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found native to the environment; namely, water, air and microorganisms. In other words,
bioleaching is the commercialization of the ability of certain bacteria and archaea, found in
nature, to catalyze the oxidation of sulfide minerals. It is the leaching of sulfide minerals that
distinguishes bioleaching from conventional acid leaching wherein only oxidized minerals are
leached.
An associated process is biooxidation. This is the oxidation of sulfide minerals associated
with but not necessarily part of the mineral of interest to be extracted. Bioleaching is used
today in commercial operations to process ores of copper, nickel, cobalt, zinc and uranium,
whereas, biooxidation is used in gold processing and coal desulfurization.
Bioleaching involves the use of microorganisms to catalyze the oxidation of iron sulfides to
create ferric sulfate and sulfuric acid. Ferric sulfate, which is a powerful oxidizing agent, then
oxidizes the copper sulfide minerals and the copper contained is then leached by the sulfuric
acid formed. In the case of uranium, the ferric sulfate oxidizes tetravalent uranium oxide,
which is insoluble in acid, to hexavalent uranium oxide, which is then leached by the sulfuric
acid. In biooxidation of refractory gold ores bacteria are used to oxidize, and therefore make
soluble, an iron sulfide matrix in which the gold particles are imbedded and thus make the
gold available for cyanide leaching. Likewise, in coal desulfurization, bacteria are used to
oxidize the pyrite contaminant in the coal thus making the sulfur soluble as ferric sulfate.
Since bioleaching is a natural process, one undesirable effect is the creation of metalliferous
acid drainage from the slow weathering of sulfide mineral outcrops and from abandoned
mines. However, as in the case of Rio Tinto, in Spain, even this can be turned into an asset
by recovery of the copper from such waters.
Bagdad, USA
Morenci, USA
Sierrita, USA
Heap Leaching
Cananea, Mexico
Collahuasi, Chile
Girilambone, Australia
Morenci, USA
Zaldvar, Chile
Ashanti, Ghana
Fairview, Zambia
Wiluna, Australia
Youanmi, Australia
Following early development work and application in the United States, Chile has become a
major developer of bioleaching on an industrial scale. In 2001, there were 13 companies
using bioleaching and 30 companies in all using leach/SXEW technology. In 2001,
bioleaching constituted approximately 10% of Chilean copper production and heap and
dump leaching, in general, constituted approximately 30% of Chilean production. 2 The first
Chilean plant to be put into operation was S.M. Pudahuel. The plant was initiated in 1982
using the Thin Layer Bacterial leach process (TLB) - a water saving process - and leaches
copper oxides and secondary sulfide minerals.
Bioleach processing differs depending on the type of resources to be processed. It is used
today in three different regimes dependent upon the raw material types to be processed:
1.
Dump leaching - waste rock, low grade ore or concentrator tailings (low grade, oxides
and secondary sulfides) are leached where placed for disposal. (Mature technology, widely
used)
2.
with acid prior to depositing on heap. (Mature technology, increasing use); Primary
sulfides; i.e., chalcopyrite, leaching (Experimental only)
3.
1.
2.
3.
Background
The results of natural microbial leaching have been known since ancient times. Pliny the
Elder (23-73 AD), who had a passion for observing the wonders of nature, discusses the
" vitreolus quasi vitrum" - a glass-like substance - found on rocks in his treatise on natural
history. 3 One of the earliest records of utilizing the effects of bioleaching is from the island of
Cyprus. Galen, a Greek physician from Pergamum, in 162 A.D., is reported to have collected
cuperiferous solutions from mine water from the mines of Skouriotissa and concentrated
them by evaporation to form crystals of copper sulfate. 4 Recent findings have revealed
evidence that predates this account. 5Indeed, observations have been made on the natural
leaching of copper and the formation of "gall springs" during the East Han Dynasty (206 BC220 AD) in China. The "Gall-Copper Process" was recorded as being used during the Song
Dynasty (960-1271AD). Copper was precipitated from solution by dipping iron into the blue
vitriol solution - a process identified as early as 150 BC in China. 6 Therefore, presumably,
the recognition of a natural copper leaching process can be identified as early as that date.
Iron-rich acidic waters draining from abandoned coal and metal mines as well as from
unmined mineralized areas are another evidence of microbial leaching. In fact, history
records that mine water problems began at the same time that mining activities began. For
example, in the area of the Iberian Pyritic Belt, exploited since prehistoric times, the
production of acid mine drainage gave names to rivers like Tinto, Tintillo, Aguas Teidas,
referring to the river's characteristic color. In fact, at Rio Tinto, in Spain, 17th-century records
describe the occurrence of copper-bearing waters. Formal microbial leaching continued at
the Rio Tinto mine until the late 1970s. The UK-based mining company, Rio Tinto, which was
formed in 1873, owes its name to these copper-bearing waters.
It was not until 1947 that these phenomena were attributed to bacteria. 7 Once identified,
however, rapid steps were taken to commercialize the process. Commercial application of
bacterial leaching began in the late 1950s at the Kennecott Utah Copper Company's
Bingham Canyon Mine near Salt Lake City, Utah where it was observed that blue coppercontaining solutions were running out of waste piles that contained copper sulfide minerals something that should not have happened in the absence of powerful oxidizing agents and
acid. Investigation revealed that naturally occurring bacteria were oxidizing iron sulfides in
the piles, and the resulting ferric sulfate and sulfuric acid was acting as an oxidizer and
leachant for copper sulfides. 8 These bacteria were given the name ferrooxidans for their
ability to oxidize iron sulfides. A second set of bacteria was also identified and given the
name thiooxidans for their ability to oxidize sulfur to yield sulfuric acid. The bacteria, which
were native to the soil, in effect created a completely natural metallurgical processing plant.
Until recently, conventional acid-leaching of copper was utilized as a means of recovering
copper from low-grade materials such as waste rock and flotation tailings and was
conducted in dumps that were already in place. At least five factors have impeded the
acceptance of leaching as a major commercial process:
1.
2.
3.
4.
5.
The inability to process chalcopyrite - the most abundant and, thus, the most
economically important copper mineral.
The inability to recover precious metals
Solutions are now in sight to rectify most of these impediments.
Prior to the development of the solvent extraction-electrowinning (SX/EW) process in 1959
(seeCopper the Green Metal ), the only way to recover copper from an acid solution was by
a process called cementation. In this process, copper was in effect "traded" for iron by
contacting the copper-bearing solution with scrap iron. Impure metallic copper was
precipitated on the iron surface while an electrochemical equivalent of iron went into
solution. The resulting cement copper was then processed in a smelter and electrolytic
refinery to produce high-purity copper. By the use of the SX/EW process, copper can now be
extracted away from the iron and other impurities in solution and further purified and reduced
to metallic metal by electrolysis without ever having to be melted.
Further, through the use of biooxidation, it is now possible to leach many of the copper
sulfide minerals present in the ore. While chalcopyrite remains refractory to ambient
temperature bioleaching, other copper sulfide minerals - the secondary sulfide minerals such as chalcocite, covellite, bornite, etc. - are leachable by today's technology.
It is well known that increasing the temperature can increase the rate of a chemical reaction.
However, microorganisms are sensitive to temperature and, until recently when new strains
of temperature-resistant microorganisms ( thermophilic) were introduced, the reaction rate of
bioleaching was too slow to consider conducting the process as a primary copper extraction
process.
A number of companies have developed biooxidation processes for use in metal extraction.
Some of these have found commercial application while others are still in the experimental
or pilot plant stages:
Newmont Mining
Chemistry of Bioleaching
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. 18
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 acidsolubility required for leaching to take place.
The overall chemical reactions for chalcopyrite are:
Microbiology of Bioleaching
As indicated above, the original bacteria used in bioleaching were those that were native to
the site where the leaching took place. However, once bioleaching gained acceptance as a
potentially viable method for the recovery of metals from low-grade ores, flotation tailings
and waste materials, efforts were undertaken to optimize the bacteria for the operation
intended. "Native" bacteria, sometimes termed mesophilic bacteria, are sensitive to elevated
temperatures and to some of the metals being extracted. Thus, microorganisms were sought
that can withstand higher temperatures, thermophilic (and even hyperthermophilic; i.e., 60C
or higher) microorganisms, and are tolerant to the metals being extracted. One of the first
locations to be investigated for suitable thermophilic bacteria was the hot springs at
Yellowstone National Park. Others have been a hot spring in Iceland, a coalmine in Western
Australia, a volcano in Italy and a slagheap in Germany.
Out of these collections have come starting cultures for a number of bacteria strains. For
example, some bacteria in use today are: Acidianus brierleyi ( Sulfolobus brierleyi ), an
aerobic, extremely acidophilic, thermophilic sulfur-metabolizing archaebacteria useful to
70C (158F); that was developed from a Yellowstone hot spring; 19 Acidianus infernos,
useful to 88C (190F), that was developed from mud from the crater of the Solfatara
volcano in Italy; 20 Sulfolobus metallicus, useful to 65C (149F), that was isolated from the
lava field of the same volcano; 21Metallosphaera sedula, useful to 65C, that was isolated
from a thermal spring; 22 Metallosphaera prunae, useful to 80C (176F), that was found in
the smoldering slagheap of a uranium mine in Thringen, Germany. 23 In fact, natural
thermophiles have been isolated from the high-temperature zones of dumps and stockpiles
where normal, low-temperature bacteria have be used. To date, approximately 30 naturally
occurring strains of microorganisms have been screened as being useful in bioleaching.
While it is common to refer to the microorganisms used in bioleaching as being bacteria,
strictly speaking, this is not the case since the thermophiles actually fall into another
classification of microbiology - the archaea. 24 Thus, iron- and sulfur-oxidizing archaea are
currently the microorganisms of choice in the bioleaching of chalcopyrite-containing ores and
concentrates.
Archaea
Bacteria
Eukaryota
At present, the strains of microorganisms used in bioleaching have been cultured from
natural strains using methods that are commonly used in other industries, for example, in
cheese making, where mesophilic and thermophilic microorganisms are also used. These
strains are identical to those found in nature. The only difference is that in some cases they
have been selected for rapid growth on the ore or concentrate concerned and to the plant
operating conditions. These strains have been characterized, many by DNA sequencing, and
listed in the major biological species indices of the world. In the future, perhaps we can
expect new, more efficient strains, introduced as a result of genetic manipulation.
Leaching Method
As indicated above, bioleaching originated by the leaching of low-grade ore dumps, flotation
tailings and other waste materials already in place. As the technology has progressed it has
moved to more processing-amenable methods: i.e., leaching on a controlled leach pad
(heap leaching) (See The Phelps Dodge Mine-for-Leach Project) or in a stirred tank. Each of
these methods has a cost and therefore, as shown in Figure 1, the ore-grade and particle
size are the controlling factors in making a leaching process choice. 25
Three of the processes introduced above have made great strides in solving these problems
for the extraction of copper from chalcopyrite:
Bioleaching is the process of using bacteria to dissolve metals instead of chemical solutions.
Bioleaching has been used to dissolve metals such as nickel, copper, zinc, cobalt, gold, lead,
arsenic and others. Bioleaching works by using specific bacteria that can essentially eat the
metal content out of ore. For example the actual bacteria name used to dissolve gold is
Acidithiobacillus. Recoveries of metals have been fairly high using bacteria, over 90% of the metal
content in ore can be recovered. Bioleaching is typically used for small quantities of metal ore or
when environmental treatment is a concern. The bioleaching process is also being researched for
use as an exploration device or even for mining small orebodies. Bacteria could be pumped
underground, allowed time to dissolve the metal content, and then flushed back to surface. This
process could be used either to identify areas and quantities of ore, or to actually mine out the
metal content of an orebody.
Bioleaching Process
Bioleaching is achieved when bacteria feed on the minerals in an orebody. This separates the
precious metals and allows them to be flushed out in a solution. The bacteria are essentially a
catalyst to oxidize the metal sulphide crystals into sulphates and pure metal. This is not an
instantaneous process; it can take many hours to dissolve a relatively small amount of metal.
When compared with chemical methods of separation bioleaching is slow, but clean and effective.
The first step is to get a supply of the proper bacteria. This is completed by cultivating a batch of
microbials, or in other words farming the bacteria similar to any other animal. The bacterium
tends to be difficult to cultivate, as precise conditions must be met to encourage rapid growth and
reproduction. The best method appears to be simulating the environment in which the particular
bacteria are found. Once a supply has been cultivated, they can be shipped to the site and pumped
into the orebody. After allowing a soaking time a recovery well is used to pump the solution back
to surface. This solution moves through a purification plant which separates the metals from the
bacterial mixture. The solution passes through an enrichment section to replenish any of the
bacteria that may have been lost in the process, then continues the cycle.
Environmental Aspect
Bioleaching is immediately recognizable as a more environmentally friendly method of separating
metals than smelting due to the bio name. However there are some effects caused by
bioleaching that may also have a negative impact on the environment. For instance sulphuric acid
can sometimes be created in the process, and if using bioleaching outdoors this would allow the
nearby groundwater to absorb the acid. Extended use could cause the pH level of the water in the
area to lower over time. Extraction of hazardous metals such as lead and arsenic can also lead to
pollution of the water table. Bioleaching researchers argue that the metals and the bacteria both
occur naturally in the ground, so these effects would happen even without human intervention.
While that may be true, pumping bacteria into the ore and flushing it back out with a solution
significantly increases the rate of dissolving when compared with the natural process. Overall
compared with smelting ore the bioleaching process releases less harmful materials into the
environment and causes less damage to the Earth.