Reducing/Replacing Hg in ASM

Operations

Marcello M. Veiga
Associate Professor of
University of British Columbia
Vancouver, Canada

Presented at the 8th CASM – Community and

Small-scale Mining Annual Conference
Brasilia October 6-12, 2008

Suriname, 2008
 Technical Solutions for Hg Pollution

Alternative Control Hg Reduce Hg

Processes to Bioavailability Use and
Replace Hg Emissions

Replace Avoid methylation Avoid exposure

amalgamation covering or to Hg and
with other dredging Hg- eliminate bad
process contaminated practices
tailings

Long-term Medium-term Short-term

 Technical Solutions

Alternative Control Hg Bioavailability Reduction of

Processes Hg Emissions
Direct
Smelting
Polluted Mercury Systemic Individual
Electrolytic Sites Dispersed Solutions Solutions
Process
Y Education Amalgamate
Cyanidation N Y concentrates
Bioaccumulation Bioaccumulation
Occurring Occurring ?
Other ?
Processing Use Hg far
Lixiviants Centers from people
Monitoring
Re-suspension Organization Retorts & special
Covering Fish of Sediments of Associations Fume hoods
Dredging Hair Change of Law
& Treatment Food Habits Activated Hg
Enforcement

Permanent
Biological Monitoring
& Technical Assistance
 Reduction of Hg Emissions Depends
on the Amalgamation Procedure

Amalgamation of Huge Hg losses, large

the Whole Ore environmental problem
and/or
Cyanidation of Hg-
contaminated tailings Hgo CH3Hg in fish

Hgo vapor lungs

Burning Health problem for miners,
Amalgams in Pans family and neighbors
 Amalgamation of Whole Ore is
the Main Cause of Hg Loss
• There is a false perception that the main
Hg loss in ASM is when miners burn the
amalgam in open air
• The main losses occur when the whole
ore is amalgamated:
– Hg is spread on the ground or in sluice boxes
– Cu-Hg plates
– Grinding with mercury
 Amalgamation of the Whole Ore
(Mercury Spread on the Ground)

Hg is spread in the pool

and pumped to the
sluice box

Hg is retained in the riffles

giving the impression that
amalgamation occurred in the
pool

Venezuela, 1995
 Amalgamation of the Whole Ore
(Mercury in the Sluice Box)

Hg is
added
here

Brazil, 1999
Hg goes with tailings
 Amalgamation of the Whole Ore
(Mercury in the Sluice Box)
(it was a common practice in North America during gold rush)

• Between 1860-1895: 6,350 tonnes

Hg lost to Carson River, Nevada

• 12,000 tonnes Hg lost in

California and Nevada

Canada, 1856
• Archives from British Columbia: 13kg of Hg/day/sluice
used by miners at Cariboo, Canada (1856)

This is 20,000 x more Hg than used by a Brazilian ASM

 Amalgamation of the Whole Ore
(Cu-Plates with Hg)

Brazil, 2008

Plates: attrition remove Hg

from plates = Hg is lost
Venezuela, 2003
Amalgamation of the Whole Ore
(Cu-Plates with Hg)

Venezuela, 2003
Amalgamation of the Whole Ore
(Cu-Plates with Hg)

Venezuela, 2003
Amalgamation of the Whole Ore
(Cu-Plates with Hg)

Use of Copper
Amalgamation
Plates
generates
tailings highly
contaminated
with Hg
(usually 50-200
Zimbabwe, 2005
ppm Hg)
Amalgamation of the Whole Ore
(Grinding with Hg)

Adding Hg into
the Grinding
Circuit

25 to 30% of the
Hg added is lost
Indonesia, Talawaan, 2001 with tailings
(“flouring”)
 Grinding with Hg
Antioquia Province - Colombia

• Colombia: Hg in the
“cocos” (ball mills)
• About 4 ounces of
Hg is added in each
“coco” (ball mill)

Colombia, 2007
 Additives used in Amalgamation
by Artisanal Miners
Miners use these methods to reduce Hg flouring
and consequently Hg losses with Tailings:
• Clean Hg with boiling water (Indonesia)
• Lime juice (Laos, Colombia)
• Caustic soda (Colombia)
• Cyanide (Zimbabwe)
• Brown sugar (Ecuador)
• Molasse (Colombia)
• Urine (Chile)
• Sodium-amalgam (Colombia, Brazil)
Brown Sugar in the Ball Mills with Hg

Ecuador, 2004
 Amalgamation in Antioquia, Colombia
30L water 70kg ore 200g Ca(OH)2
50kg balls
“coco”” 120g Hg pH 11
(1/2 volume)
4 hours
Excess Hg +
elutriator
amalgam 10mL molasse
10L lime “coco” 90g Hg pH 5
juice (with balls)
3 hours
Excess Hg + NaHCO3
amalgam elutriator

cyanidation
 Grinding with Hg
Antioquia Province - Colombia
• Tailings (up to 5000
ppm Hg) are later
leached with cyanide
• 50 - 70% of Au
recovered by
amalgamation
• 25 - 30% of Hg is lost
• 50 to 100 tonnes Hg/
Colombia, 2007 a lost in the
Antioquia Province
Using Urine to Amalgamate

Chile, 2008
 Forming Sodium-amalgam
(increase coalescence = reduces Hg
flouring = less Hg loss with tailing)
sodium-amalgam is
+ Battery
12 V
- more consistent
than pure Hg
wire
Also called
Graphite rod “Hg Activation”

Water with
NaCl (10%)
Mercury

Dr Pantoja’s Method
 Brazil, 2006
3800 miners in the GMP
site in the Amazon
adopted this technique
Zimbabwe, 2006
 What Can Be Done to Improve Amalgamation
and Reduce Hg Emissions
• Amalgamate only gravity concentrates
• Promote good contact between Hg and gold (particles
must be cleaned, e.g. detergent)
• Avoid severe grinding that causes “flouring”
• Additives to reduce Hg surface tension
• Use activated Hg (Na or K-amalgam). K-amalgam is used in
Colombia to capture alluvial Pt (Mineros de Antioquia SA)
• Centrifuge amalgam after amalgamation to remove excess
mercury
Manual Amalgamation Must Be Avoided

Tanzania, 2005
 Using an Amalgamating Barrel
to Improve Amalgamation
• One part of Hg to 100 parts of concentrate

Glass Amalgamation Barrel (3

L)
Indonesia, 2006
After Amalgamation, the Amalgam Must Be
Separated from the Heavy Minerals
• Excavated pool lined with
a plastic trap
• When the pool is full,
cover it
• CONTAMINATED
TAILINGS MUST NOT BE
RECYCLED Brazil, 2007
 PVC cups Reducing %Hg in amalgam
from 40% (manual squeeze)
to 20% (centrifuge)

amalgam filtered
piece of mercury
cloth clamps

Indonesia, 2001
Filtering Amalgam

Brazil, 2006

Manual
Centrifuge
Alternative to Reduce/Replace Hg
• Direct smelting of concentrates Ore
• Electrolytic Process
• Cyanidation Grinding

• Other lixiviants
Concentration

Cyanidation
Concentrate Tailing
Other lixiviants

Direct smelting
Gold Concentration is Fundamental
Gold Recovery is Low when Gold is not Liberated
Gold Not Liberated Liberated Gold

0.07 mm

Gravity Separation

Assuming that the dark

particles are gold
 In order to concentrate it’s necessary to
LIBERATE gold particles
• Liberation is obtained
by comminution
(crushing and grinding)
• Gold occurs occluded
in other minerals
• Manual crushing is
inefficient Tanzania, 2007
 Good Grinding Does not Need
Sophisticated Equipment

Mozambique, 2005
Indonesia, 2004

10 kg of ore ground with

14 steel balls for 45 min.
NO Hg ADDED in the ball mills
 Gold Concentration by Panning
Panning in a
closed pool (away
from rivers)

Some Hg-free gold

can be obtained
but in most cases
Hg is introduced
at the end of the
panning step to Mozambique, 2005
capture fine Au
 Zig-zag Sluice

Indonesia, 2006

Suriname, 2007
Zig-zag sluices
increase chances of
capturing gold
Concentrating Gold in Sluice Box

Indonesia, 2006
 Centrifuges
• Good for coarse and fine
gold (0.05 mm)
• Much more efficient than
sluices
• Used by mining companies
• High cost
• High maintanance and
control
• Most common: Knelson
and Falcon, both from
B.C., Canada
Why Are Centrifuges More Efficient?
• S.G. quartz = 2.7
=
• S.G. gold = 19
gold quartz

When the particles are subjected to the gravity force

(G =1), one gold particle of 0.02 mm fall in water as
fast as a quartz particle of 0.07 mm

Then there is no way to separate them

Why Are Centrifuges More Efficient?
When the particles are subjected to G = 60, the
difference in fall velocity is much higher than with G = 1

6
Difference in Fall Velocity (mm\sec)

0
0 20 40 60
Gravity (G)
 New Falcon Centrifuge for ASM

• Introducing new centrifuges

developed with UBC and the
company Falcon
Concentrators(Langley)
• Price <US$4000
• 1-2 tonnes/h
• Good for fine gold
Canada, 2006
 Magnetic Sluice Boxes
Cleangold® Sluice Box
• Ore must have
magnetite
• Iron bits from hammer
mills can also be
attracted
• Like any other gravity
concentrator,
Venezuela, 2003
uliberated gold is lost
with middlings
Using Small Cleangold

Panning Tailings with Cleangold

Sudan, 2004
 Concentrating Gold
Using Fridge Magnets

Mozambique, 2005
 Gravity Concentration of a Gold
Ore from Talaawan, Indonesia
Au (ppm or g/t)
Cleangold® HMMS Knelson®
Feed 12.60 12.30 11.50
Concentrate 64.00 117.00 16.00
Tailings 11.95 11.40 11.31
Au Recovery (%) 7% 8% 5%
HMMS = Homemade magnetic sluice

P80 = 0.25 mm
Conclusion: gold is not liberated and it’s very fine
 Concentration
• Gravity Concentration
– Depends on gold liberation (grinding) and how
fine is the gold (size of the particle)
– Gold in the middling product (unliberated) in a
problem
– For primary ore, gold recovery rarely goes
beyond 30-40% (even in industries)
 Concentration
• Flotation
– Depends on gold liberation (grinding)
– Concentrates are usually poor (200 g Au/t)
– Concentrate produced must be submitted to
amalgamation or cyanidation
– Control of pH and reagents is needed
– Little investment in flotation cell is needed
 Flotation (Chile)
• Homemade
flotation cells
• Use xanthate and
pine oil
• Miners sell the
gold and copper
concentrate
Chile, 2008
• Sun-dried
 Concentration
• Agglomeration
– Depends on gold liberation (grinding)
– Agglomerates (5 mm) of coal and oil are formed and put
in contact of a pulp of gravity concentrate in one or more
cycles.
– Recoveries of 90% were obtained in one step.
– Envi-Tech Inc of Edmonton, Canada has its own
proprietary agglomerate (gold absorbent)
– Melted paraffin to collect gold in an acidic medium
– Encouraging results but none of these methods provide a
simple, cheap and quick alternative for unskilled artisanal
miners.
 Direct Smelting
• Concentrates must be very rich
• Smelting of low grade concentrates implies
in Au losses to slag and high amounts of
borax used
• Lab tests show that the threshold is around
5,000 g Au/t in a concentrate
• To increase Au in concentrates, Au
recovery decreases, i.e more Au is lost in
middling
 Electrolytic Process
• SALTEM Process (devised by CETEM, Brazil)
– Gold ore (or concentrate) is mixed with NaCl (1 Mol/l)
which is transformed by electrolysis into a mixture of
sodium hypochorite-chlorate
– Seawater can also be used
– More than 95% of the gold dissolves within 4 hours and is
collected on a graphite cathode
– Solution is recycled minimizing effluent discharge
– NaCl = 100 kg/tonne of ore
– Energy = 170 kwh/kg of Au
– Plastic tanks are used, reducing investment cost
– Very good potential but a bit complicated for ASM
 Electrolytic Process

+ -

NaCl
solution
Cl2
AuCl4-
Pulp of ClO-
gold ore
 Cyanidation
4Au + 8CN- + O2 + 2H2O = 4Au(CN)2- + 4OH-
2Au(CN)2- + Zn = Zn(CN)42- + 2Au (Merrill-Crowe process)
• ASM are familiar with the process
• Problems with NaCN in ASM:
– Poor control of the pH
– Use of Zn precipitation followed by burning
– High investment in agitated tanks
– No CN destruction is applied
– Cyanidation of Hg-contaminated material makes
Hg more bioavailable
– Poor management of tailings with CN
 Cyanidation

• Zinc is used to
precipitate gold
from the cyanide
solution
• Zinc is evaporated
contaminating the
whole area
Ecuador, 2006
 Cyanidation

• Cyanidation of Hg-
contaminated
tailings increases
the bioavailability
of mercury
• Mercury-cyanide
species are formed

Zimbabwe, 2005
 Hg-contaminated Tailings are Submitted
to Cyanidation - São Chico, Brazil
• Abandoned
cyanidation heap
in São Chico,
Brazil near the
water stream
• Tailings are still
full of Hg when
submitted to
cyanidation Brazil, São Chico, 2003
Hg-contaminated Tailings are Submitted
to Cyanidation - São Chico, Brazil
• Carnivorous fish, Ave = 4.16 ppm Hg
• Non-carnivorous, Ave = 1.33 ppm Hg
• 60% of fish >0.5 ppm Hg (guideline for
fish consumption)
• One fish sample = 22 ppm Hg
 Amalgamation of a Pre-concentrate
Followed by Cyanidation - Ecuador

A pre-concentrate is
obtained in sluice boxes
(discharge every hour)… …and amalgamated in
barrels

Ecuador, 2007
 Amalgamation of a Pre-concentrate
Followed by Cyanidation - Ecuador
Tailings (with or without Hg)
are leached with NaCN

Ecuador, 2007

Some operations use

pH = 7 in Cyanidation
 Amalgamation of a Pre-concentrate
Followed by Cyanidation

• Tailings with Hg
cyanide are dumped
into the Amarillo River,
Ecuador
• 92 cyanidation tanks in
the town of Portovelo

Portovelo, Ecuador, 2007

 Hg is added
Misuse of Cyanidation while grinding
with Amalgamation the ore
Cu plate
• Brazil
• China
• Colombia Cyanide
• Ecuador
• Indonesia
• Peru
• Philippines
• Venezuela
• Zimbabwe

Photo AJ Gunson
China, 2002
 Cyanidation
Gold Ore from Talaawan, Indonesia
Au (ppm or g/t)

Cleangold® HMMS Knelson® Cyanidation

Feed 12.60 12.30 11.50 12.20
Concentrate 64.00 117.00 16.00 32.00
Tailings 11.95 11.40 11.31] 1.96
Au Recovery (%) 7% 8% 5% 84%
HMMS = Homemade magnetic sluice

P80 = 0.25 mm
6 hours of leaching in agitated tank
Improving Cyanidation for ASM
• Instead of using Hg in ball mills, miners
could use NaCN
• No additional investment needed
• Training is fundamental
• Quick leaching time
• High Au recovery (>90%)
 Mill-leaching
(Cyanide in Ball Mill)
Gold Ore from Talaawan, Indonesia
Grinding with NaCN for 2h + Leaching Time
Au in the
Leaching pH Final NaCN %Au
sample,
Time, h Initial Final g/L Recovered
g/tonne
2 12.3 12.2 0.88 77.9 14.7
4 12.3 12.2 0.88 85.5 16.2
6 12.1 11.9 0.78 93.1 17.5
8 11.4 11.1 0.88 93.3 15.0
24 10.7 10.7 0.86 93.6 14.8
 Field Tests in Ecuador
• Ore ground in Chilean mill 80% passing 0.150mm
• Pre-concentrate from sluice box (17.3 g Au/t):
– Amalgamation (160 kg)
– Cyanidation in agitated tank (695 kg)
– Field tests of mill-leaching (80kg)

Ecuador, 2007
 Result of Amalgamation
• Amalgamation of the
pre-concentrate was
manual
• Use of brown sugar
• 8 hours of amalgamation
in a batea
• Amalgam was burned in
a retort
Ecuador, 2007
• Gold recovery was 26%
Result of Cyanidation in Agitated Tank
• Miners are familiar but not with Carbon in Leaching
• Activated carbon was added after 7 hours of
leaching
• pH = 11
• 41% solids
• Gold dissolution in 7 hours of leaching was 62%
• Total gold recovered after 31 hours was 94%
• Gold grade of the AC was 1235 mg/kg
• NaCN consumption of 4.5 g/kg of ore.
Cyanidation in Agitated Tank

Ecuador, 2007
 Results of Mill-leaching
(Cyanide in the Grinding Circuit)
• 95% of gold extracted
in 8 h (2h grinding with
CN and 6 hours
leaching)
• Use of activated carbon
• Residual NaCN=1.7 g/L
• Free cyanide was
destroyed with bleach
before being
discharged
• The NaCN consumption Ecuador, 2007
was 0.95g/kg of ore
 Results of Mill-leaching
(Cyanide in the Grinding Circuit)
Elution of Activated Carbon (AC)
• NaCN = 2g/L, NaOH = 10 g/L
• Alcohol = 20%
• Temperature: 90 °C, 3-4 hours
• 97% Au removed from AC
• Gold was precipitated with Zinc
• Loaded zinc shavings were
leached with nitric acid and
melted with borax to produce
the gold bullion
• Zinc in the nitric solution was
precipitated with lime
Ecuador, 2007
 Advantages of Mill-leaching
(Cyanide in the Grinding Circuit)
• Faster than agitated tank leaching:
– 8h of mill-leaching = 31 h of agitated tank
• All gold remaining in the moisture in the
tailings is recovered
• This is almost 30% more gold which is
usually lost with tailings in agitated tanks
• No need for investment in equipment (in the
case of Ecuador, Colombia and Indonesia)
 Other Reagents
Name Reagent pH Complex formed with Au
Thiourea NH2CSNH2 1-4 [Au(NH2CSNH2)2]+
Bromine Br- 1-7 AuBr4-
Iodine I- 1-5 AuI2-
Thiocyanate SCN- 1-3 [Au(SCN)4]-
Thiosulfate S2O32- 8-11 [Au(S2O3)2]3-
Cl-, OCl-, Cl2
Chlorine 1-4 AuCl4-
ClO3-
Adapted from Trindade & Barbosa Filho. Reagentes Alternativos ao Cianeto. Chapter 9, p. 211-252. In:
Extração de Ouro - Princípios, Tecnologia e Meio Ambiente. CETEM/CNPq, Rio de Janeiro, Brazil
 Other Reagents
• iGoli Process (Mintek, South Africa)
– Gold from gravity concentrates (>1000 g Au/t) is
leached with hypochlorite and HCl
– Gold is precipitated with sodium metabisulfite,
or ferrous sulphate or SO2, etc.
– Solution is filtered
– Gold powder is hammered to become yellow
– Many field tests in Africa
– Great potential and open technology
– Hard to find reagents in remote areas
 iGoli

Photo: Mintek, South Africa 2001

 Conclusion
• There is no panacea
• There are many processes to replace Hg but all
cases are site-specific (level of education, level of
investment, labor organization, type of ore,
access to reagents, etc.)
• Any method must be transparent and simple
• Gravity concentration is key to reduce Hg
emissions and promote leaching of concentrates
• Gravity concentration alone is efficient in alluvial
ores or when grinding is efficient (rarely more
than 30% gold recovery is obtained)