Journal of Scientific & Industrial Research

Vol. 65, January 2006, pp. 65-67

Comparison of different extraction methods to determine gold in

geological samples
P V Sunder Raju*
National Geophysical Research Institute, Hyderabad 500 007
Received 03 May 2005; revised 25 August 2005; accepted 14 October 2005

Different petro-chemically varied lithological samples were collected from the Chitradurga schist belt, Karnataka, to
identify auriferous zones. The efficiencies of gold estimation at very low levels by different extraction methods were
compared. The extraction methods were fire-assay (FA), cyanide leach, and methyl isobutyl ketone (MIBK) solvent
extraction. The rock samples include banded iron formations (silicate, oxides, carbonate and sulphide facies), ferruginous
cherts, massive milky white quartz veins and highly sheared fractured translucent dark grey to bluish grey quartz veins.
After separation and pre-concentration of gold, MIBK solvent extraction procedures have been studied using flame atomic
absorption spectrophotometer (F-AAS).

Keywords: Chitradurga, F-AAS, MIBK

IPC Code: C22B11/00

Introduction systematically sampled to give a weight of 20 g. Prior

In nature, gold occurs as native or refractory type.
Refractory gold ores are not free milling and cannot
be leached without some form of physical, chemical
or pyro metallurgical pretreatment. Refractory gold is
found in association with sulphides (pyrite,
arsenopyrite and chalcopyrite), whereas native gold is
associated with tellurides, bismuthides, silver,
antimony and copper. In general, fire-assay (FA),
cyanide leach, open aquaregia and microwave
(closed) are some of the important extraction
methods. The present study is an attempt to find any
difference in the Au content of the splits of large
sample after crushing, to understand the efficiency of
the analytical methods based on aquaregia leach,
NaCN leach and methyl isobutyl ketone (MIBK)
extraction, and compare these methods with the
classical and widely accepted lead fire assay method.
Experimental Methods
Sampling and Powdering
Samples were collected from geologically
favorable hosts for gold mineralization from
Chitradurga and Gadag schist belts. Bulk samples
(10-15 kg) were collected and powdered
(200-250 mesh). Samples were coned, quartered and
______________
*Tel: 040-23434700; Fax: 040-23434651
E-mail: pvsraju@ngri.res.in
to chemical dissolution, the samples1 were mixed with
ammonium nitrate and subjected to open air roasting
at 600-650° C in a porcelain crucible.
Instrumentation
SpectrAA 220 (Varian, Australia) flame atomic
absorption spectrophotometer (F-AAS) with
deuterium background correction was utilized. A
model Z 300 bench top centrifuge (Hermle Labor
Technik, Germany) was employed for centrifuging
sample solutions in MIBK extraction. Gold speck
obtained by cyanidation process was weighed using a
model UMT-2 microbalance (Metler, Switzerland).
The instrumental parameters are as follows: lamp
type, hollow cathode lamp; flame type, air acetylene;
background correction, deuterium; wavelength,
242.8 nm; slit width, 1.0 nm; lamp current, 4 mA;
measurement time, 1.5 sec; airflow, 3.5 l/min; and
acetylene flow, 1.5 l/min.
Anaytical Methods
Lead Fire Assay
Finely powdered sample (80-90%<75 µm), mixed
with litharge and glass fluxes, was analyzed by FA
method, which can measure gold concentration in the
range ppb-ppm. The sample, in a crucible, was
charged at 850°C in a muffle furnace and temperature
raised and maintained well above 1000°C for
30-40 min until complete fusion occurred. The lead
66 J SCI IND RES VOL 65 JANUARY 2006

circulates through the molten mass and collects the Table 1  Comparison of gold extraction methods
precious metal forming Au-Ag-Pb alloy, which is Rock type MIBK Cyanidation Fire Assay
recovered as a button after cooling and separation µg/g µg/g µg/g
from the glassy slag containing base metal and other BIF 0.42 0.40 0.32
impurities. Bone ash and marborite cupel heated to BIF 0.52 0.40 0.60
1000°C are charged with lead button. This process BIF 0.78 0.40 0.60
results in a precious metal bead, which is parted by BIF 0.49 0.20 0.40
Metavolcanics 0.44 0.60 0.10
dissolving in nitric acid. Alternatively, lead is Metavolcanics 0.40 0.42 0.32
dissolved in aqua regia and analyzed for gold and Metavolcanics 0.52 0.40 0.60
silver by F-AAS. Lead - FA analysis was carried out
on 50 g samples at the Chemistry Laboratory of (30 ml) was added to stabilize AuCl3 complex, during
Chitradurga gold unit of Karnataka. Gold specks were evaporation on a hot plate. Each beaker was covered
weighed using a model UMTZ microbalance, with a watch glass and heated on a hot plate. Heating
Switzerland2. was continued for at least 4 h and enough aqua regia
was added at regular intervals to maintain the free
Sodium Cyanide Leach acid level at about 1 cm above the sample surface3,4.
The sample (200g) was weighed into a bottle and The watch glasses were removed and the contents
200ml of distilled water was added. The pH was evaporated slowly until the residue became nearly
adjusted to 11 by the addition of CaCO3 (3g). The dry. 3 M HCl (40 ml) was added to each beaker and
solution was made 2% with respect to NaCN .The warmed until clear solution is obtained. These
open bottle is laid on its side on a bottle roller and solutions were cooled and filtered using Whatman 40
allowed to roll on a bottle roller for 24 h. The bottle filter paper. The filtrate of each sample was
with contents was weighed before and after the transferred to a 250 ml-separating funnel. The beaker
cyanide leach to estimate the amount of evaporation. was washed with a minimum amount of 3 M HCl and
The solution was filtered and heated up to 30°C. The the washings were transferred to a separating funnel
lead acetate (2g) was added and the solution was and shaken for 5 min. After the phases were clearly
stirred. After 15-20 min, the contents were heated up separated, aqueous phase was drained off. A washing
to 60-65°C. Simultaneously, zinc dust (2g) was added solution (10 ml of conc. HCl+10 ml conc. HBr to
and contents were stirred. Then concentrated HCl 500 ml with DD water) was added and the separating
(10-12 ml) was added drop wise while keeping the funnel was shaken for 2 min. After the phases were
beaker on a hot plate for 5 min. Sponge is formed, completely separated, aqueous phase was discarded
allowed to cool to room temperature and then the and the organic phase was collected for F-AAS gold
sponge containing solution is filtered. The sponge was estimation5.
washed 2 to 3 times with distilled water. Excess water
was squeezed out and spongy mass was rolled in to Results and Discussion
lead foil after adding metallic silver granules Samples were analyzed for Au (Table 1); Lead Fire
(0.1 - 0.5g). The rolled lead foils were cupelled. The Assay method was taken as standard and each
contents are wrapped in a lead foil and heated in determination was carried out 5 times using standard
bone-ash cupell. This process of heating is designated reference materials (Table 2).
as cupelled or cupellation at 1000oC for about 1 h.
Cyanidation Processes
The complex bead containing gold and silver was
Cyanidation process is quite time consuming and
dissolved in 1:4 HNO3 for~10 min and then 1:1 HNO3
hazardous in handling. Quite often, the silicate and
to separate gold from silver. The gold speck was
iron rich samples are not dissolved completely and
weighed on a microbalance.
give quite erratic results. Large sample volumes are
required for this technique6 to counteract the
MIBK Procedure
heterogeneity problems and this technique is
Each sample (10g) was transferred into a porcelain
ineffective for the leaching of encapsulated gold.
crucible with ammonium nitrate (1g), mixed
thoroughly, and roasted for 1 h in a muffle furnace at MIBK Method
650°C. Roasted samples were transferred in glass MIBK method is suitable for treating multi-varied
beakers (250 ml each) and freshly prepared aqua regia samples especially banded iron formations (oxides,
 SUNDER RAJU: EXTRACTION METHODS TO DETERMINE GOLD IN GEOLOGICAL SAMPLES 67

Table 2  Standard reference materials used extracts the entire platinum metal group in addition to
Sample MIBK- Certified value Type gold and silver. The combination of a Fire Assay
FAAS fusion with AAS technique offers the advantage of
µg/g µg/g using large quantity sub sample together with a very
GAu – 16 @
1.08 ± 0.09 1.09 ± 0.03 Ore from sensitive technique to yield better detection limits.
sandstone gold Occasionally, interferences from elements like Fe etc.
GAu – 17@ 3.01±0.20 3.14±0.06 Ore from Silt especially in case of samples of banded iron
stone
GAu-18@ 9.96±0.57 10.00±0.20 Ore from
formation of different facies (sulphides, oxides,
faulted zone silicate and carbonate) and quartz vein containing
OX-11# 2.89±0.04 2.94±0.03 Gold bearing refractory gold will reduce instrument sensitivity.
quartz vein This study shows that both aqua regia and Sodium
OX-12# 6.49±0.37 6.60±0.08 Gold bearing
Cyanide Leach methods and MIBK solvent extraction
quartz+pyrites
S-2# 1.52±0.03 1.53±0.03 Gold bearing techniques, act as potential alternatives for the Fire
quartz+pyrites Assay method. However, explorationists looking for
WG-2# 1.39 ±0.06 1.38±0.03 Dissemenated the best resolution of low-level gold anomalies, the
gold alternative chemical procedures play a vital role for
KH-1# 0.84 ±0.01 0.85±0.02 Gold with
pyrites
the investors to decide about the economics of the
@
deposit, as proved in the case of gold exploration
Institute of Geo Physical and Geology Exploration, Lang Fai, studies in Gadag and Chitradurga Schist Belts in
102849, China
#
Rock labs, New Zealand Karnataka, India.

sulphides, silicates and carbonates). Iron interfering References

with gold wavelength during analysis was overcome
by back extraction of iron from the organic extract.
Centrifugation of colloidal materials in the organic
phase also affects aspiration of solutions in F-AAS.
Fire Assay
Traditional Fire Assay method was carried at
Chitradurga gold unit to confirm the true values
obtained in-other methods. This procedure is time
consuming but perfect gravimetrical results of gold
are obtained.
Conclusions
Different methods of analytical results vary on the
type of sample containing gold content especially on
refractory ores. Sodium cyanide leach results were
lower in comparison to Fire Assay and aqua regia
leach because of non-effective leaching of sulphide
and silica bearing samples containing gold. The
advantage of MIBK method is primarily associated
with its cheaper cost, than the Fire Assay fluxes. As
exploration samples require a better detection limit
than that offered by gravimetric procedures, Fire
Assay provides total fusion of gold as it dissolves and
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