12
Vol. 25 — N° 2-3 p.199-217
01
An Evaluation of Methods for the Chemical
Decomposition of Geological Materials for
Trace Element Determination using ICP-MS
Zongshou Yu (1), Philip Robinson* (2) and Peter McGoldrick
(1) Centre for Ore Deposit Research, University of Tasmania, GPO Box 252-79, Hobart, Tasmania, 7001, Australia
(2) School of Earth Sciences, University of Tasmania, GPO Box 252-79, Hobart, Tasmania, 7001, Australia.
* Corresponding author. e-mail: Phil.Robinson@utas.edu.au
Complete dissolution is essential to obtain accurate
analytical results using ICP-MS. In this study,
decomposition techniques (i.e. acid digestions using
Savillex  Teflon vials, a high pressure digestion
system and microwave oven, a combined lithium
tetraborate fusion - HF/HNO 3 acid decomposition
and sodium peroxide sinter) for the total dissolution
of different types of geological reference materials
have been investigated. Savillex  Teflon vial
HF/HNO 3 digestion is effective for basaltic samples.
The high pressure HF/HClO 4 digestion (PicoTrace 
TC-805 digestion system, Bovenden, Germany)
allows dissolution of basalts and ironstones.
Granites and magnetite-rich samples can be
dissolved using a high pressure HF/H 2SO 4 method.
Geological samples cannot be effectively attacked
by microwave acid digestion. A combined lithium
tetraborate fusion - HF/HNO 3 acid digestion
method allows complete dissolution of many
different types of geological materials; however, this
method precludes the determination of volatile
elements due to the high fusion temperature
(1000 °C). A sodium peroxide sinter method at
480 °C has the potential for the rapid determination
of Y, Sc and REE in different types of geological
materials. However, the lack of ultra-pure reagents
precludes the use of lithium tetraborate fusion
and sodium peroxide sinter methods for the
measurement of geological samples with low trace
element abundances.
Keywords: chemical decomposition, geological
reference materials, trace element determination,
inductively coupled plasma-mass spectrometry,
comparison of techniques.
199
GEOSTANDARDS
NEWSLETTER
The Journal of Geostandards and Geoanalysis
(1)
La dissolution complète est essentielle pour obtenir
des résultats analytiques justes par ICP-MS. Dans cette
étude, les techniques de décomposition (i.e., attaques
acides utilisant des fioles Savillex® en téflon, un système
d’attaque à haute pression et un four à micro-ondes,
une fusion au tétraborate de lithium combinée avec
une décomposition acide HF/HNO3 et un frittage
avec peroxyde de sodium) pour la dissolution totale
de différents types de matériaux géologiques de
référence ont été étudiées. L’attaque HF/HNO3 en
flacon téflon Savillex est efficace pour les échantillons
de basalte. L’attaque HF/HClO4 à haute pression
(système d’attaque PicoTrace® TC-805, Bovenden,
Allemagne) permet la dissolution des basaltes et des
roches riches en fer. Les granites et les échantillons
riches en magnétite peuvent être dissous par la
méthode HF/H2SO4 à haute pression. Les échantillons
géologiques ne peuvent pas être efficacement attaqués
par une attaque acide en four à micro ondes. Une
méthode combinée – fusion avec tétraborate de
lithium et attaque acide HF/HNO3 permet la dissolution
complète de nombreux différents types de matériaux
géologiques sauf la détermination des éléments
volatils due à une haute température de fusion
(1000 °C). Le frittage avec peroxyde de sodium à
480 °C permet la détermination rapide de Y, Sc et
des Terres Rares dans différents types de matériaux
géologiques. Toutefois, l’absence de réactifs ultra-
purs exclut l’utilisation de la fusion avec tétraborate
de lithium et du frittage avec peroxyde de sodium
pour l’analyse de faibles teneurs d’éléments en
traces dans des échantillons géologiques.
Mots-clés : décomposition chimique, matériaux
géologiques de référence, détermination d’éléments
en traces, spectrométrie de masse couplée à une
torche à plasma induit, comparaison de techniques.
Received 10 Nov 00 — Accepted 27 Jun 01
GEOSTANDARDS
NEWSLETTER
The Journal of Geostandards and Geoanalysis
Sample decomposition is a fundamental and
critical stage in the process of geochemical sample
analy sis. It is often the limiting fac tor to sample
throughput, which is particularly true with the applica-
tion of fast and modern multi-element measurement
instrumentation, such as ICP-MS and ICP-AES (Chao
and Sanzolone 1992).
Many digestion methods have been used for the
decomposition of geological samples. These include
open and closed vessel acid digestion methods
(Moselhy et al. 1978, McQuaker et al. 1979, Lechler
e t a l . 19 8 0 , C h u rc h 19 81, U c h i d a e t a l . 19 8 0 ,
McLaren et al. 1981, Hee and Boyle 1988, Karstensen
and Lund 1989, Jarvis 1990, Boer et al. 1993, Dulski
1994, Münker 1998, Liang et al. 2000), microwave
dissolution (Lamothe et al. 1986, Borman 1988,
Kingston and Jassie 1988, Mathes 1988, Matusiewicz
and Sturgeon 1989, Kemp and Brown 1990, Nölter et
al . 1990, Totland et al. 1995, Yoshida et al. 1996),
Na 2O 2 sintering (Robinson et al. 1986, Longerich et
al. 1990) and fusions with alkali fluxes such as LiBO 2,
Li 2B 4O 7, Na 2O 2 etc. (Burman et al. 1978, Bankston et
al. 1979, Walsh and Howie 1980, Brenner et al.
1980, Jarvis 1990). Totland et al. (1992) evaluated
results from open vessel acid digestion, LiBO2 fusion,
and microwave-heated sealed-vessel acid digestion
for thirty eight elements by ICP-MS analysis in nine
geological reference materials of varied composition.
Reviews of decomposition techniques in geological
materials are given in Potts (1987), Heinrichs and
Herrmann (1990), Jarvis (1992), and Chao and
Sanzolone (1992).
Despite this multitude of techniques, complete
dissolution of all sample types is still a problem. In
practical ICP-MS analysis, care must be taken when
adapting methods for multi-element determination,
since many of the digestion procedures were develo-
ped for measurement of only a few elements. The solu-
tion chemistry involved in many dissolution procedures
is poorly understood and refinements and understan-
ding of these techniques have not kept pace with the
rapid development in modern analytical instrumenta-
tion (Jarvis 1992).
Therefore, in order to achieve a complete dissolu-
tion and hence obtain reliable multi-element analytical
data using ICP-MS, a sy stematic investigation of
decomposition techniques for a range of basalt, granite
and ironstone geological reference materials is descri-
bed in this paper. The methods investigated are:
200
1. Savillex screw-top Teflon vial acid digestion
2. PicoTrace high pressure acid digestion
3. Microwave oven (sealed vessel, acid digestion)
4. Combined Li 2 B 4 O 7 fusion + HF/HNO 3 acid
digestion
5. Sodium peroxide sinter
Experimental
Instrumentation
A Finnigan MAT Element ICP-mass spectrometer
(Bremen, Germany) was used in this study. This instru-
ment was equipped with a compact, double-focusing,
magnetic sector of reversed Nier-Johnson geometry.
The mass range of the double-focusing magnetic
sector field analyser extended from 5 to 260 amu. Pre-
defined resolution settings (M/∆M at 10% valley defi-
nition) of 300 (low), 3000 (medium) and 7500 (high)
allowed the operating resolution to be adjusted,
depending mainly on the analytical matrices encoun-
tered. In this investigation, isotopes of interest were
measured using electric scanning, with the magnet
held at fixed mass. As reported in an earlier study
(Robinson et al. 1999), 45 Sc was measured using
medium resolution in order to avoid the interferences
of polyatomic species such as 29 Si 16 O, 28 Si 16 O 1 H,
13 C 16 O etc. and the remainder of trace elements
of interest were all measured using low resolution.
Instrument tuning and optimisation were performed
daily using a 10 ng g -1 multi-element solution contai-
ning the elements of interest. In general, instrument
parameters were adjusted to obtain optimum intensity
and stability. The typical instrumental settings for the
study are summarized in Table 1. Further details regar-
ding this instrument have been reported elsewhere
(Moens et al. 1994, Townsend et al. 1998, Robinson et
al. 1999, Yu et al . 2000).
Digestion apparatus
PicoTrace  high pressure digestion system: The
acid pressure digestion system used in the study was a
P i c o Tr a c e  TC - 8 0 5 P r e s s u r e D i g e s t i o n S y s t e m
(Bovenden, Germany). Digestion time and temperature
could be controlled automatically. Geological mate-
rials were digested in 30 ml PTFE (polytetrafluoroethy-
lene) digestion containers using procedures in which
temperatures and pressures did not exceed 180 °C
and 2000 kPa. During pressure digestion, the PTFE
containers were inserted in a PFA- (perfluoroalkoxy-
ethylene) coated digestion block and tightly sealed
 GEOSTANDARDS
NEWSLETTER
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Table 1.
Typical instrumental settings

Instrument Finnigan MAT ELEMENT

Resolution (M/∆M) Low = 300, Medium = 3000

RF power ~ 1250 W
Nebuliser Meinhard
Coolant argon flow rate 12-13 l min-1
Auxiliary argon flow rate 0.8-1 l min-1
Nebuliser argon flow rate 0.8-1.2 l min-1 (adjusted daily to obtain optimum signal intensity and stability)
Sample uptake rate Approximately 0.75 ml min -1
Spray chamber Scott (double pass) type cooled at 3.5 to 5 °C
Sampler cone Nickel, 1.1 mm aperture i.d.
Skimmer cone Nickel, 0.8 mm aperture i.d.
Instrument tuning Performed using a 10 ng g-1 multi-element solution
Ion transmission ~ 1,000,000 cps per 10 ng g-1 indium
Rinse time between standards or samples 200 s (with 5% v/v HNO3)
Takeup and stabilisation time 240 s
Scan type Magnetic jump with electric scan over small mass range
Ion sampling depth Adjusted daily to obtain maximum signal intensity
Ion lens settings Adjusted daily to obtain maximum signal intensity and optimum resolution

with PTFE lids, which were reinforced by pressure disks
and plates. Two sixteen container blocks on the hotplate
allowed digestion of thirty two samples at a time.
During evaporation, all PTFE containers remained in
the pressure digestion unit and were covered with one
large PTFE evaporation plate. Acid fumes were remo-
ved by a water vacuum pump and absorbed by a
strong alkaline solution. No cross contamination bet-
ween digestion containers was observed during the
evaporation stage.
Milestone microwave: Microwave decomposition
was carried out with the MLS-1200 MEGA Microwave
Digestion System (Milestone, Italy) in combination
with MDR (microwave digestion rotor) 1000/6/100/110
system and 100 ml TFM (tetrafluormethaxil) vessels.
The power emission of the microwave system could
be controlled from 10 to 1000 W (in 10 W incre-
ments). Different digestion programmes could be cho-
sen for different samples. There were several steps
with each digestion programme, and a different time
could be set for each step of digestion. The maximum
pressure in the vessel could reach as high as 11000
kPa. The properties of TFM include high density, high
insulating properties and high working temperature
( ca. 330-350 °C).
Reagents and calibration
Concentrated acids were used exclusively in this
study. Hydrochloric acid (33% w/w BDH, AR grade)
and HNO 3 (70% w/w BDH, AR grade) were used
after further double distillation in a sub-boiling
quartz distillation system. Hydrofluoric acid (50% w/w
Analar, AR grade) was doubly distilled in a sub-boiling
Teflon distillation system and ultra-pure HClO 4 (70%
w/w ARISTAR , BDH Chemicals) was also used. Ultra-
pure H 2 SO 4 (double distilled sub-boiling in quartz)
was obtained from Seastar Chemicals Inc., Canada.
Ultra-pure water (≥ 16.7 MΩ) used in the study was
prepared by distillation with a glass distillation system
and then further purified with a MODULAB Water
P u r i f i c a t i o n S y s t e m ( C o n t i n e n t a l Wa t e r S y s t e m
Corporation, Melbourne, Australia). Li 2B4O7 (AR grade,
Sigma Chemicals, WA, Australia) and Na 2 O 2 (AR
grade, Merck) were used for the fusion and sinter
experiments, respectively, in this work.
External calibration standards were prepared by
gravimetric serial dilution from 100 µg ml -1 multi-
element standards (QCD Analyst, USA). The standard
solutions were prepared at the beginning of each
analytical sequence with doubly distilled water and
2% w/w HNO 3. The indium standard solution (1000 ±
3 µg ml -1 in 2% w/w HNO 3, High-Purity Standards,
South Carolina, USA) was diluted to working concen-
tration in 2% w/w HNO 3 before use as an internal
standard for ICP-MS analysis.
Geological reference materials
A range of basalt, granite and ironstone geological
reference materials was chosen to investigate the cha-
racteristics of different digestion techniques (Table2).
International geological reference materials were
mainly used, along with two in-house rock reference

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Table 2.
A list of geological reference materials studied

Sample name Description Reference

BHVO-1 Basaltic lava from Kilauea caldera, Kilauea volcano, Hawaii, USA Govindaraju (1994)

TAFAHI Basalt collected from north Tonga, used as an in-house reference material by the Eggins et al. (1997)
Research School of Earth Sciences, Australian National University

AC-E Granite from a quarry in Ailsa Craig island in the Firth of Clyde, southwest Scotland. The Potts and Holbrook (1987),
Ailsa Craig microgranite comprises alkali feldspar (low albite with small proportions of Govindaraju (1987)
orthoclase) and quartz with less 10% of amphibole, pyroxene, aenigmatite and accessory
minerals. It contains significant amounts of both light and heavy REE giving a flat chondrite-
normalized abundance distribution at about the 100 times chondrite level

GSR-1 A grey medium-grained biotite granite from Binzhou, Hunan province, PRC. Mineralisation Xie et al. (1985, 1989)
of tungsten, tin and molybdenum occurs in the contact zone between the granite and
carbonate rocks

G-2 Westerly granite from Sullivan quarry, Bradford, Rhode Island, USA, collected by Felix Chayes, Flanagan (1967)
Geophysical Laboratory, Carnegie Institution of Washington. G-2 is rich in plagioclase Govindaraju (1994)
and biotite

MA-N Albite-lepidolite granite (“quartz albititite”), from Beauvoir (Clemont-Ferrand, Massif Central), Govindaraju (1980, 1994)
France. MA-N is a special granite in the sense that transition elements and REE are at
very low concentrations whereas elements such as Ag, Be, Cd, Cs, Ga, Li, Nb, Rb, Sn, Ta
and W are at “unusually high concentrations”, and it also contains cassiterite

YG-1 Medium-grained felsic granite with occasional feldspar megacrysts up to 20 mm from the Thompson et al. (1999)
Yewangara pluton, Wyangala batholith, Lachlan granite province, New South Wales, Australia

FeR-2 Iron formation sample (magnetite rich) from Griffith Mine, Bruce Lake, Ontario, Canada Govindaraju (1994)

FeR-4 Iron formation sample (magnetite rich) from Sherman Mine, Temagami, Ontario, Canada Govindaraju (1994)

TASBAS Basalt from Tasmania, Australia (an in-house reference material at School of Earth Sciences, Robinson et al. (1986)
University of Tasmania)

TASGRAN Granite from St Helens, N.E. Tasmania, Australia (an in-house reference material at School of Robinson et al. (1986)
Earth Sciences, University of Tasmania). Contains potassium feldspar, plagioclase, biotite
and hornblende

samples (TASBAS and TASGRAN) from the School of
Earth Sciences of the University of Tasmania.
Savillex Teflon vial acid digestion
Acid digestion in Teflon vials on a hotplate is a
simple and convenient way to decompose geological
samples for analysis. Silicon is removed as volatile SiF 4
and no extra salts are added to the solution.
Digestion procedure
shaken occasionally. The vial was removed from the
hotplate twice (at the beginning and in the middle of
the digestion) and placed in an ultrasonic bath for a
couple of minutes. The solution was evaporated on a
hotplate at 130-150 °C to incipient dryness. The eva-
poration was repeated twice more after adding 1 ml
HNO 3 each time. The residue was dissolved using 2
ml HNO3 and 3-5 ml water on the hotplate and dilu-
ted to 100 ml with ultra-pure water in a polypropylene
bottle. All solutions were freshly analysed within 24
hours of dissolution by ICP-MS.

Aliquots of rock powder (100 mg) were weighed Results

into 7 ml screw-top Savillex  Teflon vials. After wetting
with a few drops of ultra-pure water, the sample was
spiked with 0.1 ml 10 µg g -1 indium solution and then
2 ml HF and 0.5 ml HNO 3 were slowly added. After
sealing, the beaker was placed on a hotplate at 130-
150 °C for 48 hours. During the digestion, the vial was
The results in Table 3 demonstrate that the three
basalts (BHVO-1, TAFAHI and TASBAS) can be comple-
tely dissolved by the proposed Savillex  Teflon vial
acid digestion technique. Accuracy and precision for
twenty seven elements in BHVO-1 (eight digestions),

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Table 3.
Measured trace element concentrations (µg g -1 ), precision and reference
values for BHVO-1, TAFAHI and TASBAS by Savillex Teflon vial digestion

Element BHVO-1 TAFAHI TASBAS

Result % RSD Ref. Result % RSD Ref. Result % RSD Ref.

n = 8 value n = 17 value n = 14 value

Sc 31.9 1.8 31.8 44.3 3.1 45.5 14.3 3.8 14.3

Rb 9.6 3.1 11 1.8 1.4 1.75 16 1.8 16.4
Y 24.9 1.9 27.6 8.2 1.7 9.11 19 5.1 19.5
Zr 168 0.2 179 11.7 1.4 12.07 243 2.8 257
Nb 18.2 1.2 19 0.5 2.1 0.456 58.4 1.0 58.4
Mo 1.06 1.9 1.02 0.45 2.8 0.44 7.55 1.2 7.4
Sn 1.98 4.0 2.1 0.217 5.7 0.24 2.94 4.1 3.3
Cs 0.1 8.6 [0.13] 0.065 4.0 0.066 1.05 1.0 1.07
Ba 134.8 1.7 139 40.1 1.9 40.3 187 1.0 186.5
La 16 1.0 15.8 0.94 1.6 0.938 43 3.6 44.5
Ce 39 3.0 39 2.24 2.0 2.22 84.9 5.8 85.4
Pr 5.65 1.7 5.7 0.366 1.6 0.361 10.3 5.9 10.25
Nd 25.1 2.2 25.2 1.89 1.5 1.93 39.6 3.9 40.2
Sm 6.26 3.1 6.2 0.711 1.5 0.722 7.97 4.4 8.25
Eu 2.12 2.0 2.06 0.3 2.2 0.305 2.53 6.3 2.64
Gd 6.26 3.1 6.4 1.04 2.1 1.069 6.88 5.0 6.79
Tb 0.97 3.8 0.96 0.193 1.4 0.207 0.92 6.8 0.96
Dy 5.34 2.6 5.2 1.34 1.5 1.384 4.59 6.7 4.77
Ho 1.02 4.0 0.99 0.311 1.3 0.322 0.78 7.4 0.8
Er 2.59 2.4 2.4 0.94 0.9 0.98 1.83 5.3 1.82
Yb 1.99 3.5 2.02 0.94 0.9 0.992 1.25 5.6 1.27
Lu 0.28 3.7 0.291 0.148 1.7 0.153 0.18 7.2 0.17
Hf 4.34 1.2 4.38 0.391 2.0 0.395 5.51 3.1 5.43
Ta 1.23 1.8 1.23 0.028 14 0.0219 3.72 7.2 3.76
Pb 2.33 3.3 2.6 0.94 4.2 0.95 4.69 3.5 4.56
Th 1.28 4.5 1.08 0.116 2.6 0.12 4.62 5.1 4.87
U 0.44 2.8 0.42 0.073 2.6 0.0728 1.9 3.8 1.89

Digestion conditions: 2 ml HF and 0.5 ml HNO3 for 100 mg powdered rock sample. [ ] information value.
See Table 2 for sources of reference values.

TAFAHI (seventeen digestions) and TASBAS (fourteen A. 1 ml HF + 2 ml HNO 3

digestions) was generally within ± 4%. Compared with B. 1 ml HF + 1 ml HNO 3
Govindaraju’s (1994) values for Rb, Y, Cs, Pb and Th in C. 2 ml HF + 1 ml HNO 3
BHVO-1 differed by -13%, -10%, +23%, -10% and D. 2 ml HF + 0.5 ml HNO 3
-18.5% respectively, although for these elements our E. 1 ml HF + 3 ml HCl + 1 ml HNO 3
results agreed with a more recent compilation (Eggins F. 1 ml HF + 1 ml HCl + 3 ml HNO 3
et al. 1997). Yttrium was also low in TAFAHI, which was
due to low reference values (Robinson et al. 1999). Duplicate digestions were applied to each sample
Results for Nb and Ta in TAFAHI were high due to remo- and digestion condition.
bilisation of trace amounts of these elements from the
sample introduction system by HF in the HR-ICP-MS when Data plotted in Figure 1 show the comparison bet-
using the Savillex HF/HNO 3 method (Yu et al. 2000). ween the average measured results and reference
values. Under all digestion conditions, the average
Granites gave poor results due to resistant mineral recoveries of trace elements for AC-E were 82% to
phases. As well as the procedure described, further 99% compared to the reference values (Govindaraju
attempts were made to digest the granites GSR-1, 1994), whereas GSR-1 and TASGRAN showed lower
TASGRAN and AC-E using varying acid mixtures of recoveries (58-80%), indicating the presence of more
HF/HNO 3 and HF/HCl/HNO 3. resistant accessory minerals (such as zircon, magnetite,
rutile, etc.). Higher recoveries for conditions C and D
Details of the mixtures and ratios are given below: were probably due to the extra HF (2 ml instead of 1

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NEWSLETTER
The Journal of Geostandards and Geoanalysis
ICP-MS/reference
ICP-MS/reference
ICP-MS/reference
Figure 1. Comparison between the measured results and reference
values for AC-E, GSR-1 and TASGRAN using Savillex vial digestion.
Digestion conditions: A = 1 ml HF + 2 ml HNO 3; B = 1 ml HF + 1
ml HNO 3; C = 2 ml HF + 1 ml HNO 3; D = 2 ml HF + 0.5 ml HNO 3;
E = 1 ml HF + 3 ml HCl + 1 ml HNO 3; F = 1 ml HF + 1 ml HCl + 3
ml HNO 3.
ml) and, for condition E, the HF/ aqua regia mix.
Recoveries for REE were particularly low (26-69%) for
conditions B and F, where only 1 ml HF was used. This
indicates insufficient HF to break down the Si-O bond,
which leads to liberation of metals bound within the
silicate structure (Chao and Sanzolone 1992). It is
concluded that the Savillex vial method is generally
unsuitable for decomposition of granites or indeed any
rocks with resistant accessory minerals.
PicoTrace high pressure acid digestion
Three procedures were investigated: (A) HF/HClO 4;
(B) two stage HF/HClO 4 and HF/HClO 4/HNO 3; (C)
HF/H 2SO 4.
HF/HClO 4
Aliquots (100 mg) of powdered sample were
weighed into 30 ml PTFE digestion containers. After
204
wetting the sample with a few drops of ultra-pure
water and adding 0.1 ml of 10 µg g -1 indium solu-
tion to each digestion container, 3 ml HF and 3 ml
HClO 4 were slowly added. After thorough mixing
by shaking a few times, the PTFE containers were
left in the digestion block at 180 °C for 48 hours.
The digestion mixture was then evaporated to dry-
ness at 180 °C for a further 12 hours in the evapo-
ration block. Finally, 2 ml HNO 3 , 1 ml HCl and 10
ml ultra-pure water were added to the PTFE contai-
ners. The residue was dissolved by warming the
solution in the digestion block at 60-70 °C for an
hour or so. After the solution became clear, it was
transferred into a polypropylene bottle and diluted
to 100 ml.
The results for BHVO-1, FeR-2 and FeR-4 are in
good agreement with the reference values
(Govindaraju 1994). Table 4 lists the measured
results and their comparisons with reference values.
Each measured result represents the mean value of
two separate digestions. The average recovery of
thirty two elements for BHVO-1 was 100%, 108% for
FeR-2 and 104% for FeR-4. The range of recoveries
for FeR-2 and FeR-4 was 73%-152%, due to the low
concentration of trace elements in the ironstones and
the additional uncertainty associated with the many
“ p ro p o s e d ” v a l u e s ( ra t h e r t h a n “ re c o m m e n d e d ”
values) listed in the compilation o f Govindaraju
(1994).
T h e a c c u ra c y o f R E E f o r Fe R- 2 a n d Fe R-4 i s
also demonstrated by the chondrite distribution
patterns shown in Figure 2. REE chondrite distribu-
tion patterns have often been used as additional
proof of the quality of REE data (e.g. Jarvis 1988,
Ionov et al. 1992, Dulski 1994, Makishima and
Nakamura 1997, Robinson et al. 1999). The pat-
terns obtained using the high pressure HF/HClO 4
digestion method are clearly smoother than those
based on the reference values (Govindaraju
1994).
BHVO-1 was also digested for 16 hours instead of
48 hours to determine if any time saving was possible
in the procedure. Results (Table 4) show a reduced
average recovery (92%) for thirty two elements compa-
red to the reference values. Over the shorter 16 hour
digestion, recoveries for Zr, Nb, Hf and Ta were 86%,
94%, 91% and 89% respectively, 94% for light REE
and 87 to 91% for heavy REE. Thus, a digestion time of
48 hours should be applied.
 GEOSTANDARDS
NEWSLETTER
The Journal of Geostandards and Geoanalysis

Table 4.
Measured results (µg g -1 ) for basalt and ironstones using
3 ml HF/3 ml HClO 4 high pressure (PicoTrace) digestion

Element BHVO-1 FeR-2 FeR-4

Measured Measured Reference Measured Reference Measured Reference

DT = 48 hr DT = 16 hr value* DT = 48 hr value* DT = 48 hr value*
n = 2 n = 2 n = 2 n = 2

Sc 29.6 29.7 31.8 5.31 6 1.09 1.5

Rb 9.26 9.24 11 61.8 67 14.9 16
Sr 383 378 403 60.9 58 60.4 62
Y 23.3 22.1 27.6 13.2 16 7.87 9
Zr 168 153 179 45.8 39 18.4 18
Nb 18.8 17.9 19 3.95 - 0.776 -
Mo 1.13 1.21 1.02 6.05 3 0.142 -
Sn 1.97 1.62 2.1 0.99 1 1.11 1
Sb 0.161 0.168 0.16 0.692 0.7 1.12 1
Cs 0.097 0.1 [0.13] 4.95 4.5 0.667 0.7
Ba 138 129 139 243 230 38.3 39
La 15.8 15.1 15.8 13.6 12 8.47 8
Ce 38.8 37.3 39 27.8 25 13.7 11
Pr 5.61 5.37 5.7 3.35 3 1.72 2
Nd 26.2 23.7 25.2 13. 6 12 8.22 8
Sm 6.69 5.83 6.2 3.02 2.5 2.39 2.1
Eu 2.32 2.06 2.06 1.48 1.25 0.79 0.74
Gd 7.23 5.94 6.4 2.88 2 1.44 1.1
Tb 0.987 0.878 0.96 0.398 0.32 0.185 0.15
Dy 5.65 4.82 5.2 2.51 2 1.16 1
Ho 1.07 0.945 0.99 0.545 0.6 0.251 0.2
Er 2.83 2.34 2.4 1.64 1.5 0.761 0.5
Tm 0.363 0.313 0.33 0.237 0.2 0.108 -
Yb 2.18 1.83 2.02 1.59 1.25 0.717 0.7
Lu 0.308 0.252 0.291 0.239 0.2 0.112 0.1
Hf 4.64 4.01 4.38 1.35 1 0.572 0.5
Ta 1.29 1.09 1.23 0.194 0.2 0.051 -
Tl 0.041 0.042 0.058 0.228 - 0.06 -
Pb 2.17 2.04 2.6 8.48 11 7.14 8
Bi 0.017 0.015 0.018 0.189 - 0.044 -
Th 1.32 1.16 1.08 3.22 2.4 0.976 0.8
U 0.455 0.446 0.42 1.29 1.2 0.641 0.5

DT is digestion time. * Reference values are from Govindaraju (1994). - No value available.
[ ] Information value.

Two stage HF/HClO 4 and HF/HClO 4 /HNO 3

The HF/HClO 4 method described above proved

inadequate for granites. Hence GSR-1, G-2 and AC-E
ICP-MS/chondrite

were digested under different conditions to test the

efficiency of two stage HF/HClO 4 and single stage
HF/HClO 4/HNO 3 high pressure techniques. According
to the acid mixture, evaporating procedure and acid in
final solutions, digestion groups A to E are classified in
Table 5.

The results of two separate digestions for GSR-1,

Figure 2. Chondrite-normalized distribution patterns G-2 and AC-E by HF/HClO 4 and HF/HClO 4/HNO 3
of REE for FeR-2 and FeR-4 by 3 ml HF/3 ml HClO 4 high high pressure digestion techniques are available from
pressure digestion. Digestion time was 48 hours. FeR-2- the authors on request. The outcomes are summarized
reference and FeR-4-reference are from Govindaraju (1994). as follows.

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Table 5.
A list of digestion conditions (groups A to E) using high pressure (PicoTrace) digestion

Stage one Stage two Final solution

(At 180 °C for 16 hr)

Group A 3 ml HF + 2 ml HClO4 + 2 ml HNO3 None 2% w/w HNO3

Group B 3 ml HF + 2 ml HClO4 + 2 ml HNO3 None 2% w/w HNO3/1% w/w HCl

Group C 3 ml HF + 3 ml HClO4 (1) Add 5 ml HCl and evaporate to dryness. 5% w/w HCl
(2) Add 5 ml HCl again and digest at 150 °C
for 16 hr.

Group D 3 ml HF + 3 ml HClO4 (1) Add 5 ml HCl and evaporate to dryness. 2% w/w HNO3/1% w/w HCl
(2) Add 2 ml HNO3 and 1 ml HCl and digest at
150 °C for 16 hr.

Group E 3 ml HF + 3 ml HClO4 (1) Add 5 ml HCl and evaporate to dryness. 2% w/w HNO3/1% w/w HCl
(2) Add 5 ml HCl again and digest at 150 °C
for 16 hr, evaporate to dryness.

All acids used were concentrated.

Results for the determination of thirty two elements
in the three granites showed recovery rates (i.e., in
comparison with reference values) for digestion groups
A, B, C, D and E of 75%, 75%, 88%, 82% and 96%
respectively. The best results (C and E) were obtained
from a two stage pressure digestion with HF/HClO 4,
followed by HCl, similar to the procedure used by
Dulski (1994) for Ba and REE determinations. The only
difference between C and E is that E has a final acid
concentration of 2% w/w HNO 3 and 1% w/w HCl
instead of 5% w/w HCl. However, the 96% average
recovery for E hides the low yields of 80% to 92% for
Zr and Hf (see GSR-1 in Figure 3). Refractory zircon
was not completely dissolved. The REE, Th and U
recoveries were 20-30% lower using methods A, B
and D, where the second pressure stage with HCl was
not used. Niobium recovery was 100 ± 5% and Ta,
averaging 95% (90-103%), were similar for digestion
methods A to E, suggesting that Nb and Ta are pre-
sent in minerals that are easily dissolved. Granite AC-E
gave particularly poor results for the REE and HFSE
(except Nb and Ta) with methods A and B, which used
a single stage HF/HClO 4/HNO 3 pressure digestion.
Münker (1998) reported that, even after a few
hours, the sample solution may lose Nb and Ta. The
addition of a small amount of HCl can stabilize Nb
and Ta in solution before ICP-MS analysis. In this work,
all solutions were freshly prepared and ICP-MS runs
were always conducted within 24 hours. The digestions
in groups A and B were identical, apart from a final
solution prepared in 2% w/w HNO 3 instead of 2%
w/w HNO3 and 1% w/w HCl. No obvious difference
in Nb and Ta results was observed between A and B.

HF/H 2 SO 4

The procedure followed was the same as for

HF/HClO 4, except that 3ml HF and 3ml H 2SO4 were
ICP-MS/reference

used at 180 °C for 16 hours. Evaporation time was

approximately four days. HClO 4 (1 ml) was added to
the residue and dried before adding the final 2 ml
HNO 3 and 1 ml HCl. GSR-1, AC-E, G-2, MA-N, YG-1,
TASGRAN, FeR-2, FeR-4, TAFAHI and TASBAS were ana-
lysed using the HF/H 2 SO 4 high pressure digestion
method.

Table 6 shows that, except for granite MA-N, the

Figure 3. The recoveries of HFSE and REE for GSR-1 under results for the granites, ironstones and basalts are in
various HF/HClO4/HNO3 and HF/HClO4 high pressure digestion good agreement with reference values (Xie et al.
conditions (groups A to E). 1989, Govindaraju 1994, Thompson et al. 1999,

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Table 6.
Measured concentrations (µg g -1 ), precisions and reference values for GSR-1, AC-E, G-2, MA-N,
YG-1, TASGRAN, FeR-2, FeR-4, TAFAHI and TASBAS by 3 ml HF/3 ml H 2 SO 4 high pressure digestion

Element GSR-1 AC-E

Measured % RSD Reference Measured % RSD Reference

n = 4 value n = 4 value

Sc 6.2 6.02 6.1 0.916 4.31 0.11

Rb 473 1.23 466 148 5.00 152
Sr 101 2.85 106 2.74 8.14 3
Y 60.7 3.41 62 161 1.81 184
Zr 165 6.14 167 803 2.12 780
Nb 42.0 8.72 40 112 4.90 110
Mo 3.7 7.16 3.5 2.36 7.33 2.5
Sn 11.8 4.89 12.5 15.2 4.00 13
Sb 0.261 8.25 0.21 0.358 9.15 0.4
Cs 37.5 2.40 38.4 3 1.00 3
Ba 308 2.19 343 55.1 3.57 55
La 51.3 1.91 54 56.6 2.37 59
Ce 102 2.56 108 150 1.73 154
Pr 12.1 2.8 12.7 21.3 1.96 22.2
Nd 41.8 3.49 47 87.2 2.41 92
Sm 9.09 4.10 9.7 23.7 3.32 24.2
Eu 0.815 2.61 0.85 1.87 4.53 2
Gd 8.49 3.12 9.3 25.2 3.15 26
Tb 1.45 4.42 1.65 4.5 4.37 4.8
Dy 9.27 3.10 10.2 28.7 1.65 29
Ho 1.98 4.04 2.05 5.98 5.18 6.5
Er 6.17 3.14 6.5 17.4 3.21 17.7
Tm 1.01 3.10 1.06 2.58 6.60 2.6
Yb 7.13 2.96 7.4 16.5 2.69 17.4
Lu 1.11 1.94 1.15 2.34 5.51 2.45
Hf 5.88 5.72 6.3 27.1 3.15 27.9
Ta 6.18 18.54 7.2 5.9 19.94 6.4
Tl 2.09 6.23 1.93 0.929 4.74 0.9
Pb 31.1 8.08 31 35 0.33 39
Bi 0.587 13.17 0.53 0.358 12.99 0.4
Th 49.1 2.01 54 17.5 3.29 18.5
U 18.7 1.17 18.8 4.53 4.00 4.6

Element G-2 MA-N YG-1 TASGRAN

Measured Ref Measured Ref Measured Ref Measured Ref

n = 2 value n = 2 value n = 2 value n = 2 value

Sc 3.59 3.5 0.117 0.2 4.49 4.48 6.89 6.85

Rb 169 170 3047 3600 149 154 259 251
Sr 438 478 73.5 84 83.3 88.5 146 146
Y 9.28 11 0.311 0.4 49.8 54.4 31.8 33
Zr 305 309 14.2 25 268 271.4 159 160
Nb 11.9 12 84.5 173 50 48.8 13.1 13.3
Mo 0.14 [1.1] 0.283 0.3 1.6 1.86 0.32 0.35
Sn 1.56 [1.8] 99.1 900 15.7 20.00 5.85 5.8
Sb 0.04 0.07 1.34 1.7 1.17 1.50 0.12 0.11
Cs 1.47 1.34 578 640 4.19 4.08 12.8 12.1
Ba 775 1882 39.8 42 292 535 464 455
La 79.7 89 0.433 0.5 58.8 63.4 41.5 39.7
Ce 151 160 0.787 0.9 118 129.5 83.3 84.6
Pr 15.9 18 0.095 0.1 15 15.01 10.1 10.1
Nd 49.8 55 0.332 0.4 53 56.7 35.9 35.9
Sm 6.95 7.2 0.073 0.09 10.9 11.44 7.09 7.51
Eu 1.38 1.4 0.014 0.02 1.61 1.63 0.83 0.82
Gd 4.37 4.3 0.052 0.08 10.5 10.85 6.10 6.27
Tb 0.47 0.48 0.01 0.01 1.69 1.70 0.90 1.02

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Table 6 (continued).
Measured concentrations (µg g -1 ), precisions and reference values for GSR-1, AC-E, G-2, MA-N,
YG-1, TASGRAN, FeR-2, FeR-4, TAFAHI and TASBAS by 3 ml HF/3 ml H 2 SO 4 high pressure digestion

Element G-2 MA-N YG-1 TASGRAN

Measured Ref Measured Ref Measured Ref Measured Ref

n = 2 value n = 2 value n = 2 value n = 2 value

Dy 2.04 2.4 0.056 0.07 9.80 9.93 5.51 5.83

Ho 0.35 0.4 0.011 0.017 2.01 1.96 1.07 1.16
Er 0.85 0.92 0.027 0.04 5.47 5.30 3.19 3.4
Tm 0.12 [0.18] 0.004 0.007 0.79 0.74 0.45 0.507
Yb 0.68 0.8 0.031 0.04 4.78 4.73 3.06 3.19
Lu 0.10 0.11 0.003 0.005 0.72 0.69 0.44 0.48
Hf 7.49 7.9 1.94 4.5 8.34 8.07 4.63 4.63
Ta 0.84 0.88 109 290 71.9 95.6 1.86 2.09
Tl 0.86 0.91 19.4 15 0.77 0.81 1.53 1.3
Pb 26.4 30 24.8 29 19.7 22.50 25.2 26.7
Bi 0.03 0.037 1.67 - 0.33 0.30 0.24 -
Th 21.2 24.7 0.716 1.4 19.6 22.45 18.3 19.2
U 2.10 2.07 13.4 12.5 3.14 2.94 3.30 3.2

Element FeR-2 FeR-4 TAFAHI TASBAS

Measured Ref Measured Ref Measured Ref Measured Ref

n = 2 value n = 2 value n = 2 value n = 2 value

Sc 5.79 6 1.42 1.5 43.5 45.5 14.3 14.3

Rb 66.8 67 17.1 16 2.00 1.75 16.9 16.4
Sr 62.1 58 65.7 62 145 138.9 1014 1006
Y 12.7 16 8.42 9 9.94 9.11 17.9 19.5
Zr 37.5 39 20.6 18 10.7 12.07 243 257
Nb 2.67 - 1.50 - 0.442 0.456 61.5 58.4
Mo 2.69 3 1.14 - 0.503 0.44 8.06 7.4
Sn 1.03 1 1.01 1 0.166 0.24 3.04 3.3
Sb 0.64 0.7 1.26 1 0.02 0.024 0.11 1.03
Cs 4.83 4.5 0.71 0.7 0.055 0.066 1.05 1.07
Ba 205 230 40.7 39 39.4 40.3 190 186.5
La 12.2 12 7.87 8 1.03 0.938 44.3 44.5
Ce 23.8 25 12.6 11 2.41 2.22 84.6 85.4
Pr 2.90 3 1.59 2 0.414 0.361 10.2 10.25
Nd 11.4 12 7.21 8 2.16 1.93 37.8 40.2
Sm 2.40 2.5 2.01 2.1 0.834 0.722 7.68 8.25
Eu 1.18 1.25 0.64 0.74 0.378 0.305 2.48 2.64
Gd 2.16 2 1.21 1.1 1.27 1.069 6.49 6.79
Tb 0.33 0.32 0.17 0.15 0.249 0.207 0.83 0.96
Dy 2.08 2 1.07 1 1.75 1.384 4.17 4.77
Ho 0.43 0.6 0.22 0.2 0.413 0.322 0.69 0.8
Er 1.29 1.5 0.67 0.5 1.22 0.98 1.65 1.82
Tm 0.18 0.2 0.09 - 0.185 - 0.20 0.232
Yb 1.22 1.25 0.60 0.7 1.18 0.992 1.21 1.27
Lu 0.18 0.2 0.09 0.1 0.184 0.153 0.16 0.17
Hf 1.09 1 0.53 0.5 0.294 0.395 4.99 5.43
Ta 0.27 0.2 0.11 - 0.0223 0.0219 2.87 3.76
Tl 0.21 - 0.09 - 0.01 0.0142 0.09 < 0.1
Pb 9.40 11 7.06 8 0.985 0.95 6.24 4.56
Bi 0.25 - 0.19 - 0.003 - 0.19 < 0.1
Th 2.37 2.4 0.78 0.8 0.136 0.12 4.36 4.87
U 0.89 1.2 0.56 0.5 0.078 0.0728 1.83 1.89

See Table 2 for sources of reference values. - no value available. [ ] information value.

208

E g g i n s e t a l . 19 9 7, R o b i n s o n e t a l . 19 8 6 ) . T h e
H 2 SO 4 is successful in decomposing all zircon and
other accessory minerals in the granites and the
f i n a l H C l O 4 t re a t m e n t c o n v e r t s m o s t s u l f a t e s t o
soluble perchlorates, provided trace element levels
are not too high. Insoluble sulfates of Sr, Ba and Pb
would be expected to give low results. Strontium
and Pb recoveries, however, were quite good (88-
100%) although Ba recovery was variable, some-
times 100% (e.g. AC-E and TASGRAN) but with low
results for G-2 (41%) and YG-1 (55%). Thorium, Ta
and Nb (at high levels) gave low results due to
hydroly sis in the aqueous solution (Heslop and
Jones 1976, Münker 1998). Thorium was 2-14% low
and Ta, 5-24% low except for granite MA-N where
the presence of cassiterite (Govindaraju 1980) and
very high levels of Ta and Nb resulted in exceptio-
nally poor yields. Recoveries of Sn (900 µg g -1
expected), Nb (173 µg g -1 expected) and Ta (290
µg g -1 expected) were only 11%, 49% and 37%,
respectively. As reported by Hall (1980), cassiterite
is resistant to the commonly used acids (including
HF/H 2 SO 4 ). The average recovery for MA-N was
only 74% due to incomplete digestion of cassiterite,
hydrolysis and sulfate precipitation.
HF/H 2 SO 4 ratios
Although the PicoTrace  HF/H 2 SO 4 digestion
method is successful in breaking down most resistant
minerals, the high boiling point of H 2SO 4 (338 °C),
dictates a minimum of 4 days evaporation time. An
open beaker evaporation, i.e., beakers in the digestion
block on top of the hotplate without the evaporation
block, did not reduce this time. An investigation was,
therefore, made to ascertain if the volumes of HF and
H 2 SO 4 (normally 3 ml) could be reduced and so
speed up the overall analysis. Using 100 mg of each
granite, GSR-1, G-2 and AC-E, the following ratios and
digestion times were tested with the temperature kept
at 180 °C:
3 ml HF + 0.5 ml H 2SO4 16 hours
3 ml HF + 1 ml H 2SO 4 16 hours
2 ml HF + 0.5 ml H 2SO4 16 hours
2 ml HF + 1 ml H 2SO 4 16 and 48 hours
2 ml HF + 2 ml H 2SO 4 48 hours
The complete results of two independent digestions
under each HF/H 2 SO 4 ratio and digestion time are
available from the authors on request. From these
results it can be seen that:
209
GEOSTANDARDS
NEWSLETTER
The Journal of Geostandards and Geoanalysis
1. In general, the recoveries of trace elements
increased with increasing H 2SO 4 concentration; e.g.,
the average recovery (compared with reference values)
of GSR-1 increased from 69% to 93% by increasing
the H 2SO 4 from 0.5 to 2 ml.
2. Similar recoveries were found using 16 and 48
hour digestion times when the same H 2SO4 concentra-
tion (2 ml HF + 1 ml H 2SO4) was employed. The ave-
rage recoveries for GSR-1 were 90% (16 hours) and
84% (48 hours); 85% (16 hours) and 86% (48 hours)
for G-2 and 87% for AC-E (for both digestion times).
3. Unlike GSR-1 and G-2, there is not a clear
increase in the recovery of AC-E with increasing H 2SO4
concentration. This reflects differences in mineral com-
positions between AC-E and GSR-1 or G-2.
4. Granites cannot be digested completely with
less than 3 ml HF and 3 ml H 2SO4 under the propo-
sed digestion conditions.
Figure 4 shows the recoveries of HFSE and REE for
GSR-1 under various digestion conditions. The recovery
(measured/reference) increased with increasing
volumes of HF and H 2SO4. The average recovery was
ICP-MS/reference
Figure 4. The recoveries of HFSE and REE for GSR-1 under various
HF/H 2SO 4 high pressure digestion conditions. All digestions were
with100 mg rock powder at 180 °C. Digestion conditions: GSR-1a
= 16 hour digestion with 3 ml HF + 0.5 ml H 2SO 4; GSR-1b = 16
hour digestion with 3 ml HF + 1 ml H 2SO 4; GSR-1c = 16 hour
digestion with 2 ml HF + 0.5 ml H 2SO 4; GSR-1d = 16 hour
digestion with 2 ml HF + 1 ml H 2SO 4; GSR-1e = 48 hour
digestion with 2 ml HF + 1 ml H 2SO 4; GSR-1f = 48 hour digestion
with 2 ml HF + 2 ml H 2SO 4; GSR-1g = 16 hour digestion with 3
ml HF + 3 ml H 2SO 4.
GEOSTANDARDS
NEWSLETTER
The Journal of Geostandards and Geoanalysis
Table 7.
Comparison of power and pressure used in different microwave digestion studies
Parameter This work Jarvis et al. (1992)
Maximum power (W) 650 not given
Maximum pressure (kPa) 11000 828
about 97% when 3 ml HF and 3 ml H 2SO4 were used.
The low recovery for Ta was due to hydrolysis. Although
fresh solutions (within 24 hours after dissolution) were
normally analysed in this work by ICP-MS, approxima-
tely 15% Ta was lost.
Microwave digestion
In recent years, microwave digestion techniques
have been used to digest rock samples for ICP-MS
(e.g. Jarvis et al. 1992, Totland et al. 1995, Yoshida et
al. 1996). Ideally, in comparison with the high pressure
digestion method, the microwave digestion technique
should be less time-consuming, with rock samples
being digested within one hour or so. However, Jarvis
et al. (1992) found that microwave digestion did not
always allow the measurement of elements such as Zr
and Hf, especially when refractory mineral phases
were present. In some cases, measurement of the REEs
seemed to be a problem due to incomplete dissolution
of rock samples (Yoshida et al. 1996). The work repor-
t e d h e r e u s e d a M LS - 12 0 0 M E G A M i c r o w a v e
Digestion System, which is a more powerful system
(Table 7) than those used by Jarvis et al. (1992),
Totland et al. (1995) and Yoshida et al. (1996).
Digestion procedure
The sample (100 mg) was weighed into a TFM
(tetrafluormethaxil) vessel. After wetting with ultra-pure
water and spiking with indium as an internal stan-
dard, 2 ml HF and 0.5 ml HNO 3 were added to each
vessel. After thorough mixing, the vessel was introdu-
ced into the microwave oven (Milestone MLS-1200
MEGA with maximum pressure of 11000 kPa) and
digested at 250 W, 400 W, 650 W and 250 W for 5
minutes each, followed by venting for 5 min. The ves-
sel was then carefully removed onto a hotplate at
about 150 °C and the solution evaporated to a crys-
talline paste. To ensure the complete removal of HF,
two further 1 ml aliquots of HNO 3 were added and
evaporated to near dryness again. Finally, 2 ml HNO 3
and 5 to 10 ml ultra-pure water were added to the
vessel. The vessel was replaced in the microwave
210
Totland et al. (1995) Yoshida et al. (1996)
100 420
1379 483
oven and the residue was redissolved for one minute
at each power stage. The solution was finally transfer-
red to a polypropylene bottle and diluted to 100 ml
with ultra-pure water. Two other sets of conditions
were tried, (1) as above but with 10 minutes for each
power stage instead of 5 minutes and (2) 2 ml HF +
0.5 ml HNO3 + 2 ml HClO4 + 0.2 ml H 2SO 4 with 10
minutes for each power stage.
Results
An attempt was made to digest BHVO-1, GSR-1,
TASGRAN and FeR-2 by the microwave digestion
methods. Figure 5 shows the comparison between the
measured results and reference values (Govindaraju
1994).
Basalt BHVO-1 recovery was similar (about 91%)
for all three sets of conditions. Average recovery was
98.5% for U, better than 90% for the light REEs and
most trace elements, 85% for the heavy REEs and 83%
for Zr. Yttrium showed the lowest recovery with less
than 80%. These recovery values are similar to those
for the microwave digestion of basalts reported by
Yoshida et al. (1996), who found that average recove-
ries of U, Zr and Y for two Japanese basalt reference
materials (JB-1 and JB-2) were 96%, 90.5% and
84.5%, respectively.
Recoveries for the granites TASGRAN and GSR-1
were poor. TASGRAN averaged 69% recovery with little
difference between the three digestion methods. The
recovery for GSR-1 increased from 68.6% using 5
minutes for each power stage to 76% (10 minutes
each stage) and 83.7% (10 minutes), when the oxidi-
sing acids HClO 4 and H 2SO4 were present as well as
the HF and HNO3. The average REE increased similarly
from 61% to 72% to 77%. Recoveries of 100% were
found for Nb in both granites. Zirconium and Hf reco-
veries ranged from 80-100% in TASGRAN, but only
55-80% in GSR-1 indicating differences in mineralogy.
Ironstone FeR-2 gave a similar low average recovery
(85.6, 85.8 and 87.8%) for the three microwave

ICP-MS/reference
ICP-MS/reference
ICP-MS/reference
ICP-MS/reference
Figure 5. Comparison of ICP-MS results with reference values
for BHVO-1, GSR-1, TASGRAN and FeR-2 using microwave
digestion. Digestion conditions: 5 min/power = 5 minutes for
each power stage with 2 ml HF + 0.5 ml HNO3; 10 min/power-1
= 10 minutes for each power stage with 2 ml HF + 0.5 ml
HNO 3. 10 min/power-2 = 10 minutes for each power stage
with 2 ml HF + 0.5 ml HNO 3 + 2 ml HClO 4 + 0.2 ml H 2SO 4.
methods, the extra time (10 minutes at each power
stage) and addition of oxidising acids (HClO 4 and
H2SO 4) making little difference.
Li2B4O7 fusion + HF/HNO3 acid digestion
Despite the introduction of a high level of total
dissolved solids during sample preparation, which may
restrict the quantification of some trace elements by
ICP-MS (Totland et al. 1992), alkali fusion is still a very
useful alternative technique capable of the decompo-
sition of refractory minerals (Potts 1987, Chao and
Sanzolone 1992, Jarvis et al. 1992). In this work,
basalts BHVO-1, TAFAHI and TASBAS, granites (GSR-1,
AC-E and TASGRAN) and ironstones (FeR-2 and
FeR-4) were fused with Li 2B4O7. This was followed by
HF/HNO 3 treatment in an attempt to remove Si and B
as volatile fluorides and so reduce the total dissolved
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GEOSTANDARDS
NEWSLETTER
The Journal of Geostandards and Geoanalysis
solids present in the final solution. ICP-AES analysis
of the resulting solutions was made to determine any
residual Si and B.
Digestion procedure
The sample (100 mg) and 200 mg of lithium tetra-
borate (Li 2 B 4 O 7 ) were weighed into a platinum
crucible and mixed thoroughly with a plastic spatula.
The mixture was fused at 1000 °C for 30 min. in a
muffle furnace. After cooling to room temperature, 5 ml
HF and 2 ml HNO 3 were slowly added to the crucible
and the solution was evaporated on a hotplate
at 130-150 °C to incipient dryness. Two 1 ml aliquots
of HNO 3 were added to the residue and each evapo-
rated to incipient dryness. Finally, the residue was
dissolved in 2 ml HNO 3 and 10 ml ultra-pure water.
The solution was transferred to a polypropylene bottle,
spiked with 0.1 ml 10 µg g -1 indium and diluted to
100 ml with ultra-pure water.
Results
The results show that the combined Li 2B4O7 fusion
+ HF/HNO 3 acid digestion is an effective decomposi-
tion technique for trace elements in the basalts, gra-
nites and ironstones investigated. Data in Figure 6
compare the ICP-MS results with reference values (R 2 =
0.9991). A full compilation of results is available on
request from the authors.
The average accuracy (compared with reference
values) of trace elements for basalts BHVO-1, TAFAHI
and TASBAS was 2.1, 3.8 and 1.2% respectively, with a
spread of ± 4%. For the granites GSR-1, AC-E and
TASGRAN, recovery was excellent with an average
accuracy of about 1% with a spread of ± 4.4%. Good
results were obtained for elements like Y, Zr, Ba, REE,
Ta, Th and U, which often reside in resistant minerals.
Higher variations were observed in the ironstones
Fe R - 2 a n d Fe R- 4 . Fo r ex a m p l e , c o m p a re d w i t h
Govindaraju (1994), Ta and U were low by 11% and
16% in FeR-2 and Cs, Ce and the HREEs were low by
11-73%. However, for trace elements present at low
concentration levels (< 1 µg g -1) FeR-2 and FeR-4 are
not particularly well characterized as reference materials.
A s an additional assessment of the analytical
quality of REE data, REE chondrite-normalized plots
(Figure 7) show the smoothness of REE patterns for the
eight geological reference materials analysed in the
study.
GEOSTANDARDS
NEWSLETTER
The Journal of Geostandards and Geoanalysis
Reference values
Measured
Figure 6. Correlation of twenty seven trace elements
(including HFSE, REE, Sc, Rb, Sr, Y, Mo, Cs and Ba)
between the measured results by Li 2B 4O 7 fusion +
HF/HNO 3 digestion and reference values for BHVO-1,
TAFAHI, TASBAS, GSR-1, AC-E, TASGRAN, FeR-2 and FeR-4.
Although Li 2B 4O 7 fusion is a powerful decompo-
sition technique for geological materials by ICP-MS,
this method precludes the determination of volatile
elements Sn, Sb, Tl and Pb due to the high fusion tem-
perature (1000 °C). Jarvis et al. (1992) and Totland et
al. (1992), using a LiBO 2 fusion method, also reported
similar problems.
Another disadvantage of this method is the high
salt concentration, which decreases instrumental sen-
sitivity, resulting in poor detection limits and the need
for frequent cleaning of cones, nebuliser and spray
chamber. The additional HF/HNO 3 acid digestion
stage was useful in reducing the salt concentration,
by removing Si and B as volatile fluorides. Sample
solutions of basalt (TASBAS) and granites (GSR-1
and TASGRAN) were also analysed by ICP-AES to
determine how much Si and B were lost. The TASBAS
solution lost only 36% of B and 61% of the Si, whe-
reas the granites lost 64 to 66% of the B and 81 to
85% of the Si. Further experiments involving the
addition of an extra 2 ml HF during the digestion,
did not show any further reduc tion in Si and B
concentration.
Reagent contamination is also a problem. Although
relatively pure lithium borates can be obtained, blanks
are often too high for the determination of trace
212
ICP-MS/chondrite
Figure 7. Chondrite-normalized distribution patterns of
REE for BHVO-1, TAFAHI, TASBAS, GSR-1, AC-E, TASGRAN,
FeR-2 and FeR-4 using Li2B4O7 fusion + HF/HNO3 digestion.
elements at ultra low levels in ultramafic rocks. Finally,
it can be difficult to determine Li and B in subsequent
acid digestion runs due to their high background
levels in the ICP-MS instrument.
Sodium peroxide sinter
This method is a modification of that used by
Robinson et al. (1986) for the XRF determination of
REE, Sc and Y. It was of particular interest to discover
whether HFSE and other elements could be determi-
ned.
Digestion procedure
Merck Na 2O 2 (0.4 g) was weighed into a clean
platinum crucible, followed by 100 mg of finely
ground sample (note: 0.6 g of Na 2O 2 for magnetite,
chromite and sulfides). After mixing thoroughly, the
mixture was sintered for one hour at 480 °C. This was
followed by drop-wise addition of ultra-pure water
until the vigorous reaction ceased. The sinter residue
was transferred to a centrifuge tube, and washed
twice with ultra-pure water, decanting the clear liquid
each time. This removed sodium and silica salts, whe-
reas REE, Sc, Y and some HFSE were retained. Nitric
acid (2 ml ) and 10 ml ultra-pure water were added
and the residue dissolved. One drop of HF was
added to stabilize the HFSE, the solution was spiked
with 0.1 ml of 10 µg g -1 indium and diluted to 100 ml
with ultra-pure water.

Reference values
Measured
Figure 8. Correlation of Sc, Y and REE between the
measured results by the Na 2O 2 sinter method and
reference values for GSR-1, G-2, AC-E, TASGRAN, FeR-2,
FeR-4, BHVO-1, TAFAHI and TASBAS.
Results
The geological reference materials used in this
study were GSR-1, G-2, AC-E, TASGRAN, FeR-2, FeR-4,
BHVO-1, TAFAHI and TASBAS. The variation (accuracy)
between measured results and reference values was
normally within ± 10%. Excluding data for Y, where
reference values are high (Robinson et al. 1999), the
average bias for granites (AC-E and TASGRAN) is
-1.3% and +3.6% with a spread of 2 to 3%. Granites
(GSR-1 and G-2) were about 6% low with a spread
of 3 to 5%. Basalts (BHVO-1, average bias -4.9%
and TASBAS, +0.1%) had a spread of 2 to 3% and
the low level basalt (TAFAHI, +3.6%) had an expec-
ted wider spread of 6.9%, compared to the reference
values. Excluding data for Tm in FeR-4 (where the
reference value appears low), the ironstones FeR-2
and FeR-3 had an average bias of -3% and +2%
respectively, although the spread was 6 to 7%, as
elements in these reference materials are low in
concentration and not so well characterized. Precision
(1 s ) for the REE, Sc and Y for the reference materials,
which were digested between three and six times,
was generally better than 5% with the lowest average
for all elements being 1.8% for TASGRAN and the
highest average 4.1% for G-2, except for TAFAHI
(7.8%) which has lower trace element levels. Good
correlation (R 2 = 0.9979) between the measured
results and reference values can be seen in Figure 8.
213
GEOSTANDARDS
NEWSLETTER
The Journal of Geostandards and Geoanalysis
ICP-MS/chondrite
Figure 9. Chondrite-normalized distribution patterns
of REE for GSR-1, G-2, AC-E, TASGRAN, FeR-2, FeR-4,
BHVO-1, TAFAHI and TASBAS using Na 2O 2 sinter
decomposition technique.
The good quality of the REE data for the nine selec-
ted geological materials was further demonstrated by
the smooth chondrite distribution patterns (Figure 9).
Table 8 shows the recovery (in comparison with
reference values) of HFSE, Rb, Sr, Ba, Mo, Sb, Cs, Tl, Pb
and Bi for the reference materials digested between
two and four times each. Strontium and Th results
show almost complete (100%) recovery, although the
blank levels of Sr (2-5 µg g -1) and Th (0.1 µg g -1) in
our Merck Na 2 O 2 preclude determination of these
elements at low levels. Niobium had a reasonable
average recovery of 91% but the range of 76 to
100% is not consistent enough to be useful. Barium
and Bi also gave reasonable average recovery yields
of 86% and 78% respectively, and again the recovery
was variable (63-101%). Zirconium, Hf, Ta and Pb
showed 69 to 80% average yields and were affected
by variable reagent (Na 2 O 2 ) contamination. Due to
solubility in a basic environment, Sn, Sb, Tl and U
gave only 48 to 66% average yields and Rb, Mo and
Cs were almost completely lost (4-7% yields) during
the digestion.
Compared to other digestion techniques, Na 2O 2
sinter is less time consuming for the determination of
Sc, Y and REE in geological samples. A batch of
samples may be digested within 4 to 5 hours.
Therefore, it is possible to obtain REE results in the
same day by this digestion method in conjunction with
ICP-MS. However, Na 2O 2 sinter may not be suitable
GEOSTANDARDS
NEWSLETTER
The Journal of Geostandards and Geoanalysis

Table 8.
Recovery (% yield) for nine selected geological reference materials using the Na 2 O 2 sinter method

AC-E GSR-1 G2 TASGRAN BHVO1 TASBAS TAFAHI FeR-2 FeR-4 Average

n = 3 n = 2 n = 2 n = 2 n = 2 n = 4 n = 4 n = 2 n = 2 (%)

Rb 3 4.6 5 5 3 4 7 1.1 1.3 4

Sr - 104 97 105 98 89 111 117 111 104
Zr 90 53 37 85 81 90 87 - - 75
Nb 98 91 85 93 76 94 100 - - 91
Mo 1 1.1 0 2 6 12 3 - 4
Sn 86 51 60 48 59 48 100 - - 65
Sb 45 73 - - 26 - - - - 48
Cs 4 5 7 6 20 4 13 1.3 1.2 7
Ba 93 80 90 89 89 90 101 70 71 86
Hf 88 53 37 98 92 94 93 - - 79
Ta 76 73 23 96 59 86 - - - 69
Tl 67 79 72 50 65 - - - - 66
Pb 85 68 66 72 70 75 70 45 72 69
Bi 63 94 79 - - - - - - 78
Th 93 97 91 106 93 94 - 106 100 98
U 74 58 53 70 58 61 53 56 40 58

Missing data indicates elements either too low in concentration or preferred values unavailable. n = number of digestions.

Table 9.
Summary of elements measurable by different digestion methods

Savillex PicoTrace Fusion Sinter

HF/HNO 3 HF/HClO 4 HF/H 2 SO 4 Li 2 B 4 O 7 Na 2 O 2

Basalt REE, Sc, Rb, Sr, Y, Zr, Nb, REE, Sc, Rb, Sr, Y, Zr, Nb, REE, Sc, Rb, (Sr), Y, Zr, Nb, REE, Sc, Rb, Sr, Y, Zr, Nb, REE, Sc, Sr, Y and Th
Mo, Sn, Sb, Cs, Ba, Hf, Mo, Sn, Sb, Cs, Ba, Hf, Mo, Sn, Sb, Cs, (Ba), Hf, Mo, Cs, Ba, Hf, Ta, Th
Ta, Tl, Pb, Bi, Th and U Ta, Tl, Pb, Bi, Th and U Ta, Tl, (Pb), Bi, Th and U and U

Granite - - REE, Sc, Rb, (Sr), Y, Zr, REE, Sc, Rb, Sr, Y, Zr, Nb, REE, Sc, Sr, Y and Th
(Nb), Mo, Sb, Cs, (Ba), Hf, Mo, Cs, Ba, Hf, Ta, Th
(Ta), Tl, (Pb), Bi, Th and U and U

Ironstone - REE, Sc, Rb, Sr, Y, Zr, Nb, REE, Sc, Rb, (Sr), Y, Zr, Nb, REE, Sc, Rb, Sr, Y, Zr, Nb, REE, Sc, Sr, Y and Th
Mo, Sn, Sb, Cs, Ba, Hf, Mo, Sn, Sb, Cs, (Ba), Hf, Mo, Cs, Ba, Hf, Ta,
Ta, Tl, Pb, Bi, Th and U Ta, Tl, (Pb), Bi, Th and U Th and U

Elements in brackets at high concentration cannot be measured due to the formation of insoluble sulfates or hydrolysis in solution. Some low
abundance ultramafic rocks such as dunites, peridotites and serpentines can also be decomposed by the HF/HClO 4 method (Yu et al. 2000).

for the determination of elements at low abundance in
rock samples due to the lack of ultra-pure Na2O2.
Conclusions
Results of five different sample digestion proce-
dures show that geological samples should be diges-
ted using different digestion techniques according to
individual sample compositions. Table 9 gives a brief
summary of the measurable elements by Savillex  ,
PicoTrace , fusion and sinter digestion methods. The
advantages and disadvantages of the five different
digestion methods investigated in this study are sum-
marized as follows:
(1) Savillex Teflon vial acid digestion can be used
for the decomposition of basalts. The optimum ratio of
HF to HNO 3 for 100 mg powdered rock sample is 2
ml to 0.5 ml. In order to achieve a complete dissolu-
tion, rock samples should be digested on a hotplate at
about 130-150 °C for at least 48 hours. Granites can-
not be completely decomposed by Savillex  vial
digestion.
(2) Basalts and iron formation samples can be
completely digested by the HF/HClO 4 high pressure
digestion method at 180 °C for 48 hours. However,
some low abundance ultramafic rocks such as dunites,
peridotites and serpentinites can be decomposed by

214

HF/HClO 4 at about 180 °C for 16 hours (Yu et al.
2000). Generally, granites cannot be digested by the
HF/HClO 4 high pressure digestion method unless a
complicated two-stage digestion procedure is applied.
The two-stage procedure can give recoveries of 85 to
100% for more than thirty trace elements investigated
in granites.
Basalts, granites (with accessory mineral phases
such as zircon, magnetite, fluorides and monazite)
and ironstones can be completely decomposed by the
3 ml HF/3 ml H 2SO 4 high pressure digestion method
at 180 °C for 16 hours. Granites containing cassiterite
cannot be completely decomposed using this method.
In order to achieve complete decomposition, the
volumes of either HF or H2SO 4 for 100 mg powdered
samples should be controlled at 3 ml and any reduc-
tion in the volumes of HF and H 2SO 4 may result in the
incomplete dissolution of rock samples. The main
disadvantage of the HF/H 2SO 4 high pressure diges-
tion method is that the evaporation time is very long,
taking, at present, 4 days to evaporate the mixture to
dryness. Work is under way to improve the evapora-
tion process by controlled heating of the evaporation
cover plate.
(3) Microwave digestion methods used during this
study are not suitable for geological samples. The
recovery of thirty two trace elements in BHVO-1 (basalt)
was only 80-100% in comparison with reference values.
Granites TASGRAN and GSR-1 gave average recoveries
of 69-84% and ironstone FeR-2 an average recovery
of 87%.
(4) Li 2B4O7 fusion + HF/HNO 3 method can gene-
rally be used to decompose many different geological
samples such as basalts, granites and ironstones.
However, this method precludes the measurement of
volatile elements such as Sn, Sb, Tl and Pb due to the
high decomposition temperature (1000 °C). This
method increases the level of total dissolved solid in
solution and hence strongly degrades instrumental
intensity during an analytical run. In addition, this
decomposition method may not be suitable for the
decomposition of elements at low abundance in rock
samples, due to the lack of commercially available
ultra-pure Li2B4O7.
(5) Finally, most geological samples can be com-
pletely decomposed by the sodium peroxide sinter
method. This method can provide fast analysis times
for Sc, Y and REEs, and geological samples can
215
GEOSTANDARDS
NEWSLETTER
The Journal of Geostandards and Geoanalysis
normally be decomposed and analysed in the same
day. HFSE could not be measured (in this study) due
to variable yields and the high levels of HFSE in
procedural blank solutions. Again, this method is not
recommended for the measurement of elements at low
abundance in samples because of the high blank
levels.
This work also highlights the necessity of carefully
characterising decomposition procedures with respect
to specific geological matrices of interest before any
analysis is undertaken. It should be reiterated that no
single decomposition protocol will allow the measure-
ment of all trace elements in all types of geological
samples by ICP-MS.
Acknowledgements
T h i s re s e a rc h p r o j e c t w a s s u p p o r t e d b y t h e
Au stra lia n Re se a rch C o u ncil’ s Re se a rch C e ntres
Programme. The Centre of Ore Deposit Research, the
School of Earth Sciences and the Central Science
Laboratory (CSL), University of Tasmania, are gratefully
acknowledged for the use of their digestion and ICP-
MS facilities. Ashley Townsend of the CSL is particularly
thanked for his assistance with the ICP-MS analysis.
Carsten Münker and Alfred Schneider are thanked for
their assistance with the PicoTrace digestion apparatus.
Ross Large and Tony Crawford at the Centre for Ore
Deposit Research, University of Tasmania, are thanked
for their support.
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