Professional Documents
Culture Documents
Tutkimusraportti 114
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
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
1993
ODS FOR DE
GOLD IN GEOLOGICAL SA
by
Esko Kontas
Digestion
Separation
25-50
20
10
5
1
0.6
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
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of Investigation 114, 1993
Esko Kontas
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).
SAMPLE REPRESENTATIVENESS
Gold occurs in nature most commonly as native
grains or as the main component of alloys with sil-
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
- Geological Survey
Amount
of quartz
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
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.
Decompositon of samples
Fusion
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finlmzd, Report of htvestigation 114, 1993
Esko Kontas
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).
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of Investigation 114, 1993
Analytical methods for determining gold in geological samples
REFERENCES
Beamish F. E. 1966. Analytical Chemistry of the Noble
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.
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
metals. I. Sample decomposition and methods for separation. Trends Anal. Chem. 3, 10, 272.
Van Loon J. C. 1985. Accurace determination of the noble
metals. 11. Determination methods. Trends Anal. Chem.
4, 1, 24.
Warren V. H. & Horsky S. J. 1986. Thallium, a
biogeochemical prospecting tool for gold. J. Geochem.
Expl. 26, 215-221
Wedepohl K. H. Editor, 1969-1978. Handbook of Geochemistry, Vol. 11-4. Springer Verlag, Berlin.
1993
D IN GEOLOG
MATERIALS
EAD FIRE ASSAY SE ARATION
by
Riitta Juvonen and Paavo J. Vaananen
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-
EXPERIMENTAL
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
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
Furnace
temperature
"C
Time
Ramp
Hold
Internal
gas flow
ml/min
Palladium
1
2
3
4
5
Platinum
1
2
3
4
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of Investigation 114, 1993
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
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
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.
1993
by
P. Noras
INTRODUCTION
grade,
2) apparatus: Furnace for calcination (maximum
- Geological Survey
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
EXTRACTION
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
DISCUSSION
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.
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of Investigation 114, 1993
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
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.
Key words (GeoRef Thesaurus, AGI): chemical analysis, techniques, gold,
palladium, atomic absorption, sample preparation, reagents, accuracy
U. Penttinen, retired
Outokurnpu Metals & Resources
Geoanalytical Laboratory
P.O.Box 74, SF-83501 Outokunnpu, Finland
INTRODUCTION
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.
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
Number of
det's
This
work
Stand.
dev.
Coeff. of
var. %
Recommended
value
REFERENCES
Parkes A. & Murray-Smith R. 1979. A rapid method for
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.
1993
bY
E. Ojaniemi
E. Ojanienzi
Rautaruukki CO,Research Centre
SF-92170 Raahe
Finland
INTRODUCTION
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-
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of Investigation 114, 1993
E. Ojanietni
2 M HCI.
Instruments:
EXTRACTION OF PLATINUM
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.
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of Investigation 114, 1993
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.
INT.FLOW
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-
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
Parkes A. & Murray-Smith R. 1979. A rapid method for
the determination of gold and paIIadium in soils and
rocks. At. Abs. Newsl. Vol. 18, No 2. 25-27,
1993
DETERMINATION 0
DIGESTION
REG
by
E. Kontas
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-
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of Investigation 114, 1993
E. Ko~ttns
Apparatus :
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of Investigation 114, 1993
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.
depend on the detection limits required. The instrument parameters are presented in Table 1.
DISCUSSION
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
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
REFERENCES
Barnard E. & Zeeman P. B. 1958. Die Konsentrering en
Spektrgrafiese Bepaling van Edelmetale Gesteendes en
Rotse. Tegnikon 1 1, 2, 63-69.
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.
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
1993
GOLD
bY
R. J. Rosenberg, Riitta Zilliacus and Maija Lipponen
INTRODUCTION
Geologiau tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of btvestigatiort 114, 1993
R. J. Rosenberg, Riitta Zilliacus and Maija Lipporterr
EXPERIMENTAL
Standards
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-
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of Investigation 114, 1993
Neutron activation analysis of gold in geochemical samples
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
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
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of Investigation 114, 1993
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
Other laboratories
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.
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.
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.
1993
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
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
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
SAMPLE PREPARATION
Geologian tutkimuskeskus, Tutkimusraportti - Geological Survey of Finland, Report of Investigation 114, 1993
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
Size of
of team
4
2
3
2
2
2
Capacity
samples1
week
Sample
weight
Det.
limit
Method
Applications
P P ~
150
200
3 00
400
5 00
570
25-50
20
10
0.1
0.05
0.05
0.02
0.0001
0.003
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:
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.
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:
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.
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
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