Minerals Engineering 50-51 (2013) 13–29

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

Cyanide and removal options from effluents in gold mining and
metallurgical processes
Nural Kuyucak a, Ata Akcil b,⇑
Golder Associates Ltd., 32 Steacie Drive, Kanata, Ontario K2K 2A9, Canada
Department of Mining Engineering, Mineral Processing Division (Mineral-Metal Recovery and Recycling Research Group), Suleyman Demirel University, Isparta TR32260, Turkey

a r t i c l e i n f o 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 affinity 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.
Natural degradation reactions can render cyanide non-toxic, resulting in carbon dioxide and nitrogen
compounds. These natural reactions have been utilised by the mining industry as the most common
Process effluents means of attenuating cyanide. However, the rate of natural degradation is largely dependent on environ-
Wastewater treatment mental conditions and may not produce an effluent 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
Ó 2013 Elsevier Ltd. All rights reserved.


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 Ó 2013 Elsevier Ltd. All rights reserved.

. . . . 2002). .3. . . . 28 1. . . . . Because of its ability to selectively dissolve gold and silver from their ores. . . Plants. . . . . . . . . . . paints. . . Cyanide content of various materials. . respiring exhaust from is an essential raw material in producing synthetic silk. Cyanide due to smoking tobacco (0. . . . . . . . . . . . cassava (104 mg/100 g plant tissue). . . . . . . . . . . . . Some food and cosmetics (Kirk-Othmer. . . A. The technical defini. . . . . . . . . . . . . . . 2002. . .. . . . cides and fertilisers. . . . . .2. . . . . . . . medicines and while using these industries with the remaining percentage being used else- products which contain cyanide (USEPA. . . . . Varying quantities of cyanide may be one atom of carbon and one atom of nitrogen. . . . .03–15.1. . 27 References .g. . . . . . . . . . . . . . fishing in South Asia. . . . . .g. . . . .. . . . . . . . . . . . . . rubber and nylon. . . . . . microorganisms and insects can Cyanide can naturally be found in about 2000 sources (WHO ECEH. . . . . predator (coyote) poisoning devices. . . . . . . drink. . . Mudder et al. . Cyanide in daily life packed fruit juice (e. . . . . 2004). . . . . Cornell University. . . Biological cyanide degradation process. . . . . . . . . . . . . . . . . . . . . . . . smoking. . coloured photographic and television films. . 1 shows the concentration of cyanide found in several products. . . . Akcil. . . . . . . lipstick). . . . . the recovery of gold and silver is often asso- ciated with cyanide use. . . . . . . . . . . . . tion of cyanide is a triple-bonded molecule with a negative one apple. . . . . . illustrated in Fig. almond (297 mg/kg). . Relationship between HCN and CN with pH (25 °C). Humans are in close contact with cyanide in their cesses. . . . . . . . fire retardants. . . . . . . . . . eye blush. . . . . cotton and agricultural products. . . . . . . . 2010. . only about 13% of world cyanide production is consumed by daily life through food. . . . . .2. . . . . . . . . .. . . . . . 1. . . . . . For instance. . . . . . . . . 26 3. Iron cyanide is often used as an anti-cak- ing agent in both table and road salts. . . . . Electroplating. . . . . . . . The principal human-made cyanide forms are gaseous Although the use of cyanide is mostly perceived by the general hydrogen cyanide (HCN) and solid sodium or potassium cyanide public as being associated with the mining and metallurgical pro- (NaCN or KCN). . . . . . . strawberry. . . . .5 mg/cigarette). . . . . . . . . Fig. . . . 27 4. . The concentration of cyanide per kg in certain a depressant in the flotation of base metal sulphide ores (e. . 1.14 N. . as where (WHO ECEH. . . 23 2. sorghum (250 mg/100 g plant tissue). they are exposed to certain levels of cyanide 2001a. . . and using cosmetics (e. . . . . . . . . . . wild cherries (140–370 mg/100 g plant tissue). . . . . . . . . . . . Fig. Fig. . . . Summary . and cyanide compounds. . . insecti. . . . . . . . . . . . 0. . . . 2002). . .84 mg/L in orange and sour cher- ry). . also naturally produce cyanide. . . . . . . . Introduction beans (100–300 mg/100 g plant tissue). .5. . . Electrolytic oxidation . . . . . .g. Mudder and Botz. . charge. . . . . . 1976). 26 2. . . . . . . consisting of one atom of carbon in the +2 oxidation state 1976. . . . . . . . Other methods and emerging processes . . Surface waters may contain low levels of cyanide due to industrial activities associated with cyanide use such as mining/metallurgical processes. . . 2. . . . . . . . . . . . . . . for curing cancer and high blood pressure are made of cyanide 2012). . . grapes. . Akcil / Minerals Engineering 50-51 (2013) 13–29 2. . . . . . Kuyucak. . . handling certain type of pesticides. . . . . . found in other fruits and vegetables such as apricot. . al- The term ‘‘cyanide’’ refers to a chemical compound containing mond products (50 mg/kg). . . . . . . . . . Some pharmaceutical drugs used and one atom of nitrogen in the 3 oxidation state (InfoMine. . . . . Cyanide is often added as in their production. . . . . medical and pharmaceutical products. . . . Cyanides most commonly refer to salts of the anion CN. .2. . . . . . . . Process costs and selection of suitable process . 2000. . . . .. . . . 2001. . . . . . . . . . . . . Mudder and Botz. . 2000). . . . . . . . 1. . . . . road salts. iron food products has been observed as: table salt (20 mg/kg). . . . . peach and cauliflower and alcoholic beverages (USEPA. particularly for growing tobacco. synthetic vehicles (7–9 mg/km). . 2006. . lima and copper). . . . . . . . . . . . . . .4. . . . . . . galvanising products may either naturally contain cyanide or cyanide is used and jewellery making also use cyanide. .b. . . . . . . . . . . .

and ferricyanide complexes. ferrocyanide may form relatively rapidly. the cyanidation process would 1. phate. Otherwise. cyanide complex precipitation. nides which dissolve completely in aqueous solutions giving free As cyanide is strongly bound to organic matter. form soluble amine complexes with heavy metals such as copper. sulphide minerals (e. which incidentally has a significantly (at least balt complexes are the strongest ones. Nitrate is the end-product of the cyanide oxida- the general oxidation systems unaffected. pH. the strength of cya- alkali earth cations and cyanide anions as shown by nide retention on inorganic materials is unclear.3. hydrogen peroxide.g. Precipitation neither be practical and safe nor economically and environmen. Stability of cyanide– tions creates free cyanides. the majority of free cyanide can be found in the form of HCN and can be lost by volatilization. Iron cyanide complexes form insoluble precipitates with Fe. A. where they tion pH of 10. Weak ‘‘free cyanide’’ can be in the form of either cyanide anion (CN-) or acid dissociable Cu and Zn complexes are relatively unstable and hydrocyanic acid (or hydrogen cyanide. Pb. the recent treatment systems employ elevated 1.3. free ammonia NH3 or ammonium ion bearing solutions are treated with cyanide. as free cyanide or as simple 1.3. where production is accelerated if inadequate aeration is allowed 1. bio-attenuation. Cyanide and cyanide–metal complexes are adsorbed on organic Salts of hydrocyanic acid such as sodium cyanide (NaCN).1. manganese. most of the free cyanide in the solution is can undergo photochemical decomposition. Depending on the pH of the solution. Since free ammonia can tors such as the intensity of light. tween 5 and 8. 2 illustrates 1. Complex formation (chelation) compounds in cyanidation solutions. formation of dant demand and breakdown products typically include cyanate. poly- resulting from cyanidation. The rate of cyanate hydrolysis is relatively rapid at pH levels and strong acids. Hydrolysis of HCN in a zinc.3. Thiocyanate temperature oxidation principals potentially combined with a cata. and inorganic materials in the soil appears to be oxidised under clude cadmium. Thiocyanide. In addition.. moderately strong and strong). sulphides and thiosulphate) found in soils can provide potential cesses. Adsorption the relationship between pH levels and cyanide compounds. of its hydrolysis to ammonia and carbonate (or an ammonium salt mium are known to be the weakest complexes while iron and co. The dissolution and dissocia. where cyanide loss by vol- atilization is limited. which is known ammonium formate. These compounds include thiocyanate (SCN).g. phur. Fig. natural conditions. the formation of hydrogen peroxide in the initial step of cyanida- centration of cyanide and metals play a role in the quantity of tion process. 1995).5 or greater. 2013). Free sul- ter. Cu. adsorption. Ag over a pH range of 2–11.. Kuyucak. natural attenuation or treatment pro.. whereas both weak acid and is predominantly found in waters with a pH below ferro. 2012). potas. zinc and cad. ammonia (i. These complexes may 1000 times) lower inherent toxicity in comparison to that of cya- dissociate and release free cyanide in the presence of UV radiation nide. iron and sium cyanide (KCN) and calcium cyanide (Ca(CN)2) are simple cya. chalcopyrite–CuFeS2. The cyanide ion is an anion that can be found as complexes (e. seven times less toxic thiocyanate (SCN. In natural aqueous systems that have pH values be.5.. creates an oxi- oxidation to cyanate. have the potential to generate thiocyanate. where volatilization of cyanide takes place and in aqueous solutions. less than 6 or at elevated temperatures. thiocyanate and hydrolysis/saponification of free cyanide.. Solution chemistry of cyanide basis for the development of chemical and biological treatment processes. chalcocite– A variety of cyanide related compounds can form in solutions Cu2S and pyrrhotite–FeS) and their oxidation products (e. It may chemically and biologically Natural attenuation mechanisms of cyanide may include: com. feldspars and organic carbon. Mn. Thiocyanate occurs when pyrite and pyrrhotite- (OCN). Zn) that tion (or ionisation) of molecular or ionic cyanide in aqueous solu. Reaction with some sulphur species converts cyanide to about lyst to reach low parts per billion (ppb) treatment levels (Manches. the presence of ammonia may inhibit pre- neutral or acidic solution yields formate as either formic acid or cipitation of these metals at pH values of above 9. total dis. cyanate sulphur sources. 2001).e. such as those found in soils approximately 8. Zn.3. All sulphides minerals. Since some of these mechanisms provide a iron. tion from the sun releasing free cyanide in receiving lakes and riv- ers. they are briefly discussed below. Formation of cyanide compounds and pathways for cyanide in conjunction with low alkalinity conditions.  NH 4 ) and nitrate (NO3 ). in the form of the cyanide anion (CN). Akcil / Minerals Engineering 50-51 (2013) 13–29 15 1. except lead sulphide. metal complexes may vary depending on the type of metal. copper. and carbon dioxide). Conditions that .4. are much less toxic than hydrogen cyanide.3. At an optimal gold extrac. volatilisation. Cyanide adsorbed on both organic The weak and moderately strong cyanide complexes primarily in. Flynn and McGill. Iron cyanide is known to be refractory cyanide to be an effective range for the precipitation of metal hydroxides as it is a stable typically non-reactive cyanide that passes through (Kuyucak. NaCN ! Naþ þ CN ð1Þ 1. conditions. water temperature. The solution pH and the con. Ni. 1985. environmental conditions except ultraviolet (UV) light. weak. Under low alkalinity and reduced aeration pathways help decrease the reactivity of cyanide in natural envi. Cyanate does not accumulate in solutions because complex formation. that is potentially toxic itself. A larger quantity degradation/attenuation in the environment of thiocyanate is produced in the free sulphur or pyrrhotte (an iron sulphide) containing minerals. break down producing ammonia and nitrate. nickel.2. solved solids and complex concentration. and inorganic constituents such as oxides of aluminium. HCN is a relatively can release free cyanide back to the environment. carbonate and sul- plexation (chelation). certain types of clays. N. Fe.2. It has been reported that tion process and forms as a result of chemical or biological oxida- iron cyanide could break down when it is exposed to the UV radia. hypochlorite or gaseous oxygen. and if pre-oxidised iron sulphide ore contains ferrous ronment (ICMI. silver and zinc cyanide complexes.5. Cyanate Cyanide can be oxidised to less toxic cyanate (OCN) with the CN þ H2 O ! HCN þ OH ð2Þ help of a strong oxidising agent such as ozone. 2012). ICMI. Cu. can show extreme stability under most (Randol. Sn. cyanate which is normally found in cyanidation solutions due to centration of the solution is increased. These ammonia and nitrate.g. HCN). Cyanide forms ionic complexes with metals (e. tion of ammonia.3. silver and nickel.5.g. In terms of chemical stability. tally feasible. Oxidation of cyanide results in formation of These complexes form in a step-wise manner as the cyanide con. The rate of dissociation is affected by several fac. Cd.

weaker than the gold cyanide complex. e. inhalation of 2000 ppm hydrogen cyanide tion at a pH greater than 10 which may contain about 50 mg/L free causes death within one minute.b). by forming complexes. Mudder et al. 200 mg. potential interferences. If required. 2000). The amount of cya- recoverable gold having been removed. Effectiveness of this and/or longer reaction times must be employed to accomplish silver process is limited to cyanide concentrations of up to 200 ppm. [Au(CN)2] and ingestion or absorption through the eyes and skin. thereby removing gold and cyanide in metal complexes. chemical and treatment aspects of the cyanide bearing test and the results can be periodically verified with another ana. Akcil / Minerals Engineering 50-51 (2013) 13–29 could be arranged to minimize the formation of either thiocyanate et al. type of analytical method and the laboratory.g.. thereby causing suffocation of humans and animals.1% NaCN and 1% NaOH at elevated temper- and complex forms of cyanide. in- wastewater or process solutions may contain three principle types creased aeration of solution and with increasing temperature. recovery is out of the scope of this paper. except with cobalt. gold and silver cyanide complexes cyanide. Free cyanide includes the cyanide atures (Zadra Process). There are several methods used to characterise the treatment of wastewater becomes easier and more efficient samples for cyanides and cyanide containing compounds (APHA. chemistry requirements (e. nide lost through this pathway increases with decreasing pH. 1996).6. Cyanide for dissolution and recovery of precious metals inhibition of cytochrome oxidase results in toxicity to freshwater fish mainly by blocking electron transport and energy release in Gold and silver are noble metals and as such they are not solu. weak acid dissociable (CN–WAD) and free the activated carbon process. free cyanide level. For instance. weakly complexed cyanide Cyanide is also lost through volatilization from soil surfaces. Volatilization Ag2 S þ 4NaCN þ H2 O ! 2Na½AgðCNÞ2  þ NaSH þ NaOH ð4Þ At the pH typical of environmental systems. such as mercury and copper. with gaseous solids. anions to produce soluble derivatives. free cyanide will be The ‘‘pregnant liquor’’ containing these ions is separated from the predominately in the form of hydrogen cyanide. calculated as hydrogen cya- ver dissolution. Only a brief discussion time and cost). Then.. als in the solution and a decrease in selectivity for gold and silver. elemental zinc powder re- Analytical methods can determine three types of cyanide duces gold ions to its free metal form in the absence of oxygen.3. In the zinc precipitation process. gold and silver are desorbed from the sented by total cyanide values. The precious metals form complexes with the cyanide and alkali salts of cyanide can enter the body through inhalation. within 10–60 min.3. 1987. it may be of sig. the hydrogen cyanide evolving slowly over time. The use of activated carbon can decrease the concentration level and the CN–WAD level should be greater than or equal to the of undesirable metals. Although biological degradation also occurs under anaerobic con. This is called ‘‘Cyanidation’’ (Habashi. Samples need to be preserved as described by the analytical laboratory procedures if the sample 1. Gold and cya- nide can form a strong complex in relatively weak cyanide solu- 1.3.. Rubo nide. (3)): the formation of one product may promote formation of another undesirable product.. Characterization of samples for cyanides cementation. 1966. For contact with unabraded skin. which then oxidises to nitrate. consequently. In including total cyanide. dissolution due to the refractoriness of silver sulphide minerals. Mudder and Botz. of cyanide compounds: free cyanide. Although this reaction is not rapid. Similarly. Gold is recovered usually from the strip anion and molecular hydrogen cyanide.4. The use of automated on-line continuous monitoring systems is Cyanide does not accumulate in the body and does not cause becoming widespread. As a result. The iron minerals in pyrite and pyrrhotite these microorganisms. cyanide can also be analysed chronic diseases. Liquid or gaseous hydrogen cyanide ble in water.8. can be repre. 2006). solution by electro winning and a portion of the cyanide is recy- nide level should be greater than or equal to the CN–WAD cyanide cled. Cyanide and cyanide compounds toxicityand guidelines and cannot be analysed immediately. The LD50 for ingestion is 50– cyanide. can provide the maximum rate and extent of gold and sil. Kuyucak. All cyanide compounds present in the solution including are adsorbed onto active carbon sites.. it can inhibit oxygen transfer to the cells. a rapid and inexpensive method on cyanidation is given here to provide a background for toxicolog- which can provide good estimates can be used during a field pilot ical. 100–500 mg/L NaCN solu. Merrill–Crowe process) or adsorption onto activated carbon. Hydrolysis the attack on other minerals present in the ore resulting in an in- Hydrogen cyanide can be hydrolysed to formic acid or ammo. in a substance is typically expressed as the concentration or dose that order to maintain ionic form of cyanide and prevent volatilisation is lethal to 50% of the exposed population (LC50 or LD50). The appropriate method is selected based on the solution 2001a. Cyanidationof gold takes place in two reaction steps or ferrocyanide are limited because a condition that may restrict and the overall reaction is known as Elsner’s equation (Eq.7. cells (Ripley et al.g. In the absence of other metal tion of 100–300 ppm gaseous hydrogen cyanide results in death cyanide complexes. Gold can be separated from the ‘‘pregnant solution’’ bearing gold–cyanide complexes by reduction with Zn or Zn-dust (zinc 1. ores consume the highest quantity of cyanide.16 N. silver from solution. A. 2001. as the silver cyanide complex is Cyanide can degrade to ammonia by microorganisms under aer.5. site-specific A complete discussion on the cyanidation process and gold samples) and its reliability and efficiency (e. lytical method for their reliability. higher concentrations of other met- nium formate. can increase 1. reproducibility. typically pH > 10. and strongly complexed cyanide (WHO ECEH. WAD cyanide covers both the free loaded carbon using 0. which are discarded to a tailing pond or spent heap. where anaerobic conditions exist. or 1–3 mg/kg of body weight. Biodegradation tions. the LD50 is 100 mg/kg of . solutions. cyanide concentrations greater than 2 ppm are toxic to idation to some extent. Detection limits can vary for each regulations cyanide compounds. The toxicity of [Ag(CN)2] under strong alkaline conditions. 1. Aggressive condi- tions can dissolve gold twice as rapidly as silver but. stronger cyanide solution obic conditions.g. 1998). After gold is extracted. nificance in ground water. For leaching of silver.. Inhala- to hazardous hydrocyanic acid (HCN). a relatively dilute. crease in cyanide consumption. but because of its ability to bind iron in blood in a solid sample. the total cya. Zinc and copper are dissolved from sulphide minerals during cyan- ditions. (Scott and Ingles.6. 4Au þ 8NaCN þ O2 þ 2H2 O ! 4Na½AuðCNÞ2  þ 4NaOH ð3Þ 1.

The degra- experienced dramatic growth. Treatment processes to remove cyanide cyanide concentration is only controlled in drinking water. The capital and (Turkmen. Ripley (WHO) guidelines consider 0. The treatment process should not produce undesirable cyanide does not accumulate in the soil.005 and 0..1 mg/L free CN SO2/Air oxidation. Natural (i. in the last two decades. it is believed that higher than 0. evaluates its implementation. many years. electrochemical and thermal hydrolysis meth- at 0. 2010). especially infants. N. hydrogen peroxide oxidation. Canada sets fresh and marine water stan. The Cyanide Code is being imple. which is 0. and aquatic life by enhancing algae growth and thereby. produce approximately 60% of the world’s commercially-mined Cyanide in effluents resulting from gold mining is known to be gold. The treatment systems should allow recycling ecosystems. 1998). chlorination. water or air. 2013). Since organisms. Akcil / Minerals Engineering 50-51 (2013) 13–29 17 body weight as HCN.g.05 mg/L CN–WAD levels may adversely affect humans and 2. Currently. 2012). including those in Canada. 1991. biological. 173 of these already have been certified in compliance (ICMI 2012). 1992. treatment method in most mills. Nelson et al. chronic cyanide exposure det- of solutions that do not meet the discharge criteria during plant riments the thyroid gland (Bhunia et al. aquatic life) (Hagelstein and Mudder.05 mg total CN per litre (Turkmen. Treatment processes aquatic life (Randol. A. Usually. Hemlo/Golden Giant (copper and iron sulphate) and 0. ICMI. 2012). Acheampong et al. natural attenuation in enforcement to protect the human health and the environment surface ponds) to highly sophisticated plant applications. ammonia may exceed the regulation limits. decreasing dissolved oxy- 2.. UV radiation by-products and should be able to remove harmful by-products in sunlight and gaseous oxygen in air naturally degrade cyanide to such as ammonia and metals. several processes including allowable cyanide concentration in potable water is established chemical. precipitation). 1997. 2009). Inco SO2/Air and hydrogen peroxide established by the United Nations Environment Programme techniques are known to be ‘‘widely used’’ methods while other (UNEP) to administer the International Cyanide Management Code methods find limited application. 2012). 2002). 1996. 2000. and increasing fish mortality rates. 1998. 2013). munities regarding the cyanide compounds. The focus of this paper will be for the Manufacture. dation of cyanide results from a combination of naturally . The European Union (EU) is the use of highly sophisticated and automated treatment plants specifies 0. Cyanide in water is first adsorbed by soil par- specific climatic conditions (e.e. While the removal. aquatic life are lower than the standards set for the drinking water The common cyanide treatment methods include natural degra- quality. installed with on-line monitoring devices due to the increasing 2000.07 mg/L CN safe for both acute and et al. 2007. respectively. increased thiocyanate concentra- duce streams with acceptable water quality that can be discharged tions in water resources can adversely affect the fish and aquatic to the environment. dation in tailings ponds and chemical and biological degradation dards for cyanide as 0. Treatment aims to destroy cyanide. tailings with water to more complex techniques such as alkaline bon dioxide.2 mg/L (Ministry of Environment Ontario. jurisdictions to jurisdic. the World Health organisation ural degradation (Ritcey. Transport and Use of Cyanide in the Produc. 2006. standards set for both fresh and marine concerns of regulators and communities.2. operational costs should suit the mining production conditions Despite on-going concerns with regulatory agencies and com- such as production rate and life expectancy. Since the establishment of ICMI. 1989. 1985 Donato et al. ICMI. WHO ECEH. Inco ing companies should meet 1 mg/L total cyanide. 0. The nature of the treatment process may range from natural els to provide reasonable levels of safety and to promulgate their degradation in tailings impoundment (viz. Process selection criteria gen concentration in the aquatic environment. which tions are currently underway to develop methods to manage treat both solutions (spent cyanide solution and heap rinse) and ammonia and nitrate in wastewaters as well as cyanides. ticles then slowly decomposes with the help of microorganisms solution chemistry and discharge requirements. and by the Ontario Ministry of the Environment (Canada). Natural cyanide degradation in tailings ponds the safe management of cyanide at gold mines is voluntary (Akcil. However. according to a study transport operations in 48 countries throughout the world. Treatment methods range from rinsing heaps of solid many of treatment processes convert cyanide to ammonia and car. Total 2. ing device. nitrate is a relatively non-toxic compound. Although natural degradation is still used for cyanide tions and even site to site (Randol. CDS. Although slurries (tailings). ods have been developed to either supplement or supplant the nat- tection Agencies (USA/Canada EPA). where health effect may occur. ICMI promotes the adoption of the Code. Methods of removing or destroying cyanide are summarized in An International Cyanide Management Institute (ICMI) was Table 1.from removal to recovery of cyanides (USEPA. 1998. Similarly. 1998). it may cause harm to humans. temperature. ICMI. biological’’ process. sulphur dioxide oxidation and electrochemical. Kuyucak. and Christophersen. Stan- dards or criteria are established based on determined toxicity lev.2. at high concentrations 1994. whereas thiocyanate is reported to be se- Cyanide destruction plants must be reliable all the time to pro- ven times less toxic than cyanide. Smith and Mudder. The World processes..001 mg/L.. dation (alkaline chlorination). 2013). Howell precipitation and Acidification–Volatilization–Regeneration (AVR). The participation to the Code that exclusively focuses on 2. 20 cyanide production and repackaging facilities and 105 the prime candidate for treatment. Investiga. The degradation in tailings ponds has been the most commonly used standards set for the allowable concentration of ions and com.1 mg/L total cyanide and 0. the Cyanide Code has ent in tailings or holding ponds for prolonged periods. upsets and should be installed with a continuous on-line monitor- As a result of natural attenuation and dissociation phenomena. and manages the certification pro- cess. For instance. Natural degradation involves detaining cyanide-bearing efflu- 2002. There is no reported bio-magnification of cya. Akcil. Chemical processes may consist of alkaline chloride oxi- Bank requires that the effluent from base metal and iron ore min. 2012). mented at 133 gold mines including companies that collectively nide in the food chain (ATSDR. The recent tendency long-term exposure in drinking water. It should be appropriate to site- C and N compounds. Natural degradation. for pounds may vary from country to country. ammonia. generally by converting it the concentration of ammonia in treated waters is regulated in into compounds that are insoluble and cannot be taken up by Canada and is required not to exceed 10 mg/L (CCME. 2010).1. suspended solids and copper were identified as the most important contaminants in gold mining effluents rather than cyanide.2 mg/L by the United States and Canadian Environmental Pro. mainly on the ‘‘widely used’’ methods and the unique ‘‘Homestake tion of Gold (the Code). and in the human body..1. ICMI.5 mg/L CN–WAD levels (World Bank Group. wild life..

The tailings profile in a as bicarbonate and ammonia as gas and ammonium ions. Under aerobic conditions cyanide is initially converted to When the pond surface is covered with ice during winter. 1987. 2). The drop in pH induces a change in the cyanide/hydrogen cya. bulence. 2009). cyanide and cyano-metal complexes. Zaidi et al. Of these mechanisms. Conversion to Less Toxic Forms Thiocyanide conversion  Complexation Ferrocyanide conversion Cyanide Recovery by  Acidification SART. (Fig. Temperature and aeration are the most Volatilization of HCN from solution is the dominant natural important factors affecting the volatilization rate of free cyanide attenuation mechanism in most surface ponds (e. cya- cyanate and then cyanate hydrolysis occurs to form carbon dioxide nide decay may be significantly reduced. ural uptake of carbon dioxide from the air and by the addition of The studies revealed that degradation of ferricyanide to ferrocya- acidic rainwater.g. nickel and iron. ice cover). microorganisms) Chemical Addition Under Controlled Conditions  Oxidation Processes SO2–Air Oxidation  Oxidation Alkaline Chlorination  Conversion to cyanate – Chlorine gas  Hydrolysis – Hypochlorites – Electrolytic (in situ) generation Ozonation  OxidationComplexation Sunlight (UV) w/o catalyst  Hydrolyis Hydrogen Peroxide Oxidation  Precipitation  Iron Sulphide Processes  Thermal treatment under high pressure  Fe/Cu Precipitation Biological Oxidation  In reactors and under controlled conditions (e. there is a time lag for the deeper pond sections. an equilibrium nide by photolysis and photo-catalysis under solar radiation is pH ranging between 7. chemical precipitation. adsorption/uptake. However.. dissolved solids and total cyanide contents are usually higher in . a considerable amount of work In stagnant water bodies. aeration and pond conditions (e. Natural mixing of water mathematically model the natural degradation process of cyanide by wind action and convection currents caused by the temperature in tailings ponds (Ritcey. precipitation. ity and attenuation of iron–cyanide complexes in the surface ponds.. Cyanisorb  Volatilization & Condensation  Re-neutralization Absorption Processes Ion Exchange (also leads to CN recovery)  Complexation Activated Carbon Ion Flotation Electrolytic Processes Cyanide regeneration  Decomposition Cyanide destruction occurring physical. temperature.0 establishes in the tailings ponds. (6) and (7) (Young and Jordan. hydrolysis and precipitation on CN þ 1=2O2 ðþcatalystÞ ! OCN ð6Þ solids. ponds (Zaidi et al. volatilization is considered to be the most important. UV radiation affects the stabil- nide in ponds. bacteriological or mineralogical catalyst. tailings and cyano-metal complexes of zinc. Due to the carbon dioxide uptake. AVR. 1987). Over time.g. difference between pond water and air.5 to less than tration did not show any effect (Arellano and Martinez. Akcil / Minerals Engineering 50-51 (2013) 13–29 Table 1 Methods available for removing or destroying cyanide and process mechanisms involved.g. etc. chemical and biological processes including CN þ Hþ ! HCNðaqÞ ! HCNðgÞ ð5Þ volatilization. media. chemical oxidation.18 N.0 and 9.. Cyanide removing/destroying method Process mechanisms Natural Attenuation/Degradation (Collecting and Holding In Ponds)  Volatilization  Biodegradation  Oxidation (by UV. A. pond. Conversion of cyanide to cyanate requires a photochemical (15–35 m). intermediate zone (3–15 m) and reducing zone 1995). favouring the formation of HCN and its subse. Cya- ponds). copper.0.. Cyanide decay occurs in both shallow and deep sections of the tion). turbidity. area. In the 1980s. Kuyucak. induces volatilization in 1996). Home stake RBC process)  Degradation (to CO2 and NH3)  Passive systems (Wetlands and in-pit)  Oxidation to NO3. photodecomposition. Ripley et al. cyanide volatilization is directly propor- was carried out by Environment Canada to better understand and tional to the ratio of solution area to depth. More than 90% of free cyanide is removed by volatilisation. 1989. strongly affected by the water pH. Regardless of the presence or absence of catalysis in the aquatic nide equilibrium. as the initial ferricyanide concen- and the pH of the tailings slurry drops from about 10. sunlight (UV radia. microbial oxidation.. pH.. 9. bacteria present. total (sunlight). then reduction to N2)  Complexation. zone (0–3 m). tur. Natural degradation is influenced by a number OCN þ H2 O ! HCO3 þ NHþ4 þ OH ð7Þ of variables such as: cyanide species and their concentration in solution. Although all zones may have the same pH levels. These tailings pond can be divided into three zones by depth: oxidising reactions are shown by Eqs. depth. the redox reactions under sunlight exposure were strongly quent volatilization as hydrocyanic gas according to Eq. the pH in the pond is lowered by the nat. (5) dependent on the water pH. nide attenuation obeys a first order reaction with respect to free It is believed that photolysis also contributes to degradation of cya.

and H2S species are present in anaero. Fig. (11) represents the cyanide oxidation reaction be completed (Eq. partially oxidised to fer- ricyanide. Handling of chlorine gas raises safety concerns (Kilborn.to selec- nate to nitrogen and bicarbonate tively oxidise both free and complex cyanide species (CNWAD). If natural degradation cannot produce a fi. except iron cyanide and more stable cyanide–metal complexes.3 mg/L. These wastes can be batch treated by electrolytic oxidation and bic (reducing) zones. WAD content rapidly decays. by Toxicity of the intermediate products that form during the chlori- oxidation with chlorine under alkaline conditions. effluents for a long time. bacteria (e. Chemical treatment methods and metals were removed by chlorine addition in the first stage Inability to produce effluents of acceptable quality by natural and arsenic was precipitated by ferric sulphate addition in the sec- means has led to the development of chemical and biological treat. Several companies in Canada will typically be used as an intermediate step for the partial re. The complete oxidation of cyanide to nitrogen and (US Peroxide. calcium hypochlorite. As a consequence of both high cost and the and products produced by the SO2/Air process relatively low toxicity of cyanate (1/1000 the toxicity of free cya. Any potential located in the mill buildings. per lb of CN). 4. HSCN hydrolysis takes sumption is usually estimated to be 25–100% greater than the stoi- place producing H2S..5 lb of NaOCl less effective mechanism than that of aerobic bioattenuation be.1. Cyanate is also oxidised to give N2 and CO2. cop- per and iron could be reduced from 400.. gas. 2002). The treated water may require Neutralisation of acid generated and precipitation of metals are aeration or a polishing step for removal of toxicity due to residual illustrated by chlorine. The excess chlorine is consumed by oxidation of cause of its slow rate and the toxicity effect of cyanide on anaerobic organics and metal ions present in the wastewater. A conceptual flowchart of the process is given in Fig. Some treat the whole tailings slurry. N.2. NH3 and CO2. under controlled pH conditions of 8–10. A. peroxymono sulfuric acid (commonly known as Caro’s acid). Saarela and Kuokkanen. Devuyst et al.5. thiosalts and metals in low oxidation states effluents in some cases. ð10Þ 2004). The processes ‘‘widely used’’ and was discharged to a large polishing pond with a 15-day retention ‘‘used with limitations’’ are discussed below. (9)). provided in the form of gaseous chlorine or sodium or calcium and persulfates have been found to be effective alternatives to hypochlorite. have employed this method as ‘‘standard’’ until the Inco process moval of cyanide prior to chemical treatment. A conceptual flowchart of the process is illustrated in The first stage of the reaction (Eqs. time. In the Inco process. Peroxygen compounds such as hydrogen per- ent. and then hydrolyzed to cyanate NaCN þ Cl2 ! CNCl þ NaCl ð8Þ 2. 2013). emitting chlorine If reduced portions and HS. interest in using the alkaline chlorination process free cyanide.2. The process also removes iron cyanide by 8. they can be installed as a separate impact on surface waters due to cyanide use cannot persist for a treatment plant adjacent to the discharge end of the tailings ponds significant period of time after the mine–mill shuts down (Randol. Akcil / Minerals Engineering 50-51 (2013) 13–29 19 the intermediate zone.2. (10)) occurs at a pH of solution as hydroxides.4. should not be reacted with of tailings remain relatively stable. Then. and where high concentrations of cyanide are pres- has been decreasing. Ferrocyanide is not destroyed but. in process may also destroy thiocyanate. Chlorine can be oxide.2. metals are precipitated from imum pH of 11. An additional process is required for removal of iron cya- H2 SO4 þ CaðOHÞ2 ! CaSO4 2H2 O ð12Þ nide. Alkaline chlorination has been well- to less than 5. it requires costly and complex additions and installations. consume additional chlorine. respectively. The process destroys cyanide (CN–WAD). This process was developed and pat- ented by the Inco Metals Company in 1984 in Canada (Canadian CNCl þ 2NaOH ! NaCNO þ NaCl þ H2 O ð9Þ Mining Journal. 200 mg/L). Eq. some mills treat only the tailings industries have used gaseous chlorine and some have used solid pond overflows. Cyanide 2. tions show that these precipitates are quite stable over a wide low pH 11. regulatory agencies may accept the process to be carried through only at the cyanate stage. cyanide are provided in Section 2. With the exception of iron.5 and 0. 0.2. 2010).. 1985). ond stage. Cyanide is especially biodegradable in warm cli. Alkaline chlorination. While some mills was fully developed and its capabilities were demonstrated. Detailed discussions on peroxygen oxidation bicarbonate takes place in two stages. After flocculation the treated effluent from this plant ment methods (Botz et al. to cyanate (CNO) (Smith and Mudder. Nelson et al. As the total cyanide content in pore water as spent plating or stripping solutions. free cyanide. Although the chlorination units are usually mates as a result of natural attenuation processes. is oxidised. 3. During chlorination. Although the nation process and residual chlorine are of concern. 2009). Kuyucak. The presence of thiosalts may signif- nal effluent quality suitable for discharge. It was known to be Inco process. SO2/Air (INCO) process. 1991. while the second stage (Eq. hydrolysis of highly toxic cyanogen chloride gas will not range of pH. it is primarily effective on recent years. Anaerobic bioattenuation is a chiometric requirement (approximately 7 lb of Cl2 or 7.2. 1998. 250. Be. Investiga- times are required in completing both stages at a pH level of 11. 2005). In the first stage.g. 300 and 400 mg/L 2. 1991).2. CNWAD þ O2 þ SO2 þ Cu þ H2 O ! CNO þ Cu þ H2 SO4 ð11Þ nide). Sodium hypochlorite con- anaerobic bioattenuation of cyanide.2. With this process. 2 mg/L vs.2. Considerably greater reagent additions and longer retention precipitation as insoluble copper and zinc ferrocyanide.2. hypochlorite because the reaction can be violent. ex- 3Cl2 þ 2NaCNO þ 6NaOH ! 2NaHCO3 þ N2 þ 6NaCl þ 2H2 O cept iron cyanide. 2009). then natural processes icantly increase the chlorine demand. Lime is an alkaline agent that is commonly used for alkaline chlorination for destroying free and complexed cyanides pH control. oxidizable substances other than cyanide. and is reported to be easy to operate. a mixture of SO2 and air is used in the presence of copper The Second stage of the process is the further oxidation of cya- as a catalyst. such Me2þ þ CaðOHÞ2 ! MeðOHÞ2 þ Ca2þ ð13Þ . Concentrated cyanide wastes. known for a long time as an effective means of treatment for indus- Although it is possible to recover cyanide by this method for re- trial wastewaters (Cushnie. (SGS Technical Bulletin. Cyanide removal by natural means may produce acceptable such as thiocyanate. the concentration of total cyanide. (8) and (9)) takes place at a min. The process does not require a catalyst such as Cu. 0. Giant Yellowknife Mine in Canada operated a two-stage treat- ment system for the removal of both cyanide and arsenic. Therefore. thiocyanide (HSCN) forms as a result of thermal destruction (Cushnie. It has been applied to gold mill use. 1992.

Although it showed potential for development and was used at Fig. Kuyucak. 3. it has not been adapted as widely as the INCO process. wastewater. In these processes. 2012). Currently. A process royalty was charged for its use until 2004 (Nelson et al. 2009). In roaster gases containing SO2. Some mills employ the method to treat tailings pond overflow. The recent tendency is to treat tailings slurries before disposal into the tailings ponds to protect the environment and wild life.2. Addition of ferrous iron the other hand. soluble sulphite or metabisulphite (Na2S2O5). oldest methods used to detoxify free cyanide (Manoranjan et al. addition. The process can be applied to either aqueous reclaim water or directly to the tailings slurry. Copper requirements are significantly reduced or eliminated for waters containing greater than 50 mg/L copper.. where CNWAD is the weak acid dissociable cyanide that in. A. Akcil / Minerals Engineering 50-51 (2013) 13–29 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. 2003).5 mg/L for total cyanide and for each of the metals com- monly found in gold mill effluents (e. some are treating tail- ings slurries. The SO2/ Air process received worldwide attention for the treatment of gold mill effluents 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. preventing the removal of cyanide to an acceptable level. Iron/copper precipitation processes. nickel and zinc). copper. the Noranda operations. processes to destroy cyanide from mill effluents (Yang and Skryp- and depends on the concentrations of other constituents in the niuk. . The SO2/Air process offers an effective means to treat gold mill effluents and to produce effluents containing concentrations of less than 0. the presence of thiocyanates has shown quired for the process may be supplied in a variety of forms such significant inhibition to the complexation of cyanide with the me- as gaseous SO2. Conceptual INCO SO2/Air process.g. INCO Process offered distinct advantages over the two main alternative. Other sites also reported the use of modified INCO The amount of copper required to catalyse the reaction varies. iron. It has been accepted by many regulatory agen- cies throughout the world as the state-of-the-art method. While some mills are applying this process to the barren bleed solutions. yielding HCN has raised stability concerns. cludes free cyanide and weakly complexed cyanides. sodium sulphite and so.20 N. 4. The SO2 re.2. Several cyanide detox- ification processes have been developed based on the principles of Fig. Noranda developed ‘‘Noranda SO2 process’’ where both tailings slurry and effluents can be trea- ted using pure copper and SO2 without air injection (Kilborn. Carrillo-Pedroza and Soria-Agullar. decomposition of ferrocyanides observed under sunlight dium metabisulphite are being used more frequently. 1991... Conceptual alkaline chlorination treatment process. or tal ion. SO2 consumption to CNWAD ratio by weight is to form insoluble ferrocyanide at pH higher than 10 is one of the 2. 2001. alkaline chlorination and hydrogen peroxide methods. 1998). InfoMine.46. On 2.3.

divalent iron. Ferric sulphate is added in Zn complexes). be discharged to the environment requires further polishing for The final products are carbonate and ammonia ions (USEPA. it is precipitate. OK TEDI Mining Limited in Papua. In 2003. 2003). A pH of 9–10 should be maintained to avoid release of HCN (US The use of Caro’s acid made of H2O2 and sulphuric acid can signif- Peroxide. The Hemlo Process reacts the untreated oxidise cyanide to cyanate before discharge. persulphates and the use of excess H2O2 can increase the reaction rate. The gold itate formation.2. Upon addition of the wastewater. It was observed sulphate catalysis to meet the total WAD and free cyanide that the reaction rate could be significantly accelerated by the limits. the ferrous H2O2. Photoac. moves arsenic which dissolves from the ore. of wastewater resulting from Merrill–Crowe process where mer- cury (Hg) is used along with cyanide to recover gold (Howell and 2. The temperature did fying equipment and filtration.26 lb H2O2 per lb of cyanide. the types of cyanides being treated (free.2. 2011). The cyanide destruction the pH at4. (2003) con. anti.005 mg/L. the initially formed ferric hydroxide. bearing solution (Yeddue et al. ent containing less than 0. (3) carbon adsorption as a precaution to meet the desired level tion and the cyanide removal kinetics fit to pseudo-second order of Hg removal. Ferrocyanide is precipitated from the solution as cupric process is followed by a metal and trace ion removal process using ferrocyanide. The flex- copper. Increase in temperature and dosage of catalyst icantly accelerate the reaction rate. Waste barren bleed solution is treated by the addition of fer- rous sulphide (FeS) to remove both free and complexed cyanides. precipitation and separation of metal and iron with the increasing initial molar ratio of [H2O2]0/[CN] and de. ment imposed effluent quality requirements in the 1980s. mill operation throughput of 22. and acti. ferric chloride. V. The treatment plant built in where hydrogen peroxide is added at neutral pH.2. The tailings slurry is subjected to SO2/Air (H2O2) can oxidise cyanide to cyanate in the presence of a transi. It was also claimed that. The adsorption of cyanide on the FeS particles results in removal where H2O2 consumption might be significantly high. The process a mixture of thiosulphate and complexing agents (such as divalent could reduce both cyanide and heavy metals to low levels. Although H2O2 while the cupric ion is simultaneously reduced to the cuprous can successfully oxidise and destroy cyanide. operational cost savings over the traditional Inco process. or CO2 and NH3). Ferrous sulphate also re- New Guinea. The cyanide removal . the removal of metal ions including Hg and cyanide. This process is also water with a pre-mixed solution of cupric sulphate and ferrous sul. divalent cobalt or their mixtures). Ammonia in the resulting effluent may pose of copper. A final ‘‘polishing’’ stage occurs in the third step. oxidation process for the destruction of cyanide before its disposal tion metal (Cu. Ag. hydroxide sludge in a high-rate sand-blasted settling/clari- creased with increasing pH from 8 to 12.5 and a retention time of 15 min. This process is more suitable for wastewaters rather than slurries. The reaction rate increased (2) flocculation. Degussa (Cyplus) and INCO developed a new process Another method developed by Manoranjan et al. World Bank and the local 0. The pH of the process could be adjusted between 5 and on site-specific conditions. employed H2O2 to meet extremely stringent govern. Copper. N. ferricyanide. CNO þ 2H2 O ! CO2 þ Finely divided insoluble ferrous sulphide particles are prepared 3 þ NH4 ð15Þ in the mill by reacting ferrous sulphate with sodium sulphide. The H2O2 solution was directly added to the Canada. existed in effluents resulting from gold and silver the second step to ensure complete precipitation of the metals. and the system economics. The process could effectively re. Excess water in the tailings impoundment to 50 mg/L. Ohinemuri River. lime is added to control cess as a catalyst to speed up the reaction. The Hemlo process can generate a treated efflu. due to handling diffi- ion which removes free cyanide as an insoluble cuprous cyanide culties caused by its hazardous nature and economic reasons. or inert). 2013). the desired products (cyanate. Copper sulphate is added to the pro- Due to the acidity of the ferric reagent. A conceptual process flow chart cess to produce high quality water that can be discharged to the is shown in Fig. Hydrogen peroxide Christophersen. Hydrogen peroxide oxidation process. Th) as a catalyst in concentrations of 5 to to the tailings pond. Ni. who manufactures phate in the first step. The FeS heap leach piles (USEPA. nickel. 1994). The reaction is strongly pH dependent and requires a cessfully used in the USA to neutralise cyanide remaining in the pH of approximately 7. depending agents. The choice of peroxygen system depends treatment process consists of three steps: on the reaction time available. The removal of free cyanide causes the dissociation not frequently used. A. 2013). The destruction of cyanide by H2O2 is shown by 2.0002 mg/L. 1988). sodium or potassium) can oxidise cyanide beyond tivation (UV + H2O2) can destroy stable cyanide complexes such as cyanate above pH 9 and in the absence of a catalyst. 5. duce total cyanide and CN–WAD concentrations to less than At the Marlin gold mine in Guatemala.. copper cyanide) precip. removal of cyanide as cuprous cyanide. Alternatively. 2013). The oxidation requires 1. Kuyucak. ibility of the process to accommodate changes in the feed was vated carbon. with respect to cyanide. (ammonium. developed a process for cyanide removal at their property carbon-in-pulp (CIP) tailings slurry and reacted in a mixed tank to (Konigsmann et al. developed an automated and closely controlled process in iron is quickly oxidised and forms a ferric hydroxide precipitate which H2O2 is efficiently used (Degussa.5. weak acid (1) oxidation with hydrogen peroxide in the presence of copper dissociable.4. extraction (Waihigold. called CombinOx combining the advantages of Inco SO2/Air and sisted of removing free cyanide and CN–WAD from effluents using hydrogen peroxide technologies (Chemeurope. to cyanide ratio is maintained at 3–1.500 tonnes per day was a giant one The Golden Giant Mine of Hemlo Gold Mines Inc. respectively. of cyanide. not have a significant effect on the kinetics of the cyanide degrada. US Peroxide. Akcil / Minerals Engineering 50-51 (2013) 13–29 21 insoluble metal cyanide (e. by gold mill standards. the new process could offer capital and 10 with the help of lime or NaOH. Ontario. zinc. The polishing 1994. lime and flocculants.5 mg/L total cyanide and metal ions. ferrocyanide. It was suc. 1989). 2009). Sulphate salts were used to prepare complexing shown to be the key advantage.g. Newmont’s Waihi Gold Mine in New Zealand uses H2O2 method mony and molybdenum are co-precipitated from solution with to destroy cyanide in the form of free cyanide and WAD (as Cu.5 mg/L and 0. Thickened sludge 1999 was recently upgraded incorporating a reverse osmosis pro- is disposed of to the tailings pond. known as the Degussa process because Degussa. Iron sulphide (FeS) and sulphide precipitation processes and CN þ H2 O2 ! CNO þ H2 O ð14Þ SART... The precipitates resulting regulatory agencies imposed stringent standards for the discharge from the process has been claimed to be chemically stable. nickel and zinc cyanide complexes resulting in further toxicity to the fish.2. removal of Hg by a chelating polymer to below detec- addition of copper-impregnated activated carbon to the cyanide tion limit of 0.

2013). and acidification reactions was presented below: ducted to investigate the reaction in a 2% (20. At the mine. Australia.000 mg/L) solution of sodium cyanide revealed that the reaction was 95% complete 2CuðCNÞ2 3 þS 2 þ 6Hþ ! Cu2 S þ 6HCNðaqÞ ð16Þ within 1 h. and allow smooth operation. it was desirable to thiocyanate.5–1. 2012). and the solution is neutralised with sodium hydroxide or lime Lime consumption ranged from 0. step is not employed to produce an effluent of suitable quality to and recycled back to the leaching process to re-use the cyanide. brand name products such as DTOX have been intro.4 kg of 100% sulphuric precipitates are removed for possible sale or further processing. The regulated parameters in the effluent from the tailings nide (SGS Technical Bulletin. and cyanide concentrations were non-detectable with- in 2 weeks at a CN: poly S0 ratio of 1:2 by weight. acid/kg WAD cyanide to reduce the pH from about 10 to pH 4–5. containing copper as copper sulphide precip- end products released to the environment contain carbonates itate and cyanide as HCN in solution. Be- polysulfide–sulfur contained in DTOX converts hydrogen cyanide cause of economical and environmental reasons. Acid consumption was 1. In addition. The sulphide ore was treated through eral Process Control. Kuyucak. the oxide gold pond are usually below the objective limits of this process. The experiments con. meet the imposed effluent discharge limits but rather relies on fur.3 kg/kg WAD CN at a pH of . as cyanide. based on the sulphide precipitation process principles (Min. The reaction between cyanide and a flotation circuit to produce pyrite and copper concentrates. The the solution. The The resulting slurry. It is claimed that the reaction is safer and the rates where they were separated. and high grade copper ores to minimize cyanide consumption duced. heavy metal ions can be precipitated to reduce the amount of cyanide reporting to the tailings pond. Telfer Gold Mine in a remote location of Western Australia investi- ther removal of cyanide by natural degradation in the tailings gated SART as a cost-effective process to recover copper and cya- ponds. Akcil / Minerals Engineering 50-51 (2013) 13–29 Fig. and free and complex cyanides are neutralised. ore was treated in a conventional CIL circuit by blending the low Recently. Conceptual Golden Giant mine effluent treatment process. The results of the pilot tests revealed that a pH of 5 would be suffi- A process called SART (Sulphidization–Acidification–Recycle– cient to remove over 95% of the copper from tailings effluent and re- Thickening) that was developed by Lakefield and Tech in Canada cover over 94% of the cyanide. NaSH additions at 100% in early 2000s uses a reagent such as sodium hydrosulphide stoichiometric copper were sufficient to remove over 95% of the (NaHS) to precipitate copper and zinc as sulphides and convert copper from the effluent when sulphuric acid was used to acidify cyanide to HCN (Alta Metallurgical Services.22 N. 2001). 5. was fed to the SART thickener and ammonia.7–2. The process involved in sulphidization are more rapid than those of hypochlorite. A.

1998). lated with a cyanide-reducing bacterium Pseudomonas pseudo which was the amount of cyanide released in laboratory acidificat. was recovered by this method. the overall cost the costs of cyanide recovery. Four types of ered from 9 to 2. 2007. A. 2009) ery plant aimed to process tailings slurry to achieve greater than 90% cyanide recovery from tailings containing about 600– CN þ 1=2O2 ðaqÞ ! OCN ! OCN þ 3H2 O 800 mg/L WAD cyanide (as CN).. 2012). Air was used in towers to sweep HCN from the acidified bar. Microorganisms can utilise cyanide compounds as source of carbon and nitrogen for their own growth 2. Sabatini used at the Emperor Gold Mine in Fiji to remove residual cyanide et al. 1993). 2003. slimy or viscous ores revealed that the alkaliphilic autochthonous bacterium Pseudomo- (SGS Technical Bulletin.4. counter-current decantation (CCD) system. 2003. wetlands. pit-lakes. sus- the total cyanide added to the leaching circuit.5. 2009). involves acidifying waste cyanide bearing solutions to a pose a hostile environment to bacteria and reduced bacterial activ- pH of between 2 and 3 with H2SO4 or SO2. The SART process has been successfully commercialised and ap. The results indicated cesses are applied to tailings effluents rather than pulp. or alternatively referred to as the Mills–Crowe wastewaters from gold mills. in air-uplift-type fluidized bed reactors to convert inorganic cya- tion was acidified with H2SO4 solution from their zinc recovery nides to carbon dioxide and ammonia has been investigated as plant. Mani. suitability for cold climates. Relatively high consumption of ! NHþ4 þ HCO3 þ OH ð17Þ sulphuric acid and sodium hydroxide leading to high rates of scale formation in the acidification tank and stripping towers were ob. ammonia (Akcil. Biological cyanide degradation process deprivation outside the cell and metalloenzymes inhibition inside Several microorganisms (bacteria. formic acid and formamide. Therefore.2. The acidification process zyme into NH4 and formic acid. alcaligenes (UA7) in Alaska aiming to compare cyanide destruction ion tests. Ninety-one percent of the regenerable cyanide. cyanide recovery from mill tailings has been prac. plied several sites in the last decade (SGS Technical Bulletin. the use of immobilised cells of Pseudomonas putida the recovery of gold from base metal tailings. The AVR Canada. 2. This process and Canada. that cyanide could be reduced to acceptable levels by the bacte- Therefore. oxygen and resulting effluents by this process was not reported. About 90–92% sodium actors. To remove cyanide. oxidation and reduction.2. The recovered cyanide pond waters where both cyanide and metal concentrations are rel- is recycled to the cyanidation circuit for reuse. The reaction pathway and the pro- was principally employed for cyanide recovery. Kadlec and Wallace. Acidification–Volatilization–Regeneration (AVR) or Mills– Active biological processes have been neither widely practised Crowe process for recovery of cyanide. the cyanide recov. in-pit treatment) (MPERG. fungi) and their enzymes the cell occurs resulting in a cyanide-insensitive respiratory have ability to degrade cyanide and cyanide complexes including system and a cyanide degradation/assimilation pathway (Luque- .1 and was used at a silver mine operated by Compania Beneficiadora 2. Cyanides are irreversibly bound to metals. nificant amount of research has been carried out to develop micro- toba. reliability. Success of the Homestake process has increased attention in the tal sulphur at the site. not for environ. cesses are usually ruled out in cold climate countries such as tilize and Reneutralize’’ (SGS Technical Bulletin. A recent study quid components as occurs with high clay. cyanide recovery can be obtained from a solution containing about Passive systems have been investigated for their methodology and 350 mg/L WAD cyanide. Both SART and AVR pro. i. especially for their application to remote sites. from 1935 to 1978 while the company was using cyanidation for For instance.or full-scale process have been oper- ren solution and the HCN was absorbed in Ca(OH)2 for reuse in the ated using this method (Babu et al. Waste barren solu.. method due to significantly lower operating costs. the cost of solid–liquid separation must be added to rium and. 2010). application of microorganisms for degradation of cyanides. used the Mills–Crowe process for cyanide recovery biological processes with improved efficiency and performance. Three full-scale active – biological treatment processes process has also been commercialised and successfully applied have been developed and used by Homestake Mining in the USA several mining sites (SGS Technical Bulletin. HCN gas released dur. tainability and cost-effectiveness. despite the higher initial capital cost. Acidification process and cyanide recovery. are briefly discussed below in Section 2. Chapman et al. iron cyanide complexes to less toxic compounds such as nitrogen. yeast. de Pachuca in Mexico. 2004).6. Barren bleed and tailings slurries process.. The SO2 gas is produced by burning elemen. Initially. NaOH or Ca(OH)2).g.5 by spraying SO2-containing roaster gases in a enzymatic reactions can take place including substitution/addition. but no pilot.4.. Cyanide degradation can occur under both aerobic from cyanided and washed calcine after the flotation step to re.. Akcil and Mudder. such as to iron. 2010).2.. 2009). 2003).2. cess kinetics can be affected by aerobic or anaerobic conditions. Akcil et al. an alternative. information about the quality of nutrients (carbon such as sugar).3. Biological pro- ‘‘Cyanisorb’’ has also been givento AVR referring as ‘‘Acidify. The mode of application can take place in either active – fully con- which reduced the sulphuric acid consumption and eliminated trolled automated bioreactors or in passive systems (passive biore- scale formation in the process equipment. nas pseudoalcaligenes can detoxify cyanide in two ways. Thisprocess was (Saarela and Kuokkanen. Canada. Changes were made to the cyanide recovery system allow- ing the operation of a two stage CCD circuit with clear solution. longevity. A test heap was inocu- cyanidation circuit. and anaerobic conditions. Vola. Kuyucak.. and Jordan. causing iron 2. 2010). Hydratase enzyme degrades ing the process is stripped in towers and decanted to eliminate cyanide to formamide which is further hydrolysed by amidase en- cyanide emission to the atmosphere. HCN by air flushing and recovering the HCN by absorption in an Application of the biological process is more successful for tailings alkaline solution (e.2.. The reactions tised at Cerro Vanguardia in Argentina that includes multiple open showing oxidation of metal cyanide complexes and thiocyanide pits and a hybrid Merrill-Crowe and CIL circuit to recover gold and by Pseudomonas sp. 1995. pH. hydrolysis.. Microorganisms tend to form a biofilm on a support Since 1998. A specific name atively low due to natural degradation and dilution. Acidification–Volatilization– nor received a great deal of attention for treating cyanide bearing Regeneration (AVR). Aerobic oxidation process produces cover sulphides.e.2.2. 2010).7. nitrogen. A sig- Hudson Bay Mining and Smelting Company at FlinFlon.2. are illustrated in Eqs. (17) and (18) (Young silver from oxide ore (Botz et al.2. costs with INCO process (Nelson et al.3. the pH of calcine slurry is low. temperature. Akcil / Minerals Engineering 50-51 (2013) 13–29 23 3. Examples are given in Section 2. SCN þ 3H2 O þ 2O2ðaqÞ ! SO2 þ  þ 4 þ NH4 þ HCO3 þ H ð18Þ served. which accounts for about two-thirds of performance. mental protection. N. volatilizing the resulting ity may occur if cyanide and metals are in high concentrations. This can be a significant capital-cost of the treatment in the long term could be lower than the chemical burden if the tailings pulp is difficult to separate into solid and li. material in reactor applications (Maier et al. 2004.

flow) and anaerobic (subsurface flow) wetland and a polishing/fil- tration. (21).3. where Me represents metal species. (19)). they are better accepted by the public. copper as well as other metals. In addition. 1998).3. ferric sulphate and flocculent. willows). Akcil / Minerals Engineering 50-51 (2013) 13–29 Almagro et al.05 mg/L respectively in the final effluent. 2006.. thiocyanate. complex formation with iron and precipitation and sand filtration.06 mg/L. Homestake Wetlands were investigated for their ability to remove cyanide Mining has developed another unique process utilising aerobic and cyanide complexes.g. 6. The process combined biological and chemical facility was implemented at the was developed in early 1980s and. creates a nutrient-rich environment which pro- housed but all were well insulated. Despite their known drawbacks such as oxidation process is carried out in two stages (Whitlock. since then. The biological pit lakes (in-pit treatment). The full-scale plant was operated satisfactorily reactions take place (Kadlec and Wallace. ammonia and copper were sorption of trace metals. Furthermore. The full-scale 2. arsenic with tailings pond water to maintain the temperature of the com. it is known as Homestake Mining’s biological process.1. aerobic (surface moved from the effluent by clarification and dual-media sand fil. Although the and the nutrient source organic carbon is converted to carbonate removal of copper and iron in the process was high. impoundment solution and seepage. The temperature of the feed Cyanide.1 mg/L to 0. soda ash. water is raised to approximately 20 °C using a propane-fired sub- taminants found in the mixed wastewater. 1995). tion by plants (e. silver. In the second step.2. sulphate. limestone. other metals such as nickel. oxidation of thiocyanate (Eq. ingestion and metabolic degrada- biological contactors was modified by the addition of ferric chlo. Arthrobacter sp. not removed as effectively (Maier et al. As the biofilm applications.1. Thiobacil- Forty-eight RBCs with 12 foot diameter discs were used to con.3. The process takes place merged combustion water heater. from the wastewater (Eq. holds two patents for the use of specific bacteria responsible for Their applications are well-suited in remote sites with limited oxidation of cyanide and thiocyanate. and other residual metal are precipitated using lime and ferric sul- bined wastewaters at a sufficiently elevated temperature year phate. It was found that insoluble complexes with metal ions resulting in removal of metals bacteria adsorbed gold. thiocyanate. ammonia pro- shown in Fig. and neutralization/precipitation process chemicals such as US$10 million. teria such as methanol. Canada for treating tailings Homestake Mining Company at Lead. Sulphide (S2) produced makes ids content in the treated effluent was <10 mg/L. Lawrence et al. silver and copper could be recovered from the sludge by igniting the sludge and annually about US$ 2009). large space and warmer climates. which was produced following the respectively reduced from 50. the need for long retention time. Gold. In the second stage. anaerobic de-nitrification takes place impoundment wastewaters. continuously sloughs off the discs.5 million income was obtained SO2   2 4 þ 2C3 H4 O3 ðlactateÞ ! 2C2 H4 O2 ðacetateÞ þ 2CO3 þ S 2 through this practise which reduced the overall operating cost of ð19Þ the process by 25% (Whitlock. The process was successfully operated from 1984 to 2002. 2009). chromium and zinc were an important role in the SO24 reduction process (Kuyucak. The first stage consists of the bacterial oxi. The plant was con. Anaerobic wetlands may contain an organic substrate or a the effluent can be discharged directly to the environment without mixture of organic and inorganic compounds such as manure. tests for about two decades. 6. 2002.. SO2 4 .. can be reduced to sulphide 0. Since they are generally per- involved in the various stages of the process.. (20)). thio- Therefore. About 99% removal rate could be ob. 2003). nitrate and metals (Given et al. uptake by plants and ride and/or a polymer to produce a sludge before clarification microorganisms. additional treatment. 2.. volatilization. Different strains of bacteria are operators and routine maintenance.0. In the final (HDS) step. The suspended sol. cyanide and cyanate are converted to ammonia and then nitrate The Homestake Mining has still been the only company in the with the help of a two-stage aerobic activated sludge treatment world using this method to treat their combined mine and tailings process. with 95–98% as presented in Eq. Subsurface flow (SSF) and surface flow (SF) . reducing the initial cyanide concentration of tion are coupled with the chemical precipitation and chemical 4. Kuyucak. The cyanide assimilation pathway that gen. South Dakota in the USA. Metals associated with cya. duced by aerobic microorganisms such as Pseudomonas. Homestake mine biological process in the USA. accessibility. Nickel plate mine biological process in Canada. Neissarie sp. reagents added were soda ash as an inorganic carbon source to aid nitrate and ammonia phenomena by microorganisms occur (Akcil nitrification and phosphorus as a trace nutrient. chemicals. In the first step.3. sorption. Blending relatively warm mine water to reduce nitrate to nitrogen gas. bacterial nitrification occurs and their operations often do not require external energy. lime. In wetland processes. Micrococcus tact the bacteria with wastewater and air. is further incorporated into organic nitrogen. In contrast with the tering system. saw dust. Wetlands are often planted with aquatic vegeta- competing chemical treatments. phosphoric acid and sulphuric structed in 1984to treat 3600 US gpm at a capital cost of acid. in rotary biological contactors (RBC) where bacteria are attached to slowly rotating discs as a biofilm. until the closure of the mine (Maier Me2þ þ S2 ! MeSðsÞ ð20Þ et al. A. Prime reagents used in the plant include nutrients for bac- round is key to their successful operation. 1995.0 mg/L to less than 0. Anaerobic sulphate reduction. Passive biological treatment process: engineered wetlands and merged in the tanks at all times (Maier et al. sulphate and other conventional and emerging treatment technologies because ammonia. Paracoccus sp.0 and 1. cyanide. ammonia is converted to nitrate. Bacillius sp. and disposed into the tailings pond. 1998).24 N. A simplified flowchart of the process is straw. Kuyucak and Chabot. 2009). lime neutralization method for removal of cyanide. Wetlands may contain a train of settling ponds. 2009). con- employed in the cyanide and thiocyanate removal stage. denitrification and cyanide attenua- tained for cyanide. thiocyanide and ammonia. The first 24 contactors were motes microbial growth and subsequently uptake. Sulphate reducing bacteria ‘‘SRB’’ play efficiency. 2. and anaerobic biological processes and high density sludge (HDS) erates ammonium. passive methods are known to be cost-effective alternatives to dation of cyanide and thiocyanate to carbon dioxide. has been used by Nickel Plate Mine in British Columbia. Effluent from the and Mudder.1 and 0. tions. The most common passive treatment methods con- nide and thiocyanate are removed through adsorption by bacteria sist of engineered wetlands and in-pit (pit lake) or in-pond (biofilm) once the wastewater is free of cyanide. Thiocyanate. The RBCs were not spand. hydrogen peroxide and SO2/Air. the bacteria-metal sludge is re. The only version and/or precipitation of cyanide. copper and ammonia are the main con. Homestake Mining ceived as natural systems. lus sp. iron and produced effluents of the quality predicted from pilot plant complexes undergo photolytic degradation to give free cyanide. 2011).. About 40% of each disc is sub. 2009).

Biological treatment process at Homestake Mining Company. An contained cyanide.. wetlands with vegetation (e. 6. Evenly were stored. MPERG. 2007. water that results from the ability to remove metal cyanide and thiocyanide and metal ions. before discharge. The concentration of total cyanide in the treated spaced perforated pipes were placed in the inactive lined leach water had to be 1 mg/L or less to meet the local discharge require- solution pond which was then furnished with an organic matter ments.g. Kadlec and Wallace. 2007. After mine closure. Tailings resulting from beds and open limestone channels to condition the wastewater the VAT cyanide leach process to recover gold were disposed of pH and enhance the treatment process before the treatment and/ in a natural lake for storage and management at the Colomac mine or to adjust the effluent pH and further sequester contaminants located in Yellowknife.) have shown In-Pit (Pit Lake or Pond) application. The mini. 1991. USA (Mudder et al... 2009). in the pit. storage of waste materials such as tailings. Canada (Chapman et al. the efficiency of removal in vegetated ment by adding chemicals and encouraging the growth of aquatic wetland was marginally better (Kadlec and Wallace. N. from the effluent after treatment. Akcil / Minerals Engineering 50-51 (2013) 13–29 25 Fig. etc. Biolog. The treated in the water to convert to ammonia in situ in the pit. 30 days was also observed when algal growth was stimulated by . tions. Some of effluent is collected in a gravel layer and is routed to a drain field ammonia produced was further removed by uptake by algae grown where it is aerated while infiltrating into the ground. willow. NWT. collected from the heap leach pad.5 mg/L in mum retention time of the system is about 38 days. Several options including alkaline breakpoint chlorination down. 2001b). thiocyanide and ammonia in high concentra- engineered wetland treatment system was installed to treat drain. to provide an effluent and biological RBC processes were investigated for the treatment suitable for discharge into the groundwater system at the closed of seepage accumulated in the pit and the pit lake where tailings Santa Fe mine site in Nevada. A. waste rocks and/or The presence of vegetation did not show a significant difference sludge or contaminated water is directly treated in the impound- in removal of compounds. Bench and pilot tests indicated the pad is directed by gravity to the perforated pipes and distrib. that bacteria could catalyse cyanide and cyanide complexes found uted across the cross-section of the organic matter. Kuyucak. seepage originating from the Engineered wetlands also have been employed for the removal/ tailings disposal area had to be collected and pumped into a mined reduction of cyanide from mining effluents in the USA and Canada out pit as an emergency measure. Tailings pore-water and seepage (Kilborn. 2010). Zagury et al. Reduction of thiocyanate from 100 mg/L to 0. cattails. Biological RBC process was found to be prohibitively expen- consisting of composted manure and straw.. The drain-down from sive because of heat requirements. plants. The treated water is then pumped out to the environment if ical passive systems can be supplemented with limestone leach its quality meets the regulated standards. 2009).

CuCN. the equipment cost including the cost of ozone generator is 2. com- metals to reduce the cost of the treatment process. Kuyucak. Production of toxic compounds as a the treated water to be discharged.4. Another advantage is the ability of 2010). process has also been combined with UV radiation for the treat- ment of halogenated organics. As in the SART process. Ozone is generated on-site typically by the silent and ammonia could be removed to the regulated levels allowing electrical discharge method. 1992). Free cyanide. both of which can be extracted directly from pulps by anion inated with thiocyanate and copper–cyanide complexes (Soto exchange resins. Electrolytic oxidation Processes such as. plex. ion exchange process has been considered as readily adaptable to phuric acid is conditioned with hydrogen peroxide. This method has been com. Cyanide without the use of a catalystis and ferrous sulphide adsorption and cyanide complexes first become oxidised at the anode to give and thermal hydrolysis have shown potential for development cyanate ions which are further decomposed to non-toxic carbon (Kilborn 1991. mono replacing the alkaline chlorination process (Cushnie. voltage and potential to recycle cyanide associated and to generate revenue electrolyte solution. pound. it has not yet been widely used studies to develop an of copper. metal cyanide complexes chloride. Other methods and emerging processes significantly higher. cyanide complexes and concen. Electrochemical oxidation is sometimes used to de. alkaline chlorination process. 2000). quires 1. 1996). 2010). adsorption. 2009).5. CO2 Use and Sunlight/UV. trated cyanide can be handled in this process. the seepage lake received about 9 tonnes more phosphorus shown to be the prime advantage of the ozone CN destruction pro- fertiliser. 2012). 1996. acti- In the electrochemical oxidation process. produces a regenerated resin . 2006). Addition of carbon dioxide alone without are reduced to free metal ions at the cathode which can be col. where ozone is less expensive than chlorine or sodium hypo- and denitrification bacteria.8–2. electrolytic decomposition. Recycling of cyanide could also decrease environ- (2004).g.6–5.. Oxidation of cyanate resulting from the first 2. The Augment and Hannah proprietary processes. The type of the cathode and anode material af. If the revenue could offset the operating costs of the cyanide ozone. tion processes. 2004). conventional. commercial strong-base lyst requirements and associated high capital costs.2.. Cyanide. plexes directly from gold plant tailings.000 mg/L CN). Reactions and Removal/reduction of cyanide by adsorption using activated examples are depicted by carbon from mining wastewaters has been focused (Dash et al. As explained petition between ions. Hg) and other compounds rather than CN. When the loaded resin is treated with sulphuric et al. copper remains in the resin phase as a precipitate of the com- stroy concentrated cyanide wastes (e. Evaporation and potential zero discharge. the electrochemical oxidation is a very economical and mental risks by reducing loading of potentially harmful salts in environmentally friendly cyanide destruction process. mainly for removal of metal Cathode : 2CNO þ 4OH ! 2CO2 ðgÞ þ N2 ðgÞ þ 2H2 O þ 6e ð23Þ ions (e. ozonation. Carrillo-Pedroza and Soria-Agullar. Moreover.26 N. and oped industrial process used for gold and uranium recovery. oxidation step of cyanide requires excessive ozone thereby the evaporation may provide a means for achieving zero-discharge of operating cost is significantly increased. the technology could transform uneconomic ore aim to recover and recycle cyanide and other compounds and/or bodies into viable mines. 2009). According to Saarela and Kuokkanen Bulletin. This process eliminates cata. thereby also circumventing solid/liquid separa- lower WAD cyanide (Menne.1.g. innovative oxidation by nide. In arid regions.. The ammonium phosphate) were added to the tailings lake and the ozone process is effective in reducing cyanide concentrations to seepage pit lake to stimulate the algal growth in 2002.2.0 lbs to reach complete oxidation. The use of activated carbon adsorption was combined ½AgðCNÞ3 2 þ 6OH ! Ag2þ þ 3OCN þ 3H2 O þ 6e ð22Þ with other technologies to meet stringent water quality standards (Howell and Christophersen. The mainly to recover cyanide for reuse. Akcil / Minerals Engineering 50-51 (2013) 13–29 the addition of phosphorus as nutrient during the tests.. Many of these methods recovery plant. the tailings and recycle water (e. Caro’s acid process. SGS Technical fects the process kinetics.. in CuCN is intentionally precipitated in the pores of a conventional way (Cushnie. elution and associated costs. Oxidation by ozone re- process waters to the environment. earlier. Due to technically difficult and costly regeneration of acti- Anode : CN þ 2OH ! OCN þ H2 O þ 2e ð21Þ vated carbon. Later in environmentally acceptable low levels. dioxide and nitrogen gas at the cathode. A.2. which is a well-devel- hydrogen cyanide gas. Saarela and Kuokkanen. CNO.4. >50.0 lbs of ozone per pound of CN to reach the cyanate monly practised at gold mines in the United States. This method proved to be a result of oxidation of organics does not occur as is the case in the very cost-effective mine water management option (MPERG. Cushnie. the adsorption technology has not been widely used (Crini. NH3and metal cya- nides. via the sale of the copper itself (Ripley et al. alternative to the SO2/Air process (Randol. 2009). Monitoring of the lakes indicated the presence of algae cess. How- ever.g. ion exchange. 1995. anion exchange resins have idly dissociate metal–cyanide complexes and expel cyanide as been used in the resin-in-pulp (RIP) process. 2001. 2009). where pH of the barren bleed solution is lowered to 2–3 to rap.g. a catalyst to replace SO2 was tested with success as an inexpensive lected for their use. strong base resin and. ion exchange (an adsorbent resin capable of binding destroyed at the anode as metals are collected at the cathode metal cyanide complexes). Australia and stage and 4.. ion blinding. Low operational costs are 2003. can rapidly cyanide recovery. acid. Ion exchange techniques have not been widely practised de- Ag2þ þ 2e ! Ag0 ðsÞ ð24Þ spite promising results obtained from various pilot-plant opera- tions. The ozonation South Africa. storage and handling of cya- 2. Because of their ability to extract cyanide and metal cyanide com- od. CNS. and the need for transportation. About Ozone as a strong oxidising reagent has been used to destroy CN 12 tonnes and 24 tonnes of phosphorus fertiliser (e.2. ion exchange resins present the Electrolytic oxidation process is depended on pH. ozone to destroy zinc.5. was rarely used in earlier periods. hydrogen peroxide oxidation with or (Young and Jordan. 2. cyanide ions can be vated carbon.1. InfoMine. the Acidification–Volatilization–Regeneration (AVR) meth. but cyanide resins are well-suited to cyanide recovery application since the complexes formed do not remain stable and release free cyanide. How. copper and nickel cyanide complexes. in this form. and only two moles of cyanide are released per mole ever. Dissociated metal cations 2009. most common cyanide species in gold plant tailings are free cya- A method based on the use of ozone and oxygen was developed nide anions (usually 100–500 mg/L) and the tricyano copper com- to recover cyanide and copper from cyanidation effluents contam. where- electrolytic cyanide and metal recovery (CELEC) process are under. Cyanide recovery. Main issues cited are ion selectivity. where sul.

it was suggested that bacterial to free cyanide and iron hydroxide. Akcil / Minerals Engineering 50-51 (2013) 13–29 27 that is an efficient adsorbent for free cyanide ions and soluble cop. Alkaline breakpoint chlorination pro- ing cyanides are treated at elevated temperature and pressure in cess was kept as a backup process to be able to meet the required batch or continuous mode (CDS. Natural degradation in tailings ponds is still known to be the most common method. cases because of its limitation in producing a final effluent of de- specific. In a usual operation. As the environmental regulations have become more and more stringent with respect to cyanide. (25) and (26) (NMFRC. need for the removal of other metals or anions. it has been Since the cost of reagents and the degree of treatment require. In some cases. Thermal cyanide destruction. the need for developing removal 3. 2003). In case of Colomac Mine formation of strong oxidising agent of OH. The mining industry has to deal with water in of CN. cyanide treatment costs are site. in situ treatment in the pit was selected as the most cost- 2. Be- Hydrolysis takes place in a heated pressure chamber. 2013).2. the Augment process is a strong base resin extraction of cop. 1998). The residual CN can be treated by a conven- nal product.. a study conducted at the Ryan Lode Mine near the water. cause SART and AVR applications enable the use of the recovered ature (450–470°F) and pressure (600 psi) significantly increase the cyanide back in the metal extraction process and subsequently re- kinetics of hydrolysis. 2009). or fixed onto a lattice-type structure Fairbanks. 2009. NWT.3 m3 of water (Kuyucak. 2007). Operational It has been reported that the sunlight (UV) could function as a capacity and life expectancy of the mine should also be taken into strong oxidizer when wastewater is subjected to sunlight in the account while selecting and deciding on the appropriate treatment presence of a semiconductor catalyst such as titanium dioxide plant. This process was found to be suitable for the oxidation of tory and pilot tests. cyanide and metal for economical and environmental reasons. one location to another would be misleading. N.radicals that can oxidise in Yellowknife. batch basis for about 10 h and then discharged to a conventional 2009). environmentally acceptable level. AVR and ion exchange to recover and recycle the principle of the cyanide destruction process mechanism.. ing processing of ores (e. 2010). UV in combination with ozone results in the moval of cyanide from spent leach heaps. detoxification be considered as a viable alternative to affect the re- atively clear solutions. The quality of water has atmosphere. Later dur- is claimed that the process is able to destroy all cyanide complexes. Solid or liquid wastes contain. either supplemented or replaced by a chemical process in many ments may vary from site to site. conducting a series of labora- (TiO2). effective process for the site. downtime (Cushnie. Additionally. the biological RBC process due to cold temperature of the wastewater UV/ozone oxidation does not produce undesirable by-products and the cold climate of the location would require heating (Chap- such as ammonia (Spartan Environmental Technologies. In addition to cyanide. In the case of iron cyanide the compound is photolyzed low present-worth cost. 2013). For large flows. starting from excavation of the ore to the fi- give about 25 mg/LCN. and efflu- increasing the cost of the cyanide recovery process. the catalyst mixed into For instance. they are considered to be more economical than other effluent treatment processes which require destruction of cyanide. It was found that the biological method had a higher metal complexes such as ferricyanide and ferrocyanide to partially capital cost. Summary This process was developed in early 1990s and has been shown to Water is considered to be a crucial asset for mining and metal- be cost-effective for treating wastes containing high concentrations lurgical processes.2. The recent tendency is to use a pro- steps as given in Eqs.5. if time allows. Therefore. 200–280 nm (nm). cost benefit analyses including cap- iron cyanide complexes. Underground mines or open pits should be CN concentration to a lower. Even after a site closure. water management gains a significant importance. These radicals break down the cyanide where the first process to the biological degradation process were compared for product of photocatalytic oxidation of cyanides in the presence of the treatment of rinse water from spent leach heaps (Nelson polycrystalline TiO2in aqueous medium is CNO. High temper. When exposed to the sunlight. Ammonia gas generated by the unit is vented to must be practised as much as possible.000 mg/LCN can be treated to every stage of mining. extraction and recovery).. UV light causes et al. a continuous process Therefore. Processing of 1 m3 of ore requires a mini- into the high temperature and pressure vessel and treated on a mum of 1. 2013). Institutions that tested the process experienced tem- to be ensured for its compliance before its discharge to the envi- perature and pressure control problems due to seal leak (N2 and ronment as it is essential in maintaining and sustaining the aquatic oil seal) at the point of agitator entry into the vessel resulting in resources. Kuyucak and Palkovits. creating a slurry. Cost analyses for per cyanide (SGS Technical Bulletin. Ozone will absorb in this band. Cyanide wastes containing 100. It drained to be able to access to the ore during excavation. Suitable light sources emit in the range of ital and operational costs and site specific condition requirements. Specifically.. considering the actual site conditions.g. to reduce the aged for many years. NaCN þ NaOCl ! NaCNO þ NaCl ð25Þ 2NaCNO þ 3NaOCl þ H2 O ! 3NaCl þ N2 þ 2NaHCO3 ð26Þ 4. treatment plant for polishing. Process costs and selection of suitable process processes has been increasing. ore type. Canada. As Hannah refers to both capital and operating costs should be carried out for each site strong base resin extraction of free cyanide and metal cyanide spe. water is used even that of iron. Reactions occur in two effluent quality for discharge. per and cyanide (SGS Technical Bulletin. Kuyucak.. ent regulations (e. and scale-up studies should be considered as both free and complexed cyanides dissolved in wastewater (Parga a useful path in making a decision. The need for water grows as the mining activities increase. 2009). A. from nil to aggressive treatment). water may need to be man- tional method such as ozone or hydrogen peroxide. Elution of copper possibility of the use of natural degradation or zero discharge (or metal) and cyanide from the resin poses technical difficulties methods. The type of process can be cies. man et al. CN wastes are transferred as part of each process. After conducting a series of laboratory and pilot tests. production rate. et al. the capital and operating costs of the SO2/Air radicals. The direct comparison of cyanide treatment costs from sired quality. Alaska investigated the comparative costs of chemical absorbs the high-energy photons from the UV portion of the solar and biological destruction of cyanide in mine waters in cold cli- spectrum forming powerful oxidizers of reactive hydroxyl (OH) mates. where OCN is converted to ammonia and duce the consumption of cyanide in the overall metallurgical pro- bicarbonates/carbonates as shown in cesses.g. Hydrolysis is cess such as SART. the toxic effect of ammonia . selected depending on the site climate. is used and the process is controlled by adjusting the temperature Water losses have to be minimized and recirculation and reuse and pressure. but a significantly lower operating cost resulting in a dissociate. UV oxidation is limited to rel.

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