction to take place - ‘EXOPOLYSACCHARIDE’ serves as space
  • 11. The mineral dissolution reaction is not identical for all metal sulphides as it varies depending on the nature of the sulphides. The oxidation of different metal sulphides proceeds by means of one of the two main pathways via different intermediates. Pathways 1. Direct 2. Indirect 3. Thiosulphate pathway 4. Polysulfide mechanism
  • 12. Direct/contact Bacteria in physical contact with the mineral surface and resulting in the oxidation of iron sulfides
  • 13. Indirect mechanism No physical contact is here necessary Bacteria lixiviant Acid and/or iron(III) - oxidizing agents Bacteria - catalyst of the mineral dissolution, concentrating the attacking agents (i.e., protons and/or iron(III) ions) at the interface of the minerals and thus enhancing the degradation process Iron(II), elemental sulphur, sulphates, thiosulphates, and hydrogen sulphide are produced
  • 14. Recent studies - redefined pathways Acid solubility of the minerals
  • 15. Thiosulphate pathway Occurs when the acid insoluble metal sulphides such as pyrite (FeS2) and molybdenite (MoS2) are oxidized Solubilisation - ferric iron attack on the acid- insoluble metal sulphides where thiosulfate is the main or first intermediate and sulphate is the main end product
  • 16. Polysulfide mechanism Takes place when the acid soluble metal sulphides such as sphalerite (ZnS), chalcopyrite (CuFeS2) or galena (PbS) are solubilised In this case, solubilisation - combined attack by ferric iron and protons, with elemental sulphur as the main intermediate Elemental sulphur is relatively stable but may be oxidized to sulphate by the sulphur-oxidizing microbes present in the system
  • 17. In both the pathways, the ferrous iron produced gets re-oxidized to ferric iron by the iron-oxidizing microorganisms EPS layers, which provides a zone of high oxidation activity
  • 18. Factors Nutrients O2 and CO2 pH Temperature Mineral substrate Heavy metals Surfactants and organic extractants Redox potential Influencing bioleaching
  • 19. Conclusion Further scope ● Low cost carriers - Organic carriers can be used for immobilization ● Designing a well controlled reactor system – to minimize the release of GMM in environment ● Prolong the life of immobilized carriers and increase the biomass concentration