Biohydrometallugry: Extraction of metals

The conventional metallurgy involves smelting of ores at high temperature, involving high energy
cost and causing pollution. It was discovered in 1947 that copper could be leached from its ores by
the activity of a bacterium Acidothiobacillus (formerly Thiobacillus) ferroxidans, which thrives in
acidic medium and can live solely on sulphides, so commonly found in metal ores. This initially led to
the use of biohydrometallugry, for extraction of uranium in Canada in 1970 and extraction of gold in
South Africa in 1980s. Subsequently, starting in 1986 and 1990s, this technology has either been
already exploited or will be exploited commercially in several countries for extraction of Cu, Au, As,
Ni, Zn etc.

Microbes useful in metal recovery

The microbes that are suitable and useful for metal recovery differ depending upon the temperature
of the metal recovery process. At 40 C, the most important microbes are Gram negative bacteria
belonging to genera Acidothiobacillus and Leptospirillum, which include

(i) iron and sulphur oxidizing At. ferroxidans

(ii) sulphur oxidizing At. thiooxidans and At. caldus and
(iii) iron oxidizing L. ferroxidans

At 50 C, the suitable biomining microbes include At. caldus, some species of the genus Leptospirillum
and some Gram negative bacteria including the members of the genera Sulphobacillus and
Acidimicrobium and at 70 C, the useful biomining microbes are members of the group archaea
(Sulphobolus and Metallophaera).

Mechanisms of metal recovery

Metal ores are generally found as sulphides, which are insoluble in water, so that they need to be
converted into sulphates, which are readily soluble in water and therefore, can be easily leached for
further extraction of the metal. Mainly two strategies are used for the recovery of metal sulphates
for further extraction. The first of these strategies, namely bioleaching involves conversion of the
insoluble sulphide ores into soluble sulphates (due to action of ferric iron and the proteons), so that
only those metals can be recovered by this method, whose sulphides are insoluble, but the sulphates
are soluble, and the second strategy, namely biooxidation involves decomposition of the mineral
matrix to make it available for cyanidation, which is generally used for recovery of gold from
recalcitrant arsenopyrite ores.
The two methods that are available for metal extraction through formation of soluble sulphates
involve the formation of different intermediate products, which is a thiosulphate in one case (where
metal sulphides are acid insoluble and require attack of ferric iron for oxidation e.g. FeS2, MnS2, WS2)
and a polysulphide in the other (where metal sulphides are acid soluble, e.g. ZnS, CU2S, PbS),as
shown below; in both these methods, ferric iron (through biooxidation) facilitates metal dissolution
and the resulting ferrous iron (reduced form) may be reoxidized into ferric iron (oxidized form) by
iron-oxidizing microbes (e.g. At. caldus, L. ferroxidans, L ferriphilum, Leptospspirillum, Sulphobacillus
and Acidimicrobium).The main function of the microbes, therefore is the production of sulphuric
acid for the solubilization of metal sulphides, for the proton attack and to keep the iron in its
oxidized ferric state for an oxidative attack on the mineral.

All of these leaching bacteria assist in the dissolution of metals in several ways. These methods have
been termed ‘direct’ and ‘indirect’. Oxidations catalyzed ‘directly’ by bacteria include the oxidation
of iron.

4FeSO4 + O2+ 2H2SO4 2Fe2(SO4)3 + 2H2O

and the oxidation of sulphur,

S8+ 12O2+ 8H2O 8H2SO4

Certain minerals are directly oxidized by some leaching organisms. Examples include the oxidation of
pyrite, 4FeS2+15O2 + 2H2O 2Fe2(SO4)3 + 2H2SO4

and the oxidation of sphalerite,

ZnS+ 2O2 ZnSO4

Ferric iron is an effective oxidizing agent for solubilizing many minerals e.g. the solubilization of
chalcocite

CU2S + 2Fe2 (SO4)3 2CUSO4 + 4FeSO4 + S0

and uraninite

UO2 + Fe2(SO4)3 UO2SO4 + 2FeSO4

Leaching carried out by the action of ferric iron which has been generated through bacterial activity,
is termed ‘indirect’ extraction. Frequently, elemental sulphur is produced from this chemical
reaction and can be oxidized to sulphuric acid ‘directly’ by the bacteria.
Commercial processes for metal recovery

Two technologies are available for microbe mediated mineral degradation for metal recovery

(a) Heap-reactor technology

In this technology, low grade ore is piled up in a heap, which is sprayed with a leaching solution
containing Fe3+, (SO4)2- and At. ferroxidans (the sulphate provide an acidic medium for the growth
and activity of the microbe and Fe3+ brings about oxidation of sulphides). The leach solution
containing the soluble metal sulphates (produced due to Fe3+, involving microbial activity) is drained
and sent for metal recovery. The remaining leachate flows into an open pond and is used again for
spraying the heap, after getting recharged due to oxidation of Fe2+ into Fe3+ and sulphide into
sulphate (figure). Heap technology has been mainly used for the treatment of copper ores, although
it can also be used for the treatment of gold bearing ores, before recovering gold through
cyanidation. Heap reactors are cheaper and suitable for treatment of lower grade ores, but are less
efficient (also more difficult to inoculate and inadequately aerated), so that the process takes
months rather than days.

Figure: Different steps involved in mining of copper with bacteria.

(b) Stirred-tank reactor technology

In this technology, a finely ground mineral concentrate/ore along with the inorganic nutrients
(ammonia and phosphate-containing fertilizers) is added to the first tank. The suspension flows
through a series of tanks, where mineral decomposition takes place within days rather than in weeks
or months needed in heap reactors. However, stirred reactors need high capital investment and also
high running cost, so that only for value minerals, it use may be justified. Despite this, most of these
stirred reactors are used for extraction of gold ores.