CHEMICAL

GEOLOGY

n!Zi-

INCLUDING

ISOTOPE GEOSCIENCE

ELSEVIER

Chemical Geology 134 (1997) 311-326

A simple method for the precise determination of > 40 trace

elements in geological samples by ICPMS using enriched isotope
internal standardisation
S.M. Eggins *'1, J.D. Woodhead 2, L.P.J. Kinsley, G.E. Mortimer, P. Sylvester,
M.T. McCulloch, J.M. Hergt 3, M.R. Handler
Research School of Earth Sciences, Australian National University, Canberra, A.C.T. 0200, Australia

Received 9 August 1995; accepted 22 June 1996

Abstract

The combination of enriched isotopes and conventional elemental internal standards permits the precise determination of
> 40 trace elements by ICPMS in a broad spectrum of geological matrixes. Enriched isotopes expand the suite of available
reference isotopes spaced through the mass spectrum, so that the complex mass-dependent variations in sensitivity
encountered during ICPMS analysis can be monitored and deconvolved. The method we have developed is straightforward,
entailing simple sample preparation, instrument calibration, and data reduction procedures, as well as providing extended
element coverage, improved precision, and both time and cost benefits compared to alternative analytical strategies.
Analytical precision near or better than 1% RSD (relative standard deviation) is achieved for most dements with mass > 80
amu and between 1% and 4% (RSD) for elements with mass < 80 amu, while maintaining low detection limits ( < 1 to
< 10 ng g - l for elements with mass > 80 amu and < 10 ng g - i to 1 Ixg g - i for elements with mass < 80 amu). The
subtle geochemical differences which can be resolved using this method are demonstrated by analyses of Nb, Ta, Zr, and Hf
in magmas from ocean islands and subduction zones. These data reveal significant departures from chondritic Z r / H f and
N b / T a values, and systematic trends which are consistent with greater incompatibility of Zr relative to Hf and also of Nb
relative to Ta during melting of the upper mantle. The occurrence of significantly subchondritic Z r / H f and N b / T a ratios in
Nb-poor subduction zone magmas, supports the notion that the depletion of high-field strength elements in subduction
magmas is due to their removal from the mantle wedge by prior melting events.
Keywords: Inductively coupled plasma methods; Mass spectrometry; Trace element analysis; Subduction zones; Partial melting

I. Introduction
* Corresponding author.

t Present address: DepaJament of Geology, Australian National

University, Canberra, A.C.T. 0200, Australia.
2 Present address: School of Earth Sciences, University of
Melbourne, Parkeville, Vic. 3052, Australia.
3 Present address: DepaJ:tment of Geology, Australian National
University, Canberra, A.C.T. 0200, Australia.

ICPMS (inductively coupled plasma mass spectrometry) has rapidly become established as a preferred method for the analysis of trace elements in
geological samples, offering rapid analysis capabilities, an ability to measure most elements, relatively
straightforward sample preparation, very low detec-

0009-2541/97/$17.00 Copyright 1997 Elsevier Science B.V. All rights reserved.

PH S 0 0 0 9 - 2 5 4 1 ( 9 6 ) 0 0 1 0 0 - 3

312

S.M. Eggins et al. / Chemical Geology 134 (1997) 311-326

tion limits, a large dynamic range, and largely interference-free spectra. However, it is increasingly apparent that fully quantitative measurement by ICPMS
can be compromised by variation in instrument sensitivity during the course of an analytical run and
with the introduction of different sample matrixes.
Accurate and precise data may only be obtained if
these effects can be minimised or, monitored and
corrected for.
The adverse effects of sensitivity variations during ICPMS analysis can be avoided or minimised by
employing either standard addition or isotope dilution (e.g., Jenner et al., 1990; Xie et al., 1994).
However, these methods have drawbacks which
compromise the inherent capabilities of ICPMS. Isotope dilution requires accurately prepared and maintained enriched isotope spikes, and optimal "spiking" of individual samples. Furthermore, it is limited
to multi-isotope elements and, when applied to a
large number of element determinations, is expensive
and time consuming. Standard addition likewise requires preparation of accurate elemental standard
solutions, employment of optimal spiking strategies
on a sample by sample basis, and the aliquoting of
sample solutions in order to conduct the multiple
analyses necessary for analyte determination.
Faced with the rigors of standard addition and
isotope dilution, many ICPMS laboratories have resorted to external calibration (using either synthetic
or natural reference materials) with internal a n d / o r
external standardisation. These alternate strategies
offer considerable time, sample preparation, and cost
benefits but until now have not delivered good analytical reproducability due to the complex sensitivity
variations encountered during analysis. The strategies employed with most success to date include: (1)
the use of multiple elemental internal standards
(Thompson and Houk, 1987; Doherty, 1989); (2)
relatively short analytical procedure duration; and (3)
external standardisation based on multiple repeats of
the same solution run at intervals during an analytical procedure (e.g., Cheatham et al., 1993), or a
combination of the above (e.g., Schonberg, 1993).
It should be noted that most existing multi-element ICPMS studies on geological samples fall well
short of the analytical precision capabilities of modem ICPMS instruments. The ability to measure isotope ratios to a precision of ~ 0.2-0.3% RSD (rela-

tive standard deviation), should translate into an

ability to reproduce measurements to + 1% or better,
given cumulative sample preparation, analytical
methodology, and counting statistic errors. This can
be compared to reported precision usually in the
range 3-5% RSD (Jenner et al., 1990; Cheatham et
al., 1993; Schonberg, 1993; Xie et al., 1994), and
sometimes > 10% or 20% despite favourable concentration levels.
Herein we describe a straightforward method employing external calibration along with a combination of external standardisation and multiple internal
standardisation, using both elemental and enriched
isotope internal standards. Improved precision and
extended element coverage ( > 40 elements) is attained compared to other ICPMS analytical strategies
reported to date. Moreover, because mass-dependent
variations in instrument sensitivity are monitored and
deconvolved on a sample by sample basis, the method
is matrix tolerant and does not necessitate strict
matrix-matching protocols. It has been applied successfully to peridotites, a spectrum of magma types
ranging from komatiite through basalt to rhyolite,
granitic samples, banded iron formations, and mineral separates including olivine, pyroxene, spinel,
feldspar, various oxide phases, and apatite.

2. Mass-dependent sensitivity variation during

ICPMS analysis
Initial experience with our instrument (Fisons
PQ2 + ) employing a single internal standard (elemental In) revealed an inability to reproduce determinations on the same sample within analytical error, even during a single analytical run. The relative
differences between repeated analyses were found to
be a systematic but often complex function of mass.
This behaviour is symptomatic of variations occurring in instrument sensitivity as a function of mass
with time (Fig. 1), and has been described in detail
by Cheatham et al. (1993) for the restricted mass
region spanned by Ba and the rare-earth elements
(REE). We have found that the magnitude and complexity of these sensitivity variations can be severe
where the analysed isotopes span the entire mass
spectrum, particularly in the low-mass region ( < 80
amu). Interestingly, it appears that this problem is

S.M. Eggins et al. / Chemical Geology 134 (1997) 311-326

aU

~-~"

1.0

"~

0.95

IntscnalStsndards ~'Sr

"

Rh In

'47E;m Tm

Re

~'SU

"
Ot~
!
~ ~aga~m o
~...............................
i...........................~...............................
~................................
---~ 0.90 -t~.........................
O~
Q.
O0 0.85

._>

0.80

n
,-

0.75

CO

0.70

=.~..................;-~.-~'!..............i.............................i.--~,~v-i.........................-

i
I
._>
i........ l
-,,--' 0.65 :_._;.._._._1._ . . . . ~ . ~ ...............- .............................
~71 ~i
~:
I
r'

0.60

- , ' , , U i - , , , ,'i . . . .
50

100

atomic

i ........
150

mass

#5 li

I..:
# 191 :

# 12

200

"
250

units

Fig. 1. Relative sensitivity c h a n g e s for internal standard and

analyte isotopes during the course o f an analytical run, b a s e d on
repeat analyses o f the same solution at intervals during the run.
# n denotes the analysis number o f each repeat m e a s u r e m e n t
within the analysis sequence. The continuous line is a linear
interpolation between internal standard isotopes for analysis # 19.
This c o m p a r e s to the dashed curve, w h i c h is a closer a p p r o x i m a tion to the actual sensitivity changes, particularly in the l o w - m a s s
region between 6Li and 84Sr.

the principal limitation to quantitative analysis of

many low-mass eleme.nts rather than molecular interferences.
Given the complex nature of the sensitivity variations illustrated in Fig. 1, it can be readily appreciated that the conventional use of a single or even
several elemental internal standards will be inadequate to monitor and deconvolve these variations
during the course of an analytical run. If internal
standardisation is to be effective in such cases then
multiple internal standards, spaced at appropriate
intervals through the entire mass spectrum (i.e. ~ 20
mass units apart), are required. This presents an
insurmountable difficulty for conventional internal
standardisation using modern high-sensitivity instruments, as elemental internal standards are largely
restricted to ultra-trace elements (e.g., Rh, In, Re,
Bi) whose natural abundances do not contribute significantly (ideally < 0.1-0.2%) to any added internal standard.
Enriched isotopes not only expand the pool of
useable internal standards but enable the abundance
of their parent elements to be determined. The use of
particular enriched isotopes is subject to their posi-

313

tion and spacing within the mass range, stability in

dilute nitric acid solutions, cost, and the limitations
which they can place on the dynamic range and
detection limits of parent element analyte isotopes.
The latter is a product of the uncertainities arising
from subtracting the natural and enriched isotope
contributions from the internal standard and analyte
isotopes, respectively.
Multiple internal standards also contribute to improved analytical precision by offsetting the effects
of higher frequency noise in ICPMS. For example,
with a typical mass spectrometer sweep time of 1 s
to traverse the mass spectrum, ten uniformly spaced
internal standards will account for noise of < 10 Hz
whereas a single internal standard will be limited to
< 1 Hz.

3. Analytical t e c h n i q u e

3.1. Sample preparation and introduction

Samples and geochemical reference materials are
dissolved by conventional digestion methods, using
concentrated H F - H N O 3 mixtures (10:1) in 25-ml
Savillex screw-top Teflon beakers. Several times
during the digestion, the beakers are placed in an
ultrasonic bath in order to disaggregate granular
material and render it more susceptible to acid attack. In the case of samples containing resistant
phases, such as zircon, microwave or " b o m b " digestions are employed to ensure complete dissolution. Following digestion the samples are evaporated
to incipient dryness, refluxed in 6 N HNO 3, taken
again to incipient dryness, and the sample cake then
dissolved in 2 ml of concentrated HNO 3. Final sample preparation is undertaken, following transfer to
125-ml polypropylene bottles and addition of a
known weight of internal standard solution, by dilution with ultrapure H 2 0 to a sample/solution weight
ratio of 1 : ~ 1000-1250 (i.e. ~ 80-100-rag sample
in 100 g of final solution). This dilution factor is a
compromise between sample-size related heterogeneity, ease of digestion, availability of large volumes of
clean reagents, required detection limits, and analyte
suppression effects which can be severe where total
dissolved solid contents exceed 0.2%. All reagents

S.M. Eggins et al. / Chemical Geology 134 (1997) 311-326

314

Table 1
Internal standard and analyte isotopes, interferences, and internal
standard concentrations
Analyte

Isotope

Significant interferences a6 ( n g / g )

Int.
Li
Be
Sc
Ti
V
Cr
Co
Ni
Cu
Zn
Ga
Int.
Rb
Sr
Y
Zr
Nb
Mo
Int.
Cd
Int.
Sn
Sb
Cs
Ba
La
Ce
Pr
Nd
Int.
Sm
Eu

6
7
9
45
49
51
53
59
60
65
66
71
8484
85
86
89
91
93
98
103
114
115
120
121
133
137
139
140
141
146
147
149
151

Li natural 7
Li Int. Std.

Std. 6Li

Std. 84Sr

Std. Rh
Std. In

Std. 147Sm

Tb
Gd

159
160

Dy
Ho
Er

161
165
167

Int.
Yb
Lu
Hf
Ta
Int.
T1
Pb
Int.
Th
Int.
U

Std. T m

Std. Re

Std. Bi
Std. Z35U

169
173
175
178
181
187
205
208
209
232
235
238

10

COOH?

Table 1 (continued)
Analyte

Isotope

Significant interferences a

(ng/g)

Other possible internal standards:

6JNi
t34Ba
135Ba
2apb

61
134
135
204

44CaOH

a Bold typeface indicates corrected interferences.

44CAO49

TiO, 4s TiOHSO
"rio, 49 TiOHI42
Ce z+, 142Nd2+
Sr natural, s4Kr

16

Sr Int. Std., ~ K r

n4
Sn

5
10

147
Sm natural 149
Sm Int. Std. 13s

10

BaO and 134BaOH143

NdO 144
SmO, 144NdO, 16097145
NdO 149
SmO
t51 Eul6OI69
T m natural
157GdO
J59TbO
162DyO
~65HoO

10

10

235
U natural 23a
U spike

2.5

are prepared using double-distilled concentrated acids

and ultra pure water ( > 18 MII).
Sample introduction to the ICPMS is automated
via a Gilson Autosampler at a rate of ~ 1 m l / m i n - 1.
The uptake time is set to facilitate stable analyte
signals prior to analysis (typically 90-120 s). A
washout procedure incorporating a dilute surfactant
(e.g., ~ 0.5% Triton X-100 or DECON) and sufficient wash time is critical to achieving adequate
instrument blank levels. A procedure appropriate for
most applications involves a 60-90 s surfactant wash
and a 180 s wash with 2% HNO 3. The total time for
analysis of a single sample solution is ~ 10-12 min,
resulting in typical run times of between 3 and 7 hr
for the analysis of 18-36 solutions, of which 12-28
are unknowns, 2 are calibration solutions, 2 - 4 procedural blanks, and an instrument sensitivity monitoring solution which is repeated every 5 - 7 solutions.
To assure low instrument blank levels, particularly for the analysis of low-level concentrations of
elements which have poor washout characteristics
(e.g., Nb and Ta), prior analysis of samples with
high concentration levels of such elements is avoided.
The spray chamber and nebuliser are also cleaned
and replaced regularly along with the sample introduction tubing. Externally lubricated silicone tubing
is employed on the peristaltic pump in preference to
Tygon tubing, which develops internal cracking after
a short period of use. It should be noted that measured reagent blank levels for many elements with
poor-washout characteristics are often not a true
reflection of instrument blank levels during the introduction of analyte solutions, as these elements can be
more efficiently scavenged from the sample introduction system than by "blank" 2% HNO 3 acid
solutions (see also Xie et al., 1994).

S.M. Eggins et al. / Chemical Geology 134 (1997) 311-326

3.2. Internal standard,~

The elemental and enriched isotopes we employ
for internal standardi:sation are listed in Table 1,
along with several o~Lers that we have identified as
being suitable. The enriched isotopes we use are
relatively inexpensive with the exception of 84Sr,
though even with inclusion of this isotope the cost of
internal standardisation per sample is only a minor
fraction of the total cost of each analysis ( ~ 1 US $).
In conventional elemental internal standardisation
the natural isotope abundance needs to be overwhelmed by the added internal standard, though in
some cases it can be., subtracted from the internal
standard isotope signal (e.g., natural 169Tm evaluated
from Er and Yb concentrations). With enriched isotope internal standardisation the optimal concentration level to "spike" a sample can be determined
from the relationship:
Ri/.j

./]gi/j

. ipi/-f'--

mtxture ----"V~"spike "~sample

where R i/j is the ratio of isotope i to j in the spike,

sample and mixture. Any given concentration of an
enriched isotope presents an effective "dynamic
range" over which both it (the internal standard) and
any associated analyte isotopes can be measured
precisely. This dynamic range can be used to tailor a
particular internal st~mdard spike solution for the
range in element concentrations likely to be encountered. With careful selection, a particular enrichedisotope concentration can be employed to quantify a
large concentration r~mge in associated analyte isotopes, such that a single set of intemal standard
concentrations may be employed to measure a broad
spectrum of compositions likely to be encountered.
We typically employ only two sets of internal standard concentrations, one to measure basaltic and
differentiated magma compositions and another to
measure low-level samples, such as mantle peridotites and certain mineral phases.
3.3. Correction for m~ss-dependent sensitivity variation
Sensitivity variations occurring during the course
of an analytical run are monitored by ratioing the
count rate of each internal standard isotope (or ele-

315

ment) in each solution analysed, relative to that

measured in the initial solution of each run. The
reciprocal of these ratios is used to correct the count
rates of each internal standard, so that they are
equivalent to that during the first analysis of each
run. Count rates for the analyte isotopes, which lie
between internal standard masses, are corrected based
on a linear interpolation of the internal standard
correction factors as a function of mass (see Fig. 1),
and are calculated on-line using the Fisons' software.
This primary correction procedure deconvolves sensitivity variations of both matrix and instrument origin.
A second correction based on external standardisation is subsequently applied off-line to remove any
residual sensitivity differences that remain following
internal standardisation. This need arises because the
internal standard correction, which is modelled as a
linear interpolation between internal standard masses,
is unable to account for the occurrence of more
complex non-linear sensitivity variations as a function of mass (see Fig. 1). In regions of the mass
spectrum where internal standards are sufficiently
closely spaced, the linear intemai standard correction
provides a close approximation to any complex sensitivity variation and a secondary correction is usually unnecessary. However, where internal standards
are separated by large relative mass differences,
particularly between 6Li and 84Sr, and between llSIn
and 147Sm, large external standard-based corrections

1.0
o.
-0

0.95

"~

0.90

._~
0

::z.

0.85

nn

0.80
0

10

15

20

25

30

Analysis # (sequence)
Fig. 2. A graphical illustration of the external-standardisation
procedure, using either a polynomial fit to, or linear interpolation
between, the internal-standard corrected count rates for an analyte
isotope (in this case Be) as a function of the analysis sequence
[see text and also Cheatham et al. (1993), for details].

316

S.M. Eggins et al. / Chemical Geology 134 (1997) 311-326

are sometimes needed (see Fig. 1). The external

standardisation procedure employed is similar to that
described by Cheatham et al. (1993). A polynomial
fit or linear interpolation is established based on the
internal standard-corrected count rate ratios for each
analyte isotope as a function of the analysis sequence, using a reference solution measured repeatedly at intervals (every 5-7 solutions) through each
run (Fig. 2). Several criteria are employed to validate
the integrity of these external-standard corrections,
namely that neighbouring isotope masses should have
similar correction factors and, that the magnitude of
the correction should decrease to zero as isotopes
approach the mass of any intemal standard.
3.4. Instrument operating parameters and performance

Typical instrument operating parameters are listed

in Table 2 along with routine performance criteria.

bration is routinely undertaken using the natural

reference material BHVO-I following a digestion
procedure identical to that employed for the unknowns. The use of a natural reference material
offers several advantages over synthetic solutions
including: (l) a simple, equivalent, and reproducible
preparation procedure for both samples and standards; (2) avoidance of potential analyte contamination through standard solution impurities; and (3)
long shelf lives of at least 2 months but commonly
longer. The principal drawback of calibrating against
natural reference materials is the incorporation of
systematic analytical bias due to deviation of the
adopted calibration concentrations from true values.
Our preferred concentration values for BHVO-1 (Table 3) are based on a selection of published (e.g.,
Gladney and Roelandts, 1988; Govindaraju, 1989)
and unpublished data (W.F. McDonough, pers. commun., 1994). In the event of future change to these
BHVO-1 values, any existing data need only to be
corrected by the ratio of the new and old values.

3.5. Instrument calibration

3.6. Isobaric and molecular interference corrections

Instrument calibration is performed using a single

calibration solution (which is analysed in duplicate)
and by forcing the weighted linear regression through
the origin following blank subtraction. This simple
strategy is sound, given the well-established linear
dynamic range of the ICPMS, which exceeds 6
orders of magnitude (e.g., Jarvis et al., 1992). Cali-

Interference corrections are routinely applied to

correct analyte isotopes for molecular and isobaric
interferences, and are also used to subtract the natural isotope contributions to the enriched isotope internal standards (see Table 1). The generation of
oxide and doubly-charged species, and the mass

Table 2
Instrumental operating conditions
Instrument

Fisons VG PlasmaQuad PQ2 + STE

Forward power
Reflected power
Nebuliser
Nebuliser gas flow rate
Coolant gas flow rate
Auxiliary gas flow rate
Spray chamber
Detector
Sensitivity
Ion collection
Dwell time a and points/peak
Analysis time

1300 W
<3W
Meinhardt
0.85 1/min
14 1/min
1 1/min
Scott double-pass water cooled ( ~ IC)
ETP Dinode operating in PC and Analogue
(2-5) x 107 counts per second/ppm nSIn and 238U
peak hopping
2.56-20.48 ms, 3 points/peak separated by 5 DAC units
90-s acquisitions ( ~ 60 sweeps), 4 repeats

Quartz V-groove
0.92 l / m i n
141/min
1 l/min

Dwell times are varied according to individual isotope abundances and elementresponse factors, to minimise counting statistic errors.

Elemenq B H V O - I
oWE I Prefd Value
Li
4.90
Be
1.10
Sc
31.8
"It
16610
V
321
Cr
289
Co
45
Ni
120
Cu
136
7m
105
Ga
21
Rb
9.5
Sr
390
Y
28.0
71
180
Nb
19.5
Mo
1.0
C.d
0.069
Sn
2.30
Sb
0.170
Cs
0.100
Ba
133
I.at
15.5
Ce
38.0
Pr
5.45
Nd
24.7
fan
6.17
Eu
2.06
Gd
6.22
'rb
0.95
Dy
5.25
Ho
1.00
Er
2.56
Yb
1.98
Lu
0.278
HI"
4.30
Ta
1.200
11
0,059
Pb
2.10
Th
1.26
U
0.420

BIR-I
n = 15
3.32
0,116
43.8
6036
322
412
53
175
113
65
15.2
0.195
106.4
16.20
14.47
0.558
0.037
0.050
0.88
0.50
0.0053
6.52
0.604
1.897
0.378
2.38
1.117
0.524
1.850
0.379
2.53
0.585
1.734
1,649
0,247
0,562
0.041
0.004
2.97
0.0302
0.0100
2.5
4.4
1.9
9.8
4.3
23
2.5
1.3
2.4
3.6
1.5
2.9
0.8
0.6
1.1
0.8
17.1
3.5
10.3
15.1
5.1
1.3
1.2
0.9
1.1
1.0
1.5
1.0
1.0
1.3
0.9
1.1
0.8
1.1
1.0
1.3
2.3
61.5
1A
2.9
6.7

RSD%

3.00
0.030
0.010

Preferred
Value
3A
0.58
44.0
5755
313
382
51
166
126
71
16.0
0.24
110
16.5
14.5
0.55
0.50
0.I14
0.54
0.58
0,005
6.40
0.58
1.85
0.37
2.35
1.10
0.52
1.97
0.38
2.50
0.57
1.70
1.60
0.25
0.56
0,060
2.43
0,501
0,989
687
25.5
53.3
6.88
28.8
6.60
1.892
6.69
1.068
6.35
1,315
3.67
3.35
0.505
4.86
0.795
0..374
1321
6.19
1.679

0.60
0.004
7.10
0.61
1.95
0.38
2.34
1.10
0.52
1.84
0.36
2.51
0.56
1.66
1.63
025
0.51
0.030
0.010
2.94
0.031
0.0097

313
382
51
166
123
71
16.0
024
110
15.5
15.4
0.50

44.0

BCR-I
n=10
14.0
1.75
33.0
13183
401
9
39
12
19
128
21.6
48.0
326
39.0
201
13.07
1.55

Jochumet
al. 94

2.5
1.1
1.2
0.4
1.0
0.3
0.4
0.9
2.0
0.5
1.5
0.6
0.1
0.7
1.1
1.1
0.6
1.6
1.5
1.2
1.6

1.5
3.6
1.7
1.8
2.0
7.1
8.6
1.7
23.0
4.1
0.9
0,4
0.8
0.3
0.8
0.5

%RSD

405
16
37
13
19
129
22.0
46.9
330
35
187
12.5
1.80
0,130
2.30
0.62
0,956
675
24.9
53.6
6.80
28.8
6.59
1.98
6.72
1.13
6.42
1.35
3.70
3.38
0.499
4.97
0.81
0.30
135
5.91
1.70

Prcfen'ed
Value
12.9
1.60
32.6

AGV-1
n=8-12
11.2
2.55
12.6
6139
126
9
16
16
58
85
20.3
68.3
655
21.0
240
14.91
2.12
0.099
5 .27
4.46
1305
1223
38.5
68.5
8 .45
31.6
5.82
1.565
433
0.664
3.54
0.690
1.856
1.644
0.248
5.00
0.882
0.423
37.27
6.53
1,885
2.1
2.4
2.4
2.6
6.4
11.3
6.7
33
3.0
4.1
0.5
0.8
O.8
1.4
1.7
03
2.8
4.8
9.5
3.6
1.5
1.0
1.1
0.6
0.9
0.7
1.3
0.9
0.9
1.0
0.8
0.6
0.7
1.0
0.9
0.7
0.6
1.0
2.7
1.1
0.9

%RSD

Preferred
Value
12.0
2.10
12.2
6295
121
10.1
15.3
16
60
88
20.0
68.0
66O
20.0
225
14.5
2.10
0.069
4.5
4.3
1.25
1200
39.0
70.0
8.00
32.0
5.90
1.55
4.70
0.70
3.80
0.70
1.90
1.75
0.270
5.17
0.90
0.34
37.0
6.50
1.90
6.47
0.240
0.0549

f)NC-1
n=6
5.08
0.226
31.1
3141
157
291
57
264
86
57
133
3.6
141.4
18.03
36.4
1.564
0.121
0.064
2.46
0.870
0,213
104.5
3.68
8.17
1.113
4.95
1.44
0,592
102
0.390
2.71
0.638
1.945
1.915
0.292
0.955
0.089
0.9
2.1
2.2

1.8
13
1.9
11.9
4.0
2.8
1.6
1.9
2.2
6.7
1.5
1.5
0.6
0.5
0.5
0.6
13.8
3.4
11.3
1.4
3.4
0.7
1.1
0.9
0.3
0.8
1.2
0.5
0.6
1.1
O.9
1.1
1.2
0.7
0.9
1.0
1,6

%RSD

6.20
0.220
0.050

0.96
0.300
118.0
3.53
8.19
1.10
4.86
1.40
0.60
2.00
0.39
2.76
0.65
1.90
1.97
0.309
1.05
0.098

31.0
2878
148
285
55
247
96
66
15.0
4.5
145
18
41
2.0
0.70
0.180

Preferred
Value
5.1
W-2
n=l 1
9.59
0.75
36.2
6700
270
92
46
74
104
76
17.4
20.1
191.8
22.8
92.0
7.76
0A3
0.057
1.95
0394
0.916
171.0
10.59
23.08
3.027
12.95
3.31
1.093
3.69
0.622
3.79
0.798
2.26
2.03
0.299
2.30
0.483
0.132
7.81
2.21
0.497
1.8
3.7
2.6
6.O
4.8
1.9
2.4
1.5
2.3
4.6
1.2
0.9
0.8
0.8
1.5
0.8
3.3
4.5
5.2
3.1
1.2
0.7
0.9
0.7
0.7
0.5
0.5
0.6
0.7
0.7
1.1
0.9
0.8
1.4
1A
2.0
1.8
1.1
1.3
1.2
1.2

RSD%

Pre.feaa'cd
Value
9.3
1.30
35.0
6355
262
93
44
70
103
77
20.0
20.0
195
23.0
95
7.8
0.60
0.104
390
0.79
O.90
173
10.0
23.5
3.20
14.0
3.40
1.15
3.60
0.63
3.80
O.84
2.40
2.08
0.32
2.40
0.50
0.20
7.60
2.20
0.48

M e a s u r e d trace e l e m e n t c o n c e n t r a t i o n s ( p ~ g / g ) , p r e c i s i o n e s t i m a t e s , a n d p r e f e r r e d v a l u e s f o r i n t e r n a t i o n a l a n d l a b o r a t o r y r e f e r e n c e m a t e r i a l s ( I x g / g ) i n c l u d i n g c a l i b r a t i o n v a l u e s
for BHVO1

Table 3

-O

k*a
r,o
O~

Z3

"X

o~

S.M. Eggins et al. / Chemical Geology 134 (1997) 311-326

318

Table 3 (continued)

Li
Be
Sc

QLO-1
n=2
27.2
2.31
8.7

Ti

3358

V
Cr
Co
Ni
Cu
Zn
Ga
Rb
Sr
Y
Zr
Nb
Mo
CA
Sn
Sb
Cs
Ba
La
Ce
Pr
Nd
Sin
Eu
Gd
Tb
Dy
Ho
Er
Yb
Lu
Hf
Ta
TI
Pb
Th
U

48
1
7.4

Preferred
Value

25
57
17.3
72.2
329
25.8
194
10.8
2.59

1.89
8.9
3741
54
3.2
7.2
5.8
29
61
17.0
74.0
336
24.0
185
10.3
2.60

2.91
2.00
1.67
1429
26.5
50.4
5.99
22.9
4.60
1.203
4.17
0.658
3.90
0.828
2.40
2.39
0.390
4,68
0,845
0.25
23.9
4.88
1.83

2.3
2.1
1.75
1370
27.0
54.6
6.00
26.0
4.88
1.43
4.70
0.71
3.80
0.86
2.30
2.32
0.37
4.60
0.82
0.22
20.4
4.50
1.94

RGM-1
n=7
63.0
2.93
4.7
1940
12
4.9
2.1
3.7
11
30
15.9
154.7
102,4
25.1
241
9.57
2.54
0.090
5.35
1.53
10.45
831
23.16
45.9
5.32
19.08
3.94
0.547
3.56
0.605
3.60
0369
2.33
2.47
0.386
5.81
0.965
24.2
15.05
5.56

Preferred
Value
57.0
2.37
4.4
1601
13
3.7
2.0
4.4
12
32
15.0
149
108
25.0
219
8.90
2.30
0.065
4.10
1.26
9.60
807
27.0
47.0
5.30
19.0
4.30
0.66
3.70
0.66
4.08
0.95
2.60
2.60
0.41
6.20
0.95
0.93
24.0
15.1
5.80

STM-1
n=7
37.5
11.4
1.7
942
0.2
2.3
0.7
1.5
3.4
200
34.8
117.7
690
49.4
1441
289
5.19
0.24
9.87
1.61
1.573
577
153.2
264
26.2
80.8
12.34
3.35
8.83
1.454
7.92
1.543
4.35
4.25
0.623
27.3
18.71
17.73
31.2
8.53

fractionation factors necessary to correct the enriched isotope internal standard signals for isobaric
interferences are monitored on a run-to-run basis
using stock solutions. The removal of contributions
to analyte isotopes from the added enriched isotopes
is undertaken via blank subtraction. Oxide formation
levels are routinely maintained near 1% LaO relative
to La, a level which necessitates corrections to only a
handful of isotopes/elements, the most critical of
which are usually the middle REE (Eu, Gd, and Tb),

Prefexged
Value
32.0
8.6
0.7
809
2.0
0.7
4.5
237
36.0
117.0
710
42.5
1280
249
5.20
0.27
6.80
1.66
1.54
560
150
259
25.5
82.4
11.3
3.35
9.74
1.390
7.75
1,500
4.19
4.13
0.640
29.6
17.9
0.26
16.3
28.4
8.46

PCC-I
n=12
0.9
0.001
9.0
23
27
2168
105
2052
7
31
0.48
0,058
0.33
0.087
0.191
0.011
0.032
0.022
1.24
1.36
0.0045
0.76
0.029
0.053
0.0068
0.025
0.005
0.0011
0.0061
0.0012
0.0087
0.0027
0.0113
0.0213
0.0046
O.0054
0.002
8.0
0.0115
0.0039

%RSD
8.5
171
7.6
12.6
12.5
37
4.4
13.9
13.9
13.2
13.9
19.7
22
5.3
18.6
16.3
55
2,4
7.0
6.3
13.6
8.0
7.4
9.7
8.3
6.4
50.2
40,8
19.7
25.0
14.1
13.8
10.8
6.7
13.3
36.7
41.2
4.4
10.2
10.3

Literature
Value
1.2
0.050
8.4
75
31
2730
112
2380
10
42
0.64
0,066
0.38
0.087
0,200
0.040
0.020
0.020
1.60
1.400
0.0055
0.90
0.035
0,072
0.0086
0.0350
0.(}066
0.0012

DTS-I
n=2
2.0
0,002
5.3
19
9

5
35
0.39
0.078
0,31
0.038
0.253
0.012

0.99

Litea'ature
Value
2.1
3.5
ii
3990
137
2360
7
46
0.50
0.058
0.32
0.04
4.00
2.20
0.14

0.0015
0.011
0.0029
0.012
0,024
0.0057
0.0060
0.0020

0.0073
0.33
0.0246
0.100
0.0063
0.0234
0.0031
0.0013
0.0044
0.0007
0.0038
0.0014
0.0050
0.11090
0.0019
0.{)069
0,002

0.55
0.500
0.0058
1.70
0.029
0.072
0.0063
0.029
0.0046
0.0012
0.0038
0.0008
0.0030
0.0013
0.0040
0.010
0.0024
0.015
0,039

8.5
0.0100
0.0043

13.06
0.009~
0.0018

12.00
0.0100
0.0036

and Cu and Zn. Less significant corrections are also

applied to a number of other isotopes, as detailed in
Table 1.

4. Results
The measured concentrations of > 40 trace elements in a range of international and laboratory
reference materials are reported in Table 3. Also

S.M. Eggins et al. / Chemical Geology 134 (1997) 3 1 1 - 3 2 6

319

Table 3 (continued)

Li
Be
Sc

Bit
n=8
14.9
2.23
23.4

Ti
V

16194
240

Or
Co
Hi
Cu
Zn
Ga
Rb
Sr
Y
Zt
Nb
Mo
Cd
Sn
Sb
Cs
Ba
La
Ce
Pt
Nd
Sm
Ea
Gd
Tb
Dy
Ha
Er
Yb
Lu
Hf
Ta
1"1
Pb
Th
U

%RSD Prefmed
Value
1.1
13.0
2A
1.50
2A
25.0

7.2
7.1

15587
235

SY-2
n=3
95
27
6.9

7.7
3.7

839

14.3
673

9.5
8.6
9.9
5.2
248
29.0
217
271
128.0
280.0
29
1.80

95
43
54
65
115
21.6
26.0
403
33,6
212
18.98
3.18

5.70
0.250
2.400
460
75.0
175.0
18.80
73.0
16.10
2.42
17.00
2.50
18.00
3.80
12.40
17.00
2.70
7.70
2.01
1.50
85.0
379
284

16.24
0.077
0.480
337
26.7
59.3
7.80
32.5
8.76
2.16
7.06
1.074
5.98
1.176
3.08
2.50
0.359
5.03
1.140
0.230
13.4
3,13
0.628

2.1
6.4
3.4
4.3
4,4
4.1
1,1
1.3
1.4
1.2
1.1
2.3

380
52
260
72
160
19.0
47.0
1320
30
250
98
2.4

4.9
12
11
3
222
28.0
225
271
144
314
32.3
0.82

2.24
0.137
0.823
1082
82.1
152.2
17.36
66.1
12.11
3.58
9.57
1.29
6.30
1.0~/
2.59
1.806
0.251
5.62
5.79
0.074
4.77
10,87
2.46

7.6
7.7
2.8
1.4
12
1.6
0.7
02
0.6
l.l
1.0
1..~
0.~;
0,g
0.6
1.0
1.]
1.:;
1.0
2.6
3.0
0.11
1.2

2.50
0.30
1.00
1050
82
151

6.15
0.219
2.805
453
69.2
161.1
20.1
76.5
16.2
2.40
16.7
3.08
20.4
4.84
15.59
18.07
3.06
8.65
1.97
2.00
53.4

2.40
1.90
0.25
5.40
6.20
0.05O
8.00
II.00
2.50

WSE
n=5
13.6
1.26
28.0

770
49

368
56
263
71
172
17.1
48.7
1364
31.5
283
119.3
2.17

65
12.0
3.70
9.50
1.25
6.20

%RSD Prefen'ed
Value
5.2
95.0
4.0
22.0
5.1
7.0

333
247

27.3
5.1
2.4
1.5
2.5
2.0
3.1
2.3

3.1
0.6
0.9
0.6
1.1
1.3
0.8
0.7
3.3
1.9
1.8
1.2
0.7
0.2
1.4
1.3
1,4
1.8
0.6
12.4
6.0

listed are relative standard deviation (RSD) values

based on multiple determinations made in independent analytical procedures, and in most cases incorporate multiple digestions of each reference material.
The preferred values listed for each reference material provide a guide to the accuracy of the method,
its dynamic range, arid the ability to measure a broad
range of matrix compositions.
The precision able to be attained using our technique is indicated by the RSD values listed for our
laboratory standard 93-1489, a Kilauea tholeiite simi-

5.2
5.7
3.8

14198
347

PMS
n=2
7.5
0.37
32.4
6049

181
2.1
10.1
2.4
4.1
6.1
2.7
0.8
0.9
1.7
0.7
1.0

2.4
0.9
0.7
0.6
0.6
1.5
1.8
0.5
1.3
0.3
0.5
0.8
0.3
0.6
1.6
1.6
0.9
8.6
1.8
0.6

315
45
120
57
56
14.5
0.915
270
11.37
36.1
2.41
1.57
5.28
0.023
0.347
146.3
2.57
6.52
1.051
5.46
1.798
1.053
2.04
0.338
2.05
0.425
1.169
0.984
0.145
1.033
0.176
0.051
3.51
0.044
0.014

93-1489
n=23
4.8
0.918
31.6

14362
301
471
51
160
123
104
19.2
7.15
317
27,0
147.2
13.24
0.74
0.064
1.72
0.033
0.074
99.9
11.20
27.9
4.11
19.21
5.21
1383
5.59
0.878
4.96
0.966
2.51
1.974
0.279
3.58
0.820
0.022
0.95
0.853
0.274

%RSD

%RSD

1.4
2.3
1.7
2.5

Tafahi
n=12
4.O
0.185
45.5
2279

4.3

298

$.7

2.5
2.3
1.7
2.6
1.5
0.8
1.8
0.7
0.5
0.5
0.6
5.5
13.5
2.7
73
3.9
0.5
0.6
0.5
0.6
0.7
0.8
0.5
0.9
0.8
0.5
0.8
0.5
1.0
1.2
0.8
1.0
3.9
2.7
1.0
0.6

53
41
25
128
64
13.13
1350
138.9
9.11
12.07
0.456
0.44
0.031
O.24
0.024
0.066
40.3
0.938
2.22
0.361
1.93
0.722
0.305
1.069
0.207
1.384
0.322
0.980
0.992
0.153
0.395
0.0219
0.0142
O.95
0.120
0.0728

2.1
5.8
1.9
3.3
6.0
1.0
1.8
1.0
0.9
1.6
0.8
3.3
3.1
9.3
9.5
3.O
1.2
1.4
1.1
2.0
1.4
1.8
1.2
1.4
2.7
1.1
1.0
0.9
1.2
1.7
1.0
3.8
4.3
2.3
2.1
1.3

3.5
3,0
3.0
6.6

lar to BHVO-1. The data for this reference material

were acquired in 23 separate analytical procedures
and on no less than 15 separate sample digestions
over a period between May 1994 and February 1995.
The RSD values for most elements with mass > 80
amu are < 1%, and between 1% and 4% for elements with mass < 80 amu (Fig. 3). Notable exceptions occur with Mo, Cd, Sn, Sb, Cs, T1 and Pb,
which can be attributed either to counting statistic
limitations at low abundance levels in 93-1489 or the
BHVO-1 calibration solution (e.g., Be, Mo, Cd, Sb,

S.M. Eggins et aLI Chemical Geology 134 (1997) 311-326

320

Anal~ical Precision
I I I I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

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*i

Hf~ TIPb~ U

Element
R g . 3. A n ~ y ~ c a l p ~ c i s i o n v ~ u e s ( % R S D ) ~ r each element using enriched-isotope i n ~ m a l - s t a n d ~ d i s m i o n , based on the r e p r ~ u c ~ i l i ~

of

multiple i n ~ n d e n t me~u~ments (n = 23) of our l~orato~ standard 93-1489. T~se values a~ compared to t ~ ~eo~tic~ precision
l i ~ t estimated from ~p~al counting stmistics. No~ that ~eroretical values ~ling ~low ~ 0.3% are n~ shown as ~ey are unable to
ach~ved due to in~nsic instrument noise.

Cs, T1; cf. theoretical precision limits based on

counting statistics in Fig. 3), or to minor environmental contamination during sample preparation and
analysis (specifically Pb). In addition, some elements
are prone to instability in dilute nitric acid solutions
(e.g., Mo), and others to volatility during the digestion procedure (e.g., Sn, Sb). The upward bow in

RSD values between the widely spaced internal standards at low mass principally reflects an inability to
deconvolve accurately the complex sensitivity variations that occur in that region, though uncertainties
in the detector cross-calibration between pulse-counting and analogue modes and the less precise measurements able to be made in analogue mode also

Inter-Laboratory Comparison

Ii~

i i O i i i iIi iri ir! T

i i i ri i li ili l' ili ifi ri l r l r l l I I , ! ~

|-i.] ~ ~B~,ta~kt~, ~...LLL.1....i-~-i.-i--j....~.-.i...~...i...~-~....!....!....~-.!....!..R.~..;..~..i-i!

Ii +
1.0

|i

i iii

i!i~iO''i'i~Y:

i$ Zi*r i
iii

i i i i~i~i

::'!!0:!:

r*O
i i i i i i ~ ! i~!

?;
i i i~i

iiiill

i iii

i i i~i

~ . .-..r-~-~-~-~-i.-~ ............r.. - . ~ - - ~ . ~ - ~ - ~ . . . ~ . . . i ....................... ? . , . ~ - . t - i . ~ - ~ . . r - r ~ . . ! - ~ e - ~ . . . ? . . * . . ~ , -

~i i
+ ~ Y
e
i~!!iiiiiiiiiii~
[ iiii ii ! l liii i i iii ii i l $i ii l ii li !i !ii !i ii li~i ii i i* ii ii ?i l~i ii i i ! l i! li !i i i i i i i l i i i
hiiiiiiiiiiiiiiiiiiiiiiillll

iiiiiiiiiili

H ~Sc ~ i CrColiCuZnGiRbSr Y ~ l l ~ d S n t C s l ~ C e

PrldSntEuGd~Ho ~

ii~

HI~ ~ Pb~ U

Element
~g. 4. Comp~son of an~ytical precision (in %RSD) ~po~ed by laboratories employing muhi-element ~PMS an~ysis strategies on
geol~ical samples. No~ ~at d i ~ n c e s in instrument sensitivity and the number ~ elements determined in these cases have ~en offset as
far as ~ssiMe ~ c o l l ~ dam only for ~ r e n e e materiMs wi~ high trace element abund~ces.

S.M. Eggins et al. / Chemical Geology 134 (1997) 311-326

els and a corresponding counting statistic based

degradation of precision (see Fig. 3). Similar patterns
of precision have been obtained for other interna-

affect the high abundance elements. The steady increase in RSD values from the light REE to heavy
REE is consistent with decreasing concentration lev-

EnrichedlsotopelnternamStandardlsatlon(thlaatudy)

(a)

! ! !!

10

!!!!!!!!!!

!!!!!

.!.~t

-~..~

Z.Z-..L....L.L.~--L.L.~--Z~_.~.~--L.Z--L..]

ii

o<t

321

)I

~8~

IIII111

)1

#~

iIi

+ i

!!!!!!

W-2

m++,+,++,

BR

~iiiiiii

I!!

93"1~9~

......... ~--)--~-----)-

)i ii)ii iii i) i ii) iii

+i+

t,

+ i(.)+i

1+++ ++)+))))) + + +))++(i)iti+i()+(++t(

Cl

:iii~:i~ii'il:!:iiiiiiiiiiilii()ila:iiil

n":

aii

i , i~1

~ 10i

i~)

i i ) i i i i~)

:~!!)iiii:i~?.~iiiiii=

i ) i i i ) ) i i i )!!

()i~ii?iil,

i ii

;i'l'

1.0

~+,++,+++
'

+i

id))l+-

~+++,+w+U@O+a= j ~
lT~+~l$

~,x+++$

+Ot++))Yilti

iii~{ili(i(i{(~i~i{iii~{~i{161{~i{ii~ii{

'ii;iiiii;i~iiiiiiiiiiiiiiiiiiiiiiiiiiii
U BO~ ~ V Cr@o~CuZnG~RbSr Y Zr~dSnSbCs~CePrN~mE~d~DyHoEr~Lu

(b)

External

Ta TIPb~ U

Standardlsation

!!!!!~!!!!!!!!!]!!!!!!!!!(!I!$!!!!)!!!!!!

[ "=+')1];"+'++i{++'++)[1+L.1.]

10

!11

........T i f ~ I T ] [ [ [ )

))))))))iil~YiTO)lll$!~l$e+~YYT~T~lY)))
,
+

El
ft.)
rr:

l l l l : I t l l l l l : ~ : : [ l ~ l l [

1.0

w-2
))+)))l+
-i..i.-....i..i,...-.i...)......i-..)...i...i...)......i..-)-+.i-.-F-.i
...... 0 9'-'
489
AGV-1
|) ) ) ) ) ) ) )

))))))))))))))))))))))),

- ,,

~iiii!!!!!!!!iil)iiiiiiii!iiiiiiiiiiii!!)
I I I I i I i I I i Ill
q I I I it I tim
Li BeSc Ti V CrCo NiCuZnGa.RbSr

(c)

!-........ v

[iv')

......... r..,,.-.--t

. i~i

......... , ......... ,

I
! i I

r-.~ ......

ErYbLu

:~/W'

93-1489
W-2

..-

I I I

Hf TI TI Pbi'h U

'mm

i [ i i i I
i, i i i i ' t

AGV 1

~ i i ~lml i i ibJ ) i , i ) i ) i ) i iel

ii [i )ii ii., i ~

1.o

e
~,,,

..........

) 1)i ))i )i 1.1~)i

o:

i i i i I Ii

NdSmEuGdlbOyHo

External & Elemental (In) Internal Standardisation

= } i I <> I i i t J I I i
I J i i i !, J i ! i J i i i ! i
~_i i i i, i, i, i i, i ! )J,

i I i I i Ii

Y Zr NbMoCdSnSbCllBaLaCePr

,o

m.,..++.++++

...... :+......... r-.: ....

+ii);+i

i~>i i ) =$dm.~)~1
I!'

' :

~,!

i I~,T!i!il)li*~.#.@,TT)l.'71i )|

-6--4---+----+-+---)---F++.-i-------}---I----T.---)-.---.....*..+
........ $$...'..--.:'--T--------~-----..'g-........ -.."--..-.F+...---'---)-...-t

iiiiiiii

ii !i!!il

ii iiiiiiii

ii iiiii

i!V!

i! ii 1

ili[illilllili(l[iii[iiiiiiiiiiiiiiiiiil

kiOeSc Ti V CrCoNiCuZnGaRbgr Y ZrNbMoCdSnSbCsBaLaCePrNdSmEuOdTonyHoErYbLuHfTaTIPbTh U

Element
Fig. 5. Comparison of the analytical precision (in %RSD) for each element based on different data reduction strategies using our primary
data set for the reference materials, 93-1489, AGV-1, W-2, and BR. The strategies compared include: (a) enriched isotope internal
standardisation as described in detail in the text; (b) external standardisation; and (c) combined elemental internal standardisation (using In)
and external standardisation.

322

S.M. Eggins et al. / Chemical Geology 134 (1997) 311-326

tional and laboratory reference materials, though at

marginally poorer levels than obtained for 93-1489
(Table 3, Fig. 3, and also Fig. 5a below).

4.1. Accuracy and detection limits

Assessment of the method's accuracy is inherently limited by the accuracy to which elemental
concentrations are known in international reference
materials. Most measured values show reasonable
agreement (generally to better than ___I-3%) with
preferred values for the international reference materials (Table 3), particularly for those elements which
are relatively well known (e.g., Rb, Sr, Y, Zr, Pb,
Th, U and the multi-isotopic REE). The principal
source of inaccuracy with our technique stems from
the calibration values adopted for BHVO-1, which
bias all determinations where these calibration values
deviate from true values.
Detection limits vary from element to element due
to a variety of factors, but for most high mass
elements ( > 80 amu) typically fall within a range
from < 1 to 10 pg g-I ( < 1 - 1 0 ng g-1 sample
equivalent) and for lower-mass elements between 10
pg g-1 and 1 ng g-~ (10 ng g - ~ - I txg g-I sample
equivalent).

5. Discussion

5.1. Comparison with other ICPMS analytical techniques

The analytical precision obtained using our
method may be compared with the so far limited
data reported by other ICPMS laboratories that employ multi-element analytical methods. In making
such a comparison, the different calibration strategies
and drift correction techniques adopted by the various laboratories should be borne in mind, as well as
the inherent limitations stemming from different instrument performance, particularly in cases where
older, less sensitive instruments are employed. Most
laboratories report analytical precision between 3%
and 10% (e.g., Jenner et al., 1990; Cheatham et al.,
1993; Poitrasson et al., 1993; Schonberg, 1993;
Hrmond et al., 1994; Xie et al., 1994; see Fig. 4)
though some notable exceptions do occur. For exam-

pie, Xie et al. (1994) report precision better than

+ 1% for some elements in certain samples, but
upwards of + 5% and occasionally as much as + 20%
for other elements in the same sample (e.g., Hf, Ta,
Th and U in BIR-1). Incomplete washout of previous
sample signals prior to analysis is often responsible
for such poor precision and can result in measured
concentrations that are higher than accepted values.
The comparatively poor performance of existing
multi-element ICPMS analysis strategies probably
reflects the difficulty of undertaking optimum spiking in the case of standard addition or failure to
adequately correct for mass-dependent sensitivity
variations in the case of procedures employing external standardisation a n d / o r elemental internal standardisation. The latter are readily demonstrated by
comparing the precision obtained if external standardisation a n d / o r elemental internal standardisation
are used as alternative means to correct our primary
data set (Fig. 5a-c). External standardisation without
internal standardisation results in a consistent analytical precision of ~ 4-6% RSD for virtually all
elements (Fig. 5b). The magnitude and uniformity of
this precision matches closely that demonstrated by
Cheatham et al. (1993) using the same technique (cf.
Fig. 5b and 4), and is 5-10 times poorer than
achieved with the same data using enriched isotope
internal standardisation (cf. Fig. 5a and b).
The combination of a single internal standard with
secondary external standardisation dramatically improves analytical precision, particularly for elements
which are near the internal standard mass (Fig. 5c).
Analytical precision is reduced to between + 1% and
+ 5% for most elements using In, with the improvement being most notable for analyte masses nearest
the internal standard. Clearly, further improvements
can be obtained with additional internal standards
spaced through analyte mass range, and can be optimised with the use of enriched isotope internal standards (see Fig. 5a).

5.2. Applications
The ability to measure rapidly and precisely a
large number of elements over a concentration range
from the ng g-1 to % level, in a broad spectrum of
matrixes, makes ICPMS a powerful tool for the
Earth sciences. The array of potential applications of

S.M. Eggins et al. / Chemical Geology 134 (1997) 311-326

multi-element ICPMS analysis has been dealt with
previously (e.g., Jenne~r et al., 1993) and need not be
revisited here. Instead we shall focus on an application which highlights the benefits of the improved
precision and the ability to measure low concentration levels of the high-field strength elements (HFSE)
Nb, Ta, Zr and Hf. The ability to discern subtle
differences in the get)chemical behaviour of these
petrogenetically important elements has significant
implications, among others, for m a g m a petrogenesis,
the nature of chemical differentiation processes operating within the Earth, and the discrimination of
ancient tectonic envirenments.

60

+
o
o
x

55
50

323

SZB
SZ Diff*ted
BABB
OIB

OIDifl'ted
Melting Model
~ l s t
Stage
,~i2nd
Stage

"
ee
~<eee

%,0* + + ~ ~ t "

,.i..-

"I" 45
N

I .......
|
|
I
-i

40

~+ . ~ . 2

35

....

30
. . . . . . . .

illl[

. . . . .

-i-

24

Tafahi

5.3. Assessment of choi~dritic ratio values for Zr /

Nb / Ta and Y / Ho in magmatic rocks

Hf

A number of element pairs possess virtually identical ionic radii for a given coordination number and
are well known for their similar geochemical behaviour, in particular Zr and Hf, Nb and Ta, and Y
and Ho. Indeed, each of these element pairs has been
promoted as having essentially chondritic ratios in
the Earth's mantle an6 in magmas derived therefrom
(Jochum et al., 1986). However, it has been recently
observed by Dupuy et al. (1992) that the Z r / H f ratio
increases systematically as a function of total Zr
concentration in alkaline basaltic magmas and can
reach highly superchondritic values (up to ~ 100 vs.
the chondritic value of 36) in certain extremely
incompatible element--rich magmas. Accordingly it
has been suggested that Zr is more incompatible than
Hf during mantle melting. Some doubt has remained
as to the validity of the observations of Dupuy et al.,
and the data they compiled did not include relatively
incompatible element poor magmas (e.g., tholeiites),
thus the expectation has remained that most mantlederived magmas should have near chondritic Z r / H f
ratios (i.e. 36). Similar expectations also apply to
N b / T a and Y / H o ratios which are widely believed
to conform to their chondritic values of 17 and 28,
respectively (Jochum et al., 1986).
W e have measured a large number of subduction
zone and ocean island lava samples, largely of
basaltic composition, as part of our investigations
into mantle source chemistry and magma generation
processes within subduction zones and in mantle
plumes. The Z r / H f , N b / T a and Y / H o ratios mea-

::'8

.D

++4~

16
12
. . . . . . . .

ilrlll

i i t H I

40

35

o9 ~o o++

++

+ xxx

xXx ~

"1- 30

25

20

0.1

. . . . .

....

10

. . . . . .

,i

100

Nb ppm
Fig. 6. Measured Zr/Hf, Nb/Ta and Y/Ho ratio values vs. Nb
concentrations in subduction zone basalts, back-arc basin basalts,
and oceanic island basalts and more limited examples of differentiated magmas from subduction zones (SZ Diff'ted) and ocean
islands (OI Diff'ted). A simple two-stage non-modal batch melting model for a mantle source initially containing 1.0 Ixg g-l Nb
and possessing chondritic ratios of Zr/Hf (36) and Nb/Ta (17) is
shown for comparison (the extents of melting in % are given
within the symbols). The second melting stage is conducted on the
residual source composition remaining after extraction of 5% melt
in the first stage. Bulk mantle-melt partition coefficients used for
Zr, HI', Nb, and Ta were 0.044, 0.064, 0.002, and 0.005, respectively, The non-modal melting cofficients (P values) employed in
the first stage were 0.164, 0.244, 0.005, and 0.007, and in the
second stage 0.036, 0.052, 0.0018, and 0.0022, respectively.
These coefficients are based on experimentally determined solidmelt partitioning values for individual peridotite phases (see for
review Green, 1994), a source initial source mode comprising
60% olivine, 20% orthopyroxene and 20% clinopyroxene, and a
melting mode of 80% clinopyroxene and 20% orthopyroxene.
Similar results and systematics are obtained for melting of a
garnet-bearing mantle source mineralogy, and with fractional
melting employing an acceptable threshold porosity.

324

S.M. Eggins et al./ Chemical Geology 134 (1997) 311-326

sured for these samples are plotted in Fig. 6 against

their Nb concentrations. Nb is chosen here for its
typically highly incompatible behaviour during mantie melting and because it is unlikely to have been
added in significant quantities to the mantle source
region of subduction zone magmas.
Z r / H f ratios are found to increase significantly
and systematically with increasing Nb concentration,
from subchondritic values near 30 for the most incompatible element-poor subduction zone basalts up
to values approaching 60 for the most incompatible
element-rich ocean island magmas. This not only
confirms the trend observed by Dupuy et al. (1992)
but extends it across the compositional spectrum of
mantle-derived magmas. It is notable that ocean
island basalts (OIB) have superchondritic Z r / H f values and an average value of 44.6 + 2.3 (lcr) whereas
subduction zone basalts (SZB) average 37.2 + 4.1,
and range down to values as low as 30 for the more
Nb-poor samples.
N b / T a ratio variation tends to mimic that of
Z r / H f at least for the SZB, of which the most
Nb-poor tend to have subchondritic values and the
more Nb-rich to have slightly superchondritic values.
OIB cluster tightly about the chondritic value at
16.7 _ 1.2 (ltr), with the exception of several highly
silica-undersaturated magmas from Aitutaki (Cook
Islands, Polynesia) which have distinctly superchondritic values near 22. Interestingly, our laboratory
standard, a Nb-poor island arc tholeiite from north
Tonga, along with other samples from the same
region, have anomalous superchondritic N b / T a values which range to well above 20 (Fig. 6, middle).
Y / H o ratios, unlike Z r / H f and Nb/Ta, plot very
tightly about the chondritic value (Fig. 6, bottom).
Virtually all samples have values between 27 and 30,
with similar mean values for SZB (29.0 + 1.15),
back-arc basin basalts (BABB = 28.4 __+1.05) and
OIB ( 2 8 . 8 _ 1.10). Departure from the chondritic
value is uncommon and is usually found only in
some highly differentiated magmas which tend to
have superchondritic values exceeding 30 (see Fig.
6, top). The latter indicates subtle differences in the
partitioning of Y and Ho between crystallising phases
and melt during protracted magmatic differentiation.
The systematic increase in Z r / H f values along
with Nb concentrations in basaltic magmas indicates
that Zr is more incompatible than Hf during upper

mantle melting. This is consistent with most experimental and natural element partitioning studies between clinopyroxene-melt, garnet-melt and amphibole-melt (e.g., Ulmer, 1989; Hart and Dunn, 1993;
Green, 1994; Adam et al., 1995). Nb has also been
shown to be more incompatible than Ta for clinopyroxene-melt and garnet-melt pairs, but not for amphibole-melt and rutile-melt pairs (e.g., Jenner et
al., 1993; Green, 1994). The latter is of interest
because the occurrence of amphibole a n d / o r rutile
during mantle-wedge melting could explain the
strongly subchondritic N b / T a values observed in
some subduction zone magmas. However, both Nb
and Ta are relatively incompatible in amphibole
(e.g., Green, 1994), and so the presence of this phase
is unable to account for the very low Nb and Ta
abundances which characterises these subduction
zone magmas. Moreover, these particular magmas
are also highly depleted in other trace elements,
including the LREE and Th, which cannot be attributed to the presence of amphibole a n d / o r futile
during partial melting.
Despite possible differences in bulk mantle-melt
partition coefficients for Nb and Ta it will be intrinsically more difficult to fractionate Nb from Ta than
Zr from Hf in mantle-derived magmas due to the
much smaller magnitude of bulk partition coefficients for the former elements, unless an accessory
phase such as rutile is present. Any fractionation of
N b / T a from the mantle source ratio is most likely
only at tiny degrees of partial melting. This may
account for the widespread development of superchondritic Z r / H f values but not N b / T a values.
The occurrence of subchondritic Z r / H f and
N b / T a values in certain mantle-derived magmas,
particularly the most Nb-poor subduction zones magmas, can be most simply explained by depletion of
Nb relative to Ta and Zr relative to Hf in their
mantle sources. This is consistent with the expected
depletion of these elements arising from previous
melting of the mantle source. A simple two-stage
mantle melting model (cf. Fig. 6) can reproduce the
observed trends and the absolute element concentrations. This supports the hypothesis of Woodhead et
al. (1993) that the low HFSE abundances in subduction zone magmas is due to source depletion. The
low Nb concentrations (_< 1 p~g g - l ) occurring in
many subduction zone magmas assert this conclusion

S.M. Eggins et aL / Chemical Geology 134 (1997) 311-326

for they cannot be produced by reasonable amounts

of melting of a fertile mantle source with a primitive
mantle Nb concentration (i.e. 0.71 g g-Z; Sun and
McDonough, 1989), nor melting of a geochemically
"depleted" N-MOR]3-1ike source mantle with a Nb
concentration of ~ 0.2-0.4 i~g g-1 (assuming 10%
melting to produce the average N-MORB Nb concentrations of Hofmann (1988)) and Sun and McDonough (1989). Given a likely maximum limit of
20% partial melting, the mantle source of the most
Nb-poor subduction zone magmas, is estimated to
contain no more tharL 40 ng g-1 Nb. The nature and
significance of the superchondritic N b / T a value obtained for samples from north Tonga is the subject of
a continuing investigation.

6. Conclusions
The novel use of enriched isotopes along with
conventional elemenlLal internal standards enables the
complex sensitivity variations that are often encountered during ICPMS analysis to be monitored and
deconvolved. This provides the basis for a routine
method for the analysis of > 40 trace elements,
spanning the entire mass range, in a broad spectrum
of sample matrixes. The method delivers improved
precision and extended element coverage compared
to existing ICPMS analytical strategies, while maintaining low detection limits. These capabilities are
demonstrated by the measurement of subtle but significant deviations of Z r / H f and N b / T a ratios from
chondritic values in mantle-derived basaltic magmas,
and the occurrence of systematic variations in these
ratios with varying iincompatible element concentrations. This behaviour indicates greater incompatibility of Nb than Ta and of Zr than Hf during mantle
melting, and supporls the notion that the cause of Nb
and other HFSE depletions in subduction zone magmas is due to the geochemical depletion of the
mantle wedge by prior melting events.

Acknowledgements
We are indebted to Bill McDonough for his assessment of preferr,~d values for BHVO-1 and the
other international standards, and to both he and

325

Roberta Rudnick for their ongoing interest in and

critical assessment of our ICPMS technique and data.
Mike Shelley has shared with us his much valued
knowledge of and remedies for problems associated
with ICP sample introduction systems.

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