This article was downloaded by: [University of Sussex Library]

On: 19 January 2015, At: 00:39

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK

Mineral Processing and Extractive Metallurgy Review:

An International Journal
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/gmpr20

Arsenic in Gold Processing

a a
R. G. ROBINS & L D. JAYAWEERA
a
Hydromet Technologies Ltd , 31-45 Smith Street, Marrickville, NSW, 2204, Australia
Published online: 26 Apr 2007.

To cite this article: R. G. ROBINS & L D. JAYAWEERA (1992) Arsenic in Gold Processing, Mineral Processing and Extractive
Metallurgy Review: An International Journal, 9:1-4, 255-271

To link to this article: http://dx.doi.org/10.1080/08827509208952710

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained in the
publications on our platform. However, Taylor & Francis, our agents, and our licensors make no representations
or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. Any
opinions and views expressed in this publication are the opinions and views of the authors, and are not the
views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and should be
independently verified with primary sources of information. Taylor and Francis shall not be liable for any losses,
actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or howsoever
caused arising directly or indirectly in connection with, in relation to or arising out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions
 Mineral Processing and Extractive Metallurgy Review. 1992. Vol. 9. pp. 255-271
Reprints available directly from the publisher
Photocopying permitted by license only
© 1992 Gordon and Breach Science Publishers S.A.
Printed in the United States

Arsenic in Gold Processing

R. G. ROBINS and L. D. JAYAWEERA
Hydromet Technologies Ltd., 31-45 Smith Street, Marrickvifle NSW 2204, Australia
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

The processing of gold bearing sulphide minerals which contain arsenopyrite and other complex arsenic
sulphide minerals results in arsenic containing emissions and effluents which must be given careful
consideration in relation to clean air and clean water standards. The sources of arsenic and the various
process options for treating arsenical gold orcs and concentrates are briefly reviewed.
The problem relating to the removal of arsenic from gaseous emissions from roasting processes is
considered.
Residues from aqueous processing contain a variety of arsenical materials which have not been
characterised. and the long-term stability of these is suspect.
The use of lime to stabilise aqueous residues as either calcium arsenate or calcium arsenite has been
shown to be inadequate for long term disposal since both compounds are converted into calcium
carbonate due to the influence of carbon dioxide in the atmosphere.
Ferric ion solutions have been used to precipitate ferric arsenate or to form ferric hydroxide which
binds the arsenic for short term disposal. The long term stability of these ferric materials is poor. but
could lead to the acceptance of a slow release option rather than complete containment of residues.

INTRODUCTION

As the higher grade free-milling and oxidised gold ores are being depleted, the
gold mining industry is quickly moving to the exploitation and treatment of re-
fractory sulfides. In many parts of the world gold has been found in association
with arsenical sulfides and in several countries well developed treatment procedures
for these ores have been developed. Most reports of processing arsenical gold ores
detail the various procedures which result in high recoveries of gold, but do not
consider the long-term fate of arsenic in tailings and residues. Jha 1 has reviewed
the causes of the refractoriness of certain gold ores to cyanidation and the various
solutions to poor gold recoveries, and Jha and Kramer' have outlined some of the
process considerations for arsenical ores and briefly comment on the environmental
aspects but without concern. A more recent survey of the process options for
refractory sulfide gold ores, which covers technical, environmental and economic
aspects, was presented by Kontopoulos and Stefanakis', and although due mention
of environmental aspects is made there is not any detail of the problems of disposal
of arsenic containing residues.
A variety of economic process options for the recovery of gold from arsenica I
gold ores is available but the disposal of residues does present problems. It is only

255
 256 R. G. ROBINS AND L. D. JAYAWEERA

during the past ten years that the stability of disposed residues based on calcium
arsenates and ferric arsenates has been shown to be poor'>

FORMATION & MINERALOGY OF ARSENICAL GOLD ORES

Mineral phases in which arsenic is a major component have been well documented
by Onishi and Sandell" and more recently by Gonzalez and Monhernius'. The
association of arsenic with gold is very common, and this has been related to mutual
solubilities in sulfide magmas and transport in ore-forming sulfide magmas and
hydrothermal solutions''". The solubility of arsenic in hydrothermal sulfide solutions
is extremely high III, and that of gold sufficient to explain the genesis of hydrothermal
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

gold deposits"!'. Recently sorption processes have been invoked as an efficient

mechanism for deposition of gold".
Gold occurs in nature mostly as the metallic element sometimes alloyed with
silver as electrum. It also occurs as gold and gold-silver tellurides, but its association
with sulfur in various sulfide mineral assemblages leads to its association also with
arsenic. An excellent review of the host minerals of gold was published in 1944 by
Schwartzi). The most common gold bearing sulfides are arsenopyrite (FeAsS) and
pyrite (FeSz) but other arsenic containing minerals such as cobaltite (CoAsS) en-
argite (Cu ZAsS 4) gersdorffite (NiAsS) proustite (Ag)AsS)) realgar (AS4S4) orpiment
(As-S, tennantite «Cu,Fe)IZAs4SI) and others have been reported closely asso-
ciated with gold.
Gold-ore mineralogy has been investigated primarily by optical microscopy.
Henley!' reviews these studies in relation to metallurgical treatment and presents
a number of photomicrographs showing the presence of gold in arsenopyrite. Gold
has been shown optically at grain boundaries, surfaces and inclusions in arsenopyrite
crystals but in many cases it is so finely disseminated that even electron microscopy
and electron probe microanalysis have not revealed relatively high gold concen-
trations.
Arsenopyrite has been synthesised from Fe-As-S mixtures":" and the solid-sol-
ubility of gold in the resultant material shown to be substantial at temperatures of
600-700°C. Gold is exsolved during cooling and cooling-rate has much to do with
the final gold dispersion in these synthetic materials.
Although many arsenopyrite ore deposits are said to be of hydrothermal origin
there is little evidence of hydrothermal synthesis of the mineral. Gavrilov et al"
claim to have synthesised arsenopyrite in aqueous ammonium chloride solutions
at temperatures approaching 400°C (perhaps in the super-critical region) but Tahija
and Huang'? were unable to prepare the mineral during extensive experiments in
subcritical aqueous solutions. The authors of this paper have synthesised arseno-
pyrite in supercritical hydrothermal solutions (see Figure 1). Solubility equilibria
involving arsenopyrite have been calculated IU to explain mineral paragenisis from
thermodynamic extrapolations.
Arsenopyrite is not thermodynamically stable at room temperature despite hav-
ing been represented in a number of 25°C stability diagrams I7 - 19 • Its presence as
a metastable phase on these diagrams (e.g. potential-pH diagrams) is useful, how-
ever, in considering reaction chemistry in the Fe-As-S-HzO system.
 ARSENIC IN GOLD PROCESSING 257
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

FIGURE I Synthetic Arsenopyrite (FcAsS) Prepared in a Supcrcritical NaHS·}-I!O System.

Crystal-chemical studies on arsenopyrite" show compositions of the natural min-

erai varying from about FeAs".9S1 1to FeAsI.IS".9' The changes caused by increasing
arsenic content are that triclinic symmetry approaches monoclinic and that metri-
cally the cell approaches orthorhombic. Two different forms of twinning arise from
these pseudosymmetries. A fairly accurate quantitative x-ray diffraction analysis
for arsenopyrite can be obtained from the dlJl = 1.6106 diffraction peak.
Complexation of arsenic (Ill), iron (I I) and gold (I) with sulphur ( - )I) in aqueous
systems is well docurnentedv'":":" and formation stability constants are available
for various thermodynamic feasibility calculations. Table I indicates some of the
complexes that have been proposed in the Au-As-Fe-S system. Mixed complexes
in this system are likely, and further interactions by introducing chloride as a further
component, also possible.

TABLE I
Species Proposed for the complexation of Au(I). As(IIl) and Fc(II) with S( - II).

Formulae Reference

AuHS". Au(HS),' . Au,(HS),S" 9

AuHS". Au(HS),- . Au.Si 12
H,As.8~. H!As8; . HAsJS~­ 22
H!As!S~. HAs!SJ- . As!Si- . AsS.:- 10
Fe(HS)~. Fc(HS), 21
 25X R. G. ROBINS AND L. D. JAYAWEERA

Sometimes a knowledge of hydrothermal ore genesis leads to considerations of

hydrometallurgical extraction processes (the reverse reactions) but in this case the
solubilities as sulfide complexes are insufficient to allow a sulfide extraction route
despite suggestions to that effect.

PROCESS OPTIONS

In processing arsenical sulfide gold ores, flotation and sometimes gravity separation
methods are used prior to an extraction pretreatment of either roasting, hydro-
metallurgy or biological leaching. Flotation of the sulfide minerals pyrite and ar-
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

senopyrite prior to gold recovery was well described in the late 40's in relation to
a number of commercial operationsv" ". The presence of arsenic in flotation be-
haviour poses no special problems apart from the need to understand surface
chemical behaviour. A number of theories have been proposed for mineral-collector
interactions in flotation and those most applicable appear to be related to a si-
multaneous action of oxygen and collector on the mineral surface. The behaviour
of arsenopyrite in that regard was originally reported by Rand" and has since been
confirmed by other workers. Despite these fundamental studies the flotation of
arsenopyrite and separations of arsenopyrite and pyrite by differential flotation
remain more of an art than a science, and in most operations site-specific solutions
have been found.

Roasting Pretreatment of Arsenical Ores and Concentrates

Roasting of arsenical ores and concentrates to liberate gold has been practised for
many years. The subject has been well documentedz.3.23.28-JII but in most cases the
emphasis is given to those conditions which result in a maximum gold recovery in
subsequent cyanidation, process control, testing and design parameters.
A variety of roasting procedures have been adopted industrially, the most com-
mon being a two-stage procedure as shown in simplified form in Figure 2.
It has been indicated?" that the oxidation of arsenopyrite in roasting occurs in
two stages:

4FeAsS + 30 2 = 4FeS + AS~06 i

4FeS + 70 z = 2Fez03 + 4S0, l'
and on cooling the off-gas the As.0 6 will condense to its solid form of As Z0 3
(arsenolite ).
The environmental problems associated with both SOz and ASzOJ emissions are
well known. Regulations have been imposed in some countries where arsenic levels
in off-gases are limited to 10 mg I rn' (STP) and there is consideration being given
to reducing that figure further. This will be extremely difficult since most (if not
all) arsenopyrite roasting operations are not able to meet the 10 mg I m' require-
ment. The vapour pressure of AS Z0 3 was investigated by Behrens and Rosenblatt",
 ARSENIC IN GOLD PROCESSING 259

ARSENICAL ORE
OR
CONCENTRATE

t
FEED
PREPARATION Off-Gas Off-Gas

t t
Ail'
+
STAGE I
ROAST

+
GAS
CLEANING

~
r- SULPHURIC
ACID PLANT

~
-
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

Ai,' STAGE 2
t-- DUSTS TO
ROAST DISPOSAL RESIDUES
OR

Carbon + As,a, RECOVERY

Lime CALCINE Barren

Cyanide LEACH/CIP Slurry

WASTE
Call:jli<.:
+ Effluent MANAGEMENT
GOLD/SILVER
Cynnidc
RECOVERY

+
Gold. Silver

FIGURE 2 Conceptual Flow Diagram for a 2-Stage Pretreatment Roast Process for Arsenical Gold
Orcs or Concentrates.

who have related their results in the temperature range 367 to 429 K by the
relationship:
-6067
log p (atm) = -'1'- + 9.905

At lOOcC this means that As 2 0 , would have a vapour pressure of 3.4 x 10- 4 mm
Hg which is equivalent to about 4 mg / rrr' (STP) of arsenic at equilibrium. To
nucleate As,O, solid and achieve equilibrium in off-gases being generated at thou-
sands of cubic metres per minute and cooled at hundreds of degrees per second,
and to remove sub-micron sized particles of As,O, from the gas stream is extremely
difficult and very costly.
A number of attempts at gas cooling and filtering to achieve low arsenic levels
have been reported. The Hatch Gas Mixer" is a device for cooling stack gases to
about lOOcC and removing As 20 J in the condensed state. A number of commercial
operations installed this equipment and the unit at the Campbell Red Lake gold
smelter in Ontario, Canada (now Placer Dome Inc., Campbell Mine) was inves-
tigated thoroughly by the Southern Research Institute of Birmingham, Alabama
and their report issued by the U.S. Environmental Protection Agency". The total
 260 R. G. ROBINS AND L. D. JAYAWEERA

arsenic emission from the system during testing was 11 mg / m 3 (STP) and arsenic
collection efficiency exceeded 99.9%. The operation at Campbell Red Lake has
proceeded since that time, presently roasting about 60 tons / day, but studies of
alternative processes have resulted in a commitment to a pressure oxidation plant
to be operational in July 199p4.
The problems related to arsenic emission into the air from the roasting of arsenical
gold ores and concentrates are considerable. The toxic and epidemiologic problems
which arise from human contact with off-gases, even at considerable distances from
the source, are well documented" and continuing to be identified.
Gas chemistry in the roasting of arsenical gold ores and concentrates is extremely
complex, but with the aid of a number of fundamental thermodynamic studiesv>",
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

is fairly well understood. Many volatile species other than AS40 6 are formed and
comprehensive thermodynamic data Js.J9 are available for calculating equilibria in
the As-S-O system. The formation of AszO J by condensation from off-gases remains
the main problem in roasting, in terms of its hazardous nature in both air and water
contamination. Sulfur dioxide emission can be reduced to acceptable levels.
Flue dusts which are collected from the roasting of purely arsenopyrite concen-
trates can contain in excess of 50% AszO J . The material has a high solubility
(about 20 g / L) and its disposal presents difficulties. There are a number of processes
for producing pure AszO J from flue dusts" with the main use being for wood
preservation. However, it has been predicted that the arsenic content in dusts and
fumes from various current roasting and smelting operations is far in excess of
world demand for arsenic chemicals.

Hydrometallurgical Pretreatment of Arsenical Ores and Concentrates

The main purpose of hydrometallurgical pretreatment is to break down the sulfide
minerals by oxidation so that cyanide or other reagents can leach the gold from
the residues for recovery. Direct cyanidation of arsenical sulfide concentrates has
been practised'! -43 but is shown to be effective only when the gold is largely
liberated in the earlier grinding stages. Hedley and Tabachnik" concluded that the
arsenic minerals had little effect on cyanidation in the pH range 10-12. Sulfide
minerals in which the gold is finely dispersed ("invisible gold") require a pretreat-
ment stage to completely break down the sulfide mineral. The various process
options that are available have been reviewed by a number of auth o rs l.J ·44 - 46 and
some of the processes will be mentioned only briefly here.

High Pressure Acid Oxidation These processes involve reacting the ore or con-
centrate with oxygen at 1800-2200 kPa and temperatures in the range 180c-21Oc C
in large pressure autoclave reactors. The prime process of this type was developed
by Sherritt Gordon and described by Berezowski and Weir", Recently, details of
an experimental study of reaction chemistry and kinetics of acid pressure oxidation
of arsenopyrite was published's. The chemistry of the oxidation stage of the process
can be represented in simplified form by the following equations:
= 2FeSO, + 2H,SO,
2FeS, + 70, + 2H,O
FeS + 20 = FeSO + S
 ARSENIC IN GOLD PROCESSING 261

4FeAsS + 110, + 6HP = 4H)AsO) + 4FeS04

4FeS04 + 2H,S04 + 0, = 2Fe,(S04)) + 2H,O
2H)AsO) + 0, = 2H)As0 4
Fe,(S04)) + 3H,O = Fe,O) + 3H,S04
Fe,(S04h + 2H,As04 = 2FeAs0 4 + 3H,S04
The solid residue after oxidation consists not only of ferric arsenate (scorodite)
and ferric oxide (hematite) but basic ferric sulfates and jarosites and arsenic as-
sociated with ferric oxyhydroxides as well as the gangue residues and the precious
metals and sometimes elemental sulfur. Arsenic also remains in solution to an
extent of hundreds of mg / L, but can be reduced to less than I mg / L in the
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

neutralisation circuit. In the limestone neutralisation stage, calcium arsenates are

precipitated together with calcium sulfate and other basic sulphates.
The high pressure acid oxidation process is operating at several plants (California,
USA 49; Sao Bento, Brazil"; Nevada, USA 51) and is to be installed at others (Por-
gera, Papua New Guinea'"; Lihir Island": Olympias project, Greece"). A concep-
tual flow diagram for the process is shown in Figure 3.
Tailings from this process contain arsenic as ferric arsenate, calcium arsenates,
a variety of other more complex arsenates and adsorbed arsenic which is mostly
associated with ferric oxyhydroxides. Silver jarosite also remains in residues. The
authors of this paper have examined residues from the high pressure acid oxidation
process using mostly specialised TEM and XRD techniques and have been able to
identify many of the crystalline compounds which are present. The small particle
size of these compounds, particularly the arsenates (LOO-sOO nm) gives rise to
doubts of long-term stability, considering the present state of knowledge in regard
to the instability of both calcium and ferric arsenates'<". Figure 4 is a transmission
electron micrograph showing some of the materials present in the neutralised high
pressure oxidation residues.

Low Pressure Acid Oxidation A number of experimental processes have been

reported for treating sulfide gold ores and concentrates in the temperature range
of 60°-150°C, at pressures of the solution vapour pressure but using oxidants other
than oxygen or air (but sometimes together with oxygen or air). These processes
have been called "chemical oxidation" processes.
Several of the low pressure acid oxidation processes rely on the use of nitric acid
as an oxidant. Felix Schaufelberger" patented a method for leaching arsenide ores
in 1957 in which additions of 1-5% nitric acid in a sulfuric acid system were said
to have "surprisingly effective results". Prior patent application for a sulfuric-nitric
process had been made in t956 by French Companies but was not published until
195855• Recently the use of nitric acid was again investigated and several processes
developed for commercial exploitation but not yet developed industrially.
The ARSENO process'? is a "nitric acid catalysed" oxygen pressure leach at
moderate conditions of about WO°C and 700 kPa. It is reported to have a very
short reaction time for the complete oxidation of sulfides and it may be used
commercially on the City Resources project at Cinola in Canada.
The NITROX process" is a nitric acid oxidation in which the nitric acid is
 262 R. G. ROBINS AND L. D. JAYAWEERA

ARS~:NICAL OR~
DR
CONCENTRATE

'.
FEED
PREPARATION

Dltygcn
+
water OXIlJATlON

+
REPULP
....
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

Limestone

+ ~
~ '"
Lime
NEUTRALIZATION

+ +
REPULP
''"" ~ -

+
~ I--
'---- -
Carbon +
Lime
LEACHjCIP Barren
Cye nldc Slurry

Landed .. Carbon WASTE

Ceusttc
Effluent MANAGEMENT
Cyanide
GOLD,SILVER
RECOVERY

t
Gold, Silver

FIGURE 3 Conceptual Flowsheet for Acid Pressure Oxidation Pretreatment of Refractory Gold Ores
or Concentrates.

regenerated from the oxides of nitrogen produced in the reaction. Ferric arsenate
and gypsum are identified in a complex residue, Residues from nitric acid oxidation
experiments are shown in Figure 5.
The ORF process" utilises peroxymonosulfuric acid (Caro's acid) at ambient
conditions to oxidise arsenopyrite without significant oxidation of pyrite,
The CASHMAN process which is a version of the U.S. Bureau of Mines Chlo-
ride-Oxygen process'? is a calcium chloride leach with oxygen at temperatures of
60°-150°C. Developed by CSS Management Corporation, this process has recently
been given more attention for its use in the treatment of arsenical flue dusts at
 ARSENIC IN GOLD PROCESSING 263
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

(a) (b)

(c) (d)
FIGURE 4 TEM Images of Constituents in the Residue from the High Pressure Acid Oxidation of
an Arsenopyrite Concentrate. Rhombic crystals are FcAs0 4.2H20 (scorodite). The oval-shaped crystal
al the centre of both A and B is a lead arsenate. Frame C consists of mostly of CaHAsO, (weilite)
formed in the neutralisation stage after acid oxidation. Other components have been identified. (I em
~ 500 nm)
 264 R. G. ROBINS AND L. D. JAYAWEERA
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

(a) (b)

(c) (d)

FIGURE 5 TEM lmngcs of Constituents in the Residue from Nitric Acid Leaching of Arsenopyrite.
Ferric Arsenate (scorodue) is the main constituent (rhombic crystals) together with arsenic containing
ferric oxyhydroxidc of extremely small particle size as in A. (1 em = 100 nm)
 ARSENIC IN GOLD PROCESSING 265

Anaconda, Montana. The residues from this process have been investigated by the
authors and shown to consist largely of gypsum together with ferric arsenate,
calcium arsenates and arsenic adsorbed to ferric oxyhydroxide and other materials
(See Figure 6.).
The AuroMet Process" is presently being piloted in Australia. No details of this
system are available other than it being a mixed chemical oxidant. neutral pH
chloride process specifically developed for arsenopyrite concentrates and designed
to produce a residue in which the arsenic is adsorptively bound to ferric oxyhy-
droxide.

Alkaline Oxidation Processes Alkaline leaching processes for the recovery of ar-
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

senic and antimony from sulfide minerals have long been established. Sodium sulfide
solutions have been used" as well as sodium hydroxide'<. The development of an
alkaline pressure oxidation process for the Mercur gold plant in Utah. USA is
described by Mason, Wicks et al'", The U.S. Bureau of Mines has reported bench
scale studies on the development of an alkaline oxidation procedure for pretreating
gold bearing arsenopyrite?' in which arsenic is precipitated as a relatively pure
calcium arsenate.
The main advantage of alkaline oxidative processes for treating arsenopyrite gold
ores and concentrates is the use of mild operating temperatures and pressures and
the direct leaching of residues without pH change. The final residues, however,
contain arsenic in an unstable form.

Bacterial Leaching Processes Bacterial oxidation of arsenopyrite was reported by

Ehrlich" in 1964, for experiments where, in 21 days, there was "extensive solu-
bilisation" of the arsenic as a mixture of arsenic (III) and (V). The pH of his
reaction mixture dropped from 3.5 to 2.5 and arsenic concentrations reached I
mg / L. Bacterial leaching technology utilising the organism T.ferrooxidans has ad-
vanced enormously in the past 20 years and now successful pilot plant demonstra-
tions have been reported?", Organisms have now adapted to arsenic concentrations
in excess of 109 / L. Giant Bay Biotech conducted bioleach trials at the Giant
Yellowknife properties in the Northwest Territories of Canada in 1987 but details
have not been released").
In Australia a pilot bioleach system" has been developed by BacTech Pty Ltd
in Western Australia who utilise a moderately thermophilic organism which op-
erates at about 45°C. The plant has operated very successfully on I tonne per day
trials with an arsenopyrite concentrate.

ARSENIC IN PROCESS RESIDUES

The arsenic in processing of arsenopyrite ores and concentrates can be recovered

as a commercial commodity, but usually reports to the process residues and is
disposed to tailings storage. Arsenic in tailings is mostly in the form of ferric
arsenate, calcium arsenates, other complex arsenates and arsenic (V) adsorbed to
ferric oxyhydroxides and other compounds. The particle size of all of the arsenic
 266 R. G. ROBINS AND L. D. JAYAWEERA
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

'to (a) (b)

""

FIGURE 6
(c)
- (d)

TEM Images of Minor Constituents in the Residue from the Cashman Process. The
material here is mostly arsenic containing ferric oxyhydroxide « 10 nm) with many rhombic ferric
arsenate crystals. some calcium arsenate. Calcium sulfate (gypsum), the major phase in this residue,
is several orders of magnitude larger in particle size and is not shown here. (1 em = 100 nm)
 ARSENIC IN GOLD PROCESSING 267

containing solids is extremely small (sometimes with considerable quantities less

than lOa nm) and since they are mostly unstable in the tailings environment they
can easily transform to the stable phases and release arsenic to solution.
The authors of this paper have examined the residues from most of the processes
that were mentioned earlier and have performed long term water percolation leach
tests on some of them. With all of the residues that have been studied it can be
said that none are long-term stable and all release arsenic (albeit at very slow rate).
Figures 4-6 show TEM photographs of some of the crystalline phases present
in various residues.
The stability of arsenic in gold mine processing wastes has been reviewed
previously'". The precipitation of a range of compounds including calcium arse-
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

nates, mixed calcium phosphate-arsenate compounds, ferrous and ferric arsenates,

barium arsenate, titanium arsenate. magnesium-ammonium arsenate, and arsenic
sulfide has been suggested for removing arsenic from waste waters. Only two of
these arsenates are actually formed in any quantity in the commercial process
residues, calcium arsenates and ferric arsenate. The other major component of
residues is arsenic containing ferric oxyhydroxide. None of these materials is long-
term stable in an open aqueous environment which is exposed to the atmosphere.
Calcium arsenates in an aqueous system when exposed to air will take up carbon
dioxide and convert to calcium carbonate with the release of arsenic'. Ferric ar-
senate will convert to ferric oxyhydroxide" (See Figure 7). Even the high iron "basic
ferric arsenates"?" (which in fact are inner sphere adsorption complexes) will release
arsenic when leached with water. These reactions are very slow and may take many
years for appreciable changes.
Testing methods for evaluating the stability of hazardous waste residues have
been defined in the United States by the Environmental Protection Agency. Several
EP Toxicity Test Procedures have been described 7 1. 72 • These tests obviously do not
adequately assess the long term stability of residues (since they must be conducted
over periods of only hours), and improved test methods must be designed.
Long term stability of the Cashman Process residue from Anaconda flue dust
stabilisation tests was assessed" by PTI Environmental Services at Boulder, Col-
orado. in both continuous column tests and batch bottle-rolling tests for periods
up to 210 hours. Unusual arsenic release profiles were observed even in these short
experiments. EP Toxicity and TCLP tests conducted on copper smelter slag at the
University of Washington also showed unusual leaching profiles over a period of
100 hours. due to interactions of the leached components at the solid surface":'.
These examples of changing behaviour during the leach testing of residues, even
in hundreds of hours. show the need for longer term tests. Also the tests should
be conducted by water percolation leaching rather than "equilibrium" tests in a
closed system.

CONCLUSION

A number of economic processes have been developed for the recovery of gold
from arsenical gold ores and concentrates. The technologies are mostly well under-
 26R R. G. ROBINS AND L. D. JAYAWEERA
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

(a) (b)

(c) (d)

FIGURE 7 TEM Images from Samples of Pure Ferric Arsenate after water washing for Several Years.
The more transparent crystals are shown in various stages of converting to ferric oxyhydroxide (different
forms).
 ARSENIC IN GOLD PROCESSING 269

stood particularly in relation to the behaviour of gold in the various processes. The
reactions of arsenic in terms of process chemistry are also generally understood
but there still remains a lack of information on complex speciation in aqueous
systems and surface complexation and adsorption or arsenic in relation to modern
theories's. The speciation, chemistry and kinetics of the reactions which occur in
the residues from these processes is less well known particularly in relation to
arsenic.
Some biological and human epidemiological studies of the effects of arsenic are
reported by Fowler" and it is obvious that further investigation will point more to
the need for better environmental control in industrial processes which mobilise
arsenic.
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

Roasting pretreatment of arsenical ores and concentrates has long been practiced
but the off-gases which are produced contain arsenic trioxide which is extremely
difficult and costly to remove to levels which would have no environmental impact.
The move by Placer Dome Inc. from a smelter system to a pressure oxidation plant
at its Campbell Mine in Ontario)' (to be operational in 1991) must be seen as a
trend to hydrometallurgical alternatives to roasting and smelting.
A number of hydrometallurgical options to roasting pretreatment of arsenical
gold ores and concentrates are available commercially. The Sherrin Gordon high
pressure acid oxygen process" is foremost of these and the reaction chemistry has
been well defined. However, the residues from this process have not been closely
investigated either in terms of mineralogy or long term stability, and this should
be done. It is not sufficient simply to adopt U.S. EPA toxicity test extraction
procedures as indicators of environmental acceptability without a detailed scientific
study of the residues. ,
Even without the consideration of modern gold processing technology we are
left with residues from old operations that are presenting environmental concern.
Some of these are being thoroughly investigated since in the United States, at least,
the Comprehensive Environmental Response, Compensation, and Liability Act of
1980 (CERCLA) provides the U.S. Environmental Protection Agency with the
authority and responsibility to establish procedures and to evaluate waste sites and
implement remedial responses. The guidance document on remedial technologies
is the Handbook of Remedial Action at Waste Disposal Sites published in 1982
and later updated".
The new technologies should not be left to the same fates as the old.

References
I. M. C. Jha. Min. Proc. and Extractive Mel. Rev.. 2. 331 (19~7).
2. M. C. Jha and M. J, Kramer, Recovery of Gold from Arsenical Ores, in Precious Metals: Mining,
Extraction and Processing, (Kudryk, Corrigan and Liang, eds.) AIME, Met. Soc. Warrendale,
337-365 (1984).
3. A. Kontopoulos and M. Stefanakis, Process Options for Refractory Sulfide Gold Ores: Technical.
Environmental and Economic Aspects. in EPD Congress '90 (D. R. Gaskell. ed.] TMS. Warren-
dale, 393-412 (1990)
4. R. G. Robins and K. Tozawa , elM Bulletin. April. 171 (1982).
5. R. G. Robins, The Stability and Solubility of Ferric Arsenate: An Update, in EPD Congress '90
(D. R. Gaskell, ed.) TMS, Warrendale, 93-104 (1990).
o. H. Onishi and E. B. Sandell, Geochim, et Cosmochim, Acta. 7, I (1955).
 270 R. G. ROBINS AND L. D. JAYAWEERA

7. V. L. Escobar Gonzalez and A. J. Monhemius. The Mineralogy of Arscnates Relating to Arsenic

Impurity Control, in Arsenic Metallurgy Fundamentals and Applications (Reddy, Hendrix and
Oucncau. cds) TMS, Warrendale, 405-418 (1988).
8. L. A. Clark, Econ. Geol.. 55, 1345 and 1631 (1960).
9. T. M. Seward. Geochim. et Cosmochim. ACla, 37, 379 (1973).
Ill. C. A. Henrich and P. J. Eadington, Econ. Geol., 81, 511 (1986).
II. D. M. Shenberger and H. L. Barnes, Geochim. et Cosmochim. Acta. 53, 269 (1989).
12. P. J. Renders and T. M. Seward, Geochim. el Cosmochim. ACIa, 53, 255 (1989).
13. G. M. Schwartz. Econ. Geol, 39, 371 (1944).
14. K. J. Henley, Mill. Sci. and Eng .. 7. 289 (1975).
15. P. B. Barton Jr., Geochim. et Cosmochim. ACIa, 33, 841 (1969).
16. A. M. Gavrilov et al.. Trudy. Tsent. naueh. geol. inst. blag., Metall., 135, 85 (1978).
17. D. Tahija and H. H. Huang, Hydrometallurgical Formation of Iron-Arsenic Compounds, in
lmpurity Control and Disposal (Proc. CIM Hydromet. Meeting, Vancouver, Canada 1985) Paper
4,1-14.
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

18. E. Z. Bur 'Yanova, Zapisk. Vses. Mineral Obshch., 106,302 (1977).

19. K. Ossco-Asarc et al., Solution Chemistry of Cyanide Leaching Systems, in Precious Metals:
Mining. Extraction. and Processing (Kudryk, Corrigan and Liang, eds.), AIME Met. Soc.. War-
rendale, 173-197 (1984).
20. N. Morimoto and L. A. Clark, Amer. Mineral., 46, 1448 (1961).
21. I. L. Khodakovskiy. Geokhimiya, 8, 960 (1966).
22. N. F. Spychcr and M. H. Reed, Geochim. et Cosmochim. Acta, 53, 2185 (1989).
23. F. R. Archibald, ClM Trans., 52, 76 (1949).
24. O. Mathews, ClM Bull., 42, 178 (1949).
25. R. C. Gegg, CIM Bull., 42, 659 (1949).
26. R. J. C. Tait, CIM Bull., 54, 302 (1961).
27. D. A. J. Rand, 1. Electroanal. Chem., 83,19 (1977).
28. K. R. N. Hansen and J. E. Laschinger, The Roasting of Refractory Gold Ores and Concentrates,
NIM (South Africa) Research Report No. 85 (1967).
29. G. Ramadorai and R. K. Mishra, Roasting of Arsenical Gold and Silver Bearing Minerals, in
Arsenic Metallurgy Fundamentals and Applications. (Reddy, Hendrix and Oucncau. eds.), TMS,
Warrendale, 161-171 (1988).
30. F. J. Arriagada and K. Osseo-Asarc, Gold Extraction from Refractory Orcs: Roasting Behaviour
of Pyrite and Arsenopyrite, in Precious Metals: Mining: Extraction and Processing, (Kudryck,
Corrigan and Liang, eds.). AIME Met. Soc .. Warrendale. 367-385 (1984).
31. R. G. Behrens and G. M. Rosenblatt, J. Chern. Thermodynamics. 4, 175 (1972).
32. H. D. Goodfellow et al., Arsenic Removal from Roaster Off-gases, Paper presented at the Fourth
International Clean Air Conference (1978).
33. G. H. Marchant and R. L. Meek, Evaluation and Technology for Control of Arsenic Emissions
at the Campbell Red Lake Gold Smelter, USEPA Report 600/2-80-141. June (1980).
34. J. Frostiak. personal communication, July (1990).
35. B. A. Strathdee and L. M. Pidgeon, CIM Bulletin, 883. December (1961).
36. A. S. Pashinkin et al.. Zhur, Priklad. Khim., 52, 1085 (1979).
37. N. Chakraborti and D. C. Lynch. Met. Trans. B, 14.239 (1983).
38. A. D. Mah, Termodynamic Data for Arsenic Sulfide Reactions, USBM Report of Investigation
8671 (1982).
39. D. C. Lynch. A Review of the Physical Chemistry of Arsenic as it Pertains to Primary Metals
Production, in Arsenic Metollurgy Fundamentals and Applications, (Reddy. Hendrix and Oueneau,
cds.). TMS. Warrendale, 3-33 (1988).
40. Y. Kondo, Recovery and Fixation of Arsenic from Metallurgical Intermediates, Proceedings MMIJ-
AIME 4th Joint Meeting Tokyo. Japan. D-I-4, 45-58 (1980).
41. N. Hedley and H. Tabachnik , Arsenic and Antimony Sulfide Minerals in Cyanidation, in Recent
Developments in Mineral Dressing. IMM London (1953).
42. R. Carter and C. S. Sam is. ctt« Bulletin. 160. March (1952).
43. H. J. Heinen et al, USBM Report of Investigations 8458 (1980).
44. A. J. Brown, Economics of Recovering Gold from Refractory Sulfide Concentrates. Paper pre-
sented at First International Symposium on Precious Metals Recovery, Reno, Nevada, June (1984).
45. P. G. Mason and P. T. O'Kanc, Refractory Gold Process Options, Paper presented at 24th Annual
Conference of Metallurgists. Vancouver. Canada. August (1985).
46. A. Kontopoulos and M. Stcfanakis, Process Selection for the Olympias Refractory Gold Con-
centrate. in Precious Metals '89. (M. C. Jha and S. D. Hill. cds.) TMS. Warrendale. 179-209
(1988).
 ARSENIC IN GOLD PROCESSING 271

47. R. M. G. S. Bcrezowksi and D. R. Weir, Minerals and Metallurgical Processing, I, I (1984).

48. V. G. Papangelakis and G. P. Demopoulos. Call. Met. Quarterly, 29, I and 3 (1990).
49. J. R. Turney et al.. The Application of Acid Pressure Oxidation to the McLaughlin Refractory
Ore. in Precious Metals '89, (M. C. Jha and S. D. Hill, eds.), TMS, Warrendale, 25-45 (1988).
50. E. J. da Silva et aI., Process Selection, Design, Commissioning and Operation of the Sao Bento
Mineracao Refractory Gold Ore Treatment Complex, in Gold Forum on Technology and Prac-
tices-World Gold '89, SME, Littleton, 1989,322-332 (1989).
51. G. R. Wicker and J. A. Cole, The Development and Implementation of a Pressure Oxidation
Flowsbeet for the Getchell Mine, Paper presented at SME Annual Meeting, Salt Lake City (1990).
52. R. G. Robins, Mel. Trans. B, 12, 103 (1981).
53. R. G. Robins, The Stability and Solubility of Ferric Arsenate: An Update, in EPD Congress '90
(D. R. Gaskell, ed.), TMS, Warrendale. 93-104 (1990).
54. F. A. Schaufelberger, U.S. Pat. 2805936, September 10 (1957).
55. British Patent 795 793, published May 2~ (1958).
56. R. Raudsepp et aI., U.S. Patent 4647307, March 3 (1987).
Downloaded by [University of Sussex Library] at 00:39 19 January 2015

57. G. van Weert, An Update on the Nitrox Process. Randol Gold Forum 1988, Scottsdale. Arizona,
209- 210.
58. V. I. Lakshamanan et aI., Treatment of Refractory Gold Ores, paper presented CIM Annual
Hydrometallurgical Meeting, Timmins. Ontario (1984).
59. G. A. Smyres et al.. Calcium Chloride-Oxygen Leaching and Metals Recovery from an Arsenical
Copper-Cobalt Concentrate, U.S. Bureau of Mines Report of Investigation 9020 (1986).
60. E. G. Davis, (HydroMet Corporation), personal communication (1990).
61. R. I. Agladze et al., Trudy lnst. Metal. i Gornogo Dela, Akad. Nauk. Gruzin. SSR., 8, III (1957).
62. A. V. Nikolaev et al. Tsvet. Metal., 38. 44 (1965).
63. P. G. Mason, F. D. Wicks et aI., Selection of the Process Flow Sheet for the Mercur Gold Plant,
in Precious Metals: Mining, Extraction, and Procesing, (Kudrick, Corrigan and Liang, eds.), AIME
Met. Soc., warrendale. 1984,435-445 (1984).
64. P. Bhakta et al.. Alkaline Oxidative Leaching of Gold Bearing Arsenopyrite Ores, US Bureau
of Mines Report of Investigations 9258 (1989).
65. H. L. Ehrlich, Econ, Gcot., 59, 1306 (1964).
66. R. W. Lawrence and P. B. Marchant, Biochemical Pretreatment in Arsenical Gold Ore Processing,
in Arsenic Metallurgy Fundamentals and Applications. (Reddy. Hendrix and Ouencau , cds.). TMS.
Warrendale (1988).
67. K. B. DeGraaff, personal communication (1990).
68. P. A. Spencer and J. R. Budden. Metallurgical Considerations in the Design of a Bio-oxidation
Plant: A Case Study for a Refractory Arsenopyrite Concentrate in EPD Congress '90 (D. R.
Gaskell. ed.). TMS, Warrendale, 295-303.
69. R. G. Robins, The Stability of Arsenic in Gold Mine Processing Wastes, in Precious Metals:
Mining, Extraction and Processing, (Kukryck, Corrigan and Liang, eds.). AIME Met. Soc., War-
rendale, 24t-249 1984).
70. E. Krause and V. A. Ettel, Hydrometallurgy ; 22, 311 (1989).
7l. U.S. EPA. Background Document, Section 261.24. Characteristic of Extraction Procedure Tox-
icity, NTIS Report PB 81-185-027, Springfield, Virginia, May (1980).
72. U.S. EPA. Background Document for Toxicity Characteristic Leaching Procedure, Washington.
D.C. (See also Federal Register, Vol 51, Nos. 114,216. t986) (1985).
73. A. O. Davis, personal communication (1990).
74. L. G. Twidwell. personal communication (1990).
75. J. A. Davis and D. B. Kent, Surface Comptexation ModeOing in Aqueous Geochemistry, in
Mineral-Water lnterjace Geochemistry, (Hochella and White. eds.), Vol 20 of Reviews in Miner-
alogy. Min. Soc. Amer. (1990).
76. B. A. Fowler, ed., Biological and Environmental Effects of Arsenic, Elsevier, Amsterdam (1983).
77. K. Wagner et al., Remedial Action Technology for Waste Disposal Sites. Noyes Data Corp.. New
Jersey (1986).