BIOMINERALIZATION

Microorganisms can mediate the formation of minerals by a process called biomineralization. This
process offers an efficient way to sequester inorganic pollutants within relatively stable solid
phases. The main mechanisms involved in the mediation of mineral precipitation by
microorganisms includes supersaturation caused by metabolic activity, the triggering of nucleation
by production of more or less specific organic molecules, and the impact of mineral growth. Three
different types of bacterially mediated biomineralization processes have been distinguished (1)
biologically controlled biomineralization, referring to cases in which a specic cellular activity
directs the nucleation, growth, morphology, and nal location of a mineral; the emblematic
example for that process in the case of bacteria is the formation of intracellular chemically pure
magnetite crystals in magnetotactic bacteria, but no signicant impact on immobilization of metal
pollutants has been reported so far; (2) biologically induced biomineralization resulting from
indirect modication of chemical conditions, such as a pH shift or redox transformations, in the
environment by biological activity and (3)biologically inuenced biomineralization, which is
dened as passive mineral precipitation in the presence of organic matter, such as cell surfaces or
extracellular polymeric substances (EPS), whose properties inuence crystal morphology and
composition. The term organomineralization encompasses biologically inuenced and biologi-
cally induced biomineralization.

BIOMINING

Introduction: Biomining is an increasingly applied biotechnological procedure for processing of

ores in the mining industry (biohydrometallurgy). Biomining, as it is called, also makes for better
economics, especially in extracting minerals from low-grade ores, which are being used
increasingly because of depleting high-grade reserves. It improves recovery rates of minerals and
reduces capital and operating costs.

The first miners to exploit microbes, albeit unknowingly, were probably the Romans who worked
the Rio Tinto copper mine in Spain 2,000 years ago. They noticed that the fluid running off the
mine tailings was blue, an indication that it contained copper salts, from which they then recovered
the valuable metal. However, not until 40 years ago did it become clear that the copper in the fluid
was in fact the handiwork of a bacterium named Thiobacillus ferrooxidans (T ferrooxidans). The
tiny miner has proved to be a godsend for the copper mining industry, which has been left with the
low-grade ores that need to be smelted more to produce the same amount of copper. With each
new smelter costing $1 billion, the world is running short of smelters. T ferrooxidans, however,
can chew up the poor-quality ore which has been treated with sulphuric acid, releasing the copper
that is collected in a solution at lower costs. Today, at least 25 per cent of all copper produced
worldwide, worth more than $1 billion annually, is extracted using this bug. Of late, biomining
has struck gold, too. With depleting high-grade reserves of gold, not only are these microbes
cheaper to use than conventional energy-intensive techniques, they also increase the rate of gold
recovery from 70 to 95 per cent.

Phosphates have traditionally been extracted from ores either by burning them at high temperatures
to yield solid phosphorus or by treating them with sulphuric acid to produce phosphoric acid. But
last year, Alan Goldstein of California State University in Los Angeles and Robert Rogers of the
Idaho National Engineering Laboratory in Idaho Falls evolved a pair of bacterial strains,
Pseudomonas cepacia E-37 and Erwinia herbicola, which can remove the phosphate from the ore
at room temperatures, without using corrosive sulphuric acid.

Nowadays the production of copper from low-grade ores is the most important industrial
application and a significant part of world copper production already originates from heap or
dump/stockpile bioleaching. Conceptual differences exist between the industrial processes of
bioleaching and biooxidation. Bioleaching is a conversion of an insoluble valuable metal into a
soluble form by means of microorganisms. In biooxidation, on the other hand, gold is
predominantly unlocked from refractory ores in large-scale stirred-tank biooxidation arrangements
for further processing steps. In addition to copper and gold production, biomining is also used to
produce cobalt, nickel, zinc, and uranium. Up to now, biomining has merely been used as a
procedure in the processing of sulfide ores and uranium ore, but laboratory and pilot procedures
already exist for the processing of silicate and oxide ores (e.g., laterites), for leaching of processing
residues or mine waste dumps (mine tailings), as well as for the extraction of metals from industrial
residues and waste (recycling).

Copper Biomining: Copper has been one of mankind's most important metal resources since the
beginning of civilization, and to this day it holds and important role in the functioning of modern
society. It's main uses include piping, coinage, electronics, and even antibiotics. The majority of
copper minerals are sulfides, with chalcopyrite (CuFeS2) being the most abundant and thus
economically the most important. Others of economic importance are bornite (Cu 5FeS 4),
chalcocite (Cu 2S) and covellite (CuS). Sulfide minerals are insoluble in water or acid solutions
unless they are first oxidized. While exposure to air is sufficient to oxidize these minerals the
process is slow and inefficient. The kinetics of the oxidation process are vastly improved by the
introduction of Thiobacillus ferrooxan and Thiobacillus thiooxan bacteria to the system. The
former catalyzes the oxidation of iron whereas the latter catalyzes the oxidation of sulfur.

Heap Irrigation
The ores obtained from mining are crushed and piled up to 10 meters high atop plastic irrigation
pads, whereupon water seeded with acid, called the lixiviant, is irrigated through the heaps and
collected. After performing the next steps to extract the copper dissolved in the leach liquor, it is
recycled and used to irrigate the heap again.

Copper Extraction from Leach Liquor

The isolation of copper metal from leach liquor is a two-step process. The leach liquor obtained
after heap irrigation has a very low concentration of copper dissolved into it, around 0.5 - 2.0 g/L.
Through solvent extraction, the copper is transferred from the dilute liquor to a more concentrated
solution. Afterward, the dissolved copper ions are transformed to solid copper metal through a
process called electrowinning that uses an electric current to reduce the dissolved metal and deposit
it onto a cathode, at which point the solid elemental copper metal can be employed for its many
uses.

Chemistry of Biomining: There are two dominant views on the mechanisms involved in
bioleaching. The first is that the overall leaching process occurs by the microbial oxidation of
ferrous to ferric ions followed by the chemical oxidation of the sulfide mineral by the ferric ion.
This is known as the indirect mechanism. The second view envisages the microbial catalysis of
the overall dissolution of the mineral. It has been proposed that the microorganisms interact with
the mineral directly, enhancing the rate of oxidation, over and above that achieved by chemical
oxidation. This is known as the direct mechanism. Regardless of the mechanism, it is the enhanced
oxidation of the mineral created by the microorganism that creates the acid-solubility required for
leaching to take place.

The overall chemical reactions for chalcopyrite are:

4CuFeS 2 + 11O 2 + 6H 2O Thiobacillus ferrooxin >> 4CuSO 4 + 4Fe(OH) 3 + 4S (1)

2S + 3O 2 + 2H 2O Thiobacillus thiooxan >> 2H 2SO 4 (2)