Universidade de So Paulo, Escola Politcnica, Dept Engenharia de Minas PMI 5003

Studying Gold Ores: Mineralogy, Cyanidation, Toxicity and Environmental Issues

Dr. Arthur Pinto Chaves
(Universidade de So Paulo, Dept Engenharia de Minas)

Gold Process Mineralogy

Dr. Marcello Veiga

(University of Britsh Columbia, Dept Mining Engineering, Canada)

Common Gold Minerals

Gold Electrum Cuproauride Porpezite Rhodite Iridic gold Calaverite Krennerite Montbrayite Petzite (antamokite) Uytenbogaardtite Aurostibite Fischesserite Au (Au,Ag) (Au,Cu) (Au,Pd) (Au,Rh) (Au,Ir) AuTe 2 (Au,Ag)Te 2 (Au,Sb)2Te 3 Ag3 AuTe 2 Ag3AuS2 AuSb2 Ag3AuSe2

Common Gold Minerals

Platinum gold Bismuthian gold Gold amalgam Maldonite Auricupride Palladium Curoauride (Au,Pt) (Au,Bi) Au 2 Hg 3 (?) Au 2 Bi AuCu3 (Cu,Pd)3 Au 2 (Ag,Au)Te (Au,Ag)Te 4 AuCuTe 4 Pb 5 Au(Te,Sb)4 S5-8

Muthmannite Sylvanite Kostovite Nagyagite

Physical Properties of Gold

Property % Au SG Mohs Hardness Native Gold >75 16-19.3 2.5-3 Electrum 45-75 13-16 2-2.5

Physical Properties of Gold Tellurides

Mineral Calaverite Krennerite Sylvanite Montbroyite Petzite Hessite %Au 39.2-42.8 30.7-43.9 24.2-29.9 38.6-44.3 19-25.2 4.7 SG 9.2 8.6 8.2 9.9 9.1 8.4 Hardness 2.5-3 2.5 1.5-2 2.5 2.5 2.5-3

Physical Properties of Gold Minerals

Mineral Nagyagite Kostovite Aurostibnite Maldonite Au% 7.4-10.2 25.2 43.5-50.9 64.5-65.1 9.9 15.5 SG 4.5 Mohs Hardness 1.5 2-2.5 3 1.5-2

Gold Mineral Associations and Size

Gold occurs in several forms Free gold is liberated Attached to gangue along grain boundaries or completely occluded within a particle grain Finely disseminated within a mineral structure. GOLD

GANGUE

HENLEY, K.J,(1975). Gold-ore mineralogy and its relation to metallurgical treatment. Minerals Sci. Engng, vol.7, n. 4, p. 289-312

Gold in the Electron Microscope

History of Gold Ore Processing

1700 to early 1900s
Mostly alluvial gold Gold pans, sluice boxes and mercury amalgamation

Late 1800s to mid 1900s

Cyanidation Invented Depletion of alluvial gold Increase in hardrock gold mining Processing evolved towards cyanidation, although mercury still used in some large scale operations

1970s to present
Development of heap cyanidation New technologies for refractory gold ores Mercury use in large scale mines almost completely disappears Centrifugal gravity concentrators developed Escalation of ASM in developing countries

Image of back-scattered electrons

Process Design for Large Scale Gold Mines

Process designs are based on ore specific mineralogy Processes are kept as simple as possible with minimum number of stages Usually coarse gold is removed first from the leaching circuit Cyanidation is usually applied for gold particles finer than 0.15 mm (100 mesh)

Typical Terminology for Gold Ores

Alluvial (usually free naturally gold) sands and gravels, rivers, beaches usually gold particles are liberated Free milling surface and underground hard rock mines gold associated with silicates Refractory not amenable to conventional cyanidation usually associated with sulfides

Gold Ore Processing Practices (Alluvial)

USUALLY gold is liberated in alluvial ore, but sometimes it is not Sometimes gold is aggregated with clay scrubbing is needed In Coluvial and Eluvial ores, gold IS PARTIALLY liberated and this is the reason why the Au recovery is low, as many miners do not grind the ore before concentration
Gravity and/or Flotation Concentration

Gold Ore Processing Practices (Alluvial)

Scrubbing

Free gold

Brazil, 1993 (BBC Documentary) Dredging alluvial gold in the Amazon

Brazil, 2006 Mining coluvial gold ore in the Amazon

Gold Ore Processing Practices (Alluvial)

Gold Ore Processing Practices (free milling ores)

Comminution Comminution

Cyanide Leach

Gravity and/or Flotation Concentration

Free gold

Gold

Cyanide Leach

Concentration of alluvial gold by flotation. Photo H. Wotruba

Gold

Gold Ore Processing Practices (refractory)

Comminution

Typical Terminology for Gold Ores

Attached (occluded) gold sulfides Silicates Invisible gold Au grains sizes range from: very coarse >1 mm coarse >0.15 mm fine <0.074 mm to very fine <0.010 mm

Gravity Sep

Flotation

Oxidation

25 m

Free gold

Cyanide Leach

Reflected light in optical microscope Fine gold in pyrite grain

Gold

Free Gold Particle

Gold Associated with sulfides Gold rarely forms solid solution with sulfides but it is possible Gold can be occluded in sulfides in grains <0.02 m Invisible Au can be sub microscopic gold or gold in the sulfide lattice Invisible Au is preferentially concentrated in arsenopyrite which is apparently related to crystal chemistry

25 m

When an ore has fine and coarse grained arsenopyrite, Au concentrates in finer grained

Gold Associated with sulfides

Reflected light in optical microscope

Gold Associated with sulfides

Polished-thin Section, reflected light, optical microscope

Ga

Au

Chalcopyrite CuFeS2
Si

Gold with Galena and Silicates

Gold is usually difficult to polish (lots of scratches)

Reflected light

Very often in the optical microscope, chalcopyrite looks like gold, but gold is much brighter
HENLEY, K.J,(1975). Gold-ore mineralogy and its relation to metallurgical treatment. Minerals Sci. Engng, vol.7, n. 4, p. 289-312

Gold Associated with sulfides

Reflected Light

Gold Associated with Sulfides

To differentiate Au from Chalcopyrite Reflected Light gold

gold chalcopyrite

gold

sulfides (chalcopyrite and pyrite) become oxidized in the optical microscope when the specimen is attacked by diluted HNO3 (10%) for one day

Studying of Liberation of Gold Ores

It is difficult to establish gold liberation as this is usually a trace element in most ores, hardly visible in microscope. Liberation of gold can be obtained by indirect methods, such as heavy liquid separation, gravity concentration, flotation, etc.. One technique (very common) to establish the gold liberation is grinding in different times followed by concentration

Studying Gold Liberation

Studying Liberation by Flotation or Gravity Concentration

Studying Liberation by Flotation or Gravity Concentration

3 2.5

Increasing grinding time

increasing liberation.

Example

The average gold grade of this tailing from Crixs, Brazil is around 0.7 to 1 g/tonne. Gold liberation was studied as follows::
Composite Sample Grinding (various time) Batch Flotation tail. conc. Fire Assay

Grain size distribution of a garimpo tailing before grinding.

Au 1.5 (g/t) 1
0.5 0

# 48

grinding time - no grinding - 5 min. - 10 min. - 20 min. - 30 min.

Gold grades in screened fractions

Grain size analyses

It is noticeable that the Artisanal Miners could not recover the fine gold (they used sluice boxes) and the unliberated gold in the coarse fractions.

25

Au 20 15 distr.10 (%) 5
0

Gold distribution in screened fractions

Studying Liberation by Flotation or Gravity Concentration

Concentration of the different ground sub-samples indicates that the liberation must be around 10 minutes of grinding. Taking this information to the grain size distribution graphic, we can obtain the liberation size of the gold particles.

Studying Liberation by Flotation or Gravity Concentration

100 80 60 40 20 0 16 20 28 35 48 65 100 150 200 270 400 -400 grinding time 1 min 5 min 10 min 20 min

100 90

%Gold recovery 80 by concentration 70

60 50 0 5 10 20 30

% Mass Passing

D80 for 10 min of grinding (probable gold liberation)

Tyler Mesh

Grinding time (min.)

65 # 10 0# 15 0# 20 0# 27 0# 40 0# -4 00 #

20 #

28 #

35 #

48 #

# 10 0# 15 0# 20 0# 27 0# 40 0# -4 00 #

# 28

35

20

65

Mesh

Mesh

Studying of Liberation of Gold Ores

Very often the concept of gold liberation is usually replaced by accessibility of gold to reagents such as mercury, cyanide, etc. In other words: submit the sample (or concentrates) to cyanidation and amalgamation. The grain size distribution must be known .or make cyanidiation or amalgamation of the sized fractions

Studying of Liberation of Gold Ores

For amalgamation a gold particle must be at least >90% liberated Amalgamation is difficult for -200 mesh fractions unless the mercury is activated For cyanidation gold does not need to be liberated; it can be exposed
Au exposed but not liberated Quartz particle

Hg Activation Improves Amalgamation

Usually Hg becomes oxidized (dirty) when it is old The efficiency of amalgamation is low (usually 70%) Hg doesnt grab Aut Hg forms droplets and loses coalescence Lots of Hg is lost to amalgamation tailings (usually have 60-300 ppm Hg)

Hg Activation Improves Amalgamation

Boil water (Indonesia) Detergent (Brazil, Zimbabwe, Tanzania) Lime juice (Laos) Dilluted nitric acid (Peru) Brown sugar (Ecuador) Molasse, guava leaves, lime juice, bicarbonate (Colombia, Antioquia) Urine (Chile) Electrolytic formation of Na- or K-amalgam (Colombia, Narios)

Activating Hg before amalgamation (increase coalescence = reduces Hg flouring = less Hg loss with tailing)

+
wire Graphite rod

Battery 12 V

It forms sodiumamalgam which is more consistent than pure Hg

Mercury

Water with 10% of salt NaCl or KCl

Brazil, 2006

Zimbabwe, 2006

Brown Sugar in the Amalgamation Barrel

Amalgamation Barrel

Ecuador, 2004

It is not know the role of brown sugar in improving amalgamtion. This is widely used in Ecuador and some parys of Colombia

Indonesia, 2006

Studying of Liberation of Gold Ores

A Simple Methodology: screened fractions are submitted to heavy liquid separation. The floats are assayed for gold. The sinks are submitted to amalgamation. The mineral residue is submitted to cyanidation. This will determine the gold portion accessible to mercury (almost free gold) and accessible to cyanide (not quite free). The final residue, after cyanidation is analyzed by fire assay, in which all ore is melted. This determines the portion of mineral-locked gold (not amalgamated or leached).

Studying of Liberation of Gold Ores

ATTENTION:

This is just a lab test This must not be used in an actual processing plant Hg-contaminated tailings must not be leached with cyanide since this forms Hg-cyanide which is very bioavailable

Studying of Liberation of Gold Ores

Gold Ore (8g/tonne Au)
Results:

Studying of Liberation of Gold Ores

All fractions finer than 48 mesh had similar Au recovery (~60%) in heavy liquid. Amalgamation showed that particles coarser than 48 mesh did not show enough exposure to be amalgamated.
Fraction (Tyler mesh) -28 +35 -35 +48 -48 +65 -65 +100 -100 +150 -150 +200 -200 +270

Crushing ((-28#) Screening 35, 48, 65, 100, 150, 200, 270 mesh Chemical Analysis Nitric Acid Hg-Dissolution Hg Chemical Analysis gold gold

(60% solids; Hg:solids = 1:20)

light fractions Heavy Liquid Separation heavy fractions amalgams Amalgamation residue Cyanidation
(*) (*)

solutions

(10g/L NaCN, NaCN, pH=10, 40%sol, 24 h)

residue Fire Assay

(*)

Gold in Heavy Products (%) 32 68 57 55 62 60 n.a.

Amalgamated Gold (%) 4 1 21 48 67 87 n.a

CN Leached Gold (%) n.a n.a n.a 88.0 93.2 95.0 99.0

gold

Just the -48 mesh fractions were leached by cyanide. High concentration of CN was used to avoid CN consumpion control

We should expect to extract up to 60% of the gold from this ore ground -65 mesh and subjected to gravity separation. Cyanidation of -200 mesh recovers almost all gold.

Studying of Liberation of Gold Ores

Example: Gold liberation of an ore from Texada Island, BC, Canada As the ore had more than 30% of heavy minerals (pyrite, bornite, iron oxides) (sg>2.89) and high gold grade (7.3 g/t), the heavy liquid separation was not used, just amalgamation followed by cyanidation and fire-assay (fusion) of final residues. It is possible to notice the gold liberation increasing with particle size decreasing.

Studying of Liberation of Gold Ores

Representative sample Chips of sample selected Crushing sub-sample - 6 Mesh (3.4 mm) sub-samples Store in bags Grinding - 28 M (0.6 mm) Screening fractions Heavy Liquid Separation heavies Amalgamation residues Cyanidation Optical and electron microscopy
(polished thin sections)

DAu (%) 100

75

- +100#
-200+400# -400# -100+200#

Fusion Cyanidation

50
25

Liberation of Sulfides (Microscopy) Chemical Analysis

Grinding with different times Gravity Sep. tailing Flotation conc. Cyanidation residue Diagnosis Leaching

Amalgamation

Overall Gold recovered by:

Fusion: Cyanidation: Amalgamation:

11.4 % 64.0 % 24.6 %

residues Fire Assay = splitting = optional

Studying of Liberation of Gold Ores

Clifton et al. (1969) calculated the size of sample required to contain 20 particles of gold (spheres) as a function of gold particles and grade, assuming that Au particles are uniform and randomly distributed. Size of Gold Particle (mm) 2.0 The mass of sample to be used is a function of the gold particle shape, size and distribution. 1.0 0.5 0.25 0.125 0.062 0.031 0.015 0.008 kg of sample required 4 ppm Au 400 50 8 1 0.1 0.02 0.002 0.0002 0.00002 1 ppm Au 1000 200 30 4 0.5 0.05 0.006 0.002 0.0001

Studying of Liberation of Gold Ores

According to Clifton et al. (1969) a precision of 50% is achieved at 95% certainty when a sample for analysis contains a minimum of 20 gold particles Usually 100 kg of a representative sample crushed below 1/4" (6.35 mm) is a good starting material. If gold particles are not larger than 0.25 mm (no nuggets), material can be stored in 1 kg bags after crushed below 6 Mesh (3.4 mm). When there is indication of presence of >1mm nuggets the entire process becomes complex as we cannot work with small samples. When the amount of sulfides in the ore is low (<2%) it is convenient to concentrate the screened fractions in heavy liquids before the microscopy (Gaudin Method)

History of Gold Cyanidation

Date 6th Century 1704 Name Jabir Hayyan Discovery Discovered aqua regia & that it dissolved gold 6HCl + 2HNO3 + 2Au 2AuCl3 + 2NO + 4H2O Discovered Prussian Blue (Fe4[Fe(CN)6]3) by accidentally combining dried blood with potash (K2CO3) and treating with iron vitriol (FeSO4) C.W. Schule K.F. Plattner Discovered chlorine & that it dissolved gold Applied chlorination to gold recovery 2Au + 3Cl2 2AuCl3

Gold Cyanidation

1774 1852 Early 1700s 1782

P.J. Discovered potassium ferrocyanide Macquer (K4[Fe(CN)6]) by combining Prussian Blue with Alkali (KOH) C.W. Schule Discovered Blue Acid by heating Prussian Blue with Dilute Sulphuric Acid

Date 1811 1834

Name J.L. GayLussac

Discovery Determined Blue Acid was HCN Potassium cyanide produced by fusing potassium ferro cyanide with potash K4[Fe(CN)6] + K2CO3 6KCN + FeCO3

Cyanidation Process (theories)

1. Oxygen Theory, L. Elsner (1846)
4Au + 8NaCN + O2 + 2H2O 4NaAu(CN)2 + 4NaOH

1840 1846

Elkington L. Elsner

Patented process using KCN to prepare electrolyte for electroplating Au and Ag Recognized importance of oxygen to dissolution of Au with cyanide 4Au + 8KCN + O2 + 2H2O 4KAu(CN)2 + 4KOH Patented process for dissolution of Au from ore using weak cyanide solution and to precipitate Au with zinc shavings. Process was considered a significant improvement over amalgamation and chlorination.

2. Hydrogen Theory, L. Janin (1888)

2Au + 4NaCN + 2H2O 2NaAu(CN)2 + 2NaOH + H2

3. Hydrogen Peroxide Theory, G. Bodlander (1896)

2Au + 4NaCN + O2 + 2H2O 2NaAu(CN)2 + 2NaOH + H2O2 H2O2 + 2Au + 4NaCN 2NaAu(CN)2 + 2NaOH 4Au + 8NaCN + O2 + 2H2O 4NaAu(CN)2 4NaOH

1887

J.S. MacArthur, R.W. Forrest, W. Forrest

Cyanidation Process (theories)

4. Cyanogen Formation, S.B. Christy (1896)
O2 + 4NaCN + 2H2O 2(CN)2 + 4NaOH

Factors Affecting Cyanidation

Hedley and Tabachnick (1968) listed the main factors affecting cyanidation: dissolved oxygen pH stability of cyanide solutions cyanide concentration gold particle size and shape accessibility of cyanide to gold (exposure) silver content (silver dissolves slower than gold) temperature presence of minerals consuming oxygen presence of cyanicides
Hedley, N. and Tabachnick, H., 1968. Chemistry of Cyanidation. Mineral Dressing Notes, n. 23. American Cyanamid Co. Veiga, M.M. and Klein, B. (2005). Cyanide in Mining. Edumine.com.

5. Corrosion Theory, B. Boonstra (1943)

O2 + 2H2O + 2e H2O2 + 2OHAu Au+ + e Au+ + CN- AuCN AuCN + CN- Au(CN)2 Au + O2 + 2CN- + 2H2O + e- Au(CN)2- + 2OH- + H2O2

Cyanide Stability
CN- + H2O = HCN + OHAu Dissolution Rate

pH of Gold Cyanidation
NaOH Ca(OH)2 10.5

bitter almond smell

pH Au cyanidation is more efficient at pH=10.5 Ca(OH)2 precipitates on gold surface inhibiting the cyanide attack .avoid high pHs

Oxygen in Cyanidation

Cyanidation Process
Mechanisms Oxygen adsorption into solution Transport of dissolved O2 and CN- to S/L interface Adsorption of O2 and CN- onto gold surface Electrochemical reaction Desorption of soluble Au-CN complexes (e.g. Au(CN)2-) and other reaction products from solid surface Transport of soluble products into solution

The level of dissolved oxygen controls the kinetics of gold cyanidation The concentration of cyanide does not usually determine the rate of the gold cyanidation reaction The level of dissolved oxygen required for the cyanidation process depends on the cyanidation reactions and cyanide consumption by other substances (cyanicides). The concentration of dissolved oxygen also depends on: - pressure (altitude) - temperature - agitation - ionic strength of the solution

Normal Cyanidation
In normal conditions of cyanidation, the minimum NaCN concentration to extract gold is 75 mg/L. 4 Au + 8 NaCN + O2 + 2 H2O = 4 Na[Au(CN)2] + 4 NaOH Gold cyanidation employs diluted sodium or potassium cyanide solutions containing 100 to 1000 mg/L. In average 100 tonnes of NaCN are needed to extract 1 tonne of gold Most plants operate at between pH 9.5 and 11.5. Cyanide consumption usually is between 0.05 and 5 kg NaCN/tonne of ore .for cyanidation of concentrates, the cyanide consumption can be higher (>5 kg/t)

Silver Slows Down Cyanidation

Some Minerals Consume Cyanide

Some of the cations that form stable complexes with cyanide, and in the process consume cyanide, are: Cu+, Cu2+, Fe2+, Fe3+, Mn2+, Ni2+, Zn2+. One way to eliminate the cyanide consumption problem is to remove cyanicide, e.g. pyrrhotite, by magnetic separation or flotation (assuming it does not contain a significant amount of associated gold) prior to cyanidation. Other methods include adding lead nitrate, or oxidation of the sulfides by pre-aeration, oxygen or peroxide.

Effect of Lead Nitrate

Lead nitrate reduces cyanide consumption and speed up the gold leaching reaction Pb forms insoluble PbS removing passivation ions (S2+) from gold surface Local galvanic cells between is also formed on gold surface In a cyanide solution, lead nitrate, lead sulfide and lead sulphite react with gold to form AuPb2, AuPb3 and metallic lead, which clearly accelerate the gold dissolution

Deschenes et al (2000/ Minerals Engineering v.13, n.12, p.1263-1279.

10

Effect of Lead Nitrate

50 g/t Pb(NO3)2

Some Minerals Consume Cyanide

Au Extraction (%)

No Pb(NO3)2

Time (h)

Ore: 4.2 g/t Au, 0.9 g/t Ag, 3.1 pyrrhotite, 0.4% pyrite, Conditions: 0.38 g/L NaCN, pH 10
Deschenes et al (2000/ Minerals Engineering v.13, n.12, p.1263-1279.

Some Minerals Consume Cyanide

Some Minerals Consume Cyanide

Pyrrhotites range from Fe5S6 to Fe16S17

Some Minerals Consume Cyanide

Some Minerals Consume Cyanide

When high concentrations of cyanideconsuming minerals (in particular Cu minerals) exist in a ore, cyanidation may become uneconomical as this results in poor gold recovery and high operating costs The ammonia-cyanide leaching system is an alternative approach. It is proposed that the ammonia stabilizes a copper(II)-ammoniacyanide complex such as Cu(NH3)4(CN)2 that is responsible for gold dissolution

11

Preg-Robbing Ore
Gold in solution can also be adsorbed by some mineralogical components of the ore. These are known as 'preg-robbing' substances. The most common preg-robbing substances are carbonaceous materials which are organic substances with high surface area. Not all carbonaceous material is activated

Preg-Robbing Ore
One way to eliminate this effect, in milder cases, is addition of diesel or kerosene to the leach to deactivate the carbonaceous matter, This has to be done with caution otherwise the posterior carbon-in-pulp (CIP) process (adsorption of gold on activated charcoal) could be adversely affected. The addition of kerosene can effectively passivate the carbonaceous material by coating it. This process is suitable for ore with less than 1% carbonaceous material.

Preg-Robbing Ore
In other circumstances, the organic matter must be eliminated prior to cyanidation by flotation or by oxidization / burning Most common procedure to overcome this effect is the CIL (carbon-in-leach) process. AC is introduced into the leaching process and soluble gold is immediately adsorbed by the charcoal. The process takes advantage of the fact that the adsorption kinetics of gold on charcoal is faster than it is on the preg-robbing mineralogical species

Preg-Robbing Ore

Source: Marsden, J.O, House I. 2006. The chemistry of gold extraction. 2nd ed. Littleton, CO: SME Society for Mining, Metallurgy and Exploration. 651p

Recovering Gold from Cyanide Solutions

Gold can be recovered from CN solution by 3 methods: Activated Charcoal (AC) Adsorption Zinc precipitation (Merrill-Crowe Resin Adsorption The first two are the most popular methods Adsorption with Activated Charcoal (AC) Carbon-in-Pulp (CIP) Carbon-in-Leach (CIL) Carbon-in-Columns (CIC)

Recovering Gold with Activated Charcoal

Ore or Conc. Cyanidation
pulp

Ore or Conc. Cyanidation with AC

AC

Ore or Conc. Cyanidation

solution

CIP
AC

Separation S/L
solution

Elution
Au rich solution

Elution Electrolysis Gold

Columns with AC
AC

Au rich solution

Electrolysis Gold

Elution
Au rich solution

Electrolysis Gold

AC = activated chacoal

12

Recovering Gold with Activated Charcoal

Activated Charcoal (AC) Properties: - Adsorptive Capacity (porous) - Adsorption Rate - Mechanical Strength and Wear Resistance - Reactivation Characteristics - Coarse Grain Size Most AC are manufactured from coconut shell Other materials can also be used anthracite, peat, etc.

Recovering Gold with Activated Charcoal

The CIP method (Carbon-in-Pulp ) makes use of the physical affinity that activated charcoal (AC) has for gold (it can attract 7% of its weight in gold), which it readily attracts to its surface in cyanide solution. Usually the industry does not load the AC with more than 8000 g Au/t charcoal = 0.8% The following figure shows that less gold stays in solution when the max load is 5000 ppm Adsorption rate on AC is rapid initially as Au adsorbs to most accessible sites but then decreases as rate controlled by diffusion along pores.

Recovering Gold with Activated Charcoal

Recovering the AC
As the particles of AC are coarser than the ground ore, the AC is screened after the cyanidation The fine material is sent to cyanide destruction Some fine AC particles (with Au) can be lost if the charcoal does not have good physical properties
Ecuador, 2009

Source: Marsden, J.O, House I. 2006. The chemistry of gold extraction. 2nd ed. Littleton, CO: SME Society for Mining, Metallurgy and Exploration. 651p

Elution of Activated Charcoal

After loading the AC, gold must be extracted (eluted) from the charcoal surface Elution procedures are very variable. Just a high pH solution can strip Au from the AC, but this takes time. Usually companies use a cyanide solution 1-2 g/L and 10 g/L of NaOH and temperature 90-100 oC and up to 72 hours to strip >97% gold from AC Elution is not done everyday. Wait for the charcoal to be loaded (5000 8000 gAu/t AC)

Elution of Activated Charcoal

Solvents such as ethanol (10 to 20% vol) can speed up the process to be completed in 8 hours The elution solution, now with 1000 to 3000 mg Au/L (ppm) is submitted to electrolysis Some people use Zn to precipitate Au from the elution solution Excess zinc is dissolved with acid, and gold is melted

13

Elution - Stripping of Au from AC

Recovering Gold with Activated Charcoal

Figure: the elution solution (7 m3) is heated in a diesel oil burning column and pumped through two columns filled with the loaded activated charcoal Stainless steel columns work in series to the electrolysis cell and then to a large holding tank, insulated with Styrofoam in a wooden box which in turn feeds the heating vessel.

Elution columns in Portovelo, Ecuador

Recovering Gold with Activated Charcoal

After elution, the AC must be treated with nitric or hydrochloric acid to remove contaminants. Usually the charcoal is treated after 10 to 12 times of use After acid treatment, the AC is heat to 500 C. Impurities are removed as gases or remain as a tar-like residue. Then the charcoal is exposed to an oxidizing atmosphere of steam containing CO2 and O2 at 700 1000 C. This burns off the tar-like residue, develops internal pore structure, and the carbon atoms at the edges of crystallites become 'active sites' due to unsaturated valencies.

Typical Carbon-in-Pulp Process Flowsheet

Ore or Conc. Re-cycle to Process Comminution Cyanide Leach
pulp

CIP
AC

Cyanide Destruction Tailings Pond

solution

Elution Electrolysis Gold

solution

In the case of leaching concentrates, comminution is not always needed

Recovering Gold with Zinc

The Merrill-Crowe process is usually preferred over the charcoal process when the pregnant solution is high in Ag, or other metals like Hg, as these metals very quickly plug the pores of the charcoal 4Au + 8CN- + O2 + 2H2O = 4Au(CN)2- + 4OH2Au(CN)2- + Zn = Zn(CN)42- + 2Au (Merrill-Crowe process) Pulp is filtered and the clarified solution is then passed through a vacuum de-aeration tower where oxygen is removed from the solution. Zinc powder is added to the solution with a dry chemical feeder. The reaction of the special fine powder zinc with the solution is almost instantaneous. Precipitated gold is recovered by filtering.

Merrill-Crowe Process
(Factors Affecting Zinc Precipitation) Suspended solids - interfere with the process possibly by coating the Zn particles and contaminate the final concentrate. Therefore, leach slurries are filtered to remove solids prior to Zn precipitation. Dissolved Oxygen - oxygen reduction competes with Au reductions, therefore, dissolved oxygen reduces precipitation kinetics. De-aeration is required to lower dissolved oxygen levels to <0.5 - 1.0 mg/l prior to precipitation. pH - the process is not very sensitive over pH range of 9 to 12. Above and below this range, precipitation decreases

14

Merrill-Crowe Process
(Factors Affecting Zinc Precipitation) Cyanide concentration - minimum concentration required otherwise rate of precipitation is reduced (Typically > 0.05 - 0.20 g/L)

Typical Merrill-Crowe Process Flowsheet

Ore or Conc. Comminution
solution

Re-cycle to Process

Temperature - precipitation kinetics are accelerated at elevated temperatures Gold concentration - precipitation rate increases with Au grade of solution Zinc concentration - at high Zn concentrations, the dissolution rate of Zn can be slow. Also, high Zn concentrations can lead to formation of insoluble Znhydroxide which passivates Zn surface. Zn added at 5 to 30 times the stoichiometric Au requirement.

Cyanide Leach
pulp pulp

S/L Separation
solution

Settling Tank
pulp

solution

pulp

Precipitation w/ Zn Leach with Acid Precipitate w/Al

Cyanide Destruction
pulp

Tailings Pond
In the case of leaching concentrates, comminution is not always needed

Gold

Zinc

Electrowinning
Instead of Zn precipitation, electrolysis can be used to treat high-grade gold solutions (carbon eluates) to produce loaded cathodes or cathode cell sludges Au(CN)2- + e- Au + 2CN Advantages (over Zn precipitation) No chemicals or metals introduced in process More selective for Au and Ag over Cu Higher purity product Disadvantages Low single pass efficiency per unit cell requiring recirculation of solution to achieve acceptable extraction It needs high Au concentration in solution

Main Cyanidation Practices

Agitated Tanks
CIP (Carbon-in-Pulp) CIL (Carbon-in-Leach)

Static leaching
Vat leaching with Carbon-in-Column or Zinc ppt Heap leaching with Carbon-in-Column or Zinc ppt

Intensive cyanidation (for concentrates)

Gekko Acacia Mill-leaching (cyanidation in a small ball-mill)

Cyanidation in Agitated Tanks in Small-scale Cyanidation is being used in 160 tanks in Zaruma-Portovelo region Tanks range from 10 to 20 m processing from 4 to 20 tonnes/day Some plants use either MerrillCrowe or CIP (Carbon-in-Pulp) techniques
Ecuador, 2009

Cyanidation in Agitated Tanks in Small-scale CIP: 3 tanks = 9 hours, 100 tonnes/d, 2 g Au/t 0.7 g NaCN/L, consumption = 2.5 kg NaCN/t of ore

Ecuador, 2009

15

Cyanidation in Agitated Tanks in Small-scale

Merrill-Crowe process in Ecuador The concrete tanks are loaded with 3,600-4,500 kg of sluice (canalone) concentrate and filled with about 11 m3 of cyanide solution that ranges from 2 to 4 g NaCN/L. After 12 hours, agitation is stopped to allow the pulp to settle. The semi-clarified solution flows by gravity to a holding tank and then through 4 clusters of 4 PVC columns containing a total of 11 kg of zinc shavings. Gold precipitation is not efficient as it is not conducted in vacuum. Miners do not leach Zn with acid to obtain gold, they simply evaporate the zinc (bad practice!!!)

Cyanidation in Agitated Tanks in Small-scale Merrill-Crowe process in Ecuador

Ecuador, 2007

Cyanidation in Agitated Tanks in Small-scale Merrill-Crowe process in Ecuador

Cyanidation in Vats Vat leaching: cyanide solution slowly percolates through ore in a static tank. Ore can be coarser than in agitation leaching, with sizes of <1 cm. Ore is not agitated and coarse material must have good permeability. Very fine grain sizes of <1 mm may tend to block the free circulation of the leaching agent. The leaching period is 2 to 4 days and gold recovery is approximately 70 to 80%.

Ecuador, 2007

Some artisanal miners leach for 30 days

Cyanidation in Vats

Vat-leaching in the Tapajs Region, Amazon, Brazil

Tailing pond (baixao)

Vat-leaching tank

Pool with CN solution

Artisanal Gold Miners in Zimbabwe using Amalgamation Tailings to fill the cyanidation vat
Tanks with activated charcoal

Pool with pregnant solution

96

16

Cyanidation in Heaps Heap Leaching: the cheapest but slowest technique of gold cyanidation It is a process usually applied to low-grade gold ore. The ore is piled to a given height on an inclined impermeable surface, a so-called leach pad. A sprinkler system provides a continuous spray of alkaline cyanide solution that percolates through the ore, dissolving the gold. The gold-bearing or pregnant solution is collected and pumped to a gold recovery plant.

Heap Leaching

http://www.sulliden.com/projects/shahuindo-gold-project.aspx

Cyanidation in Heaps The amount of material contained in a heap can reach 400 million tonnes (Yanacocha). Leaching time ranges from several weeks to a few months. Gold recovery rarely exceeds 70%

Cyanidation in Heaps
Yanacocha Mine, the 4th gold producer in the world. Location: Cajamarca, Peru, 4700 m above sea level Started in 1993. In 2005, produced: 3.3 Moz gold Ore Production: 544,000 tonnes/d @ 0.9 g Au/t Rock is crushing and agglomerated with cement before going to the heap. Au recovery = 74% Waste:Ore Ratio ~0.40 Solution: 0.1 g/L NaCN, pH 10.5, 10 L/h/m2, NaCN consumption 0.06 kg/t ore

Installing the plastic pads

http://www.mining-technology.com/projects/minera/

Yanacocha Mine, Peru

http://www.mining-technology.com/projects/minera/minera2.html

Au is adsorbed on activated charcoal, and then eluted solution is precipitated with zinc or submitted to electrolysis
http://www.geomineinfo.com/Complimentary%20Downloads/Yanacocha.pdf

Intensive Cyanidation
Many mining companies do not concentrate gold before leaching it with cyanide The whole ore cyanidation is a common practice usually when gold is very fine, hard to liberate but the rock is prorous to allow penetartion of cyanide solution The operating cost of whole ore leachingis higher than cyanidation of concetrates also called intensive cyanidation The cost of destroying cyanide is high when the whole ore is leached

Intensive Cyanidation
Coarse gold takes a long time to be dissolved in normal cyanidation solutions. In normal conditions of cyanidation the solubility rate of pure metallic gold is 3.25 mg/cm2/hour. Pure silver dissolution rate is 1.54 mg/cm2/hour. The more silver, the slower is the dissolution of the Au-Ag alloy Then a pure gold grain of 44 m (400 mesh) would take about 13 hours to dissolve. A 150 micron (100 mesh) diameter pure gold particle would need almost 44 hours to dissolve.
Hedley, N. and Tabachnick, H., 1968. Chemistry of Cyanidation. Mineral Dressing Notes, n. 23. American Cyanamid Co.

17

Intensive Cyanidation
In the past many companies used gravity concentration followed by amalgamation of the gold in the concentrate. Amalgamation was used to remove the coarse (100 m) gold The tailings from amalgamation was leached with cyanide. Problem: this forms mercury cyanide which is very toxic and also consumes cyanide. Most organized mining companies no longer use amalgamation artisanal miners use 1000 tonnes Hg/annum

Intensive Cyanidation
If the ore has coarse gold (>100 m), companies use gravity concentration and/or flotation. They concentrate gold until >3000 g Au/tonne and melt it with borax. Problem: gold can be in the slag and this must be leached with cyanide or all middling products in the gravity sep. must be recyled Recently, mining companies are concentrating gold (gravity or flotation) followed by leaching the concentrate: Intensive Cyanidation

Intensive Cyanidation
To leach coarse gold a strong oxidant is needed. The concentration of the oxidizing agent is more important than a high cyanide concentration. High concentration of cyanide is used because, in an oxidant environment, cyanide will be oxidized as well, forming cyanate (CNO-). 5 to 20 g/L of NaCN is used Use of catalysts Leachwell or LeachAid or hydrogen peroxide (up to 0.5 g/L) is common Temperature can also increase cyanidation rate

Intensive Cyanidation
Intensive cyanidation of gravity and flotation systems have been used by GEKKO and Acacia Systems The GEKKO process is a thin film in a drum

Intensive Cyanidation
Acacia System CS 250: 375 kg conc./cycle Knelson Centrifuge provide concentrates for the reactor

Intensive Cyanidation
Acacia System:
Pre-washing of the gold concentrate to remove ultra-fine solids (slimes) NaOH, NaCN and LeachAid Agitation for 16 hours with warm CN solution Decanting and wash the solids with water Electrowinning Tailings sent to the normal cyanidation circuit

http://www.knelsongravitysolutions.com/page361.htm http://www.knelsongravitysolutions.com/page361.htm

18

Intensive Cyanidation
A good methodology to investigate intensive cyanidation of gravity concentrates can be: Concentrate is ground with different times and leached with cyanide (5 to 20 g/L) for 1 to 12 hours, 40% solids and pH 10.5 to 11 and presence of H2O2 (0.3 g/L = 100mL of 3% v.v. H2O2 solution in 1 L of water) It is always useful to do CIL Carbon-in-Leach process to avoid any preg-robbing effect

Intensive Cyanidation
(Mill-leaching)
The ore is not primarily finely ground (this can be conducted in a hammer-mill) Gold concentration in centrifuge or in sluice boxes or jig or flotation Unliberated gold is also concentrated = pre-concentration Concentrate is taken to a small batch ball-mill with cyanide and a capsule of activated charcoal Leached for 8 hours with 10-20 g/L NaCN and 0.3 g/L H2O2, pH 10.5. Remove the capsule of activated charcoal Elution Electrolysis or precipitation with zinc and leaching with acid

Veiga,M.M.; Nunes,D.; Klein,B.; Shandro,J.A.; Velasquez,P.C.; Sousa,R.N. (2009). Replacing Mercury Use in Artisanal Gold Mining: Preliminary Tests of Mill-Leaching. J. Cleaner Production, v.17, p.13731381

Small-scale Intensive Cyanidation implemented in Tapajs, Brazil

+2mm Screen 2 mm -2mm Icon centrifuge tailing Icon centrifuge tailing flotation Hammer mill Gold ore

A Simple Intensive Cyanidation System

Icon centrifuge: 2 tonnes/h of ore

co nc .
conc. Intensive Cyanidation activated charcoal elution

. nc co

final tailing

electrolisis

meting gold

Icon (Falcon) centrifuge

A Simple Intensive Cyanidation System

Re-grinding the centrifuge concentrates

Source: Falcon website, 2009

Capacity: 2t/h Pulp: 30% solids Cycle: 15 to 30 minutes Bowl: 1kg concent. (dry) Day: 40 to 80kg conc Au recovery: 50 to 65%

Capsule of activated charcoal in the ball mill

Sousa,R.N.; Veiga,M.M.; Klein,B.; Telmer,K.; Gunson,A.J.; Bernaudat,L. (2010). Strategies for Reducing the Environmental Impact of Reprocessing Mercury-contaminated Tailings in the Artisanal and Small-scale Gold Mining Sector: Insights from Tapajos River Basin, Brazil. In press by Journal of Cleaner Production.

19

Intensive Cyanidation in Ball Mill

This is an easy procedure Replace the use of Hg in these small ball-mills Capsule of activated charcoal can be added together with rods or balls but this depends on the resistance of the capsule If necessary grind first, remove rods and add the AC capsule later

Centrifuge concentrate [CN] 20 g/L, 0.3 g/L H2O2 grinding Same but no grinding

Conventional cyanidation Head sample, [CN] 1g/L, pH 10-11, no grinding

Ecuador, 2009

Sousa,R.N.; Veiga,M.M.; Klein,B.; Telmer,K.; Gunson,A.J.; Bernaudat,L. (2010). Strategies for Reducing the Environmental Impact of Reprocessing Mercury-contaminated Tailings in the Artisanal and Small-scale Gold Mining Sector: Insights from Tapajos River Basin, Brazil. In press by Journal of Cleaner Production.

Intensive Cyanidation Tests in Ecuador

Concentrate from sluice boxes (17,3 g Au/t) was split in 3 subsamples: Amalgamation (160 kg) Conventional cyanidation in tank (695 kg) Intensive cyanidation in ball mill (80kg)

Result of Amalgamation
Manual amalgamation 8 hours in a batea with mercury and brown sugar Gold recovery from the gravity concentrate after amalgamation was: 26%

Ecuador, 2007

Ecuador, 2007

Result of Conventional Cyanidation

In agitated tank pH = 11 Gold recovery from the gravity concentrate after 31 horas was: 94% NaCN consumption was 4.5 kg/t of concentrate

Result of Intensive Cyanidation in Ball Mill Gold recovery after 8 hours of millleaching the concentrate was: 95% Cyanide consumption was 0.95 kg/t of concentrate

Ecuador, 2007

20

Results of Elution of Activated Charcoal

NaCN = 2g/L, NaOH = 10 g/L Alcohol = 20% Temperature: 90 C, 8 h 97% of gold removed from the activated charcoal Gold precipitated with small amount of zinc Zinc leached with HNO3 Zinc can also be precipitated with aluminum (cementation)
Ecuador, 2007

Intensive Cyanidation (conclusion)

For environmental and economic reasons, intensive cyanidation of gravity and flotation concentrates must be the future of gold mining industry. Coarse gold particles (up to 1 mm) can be leached in intensive cyanidation circuits the use of catalysts (oxidants) is fundamental. This reduces liability and operating costs Capital costs is not much higher but depends on flotation and gravity concentration circuits

Diagnosis Leaching
This is a procedure to assess why the gold is not being extracted by classical cyanidation (low CN concentration and no peroxide)

Tests to Check Accessibility of Cyanide to Gold Particles

First of all, the sample must be ground below 0.1 mm, homogenized and 30g obtained to make a fire assay Fire assay is a procedure to melt (~1200 oC) the whole material with borax, lead oxide and a source of carbon (e.g. flour). The carbon reduces the PbO and the lead carries the precious metals to the bottom of the crucible. The lead button is placed into a cupel, which is a small dish made from fishbone ash, and placed into a furnace. Lead volatilizes and soaks into the cupel, leaving a small "bead" of precious metals. The bead is leached with aqua regia and analyzed by atomic absorption spectrometry

Diagnosis Leaching
Another subsample of the ground material (200 g) is leached with cyanide 1 g/L (467 mL) for 24-48 hours (rolling bottles or agitated beaker) using 30% of solids, pH 10.5, ambient temperature. During the test, check free cyanide consumption (titration with AgNO3) and eventually add more cyanide if needed. Some people keep the rolling bottles for 72 h, but this depends on how much coarse gold has the material. You can pan a bit of the material to check the presence of coarse (>0,1mm) gold Filter the solution and send it to be analyzed by atomic absorption. Wash, dry and keep the residue. With the result from the atomic absorption you can check if the total gold was dissolved in cyanide

Diagnosis Leaching
%Au extracted = mg gold in solution (volume was 467mL) mg of gold in sample (weight was 200g) If total gold was not extracted use the filtration residue (now it its dried). Regrind it, weigh it and leach it again with cyanide in most cases this solve the problem but the question is how fine you must grind the material (ore or concentrate)? It is not suggested to grind too fine since this is a very expensive operation in a real plant Grind below 200 mesh (0.074mm) and use same leaching with CN conditions as above Filter and send solution to atomic absorption. Wash, dry and keep the residue.

21

Diagnosis Leaching
If the total gold was not extract yet, gold can be occluded in the sulfide minerals. Weigh the dry residue. Oxidize sulfides using 2M HCl and 100 g/L as FeCl3, at boiling temp. for 6 to 24 h, L:S=2:1. Use an agitated beaker. Filter the sample, wash it and keep solution (measure the volume). If you notice in the wet solids some sulfides, add on the wet sample nitric acid 1:1 (HNO3 55%: distilled water) L:S=10:1 (approximately) Filter it, wash it well (measure the volume of solution). All acid solutions must be analyzed as acid + oxidizing agent can dissolve some gold (some authors found gold in solution) Dry and weigh residue Fe3+

Diagnosis Leaching
Leach the residue with cyanide using similar conditions as above. Filter and keep residue. Send solution to atomic absorption If the total gold was not extracted yet and the sample has organic matter (dark color), use the filtration residue from the previous leaching step Check if gold is adsorbed on organic matter. Extract gold using 40% v/v acetonitrile in distilled water, 10 g/L sodium cyanide, and 2 g/L NaOH, 16 hours, L:S = 5:1 filter, wash and analyze solution. Dry residue. If total gold was not extracted yet use filtration residue. Probably the acetonitrile was not enough to extract all organic matter

Diagnosis Leaching
An ultimate test is to burn carbonaceous material off in a furnace at 700 C for 6 hours and repeat cyanidation. This can also roast any residual sulfide Leach silicates with HF and filter. L:S=10:1 Residual gold: leach the residue with aqua regia: 3 HCl + 1 HNO3. L:S=10:1 Analyze solution now the total gold was definitely extracted. Based on the weight of each leaching step calculate the % gold extracted in each step. The sequence of leaching can have more steps depending on the mineralogical phases to be investigated
Adapted from Lorenzen, L. (1995). Minerals Engineering, v. 8, n. 3, p. 247-256

Environmental Management of Cyanide

Use of Cyanide
About 1.4 million tonnes of hydrogen cyanide (HCN) are produced annually worldwide. Cyanide price is around US$ 1.1 and 1.3 per kilogram but now increased to near US$ 3/kg

Use of Cyanide
According to the ICMI International Cyanide Management Institute, 1.4 million of HCN is produced annually in the the world. This is equivalent to 2.5 million tonnes of NaCN. About 13% is used in the gold mining industry. This is equivalent to 325,000 tonnes/a of NaCN.

Gold Mining 13% Other 2%

Used in production of Organic Chemicals 85%

Used for NaCN production

ICMI (2010). International Cyanide Management Institute. http://www.cyanidecode.org/cyanide_use.php

22

Gold Uses

Gold Uses

Source: Elma van der Lingen (2005). Golds Other Uses, The LBMA Precious Metals Conference 2005, Johannesburg, p.75-80

Source: Elma van der Lingen (2005). Golds Other Uses, The LBMA Precious Metals Conference 2005, Johannesburg, p.75-80

Gold Mine Production 2009

(tonnes) 1. China (314) 2. Australia (227) 3. United States (216) 4. South Africa (205) 5. Russia (205) 6. Peru (180) 7. Canada (95) 8. Ghana (90.2) 9. Indonesia (90) 10. Uzbekistan (80)

Gold Consumption
The total gold produced in the world: 161,000 tonnes; enough to fill 2 Olympic swimming pools India is the largest gold consumer. In 2008 consumed 660.2 tonnes Au In 2008 China consumed 395.6 tonnes of gold

Photo: http://goldprice.org/buyinggold/uploaded_images/indian-gold-742896.jpg

Total: 2572 tonnes

Others (854)

Source: Goldsheet. http://www.goldsheetlinks.com/production.htm

Use of Cyanide
Cyanidation employs diluted sodium or potassium cyanide solutions containing 50 to 500 mg/L (free cyanide is typically 50 to 100 mg/L). Cyanide consumption is typically 300 to 2000 g NaCN per tonne of ore. In average 100 tonnes NaCN is used to produce 1 tonne of gold. Cyanide concentration in effluents (Canadian gold industry) range from 0.3 to 30 mg/L (ppm). Cyanide is also used as a depressant to separate multiple sulfide ores by flotation (e.g.: depress chalcopyrite to float galena). Concentration of total cyanide in flotation effluents is <0.03 mg/L (ppm). Species Rainbow trout

Cyanide Toxicity
Temperature (C) 6 10 12 18 15 21 20 96-h LC50 (mg/L) 0.028 0.057 0.042 0.068 0.090 0.102 0.432

Yellow perch Snail

Higher temperature, lower toxicity

23

Cyanide Toxicity
Adverse effects on fish swimming and reproduction usually occur between 0.005 and 0.007 mg of free cyanide/L. Free cyanide concentrations between 0.05 and 0.2 mg/L are fatal to the more-sensitive species

Cyanide Toxicity
Public perception is that cyanide is very dangerous...
chemical warfare judicial executions mass suicides the Tylenol affair

A large majority of the public believes that cyanide is more dangerous than mercury...however cyanide is not persistent in the environment and Hg is. Problems: spills misuse of cyanide by Artisanal Gold Miners

Cyanide Toxicity
Jim Jones was the founder and leader of the Peoples Temple, in Jonestown, Guyana On November 18, 1978, 909 Temple members, including 276 children, drunk cyanide with Cool Aid

Cyanide Toxicity

Source: Infoczarina, 2008

http://www.chicagostagereview.com/wp-content/uploads/2008/09/jonestown1.jpg

Cyanide Spills
Baia Mare, Romania, mine re-opened in 1999. Intense rain in Jan 2000 = overflow 100,000 of tailings with cyanide released to the river 50 to 100 tonnes of cyanide released m3

Cyanide Spills
1000 tonnes of fish killed CN in the Danudbe Public reaction was horrible

24

Cyanide Spills
1995 Omai Mine in the Esequibo region in Guyana 4 millions m3 of cyanide contaminated tailings entered the Essequibo River Until now the use of cyanide in mining is not allowed in Guyana The use of Hg has increased

Rudimentary Cyanidation Plant made by Artisanal Miners in Zimbabwe

Amalgamation tailings (full of Hg) are submitted to cyanidation

http://www.ec.gc.ca/inre-nwri/default.asp?lang=En&n=0CD66675-1&offset=14&toc=show

Rudimentary Cyanidation Plant made by Artisanal Miners in Zimbabwe

Misuse of Cyanide
Increasing the use of Hg-amalgamation followed by cyanidation in Artisanal Mining. Cyanidation of Hg-rich tailings forms Hg(CN)42which is a very stable and persistent compound. This can be transformed into highly toxic compounds, e.g. Methylmercurycyanide

...at least they know that cyanide is dangerous!!!

Artisanal Gold Miners (Sulawesi, Indonesia)

Artisanal Gold Miners (Sulawesi, Indonesia)

Rudimentary tailing pond; often CN-rich tailings reach the streams

Recovering loaded charcoal (retained in a screen)

Only CN destruction method = NATURAL = sun light False perception that this destroys all cyanide complexes

25

Cyanide Toxicity
Free cyanide criteria currently proposed for the protection of natural resources: Free cyanide (CN- or HCN) criteria for the protection of aquatic life of natural resources: <0.005 mg/L (Canadian Water Quality Guidelines, 2001). for human protection:
drinking water in USA and Canada: MAC = 0.2 mg/L in drinking water in Sweden: 0.05 mg/L WHO Drinking water quality guideline: 0.07 mg/L (12 g/kg body weight) <50mg/kg in diet <5mg/m in air

Cyanide Toxicity
The cyanide toxicity depends on the cyanide species. The predominance of free cyanide (CN- and HCN) depends on the pH In solutions with pH above 10, free cyanide is as CN- and not as HCN gas The gold cyanidation is usually conducted at pH 10.5 to 11

Cyanide Toxicity (humans)

In solution, 3 to 5 mg of cyanide/kg body weight is lethal

Cyanide Toxicity (humans)

Cyanide is readily absorbed through inhalation, ingestion or skin contact. In respiratory exposure to hydrocyanic acid (HCN gas), death occurs at 0.1 to 0.3 g/m Cyanide is a potent asphyxiant. It induces tissue anoxia through inactivation of cytochrome oxidase due to the reaction of CN- and Fe3+. Oxygen cannot be utilized and death results from the depression of the central nervous system.

If a mine uses a CN solution of 300 mg/L A 100-kg person should drink 1.5 L to die You need to drink a lot of Cyanide solution to die

Cyanide Toxicity (humans)

Some plants such as sorghum, cassava, bamboo and lima beans can contain over 2,000 mg/kg total cyanide. At this level, ingestion of 170 g of the plant can be lethal to a 80 kg-human being. Congenital hypothyroidism (cretinism) is present in 15% of newborns in certain areas of Zaire where cassava is a staple food. This incidence is approximately 500 times that observed in industrial countries.

Fishing with Cyanide

Its forbidden to fish with cyanide and explosives

Ecuador, 2006

26

Cyanide Toxicity (humans)

Cyanide is detoxified by an enzyme called rhodanase forming thiocyanate CNS The major route of cyanide elimination from the body is via urinary excretion of thiocyanate (CNS). The toxicity of thiocyanate is significantly less than that of cyanide, but chronically elevated levels of thiocyanate in blood can inhibit the uptake of iodine by the thyroid gland, thereby reducing the formation of thyroxine.

Cyanide Toxicity (humans)

Cyanide does not accumulate in the blood and tissues following oral exposure to inorganic cyanide and no cumulative effect on the organism during repeated exposure has been demonstrated. There is a cumulative effect of exposure to thiocyanate resulting in thyroid toxicity, including goitre and cretinism.

Cyanide Toxicity (humans)

Organs affected by Chronic intoxication with cyanide (oral exposure):

Cyanide Toxicity (humans)

Organs affected by Chronic intoxication with cyanide (inhalation):

Central nervous system: neuropathies and amblyopia (partial or complete loss of vision in one eye caused by conditions that affect the normal development of vision) Thyroid: increase thyroid weights and depress thyroid function Reproduction and Development: congenital hypothyroidism was reported in human newborns Kidneys

Central nervous system: vertigo, equilibrium disturbances, nystagmus, nervousness, headache, weakness, loss of appetite, changes in smell and taste Cardiovascular and/or respiratory system: breathing difficulties Gastrointestinal tract: nausea, and gastritis Thyroid: Enlarged thyroids Reproduction and Development: risk of giving birth to low body weight infants and of perinatal death.

Cyanide Toxicity (hypothyroidism)

The main purpose of thyroid hormone is to "run the body's metabolism. It takes iodine, found in many foods, and convert it into thyroid hormones. Hypothyroidism results in inflammation of the thyroid gland and reduction of hormone production.

Cyanide Toxicity (congenital hypothyroidism)

Cretinism: Poor length growth Adult stature without treatment ranges from 1 to 1.6 m Neurological impairment Thickened skin Enlarged tongue Protruding abdomen
Sources: http://www.gidabilimi.com/images/kretenizm1.png Wikipedia

goitre
Sources: http://www.endocrineweb.com/thyfunction.html http://en.wikipedia.org/wiki/Goitre

thyroid gland normally weighs <30g

27

Important Toxicological Facts

The greatest source of cyanide exposure to humans and some animals is cyanogenic food plants and forage crops, not mining operations. Free cyanide is the primary toxic agent Cyanides are not mutagenic or carcinogenic. There is no indication that cyanide is biomagnified in food web. Cyanide has low persistence in the environment In general, the toxicity of free cyanide is reduced when a complex is formed.

Types of Cyanide
1. Free cyanide (HCN/CN-) and simple cyanide salts (NaCN, KCN) which dissolve in water to form free cyanide. Free cyanide is the active form to leach gold 2. Weak and moderately strong cyanide complexes such as cyanides of Zn(CN)42-, Cd(CN)3-, Cd(CN)42-, Cu(CN)2-, Cu(CN)32-, Ni(CN)42-, Ag(CN)2- These cyanides are known as Weak Acid Dissociable Cyanides (WAD) as they can be decomposed in weak acid (pH 3 to 6). 3. Strongly bound cyanide complexes such as Co(CN)64-, Au(CN)2-, Fe(CN)64-. These are stable under ambient conditions of pH and temperature

Free Cyanide
Determined by tritation with AgNO3 Silver will complex with free CN and excess of Ag+ is detected by p-dimethylaminobenzalrhodanine or by potassium iodide (KI) whihc are indicators AgNO3 + 2NaCN = NaAg(CN)2 + NaNO3 Color will change from yellow to blue (dimetyl) or a white bluish color in the case of KI Free cyanide is determined based on the volume of silver nitrate used in the titration Total CN is determined by another method... distillation

Complexes with Heavy Metal

In the leaching of gold, many other metals can be dissolved in cyanide forming complexes. Example of minerals soluble in cyanide:
Pyrrhotite - FeS Argentite - AgS Malachite - CuCO3.Cu(OH)2 Chalcocite - Cu2S Bornite - Cu5FeS4 Orpigment - As2S3 Galena - PbS, partially soluble Sphalerite - ZnS, partially soluble Pyrite - FeS2, sparingly soluble

Fate of Free Cyanide

Free cyanide seldom remains biologically available in soils and sediments because it is either complexed by trace metals, metabolized by various microorganisms, or lost through volatilization. Under aerobic conditions, cyanide salts in the soil are microbiologically degraded to nitrites or form complexes with metals. Under anaerobic conditions, cyanides denitrify to gaseous nitrogen compounds and enter the atmosphere. All cyanide complexes are subjected to (biotic and abiotic) oxidation.

Main Cyanide Reactions

Hydrolysis Oxidation of HCN/CNCN- + H2O = HCN + OH2HCN + O2 = 2HCNO 2CN- + O2 + catalyst = 2CNO-

Hydrolysis of CNO HCNO + H2O = NH3 + CO2 Hydrolysis/saponification of HCN + 2H2O = NH4COOH or HCN + 2H2O = NH3 + HCOOH HCN Aerobic biodegradation Thiocyanate formation Cyanide compound dissociation Metal-cyanide complexation Anaerobic biodegradation 2HCN + O2 + enzyme = 2HCNO
2 S2 x + CN = S x 1 + CNS

2 2 S2O 3 + CN- = SO 3 + CNSNaCN = Na+ + CN Zn2+ + 4CN- = Zn (CN ) 2 4

CN- + H2S = HCNS + H+ HCN + HS- = HCNS + H+

28

Cyanide Cycle
NH3 + CO2 HCN/CNcyanidation tank evaporation and decomposition spill tailing pond River NH3 + HCO3or

Cyanide Treatment Processes

Natural Degradation (Lagooning) Oxidation Processes Alkaline Chlorination Electrochemical Processes Ozonation Hydrogen Peroxide INCOs SO2/Air Process Precipitation (Cuprous Process)

tailing with cyanide HCN/CNNO3-

Fe(CN)63Fe(CN)64-

CO32-

CH4 + CO2

Cyanide Treatment Processes (cont.)

Conversion to Less Toxic Forms Biological Treatment Cyanide Recovery Processes Acidification/Volatilization/Reneutralization AVR Ion Exchange Activated Charcoal Electrolytic Processes

Natural Degradation
It is the oldest treatment method used by Canadian gold mines to remove cyanide from effluents. Volatilization is the main mechanism. The most important variables are:
pH temperature UV light aeration biodegradation precipitation conversion to thiocyanate

Other variables:

Natural Degradation
The equilibrium between free cyanide species (CNand HCN) is pH dependent: HCN = H+ + CN[ H ].[ CN ] = 4 .93 x10 10 [ HCN ] Molecular HCN has high vapor pressure and therefore can readily be volatilized to the atmosphere. At pH 7, 99.5% of free cyanide exists as molecular HCN. Kd =

Stability of Cyanide Complexes

Cyanide Complex Co(CN) 4 6
Fe(CN ) 4 6 Hg( CN ) 2 4

Dissociation Constant 10-50 10-47 10-39 10-37 10-33 10-30.7 10-30 10-29.2 10-21 10-21 10-20.4 10-19

Dissociation constant

Au( CN ) 2
Cr ( CN ) 3 6 Cu( CN ) 2 4 Ni( CN ) 2 4 Cu( CN ) 2 3 Cr ( CN ) 4 6 Zn( CN ) 2 4

Free cyanide is rare in mining tailings because of the high reactivity of the CN- molecule with metal ions.

(CN-/HCN)

Ag( CN ) 2
Cd ( CN ) 2 4

29

Natural Degradation

Cyanide Guidelines (Canadian Legislation)

Strong-acid dissociable cyanide plus thiocyanate g/L (as CN) 200 g/L Strong-acid dissociable cyanide g/L (as CN) Not applicable Weak-acid dissociable cyanide g/L (as CN) Not applicable < or = 5 g/L 10 g/L

3 4 Ferrocyanides ( Fe( CN ) 6 ) and Ferricyanides ( Fe (CN ) 6 ) are very stable compounds. They can form complexes with trace metals. Most complexes are insoluble, e.g.: SnFe (CN ) 6 = tin(IV) ferrocyanide

Water Use

Fe 4 [ Fe( CN ) 6 ]3 = ferric ferrocyanide

Co 3[ Fe( CN ) 6 ]2 = cobalt ferricyanide

Sn 3 [Fe(CN ) 6 ]2 = tin(II) ferricyanide

Raw Drinking Water (maximum) Freshwater Aquatic Life (30-day average) Freshwater Aquatic Life (maximum) Marine and Estuarine Aquatic Life (maximum at any time)

Not applicable None proposed Not applicable None proposed

Major environmental concern:

ferrocyanides and ferricyanides (usually in the sediments) can form free cyanide by influence of ultraviolet light This reaction can take hundreds of years

Not applicable None proposed

1g/L

British Columbia Approved Water Quality Guidelines (Criteria) 1998 Edition

Cyanide Guidelines
The Canadian MMER (Metal Mining Effluent Regulation, 2002): maximum level of total cyanide to be released in a mining effluent is 1.0 mg/L (ppm) as a monthly average concentration, 1.5 mg/L in a composite sample and 2 mg/L in a grab sample. In Yukon Territory, the discharge limits are 0.5 mg/L of total cyanide and 0.2 mg/L of WAD (weakly acid dissociable) The World Bank guidelines (1995) for discharge into the environment are:
Free Cyanide: 0.1 mg/L Weak Acid Dissociable: 0.5 mg/L Total Cyanide: 1.0 mg/L. In no case should the concentration in the receiving water outside of a designated mixing zone exceed 0.022 mg/L.

Natural Degradation
Before the mid 1970s, natural degradation was the only treatment method used by the Canadian mining industry Photodegradation is affected by turbidity, color and depth, intensity and wavelength of light, angle of light incidence and cloud cover. Degradation: free cyanide in the concentration range of 0.1 to 0.5 mg/L is volatilized at a rate of 0.021 mg CN/ft2.hr in still waters. Rates in agitated water are up to 3 times as great. A temperature increase of 10C causes the free cyanide removal rate to increase by more than 40%

Natural Degradation
Natural degradation is: suitable for removal of free cyanide, removes partially Zn and Cd cyanide complexes and thiocyanate (CNS) does not remove Cu and Ni complexes and Iron-cyanides. Natural degradation is more effective when barren solutions (barren bleed ponds) are stored separately from solid tailings in shallow ponds.

Oxidation by Chlorine
Alkaline chlorination is the oxidation of cyanide in an alkaline solution by chlorine or hypochorite. The complete oxidation of cyanide proceeds in two stages at different pHs: In the first stage, cyanide is transformed to cyanate (CNO) (which is considered approximately onethousandth as toxic as hydrogen cyanide). The oxidation of cyanide is represented by the equations: Any pH: High pH: CN- + Cl2 = CNCl + ClCNCl + 2OH- = CNO- + Cl- + H2O

With hypochlorite: CN- + OCl- = CNO- + Cl-

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Oxidation by Chlorine
The second stage consists of cyanate being converted to bicarbonate and nitrogen: 2CNO- + 3Cl2 + 4H2O = (NH4)2CO3 + 3Cl2 + CO32(NH4)2CO3 + 3Cl2 + 6OH- + CO32- = 2HCO3- + N2 + 6Cl- + 6H2O

Oxidation by Chlorine
Advantages of the process: Easy to operate Reactions reasonably rapid Free and WAD cyanides as well as thiocyanates are destroyed Chlorine or hypochlorite readily available in several forms Capital outlay relatively low

Oxidation by Chlorine
Disadvantages: High operating cost (reagents are costly) Requires pH control to prevent cyanogen chloride which is highly toxic Ferro and Ferricyanides are not destroyed High content of chloride and chlorine in effluents Some chlorination products (e.g. Nahypochlorite, chloro-lime, etc.) are degradable: storage problems in remote regions.

Electrochemical Processes
Electroreduction: Complex metal cyanide ions reduce at the cathode to deposit or precipitate the metal, regenerating free cyanide: n Me( CN ) 2 + 2 e = n CN + Me ( Me = divalent metal) n Electrochlorination : Anode reaction: Cathode reaction:

Cl = Cl + e 2Cl = Cl 2 (g)

H 2 O + e = H + OH 2 H = H 2 (g )

Introducing NaCl into the solution, chlorine is produced by electrolysis. Hypochlorite and chlorate can also be formed. Free cyanide, WAD cyanides and thiocyanates are destroyed. Ironcyanides are not destroyed Cyanide can be regenerated

Oxidation with Hydrogen Peroxide

Cyanide oxidation with H2O2 is a fast, one-step reaction, forming non-toxic intermediates. H2O2 oxidizes free and Zn & Cd cyanides to cyanate which is further hydrolyzed yielding biodegradable ammonia and carbonate. CN- + H2O2 = CNO- + H2O (Cu2+ is a catalyst) CNO- + 2H2O = NH4+ + CO32(pH just < 7)

Oxidation with Hydrogen Peroxide

Cu and Ni cyanides are partially destroyed and Iron-cyanides are partially precipitated. Since copper and other metal ions are already in many mining effluents, additional metallic catalyst may not be required to enhance the reaction rate. Degussa process uses borate compounds as catalysts resulting in a substantial saving of hydrogen peroxide consumption (up to 60%).

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Oxidation with Hydrogen Peroxide

There are a variety of processes combining hydrogen peroxide with other compounds, such as glycolonitrile (Kastone process), H2SO4 (Caros acid), SO2, etc. Formation of thiocyanate by H2O2 is slow (in contrast to chlorination). H2O2 consumption is estimated to be around 3 kg/kg CN-. Theoretical dosage: 1.5 kg H2O2/kg CN The process is not very suitable for slurries. High operating cost. First used at Ok Tedi in 1984 and in Canada at Teck Corona in 1985. Many plants in Canada use peroxide.

Oxidation with Hydrogen Peroxide (Example)

Species As Cu total CN Fe Se Ag Zn Effluent (mg/L) Before After 0.2 <0.05 4.5 <1 280 3 16 <0.015 5 4 3.2 1 157 <1 EPA dws (mg/L) 0.05 9.0 0.05 0.3 0.01 0.05 5

Note: H2O2 dosage = 2.5 mL/L dws = drinking water standard

INCO SO2/Air Process

INCO SO2/Air Process

Invented by INCO in 1984 as a result of a research to destroy cyanide used to depress pyrrhotite during flotation of pentandite (NiFe9S8) and Chalcopyrite (CuFeS2). A mixture of sulphur dioxide and air rapidly oxidizes free cyanide and WAD metal cyanide complexes in the presence of Cu2+ as catalyst. CN + SO2 + O2 + H2O = CNO + H2SO4 (Cu2+ is a catalyst)
-

Copper should be present in minimum concentration of 50 mg/L and can be added as copper sulphate. Cu2+ additions depend on the iron content of the effluent and are in the range 0 to 0.5 g/g total CN. Free cyanide, Zn, Cd, Cu, Ni cyanides are destroyed. Iron-cyanides are partially precipitated. Thiocyanide is partially (10 to 20%) destroyed. The process is usually performed in one or two stages, bubbling SO2-air or adding sodium metabisulphite. Air flowrate is around 1 L/min per liter of solution. In practice 3-4 kg SO2 (or 5-8 kg of sodium metabisulphite) is required per kg of cyanide. Stoichiometrically the reactions require 2.46 kg SO2 per kg of WAD cyanides. Retention time ranges from 20 min to 2 hours.

2+ Me(CN) 2 4 + 4 SO 2 + 2 O 2 + 4H 2 O = 4 CNO + 4 H 2 SO 4 + Me

Me2+ = Zn2+, Cu2+, Ni2+, Cd2+, etc. (neutralization): H2SO4 + Ca(OH)2 = CaSO4.2H2O (pH>8) (precipitation): Me2+ + Ca(OH)2 = Me(OH)2 + Ca2+ 4 2 Me 2 + + Fe(CN ) 6 = Me 2 Fe(CN ) 6

INCO SO2/Air Process

The process has been licensed at over 100 project sites worldwide. The process has been used to treat effluents containing > 200 mg/L total cyanide and routinely reduces this to <1 mg/L Capital cost for an installation to destroy 3,000 tonnes of slurry/d is Cn$ 1.2 million (installed) Typical operating cost to treat tailings from a plant using CIP is Cn$0.8/tonne Patent expired in 2004
Species

INCO SO2/Air Process

Liquid Effluent (mg/L) Before After 365.8 0.69 225 0.15 44.6 100.7 35.45 45.82 4.13 324.2 82.5 1.21 0.26 0.25 Final Tailing (mg/L) 29.4 12.2 52.9 18.9 7.7 5.35 0.51

Total cyanide WAD cyanides Cyanate Thiocyanate Cu Fe Ni

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Combinox Process
Developed in Germany by CyPlus, this is a variation of the INCO Process, when the patent expired (May 2008) This process is a combination of SO2/Air and Peroxide (Degussa Process) Thiocyanate (CNS) is destroyed It destroys free and Zn, Ag, Cd, Cu, Ni cyanides Fe cyanides are precipitated in presence of copper: Fe(CN)64- + 2Cu2+ Cu2Fe(CN)6 (solid) Final product: CO2 + NH4+ It is considered one of the most effective cyanide destruction processes

Combinox Process
Applied in Las Crucitas Project, in Costa Rica 7500 tonnes/day of saprolite In the future 5000 tonnes/d hard rock (1.5-2 g/t) All material is leached with 150-200 mg/L CN: CIP
Compound (mg/L) Total CN Free CN WAD CN (moderately complexed) Solution after Combinox 0.58 <2 0.31 Solution after 10 days 0.03 <0.02 <0.01

Biological Treatment
Cyanide is degraded by aerobic and anaerobic microbes First applied in 1984 at Homestake Lead Mine, South Dakota to treat 800 t/h of mixed mine water and tailings. Sensitive to temperature (optimum: 30 C, pH 7 8.5). Process requires gradual acclimatization of mutant strains of bacteria (Pseudomonas) to the high concentration of cyanides and thiocyanate. Oxidation rate of cyanide to cyanate is increased by the bacteria.

Cyanide Recovery
Acidification - Volatilization - Reneutralization AVR Processes was used successfully at Flin Flon (Canada) from 1930 to 1975 and in several other commercial operations. The process consists of acidification of the alkaline cyanide leach solution producing hydrogen cyanide (HCN) which is removed by volatilization in a stream of air to be reabsorbed into an alkaline solution. Acidification: CN- + H+ = HCN Absorption: 2HCN + NaOH = NaCN + 2H2O

Cyanide Recovery
Golconda (Australia) has reduced the total cyanide concentration in effluents from >200 mg/L to < 5 mg/L. Reagent consumption is 0.6 kg H2SO4/t solution and 0.45 kg NaOH/t. Cyanide recovery 50 to 85%. The Cyanisorb is an AVR process that uses high efficiency packed towers, low pressures and moderate pH levels. It recovers about 90% of the cyanide from tailings: Gold mine in Waihi (New Zealand), AngloGold in Argentina, DeLamar (U.S.), Marlin Mine (Guatemala) are using Cyanisorb method AVR technology has been developed to allow treatment of slurry streams directly without the need for solid-liquid separation.
H2SO4
10%

Cyanisorb Process
Barren solution
300 ppm HCN HCN ladden air bleed air

pH 5 - 7.5 Ca(OH)2

air

stripped slurry NaCN (recovered) solution

Pulp to tailing pond

Metals precipitation

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Cyanide Recovery: Ion Exchange

Developed in the mid-1950s for the recovery of cyanide from electroplating solutions. Resin impregnated with copper (to tie up all free cyanide as complex) precipitates cuprous cyanide in the resin matrix. Strong-base anion exchange resins remove cyanide complexes of iron, zinc, copper, nickel, cobalt, gold and silver can be removed effectively followed by elution of the resin. Practical problems: Efficient elution of all species that load onto the resin is hard to achieve Resin must be regenerated or new resin must be used to maintain process efficiency High costs involved

Cyanide Recovery: Activated Charcoal

Activated Charcoal has been used for recovery of metals from cyanide solutions. Activated charcoal is capable of adsorbing up to 5 mg CN-/g from aerated alkaline cyanide solutions. This can reach 25 mg CN/g in the presence of a catalyst such as copper. Cyanide can be recovered (elution) from the AC into low ionic strength solution at elevated temperature.

You and me, we used to mine together Cyanide together, always I really felt, a bitter almond smell When the pH fell, and I ran You dont know, where the pH goes 10.5 is good to leach the gold Don't leach if you dont have control pH cannot be low Be careful cause it hurts Don't leach if you forgot the lime the smell can be sublime, but Be careful cause it hurts

In long term, the cyanide effect, A lump in your neck, you will cry Thyroidism, this can appear And them it will be to late youre gonna die Don't leach gold or even silver, Dumping cyanide in rivers Be careful cause it hurts Don't leach if you think the fish wont feel Cyanide in their gills, Be careful cause it hurts You dont agree, but with 5 ppb, fish can die

You told me, youve never had destroyed The cyanide you have employed, you fool Youve just trust, what the sun can do Youve just left the tailings in a pool Don't leach what youre doing is quite insane Cyanide still remains Be careful cause it hurts Don't leach I dont need your reasons Telling this is sunny season Be careful cause it hurts THE END

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