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Minerals Engineering
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Golder Associates Ltd., 32 Steacie Drive, Kanata, Ontario K2K 2A9, Canada
Department of Mining Engineering, Mineral Processing Division (Mineral-Metal Recovery and Recycling Research Group), Suleyman Demirel University, Isparta TR32260, Turkey
a r t i c l e
i n f o
Article history:
Received 18 April 2013
Accepted 27 May 2013
Available online 28 June 2013
Keywords:
Cyanide
Hydrometallurgy
Leaching
Process efuents
Wastewater treatment
a b s t r a c t
Cyanide has been widely used as an essential raw material in several industries including textile, plastics,
paints, photography, electroplating, agriculture, food, medicine and mining/metallurgy. Because of its
high afnity for gold and silver, cyanide is able to selectively leach these metals from ores. Cyanide
and cyanide compounds in wastewater streams are regulated. Residues and wastewater streams containing cyanide compounds have to be treated to reduce the concentration of total cyanide and free cyanide
below the regulated limits.
Natural degradation reactions can render cyanide non-toxic, resulting in carbon dioxide and nitrogen
compounds. These natural reactions have been utilised by the mining industry as the most common
means of attenuating cyanide. However, the rate of natural degradation is largely dependent on environmental conditions and may not produce an efuent of desirable quality in all cases year round. Technologies that include chemical, biological, electrochemical and photochemical methods have been
developed to remove cyanide and cyanide compounds to below the regulated limits in wastewaters. This
paper discusses commercially available and emerging methods for removing cyanide from waste
streams, particularly from tailings and tailings reclaim waters that are generated in the gold mining
processes.
2013 Elsevier Ltd. All rights reserved.
Contents
1.
2.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1.
Cyanide in daily life . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2.
Solution chemistry of cyanide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.
Formation of cyanide compounds and pathways for cyanide degradation/attenuation in the environment . . . . . . . . . . . . . . . . . . . . . . . .
1.3.1.
Complex formation (chelation) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.2.
Precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.3.
Adsorption. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.4.
Cyanate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.5.
Thiocyanate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.6.
Volatilization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.7.
Biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.8.
Hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.4.
Characterization of samples for cyanides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.5.
Cyanide for dissolution and recovery of precious metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.6.
Cyanide and cyanide compounds toxicityand guidelines and regulations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Treatment processes to remove cyanide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Process selection criteria. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Treatment processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1.
Natural cyanide degradation in tailings ponds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.2.
Chemical treatment methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Corresponding author. Tel.: +90 246 2111321; fax: +90 246 2370859.
E-mail address: ataakcil@sdu.edu.tr (A. Akcil).
0892-6875/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mineng.2013.05.027
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3.
4.
2.2.3.
Biological cyanide degradation process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.4.
Other methods and emerging processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.5.
Electrolytic oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Process costs and selection of suitable process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
1.1. Cyanide in daily life
The term cyanide refers to a chemical compound containing
one atom of carbon and one atom of nitrogen. The technical denition of cyanide is a triple-bonded molecule with a negative one
charge, consisting of one atom of carbon in the +2 oxidation state
and one atom of nitrogen in the 3 oxidation state (InfoMine,
2012). Cyanides most commonly refer to salts of the anion CN.
Cyanide can naturally be found in about 2000 sources (WHO ECEH,
2000). The principal human-made cyanide forms are gaseous
hydrogen cyanide (HCN) and solid sodium or potassium cyanide
(NaCN or KCN). Humans are in close contact with cyanide in their
daily life through food, drink, smoking, medicines and while using
products which contain cyanide (USEPA, 1976). For instance, as
illustrated in Fig. 1, they are exposed to certain levels of cyanide
due to smoking tobacco (0.5 mg/cigarette), respiring exhaust from
vehicles (79 mg/km), handling certain type of pesticides, insecticides and fertilisers, particularly for growing tobacco, cotton and
grapes, and using cosmetics (e.g., eye blush, lipstick). Some food
products may either naturally contain cyanide or cyanide is used
in their production. The concentration of cyanide per kg in certain
food products has been observed as: table salt (20 mg/kg), lima
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NaCN ! Na CN
The weak and moderately strong cyanide complexes primarily include cadmium, copper, nickel, silver and zinc cyanide complexes.
These complexes form in a step-wise manner as the cyanide concentration of the solution is increased. The solution pH and the concentration of cyanide and metals play a role in the quantity of
complex formation. In terms of chemical stability, zinc and cadmium are known to be the weakest complexes while iron and cobalt complexes are the strongest ones. These complexes may
dissociate and release free cyanide in the presence of UV radiation
and strong acids. The rate of dissociation is affected by several factors such as the intensity of light, water temperature, pH, total dissolved solids and complex concentration. Hydrolysis of HCN in a
neutral or acidic solution yields formate as either formic acid or
ammonium formate. Iron cyanide is known to be refractory cyanide
as it is a stable typically non-reactive cyanide that passes through
the general oxidation systems unaffected. It has been reported that
iron cyanide could break down when it is exposed to the UV radiation from the sun releasing free cyanide in receiving lakes and rivers. In addition, the recent treatment systems employ elevated
temperature oxidation principals potentially combined with a catalyst to reach low parts per billion (ppb) treatment levels (Manchester, 2013).
A variety of cyanide related compounds can form in solutions
resulting from cyanidation, natural attenuation or treatment processes. These compounds include thiocyanate (SCN), cyanate
(OCN), ammonia (i.e., free ammonia NH3 or ammonium ion
NH
4 ) and nitrate (NO3 ).
1.3. Formation of cyanide compounds and pathways for cyanide
degradation/attenuation in the environment
Natural attenuation mechanisms of cyanide may include: complexation (chelation), cyanide complex precipitation, adsorption,
oxidation to cyanate, volatilisation, bio-attenuation, formation of
thiocyanate and hydrolysis/saponication of free cyanide. These
pathways help decrease the reactivity of cyanide in natural environment (ICMI, 2012). Since some of these mechanisms provide a
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1.3.6. Volatilization
At the pH typical of environmental systems, free cyanide will be
predominately in the form of hydrogen cyanide, with gaseous
hydrogen cyanide evolving slowly over time. The amount of cyanide lost through this pathway increases with decreasing pH, increased aeration of solution and with increasing temperature.
Cyanide is also lost through volatilization from soil surfaces.
1.3.7. Biodegradation
Cyanide can degrade to ammonia by microorganisms under aerobic conditions, which then oxidises to nitrate. Effectiveness of this
process is limited to cyanide concentrations of up to 200 ppm.
Although biological degradation also occurs under anaerobic conditions, cyanide concentrations greater than 2 ppm are toxic to
these microorganisms.
1.3.8. Hydrolysis
Hydrogen cyanide can be hydrolysed to formic acid or ammonium formate. Although this reaction is not rapid, it may be of signicance in ground water, where anaerobic conditions exist.
1.4. Characterization of samples for cyanides
Analytical methods can determine three types of cyanide
including total cyanide, weak acid dissociable (CNWAD) and free
cyanide. All cyanide compounds present in the solution including
cyanide in metal complexes, except with cobalt, can be represented by total cyanide values. WAD cyanide covers both the free
and complex forms of cyanide. Free cyanide includes the cyanide
anion and molecular hydrogen cyanide. As a result, the total cyanide level should be greater than or equal to the CNWAD cyanide
level and the CNWAD level should be greater than or equal to the
free cyanide level. There are several methods used to characterise
samples for cyanides and cyanide containing compounds (APHA,
1998). The appropriate method is selected based on the solution
chemistry requirements (e.g., potential interferences, site-specic
samples) and its reliability and efciency (e.g., reproducibility,
time and cost). For instance, a rapid and inexpensive method
which can provide good estimates can be used during a eld pilot
test and the results can be periodically veried with another analytical method for their reliability. Samples need to be preserved
as described by the analytical laboratory procedures if the sample
cannot be analysed immediately. Detection limits can vary for each
cyanide compounds, type of analytical method and the laboratory.
The use of automated on-line continuous monitoring systems is
becoming widespread. If required, cyanide can also be analysed
in a solid sample.
1.5. Cyanide for dissolution and recovery of precious metals
Gold and silver are noble metals and as such they are not soluble in water. The precious metals form complexes with the cyanide
anions to produce soluble derivatives, e.g., [Au(CN)2] and
[Ag(CN)2] under strong alkaline conditions, typically pH > 10, in
order to maintain ionic form of cyanide and prevent volatilisation
to hazardous hydrocyanic acid (HCN). In the absence of other metal
cyanide complexes, a relatively dilute, 100500 mg/L NaCN solution at a pH greater than 10 which may contain about 50 mg/L free
cyanide, can provide the maximum rate and extent of gold and silver dissolution. This is called Cyanidation (Habashi, 1966; Rubo
body weight as HCN. There is no reported bio-magnication of cyanide in the food chain (ATSDR, 2006; ICMI, 2012).
Cyanide in efuents resulting from gold mining is known to be
the prime candidate for treatment. However, according to a study
by the Ontario Ministry of the Environment (Canada); ammonia,
suspended solids and copper were identied as the most important
contaminants in gold mining efuents rather than cyanide. Total
cyanide concentration is only controlled in drinking water, which
is 0.2 mg/L (Ministry of Environment Ontario, 2013). Currently,
the concentration of ammonia in treated waters is regulated in
Canada and is required not to exceed 10 mg/L (CCME, 2013). Since
many of treatment processes convert cyanide to ammonia and carbon dioxide, ammonia may exceed the regulation limits. Investigations are currently underway to develop methods to manage
ammonia and nitrate in wastewaters as well as cyanides. Although
nitrate is a relatively non-toxic compound, at high concentrations
it may cause harm to humans, especially infants; and aquatic life
by enhancing algae growth and thereby, decreasing dissolved oxygen concentration in the aquatic environment; and increasing sh
mortality rates. Similarly, whereas thiocyanate is reported to be seven times less toxic than cyanide, increased thiocyanate concentrations in water resources can adversely affect the sh and aquatic
ecosystems, and in the human body, chronic cyanide exposure detriments the thyroid gland (Bhunia et al., 2000; ICMI, 2012).
As a result of natural attenuation and dissociation phenomena,
cyanide does not accumulate in the soil, water or air. UV radiation
in sunlight and gaseous oxygen in air naturally degrade cyanide to
C and N compounds. Cyanide in water is rst adsorbed by soil particles then slowly decomposes with the help of microorganisms
(Turkmen, 1998).
Despite on-going concerns with regulatory agencies and communities regarding the cyanide compounds, where health effect
may occur, it is believed that higher than 0.1 mg/L total cyanide
and 0.05 mg/L CNWAD levels may adversely affect humans and
aquatic life (Randol, 1985 Donato et al., 2007; ICMI, 2012). Standards or criteria are established based on determined toxicity levels to provide reasonable levels of safety and to promulgate their
enforcement to protect the human health and the environment
(i.e., wild life, aquatic life) (Hagelstein and Mudder, 1998). The
standards set for the allowable concentration of ions and compounds may vary from country to country, jurisdictions to jurisdictions and even site to site (Randol, 1992; ICMI, 2012). While the
allowable cyanide concentration in potable water is established
at 0.2 mg/L by the United States and Canadian Environmental Protection Agencies (USA/Canada EPA), the World Health organisation
(WHO) guidelines consider 0.07 mg/L CN safe for both acute and
long-term exposure in drinking water. The European Union (EU)
species 0.05 mg total CN per litre (Turkmen, 1998; WHO ECEH,
2000; Akcil, 2002). Usually, standards set for both fresh and marine
aquatic life are lower than the standards set for the drinking water
quality. For instance, Canada sets fresh and marine water standards for cyanide as 0.005 and 0.001 mg/L, respectively. The World
Bank requires that the efuent from base metal and iron ore mining companies should meet 1 mg/L total cyanide, 0.1 mg/L free CN
and 0.5 mg/L CNWAD levels (World Bank Group, 1997; Howell
and Christophersen, 2009).
An International Cyanide Management Institute (ICMI) was
established by the United Nations Environment Programme
(UNEP) to administer the International Cyanide Management Code
for the Manufacture, Transport and Use of Cyanide in the Production of Gold (the Code). ICMI promotes the adoption of the Code,
evaluates its implementation, and manages the certication process. The participation to the Code that exclusively focuses on
the safe management of cyanide at gold mines is voluntary (Akcil,
2002, 2010). Since the establishment of ICMI, the Cyanide Code has
experienced dramatic growth. The Cyanide Code is being imple-
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Table 1
Methods available for removing or destroying cyanide and process mechanisms involved.
Cyanide removing/destroying method
Process mechanisms
Volatilization
Biodegradation
Oxidation (by UV, microorganisms)
Oxidation
Conversion to cyanate
Hydrolysis
OxidationComplexation
Hydrolyis
Precipitation
Decomposition
The Second stage of the process is the further oxidation of cyanate to nitrogen and bicarbonate
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CN H2 O2 ! CNO H2 O
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The results of the pilot tests revealed that a pH of 5 would be sufcient to remove over 95% of the copper from tailings efuent and recover over 94% of the cyanide. NaSH additions at 100%
stoichiometric copper were sufcient to remove over 95% of the
copper from the efuent when sulphuric acid was used to acidify
the solution. Acid consumption was 1.72.4 kg of 100% sulphuric
acid/kg WAD cyanide to reduce the pH from about 10 to pH 45.
Lime consumption ranged from 0.51.3 kg/kg WAD CN at a pH of
3. The SART process has been successfully commercialised and applied several sites in the last decade (SGS Technical Bulletin, 2010).
2.2.2.6. Acidication process and cyanide recovery. Thisprocess was
used at the Emperor Gold Mine in Fiji to remove residual cyanide
from cyanided and washed calcine after the otation step to recover sulphides. To remove cyanide, the pH of calcine slurry is lowered from 9 to 2.5 by spraying SO2-containing roaster gases in a
counter-current decantation (CCD) system. HCN gas released during the process is stripped in towers and decanted to eliminate
cyanide emission to the atmosphere. The acidication process
was principally employed for cyanide recovery, not for environmental protection. Therefore, information about the quality of
resulting efuents by this process was not reported.
Since 1998, cyanide recovery from mill tailings has been practised at Cerro Vanguardia in Argentina that includes multiple open
pits and a hybrid Merrill-Crowe and CIL circuit to recover gold and
silver from oxide ore (Botz et al., 2004). Initially, the cyanide recovery plant aimed to process tailings slurry to achieve greater than
90% cyanide recovery from tailings containing about 600
800 mg/L WAD cyanide (as CN). Relatively high consumption of
sulphuric acid and sodium hydroxide leading to high rates of scale
formation in the acidication tank and stripping towers were observed. Changes were made to the cyanide recovery system allowing the operation of a two stage CCD circuit with clear solution,
which reduced the sulphuric acid consumption and eliminated
scale formation in the process equipment. About 9092% sodium
cyanide recovery can be obtained from a solution containing about
350 mg/L WAD cyanide, which accounts for about two-thirds of
the total cyanide added to the leaching circuit.
2.2.2.7. AcidicationVolatilizationRegeneration (AVR) or Mills
Crowe process for recovery of cyanide. AcidicationVolatilization
Regeneration (AVR), or alternatively referred to as the MillsCrowe
process, involves acidifying waste cyanide bearing solutions to a
pH of between 2 and 3 with H2SO4 or SO2, volatilizing the resulting
HCN by air ushing and recovering the HCN by absorption in an
alkaline solution (e.g., NaOH or Ca(OH)2). The recovered cyanide
is recycled to the cyanidation circuit for reuse. A specic name
Cyanisorb has also been givento AVR referring as Acidify, Volatilize and Reneutralize (SGS Technical Bulletin, 2009). The AVR
process has also been commercialised and successfully applied
several mining sites (SGS Technical Bulletin, 2010). This process
was used at a silver mine operated by Compania Beneciadora
de Pachuca in Mexico. The SO2 gas is produced by burning elemental sulphur at the site.
Hudson Bay Mining and Smelting Company at FlinFlon, Manitoba, Canada, used the MillsCrowe process for cyanide recovery
from 1935 to 1978 while the company was using cyanidation for
the recovery of gold from base metal tailings. Waste barren solution was acidied with H2SO4 solution from their zinc recovery
plant. Air was used in towers to sweep HCN from the acidied barren solution and the HCN was absorbed in Ca(OH)2 for reuse in the
cyanidation circuit. Ninety-one percent of the regenerable cyanide,
which was the amount of cyanide released in laboratory acidication tests, was recovered by this method. Both SART and AVR processes are applied to tailings efuents rather than pulp.
Therefore, the cost of solidliquid separation must be added to
the costs of cyanide recovery. This can be a signicant capital-cost
burden if the tailings pulp is difcult to separate into solid and liquid components as occurs with high clay, slimy or viscous ores
(SGS Technical Bulletin, 2010).
2.2.3. Biological cyanide degradation process
Several microorganisms (bacteria, fungi) and their enzymes
have ability to degrade cyanide and cyanide complexes including
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The mode of application can take place in either active fully controlled automated bioreactors or in passive systems (passive bioreactors, wetlands, pit-lakes, i.e., in-pit treatment) (MPERG, 2010).
Passive systems have been investigated for their methodology and
performance, reliability, suitability for cold climates, longevity, sustainability and cost-effectiveness, especially for their application to
remote sites. Examples are given in Section 2.2.5.3.
Active biological processes have been neither widely practised
nor received a great deal of attention for treating cyanide bearing
wastewaters from gold mills. Barren bleed and tailings slurries
pose a hostile environment to bacteria and reduced bacterial activity may occur if cyanide and metals are in high concentrations.
Application of the biological process is more successful for tailings
pond waters where both cyanide and metal concentrations are relatively low due to natural degradation and dilution. Biological processes are usually ruled out in cold climate countries such as
Canada. Three full-scale active biological treatment processes
have been developed and used by Homestake Mining in the USA
and Canada, are briey discussed below in Section 2.2.4.1 and
2.2.4.2.
Success of the Homestake process has increased attention in the
application of microorganisms for degradation of cyanides. A signicant amount of research has been carried out to develop microbiological processes with improved efciency and performance.
For instance, the use of immobilised cells of Pseudomonas putida
in air-uplift-type uidized bed reactors to convert inorganic cyanides to carbon dioxide and ammonia has been investigated as
an alternative, but no pilot- or full-scale process have been operated using this method (Babu et al., 1993). A test heap was inoculated with a cyanide-reducing bacterium Pseudomonas pseudo
alcaligenes (UA7) in Alaska aiming to compare cyanide destruction
costs with INCO process (Nelson et al., 1998). The results indicated
that cyanide could be reduced to acceptable levels by the bacterium and, despite the higher initial capital cost, the overall cost
of the treatment in the long term could be lower than the chemical
method due to signicantly lower operating costs. A recent study
revealed that the alkaliphilic autochthonous bacterium Pseudomonas pseudoalcaligenes can detoxify cyanide in two ways. Cyanides
are irreversibly bound to metals, such as to iron, causing iron
deprivation outside the cell and metalloenzymes inhibition inside
the cell occurs resulting in a cyanide-insensitive respiratory
system and a cyanide degradation/assimilation pathway (Luque-
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Almagro et al., 2011). The cyanide assimilation pathway that generates ammonium, is further incorporated into organic nitrogen.
2.2.3.1. Homestake mine biological process in the USA. The process
was developed in early 1980s and, since then, has been used by
Homestake Mining Company at Lead, South Dakota in the USA.
Therefore, it is known as Homestake Minings biological process.
The Homestake Mining has still been the only company in the
world using this method to treat their combined mine and tailings
impoundment wastewaters. Blending relatively warm mine water
with tailings pond water to maintain the temperature of the combined wastewaters at a sufciently elevated temperature year
round is key to their successful operation. The plant was constructed in 1984to treat 3600 US gpm at a capital cost of
US$10 million.
Cyanide, thiocyanate, copper and ammonia are the main contaminants found in the mixed wastewater. The process takes place
in rotary biological contactors (RBC) where bacteria are attached to
slowly rotating discs as a biolm. About 40% of each disc is submerged in the tanks at all times (Maier et al., 2009). The biological
oxidation process is carried out in two stages (Whitlock, 1995;
Lawrence et al., 1998). The rst stage consists of the bacterial oxidation of cyanide and thiocyanate to carbon dioxide, sulphate and
ammonia. In the second stage, bacterial nitrication occurs and
ammonia is converted to nitrate. Different strains of bacteria are
involved in the various stages of the process. Homestake Mining
holds two patents for the use of specic bacteria responsible for
oxidation of cyanide and thiocyanate. Metals associated with cyanide and thiocyanate are removed through adsorption by bacteria
(biolm) once the wastewater is free of cyanide. As the biolm
continuously sloughs off the discs, the bacteria-metal sludge is removed from the efuent by clarication and dual-media sand ltration, and disposed into the tailings pond. In contrast with the
competing chemical treatments, hydrogen peroxide and SO2/Air,
the efuent can be discharged directly to the environment without
additional treatment. A simplied owchart of the process is
shown in Fig. 6.
Forty-eight RBCs with 12 foot diameter discs were used to contact the bacteria with wastewater and air. The RBCs were not
housed but all were well insulated. The rst 24 contactors were
employed in the cyanide and thiocyanate removal stage. The only
reagents added were soda ash as an inorganic carbon source to aid
nitrication and phosphorus as a trace nutrient. Efuent from the
biological contactors was modied by the addition of ferric chloride and/or a polymer to produce a sludge before clarication
and sand ltration. The full-scale plant was operated satisfactorily
and produced efuents of the quality predicted from pilot plant
tests for about two decades. About 99% removal rate could be obtained for cyanide, reducing the initial cyanide concentration of
4.1 mg/L to 0.06 mg/L. Thiocyanate, ammonia and copper were
respectively reduced from 50.0, 6.0 and 1.0 mg/L to less than 0.1,
0.1 and 0.05 mg/L respectively in the nal efuent. Although the
removal of copper and iron in the process was high, with 9598%
efciency; other metals such as nickel, chromium and zinc were
not removed as effectively (Maier et al., 2009). The suspended solids content in the treated efuent was <10 mg/L. It was found that
bacteria adsorbed gold, silver, copper as well as other metals. Gold,
silver and copper could be recovered from the sludge by igniting
the sludge and annually about US$0.5 million income was obtained
through this practise which reduced the overall operating cost of
the process by 25% (Whitlock, 1995). The process was successfully
operated from 1984 to 2002, until the closure of the mine (Maier
et al., 2009).
2.2.3.2. Nickel plate mine biological process in Canada. Homestake
Mining has developed another unique process utilising aerobic
19
Me2 S2 ! MeSs
20
25
In-Pit (Pit Lake or Pond) application, water that results from the
storage of waste materials such as tailings, waste rocks and/or
sludge or contaminated water is directly treated in the impoundment by adding chemicals and encouraging the growth of aquatic
plants. The treated water is then pumped out to the environment if
its quality meets the regulated standards. Tailings resulting from
the VAT cyanide leach process to recover gold were disposed of
in a natural lake for storage and management at the Colomac mine
located in Yellowknife, NWT, Canada (Chapman et al., 2007;
MPERG, 2010). After mine closure, seepage originating from the
tailings disposal area had to be collected and pumped into a mined
out pit as an emergency measure. Tailings pore-water and seepage
contained cyanide, thiocyanide and ammonia in high concentrations. Several options including alkaline breakpoint chlorination
and biological RBC processes were investigated for the treatment
of seepage accumulated in the pit and the pit lake where tailings
were stored. The concentration of total cyanide in the treated
water had to be 1 mg/L or less to meet the local discharge requirements. Biological RBC process was found to be prohibitively expensive because of heat requirements. Bench and pilot tests indicated
that bacteria could catalyse cyanide and cyanide complexes found
in the water to convert to ammonia in situ in the pit. Some of
ammonia produced was further removed by uptake by algae grown
in the pit. Reduction of thiocyanate from 100 mg/L to 0.5 mg/L in
30 days was also observed when algal growth was stimulated by
26
21
22
23
24
that is an efcient adsorbent for free cyanide ions and soluble copper cyanide (SGS Technical Bulletin, 2010). As Hannah refers to
strong base resin extraction of free cyanide and metal cyanide species, the Augment process is a strong base resin extraction of copper and cyanide (SGS Technical Bulletin, 2009). Elution of copper
(or metal) and cyanide from the resin poses technical difculties
increasing the cost of the cyanide recovery process.
It has been reported that the sunlight (UV) could function as a
strong oxidizer when wastewater is subjected to sunlight in the
presence of a semiconductor catalyst such as titanium dioxide
(TiO2). This process was found to be suitable for the oxidation of
both free and complexed cyanides dissolved in wastewater (Parga
et al., 2003). When exposed to the sunlight, the catalyst mixed into
the water, creating a slurry, or xed onto a lattice-type structure
absorbs the high-energy photons from the UV portion of the solar
spectrum forming powerful oxidizers of reactive hydroxyl (OH)
radicals. These radicals break down the cyanide where the rst
product of photocatalytic oxidation of cyanides in the presence of
polycrystalline TiO2in aqueous medium is CNO. UV light causes
metal complexes such as ferricyanide and ferrocyanide to partially
dissociate. In the case of iron cyanide the compound is photolyzed
to free cyanide and iron hydroxide. UV oxidation is limited to relatively clear solutions. UV in combination with ozone results in the
formation of strong oxidising agent of OH- radicals that can oxidise
iron cyanide complexes. Suitable light sources emit in the range of
200280 nm (nm). Ozone will absorb in this band. Additionally, the
UV/ozone oxidation does not produce undesirable by-products
such as ammonia (Spartan Environmental Technologies, 2013).
2.2.5.2. Thermal cyanide destruction. Solid or liquid wastes containing cyanides are treated at elevated temperature and pressure in
batch or continuous mode (CDS, 2013). Reactions occur in two
steps as given in Eqs. (25) and (26) (NMFRC, 2013). Hydrolysis is
the principle of the cyanide destruction process mechanism.
Hydrolysis takes place in a heated pressure chamber. High temperature (450470F) and pressure (600 psi) signicantly increase the
kinetics of hydrolysis, where OCN is converted to ammonia and
bicarbonates/carbonates as shown in
25
26
This process was developed in early 1990s and has been shown to
be cost-effective for treating wastes containing high concentrations
of CN. Cyanide wastes containing 100,000 mg/LCN can be treated to
give about 25 mg/LCN. The residual CN can be treated by a conventional method such as ozone or hydrogen peroxide, to reduce the
CN concentration to a lower, environmentally acceptable level. It
is claimed that the process is able to destroy all cyanide complexes,
even that of iron. In a usual operation, CN wastes are transferred
into the high temperature and pressure vessel and treated on a
batch basis for about 10 h and then discharged to a conventional
treatment plant for polishing. For large ows, a continuous process
is used and the process is controlled by adjusting the temperature
and pressure. Ammonia gas generated by the unit is vented to
atmosphere. Institutions that tested the process experienced temperature and pressure control problems due to seal leak (N2 and
oil seal) at the point of agitator entry into the vessel resulting in
downtime (Cushnie, 2009).
3. Process costs and selection of suitable process
Since the cost of reagents and the degree of treatment requirements may vary from site to site, cyanide treatment costs are sitespecic. The direct comparison of cyanide treatment costs from
27
4. Summary
Water is considered to be a crucial asset for mining and metallurgical processes. The mining industry has to deal with water in
every stage of mining, starting from excavation of the ore to the nal product. Even after a site closure, water may need to be managed for many years. Underground mines or open pits should be
drained to be able to access to the ore during excavation. Later during processing of ores (e.g., extraction and recovery), water is used
as part of each process. Processing of 1 m3 of ore requires a minimum of 1.3 m3 of water (Kuyucak, 2009; Kuyucak and Palkovits,
2009). The need for water grows as the mining activities increase.
Therefore, water management gains a signicant importance.
Water losses have to be minimized and recirculation and reuse
must be practised as much as possible. The quality of water has
to be ensured for its compliance before its discharge to the environment as it is essential in maintaining and sustaining the aquatic
resources.
As the environmental regulations have become more and more
stringent with respect to cyanide, the need for developing removal
processes has been increasing. Natural degradation in tailings
ponds is still known to be the most common method, it has been
either supplemented or replaced by a chemical process in many
cases because of its limitation in producing a nal efuent of desired quality. In addition to cyanide, the toxic effect of ammonia
28
is of concern to the regulatory agencies and investigations to reduce ammonia concentrations in efuents are underway. Despite
its wide use in the last two decades, the use of alkaline chlorination
process has become limited due to toxic nature of intermediate
and by-products. Unique methods, such as Homestake biological
process and the Hemlo/Golden Giant copper and iron sulphate precipitation processes, are mainly developed and used by their
respective companies. In addition to the conventional SO2/Air process, SART, AVR and ion exchange processes have been receiving
worldwide attention. The application of hydrogen peroxide also
has been increasing. Investigations for the development of new
processes have been ongoing. In arid climates, evaporation is used
to obtain zero discharge.
Since the cost of reagents and the degree of required treatment
may vary from site to site, cyanide treatment costs are site specic.
Some processes may require up front high capital costs and may
provide lower operational costs (e.g., reagent cost, energy and
maintenance requirements), while some processes can be implemented to a site with small capital costs, but operation using these
methods might be expensive. During the project planning stage,
cost-benet analyses should be conducted for potential alternative
treatment methods to determine the most appropriate process for
a given site.
References
Acheampong, M.A., Meulepas, J.W., Lens, P.N., 2010. Removal of heavy metals and
cyanide from gold mine wastewater. Journal of Chemical Technology,
Biotechnology 85, 590613.
Akcil, A., 2002. First application of cyanidation process in Turkish gold mining and
its environmental impacts. Minerals Engineering 15, 695699.
Akcil, A., 2003. Destruction of cyanide in gold mill efuents: biological versus
chemical treatments. Biotechnology Advances 21, 501511.
Akcil, A., 2006. Managing cyanide: health, safety and risk management practices at
Turkeys Ovacik goldsilver mine. Journal of Cleaner Production 14, 727735.
Akcil, A., 2010. A New global approach of cyanide management: international
cyanide management code for the manufacture, transport, and use of cyanide in
the production of gold. Mineral Processing and Extractive Metallurgy Review 31
(3), 135149.
Akcil, A., Mudder, T., 2003. Microbialdestruction of cyanidewastes in goldmining:
process review. Biotechnology Letters 25, 445450.
Akcil, A., Karahan, A.G., Ciftci, H., Sagdic, O., 2003. Biological treatment of cyanide by
natural isolated bacteria (Pseudomonas sp.). Minerals Engineering 16 (7), 643
649.
Alta Metallurgical Services, Australia, 2012. <http://www.altamet.com.au/wpcontent/uploads/2012/12/Gold-Technology-Developments-and-Trends.pdf>.
American Public Health Association (APHA), 1998. Standard Methods for the
Examination of Water and Wastewater.20th Ed, Edited by L.S. Cleseri, A.E.
Greenberg and A.D. Eaton.
Arellano, C.A.P., Martinez, S.S., 2009. Effects of pH on the degradation of aqueous
ferricyanide to ferrocyanide by photolysis and photocatalysis under solar
radiation. Solar Energy Materials and Solar Cells 94 (2), 327332.
Agency for Toxic Substances and Disease Registry (ATSDR), 2006. Toxicological
Prole for Cyanide. US Department of Health and Human Services, Public Health
Service, Atlanta, GA, p.298.
Babu, G.R.V., Wolfram, J.H., Chapatwala, K.D., 1993. Degradation of Inorganic
Cyanides ByPseudomonas putida Cells. In Biohydrometallurgical Technolgies:
Fossil Energy Materials, Bioremediation, Microbial Physiology. In: Torma, A.E.,
Apel, M.L., Brierley, C.L. (Eds.), Proceedings of an International
Biohydrometallurgy Symposium, Jackson Hole, Wyoming, USA. August 2225,
1993, vol. II., pp. 159165.
Bhunia, F., Saha, N.C., Kaviraj, A., 2000. Toxicity of thiocyanate to sh, plankton,
worm, and aquatic ecosystem. Bulletin of Environmental Contamination and
Toxicology 64 (2), 197204.
Botz, M.M., Scola, J.C., Fueyo, R., de Moura, W., 2004. Cyanide recovery practice at
Cerro Vanguardia, In: Proceeding of 2004 SME Annual Meeting and Exhibit
February 2325, Denver, CO.
Botz, M., Mudder, T., Akcil, A., 2005, Cyanide treatment: physical, chemical and
biological processes. In: Adams, M. (Ed.), Advances in Gold Ore Processing,
Elsevier Ltd., Amsterdam, pp. 672700. (Chapter 15).
Canadian Mining Journal, 2002. INCO R&D Process Development, Product
Development and Cyanide Destruction, April 2002.
Carrillo-Pedroza, F.R., Soria-Agullar, M.J., 2001. Destruction of cyanide by ozone in
two gasliquid contacting systems. European Journal of Mineral Processing and
Environmental Protection 1, 5563.
CCME, 2013. Canadian Environmental Quality Guidelines and Summary Table.
<http://www.ccme.ca/publications/ceqg_rcqe.html>.
SGS
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