Geochemical Journal, Vol. 43, pp.

133 to 141, 2009

NOTE

A simple method for the precise determination of boron, zirconium, niobium,

hafnium and tantalum using ICP-MS and new results for rock reference samples

K AZUYA NAGAISHI 1,2* and TSUYOSHI ISHIKAWA3

1
Marine Works Japan Ltd., 200 Monobe-otsu, Nankoku, Kochi 783-8502, Japan
2
Graduate School of Science and Engineering, Shizuoka University, 836 Oya, Shizuoka 422-8529, Japan
3
Kochi Institute for Core Sample Research, Japan Agency for Marine-Earth Science and Technology (JAMSTEC),
200 Monobe-otsu, Nankoku, Kochi 783-8502, Japan

(Received August 6, 2008; Accepted October 23, 2008)

An analytical technique for determining boron, zirconium, niobium, hafnium and tantalum contents in rock samples
by inductively coupled plasma mass spectrometry (ICP-MS) is described. The rock samples (<30 mg) were decomposed
with mannitol-added HF, and dissolved in a 0.015 M HF/0.12 M HNO3 acid mixture for ICP-MS analysis. Boron, zirco-
nium, niobium, hafnium and tantalum concentrations were measured by the internal calibration curve method using three
internal standard elements, beryllium for boron, indium for zirconium and niobium, and rhenium for hafnium and tanta-
lum. Seventeen rock reference samples from the Geological Survey of Japan and the U.S. Geological Survey were analyzed,
and the determined concentrations showed good agreement with the reported values obtained by isotope dilution method,
as well as with the recommended values. This technique is a simple method for the precise determination of boron,
zirconium, niobium, hafnium and tantalum concentrations, and it has wide potential for geochemical application, particu-
larly for the determination of boron.

Keywords: ICP-MS, analytical method, rock reference samples, boron, high field strength elements

1990; Ishikawa and Nakamura, 1994; Ishikawa and Tera,

INTRODUCTION
Boron, zirconium, niobium, hafnium and tantalum all
behave as incompatible elements during magmatic proc-
esses (Sun and McDonough, 1989; Ryan and Langmuir,
1993). In aqueous fluid-related processes, however, the
behavior of boron is in striking contrast to that of zirco-
nium, niobium, hafnium and tantalum. Boron is one of
the most fluid-mobile elements during high-temperature
fluid-rock interactions (Seyfried et al., 1984; Morris et
al., 1990; Brenan et al., 1998). In contrast, zirconium,
niobium, hafnium and tantalum, which are known as typi-
cal high field strength elements (HFSEs), are essentially
fluid-immobile (Keppler, 1996; Kogiso et al., 1997).
These distinctive chemical characteristics of boron and
HFSEs make it possible to utilize B/HFSE ratios, such as
B/Nb and B/Zr, as powerful geochemical tracers for elu-
cidating fluid-induced processes in the crust and mantle,
especially dehydration of subducting oceanic slab and the
genesis of arc magma in mantle wedge (Leeman et al.,
*Corresponding author (e-mail: nagaishik@mwj.co.jp)
Copyright © 2009 by The Geochemical Society of Japan.
1997; Tonarini et al., 2001). Although the isovalent ele-
ment pairs zirconium–hafnium and niobium–tantalum
have very similar ionic radii and generally behave coher-
ently during magmatic processes, the Zr/Hf and Nb/Ta
ratios of some mantle-derived igneous rocks deviate sub-
stantially from the chondritic values (Xie and Kerrich,
1995; Stolz et al., 1996; Eggins et al., 1997; Niu and
Batiza, 1997; Münker, 1998), leading to an increased in-
terest in using these element ratios as tools for studying
geochemical processes in the mantle.
Despite the geochemical importance of boron, it is
uncommon for boron concentrations of rock samples to
be routinely determined along with other trace elements,
including HFSEs, because boron is easily volatilized from
acid solution, causing loss of boron during sample diges-
tion with HF and subsequent chemical treatments. This
problem is avoidable when boron is determined by in-
ductively coupled plasma-atomic emission spectrometry
(ICP-AES) after sample digestion using the alkali fusion
technique (Ryan and Langmuir, 1993) or by prompt γ-ray
neutron activation analysis (PGNAA) without sample di-
gestion (Gladney et al., 1976). However, these methods
are of limited utility for the analysis of low levels of bo-
ron as well as for the determination of HFSEs. In con-

133
 Table 1. ICP-MS operating conditions

ICP Ion Source

RF power 1.6 kW, frequency 40.68 MHz
Torch Fassel type, made of quartz glass
Plasma Ar flow rate 17 L/min
Auxiliary Ar flow rate 1.7 L/min
Nebulizer Ar flow rate 1.0 L/min (typical)
Nebulizer Concentric type, made of quartz glass
Spray chamber Cyclonic type, made of quartz glass (ambient temperature)
Solution uptake rate 0.25 mL/min (pumped)

Interface
Sample cone Pt tip insert in a Ni base, 1.1 mm orifice diameter
Skimmer cone Pt tip insert in a Ni base, 0.9 mm orifice diameter

Data Acquisition
Dwell time 50 ms/isotope (pulse counting mode)
Integration time 300 ms/isotope
Replication 3 times

trast, Makishima et al. (1997, 1999) developed a tech-
nique for analyzing boron and HFSEs by inductively cou-
pled plasma mass spectrometry (ICP-MS) with a flow
injection system. In their method, rock samples were de-
composed by mannitol-added HF to avoid boron loss
(Ishikawa and Nakamura, 1990; Nakamura et al., 1992)
and the concentrations of boron and HFSEs dissolved in
a 0.5 M HF solution were determined either by the iso-
tope dilution method (boron, zirconium and hafnium) or
by the external calibration curve method (niobium and
tantalum). Boron and HFSEs are soluble in the HF-
mannitol solution as a stable boron-mannitol complex ion
and as fluoro-HFSE complex ions such as NbF 6– and
ZrF 62–, respectively, making it possible to analyze these
elements precisely and simultaneously. However, the
method of Makishima et al. (1997, 1999) requires some
special apparatuses, including a HF-resistant spray cham-
ber, a nebulizer and a torch, and a flow injection system,
and also necessitates careful control of the spike/sample
weight ratio to avoid uncertainty propagation in isotope
dilution, both of which tend to prevent this method from
being used along with other analytical laboratory routines.
Thus the development of a method that is capable of
analyzing boron (and HFSEs) easily and precisely still
has great significance.
In this paper, we present a simple method for the pre-
cise determination of boron, zirconium, niobium, hafnium
and tantalum concentrations in rock samples, in which
the samples decomposed with HF-mannitol are dissolved
in a 0.015 M HF/0.12 M HNO3 acid mixture, and analyzed
by an internal calibration curve method with the standard
ICP-MS instrumental setting. This technique makes it
possible to determine boron, zirconium, niobium, hafnium
and tantalum easily and precisely without using the iso-
tope dilution method. We also present new analytical re-
sults for boron, zirconium, niobium, hafnium and tanta-
lum in 17 rock reference samples of the Geological Sur-
vey of Japan (GSJ) and the U.S. Geological Survey
(USGS), including the recently issued samples JB-1b, JB-
2a, JB-3a and JA-1a.
EXPERIMENTAL
Instrumentation
The instrument used in this study was the quadrupole
ICP-MS, ELAN DRC II (Parkin Elmer, USA) at the Kochi
Core Center in Japan. Operating conditions are shown in
Table 1. To decrease susceptibility to matrix effects, the
ICP was operated at a higher power (1600 W) than usual
(1100 W), in accordance with the technique reported by
Makishima et al. (1999). The nebulizer gas flow and aux-
iliary gas flow were adjusted so as to obtain CeO/Ce <
0.03.
Typical sensitivities for 9Be, 115In and 185Re in this
study were 1200, 33000 and 39000 cps ng–1 mL, respec-
tively. The ELAN DRC II does not equip high-voltage
ion-extraction lenses, which results in lower sensitivities
for low-mass elements (e.g., beryllium and boron) but on
the other hand effectively reduces background levels and
background equivalent concentrations of elements, pro-
ducing high signal-to-background ratios in ICP-MS analy-
sis.
Reagents and standard solutions
All solutions used in this study were prepared with 18
MΩ H 2 O produced by a Milli-Q Element system
(Millipore, USA). To reduce boron blank, analytical grade
HF and HCl were purified by subboiling in a two-bottle

134 K. Nagaishi and T. Ishikawa

Teflon still in the presence of mannitol (Nakamura et al.,
1992). For HNO 3 , either an analytical grade reagent
subboiled in a two-bottle Teflon still or a commercially
supplied high-purity reagent (TAMAPURE AA-100, Tama
Chemical, Japan) was used. A 1% mannitol solution was
prepared by dissolving mannitol powder (MERCK, Ger-
many) in 0.015 M HF.
Internal standard solutions (400 ng/mL Be and 10 ng/
mL In and Re) were made by diluting a 1000 µg/mL Be
atomic absorption standard solution (Kanto Kagaku, Ja-
pan), a 1000 µ g/mL In plasma standard solution
(CertiPUR, Merck) and a 100 µg/mL plasma standard
solution of precious metals (Ir, Os, Pd, Pt, Re, Rh and
Ru) (Specpure, Alfa Aeser, USA), in either a 0.015 M HF
solution (internal standard solution-I) or a 0.015 M HF/
0.15 M HNO3 acid mixture (internal standard solution-
II).
A multi-element standard solution for ICP-MS analy-
sis (50 ng/mL B, 110 ng/mL Zr and 10 ng/mL Nb, Hf and
Ta in 0.015 M HF/0.12 M HNO 3 and 0.004% mannitol)
was prepared by dilution of a 100 µg/mL plasma stand-
ard solution of refractory metals (B, Al, Si, Ti, V, Cr, Zr,
Nb, Mo, Hf, Ta and W) (Specpure, Alfa Aeser), a 1000
µg/mL B atomic absorption standard solution (Kanto
Kagaku), a 1000 µg/mL Zr plasma standard solution
(Specpure, Alfa Aeser) and the 1% mannitol solution, in
a mixed internal standard solution (I:II = 1:4).
Rock reference samples
Fourteen GSJ “Igneous rock series” rock reference
samples and three USGS rock reference samples were
analyzed in this study. They comprised basalt (JB-1, JB-
1a, JB-1b, JB-2, JB-2a, JB-3, JB-3a, BIR-1, BCR-2 and
BHVO-2), andesite (JA-1, JA-1a, JA-2 and JA-3) and
rhyolite (JR-1, JR-2 and JR-3) samples.
Sample preparation
Typically, 15 mg of rock powder (from 8 to 33 mg in
this study) was weighed in a 7-mL PFA Teflon vial. The
sample was soaked in 0.1 mL H2O, and then 0.1 mL 1%
mannitol solution, 0.1 mL 6 M HCl and 0.5 mL 30 M HF
were added. The vial was tightly capped, and the sample
was decomposed at 70°C on a hot plate. After it cooled to
room temperature, the sample was evaporated to dryness
at 60°C overnight. During this stage, it is essential to keep
the evaporation temperature well below 100°C.
Volatilization of boron during evaporation of the HF and
HCl solutions are completely suppressed when the man-
nitol/boron mole ratio in the solution is more than unity
because BF4– or B(OH)3 in these solutions reacts with
mannitol to form [BL]– complex, where L is mannitol,
and the resultant complex is not volatilized during evapo-
ration of the solution (Ishikawa and Nakamura, 1990).
However, the long extra heating after complete evapora-
A simple method for the precise determination of B, Zr, Nb, Hf and Ta using ICP-MS 135
tion of the solution at >70°C tends to destabilize the
boron-mannitol complex and cause loss of boron
(Ishikawa and Nakamura, 1990). In addition, hafnium is
not recovered perfectly from the fluoride residues when
the evaporation temperature is >100°C (Salters and Hart,
1991).
Subsequently, 5 mL of internal solution-I was added
to the dried sample, and the vial was again tightly capped.
The vial was heated at 70°C for an hour to dissolve boron
and HFSEs into the solution. After it cooled to room tem-
perature, the vial was centrifuged at 3000 rpm for 5 min-
utes, and then a 1 mL aliquot of the supernatant was trans-
ferred into another 7-mL PFA Teflon vial. Then 4 mL of
internal solution-II was added to the supernatant aliquot.
The resultant 5 mL of sample solution with 0.015 M HF/
0.12 M HNO3 and 0.004% mannitol was used for the ICP-
MS analysis.
To minimize the contamination of boron from experi-
mental environment, all chemical operations were car-
ried out in a clean room, and an evaporation apparatus
equipped with ULPA filter was used for evaporation of
the sample solutions.
ICP-MS measurement
The samples were introduced into the ICP-MS instru-
ment at a solution uptake rate of 0.25 mL/min. During
the ICP-MS analysis, ion counts of 9Be, 10B, 11B, 91Zr,
93
Nb, 115In, 178Hf, 179Hf, 181Ta and 185 Re were measured,
and ion count ratios of 11 B/9Be, 91Zr/ 115In, 93Nb/ 115In,
(178Hf+179Hf)/ 185Re and 181Ta/185Re were used for deter-
mination of the boron, zirconium, niobium, hafnium and
tantalum concentrations, respectively. An analytical se-
quence consisted of seven measurements, in which meas-
urements of three unknown samples were bracketed by
those of standard and blank solutions. Each sample meas-
urement took about 2 minutes, which was followed by 5
minutes of sample-washout with 0.015 M HF/0.15 M
HNO3.
The 3σ detection limits determined by replicate meas-
urements of blank solutions were 22 pg/mL for boron, 8
pg/mL for zirconium, 0.5 pg/mL for niobium and hafnium
and 0.3 pg/mL for tantalum.
The use of HF/HNO3 acid mixture not only stabilize
the signals of boron and HFSEs but also enables effec-
tive washout of boron, HFSEs, beryllium, indium and
rhenium. A five-minute sample-washout after the meas-
urement of standard solution reduces back ground levels
typically to 20 cps for 9Be, 150 cps for 11B, 20 cps for
91
Zr, 10 cps for 93Nb, 20 cps for 115In, 5 cps for 178Hf, 3
cps for 179Hf, 50 cps for 181Ta, and 20 cps for 185Re, which
are low enough compared with signals of >5000 cps for
most of rock samples. The damage of glass-made appa-
ratus (e.g., nebulizer) by HF is regarded as negligible in
our analytical condition, and we did not observe any
 Table 2. B, Zr, Nb, Hf and Ta concentrations of BIR-1 and JB-3

B (µg/g) Zr (µg/g) Nb (µg/g) Hf (µg/g) Ta (µg/g) Zr/Hf Nb/Ta

This 1SD RSD This 1SD RSD This 1SD RSD This 1SD RSD This 1SD RSD This 1SD This 1SD
study (%) study (%) study (%) study (%) study (%) study study
BIR-1 #1 0.169 13.8 0.543 0.557 0.0348 24.8 15.6
BIR-1 #2 0.142 13.9 0.545 0.562 0.0354 24.7 15.4
BIR-1 #3 0.138 14.3 0.545 0.555 0.0343 25.7 15.9

136 K. Nagaishi and T. Ishikawa

BIR-1 #4 0.144 14.6 0.543 0.563 0.0342 25.9 15.9
BIR-1 #5 0.143 14.3 0.548 0.566 0.0351 25.3 15.6
Average 0.147 0.012 8.4 14.2 0.3 2.3 0.545 0.002 0.4 0.560 0.005 0.8 0.0348 0.0005 1.5 25.3 0.5 15.7 0.2

(1)
ID-MC-ICP-MS 13.96 0.07 0.5 0.548 0.013 2.4 0.582 0.004 0.6 0.0356 0.0004 1.3 24.0 0.2 15.4 0.4
(2)
ICP-MS 14.47 0.16 1.1 0.558 0.004 0.8 0.562 0.007 1.3 0.041 0.001 2.3 25.7 13.6

Internal calibration curve method

JB-3 #1 20.7 93.6 2.01 2.68 0.118 34.9 17.0
JB-3 #2 21.0 94.1 2.00 2.71 0.125 34.8 16.0
JB-3 #3 20.7 93.5 2.03 2.69 0.123 34.8 16.5
JB-3 #4 20.0 92.9 2.00 2.64 0.121 35.2 16.5
JB-3 #5 20.8 93.7 2.02 2.68 0.121 34.9 16.7
JB-3 #6 20.7 93.4 2.03 2.67 0.121 35.0 16.8
JB-3 #7 20.8 95.6 2.05 2.71 0.119 35.3 17.3
Average 20.7 0.3 1.6 93.8 0.9 0.9 2.02 0.02 0.9 2.68 0.02 0.9 0.121 0.002 2.0 35.0 0.2 16.7 0.4

Standard addition method

JB-3 #8 21.0 93.2 2.02 2.81 0.148 33.2 13.7
JB-3 #9 21.3 92.4 2.01 2.73 0.127 33.8 15.9
JB-3 #10 20.8 92.5 1.99 2.78 0.136 33.3 14.6
JB-3 #11 20.3 91.8 1.98 2.77 0.123 33.2 16.1
JB-3 #12 20.8 92.3 1.99 2.79 0.138 33.1 14.4
Average 20.8 0.4 1.9 92.4 0.5 0.5 2.00 0.01 0.5 2.78 0.03 1.1 0.134 0.010 7.5 33.2 0.3 14.9 1.0

ICP-AES
JB-3 (n = 12) 20.1 0.5 2.5

(3)
ID-TIMS 20.3
(4)
ID-ICP-MS/ICP-MS 20.7 0.2 0.9 86.2 0.6 0.7 1.87 2.65 0.03 1.3 0.114 32.5 16.4
(5)
ICP-MS 100 0.8 0.8 2.18 0.03 1.4 2.88 0.01 0.5 0.153 0.002 1.5 34.7 14.2
(6)
Recommended value 18.0 3.1 17 97.8 7.4 7.6 2.47 0.85 34 2.67 0.12 4.5 0.15 0.045 30 36.6 16.5

(1) (2) (3) (4) (5) (6)

Refs: Weyer et al. (2002), Eggins et al. (1997), Ishikawa and Nakamura (1994), Lu et al. (2007), Kelley et al. (2003), Imai et al. (1995).
 Table 3. B, Zr, Nb, Hf and Ta concentrations of GSJ and USGS rock reference samples

B (µg/g) Zr (µg/g)
n ICP-MS 1SD ICP-AES Ref. ICP-MS 1SD Ref.
(1)
BCR-2 3 4.10 0.06 4.37* 191 3 184 , 188(2)
BHVO-2 3 2.44 0.09 2.58* 155 3 166(1), 172(2)
JB-1 3 8.18 0.19 8.20(3), 8.45(4), 9.0(10) 128 3 126(4), 141(5)
JB-1a 6 7.75 0.20 7.56 7.88(5) 132 4 144 (5)
JB-1b 3 4.68 0.09 4.8 (10) 125 2 122 (6)
JB-2 3 30.5 0.4 30.3* 31.2(4), 30.2(5), 31.2(7), 29.9(10) 49.1 0.2 42.9(4), 51.2(5), 44.1(6)
JB-2a 3 30.8 0.5 55.3 0.4
JB-3a 3 20.7 0.3 97.9 2.1
JA-1 4 24.1 0.5 23.0 23.7(4), 21.0(5), 23.8(7) 85.1 1.4 76.3(4), 88.3(5)
JA-1a 3 25.4 0.5 85.5 3.3
JA-2 3 21.6 1.0 21.2 22.7(4), 20.7(5), 22.7(8) 114 3 106(4), 116(5)
JA-3 4 26.5 0.6 26.2 25.5(3), 26.1(4), 24.8(5) 116 1 105(4), 118(5)
JR-1 3 132 1 134 117 (5) 96.9 1.6 99.9(5)
JR-2 4 158 6 154 145 (5), 149 (10) 93.5 2.0 96.3(5)
JR-3 4 10.5 0.3 10.1 11.4 (10) (355)** (12)** 1494(9)

Nb (µg/g) Hf (µg/g) Ta (µg/g)

n ICP-MS 1SD Ref. ICP-MS 1SD Ref. ICP-MS 1SD Ref.
(1) (1) (1)
BCR-2 3 12.8 0.1 13.0 5.09 0.08 5.00 0.759 0.006 0.738
BHVO-2 3 18.5 0.2 4.19 0.06 4.50(1), 4.1(2) 1.15 0.02 1.11(1)
JB-1 3 35.3 1.5 34.6(4), 33.3(5) 3.45 0.12 3.44(4), 3.31(5) 2.48 0.17 2.32(4), 2.93(5)
JB-1a 6 28.3 0.7 26.9(5) 3.47 0.09 3.41(5) 1.66 0.03 1.93(5)
JB-1b 3 26.1 0.3 26.6(6) 3.32 0.09 3.24(6) 1.46 0.03 1.85(6)
JB-2 3 0.514 0.002 0.459(4), 0.448(6) 1.53 0.02 1.45(4), 1.49(5), 1.44(6) 0.0330 0.0016 0.0307(4), 0.13(5), 0.0317(6)
JB-2a 3 0.480 0.002 1.67 0.01 0.0403 0.0003
JB-3a 3 2.00 0.04 2.80 0.03 0.121 0.001
JA-1 4 1.31 0.02 1.17(4), 1.85(5) 2.56 0.05 2.45(4), 2.42(5) 0.0892 0.0059 0.0833(4), 0.13(5)
JA-1a 3 1.23 0.02 2.62 0.08 0.0915 0.0010
JA-2 3 9.33 0.12 8.31(4), 9.47(5) 3.05 0.04 2.92(4), 2.86(5) 0.644 0.007 0.592(4), 0.80(5)
JA-3 4 3.23 0.02 2.86(4), 3.41(5) 3.36 0.07 3.19(4), 3.42(5) 0.237 0.008 0.220(4), 0.27(5)
JR-1 3 16.0 0.3 15.2(5) 5.08 0.11 4.51(5) 1.65 0.04 1.86(5)
JR-2 4 19.0 0.4 18.7(5) 5.55 0.11 5.14(5) 2.10 0.03 2.29(5)
JR-3 4 564 16 510 (9) (13.0)** (0.3)** 40.3(9) 35.1 0.7 36.8(9)

*Values determined in this study. Other ICP-AES data are from Ishikawa et al. (1997). Analytical uncertainties for these data are 3–5%.
**Zr and Hf in JR-3 were not determined accurately probably because of incomplete decomposition of zircon (see text).
Refs: (1)Weyer et al. (2002, ID-MC-ICP-MS), (2)Plumlee (1998a, b, recommended value), (3)Makishima et al. (1997, ID-TIMS), (4)Lu et al. (2007, ID-ICP-MS/ICP-MS), (5)Imai et al. (1995,
recommended value), (6)Ingle et al. (2007, ICP-MS), (7)Ishikawa and Nakamura (1994, ID-TIMS), (8)Ishikawa (unpublished data, ID-TIMS), (9)Imai et al. (1999, recommended value), (10)Terashima
et al. (1998a, ICP-AES).

A simple method for the precise determination of B, Zr, Nb, Hf and Ta using ICP-MS 137
 40
a b
30
B (µg/g) ICP-MS
20
10
0 0
0 10 20
B (µg/g) ID-TIMS
Fig. 1. B concentrations of GSJ rock reference samples measured by ICP-MS plotted against those obtained by ID-TIMS (a) and
ICP-AES (b). The ID-TIMS data are from Ishikawa and Nakamura (1994), Makishima et al. (1997) and Ishikawa (unpublished
data), and the ICP-AES data are from this study and Ishikawa et al. (1997). Error bars represent one standard deviations of each
value. The errors in ICP-AES analyses are assumed to be 5% for all samples.
change in analytical sensitivity and signal stability of ICP-
MS throughout our analyses for two years.
Boron determination by ICP-AES
Boron concentrations of four rock reference samples,
JB-2, JB-3, BCR-2 and BHVO-2, were determined by
ICP-AES in addition to ICP-MS. The ICP-AES analysis
was carried out at Shizuoka University after sample prepa-
ration consisting of HF-mannitol digestion of 400 mg of
rock powder and subsequent removal of major cations
with an ion-exchange column (Ishikawa and Tera, 1997).
The removal of major cations reduces spectral interfer-
ences effectively and enables precise determination of
boron using ICP-AES, although the whole chemical pro-
cedure takes about three days.
RESULTS AND DISCUSSION
Interferences and blanks
When beryllium is used as an internal standard ele-
ment, the natural abundance of beryllium in the rock sam-
ples must be low enough not to affect the accuracy of
boron determination using the 11B/9Be ratio. Most natu-
ral rock samples have a beryllium content lower than 4
µg/g, which influences the determined boron concentra-
tion by <0.6% when the standard procedure with a dilu-
tion factor of 1700 and an internal standard solution with
400 ng/mL beryllium are used. Although some alkali rocks
such as alkali syenites contain >4 µg/g beryllium, such
rocks are usually enriched in boron (and in zirconium,
niobium, hafnium and tantalum) as well as in beryllium
because of the incompatible characteristics of these ele-
ments. In such samples, interference from natural beryl-
138 K. Nagaishi and T. Ishikawa
40
30
B (µg/g) ICP-MS
20
200
10 100
0
0 100 200
30 40 0 10 20 30 40
B (µg/g) ICP-AES
lium is avoidable by analyzing the samples with larger
dilution factors.
In the HFSE analysis, interference from the oxide ions
75
As16O+, 77Se16O+, 162Dy16O +, 163Dy16O + and 165Ho 16O+
on 91Zr+, 93Nb+, 178 Hf+, 179Hf+ and 181Ta+, respectively,
may occur. In our analytical condition, the ion count of
77
Se for rock samples was as low as a few times the de-
tection limit. The count ratio of 75As/91Zr was <0.05 for
basalts and andesites and <0.15 for rhyolites, which gives
75
As16O+/91Zr < 0.005 assuming oxide forming rate of 3
%. Therefore interference from the arsenic and selenium
oxides is considered negligible. In this study, the sam-
ples were dissolved in 0.015 M HF after decomposition
with HF-HCl-mannitol. The use of HF as a solvent effec-
tively removes insoluble rare earth element fluoride com-
pounds from the sample solution, thus reducing interfer-
ences from oxide ions of dysprosium and holmium to
negligible levels (Makishima et al., 1999).
The total procedural blanks observed during this study
were 55–100 pg for boron, and <8 pg for zirconium, <0.5
pg for niobium and hafnium and <0.3 pg for tantalum,
and negligible in our analysis.
Analysis of rock reference samples
Analytical results obtained for the 17 rock reference
samples are listed in Tables 2 and 3. To evaluate the re-
producibility of the analyses in this study, five and seven
separate analyses were carried out for BIR-1 and JB-3,
respectively (Table 2). BIR-1 was chosen for evaluating
the analyses of low levels of boron, zirconium, niobium,
hafnium and tantalum. JB-3 was used as a standard mate-
rial for daily checking of the sample preparation and the
ICP-MS analysis, and concentrations of boron, zirconium,
 100
JB-1 series
10
Sample / MORB
JB-3 series
1 rate for samples with a wide range of boron concentra-
JA-1 series
JB-2 series
0.1
B Nb Ta Zr
Fig. 2. MORB-normalized ratios of B, Zr, Nb, Hf and Ta for
JB-1 series, JB-2 series, JB-3 series and JA-1 series rock ref-
erence samples. MORB values are from Sun and McDonough
(1989) and Ryan and Langmuir (1993).
niobium, hafnium and tantalum were determined by the
standard addition method in addition to the usual internal
calibration curve method. For the other 15 rock reference
samples, three to six separate analyses were made (Table
3).
Boron analysis
Analytical reproducibility of boron determination in
this study ranged from ±1 to 5% RSD at boron concen-
tration levels between 2.4 and 158 µg/g (Tables 2 and 3).
BIR-1 showed a very low boron concentration (0.15 µg/
g), and the analytical reproducibility was ±8% RSD. Bo-
ron contents determined for JB-1a, JB-2, JB-3, JA-1, JA-
2, JA-3, JR-1 and JR-2 were consistent with the recom-
mended values (Imai et al., 1995) within analytical un-
certainties, although unfortunately the recommended val-
ues are not always precise enough to be used for com-
parison in this study (±12–38% RSD, except for ±6% RSD
for JR-2).
The boron content of JB-3 determined by the internal
calibration curve method was 20.7 ± 0.3 µg/g (1 SD un-
certainty, n = 7). This value was identical to the value
obtained by the standard addition method, 20.8 ± 0.4 µg/
g (n = 5). For six rock reference samples, JB-1, JB-2, JB-
3, JA-1, JA-2 and JA-3, boron concentration values de-
termined by the isotope dilution-thermal ionization mass
spectrometry (ID-TIMS) are available (Ishikawa and
Nakamura, 1994; Makishima et al., 1997; Ishikawa, un-
published data), and can be used as benchmarks. The data
A simple method for the precise determination of B, Zr, Nb, Hf and Ta using ICP-MS 139
for these six samples in this study showed good agree-
JB-1
JB-1a
ment with the values obtained by ID-TIMS, with differ-
JB-1b ences of 0.3–5% (Tables 2 and 3 and Fig. 1a). The data
JB-2 for JB-1a, JB-2, JB-3, JA-1, JA-2, JA-3, JR-1, JR-2, JR-
JB-2a
3, BCR-2 and BHVO-2 were also compared with the ICP-
JB-3
JB-3a AES data (analytical reproducibility = ±3–5% RSD) ob-
JA-1 tained in this study as well as by Ishikawa et al. (1997).
JA-1a
These two data sets agree well with each other, with
<6.5% differences (Tables 2 and 3 and Fig. 1b). These
observations indicate that boron concentrations deter-
mined in this study are satisfactorily precise and accu-
tions and varied major element compositions.
HFSE analysis
The analytical reproducibility of HFSE determination
(expressed as RSD%) in this study was ±0.4–4% for zir-
Hf conium and niobium, ±1–4% for hafnium and ±1–5% tan-
talum, except for ±7% RSD for tantalum observed in JB-
1 and JA-1 (Tables 2 and 3). Less reproducible tantalum
values for JB-1 and JA-1 compared with other rock refer-
ence samples have also been reported by Lu et al. (2007),
and may result from the heterogeneity of these samples
at milligram levels. Zirconium, niobium, hafnium and
tantalum concentrations determined for JB-1, JB-1a, JB-
2, JB-3, JA-1, JA-2, JA-3, JR-1 and JR-2 were consistent
with recommended values (Imai et al., 1995), which have
RSDs of ±6–16% for zirconium, ±7–38% for niobium,
±5–21% for hafnium and ±18–52% for tantalum. Zirco-
nium and hafnium contents of JR-3 observed in this study
were very low compared with recommended values (Imai
et al., 1999), and seem inadequate (Table 3). This is prob-
ably because JR-3 contains zircon, which is not decom-
posable by the HF-mannitol method.
Weyer et al. (2002) developed a technique for the pre-
cise determination of zirconium, niobium, hafnium and
tantalum using a multiple collector ICP-MS, in which
zirconium, hafnium and tantalum concentrations were
measured by isotope dilution method, whereas mono-
isotopic niobium was measured using the 93Nb/90Zr ra-
tio, after quantitative separation of the HFSEs from the
matrix. They carried out replicate analyses (n = 5) of BIR-
1, which has low levels of HFSEs, and reported concen-
trations of 13.96, 0.548, 0.582 and 0.0356 µg/g for zirco-
nium, niobium, hafnium and tantalum, respectively. Our
values for BIR-1 (n = 5), 14.2, 0.545, 0.560 and 0.0348
µg/g for zirconium, niobium, hafnium and tantalum, re-
spectively, show good agreement with the values of Weyer
et al. (2002), with differences of 0.6–4% (Table 2). The
data for BCR-2 in this study and that of Weyer et al. (2002)
also agree, with <4% differences (Table 3). These obser-
vations indicate that concentrations of HFSEs were ac-
curately measured in this study. The accuracy of HFSE
determination is also confirmed by the consistency within
the data of JB-3 between the internal calibration curve
and the standard addition methods (±8% RSD, Table 2).
Boron and HFSE compositions of JB-1 series, JB-2 se-
ries, JB-3 series and JA-1 series rock reference samples
Among the GSJ rock reference samples, samples of
each series, the JB-1 (JB-1, JB-1a and JB-1b), JB-2 (JB-
2 and JB-2a), JB-3 (JB-3 and JB-3a) and JA-1 (JA-1 and
JA-1a) series, were from rocks collected from the same
locality. The source rock of JA-1a was re-sampled at the
same position as JA-1 (andesitic lava, Hakone Volcano,
Kanagawa, Japan) (Okai et al., 2003). JB-1a and JB-1b,
JB-2a and JB-3a were re-prepared by using the remain-
der samples of JB-1 (basaltic lava, Kitamatsuura, Naga-
saki, Japan), JB-2 (basaltic lava, Oshima Volcano, To-
kyo, Japan) and JB-3 (basaltic lava, Fuji Volcano,
Yamanashi, Japan), respectively (Imai et al., 1995;
Terashima et al., 1998b; Okai et al., 2006). It is mean-
ingful to compare their boron and HFSE compositions
and evaluate within-series variations.
Boron and HFSE compositions of these four sample
series are plotted as mid-ocean ridge basalt (MORB)-
normalized ratios in Fig. 2. Within the JB-3 series and
the JA-1 series, the boron, niobium, tantalum, zirconium
and hafnium compositions were similar, and the observed
within-series differences were <6% for all elements. The
concentrations of niobium, tantalum, zirconium and haf-
nium in JB-2 and JB-2a showed variations of 7–20%,
whereas their boron concentrations were almost identi-
cal. Differences of 30–40% were also observed between
boron, niobium and tantalum concentrations of JB-1 se-
ries rocks, although their zirconium and hafnium concen-
trations were consistent, with differences of <4%. Dis-
tinctly low boron content of JB-1b compared with JB-1
and JB-1a may be derived from heterogeneity of boron
content in the original lava sample caused by loss of bo-
ron during post-eruptive degassing, which has been re-
ported for a thick lava flow of trachytic andesite in the
Rishiri Volcano, northern Japan (Kuritani and Nakamura,
2006). In fact, cesium content reported for JB-1b (0.806
µg/g: Ingle et al., 2007) is distinctly lower than those for
JB-1 (1.23 µg/g: Imai et al., 1995) and JB-1a (1.31 µg/g:
Imai et al., 1995), being consistent with degassing-related
loss of cesium as observed in the Rishiri Volcano (Kuritani
and Nakamura, 2006).
Utility of the method
The ICP-MS technique described here makes it possi-
ble to determine boron, zirconium, niobium, hafnium and
tantalum concentrations of relatively small samples (<30
mg) with satisfactory precision and accuracy without us-
ing the isotope dilution method. This simple method ena-
bles us to analyze these elements, particularly boron, with
standard ICP-MS instrumental setting along with other
140 K. Nagaishi and T. Ishikawa
analytical routines, an essential feature allowing wide
geochemical application.
Acknowledgments—We thank Dr. M. Tanimizu for many sug-
gestions and helpful comments for the ICP-MS analysis. We
are grateful to Dr. T. Okai, GSJ, for providing the JB-2a and
JB-3a samples. We also thank Dr. T. Hirata and Dr. S. Nakai
for their constructive reviews of the manuscript. This work was
partly supported by a Grant-in-Aid for Scientific Research from
JSPS.
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