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By George O. Lower

The use of cyanides in the extraction of gold and silver is well known.1 Such extractions employ con¬centrations of cyanide in the range of 0.02-0.25 % sodium cyanide equivalent in leaching cycles of 24-48 hours and frequently longer. Copper minerals, even though minor components of precious metal ores, dissolve in these cyanide leaching solutions, consume cyanide, cause fouling of mill solutions, and thus interfere with the precipitation and recovery of gold and silver. 2,3,4 This paper presents a summary of laboratory investigations on the use of cyanide solutions as extractants for copper from various copper-bearing ore fractions. In view of the metal contents involved, it will be apparent that larger quantities of cyanide are required to extract copper than for the extraction of precious metals. In cyanide solutions of concentrations generally favorable to copper extraction, sulfide and oxide copper minerals were found to dissolve rapidly at room temperature and atmospheric pressure. For example, on products in the flotation size range, the major portions (e.g. 65-85%) of the extractable copper frequently dissolved in 2-10 minutes. At coarser grinds, e.g. 100% minus 28 mesh and 100% minus 10 mesh, 75-85% of the total copper was extracted in 30 minutes.

Jan 1, 1966

By Robert M. Mann

The Ag/S specific ion electrode has been evaluated for analysis of both free and total cyanide. Metal cyanide solutions were prepared from reagent grade compounds and by stoichiometric fixture of the metal with a potassium cyanide solution. Solutions containing Cu+1, Ni+2, Fe+2, Fe+3 and Zn+2 complexes were analyzed prior to and following EDTA pre treatment. This effort provides an understanding of the effect of each metal cyanide complex on the SIE analysis of free and "total" cyanide.

Jan 1, 1981

By G. S. Walker, W. van Bronswijk

The accurate determination of free cyanide and metal cyanide complexes is of increasing interest to Carbon-in-Pulp (CIP) gold extraction operations as cyanide consumption is an important economic factor in the processing of complex ores. Characteristically complex ores are high cyanide consumers and these ores usually contain a range of sulfide minerals e.g. covellite (CuS), digenite (Cu1,S), chalcocite (Cu, S), Pyrrhotite (Feci-x)S), marcasite (FeS2), arsenic and antimony sulfides and zinc sulfide. These minerals can consume significant quantities of cyanide, e.g. various copper(!) cyanide complexes such as CuCN, Cu(CN)2·, Cu(CN)/ and Cu(CN)/ can form, depending on the cyanide to copper ratio in solution. Measurement of free and complexed cyanide is thus a prerequisite for efficient cyanide dosage control. Free cyanide can be determined potentiometrically or amperometrically but the methods are prone to error and are laborious [1]. Metal cyanide complexes can be determined by reverse phase HPLC, however, the species ofa single cation (e.g. Cu(CN)i-, Cu(CN);2 and Cu(CN)/) elute as one species [2]. Additionally the high amount of suspended matter in CIP leach solutions tends to introduce errors. Raman spectroscopy has the potential to be used as an in­line or on-line method of analysis. Free cyanide and the cyanides of gold, silver, copper and iron have been studied in aqueous alkaline solutions with a view to developing such a method. Spectra were obtained with a Bruker RFSl00 FT-Raman spectrometer using a 1064 nm laser delivering 800 mW of power at the sample. Depending on the solution, 250, 1000 or 4000 scans at 4 cm-1 resolution were accumulated. The cyanide stretches observed were relatively narrow (10 15 cm-1 full width at half height) and well resolved (Figure 1 ).

Jan 1, 1995

By Mike Wardell-Johnson, Chris Campbell-Hicks, Craig Bitmead

Faster, simpler, cheaper and more accurate cyanide ex­tractable gold procedures are now available for grade control assay. Cyanide 'bulk leach extractable gold' or BLEG assays have previously been seen as desirable, due to the large sample size that can be treated, but not in common use due to the 24hr total assay time required. Sample sizes from 50g to several kilos can now be accurately assayed in less than 4 hours total time with the larger sample size increasing accuracy, without loss of precision, while greatly reducing the 'nugget effect' or coarse gold bias. Typical assay size is 200g, equivalent to 4 x 50g Fire Assays or 10 x 20g Aqua Regia Assays. Ongoing modifications and refinement of the procedures and reagents used also indicate applicability to the treatment of coarse gravity gold where substantial savings in both capital and operating costs for these circuits are possible. The successful use of this cyanide assay at the Bannockburn and Windine Well operations are cited to-gether with a compre­hensive comparative testwork program by Newcrest. Testwork at Gidgee and Lynas Gold operations is currently being initiated. Other operations using the method include Red Dome and Kidston; with Placer(Granny Smith) and PMA's Palm Springs operations to commence shortly.

Jan 1, 1995

By G. Piegols, J. A. Lombardi

Substantial volumes of cyanide are consumed in precious metals mining due to the purposeful destruction of base metal cyanide complexes and free cyanide to meet surface discharge regulations. This destruction of cyanide resource runs counter to the prevailing social ethic of resource conservation wherein cyanide recovery-and-reuse is considered a more socially responsible cyanide use pattern than systematic cyanide destruction. HW Process Technologies, Inc. (HWPT) has developed membrane based methods for the recovery of cyanide from barren solution as a means to reduce cyanide waste. The HWPT Engineered Membrane Separation (EMS™) system uses state-of-the-art spiral wound membrane elements that are engineered specifically for the treatment of high pH cyanide process solutions. The membranes fully reject WAD CN, SAD CN and most minor metals, and partially reject SCN, Free CN and precious metal cyanide from a high clarity barren solution feed to a small volume EMS™ “concentrate” stream. The EMS™ “concentrate” stream is returned to the process. The large percentage of the EMS™ process feed exits the system as cyanide lean EMS™ “permeate.” The EMS™ permeate, after residual cyanide destruction, polishing, and pH adjustment, is, thereafter, typically suitable for discharge. Separately, the HWPT EMS™-PLS method of cyanide recycling is an internal plant cyanide recovery step that removes base metal cyanides from a pregnant leach solution to a small volume EMSTM concentrate stream. The concentrate stream is then typically processed further for the recovery of metals and recovery-recycling of cyanide. The method makes it economically practical to recover gold from Merrill-Crowe or car-bon plant “fouling” solutions, e.g., those with greater than 400 ppm Cu, as might result from the use of the EMS™ method wherein EMS™ concentrate is constantly thrown back into the mine leach solution pool as part of the free cyanide recycle process, or as might result from the single-pass leach treatment of high copper content ores or concentrates. The EMS™ cyanide recovery method for barren solution treatment is shown to be “economic” for the treatment of clear solutions at the approximately 200 ppm total cyanide level (CNT), and for slurries at the approximately 400 ppm total cyanide level, where economic is defined as a 2 year EMS™ plant payback. The EMS™ plant payback calculation includes the beneficial monetary impacts of gold and free cyanide recycling and the avoided operating cost of cyanide destruction.• The cyanide recovery plant payback period is reduced further when the avoided capital costs for cyanide destruction (EMS™ permeate “clear solution CN destruction polish” only required) and/or metals precipitation are considered.

Jan 1, 2004

By Adrian Smith

14.1 INTRODUCTION From the time the last recoverable gold is extracted from ore on a heap leach, the ore - now spent ore - changes from being the resource, indeed the raison d'etre of the operator, to a potential liability. The spent ore contains process chemicals and constituents leached from the ore both in the interstitial pore water in the heap and on the surfaces of spent ore. If these chemical species were released to the environment, it could have a potential impact on the quality of both surface water and groundwater resources. Accordingly, the spent ore must be left in a condition where it does not present a potential environmental liability. This can be accomplished either on a decommissioned pad or, if the heap leach is operated as a load/unload scheme, in a waste facility. In general, the residual cyanide level in the spent ore is the perceived controlling factor when determining whether the leached material is suitable for abandonment. Regulatory authorities set permit conditions for heap leach abandonment in terms of residual cyanide levels, for example, Smith and Struhsacker (1987). This chapter discusses cyanide degradation and methods for detoxifying a heap leach in order to meet regulatory limits/permit conditions for abandonment. Cyanide degradation and detoxification by "natural" processes are described initially, based on the chemistry and geochemistry discussed in Chapter 13. This leads to a review of chemical treatment processes for detoxification of spent ore. The advantages and apparent disadvantages are then appraised. 14.2 NATURAL DEGRADATION AND DETOXIFICATION For the purposes of discussion, "natural" detoxification processes can be divided into two alternatives: • Passive abandonment (the so-called "do nothing" option); and • Water In the first alternative, the spent ore is merely left on the leach pad to age; the second alternative involves the flushing of the spent ore with water.

Jan 1, 1988

By P. J. Arps

Cyanide (CN) is used to recover gold from its ores in many locations worldwide. In spite of the established history of gold mining in Alaska, modern cyanidation methods have been used at only one location, the Ryan Lode Mine at Ester Dome, near Fairbanks. Ore was processed by heap leaching between 1987 and 1989, when permitting issues caused operations to be terminated. Those issues have since been resolved, and plans to reopen the mine are currently being discussed. Plans are also proceeding to develop several other ore deposits in the state, all of which include the use of cyanide for gold recovery [6]. Since tailings and effluent water produced from these mines will require treatment, it is important to develop detoxification methods suitable for the Arctic and sub-Arctic conditions found in Alaska. Several methods exist for removing cyanide from mining wastewater. However, most industrial users prefer chemical treatment systems, and typically use sodium hypochlorite, hydrogen peroxide, or sulfur dioxide/air/copper to oxidize free and complexed cyanides [9]. Biological treatment has been used successfully at two sites in the United States [30,32] and field tested at several others [20,27,28]. In addition, one mine uses "natural processes", which include natural oxidation, photodegradation, and degradation by naturally occurring bacteria [33].

Jan 1, 1994

By James L. Hendrix, Michael R. Straka, Emil B. Milosavljevic, Ljiljana Solujic, Neil P. Gallagher

Analysts that utilize the classical distillation procedures for cyanide analysis are often frustrated by the poor reproducibility and repeatability of these techniques. Capital intensive business decisions and environmental management regulations are exas­perated by the fact that the EPA/ASTM approved cyanide deter­mination methods produce data of questionable quality. Reliable cyanide values are important in monitoring the effec­tiveness of the cyanide detoxification procedures. Efficiency and cost of gold and silver cyanidation recovery can also be improved by precise cyanide monitoring in the process itself.

Jan 1, 1996

By Val Cachic, Harry M. Castrantas, Craig McKenzie

In April 1986, FMC- Paradise Peak Corporation began milling at the Paradise Peak Mine, which is located eight miles southeast of Gabbs, Nevada. The mill processes about 4DOO tons per day of ore through the mill and cyanide leaching circuit. Gold and silver are recovered via the Merrill-Crowe zinc precipitation process. Tailings are routed to a tailings pond located about one half mile southeast of the mill facility. The pond, lined with 60 mil MDPE, was 25 acres at the start of the cyanide detoxification, covers 90 acres and will ultimately cover 180 acres. Solution is reclaimed from the pond and circulated back to the mill.

Jan 1, 1998

By W. J. C. Meynink

In drier regions of the world, total containment of cyanide liquors for rainfalls less than a specific design value is often required by government regulation. For example, in Queensland total containment is required for rainfalls up to 'the 1% annual exceedence probability. In equatorial regions, where rainfall greatly exceeds evaporation, a total containment requirement is unrealistic and this is recognized by regulatory authorities. Regulatory constraints typically require that cyanide concentrations at an agreed downstream compliance point not exceed a specific value more than a specified fraction of the time. While the excessive rainfall prevents total containment, it does provide substantial dilution. This paper outlines a methodology for assessing the distribution of cyanide concentrations at a downstream compliance point in an equatorial region with limited hydrometeorological data. Consider the hypothetical mine environs depicted in Figure 1. The mine is located near the catchment divide and draws its water supply via a gravity line. Tailings from the process plant are piped to a tailings dam on a sub-catchment below the plant site. The objective is to determine the distributions of cyanide species concentrations at a compliance point just upstream of a major settlement to ensure they do not exceed regulatory limits.

Jan 1, 1991

By Adrian Smith, Debra W. Struhsacker

13.1 INTRODUCTION Cyanide is, a generic term indicating the presence of the cyanide ion (CN-). Cyanide is a very common, naturally occurring compound produced by many biochemical reactions. Many plant species synthesize organic compounds which contain cyanide in the form of cyanogenic glycosides (Knowles, 1976). For example, trace amounts of cyanide are present in the seeds and leaves of many members of the Rosaceae (rose) family (Kingsbury, 1964). Many common items such as lettuce, maize, sweet potatoes, kidney beans, (Oke, 1969) almonds, and cigarette smoke contain cyanide. As examples, a recent chemical analysis of chocolate-covered almonds measured a total cyanide content of about two ppm (Steffen Robertson and Kirsten, 1987); and the U.S. Surgeon General (U.S. Department of Health, 1964) has shown that cigarette smoke contains up to 1,600 ppm total cyanide. The chemistry of cyanide solutions is complicated because the cyanide ion forms compounds and complexes with many elements. Some cyanide species are highly toxic whereas others are relatively inert and harmless. Molecular hydrogen cyanide (HCN) is the most toxic form of cyanide. Under most conditions, HCN exists as a gas which readily dissipates or reacts with the environment to form less toxic or nontoxic forms of cyanide. Thus HCN is an ephemeral toxin, and many naturally occurring geochemical processes reduce the HCN concentration of a heap system with time. As discussed below, free cyanide includes the two species, ionic cyanide (CN-) and molecular hydrogen cyanide. Free-cyanide toxicity in man, mammal s, and aquatic species is we1 1 documented (Doudoroff, 1976; Ecological Analysts, 1979; Towill et al., 1978). The lethal doses reported for human adults vary with the type of exposure as follows: • One to three mg/kg body weight if ingested; • One hundred to 300 ppm if inhaled; and • One hundred mg/kg of body weight if absorbed. Acute toxicity of free cyanide to freshwater invertebrates ranges from 0.028 to 2.295 mg/l, depending on species and test conditions. Generally, free-cyanide concentrations greater than 0.1 mg/l are expected to kill sensitive species in freshwater or marine environments (Doudoroff, 1976;

Jan 1, 1988

By Adrian Smith, Debra W. Struhsacker

There is now overwhelming evidence that, despite concerns to the contrary, natural degradation of cyanide and cyanide attenuation by hydrogeochemical processes are capable of minimizing or eliminating potential water qua1ity impacts from heap leach systems. A1 though there was some recognition of these data by the regulatory authorities, for example the initial USEPA modification of cyanide standards to an advisory level, many states have codified standards inappropriate to the clearly site specific nature of heap leach operations. As an overview to this problem, this paper will integrate the theoretical chemical data on cyanide with the observed geochemical behavior of cyanide in the decommissioned heap leach environment. The cyanide species that are likely to exist within an abandoned heap leach system will be identified, and the relative toxicity and potential environment effect of these cyanide species will be discussed. These data will then be used to evaluate cyanide detoxification regulations for decommissioned heap leach projects in 14 states.

Jan 1, 1987

By Diane M. Jordan Tom M. Malloy

As part of the Mine Waste Technology Program (MWTP), a large-scale column test utilizing bacteria and a sulfide ore was conducted at McClelland Laboratories, Inc., in Sparks, Nevada. The MWTP is funded by the U.S. Environmental Protection Agency (EPA) and is jointly administered through an interagency agreement with the U.S. Department of Energy (DOE). The project was intended to illustrate the viability and feasibility of biodegradation technologies to reduce the cyanide to the regulatory level of 0.2 parts per million (ppm) within an acceptable time frame and with low operational costs.

Jan 1, 1999

By W. P. Staunton, K. Jones

INTRODUCTION The increased activity in the Aus­tralian gold industry over the last decade has resulted in a concomitant increase in the use of sodium cyanide, with a projected consumption of 80,000 tonnes in 1991. Growing environmental awareness by government, industry and the public has generated increased interest in the fate of cyanide near gold mine tailings dams and has highlighted the lack of basic knowledge in the area, particularly for Australian conditions. In 1989 the Chemistry Centre (W.A,) commenced a' project, under the auspices of the Australian Mineral Industries Research Association entitled "Fate of cyanide in the Enviroment Near Mine Tailings" to investigate some of the issues arising from the management of tailings containing cyanide, The project, which has been supported by thirteen companies has three broad aims:

Jan 1, 1991

By James L. Hendrix

This paper is intended to give the reader an update on the work being done at the Mackay School of Mines about the fate of cyanide on precious metals mill tailings waste. During the last two years several tailings impoundments have been sampled and analyzed for total and free cyanides. From our sampling program we are beginning to learn valuable information concerning the fate of cyanides in precious metals mill wastes. Included in this paper is a detailed description of our sampling and analytical techniques. Also, some of the data obtained from five sites are given.

Jan 1, 1986

By C. A. Young

Cyanide is a fast-acting, highly toxic substance but, at the same time, is deemed essential for sustaining life as well as our standard of living. In this manuscript, the facts about cyanide are presented beginning with a brief history and definition and ending with a discussion on cyanide alternatives. Other topics include speciation, physical characteristics, toxicity, manufacturing, cyanogenics, cyanide cycle, separation, destruction, and markets including those outside the mining industry. Emphasis, of course, is placed on gold production by leaching and how it is influenced by ore type, mineral characteristics and economics as well as its advantages and disadvantages.

Jan 1, 2001

By P. L. Sibrell

Previous research by the U.S. Bureau of Mines showed that autoclave cyanide leaching of used automobile exhaust catalysts for recovery of platinum group metals (PGM) was technically feasible. This work involves a more detailed investigation of the chemistry of the dissolution of PGM in cyanide solutions. The PGM species in solution identified by ultraviolet spectroscopy. Pt and Pd cyanide complexes were square were The planar in geometry, while the Rh complex was octahedral. The rate of dissolution of the PGM was also investigated using a rotating disk technique. Dissolution rates increased in the order of Rh, pt, and Pd, respectively.

Jan 1, 1994

By K. Barbetti, D. C. Wright, L. J. Warren, J. A. Rumball

This paper describes the advantages and disadvantages of cyanide sensors in gold processing operations, and their role in reducing process variability and lowering cyanide consump­tion. The importance of understanding the chemistry of the sensing principle, and the role of impurities, in order to choose the correct sensor setting, is demonstrated.

Jan 1, 1997

By E. A. Devuyst, G. Robbins

A unique process for removing cyanide and base metal complexes from industrial waste streams was patented by G.J. Borberly et al. (1984). The process uses SO2 (liquid or gas, or solutions of sulfite salts, or from burning elemental sulfur), plus air that is dispersed in the effluent using a well agitated vessel. Acid produced in the oxidation reactions is neutralized with lime at a controlled pH generally in the range 7 to 10. The reaction requires the presence of soluble copper as a catalyst which can be supplemented by copper sulfate if necessary. The process can be applied to the detoxification of gold and silver mining waste streams, such as carbon-in-pulp (CIP) tailing pulps, barren solution bleeds, pond waters and heap leach rinse solutions and also to plating shops wastewaters. The SO.jAir process has substantial advantages over two of the main alternative methods of cyanide destruction, namely alkaline chlorination and hydrogen peroxide. Alkaline chlorination is highly penalized in terms of reagent consumption. Chlorine is a strong oxidant reacting with species other than cyanide present in the effluent such as thiocyanate and sulfides. Furthermore alkaline chlorination is an incomplete detoxification process. Iron cyanide is not removed and the potential for harmful by-products species exist. Consequently final effluents may be subject to additional treatment in order to comply with regulatory demands.

Jan 1, 1991

By Steve Rule, Jose Roberto Vago, Walter de Moura

Cerro Vangaurdia Gold Mine is a joint venture between AngloGold (the operator), Perez Companc and Formicruz and is situated in the southern province of Santa Cruz, in Argentina, approximately 2,150 km south of the capital, Buenos Aires. The mine is located in a severe, semi-arid environment with very cold winters and little annual rainfall (200mm). It is an open-pit operation, mining several narrow, shallow epithermal quartz veins with . gold and silver mineralisation. Commissioning of the plant commenced in September 1998 and the first dore bar was poured towards the end of the same month. The nominal capacity of the plant is 55,000 tonnes per month, with a design capacity of 60,000 tonnes per month. Prior to finalising the design, an extensive testwork programme was undertaken at Nova Lima, in Brazil, in which all parts of the process were evaluated together on a pilot-plant scale. The process flowsheet selected at Ce1rn Vanguardia is quite novel, in that it includes milling in cyanide, as well as a cyanide recovery and recycling plant on the tailings section of the treatment plant is included. The cyanide recovery process selected was a version of the acidification - volatilization - reabsorption (AVR) process, known as Cyanisorb™. The selection of the Cyanisorb™ process in the plant design was as a direct consequence of two factors:

Jan 1, 2000