Treatment of Tailings From Artisanal Gold Mining in Nicaragua

Faculty of Bioscience Engineering
Academic year 2012 – 2013
Treatment of tailings from artisanal gold mining in

Nicaragua
Brecht Annicaert
Promotors: Prof. dr. ir. Gijs Du Laing

Dr. Lieven Machiels
Tutor: Prof. dr. ir. Gijs Du Laing
Master’s dissertation submitted in partial fulfilment of the requirements

for the degree of Master of science in bioscience engineering:
Chemistry and Bioprocestechnology
Faculty of Bioscience Engineering
Academic year 2012 – 2013
Treatment of tailings from artisanal gold mining in

Nicaragua
Brecht Annicaert
Promotors: Prof. dr. ir. Gijs Du Laing

Dr. Lieven Machiels
Tutor: Prof. dr. ir. Gijs Du Laing
Master’s dissertation submitted in partial fulfilment of the requirements

for the degree of Master of science in bioscience engineering:
Chemistry and Bioprocestechnology
i
Copyright
The author and the promotor give permission to use this thesis for consultation and to copy
parts of it for personal use. Every other use is subject to the copyright laws, more specically
the source must be extensively specied when using results from this thesis.
Ghent, June 2013
The promotor, The author,
Prof. dr. ir. Gijs Du Laing Brecht Annicaert

ii
A word of gratitude
This thesis would not have been possible without the help and guidance of several people
who put their time and experience at my disposal.
Firstly I would like to express my gratitude to promotor prof.dr.ir. Gijs Du Laing and my
co-promotor dr. Lieven Machiels to oer me the opportunity to do my thesis partly abroad
and gain some invaluable life experiences. Furthermore their guidance and good advice made
the rough route seem a little smoother
My stay in Nicaragua would not have been the same if not for the warm welcome of the
family Icaza as a guest in their house. Thank you, Harold, Carol, Kendra, Kristel, Keira,
Titi, Carolita, Harolito,..., for feeling a part of the family if we watched together 'Porque el
amor que manda'. I owe thanks for the succesfull sampling campaign to Roger Midence who
assisted me with his diplomatic and scientic advice and learnt me the ways of how Nicas live.
Without the help of Leopoldo Marin en Juan Carlos Chavarria no sampling campaign could
be conducted and made me appreciate good company and rudimentary karaoke.
I would like to thank Ria, Kathy, Joachim, David and Frederik for their precious time and
advice that were indispensible for doing my experiments in the laboratory.
My appreciation goes out to Dorien Nijs who made the eort to read and corrected my thesis
although this resulted in an improved reading experience it also gave me hours of extra work
which I could have spent enjoying the good weather.
A word of thank is attributed to my friend and family for their non-stop support and pressure
to make this thesis a worthwhile experience.
Finally my dubious thanks go out to mercury for becoming my thesis subject and always
giving the best of yourself, as shown in the gure below.
Figure 1: (Freddy) Mercury, giving the best of himself

iii
Abstract
Artisanal and small-scale gold mining surpassed all other industries and recently became the
largest contributor to intentional mercury releases. Reducing this growing source of mercury
pollution became a priority if we want to live on a healthy planet. The solid waste generated by
artisanal and small-scale gold mining activities and contaminated with mercury poses a great
risk towards the health of nearby communities and environment when they are not properly
disposed or treated.
The objective of this thesis is to nd a remediation technique which is environmental and
economical sound. The solutions studied in this thesis is the removal of mercury by thermal
treatment or the simultaneous recovery of mercury and gold by coal gold agglomeration from
the tailings.
Firstly a sampling campaign was conducted in the artisanal gold mining community of la
Libertad, Nicaragua. Several sites were visited where contaminated mercury tailings were
disposed. At the same time a questionnaire was drawn from the artisanal miners to create
a better understanding of the mercury use throughout the process. Afterwards the samples
were subjected to dierent treatment and their eciency on mercury removal was measured
by cold vapour atomic absorption spectrometry.
It could be shown that in la Libertad alone about 56 tonnes of contaminated tailings are
discarded per day with an average content of 8,12 mg mercury and 3,82 mg gold per kg
tailing. In the surrounding area of the tailing mercury and gold content were estimated on
1,94 mg/kg and 1,23 mg/kg, respectively.
The results from thermal treatment show that the removal eciency of mercury increases
when the treatment temperature is raised. No signicant improvements of mercury removal
eciency in the tailings were observed when the temperature was raised above 300
◦ C and
all samples, except for one, had an content lower than 1 ppm mercury at 300
◦ C. An average
of 66 % mercury removal eciency was obtained when samples from four tailing sites were
subjected to a treatment of one hour and 250

◦ C. Mimicking the conditions of in-situ thermal
treatment on a soil from an industrial site in Belgium resulted in a slow temperature rise in
the soil compartment and signicant dierence in mercury removal at the locations closest
and furthest from the heating element. This resulted in respective concentrations of 3,93 ppm
and 13,81 mg mercury per kg after 36 days and when the temperature in the reactor reached
310
◦ C for seven days. From the initial concentration of 44 mg mercury per kg soil about 76
% was removed after 36 days of treatment.
The simultaneous recuperation by coal gold agglomeration was successful and concentrations
of up to 8 mg Hg and 2 mg Au was found in one kilogram of coal. The recovery eciency
of gold and mercury from the tailing under the given conditions was only 22 % and 11 %,
respectively.
iv
An outline shows that the operating cost for thermal treatment are about 305 $ per ton tailing.
The operating costs of coal gold agglomeration are, under the current experimental conditions,
estimated at 618 $. If, however, the process is optimized costs can decrease to 26 $ per ton
tailing.
Future research could be done to further shorten the duration of thermal treatment without
compromising mercury removal eciency and dening the optimal conditions at which the
coal gold agglomeration have the highest mercury and gold concentration in the activated
carbon while separating the activated carbon from the tailings is easy.
v
Samenvatting
Ambachtelijke en kleinschalige goudwinning overtrof alle andere sectoren en werd recentelijk
de sector met de grootste bijdrage aan het opzettelijk vrijkomen van kwik. Het verminderen
van deze groeiende bron van kwikverontreiniging werd een prioriteit als we willen leven op een
gezonde planeet. De vaste afvalstoen gegenereerd door ambachtelijke en kleinschalige goud-
winning activiteiten en verontreinigd met kwik vormt een groot risico in de voor de gezondheid
van de nabijgelegen gemeenschappen en het milieu als ze niet goed worden afgevoerd of be-
handeld.
Het doel van deze thesis is om een saneringstechniek te vinden die aan de huidige milieu
voorwaarden doet en economisch haalbaar is. De, in dit proefschrift onderzochtte oplossingen
is de verwijdering van kwik door thermische behandeling of de gelijktijdige terugwinning van
kwik en goud door coal gold agglomeratie van de tailings.
Eerst werd een veldproef uitgevoerd in de goudmijnbouwersgemeenschap van La Libertad,
Nicaragua. Verschillende sites werden bezocht waar verontreinigde kwik residuen werden
afgevoerd. Tegelijkertijd werd een vragenlijst opgesteld van de artisanale mijnwerkers tot een
beter begrip van het gebruik van kwik gedurende het gehele proces te creëren. Daarna werden
de monsters onderworpen aan verschillende behandelingen en hun eciëntie op kwikverwi-
jdering werd gemeten door koude-damp-atomaire-absorptiespectrometrie.
Het kan worden aangetoond dat in la Libertad alleen al ongeveer 56 ton verontreinigde residuen
worden per dag gegenereerd met een gemiddeld gehalte van 8,12 mg kwik en 3,82 mg goud
per kg tailing. In de omgeving van deze residues het kwik en goudgehalte werd geschat op
1,94 mg / kg en 1,23 mg / kg, respectievelijk.
Uit de resultaten van thermische behandeling blijkt dat de verwijderingseciëntie van kwik
toeneemt wanneer de behandelingstemperatuur wordt verhoogd. Geen signicante verbeterin-
gen van kwik verwijdering eciëntie in de tailings werden waargenomen wanneer de temper-
atuur boven de 300 werd verhoogd

◦ C en alle monsters, met uitzondering van een, had een
gehalte van minder dan 1 ppm kwik bij 300

◦ C. Een gemiddelde van 66 % kwik verwijder-
ingseciëntie werd verkregen wanneer monsters van vier tailing sites werden onderworpen
aan een behandeling van één uur en 250 graden C. Het nabootsen van de omstandigheden
in situ thermische behandeling op een bodem van een industriële site in België resulteerde in
een langzame temperatuurstijging in het bodem compartiment en signicante verschillen in
verwijdering van kwik op de plaatsen dichtstbijzijnde en verst van het verwarmingselement.
Dit resulteerde in respectievelijke concentraties van 3,93 ppm en 13,81 mg kwik per kg na 36
dagen en wanneer de temperatuur in de reactor 310

◦ C bereikte gedurende zeven dagen. Van
de aanvankelijke concentratie van 44 mg kwik per kg bodem werd na 36 dagen behandeling
ongeveer 76 % verwijderd.
De gelijktijdige recuperatie door coal gold agglomeratie was succesvol en concentraties tot 8
vi
mg Hg en 2 mg ceAu werd gevonden in een kilo actieve kool. De terugwinningseciëntie
van goud en kwik uit de tailings onder de gegeven omstandigheden is slechts 22 % en 11 %,
respectievelijk.
Uit een economische schets blijkt dat de operationele kosten voor de thermische behandeling
ongeveer 305 $ bedragen per ton tailing. De exploitatiekosten van coal gold agglomeratie
zijn, onder de huidige experimentele conditie, geschat op 618 $ als echter het proces verder
geoptimaliseerd wordt kan dit dalen tot 26 $ per ton Wtextittailing.
Toekomstig onderzoek zou nodig zijn om verdere verkorting van de tijdsduur van de thermische
behandeling te veriëren op zijn kwikverwijderingseciëntie en het deniëren van de optimale
omstandigheden waarbij de coal gold agglomeratie de hoogste kwik en goudconcentratie in de
actieve kool bereikt en de scheiding van de actieve kool en het gouderts eenvoudig is.
Contents
Contents vii
List of Figures x
List of Tables xii
1 Introduction 1
I Literature overview 3
2 Mercury 4
2.1 Mercury emission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1.1 Natural emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.2 Anthropogenic emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.3 Re-emissions and remobilization . . . . . . . . . . . . . . . . . . . . . . 7
2.2 Mercury speciation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2.1 Elemental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2.2 Inorganic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2.3 Organic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.3 Impact on human health . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3.1 Exposure pathways . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3.2 Health eects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3.3 Environmental guidelines . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3 Artisanal and small-scale gold mining 12

3.1 Gold in Nicaragua . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.2 Gold process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.3 Mercury use in ASGM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.4 Combatting mercury pollution in ASGM . . . . . . . . . . . . . . . . . . . . . . 19
3.4.1 Improving awareness and training . . . . . . . . . . . . . . . . . . . . . . 19
3.4.2 Public opinion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.4.3 Mercury reducing approaches . . . . . . . . . . . . . . . . . . . . . . . . 20
vii
CONTENTS viii
3.4.4 Mercury free techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.4.5 Mercury removal from tailings . . . . . . . . . . . . . . . . . . . . . . . . 22
3.4.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
II Material and methods 25

4 Sampling Campaign 26
4.1 Sample preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
5 Laboratory experiments 28
5.1 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
5.2 Analytical methods for soil characterization . . . . . . . . . . . . . . . . . . . . 28
5.2.1 2
pH-H O and pH-KCl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
5.2.2 Electrical conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.2.3 Organic matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.2.4 Chloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.2.5 Soil texture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.2.6 Particle size distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.3 Digestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.3.1 Mercury analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.3.2 Gold analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
5.3.3 Sulphur analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
5.4 Mercury fractionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
5.4.1 Step I (Active mercury fraction) . . . . . . . . . . . . . . . . . . . . . . 32
5.4.2 Step II (HCl-dissoluble mercury) . . . . . . . . . . . . . . . . . . . . . . 32
5.4.3 Step III (Organic-bound mercury) . . . . . . . . . . . . . . . . . . . . . 33
5.4.4
0
Step IV (Elemental mercury or Hg ) . . . . . . . . . . . . . . . . . . . . 33
5.4.5 Step V (Residual mercury) . . . . . . . . . . . . . . . . . . . . . . . . . 33
5.5 Thermal treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
5.5.1 Experiment to asses the removal eciency as function of temperature . 33
5.5.2 Experiment to optimize treatment time and temperature . . . . . . . . . 33
5.5.3 Pilot setup: in-situ thermal treatment . . . . . . . . . . . . . . . . . . . 34
5.6 Coal gold agglomeration experiment to extract gold . . . . . . . . . . . . . . . . 36
5.6.1 Experimental conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
5.6.2 Pre-treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
III Results and discussion 39

6 Sampling campaign 40
CONTENTS ix
7 Laboratory experiments 42
7.1 Soil characteristics of the tailings . . . . . . . . . . . . . . . . . . . . . . . . . . 42
7.1.1 General properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
7.1.2 Soil texture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
7.1.3 Particle size distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
7.1.4 Mercury and gold in tailings . . . . . . . . . . . . . . . . . . . . . . . . . 45
7.2.1 Removal eciency as aected by temperature . . . . . . . . . . . . . . . 50
7.2.2 Eect of time and temperature to optimize remediation . . . . . . . . . 50
7.2.3 Pilot: in-situ thermal treatment . . . . . . . . . . . . . . . . . . . . . . . 51
7.3 Coal gold agglomeration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
7.3.1 Inuence of experimental conditions on recovery . . . . . . . . . . . . . 57
8 Discussion 60
8.2 Coal Gold Agglomeration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
8.3 Suggestions for future research . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
IV Conclusion 64
Bibliography 67
A Sampling campaign I
A.1 Sampling procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I
List of Figures
1 (Freddy) Mercury, giving the best of himself . . . . . . . . . . . . . . . . . . . . ii
2.1 Anthropogenic mercury emissions classied by sector [UNEP, 2013] and [UNEP,
2008] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2 Mercury emissions and cycle in air and water, amount noted in tonnes/yr
[UNEP, 2013] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1 Mean total mercury released in ASGM with: no estimate made (•), 0 to 1(•),
1 to 5(•), 5 to 10(•), 10 to 25(•), 25 to 50(•), 50 to 500(•) in tonnes/a (from
www.mercurywatch.org, online accessed on 12 may 2013) . . . . . . . . . . . . 13
3.2 Gold mining in Nicaragua with mines in operation (•) and prospected conces-
sion of Cassius Venture Ltd (•) (www.cassiusventures.com ) . . . . . . . . . 14
3.3 Methods used in artisanal mining operations to extract gold with mercury
[Sousa et al., 2010] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.4 Gravity separation methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.5 Retorts used in artisanal mining activities . . . . . . . . . . . . . . . . . . . . . 21
4.1 Arrastra sites sampled in la Libertad (•) and reference sites (•) . . . . . . . . . 26
5.1 The cross section of the thermal treatment reactor . . . . . . . . . . . . . . . . 35
5.2 Schematic overview of the pilot setup with 1) reactor with soil, 1a) isolation,
1b) soil, 1c) heating element, 2) water cooling, 3) condensate collector, 4) active
coal lters, 5) pump. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
5.3 Flow diagram of the experimental setup of coal gold agglomeration [Kotze and
Petersen, 2000] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
7.1 Soil texture of tailing samples: CMT2015, FOT11530, FMT1015, AYNT11530,
PENT11530 (•),YAHS2, HPHS1(•), FMHS2, FONT2015, GDNT2015(•) . . . . 44
7.2 Size distribution of the particles in tailings from 4 sites . . . . . . . . . . . . . . 44
7.3 Overview of the gold extraction process in la Libertad . . . . . . . . . . . . . . 47
7.4 Distribution of gold and mercury in function of particle size . . . . . . . . . . . 47
x
LIST OF FIGURES xi
7.5 Mercury fractionation in the four tailings with I) active mercury, II) acid-
dissoluble mercury, III) organic-bound mercury, IV) elemental mercury and
V) residual mercury . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
7.6 Removal eciency of mercury in function of temperature . . . . . . . . . . . . . 50
7.7 Thermal treatment optimization in function of temperature and time . . . . . . 51
7.8 Temperature in reactor in function of time with T1) heating element, T2)inner
wall in between heating element and soil T3, T4 and T5) outer circle of soil
compartment T6) inner circle of soil compartment and T7) the outside of the
reactor (gure 5.1) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
7.9 Mercury content before and after thermal treatment and at dierent locations
in the soil compartment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
7.10 Distribution of the weight according to particle size . . . . . . . . . . . . . . . . 55
7.11 Mercury content in activated carbon lters after each thermal treatment (TT1,
TT2 and TT3) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
7.12 Inuence of coal:oil ratio on the concentration of gold and mercury in coal . . . 58
A.1 Mill facilities in la Libertad . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV

List of Tables
2.1 Overview of mercury sources and exposure routes [Bose-O'Reilly et al., 2010] . 10
5.1 Dierent steps and fractions of sequential procedure with reagents used . . . . . 32
5.2 Overview of treatments used when studying mercury removal as function of
temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
6.1 Summary of the results of the self-reported questionnaire . . . . . . . . . . . . . 41
7.1 Soil characteristics of the tailing samples . . . . . . . . . . . . . . . . . . . . . . 42
7.2 Chloride content of tailings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
7.4 Mercury and gold content of the composed sample per tailing site . . . . . . . . 45
7.3 Mercury and gold content in tailing and distribution samples . . . . . . . . . . 46
7.5 Gold and mercury content and their distribution among particles size fractions
for tailings pile from the sites AY and FO . . . . . . . . . . . . . . . . . . . . . 48
7.6 Desorption temperatures for dierent mercury phases [Navarro et al., 2009] . . 49
7.7 Mass balance of Hg in reactor after three thermal treatments . . . . . . . . . . 57
7.8 Inuence of coal type on gold and mercury content . . . . . . . . . . . . . . . . 59
8.1 CGA estimated operation cost of processing one ton tailing . . . . . . . . . . . 63
A.1 Sampling questionnaire . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II
A.2 List of arrastras in la Libertad on April 2012, sampled arrastras . . . . . . . . III
A.3 Build up of sample labels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V
xii
Chapter 1
Introduction
"Pollution is nothing but the resources we are not harvesting. We allow them to disperse
because we've been ignorant of their value"
-R. Buckminster Fuller-
Published in 1962, Silent Spring of Rachel Carson has generally been regarded as the start-
ing point of the environmental movement. The book focuses on the use of the pesticide
dichlorodiphenyltrichloroethane or better known as DDT and its devastating eects world-
wide. Although the book is not scientically correct, it made scientist and policy makers
aware of the consequences of the hazardous substances coming from industrialization.
Analogies between DDT and (methyl)mercury can be found in the fact that they both bioac-
cumulate and are transported across the globe. The disruptive eects of mercury poisoning
became clear after the Minimata incident (Japan) in the 50's of the past century. This at-
tracted the attention of scientist and policy-makers worldwide. The internationally awareness
was risen towards combatting mercury pollution and was consolidated when the United Nation
Environment Programme put mercury pollution on its priority list.
Fossil fuels, the chlor-alkali industry are well-known polluters of mercury but the recent grow
in number of the artisanal and small-scale gold mining activities has made that it surpasses
all other sectors and became the largest contributor to anthropogenic mercury emissions. Re-
placing the amalgamation process in the artisanal and small-scale gold mining by mercury-free
gold extraction process is the solution on the long run. To date, however, there is no process
in the given circumstances which is as cheap, simple, eective and ecient as amalgamation.
Mercury reducing approaches could minimize the extent in which the pollutant nds it way
into the environment but waste and residues originating from the mining activities continue
to contaminate the surrounding with mercury.
The need to remediate this contaminated tailings arise as they are often located close to
streams and in villages. The current technologies that exist to remediate mercury contami-
1
2
nated soils are solidication and stabilization, soil washing and acid extraction, vitrication,
phytoremediation and thermal treatment [Otto and Bajpai, 2007]. Although these technolo-
gies eliminate the mercury pollution, they bring high capital and operating costs [Kucharski
et al., 2005]. As ASGM, in general, occurs in countries with a weak government and low
education level, mercury pollution is often seen as a necessary evil and remedation project as
costly aairs.
In order to overcome these shortcomings ways to cut the costs and optimize the eciency of
remediation techniques could oer a step in the good direction. Another alternative is the
simultaneous recuperation of mercury and gold that is still present in the tailings. Methods like
electroleaching with sodium chloride or coal gold agglomeration are capable to lower operating
cost by vending the recovered gold [de Andrade Lima et al., 2008].
The general objective of this thesis is to study a possible treatment of the mercury contami-
nated tailings in la Libertad (Nicaragua), this can be divided in the following categories:
Create an understanding of the gold extraction process executed in the artisanal mining
community in la Libertad (Nicaragua) and the mercury-use herein.
Study the soil properties of the tailings and determine the mercury and gold content
present in the tailings.
Evaluate the eciency of mercury removal by thermal treatment on the tailings and
determine the optimal temperature and time.
Mimick in-situ thermal treatment conditions in a pilot setup on soil originating from an
old mercury contaminated industrial site.
Asses the recuperation eciency of gold and mercury by coal gold agglomeration.
Firstly, in chapter 2, it is explained how mercury enters the environment and which health
eects are associated with mercury pollution. Subsequently the link between artisanal and
small-scale gold mining and mercury is made in chapter 3. It explains why mercury is still
in use, what the mercury reducing approaches are and which mercury-free methods exist.
Chapter 4 describes how the sampling campaign was performed while chapter 5 explains which
methods in the laboratory experiments were used to achieve the goals of this study. In chapter
6 and 7 the results from respectively the sampling campaign and laboratory experiments are
explained. An outline of the economic framework for the investigated methods is given in the
discussion in chapter 8. Finally the most important results form the study are summarized in
the conclusion.
Part I
Literature overview
3
Chapter 2
Mercury
Mercury is a constituent element of the earth and has an atom number of 80. As an element,
mercury cannot be destroyed nor created which makes that once liberated or emitted it ac-
cumulates in the environment [UNEP, 2002]. Furthermore, in contrast with other pollutants,
mercury is not restricted in its range and in the size and number of populations it aects.
Due to its high volatility it can travel thousands of kilometres from the original place where it
has been emitted or discarded [UNEP, 2012a]. A striking example is the doubling of mercury
content over the last 100 years in the top 100 meters of the oceans. This results into a 12
times higher concentration of mercury than normal in some species of Arctic animals. Over
90% of this mercury is believed to be from anthropogenic sources [UNEP, 2013].
The mobile, persistent and toxic nature of mercury to human and environment makes a global
solution necessary. This is the reason why the United Nations Environmental Programme
(UNEP) has put combating mercury pollution on its priority list. Recently in January 2013,
the fth session of the Intergovernmental Negotiating Committee (INC5) was held in Geneva
(Switzerland) to prepare a global legally binding instrument on mercury. It gave birth to the
Minamata Convention on Mercury", named after the mercury pollution incident 50 years
earlier. On the same location where the tragedy occurred the the treaty will be signed in
October 2013.
2.1 Mercury emission
Mercury emissions are currently estimated between 5500-8900 tonnes per year. Those emis-
sions can be subdivided into three main categories: natural emissions, anthropogenic emissions
and re-emissions or remobilization [Pirrone et al., 2010].
4
MERCURY EMISSION 5
2.1.1 Natural emissions

Natural releases to air and water are caused by weathering of mercury-containing rocks, vol-
canic eruptions and geothermal activities. They account for almost 10% of the total emissions
[Pirrone et al., 2010] .
2.1.2 Anthropogenic emissions

Research on ice cores in Arctic regions shows that mercury concentrations in the air have
risen drastically from the beginning of the 20th century. This rise is related to the fast
industrialization and intensication of human activities as coal burning and mining [Pirrone
et al., 2010].
Anthropogenic emissions can be subdivided in unintentional and intentional emissions:
Unintentional emissions are considered mercury releases from processes where mercury
is a by-product or waste. A school example is the burning of coal and to a lesser
extent fossil fuels in general. Coal contains a small amount of mercury which is released
into the environment when combusted. Although these mercury concentrations are in
general fairly low the large scale makes that coal burning is one of the main contributes to
mercury emissions. Other examples of unintentional emissions are mining and smelting
of iron and non-ferrous materials, oil rening and cement production.
To reduce these unintentional emissions, pollution control measures on industrial plants
and power plants can be a step in the good direction where for coal combustion up to
95 % of the mercury can be removed by using the latest technologies. By rening the
captured mercury, which enters the supply chain, the demand for mercury is lowered
and so the need to mine mercury [UNEP, 2013].
Intentional emissions happen when mercury is needed in a process due to it specic char-
acteristics. The high specic density and liquid state, for example, made it have excellent
properties for manometers and thermometers. The unique electrochemical characteris-
tics of mercury led to the incorporation into batteries and the use as electrolytic cell in
the chlor-alkali industry[Yera, 2012]. Other consumer products are cosmetics, fungicides,
dental amalgams and uorescent bulbs. Also in industrial processes mercury is being
used as catalyst in the vinyl chloride monomer industry. However, the largest consumer
of mercury can be found in the gold mining industry, more specic the artisanal and
small scale gold mining sector. As mercury forms an amalgam with the gold particles
present in an ore slurry it facilitates the recovery of gold and so reducing the time spent
for the miners to concentrate gold [UNEP, 2013].
The mercury pollution occurs when no attention is paid to consumer products containing
mercury at the end of their life cycle and dumped together with other household waste.
MERCURY EMISSION 6
This results in landlls which slowly leach out mercury into the environment. The waste
coming from chlor-alkali processes and amalgamation by gold miners cause a similar
problem as soil with an elevated mercury concentration is discarded without proper
treatment.
To phase out the current practices, alternative processes and products need to be devel-
oped. This is already the case in the chlor-alkali industry. More ecient use of mercury
in uorescent bulbs also leads to less pollution from these sources.
Coal burning and the artisanal and small-scale gold mining (ASGM) together account cur-
rently for more than half of the total anthropogenic emissions worldwide. This can be clearly
seen in the gure 2.1.
Figure 2.1: Anthropogenic mercury emissions classied by sector [UNEP, 2013] and [UNEP,
2008]
More ecient combustion and better pollution control resulted in a drop of mercury releases
caused by fossil fuel from an estimated 878 tonnes a year in 2005 to around 483,9 in 2010.
The burning of coal contributes to more than 90 % to those gures.
In contrast, in the ASGM sector the large demand for gold, the absence of advanced extraction
technology and the unawareness of the toxicity of mercury causes a steep rise of mercury
emissions to the environment. For 2005 UNEP estimated that about 350 tonnes where released
every year, whereas only 5 years later this gure more than doubled to 727 tonnes.
The total anthropogenic emission reached its highest amount in 1995 with about 2235 tonnes
a year [UNEP, 2008]. Thereafter in the last 10 years the level of emissions stabilized just
MERCURY SPECIATION 7
below 2000 tonnes, with 1930 tonnes in 2005 and 1960 tonnes in 2010. These gures account
for 30 % of the total mercury emissions [UNEP, 2008] [UNEP, 2013].
2.1.3 Re-emissions and remobilization

Re-emissions and remobilization occur when mercury that has been previously deposited on
the surface is released again to the environment. Remobilization occurs when rains and oods
liberate mercury into the aquatic system. Re-emission on the other hand refers to direct
mercury vaporization, for example during forest res or biomass burning [UNEP, 2008].
Due to this fact mercury can enter several times the atmosphere and aquatic environment
before nal deposition. This signies that although mercury emissions stopped rising, the
results will only be visible in several decades. From those considerations UNEP emphasizes
that mercury pollution should be tackled now before the burden on human and nature is
unbearable [UNEP, 2013].
The original source of those emissions can not be determined and so they can not be considered
naturally, as can be seen in gure 2.2. Estimations of the total amount of re-emission use the
understanding of the mercury cycle in air, soil and water and mercury concentrations in the
atmosphere and ice cores [UNEP, 2008]. Remobilization and re-emission are responsible for
60 % of the total mercury emission.
2.2 Mercury speciation
Mercury occurs in several forms in the environment and various processes control its form
and fate. Speciation determines toxicity ( see 2.3), transport pathways and residence time
of mercury in dierent compartments of the environment. The speciation of mercury can be
classied into three groups: elemental, inorganic and organic mercury.
2.2.1 Elemental
Hg
0 or elemental mercury is volatile and sparingly soluble in water. Due to the high vapor
pressure of elemental mercury it is the dominant form in the atmosphere and has a residence
time of 1 to 2 years [O'Driscoll et al., 2005]. Elemental mercury is used in the chlor-alkali
industry, electronic instruments, thermometers and for the extraction of gold particles in
artisanal gold mining.
2.2.2 Inorganic
When elemental mercury is deposited onto the soil, environmental conditions (pH, tempera-
ture, humic acid content, micro-organism) cause Hg

0 to be oxidized to Hg+2 [Gavilan-Garcia,
MERCURY SPECIATION 8
Figure 2.2: Mercury emissions and cycle in air and water, amount noted in tonnes/yr [UNEP,
2013]
2008]. This mercury ion is highly soluble and reacts with chloride, oxygen and sulphur re-
sulting in inorganic compounds or mercury salts [O'Driscoll et al., 2005] like HgS, HgCl 2 or
2 2
Hg Cl . These mercury salts exist as white powders or crystals with the exception of cinnabar
which turns from red to black if exposed to sunlight [Risher and DeWoskin, 1999]. Mining
cinnabar is the main route for producing metallic mercury.
2.2.3 Organic
Organic mercury compounds can be formed via two routes. The rst is by industrial processes
as there are the production of vinyl chloride and acetaldehyde (the Minimata case) which con-
verts respectively dichloride mercury and sulphuric mercury to methylmercury. Methylmer-
cury is also formed by micro-organisms in aquatic environments and accumulates through the
trophic levels into (predatory) sh. According to Selin [2009] almost 90 % of the mercury found
in sh consist of methylmercury. It is the predominant organic species in the environment.
Other organic compounds of mercury are phenylmercury and ethylmercury.

IMPACT ON HUMAN HEALTH 9
2.3 Impact on human health
The expression 'as mad as a hatter' is derived from the neurological problems associated with
hat makers by inhaling mercurious nitrate. Although the toxicity of mercury is widely known,
the related health eects are less known due to their indirect nature [Poulin et al., 2008].
2.3.1 Exposure pathways

The speciation of mercury has a big inuence on the exposure pathway. In the case of metallic
mercury ingestion poses almost no risk to human health due to an uptake of less than 0,01%
through intestines and stomach. On the other hand most of the inhaled elemental mercury
(about 80%) goes from the lungs directly into the bloodstream and then to the brain and
kidneys. For organic (MeHg) and inorganic mercury (Hg

+2 ) the main pathway of exposure is
ingestion. Respectively 95% and 10% of the ingested amount is absorbed in the gastrointestinal
tract [Risher and DeWoskin, 1999] [Poulin et al., 2008]. An overview of the link between source,
mercury species, pathway and associated disease can be found in table 2.1.
2.3.2 Health eects

Elemental and methylmercury are toxic to the central and peripheral nervous system. The
inhalation of mercury vapour can produce harmful eects on the nervous, digestive and im-
mune systems, lungs (with shortness of breath as result) and kidneys. The inorganic salts of
mercury are corrosive to the skin, eyes and gastrointestinal tract, and can cause renal failure
if ingested [Risher and DeWoskin, 1999].
Neurological and behavioural disorders may be observed after inhalation, ingestion or dermal
application of dierent mercury compounds. Symptoms include tremors, insomnia, memory
loss, neuromuscular eects, headaches and cognitive and motor dysfunction. Studies of work-
ers in uorescent tube manufacturing, wood processing, chlor-alkali and thermometer plants
exposed to an elemental mercury level in the air of 20 µg/m3 or more for several years show
mild subclinical signs of central nervous system toxicity. Kidney and immune eects have
been reported. There is no conclusive evidence linking mercury exposure to cancer in humans
[Poulin et al., 2008].
Special attention should be paid to exposure of mercury to children as it seriously hinders
there development. Methylmercury bioaccumulated in sh and consumed by pregnant women
may lead to neurodevelopmental problems in the developing foetus. Transplacental exposure
is the most dangerous, as the fetal brain is very sensitive. Several studies ([Kakita et al.,
2000, Tamura et al., 1978, Matsumoto et al., 1978] report neurological symptoms, associated
with transplacental exposure, including mental retardation, seizures, vision and hearing loss,
delayed development, language disorders and memory loss. In children, a syndrome character-
ized by red and painful extremities called acrodynia has been reported to result from chronic
mercury exposure [WHO, 2007].
Table 2.1: Overview of mercury sources and exposure routes [Bose-O'Reilly et al., 2010]
Mercury Sources Routes of Elimi- Toxicity

exposure nation
Elemental Artisanal gold mining Inhalation Urine CNS
(metallic) Dental amalgams Feces Kidneys
Crematoria Lungs
Thermometers and other Skin (acrodynia
measuring devices in children)
Folk remedies
Volcanoes
Combustion
Waste incineration
Housing on former tailings
Inorganic Food grown in Ingestion Urine CNS
(mercuric contaminated sites Dermal Kidneys
chloride) Thiomersal Gastrointestinal
Cosmetics tract
Folk medicine Skin (acrodynia
Lamps in children)
Photography
Disinfectants
Organic Fish Ingestion Feces CNS
(methyl;
ethyl) Preservatives Parenteral Cardiovascular
Fungicides Transplacen-
tal
2.3.3 Environmental guidelines

International and national guidelines have been set by dierent authorities for air, water, food,
seafood and soil.
Air: The World Health Organization (WHO) set the value for elemental and inorganic
mercury vapor at 0,2 µg/m3 and 1 µg/m3 , respectively, for long-term inhalation expo-
sure. [Bose-O'Reilly et al., 2010].

Water: The WHO guideline value is 1 µg/l for total mercury.
Food: As methylmercury is the main contributor mercury in our diet the tolerable
intake is 1,6 µg methylmercury/kg body weight per week. The tolerable intake of total
mercury has been set at 2,0 µg/kg body weight per day.
Seafood: Methylmercury bioaccumulates throughout the food chain. For this reason
it is not recommended to eat predatory sh or sea animals. Dierent standards have
been set for sh and predatory sh/sea animals (sharks, swordssh, seals, tuna) with
respective values of 0,5 mg/kg and 1 mg/kg.
Soil: The UNEP has set preliminary critical limits to prevent ecological eects at 0,07-
0,3 mg/kg for total mercury content in soil [UNEP, 2002][Bose-O'Reilly et al., 2010]. For
the USA, the Environmental Protection Agency (EPA) dierentiates between the use of
soil for industrial, allotment and residential purpose where the latter has a upper limit
of 1 mg/kg of total mercury in soil [EPA, 2004]. In Flanders new regulation concerning
soil pollution has stringent the values of mercury in soil for residential use to 4,8 mg/kg
[OVAM, 2010].
Chapter 3
Artisanal and small-scale gold mining
When in 1971 the gold standard was abandoned by the United States the price of gold rapidly
rose from 32 $ to about 500 $ in the early eighties and around 1500 $ per ounce nowadays [Ali,
2006]. Beating ination by a tenfold it is clear that investing in gold was a very attractive
investment.
This fact initiated in the 80's a new gold rush. In contrast to the gold rush in the 19th century
its centre was not the United States, Canada or Australia, but third world countries, located in
South and Central America, Africa and South-East Asia, like Peru, Brazilia, Ecuador, Ghana,
Indonesia, etc. In gure 3.1 the estimated mean mercury release of ASGM per country can
be found.
Giving a denition of artisanal and small-scale gold mining is dicult due to the big dierence
in denitions between countries [UNEP, 2012b]. ASGM can be formal or informal, legal or
illegal and can process primary or secondary ores. The sector may be better characterized by
the lack of long term mine planning/control and use of rudimentary techniques [Hinton et al.,
2003].
13% of the worldwide gold supply (330 tonnes) comes from artisanal and small-scale gold
mining but the global workforce is equivalent to that of large scale mining [UNEP, 2010].
Even very conservative estimates suggest that around 20 to 30 million persons are directly
involved with the artisanal and small-scale gold mining industry in more than 70 countries
[Spiegel and Veiga, 2010]. It can be further extrapolated that worldwide 80 to 100 million
people are directly and indirectly dependent on this activity for their livelihood [Veiga et al.,
2009]. This is mainly because of two reasons. The rst is that in contrast to other export
products like coee or cacao, gold can easily be sold at 70 % of its the market value and is
not inuenced by the instability of local governments. The ease of transportation of the noble
metal makes it an appropriate mean to alleviate poverty for marginalized communities. The
second reason is that initial capital investment and operational costs are low, leading to a fast
shift of employment from farmer to miner once gold ore is discovered.
12
GOLD IN NICARAGUA 13
Figure 3.1: Mean total mercury released in ASGM with: no estimate made (•), 0 to 1(•), 1 to
5(•), 5 to 10(•), 10 to 25(•), 25 to 50(•), 50 to 500(•) in tonnes/a (from www.mercurywatch.

org, online accessed on 12 may 2013)
Due to its rudimentary nature, ASGM activities often leave a legacy of extensive degradation
and deplorable social conditions in its wake [Vieira, 2006]. Driven signicantly by poverty,
ASGM is often undertaken by workers with limited economic capacities and limited or no
formal technical training on ways to mitigate the long-terms impacts of their mining activities
on the environment and their health [Spiegel and Veiga, 2010]. These activities are often
conducted close to where the miners live leading to alarming concentrations of mercury in air
(up to 10 000 µ g/ m3 in gold shops) and soil and exposing vulnerable groups like women and
children to the hazardous eects of mercury pollution [van Straaten, 2000]. Contaminating the
water sources and aecting the sh it is clear that the nearby communities are often unaware
of the extent that the insidious poison, mercury, induces.
3.1 Gold in Nicaragua
Due to Nicaragua's slow economic recovery after the revolution and subsequently civil war
between 1979 and 1989, it still is lagging behind its neighbouring countries on the subject
of export, infrastructure and tourism. Nevertheless in recent years the economic growth of
Nicaragua have surpassed that of Costa Rica and Guatemala [AmericaData, 2011].
In 2012, Nicaragua exported $ 422 million of gold, surpassing beef as the country's number
2 export product and just behind coee. Nicaragua's gold exports climbed 16 % last year
[Dispatch, 2013].
GOLD PROCESS 14
The reason for this vast climb is the pro-mining policies, by the current government under
Daniel Ortega, attracting Vancouver-based companies like B2Gold Corp., Golden Reign Re-
sources Ltd. and Cassius Venture Ltd. to invest in the gold mining sector.
Gold-rich areas can be found all over the country. From the North Atlantic Autonomous
Region (RAAN) in the east, Neuvo Segovia in the north, Leon in the west and the Chontales
province in the centre of Nicaragua. An overview can be found in gure 3.2[Journal, 2012].
Figure 3.2: Gold mining in Nicaragua with mines in operation (•) and prospected concession
of Cassius Venture Ltd (•) (www.cassiusventures.com )
Altough these Canadian companies bring employment towards marginalized regions they often
come in contact with existing artisanal and small-scale gold mining communities, the so-called
guiriseros.
According to Veiga [1997] the artisanal mining community in Nicaragua existed of about
3000 to 6000 guiriseros producing between 1 to 2 tonnes of gold. These gures however are
outdated. At present, in la Libertad alone about 3000 guiriseros are active resulting towards a
conservative estimation of a population of 20 000 to 30 000 persons involved in ASGM. About
1,5 tonnes of mercury per annum is released due to ASGM activites in Nicaragua.
3.2 Gold process
Gold reserves mined by artisanal miners can be divided into two categories [Hinton et al.,
2003].
GOLD PROCESS 15
Primary ore Gold particles enclosed in quartz veins, gold-pyrite bearing conglomerates or
sulphide associated gold are examples of primary gold ore [de Andrade Lima et al., 2008]
[Hinton et al., 2003] and are often found at depth. The main characteristics are that the gold
is locked in a rock matrix and has in general a low grade (5-40 g gold/ton) [Spiegel and Veiga,
2010]. To separate the gold from the gangue the ore rst needs to be comminuted.
Secondary ore Placer gold or gold in alluvial, colluvial or elluvial material are considered
secondary ore. These gold reserves can be found in river banks and comes from weathered
primary ore. It can form when highly saline groundwater redissolves primary gold in the near-
surface weathering environment and transports that gold in solution to the air-water interface.
As the gold ore often has already the suitable particle size it can be directly subjected to direct
amalgamation, also called whole ore amalgamation (3.3), or rst concentrated to a high grade
ore.
Figure 3.3: Methods used in artisanal mining operations to extract gold with mercury [Sousa
et al., 2010]
Several techniques are involved in artisanal gold mining:

GOLD PROCESS 16
Communition Communition involves the crushing and grind of ore te reduce particles to
a size suitable to liberate gold from gangue minerals. Sledge hammers are the most primitive
way to reach the desirable particle size, while hammer mills and ball mills oer a mechanized
alternative. In many countries local variants, like arrastras in Nicaragua, chancas in Ecuador
[Velásquez-López et al., 2010] and cocos in Columbia [Cordy et al., 2011], are used instead of
hammer or ball mills often consisting of large stones which, by their weight and movement,
crush the ore [Vieira, 2006]. They oer a cheaper but still mechanized way to liberate gold.
Although these are relative simple mechanical processes they are the most expensive unit
operations in mineral processing because of the high energy consumption and wearing down
rate [Hinton et al., 2003]. Once the gold is liberated it can be subjected to amalgamation or
gravity concentrated as described in the next paragraph.
Gravity separation All concentrating techniques make use of the dierence in weight be-
3
tween the density of gold particles (19,30 g/cm ) and the gangue material (often quartz, 2,65
g/cm ).
3
Sluices boxes, with or without mats, appear crude but are due to their low capital and op-
erating cost still the method of choice for artisanal gold miners. From an operating point
view it makes sense as concentration ratios are obtained between 10 000:1 to as high as 500
000:1 [Vieira, 2006]. As gold particles, even after communition, vary in size, sluice boxes are
better operated in catch swings of larger to ne particles rather than trying to catch the mean
particle size.
More advanced gravity separation techniques are centrifugal gravity concentrators which make
use of a uidized bed spinning-bowl that generates a centrifugal force. In two stages gold
grades of more than 20000 g gold/tonne can be reached which can be directly melted and
avoiding an amalgamation step [Hinton et al., 2003]. Falcon and Knelson concentrators are
school examples of this type of gravity separators. A schematic overview is given in gure
3.4b.
Shaking tables make us of the generation of motion on angled surface covered in parallel
ries to separate the particles based on density and size. Shaking tables, like centrifugal
concentrators, can obtain a higher grade ore. The cost of, for example, the gemini table (as
seen in gure 3.4c) is around 8000 $, an exorbitant amount for artisanal miners.
The capital cost entailed with and the required skilled-labor for the latter two techniques make
that the use is reserved for more advanced mining activities [Hinton et al., 2003].
MERCURY USE IN ASGM 17
(a) Sluice box with matted bottom (b) Centrifugal concentrator
(c) Gemini table with 1) inlet uidized gold ore, 2) ries, 3) water faucet, 4)
outlet tailings, 5) outlet concentrate
Figure 3.4: Gravity separation methods
3.3 Mercury use in ASGM
Mercury amalgamation is currently the most commonly used method to extract gold in arti-
sanal and small-scale gold mining due to its following characteristics:
Ease of use: under the eld conditions in which ASGM operates, mercury provides a
quick and easy method to concentrate gold particles. It is a necessity to avoid robbery
of the gold and if no labour skills are present.
Independent: as almost no skill is required the whole mining process can be accom-
plished by only one person.

MERCURY USE IN ASGM 18
Eective: From a theoretical point of view more ecient methods exist to extract gold
but under the given socio-economic and political conditions amalgamation is often the
optimal method.
Accessible: mercury moves as easily or more easily than many other contraband ma-
terials. So a ban on mercury only results that mercury trade moves into illegality.
Cheap: the cost of mercury is very small if compared to the prot gained by gold.
Current market prices of mercury are around 15 eper kg. In mining camps these prices
are often much higher reaching up to 150 eper kg. If gold is sold at 70 % (22.4e/g) of
its market value and the ratio mercury:gold is 2:1 only 1.3 % of the revenue is used to
purchase mercury [Telmer and Veiga, 2009].
The mercury is largely released into the environment, reaching in 2008 an estimated 1000
tonnes whereof 40 % is emitted directly into the atmosphere. The Mercury Watch database
estimates that releases from small-scale gold mining have increased roughly 30 percent to
1,320 tonnes per year in 2011 due to increased gold mining driven by the high gold price and
high poverty rates in the countries where it is practised [UNEP, 2011a]. By this ASGM is the
single largest source of intentional-release mercury in the world: even larger than coal-red
power generation (as seen in section in 2.1.2).
When amalgamation is applied in the gold extraction process, how the amalgam is processed
and mercury is recovered has a big inuence on the mercurylost :goldproduced ratio. On the
other hand up to only 1 gram Hg or less is lost to produce 1 gram of gold when good mining
practices are applied [Velásquez-López et al., 2010][Veiga and Baker, 2004].
Whole ore amalgamation In this process, mercury is added to all the ore being processed
crushed, ground or sluiced. Whole ore amalgamation is an intensive use of mercury and dra-
matically increases the amount of mercury released to the environment compared to treating
concentrates. When mercury is mixed with the ore the turbulence makes that the mercury
ours rendering it unable to amalgamate with gold and resulting in heavily contaminated
discharges. Ratios of mercurylost :goldproduced can be as high as 100:1, as seen in Indonesia
when excessive amounts of mercury when added with the whole ore into a steel-grinding mill,
likely one of the highest ratios recorded. On average this ratio ranges between 50:1 and 10:1
[UNEP, 2011b]. In this way the whole ore amalgamation contributes to more than 50% of
mercury losses in ASGM [Spiegel and Veiga, 2007].
Open burning This process contributes to 20-30% of mercury losses in ASGM [Spiegel and
Veiga, 2007]. Miners heat amalgam to recover gold. Amalgam is burned openly without a
vapor capture system such as a retort or fume hood. This is done with a torch and crucible or
COMBATTING MERCURY POLLUTION IN ASGM 19
even more crudely in a shovel or metal pan over an open re or directly on wood coals. The
vapors, originating from the burned amalagam, are released to the air and are inhaled by the
miners, their families and others nearby. Eventually it will contributes to the global mercury
pollution and cycle throughout the atmosphere. As the amalgam consist of an approximate 1
unit mercury per unit gold the ratio of this process has an average of 1.3 [UNEP, 2011b].
3.4 Combatting mercury pollution in ASGM
In the previous sections it was stated that mercury pollution is a global concern. Because
of this the United Nations have initiated the 'Global Mercury Project' a program conceived
to support the livelihoods of miners and their communities through stakeholder training ac-
tivities, and the demonstration of safer and more ecient technologies [Spiegel and Veiga,
2010].
3.4.1 Improving awareness and training

Artisanal miners are often not aware of the health eects associated with mercury. Addressing
the miners should be done in a way that considers the cultural background and the restrictions
like illiteracy and small scientic background. Illustrative brochures, comics and videos are
good in capturing the miners attention about the eects of mercurialism. Mentioning impo-
tence as one of the common symptoms is not entirely accurate but it is very eective [Veiga
et al., 2006].
At the same time training should be provided towards the adoption of mercury reducing tech-
niques (as can be seen in the next section) and eventually in instating mercury free techniques.
Education and training should be conducted for a long period of time and adequate follow-
up should be provided. Cooperation with local authorities and equipping them with the
resources needed to encourage cleaner techniques in the miners daily practices can establish
a more sustainable approach. The eorts from UNIDO to implement a "safe-life" programme
in 9 days were noble but pass by to the reality that miners are suspicious about the trainers
intentions and trust rst need to be earned before implementing new practices [Shandro et al.,
2009].
3.4.2 Public opinion

The growing awareness of consumers about the origin of its products also aected gold. In
February 2004, Oxfam-America and 12 other activist groups around the world launched a No
Dirty Gold Campaign. Their activities inform consumers about the heavy cost of gold mining
and to enlist consumer support for reform of mining practices [Ali, 2006]. This resulted
eventually in a Fairtrade and Fairmined label for gold which contributes to the development
of miners communities while protecting the environment and human health. Oro Verde,
SOTRAMI and Cotapata in South-America are projects which are granted to use the label.
3.4.3 Mercury reducing approaches

The two processes, whole ore amalgamation and open amalgam burning, which contributes
together to 70 % of the mercury releases can be tackled adopting some simple techniques:
Amalgamate concentrate When mercury is not added to the whole ore but the gold is
rst concentrated by the sluice boxes, shaking tables or centrifugal concentrators, a lesser
amount of mercury is needed to trap the gold. The biggest incentives for miners to switch to
concentrate amalgamation is the high price of mercury.
Retort When the amalgam is burned mercury is vaporized while the gold stays behind. To
eliminate the exposure of mercury vapours and to recover the mercury retorts are used. The
reluctance to adopt retorts for burning the amalgam have various reasons: loss of gold due
to the 'black-box' eect, not fast enough as robberies mostly occur in this process stage and
the cost associated with retorts [Veiga and Baker, 2004]. Tackling the rst reason UNIDO
introduced the Thermex retort, as can be seen in gure 3.5a. The transparent retorts allows
miners to observe the colour change from silver to gold during heating. Because of the high
cost, small capacity and fragility it only serves training purposes [Babut et al., 2003]. Inex-
pensive retorts can be easily made from plumber material, costing only a few dollars, or even
from scrap ,such as the tin-sh-tin retort (gure 3.5b). As air concentrations can be reduced
from 6000 µg/m3 to 30 µg/m3 of mercury, the importance towards health eects should be
stressed to implement these techniques [Veiga and Baker, 2004].

(a) Retors used for training purpose [Babut et al., 2003] (b) Tin-sh-tin retort [Hinton et al., 2003]
Figure 3.5: Retorts used in artisanal mining activities
Recycle After the mercury is used to amalgamate the gold, it is often oxidized due to
the burning process or contaminated with other minerals. Recycle techniques exist from the
advanced ultrasonic bath to more simple techniques adding a spoon of table salt and using two
radio batteries or a car battery to reactivate the mercury. Discharges of the 'sick' mercury,
which suits no further to capture gold particles, is avoided when these methods are applied
[Shandro et al., 2009].
3.4.4 Mercury free techniques

Depending on the skills and nancial resources of miners, other benecation techniques can
be used [Hinton et al., 2003]:
Chemical extraction
The search for other lixiviants than mercury to extract gold from the ore has a long history.
In 1848 chlorine was added for the treatment of ne gold particles and gold sulphide but
lost popularity once cyanidation was discovered [Vieira, 2006]. Cyanide is the most impor-
tant chemical used in the gold industry because of its wide adoption in industrial mining.
The process requires a pH of more than 11 to prevent formation of poisonous gasses. If
cyanidation is applied after amalgamation it worsens only the pollution problem due to en-
hanced mercury mobilization. Its inherent toxicity and environmental consequences makes it
not advisable for durable ASGM [Cordy et al., 2011]. Further research led to chemicals like
thiourea, thiocyanate thiosulphate, etc., all of them obtaining good recovery in laboratory
experiments. However because of their limited availability their adoption in ASGM is very
small [Swaminathan et al., 1993].

Froth otation
Chemical surfactants are used to recover ne mineral particles from a feed slurry by adsorbing
to the particle surface and rendering it hydrophobic [Hinton et al., 2003]. Concentrates of
up to 3000 g Au can be obtained but skilled workers are required for the operations of these
devices.
Direct smelting
Once a high grade concentrate is obtained after gravity separation of froth otation direct
smelting can be applied. Direct smelting is a high-temperature melting process where uxes
are added to the concentrate to assist melting and react with impurities, separating the metal
from the glassy slag [UNEP, 2011b].
Clean gold sluice

Polymeric magnetic sheets are inserted into an aluminium sluice boxes [Vieira, 2006]. Gold
ore associated with magnetite will form a corduroy-like bed on the sluice oor and eectively
recovers the ne gold. Due to the high prices (75 $ per sluice box), the limited capacity and
availability the use is not widespread.
Coal gold agglomeration

In 1980 Australian engineers from BP discovered a process to recover gold with ne coal
particles. The hydrophobic surface of gold nes agglomerates with the coal nes and by
adding oil to the suspended mixture aggregates are formed. These aggregates can be used
again for a next batch of gold ore or can be ashed to release the gold from the coal-oil matrix
[Sen et al., 2005]. The starting materials, charcoal with a low ash content and gasoline or
vegetable oils, are easily obtained or already available on the mining site, this process can be
considered as an good alternative for the amalgamation practices.
3.4.5 Mercury removal from tailings

When the tailings of artisanal gold mining are discarded without proper waste management
the mercury present will leach out and pose a long-term health hazard towards the surrounding
environment and communities. By applying dierent techniques, the hazard originating from
the presence of mercury could be reduced to a minimum.

solidication/stabilization
Immobilizing the hazardous contaminants in the environment by means of physical and chem-
ical agents is called solidication/stabilization. Solidication uses physical means to bind
the toxic substances within stabilized mass while stabilization uses chemical means to induce
chemical reaction between the stabilizing agent, like sulfur polymer cement, Portland cement
or polyester resins, and the pollutants to reduce the mobility [Otto and Bajpai, 2007].
Soil washing and acid extraction

Pollutants which preferable adsorb on the ne soil fraction can be treated by soil washing.
By suspending the ne fraction, separating it and further treating it to remove the pollutant
from the particle surface the contamination can be reduced.
2 4 3
Acid washing makes use of a strong acid (H SO , HCl or HNO ) to extract the mercury from
the soil. This simple method only can be applied to certain forms of mercury occurring in the
soil [Otto and Bajpai, 2007].
Vitrication
Applying high-temperature to the soil results in vitrication rendering the pollutant present
immobile. The mercury will not leach out and the vitried end product is chemically durable
[Otto and Bajpai, 2007].
Phytoremediation
Biological, chemical and physical processes that are associated with plants and that help
remove the toxicants are applied in phytoremediation. The plants remove the mercury by
root take up and incorporate it into their bodies. This makes remediation possible for a fairly
low cost. Subsequently the plants need to be treated to extract the pollutant and give it a
nal destination [Wang et al., 2012].
Thermal treatment
The volatility of mercury makes it possible to transfer it from solid phase in the soil to the gas
phase by heating at a relatively low temperature, compared to other metals. Theoretically, if
no HgO or HgS is present the temperature needed to remove all mercury is less ten 600
◦ C.
Ex-situ When the waste or soil is excavated and transferred into an oven to be thermally
treated the term ex-site thermal treatment is applied. The o-gasses are cooled down to
adsorb the mercury vapours onto activated carbon or form liquid mercury.
In situ Subsurface soils are heated with the aid of surface heater blankets or an array of
vertical heater/vacuum wells. A combination of dierent processes, evaporation into the air
stream, steam distillation into the water vapor stream, boiling, oxidation and pyrolysis, help in
the removal of mercury by vaporization. Subsequently, the vapours are treated as previously
mentioned [Park, 2012][Vos et al., 2012].
3.4.6 Conclusion
The alternatives to amalgamation are still in their infancy and need to be translated from
laboratory scale to application in the eld. As none of them will provide the same robustness
and ease of use of mercury proper training should be given to the artisanal miners. As this
will take a long time the UNEP's focus now lies in the reduction and recovery of mercury
throughout the process, it even has assembled an illustrated guide to educate artisanal miners
in good mining practices [UNEP, 2012b]. Mercury-reducing approaches will not only have a
positive eect on the environment and human health, they can also be economically driven
as the cost of acquiring mercury begin to rise [Ali, 2006]. In the long term amalgamation
practices will be phased out as mercury-free techniques become economical alternatives and
the consumers awareness has drawn artisanal miners to simultaneously alleviate them self
from poverty and protect the environment.

Part II
Material and methods
25
Chapter 4
Sampling Campaign
Samples were collected during a two-month eld study from October until December 2012
in la Libertad in the region Chontales, Nicaragua. The sampling campaign included in total
10 arrastras and 3 reference sites which were visited. The locations are presented in gure
4.1. During this visit a self-reported questionnaire was conducted. All samples were labelled,
dried at room temperature and stored in air-tight plastic bags. The details of the sampling
campaign are discussed in Appendix A.
Figure 4.1: Arrastra sites sampled in la Libertad (•) and reference sites (•)
26
SAMPLE PREPARATION 27
4.1 Sample preparation
Part of the tailings samples from one site were mixed together to obtain a representative
sample from the tailing site itself for further use in the experiments: thermal treatment and
coal-oil-gold agglomeration (5.5 and 5.6).

Chapter 5
Laboratory experiments
5.1 Reagents
All reagents used in the following experiments were analytical grade or better. Exceptions are
the corn oil, acquired at the local supermarket, and the biochar acquired from the department
of Biosystems Engineering (Ghent University). For the analyses Milli-Q was used to prepare
the standards and extraction reagents.
5.2 Analytical methods for soil characterization
2
Soil characteristics which were determined include pH-KCl, pH-H O, total organic matter,
chloride content, electrical conductivity and soil texture. All procedures are describe in 'Man-
ual for the soil chemistry and fertility laboratory: analytical methods for soils and plants
equipment and management of consumables' [Van Ranst et al., 1999] except for the soil tex-
ture and chloride analyses.
5.2.1 pH-H2 O and pH-KCl

Ten gram of soil was weighed and transferred into a 50 ml beaker where 50 ml of distilled
water was added. After 18 hours of equilibration the pH of the supernatant was measured
with a pH glass-electrode (Orion A).
To determine the pH-KCl 10 g of soil was mixed with 25 ml of 1 M KCl in a 50 ml beaker.
After 10 minutes of equilibration the pH was measured with a pH glass-electrode (Orion A).
28
ANALYTICAL METHODS FOR SOIL CHARACTERIZATION 29
5.2.2 Electrical conductivity

After weighing 10 gram of soil and addition of 50 mL distilled water in a 250 mL Erlenmeyer
ask, the sample was shaken on a shaking plate for 30 minutes. Electrical conductivity was
determined in the suspension, which was ltered over white ribbon lter paper (Machery-
Nagel MN 640 m, φ 125 mm), using a Microprocessor Conductivity Meter (Wissenschaftlich
Technischen Werkstaten, Weilheim, Germany).
5.2.3 Organic matter

The organic matter of the tailings was determined by measuring the dierence in weight of a
2 g sample after 2 hours at 550 °C in a mue furnace.
5.2.4 Chloride
To determine the chloride content an adapted Volhard method was used. Ten gram of soil
was weighed, transferred into a 250 ml Erlenmeyer together with 50 ml 0,15 M HNO 3 and the
Erlenmeyer was shaking for half an hour. Afterwards the solution was ltrated into a beaker
and the lter was rinsed with 20 ml of 0,15 M HNO . 3

The titration reagent was 0,05 M AgNO 3 where its titer was determined by titrating 0,01 M
NaCl. The ltrate was then titrated and the equivalence point was determined by potentio-
metric measurements using a combined silver electrode.
5.2.5 Soil texture

Soil texture was determined by the Bouyoucos procedure [Goh et al., 1999]. Forty gram of
oven-dried soil was weighed and transferred into a 1 L plastic bottle. After addition of 100 mL
of dispersing agent and 250 mL distilled water, the bottle was covered with a cap and shaken
overnight. Afterwards the dispersed soil sample solution was transferred into a sedimentation
cylinder and distilled water was added to reach 1 L total volume. The sedimentation cylinders
were placed in a water bath to ensure a constant temperature of 22

◦ C. To examine the soil
texture the cylinder was closed with a rubber stopper and shaken thoroughly for a minute.
As soon as mixing was complete, the hydrometer was carefully lowered into the suspension.
A reading was performed at time 0 and after 1, 5, 90, 120, 960 and 1440 minutes. Based on
the calculation from the recordings, soil texture was determined.
5.2.6 Particle size distribution

A fractionation into dierent particle size classes was executed to determine the particle size
distribution. The samples were screened through a series of 8 sieves with sizes 700, 500, 400,
DIGESTION 30
300, 200, 150, 100, 63 µm. The sample was divided into 9 categories and the average particle
size of each fraction was calculated by taking the average of the two adjacent sieve sizes except
for the largest and smallest particle size fraction.
5.3 Digestion
To determine mercury by CVAAS (5.3.1), gold by ICP-MS (5.3.2) and sulphur by ICP-OES
(5.3.3) the samples require an important and indispensable pre-treatment step involving dis-
solution and release of the element from the soil matrix.
The aqua regia digestion procedure (ISO 11466:1995 and European Standard EN 13650, EN
13657) is regarded adequate for analysis of total recoverable mercury, gold and sulphur in soil
[Tara²kevi£ius et al., 2013].
The procedure consists of digesting samples on a hot plate with 3 parts of HCl (37 % m/m )
and 1 part of HNO 3 (65 % m/m ). The HNO 3 provides the oxidizing power and reacts with
the concentrated HCl to form NOCl, as can be seen in the following reaction:
3 HCl + HNO3 −−→ 2 H2 O + NOCl + Cl2
For soil samples about 1 gram of soil together with 10 ml aqua regia is mixed into a 100 ml
erlenmeyer and sealed with a watch glass to prevent loss by evaporation. The mixture was
left to react overnight and afterwards the erlenmeyer is put on a hot plate at 150
◦ C for 2
hours. When the sample solution has cooled it is ltered through lter paper (Machery-Nagel
MN 640 m, φ 125 mm) to remove undigested solid material. The lter and the residue were
3
rinsed multiple times with 1% HNO . The ltrate is collected in a 100 ml volumetric ask.
5.3.1 Mercury analyses

For the analyses of mercury present in the samples a method called Cold Vapour Atomic
Absorption Spectrometry (CVAAS) was used.
The low vapour pressure of metallic mercury, 0,0016 mbar at 20

◦ C, results in concentration
2
of 14 mg/m . For this reason no atomizer is needed to analyse mercury.
As the mercury should be in its metallic form a reducing agent is fed to the sample. This is
done by SnCl 2 according to the following reaction:
Sn
+2 + Hg+2 −−→ Sn+4 + Hg0
After the reduction, mercury is separated from the sample matrix by vaporization and trans-
port by the inert gas, argon, towards to absorption cell. The absorption of light by Hg
0 occurs
MERCURY FRACTIONATION 31
at 253,7 nm and a measurement is conducted at this wavelength with a hollow cathode lamp
as light source. The mercury content of the sample is then determined by comparing the
intensity of absorption with the standards curve.
The apparatus used in this study to determine mercury is the QuickTraceM-7500 (CETAC).
5.3.2 Gold analyses

The analysis of trace metals present in the ppb range is generally executed by using an
Inductivly Coupled Plasma Mass Spectrometer apparatus (ICP-MS) because of its higher
sensitivity and precision.
The ICP-MS apparatus used in this study is an ELAN

® DRC-e ICP-MS (PerkinElmer) and
consists of an ionization and segregation part. The sample is vaporized, transported by argon
and fed to a torch which is placed in a coil supplied with a radio-frequency electric current. Due
to the fast changing magnetic eld, the electrons, originated from a spark, change directions
and initiate collisions with the gas atoms and by doing so forming a plasma. The plasma
ionizes the atoms present in the sample. The ionized atoms are fed to a mass spectrometer
which executes the segregation based on the mass of the atoms.
To determine the content of gold present in the soil the intensity in the mass spectrometer
was measured for the mass of 197. The concentration was then calculated by means of the
standard curve, the respective intensities and adjusted with the internal standards of Ga and
Rh [Elzey et al., 2013] [Cherevko et al., 2013].
5.3.3 Sulphur analyses

The sulphur content of the soil was determined by means of an Inductive Coupled Plasma
Optical Emission Spectrometry (ICP-OES).
The ICP-OES also consist of a torch which, by the supplying of a strong radio-frequency
changed magnetic eld, induces a plasma. Elements introduced into the plasma will emit
light at certain wavelengths. These spectral lines are unique for each element. For sulphur
analysis the wavelengths at 393,3 and 543,8 nm are measured [Ackerman et al., 2012] [Khan
et al., 2012].
The ICP-OES apparatus used for sulphur analysis is a Vista-Pro CCD Simultaneous ICP-
MS (Varian).
5.4 Mercury fractionation
To asses the type and binding forms of mercury in the soil a sequential extraction previously
described by Coufalk et al. [2012] was carried out. By subjecting the soil to dierent envi-
MERCURY FRACTIONATION 32
ronmental conditions dierent fractions can be extracted. This is done by the use of various
chemical extractants.
The sequential fractionation compromises 5 steps identifying the following fractions: (a) active
mercury, (b) HCl-dissoluble mercury, (c) organic-bound mercury, (d) Hg 0 form and (e) residual
mercury. The sequential extraction procedure steps and the reagents used are described in
table 5.1
Table 5.1: Dierent steps and fractions of sequential procedure with reagents used
Step Mercury species Reagents
Active mercury
I (including soluble mercury 20 ml of 0.1 M CaCl 2

and exchangeable mercury)
20 ml of 1 M HCl
II HCl-dissoluble mercury
+ 0.5 ml of 1% CuSO 4
III Organic-bound mercury 20 ml of 1% KOH
0
IV Elemental mercury (Hg ) 10 ml of 2 M HNO 3
V Residual mercury 10 ml of aqua regia
5.4.1 Step I (Active mercury fraction)

One gram of soil sample was weighed into 50 mL polypropylene centrifugal tubes and twenty
milliliter of 0.1 M CaCl 2 solution was added into the tubes. The tubes were thoroughly shaken
on a shaking plate for half an hour and centrifuged at 3500 rpm for 10 minutes. The complete
supernatant was separated and put into an Erlenmeyer ask to be heated for digestion at 150
◦ C for 2 hours after the addition of aqua regia. The Erlenmeyer ask was covered by a watch
glass during the digestion. After digestion, the extracted solution was transferred into the 50
mL volumetric ask with 9.5 mL of HCl after being ltered over a ltration paper (Machery-
Nagel MN 640 m, φ 125 mm). Total mercury from the extracted solution was determined
using the method described in 5.3.1.
5.4.2 Step II (HCl-dissoluble mercury)

The residue of Step I was brought back in solution in a 50 mL polypropylene centrifugal tube
after addition of 20 ml of 1 M HCl and 0.5 ml of 1 % CuSO 4 solution. Afterwards, shaking,
centrifugation, sampling, and the analysis procedure described in Step I were applied.
THERMAL TREATMENT 33
5.4.3 Step III (Organic-bound mercury)

For the determination of the organic-bound mercury the residue of step II is resuspended with
20 ml of KOH solution. Afterwards, shaking, centrifugation, sampling, and analysis procedure
described in Step I were applied.
5.4.4 Step IV (Elemental mercury or Hg0 )

In Step IV, 10 ml of 2 M HNO 3 was added into the residue of Step III to determine the
elemental mercury. Afterwards, shaking, centrifugation, sampling, and analysis procedure
described in Step I were applied.
5.4.5 Step V (Residual mercury)

The residue of step IV was subjected to the following procedure to determine the residual
mercury. Aqua regia was added to the residue and after mixing the sample tube was set in a
water bath at 90
◦ C for 4 hours to digest. After the sample was cooled down it was ltered
over a lter paper (Machery-Nagel MN 640 m, φ 125 mm) and into a 100 ml volumetric ask.
The analysis is as described in 5.3.1.
5.5 Thermal treatment
5.5.1 Experiment to asses the removal eciency as function of temperature

By heating the contaminated soil at a certain temperature the removal of mercury can be
estimated and an image of the dierent forms in which mercury is present in the soil can be
formed.
A total of 10 samples were randomly drawn from the tailings population (HS, NT and T as
can be seen in table A.3) and 5 samples of the surroundings of the arrastra site or distributions
(D). From each sample 1 gram was weighed and transferred into a crucible cup.
The soil samples were subjected for 24 hours to 100

◦ C, 150 ◦ C, 200 ◦ C, 250 ◦ C, 350 ◦ C, 400
◦ C and 450 ◦ C in a mue furnace. An overview of the treatment can be found in table 5.2.
Afterwards the treated soil samples were subjected to the analysis described in section 5.3.
5.5.2 Experiment to optimize treatment time and temperature

To determine if thermal treatment temperature and duration could be lowered without signif-
icantly aecting the mercury removal eciency, the following experiment was conducted.
Table 5.2: Overview of treatments used when studying mercury removal as function of tem-
perature
temperature (°C) 0 100 150 200 250 300 350 400
tailings (# samples) 10 10 10 10 10 10 10 10
distribution (# samples ) 5 5 5 5 5 5 5 5
time (h) 24 24 24 24 24 24 24 24
From each arrastra site a representative sample was composed and giving the associated owner
initials as reference, as can be seen in table A.3. From each representative sample 1 gram was
weighed and transferred into a crucible cup.
The tailings of the 4 selected sites where subjected to 4 dierent temperatures: 250
◦ C, 270
◦ C, 290 ◦ C, 300 ◦ C. At each temperature, 4 thermal treatment durations were applied: 1, 2,
3 and 5 hours.
Afterwards the treated tailing samples were subjected to the analysis described in section 5.3
to determine the mercury content.
5.5.3 Pilot setup: in-situ thermal treatment

Thermal treatment can be executed by feeding the contaminated soil to a furnace which is
called an ex-situ method. An in-situ method exist of applying heat to into the soil at the site.
The heating can be done by injecting hot air or steam to the soil. We used a pilot setup to
mimick in situ thermal treatment.
The soil used in the experiment was excavated at an old mercury-contaminated industrial site
in Belgium. Homogenization was done manually before thermal treatment.
Pilot setup
The reactor in which the thermal treatment is executed consist of three concentric cylinders.
The inner cylinder is the heating element and is in contact with the soil in the middle. The
outer cylinder contains insulation to ensure a homogeneous temperature in the soil sample.
A total of 23,95 kg of soil was loaded into the second compartment. Seven temperature
sensors are placed for adequate follow up of the temperature evolution in and outside the
reactor. A rst sensor (T1) is placed to regulate the temperature of the heating element by a
PID controller. The second (T2) measures the temperature of the wall between the heating
element and the soil. To quantify the temperature in the soil one sensor (T6) is located near
the heating element and the other three sensors (T3, T4 and T5) are put closer to the outside
of the reactor. The last sensor (T7) is located at the outside of the reactor where an extra
layer of insulation has been placed to minimize cooling down from the forced convection by
the air ow of the fume hood. A cross section of the reactor is presented in gure 5.1.
Figure 5.1: The cross section of the thermal treatment reactor
The vapours produced by the treatment are transported through two in series water-cooling
elements and the condensate is collected in a 3 l Erlenmeyer. The cooled air is forced into
two activated mercaptan coated carbon lters (Norit

® ) by means of a pump. The activated
carbon lters capture the mercury in the ue gasses. The pump outlet is located in a fume
hood.
An overview of the pilot setup is given in gure 5.2. The reactor is directly connected to the
conical hood in the experiments, where in the gure a gap is drawn to have an insight into
the reactor.
Treatment
The temperature set point of the heating element was xed at 300
◦ C. Once the moisture in
the reactor was removed and the temperature of the soil reached a stable level, the reactor
was operated for seven days at this temperature. Subsequently the set point for the heating
element was raised to 400

◦ C and afterwards 500 ◦ C, where after each time the temperature
in the soil stabilized, the reactor was kept at these temperatures for seven days.
Before each adjustment to the set point temperature a sampling was performed to determine
the removal eciency of the treatment, as is described in the next paragraph.

COAL GOLD AGGLOMERATION EXPERIMENT TO EXTRACT GOLD 36
Figure 5.2: Schematic overview of the pilot setup with 1) reactor with soil, 1a) isolation, 1b)
soil, 1c) heating element, 2) water cooling, 3) condensate collector, 4) active coal lters, 5)
pump.
Sampling
Prior to the treatment, 4 samples were taken from the homogenized soil sample. After each
seven-day thermal treatment, 4 soil samples were taken from the pilot setup. Two of them
are located close to the wall with the heating element (at 0 cm) and the two other at 10
centimetres of the wall.
Each soil sample was seperated into three size fractions size of < 1 mm, 1-2 mm and > 2 mm.
For each of the samples the mercury content was determined by the method described in 5.3.
Before a next treatment was performed the activated mercaptan coated carbon (Norit
® )
lters were replaced with new uncontaminated carbon. The removed carbon was crushed and
following the procedure described in 5.3 the mercury content was determined.
5.6 Coal gold agglomeration experiment to extract gold
The contacting and adhesion process of gold particles with agglomerates is the key element
that lies at the heart of the coal gold agglomeration process. The recovery of gold by the use
of coal is based on the hydrophobic characteristics of gold. As mercury is also hydrophobic
simultaneous adsorption onto the coal particles is possible. Due to the thorough mixing of
the tailings with the oil and coal nes, absorption occurs at the oil water interface and the
metal are nally deposited on the coal nes. The coal nes form spherical aggregates under
the sheer conditions in the reactor [Wu et al., 2004a]. In essence, the agglomerates can be
considered as a kind of carrier or absorbent of gold particles.
In general a xanthate collector is added and adsorbs on the gold particles surface facilitating
the recovery by increasing the attachment probability (Pa ). The longer the hydrocarbon chain
the higher the Pa [Wu et al., 2004b] and the better the recovery of gold.
A ow diagram of the experimental setup is presented in gure 5.3.
Figure 5.3: Flow diagram of the experimental setup of coal gold agglomeration [Kotze and
Petersen, 2000]
5.6.1 Experimental conditions

The coal gold agglomeration was conducted in a 250 ml beaker with 180
◦ baes. To ensure
sucient mixing the solution was magnetically stirred at 1200 rpm.
The oil used in the experiments was corn oil obtained at a local supermarket. It has a density
of 0,92 g/cm
2 and a viscosity of 52,3 cP at 24 ◦ C [Noureddini et al., 1992].
In the experiments three coals were used to asses the recovery of gold and mercury. Normal
activated carbon (SAK), activated mercaptan coated carbon (MAK) and biochar (BC) ob-
tained from the Laboratory of Biosystem Engineering at the Faculty of Bioscience Engineering,
(Ghent University). As collector, potassium ethyl xanthate (PEX) was used, a commercial
3
yellow powder(bulk density 0.62 g/cm , water soluble, purity over 90 %), recently acquired
from Merck.
Factors adjusted to optimize recovery were oil:coal ratio, coal:tailings ratio and % solids (by
weight).
The experiments consisted out of three parts: the agglomeration, contact phase and recovery
phase
The agglomeration phase 100 ml of water is added to a certain amount of coal and oil in
a 250 ml beaker and thoroughly mixed for 15 minutes.
Contact phase After the 15 minutes of agglomerating the gold ore was added together with
the potassium ethyl xanthate collecter and mixing was continued for one hour.
Recovery If small agglomerates were formed the mixture was passed through a 300 µm
sieve to separate the coal aggregates from the ore. If no agglomerates were formed the coal
was scraped of from the top of the solution. The coal nes or agglomerates and processed
gold ore were stored in an aluminium tray for further treatment.
5.6.2 Pre-treatment
The ore and coal samples were dried overnight at 50
◦ C to limit mercury evaporation and
preserve the mercury present in the particles. After drying 1 gram was subjected to the
procedure described in 5.3 to determine the mercury and gold content (5.3.1 and 5.3.2).
The coal was ashed and then analysed for gold. This was done to evaluate the eciency of
previous method on gold extraction. One gram of coal was weighed and transferred into a
◦
crucible cup and ashed at 800 C for 1 hour. Afterwards, the ash was digested according to
procedure described in section 5.3 and gold analysis was performed as described in 5.3.2.
Part III
Results and discussion
39
Chapter 6
Sampling campaign
By sampling from 10 dierent sites, where in total 18 milling facilities were located, the results
can be considered as representative with respect to the total population of 53 grinding facilities
on the arrastra sites in la Libertad.
The results of the questionnaire, as presented in table 6.1, give a good idea of the impact of
artisanal gold mining in la Libertad. The typical grinding facility is an arrastra or bolillon,
as described in appendix A.1. The main dierence between these two types is the amount of
ore that can be pulverized per day. The average tonnage of ore that can be processed in one
milling facility per day is 1,1 and about 31,7 g of mercury is used to extract 10,6 g of gold, as
seen in table 6.1. Thus, in total, a daily amount of 58 ton gold ore is processed in the milling
facilities in la Libertad resulting in an average of 562 g gold extracted. The ratio gold extracted
per mercury used is about 1 to 3 and leads to an estimated 1686 g mercury used daily for the
amalgamation process. The ratio mercuryl ost:goldp roduced will be lower than the previously
mentioned 3 to 1. Firstly the excess mercury obtained when the amalgam is passed through a
piece of cloth is recovered and reused. Secondly the use retorts are widespread in la Libertad
and mercury is recycled. These practices are economically driven because of the high price of
mercury (3000 C$ per libra of 250 $ per kg mercury).
The renting cost of the grinding facility reported by the guiriseros does not dier greatly and
is 1500 cordobas or 63 US$ per day. About half of this amount is used to cover the cost of
the electricity and accounts on a month basis for about 1000 US$ per grinding facility.
40
Table 6.1: Summary of the results of the self-reported questionnaire
arrastra owner arrastra ore processed gold extracted mercury used Au:Hg renting cost
type per day (t) per ton ore (g) per ton ore (g) (C$/day)
Leopoldo Marin arrastra 0,5 7,0
Ayvin Ulises bolillon 2,0 5,0
bolillon 2,0 5,0
Juan Carlos bolillon 0,6 16,0 12,5 1 2/7
arrastra 1,6 6,2 12,5 1/2
Yasser Alleman trapiche 3,5 15,0 32,4 1/2
Wilder Mareina arrastra 0,5 12,0 84,0 1/7 1200
bolillon 1,0 12,0 42,0 2/7 1500
Humberto Perez bolillon 1,0 15,0 14,0 1 1500
Carlos Marin bolillon 1,0 15,0 42,5 1/3 1500
bolillon 1,0 15,0 42,5 1/3 1500
bolillon 1,0 15,0 42,5 1/3 1500
bolillon 1,0 15,0 42,5 1/3 1500
Fernando Obregon arrastra 0,5 15,0 61,8 1/4 1500
arrastra 0,5 15,0 61,8 1/4 1500
Gustavo Diaz bolillon 1,5 8,0 30,2 1/4 1500
bolillon 1,0 8,0 30,2 1/4 1500
bolillon 1,0 8,0 30,2 1/4 1500
Pablo Emilio arrastra 1,0 5,0 18,1 2/7 1500
bolillon 0,5 10,0 36,1 2/7 1500
average 1,1 10,6 31,7 1/3 1479
1st quartile 0,6 7,8 30,2 1/4
3d quartile 1,1 15,0 42,5 1/3
41
Chapter 7
Laboratory experiments
7.1 Soil characteristics of the tailings
7.1.1 General properties

Results from the analyses conducted on the tailing samples are presented in table 7.1. As
tailings mostly exist of crushed ore the data follow the expectation of having little organic
matter, carbonate, nitrogen and sulphur. The tailing samples exhibit a pH ranging from
slightly acid to slightly alkaline. The high pH (above 8) in some samples could be caused
by the relatively high carbonate content (of more then 1 %). A low electrical conductivity
indicates that almost no soluble salts are present in the sample.
Table 7.1: Soil characteristics of the tailing samples
sample pH H2 O pH KCl EC at 20,4°C total organic total CaCO3 total N total S

reference (µS/cm) matter (%) (g/kg) (g/kg) (mg/kg)
CMT2015 6,92 7,06 28,3 0,71 3,75 0,23 8,2
FOT11530 5,41 5,17 129,1 0,80 1,25 0,15 205,3
FMT1015 8,18 8,57 328,0 1,29 13,75 0,22 55,5
YAHS2 6,80 6,24 48,6 0,33 6,25 0,24 60,4
HPHS1 8,26 7,68 17,7 1,19 6,25 0,23 3,3
FMHS2 8,42 8,45 44,8 1,73 13,75 0,16 21,1
FONT2015 6,89 6,17 244 1,40 8,75 0,17 210,4
GDNT2015 8,43 8,34 23,4 0,44 20 0,25 3,5
AYNT11530 8,21 8,49 35,4 0,85 6,25 0,29 4,4
PENT11530 6,37 5,24 44,5 1,50 3,75 0,33 25,9
average 7,39 7,14 94,39 1,02 8,38 0,23 59,80
st. dev. 1,05 1,36 107,48 0,47 5,78 0,06 80,70
The chloride content, only determined on 4 tailing sites, is very low. This conrms that almost
42
SOIL CHARACTERISTICS OF THE TAILINGS 43
no soluble salts are present.
Table 7.2: Chloride content of tailings
tailingssite total chloride

(mg/kg tailing)
JC 13,58
AY 13,46
FO 12,99
GD 8,08
average 12,03
st.dev 2,65
7.1.2 Soil texture

The samples were classied according to the United Stated Department of Agriculture (USDA)
soil texture triangle according to their percentage of clay, silt and sand (7.1). It can be
concluded that all tailings have a low clay fraction and can be classied as loamy sand, silt
loam or sandy loam.

Figure 7.1: Soil texture of tailing samples: CMT2015, FOT11530, FMT1015, AYNT11530,
PENT11530 (•),YAHS2, HPHS1(•), FMHS2, FONT2015, GDNT2015(•)
7.1.3 Particle size distribution

In gure 7.2the particle size distribution is presented. The characteristic diameter that retains
half of the particles population (d50 ) varies between below 63 µm for one tailing site (JC) and
83µm for the other three. For all four samples 95% of the weight was contributed by particles
smaller than 250 µm.
(a) (b)
Figure 7.2: Size distribution of the particles in tailings from 4 sites

7.1.4 Mercury and gold in tailings

The samples taken from the dierent sites where divided according to their origin: the tailings
and the surrounding area (distribution).
The gold present in the tailings has an average concentration of 3,82 g/ton tailing but shows
a great variation in concentration ranging from above 5,6 to below 1,94 g/t. This could be
addressed to the eciency by which the gold miners recover their gold. According to Murthy
et al. [2003], all of the samples are above the cut-o level (of 1,75 g/ton) below it will be not
anymore economically viable to use the ore directly.
In the distribution samples, the gold content is more then 3 times lower, i.e. 1,23 g/ ton soil.
The mercury content in tailings exhibit an even greater variation in concentration than that
of gold. The heterogeneity can be explained by the dierence in operation of the extraction
process and the sampling method. No relation between the mercury content and the examined
soil characteristics could be revealed. On average 8,12 g Hg/ton tailing is present. Compared
to the worldwide background level of mercury, ranging between 0.01 and 0.5 ppm, the con-
centration is 16 to 800 times higher [Park, 2012]. It also exceeds the tolerable levels declared
by the US EPA (1 ppm) and the Flemish organisation, OVAM (4,8 ppm) [EPA, 2004][OVAM,
2010].
A much lower content can be found in the surrounding area. These concentration however are
still higher then the natural background concentration of mercury [Park, 2012].
Analysis of the composed samples per tailing site, conducted in duplicate, shows similar results.
Remarkable is that with a higher content of gold a higher content of mercury is found. A
possible explanation could be that for higher gold grades more mercury is used or that by a
using mercury concentration higher then a critical point the mercury starts ouring, capturing
the ne gold but rendering it more susceptible to be washed out [Hinton et al., 2003]. This
latter process shows that by applying excess mercury gold recovery may be decreased in
contrast to what the artisanal gold miners often believe.
It could be noted that tailings with a ner characteristic particle size diameter have higher
content of gold and subsequently mercury if the gure 7.2 and table 7.4 are compared.
Table 7.4: Mercury and gold content of the composed sample per tailing site
tailing site total Hg (mg/kg) total Au (mg/kg)

JC 8,52 ± 0,12 5,47 ± 0,10
AY 6,12 ± 0,01 4,11 ± 0,45
FO 11,46 ± 0,24 5,76 ± 0,08
GD 3,46 ± 0,03 3,13 ± 0,18

Table 7.3: Mercury and gold content in tailing and distribution samples
sample reference gold (mg/kg) mercury (mg/kg)

CMT2015 3,62 15,21
FOT11530 5,30 14,81
FMT1015 4,26 2,10
YAHS2 1,94 3,98
HPHS1 4,25 15,92

tailings
FHS2 5,30 16,86
FONT2015 4,83 3,09
GDNT2015 4,06 6,39
AYNT1530 3,15 4,19
PENT11530 2,97 3,59
PET1015 2,70 7,90
PEHS2 3,41 3,43
average 3,82 8,12

st. dev. 1,04 5,82
distribution
FOD21530 2,16 2,41
GDD1015 0,79 1,77
RPD2015 1,42 2,01
CMD21530 0,55 1,57
average 1,23 1,94

st. dev. 0,72 0,36
A simplied overview of the gold extraction process, executed in la Libertad, can be found in
7.3 based on the data from the questionnaire and the analysis of the tailings.
Figure 7.3: Overview of the gold extraction process in la Libertad
Mercury and gold by fraction

The analyses of the dierent particle size fractions from the two tailing sites, AY and FO, were
conducted in triplicate. A similar trend in average gold and mercury concentrations as function
of particle size could be derived from gure 7.4. Mercury and gold seem to be associated with
an average ratio of 2:1 mercury:gold. Higher concentrations of mercury can be found in the
ner and coarser particles while for gold only the nest fraction contains signicantly higher
amounts then the coarser one. According to Hinton et al. [2003], amalgamation is only ecient
for particles coarser then 74 µm, resulting in the remarkable high gold content in the minus
64 µm fraction.
(a) Mercury content in function of particle size (b) Gold content in function of particle size
Figure 7.4: Distribution of gold and mercury in function of particle size
From table 7.5 it is clear that due to the high content of gold and mercury in the ner fractions
and their large share in the weight of the samples they deserve the most attention towards
recuperation of gold and remediation. More than half of the gold and mercury is located in
the minus 64 µm fraction while more than 90 % of the gold and mercury can be found in the
minus 150 µm fraction.
Table 7.5: Gold and mercury content and their distribution among particles size fractions for
tailings pile from the sites AY and FO
average weight mercury content gold content mercury gold

size (µm) distribution (%) (mg/kg) (mg/kg) distribution(%) distribution(%)
<63 40,25 15,53 9,69 59,26 66,99
81,5 20,37 8,79 4,08 16,97 14,26
125 25,11 6,28 2,58 14,95 11,12
175 6,64 4,49 2,59 2,83 2,95
250 3,30 6,25 2,75 1,95 1,56
350 1,53 8,33 3,71 1,21 0,97
450 1,30 13,06 5,85 1,61 1,31
600 1,01 12,60 4,82 1,21 0,84
700 0,48 - - - -
Mercury fractionation
Tailings from four sites, JC, AY, FO and GD, were subjected to sequential extraction and this
was done in duplicate. According to Coufalk et al. [2012] fraction I, in gure 7.5, contains the
water soluble and exchangeable mercury and is likely the most labile and being able to end
up in water streams and ground water. An average of 0,5 mg/kg mercury was found in this
fraction.
The second fraction, II, contains the mercury which becomes soluble under acidic conditions
and is potentially available for the human digestive system. As can be seen in gure 7.5 it
is the second largest fraction and accounts, on average, for about 37 % of the total mercury
present in the tailings. Concentrations in the four tailings in this fraction range between 1,94
mg/kg and 6,25 mg/kg. These rst two fractions are probably the most important in relation
towards environmental concerns [Liu et al., 2006].
The mercury associated with humic substances and in general organic matter is represented
by the third fraction, III. The procedure for the fourth fraction, IV, extracts the elemental
0
mercury (Hg ). Fractions III and IV both have a very low mercury content, containing only
1 % (0,14 ppm) and 3 % (0,26 ppm) respectively of the total mercury present in the tailings.
The low concentration in the third fraction coincides with the low organic matter content in
the tailings.
The mercury which has not been extracted in the previous steps is collected in the fth or
residual mercury fraction, V. It consist of mercury suldes (HgS) and mercury oxides (HgO)
[Coufalk et al., 2012]. It is by far the biggest fraction containing, on average, 55 % of the total
mercury in the four tailings.
Figure 7.5: Mercury fractionation in the four tailings with I) active mercury, II) acid-dissoluble
mercury, III) organic-bound mercury, IV) elemental mercury and V) residual mercury
As mercury occurs in dierent species remediation of contaminated tailings by thermal treat-
ment is not straightforward. The various desorption temperatures are presented in table 7.6
and demonstrate that depending on the mercury species a dierent temperature should be
applied.
Table 7.6: Desorption temperatures for dierent mercury phases [Navarro et al., 2009]
Phase Desorption temperature (◦ C)

Hg 0 100
Hg2 Cl2 170
HgCl2 120-250
Hg matrix-bound 200-300
HgS (cinnabar) 310-330
HgO 420-550
HgSO 4 450-500
Hg in pyrite >450
Hg in Sphalerite 600
7.2.1 Removal eciency as aected by temperature

In gure 7.6 the removal of mercury in the tailing samples by heat can be clearly seen.
According to table 7.6 the mercury which is removed at 100

◦ C or less should be attributed
to the vaporization of metallic mercury

0
Hg . The average of mercury removed at 100
◦ C of
all tailing samples is about 20 %.
The steepest slopes however are seen in the range between 100 and 200
◦ C. Removal of mercury
2 2
chloride species (Hg Cl and HgCl 2 ) could explain the drop from an average of 80 % to only
27 % as the desorption temperature of these mercury phases are 170

◦ C and 120-250 ◦ C
respectivel (table 7.6).
Higher temperatures results in greater mercury removal as clearly showed by Huang et al.
[2011]. After thermal treatment at 250 and 350

◦ C respectively 16 % and 6 % remains of the
mercury present in the untreated soil. At 350

◦ C all samples, except one, contain less then 1
ppm mercury.
Higher temperature (400 and 450

◦ C) show only minor improvements in mercury removal,
indicating that there are almost no mercury oxides, mercury sulphates and mercury associated
with sphalerite or pyrite is in the tailings.
Figure 7.6: Removal eciency of mercury in function of temperature
7.2.2 Eect of time and temperature to optimize remediation

The four sites, JC, AY, FO and GD, were subjected to a thermal treatment with temperatures
at 250, 270, 290 and 310

◦ C and a duration of 1, 2, 3 and 5 hours. Huang et al. [2011] reported
that raising the temperature has a bigger inuence on the mercury removal than a prolonged
treatment. From the results given in gure 7.7, however, no signicant dierence was made in
mercury removal by changing time and temperature. Mercury removal eciency ranged from
67 % to 75 % for all treatments with no visible trend in time and temperature. Thus lowering
temperature to 250
◦ C instead of 310 ◦ C and conducting the treatment to only one hour and
not ve could signicantly reduce the energy consumption of the thermal treatment without
compromising on mercury removal eciency.
From previous results in gure 7.6 an average mercury removal eciency of 84 % was obtained
after thermal treatment of 24 hours and 250

◦ C.
(a) one hour thermal treatment (b) two hour thermal treatment
(c) three hour thermal treatment (d) ve hour thermal treatment
Figure 7.7: Thermal treatment optimization in function of temperature and time
7.2.3 Pilot: in-situ thermal treatment

To mimic in-situ thermal treatment 23,5 kg soil, from an old industrial site in Belgium, was
heated in a cylindrical vessel.

Temperature
Figure 7.8 presents the temperature recorded by the temperature sensors inside and outside
the reactor, as seen in gure 5.1. The setpoint temperature of the heating element was rst
set at 300
◦ C and the temperature of the soil compartment (T3-T6) in the reactor slowly
increased but after 2 days of treatment no further increase was noted. When at day 6 the
reactor was insulated the cooling down eect was eliminated and the soil temperature rose
again. After the removal of the moisture in the soil at day seven the temperature in the
was stabilized in the soil compartment at an average of 135

◦ C. The reactor was kept at this
temperature for seven days and this is further referred as the rst thermal treatment (TT1).
Subsequently after TT1 the temperature setpoint of the heating element was set at 400
◦ on
day 20 and initiated the second thermal treatment (TT2) at day 21 when the soil temperature
was stabilized around 220

◦ C and kept at this temperature untill day 28 of the experiment.
Finally the heating element rose up to 500

◦ C and the third thermal treatment (TT3) begun
at day 29. The average soil temperature of TT3 was 310

◦ C.
Figure 7.8: Temperature in reactor in function of time with T1) heating element, T2)inner
wall in between heating element and soil T3, T4 and T5) outer circle of soil compartment T6)
inner circle of soil compartment and T7) the outside of the reactor (gure 5.1)
Treated soil
In gure 7.9 the mercury content in the samples taken after each thermal treatment are
displayed and compared to the untreated soil. The samples are divided according to their
particle size and at which location they are taken: from the inner circle (closest to the heating
element or at '0 cm') or the outer circle (furthest of the heating element or at '10 cm').
The untreated soil samples dier strongly in their content of mercury. In the ner fractions
(less then 1 mm) the lowest concentrations can be found (21,6 mg/ kg soil The soil fraction
from 1 to 2 mm and larger than 2 mm have a concentration of 38,6 and 51,6 mg Hg/ kg soil,
respectively. It could be noted that with the fraction becoming coarser the concentration rises
as well as the standard variation (of the four samples).
An explanation of the elevated concentration of mercury with elevated particle size can be
found in the reduction of the surface/volume ratio. As the soil originates from an old industrial
site the mercury occuring at the surface of the particles probably already leached out, with
this process being more prominent in the ner fractions.
In gure 7.9 it can be noted that the mercury removal increases if the samples are taken closer
to the heating element (at '0 cm' in comparison to '10 cm'). Although the temperature sensors
measure a uniform temperature of the soil in the reactor (gure 7.8), the signicantly higher
mercury removal at '0 cm' than '10 cm' indicates an elevated thermal treatment temperature
for the samples taken at '0 cm'. This could be due to the fact that the temperature sensor
T6 is not exactly placed at the place were the samples. A more representative temperature
for the samples taking at '0 cm' or the inner circle of the soil compartment could be the
average between the temperature recorded at T2, the wall between heating element and soil
compartment, and T6.
Another trend is that the mercury content decreases with each thermal treatment and thus
with increasing temperature, which is however not observed for the mercury content after the
second treatment (TT2) at 220

◦ C. The concentration in the soil samples does not decrease
in comparison to the rst treatment (TT1) but signicantly increased.This is the case for all
particle size fractions (less than 1 mm, from 1 to 2 mm and larger than 2 mm) if they are
compared to the sample taken from the same location in the soil compartment (at '0 cm' or
'10 cm' from the heating element) ( gure 7.9).
By visual inspection it could be clearly seen that most particles existed out of aggregated sand
particles which after thermal treatment collapse in ner particles. As mentioned before, this
could expose mercury which was previously occluded in the particles. In gure 7.10 this can
be clearly observed. The ner fraction, less then 1 mm, increases relative in weight and the
coarser fraction, larger than 2 mm, decreases while the intermediate fraction, 1-2 mm, remains
unchanged.
Another explanation for the elevated mercury concentrations after the second thermal treat-
ment can be found in the sampling method. Samples were taken from the soil surface which
could possibly be not representative for the soil layers more at the bottom of the reactor. It
could be assumed that the temperature at the bottom of the cylindrical vessel is higher then
at the soil:air interface. This assumption may lead to mercury being faster vaporized in the
deeper soil layers and is redeposited closer to the soil surface where the temperature is lower.
In this process mercury accumulates at the soil:air interface. At 135

◦ C (TT1) not enough
mercury was vaporized to induce this eect while at 310

◦ C (TT3) most mercury was already
removed.
In the results reported by Park [2012] obtained with the same soil a similar trend could be
noted. When the temperature was raised to 250

◦ C the mercury content increased slightly in
comparison to the 200

◦ C treatment.
After the third thermal treatment the soil closest to the heating element reached an average
content of 3,93 mg mercury per kg soil whereas the samples from the outer cylinder of the soil
compartment have an average mercury content of 13,81 mg/kg. As the latter concentration
represent twice the volume of the rst the average concentration after TT3 was estimated at
10,52 mg/kg. The average concentration of the untreated soil was 44,25 mg/kg untreated soil.
So after a thermal treatment of 36 days and reaching a temperature of 310

◦ C, the average
mercury removal in the soil compartment reached 76 %.
Figure 7.9: Mercury content before and after thermal treatment and at dierent locations in
the soil compartment

Figure 7.10: Distribution of the weight according to particle size
Activated carbon lters

The lters existed out of an activated carbon column where the o gasses were send through.
This column is stratied into three zones: upper layer, the middle layer and the lower layer
where the gasses enter the lter. After each treatment the lters were replaced with uncon-
taminated activated carbon and the spent lters were analysed for their mercury content. The
data is presented in gure 7.11.
From gure 7.11a the mercury concentration in the lower layer reach up to 3300 mg mercury
per kg activated carbon while for the middle and upper layer the concentration are 1395 and
740 mg/kg, respectively. A similar trend could be noted after the second an third thermal
treatment showing a decreasing mercury content higher up the lter. This seems logical as
the o gasses arrive rst at the bottom of the activated carbon lter and are loaded with
vaporized mercury which is readily adsorbed on the activated carbon. Gasses with a lower
mercury concentration continue there way through the lter and less mercury can be adsorbed.
This also explains why the mercury content in the rst lter is a 1000 times higher then in
the second lter. In the second activated carbon lter ( gure 7.11b) no similar trend could
be noted in the upper, middle and lower layer. This could be attributed to the low amount
of mercury adsorbed and thus more susceptible to small variations in the vapours originating
from the reactor.
The second lter adsorbed over 36 days of thermal treatments only 0,22 mg mercury while
for the rst lter this was 228 mg. This shows that the second activated carbon lter is not
a necessity.
Another trend seen in 7.11a is that after each thermal treatment a lower mercury content is
found in the rst activated carbon lter resulting in lesser amount of mercury adsorbed after
each treatment.
(a) Mercury content in rst activated carbon lter (b) Mercury content in second activated carbon lter
Figure 7.11: Mercury content in activated carbon lters after each thermal treatment (TT1,
TT2 and TT3)
Mass balance
In table 7.7 the total amount of mercury was calculated for the untreated soil by multiplying
the mercury concentration of each fraction with its relative weight and the total mass of soil
presented in the reactor. After each thermal treatment the same procedure was followed to
determine the total amount of mercury still present in the reactor. Closing the mass balance
for mercury was done by dening how much mercury was adsorbed on the activated carbon
lters after each thermal treatment. The 'total mercury' presented in table 7.7 is the sum
of the mercury present in the reactor after each thermal treatment and that of all activated
carbon lters up to the calculated thermal treatment.
It should be mentioned that the condensate originating from the treated soil after the rst
treatment (TT1) had a volume of 3,1 l and did contain 6 ppb mercury. This amount could
be neglected in comparison to the content found in the soil and activated carbon lter and
should thus not be taking into account into the mass balance.
The mass balance in table (7.7) show some oddities. After the rst thermal treatment the mass
balance is not closed and about 300 mg mercury have disappeared. This could be attributed
to the fact that the reactor and the connections of the pilot setup were not air-tight and thus
vaporized mercury could escape. This is also the case for the total amount of mercury in the
mass balance after the third thermal treatment.
Although the total mercury after the second thermal treatment is in the same order of magni-
tude as before the thermal treatments this is caused by the high mercury concentrations in the
reactor. These are, however, erroneous because of the unrepresentative samples taken from
COAL GOLD AGGLOMERATION 57
the treated soil given their elevated mercury concentrations as explained in the subsection
'treated soil'.
Table 7.7: Mass balance of Hg in reactor after three thermal treatments
start of treatment TT1 TT2 TT3

fractions total mercury total mercury total mercury total mercury
(mg) (mg) (mg) (mg)
<1mm 171,89 55,45 148,43 92,94
1-2mm 97,65 44,21 108,73 43,31
<2mm 770,24 445,32 526,92 110,90
mercury present in reactor 1039,78 544,98 784,08 247,15
activated carbon lter 0,00 170,71 51,28 6,32
total mercury 1039,78 715,69 1006,07 475,46
7.3 Coal gold agglomeration
The possibility to simultaneously remediate the mercury contaminated soil and meanwhile
also recovering gold from it was examined by using coal agglomerates.
7.3.1 Inuence of experimental conditions on recovery

The essence of the coal gold agglomeration process is the formation of coal oil agglomerates
and the contact with ne gold particles (and eventually mercury). Important parameters in
these process is the coal:oil and coal:ore ratio as it denes respectively the agglomerate size
and the collision probability [Kotze and Petersen, 2000].
In gure 7.12 experiments with dierent oil:coal ratios were conducted but the same coal:ore
ratio of 1 and synthetic activated carbon was used. The results for the gold and mercury
concentration in the activated carbon show that for an oil:coal ratio of 0,2 respectively 2,01
and 8,58 mg/kg was obtained. While for a much higher oil:coal ratio of 0,8 only 0,41 mg gold
and 1,18 mg mercury per kg activated carbon was measured. It could be concluded that the
mercury and gold content in the activated carbon decreases with increasing oil:coal ratio.
According to Wu et al. [2004a] gold recovery increases with decreasing agglomerates size
based. As very ne agglomerates are formed when few oil is added to the mixture this could
explain the increased recovery of not only gold but also mercury. The major drawback of ne
agglomerate sizes is the increased diculty to recover the agglomerates as the sieves used to
separate the agglomerates will also retain the particles in the tailing. A good balance should
found between a high mercury and gold concentrations and ease of separation.
Figure 7.12: Inuence of coal:oil ratio on the concentration of gold and mercury in coal
Not only the oil:coal and coal:ore ratio inuence the coal gold agglomeration the recovery of
gold and mercury but also the type of coal on . In table 7.8 the mercury and gold concentration
are presented for the dierent coal types used in the coal gold agglomeration process. The
results show that mercaptan activated carbon (MAK) has mercury concentration similar to
that of synthetic activated carbon (SAK) when the coal:ore ratio was 0,5. When the coal:ore
ratio was 1 the MAK had a three to six time higher mercury concentration then the SAK. For
gold recovery, however, is the use of MAK not suited as very little or no gold at all was found
in the coal. In general the recovery of gold by Biochar (BC) is in the same order of magnitude
as that of SAK experiments. But mercury recover with BC is much higher, especially when no
oil was used. In this case a ten times higher concentration was determined than encountered
in experiments were SAK was used.
A mercury and gold content of respectively 8,58 mg and 2,01 mg per kg coal only resulted in
a 22 % recovery for mercury and 11 % for gold.

Table 7.8: Inuence of coal type on gold and mercury content
coal type oil:coal coal:ore net concentration Hg concentration Au

(mg/kg coal) (mg/kg coal)
SAK 0,72 1 3,22 1,18
SAK 0,72 1 2,88 1,36
MAK 0,72 1 1,77 0,02
MAK 0,72 1 3,77 0,00
BC 0,72 1 4,78 0,73
BC 0,72 1 4,90 0,63
SAK 0,7 0,5 2,31 0,89
MAK 0,7 0,5 6,86 0,07
MAK 0,7 0,5 12,37 0,07
BC 0,7 0,5 7,64 1,26
BC 0,7 0,5 8,08 1,54
BC - 0,5 22,85 1,00
BC - 0,5 18,75 0,63

Chapter 8
Discussion
As mercury pollution in the tailings is invisible for the naked eye and the health eect as-
sociated with mercury poisoning is only visible on the long term, initiaves to remediate the
aected areas are almost unexistent. Application of remediation techniques to remove mercury
is then often seen as a capital intensive operation with no net benet other then a healthier
environment, which is hard to prove. Characterizing the cost of a polluted environment can
be a challenging task as you have to take into account the eects of the global burden by
the mercury pollution and the direct implications on human health. Estimating the cost of
the latter was done by Hylander and Plath [2006] and by adjusting the gures it could be
extrapolated to la Libertad.
The health cost, calculated by Hylander and Plath [2006], is the loss of intelligence due
to mercury poisoning. Studies conducted at the Faroe Islands and New Zealand concluded
that development eects become apparent at levels around 5,8 µg Hg per litre cord blood
of a newborn child. If this limit is surpassed a linear relationship was found where for each
doubling of the mercury concentration a loss of 1.5 IQ points was found. A study done by
the Universidad CentroAmericana (UCA) in the village of la Libertad in 2009 showed that
half of the examined persons had an elevated mercury concentration higher than 5,14 µg per
litre whereas a quarter of them reached concentrations higher than 15,16 µg per litre blood.
The loss of one IQ point corresponds to a 2,578 % decrease in lifetime expected earnings. The
value of lifetime earnings discounted to present value used in this study is 897 735 US$, which
is the average for an American child born in 2000 [Hylander and Plath, 2006]. Converting the
given gures to the situation of la Libertad (by using the GDP per person of the USA and
Nicaragua), about one in ve children are born with a a substantial loss of 1.5 IQ points. The
lifetime expected earnings of this child is reduced from 31569 to 30348 $ signifying a loss of
about 1221 $ or 244 $ per child born in this aected region.
Keeping this gure in mind and considerating that it is only the tip of the iceberg of the
environmental damage done by mercury pollution, remedation of the aected area becomes
60
not only sound on an ecological base but also on an economic base.
Thermal treatment requires a soil with a low amount of organic matter or pyrite to avoid
explosion. Properties which facilitate the removal of mercury are sandy texture and a low
humic acid content [Vos et al., 2012]. The implementation of the thermal treatment in this
study is facilitated due to the fact that the soil properties of the tailings comply with those
characteristics ( subsection7.1.2). Only a pre-treatment should be conducted to lower the
moisture content from 20 to about 3 % to minimalize treatment time and lower operating
cost.
From the experiments it can be concluded that the mercury removal in the four tailings treated
for one hour and at 250

◦ C reached, on average, 70 %, with values for the residual mercury
ranging from 1,63 to 4,59 mg per kg tailing. This ex-situ treatment at relative low temperature
and during a short period complies with the standards set by OVAM but not the EPA for
soils [OVAM, 2010][EPA, 2004]. It can be assumed that under these conditions the most
mobile fractions, like the water-soluble, HCl-dissoluble and elemental mercury, are removed
because of their low desorption temperature [Navarro et al., 2009] and thus lowering the risk
of mercury exposure to environment and humans.
Results from the pilot setup to mimic in-situ thermal treatment show that a temperature
gradient is present in the soil compartment indicated by the dierence in mercury content in
the inner and outer cylinder of the soil compartment. The moisture content of 6 % slowed the
thermal treatment down for several days before reaching temperatures higher than 100
◦ C.
When temperatures in the reactor reached 300

◦ C and the treatment was conducted for seven
days, a 76 % mercury removal was accomplished. The resulting mercury content however was
still higher then the OVAM and EPA standards as the soil still contained on average 10,3 mg
Hg/kg soil.
According to estimates from Otto and Bajpai [2007] the operating cost for thermal treatment
ranged from 68 up to 125 $ per tonne contaminated soil. It should be noted however that
these estimates originate from 1995. More recent literature states that for the ex-situ thermal
treatment process conducted at 450

◦ C and for a period of one hour the operation cost are
293 496 $ for treating 960 tonnes of waster per year. This results in a cost of 305 $ per tonne
contaminated soil [Yera, 2012]. The artisanal gold mining industry in la Libertad however
produces around 56 tonnes tailing a day. The big volume of contaminated soil and a rather
low contamination level (8 mg Hg/kg tailing) makes that most remediation techniques are not
economically feasible.
8.2 Coal Gold Agglomeration
To counter the problem of the high cost associated with mercury removal, the recuperation of
the gold still present in the tailings could oer a solution.
The gold content in the tailings is on average 3,82 g/ton the process executed by the artisnal
miners only recovers about 70 % of the gold by the amalgamation technique. Data shows that
66 % of the gold and almost 60 % of the mercury is present in the minus 64 µm fraction. This
makes it almost out of reach for gravity separation and amalgamation.
Another method, coal gold agglomeration, is known to be able to recover gold particles as ne
as 5 µm up to 300 µm [Sen et al., 2005]. The results show that mercury could be recuperated
simultaneously with gold. Gold and mercury follow the same trend and have its highest
recuperation when the oil:coal ratio is 0,2 and the coal:ore ratio is 0,5. These conditions result
in 8,58 mg Hg and 2,01 mg Au per kg activated carbon.
To facilitate the calculation of the economic feasability of the coal gold agglomeration process
an overview of the current operating cost can be found in table 8.1. As can be seen is the CGA
process not at all protable and are even more cost involved than with thermal remediation.
With only 1 gram of gold and 4,29 gram of mercury recovered per ton of processed tailing the
eciency is low. Analysis of the tailing, from FO, used in the experiments showed that 5,8 g
gold and 12,18 g mercury per ton was present resulting in a recovery eciency of respectively
17 and 35 %.
If, however, the coal gold agglomeration process could be improved in terms of mercury and
gold recovery it will have a great inuence on operating costs. Studies showed that by optimiz-
ing the conditions a gold recovery of 80 % could be achieved [Kotze and Petersen, 2000][Wu
et al., 2004a]. According to Marciano et al. [1994] the agglomerates formed by the activated
carbon and gasoline could be reused in a next recovering step and this up to 5 cycles without
considerable loss in recovery eciency. If these considerations are taken into account the op-
erating cost of the CGA process can be decreased to only 26 $ per ton tailings, as presented
in table 8.1.
Although the CGA sounds promising strong objections should be made in relation to the emis-
sion of CO 2 and subsequently the environmental impact and contribution to global warming.
8.3 Suggestions for future research
The study conducted focussed on nding the most economically viable solution for mercury
contaminated tailings originating from artisanal and small-scale gold mining industry. Still a
long road needs to be followed before this becomes reality. Suggestions for further research
that could contribute toward reaching this goal can be identied:

SUGGESTIONS FOR FUTURE RESEARCH 63
Table 8.1: CGA estimated operation cost of processing one ton tailing
amount current costs optimized costs

activated carbon 500 kg -326,5 100 kg -65,3
PEX 40 kg -52 40 kg -52
gasoline 150 kg -244,2 30 kg -49
electricity cost 100 kW -40 100 kW -40
gold recuperation 1 g 45 4 g 180
-618 -26
Thermal treatment experiments where time is further shortened (5, 15 and 30 minutes)
at 250
◦ C and 300 ◦ C. Operating cost associated with thermal treatment depend strongly
on the time and temperature needed to treat a given amount of soil.
Investigating the mercury specation and conducting a TLCP on the thermally treated
tailings and tailings subjected to CGA process. Tailings could be used as building
material if no hazard of mercury exposure is present. This means that no water-soluble,
elemental and acid-dissoluble mercury should be present, and the tailings should comply
with the EPA guideline of less then 0,2 mg Hg /litre in TLCP test.
Optimizing the conditions of the CGA process towards accumulating a high mercury
and gold concentration in the activated carbon and an easy recovery by formation of big
agglomerates.
Investigating the possibility to reuse the agglomerates in several cycles with no substan-
tial loss of recovery eciency.
By closing the mass balance in the pilot setup for in-situ treatment a better understand-
ing could be created of how the process works and about the mobility of mercury inside
the soil. This could be done by not treating a soil subsequently to dierent tempera-
tures but after each treatment replacing the treated soil with new soil from the same
bulk sample and by taking samples at dierent depths in the reactor.

Part IV
Conclusion
64
65
Conclusion
The gold extraction process in la Libertad (Nicaragua) could be improved by following the
guidelines described in "a practical guide: reducing mercury use in artisanal and small-scale
gold mining" [UNEP, 2012b]. Abolishing the whole ore amalgamation by rst appling some
sort of concentration techniques like sluice boxes, shaking tables or centrifugal concentrators
could reduce the current ratio of 3 units of mercury used per unit of gold extracted to less then
one. By doing so reducing greatly reducing the current 56 tonnes of mercury contaminated
tailing discarded per day.
The tailings in this study had an average mercury and gold content of respectively 8,13 and
3,82 mg per kg tailing. They also showed a characteristic particle diameter of 83 µm and more
then half of the mercury and gold present could be found in the minus 63 µm fraction.
Thermal treatment at various temperatures made clear that largest reduction in mercury con-
centration in the tailings could be noted between 100 and 200

◦ C. No signicant improvements
were made on the mercury removal eciency if temperatures were raised above 300
◦ C. At
this temperature allmost all samples meet the standards of the US EPA of containing less then
1 ppm mercury. Reducing time and temperature to one hour at 250

◦ C reached a mercury
removal eciency of 66 %. It showed no signicant dierence in mercury removal with a

◦
treatment at 310 C and 5 hours and thus saving not only time but also money by lowering
the energy cost.
The experiments to asses the eects of an in-situ thermal treatment showed that the duration
is much longer than that of ex-situ and should be in the great order of days or weeks rather
than hours to secure an uniform temperature throughout the soil and evaporate the water
present. Another reason could be to eliminate the delaying eect coming from the mercury
evaporation from and redeposition on the soil particles. Furthermore signicant dierences in
the mercury removal eciency were found in the treated soil in relation to the distance of the
soil to the heating element.
The coal gold agglomeration process oers a possibility to recover gold and mercury in the
same process allowing remediation of a contaminated site while the gold recupertion could pay
back some of the operating costs. A mercury and gold content of respectively 8,5 mg and 2,13
mg per kg coal was achieved but due to dicult separation of the coal from the ore recovery
percentages of only 22 % for mercury and 11 % for gold are achieved. Nevertheless this study
could be used as a starting point for further optimizing this process in terms of clean up and
precious metal recovery.
Finally mercury-reducing approaches could minimalize the extent of contamination and even-
tually mercury-free techniques can make artisanal and small-scale gold mining a sustainable
sector but mercury contaminated tailings will continue to pollute the environment even after
mining activites have ceased if they are not properly treated. Remediation technologies are a
66
nancial loss and the search to nd the most appropriate technology for tailings with a high
mercury and gold content could lower these costs. In the end, however, the real costs for not
treating the contaminated sites could by a multitude higher than the initial remediation cost.
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Appendix A
Sampling campaign
In cooperation with Universidad de Centroamericana (UCA) and the cooperative of arras-

tra owners Cooperativa de Rastreros y Mineros la Libertad Chontales (COOPROMILICH) a
sampling campaign was conducted in the village of la Libertad in Nicaragua.
The objective of this campaign was to obtain representative samples for further remediation
of the tailings. In the period from the end of October until the beginning of December a total
of 10 arrastras sites were visited as can be seen in table A.2. A self-reported questionnaire was
conducted at each site, the questions can be seen in table A.1. Samples were taken according
to a predened procedure described in A.1.
A.1 Sampling procedure
Soil samples were taken at each site by a core drill and preserved in air-tight plastic bags.
Each sample was labelled with an unique code(table A.3). The exact location was determined
by GPS and registered. Afterwards samples were dried at ambient temperature (out of direct
sunlight) and subsequently sealed for further analysis.
From each site the following types of soil samples were collected in duplicate and stratied
according to depth:
Hot spot: The area in the tailing site that is considered to be most heavily contami-
nated. Normally located where the sand and water leave the grinding process. Due to
the liquid state no stratication according to depth was applied.
New tailings: The area where the most recent tailings are located. These are the most
humid places at the tailing site.
Tailings: The area which is part of the tailing site but not considered as hot spot or
new tailings.
I
SAMPLING PROCEDURE II
Distribution: The area located downstream of the tailing site, considered to be con-
taminated with mercury.
Background: Soil which is considered as uncontaminated (upstream and without hu-
man activity in its surroundings), used as background sample or reference.
1) Since when is the arrastra processing gold ore (brosa)?
2) What is the average of tons gold ore processed daily in the arrastra?
3) What is the average amount of mercury used daily?
4) Which type of arrastra is this?
5) How much gold is extracted daily?
6) What is the price to rent the arrastra ?
Table A.1: Sampling questionnaire

SAMPLING PROCEDURE III
Nº Name and Surname Coordinates # Rastras

longitude latitude
1 Wilder Mairena Barrillas -85,1698 12,2131 2
2 Yasser Alemán Soto -85,1594 12,2209 1
3 Juan Carlos Chavarría -85,1707 12,2118 2
4 Aybin Ulises Altamirano -85,1607 12,2227 1
5 Gustavo Díaz Olivares -85,1709 12,2126 3
6 Humberto Perez -85,1610 12,2197 1
7 Carlos Marin -85,1635 12,2143 4
8 Leopoldo Marin -85,1651 12,2131 1
9 Fernando Obregon -85,1623 12,2129 2
10 Pablo Emilio Martinez -85,1631 12,2150 1
11 Yoel Aristegui Miranda -85,1697 12,2134 2
12 Brenda Kauman García -85,1657 12,2180 1
13 Cristina González Reyes -85,1659 12,2182 1
14 Gloria Elena Lazo -85,1654 12,2182 2
15 Manuel Antonio Obregón -85,1645 12,2181 1
16 José Manuel Lazo Altamirano -85,1607 12,2227 1
17 Gilder Marenco Alarcón -85,1702 12,2126 3
18 Rubner Jirón Suarez -85,1614 12,2206 1
19 Francisco José Siles Núñez -85,1626 12,2148 1
20 Sociedad Trapiche Minero -85,1674 12,2296 1
21 Juan Mairena -85,1626 12,2301 1
22 Auxiliadora García -85,1677 12,2140 1
23 Alberto Sandoval Mairena -85,1620 12,2144 2
24 Fco García/Domingo Martínez -85,1620 12,2123 1
25 Sociedad Pajaritos -85,1703 12,2136 1
26 Javier Díaz Olivares -85,1685 12,2154 2
27 Germán Mena -85,1678 12,2177 3
28 Narciso Rivera 2
29 Hernaldo Halleslevens 1
30 Segundo Amador 1
31 Manuela Olivares Lopez 1
32 Miguel Angel castro 4
33 Isidoro Lorio 1
Total 53
Table A.2: List of arrastras in la Libertad on April 2012, sampled arrastras
SAMPLING PROCEDURE IV
The dierent types of arrastras can be subdivided as follows:
Bolillon : Two or four heavy rocks rotate in a paved basin to grind the ore. Processes
more then one ton per 24 hours ( gure A.1c).
Arrastra : Similar as bollilon but smaller dimensions and process less then one ton ore
per 24 hours ( gure A.1a).
Bolillo : A ball shaped rock is manually operated. It can grind only a few kilograms of
ore inside a paved cavity. It is used to prospect the ore and estimate the concentration.
Trapiche : Originated from Chili. It is an advanced system of two big concrete and
steel enforced wheels which rotate to crush the ore (gure A.1b).
(a) arrastra mill type (b) trapiche mill type
(c) arrastra in foreground and in the background a bolillon mill type
Figure A.1: Mill facilities in la Libertad

SAMPLING PROCEDURE V
First pair of characters Second pair of characters Numbers

reference to arrastra reference to type of sample Replicates Depth
Wilder Mairena FM
Hot spot HS
Yasser Alleman YA
Juan Carlos JC
Aybin Ulise AY according to depth

New tailings NT
Gustavo Diaz GD number 1, 2 or 3 0 to 15 cm were
Humberto Perez HP was assigned assigned '015' and
Carlos Marin CM 15 to 30 cm '1530'

Tailings T
Leopoldo Marin RP
Fernando Obregon FO
Pablo Emilio PE
Distribution D
Background REF
Table A.3: Build up of sample labels

Treatment of Tailings From Artisanal Gold Mining in Nicaragua

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Treatment of Tailings From Artisanal Gold Mining in Nicaragua

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Faculty of Bioscience Engineering

Academic year 2012 – 2013

Treatment of tailings from artisanal gold mining in

Promotors: Prof. dr. ir. Gijs Du Laing

Tutor: Prof. dr. ir. Gijs Du Laing

Master’s dissertation submitted in partial fulfilment of the requirements

Academic year 2012 – 2013

Treatment of tailings from artisanal gold mining in

Promotors: Prof. dr. ir. Gijs Du Laing

Tutor: Prof. dr. ir. Gijs Du Laing

Master’s dissertation submitted in partial fulfilment of the requirements

Ghent, June 2013

The promotor, The author,

Prof. dr. ir. Gijs Du Laing Brecht Annicaert

who put their time and experience at my disposal.

the rough route seem a little smoother

be conducted and made me appreciate good company and rudimentary karaoke.

advice that were indispensible for doing my experiments in the laboratory.

which I could have spent enjoying the good weather.

to make this thesis a worthwhile experience.

giving the best of yourself, as shown in the gure below.

Figure 1: (Freddy) Mercury, giving the best of himself

by cold vapour atomic absorption spectrometry.

1,94 mg/kg and 1,23 mg/kg, respectively.

when the treatment temperature is raised. No signicant improvements of mercury removal

subjected to a treatment of one hour and 250

% was removed after 36 days of treatment.

of up to 8 mg Hg and 2 mg Au was found in one kilogram of coal. The recovery eciency

gezonde planeet. De vaste afvalstoen gegenereerd door ambachtelijke en kleinschalige goud-

is de verwijdering van kwik door thermische behandeling of de gelijktijdige terugwinning van

kwik en goud door coal gold agglomeratie van de tailings.

Eerst werd een veldproef uitgevoerd in de goudmijnbouwersgemeenschap van La Libertad,

de monsters onderworpen aan verschillende behandelingen en hun eciëntie op kwikverwi-

jdering werd gemeten door koude-damp-atomaire-absorptiespectrometrie.

1,94 mg / kg en 1,23 mg / kg, respectievelijk.

toeneemt wanneer de behandelingstemperatuur wordt verhoogd. Geen signicante verbeterin-

atuur boven de 300 werd verhoogd

gehalte van minder dan 1 ppm kwik bij 300

een langzame temperatuurstijging in het bodem compartiment en signicante verschillen in

verwijdering van kwik op de plaatsen dichtstbijzijnde en verst van het verwarmingselement.

dagen en wanneer de temperatuur in de reactor 310

de aanvankelijke concentratie van 44 mg kwik per kg bodem werd na 36 dagen behandeling

mg Hg en 2 mg ceAu werd gevonden in een kilo actieve kool. De terugwinningseciëntie

van goud en kwik uit de tailings onder de gegeven omstandigheden is slechts 22 % en 11 %,

geoptimaliseerd wordt kan dit dalen tot 26 $ per ton Wtextittailing.

behandeling te veriëren op zijn kwikverwijderingseciëntie en het deniëren van de optimale

omstandigheden waarbij de coal gold agglomeratie de hoogste kwik en goudconcentratie in de

2.1.1 Natural emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

2.1.2 Anthropogenic emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

2.1.3 Re-emissions and remobilization . . . . . . . . . . . . . . . . . . . . . . 7

2.2 Mercury speciation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

2.3 Impact on human health . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

2.3.1 Exposure pathways . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

2.3.2 Health eects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

2.3.3 Environmental guidelines . . . . . . . . . . . . . . . . . . . . . . . . . . 10

3 Artisanal and small-scale gold mining 12

3.2 Gold process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

3.3 Mercury use in ASGM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

3.4 Combatting mercury pollution in ASGM . . . . . . . . . . . . . . . . . . . . . . 19

3.4.1 Improving awareness and training . . . . . . . . . . . . . . . . . . . . . . 19

3.4.2 Public opinion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

3.4.3 Mercury reducing approaches . . . . . . . . . . . . . . . . . . . . . . . . 20

3.4.4 Mercury free techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

3.4.5 Mercury removal from tailings . . . . . . . . . . . . . . . . . . . . . . . . 22

giving the best of yourself, as shown in the gure below.

when the treatment temperature is raised. No signicant improvements of mercury removal

of up to 8 mg Hg and 2 mg Au was found in one kilogram of coal. The recovery eciency

gezonde planeet. De vaste afvalstoen gegenereerd door ambachtelijke en kleinschalige goud-

de monsters onderworpen aan verschillende behandelingen en hun eciëntie op kwikverwi-

toeneemt wanneer de behandelingstemperatuur wordt verhoogd. Geen signicante verbeterin-

een langzame temperatuurstijging in het bodem compartiment en signicante verschillen in

mg Hg en 2 mg ceAu werd gevonden in een kilo actieve kool. De terugwinningseciëntie

behandeling te veriëren op zijn kwikverwijderingseciëntie en het deniëren van de optimale

2.3.2 Health eects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

5.5.1 Experiment to asses the removal eciency as function of temperature . 33

7.2.1 Removal eciency as aected by temperature . . . . . . . . . . . . . . . 50

7.2.2 Eect of time and temperature to optimize remediation . . . . . . . . . 50

7.3.1 Inuence of experimental conditions on recovery . . . . . . . . . . . . . 57

coal lters, 5) pump. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36

7.6 Removal eciency of mercury in function of temperature . . . . . . . . . . . . . 50

reactor (gure 5.1) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

7.8 Inuence of coal type on gold and mercury content . . . . . . . . . . . . . . . . 59

dichlorodiphenyltrichloroethane or better known as DDT and its devastating eects world-