CHEMICAL

GEOLOGY
ISOTOPE GEOSCIENCE
ELSEVIER Chemical Geology 124 (1995) 47-53

Detection of noble metal depletion in layered mafic intrusions: a

potential aid to exploration for platinum-group element deposits
Bruce J. Perry "*, D.V. Speller b, Ronald R. Barefoot c, Jon C. Van Loon c
aClaimstaker Resources Ltd., Suite 1440, 1188 West Georgia St., Vancouver, B.C. V6E 4A2, Canada
b INCO Ltd., J. Roy Gordon Research Laboratory, Sheridan Park, Mississauga, Ont. LSK 1zg, Canada
c Deparunent of Geology, University of Toronto, 22 Russell St., Toronto, Ont. M5S 3El,Canada
Received 1 October 1993; accepted after revision 4 January 1994

Abstract

In layered marie in~sions, economically important platinum-group element (PGE) mineralisation can result from collection
of PGE and Au from the silicate melt by Ni( + Cu) S droplets, which settle to form PGE- and Au-enriched layers. An important
consequence is that the PGE and Au are depleted in the remaining silicate fraction. The ability to recognise PGE and Au depletion
in rocks crystallised from a depleted melt would be useful in exploration for discriminating between favourable (containing
PGE- and Au-depleted :silicates) and unfavourable layers (those that had not experienced NiS collection of PGE and Au). Dry-
chlorination was applied to drill core samples of the Fox River Sill (Manitoba, Canada) in order to remove metallic minerals.
The remaining silicate fractions were digested by microwave heating in a mixture of HF-HCI-HNO3, evaporated to near dryness,
re-digested in aqua regia, and re-constituted in distilled de-ionized water. The solutions were analysed by ICP-MS for PGE and
Au. The PGE and Au contents of the silicate fractions of samples collected from mineralised layers were significantly depleted
relative to the PGE and Au contents of silicate fractions of samples collected from a non-mineralised layer. Verification of the
ICP-MS method for the determination of Pd was carried out by means of DCP-AES. Instrumental neutron activation analysis
(INAA) was used to v¢;rifythe method for Au and Ir.

1. Introduction by Ni( 5: Cu)S droplets, Rock-forming silicate miner-

In layered mafic intrusions, economically important
platinum-group element (PGE) mineralisation can
result from the coUection of PGE and Au by immiscible
Ni ( 5: Cu) S droplets as they segregate from the magma,
followed by the accumulation of the dense, PGE- and
Au-bearing Ni(-I-Cu) S droplets as they settle toward
the floor of the magma chamber ( Naldrett, 1989). PGE
and Au concentrations in the remaining silicate melt
should be smaller than those in earlier or later magma
pulses that had not experienced PGE and Au collection
* Corresponding author.
als crystallised from PGE- and Au-depleted silicate
melts should contain smaller PGE and Au concentra-
tions, all else being equal, than rock-forming silicate
minerals crystallised from a melt that had not experi-
enced such depletion.
As an aid to exploration for PGE deposits, an ability
to recognise PGE and Au depletion in rocks crystallised
from a PGE- and Au-depleted melt would help explo-
ration geologists to distinguish favourable marie layers
from unfavourable ones. Favourable layers would have
experienced Ni( + C u ) S collection of PGE and Au;
they should contain silicate rock-forming minerals
crystallised from a silicate melt depleted of PGE and

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48 B.J. Perry et al. / Chemical Geology 124 (1995) 47-53

Au. Unfavourable layers would not have experienced Table 1

Fox River Sill samples studied (ddh Fox 86-2) and lead collection
Ni( _ C u ) S collection of PGE and Au; they should
fire-assay data
contain rock-forming silicate minerals crystallised
from a silicate melt that had not been depleted in these Depth Rock type PGE content (ng g - 1)
elements. Consequently, the concentrations of PGE and (ft)
Au in the silicate fractions of rocks representing a Pt Pd Au

favourable layer should be smaller than the concentra- Layer A (non-mineralised):

tions of these elements in the silicate fractions of rocks
representing an unfavourable layer. 133 pyroxenite < 15 <2 4
138 pyroxenite < 15 <2 73
Inductively coupled plasma-mass spectroscopy 142 pyroxenite < 15 <2 < 1
(ICP-MS) has been established as a sensitive, multi- 146 pyroxeaite < 15 <2 4
element technique for the detection and determination 169 pyroxenite < 15 <2 < 1
of more than 70 elements. It is of particular value in
Layer B (mineralised):
analysis of geological samples where concentrations of
elements range from major to ultra-trace levels. A num- 220 orthopyroxenite < 30 23 2
ber of reports of ICP-MS analyses for PGE and Au in 225 orthopyroxenite < 30 21 <2
236 orthopyroxenite 55 49 3
rocks and minerals have been published (Grtgoire, 237 orthopyroxenite 33 37 3
1988; Sen Gupta and Grtgoire, 1989; Jackson et al., 238 orthopyroxenite 92 75 7
1990; Perry et al., 1992; Totland et al., 1993). Most of
the procedures require the preparation of sample solu- Layer C (mineralised):
tions for analysis by ICP-MS. However, acid diges- 285 orthopyroxenite < 45 <6 <3
tions may not dissolve refractory, PGE-bearing 289 orthopyroxenite < 45 91 < 13
minerals (Gowing and Potts, 1991). If alkali fusions 299 orthopyroxenite < 45 29 <3
are used to digest samples, the large quantities of rea- 1 fl=0.3048 m.
gents required causes problems by increasing the
blanks. Furthermore, in order to reduce the total dis- Dry-chlorination has been used successfully (Perry
solved solids content to levels compatible with ICP- et al., 1992) for the removal of traces of PGE and Au
MS analysis, solutions resultant from alkali fusion tech- from rocks and determination of these elements in the
niques must be severely diluted, usually to the extent resultant solution by ICP-MS. In this method, contam-
that small concentrations of PGE and Au in the sample ination contributions from reagents were very small,
can then no longer be detected. Fire-assay methods for and the solutions could be analysed without further
the separation and concentration of precious metals are chemical or mechanical manipulation. In addition, the
well known (Van Loon and Barefoot, 1991). However, method did not suffer from limitations of sample size,
contamination from chemicals and reagents is still a since large samples of > 200 g were accommodated
problem in the determination of traces of PGE and Au. (Perry et al., 1993a).
Coprecipitation with Te has been used to separate PGE In this paper, the dry-chlorination method has been
and Au from matrix elements, but this fails to overcome applied to drill core (ddh Fox 86-2) samples of the Fox
the problem of high blanks. River Sill (Manitoba, Canada). This 250-km-long
Slurry nebulisation of solid samples has been stratiform, ultramafic intrusion of Proterozoic age hosts
reported as a method for the direct determination of weak, sporadic concentrations of disseminated sulphi-
PGE and Au in solid samples (Totland et al., 1993). des which contain PGE abundances ranging up to 1200
In this method of analysis, 0.2-g samples are ground to ng g-1 (Scoates and Eckstrand, 1986). The lithologi-
< 5/zm in the presence of an acidified dispersing agent. cal compositions of the samples, the sample depths,
It was successfully applied to several reference mate- and their PL Pd and Au contents as determined by lead
rials, but the detection limits obtained make the method collection fire assay are listed in Table 1. The insoluble
suitable only for the determination of these elements in silicate fractions which remained after dry-chlorination
mineralised samples. were digested by microwave heating in an acid mixture
 B.J. Perry et al. / Chemical Geology 124 (1995) 47-53
containing HF-HCI-HNO3. The solutions resultant
from the microwaw: digestion were evaporated, the
residues dissolved in a small volume of aqua regia, and
the samples reconstituted as aqueous solutions before
ICP-MS analysis for PGE and Au.
2. Sample preparation
Dry-chlorination (Beamish, 1966; Van Loon et al.,
1984; Van Loon and Barefoot, 1991; Perry et al., 1992,
1993a) was applied to 13 drill core (Fox 86-2) rock
samples collected from three layers of the Fox River
Sill in order to remove metallic minerals from these
rock pulps. Dry-ch]lorination was accomplished by
heating a rock sample pulp, along with a small amount
of NaCI (0.1 g NaCI/15 g rock pulp), for 3.5 hr at
580°C in the presence of flowing chlorine. PGE and Au
that were present in the rock sample as native metals,
natural alloys, or contained in sulphide group minerals
were converted into salts which were soluble in weak
HCI. The chlorinated sample and the chlorination tube
were washed with weak HCI and distilled deionised
water. The resultant solution can be analysed by ICP-
MS for PGE and Au, in order to determine the concen-
trations of these elements in the metallic fraction of the
rock sample.
Following procedures modified slightly from our
previous work (Perry et al., 1993b), the residual sili-
cate fractions remaining after dry-chlorination were
digested by microwave heating 1.0 g of dry-chlorina-
tion residue in a mixture of 5 ml 29 M HF, 5 ml 12 M
HCI and 4 ml 16 M HNO3, all of which was contained
in a 23-ml Parr ® microwave acid digestion bomb.
Microwave heating was applied at high power for three
1-min heating periods. Between each heating period,
the bomb was allowed to cool in the draught of the
fume hood for 5 min. The bomb was allowed to cool
for 30 min in the draught of the fume hood before it
was opened. After the final cooling period, the bomb
was opened and the digestate was poured into a 30-ml
Nalgene* high-density polypropylene bottle. Five ml
of sample solution were taken to near dryness in 23-ml
Teflon* cups by heating the cups and their contents on
a hotplate at low temperature (75-80°C). The residues
remaining in the cups were dissolved in 400/xl aqua
regia. Two ml of distilled deionised water (ddw, > 18
M/-2) were added to the warm cup containing the dis-
49
solved residue. The solutions were transferred from the
cups to small polypropylene funnels lined with 9-cm-
diameter Whatman ® #40 filter papers, the filtrates
passing into 5-ml volumetric flasks. The cups were
rinsed twice with 1 ml ddw each time. The rinses were
passed through the filter papers into the volumetric
flasks. The filters were rinsed twice with ddw into the
volumetric flasks, which were then brought up to vol-
ume with ddw. The contents of the volumetric flasks
were transferred to test tubes. These were sealed with
Parafilm®, and then stored under refrigeration until the
solutions were analysed.
3. Instrumentation
A SCIEX ELAN 250 ICP-MS, with ion optics
upgraded to Perkin-Elmer* SCIEX ELAN 500 speci-
fications, was operated at 1.2-kW forward power with
< 5-W reflected power. Torch Ar gas parameters were:
plasma, 12.0 1 min-l; nebuliser, 38 psi (262 kPa);
auxiliary, 1.41 min- 1. A peristaltic pump provided 0.9
ml min- 1of sample solution to a Meinhard ® concentric
nebuliser (TR-30-C3, high-solids) mounted in a Scott-
type double-pass spray chamber. The instrument was
optimised according to procedures specified in the
operations manual supplied by the manufacture. The
mass spectrometer was programmed to detect I°2Ru,
l°3Rh, l°Spd, 192Os, 193Ir,195ptand 197Au,and to correct
for (elemental) isobaric interferences. Sequential peak
hopping was employed. Dwell time was 50 ms in a
measurement cycle that included ten sweeps. The peak
hopping sequence was performed six times for each
analysis.
Each sample solution was diluted with ddw by a
factor of 5, and was then analysed by a standards addi-
tions method. Spiked sample and spiked blank solu-
tions ( + 10 ng g-~ each PGE and Au; and + 2 0 ng
g-1 each PGE and Au) were prepared immediately
preceding instrumental analysis. For the + 10 ng g -
spiked sample, 20/zl of 1/zg g - 1 multi-element PGE
and Au standard (Johnson Matthey Specpure ® ICP
precious metals multi-element standard; diluted with
ddw, carried in 1% aqua regia) were added to 2 ml of
the sample solution. Similarly, for the + 20 ng g - t
spiked sample, 40/.d of 1/~g g - ~ multi-element PGE
and Au standard were added to 2 ml of the sample
solution. The sample solution was analysed, followed
 50 B.J. Perry et al. /Chemical Geology 124 (1995) 47-53

by a 60-s rinse out with 0.16 M HNO 3. The 0.16 M • :. 8}) 16o ,~o l~ORu,~o
Blan ng g-1
HNO3 was then analysed in order to detect carry-over.
110 jm~:,,~...,, . . . . . . .
Blank intensities were usually achieved after only one 160 .........
rinse. The spiked samples were then analysed. Quan- 210 B ....... .
titation (ng g - l ) was achieved by: deducting the 260 C'~2.1T;Li'.i~i '. "
counts per second (cps) recorded for the 10 ng g -
spiked sample solution from the cps recorded for the
!0 ~0 160 l~0 140
O s ng g-I
20 ng g - 1 spiked sample solution to yield the net cps e-
160
for 10 ng g-~ for each element; dividing the sample ~"~210
"°11"
B"";'~i".--
"-""..... """
cps by the net cps for 1 ng g-~; multiplying by the 260
appropriate dilution correction factors. The concentra-
~..I 1~0 I 2~0 I 340 I 4~0 I 540 I 6~0 [ 7~0LSng~Og I
tions of PGE and Au in the blanks were also determined A" Blanks
in this manner. The results for the blanks were deducted 110 ..... -..... ~..~...-....... ~ ..
from the results for the samples. 160
n~..
2602'° :
4. Results and discussion Fig. 2. Concentrations(ng g- t, n = 146) of Ru, Os and Au in Fox
RiverSill chlorination-resistantfractionsand blanks.
4.1. Case study results as plots of concentration vs. depth in the diamond drill
hole (Figs. 1 and 2). Concentrations of PGE and Au,
In order to more easily compare PGE and Au con- as sample equivalent concentrations, in reagent blanks
centration data obtained for the silicate fractions (n = 9) are also shown in each plot. These figures show
remaining after dry-chlorination of rock samples that depletion of PGE and Au occurred in the silicate
obtained from the three layers, these data are presented melts responsible for the formation of layers B and C,
but this did not occur in the silicate fractions of layer
260 460 6~0 8~0 10100 12100
Blanks Pt14~0
ng g-I
A. Layers B and C contain PGE-bearing Ni( + C u ) S
IIOIA'..':~'- ...-..-.~...,... .... . . mineralisation, while layer A does not. PGE and Au
160 . . . . depletion in the silicate fractions, due to natural
210 B . , , _ . . . .
Ni( + C u ) S collection of PGE and Au in the magma,
26oJC:.~...-. ..-
distinguished the mineralised layers from the non-
i " lOlOo 15100 20~ 2511303(~00 35100 4~00 mineralised layer. The data for Pt, Pd, Ir, Au and Os
110 -~.. ...: :.. " . . . . ~,... .,. . •
were particularly useful in highlighting the differences
160 between the layers. While the silicate fractions of
~ 210 mineralised layer B were strongly depleted of Rh, the
260 jr% . . . . . . . - - ~ ,- . silicate fractions of mineralised layer C did not appear
•~ .:: lO ~0 30 20 t0 to be depleted of Rh. Ru concentrations did not vary
[:) " Blanks Rh°~gg-I significantly between the three layers.
llO .a...."'." 2:" ."" ..... : . . . . . . . . . .
160
4.2. Analytical reproducibility
260 "." .. :'. . . . . . . . . . . .

'~ Blanksl~O 260 3~0 4~0 5~0 Ir6~n~g-1 Low relative standard deviations (RSD) were usu-
ll0 A ""-":'=~''''" •. . . . ally obtained for repeated measurements of single solu-
tions (RSD< 10%). However, analytical reproduc-
210 " " " ibility was often very poor ( R S D > 3 0 % ) between
260
solutions resultant from microwave digestions of ali-
Fig. 1. Concentrations(rigg- t, n = 146) of Pt, Pd, Rh and Ir in Fox quots of the chlorination residual from any single sam-
RiverSillchlorination-resistantfractionsand blanks. ple. Reproducibility between samples representing the
 B.J. Perryet al. / ChemicalGeology124 (1995)47-53 51

Table 2 Table 3
DCP-AESand ICP-MSrecruitsfor Pd (ng g - 1) in solutionsresultant Radionuclidesdeterminedby 1NAA
from microwavedigestionof dry-chlorinationresidues
Element Radionuclide Half-life Energy
Sample Method (keV)

DCP-AES ICP-MS Rh W4Rh 4.34 min 51

MW-95 (2 g, 0.1 S-1800) 220 302
MW-IOI (2 g, 0.1 S-1800) 200, 200 103, 207
MW-101 ( 1 g, 0.1 S-1800) 90
same layer was also very poor ( R S D > 30%). None-
theless, the strong depletion signature resultant from
the removal of PGE and Au from the silicate melt by
the natural NiS collec, tion is not obscured.
4.3. Verification stua~
The PGE and Au concentrations, as determined by
ICP-MS, in the chlorination residues (silicate frac-
tions) of these rock samples were much larger than
expected. From preliminary work (Table 2), the pres-
ence of large concentrations of Pd, not detectable by
fire assay, was confi:rmed by DCP-AES analyses of
chlorination residues obtained from INCO ® in-house
precious metal standard (0.1)S-1800, a ten times dilu-
tion with floated silica powder of S-1800. The validity
of the method for Pd received some support from com-
parisons of ICP-MS results with DCP-AES results for
analyses. However, the sensitivity of DCP-AES anal-
ysis for the remaining PGE and Au was insufficient to
obtain quantitative da*La.Consequently, during the pres-
ent work, attempts were m a d e t o obtain cross-check
analyses by INAA. Two sample solutions, MW159c
from the depleted layer B and MW166c from the non-
depleted layer A, along with spiked sample solutions
( + 20 ng g - ~PGE and Au), and a reagent blank solu-
tion were analysed by INAA. For each of these test
solutions and for the reagent blank solution, 400/zl of
the solution were deposited on a 1.5-cm2 Whatman ®
# 4 0 filter paper in 50-/xl aliquots. Each aliquot was
allowed to evaporate before the next aliquot was depos-
ited on the filter paper. The filter papers containing the
dried samples were then each heat-sealed in plastic film.
4.3.1. Short-lived radio-isotopes: l°4Rh and wgPd
For the determination of Pd and Rh only, the samples
were placed in a Cd sleeve in order reduce the thermal
neutron flux. They were activated by epithermal neu-
Pd l°gPd 4.69 min 188
Ru l°3Ru 39.3 days 497
Os 19lOs 15.4 days 129
Ir 1921r 73.8 days 468
Pt 199Au 3.14 days 158
Au 19aAu 2.69 days 412
tron flux in the SLOWPOKE Reactor (University of
Toronto) for 5 min at 5 kW. Immediately after irradi-
ation, each sample was counted for three regions of
interest in the ~-ray spectrum (two background regions
and the analyte region) on an intrinsic Ge detector
based, ~/-ray spectrometer for 5 min. The radionuclides
analysed, their half-lives and 3,-ray energies are listed
in Table 3.
Neither Pd nor Rh were detectable in either the sam-
ple solution or the spiked ( + 20 ng g - 1) sample solu-
tion. From the data collected for this spiked sample, the
INAA detection limits (D.L.) for Pd and Rh in this
matrix were determined to be 4700 and 62 ng g-1,
respectively. Pd and Rh in MW solution 166c were
determined by ICP-MS to be 9.9 and 0.2 ng g-1,
respectively. Thus, the concentrations of Pd and Rh in
the spiked sample (30 ng g - l Pd; 20.2 ng g-1 Rh)
were much less than the D.L.'s for these elements in
this matrix. It is important to note that had a spiked
solution not been analysed, the absence of signal for
Pd in the non-spiked sample solution may erroneously
have been construed to mean that Pd was not present.
This exemplifies the importance of determining D.L.'s
within the geological sample matrix for each analyte,
rather than assuming that instrumental detection limits,
or detection limits obtained by other methods, apply.
Hoffman et al. (1978), using the same facility,
obtained much lower D.L.' s (ng g - 1) for PGE and Au
in residues resultant from NiS fire assays of rocks (Pd,
50; Rh, 1; Pt, 5; Ir, 0.1; Ru, 3; Os, 2; Au, 0.1).
4.3.2. Long-lived radio-isotopes: WgAu, WSAu, 192Ir,
1930s and W3Ru
The test samples were irradiated overnight ( 16 hr)
at 5 kW. The irradiated samples were counted on an
intrinsic Ge detector based, 3,-ray spectrometer for
52 B.J. Perry et al. / Chemical Geology 124 (1995) 47-53

Table 4 verification studies, ICP-MS determinations for Pd, Au

INAA and ICP-MS results for Au and Ir in solutions resultant from and Ir were supported by results from DCP-AES and
microwave digestions of Fox River Sill dry-chlorination residues
INAA. Poor reproducibility between sub-samples of
Sample Method Element (ng g - ~) the chlorination-resistant fractions necessitated multi-
ple analyses of each chlorination-resistant fraction.
Au Ir

MW166c INAA 7.0 3.9

ICP-MS 8.1 2.5
MW159c INAA 0.9 b.d.
ICP-MS 1.2 0.5
Reagent blank INAA 1.3 b.d.
ICP-MS 0.3 0.1
b.d. = below detection.
three regions of interest in the T-ray spectrum for each
analyte (two background regions and the analyte
region) after 5, 7, 8, 14, 18, 20, 42, 75 and 88 days.
Only Au and Ir could be determined (Table 4). At no
times were the 20 ng g-~ spikes of Pt, Os and Ru
observed in the spiked sample solutions. Therefore, no
determination of the concentrations of these elements
in these solutions could be made.
Gold concentrations were determined eight days
after the overnight irradiation. Each sample was
counted for 30,000 s. The INAA results, along with the
ICP-MS results, are shown in Table 4. There were good
agreements between the results from the two analytical
methods for both test samples.
Seventy-five days after the overnight irradiation, Ir
was determined. The INAA results, along with the ICP-
MS results, are shown in Table 4. There was good
agreement in the results from sample MW166c. Iridium
was not detected by INAA in MW159c; only 0.1 ng
g - 1 was detected by ICP-MS.
5. Conclusions
A new method based upon ICP-MS has been inves-
tigated for the detection of noble metal depletion in
layered marie intrusions. The PGE and Au contents of
silicate fractions of samples collected from the miner-
alised horizons were significantly depleted relative to
PGE and Au contents of silicate fractions of samples
collected from the non-mineralised horizon. PGE and
Au depletion in the silicate phase distinguished the
mineralised layers from the non-mineralised layer. In
Acknowledgements
The authors thank INCO ® Exploration and Techni-
cal Services (I.E.T.S.) for the generous funding that
has made this work possible. In particular, we are grate-
ful for the support, encouragement and guidance of Dr.
R.A. Alcock, Manager, Geological Research and Lab-
oratories, INCO Ltd./I.E.T.S. We gratefully acknowl-
edge help received from Perkin-Elmer® SCIEX; in
particular, Ken Halligan (SCIEX) most generously
shared his great technical expertise. We wish to thank
the Geological Survey of Canada for supplying the Fox
River Sill rock samples and fire-assay data. This
research benefited from financial support received from
the Natural Sciences and Engineering Research Coun-
cil of Canada through an NSERC Operating Grant
(OGPIN 026, J.C.V.L.).
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