Analytical Methods For Determining Gold

GEOLOGIAN TUTKIMUSKESKUS
Tutkimusraportti 114
GEOLOGICAL SURVEY OF FINLA

Report of Investigation 114
Esko Kontas (ed.)
ANALYTICAL METHODS FOR DETERMINING GOLD IN GEOLOGICAL SAMPLES
Espoo 1993
Kontas, Esko (ed.), 1993. Analytical methods for determining gold in geological
samples. Geologian tutkimuskeskus, Tutkimusraportti-GeologicalSurvey of Finland,
Report of bwestigation 114, 41 pages, 16 tables, 1 appendix.
Key words (GeoRef Thesaurus, AGI): chemical analysis, gold, sample preparation,
methods, spectroscopy, atomic absorption, techniques, neutron activation analysis,
accuracy
Esko Kontas, Geological Survey of Finlmd, P.O.Box 77,SF-96101 Rovmtiemi, Finland

ISBN 95 1-690-476-9
ISSN 0781-4240
CONTENTS
Foreword
EskoKontas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Analyttcal methods for determining gold in geological samples
EslwKontas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Determination of gold by atomic absorption after lead fire assay separation
Riitta Juvonen and P. J. Vaananen . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Determination of gold by aqua regia-potassium bromate digestion, methyl
isobutyl-ketone extraction and flame atomic absorption
P.Noras . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Determination of gold and palladium by aqua regia digestion, dibutylsulphide-di-isobutyl-ketone extraction and flame atomic absorption
U. Penttinen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Determination of gold, palladium and platinum by aqua regia digestion,
dibutylsulphide-di-isobutyl-ketone extraction and flameless atomic absorption
E.Ojaniemi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Determination of gold and palladium by aqua regia digestion, stannous
chloride-mercury coprecipitation and flameless atomic absorption
E.Kontas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Neutron activation analysis of gold in geological samples
R. Rosenberg, Maija Lipponen and Riitta Zilliacus . . . . . . . . . . . . . . . . .
Gold concentrations of some reference samples - discussion
E.Kontas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
APPENDIX: The effect of sample weight and digestion and separation
method on the results of gold determinations.
4
5
13
17
21
25
29
33
39
FOREWORD
This collection of papers documents the analytical methods on which geological gold
studies in Finland are mainly based. It includes a general review of the problems associated
with the determination of gold, and details of six procedures used by the laboratories of
the Geological Survey of Finland, the Geoanalflcal Laboratory of Outokumpu Metals
& Resources, the Research Centre of Rautaruukki Co. and the Reactor Laboratory of
Technical Research Centre of Finland. Being very similar to those for gold, the analytical
methods for palladium and platinum are also described. Finally, the gold contents of five
reference samples analysed by each laboratory are presented, and their applicability for
different purposes is discussed. As the procedures have all been reported previously or
are otherwise well known, no new scientific features are presented. However, many of
the methods have been developed and improved over the years, and thus a close look
at the procedures may reveal useful information for chemists confronted by problems
when analysing noble metals. Because the correct selection of analytical methods is crusial
in gold studies, the topic is worth a document of its own.
I thank all chemists and all the other persons who have contributed to this work in
one way or another and so made publication possible. In particular I thank Dr. Pekka
A. Nurmi and Olli Lehto, Geological Survey of Finland, who reviewed the report and
made many useful suggestions, and Pentti Noras, Geological Survey of Finland, and Pertti
Hautala, Outokumpu Oy, for critical discussions and valuable comments. The English
of the manuscript was corrected by Gillian Hakli.
Rovaniemi 25.2.1992
Esko Kontns
Geological Survey of Finland
Analytical methods for determining gold in geological samples

Edited by Esko Kontas
Geologian tutkimuskeskus, Tutkimusraportti Geological Survey of Finland, Report of Investigation 114, 5-11,
1993
ODS FOR DE
GOLD IN GEOLOGICAL SA
by
Esko Kontas
Kontas E. 1993. Analytical methods for determining gold in geological

samples. Geologian tutkimuskeskus, Tutkimusraportti - Geological
Survey of Firzland, Report of Investigation 114, 5-1 1, 2 tables,
Because of the heterogenous mode of occurrence, or "nugget effect", the
preparation and representativeness of analytical samples pose special
problems in assaying gold. Field samples of gold ores and their host rocks
should be crushed to a grain size of at least 95% below 2 mm or preferably
below 1 mm before splitting and subsequent milling to analysis grain size.
About 100 g of powder is needed for analyses and possible control analyses.
The six analytical procedures presented below are those most often used
for gold studies in Finland. The principles of the procedures, including
sample weight, digestion, separation, determination, detection limits and
capacities, are presented in Table 1.
Table 1. The principles of the analytical procedures.
Sample
weight
g
Digestion
Separation
25-50
20
10
5
1
0.6
lead fire assay

aqua regia-KBrO,
aqua regia
aqua regia
aqua regia
EN A A
MIBK
DBS-DIBK
DBS-DIBK
SnC1,-Hg
Determination
Detect. Capacity
limit
ppm
sampleslw
FAAS
FAAS
FAAS
GAAS
GAAS
0.1
0.05
0.05
0.02
0.001
0.003
150
200
300
400
500
570
(Abbreviations: AAS = atomic absorption spectrometry, FAAS = flame AAS,

GAAS = graphite furnace AAS, MIBK = methyl isobutyl ketone, DBS = dibutyl
sulphide, DIBK = di-isobutyl ketone, ENAA = instrumental epithermal neutron
activation analysis).
For the evaluation of methods, five internal reference samples prepared

by the Geological Survey were analyzed several times with the above
procedures. The relative standard deviations varied from below 10% up to
90%, being, as expected, largest for the methods that used the smallest
sample weights.
The classical lead fire assay method (with a sample weight of 5 0 g) is
suited best for inventories of gold deposits and for assaying gold concentrates. The methods with sample weight of 5-20 g and aqua regia digestion are appropriate for exploration analyses of gold ores and for geochemical prospecting. Owing to their low detection limits and high capacities,
the last two methods in the above table are suitable for the geochemical
mapping and prospecting on a regional scale and for basic research.
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of Investigation 114, 1993
Esko Kontas
Key words (GeoRef Thesaurus, AGI): chemical analysis, gold, sample

preparation, methods, spectroscopy, atomic absorption, techniques, neutron
activation analysis, accuracy
Esko Kontas, Geological Survey of Finland, P.O.Box 77, SF-96101

Rovanierni, Finland
INTRODUCTION
There are three factors due to which exploration
for gold may be viewed almost as its own branch of
science. The first is the rarity of gold, the second is
its heterogenous, nugget like mode of occurrence of
the metal in the nature, and the third is its high economic value. As a result sampling, sample preparation and analytical methods have to meet more stringent requirements than other element.
The average crustal gold content is estimated
0.0035 ppm (Li & Yio 1966). The lower limit of the
abundances in gold ores is about a thousand times
higher. For geochemical exploration and for studies
of the richest ores, the analybcal methods of gold
should cover a concentration range of 104 to 102
PPm.
The gold concentrations in common geological
materials are as follows:
1) Igneous rocks (median): ultramafic 0.0032, mafic
0.0032 and granites 0.0023 ppm (Wedepohl
1969-1978),
2) sedimentary rocks (median): limestones 0.005,
sandstones and quartzites 0.005 and shales 0.004
ppm (Wedepohl 1969-1978),
3) soils (average): 0.002 ppm (Brooks 1972) and
4) fresh water (median): 0.002 ppb (Turekian 1977).
The mineralogical mode of occurrence of gold in

nature varies widely but native gold is predominant
(Boyle 1979). Even in very low concentrations it
usually appears as discrete particles of considerable
size, and is rarely, if ever, uniformly distributed. The
discrete particles tend to segregate easily due to their
high density relative to other minerals (Brown &
Hilchey 1974). Being soft and malleable, gold grains
are not easily reduced in milling; moreover in intense milling the grains may adhere to the walls of
milling vessels and thus cause losses of gold from
the sample (Harris 1982, Riddle 1983, Burn 1984).

Because of this uneven distribution, the main problem in the gold analyse and one which is often very
difficult to resolve, is the representativeness of samples. Owing to its high economic value, gold should
be determined with high accuracy and reliability. For
instance, the gold in many base metal concentrates
has a major effect on their price, and even small errors in assays may have marked economical significance when translated into masses of material.
In practice, the analytxal capacities, detection
limits and operating costs of procedures also have to
be taken into account. Therefore no single procedure
can effectively and economically meet all these requirements. For one procedure, the representativeness of an analybcal sample may be good enough but
the detection limit may be too high and capacity too
low; for another, the representativeness may be poor
but the capacity high, and so on. Furthermore, there
are very many procedures that are very similar in
principle and chemistrybut very different in practice.
The difference is particularly marked in the analytical apparatus and other facilities. The classical f ~ e
assay with lead collection requires only a simple
fusion furnace and a microbalance. Two advanced
instruments often used are the rather simple and
cheap flame atomic absorption spectrometer (FAAS)
and the more complex and expensive graphite furnace atomic absorption spectrometer (GFAAS). A
tool that is rapidly gaining popularity is the very
powerful plasma mass spectrometer (ICP-MS) (Date
et al. 1987, Jackson et al. 1990). Most powerful of
all is the nuclear reactor, which is used for the neutron activation analysis (NAA) (Hoffman et al. 1978,
Hoffman and Brooker 1982). The following takes a
look at all these procedures except the plasma-based
techniques.
SAMPLE REPRESENTATIVENESS
Gold occurs in nature most commonly as native
grains or as the main component of alloys with sil-
ver, copper or platinum-group metals. Some gold

and gold-silver tellurides, stibnites, selenides and
Geologian tutkimuskeskus, Tutkimusraportti
- Geological Survey of Finland, Report of I~zvestigation114, 1993

bismuthides are also known. But the predominant ore

minerals are native gold, aurostibnite and various
tellurides (Boyle 1979).
Gold tellurides are brittle and readily grindable
minerals (Burn 1984). However, gold deposits also
contain native gold as grains, which are not pulverized in milling. These grains may be extremely variable in size. Furthermore, gold can be incorporated
in common sulphide minerals. Discrete inclusions,
smaller than 0.1 pm, are termed "invisible gold", as
they are not detectable by optical and scanning electron microscopy. The concentrations of invisible
gold range from less than 0.5 ppm to more than 1000
ppm in sulphide grains from 12 different ore deposits, as determined by ion-probe microanalysis (Cook
& Chryssoulis, 1990). The most important gold
carriers are arsenopyrite and arsenic-rich varietes of
pyrite. In the extended gold province of Witwatersrand, the average grain size of gold is 80 pm
(Boyle 1979). In placer deposits gold grains may
weigh thousands of grams although weighths of a
few milligrams are more common.
The representativeness of samples containing gold
particles has been theoretically and experimentally
studied by Clifton et al. (1969). According to them:
"It can be shown mathematically that the number of
gold particles in the sample is the only factor controlling the precision of the chemical analysis. If the
following assumptions are valid:
1) gold particles are of uniform mass,
2) gold particles comprise less than 0.1% of all particles,
3) the sample contains a total of over 1000 particles,
4) analyt~calerrors are disregarded
5) gold particles are randomly distributed within the
sample,
a precision of S O % at the 95% confidence level will
be achieved when the sample taken for analysis
contains twenty particles of gold. For reconnaissance
studies, a smaller sample containing fewer particles
of gold may suffice. It is important, however, to note
that as the expected number of particles per sample
falls below five, the chance of having no gold particles in a given sample greatly increases."
In fact the above assumptions are never valid,
especially those concerning uniform grain sizes and
analytical errors. Nevertheless, they provide a practical starting point for estimating the representativeness of a sample, as long as something is known
about the grain size. If the size distribution of the
gold particles is unknnown and analyses of splits are
not available, an adequate sample size can be determined by assuming that all the gold in the sample
occurs uniformly in grains as large as the maximum

size which has an effect on the total gold content
(Clifton et al. 1969).
The analytical representativeness of samples with
discrete particles has been studied at lenght by Gy
(1982). The standard deviation of the fundamental
sampling error for particulate materials can be estimated theoretically from some basic properties of the
material to be sampled. Gy (1982) derived the following equation for making the estimation:
where b is the relative standard deviation of the

fundamental sampling error, M, the mass of the sample, M, the mass of the lot to be sampled, Z and C
the sampling constants and d the dimension of the
largest pieces in the lot to be sampled. Because M, is
large related to MSthe equation can be simplified:
where Z is defined as Cd3. The sampling constant C

for the particular material to be sampled contains
four parameters characteristic of the material:
C = f g l c, where f is the particle shape factor, g the
size range factor, 1 the liberation factor and c the
composite factor. Approximations or calculations for
these factors has been briefly and clearly presented
by Minkkinen (1987). The sampling constants C or
Z can also be estimated empirically by determining
the relative standard deviation of the sampling error
and calculating it from the original equation. This
requires a number of analyses of subsamples having
the same size for fine materials and analyses of individual fragments for coarse materials (Gy 1982).
On the basis of Gy's theory of sampling,
Minkkinen (1987) developed a computer program
(SAMPEX) for solving practical sampling problems.
The method involves estimating the sampling constant C. For well-characterized materials, C can be
estimated from the material properties; for unknown
materials it can be evaluated experimentally. The
program can be used to solve the following problems: the minimum sample size for a tolerated relative standard deviation of the fundamental sampling
error; relative standard deviation for a given sample
size; the maximum particle size of the material for a
specified standard deviation and sample size; the
balanced design of a multi-stage sampling and sample-reduction process; and sampling for particle size
determination.
When the grade is low and the gold particles are
large the sample size required increases very rapidly.
However, normal laboratory instruments and other
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of I?zvestigatio~t114, 1993

Esko Korltas
facilities often restrict the use of large analytical

samples. In many production geared, commercial laboratories sample weights range from 10 g to 30 g.
For very inhomogeneous materials it may be best to
use physical methods of concentration for the determination of coarse-grained gold and the chemical
analysis of fine-grained gold (Nichol 1985). However, the more complex procedure the higher are the
operation costs.
Mathematical determination of the representative
sample weight always calls for some information
about the mode of occurrence of gold and its mineralogy.
In practice, when gold explorations begin in a new

area, laboratories have to rely on assumptions. No
data are available, not even on the possible existence
of gold.
Since the precision and accuracy of analyses are
highly dependent on the mode of occurrence of gold
in samples, chemists need all the information geologists can give them about the samples. With good
cooperation between geologists and chemists, it is
possible to choose the methods that are the most advantageous and economically viable for each purpose.
SAMPLE PREPARATION
The physical preparation of rock samples involves about 100 g of the crushed sample is then pulverized
drying, crushing, splitting and pulverizing. Because for analysis.
A jaw crusher is a cost-effective apparatus univerof the heterogeneous distribution of gold, the normal
rules for safely reducing sample weight do not apply sally used for crushing rocks. It is quick and easy to
(Gy, 1979). The laboratory should therefore work use and contaminates the sample only very slightly.
with the complete sample submitted as far as possi- However, the grain size achieved is at most 95% less
ble (Riddle 1983). The Geological Survey of Finland than 2 mm. Nevertheless, a jaw crusher is fully adeobtained acceptable accuracies and precisions for quate for precrushing. A grain size of 95% less than
gold in different types of ore and their host rocks 1 mm is easily obtained by precrushing material in a
roller mill, but then contamination of samples by
using the following procedure: Bulk samples (2-5
kg) were crushed in two steps in a jaw crusher to a rollers is a considerable problem. Samples, particugrain size of 95% less than 2 mm. The samples were larly those containing metallic gold, need frequent
then split in a rotatory tube divider to obtain a and very careful cleaning because the gold grains can
subsample of about 100 g, which was then milled for smear and stick to the surface of the rollers. A disk
analysis in a swing mill. There were 137 samples in mill, which is very effective for fine crushing down
all and their concentration range was from back- to grain sizes of approximately 0.15 mm and is freground to ore grade (Nurmi et al. 1991). Samples quently employed at laboratories specializing in the
weighing 20 g were analysed for gold both by fire appraisal of gold ores. The disks, however, wear
assay and by GFAAS after aqua regia digestion. The easily when hard rocks are milled and produce concorrelation coefficient obtained between these deter- tamination by iron and its alloys, which is harmful if
the same powder is used for other geochemical studmination~was 0.93 (Appendix).
Geoanalytical Laboratory of Outokumpu Metals & ies (Olli Lehto, pers. commun.).
Grinding ore-grade samples may smear rather than
Resources (Olli Lehto, P.O. Box 74, SF-83501
Outokumpu, Finland, pers. commun.) uses the fol- grind the gold grains. Thus the grinding vessels conlowing procedure for preparing rock and drill core taminated with gold whereas the sample is slightly
samples: Samples are crushed in a jaw chrusher to a depleted in gold (Riddle, 1983, Burn, 1984). E.
grain size of 90% less than 4 mm. All coarse mate- Ojaniemi (Rautaruukki CO,Research Centre, Raahe,
rial is then crushed in a roller mill to a grain size of Finland) performed quantitative experiments to test
95% less than 1mm. The sample is split in a rotatory the smearing of gold on the surfaces of grinding vestube divider into eight fractions. Depending on the sels in a swing mill as follows: Three samples with
amount of the sample one or more fractions are varied gold concentrations were milled for different
pulverized completely in a swing mill to obtain length of time. After each milling the grinding pots
were washed with water before milling sterile quartz.
about 60 g powder.
Based on the above methods of preparation, a rec- The gold concentrations of the milled quartz were
ommended procedure might be as follows: Before determined to check whether or not any gold had
the first splitting a whole field sample is crushed to smeared (Table 2).
a grain size of 95% less than 1 mm; a portion of
The relative depletion of gold during the usual

milling time of about 60 S is insignificant. But the
contamination of subsequent samples may become
significant if samples of ore grade and of background contents are crushed and milled in the same
batch and with the same equipment.
Soil samples are usually dried and sieved to specific fractions. The "nugget effect" of sediment samples
is much more problematic than that of ore samples
because the grade is generally low whereas the gold
grains are often relatively coarse (Clifton et al.,
1969). Plant and other organic samples are usually
ashed before digestion. Warren and Horsky (1986)
have successfully determined gold and thallium
directly on pulverized plant samples after nitric acid
and aqua regia digestion.
- Geological Survey
of Firrland, Report of brvestigatiorz 114, 1993

~ n a l ~ t i c methods
al
for determining gold in
samples
Table 2. Gold concentrations in 20 g portions of cleaning quartz

(milling time 60 S) in relation to the milling times of three samples.
Milling
time of
sample
Amount
of quartz
Au i n quartz after cleaning
Sample 1
PPm
Sample 2
PPm
Sample 3
PPm
30
60
120
240
20
20
20
20
0.016
0.014
0.030
0.056
0.003
0.007
0.073
0.119
0.024
0.020
0.087
0.127
Sample 1 = copper concentrate with 32.0 ppm Au,

sample 2 = albitisized schist with 1.2 ppm Au and
sample 3 = albitized schist with 13.5 ppm Au.
GOLD RING CONTAMINATION
Experiences has shown that a gold ring may be a

source of heavy contamination, especially during
sampling but also during sample preparation. Gold
ring contamination becomes significant when the
gold concentration of samples is at the ppb level. For
example, gold concentrations of 500-600 ppb were
found in a fine fraction of till when samples were
handled after sampling by a person wearing a gold
ring. Also rather soft materials such as plant samples
are easily contaminated by a ring. The plastic capsules used in neutron activation analysis may pick up
significant quantities of gold from a ring. After slight
contamination, Au contents of 15-170 ng were
found on capsules (Kontas 1990). It should be remembered that the neutron activation method measures all the gold in a capsule regardless of whether
the gold is outside or inside the capsule.
REVIEW ON ANALYTICAL METHODS
The physical preparation of samples is usually

followed three stages:
1) decomposition of the sample,
2) separation and preconcentration of the gold and
3) measurement.
Neutron activation analysis is the only method that

allows gold to be determined directly on samples
with a relatively low detection limit without any
preconcentration. However, in most activation laboratories, the direct method restricts the size of the
sample, making it too small and unrepresentative.
Decompositon of samples
Fusion
lector in the fire assay of noble metals (Robert et al.

1971).
Fire assay for gold uses reductive fusion and the

classic collection by lead in a procedure that has Acid treatment
been used since ancient times to concentrate andisolate the noble metals (Beamish & Van Loon 1977,
Mixtures of hydrochloric and nitric acids or aqua
Van Loon 1984). Lead oxide is added to the fusion regia are most commonly used in acid treatment
pot. The oxide is reduced to lead metal in the fusion procedures. A normal mixture is HCl+HNO, = 3+1
process, which then quantitatively extracts and but others can also be used. Even if aqua regia discollects any gold or silver in the sample. More re- solves silicate minerals only to some degree, partial
cently, nickel sulphide has also been used as a col- attack with aqua regia usually results almost total
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finlmzd, Report of htvestigation 114, 1993
Esko Kontas
dissolution of gold from geological materials when

samples are roasted (Signiholfi et al. 1984). Silicate
samples can also be digested with hydrofluoric and
perchloric acids before gold is dissolved in aqua
regia (Rubeska et al. 1977). Hydrobromic acid with

bromium is also useful in dissolving gold from roasted samples (Thompson et al. 1968).
Separation and preconcentration

In the conventional fire assay, lead is separated
from the fusion slag, hammered into a cube or button
and placed on a heated cupel of bone ash or magnesia. This in turn is placed in a cupellation furnace
where the lead is oxidated into lead oxide, which is
absorbed by the cupel leaving behind a small goldsilver alloy bead that contains all the gold to be determined. Gold is determined either gravimetrically
or instrumentally. In the ~zickelsulphide fire assay
procedure the NiS button obtained by fusion is
milled and dissolved in hydrochloric acid. Gold and
the other noble metals precipitate as sulphides or
metals.
The precipitate is filtered, rinsed and dissolved for
measurement (AAS, ICP, ICP-MS) or the noble
metals are measured directly from the precipitate by
neutron activation (Hoffman et al. 1978).
Solvent extraction
The gold in a solution may be separated and concentrated with liquid-liquid extraction. Numerous
solvents and complexing agents are in use and summaries of the methods have been given by Beamish
and Van Loon (1977). The most common method
involves extraction of gold(II1) from a hydrochloric
or hydrobromic acid solution with methyl isobutyl
ketone (MIBK). In Rubeska et al. (1977), acid attack
is followed by extraction into dibutylsulphide in toluene and in Parkes and Murray-Smith (1979) into
dibutylsulphide in di-isobutyl ketone.
Coprecipitation
In accordance with its character, metallic gold is
easily precipitated by reductants. Since solutions are
highly diluted in relation to gold, a coprecipitant is
necessary. Tellurium is the usual coprecipitant and
stannous chloride (Fryer and Kerrich 1978) or
hypophosphorous acid the most common reductant
(McHugh 1983). Stannous chloride-mercury coprecipitation is another attractive method for separating
gold (Kontas 1981, Kontas et al. 1986) and some
other readily reduced elements such as the platinum-
group metals, silver, tellurium and selenium (Niskavaara and Kontas 1990). An advantage of
coprecipitation is that the analyses can be performed
in water solutions, which are more stable and easier
to handle than the organic solutions and solvents.
Measurement
In the classical lead cupellation method gold is
determined gravimetrically. The silver-noble metal
bead or prill obtained by fusion and cupellation is
treated with dilute nitric acid to separate the gold as
pure metal, which is then weighed. The detection
limit is generally 0.1 ppm. Fire assay separation has
not changed much down the ages, but gravimetry
has, being first replaced by optical emission spectrometry and then by atomic absorption spectrometry.
The method is easy to apply and is used for gold ores
and concentrates. Various separation and pre-concentration methods can be combined with different
instrumental measuring methods. Nowadays atomic
absorption instruments are very popular (Van Loon
1985). If a detection limit of 0.05 ppm is sufficient,
flame atomic absorption is a cost-effective method.
Graphite furnace atomization readily permits a ppb
level, but measuring is slower and the equipment is
more expensive than in flame atomization. Emission
spectrometry had became almost obsolete until the
new plasma emission and plasma mass instruments
gave it a new lease of life. The most sensitive measuring method, plasma mass spectrometry, permits
ultra trace contents to be determined. Neutron activation analysis is nowadays also widely applied, and if
it is combined with a suitable preconcentration method, a small sample size does not impair its
representativeness. The sensitivity of X-ray analysis
is very low. However, based on X-ray analysis an
interestingmethod has been developed for reconnaissance determination of gold in the field: gold is dissolved from a sample into a cyanide solution and
adsorbed and concentrated on the surface of a carbon
disk. Gold is then determined from the disk with a
portable X-ray instrument (ASOMA Instruments,
Austin, Texas).
REFERENCES
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Metals. Pergamon Press Inc. Oxford, 609 p.
Beamish F. E. & Van Loon J. C. 1977. Analysis of Noble
Metals. Overview and Selected Methods. Academic
Press, New York, 327 p.
Boyle R. W. 1979. The Geochemistry of Gold and Its Deposits. Bull. Geol. Surv. Can. 280, 584 p.
Brooks R. R. 1972. Geobotany and Biogeochemistry in
Mineral Exploration. Harper and Row, New York, 290 p.
Brown B. W. & Hilchey G. R. 1975. Sampling and analysis
of geochemical materials for gold.683-690 in Geochemica1 Exploration 1974, ed. by I. L. Elliott and W. K. F1etcher. Elsevier Scientific Publishing CO, Amsterdam
1975, 720 p.
Burn R. G. 1984. Factors affecting the selection of the
methods of gold analysis. Mining Magazine 150, 5, p.
468.
Clifton E. H., Hunter R. E., Swanson F. J. & Phillips R.
L. 1969. Sample size and meaningful gold analysis. U. S.
Geol. Surv. Prof. Paper 625-C, 17 p.
Cook N. J. & Cryssoulis S. L. 1990. Concentration of "invisible gold" in the common sulfides. Can. Mineral. 28,
1-16.
Date A. R., Davis A. E. & Cheung Y. Y. 1987. The potential of fire assay and inductively coupled plasma source
mass spectrometry for the determination of platinum
group elements in geological materials. Analyst, 112, 9,
1217-1222.
Fryer B. J. & Kerrich R. 1978. Determination of precious
metals a t ppb levels in rocks by combined wet chemical
and flameless atomic absorption method. Atom. Abs.
Newsl. 17, 1, 4 - 4 .
Gy P. M. 1982. Sampling of Particulate Materials. Theory
and Practice. Elsevier Publishing CO, Amsterdam, 431 p.
Harris J. F. 1982. Sampling and analytical requirements for
effective use of geochemistry in exploration for gold.
53-67 in Precious Metals in the Northern Cordillera ed.
by A. A. Levinson. Published by the Association of
Exploration Geochemists, 1982, 214 p.
Hoffman E. L., Naldrett A. J., Van Loon J. C., Hancock

R. G. V. & Manson A. 1978. The determination of all
platinum-group elements and gold in rocks and ore by
neutron activation analysis after precoucentration by a
nickel sulfide fire assay technique on large samples.
Anal. Chim. Acta 102, 157-166.
Hoffman E. L. & Brooker E. J. 1982. The determination of
gold by neutron activation analysis.69-77. bl Precious
Metals In the Northern Cordillera ed. by A. A. Levinson.
Published by the Association of Exploration Geochemists
1982,214 p.
Jackson S. E., Fryer B. J., Gosse W., Healey D. C.,
Longerich H. P. & Strong D. F. 1990. Determination of
the precious metals in geological materials by inductively
coupled plasma-mass spectrometry (ICP-MS) with nickel
sulphide fire assay collection and tellurium coprecipitation. Chem. Geol. 83, 1 19-132.
Kontas E. 1981. Rapid determination of gold by flameless
atomic absorption spectrometry in the ppb and ppm ranges without organic solvent extraction. Atomic Spectroscopy, 2, NO 2, 59-61.
Kontas E., Niskavaara H. & Virtasalo J. 1986. Flameless
atomic absorption determination of gold and palladium in
geological reference samples. Geostandards Newsletter
Vol. 10. No 2, 169-171.
Kontas E. 1991. Gold contamination of the fine fraction of

till during sampling and sample preparation. J. Geochem.
Expl. 39, 289-294.
Li T. & Yio C-L. 1966. The abundance of chemical elements in the earth's crust and its major tectonic units.
Sei. Sin. Vol. 15, No 2, 258-272.
McHugh J. B. 1983. Determination of gold in water in the
nanogram range by electrothermal atomization after
coprecipitation with tellurium. Atomic Spectroscopy Vol.
4, No 2, 66.
Minkkinen P. 1987. Evaluation of the fundamental sampling error in the sampling of particulate solids. Anal.
Chim. Acta, 196, 237-245.
Nichol I. 1985. Gold Exploration 8.-10. May 1985. Course
Notes, Department of Geological Sciences, Queers University, Kingston, 51 p.
Niskavaara H. & Kontas E. 1990. Reductive
coprecipitation as a separation method for the determination of gold, palladium, platinum, rhodium, silver, selenium and tellurium in geological samples by graphite furnace atomic absorption spectrometry. Anal. Chim. Acta,
231, 273-282.
Nurmi P. A., Lestinen P. & Niskavaara H. 1991. Geochemical characteristics of mesothermal gold deposits in
the Fennoscandian shield and a comperison with selected
Canadian and Australian deposits. Geol. Surv. Finland,
Bulletin 351, 101 p.
Parkes A. & Murray-Smith R. 1979. A rapid method for
the determination of gold and palladium in soils and
rocks. Atomic Abs. Newsl. Vol. 18, No 2, 57-58.
Riddle C. 1983. Analytical methods for gold. 272-278 in
The Geology of Gold in Ontario, ed. by A. C. Colvine.
Ont. Geol. Surv. Miscellaneous Paper 110, 450 p.
Robert R. V. D., Van Wyck E. & Palmer R. 1971. The
collection and determination of the noble metals in ores
and concentrates by the fusion technique using nickel
sulphide as a collector. National Institute for Metallurgy
(South Africa) Report 1371.
Rubeska I., Koreckova J. & Weiss D. 1977. The determination of gold and palladium in geological materials by
atomic absorption after extraction with dibutylsulfide.
Atomic Abs. Newsl. Vol. 16, No 1, 1-3.
Signiholfi G. P., Gorgoni C. & Mohamed A. H. 1984.
Comprehensive analysis of precious metals in some
geological standards by flameless A.A. spectrocopy.
Geostandards Newsletter, Vol. 8, No 1, 25-29.
Thompson C. E., Nagakava H. M. & Vansickle G. H.
1968. Rapid analysis for gold in geologic materials. U. S.
Geol. Surv. Prof. 600-B, 130-132.
Turekian K. K. 1977. Geochemical distribution of elements. 111 Encyclopedia of Science and Technology, 4th
edn. 627-630. McGraw-Hill, New York.
Van Loon J. C. 1984. Accurace determination of the noble
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Van Loon J. C. 1985. Accurace determination of the noble
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4, 1, 24.
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Wedepohl K. H. Editor, 1969-1978. Handbook of Geochemistry, Vol. 11-4. Springer Verlag, Berlin.

Geologian tutkimuskeskus, Tutkimusraportti Geological Survey of Finland, Report of Investigatioti 114, 13-16,
1993
D IN GEOLOG
MATERIALS
EAD FIRE ASSAY SE ARATION
by
Riitta Juvonen and Paavo J. Vaananen
Juvonen, R. & Vaananen, P.J. 1993. Determination of gold in geological

materials by atomic absorption after lead fire assay separation. Geologian
tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report
of Investigation 114, 13-16, 3 tables.
Key words (GeoRef Thesaurus, AGI): chemical analysis, techniques, gold,
atomic absorption, reagents, accuracy
Riitta Juvonen and Paavo J. VaanZinen, Geological Survey of Finland,
SF-02150 Espoo, Finland
INTRODUCTION
Analysis of gold and silver with the classical
fire assay technique has been in use at the Geological Survey of Finland for decades. The
method with its many variations is well documented in numerous publications and monographes (e.g. Haffty et al. 1977, Beamish et al.
1977, Moloughney 1986). The method is widely
used all over the world not only for analysing
gold but also for silver, platinum and palladium.
It permits use of a large sample, which is neces-
sary because of the uneven distribution of gold

in geological material (Moloughney 1986).
The demand for gold analyses in our laboratory has increased. We have therefore studied the
method carefully, seeking to make it faster and
easier to perform without sacrificing the quality
of the results. The following describes the method as it is currently performed at the laboratory
of the Geological Survey of Finland.
REAGENTS AND APPARATUS

1) Naber N-41 H, muffle furnace with a vent on
top of the furnace,
2) Perkin-Elmer Model 5000, atomic absorption
spectrophotometer equipped with AS 50,
autosampler
3) Perkin-Elmer Model 2380 with HGA-500
graphite furnace equipped with AS 40 autosampler,
4) Atlantic-Schmelztiegel GmbH, fusion crucibles, roasting dishes and cupels,

5) Merck, fusion flux reagents and lead oxide
(PbO), extra pure grade,
6) Merck, HNO, (G%), HCI (37%) and AgNO,,
reagent grade,
7) BDH Chemicals Ltd, gold, platinum and
Geologiau tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of I~westigation114, 1993
Riitta Juvonen and Pnavo J. ViiZi~zlinen
palladium standard solutions and

tartrate and 0.6 kg of glass powder are mixed
8) Fusion flux: 0.8 g Na2C03, 1.3 kg K2C03, well in a ball mill.
1.0 kg Na2B,0,, 1.3 kg of potassium hydrogen
EXPERIMENTAL
A 25 g sample of ground rock is mixed well

with 50 g of lead oxide (litharge) in a plastic
bag. About 130 g of the fusion flux is added and
the contents of the plastic bag are mixed well. A
known amount of silver is added in the form of
a silver nitrate solution. The plastic bag is
placed into a fusion pot and the pot is transferred to a preheated furnace at 1100C. The
sample is left in the furnace for 1 hour, after
which the melt is poured into an iron mould to
cool. Most of the slag is hammered off, and the
lead regulus is further cleaned by soaking in
10% HCI. The regulus is hammered into the
form of a cube, brushed clean and cupelled. The
lead is oxidized by air to lead oxide at a furnace
temperature of 940C. The liquid lead oxide is
absorbed by the magnesite cupel and a small
bead of silver is left behind. It contains the gold
and silver and the platinum-group metals to
varying degrees. Twelve samples are fused and
cupelled at a time, using the same furnace type
for both operations.

The silver bead obtained by fire assay is flattened and placed in a 10-m1 graduated test tube.
A small glass bead is added to avoid overboiling
the solution. HNO, (65%), 0.5 ml, is added and
the test tube is warmed carefully in a water bath
for about one hour. The tube is cooled and 1.5
m1 of HCl (37%) is added. The solution is agitated, allowed to stand overnight at room temperature, and warmed very carefully, avoiding
overboiling, on a water bath for about 30 minutes. When the dissolution is complete, the tube
is cooled and filled to the mark with 6 M HCl.
Gold standards are prepared to contain the same
amount of acids as the samples. Silver need not
be added to the standard solutions. Gold is determined by flame atomic absorption. The solution obtained is also used for determining platinum and palladium by graphite furnace atomic
absorption.
THE LEAD FIRE ASSAY METHOD
Extraction of noble metals into lead

The well ground sample is melted together
with lead oxide and a reducing fusion flux mixture, in which gold and the platinum-group
metals together with added silver are reduced
and dissolved in the simultaneously reduced
metallic lead. Quantitative extraction of the
noble metals into lead requires a complete reaction between the sample and the fusion flux. The
sample must be finely ground and well mixed
with the reagents before fusion. The viscosity of
the flux should be such that the noble metals are
dissolved by the metallic lead as it sinks to the
bottom of the fusion pot. If the flux is too fluid,
the lead will sink too fast to bring the noble
metals down with it. If the flux is too viscous,
lead globules will remain in the slag, resulting

in low metal values.
The best possible fusion flux has been devised
for each rock type (Haffty et al. 1977). However, in routine work it is not generally possible to
prepare the optimum fusion mixture for each
sample. The flux, mentioned above, in routine
use at the laboratory of the Geological Survey of
Finland, generally works well. To control the fusion process, a check is kept on the weight and
the appearance of the lead regulus. Reference
samples are frequently analysed along with the
sample series. Samples with more than 2% sulphur are roasted at 600C in special roasting
dishes before fusion.
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Fiidmrd, Reporr of Iirvestigntiora 114. 1993
Determination of gold in geological materials by atomic absorption after lead fire assay separation
SCORIFICATION OF THE LEAD REGULUS
The lead regulus may be further purified by a

process called scorification if the sample contains high concentrations of interfering elements,
mainly copper and nickel. In the fusion process
copper, cobalt and nickel are partly reduced
along with the lead and noble metals. Cobalt
will not dissolve in the lead, but copper and
nickel will.
If the sample contains appreciable amounts of
copper or nickel, further purification of the lead
regulus is necessary. The regulus along with
about 1 g of borax is put into a shallow

scorification crucible, which is transferred to a
furnace with ample air flow, at 1000C. In the
furnace, part of the lead is oxidized and simultaneously copper and nickel are oxidized and
dissolved in the slag. The scorification is repeated, and metallic lead is added until a clear,
smooth and malleable lead regulus is obtained.
For example, the scorification of one gramme of
copper requires 50 g of lead.
CUPELLATION
The lead is oxidized by a process called cupellation: the lead regulus is heated in the furnace on a cupel, made of magnesite, which absorbs
the forming lead oxide. A small bead of silver
containing the noble metals is left.
In practice, the cupels are first heated in the
furnace at 940"C, after which the lead reguli are
placed on the cupels. The regulus melts almost

instantly, the lead begins to oxidize and is absorbed by the cupel. In the last stages of the
cupellation, only a small spot remains in the
centre of the cupel. This finally disappears, giving off a bright flash of light at the end. Prolonged heating causes losses of silver.
DETERMINATION OF NOBLE METALS
In the conventional method of analysis, the

silver bead is flattened by hammer and anvil, the
flattened bead is weighed, silver is dissolved in
dilute nitric acid, and the resulting flake of gold
is weighed. The difference gives the total
amount of silver. Along with the gold, any rhodium and iridium together with small amounts
of platinum and palladium remain undissolved in
nitric acid treatment (Beamish et al. 1977). The
samples should contain about three times more
silver than gold for a good partition of the two.
The addition of silver also increases the size of
bead, making it easier to handle.
Analysis with atomic absorption has replaced
gravimetry in many laboratories (Kallmann et al.
1970, Moloughney 1986). At the laboratory of
the Geological Survey of Finland, the flattened
silver bead is dissolved in aqua regia and the
gold is analysed by flame absorption and
Table 1. Graphite furnace programme for palladium and platinum.

Step
No.
Furnace
temperature
"C
Time
Ramp
Hold
Internal
gas flow
ml/min
Palladium
1
2
3
4
5
Platinum
1
2
3
4
platinum and palladium by graphite furnace

atomic absorption.
Riittn Juvonen and P a m o J. Viiiiniinen
Table 2. Gold concentrations of five Canadian reference samples.
Sample
F:
CH-1
CH-2
MA- l a
MA-3
GTS-1
This work
AU P Q ~
Number of
determinations
Weight
Recommended
values ppm
10
10
5
5
10
Data collected over three years.
Table 3. Platinum and palladium concentrations of reference samples.
S ample
Weight
Number of det's
This work
Pt
Pd
Pt
PPn'
Pd
PPm
Pt
PP"'
Pd
PPm
3
4
3.4550.22
1.4950.21
0.3850.02
3.740
-
1S 3 0
0.37
SARM-7
SU-la
25
5
Recommended values
Data collected over three years.
PRECISION AND ACCURACY
Five gold ores of the Canadian Reference

Materials Project were analysed with the present
method but with reduced sample weights. Cornparison of the results with the recommended
values is presented in Table 2. Platinum and
palladium were determined from the reference

samples SARM-7 (South African Committee for
Certified Reference Materials) and SU-l a (Canadian Certified Reference Materials Project). The
results are presented in Table 3.
REFERENCES
Beamish P. E. & Van Loon J. C. 1977. Analysis of Noble
Metals. Overview and Selected Methods. Academic
Press, New York, 327 p.
Hafty J., Riley L. B. & Goss W. D. 1977. A Manual on
Fire Assaying and Determination of the Noble Metals in
Geological Materials. U. S. Geol. Surv. Bull. 1445, 58 p.
Kallmann S. & Wobart E. W. 1970. Determination of

silver gold and palladium by combined fire assay atomic
absorption. Talanta 17, 845-850.
Moloughney P. E. 1986. Assay methods used in CANMET
for the determination of precious metals. CANMET SP
86-lE, 33 p.

Geologian tutkimuskeskus, Tutkimusraportti Geological Survey of Finlmzd, Repori of Investigation 114, 17-19,
1993
by
P. Noras
Noras, P. 1993. Determination of gold by aqua regia-potassium bromate

digestion, methyl isobutyl ketone extraction and flame atomic absorption.
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of
Finlmzd, Report of bwestigation 114, 17-19, 1 table.
Key words (GeoRef Thesaurus, AGI): chemical analysis, gold, techniques,
atomic absorption, sample preparation, reagents, accuracy
P. Noras, Geological Survey of Finland, SF-02150 Espoo, Finland
INTRODUCTION
In the late 1960s the need arouse for a rapid

method to determinate gold, particularly owing
to the increase in geochemical exploration,
where both speed and cost are of paramount
importance. Thompson et al. (1968) introduced
a method based on Br,-HBr digestion, methyl
isobutyl ketone (MIBK) extraction of AuBr, and
AAS determination of Au. The method, described here uses aqua regia and potassium bromate for digestion before extraction of Auhalogenide complexes and determination of Au
in very much the same way as the method of
Thompson et al. The present method was developed and used extensively by the Mineral Project of the U.N. Development Programme in
Colombia on which the author was employed in

1974-77. Practical improvements were made to
the procedure in the Geological Survey of Finland.
The method, which allows sample weights of
up to 20 g to be used, offers a detection limit of
0.05 ppm Au in the sample, and accepts most
types of material encountered in geochemical
exploration. MIBK extraction has the advantage
over the conventional fire assay method that it
saves labour and materials expence, and can be
operated by less trained technicians. The disadvantage is that it cannot be used to extract other
precious metals. Moreover some interference is
caused by high contents of iron in the MIBK
phase.
1) Reagents: HCI 37%, HNO, 65%, KBrO,,

methyl isobutyl ketone (MIBK), all reagent
grade,
2) apparatus: Furnace for calcination (maximum

P. Noras
- Geological Survey
temperature preferably 1000C and

3) atomic absorption spectrophotometer Perkin-
of Firrlmld, Report of Investigation 114, 1993
Elmer Model 460 equipped with three-slot burner head.
SAMPLE PRETREATMENT AND DIGESTION
If samples are to be pulverized, avoid grinding them too fine to prevent the formation of
emulsions during the extraction stage.
Weigh 20 g of dry sample powder into a wide
roasting dish. To destroy organic matter, calcine
sediment samples at 600C for 2-5 hours, and
rock samples at 700C for one hour to decompose sulphides. Transfer the calcined sample
to a 250-m1 Erlenmeyer flask, add 25 m1 of

concentrated HC1, 5 m1 of concentrated HNO,
and 0.5 g of KBrO,, shake the flask, stopper it
lightly and allow it to stand at room temperature
overnight. Then add 0.5 g of KBrO,, shake the
flask again and place it in a water bath at 90C
for one hour.
EXTRACTION
Cool and dilute the sample solution by adding

170 m1 of water and shaking the flask. Then add
20.0 m1 of MIBK, stopper the flask and shake it
vigorously for 2 min. Let it stand until the clear
organic phase has settled out. Rapping the neck
of the flask helps to separate the two phases.

Difficulty in breaking up the emulsion in the
acid phase may be encountered with very fine
grain sizes. It is recommended that such sample
solutions be filtered before the MIBK is added.
INSTRUMENTAL CONDITIONS AND DETERMINATION OF GOLD
Gold is determined by AAS in an air-acetylene flame at a wavelength of 242.8 nm. A threeslot burner head is employed, and the flame is
adjusted to lean blue when aspirating MIBK.
The flame is just beginning "jump up" when the
water is aspirated. The spectrometer is calibrated

using standard MIBK solutions of gold prepared
in the same way as the unknown samples. The
working curve is linear, typically up to 2 pg Au
in 1 m1 of MIBK.
DISCUSSION
The precision and accuracy of the method

were studied by determining Au in some international standard reference samples and in-house
reference samples. Due to the high gold value of
the international materials, sample weights were
limited to 2 g (Table 1).
At higher concentration levels (more than
0.15 ppm) the method shows good agreement
with recommended values and acceptable precision. Unfortunately, for assessing the precision
of the method at lower levels, the data mainly
derive from the 2-g samples. The detection limit
(3xb) of the method is estimated to be 0.05 ppm
Au in sample.
The only serious interference is due to the
high contents of acid soluble iron in the sample.
Iron extracted from an acid solution to MIBK
gives "false" absorption at the measuring wavelength. It has been shown that 15% acid soluble
iron in a sample is critical. Fortunately, the iron
content is not that high in most sample types,
although the critical concentration may be
reached in pyrite ores. To overcome the possible
interference, the MIBK phase should be washed
with 0.1 M HCl solution until free of yellow colour.
Determination of gold by aqua regia-potassium bromate digestion, methyl isobutyl ketone extraction and flame atomic absorption
Table 1. Gold concentrations of some reference samples determined by the above method and the recommended values (in ppm).
S ample
number
Weigh
Number
of det's
Au
a
USBM G 2
USGS 2.6
GXR- 1
Stand.
dev.
Recommended
value1
P P ~
10
10
2
Gladney and Burns (1984).
The determination limit of this method is

fairly acceptable for rock samples, alluvial sediments and residual soil samples. However, the
method is certainly not sensitive enough for
studying regional geochemical patterns e. g. till
samples. For lower levels of Au and Ag, Bratzel
et al. (1972) have described a method in which
digestion and extraction are similar to the above
but determination of Au is by carbon-rod AAS.
The daily rate of the method run by two technicians is 30-50 effective determinations. The
method does not need highly trained staff or
sophisticated instruments and thus is easily
applicable in developing countries. Since MIBK
is a flammable chemical and harmful for health,
proper fume cupboards and ventilation are
essential.
REFERENCES
Bratzel M. P. Jr., Chakrabarti C. L., Sturgeon R. E.,
MacIntyre M. V. & Agemian H. 1972. Determination of
gold and silver in parts per billion or lower levels in
geological and metallurgical samples by atomic absorption spectrometry with carbon rod atomizer. Anal Chem
44, 372.
Gladney E. S. & Burns C. E. 1984. 1982 Compilation of
elemental concentration data for the United States Geological Survey's geochemical exploration reference samples GXR-1 to GXR-6. Geostandards Newsletter Vol. 8,
No. 2, 119-154.
Thompson C. E., Nagakava H. M. 82 Vansickle G . H.
1968. Rapid analysis for gold in geological matrials. U.
S. Geol. Surv. Prof. P. 600-B, 130-132.

1993
DETERMINA
A DIGESTION,
EXTRACTION
by
U. Penttinen
Penttinen, U. 1993. Determination of gold by aqua regia digestion, dibutylsulphide-di-isobutyl ketone extraction and flame atomic absorption.
Geologian tutkimuskeskus, Tutkimusraportti - Geological Srmey of
Finland, Report of Investigation 114, 21-23, 1 table.
palladium, atomic absorption, sample preparation, reagents, accuracy
U. Penttinen, retired
Outokurnpu Metals & Resources
Geoanalytical Laboratory
P.O.Box 74, SF-83501 Outokunnpu, Finland
INTRODUCTION
Prospecting for the gold and platinum metals

has increased greatly, giving rise to a need for a
fast and sufficiently accurate analytical method.
Introduction of the method described below has
definitely improved the effectiveness of the
prospecting for gold and platiniferous deposits
undertaken by the Exploration Department of
Outokurnpu Oy. The use of dibutylsulphide in

gold determination was first described by
Yudelevich et al. in 1970. The method has since
been refined by Rubeska et al. (1977) and
Parkes and Murray-Smith (1979). We developed
our gold and palladium determinations from
these methods in 1980.
THE PRINCIPLES OF THE METHOD
A sample should be well-homogenized and

preferably large. Organic material and sulphide
sulphur are eliminated by roasting at 600C
(Strong and Murray-Smith 1974). The graphite,
if present, should then be burned in the oxygen
stream at 600C. If gold occurs as inclusions in
silicate particles, very fine grinding is needed
or, alternatively, the sample should be submitted

to total digestion with hydrofluoric and nitric
acids. The gold is dissolved in aqua regia. This
is preceeded by hydrochloric acid treatment to
dissolve the iron precipitates on the surface of
the gold particles. The gold and the palladium
are extracted from 2M hydrochloric acid solu-
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of I?n~estigation114, 1993

U. Penttinen
tion with dibutylsulphide dissolved in di-isobutyl ketone. The gold and palladium concentrations are determined by flame atomic absorption
from the washed and centrifugued organic extract. The other elements do not interfere with
the determination.

1) HCl 37%, HNO 65%, reagent grade,
2) Dibutylsulphide solution: Dissolve 17.4 m1
dibutylsulphide in 500 m1 of di-isobutyl ketone,
3) Atomic absorption spectrophotometer: PerkinElmer Model 5000 and

4) Shaking machine: Buhler Model B.
Procedure
Weigh 10 g of fine ground and well mixed
sample into a porcelain crucible and roast it at
600C for 2-3 hours. Mix as needed. If the
sample contains arsenic, roast it at first for 2
hours at 450C and then for 2 hours at 600C to
avoid partial evaporation of gold. If graphite is
to be eliminated, burn it afterwards in a tube
furnace in oxygen stream at 600C.
Transfer the roasted sample to a 250 m1 beaker, add 80 m1 of diluted HCl (1+1), cover it with
a watch glass and keep it at 80-100C for two
hours. Add 20 m1 of concentrated HNO,, and
keep it covered at the same temperature for one
hour, stirring from time to time. Evaporate to
"wet salts". If evaporated to dryness, gold may
be reduced to a lower valence and cannot be extracted.
Add 15 m1 of concentrated HCl and 20 m1 of
water. Heat to dissolve the salts. Filter through
a Whatman GFIB glass fibre filter and wash

with water. Rinse into a 100-m1 measuring flask,
cool, fill to the mark with water and stir.
Transfer a 50-m1 aliquot to a 100-m1
separatory funnel. Add 5 m1 of dibutylsulphide
solution and shake using the full effect and shaking amplitude of the machine for two minutes.
Let the phases separate. Wash the organic extract with 25 m1 of 2M HCI. Centrifuge for 10
minutes at 3500 rpm.
Flame atomic absorption of gold is measured
at a wavelenght of 242.8 nm using background
correction. The intergation time is 0.5 S and the
reading an average of ten measurements. Palladium is measured using a wavelength of 244.8
nm and background correction.
For calibration, the extraction is done using 1,
2 and 3 m1 of solution containing 10 pglml of
gold and palladium in 2M HCl.
ACCURACY AND PRECISION

The following samples were analysed to check
the accuracy and precision of the method:
Mine (Sample B) and

3) gold ore MA-2, Canmet (Sample C).
1) Cu-Bi-CO matte, Falconbridge (Sample A),

2) Cu concentrate, Outokumpu Oy, Pyhasalmi
The results are presented in Table 1.
DETECTION LIMIT AND CAPACITY

If a 10 g sample, a 100 m1 measuring bottle, a
50 m1 aliquot and 5 m1 of dibutylsulphide solution are used, the detection limit for gold and
palladium is about 0.05 ppm. A team of three

laboratory workers can make 60 determinations
a day.
Geologian tutkimuskeskus, Tutkimusraportti - Geologicnl Survey of Finlrn~d,Report of bwestigation 114, 1993

Determination of gold by aqua regia digestion, dibutylsulphide-di-isobutyl ketone extraction and flame atomic absorption
Table 1. Gold and palladium concentrations in some reference samples.
S ample
Number of
det's
This
work
Stand.
dev.
Coeff. of
var. %
Recommended
value
REFERENCES
the determination of gold and palladium in soils and
rocks. At. Abs. Newsl. Vol. 18, No 2, 57-58.
Rubeska I., Koreckova J. & Weiss D. 1977. The determination of gold and palladium in geological materials by
atomic absorption after extraction with dibutylsulphide.
At. Abs. Newsl. Vol. 16, No 1, 1-3.
Strong B. & Murray-Smith R. 1974. Determination of gold

in copper-bearing sulphide ores and metallurgical flotation products by atomic absorption spectrometry. Talanta
21, 1253.
Yudelevich I. G., Wall G. A., Torgov V. G. & Korda T.
M. 1970. Extraction-atomic absorption determination of
gold in solutions. Zh. Anal. Khim. 25, 870.

Edited by Esko Koutas
Geologian tutkirnuskeskus, Tutkimusraportti Geological Survey of Finland, Report of Irzvestigation 114, 25-27,
1993
bY
E. Ojaniemi
Ojaniemi, E. 1993. Determination of gold, palladium and platinum by

aqua regia digestion, dibutylsulphide-di-isobutyl ketone extraction and flameless atomic absorption. Geologian tutkimuskeskus, Tutkimusraportti Geological Survey of Fidand, Report of Investigation 114, 25-27,
2 tables.
palladium, platinum, atomic absorption, sample preparation, reagents
E. Ojanienzi
Rautaruukki CO,Research Centre
SF-92170 Raahe
Finland
INTRODUCTION
The method was developed for the exploration

of platinum-group metal deposits containing
gold as well as for the determination of gold.
The preparation and dissolution of a sample also
allow the determination of palladium and platinum. The method is based on hot aqua regia
digestion and two successive liquid-liquid ex-
tractions. First gold and palladium are extracted

from 2M hydrochloric acid solution into dibutyl
sulphide in di-isobutyl ketone (Parkes and
Murray-Smith 1979). After reduction with stannous chloride, platinum can be extracted into the
same reagent (Simonsen 1970). Measurements
are made by flameless atomic absorption.
Reagents:
1) HCl 37%, HNO, 65%, reagent grade,
2) 0.2M DBS in DIBK: 14.6 g of dibutyl sulphide dissolved into 500 m1 of di-isobutyl ke-
tone. The solution is kept out of the daylight in

a refrigerator,
3) Stannous chloride solution: 100 g of SnCl,
dissolved in 1000 m1 of 2M HCl. New solution
is required daily,
E. Ojanietni
4) Ferric chloride solution: 25 mg Felml in
2 M HCI.
Instruments:
spectrophotometer equipped with an HGA 500

graphite furnace and an AS 40 autosampler,
2) Shaking machine: Desaga, tube mixer:
Heidoplh.
1) Perkin-Elmer Model 5000 atomic absorption
Before digestion, roast the samples at 800C

for 1.5 h to decompose sulphides and organic
matter.
Weigh 5.00 g of sample into a porcelain crucible. After roasting, transfer it to a 50-m1 test
tube having a plug and a magnetic stirrer on the
bottom. Add 20 m1 of 6M HCl and shake well.
Heat the tube on an aluminium block for 1 h at
90C. Remove the tube from the block and allow
it to cool for about 15 rnin at room temperature.
Add 5 m1 of concentrated HNO, and shake well.

Put the tube back on the aluminium block and
leave the solution to evaporate overnight. Remove the tube from the block in the morning.
The residue must be pulpy; very dry or roasted
residue does not give correct results. Dissolve
the residue in 35 m1 of 2M HCl, shake the tube
well and make sure that all the particles have
disintegrated. Warm the tube again at 90C for
30 min.
EXTRACTION OF GOLD AND PALLADIUM
Remove the solution from the test tube into a

100-m1 measuring bottle. Rinse the tube and fill
the bottle up to the mark with 2M HC1, and
shake. Let the silicates settle overnight, or centrifuge the required aliquot of the solution
(3 min, 3500 rpm). Pipette an aliquot of 50 m1
into a 100-m1 separatory funnel and add 5.00 m1
of DBS-DIBK-solution. Extract Au and Pd into
the organic phase by shaking the funnel for 2

rnin manually or for 10 rnin mechanically. Allow the phases to separate. Transfer the water
phase to another 100-m1 separatory funnel for
the extraction of platinum. Remove the organic
phase to a 10-m1 test tube for the determination
of gold and palladium. If necessary, clear the
phases by centrifuging (3 min, 2000 rpm).
EXTRACTION OF PLATINUM
Add 2 m1 of stannous chloride solution to the

separatory funnel with the water phase, and,
while stirring, add smaller amounts (about
0.5 ml) until the yellowish brown colour of the
ferric iron has disappeared. Add another 5 ml,
stir and let the solution stand for 10 min. Extract
Pt into 5.00 m1 of DBS-DIBK solution by shaking manually for 2 rnin or mechanically for
10 min. When the phases have separated, transfer the aliquot needed for the measurement into
a 10-m1 test tube. If necessary, clear the phases
by centrifuging. If platinum need not be determined gold and palladium can be extracted
directly from the 2M HCl solution in the test
tube that contains the sample residue.
STANDARD SOLUTIONS AND CALIBRATION
The standard stock solutions of gold and

palladium, with concentrations of 1000 pmlml,
are prepared from pure metals by dissolving
them in small volumes of aqua regia. After

careful evaporation, the residues are dissolved i n
hydrochloric acid to yield a concentration of
Determination of gold, palladium and platinum by ...
HCl of 0.6 M in the final solutions. The solutions are kept in dark bottles. The standard stock
solution of platinum, with a concentration of
100 pglml, is prepared in the same way by dissolving pure metal in aqua regia. Before evaporation some potassium chloride is added. The
final solution should be 1.2M in respect of HCl.
Standards are calibrated by preparing a working solution from the stock solutions. It contains Au 0.5 yglml, Pd 1.0 ~ g l r n l and Pt
2.5 pglml. Aliquots of 0.0, 0.25, 0.50, 1.O, 1.50,
2.00, 3.00 and 4.00 m1 are pipetted into
separatory funnels. Then 5 m1 of FeC1, solution
is added and the solution is diluted to 50 m1
with 2M HCl. Gold and palladium are extracted
into 5.00 m1 of the DBS-DIBK solution. The
water phases are separated from the organic
phases, and after the adding of stannous chloride
solution platinum is extracted into 5.00 m1 of
DBS-DIBK solution.
If only Au and Pd have to be determined the
standard solutions are prepared in the same way
as the samples but without adding of FeC1,.
The sample extracts remains fresh in closed test
tubes for a month and the pure standard solutions for at least two months.
Table 1. Instrument parameters for Au in DBS-DIBK solution

STEP
TEMP. RAMP HOLD READ REC

"C
S
S
INT.FLOW
Tube: pyrocoated graphite tube, sample volume 10 p1.

Purge gas: argon.
DISCUSSION
The accuracy of the method was controlled by
analysing reference samples SARM-7 and Konttijarvi over several months. The results are presented in Table 2.
The detection limits achieved with the meth-
od described are 0.02 ppm for Au and Pd and

0.1 ppm for Pt.
Two technicians working together are able to
prepare 40 samples and to make 120 determinations a day.
Table 2. Gold, palladium and platinum concentrations (ppm) in reference samples SARM-7 and Konttijarvi.
Element
Au
Pd
Pt
Sample
SARM-7
Konttijarvi
SARM-7
Konttijarvi
SARM.
Konttijarvi
Numb.det's
Average
Stand.dev.
C. V. %
Recomm. val.
15
0.27
0.05
19.0
0.31
15
0.16
0.017
10.6
0.17
15
1.41
0.08
5.7
1.53
15
5.98
0.38
6.4
6.3
15
3.87
0.57
14.7
3.74
15
1.78
0.16
9.0
1.80
REFERENCES
the determination of gold and paIIadium in soils and
rocks. At. Abs. Newsl. Vol. 18, No 2. 25-27,
Simonsen A. 1970. Determinaton of platinum in basic rocks

by solvent extraction and atomic absorption spectroscopy.
Anal. Chim. Acta 49, 368-370.

1993
DETERMINATION 0
DIGESTION
REG
by
E. Kontas
Kontas, E. 1993. Determination of gold and palladium by aqua regia

digestion, stannous chloride-mercury coprecipitation and flameless atomic
absorption. Geologian tutkimuskeskus, Tutkimusraportti - Geological
Survey of Finland, Report of Investigation 114, 29-32, 2 tables.
palladium, atomic absorption, sample preparation, reagents, accuracy
E. Kontas
Geological Survey of Finland
P. 0. Box 77
SF-96101 Rovanierni, Finland
INTRODUCTION
Geochemical prospecting for gold and palladium requires a rapid method of analysis with
sensitivity reaching the ppb level and sometimes
even sub ppb level. This method, which was
earlier reported for gold analyses (Kontas 1981),
has now been refined to apply to both gold and
palladium (Kontas et al. 1986). In the original
method the detection limit for gold was about
2 ppb, but it is now about 0.2 ppb for Au and
Pd. The method is based on a sample weighing
1 g and overnight aqua regia digesting at the
room temperature. Heating is partly compensated for the long digestion time. Gold and palladium are separated from analyte solution by re-
ductive precipitation using stannous chloride as

a reductant and mercury as a coprecipitant
(Barnard and Zeeman 1958). For the determinat i o n ~ the
, Hg(Au-Pd) precipitate is dissolved in
aqua regia and diluted with water. Mercury does
not interfere with the determination of gold or
palladium by graphite furnace AAS.
Centrifugation is used to separate a clear sample solution after digestion and Hg(Au-Pd) precipitation from the bulk of the analyte solution.
Centrifugation makes the method faster and
more suitable for handling large batches of samples than conventional filtering.
E. Ko~ttns
Apparatus :
Reagents, all reagent grade:

1) HCI 37%, HNO, 65%,
2) stannous chloride solution: 20% SnC12.2H,0
in 1M HC1,
3) mercurous nitrate solution: 1 mg Hg/ml in
0. I M HNO, and
4) mercury chloride solution: 0.5 mg Hg/ml in
5 0 vol-% aqua regia.
Standard stock solutions:
Merck Titrisol
1) Retsch Rhetoterm roasting apparatus,

2) Beckman centrifuge with receptables for 56
test, tubes (100X16mm),
3) Perkin-Elmer Model 2280 atomic absorption
spectrophotometer equipped with a D, background corrector and an HGA 500 graphite furnace equipped with an AS 40 autosampler and
4) Perkin-Elmer Model 3030 Zeeman atomic absorption spectrophotometer equipped with an
HGA 600 graphite furnace and an AS 60
autosampler.
Samples with carbon, graphite or large

amounts of sulphides are roasted at 750C for
20 min. If sulphides exist only in moderate
abundaces, roasting is not necessary.
Weigh l g of samples into plastic tubes
(100x16 mm) or into porcelain crucibles if
roasting is necessary. After roasting transfer
them into tubes. Add 2.5 m1 of conc. HCI and
shake; then add 0.5 m1 of conc. HNO, and
shake. Let them stand overnight at room tem-
perature. In the morning shake them again and

add 4 m1 of water; centrifuge for 10 min at
2000 rpm. Pour the clear, supernatant solutions
into conical glass tubes (100x16 mm) or take
aliquots for further separation of Au and Pd.
If the samples are ashes of organic materials,
reduce the weight of samples 29-32, g), replace
HNO, with 0.5 m1 of H202,and the water in the
morning with 4 m1 of 3M HCI.
Separation of gold and palladium
Add 2 m1 of SnCl, solution and 1 m1 of

Hg2(NO,), solution to the sample solutions. Wait
for about five minutes and centrifuge the s o h tions for 10 min at 2200 rpm. Pour the solutions
away; rinse the Hg(Au-Pd) precipitates and the
tubes by filling them with water and then pouring it away. One rinsing is often enough. Cen-
trifugation is not generally required in rinsing,

since the Hg precipitate remains on the bottom
or the walls of the tubes. Make sure that this has
happened.
For organic ashes, use only 0.5 m1 of
Hg,(NO,), solution.
Dissolving the Hg(Au-Pd) precipitate and calibration
Add 0.7 m1 of conc. HCI and 0.3 m1 of conc.

HNO, to the tubes containing the Hg(Au-Pd)
precipitate. Shake the tubes and let them stand
for about one hour. Then add 0.9 m1 of 3M
HNO,, shake the tubes once more and let them
stand overnight. The analysis can then be done
by graphite furnace AAS. The final volume of

the sample solutions is 2 ml, because about 0.1
m1 of water is left in the tubes after rinsing.
From the stock solutions, the calibration standards are diluted with mercury chloride solution.
Determination of gold and palladium by ...
Table 1. Instrument parameters for gold' and palladium2.
Au
STEP
TEMP. "C
RAMP s
HOLD s
READ
REC
BASELINE
1NT.FLOW
Pd
200
15
15
500
15
15
1900
0
2500
1
5
100
5
5
300
300
0
2
300
25
300
' p e r k i n - ~ l m e rModel 30302 AAS and HGA 600 graphite furnace. Au wavelength 242.8 nm, slit 0.7 nm. Pyrocoated graphite tube
with L'vov's platform, peak area integration, purge gas argon.
'Perkin-Elmer Model 2280 AAS with HGA 500 graphite furnace. Pd wavelength 244.8 nm, slit 0.2 nm. Pyrocoated graphite tube,
peak height integration, purge gas argon.
The concentration range of the standards, which

varies from 5 to 100 nglml of Au or Pd, and the
solution volumes injected into a graphite furnace
depend on the detection limits required. The instrument parameters are presented in Table 1.
DISCUSSION
The precision and accuracy of the method was

tested for gold by analysing USGS reference
samples GXR 1-6 (Table 2). Except for the
sample GXR 1, the recommended values
(Gladney and Burns 1984), were not precise
enough for accuracy to be assessed. Therefore the
results of Meier (1980) are shown. Meier also
used graphite furnace AAS but after HBr-Br2
digestion and methyl isobutyl ketone (MIBK)
extraction. Recommended values for palladium
were not found in the litterature for GXR's and
so reliability could not be evaluated. However,
the precision for Pd determinations observed
from replicate weighings was very good.
Despite good agreement with the values of
Meier (1980), the small size of the analytical
sample is a disadvantage in the above method
and thus the poor representativeness of samples
with coarse gold grains. On the other hand, the
use of small samples is an advantage in
analysing ashes of organic materials. As we can
assume that gold exists homogeniously in organic material, there is no need to collect and
burn big samples.
The method seems to be very suitable for
determining the background contents of gold and
palladium in silicate rocks (Kontas et al., 1986)
and other geological materials. The detection
limits are low enough for many purposes. Contamination by reagents is improbable, because
their amounts are small and they are generally
very pure. Except for platinum-rich samples,
partial attack with aqua regia after roasting
usually ensures almost total dissolution of gold

and palladium from geological materials of
different composition (Signiholfi et al. 1984).
This method is mainly used for the geochemical exploration of gold and palladium, of which
the latter is a good pathfinder element for all
platinum-group metals. The main sample materials are fine till fraction (-0.064 mm) and bedrock. Stream sediment, peat and vegetable samples have also been analysed.
Carbon and graphite are the matrix substances, that cause the worst interference as they
adsorb the gold from solutions quantitatively
(Lakin et al. 1974). Fortunately, even small amounts are easily detected at the digestion stage,
and new portions can be taken and roasted before the digestion. The ashes of organic samples
often contain finely divided carbon which can be
destroyed with hydrogen peroxide. Therefore
hydrogen peroxide is used instead of nitric acid
as the oxidizing agent for ashes.
Samples exceedingly rich in iron oxides or
base metal sulphides are somewhat troublesome
since sample solutions become concentrated in
iron or other metals, which severely interfere
with the separation. This difficulty can be avoided by taking a fifth or tenth part of the sample
solution for follow-up analysis. The detection
limits are then five or ten times higher, respectively. In favourable cases the detection limit is
0.1 ppb for gold and 0.5 ppb for palladium. The
capacity is about 2000 samples per one month
and two persons.
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of hrvestigation 114, 1993
E. Kontas
Table 2. Gold and palladium concentrations of GXR reference samples (aritmetic meanrtstandard deviation). Recommended values
after Gladney and Burns (1984) and the results obtained by Meier (1980).
Au P P ~
S ample
GXR l
GXR 2
GXR 3
GXR 4
GXR 5
GXR 6
No. of
det's
Recommended
values
3 1005200
46f 19
3-600
440rt160
80560
70rt10
3
3
3
3
5
The method is easy to modify. If necessary

digestion can be intensified by heating; the
sample weight can be increased and an aliquot
taken for follow-up analysis. Nowadays the
Pd P P ~
Meier
This work
This work
2950
22
3
353
7
63
3 1005200
10.0rt0.3
2.4rt1.7
419rt14
7.0rt0.9
86+6
0.1
0.1
0.2
0.2
0.4
2.2
method is run on the basis of a 20 g sample.

Results are in good agreement with those obtained by fire assay method (Appendix).
REFERENCES
Barnard E. & Zeeman P. B. 1958. Die Konsentrering en
Spektrgrafiese Bepaling van Edelmetale Gesteendes en
Rotse. Tegnikon 1 1, 2, 63-69.
No 2, 119-154.
Kontas E. 1981. Rapid determination of gold by flameless
atomic absorption spectrometry in the ppb and ppm ranges without organic solvent extraction. At. Spectr. Vol. 2,
NO 2, 59-61.
Kontas E., Niskavaara H. & Virtasalo J. 1986. Flameless
atomic absorption determination of gold and palladium in

geological reference samples. Geostandards Newsletter
Vol. 10. NO 2, 169-171.
Lakin H. W., Curtin C. G. & Hubert A. E. 1974. Geochemistry of Gold in the Weathering Cycle. U. S. geol.
Surv. Bull. 1330, 80 p.
Meier A. L. 1980. Flameless atomic absorption determination of gold in geological materials. J. Geochem. Expl.
13, 77-85.
Signiholfi G. P., Gorgoni C. & Mohamed A. H. 1984.
Comprehensive analysis of precious metals in some
geological standards by flameless A. A. spectroscopy.
Geostandards Newsletter, Vol. 8, No 1, 25-29.
Analytical methods for determining gold i n geological samples

Geologian tutkimuskeskus, Tutkimusraportti Geological Survey of Finland, Report of bzvestigation 114, 33-37,
1993
GOLD
bY
R. J. Rosenberg, Riitta Zilliacus and Maija Lipponen
R. J. Rosenberg, Riitta Zilliacus and Maija Lipponen. 1993. Neutron

activation analysis of gold in geochemical samples. Geologian
tutkimuskeskus, Tutkimusraportti - Geological Survey of Fiiinlatzd, Report
of Irwestigation 114, 33-37, 2 tables.
The analytical techniques used for the analysis of gold in geochemical
materials at the Reactor Laboratory of the Technical Research Centre of
Finland are described. These are epithermal instrumental neutron activation
analysis of solid samples, thermal neutron activation analysis of freezedried water and snow samples and radiochemical neutron activation
analysis of inorganic and organic samples. The detection limits are 3 ppb,
5 ng/l and 0.1 ppb, respectively. The accuracy and capacity of the methods
are discussed.
Key words (GeoRef Thesaurus, AGI): chemical analysis, gold, till, methods, reliability
R. J. Rosenberg, Riitta Zilliac~isand Maija Lipponen

Technical Research Centre of Firilnnd
Reactor Laboratory
SF-021 50 Espoo, Finland
INTRODUCTION
At the Reactor Laboratory gold is determined

from geological samples on an analytical service
basis. The annual number of samples has been
about 13,000 since 1982. The main customers
are mining companies, geological surveys and
universities in Finland and Sweden.
Three methods are in use: Instrumental
epithermal neutron activation analysis (ENAA)
for pulverized samples. With this technique 23
other elements are determined simultaneously
with gold (Rosenberg et al. 1982). Thermal neutron activation analysis (NAA) for water sam-
ples evaporated by freeze-drying. Radiochemical

neutron activation analysis (RNAA) for very low
gold concentrations, especially in biological
materials (Zilliacus 1983). Because the number
of samples needed in geochemical exploration is
fairly large the cost must be reasonable. The low
limit of detection is also critical if all anomalies
are to be detected. Therefore special emphasis
was laid on detection limit and cost in addition
to accuracy. The analytical techniques and the
organization of the work are described in the
following.
Geologiau tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of btvestigatiort 114, 1993
R. J. Rosenberg, Riitta Zilliacus and Maija Lipporterr
EXPERIMENTAL
Standards
Two different kinds of standard are used.

Solutions of gold are used for the analysis of all
except pulverized geological samples. Stock
solutions of 1000 ppm are prepared by dissolving metallic gold in aqua regia. Suitable dilutions are made with deionized water before use.
Powdered standards prepared according to the
procedure of Date (1977) are used for ENAA. A
solution of gold is dissolved in ethylene silicate

with the aid of ethanol. This mixture is hydrolyzed with ammonia, dried and ignited so as to
yield a dry silicate powder homogeneously
doped with gold.
A composite standard containing several other
elements is usually prepared.
Equipment
A Triga Mk I1 research reactor is used for
irradiations. The reactor is run for about 7 h per
day from Monday to Friday. Sometimes Monday
is needed for service work. The rotary specimen
rack contains 40 irradiation positions. The thermal flux is 1.2 xlO1' cm-'s-' and the Cd ratio for
gold is 2. Twenty of the positions are used for
thermal irradiations and twenty for epithermal
irradiations. The epithermal flux is obtained by
using containers of aluminium 30 cm X 25 cm in
size, lined with 1 mm of cadmium and again
with 0.2 mm of aluminium. These containers are
permanently located in the reactor and are only
taken up to change samples. One container holds
32 capsules of 0.5 ml, and thus 640 sam-
ples can be irradiated simultaneously in an

epithermal flux. For RNAA the samples are
irradiated in the central thimble, where the thermal neutron flux is 1013cm-'s-l.
Measurements are performed with automatic
gamma-spectrometers comprising a Ge(Li) or Ge
detector with auxiliary electronics, a sample
changer, a multichannel analyzer, a microcomputer and inputloutput devices (Vanska et al.
1983, Rosenberg et al. 1985). Such a system
measures a series of samples automatically and
simultaneously calculates the elemental concentrations which are printed on paper and cassette.
Five gamma-spectrometers of this kind are
available for activation analysis.
Procedure for ENAA
The standards and powdered samples are

weighed into polyethylene capsules with an
inner volume of 0.5 ml. Thus the sample size is
0.5-1 g, depending on the density. The samples
are transported and stored in styrox boxes holding 100 capsules each. The samples are often
weighed by the customers, and a list of the
weights accompanies the box on its arrival at the
laboratory. 32 capsules, four in a plane, are
wrapped in aluminium foil. One irradiation
series comprises four standards, 12 control samples and 144 samples. These are inserted into
cadmium containers. The samples are irradiated
for one week (25-35 h) and measured after a
decay time of 4-5 days with an automatic gamma-spectrometer. The measurement time is 20
min per sample. Thus measurement of one series
takes almost two and a half days.
The 41 1.8 keV of l g 8 ~isuused for calculating

the results. The half-life is 2.7 days. A peak
with a statistical error of 30% or less is accepted. If a peak is not found, the upper level is calculated according to the principles of Currie
(1968). The detection limit for most sample
types is 3 ppb.
The work is organized in such a way that two
series are inserted in the reactor on Monday
morning and two on Thursday morning. The two
series taken out of the reactor are allowed to
decay and thenloaded onto the sample changer on
Wednesday and Monday, respectively. Thus two
gamma-spectrometers are needed for analysing
576 net samples per week. During week-ends the
analyzers are free for other measurements. Excluding the weighing, one person can handle
these samples and wrap them in aluminium foil,
Neutron activation analysis of gold in geochemical samples
load and unload them into and out of the reactor

and sample changers, and the prepare the data
files. The sample codes and weights are printed
on floppy discs from which they are copied onto

a cassette for input into the memory of the computer at the start of a measurement series.
Procedure for NAA of water samples

Melted snow and ice as well as water samples
are preconcentrated by evaporation before irradiation. This is performed by freeze drying. The
samples are collected into polyethylene bottles
and then preserved with the addition of 1 m1 of
suprapure nitric acid (Merck) per litre of water.
200 m1 of sample is dropped onto a sheet of
polyethylene foil in a Petri beaker and freeze
dried with a WKF L 0 5 lyophilizer. This takes
about 40 h. Standards and blanks are treated in
the same way. The polyethylene sheets are
wrapped and inserted in polyethylene capsules

for irradiation. Then the samples are irradiated
for 25 h in a thermal flux of 1 . 2 ~ 1 0 ~ ~ c m - ~ s - ~ .
After a decay time of five days the samples are
measured with an automatic gamma-spectrometer. The measurement time is 1 h per sample.
The average blank is 1 ng and thus an effective
detection limit using 200 m1 samples is 5 ngll.
The number of samples is limited by the low
capacity of the lyophilizer. Only 15 samples a
week can be dried.
Procedure for RNAA

This method is intended for solid geochemical
samples when concentrations lower than 3 ppb
have to be determined. Because the method is
more expensive than the instrumental ENAA, it
is used more seldom. The method is also suitable for plants and other organic materials. The
method has been described in detail by Zilliacus
(1983) and in this context will be described only
briefly. 2 0 0 4 0 0 mg samples are weighed into
ampoules of quartz and irradiated for 25 h in a
thermal neutron flux of 10i3 ~ m - ~ s -After
'.
a
decay time of 2 - 4 days the samples are subjected to chemical separation. 1 mg of gold
carrier is added. Mineral samples are dissolved
in hydrochloric acid followed by aqua regia. The
sample is evaporated to dryness three times with
aqua regia. Organic samples are first wet-ashed
with nitric acid and hydrogen peroxide and then
treated with aqua regia. After this 2 m1 of satu-
rated boric acid solution are added to the dry

sample followed by 3 m1 of hydrochloric acid.
The sample is diluted to 20 m1 with water and
filtered through 50 mg of activated carbon
through a chimney. The carbon is washed with
Cr-carrier solution and water. The filter papers
are inserted into polyethylene capsules and measured with an automatic gamma-spectrometer.
The measurement time is 2 h.
The yield of the chemical separation is determined by reactivation. It varies between 60 and
90%. The detection limit for gold is 0.04 ng
corresponding to 0.1 ppb in a sample when a
400 mg weighing is used.
The method is rather fast. One person can
make 12 separations per day and the same number of samples can be measured with one counting system.
Evaluation of the method

There are a number of possible sources of
error in activation analysis. Some of these can
be avoided almost completely and others only at
unreasonable expense. In the following these
sources are discussed in some detail, and the
overall accuracy of the techniques is evaluated.
The discussion applies mainly to ENAA be-
cause this is the principal technique in use. The

specific problems of the other techniques are
discussed at the end of this chapter. The subjects
discussed here are:
1) representativeness of the sample,
2) contamination,
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finlnnd, Report of Investigation 114, 1993
R. J. Rosenberg, Riitta Zilliacris and Maijn Lipponen
Table 1. The gold concentrations in the US Geological Survey geochemical standards (GXR 1-6) according to this work (ENAA and
RNAA, RNAA from Zilliacus 1983) and other authors (in ppm). Allcott a is the arithmetic mean of 50 determiuations and b the arithmetic mean of 76 determinations. Maier a was made by flame and b by graphite furnace atomic absorption spectrometry.
ENA A
RNAA
Allcott 1974 a
- "- 1974 b
Motooka 1979
Kontas in this issue
Maier 1980 a
- "- 1980 b
Gladney 1984
3)
4)
5)
6)
7)
8)
GXR l
GXR 2
GXR 4
GXR 5
3.6k0.2
3.65
2.8
3.7
3.4
3.1
3.0
2.95
3.1k0.2
0.03 3kO.004
0.031
0.038
0.056
0.52k0.02
0.52
0.58
0.74
0.65
0.419
0.35
0.353
0.44k0.16
0.01 l + 0.002
0.008
0.12
0.058
0.010
0.070
0.022
0.046+0.019
neutron flux distribution,

neutron absorption,
competitive reactions,
counting geometry,
peak evaluation and
counting statistics.
The small sample size, 0.5-1 g, causes a

problem in some cases because of the
inhomogeneous distribution of gold in many
samples. But, according to investigations by the
authors, increasing the sample size from 1 g to
10 g does not significantly alter the situation.
Contamination is a special problem in analysing gold. The reasons for this are the low
concentrations dealt with and the fact that so
many people wear gold rings. Metallic gold is
soft and contaminates easily. Contamitions of
different kind have been encountered during the
work. In some cases the samples themselves
have been contaminated during preparation and
sometimes the surfaces of the polyethylene
capsules have been contaminated during weighing. The only way to avoid this is to control
rigorously that people handling the samples are
not wearing gold rings.
The production of the radionuclide on which
the analysis is based depends on the neutron
flux reaching the gold atoms. Variations in this
flux can be caused by the natural variation of
the flux in the reactor and neutron absorption in
the sample itself. The neutron flux varies by
tens of percent depending on irradiation positions. Most of this can be compensated by mapping the flux and inserting flux monitors. But it
would be too expensive to measure the flux
separately for every sample. The horizontal flux
variation inside a cadmium container is little
more than 5% and because the positions of the
samples in the reactor cannot be controlled the
error caused by this variation is not compen-
GXR 6
0.007
0.007
0.080~0.060
sated.
Another problem is neutron absorption in the
sample. This is a problem specific to gold. Gold
is usually present in the form of small grains.
Therefore the resonance neutron neutron absorption in these grains may be significant, even if
the average concentration is small. Because the
grain size cannot be controlled, this error cannot
be controlled either. In average gold concentrations of less than 1 ppm it has not been of significance. But in some cases intercomparisons
with other analytical techniques have shown a
10% negative error in concentrations of 10 ppm
or higher.
Competitive reactions are no problem for
gold. Errors in the counting geometry may be
caused by variations in the sample position
during measurement and variations in sample
size. Sample positioning by the sample changer
is precise, and customers are requested to B11 the
capsules to avoid variations in sample size.
The only possible spectral interference is
~ ~ a, europium concentration of
caused by 1 5 2 but
50 ppm is needed to give the number of counts
corresponding to the detection limit, 3 ppb of
gold. Such europium to gold ratios are highly
unlikely. Because the peak of gold is situated on
an undisturbed smooth part of the Compton
continuum in geological samples, evaluation of
the peak area causes no significant errors apart
from that caused by the counting statistics,
which depends on the sample type and gold
concentration.
When water samples are analysed, two additional problems arise: the possible loss of gold
during handling and the high risk of contamination because of the extremely low concentrations. Investigations with tracers have shown
that no loss occurs through absorption on the
walls of the collection vessel or during evaporation. The polyethylene foils onto which the
Neutron activation analysis of gold in geochemical samples
samples are evaporated contain gold and therefore a blank cannot be avoided. The blank varies
between 0.6 and 1.2 ng per 200 m1 sample, leading to a corresponding uncertainity in the analysis.
In RNAA the special problem is the variable
yield of the separation. This is corrected as
described and does not cause an additional error.
The results of control samples were monitored
to investigate the average precision of the method. 26 samples were chosen at random from
runs during two months. The result was as follows. The nominal concentration of the sample
is 0.59 ppm. The mean of 26 determinations was
0.586 ppm, and the standard deviation
0.028 ppm. Consequently, the average relative
precision at the 95% confidence level is +9.8%.
Because of the random character of this error
Table 2. Results of an intercomparison conducted by IAEA

(1985). The sample is marine sediment SD-N-112.
This work
Other laboratories
the error caused by counting statistics starts

influencing the total precision significantly from
60 ppb downwards. Theoretically a total precision of +1.7% is reached at 30 ppb and +22% at
10 ppb at the 95 % confidence level.
The overall reliability of the method was
investigated by analysing standard reference
samples and by making intercomparisons.
REFERENCES
Allcott G. H. & Lakin H. W. 1975. The homogeinity of six
geochemical exploration reference samples. Pp 659-681
in Geochemical Exploration 1974, ed. by I. L. Elliott and
W. K. Fletcher. Elsevier Scientific Publishing Co. Amsterdam, 720 p.
Currie L. A. 1968. Limits for quantitative detection and
quantitative determination. Anal. Chem. 40, 586-593.
Date A. R. 1977. Preparation of trace element reference
materials by a CO-precipitatedgel technique. Institute of
Geological Sciences, Geochemical Division, Analytical et
Ceramics Unit, Report No 101. 16 p.
NO. 2, 119-154.
Intercomparison of trace element measurements in marine sediment sample SD-N-112. International Atomic
Energy Agency, Report No 24, 18 p.
Meier A. L. 1980. Flameless atomic absorption determination of gold in geological materials. J. Geochem. Expl.
13, 77-85.
Motooka J. M., Mosier E. L., Sutley S. J. & Viets J. G.
1979. Induction-coupled plasma determination of Ag, Au,
Bi, Cd, Cu, Pb and Zn in geological materials using a selective extraction technique - preliminary investigation.
Appl. Spectr. 33, 456-460.
Rosenberg R. J., Kaistila M. & Zilliacus R. 1982. Instrumental epithermal neutron activation analysis of solid
geochemical samples. J. Radioanal. Chemistry 71,
419-428.
Rosenberg R. J. & Vanska L. 1985. STOAV84, a computer
program for an automatic gamma spectrometer used for
activation analysis. Technical Research Centre of Finland, Research reports No 415, 49 p.
Vanska L., Rosenberg R. J. & Pitkanen V. 1983. An automatic gamma spectrometer for activation analysis. Nuclear Instruments and Methods 213, 343-347.
Zilliacus R. 1983. Radiochemical neutron activation analysis of gold. Radiochemical and Radioanalytical Letters
57, 137-144.

Geologian tutkimuskeskus. Tutkimusraportti Geological Survey of Fidand, Report of I~westigation114, 39-41,
1993
GOLD CONCENTRATIONS OF SOME REFERENCE

SAMPLES - DISCUSSION
bY
E. Kontas
Kontas, E. 1993. Gold concentrations of some reference samples - discussion. Geologian tutkimuskeskus, Tutkimusraportti -Geological Survey
of Finland, Report of bzvestigation 114, 39-41, 3 tables.
The gold concentrations of five reference samples, AAV-1, AAV-2,
AAV-3, SUK-1 and SUK-2 were determined in six laboratories using the
methods described in this volume. The sample material was the fine
fraction of till (-0.064 mm); all samples contained metallic gold grains.
The sample weights ranged from 0.6 to 50 g, depending on the procedure.
Several determinations were made in each laboratory. When the highest
and lowest outlier values for each sample were omitted, the following
ranges of gold concentrations were obtained: AAV-1, 24-120 ppb; AAV2, 198-1100 ppb; AAV-3, 127-1000 ppb; SUK-1, 19-83 ppb; and
SUK-2, 28-95 ppb. The variations were greatest for the samples with the
lowest weights. However, anomalously high gold values were found in
every determination at all laboratories.
From the capacities, detection limits and representativeness of the
analytical samples, the best applications of the methods are as follows: fire
assay with sample weights of 25-50 g for the assessment of gold deposits, analysis of concentrates and quality control when cheap methods are
called for; methods based on aqua regia digestion and solvent extraction
with sample weights of 5-20 g for the analysis of ores and local geochemical prospecting; the method based on aqua regia digestion and separation by coprecipitation with a l-g sample weight for regional geochemical mapping, preliminary prospecting and some basic research; instrumental neutron activation analysis (NAA) with a sample weight of about 0.6 g
for regional geochemical prospecting and some special analyses.
Key words (GeoRef Thesaurus, AGI): chemical analysis, gold, till, methods, reliability
E. Kontns. Geological Survey of Finland

P . 0 Box 77
SF-96101 Rovaniemi. Finland
INTRODUCTION
To help readers and clients compare the different analytical methods described in this volume, five reference samples were prepared at the
laboratory of the Geological Survey of Finland
(Rovaniemi), and subsequently submitted to

analysis at the six participating laboratories.
Since laboratories employ several methods for
analysing gold, the methods were divided be-
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of bnlestigation 114, 1993
E. Kontas
tween the laboratories to cover as many as possible of the procedures required by this study.
The samples were known to contain varying
amounts of gold, at least partly in native grains.
The analysed sample material consisted of the
fine fraction of till (-0.064 mm) commonly
used in prospecting for gold and base metals in
all Fennoscandian countries, Canada and parts of
the United States.
Gold typically occurs in till as native grains
varying greatly in size. The maximum size is
defined by the mesh number of a sieve, but not
absolutely, because the oblong or threadlike

shape of the grains enables even larger grains to
pass the sieve. The representativeness of the
analytical portion is a problem, as it is dependent not only on the grain size but also on the
grade of gold in a sample (Clifton et al. 1969).
In addition, it is very difficult to homogenize
such samples, because the gold grains separate
gravitatively in the sample powder. The fine
fraction of till consists mainly of minerals of
very low density; gold, however, has the highest
density of all minerals.
SAMPLE PREPARATION
The samples, each weighing about 40 kg,

were collected from Outokumpu Oy prospects in
Kittila district, Finnish Lapland. The material is
till, much of it of local origin.
Samples AAV-1, AAV-2, AAV-3, SUK-l and
SUK-2 were dried at 70C, after which the
-0.064 fraction was sieved for chemical analy-
ses. Two 250 g aliquots of the fine fractions

were sent to each laboratory for analyses. The
homogeneity of aliquots was studied by
analysing them for base metals (Cu, Mn, CO
etc.). These elements turned out to be very
homogeneously distributed in the different batches.
RESULTS AND DISCUSSION
The precisions are clearly poorest with the

methods which used the smallest sample
weights. In some the variations are even significant with greater sample weights. The "real"
gold contents of all aliquots were probably not
exactly the same.
The results suggest (Table 1) that the analytical portions of the samples studied in this work
should be about 10 g or more, if relative standard deviations of f 5 0 % or below are aimed at.
The methods of Kontas used both l-g and 9-g
portions of samples. The results (Table 1) show
that precision improved dramatically when larger analytical samples were used. The results of
the two fire assay procedures, with 30-g and
50-g samples, showed almost ideal agreement.
Generally, when subsampling is deficient, analytical results tend to be too low rather than too
high (Ingamells and Switzer 1973, Ingamells
1981).
Very important characteristics of analytical
methods for gold are detection limit, capacity,
the representativeness of the analytical portion
and the costs per analysis. The costs are difficult
to estimate, since the prices of instruments and
other equipment vary markedly. Generally, large

capacity and little need for attendance mean low
costs per analysis.
The general trend is that the higher the capacity, the lower the weight (Table 2). At the same
time, the representativeness of the analytical
portion declines, which is a serious drawback of
these effective methods. But different methods
are applicable for different purposes. When gold
ores or gold bearing concentrates are analysed,
representativeness, precision and accuracy are
the most important criteria. A detection limit of
0.05-0.1 ppm is usually low enough and a
lower capacity is acceptable. A very high capacity and a low detection limit are particularly
important in geochemical exploration. The feasibilities of different procedures are evaluated i n
Table 3.
In general, a low detection limit is necessary
in basic research because the background values
of gold in geological materials are usually very
low. A small analytical portion is not always a
disadvantage, because the gold at background
levels is often homogeneuously distributed.
Gold concentrations of some reference samples - discussion
Table 1. Gold concentrations (Au ppb) in reference samples AAV-I. AAV-2, AAV-3, SUK-1 and SUK-2 determined by different
laboratories. (arithmetic mean 5 standard deviation).
Procedure
2A
Sample weight g
Numb. of det's
AAV- 1
AAV-2
AAV-3
SUK-1
SUK-2
0.6
8
49518
398rt262
4595362
2757
33rt10
1
6
4 852 8
7455435
6035522
44rt22
3 858
9
3
3956
699577
636567
3059
4551 l
Procedures: 1 Rosenberg et al., 2 and 2A Kontas, 3 Ojaniemi, 3A Ojaniemi, lead fire assay, 4 Penttinen, 5 Noras, 6 Juvonen and
Vaananen.
Table 2. Some important characteristics of the analytical methods for gold described above.
Table 3. Evaluation of the best applications of different analytical methods for gold.
Procedure
Juvonen and Vaananen

Noras
Penttinen
Ojaniemi
Kontas
Rosenberg et al.
Size of
of team
4
2
3
2
2
2
Capacity
samples1
week
Sample
weight
Det.
limit
Method
Applications
P P ~
Juvonen and Vaananen
150
200
3 00
400
5 00
570
25-50
20
10
0.1
0.05
0.05
0.02
0.0001
0.003
Assessment of gold deposits and

analysis of concentrates, quality
control
Analysis of ores, local geochemical
prospecting
Analysis of ores, local geochemical
prospecting
Geochemical prospecting, analyses
of gold and platinum ores
Regional geochemical mapping and
preliminary prospecting, basic research
Regional geochemical prospecting
and mapping, special analyses
5
1
0.5-1
Noras
Penttinen
Ojaniemi
Kontas
Rosenberg et al.
REFERENCES
Clifton E. H., Hunter R. E., Swanson F. J. & Phillips R.
L. 1969. Sample size and meaningful gold analysis. U. S.
Geol. Surv. Prof. Paper 625-C, 17 p.
Ingamells C. 0.& Switzer P. 1973. A proposed sampling
constant for use in geochemical analysis. Talanta, 20,
547-568.
Ingamells C. 0. 1981. Evaluation of skewed exploration
data - the nugget effect. Geochim. Cosmochim. Acta,
45, 1209-1216.
APPENDIX. The effect of sample weight and digestion and separation method on the results of gold
determinations.
Effects of sample weights and digestion and separation methods on the detection of gold were
studied by analysing 137 samples collected from 53 gold deposits and their host rocks (Nurmi et al.,
1991). With some exceptions, the samples were taken from drill core profiles: one sample from the
orebody itself and one sample from either side of it. Gold contents were determined from samples
weighing 1 and 20 g, using aqua regia digestion and stannous chloride-mercury coprecipitation as
a separation method (Kontas, this volume). Sample weights of 20 and 25 g were used in the lead fire
assay method (XRAL, Canada, Juvonen and Vaananen, this volume).
The results show that gold ores and their closest haloes in the bedrock can generally be detected
with all the sample weights used. Therefore a quick and effective method with a sample weight of
1 g would seem to be very useful in reconnaissance prospecting for gold. However, even the sample
weight of 20 g does not always seem to be reliable for the inventories of gold deposits.
Table 1. Gold concentrations (in ppb) in 53 gold deposits and their closest haloes in bedrock. Aqua regia digestion method with sample weights of 1 and 20 g (Kontas, this volume). Lead fire assay with sample weight of 20 g (XRAL, Canada) and 25 g when the gold
concentration exceeds 10000 ppb (Juvonen and Vaananen, this volume).
Method:
Sample:
Aqua regia, GFAAS

1g
Aqua regia, GFAAS

20 g
Gold deposit
Mont Charlotta
New Celebration
MA-la, CANMET #
Hoyle Pond
Owl Creek
Kerr Addison
Renabie
Ferderber
Page Williams
Lokkiluoto
_"_
Muurinsuo
-'l-
Korvilansuo
Ramepuro
Kuittila
_"_
- -
Lalleanvuoma
-'l-
-Sukseton
n. d. = not determined
# = Reference sample, CCRM, MA-la, recomended value for gold 21400+400 ppb.
Lead fire assay

20 or 25 g
Table 1. (continued.) Gold concentrations (in ppb) in 53 gold deposits and their closest haloes in bedrock. Aqua regia digestion
method with sample weights of 1 and 20 g (Kontas, this volume). Lead fire assay with sample weight of 2 0 g (XRAL, Canada) and
2 5 g when the gold concentration exceeds 10000 ppb (Juvonen and Vaananen, this volume).
Aqua regia, GFAAS
1g
Method:
Sample:
Aqua regia, GFAAS

20 g
Gold deposit
Kivimaa
_'l_
_"_
Suurikuusikko
Hirvilavanmaa
_"_
_'I_
Rovaselka
- -'l-
Saattopora N
_"_
_"_
Saattopora S
- - Isokuotko
- - Soretiavuoma
- - Sirkka W
_'I_
Bidjovagge
Juomasuo
-Saynajavaara
-Sivakkaharju
-Konttiaho
"_
Makararova
_"_
Laivakangas
- - -
Jokisivu
- - Isovesi
"_
- Antinoja
-Vesipera
_"_
~n~esueva
_"_
- n. d. = not determined
# = Reference sample, CCRM, MA-la, recomended value for gold 21400!~400 ppb.
Lead fire assay

20 or 25 g
Table 1. (continued.) Gold concentrations (in ppb) in 53 gold deposits and their closest haloes in bedrock. Aqua regia digestion
method with sample weights of 1 and 20 g (Kontas, this volume). Lead fire assay with sample weight of 20 g (XRAL, Canada) and
25 g when the gold concentration exceeds 10000 ppb (Juvonen and Vaananen, this volume).
Method:
Sample:
Gold deposit
Kiimala
_l1_
Pirila S
_rl_
_tp_
Kalliosalo
_I(_
-l1-
Kurula
- -
--
Pirila N
- - Kaapeliukulma
-II-
- Laivakangas S
- - Pohlola
_l1_
-lt-
Kopsa
- Kangaskyla
- Osikonmaki E
_qv_
-Osikonmaki W
- - Bjorkdahl
Aqua regia, GFAAS

1g
Aqua regia, GFAAS

20 g
Lead fire assay

20 or 25 g
100
1600
30
40
12000
10
160
2650
60
100
32000
60
280
6700
120
80
1280
300
240
3100
40
210
3250
260
450
3500
120
410
12800
60
410
3 800
340
2300
520
540
7000
1280
620
5400
270
2850
170
2600
62
60
9500
56
3 40
7500
90
72
1100
240
260
2800
64
240
3200
140
3 60
5500
100
320
12500
49
310
3500
280
2000
340
550
7000
l200
680
5000
430
3600
210
5000
30
40
1000
100
100
1700
30
100
1700
70
200
3900
10
840
8800
40
890
2400
290
2100
250
350
5800
2060
350
3400
100
1000
n. d. = not determined
# = Reference sample, CCRM, MA-la, recomended value for gold 21400rt400 ppb.
REFERENCE
Nurmi P. A., Lestinen P. & Niskavaara H. 1991. Geochemical characteristics of mesothermal gold deposits in
the Fennoscandian shield, and a comparison with selected
Canadian and Australian deposits. Geol. Surv. Finland,

Bulletin 351, 101 p.

Analytical Methods For Determining Gold

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GEOLOGIAN TUTKIMUSKESKUS

GEOLOGICAL SURVEY OF FINLA

Esko Kontas (ed.)

ANALYTICAL METHODS FOR DETERMINING GOLD IN GEOLOGICAL SAMPLES

Esko Kontas, Geological Survey of Finlmd, P.O.Box 77,SF-96101 Rovmtiemi, Finland

Analytical methods for determining gold in geological samples

Kontas E. 1993. Analytical methods for determining gold in geological

lead fire assay

(Abbreviations: AAS = atomic absorption spectrometry, FAAS = flame AAS,

For the evaluation of methods, five internal reference samples prepared

Key words (GeoRef Thesaurus, AGI): chemical analysis, gold, sample

Esko Kontas, Geological Survey of Finland, P.O.Box 77, SF-96101

The mineralogical mode of occurrence of gold in

the sample (Harris 1982, Riddle 1983, Burn 1984).

ver, copper or platinum-group metals. Some gold

Geologian tutkimuskeskus, Tutkimusraportti

- Geological Survey of Finland, Report of I~zvestigation114, 1993

bismuthides are also known. But the predominant ore

occurs uniformly in grains as large as the maximum

where b is the relative standard deviation of the

where Z is defined as Cd3. The sampling constant C

Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of I?zvestigatio~t114, 1993

facilities often restrict the use of large analytical

In practice, when gold explorations begin in a new

Geologian tutkimuskeskus, Tutkimusraportti

The relative depletion of gold during the usual

of Firrland, Report of brvestigatiorz 114, 1993

Table 2. Gold concentrations in 20 g portions of cleaning quartz

Au i n quartz after cleaning

Sample 1 = copper concentrate with 32.0 ppm Au,

GOLD RING CONTAMINATION

Experiences has shown that a gold ring may be a

REVIEW ON ANALYTICAL METHODS

The physical preparation of samples is usually

Neutron activation analysis is the only method that

lector in the fire assay of noble metals (Robert et al.

Fire assay for gold uses reductive fusion and the

dissolution of gold from geological materials when

regia (Rubeska et al. 1977). Hydrobromic acid with

Separation and preconcentration

Hoffman E. L., Naldrett A. J., Van Loon J. C., Hancock

Kontas E. 1991. Gold contamination of the fine fraction of

Analytical methods for determining gold in geological samples

Juvonen, R. & Vaananen, P.J. 1993. Determination of gold in geological

sary because of the uneven distribution of gold

REAGENTS AND APPARATUS

4) Atlantic-Schmelztiegel GmbH, fusion crucibles, roasting dishes and cupels,

Geologiau tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of I~westigation114, 1993

Riitta Juvonen and Pnavo J. ViiZi~zlinen

palladium standard solutions and

A 25 g sample of ground rock is mixed well

for both operations.

THE LEAD FIRE ASSAY METHOD

Extraction of noble metals into lead

lead globules will remain in the slag, resulting

SCORIFICATION OF THE LEAD REGULUS

The lead regulus may be further purified by a

about 1 g of borax is put into a shallow

placed on the cupels. The regulus melts almost

DETERMINATION OF NOBLE METALS

In the conventional method of analysis, the

Table 1. Graphite furnace programme for palladium and platinum.