Green Mining Case Study

1. Gold mining
1.1 Reserves Reserves data are dynamic because they may be reduced as ores are mined and/or the extraction feasibility decreases, or more commonly, they may continue to increase as further deposits (known or recently discovered) are developed, or currently exploited deposits are more completely explored and/or new technology or economic variables enhance their economic feasibility. Hence, reserves data are a major issue because they betray where the largest resources are, allowing us to be aware of the countries that must improve its mining methods in order to extract in the best possible way. [1]

1.2 Production Details of world gold production over the past 150 years appear in Fig. 1. The effects of the California gold rush in 1849, followed by the gold rushes in Australia in 1851 and South Africa in 1884 are evident. The development of new cyanide milling technology (carbon-inpulp) and the major rise in the real price of gold in the 1970s led to expanded production from 1980 onwards. [2]

Figure 1. World gold production [2]

The gold mining boom since the late 1970s has been facilitated by the combination of a real price rise, the development of carbon-in-pulp (CIP) milling technology, and to a lesser extent the evolution in large-scale bulk earth-moving vehicles and mining techniques. These factors led to more exploration, focused initially on previous gold producing provinces, along with the development of many new gold mines around the world. These mines have often been based on open cut mining techniques, which allow more complete extraction and processing of all gold-mineralised ore. The economics of gold mining were radically redefined during this period. It led to an extra-ordinary renaissance in some countries such as Australia, the United States and Canada for about 20 years. In South Africa, by contrast, this pattern did not emerge, due to the deep underground nature of their gold mines as well as political and social issues. From a global view, based on gold resources data presented, there is only sufficient known economic resources to sustain existing levels of newly mined production for less than 20 years. The future extent of economic resources and production is, of course, difficult to predict but will continue to depend on exploration effort, economics, social and environmental issues, technology as well as the recycling of the world gold stockpile. [2] 1.3 Gold mine wastewater production Gold is generally extracted from ores or concentrates by the alkaline cyanidation (Elsner) process. The gold-bearing ore is crushed and ground to approximately 100 microns. Next, it is transported to a leaching plant where lime, cyanide and oxygen are added to the ground and slurried ore. The lime raises the pH, while the oxygen and cyanide oxidize and complex the gold. [3] The cyanide solution thus dissolves the gold from the crushed ore. Next, the gold-bearing solution is collected. Finally, the gold is precipitated out of the solution. [3] The common processes for recovery of the dissolved gold from solution are carbon-in-pulp, the Merrill-Crowe process, electrowinning and resin-in-pulp. In the carbon-in-pulp (CIP) technique, the gold cyanide complex is adsorbed onto activated carbon until it comes to equilibrium with the gold in solution. Because the carbon particles are much larger than the ore particles, the coarse carbon can be separated from the slurry by screening using a wire
`

mesh. The gold-loaded carbon is then removed and washed before undergoing elution or desorption of gold cyanide at high temperature and pH. The rich eluate solution that emerges from the elution process is passed through electrowinning cells where gold and other metals are precipitated onto the cathodes. Smelting of the cathode material further refines the gold and produces gold ingots suitable for transport to a refinery. [3] Mercury amalgamation and gravity concentration are the other processes for obtaining gold concentrate from gold ore. The tailings, contaminated with metal and cyanide ions, are usually stored in tailings ponds, with the potential for groundwater contamination and high risk of failure, which can lead to spillage of the toxic metals and cyanide-bearing solution into the environment. The types of heavy metals present depend on the nature of the gold ore. Acid mine drainage is another type of mine effluent, which is produced when sulphide ores are exposed to the atmosphere as a result of mining and milling processes where oxidation reactions are initiated. Mining increases the exposed surface area of sulphurbearing rocks allowing for excess acid generation beyond the natural buffering capabilities found in host rock and water resources. Collectively, the generation of acidity from sulphide weathering is termed acid mine drainage (AMD). Concentrations of common elements such as Cu, Zn, Al, Fe, As and Mn all dramatically increase in waters with low pH. [3] Gold mining operations result in contamination of soils and water with tailings that release toxic metals such as Cu, As, Pb, Mo, Fe, Ni and Zn. Various regulatory bodies have set the maximum prescribed limit for discharge of toxic heavy metals into the aquatic ecosystem. Table 1 shows the maximum contaminants level (MCL) values set by the US EPA and the position in the Comprehensive Compliance Environmental Response, Compensation and Liability Act (CERCLA), 2005 list of priority chemicals of some of the toxic heavy metals. Nevertheless, metal ions are discharged into water bodies at much higher concentrations than the prescribed limit by industrial activities such as gold mining, thus leading to health hazards and environmental degradation.

Table 1. Maximum permissible concentrations for heavy metals in gold mines wastewaters Heavy metal Arsenic (As) Lead (Pb) Mercury (Hg) Cadmium (Cd) Chromium (Cr(VI)) Zinc (Zn) Manganese (Mn) Copper (Cu) Selenium (Se) Silver (Ag) Antimony (Sb) Iron (Fe) Concentration, mg/L 0.01 0.015 0.002 0.005 0.01 5.0 0.05 1.3 0.05 0.05 0.006 0.3

1.4 Health and environmental risks of heavy metals and cyanide Heavy metal pollution is one of the important environmental problems today. These heavy metals are of special concern due to their toxicity, bioaccumulation tendency and persistency in nature. The removal of heavy metals from water and wastewater is important in terms of protection of public health and environment due to their accumulation in living tissues through the food chain as a non-biodegradable pollutant. Heavy metals (such as lead, copper and arsenic) are toxic to aquatic flora and fauna even in relatively low concentrations. [3] The excessive intake of copper by man leads to severe mucosal irritation, widespread capillary damage, hepatic and renal damage, central nervous system problems followed by depression, gastrointestinal irritation and possible necrotic changes in the liver and kidney. Arsenic dissolved in water is acutely toxic and leads to a number of health problems, including disturbances to the cardiovascular and nervous system functions and eventually death. Other heavy metals (such as Hg, Cd, Se, Pb, Ni, Zn, etc.) produce similar health effects when injected in significant quantities. [3] Cyanide is acutely toxic to humans. Toxicological studies have indicated that short-term exposure to high levels of cyanide causes rapid breathing, tremors and other neurological
`

effects; while long-term exposure causes weight loss, thyroid effects, nerve damage and death. Skin contact with liquids containing cyanide may produce irritation and sores. Clearly, heavy metal and cyanide pollution of the environment is of paramount concern due to their health risk to humans and threats to the ecosystem. [3] 2. Treatment methods of gold mine wastewater The conventional methods for removing heavy metal ions from wastewater include chemical precipitation, coagulationflocculation, flotation, filtration, ion-exchange, reverse osmosis, membrane-filtration, evaporation recovery and electrochemical technologies. Advantages and drawbacks of these methods are presented in Table 2. [3] Table 2. Advantages and limitations of physicochemical treatments of industrial wastewater Type of treatment Target of removal Advantages Disadvantages References

Reverse osmosis

Electrodialysis

Ultrafiltration

Ion exchange

High energy consumption due Organic and High rejection rate, to high pressure inorganic able to withstand required (20100 Compounds high temperature bar), susceptible to membrane fouling Formation of metal hydroxide, high energy cost, Suitable for metal can not treat a Heavy metals concentration less metal than 20 mg L1 concentration higher than 1000 mg/l High operational High molecular cost, prone to weight membrane Smaller space compounds fouling, requirement (100010 000 generation of Da) sludge that has to be disposed off Dissolved No sludge Not all ion compounds, generation, less exchange resins cations/anions time consuming are suitable for

Potts et al.32, Kurniawan et al.33

Bruggen and Vandecasteele34, Ahluwalia and Goyal28

Vigneswaran35

Vigneswaran35, Ahluwalia and Goyal28,

Table 2. Advantages and limitations of physicochemical treatments of industrial wastewater Type of treatment Target of removal Advantages Disadvantages References Kurniawan et al.33 Ahluwalia and Goyal28, Bose et al.36, Wingenfelder et al.37 Shammas38, Semerjian and Ayoub39, Ayoub et al.40

metal removal, high capital cost Sludge generation, extra Chemical Heavy metals, Low capital cost, operational cost precipitation divalent metals simple Operation for sludge disposal Shorter time to Sludge production, extra Heavy metals settle out Coagulation and suspended suspended solids, operational cost flocculation improvedsludge for sludge Solids settling disposal Subsequent treatments are Heavy metals Low cost, shorter required to Dissolved air and suspended hydraulic retention improve the flotation Solids time removal efficiency of heavy metal Sulphate salts Costly, prone to and hardness Lower pressure Nanofiltration membrane ions such as than RO (730 bar) fouling Ca(II) and Mg(II) Can work under both acidic and basic conditions, Electrochemical can treat effluent High capital and Heavy metals precipitation with a metal operational costs concentration higher than 2000 mg/l Can treat wastewater with metal Membrane Metal High energy concentration of electrolysis impurities consumption less than 10 mg L1 or higher than 2000 mg L1

Lazaridis et al.41

Ahn et al.42

Subbaiah et al.43

Kurniawan et al.33 (2006)

Precipitation is most applicable among these techniques and considered to be the most economical. However, this technique produces a large amount of sludge precipitate that requires further treatment. Reverse osmosis and ion-exchange can effectively reduce the metal ions, but their use is limited due to a number of disadvantages such as high materials and operational cost, in addition to the limited pH range for the ion-exchange resin. Table 3 gives performance characteristics of some conventional heavy metal removal and recovery technologies while Table 4 summarizes research work on heavy metal removal using physicochemical techniques. [3] Table 3. Performance characteristics of some conventional heavy metal removal and recovery technologies Performance characteristics Metal Influence of Tolerance to working Metal Technology pH change suspended organic level (mg selectivity solids molecules L1) Adsorption Limited tolerance Moderate Moderate Fouled Can be poisoned < 10 > 10

Electrochemical Tolerant Limited tolerance Tolerant Some tolerant systems

Can be Can be engineered to accommodated tolerate

Ion exchange Precipitation as hydroxide Solvent extraction

Some selectivity (e.g. Fouled chelating resin) Non-selective Tolerant

Can be poisoned < 100 Tolerant > 10

Metal-selective extractants Fouled available

Table 4. Summary of heavy metal removal data by physicochemical treatment methods Initial metal Removal Power Treatment method Metal conc. pH efficiency consumption References 3 (mg (%) (kWh m ) L1) Chemical precipitation Zn(II) 450 Cd(II) 150 11.0 99.77 11.0 99.76 NA NA Cherernnyavak45

Table 4. Summary of heavy metal removal data by physicochemical treatment methods Initial metal Removal Power Treatment method Metal conc. pH efficiency consumption References (%) (kWh m3) (mg L1) Mn(II) 1085 11.0 99.30 NA Tnay and Cu(II) 16 9.5 80 NA Kabdalsi46 Electrochemicalcoagulation/ As 442 99.90 NA Mavrov et al.31 Membrane Filtration Se 2.32 98.70 NA 8.5 100 NA Juang et al.47 Ultrafiltration Cu(II) 78.74 9.5 8.5 Zn(II) 81.10 95 NA 9.5 Aliane et al.48 Cr(III 200 6.0 95 NA Nanofiltrattion Ni(II) 2000 37 94 NA Ahn et al.43 Mohammad et Reverse osmosis Cu(II) 200 4-11 99 NA al.49 Cd(II) 200 4-11 98 NA Froatation Cu(II) 3.5 5.5 98.26 NA Rubio et al.50 Ni(II) 2.0 5.5 98.6 NA Zn(II) 2.0 5.5 98.6 NA Zn(II) 50 7-9 100 NA Matis et al.51 Tzanetakis et Electrodialysis Ni(II) 11.72 NA 69 NA al.52 Co(II) 0.84 NA 90 NA Membrane electrolysis Cr(VI) 130 8.5 99.6 7.9 103 Martnez et al.53 3 Ni(II) 2000 5.5 90 4.2 10 Orhan et al.54 Electrochemical 570Kongsricharoern Cr(VI) 4.5 99 20 precitipation 2100 and Polprasert55 215Kongsricharoern Cr(VI) 1.5 99.99 14.720 3860 and Polprasert56 3 Ni(II) 40 000 NA 85 3.43 10 Subbaiah et al.44 Ion exchange Ni(II) 100 90 NA Cr(III) 100 3-5 100 NA Rengaraj et al.57 Ni(II) 100 90 NA Sapari et al.58 Cu(II) 100 100 NA Cr(VI) 9.77 NA 100 NA Kabay et al.5

NA not available

3. Gold Mine in South Africa

Gold Mine located in the Far West Rand Gold field is the object of current case study. It is situated in the geologically unique and world renowned Witwatersrand Basin, one of the worlds premier gold regions. The Witwatersrand Basin has made significant contributions to South Africas economy and remains the most important gold depository in the history of mining. Since the establishment of the first shaft in 1934, mine has produced more than 70 Moz of gold. Gold Mine operates two gold plants and the underground workings are accessed from surface through five shaft systems to a depth of 3,347 m below surface. It is estimated that the current Mineral Reserves will be depleted in 2030. [4]

3.1 Geological Settings and Mineralization All of Gold Fields South African operations are located in the Witwatersrand Basin and are intermediate to deep level underground mines exploiting gold bearing, shallowly dipping tabular ore bodies. The gold mineralisation in the Witwatersrand Basin occurs within quartz pebble conglomerates termed reefs. Considered gold mine is located in the West Wits Line Goldfi eld of the Witwatersrand Basin. This gold field is geographically divided into the Far West Rand and the West Rand areas. The mining area is underlain by outliers of Karoo Supergroup shales and sandstones, followed by Pretoria Group sediments and the Chuniespoort Group dolomites. The Dolomites overlie the Klipriviersberg Group volcanic rocks, which in turn cap the Ventersdorp Contact Reef and sediments of the Central Rand Group that hosts the other gold-bearing reefs exploited by gold mine. [4]

3.2. Mining method The predominant mining layout at considered gold mine is breast stoping with dip pillars, with a minor contribution from scattered mining. Breast stoping with dip pillars has been selected for the below infrastructure projects. Mining spans and pillar widths depend on the location, the reef being mined and the depth of working. [4]

3.3. Mineral processing Company has two operational metallurgical facilities using proven metallurgical processes, with a central elution and smelting facility. The third metallurgical facility that processed surface material was closed in April 2005. The facility was demolished and all gold recovered. 1 Plant was commissioned in 1968 to treat underground ore. This plant comprises three stage crushing, utilising open circuit rod mills for primary milling and closed circuit pebble mills for secondary milling. After milling, the pulp is thickened and then processed through air agitated leaching, drum filtration, zinc precipitation and smelting to dor. In June 2001 an AAC Pump Cell CIP circuit was installed to replace the less efficient drum filtration and Zinc precipitation. Smelting was also discontinued, with loaded carbon being transported to 2 Plant for elution and thermal regeneration. The current operational capacity of 1 Plant is 180 ktpm. 2 Plant was commissioned in November 1990. This Plant receives underground Run-of-Mine ore (RoM), which is crushed and delivered to a stacker reclaimer system, where the ore is stored and blended prior to reclamation and delivery to the mills. Surface material is also delivered to the stacker pad to utilise plant capacity. There are two Semi-Autogenous Grinding (SAG) mills, which are equipped with variable-speed ring motor drives, and can be operated as fully autogenous units or as semiautogenous units by adding steel grinding balls. Milled ore is thickened ahead of cyanide leaching in air-agitated tanks and adsorption onto activated carbon in a conventional CIP circuit. Loaded carbon is eluted in an AARL elution circuit, which was upgraded in June 2001 and further in October 2003. It now serves as the central elution facility. The upgrade included the installation of Continuous Electrowinning Sludge Reactors, which are working very efficiently. Cathode sludge is filtered and smelted to produce dor. The current operational capacity of 2 Plant is 150 ktpm. [4]

3.4. Gold Mine Tailings Since gold mining started more than a century ago, South Africa has been the largest producer of gold in the world. In 1996 alone, 377 million tons of mine waste was produced, accounting for 81% of the total in South Africa. These mine wastes contain large amounts (between 10 and 30 kg/ton) of sulphide minerals, such as pyrite, which are prone to generate acid mine drainage (AMD). AMD is a global pollution problem and is generally

reflected by high salt loads and acidification of the affected environment. In addition, AMD is often associated with significant concentrations of toxic trace elements and radionuclides. These contaminants remobilise under acidic conditions and migrate into the vadose zone and groundwater system. More than 270 tailings dams related to gold mining and covering a total area of about 180 km2 have been identified in South Africa. Most of the tailings dams are situated either in highly urbanised areas or close to valuable agricultural land. A conceptual model of the various pollution pathways from gold mining tailings is presented in Figure 2. [6]

Fig.2. Conceptual model of tailing dam and affected subsurface [6]

The vadose (unsaturated) zone is considered to be a geochemical and physical barrier between the primary source of contamination (i.e. tailings dam) and the recipient groundwater system. Moisture movement and attenuation processes such as adsorption in the vadose zone have the potential to mitigate the contamination of the groundwater.

However, once this barrier has become contaminated, it can also act as a continuous source of pollution. Furthermore, it must be stressed that gold mine tailings from the Witwatersrand can contain significant amounts of radionuclides such as uranium and radium. As a result, this material is classified as low level radioactive waste. Composition of wastewater from considered gold mine is presented in Table 5. [3] Amount of wastewater stored in tailings is estimated to be 234.9 Mt. [4]
Table 5. Composition gold mine wastewater Parameter PH Conductivity (S cm1) TDS (mg L1) TSS (mg L1) Temperature ( C) Cyanide (mg L1) As (mg L1) Fe (mg L1) Pb (mg L1) Cu (mg L1) Zn (mg L1) Gold mine wastewater 7.40 5600 2900 22 31.3 9 7.350 0.114 0.140 5.063 0.042

3.5. Task Due to environmental legislation restrictions the problem of gold mine tailings should be solved by the company as soon as possible. Currently wastewaters are stored in tailings without any treatment system. Recently two mining companies in South Africa suggested to test their waste materials (iron hydroxide and fly ash) for the purification of wastewaters. These companies are ready to provide their wastes to gold mine for free. Only transportation costs should be

covered by gold mine. Steel sand is a waste from considered gold mine and it was tested together with iron hydroxide and fly ash. Results of conducted research are presented below. Laboratory has received three different materials from two different companies, such as iron hydroxide, steel sand and fly ash. These materials are waste products from some industries. The composition of these materials has been studied by XRF (Table.6), surface area by BET (Table.7) and morphology by SEM (Fig.3), and adsorption properties of these materials by mining wastewaters purification from As (III), As (V), Ni (Table.8), Fe and Mn. Different amount of adsorbents such as 0.5, 1, and 2 g/l were studied for 26 hours. Also adsorption of different elements was studied (0 - 300 ppm). It was found out that the optimum amount of adsorbent is 2 g/l. At a concentration of elements 200 ppm removal was almost 100%. In most of solutions with concentration 100 ppm adsorption occurs within three hours (Fig.4). After this, the system is became balanced. In the course of the experiment it was found that iron and manganese are precipitated on the sulfate forms. However, adsorption of arsenic and nickel on different materials was observed and these results are presented in Table 8. Table 6. Composition of materials by XRF method Elements Al Si S K Ca Ti Cr Mn Fe Ni Cu Zn Rb Sr Zr Iron hydroxide, % 1,7 0,2 17,6 0,3 14,4 2,3 0,031 0,27 7,2 + 0,002 0,018 0,001 0,021 0,010 Steel sand, % 3,1 23,0 0,03 0,3 0,84 0,13 0,145 0,022 1,1 + 0,001 0,006 0,003 0,007 0,012 Fly ash, % 4,2 12,4 0,19 0,33 1,45 0,28 0,014 0,006 3,7 0,007 0,002 0,004 0,033 0,02

Table 7. Characterization of materials by BET-method Material Specific surface area of product BET, m /g 62,5 0,7 1,7 500
2

Adsorption capacity, cm3/g 0,130 0,002 0,009 0,970

Iron hydroxide Steel sand Fly ash Activated carbon (for comparison)

a.

b.

c.

Fig.3. SEM pictures of waste materials, a. iron hydroxide, b. steel sand, c. fly ash

Table 8. Adsorption of As (III), As (V) and Ni from wastewater in batch system Material Iron hydroxide Steel sand Fly ash Activates carbon (for comparison) Adsorption of As III from wastewater, % 98 17 16 98 Adsorption of As V from wastewater, % 93 23 17 ~100 Adsorption of Ni II from wastewater, % 93 83 65 ~100

100 80 60 40 20 0 0,5 10,5

Fig.4. Wastewater treatment by iron hydroxide (1b) and steel sand 2(b), concentration of adsorbents 2g/L, initial concentration of As (III), As (V) and Ni were 200 ppm

1b_As III 2b_As III 1b_As V 2b_As V 1b_Ni 20,5 30,5 2b_Ni

Based on presented data please do following: 1. Characterize each material as probable adsorbent for treatment of wastewaters a. material composition b. surface area c. morphology d. adsorption capacity 2. Choose the best treatments method for purification of gold mine wastewater from the environmental, economic and technological point of view (estimation of technological solutions and costs can be found in following document: Technologies and Costs for removal of Arsenic from drinking Water).

References
[1] Adriana Dominguez and Alicia Valero, Global Gold Mining: Is technological learning overcoming the declining in ore grades? Proceedings of ECOS 2012 The 25th International Conference on Efficiency, Cost, Optimization, Simulation and Environmental Impact of Energy Systems, June 26-29, 2012, Perugia, Italy [2] Gavin M. Mudd, Global trends in gold mining: Towards quantifying environmental and resource sustainability? Resources Policy 32 (2007), p. 42-56 [3] Mike A. Acheampong, Roel J.W. Meulepas and Piet N.L. Lens, Removal of heavy metals and cyanide from gold mine wastewater, J Chem Technol Biotechnol 2010; 85; 590-613 [4] Kloof gold mine, Technical Short Form Report [5] Frank Winde, Peter Wade and Izak Jacobus van der Walt, Gold tailings as a source of waterborne uranium contamination of streams The Koekemoerspruit (Klerksdorp goldfield, South Africa) as a case study. Part I of III: Uranium migration along the aqueous pathway, Water S A Vol.30 No.2, 2004, p.219-225 [6] T. Rsner, A van Schalkwyk, The environmental impact of gold mine tailings footprints in the Johannesburg region, South Africa, Bull Eng Geol Env (2000) 59: 137-148