12
Vol. 22 N2 p.187-194
98
Determination of the Platinum-Group Elements and
Gold in Twenty Rock Reference Materials by Inductively
Coupled Plasma-Mass Spectrometry (ICP-MS) after
Pre-Concentration by Nickel Sulfide Fire Assay
Hans-Gerrit Plessen* and Jrg Erzinger
GeoForschungsZentrum Potsdam, Projektbereich 4.2, Telegrafenberg, 14473 Potsdam, Germany
*Present address: Jgerallee 39, 14469 Potsdam, Germany. e-mail: gerrit@snafu.de
The platinum-group elements (PGE) and gold have
been determined in twenty international rock refe-
rence materials by inductively coupled plasma-mass
spectrometry (ICP-MS) after pre-concentration by a
nickel sulfide fire assay. It was possible to achieve
determination limits for a 50 g sample that ranged
from 1 pg g -1 (Rh) to 23 pg g -1 (Au). Compared to
published certified and recommended values for
rock reference materials, the trueness of the method
was found to be good. However, in some cases we
observed large deviations for all elements in the
sub 10 ng g -1 range within individual reference
sample splits. Our results show that the PGE and Au
are inhomogeneously distributed in the reference
materials analysed here, where they are present in
low concentrations, using 50 g test portions.
Keywords: platinum-group elements, gold,
determination, ICP-MS, nickel sulfide fire assay,
reference materials.
The highly siderophile platinum-group elements
(PGE) Ru, Rh, Pd, Ir and Pt as well as Au are becoming
increasingly important as powerful indicators of specific
geological processes. Due to developments in analyt-
ical technology (e.g. inductively coupled plasma-mass
spectrometry), it is now possible to determine this coher-
ent group of elements in the pg g -1 concentration
range within common rocks. The increasing attention
being paid to the PGE means that it is important to
expand data sets of existing international rock reference
materials to facilitate the comparison of published PGE
concentrations by different methods.
Due to their low concentrations in common rocks, it is
not possible to determine directly the PGE quantitatively.
187
GEOSTANDARDS
NEWSLETTER
The Journal of Geostandards and Geoanalysis
Les lments du groupe du platine (PGE) et l'or ont
t analyss dans vingt matriaux de rfrence
internationaux, par ICP-MS aprs une prconcentration
par fusion au sulfure de nickel. Il a t possible
d'obtenir des limites de dtermination de l'ordre de
1 pg g-1 (Rh) 23 pg g-1 (Au). Par comparaison
avec des valeurs certifies et recommandes dj
publies, la mthode a dmontr sa justesse.
Nanmoins, nous avons observ des variations
importantes des concentrations situes dans la
gamme des 10 ng g-1, pour tous les lments dans
certains aliquotes. Nos rsultats montrent que les PGE
et l'or sont distribus de faon inhomogne dans les
matriaux de rfrence que nous avons analyss
lorsquils sont prsents des concentrations trs
basses. Ceci est dtectable sur des aliquotes de 50 g.
Mots-cls : lments du groupe du platine, or,
dtermination, ICP-MS, prconcentration par fusion au
sulfure de nickel, matriaux de rfrence.
Several methods for separation and pre-concentration
of the PGE are commonly used. Overviews describing
these methods are given in two monographs (Van Loon
and Barefoot 1991, Potts 1992) and in one article (Hall
and Bonham-Carter 1988). The determination of the
PGE is mostly performed using three steps. After
sample decomposition, a pre-concentration step is
implemented followed by the determination of the ele-
ments using a variety of instrumental methods. The
three most widely used decomposition methods are
acid decomposition, fusion with an alkaline flux and
fire assay. All these methods require a chemically com-
plex treatment to guarantee complete dissolution of all
possible PGE-bearing phases and to prevent loss of
volatile elements.
Received 19 Jun 97 Accepted 17 Mar 98
GEOSTANDARDS
NEWSLETTER
The Journal of Geostandards and Geoanalysis
5 g CaF2 50 g sample
60 g Na2B4O7 5 g Ni-powder
30 g Na2CO3 5 g sulfur
1150 oC 60 min
2 parts
10 ml
HCl
Figure 1. Nickel sulfide fire assay.
Before we finally decided to use the nickel sulfide
fire assay procedure, we evaluated other methods for
their effectiveness in determining the PGE in common
rocks. Both acid attack and alkaline fusion methods
were tested following the procedures outlined in
Kritsotakis and Tobschall 1985, Sen-Gupta and
Gregoire 1989 and Sen Gupta 1989. However, we
were not able to adopt successfully any of these pro-
cedures as a quasi routine-procedure for the determi-
nation of the PGE in common rocks.
Thus, we adopted the nickel sulfide fire assay pro-
cedure firstly described by Robrt et al. (1971). Several
studies (Gregoire 1988, Asif and Parry 1990, Frimpong
et al. 1992, Jackson et al. 1990, Reddi et al. 1994
and Zereini 1994a) have suggested ways of optimi-
sing the original work and thus achieving a functional
procedure. Modifications include: varying the flux-
reagents; reducing the bead size (Van Loon and
Barefoot 1991, Asif and Parry 1990, Frimpong et al.
1992 and Reddi et al. 1994); varying the nickel-sulfur
ratio; using different homogenisation treatments (Van
Loon and Barefoot 1991, Zereini et al. 1994b); varying
temperature of fusion and handling, and changing the
decomposition and pre-concentration procedures.
on
off
ground
200 ml HCl button
1 part
H2O2
90 oC
16 h
Analytical Techniques
NiS fire assay
A fire assay flux consisting of 30 g sodium carbo-
nate (dehydrated), 60 g sodium tetraborate, 5 g cal-
cium fluoride and a sulfur oversaturated collector [not 5 g
sulfur and 5 g nickel (Fluka carbonyl nickel powder)]
was carefully weighed into a polypropylene container
(a schematic overview of the entire procedure is given
in Figure 1). After adding 50 g of sample powder, the
mixture was homogenised with an agate-piston and
transferred into fire clay crucibles (Atlantic Standard:
Atlantic GmbH). The crucibles were placed in a fur-
nace and heated to 1150 C. This temperature was
then held constant for one hour, after which the oven
was turned off. The crucibles were left in the oven until
they had cooled down to room temperature. The cold
crucibles were broken by a hammer to separate the
NiS-button from the slag. The buttons were ground in a
micro-fast-mill, transferred to 300 ml Erlenmeyer-flasks,
and dissolved in 200 ml HCl (38% v/v, analytical
grade). The Erlenmeyer-flasks were capped with splash-
head adapters and placed in a water bath at a
constant temperature of 90 C. The entire procedure
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 GEOSTANDARDS
NEWSLETTER
The Journal of Geostandards and Geoanalysis

was carried out in a fume cupboard. After approxi-
mately fourteen hours, the dissolution was complete
and the cold solutions were vacuum-filtered through
glass micro filter discs (Schott, porosity 4) fitted
within screw filter devices. The PGE-containing resi-
instrument was optimized on 115In and 205Tl masses.
Data were acquired and calculated using PQ-vision
4.0 Software. The isotopes used for PGE and Au deter-
+
mination were 101 Ru (corrected for 61 Ni 40 Ar and
+
64 Ni 37 Cl , other interferences were found to be insigni-

dues were washed carefully with HCl (40% v/v, ficant), 103Rh, 105Pd, 193Ir, 195Pt and 197Au. A PGE multi-
twice-distilled). After placing the filter discs in 100 ml element stock solution was prepared from 1.000 g l -1
beakers, the solids were dissolved with a mixture of Johnson-Matthey single element solutions at a concen-
2 parts HCl (25 ml, 40% v/v, twice-distilled) and one tration of 10 g ml-1 in 2 % v/v HCl. This stock solution
part H 2 O 2 (12.5 ml, 30% v/v, analytical grade). was found to be stable over several months.
Once the evolution of gases had ceased, 5 ml HCl + Calibration solutions with concentrations of 0.001, 0.01,
2 ml H 2O 2 was added. Finally, the solution was pas- 0.1, 1 and 10 ng ml -1, covering the range of expected
sed through a filter paper, transferred to 250 ml concentrations, were freshly prepared from the stock
beakers and evaporated on a hot plate to a volume solution before each analysis.
of 1-2 ml. After adding a further 5 ml HCl + 2 ml
H 2O 2, the solution was again evaporated to 1-2 ml, The investigated rock reference materials
cooled, transferred to volumetric flasks and diluted
with 2% HCl to a volume of 10 ml. Each sample was The investigated rock reference materials in this
independently decomposed at least three times and study came from four different sources. The rock refe-
each dissolution was analysed twice. rence materials TDB-1 (diabase), WGB-1 (gabbro),
WMG-1 (mineralized gabbro) and WPR-1 (altered per-
idotite) were purchased from the CCRMP, CANMET
Table 1. (NRCan), 555 Booth Street, Ottawa, Ontario, Canada,
Typical instrument operating conditions for our VG K1A 0G1. The samples NIM-S (syenite), NIM-D (dunite),
PlasmaQuad PQ 2+ upgraded to the PQ-XS mode NIM-N (norite), NIM-P (peridotite) and NIM-G (granite)
ICP: are rocks from the Bushveld complex and have been
Forward power (at 27 MHz) 1.35 kW prepared by the former National Institute for
Reflected power <7W Metallurgy, South Africa. These samples are available
Coolant gas-flow (Ar) 12.75 l/min
Auxiliary gas-flow (Ar) 0.95 l/min
from MINTEK, 200 Hans Strijdom Drive, Randburg,
Nebulizer gas-flow (Ar) 0.87 l/min Private Bag 3015, Randburg, 2125 South Africa. The
Nebulizer type Meinhardt TR-30-A3 former Zentrales Geologisches Institut, Berlin (former
Sample uptake 1 ml/min
GDR) prepared the samples TS (black shale), GM (gra-
Spray chamber cooled to 1 C
nite), BM (basalt), SW (serpentinite), TB (clay shale) and
Interface: GnA (greissen). Now these reference materials are dis-
Cone-material Nickel
tributed by Breitlnder GmbH, Hans-Sachs-Str. 12,
Acquisition time: 59077 Hamm, Germany. Dr. Noboru Imai from the
Uptake 90 s Geological Survey of Japan made the following
Acquisition 60 s/run (3) samples available: JG-1a (granodiorite), JG-2 (granite),
Washout 180 s
JB-3 (basalt), JSy-1 (syenite) and JMn-1 (manganese
Data acquisition: nodule). Samples can be obtained from Dr. Noboru
Detector type Galileo # 4870 Imai, Geochemistry Dept., Geological Survey of Japan,
Detector mode pulse counting
1-1-3, Higashi, Tsukuba, Ibaraki, 305 Japan.
Peak jumping mode acquisition:
No. points per peak 5 Results and Discussion
Dwell time per point 5120 s

Reagent blank and limit of determination

ICP-MS instrumentation,
operating conditions and data aquisition
In this study we used a VG PlasmaQuad PQ-XS.
Typical instrumental operating conditions using the S
option (enhanced sensitivity) are given in Table 1. The
In the concentration range from pg g-1 to g g -1, it
was not possible to determine directly the PGE-concen-
tration blank of individual reagents used in the fire
assay procedure. The reagent being tested must be
substituted to maintain detectable PGE concentrations in

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NEWSLETTER
The Journal of Geostandards and Geoanalysis

Table 2. Table 3.
Optimized low reagent blanks (sample Reference values (Govindaraju, 1994) vs.
equivalent concentration) and the concentrations from this work. Data in italics
method detection limits (calculated as 3) are certified values, other values are proposed

[ng g -1 ] Ru Rh Pd Ir Pt Au [ng g -1 ] Ru Rh Pd Ir Pt Au
Reagent blanks WGB-1 (CCRMP)
1 0.014 0.001 0.047 0.014 0.027 0.047 Reference 0.30 0.32 14 0.33 6.1 2.9
1 - 0.13 14 0.14 3.6 25
2 0.013 0.001 0.045 0.014 0.026 0.052 2 - 0.16 13 0.15 2.7 1.5
3 0.014 0.001 0.051 0.015 0.027 0.041 3 0.21 0.12 13 0.21 3.1 1.8
4 0.015 0.001 0.046 0.014 0.025 0.055 4 0.23 0.13 11 0.16 2.7 1.7
5 0.18 0.13 14 0.19 3.6 1.5
5 0.014 0.001 0.047 0.015 0.024 0.053 6 0.22 0.15 13 0.21 3.7 1.5
6 0.014 0.001 0.039 0.014 0.025 0.052 7 0.11 0.13 15 0.19 3.0 3.4
7 0.014 0.002 0.044 0.014 0.028 0.050 8 0.23 0.16 14 0.24 4.1 3.5
9 0.19 0.13 14 0.21 4.3 2.6
8 0.015 0.001 0.045 0.015 0.024 0.054
10 0.18 0.15 13 0.21 4.1 2.0
9 0.014 0.001 0.044 0.014 0.026 0.049 11 0.19 0.14 14 0.20 3.9 3.5
10 0.014 0.001 0.046 0.015 0.024 0.053 12 0.22 0.14 13 0.18 2.8 3.4
11 0.014 0.001 0.047 0.014 0.023 0.050 13 0.20 0.15 14 0.24 3.7 3.0
14 0.18 0.13 14 0.18 3.1 1.9
12 0.015 0.001 0.042 0.015 0.025 0.055 15 0.19 0.14 14 0.18 3.4 0.69
13 0.014 0.001 0.045 0.014 0.024 0.052 16 0.19 0.13 14 0.17 3.5 2.4
17 0.17 0.17 13 0.23 3.6 1.8
mean 0.014 0.001 0.045 0.014 0.025 0.051 18 0.18 0.14 14 0.19 4.0 0.78
s 0.0005 0.0002 0.0027 0.0004 0.0015 0.0038 19 0.20 0.13 12 0.18 3.0 2.3
20 0.19 0.14 14 0.18 3.9 1.4
DL 0.0015 0.0007 0.008 0.0012 0.0045 0.0113
21 0.17 0.4 12 0.21 4.3 1.0
22 0.15 0.14 14 0.31 7.1 2.1
23 0.20 0.13 14 0.23 3.4 0.78
24 0.21 0.12 14 0.22 4.1 2.8
25 020 0.14 14 0.23 3.3 0.42
the fire assay mixture. In order to determine the proced- 26 0.18 0.14 14 0.25 6.8 2.3
27 0.29 0.11 11 0.14 2.7 1.5
ural PGE blanks, it was necessary to replace the real 28 0.33 0.15 14 0.21 4.3 2.7
samples with a material that is likely to be free of PGE 29 0.19 0.14 9.8 0.23 3.5 1.7
30 0.23 0.16 13 0.25 3.8 1.0
(such as SiO2 powder), because the fire assay flux is very mean 0.20 0.14 13 0.20 3.8 2.0
aggressive and would otherwise attack the crucible. The s 0.040 0.013 1.1 0.037 1.00 0.87
RSD (%) 19.7 9.2 8.1 8.6 26.5 43.8
PGE-concentrations of the chemicals used in the proce-
TDB-1 (CCRMP)
dure varied between production batches and for this Reference 0.30 0.70 22 0.15 5.8 6.3
1 - 0.30 19 0.15 3.7 hB
reason we were not able to present a generalized total 2 - 0.40 22 0.13 3.5 hB
blank concentration. The only way to minimise the conta- 3 - 0.36 21 0.14 3.4 5.6
4 - 0.31 20 0.098 4.5 4.9
mination was to identify and use the purest reagents, to 5 - 0.34 21 0.13 4.3 3.9
6 - 0.38 22 0.11 4.0 5.4
include at least one reagent blank in each fire assay run, 7 - 0.36 21 0.097 4.2 4.6
8 - 0.34 22 0.13 4.5 5.6
and to analyse every sample at least three times. In 9 0.25 0.29 20 0.11 2.9 5.9
Table 2 we present best reagent blanks, expressed as 10 0.23 0.26 19 0.092 4.0 5.0
11 0.34 0.36 22 0.13 4.7 5.7
sample equivalent concentration, as well as the 12 0.38 0.41 21 0.15 3.6 4.4
13 0.31 0.39 21 0.13 3.5 5.4
method detection limits. The instrumental detection 14 0.25 0.30 19 0.12 4.2 5.1
limits (reflecting the ability of the instrument) are signifi- 15 0.44 0.34 21 0.13 3.5 3.6
16 0.48 0.32 21 0.13 3.8 5.3
cantly lower. The detection limit of the method was 17 0.36 0.31 19 0.10 2.9 5.5
18 0.24 0.39 21 0.14 3.8 2.4
calculated as three times standard deviation of the 19 0.33 0.34 20 0.12 4.4 5.1
reagent blanks. The reagent blanks were subtracted in 20 0.31 0.33 20 0.090 4.1 3.9
21 0.27 0.28 22 0.086 2.4 2.1
this work from each PGE data set. However, we 22 0.37 0.29 13 0.11 4.0 5.5
23 0.29 0.32 21 0.12 4.2 5.3
were not able to achieve these low PGE concentration 24 0.48 0.32 20 0.15 3.3 4.1
25 0.35 0.26 22 0.12 2.7 5.0
blanks throughout this work. Thus, we determined
mean 0.34 0.33 20 0.12 3.8 4.8
individual reagent blank values for each batch of che- s 0.079 0.042 1.7 0.019 0.59 1.0
RSD (%) 23.7 12.6 8.4 15.9 15.6 21.1
micals. Consequently, detection limits given in Table 4
WMG-1 (CCRMP)
may be different from those in Table 2. Reference 35 26 382 46 731 110
1 27 26 396 48 720 107
2 24 26 363 47 699 108
Accuracy and precision 3 26 26 401 48 655 108
4 26 26 383 42 719 95
5 28 25 350 48 715 106
The results for three geological reference materials 6 27 26 386 48 718 104
mean 26 26 380 47 705 105
CCRMP gabbro WMG-1, diabase TDB-1 and gabbro s 1.3 0.49 20 2.3 25 4.9
WGB-1 are compared to reference values (Govindaraju RSD (%) 5.1 1.9 5.2 4.8 3.6 4.7

190
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The Journal of Geostandards and Geoanalysis

Table 4.
PGE concentrations of seventeen international reference rocks

[ng g -1 ] Ru Rh Pd Ir Pt Au [ng g -1 ] Ru Rh Pd Ir Pt Au

WGB-1 (CCRMP) TS (ZGI)

1 23 12 218 14 247 42 1 0.83 0.38 37 0.15 10 8.7
2 22 11 225 13 269 48 2 0.65 0.38 40 0.15 12 10
3 23 13 205 13 259 47 3 1.1 0.42 39 0.15 11 10
4 21 12 230 13 283 37
4 0.87 0.35 38 0.17 13 9.6
mean 22 12 220 13 265 43 5 0.83 0.40 41 0.14 10 11

NIM-G (NIM) mean 0.85 0.38 39 0.15 11 9.9

1 <0.3 0.051 0.73 0.034 0.21 <0.13
2 <0.3 0.046 0.87 0.031 0.30 <0.13 SW (ZGI)
3 <0.3 0.052 0.68 0.030 0.20 <0.13 1 4.1 0.71 1.0 2.1 2.8 1.2
mean <0.3 0.050 0.76 0.031 0.24 <0.13 2 5.4 0.75 1.2 2.2 2.9 0.76
3 5.0 0.71 1.2 1.9 2.7 1.5
NIM-S (NIM)
4 3.7 0.73 1.3 2.0 2.4 1.2
1 <0.3 0.012 0.078 0.011 0.11 0.048
2 <0.3 0.011 0.059 0.010 0.087 0.071 5 5.8 0.68 1.1 1.9 3.1 1.0
3 <0.3 0.015 0.065 0.008 0.10 0.068 mean 4.8 0.72 1.2 2.0 2.8 1.1
mean <0.3 0.013 0.067 0.010 0.099 0.062
TB (ZGI)
NIM-D (NIM) 1 0.025 0.011 0.25 0.018 0.13 0.64
1 2.0 1.2 0.90 0.46 14 0.98 2 0.019 0.014 0.30 0.022 0.096 0.55
2 1.8 1.2 0.83 0.44 13 0.61
3 0.018 0.012 0.23 0.022 0.12 0.43
3 2.1 1.1 0.89 0.43 12 0.42
4 0.027 0.009 0.22 0.019 0.17 0.52
mean 1.9 1.2 0.88 0.44 13 0.67
5 0.024 0.010 0.28 0.021 0.12 0.69
NIM-N (NIM) mean 0.023 0.011 0.26 0.020 0.13 0.56
1 0.50 0.37 1.3 0.092 3.5 0.56
2 0.58 0.34 0.94 0.092 3.8 0.82 JG-1a (GSJ)
3 0.53 0.39 1.1 0.085 3.2 0.58 1 <0.01 <0.001 0.051 <0.05 0.042 0.15
mean 0.53 0.37 1.1 0.090 3.5 0.66 2 <0.01 <0.001 0.087 <0.05 0.048 0.23
3 <0.01 <0.001 0.070 <0.05 0.058 0.24
NIM-P (NIM)
1 9.1 3.0 5.7 1.8 12 0.19 mean <0.01 <0.001 0.069 <0.05 0.049 0.21
2 8.3 3.1 5.1 1.9 11 0.18
3 9.6 2.9 5.4 2.1 8.7 0.19 JG-2 (GSJ)

mean 9.0 3.0 5.4 1.9 11 0.19 1 <0.002 <0.001 0.021 <0.002 <0.005 <0.020
2 <0.002 <0.001 0.028 <0.002 <0.005 <0.020
GM (ZGI) 3 <0.002 <0.001 0.023 <0.002 <0.005 <0.020
1 <0.002 <0.001 <0.05 <0.001 <0.005 0.24
2 <0.002 <0.001 <0.05 <0.001 <0.005 0.14 mean <0.002 <0.001 0.024 <0.002 <0.005 <0.020
3 <0.002 <0.001 <0.05 <0.001 <0.005 0.23
JB-3 (GSJ)
4 <0.002 <0.001 <0.05 <0.001 <0.005 0.37
5 <0.002 <0.001 <0.05 <0.001 <0.005 0.14 1 0.16 0.053 2.3 <0.01 1.6 0.35
2 0.14 0.045 1.8 <0.01 1.2 0.26
mean <0.002 <0.001 <0.05 <0.001 <0.005 0.22
3 0.10 0.031 1.6 <0.01 1.3 0.58
BM (ZGI)
mean 0.13 0.043 1.9 <0.01 1.4 0.40
1 <0.002 <0.001 0.099 <0.001 <0.005 0.16
2 <0.002 <0.001 0.072 <0.001 <0.005 0.11
JSy-1 (GSJ)
3 <0.002 <0.001 0.12 <0.001 <0.005 0.14
1 0.030 0.010 0.13 0.017 0.11 0.093
4 <0.002 <0.001 0.12 <0.001 <0.005 0.13
5 <0.002 <0.001 0.12 <0.001 <0.005 0.18 2 0.027 0.012 0.11 0.017 0.071 0.096
3 0.032 0.008 0.15 0.015 0.091 0.094
mean <0.002 <0.001 0.10 <0.001 <0.005 0.14
mean 0.030 0.010 0.13 0.016 0.089 0.094
Gn-A (ZGI)
1 <0.1 <0.005 0.055 <0.05 <0.08 9.9 JMn-1 (GSJ)
2 <0.1 <0.005 0.074 <0.05 <0.08 8.0 1 4.4 2.0 1.6 0.59 42 1.1
3 <0.1 <0.005 0.063 <0.05 <0.08 12
2 5.5 1.8 1.6 0.58 40 1.1
4 <0.1 <0.005 0.071 <0.05 <0.08 10
3 5.1 2.0 1.6 0.58 41 1.1
5 <0.1 <0.005 0.073 <0.05 <0.08 14
mean <0.1 <0.005 0.067 <0.05 <0.08 11 mean 5.0 1.9 1.6 0.58 41 1.1

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The Journal of Geostandards and Geoanalysis

1994) in Table 3. The differences between the reference
values and our data for WMG-1 are below 5%, with
the exception of Ru, and therefore show very good
recovery and accuracy. In most cases our results are
lower, for example for gabbro WGB-1 and diabase
TDB-1, these being the most readily available geolog-
ical reference materials with the lowest certified PGE
values. The recovery of Pd is good for these reference
rocks (< 9% difference), but poor for Pt and Au. The
question arises as to whether this is due to inefficient
recovery of our procedure, sample inhomogeneity or
bias in certified values. The accuracy of certified values
in this low concentration range must be questioned,
taking into account the critical comments of Hall and
Bonham-Carter (1988) concerning the sample homo-
PGE-data of a further seventeen
international reference rocks
Our PGE data of a further seventeen international
reference materials are compiled in Table 4. Data are
grouped according to the supplier of the reference
material. Mantle-normalized PGE-plots (mantle values
from Barnes et al. 1985, corresponding to 0.815%
chondrite values) have been plotted for CCRMP and
NIM samples (Figures 2 and 3).

Sample/mantle
geneity and accuracy of PGE values in other reference
materials as well as the poor recovery for all PGE
reported in some other studies (e.g. Reddi et al. 1994).
A recent study (Verma 1996) predicts errors in the
characterisation of certified data for most elements of
between 10% and > 100%.

To investigate the observed poor recovery and the

concentration variations, we carried out numerous Figure 2. Mantle-normalized PGE patterns of CCRMP samples.
independent NiS fire assays, including thirty fire assays
of gabbro reference rock WGB-1. We found a broad
concentration range for all elements from one sample
batch to another, and also within each individual
sample container. For example, the mean Pt-concentration
Sample/mantle

within the sample container with the lowest average Pt-

concentration is about 3.3 ng g-1 (minimum concentra-
tion 2.7 ng g-1), and within the sample container with
the highest average Pt-concentrations about 6.4 ng g-1
(maximum concentration 7.1 ng g-1), compared to the
certified value of 6.1 ng g-1. These results support the
presumption that the PGE and Au are inhomogeneously
distributed in rocks where they are present in low
concentrations, and that it seems impossible to homoge-
nise samples with low PGE and Au contents entirely. Figure 3. Mantle-normalized PGE
Despite our lower values and the reported variations we patterns of NIM (MINTEK) samples.
believe our results are acceptable.
CCRMP samples gabbro WGB-1, diabase TDB-1
The precision of our PGE data of WMG-1 expres- and gabbro WMG-1 were discussed previously and
sed as the relative standard deviation (RSD) is very are plotted, together with peridotite WPR-1 and litera-
good (< 5.3%). If one considers the low PGE-contents of ture values, in Figure 2. The shapes of the patterns of
TDB-1 and WGB-1 and the homogeneity problems, each individual reference rock, resulting from this work,
the precision is still good for all PGE (< 27%) with the match the shapes of the patterns resulting from the
exception of Au (43.8% in WGB-1). The high RSD for values from Govindaraju 1994.
Au suggest, either that there was a loss of Au during
the preparation procedure, caused by incomplete Mantle-normalized values for dunite NIM-D, granite
collection of the NiS-button or an extremely inhomoge- NIM-G, norite NIM-N, pyroxenite NIM-P and syenite
neous distribution of Au in the sample. NIM-S are presented in Figure 3. Iridium in some of

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Table 5.
Concentrations from this work vs. values from low PGE and Au values in common rocks, as there could
Sen Gupta & Gregoire (1989) by co-precipitation with be concentration variations of up to 100% both
tellurium using electrothermal vaporisation (ETV) for between and within sample splits.
sample introduction
Our experience is, that it is important to plot all
[ng g -1 ] Ru Pd Ir
this work S.G.&G. this work S.G.&G. this work S.G.&G. PGE data normalized to chondrite or mantle values in
order to evaluate and interpret low PGE-concentrations
NIM-P 9 5.6 5.4 4 1.9 4 in rock samples. This is a promising way of evaluating
NIM-D 1.9 24 0.88 4 0.44 6
the quality of the data and of minimising the risk of
NIM-N 0.53 7 1.1 4 0.090 1
NIM-G < 0.3 7.8 0.76 2 0.031 0.6 misinterpreting results.
NIM-S < 0.3 3 0.067 nd 0.010 2.5
Acknowledgement
nd not determined

Thanks are expressed to Antje Mller for her skilled

these samples could not be detected. Compared to
previously published data for these reference samples
(Sen Gupta and Gregoire 1989 and Table 5), there
are large differences (in some cases up to two orders
of magnitude), our values being generally lower.
Although many aspects of the behaviour of the PGE in
magmatic rocks are still controversial, there is for
example no geochemical reason why a granite (NIM-G)
should have higher Ru values [7.8 ng g -1 (Sen Gupta
and Gregoire 1989)] than a peridotite (NIM-P) [5.6 ng g-1
(Sen Gupta and Gregoire 1989)]. Following the PGE-
literature (e.g. Barnes et al. 1988, Barnes et al. 1985)
a peridotite, as a mantle rock, should have higher
PGE-concentrations than a diorite, a norite, a syenite
or a granite, because during magmatic differentiation
the PGE-content normally decreases. Taking into
account these facts, our data are in good agreement
with the theoretical background and seem to be more
plausible than previously published data (Sen Gupta
and Gregoire 1989).
Conclusions
We modified the NiS fire assay procedure to achieve
low detection limits for Ru (3 pg g -1), Rh (1 pg g -1), Pd
(16 pg g-1), Ir (2 pg g- 1), Pt (9 pg g -1) and Au (23 pg
g -1). For samples with high PGE-concentrations (more
than 10 ng g -1), we obtained very good accuracy and
precision; for samples with low PGE-concentrations our
results are still acceptable, compared to published
data for international reference rocks.
The results of this work support the presumption of
other authors that the PGE and Au are inhomoge-
neously distributed in rocks where they are present in
low concentrations, and that it seems impossible to enti-
rely homogenise rock samples with low PGE and Au
contents. Hence, care should be taken in interpreting
technical assistance, to Jan Lindsay for checking the
English text and to two anonymous referees for their
constructive criticism.
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