Minerals Engineering, Vol. 8, Nos 1/2, pp.

147-158, 1995
Elsevier Science Lid
Pergamon Printed in Great Britain
0892'-6875(94)00109.-X 0892-6875/95 $9.50+0.00

BIOOXIDATION OF AN ARSENIC-BEARING REFRACTORY GOLD ORE

D. L A N G H A N S , A. L O R D , D. L A M P S H I R E , A. B U R B A N K , a n d E. B A G L I N

U.S. Bureau of Mines, Reno Research Center, Reno, Nevada, USA

(Received 14 July 1994; accepted 2 September 1994)

ABSTRACT

Biological oxidation era refi'actory arsenic-bearing gold ore was investigated to determine
the fate of arsenic during processing and to assess the effect of biological pretreatment
on gold extraction. Experiments were conducted using a consortium of iron and sulfide
oxidizing bacteria in semi-batch and continuous-flow stirred bioreactors, attclalso in a tall
column bioleaching system. Sulfide oxidation and arsenic solubilization were monitored
during biooxidation and the data were correlated with precious metals extraction during
subsequem~ cyanidation tests. In addition, the concentrations of arsenite [As(Ill)] and
arsenate [AS(V)] species present in the liquors were monitored as a function of time using
an anion exchange high performance liquid chromatography~atomic absorption
spectroscopy technique. The stabilities of the final tailings and the arsenic-bearing
sludges obtained by neutralization of the biooxidation liquors were also assessed.

Leaching results showed that over 95 % sulfide oxidation and 47% arsenic extraction could
be obtained fi'om this ore using the biooxidation process. Gold extraction during
subsequem! cyanidation was increased from 49% to about 80% after biological
pretreatment. Total arsenic concentrations as high as 17 g/L in solution were obtained
with no apparent detrimental effect on the bacterial populations. In all cases, arsenic was
initially slubilized as As(Ill). Typical leaching solutions contained up to 18 times as
much As(IH) as As(V). Since As(Ill) compounds are less stable and much more toxic than
As(V) compounds, long-term stability of sludge materials in the environment is of concern.
Results fi'om Toxicity Characteristic Leaching Procedure stability tests performed on the
sludges will be discussed.

Keywords
Biooxidation, arsenic, speciation, arsenopyrite, gold, bacteria.

INTRODUCTION

Many sulfidie gold and silver ores contain varying amounts of arsenic, often in the form of arsenopyrite,
FeAsS. In almost all cases, the arsenic is an unwanted impurity and its presence can cause concern due
to its potential impact on process chemistry and its involvement in the disposal of waste products to the
environment.

For refractory, ata;enic-bearing sulfide gold ores, much of the finely disseminated gold is encapsulated
in the sulfide matrix of FeAsS, and in the usually more dominant accompanying mineral pyrite, FeS 2.
Due to this sulfide encapsulation, the gold cannot be recovered using conventional leaching techniques,

147
148 D. LANGHANS et al.

including eyanidation. To effectively extract the gold from these ores, an oxidative pretreatment, such
as biooxidation, roasting, or pressure oxidation is necessary to break down the sulfide matrix. Once the
sulfides are oxidized, the gold is free to be contacted by the leaching agent.

Unfortunately, arsenic is solubilized during the biological oxidation pretreatment process and can be
present in the leach solutions as As(Ill), As(V), or as a combination of both oxidation states. Trivalent
arsenic is much more toxic than pentavalent arsenic, therefore, its release into the environment could have
a more significant impact. Consequently, it is important to identify the arsenic species present in the leach
solutions and to understand the chemical interaction of arsenic and other metals solubilized during the
biooxidation process. Complete processing schemes for the treatment of arsenic-bearing ores must allow
for the treatment and disposal of all liquid and solid arsenic-containing wastes in an environmentally
acceptable form.

Most reports on biological processing of arsenical gold ores detail the various procedures which result
in high recoveries of gold, but do not address arsenic speciation and do not consider the long term fate
of arsenic in tailings and residues [1,2]. In fact, many reports state that all arsenic solubilized is in the
form of As(V) and that a stable ferric arsenate product will be precipitated upon neutralization of the leach
solutions [3-5]. Some researchers are now reporting that arsenic is initially solubilized as As(III), but that
it is oxidized to As(V) by contact with water, oxygen, or ferric iron during the biooxidation process [6-9].
However, other researchers suggest that arsenic is solubilized as As(III) during biooxidation and that
arsenic will remain in the trivalent oxidation state unless a strong oxidant, such as ozone, is present [10].
The lack of consistent results indicates that further research in this area is needed.

The U.S. Bureau of Mines, Reno Research Center conducted research to determine the fate of arsenic
liberated during the biooxidation of an arsenic-bearing refractory gold ore. The research incorporated
the use of semi-batch and continuous flow stirred reactors, as well as a column leaching system. A novel
approach to identify and quantify arsenic species in biooxidation leach solutions was developed.
Correlations between arsenic species in solution and the conditions established during biooxidation are
discussed, as is the relationship between arsenic and sulfide solubilized during biooxidation and precious
metals extraction during subsequent cyanidation. A flow diagram for processing the arsenopyrite ore is
shown in Figure 1.
~ W
Oat ~ t4e~3,

1
TCtP ~Jng

. . . . . . . . . . . .

i U"V/U~II~'I'IIO~

-i m i -
I
Fig. 1 Flow diagram for processing arsenopyrite ore.
 Arsenic-bearingrefractorygold ore 149

DESCRIPTION OF MATERIAL, NUTRIENT MEDIUM, AND MICROORGANISMS

Material

The ore sample used for this study was obtained from a deposit in northern Washington. Mineralogical
characterization of the ore using scanning electron microscopy (SEM) and X-ray analyses showed the ore
to contain arsenopyrite, pyrite, sphalerite, galena, and an iron-arsenate in a gangue of quartz and
potassium/sodium feldspars. The analyses of the principal constituents of the ore sample are shown in
Table 1. The ore; was crushed to minus 1.9 em for column testing. Ore used in semi-batch and
continuous flow stirred bioreactor systems was crushed and pulverized to minus 100 mesh.

T A B L E 1 Analysis of arsenopyrite ore sample, percent

Fe ........... 8.7 Si . . . . . . . . . . . . . . 25.1

As ........... 6.2 S-rotat . . . . . . . . . . . . 3.5
A:[ . . . . . . . . . . . . 4.7 S2" . . . . . . . . . . . . . 2.5

K ............ 2.2 Au 1 . . . . . . . . . . . . . 0.45

10z/ton.
Medium

The nutrient medium used for both the semi-batch and the continuous leaching systems was a simple basal
salts medium, containing 0.6 g/L (NH4)2SO4 and 0.5 g/L K2HPO 4 in deionized water. The pH was
adjusted to approximately 2.0 using concentrated sulfuric acid. The remaining nutrients required by the
bacteria were provided by the ore. Ordinary tap water with no pH adjustment was used as the leaching
solution for the column test.

Microorganisms

A mixed culture of autotrophic, acidophilic, iron and sulfide oxidizing bacteria was adapted to the
arsenopyrite ore over a period of several months by adding small amounts (approximately 0.1 g) of the
ore substrate to culture tubes containing nutrient medium. The cultures were transferred biweekly until
consistent growth in the presence of the ore was achieved.

Inoculum for the semi-batch bioreactor leaching test was prepared by adding 10 mL of the mixed bacterial
culture to 500 mL of pH 2.0, non-sterile nutrient medium. Fifty grams of non-sterile ore was also added
to the inoculum to further acclimate the cultures. The mixture was grown in a 35C incubator until the
cell population, as determined by direct count using a Petroff-Hausser 1 counting chamber, was on the
order of 108 cells/niL. Inocula for the continuous-flow leach and column leach systems were obtained
by taking a portion of leach liquor from the semi-batch reactor test after the bacterial population was well
established. This culture was mixed with nutrient medium and ore using the same procedure as described
for the semi-batch reactor.

SAMPLE ANALYSES

Biological leach so]miens were analyzed for total arsenic, total iron, and other metals, as well as for total
sulfur by inductively coupled plasma (ICP)/atomic emission spectroscopy (AES). Total arsenic, gold, and
silver concentrations were measured using atomic absorption spectroscopy (AAS). Solid samples were
analyzed for arsenic and other metals by ICP/AES and AAS, gold and silver by fire assay, total sulfur

1. Referenceto specificproductsdoes not imply endorsementby the U.S. Bureauof Mines

150 D. LANGHANSet al.

using an oxygen combustion technique, sulfate using ion chromatography (IC), and elemental sulfur using
a carbon disulfide dissolution technique. The sulfide content of the solids was calculated as the difference
between total sulfur and elemental and sulfate sulfur. Net sulfide oxidation and arsenic solubilization were
used as indicators to determine the extent of biological oxidation.

Arsenic(III) and As(V) levels in the leach liquors were determined using High Performance Liquid
Chromatography (HPLC) coupled with an AAS unit. The HPLC was used to separate the mixtures of
As(III) and As(V) in the leach liquors using an anion exchange column with an ammonium carbonate
buffer. The AAS unit was used as a selective detector by recording arsenic emissions at the 193.7 nm
line using an Ar/H 2 flame. A Bio-Rad model 800 HPLC computer system was used to convert the analog
signal from the AAS as well as to automate peak integration and data collection. Liquid samples were
filtered through disposable 0.22 ~m filters to remove microbial and other impurities prior to speeiation
analyses. If not analyzed immediately, filtered samples were placed in sealed vials and refrigerated until
analyses were complete. Known standards were analyzed each time samples were run to ensure that
accurate speciation and concentration results were obtained.

Semi-batch leaching test

The semi-batch stirred bioreactor experiment was conducted in a jacketed 3-L reactor. The reactor
contained 10 wt pct pulp of ore in nutrient medium with a 10 wt pet solution of mixed iron and sulfide
oxidizing bacteria. The slurry was sparged with water-saturated air to produce a dissolved oxygen content
of at least 2 mg/L in solution. The slurry was stirred at approximately 200 rpm, and the temperature of
the slurry was maintained at 30-35C using a circulating water bath. The test was conducted using a
semi-batch technique to enhance the rate of biooxidation. In semi-batch operation, agitation was
periodically stopped to allow the solids to settle, after which the leach solution was decanted, fresh
nutrient solution was added, and agitation was reinitiated. Samples of the slurries were taken periodically
to monitor pH, Eh, sulfate and metal ion concentrations in the solution, and sulfide and metal content of
the solids.

Continuous flow leaching test

The continuous stirred tank bioreactor system (CSTR) included a stirred 30-L feed tank and three stirred,
7-L baffled leach reactors placed in series. The feed tank contained a 15 wt % slurry of ore in nutrient
medium. The pH in the feed tank was controlled at 2.0 using additions of 25 i% H2SO4. The temperature
of the slurry in each leach reactor was regulated at 32C using an immersion probe heater connected to
a variable voltage controller. The slurries were sparged with water-saturated air to maintain the dissolved
oxygen content above 2 mg/L. Prior to the start of the test, the first reactor was filled with feed slurry
and inoculated with bacteria previously adapted to the ore. Once the bacterial population of the reactor
solution reached 108 cells/mL, the test was initiated by pumping the feed slurry into the first leach reactor
at a rate which produced an overall CSTR residence time of 9.5 days. The slurry and bacteria progressed
from the first reactor into reactors 2, 3, and the catch reservoir by gravity overflow. Slurry samples were
taken from each leaching reactor every 2-3 days for chemical analyses and to provide material for
standard bottle roll cyanidation tests.

Column leaching test

A 20.3-cm-diam PVC column, 6 m high was designed and constructed in four 1.5-m sections for ease
of loading and sampling. Each section of the column contained ports to obtain solid, liquid, and gas
samples at various levels throughout its length.

The ore sample for column leaching was thoroughly mixed to obtain homogeneity using splitting and cone
and quarter mixing techniques. Assays were performed on head samples to determine the baseline
concentrations of gold, silver, sulfide, arsenic, and other metals present in the ore. The ore was
inoculated with 20 L of bacterial culture containing 107 cells/mL by hand mixing during loading. The
column, after each section was assembled and loaded, contained 241 kg of ore.
 Arsenic-bearingrefractory gold ore 151

Forty liters of pH 6.6 tap water leaching solution was initially percolated through the column in a cyclical
2 week on/2 week off pattern. The application rate was 0.02 mL/em2/min, which was slow enough to
prevent saturation or flooding of the column. The 40 L solution was circulated twice during each 2-week
leach period. After 7 days, the leaehant in the collection reservoir was replenished to 40 L with tap
water, then recyck~ back through the column. After 2 weeks of leaching, a 2 week rest cycle was
allowed. These rest cycles, in which solution flow was halted, allowed the drain down of leach solution
into the reservoir. The drain down also allowed air to permeate back into the void spaces between ore
particles and replenish the oxygen that was consumed during the biooxidation cycle. At the end of the
rest period, solution flow was reinstated with 40 L of fresh tap water.

Samples were obtaiined during each leach cycle from the four liquid sample ports along the height of the
column and from the solution reservoir at the bottom of the column. Samples were analyzed for bacterial
population, metal and sulfate ion concentration, Eh, and pH. Solid samples, which were taken
periodically throughout the test, were analyzed for metal and sulfide content. The interparticle void space
oxygen levels were measured using a hand held oxygen monitor during both leach and rest cycles to
determine if bacterial activity was related to the oxygen profile along the height of the column.

Cyanide bottle roll tests

Cyanide leach test,; to extract the precious metals were conducted using a standard bottle roll method.
Fifty grams of raw ore or biooxidized material from the semi-batch stirred reactor tests were added to
150 mL of deionized water in a 1-L plastic bottle. The pH of the slurry was adjusted using lime to
approximately 11.5, after which 0.15 g NaCN was added. The bottles were capped and placed on a roll
for 24 h at ambient temperature. After test completion, the slurries were filtered and washed with
deionized water, and the solutions and solids were analyzed.

Cyanide tests conducted on samples from the CSTR and column were conducted in a similar fashion,
except larger quantities of ore, and proportionally more water and cyanide were used to provide sufficient
residue for railings stability tests. Also, sodium hydroxide was used to adjust the pH for some of the
CSTR samples.

Tailings and Sludge Stability

Samples of the ore., as well as the residues after biooxidation and cyanidation, were subjected to the
Environmental Protection Agency's Toxicity Characteristic Leaching Procedure (TCLP) test [ 11] to obtain
an indication of the short-term stability of arsenic in these materials.

Sludges produced from the neutralization of the CSTR leach liquors were also subjected to TCLP testing.
The sludges were produced by adding a 15 wt % lime slurry to the final leach liquors from each leach
reactor and the catch reservoir to precipitate the contained metals from solution. The pH of the solutions
was increased to 7 by the addition of lime. The resultant slurry was stirred for 1 hour and then filtered.
The sludge was dried at 50C for 48 h and then subjected to TCLP testing. The clear filtrate was also
analyzed to determine if it would meet drinking water standards.

RESULTS AND DISCUSSION

Semi-batch, CSTR, and column biooxidation tests were performed to obtain data relating arsenic and gold
extractions to various levels of sulfide oxidation, as well as to compare sulfide oxidation rates obtained
with different reactor systems and to elucidate arsenic speciation during leaching. The semi-batch reactor
was operated for a total of 87 days, well past the time needed for complete sulfide oxidation, in an effort
to determine the maximum level of arsenic solubilization possible. The CSTR test was conducted for a
total of 23 days, which was deemed long enough to ensure that a steady state had been attained in the
system. The column experiment has been in operation for over 300 days. Short term (TCLP) stabilities
of the cyanide tailings from both semi-batch and CSTR tests, as well as sludges produced from the
neutralization of CSTR biooxidation leach liquors were also determined.
152 D. LANGHANSet al.

Arsenic Chemistry

A detailed study of arsenic chemistry was conducted to help elucidate the reactions occurring during
biooxidation of the arsenopyrite ore. Bacterial oxidation of arsenopyrite may proceed either directly or
indirectly. Direct mechanisms involve enzymatic attack by bacteria attached to the arsenopyrite surfaces,
while indirect mechanisms involve chemical oxidation by bacterially produced ferric sulfate. According
to various authors [2,6,12] direct biological oxidation of arsenopyrite can result in the formation of
trivalent and/or pentavalent arsenic and ferrous sulfate, as shown in the following Eqs.:

4FeAsS + 1102 +2H20 _.Bacteria__> 4HAsO2 + 4FeSO4 (i)

4FeAsS + 1302 + 6H20 __Bacteria__> 4H3AsO4 + 4FeSO4 (2)

Ferrous iron can then be biologically oxidized to ferric iron which will then be used for chemical leaching
by:

4FeSO4 + 02 + 2H2SO4 ._Bacteria__> 2Fe2(SO4)3 + 2H20 (3)

Chemical oxidation of FeAsS by biologically generated ferric sulfate is another important reaction that
may accompany the biooxidation process [2,6,13]. Either As(Ill) or As(V) can be produced:

4FeAsS + Fe2(SO4)3 + 10.502 + 3 H 2 0 - - > 6FeSO 4 + 4HAsO 2 + H2SO4 (4)

2FeAsS + Fe2(SO4)3 + 602 + 4 H 2 0 - - > 4FeSO 4 + 2H3AsO4 + H2SO4 (5)

According to some researchers [7,14], the As(Ill), whether generated by direct or indirect leaching of
FeAsS, is thermodynamically oxidizable to the pentavalent state by either oxygen or ferric iron as follows:

2HAsO 2 + 02 + 2H20--> 2H3AsO4 (6)

HAsO 2 + Fe2(SO4)3 + 2H20--> H3AsO4 + 2FeSO 4 + H2SO4 (7)

However, other researchers [10] state that As(III) is stable in the biooxidation process, and that the
addition of a stronger oxidant would be necessary to achieve oxidation of As(III) to As(V).

Speciation studies conducted in the current investigation on leach liquors from the semi-batch biooxidation
of an arsenopyrite ore have shown that arsenic is primarily solubilized as As(Ill). In fact, As(III) to
As(V) ratios of over 18:1 were measured in the leach solutions which contained up to 4 g/L arsenic. The
semi-batch reactor was continuously sparged with air during testing, and dissolved oxygen measurements
were typically greater than 4 mg/L. Ferric iron concentrations of up to 5 g/L were also present in the
leach liquors during testing. Both these parameters, along with high Eh (800 mV), low pH (1.2-1.4), and
high biological population (108-109 cells/mL), indicate oxidizing conditions existed in the reactor.
However, little oxidation of As(Ill) to As(V) occurred during the experiment.

The data showed that, in general, when the total arsenic and iron concentrations in the leach liquor were
high, i.e. in the grams per liter range, very little As(V) was observed. Because of the low solubility of
FeAsO4, the high concentration of ferric iron present in biooxidation liquors probably scavenges any
As(V) produced and carries it into the solids, as shown in the following Eq. [15]:

Fe2(SO4)3 + 2H3AsO4 --> 2FeAsO4! + 3H2SO4 (8)

However, after sulfide oxidation was nearly complete, the rate of arsenic leaching slowed and total arsenic
concentrations in the leach liquor decreased dramatically to approximately 500 tng/L. This decrease was
prinmrily due to dilution factors resulting from the periodic nutrient medium addition and replacement.
At this point, up to 20 % of the arsenic in solution was As(V). It is not known whether As(V)was formed
 Arsenic-bearingrefractorygold ore 153

due to partial oxidation of As(III) or whether it was due to slow solubilization of other arsenic-bearing
minerals in the ore or ferric arsenate precipitate formed during leaching.

Arsenic was also solubilized as As(III) during biooxidation in the CSTR and remained in that oxidation
state throughout the 23 day test. Eh and pH values for the leach reactors ranged from 670 to 740 mV
and 1.4 to 2.0, respectively, during the course of testing. Bacterial populations stayed high throughout
the test and varied from 108 to 109 cells/mE Although these conditions indicate an oxidizing environment
existed within the reactors, it appears the kinetics of As(III) to As(V) conversion were not favorable.

Somewhat strongex oxidizing conditions were observed during column bioleaching than in the stirred
reactor experiments. Solution pH averaged about 1.5, while Eh rose to approximately 900 inV. Even
under these conditions, arsenic was solubilized principally as As(Ill). Total arsenic concentrations in the
leach liquor rangexl from a few hundred milligrams per liter to over 17 g/L, depending on the sample port
and the time of sampling. Bacterial populations of up to 108 cells/mL were measured, which indicates
the bacteria were able to tolerate the high levels of As(III) and other metals in solution. After 300 d of
leaching, some As(V) began to be detected in the leach liquors. Again, the specific reactions occurring
to produce As(V) are not known. However, its presence is most likely due to solubilization of other
arsenic-bearing minerals from the ore or gradual solubilization of ferric arsenate precipitate.

Ferrous and ferric iron were added in separate tests to some stirred bioreactor media and slurries to
determine if increasing the molar ratio of iron to arsenic in solution from a typical value of 2:1 would
enhance the oxidation of As(III) to As(V). Results indicated that As(III) remained stable in the bioleach
solutions even with iron:arsenic ratios as high as 6:1. In fact, only partial oxidation of As(III) to As(V)
was achieved in the presence of iodine, a strong oxidant. This leads to the conclusion that even though
Eqs. 6 and 7 are thermodynamically feasible, they were not taking place to any extent during biooxidation
of the arsenopyrite ore. Therefore, for this ore and these test conditions, Eqs. I and/or 4 appear to best
represent the leaching chemistry.

Gold Extraction From Biooxidation Residues

Semi-batch and continuous flow reactor tests: Table 2 sununarizes the semi-batch bioreactor and CSTR
biooxidation experiments and results from cyanidation of the biooxidized residues. The data show that
the sulfide in this ore was readily biooxidized in both stirred reactor systems. Although the total
percentage of sulfide oxidized was less in the CSTR than in the semi-batch test, the initial rates of
oxidation were approximately the same: both systems achieved about 80% oxidation in 9.5 d. Arsenic
extractions ranged from 34 to 41% in the CSTR system, while the extraction achieved in the semi-batch
test was 47 %. Over 35 % of the iron was also extracted from the ore during biooxidation in both reactor
systems. The low arsenic and iron extractions in comparison to sulfide oxidation suggests that more
arsenic was solubilized during leaching but precipitated as ferric arsenate before being removed from the
system. An increase in gold extraction from 49 % for the untreated ore to over 75 % for the biooxidized
residues was observed, which indicates that biological pretreatment does significantly decrease the
refractory nature of this ore.

Figure 2 presents the overall results of the continuous flow investigation with gold and arsenic extractions
plotted as a function of sulfide oxidation for the entire CSTR system. The final data from the semi-batch
test are also included for comparison. Arsenic extraction follows a straight line to a maximum of 47 %,
which was achieved in the semi-batch test. Gold extraction increases with increasing sulfide oxidation
up to about 50% sulfide oxidation. After 50 % sulfide oxidation, gold extraction levels off at 76 to 82%.
Although additional gold extraction is not realized above 50% sulfide oxidation, additional arsenic
solubilization can be achieved with higher sulfide oxidation.
154 D. LANGHANSet al.

T A B L E 2 Summary of results of CSTR and semi-batch tests

Biooxidation Cyanidation

Material Arsenic Iron Sulfide Gold TCLP

extraction, extraction, oxidation, extraction, test, l,
pct pet pct pet pass/fail

Head sample . . -. . . . . 49 Fail

CSTR Reactor 1
residue . . . . . 37 46 68 76 Fail

CSTR Reactor 2
residue . . . . . 34 41 71 82 Fail
CSTR Reactor 3
residue . . . . . 41 43 81 77 Fail
Semi-batch
residue . . . . . 47 35 95 76 Fail

lWith respect to arsenic.

100 I I I I

~. 80
~e es
~ "o o o

i 60 ~"
" ~"J~~ KEY
(vsS)
= j ~ ~=
SEMI-BAT(:(
Au
As

20 ~~=,~r~,~.~B~ m-

O_ ~''~ I I I I
20 40 60 80 100
SULFIDE EXTRACTION, pct
Fig.2 Arsenic and gold extraction in the CSTR as a function of sulfide oxidation for arsenopyrite ore

Column leaching test

The ongoing tall column biooxidation test is being conducted to simulate heap, stope, or in situ
bioleaehing conditions. Solution and solid samples were taken periodically to monitor the level of sulfide
oxidation as well as the solubilization and mobilization of arsenic, iron, and other metals as a function
of depth in the column. Figure 3 shows overall extractions o f arsenic, iron, and sulfur as a function of
time. These numbers are based on solution concentrations in the reservoir and do not take into account
any metals that may have been solubilized but that precipitated within the ore bed. A gradient in arsenic
 Arsenic-bearin8 refractory gold ore 155

and iron solubiliz~Ltion and sulfide oxidation was observed during the first 100 d of leaching, with higher
extractions at the top of the column. However, after 300 d, extractions appeared uniform throughout the
column.

18 I I I I I I I I

16 40L 80L
loach leach
solution solution
r& 14
40L
leach
solution
1o KEY
S
ks As
Fo
6
U.

-- I I I I I I I I

0 50 100 150 200 250 300 350

TIME, days
Fig.3 Column biooxidation of arsenopyrite ore.

The 2 week on/2 week off cyclical pattern of leaching described in the experimental section was
conducted for 3 complete leach/rest cycles (90 days). Arsenic, iron, and sulfate levels as high as 17, 23,
and 43 g/L, respectively, were measured in solution, and overall rates of arsenic and iron removal were
high. Migration of ore fines and formation of an amorphous yellow precipitate containing principally iron
and arsenic caused the second section of the column to plug, and subsequently flood near the end of the
third leaching cycle. Precipitation was apparently promoted by the relatively high concentrations of iron
and arsenic in the recycle liquor, as formation of the precipitate was accompanied by decreased
concentrations of these species in the leach solution.

The leachant volume was subsequently increased to 80 L and the liquid was applied in a single pass in
an effort to minimize or eliminate the precipitation problem. Several leach cycles were conducted in this
way with no further precipitation problems. However, the levels of arsenic and iron in solution decreased
dramatically. The 80 L modified leach cycle was continued until day 232 at which time solution
application was restored to the original 40 L recycle in an effort to improve the rate of arsenic
solubilization and ,mlfide oxidation.

The rate of arseni,: and iron removal remained low, as seen in Figure 3, even after the decrease in
solution volume. Solid samples were collected from each section of the column and inspection showed
that a uniform coating covered the entire particle surface. When the particles were broken open, the
interior surfaces were dry and showed very little penetration of leach solution along fracture zones. A
second surface layer was also observed and could represent a reaction layer. These facts lead to the
conclusion that this ore is probably not a good candidate for heap, stops, or in situ bioleaehing, which
use much larger pa]~icle sizes than those used in stirred reactor leaching. Results from cyanide leach tests
showed that no improvement in gold extraction over the original 50 % obtained from the untreated ore was
achieved even after 300 days of leaching, confirming the unsuitability of this ore for heap, stope, or in
situ bioleaching.
156 D. L A N G H A N S et al.

The interparticle void space oxygen content was measured in the column as a function of depth. At the
beginning of a leach cycle, the interparticle oxygen content was fairly uniform throughout the column and
averaged 16%. During leaching, a gradient in oxygen was observed, with the highest values at the top
and progressively lower values with increasing depth, decreasing to about 5 % at the bottom of the
column. The decrease in oxygen during the leach cycle is associated with increased bacterial utilization
of oxygen and the displacement of air by the leach solution. The drain down of leach solution caused an
increase in oxygen content back up to 16 % due to the drawing action created as the solution migrated
through the column. Bacterial populations were uniform (about 108 cells/mL) throughout the 6 m length
of column, which indicates that oxygen concentration was not a limiting factor for bacterial activity.

Important information regarding metals mobilization was obtained from the column study even though
column biooxidation of this arsenopyrite ore proved unsuccessful for improving gold recovery. Arsenic
was solubilized primarily as As(Ill) and that it migrated through the column during leaching with neutral
pH water. Although some of the arsenic was attenuated by iron in the ore bed, a considerable amount
was present in the column effluent. This indicates that careful analysis and control would be necessary
to prevent the migration of toxic metals, such as arsenic, into the environment if biooxidative heap, stope,
or in situ leaching of arsenical ores was applied on an industrial scale.

Tailings stability
Cyanide residues: The EPA TCLP test bases the toxicity of a solid waste on the levels of eight toxic
metals, including arsenic, in the leachate after acetic acid leaching at pH 5. The TCLP limit for arsenic
in the extract is 5.0 mg/L. As shown in Table 2, the ore did not pass the toxicity test nor did the tails
after biooxidation and subsequent cyanidation. Arsenic concentrations in the TCLP extracts from the
CSTR solids after neutralization with NaOH and cyanidation ranged from 6.4 to 10.7 mg/L, with the
lowest concentration from the first reactor sample and the highest from the third reactor sample.

Arsenic concentrations in the cyanidation solutions were very high, ranging from 6 to 8 g/L. The arsenic
was present as As(V), giving further evidence of FeAsO4 precipitation in the solids during biooxidation.
Arsenic levels of less than 100 mg/L were observed when lime was used for pH adjustment during
cyanidation. The cyanide tails still failed the TCLP test, with arsenic concentrations in the extract very
similar to those seen in tests that used NaOH for pH adjustment.

Other researchers have shown that the stability of ferric arsenate precipitates varies with pH. In general,
as the pH increases above the neutral pH range, the stability decreases and arsenic can be resolubilized
[16,17] according to the following reaction:

FeAsO4 + 3OH---> FeO(OH)I + AsO43- + H20 (9)

The extremely high levels of arsenic in the sodium hydroxide-cyanide leach solutions indicate that arsenic
is being resolubilized while lime neutralization does not free as much As(V) because of the low solubility
of calcium arsenate. Since it is not likely that NaOH would solubilize arsenic from arsenopyrite under
ambient conditions, other forms of arsenic must be present in the biooxidation residues. As stated earlier,
evidence shows that more arsenic was leached than reported to solution during biooxidation, but some of
it precipitated in the residue, probably as ferric arsenate. However, X-ray analysis of the residue showed
only amorphous compounds, so ferric arsenate could not be positively identified.

Due to its toxicity, and therefore the need for treatment prior to disposal, it would Ix) preferable to
prevent as much arsenic as possible from entering the cyanide circuit. Therefore, a NaOH leach was
conducted on the biooxidation residues to doterndne if arsenic could be solubilized prior to cyanidation.
Final biooxidation residues from reactors 1, 2, and 3 produced in the CSTR test were slurried with water,
pH adjusted to 11.5 to 12 with NaOH pellets, and stirred for 24 h. The slurries were filtered and the
solids subjected to cyanidation tests using lime to readjust the pH.
 Arsenic-bearing refractory gold ore 157

Arsenic was solubilized during the NaOH leach, as concentrations in the caustic leach filtrate were 1.5
to 2.0 g/L, with essentiaUy all arsenic in the pentavalent oxidation state. However, this represents only
15 to 20 % of the arsenic contained in the biooxidation residues. The cyanide tails again did not pass the
TCLP test, with almost identical levels of arsenic in the TCLP extract as were seen in the cyanide tails
that had not bee]a previously subjected to the intermediate NaOH leach. While some arsenic was
resolubilized, these results emphasize that more complete arsenic extraction and recovery in the
biooxidation circuit is necessary to avoid environmental complications in the cyanide circuit.

Sludge: Arsenic concentrations in the final bioleach liquors from the three CSTR reactors and the catch
reservoir ranged from 3.0 to 4.0 g/L, while iron concentrations were on the order of 3.3 to 4.8 g/L.
Lime neutralization to pH 7 reduced arsenic concentrations in the filtrates to 5 to 18 rag/L, while iron
levels were decreased to 0.14 mg/L. Sulfate ion concentrations were reduced from 15 g/L to 2.2 g/L,
while calcium cottcentrations increased from 85 to 570 mg/L. Although these solutions would not meet
discharge standards, the reduced metal content would allow for water recycle to either the biooxidation
or cyanide circuits.

The sludges that were produced during solution neutralization did not pass the TCLP test, with arsenic
concentrations in the TCLP leachate averaging 160 mg/L. Typically, initial ferric iron:arsenic molar
ratios greater than three are needed to produce stable sludges from As(V)-bearing liquors [17-19]. At the
time of neutraliz~Ltion, the iron:arsenic molar ratio in the CSTR reactor solutions was only about 1.6.
Also, arsenic was; in the less stable As(Ill) oxidation state, which would lead to the formation of more
toxic and less stable ferric arsenite upon precipitation. These two factors, the oxidation state of the
arsenic and the low molar iron:arsenic ratio, are suspected as the principal reasons why the sludges did
not meet TCLP standards. However, sludging does significantly reduce the volume of arsenic-bearing
waste to be disposed.

SUMMARY AND CONCLUSIONS

Biooxidation of an arsenic-bearing refractory gold ore was conducted using semi-batch and continuous
flow stirred bioreactors, as well as a tall column bioleaching system. Arsenic speciation during
biooxidation showed that arsenic in solution was primarily As(III) in all three systems. The As(III)
proved to be stable in the bioleach solutions, as only partial conversion to less toxic As(V) was achieved
even in the presence of excess iron or strong chemical oxidant. The low concentration of As(V) was
attributed to precipitation of ferric arsenate during biooxidation.

Biooxidation of the arsenopyrite ore proved successful with the fine particle size used in the stirred
bioreactor systems. Over 95 % sulfide oxidation was achieved, and gold extraction by eyanidation was
increased from 49% to about 80% after biological pretreatment. A direct correlation was apparent
between arsenic and sulfide removal from the ore--the higher the sulfide oxidation, the higher the arsenic
extraction. Approximately 50% of the arsenic was removed with 95% sulfide oxidation. Column
biooxidation was unsuccessful because of the low porosity of the relatively large minus 1.9 cm ore
particles used in the test. Although arsenic was attenuated by iron in the column, a significant amount
was measured in ~fhecolumn effluent, which indicates that arsenic mobilization and migration did occur
during leaching of this ore.

The final residues after biooxidation and cyanidation did not pass the TCLP toxicity test. Research
showed that it w~.s critical to remove as much arsenic as possible during biooxidation to minimize the
amount of arsenic reporting to the cyanide circuit. Also, an intermediate sodium hydroxide leach between
biooxidation and cyanidation could be used to solubilize some of the arsenic prior to cyanidation.
However, even with this treatment, the final residues did not pass TCLP testing.

Treatment of the bioleach solutions with lime reduced the metals content significantly. Although the
remaining liquid did not meet water discharge requirements, it was clean enough to be recycled back to
the leaching circuit. The sludge formed during solution treatment also failed TCLP testing. However,
adjustment of the solution ferric iron:arsenic ratio and oxidation of As(III) to As(V) prior to neutralization
HE 8-1/2-K
158 D. LANGHANSet al.

should result in a final sludge residue that would meet toxicity standards. Continued research is planned
to identify conditions necessary to oxidize As(III) to As(V) in biooxidation leach liquors.

REFERENCES

. Jha, M.C., Refractoriness of Certain Gold Ores to Cyanidation: Probable Causes and Possible
Solutions. Miner. Process. and Extr. Metall. Rev., 2, 331-352 (1987).
2. Marchant, P.B., Plant Scale Design and Economic Considerations for Biooxidation of an
Arsenical Sulfide Concentrate. Presented at The International Symposium of Complex Sulfides,
San Diego, CA (Nov. 1985).
. Broadhurst, L.L., The Nature and Stability of Arsenic Residues From the Biox Process.
BIOMINE 93. Australian Mineral Foundation, 13-1 - 13-10 (1993).
4. van Aswegen, P.C., Commissioning and Operation of Bio-Oxidation Plants for the Treatment of
Refractory Gold Ores. Fulwlamentals, Technology, and Innovations. J. B. Hiskoy and G. W.
Warren, Eds., SME, 709-725 (1993).
. Spencer, P.A. & Budden, J.R., Is Complete Sulfur Oxidation Desirable? The Benefits of Partial
Bacterial Oxidation Using Bactech's Moderate Thermophile Culture. EPD Congress, 1992. J.
P. Hager, Ed., The Minerals, Metals, and Materials Society, 173-181 (1991).
. Torma, A.E., The Microbiological Extraction of Less Common Metals. Journal of Metals,
41(6), 32-45 (1989).
7. Bruynesteyn, A., Hackl, R.P. & Wright, F., The BIOTANK Leach Process. Extractive
Metallurgy of Gold. South African Institute of Mining and Metallurgy, Johannesburg, 2, 353-365
(1986).
. Rossi, G., Biohydrometallurgy. McGraw-Hill Book Company, Hamburg, 512-514 (1990).
9. Lawrence, L.R.W. & Marchant, P.B., Biochemical Pretreatment in Arsenical Gold Ore
Processing. Prec. of Arsenic Metallurgy Fundamentals and Applications Symposium. R. G.
ReAdy, J. L. Hendrix, and P. B. Queneau, Eds., TMS, 199-211 (1988).
10. Mahdi, M., Matulova, P. & Docekalova, H., Migration of Arsenic(III) During Bacterial
Oxidation of Arsenopyrite in Chalcopyrite Concentrate by Thiobacillusferrooxidans. Applied
Microbiology and Biotechnology. Springer Verlag, 429-431 (1992).
11. Test Methods for Evaluating Solid Wastes (Physical and Chemical Methods), EPA Method No.
1311, SW-846. Federal Register, Rules and Regulations, 55(61) (Thursday, March 29, 1990).
12. Pinches, A., Bacterial Leaching of an Arsenic-Bearing Sulfide Concentrate. Randollnternational
LTD, Gold and Sih,er Recovely Innovations Phase II1, 3, 1453-1460 (1987).
13. The Chemistry of Gold Extraction. J. Marsden and I. House, Eds., Ellis Howard, 221-234
(1992).
14. Karavaiko, G.I., Chuchalin, L.K., Pivovarova, T.A., Yemel'Yanov, B.A. & Dorofeyev, A.G.,
Microbiological Leaching of Metals from Arsenopyrite Containing Concentrates. Fundamental
and Applied Biohydrometallurgy. R.W. Lawrence, R. M. R. Branion, and H. G. Ebner, Eds.,
Elsevier, 115-126 (1986).
15. Collins, M.J., Berezowsky, R.M. & Weir, D.R., The Behavior of Arsenic in the Pressure
Oxidation of Uranium and Gold Feedstocks. Prec. of Arsenic Metallurgy Fundamentals and
Applications Symposium. R. G. ReAdy, J. L. Hendfix, and P. B. Queneau, Eds., TMS, 115-134
(1987).
16. Robins, R.G., The Stability and Solubility of Ferric Arsenate: An Update. EPD Congress, 1990.
D. R. Gaskell Ed., The Minerals, Metals and Materials Society, 93-104 (1990).
17. Krause, E. & Ettel, V. A., Solubilities and Stabilities of Ferric Arsenate Compounds.
Hydrometallurgy, 22, 311-377 (1989).
18. Papassiopi, N., Stefanakis, M. & Kontopoulos, A., Removal of Arsenic from Solutions by
Precipitation as Ferric Arsenates. Prec. of Arsenic Metallurgy Fundamentals and Applications
Symposium. R. G. ReAdy, J. L. Hendrix, and P. B. Queneau, Eds., TMS, 321-334 (1987).
19. Harris, G.B. & Monette, S., The Stability of Arsenic-Bearing Residues. Prec. of Arsenic
Metallurgy Fundamentals and Applications Symposium. R. G. ReAdy, J. L. Hendrix, and P. B.
Queneau, Eds., TMS, 469-488(1987).