Minerals Engineering 50-51 (2013) 1329

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Cyanide and removal options from efuents in gold mining and

metallurgical processes
Nural Kuyucak a, Ata Akcil b,
a
Golder Associates Ltd., 32 Steacie Drive, Kanata, Ontario K2K 2A9, Canada
b
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 a b s t r a c t

Article history: Cyanide has been widely used as an essential raw material in several industries including textile, plastics,
Received 18 April 2013 paints, photography, electroplating, agriculture, food, medicine and mining/metallurgy. Because of its
Accepted 27 May 2013 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 contain-
ing cyanide compounds have to be treated to reduce the concentration of total cyanide and free cyanide
Keywords: below the regulated limits.
Cyanide
Natural degradation reactions can render cyanide non-toxic, resulting in carbon dioxide and nitrogen
Hydrometallurgy
Leaching
compounds. These natural reactions have been utilised by the mining industry as the most common
Process efuents means of attenuating cyanide. However, the rate of natural degradation is largely dependent on environ-
Wastewater treatment mental conditions and may not produce an efuent of desirable quality in all cases year round. Technol-
ogies 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. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.1. Cyanide in daily life . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.2. Solution chemistry of cyanide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.3. Formation of cyanide compounds and pathways for cyanide degradation/attenuation in the environment . . . . . . . . . . . . . . . . . . . . . . . . 15
1.3.1. Complex formation (chelation) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.3.2. Precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.3.3. Adsorption. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.3.4. Cyanate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.3.5. Thiocyanate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.3.6. Volatilization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.3.7. Biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.3.8. Hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.4. Characterization of samples for cyanides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.5. Cyanide for dissolution and recovery of precious metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.6. Cyanide and cyanide compounds toxicityand guidelines and regulations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2. Treatment processes to remove cyanide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.1. Process selection criteria. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2. Treatment processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2.1. Natural cyanide degradation in tailings ponds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2.2. Chemical treatment methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

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
14 N. Kuyucak, A. Akcil / Minerals Engineering 50-51 (2013) 1329

2.2.3. Biological cyanide degradation process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

2.2.4. Other methods and emerging processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.2.5. Electrolytic oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3. Process costs and selection of suitable process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

1. Introduction beans (100300 mg/100 g plant tissue), cassava (104 mg/100 g

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 deni-
tion 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, insecti-
cides 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
plant tissue), wild cherries (140370 mg/100 g plant tissue),
packed fruit juice (e.g., 0.0315.84 mg/L in orange and sour cher-
ry), sorghum (250 mg/100 g plant tissue), almond (297 mg/kg), al-
mond products (50 mg/kg). Varying quantities of cyanide may be
found in other fruits and vegetables such as apricot, strawberry,
apple, peach and cauliower and alcoholic beverages (USEPA,
1976; Cornell University, 2002). Some pharmaceutical drugs used
for curing cancer and high blood pressure are made of cyanide
and cyanide compounds. Plants, microorganisms and insects can
also naturally produce cyanide.
Although the use of cyanide is mostly perceived by the general
public as being associated with the mining and metallurgical pro-
cesses, only about 13% of world cyanide production is consumed by
these industries with the remaining percentage being used else-
where (WHO ECEH, 2000; Mudder and Botz, 2001; Mudder et al.,
2001a,b; Akcil, 2002, 2006, 2010; Mudder and Botz, 2004). Cyanide
is an essential raw material in producing synthetic silk, synthetic
rubber and nylon, paints, medical and pharmaceutical products,
agricultural products, coloured photographic and television lms,
and cosmetics (Kirk-Othmer, 2002). Electroplating, galvanising
and jewellery making also use cyanide. Cyanide is often added as
a depressant in the otation of base metal sulphide ores (e.g., iron
and copper). Because of its ability to selectively dissolve gold and
silver from their ores, the recovery of gold and silver is often asso-
ciated with cyanide use. Iron cyanide is often used as an anti-cak-
ing agent in both table and road salts. Surface waters may contain
low levels of cyanide due to industrial activities associated with
cyanide use such as mining/metallurgical processes, road salts, re
retardants, predator (coyote) poisoning devices, shing in South
Asia. Fig. 1 shows the concentration of cyanide found in several
products.

Fig. 1. Cyanide content of various materials. Fig. 2. Relationship between HCN and CN with pH (25 C).
 N. Kuyucak, A. Akcil / Minerals Engineering 50-51 (2013) 1329
1.2. Solution chemistry of cyanide
The cyanide ion is an anion that can be found as complexes (e.g.,
weak, moderately strong and strong), as free cyanide or as simple
compounds in cyanidation solutions. The dissolution and dissocia-
tion (or ionisation) of molecular or ionic cyanide in aqueous solu-
tions creates free cyanides. Depending on the pH of the solution,
free cyanide can be in the form of either cyanide anion (CN-) or
hydrocyanic acid (or hydrogen cyanide, HCN). HCN is a relatively
weak acid and is predominantly found in waters with a pH below
approximately 8.5, where volatilization of cyanide takes place
(Randol, 1985; Flynn and McGill, 1995). At an optimal gold extrac-
tion pH of 10.5 or greater, most of the free cyanide in the solution is
in the form of the cyanide anion (CN), where cyanide loss by vol-
atilization is limited. Otherwise, the cyanidation process would
neither be practical and safe nor economically and environmen-
tally feasible. In natural aqueous systems that have pH values be-
tween 5 and 8.5, the majority of free cyanide can be found in the
form of HCN and can be lost by volatilization. Fig. 2 illustrates
the relationship between pH levels and cyanide compounds.
Salts of hydrocyanic acid such as sodium cyanide (NaCN), potas-
sium cyanide (KCN) and calcium cyanide (Ca(CN)2) are simple cya-
nides which dissolve completely in aqueous solutions giving free
alkali earth cations and cyanide anions as shown by
NaCN ! Na CN 1 1.3.4. Cyanate
CN H2 O ! HCN OH 2 help of a strong oxidising agent such as ozone, hydrogen peroxide,
The weak and moderately strong cyanide complexes primarily in-
clude cadmium, copper, nickel, silver and zinc cyanide complexes.
These complexes form in a step-wise manner as the cyanide con-
centration of the solution is increased. The solution pH and the con-
centration of cyanide and metals play a role in the quantity of
complex formation. In terms of chemical stability, zinc and cad-
mium are known to be the weakest complexes while iron and co-
balt 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 fac-
tors such as the intensity of light, water temperature, pH, total dis-
solved 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 radia-
tion from the sun releasing free cyanide in receiving lakes and riv-
ers. In addition, the recent treatment systems employ elevated
temperature oxidation principals potentially combined with a cata-
lyst to reach low parts per billion (ppb) treatment levels (Manches-
ter, 2013).
A variety of cyanide related compounds can form in solutions
resulting from cyanidation, natural attenuation or treatment pro-
cesses. 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: com-
plexation (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 envi-
ronment (ICMI, 2012). Since some of these mechanisms provide a
15
basis for the development of chemical and biological treatment
processes, they are briey discussed below.
1.3.1. Complex formation (chelation)
Cyanide forms ionic complexes with metals (e.g., Fe, Cu, Zn) that
are much less toxic than hydrogen cyanide. Stability of cyanide
metal complexes may vary depending on the type of metal. Weak
acid dissociable Cu and Zn complexes are relatively unstable and
can release free cyanide back to the environment; whereas both
ferro- and ferricyanide complexes, such as those found in soils
and in aqueous solutions, can show extreme stability under most
environmental conditions except ultraviolet (UV) light, where they
can undergo photochemical decomposition.
1.3.2. Precipitation
Iron cyanide complexes form insoluble precipitates with Fe, Cu,
Ni, Mn, Pb, Zn, Cd, Sn, Ag over a pH range of 211.
1.3.3. Adsorption
Cyanide and cyanidemetal complexes are adsorbed on organic
and inorganic constituents such as oxides of aluminium, iron and
manganese, certain types of clays, feldspars and organic carbon.
As cyanide is strongly bound to organic matter, the strength of cya-
nide retention on inorganic materials is unclear.
Cyanide can be oxidised to less toxic cyanate (OCN) with the
hypochlorite or gaseous oxygen. Cyanide adsorbed on both organic
and inorganic materials in the soil appears to be oxidised under
natural conditions. Oxidation of cyanide results in formation of
cyanate which is normally found in cyanidation solutions due to
the formation of hydrogen peroxide in the initial step of cyanida-
tion process. Cyanate does not accumulate in solutions because
of its hydrolysis to ammonia and carbonate (or an ammonium salt
and carbon dioxide), which incidentally has a signicantly (at least
1000 times) lower inherent toxicity in comparison to that of cya-
nide. The rate of cyanate hydrolysis is relatively rapid at pH levels
less than 6 or at elevated temperatures. Since free ammonia can
form soluble amine complexes with heavy metals such as copper,
zinc, silver and nickel, the presence of ammonia may inhibit pre-
cipitation of these metals at pH values of above 9, which is known
to be an effective range for the precipitation of metal hydroxides
(Kuyucak, 2001). Nitrate is the end-product of the cyanide oxida-
tion process and forms as a result of chemical or biological oxida-
tion of ammonia.
1.3.5. Thiocyanate
Reaction with some sulphur species converts cyanide to about
seven times less toxic thiocyanate (SCN, ICMI, 2012). Free sul-
phur, sulphide minerals (e.g., chalcopyriteCuFeS2, chalcocite
Cu2S and pyrrhotiteFeS) and their oxidation products (e.g., poly-
sulphides and thiosulphate) found in soils can provide potential
sulphur sources. Thiocyanate occurs when pyrite and pyrrhotite-
bearing solutions are treated with cyanide. All sulphides minerals,
except lead sulphide, have the potential to generate thiocyanate,
where production is accelerated if inadequate aeration is allowed
in conjunction with low alkalinity conditions. A larger quantity
of thiocyanate is produced in the free sulphur or pyrrhotte (an iron
sulphide) containing minerals. It may chemically and biologically
break down producing ammonia and nitrate, carbonate and sul-
phate. Thiocyanide, that is potentially toxic itself, creates an oxi-
dant demand and breakdown products typically include cyanate,
ammonia and nitrate. Under low alkalinity and reduced aeration
conditions, and if pre-oxidised iron sulphide ore contains ferrous
iron; ferrocyanide may form relatively rapidly. Conditions that
16 N. Kuyucak, A. Akcil / Minerals Engineering 50-51 (2013) 1329
could be arranged to minimize the formation of either thiocyanate
or ferrocyanide are limited because a condition that may restrict
the formation of one product may promote formation of another
undesirable product.
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 cya-
nide lost through this pathway increases with decreasing pH, in-
creased 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 aer-
obic 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 con-
ditions, cyanide concentrations greater than 2 ppm are toxic to
these microorganisms.
1.3.8. Hydrolysis
Hydrogen cyanide can be hydrolysed to formic acid or ammo-
nium formate. Although this reaction is not rapid, it may be of sig-
nicance 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 repre-
sented 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 cya-
nide 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 ana-
lytical 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 solu-
ble 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 solu-
tion 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 sil-
ver dissolution. This is called Cyanidation (Habashi, 1966; Rubo
et al., 2006). Cyanidationof gold takes place in two reaction steps
and the overall reaction is known as Elsners equation (Eq. (3)):
4Au 8NaCN O2 2H2 O ! 4NaAuCN2  4NaOH 3
Ag2 S 4NaCN H2 O ! 2NaAgCN2  NaSH NaOH 4
The pregnant liquor containing these ions is separated from the
solids, which are discarded to a tailing pond or spent heap, the
recoverable gold having been removed. After gold is extracted,
wastewater or process solutions may contain three principle types
of cyanide compounds: free cyanide, weakly complexed cyanide
and strongly complexed cyanide (WHO ECEH, 2000). Gold and cya-
nide can form a strong complex in relatively weak cyanide solu-
tions. For leaching of silver, as the silver cyanide complex is
weaker than the gold cyanide complex, stronger cyanide solution
and/or longer reaction times must be employed to accomplish silver
dissolution due to the refractoriness of silver sulphide minerals.
Zinc and copper are dissolved from sulphide minerals during cyan-
idation to some extent. The iron minerals in pyrite and pyrrhotite
ores consume the highest quantity of cyanide. Aggressive condi-
tions can dissolve gold twice as rapidly as silver but, can increase
the attack on other minerals present in the ore resulting in an in-
crease in cyanide consumption, higher concentrations of other met-
als in the solution and a decrease in selectivity for gold and silver.
Gold can be separated from the pregnant solution bearing
goldcyanide complexes by reduction with Zn or Zn-dust (zinc
cementation, MerrillCrowe process) or adsorption onto activated
carbon. In the zinc precipitation process, elemental zinc powder re-
duces gold ions to its free metal form in the absence of oxygen. In
the activated carbon process, gold and silver cyanide complexes
are adsorbed onto active carbon sites, thereby removing gold and
silver from solution. Then, gold and silver are desorbed from the
loaded carbon using 0.1% NaCN and 1% NaOH at elevated temper-
atures (Zadra Process). Gold is recovered usually from the strip
solution by electro winning and a portion of the cyanide is recy-
cled. The use of activated carbon can decrease the concentration
of undesirable metals, such as mercury and copper, consequently,
the treatment of wastewater becomes easier and more efcient
(Scott and Ingles, 1987; Mudder and Botz, 2001; Mudder et al.,
2001a,b).
A complete discussion on the cyanidation process and gold
recovery is out of the scope of this paper. Only a brief discussion
on cyanidation is given here to provide a background for toxicolog-
ical, chemical and treatment aspects of the cyanide bearing
solutions.
1.6. Cyanide and cyanide compounds toxicityand guidelines and
regulations
Cyanide does not accumulate in the body and does not cause
chronic diseases, but because of its ability to bind iron in blood
by forming complexes, it can inhibit oxygen transfer to the cells,
thereby causing suffocation of humans and animals. Similarly,
inhibition of cytochrome oxidase results in toxicity to freshwater
sh mainly by blocking electron transport and energy release in
cells (Ripley et al., 1996). Liquid or gaseous hydrogen cyanide
and alkali salts of cyanide can enter the body through inhalation,
ingestion or absorption through the eyes and skin. The toxicity of
a substance is typically expressed as the concentration or dose that
is lethal to 50% of the exposed population (LC50 or LD50). Inhala-
tion of 100300 ppm gaseous hydrogen cyanide results in death
within 1060 min, inhalation of 2000 ppm hydrogen cyanide
causes death within one minute. The LD50 for ingestion is 50
200 mg, or 13 mg/kg of body weight, calculated as hydrogen cya-
nide. For contact with unabraded skin, the LD50 is 100 mg/kg of
 N. Kuyucak, A. Akcil / Minerals Engineering 50-51 (2013) 1329
body weight as HCN. There is no reported bio-magnication of cya-
nide 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 car-
bon dioxide, ammonia may exceed the regulation limits. Investiga-
tions 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 oxy-
gen concentration in the aquatic environment; and increasing sh
mortality rates. Similarly, whereas thiocyanate is reported to be se-
ven times less toxic than cyanide, increased thiocyanate concentra-
tions in water resources can adversely affect the sh and aquatic
ecosystems, and in the human body, chronic cyanide exposure det-
riments 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 par-
ticles then slowly decomposes with the help of microorganisms
(Turkmen, 1998).
Despite on-going concerns with regulatory agencies and com-
munities 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). Stan-
dards or criteria are established based on determined toxicity lev-
els 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 com-
pounds may vary from country to country, jurisdictions to jurisdic-
tions 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 Pro-
tection 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 stan-
dards for cyanide as 0.005 and 0.001 mg/L, respectively. The World
Bank requires that the efuent from base metal and iron ore min-
ing 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 Produc-
tion of Gold (the Code). ICMI promotes the adoption of the Code,
evaluates its implementation, and manages the certication pro-
cess. 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-
17
mented at 133 gold mines including companies that collectively
produce approximately 60% of the worlds commercially-mined
gold, 20 cyanide production and repackaging facilities and 105
transport operations in 48 countries throughout the world; and
173 of these already have been certied in compliance (ICMI 2012).
2. Treatment processes to remove cyanide
Treatment aims to destroy cyanide, generally by converting it
into compounds that are insoluble and cannot be taken up by
organisms. Treatment methods range from rinsing heaps of solid
tailings with water to more complex techniques such as alkaline
chlorination, sulphur dioxide oxidation and electrochemical, which
treat both solutions (spent cyanide solution and heap rinse) and
slurries (tailings),from removal to recovery of cyanides (USEPA,
1994; Acheampong et al., 2010).
2.1. Process selection criteria
Cyanide destruction plants must be reliable all the time to pro-
duce streams with acceptable water quality that can be discharged
to the environment. The treatment systems should allow recycling
of solutions that do not meet the discharge criteria during plant
upsets and should be installed with a continuous on-line monitor-
ing device. The treatment process should not produce undesirable
by-products and should be able to remove harmful by-products
such as ammonia and metals. It should be appropriate to site-
specic climatic conditions (e.g. temperature, precipitation),
solution chemistry and discharge requirements. The capital and
operational costs should suit the mining production conditions
such as production rate and life expectancy.
2.2. Treatment processes
The nature of the treatment process may range from natural
degradation in tailings impoundment (viz. natural attenuation in
surface ponds) to highly sophisticated plant applications. Natural
degradation in tailings ponds has been the most commonly used
treatment method in most mills, including those in Canada, for
many years. Although natural degradation is still used for cyanide
removal, in the last two decades, several processes including
chemical, biological, electrochemical and thermal hydrolysis meth-
ods have been developed to either supplement or supplant the nat-
ural degradation (Ritcey, 1989; Smith and Mudder, 1991; Ripley
et al., 1996; Nelson et al., 1998; CDS, 2013). The recent tendency
is the use of highly sophisticated and automated treatment plants
installed with on-line monitoring devices due to the increasing
concerns of regulators and communities.
The common cyanide treatment methods include natural degra-
dation in tailings ponds and chemical and biological degradation
processes. Chemical processes may consist of alkaline chloride oxi-
dation (alkaline chlorination), hydrogen peroxide oxidation, Inco
SO2/Air oxidation, Hemlo/Golden Giant (copper and iron sulphate)
precipitation and AcidicationVolatilizationRegeneration (AVR).
Methods of removing or destroying cyanide are summarized in
Table 1. Natural degradation, Inco SO2/Air and hydrogen peroxide
techniques are known to be widely used methods while other
methods nd limited application. The focus of this paper will be
mainly on the widely used methods and the unique Homestake
biological process.
2.2.1. Natural cyanide degradation in tailings ponds
Natural degradation involves detaining cyanide-bearing efu-
ent in tailings or holding ponds for prolonged periods. The degra-
dation of cyanide results from a combination of naturally
18 N. Kuyucak, A. Akcil / Minerals Engineering 50-51 (2013) 1329
Table 1
Methods available for removing or destroying cyanide and process mechanisms involved.
Cyanide removing/destroying method
Natural Attenuation/Degradation (Collecting and Holding In Ponds)
Chemical Addition Under Controlled Conditions
 Oxidation Processes
SO2Air Oxidation
Alkaline Chlorination
Chlorine gas
Hypochlorites
Electrolytic (in situ) generation
Ozonation
Sunlight (UV) w/o catalyst
Hydrogen Peroxide Oxidation
 Iron Sulphide Processes
 Thermal treatment under high pressure
 Fe/Cu Precipitation
Biological Oxidation
 In reactors and under controlled conditions (e.g., Home stake RBC process)
 Passive systems (Wetlands and in-pit)
Conversion to Less Toxic Forms
Thiocyanide conversion
Ferrocyanide conversion
Cyanide Recovery by
SART, AVR, Cyanisorb
Absorption Processes
Ion Exchange (also leads to CN recovery)
Activated Carbon
Ion Flotation
Electrolytic Processes
Cyanide regeneration
Cyanide destruction
occurring physical, chemical and biological processes including
volatilization, photodecomposition, chemical oxidation, microbial
oxidation, chemical precipitation, hydrolysis and precipitation on
solids. Of these mechanisms, volatilization is considered to be
the most important. Natural degradation is inuenced by a number
of variables such as: cyanide species and their concentration in
solution, pH, temperature, bacteria present, sunlight (UV radia-
tion), aeration and pond conditions (e.g., area, depth, turbidity, tur-
bulence, ice cover). In the 1980s, a considerable amount of work
was carried out by Environment Canada to better understand and
mathematically model the natural degradation process of cyanide
in tailings ponds (Ritcey, 1989; Zaidi et al., 1987; Ripley et al.,
1996).
Volatilization of HCN from solution is the dominant natural
attenuation mechanism in most surface ponds (e.g., tailings
ponds). More than 90% of free cyanide is removed by volatilisation.
It is believed that photolysis also contributes to degradation of cya-
nide in ponds. Over time, the pH in the pond is lowered by the nat-
ural uptake of carbon dioxide from the air and by the addition of
acidic rainwater. Due to the carbon dioxide uptake, an equilibrium
pH ranging between 7.0 and 9.0 establishes in the tailings ponds,
and the pH of the tailings slurry drops from about 10.5 to less than
9.0. The drop in pH induces a change in the cyanide/hydrogen cya-
nide equilibrium, favouring the formation of HCN and its subse-
quent volatilization as hydrocyanic gas according to Eq. (5)
(Fig. 2). Under aerobic conditions cyanide is initially converted to
cyanate and then cyanate hydrolysis occurs to form carbon dioxide
as bicarbonate and ammonia as gas and ammonium ions. These
reactions are shown by Eqs. (6) and (7) (Young and Jordan,
1995). Conversion of cyanide to cyanate requires a photochemical
(sunlight), bacteriological or mineralogical catalyst.
Process mechanisms
 Volatilization
 Biodegradation
 Oxidation (by UV, microorganisms)
 Oxidation
 Conversion to cyanate
 Hydrolysis
 OxidationComplexation
 Hydrolyis
 Precipitation
 Degradation (to CO2 and NH3)
 Oxidation to NO3; then reduction to N2)
 Complexation, adsorption/uptake, precipitation, etc.
 Complexation
 Acidication
 Volatilization & Condensation
 Re-neutralization
 Complexation
 Decomposition
CN H ! HCNaq ! HCNg 5
CN 1=2O2 catalyst ! OCN 6
OCN H2 O ! HCO3 NH4 OH 7
Cyanide decay occurs in both shallow and deep sections of the
pond. However, there is a time lag for the deeper pond sections.
In stagnant water bodies, cyanide volatilization is directly propor-
tional to the ratio of solution area to depth. Natural mixing of water
by wind action and convection currents caused by the temperature
difference between pond water and air, induces volatilization in
ponds (Zaidi et al., 1987). Temperature and aeration are the most
important factors affecting the volatilization rate of free cyanide
and cyano-metal complexes of zinc, copper, nickel and iron. Cya-
nide attenuation obeys a rst order reaction with respect to free
cyanide and cyano-metal complexes. UV radiation affects the stabil-
ity and attenuation of ironcyanide complexes in the surface ponds.
The studies revealed that degradation of ferricyanide to ferrocya-
nide by photolysis and photo-catalysis under solar radiation is
strongly affected by the water pH, as the initial ferricyanide concen-
tration did not show any effect (Arellano and Martinez, 2009).
Regardless of the presence or absence of catalysis in the aquatic
media, the redox reactions under sunlight exposure were strongly
dependent on the water pH.
When the pond surface is covered with ice during winter, cya-
nide decay may be signicantly reduced. The tailings prole in a
tailings pond can be divided into three zones by depth: oxidising
zone (03 m); intermediate zone (315 m) and reducing zone
(1535 m). Although all zones may have the same pH levels, total
dissolved solids and total cyanide contents are usually higher in
 N. Kuyucak, A. Akcil / Minerals Engineering 50-51 (2013) 1329
the intermediate zone. As the total cyanide content in pore water
of tailings remain relatively stable, WAD content rapidly decays.
If reduced portions and HS- and H2S species are present in anaero-
bic (reducing) zones, thiocyanide (HSCN) forms as a result of
anaerobic bioattenuation of cyanide. Then, HSCN hydrolysis takes
place producing H2S, NH3 and CO2. Anaerobic bioattenuation is a
less effective mechanism than that of aerobic bioattenuation be-
cause of its slow rate and the toxicity effect of cyanide on anaerobic
bacteria (e.g., 2 mg/L vs. 200 mg/L).
Cyanide removal by natural means may produce acceptable
efuents in some cases. If natural degradation cannot produce a -
nal efuent quality suitable for discharge, then natural processes
will typically be used as an intermediate step for the partial re-
moval of cyanide prior to chemical treatment. While some mills
treat the whole tailings slurry, some mills treat only the tailings
pond overows. Cyanide is especially biodegradable in warm cli-
mates as a result of natural attenuation processes. Any potential
impact on surface waters due to cyanide use cannot persist for a
signicant period of time after the minemill shuts down (Randol,
1985).
2.2.2. Chemical treatment methods
Inability to produce efuents of acceptable quality by natural
means has led to the development of chemical and biological treat-
ment methods (Botz et al., 2005). The processes widely used and
used with limitations are discussed below.
2.2.2.1. Alkaline chlorination. Alkaline chlorination has been well-
known for a long time as an effective means of treatment for indus-
trial wastewaters (Cushnie, 2009). It has been applied to gold mill
efuents for a long time. The process destroys cyanide (CNWAD),
except iron cyanide and more stable cyanidemetal complexes, by
oxidation with chlorine under alkaline conditions. Although the
process may also destroy thiocyanate, it is primarily effective on
free cyanide, and where high concentrations of cyanide are pres-
ent. Cyanate is also oxidised to give N2 and CO2. Chlorine can be
provided in the form of gaseous chlorine or sodium or calcium
hypochlorite. Lime is an alkaline agent that is commonly used for
pH control. The complete oxidation of cyanide to nitrogen and
bicarbonate takes place in two stages. In the rst stage, cyanide
is oxidised, and then hydrolyzed to cyanate
NaCN Cl2 ! CNCl NaCl 8 2.2.2.2. SO2/Air (INCO) process. This process was developed and pat-
CNCl 2NaOH ! NaCNO NaCl H2 O 9 Mining Journal, 2002). It was known to be Inco process. In the Inco
The Second stage of the process is the further oxidation of cya-
nate to nitrogen and bicarbonate
3Cl2 2NaCNO 6NaOH ! 2NaHCO3 N2 6NaCl 2H2 O
10
The rst stage of the reaction (Eqs. (8) and (9)) takes place at a min-
imum pH of 11, while the second stage (Eq. (10)) occurs at a pH of
8.5. Considerably greater reagent additions and longer retention
times are required in completing both stages at a pH level of 11. Be-
low pH 11, hydrolysis of highly toxic cyanogen chloride gas will not
be completed (Eq. (9)). As a consequence of both high cost and the
relatively low toxicity of cyanate (1/1000 the toxicity of free cya-
nide), regulatory agencies may accept the process to be carried
through only at the cyanate stage. The treated water may require
aeration or a polishing step for removal of toxicity due to residual
chlorine. Ferrocyanide is not destroyed but, partially oxidised to fer-
ricyanide. An additional process is required for removal of iron cya-
nide. The process does not require a catalyst such as Cu, and is
reported to be easy to operate. Concentrated cyanide wastes, such
19
as spent plating or stripping solutions, should not be reacted with
hypochlorite because the reaction can be violent, emitting chlorine
gas. These wastes can be batch treated by electrolytic oxidation and
thermal destruction (Cushnie, 2009). Sodium hypochlorite con-
sumption is usually estimated to be 25100% greater than the stoi-
chiometric requirement (approximately 7 lb of Cl2 or 7.5 lb of NaOCl
per lb of CN). The excess chlorine is consumed by oxidation of
organics and metal ions present in the wastewater.
During chlorination, oxidizable substances other than cyanide,
such as thiocyanate, thiosalts and metals in low oxidation states
consume additional chlorine. The presence of thiosalts may signif-
icantly increase the chlorine demand. Several companies in Canada
have employed this method as standard until the Inco process
was fully developed and its capabilities were demonstrated. Some
industries have used gaseous chlorine and some have used solid
calcium hypochlorite. Although the chlorination units are usually
located in the mill buildings, they can be installed as a separate
treatment plant adjacent to the discharge end of the tailings ponds
(SGS Technical Bulletin, 2010).
Giant Yellowknife Mine in Canada operated a two-stage treat-
ment system for the removal of both cyanide and arsenic. Cyanide
and metals were removed by chlorine addition in the rst stage
and arsenic was precipitated by ferric sulphate addition in the sec-
ond stage. After occulation the treated efuent from this plant
was discharged to a large polishing pond with a 15-day retention
time. A conceptual owchart of the process is given in Fig. 3. With
this process, the concentration of total cyanide, free cyanide, cop-
per and iron could be reduced from 400, 250, 300 and 400 mg/L
to less than 5, 0.2, 0.5 and 0.3 mg/L, respectively.
Although it is possible to recover cyanide by this method for re-
use, it requires costly and complex additions and installations.
Handling of chlorine gas raises safety concerns (Kilborn, 1991).
Toxicity of the intermediate products that form during the chlori-
nation process and residual chlorine are of concern. Therefore, in
recent years, interest in using the alkaline chlorination process
has been decreasing. Peroxygen compounds such as hydrogen per-
oxide, peroxymono sulfuric acid (commonly known as Caros acid),
and persulfates have been found to be effective alternatives to
alkaline chlorination for destroying free and complexed cyanides
(US Peroxide, 2013). Detailed discussions on peroxygen oxidation
are provided in Section 2.2.2.4.
ented by the Inco Metals Company in 1984 in Canada (Canadian
process, a mixture of SO2 and air is used in the presence of copper
as a catalyst, under controlled pH conditions of 810,to selec-
tively oxidise both free and complex cyanide species (CNWAD), ex-
cept iron cyanide, to cyanate (CNO) (Smith and Mudder, 1991;
Devuyst et al. 1992; Nelson et al., 1998; Saarela and Kuokkanen,
2004). A conceptual owchart of the process is illustrated in
Fig. 4. With the exception of iron, metals are precipitated from
solution as hydroxides. The process also removes iron cyanide by
precipitation as insoluble copper and zinc ferrocyanide. Investiga-
tions show that these precipitates are quite stable over a wide
range of pH. Eq. (11) represents the cyanide oxidation reaction
and products produced by the SO2/Air process
CNWAD O2 SO2 Cu H2 O ! CNO Cu H2 SO4 11
Neutralisation of acid generated and precipitation of metals are
illustrated by
H2 SO4 CaOH2 ! CaSO4 2H2 O 12
Me2 CaOH2 ! MeOH2 Ca2 13
20 N. Kuyucak, A. Akcil / Minerals Engineering 50-51 (2013) 1329
Fig. 3. Conceptual alkaline chlorination treatment process.
The amount of copper required to catalyse the reaction varies,
and depends on the concentrations of other constituents in the
wastewater. Copper requirements are signicantly reduced or
eliminated for waters containing greater than 50 mg/L copper. On
the other hand, SO2 consumption to CNWAD ratio by weight is
2.46, where CNWAD is the weak acid dissociable cyanide that in-
cludes free cyanide and weakly complexed cyanides. The SO2 re-
quired for the process may be supplied in a variety of forms such
as gaseous SO2, soluble sulphite or metabisulphite (Na2S2O5), or
roaster gases containing SO2. Currently, sodium sulphite and so-
dium metabisulphite are being used more frequently.
Fig. 4. Conceptual INCO SO2/Air process.
Because of its ability to handle slurries with ease and to remove
total cyanide speciation with low-cost reagents in a single-stage
continuous treatment, INCO Process offered distinct advantages
over the two main alternative, alkaline chlorination and hydrogen
peroxide methods. It has been accepted by many regulatory agen-
cies throughout the world as the state-of-the-art method. The SO2/
Air process received worldwide attention for the treatment of gold
mill efuents and it has been applied to over 100 operations world-
wide. Companies previously using alkaline chlorination have con-
verted to the SO2/Air process to overcome iron removal problems
and/or high reagent costs. A process royalty was charged for its
use until 2004 (Nelson et al., 1998). While some mills are applying
this process to the barren bleed solutions, some are treating tail-
ings slurries. Some mills employ the method to treat tailings pond
overow. The recent tendency is to treat tailings slurries before
disposal into the tailings ponds to protect the environment and
wild life.
The SO2/Air process offers an effective means to treat gold mill
efuents and to produce efuents containing concentrations of less
than 0.5 mg/L for total cyanide and for each of the metals com-
monly found in gold mill efuents (e.g., copper, iron, nickel and
zinc). The process can be applied to either aqueous reclaim water
or directly to the tailings slurry. Noranda developed Noranda
SO2 process where both tailings slurry and efuents can be trea-
ted using pure copper and SO2 without air injection (Kilborn,
1991; Carrillo-Pedroza and Soria-Agullar, 2001; InfoMine, 2012).
Although it showed potential for development and was used at
the Noranda operations, it has not been adapted as widely as the
INCO process. Other sites also reported the use of modied INCO
processes to destroy cyanide from mill efuents (Yang and Skryp-
niuk, 2009).
2.2.2.3. Iron/copper precipitation processes. Addition of ferrous iron
to form insoluble ferrocyanide at pH higher than 10 is one of the
oldest methods used to detoxify free cyanide (Manoranjan et al.,
2003). In these processes, the presence of thiocyanates has shown
signicant inhibition to the complexation of cyanide with the me-
tal ion, preventing the removal of cyanide to an acceptable level. In
addition, decomposition of ferrocyanides observed under sunlight
yielding HCN has raised stability concerns. Several cyanide detox-
ication processes have been developed based on the principles of
 N. Kuyucak, A. Akcil / Minerals Engineering 50-51 (2013) 1329
insoluble metal cyanide (e.g. ferrocyanide, copper cyanide) precip-
itate formation.
The Golden Giant Mine of Hemlo Gold Mines Inc., Ontario,
Canada, developed a process for cyanide removal at their property
(Konigsmann et al., 1989). The Hemlo Process reacts the untreated
water with a pre-mixed solution of cupric sulphate and ferrous sul-
phate in the rst step. Upon addition of the wastewater, the ferrous
iron is quickly oxidised and forms a ferric hydroxide precipitate
while the cupric ion is simultaneously reduced to the cuprous
ion which removes free cyanide as an insoluble cuprous cyanide
precipitate. The removal of free cyanide causes the dissociation
of copper, nickel and zinc cyanide complexes resulting in further
removal of cyanide as cuprous cyanide. Copper, nickel, zinc, anti-
mony and molybdenum are co-precipitated from solution with
the initially formed ferric hydroxide. Ferric sulphate is added in
the second step to ensure complete precipitation of the metals.
Due to the acidity of the ferric reagent, lime is added to control
the pH at4. Ferrocyanide is precipitated from the solution as cupric
ferrocyanide. A nal polishing stage occurs in the third step,
where hydrogen peroxide is added at neutral pH. Thickened sludge
is disposed of to the tailings pond. A conceptual process ow chart
is shown in Fig. 5. The Hemlo process can generate a treated efu-
ent containing less than 0.5 mg/L total cyanide and metal ions.
Another method developed by Manoranjan et al. (2003) con-
sisted of removing free cyanide and CNWAD from efuents using
a mixture of thiosulphate and complexing agents (such as divalent
copper, divalent iron, divalent cobalt or their mixtures), and acti-
vated carbon. Sulphate salts were used to prepare complexing
agents. The pH of the process could be adjusted between 5 and
10 with the help of lime or NaOH. The process could effectively re-
duce total cyanide and CNWAD concentrations to less than
0.5 mg/L and 0.005 mg/L, respectively. The precipitates resulting
from the process has been claimed to be chemically stable.
2.2.2.4. Hydrogen peroxide oxidation process. Hydrogen peroxide
(H2O2) can oxidise cyanide to cyanate in the presence of a transi-
tion metal (Cu, Ag, V, Th) as a catalyst in concentrations of 5 to
50 mg/L. The oxidation requires 1.26 lb H2O2 per lb of cyanide.
The nal products are carbonate and ammonia ions (USEPA,
1994; US Peroxide, 2013). The choice of peroxygen system depends
on the reaction time available, the desired products (cyanate, or
CO2 and NH3), the types of cyanides being treated (free, weak acid
dissociable, or inert), and the system economics. It was observed
that the reaction rate could be signicantly accelerated by the
addition of copper-impregnated activated carbon to the cyanide
bearing solution (Yeddue et al., 2011). The reaction rate increased
with the increasing initial molar ratio of [H2O2]0/[CN] and de-
creased with increasing pH from 8 to 12. The temperature did
not have a signicant effect on the kinetics of the cyanide degrada-
tion and the cyanide removal kinetics t to pseudo-second order
with respect to cyanide.
A pH of 910 should be maintained to avoid release of HCN (US
Peroxide, 2013). Increase in temperature and dosage of catalyst
and the use of excess H2O2 can increase the reaction rate. Photoac-
tivation (UV + H2O2) can destroy stable cyanide complexes such as
ferricyanide. The destruction of cyanide by H2O2 is shown by
CN H2 O2 ! CNO H2 O 14
CNO 2H2 O ! CO2
3 NH4 15
This process is more suitable for wastewaters rather than slurries,
where H2O2 consumption might be signicantly high. It was suc-
cessfully used in the USA to neutralise cyanide remaining in the
heap leach piles (USEPA, 1994). OK TEDI Mining Limited in Papua,
New Guinea, employed H2O2 to meet extremely stringent govern-
21
ment imposed efuent quality requirements in the 1980s. The gold
mill operation throughput of 22,500 tonnes per day was a giant one
by gold mill standards. The H2O2 solution was directly added to the
carbon-in-pulp (CIP) tailings slurry and reacted in a mixed tank to
oxidise cyanide to cyanate before discharge. This process is also
known as the Degussa process because Degussa, who manufactures
H2O2, developed an automated and closely controlled process in
which H2O2 is efciently used (Degussa, 1988). Although H2O2
can successfully oxidise and destroy cyanide, due to handling dif-
culties caused by its hazardous nature and economic reasons, it is
not frequently used. Ammonia in the resulting efuent may pose
toxicity to the sh.
Newmonts Waihi Gold Mine in New Zealand uses H2O2 method
to destroy cyanide in the form of free cyanide and WAD (as Cu, Ni,
Zn complexes), existed in efuents resulting from gold and silver
extraction (Waihigold, 2013). Copper sulphate is added to the pro-
cess as a catalyst to speed up the reaction. The cyanide destruction
process is followed by a metal and trace ion removal process using
ferric chloride, lime and occulants. The treatment plant built in
1999 was recently upgraded incorporating a reverse osmosis pro-
cess to produce high quality water that can be discharged to the
Ohinemuri River.
In 2003, Degussa (Cyplus) and INCO developed a new process
called CombinOx combining the advantages of Inco SO2/Air and
hydrogen peroxide technologies (Chemeurope, 2003). The process
could reduce both cyanide and heavy metals to low levels. The ex-
ibility of the process to accommodate changes in the feed was
shown to be the key advantage. It was also claimed that, depending
on site-specic conditions, the new process could offer capital and
operational cost savings over the traditional Inco process.
At the Marlin gold mine in Guatemala, World Bank and the local
regulatory agencies imposed stringent standards for the discharge
of wastewater resulting from MerrillCrowe process where mer-
cury (Hg) is used along with cyanide to recover gold (Howell and
Christophersen, 2009). The tailings slurry is subjected to SO2/Air
oxidation process for the destruction of cyanide before its disposal
to the tailings pond. Excess water in the tailings impoundment to
be discharged to the environment requires further polishing for
the removal of metal ions including Hg and cyanide. The polishing
treatment process consists of three steps:
(1) oxidation with hydrogen peroxide in the presence of copper
sulphate catalysis to meet the total WAD and free cyanide
limits; removal of Hg by a chelating polymer to below detec-
tion limit of 0.0002 mg/L;
(2) occulation, precipitation and separation of metal and iron
hydroxide sludge in a high-rate sand-blasted settling/clari-
fying equipment and ltration;
(3) carbon adsorption as a precaution to meet the desired level
of Hg removal.
The use of Caros acid made of H2O2 and sulphuric acid can signif-
icantly accelerate the reaction rate. Alternatively, persulphates
(ammonium, sodium or potassium) can oxidise cyanide beyond
cyanate above pH 9 and in the absence of a catalyst.
2.2.2.5. Iron sulphide (FeS) and sulphide precipitation processes and
SART. Waste barren bleed solution is treated by the addition of fer-
rous sulphide (FeS) to remove both free and complexed cyanides.
Finely divided insoluble ferrous sulphide particles are prepared
in the mill by reacting ferrous sulphate with sodium sulphide.
The adsorption of cyanide on the FeS particles results in removal
of cyanide. The reaction is strongly pH dependent and requires a
pH of approximately 7.5 and a retention time of 15 min. The FeS
to cyanide ratio is maintained at 31. Ferrous sulphate also re-
moves arsenic which dissolves from the ore. The cyanide removal
22 N. Kuyucak, A. Akcil / Minerals Engineering 50-51 (2013) 1329
Fig. 5. Conceptual Golden Giant mine efuent treatment process.
step is not employed to produce an efuent of suitable quality to
meet the imposed efuent discharge limits but rather relies on fur-
ther removal of cyanide by natural degradation in the tailings
ponds. The regulated parameters in the efuent from the tailings
pond are usually below the objective limits of this process.
Recently, brand name products such as DTOX have been intro-
duced, based on the sulphide precipitation process principles (Min-
eral Process Control, 2013). The reaction between cyanide and
polysuldesulfur contained in DTOX converts hydrogen cyanide
to thiocyanate. In addition, heavy metal ions can be precipitated
as cyanide, and free and complex cyanides are neutralised. The
end products released to the environment contain carbonates
and ammonia. It is claimed that the reaction is safer and the rates
are more rapid than those of hypochlorite. The experiments con-
ducted to investigate the reaction in a 2% (20,000 mg/L) solution
of sodium cyanide revealed that the reaction was 95% complete
within 1 h, and cyanide concentrations were non-detectable with-
in 2 weeks at a CN: poly S0 ratio of 1:2 by weight.
A process called SART (SulphidizationAcidicationRecycle
Thickening) that was developed by Lakeeld and Tech in Canada
in early 2000s uses a reagent such as sodium hydrosulphide
(NaHS) to precipitate copper and zinc as sulphides and convert
cyanide to HCN (Alta Metallurgical Services, Australia, 2012). The
precipitates are removed for possible sale or further processing,
and the solution is neutralised with sodium hydroxide or lime
and recycled back to the leaching process to re-use the cyanide.
Telfer Gold Mine in a remote location of Western Australia investi-
gated SART as a cost-effective process to recover copper and cya-
nide (SGS Technical Bulletin, 2001). At the mine, the oxide gold
ore was treated in a conventional CIL circuit by blending the low
and high grade copper ores to minimize cyanide consumption
and allow smooth operation. The sulphide ore was treated through
a otation circuit to produce pyrite and copper concentrates. Be-
cause of economical and environmental reasons, it was desirable
to reduce the amount of cyanide reporting to the tailings pond.
The resulting slurry, containing copper as copper sulphide precip-
itate and cyanide as HCN in solution, was fed to the SART thickener
where they were separated. The process involved in sulphidization
and acidication reactions was presented below:
2CuCN2
3 S
2
6H ! Cu2 S 6HCNaq 16
The results of the pilot tests revealed that a pH of 5 would be suf-
cient to remove over 95% of the copper from tailings efuent and re-
cover 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
 N. Kuyucak, A. Akcil / Minerals Engineering 50-51 (2013) 1329
3. The SART process has been successfully commercialised and ap-
plied 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 re-
cover sulphides. To remove cyanide, the pH of calcine slurry is low-
ered from 9 to 2.5 by spraying SO2-containing roaster gases in a
counter-current decantation (CCD) system. HCN gas released dur-
ing 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 environ-
mental protection. Therefore, information about the quality of
resulting efuents by this process was not reported.
Since 1998, cyanide recovery from mill tailings has been prac-
tised 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 recov-
ery 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 ob-
served. Changes were made to the cyanide recovery system allow-
ing 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, Vola-
tilize 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 elemen-
tal sulphur at the site.
Hudson Bay Mining and Smelting Company at FlinFlon, Mani-
toba, 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 solu-
tion was acidied with H2SO4 solution from their zinc recovery
plant. Air was used in towers to sweep HCN from the acidied bar-
ren 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 acidicat-
ion tests, was recovered by this method. Both SART and AVR pro-
cesses 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 li-
quid 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
23
iron cyanide complexes to less toxic compounds such as nitrogen,
formic acid and formamide. Microorganisms can utilise cyanide
compounds as source of carbon and nitrogen for their own growth
(Saarela and Kuokkanen, 2004; Chapman et al., 2007; Sabatini
et al., 2012). Cyanide degradation can occur under both aerobic
and anaerobic conditions. Aerobic oxidation process produces
ammonia (Akcil, 2003; Akcil and Mudder, 2003). Four types of
enzymatic reactions can take place including substitution/addition,
hydrolysis, oxidation and reduction. Hydratase enzyme degrades
cyanide to formamide which is further hydrolysed by amidase en-
zyme into NH4 and formic acid. The reaction pathway and the pro-
cess kinetics can be affected by aerobic or anaerobic conditions,
nutrients (carbon such as sugar), nitrogen, yeast, pH, oxygen and
temperature. Microorganisms tend to form a biolm on a support
material in reactor applications (Maier et al., 2009). The reactions
showing oxidation of metal cyanide complexes and thiocyanide
by Pseudomonas sp. are illustrated in Eqs. (17) and (18) (Young
and Jordan, 1995; Akcil et al., 2003; Kadlec and Wallace, 2009)
CN 1=2O2 aq ! OCN ! OCN 3H2 O
! NH4 HCO3 OH 17
SCN 3H2 O 2O2aq ! SO2 
4 NH4 HCO3 H 18
The mode of application can take place in either active fully con-
trolled automated bioreactors or in passive systems (passive biore-
actors, 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, sus-
tainability 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 activ-
ity 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 rel-
atively low due to natural degradation and dilution. Biological pro-
cesses 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 sig-
nicant amount of research has been carried out to develop micro-
biological 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 cya-
nides to carbon dioxide and ammonia has been investigated as
an alternative, but no pilot- or full-scale process have been oper-
ated using this method (Babu et al., 1993). A test heap was inocu-
lated 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 bacte-
rium 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 Pseudomo-
nas 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-
24 N. Kuyucak, A. Akcil / Minerals Engineering 50-51 (2013) 1329
Almagro et al., 2011). The cyanide assimilation pathway that gen-
erates 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 com-
bined wastewaters at a sufciently elevated temperature year
round is key to their successful operation. The plant was con-
structed in 1984to treat 3600 US gpm at a capital cost of
US$10 million.
Cyanide, thiocyanate, copper and ammonia are the main con-
taminants 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 sub-
merged 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 oxi-
dation 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 cya-
nide 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 re-
moved from the efuent by clarication and dual-media sand l-
tration, 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 con-
tact 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 chlo-
ride 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 ob-
tained 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 sol-
ids 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
and anaerobic biological processes and high density sludge (HDS)
lime neutralization method for removal of cyanide, thiocyanide
and ammonia, nitrate and metals (Given et al., 1998). The full-scale
combined biological and chemical facility was implemented at the
Nickel Plate Mine in British Columbia, Canada for treating tailings
impoundment solution and seepage. In the rst step, cyanide, thio-
cyanide and cyanate are converted to ammonia and then nitrate
with the help of a two-stage aerobic activated sludge treatment
process. In the second step, anaerobic de-nitrication takes place
to reduce nitrate to nitrogen gas. In the nal (HDS) step, arsenic
and other residual metal are precipitated using lime and ferric sul-
phate. Prime reagents used in the plant include nutrients for bac-
teria such as methanol, soda ash, phosphoric acid and sulphuric
acid, and neutralization/precipitation process chemicals such as
lime, ferric sulphate and occulent. The temperature of the feed
water is raised to approximately 20 C using a propane-red sub-
merged combustion water heater.
2.2.3.3. Passive biological treatment process: engineered wetlands and
pit lakes (in-pit treatment). Despite their known drawbacks such as
the need for long retention time, large space and warmer climates;
passive methods are known to be cost-effective alternatives to
other conventional and emerging treatment technologies because
their operations often do not require external energy, chemicals,
operators and routine maintenance. Since they are generally per-
ceived as natural systems, they are better accepted by the public.
Their applications are well-suited in remote sites with limited
accessibility. The most common passive treatment methods con-
sist of engineered wetlands and in-pit (pit lake) or in-pond
applications.
Wetlands may contain a train of settling ponds, aerobic (surface
ow) and anaerobic (subsurface ow) wetland and a polishing/l-
tering system. Wetlands are often planted with aquatic vegeta-
tions. Anaerobic wetlands may contain an organic substrate or a
mixture of organic and inorganic compounds such as manure,
straw, saw dust, limestone. In wetland processes, ammonia pro-
duced by aerobic microorganisms such as Pseudomonas, Thiobacil-
lus sp, Bacillius sp, Arthrobacter sp, Paracoccus sp, Micrococcus
spand, Neissarie sp, creates a nutrient-rich environment which pro-
motes microbial growth and subsequently uptake, sorption, con-
version and/or precipitation of cyanide, thiocyanate, sulphate,
nitrate and ammonia phenomena by microorganisms occur (Akcil
and Mudder, 2003). In addition, ingestion and metabolic degrada-
tion by plants (e.g., willows), volatilization, uptake by plants and
microorganisms, complex formation with iron and precipitation
reactions take place (Kadlec and Wallace, 2009). Furthermore, iron
complexes undergo photolytic degradation to give free cyanide.
Anaerobic sulphate reduction, denitrication and cyanide attenua-
tion are coupled with the chemical precipitation and chemical
sorption of trace metals. SO2 4 , which was produced following the
oxidation of thiocyanate (Eq. (19)), can be reduced to sulphide
and the nutrient source organic carbon is converted to carbonate
as presented in Eq. (21). Sulphate reducing bacteria SRB play
an important role in the SO24 reduction process (Kuyucak, 2002,
2006; Kuyucak and Chabot, 2009). Sulphide (S2) produced makes
insoluble complexes with metal ions resulting in removal of metals
from the wastewater (Eq. (20)).
SO2   2
4 2C3 H4 O3 lactate ! 2C2 H4 O2 acetate 2CO3 S
2
19
Me2 S2 ! MeSs 20
where Me represents metal species.
Wetlands were investigated for their ability to remove cyanide
and cyanide complexes. Subsurface ow (SSF) and surface ow (SF)
 N. Kuyucak, A. Akcil / Minerals Engineering 50-51 (2013) 1329
Fig. 6. Biological treatment process at Homestake Mining Company.
wetlands with vegetation (e.g., willow, cattails, etc.) have shown
ability to remove metal cyanide and thiocyanide and metal ions.
The presence of vegetation did not show a signicant difference
in removal of compounds; the efciency of removal in vegetated
wetland was marginally better (Kadlec and Wallace, 2009). Biolog-
ical passive systems can be supplemented with limestone leach
beds and open limestone channels to condition the wastewater
pH and enhance the treatment process before the treatment and/
or to adjust the efuent pH and further sequester contaminants
from the efuent after treatment, before discharge.
Engineered wetlands also have been employed for the removal/
reduction of cyanide from mining efuents in the USA and Canada
(Kilborn, 1991; Zagury et al., 2007; Kadlec and Wallace, 2009). An
engineered wetland treatment system was installed to treat drain-
down, collected from the heap leach pad, to provide an efuent
suitable for discharge into the groundwater system at the closed
Santa Fe mine site in Nevada, USA (Mudder et al., 2001b). Evenly
spaced perforated pipes were placed in the inactive lined leach
solution pond which was then furnished with an organic matter
consisting of composted manure and straw. The drain-down from
the pad is directed by gravity to the perforated pipes and distrib-
uted across the cross-section of the organic matter. The treated
efuent is collected in a gravel layer and is routed to a drain eld
where it is aerated while inltrating into the ground. The mini-
mum retention time of the system is about 38 days.
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 impound-
ment 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 concentra-
tions. 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 require-
ments. Biological RBC process was found to be prohibitively expen-
sive 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 N. Kuyucak, A. Akcil / Minerals Engineering 50-51 (2013) 1329
the addition of phosphorus as nutrient during the tests. About
12 tonnes and 24 tonnes of phosphorus fertiliser (e.g., mono
ammonium phosphate) were added to the tailings lake and the
seepage pit lake to stimulate the algal growth in 2002. Later in
2003, the seepage lake received about 9 tonnes more phosphorus
fertiliser. Monitoring of the lakes indicated the presence of algae
and denitrication bacteria. Cyanide, metal cyanide complexes
and ammonia could be removed to the regulated levels allowing
the treated water to be discharged. This method proved to be a
very cost-effective mine water management option (MPERG,
2010).
2.2.4. Other methods and emerging processes
2.2.4.1. Evaporation and potential zero discharge. In arid regions,
evaporation may provide a means for achieving zero-discharge of
process waters to the environment. This method has been com-
monly practised at gold mines in the United States, Australia and
South Africa.
2.2.5. Electrolytic oxidation
In the electrochemical oxidation process, cyanide ions can be
destroyed at the anode as metals are collected at the cathode
(Young and Jordan, 1995; Saarela and Kuokkanen, 2004). Cyanide
and cyanide complexes rst become oxidised at the anode to give
cyanate ions which are further decomposed to non-toxic carbon
dioxide and nitrogen gas at the cathode. Dissociated metal cations
are reduced to free metal ions at the cathode which can be col-
lected for their use. Free cyanide, cyanide complexes and concen-
trated cyanide can be handled in this process. Reactions and
examples are depicted by
Anode : CN 2OH ! OCN H2 O 2e 21
AgCN3 2 6OH ! Ag2 3OCN 3H2 O 6e 22
Cathode : 2CNO 4OH ! 2CO2 g N2 g 2H2 O 6e 23
Ag2 2e ! Ag0 s 24
Electrolytic oxidation process is depended on pH, voltage and
electrolyte solution. The type of the cathode and anode material af-
fects the process kinetics. According to Saarela and Kuokkanen
(2004), the electrochemical oxidation is a very economical and
environmentally friendly cyanide destruction process.
2.2.5.1. Cyanide recovery, ion exchange, innovative oxidation by
ozone, adsorption, CO2 Use and Sunlight/UV. Many of these methods
aim to recover and recycle cyanide and other compounds and/or
metals to reduce the cost of the treatment process. As explained
earlier, the AcidicationVolatilizationRegeneration (AVR) meth-
od, where pH of the barren bleed solution is lowered to 23 to rap-
idly dissociate metalcyanide complexes and expel cyanide as
hydrogen cyanide gas, was rarely used in earlier periods, and
mainly to recover cyanide for reuse. Caros acid process, where sul-
phuric acid is conditioned with hydrogen peroxide, can rapidly
lower WAD cyanide (Menne, 2000). This process eliminates cata-
lyst requirements and associated high capital costs, but cyanide
complexes formed do not remain stable and release free cyanide.
A method based on the use of ozone and oxygen was developed
to recover cyanide and copper from cyanidation efuents contam-
inated with thiocyanate and coppercyanide complexes (Soto
et al., 1996). Electrochemical oxidation is sometimes used to de-
stroy concentrated cyanide wastes (e.g., >50,000 mg/L CN). How-
ever, it has not yet been widely used studies to develop an
electrolytic cyanide and metal recovery (CELEC) process are under-
way (Cushnie, 2009).
Ozone as a strong oxidising reagent has been used to destroy CN
replacing the alkaline chlorination process (Cushnie, 2009). The
ozone process is effective in reducing cyanide concentrations to
environmentally acceptable low levels. Low operational costs are
shown to be the prime advantage of the ozone CN destruction pro-
cess, where ozone is less expensive than chlorine or sodium hypo-
chloride. Ozone is generated on-site typically by the silent
electrical discharge method. Production of toxic compounds as a
result of oxidation of organics does not occur as is the case in the
alkaline chlorination process. Another advantage is the ability of
ozone to destroy zinc, copper and nickel cyanide complexes. How-
ever, the equipment cost including the cost of ozone generator is
signicantly higher. Oxidation of cyanate resulting from the rst
oxidation step of cyanide requires excessive ozone thereby the
operating cost is signicantly increased. Oxidation by ozone re-
quires 1.82.0 lbs of ozone per pound of CN to reach the cyanate
stage and 4.65.0 lbs to reach complete oxidation. The ozonation
process has also been combined with UV radiation for the treat-
ment of halogenated organics.
Processes such as, electrolytic decomposition, ozonation, acti-
vated carbon, ion exchange (an adsorbent resin capable of binding
metal cyanide complexes), hydrogen peroxide oxidation with or
without the use of a catalystis and ferrous sulphide adsorption
and thermal hydrolysis have shown potential for development
(Kilborn 1991; Carrillo-Pedroza and Soria-Agullar, 2001; Cushnie,
2009; InfoMine, 2012). Addition of carbon dioxide alone without
a catalyst to replace SO2 was tested with success as an inexpensive
alternative to the SO2/Air process (Randol, 1992).
Removal/reduction of cyanide by adsorption using activated
carbon from mining wastewaters has been focused (Dash et al.,
2009). Due to technically difcult and costly regeneration of acti-
vated carbon, the adsorption technology has not been widely used
(Crini, 2006). The use of activated carbon adsorption was combined
with other technologies to meet stringent water quality standards
(Howell and Christophersen, 2009), mainly for removal of metal
ions (e.g., Hg) and other compounds rather than CN.
Ion exchange techniques have not been widely practised de-
spite promising results obtained from various pilot-plant opera-
tions. As in the SART process, ion exchange resins present the
potential to recycle cyanide associated and to generate revenue
via the sale of the copper itself (Ripley et al., 1996; SGS Technical
Bulletin, 2010). Recycling of cyanide could also decrease environ-
mental risks by reducing loading of potentially harmful salts in
the tailings and recycle water (e.g. CNS, CNO, NH3and metal cya-
nides, and the need for transportation, storage and handling of cya-
nide. If the revenue could offset the operating costs of the cyanide
recovery plant, the technology could transform uneconomic ore
bodies into viable mines. Main issues cited are ion selectivity, com-
petition between ions, ion blinding, elution and associated costs.
Because of their ability to extract cyanide and metal cyanide com-
plexes directly from gold plant tailings, anion exchange resins have
been used in the resin-in-pulp (RIP) process, which is a well-devel-
oped industrial process used for gold and uranium recovery. The
ion exchange process has been considered as readily adaptable to
cyanide recovery, thereby also circumventing solid/liquid separa-
tion processes. Moreover, conventional, commercial strong-base
resins are well-suited to cyanide recovery application since the
most common cyanide species in gold plant tailings are free cya-
nide anions (usually 100500 mg/L) and the tricyano copper com-
plex, both of which can be extracted directly from pulps by anion
exchange resins. When the loaded resin is treated with sulphuric
acid, copper remains in the resin phase as a precipitate of the com-
pound, CuCN, and only two moles of cyanide are released per mole
of copper. The Augment and Hannah proprietary processes, where-
in CuCN is intentionally precipitated in the pores of a conventional
strong base resin and, in this form, produces a regenerated resin
 N. Kuyucak, A. Akcil / Minerals Engineering 50-51 (2013) 1329
that is an efcient adsorbent for free cyanide ions and soluble cop-
per cyanide (SGS Technical Bulletin, 2010). As Hannah refers to
strong base resin extraction of free cyanide and metal cyanide spe-
cies, the Augment process is a strong base resin extraction of cop-
per 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 rel-
atively 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 contain-
ing 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 temper-
ature (450470F) and pressure (600 psi) signicantly increase the
kinetics of hydrolysis, where OCN is converted to ammonia and
bicarbonates/carbonates as shown in
NaCN NaOCl ! NaCNO NaCl 25
2NaCNO 3NaOCl H2 O ! 3NaCl N2 2NaHCO3 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 conven-
tional 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 tem-
perature 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 require-
ments may vary from site to site, cyanide treatment costs are site-
specic. The direct comparison of cyanide treatment costs from
27
one location to another would be misleading. Cost analyses for
both capital and operating costs should be carried out for each site
considering the actual site conditions. The type of process can be
selected depending on the site climate, production rate, ore type,
possibility of the use of natural degradation or zero discharge
methods, need for the removal of other metals or anions, and efu-
ent regulations (e.g., from nil to aggressive treatment). Operational
capacity and life expectancy of the mine should also be taken into
account while selecting and deciding on the appropriate treatment
plant. In some cases, if time allows, conducting a series of labora-
tory and pilot tests, and scale-up studies should be considered as
a useful path in making a decision.
For instance, a study conducted at the Ryan Lode Mine near
Fairbanks, Alaska investigated the comparative costs of chemical
and biological destruction of cyanide in mine waters in cold cli-
mates. Specically, the capital and operating costs of the SO2/Air
process to the biological degradation process were compared for
the treatment of rinse water from spent leach heaps (Nelson
et al., 1998). It was found that the biological method had a higher
capital cost, but a signicantly lower operating cost resulting in a
low present-worth cost. Therefore, it was suggested that bacterial
detoxication be considered as a viable alternative to affect the re-
moval of cyanide from spent leach heaps. In case of Colomac Mine
in Yellowknife, NWT, Canada, cost benet analyses including cap-
ital and operational costs and site specic condition requirements,
biological RBC process due to cold temperature of the wastewater
and the cold climate of the location would require heating (Chap-
man et al., 2007). After conducting a series of laboratory and pilot
tests, in situ treatment in the pit was selected as the most cost-
effective process for the site. Alkaline breakpoint chlorination pro-
cess was kept as a backup process to be able to meet the required
efuent quality for discharge. The recent tendency is to use a pro-
cess such as SART, AVR and ion exchange to recover and recycle
cyanide and metal for economical and environmental reasons. Be-
cause SART and AVR applications enable the use of the recovered
cyanide back in the metal extraction process and subsequently re-
duce the consumption of cyanide in the overall metallurgical pro-
cesses, they are considered to be more economical than other
efuent treatment processes which require destruction of cyanide.
4. Summary
Water is considered to be a crucial asset for mining and metal-
lurgical 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 man-
aged for many years. Underground mines or open pits should be
drained to be able to access to the ore during excavation. Later dur-
ing processing of ores (e.g., extraction and recovery), water is used
as part of each process. Processing of 1 m3 of ore requires a mini-
mum 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 envi-
ronment 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 de-
sired quality. In addition to cyanide, the toxic effect of ammonia
28 N. Kuyucak, A. Akcil / Minerals Engineering 50-51 (2013) 1329
is of concern to the regulatory agencies and investigations to re-
duce 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 pre-
cipitation processes, are mainly developed and used by their
respective companies. In addition to the conventional SO2/Air pro-
cess, 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 imple-
mented 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.
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