Simultaneous Measurement of Major, Trace Elements and Pb

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Simultaneous Measurement of Major, Trace Elements and Pb
Journal of Earth Science, Vol. 28, No. 1, p. 092–102, February 2017
Printed in China
DOI: 10.1007/s12583-017-0742-8
ISSN 1674-487X
Simultaneous Measurement of Major, Trace Elements and Pb
Isotopes in Silicate Glasses by Laser Ablation Quadrupole and
Multi-Collector Inductively Coupled
Plasma Mass Spectrometry
Mengning Dai , Zhi’an Bao, Kaiyun Chen, Chunlei Zong, Honglin Yuan *
State Key Laboratory of Continental Dynamics, Department of Geology, Collaborative Innovation Center of Continental Tectonics,
Northwest University, Xi’an 710069, China
Mengning Dai: http://orcid-org/0000-0003-0619-6174; Honglin Yuan: http://orcid-org/0000-0002-5234-8549
ABSTRACT: A method was developed for the rapid in situ analysis of major and trace elements and Pb
isotopes in silicate glass samples that combines laser ablation quadrupole and multi-collector inductively
coupled plasma mass spectrometry (LA-Q-ICP-MS/MC-ICP-MS). Major, trace elements, and Pb isotope
ratio compositions were clearly affected by laser conditions. Using a laser spot size of 160 μm, a laser ablation frequency of 15 Hz, an energy density 18 J/cm2, and a 1 : 9 ratio of laser ablation aerosol to the corresponding makeup gas, we obtained accurate major and trace element contents and Pb isotope ratios. Using
Ca as the internal standard element, and GSE-1G and NIST 610 as the external standards for calibration,
element contents generally matched the preferred values within 15%. Higher relative errors for some elements (e.g., Cr, Ga, Ge) may have been caused by lower than recommended values in some standards. The
exponential law correction method for Tl normalization, with optimum adjusted Tl ratio, was utilized to
obtain Pb isotopic data with good precision and accuracy. Pb isotopic ratios of the glass reference materials
were in good agreement with the reference or published values to within 2 s measurement uncertainties, and
the analytical precision was better than 0.17% (e.g., 208Pb/206Pb). The developed method is a simple, reliable,
and accurate technique for determining major, trace elements, and Pb isotope compositions of silicate
glasses and minerals within a single ablation event.
KEY WORDS: major, trace elements, Pb isotope, laser ablation, Q-ICP-MS, MC-ICP-MS, silicate
glasses.
0
INTRODUCTION
Whole-rock and mineral trace elements have been proved
useful for tracing geological processes, environmental evolution,
and the formation of rocks and related ore deposits (Huang et al.,
2016; Xin et al., 2016; Chung et al., 2015; Scarpelli et al., 2015;
Regelous et al., 2014; Wu et al., 2014; Zhao et al., 2011; Jarvis
and Williams, 1993). Laser ablation quadrupole inductively coupled plasma mass spectrometry (LA-Q-ICP-MS) technology is
widely used for in situ analysis of trace elements in minerals and
fluid inclusions (Huang et al., 2016; Otamendi et al., 2016; Bauer
and Limbeck, 2015; Chung et al., 2015; Lin et al., 2015; Scarpelli
et al., 2015; Tomlinson et al., 2015; Regelous et al., 2014; Wu et
al., 2014; Zhao et al., 2011; Gao et al., 2002; Jarvis and Williams,
1993). Through a combination of a Nd: YAG laser ablation system and inductively coupled plasma mass spectrometry, Jarvis
*Corresponding author: [email protected]
© China University of Geosciences and Springer-Verlag Berlin
Heidelberg 2017
Manuscript received December 5, 2015.
Manuscript accepted April 27, 2016.
and Williams (1993) firstly obtained precise major and trace
element compositions for 7 international standard samples. Similarly, Gao et al. (2002) derived 42 element contents by combining
the 193 nm ArF excimer laser ablation system with inductively
coupled plasma mass spectrometry, and Liu et al. (2008) obtained
54 major and trace element compositions of 100% standard geological samples by means of 193 nm ArF LA-ICP-MS without
applying an internal standard. Furthermore, many other researchers analyzed the major and trace elements geochemistry of various samples (Otamendi et al., 2016; Bauer and Limbeck, 2015;
Tomlinson et al., 2015; Audétat et al., 1998).
Pb isotopic compositions of minerals and whole rocks
have been used as an effective tool in the study of environmental change, crust-mantle interaction, formation of rocks and
ore deposits, geochronology, Earth evolution, and archaeology
(Gu et al., 2016; Lu et al., 2016; Munoz et al., 2016; Cloquet et
al., 2015; Han et al., 2015; Zhou et al., 2014; Yuan et al., 2008;
Baker et al., 2004). The traditional analysis procedure is to
dissolve the rock powder or mineral grains in solution, separate
Pb by anion-exchange resin (Zhang et al., 2008), and then analyze Pb isotopic compositions by TIMS or MC-ICP-MS (Noble
et al., 2015; Jochum et al., 2011; Baker et al., 2004; Pomiès et
Dai, M. N., Bao, Z. A., Chen, K. Y., et al., 2017. Simultaneous Measurement of Major, Trace Elements and Pb Isotopes in Silicate
Glasses by Laser Ablation Quadrupole and Multi-Collector Inductively Coupled Plasma Mass Spectrometry. Journal of Earth Science, 28(1): 92–102. doi:10.1007/s12583-017-0742-8. http://en.earth-science.net
Simultaneous Measurement of Major, Trace Elements and Pb Isotopes in Silicate Glasses
al., 1998). However, most natural minerals usually have heterogeneous isotopic compositions, therefore traditional methods cannot provide detailed and precise Pb compositions for
different parts of the mineral grains (Yuan et al., 2015; Gagnevin et al., 2005). In situ Pb isotope analysis by
LA-MC-ICP-MS has been widely used in mineral chemistry,
rock geochemistry, and archaeology (Bao et al., 2016; Yuan et
al., 2015; Zhang et al., 2015; Chen et al., 2014; Bellucci et al.,
2011; Yip et al., 2008; Gagnevin et al., 2005; Reuera et al.,
2003; Collerson et al., 2002). For example, Chen et al. (2014)
successfully analyzed Pb isotope compositions in 21 international reference materials using femtosecond laser ablation
coupled with MC-ICP-MS (fsLA-MC-ICP-MS) and Zhang et
al. (2015) determined in situ Pb isotope compositions of <10
ng/g international reference materials through a combination of
ion counter and Faraday cup methods. However, traditional
methods obtain trace element and Pb isotope compositions by
ablation of the interfaced spots, which, considering the inhomogeneity of natural geological samples may result in the decoupling of trace element and Pb isotope compositions. Recent
studies have demonstrated methods to collect U-Pb isotopes
and trace elements together with Hf isotopes (Yuan et al., 2008),
simultaneous measurement of Rb-Sr/Sm-Nd or Sm-Nd/Lu-Hf
isotopes from the same laser ablation spot (Huang et al., 2015).
In this study, we firstly combine laser ablation, quadrupole
inductively coupled plasma mass spectrometry, and multicollector inductively coupled plasma mass spectrometry in
order to determine major, trace element, and Pb isotope compositions from a single spot. The bulk silicate rock samples
could be prepared by pressed powder pellet (Xu et al., 2005) or
lithium-borate or flux-free fusion glasses (Bao et al., 2016;
Diwu et al., 2007).
1 EXPERIMENT
1.1 Samples and Reagents
In this study, we used high purity water produced through
the Milli-Q system with a resistivity of 18.2 MΩ·cm-1
(Elix-Millipore, USA), and nitric acid purified by DST-1000
sub-boiling distiller (SavillexTM Minnetonka, USA). The Tl
solution of internal standardization was prepared by diluting
pure Tl metal (SRM 997), from the National Institute of Standards and Technology (NIST), to 25 μg/L with 2% HNO3.
The certified reference materials for microanalysis were silicate glasses NIST 610 and 612, basalt glasses GSD-1G, GSE-1G,
and CGSG-1G, CGSG-2G, CGSG-4G, and CGSG-5G, purchased
from the National Institute of Standards and Technology (NIST),
the United States Geological Survey (USGS) and the National
Research Center for Geoanalysis (NRCG), respectively.
Firstly, the samples were fixed on a slide using doublesided tape. After sheathing a PVC ring, the epoxy resin and
curing agent were fully mixed and injected into the PVC ring.
When the epoxy resin was completely cured, the sample was
peeled from the slide and then polished. Before analysis, the
sample surface was cleaned with 2% HNO3 and ethanol to remove any contaminants (Dai et al., 2016).
1.2
Instruments
The instruments used are a Nu Plasma HR MC-ICP-MS
93
(Nu Instruments Ltd., UK), an Agilent 7700x Q-ICP-MS
(Agilent Technologies, USA), and a GeoLas 2005 excimer ArF
laser-ablation system (MicroLas™ Beam Delivery Systems,
Lambda Physik AG, Germany), all housed at the State Key
Laboratory of Continental Dynamics, Northwest University,
Xi’an, China. The GeoLas 2005 laser-ablation system consists of
a COMPexPro 102 ArF excimer laser (wavelength 193 nm,
maximum energy 200 mJ, and maximum pulse rate 20 Hz) and a
GeoLas 2005 PLUS package (including a laser-beam homogenizing system, a motorized sampling stage, and a viewing system
coupled with an Olympus microscope and color CCD). The Nu
plasma HR MC-ICP-MS is a third-generation double-focusing
MC-ICP-MS with 3 ion counters and 12 Faraday cups, used to
measure Pb isotopic ratios. MC-ICP-MS was prepared for the
introduction of the Tl solution through the DSN 100 desolvating
nebulizer system. The thallium solution was self-aspirated at an
uptake rate of 100 μL/min through the PFA nebulizer and desolvated by the DSN. The detector arrangements and instrument
parameters are summarized in Table 1.
The ablated aerosol was split via a T-shaped connector into
two outlet streams that were transported into Q-ICP-MS and
MC-ICP-MS (Fig. 1). The gas flow was then distributed into the
two instruments by a valve, which ensured sensitivity and accuracy in the major-trace element and Pb isotope analysis.
1.3
Analytical Method
High-purity helium (99.999 5%) was used as the carrier
gas for laser ablation, and the ablated aerosol was separated
into two streams. The aerosol in stream 1 passed through the
regulating valve, mixed with argon makeup gas in the homemade homogenizers, and was then transported into an Agilent
7700x Q-ICP-MS to measure major and trace element contents.
To conduct quantitative analysis by LA-Q-ICP-MS, the relative
element sensitivity for each element was calibrated using both
external calibration (NIST 610 and GSE-1G) and internal standardization (Si and Ca) (Nunes et al., 2016; Peacock et al.,
2016; Liu et al., 2007), and the effect of analytical precision in
different calibration modes was evaluated. The LA-ICP-MS
data was reduced using ICPMS DataCal software (Liu et al.,
2008). The aerosol from stream 2 was mixed with Tl (Tl aerosol from the desolvating nebulizer system) in the glass aerosol
homogenizer and then introduced into the ICP for atomization
and ionization. Thallium was used to monitor and correct for
instrumental mass discrimination and adjusted for instrumental
mass fractionation as monitored by the 205Tl/203Tl ratio. In this
study, the optimum 205Tl/203Tl ratio (2.388 69) used was obtained from Collerson et al. (2002). 202Hg was used to correct
for the isobaric overlap of 204Hg on 204Pb. Hg was purified using an in-house filtration column with gold-plated filters, which
can remove more than 90% of Hg in the laser ablated aerosol
(Yuan et al., 2015). The interference of 204Hg on 204Pb was determined using the natural abundance ratio 204Hg/202Hg=
0.229 883 (Noble et al., 2015; Yuan et al., 2015; Zhang et al.,
2008), meanwhile, the analytical precision of Pb isotope ratio
calculations was monitored by NIST 610. The background
values of 205Tl and 203Tl were detected by 2% HNO3 through
the DSN, and background values of Pb and Hg were integrated
from the first 30 s (Table 1).
Mengning Dai, Zhi’an Bao, Kaiyun Chen, Chunlei Zong and Honglin Yuan
94
Table 1 Instrumental parameters of laser ablation-quadrupole/multi-collector ICP-MS
Laser ablation (GeoLas 2005)
Parameters
Q-ICP-MS (Agilent 7700x)
Parameters
Spot size
90–160 μm
RF power
1 390 W
Frequency
10–20 Hz
Coolant gas flow
1.04 L/min
238
Energy output
45–75 mJ
Sensitivity
Carrier gas flow
~1.0 L/min
Dwell time
6–10 ms
Ablation mode
Single spot
Integration time
40 s
MC-ICP-MS (Nu plasma HR)
Parameters
RF power
1 300 W
Coolant gas flow
13 L/min
Auxiliary gas flow
0.8 L/min
U>4 000 cps/ppm
Accelerating voltage
4 000 V
Sensitivity and background
208
Pb: 7.3 mV/ppm (160 μm, 15 Hz, 18 J/cm2), all isotopes<0.05 mV
Faraday cup arrangement
202
Hg (L2), 203Tl (L1), 204Pb+204Hg (Ax), 205Tl (H1), 206Pb (H2), 207Pb (H3), 208Pb (H4)
Integration time of TRA signal
0.1 s
Integration time per data point (TRA mode)
Background 30 s + signal 50 s
Argon
Regulating valve
Q - ICP - MS
Laser
Stream 1
Helium
Sample
Stream 2
Hg filter
MC - ICP - MS
Argon
Dry aerosol
Desolvator
Thallium
Solvent
Figure 1. Schematic diagram of laser ablation Q/MC-ICP-MS system setup. The ablated silicate aerosol carried in helium is split via a T-shaped connector into
two outlet streams that are separately flushed into homemade homogenizers via tygon tubes of 2 mm inner diameter. The aerosol is mixed with argon makeup
gas in the homogenizers. The two streams of aerosol are finally transported into an Agilent 7700x Q-ICP-MS (for measurements of major and trace element
concentrations) and a Nu plasma HR MC-ICP-MS (for simultaneous lead isotope analysis).
The sensitivity of MC-ICP-MS was 7.3 mV/ppm (e.g.,
Pb) using laser ablation conditions of 160 μm, 15 Hz, and 18
J/cm2. In order to obtain accurate and precise results with sufficient signal intensity, only the high Pb content samples (Pb>20
ppm) and large spot sizes (≥90 μm) were chosen for this study.
208
2 RESULTS AND DISSCUTION
2.1 Effect of Aerosol Distribution Ratio
When the aerosol distribution ratio between Q-ICP-MS
and MC-ICP-MS is bigger than 1 : 8, the ion beam signal of
Q-ICP-MS could vary over the full range. Hence, this study
only discusses the effect of aerosol distribution ratios <1 : 8 on
the analytical results of major and trace elements.
Using the same connecting method, the aerosol distribution ratio between Q-ICP-MS and MC-ICP-MS does not affect
the distribution of carrier gas between the two gas streams.
When the aerosol distribution ratio was 1 : 9, He flow rate was
95 mL/min; yet with a lower aerosol distribution ratio of 1 : 24,
He flow rate was only 37 mL/min. The latter case led to a
longer aerosol retention time in the line of extension, manifested by a clear tail in the signal (Fig. 2). Although the signal
intensity of Q-ICP-MS was 2.5 times lower, the relative error
of most analyzed elements, compared to reference values, was
less than 5%. Fe is an exception as it showed a larger relative
error (e.g., a signal to noise ratio <30 when the aerosol distribution ratio was 1 : 24), as a result of its low NIST 610 content
Simultaneous Measurement of Major, Trace Elements and Pb Isotopes in Silicate Glasses
2.2
Effect of Laser Ablation Conditions
Analytical results are also affected by laser ablation frequency, ablation spot size, and energy density (Dai et al., 2016;
Horn et al., 2000). To determine the effect of ablation frequency,
we used three different frequencies: 10, 15, and 20 Hz, and
fixed the ablation spot size at 160 μm and energy density at 18
J/cm2. The relative errors for most analyzed elements were
within 3%, except those for Fe and Zn (>5%). An increase in
ablation frequency led to an increase in Q-ICP-MS signal intensity e.g., Pb increased by 3.6 times with a frequency increase
from 10 to 20 Hz. Taking Si and Ca as the internal standards,
all the analytical results of elemental concentrations agreed
with the reference values (Figs. 5a and 5b). Meanwhile, the
signal strength of MC-ICP-MS increased by 1.6 times, and the
relative error in the Pb isotope ratio at 20 Hz was smaller than
those at lower frequency (Figs. 6a and 6b). Internal precision of
higher frequency is better than lower frequency since higher
intensity can be achieved by more material ablated in higher
frequency. However, the external precision of 15 Hz is better
than 10 Hz, but similar to 20 Hz. The Pb isotope can be acceptable in terms of both external and internal precision as long
as the laser frequency is higher than 15 Hz.
With an optimized ablation frequency of 20 Hz and energy
density of 18 J/cm2, we varied the ablation spot size between 90,
120, and 160 μm. With a laser spot size of 90 μm, the relative
10 6
Signal intensity (cps)
(0.058 9 wt.%). When the aerosol distribution ratio was between 1 : 9~1 : 19, measured values agreed with the reference
values, with relative errors of less than 2%, whereas with an
aerosol distribution ratio of 1 : 24, the analytical results of rare
earth elements were lower than reference values (Fig. 3). With
an aerosol distribution ratio range of 1 : 9 to 1 : 24 (i.e., more
than 90% of total aerosols assigned to MC-ICP-MS), the signal
intensity of Pb using MC-ICP-MS increased from 3.9 to 4.1 V,
and analyzed Pb isotope ratios agreed with reference values
within the error range (Fig. 4). Therefore, in order to eliminate
the signal tail and optimize analytical results, we chose to analyze major elements, trace elements, and Pb isotopes using an
aerosol distribution ratio of 1 : 9.
95
1:9
1 : 14
1 : 19
1 : 24
10 5
10 4
10 3
10 2
0
10
20
30
40
50
Time (s)
60
70
80
Figure 2. Effect of different sampling ratios on in situ measurement of
ICP-MS signals (29Si).
10
1:9
1 : 14
1 : 19
1 : 24
RE (%)
6
2
-2
-6
-10
Li Na Al P
Ca Ti Cr Fe Ni Zn Ge Sr Zr Cs La Pr Sm Gd Dy Er Yb Hf W Th
Be Mg Si K Sc V Mn Co Cu Ga Rb Y Nb Ba Ce Nd Eu Tb Ho Tm Lu Ta Pb U
Figure 3. Effect of different sampling ratios on the relative error (RE%) of major and trace elements (NIST 610).
0.04
1:9
1 : 14
1 : 19
1 : 24
RE (%)
0.02
0.00
-0.02
-0.04
208
Pb/ 206Pb
207
Pb/ 206Pb
206
Pb/ 204Pb
207
Pb/ 204Pb
208
Pb/ 204Pb
Figure 4. Effect of different sampling ratios on the relative error (RE%) of
Pb isotopes (NIST 610).
errors for most elemental contents were less than 3% (taking Ca
and Si as internal standardization elements). However, the relative error was smaller when taking Ca as the internal standard
rather than Si, i.e., the relative error of P and Zr for the former
case was 3%–5% and >5% for the latter. When laser ablation
spot sizes were 120 and 160 μm, all of the analyzed elements
agreed with the preferred value with a 3% relative error, yet the
160 μm spot size showed slightly better analytical results (Figs.
5c and 5d). MC-ICP-MS signal intensity using the 160 μm
laser ablation spot size was 1.7 and 3.9 times higher than that
when using 120 and 90 μm spot sizes, respectively. Because the
bigger laser ablation spot size could get higher signal intensity,
and obtain better analytical accuracy. Therefore, the relative
errors of measured Pb isotope ratios using 90 and 120 μm ablation spot sizes are 13.8 and 1.3 times higher than that obtained
Mengning Dai, Zhi’an Bao, Kaiyun Chen, Chunlei Zong and Honglin Yuan
96
10
(a)
Si
RE (%)
5
0
2
160 μm, 10 Hz, 18 J/cm
-5
2
160 μm, 15 Hz, 18 J/cm
160 μm, 20 Hz, 18 J/cm 2
-10
10
(b)
Ca
RE (%)
5
0
160 μm, 10 Hz, 18 J/cm 2
-5
2
160 μm, 15 Hz, 18 J/cm
160 μm, 20 Hz, 18 J/cm 2
-10
10
(c)
Si
RE (%)
5
0
2
90 μm, 20 Hz, 18 J/cm
2
120 μm, 20 Hz, 18 J/cm
160 μm, 20 Hz, 18 J/cm 2
-5
-10
10
(d)
Ca
RE (%)
5
0
90 μm, 20 Hz, 18 J/cm 2
120 μm, 20 Hz, 18 J/cm 2
2
160 μm, 20 Hz, 18 J/cm
-5
-10
10
(e)
Si
RE (%)
5
0
160 μm, 20 Hz, 13 J/cm 2
2
160 μm, 20 Hz, 18 J/cm
160 μm, 20 Hz, 22 J/cm 2
-5
-10
10
(f)
Ca
RE (%)
5
0
2
-5
-10
160 μm, 20 Hz, 13 J/cm
2
160 μm, 20 Hz, 18 J/cm
2
160 μm, 20 Hz, 22 J/cm
Li Na Al P Ca Ti Cr Fe Ni Zn Ge Sr Zr Cs La Pr Sm Gd Dy Er Yb Hf W Th
Be Mg Si K Sc V Mn Co Cu Ga Rb Y Nb Ba Ce Nd Eu Tb Ho Tm Lu Ta Pb U
Figure 5. Effect of different laser ablation conditions (frequency, spot size, energy output) on the relative error (RE%) of major and trace elements by in situ
measurements (NIST 610).
Simultaneous Measurement of Major, Trace Elements and Pb Isotopes in Silicate Glasses
using 160 μm (Figs. 6c and 6d).
Finally, using a fixed laser ablation spot size of 160 μm at
a frequency of 20 Hz, we determined the effect of using energy
densities of 13, 18, and 22 J/cm2. Using Si or Ca as internal
standards, all element contents matched the reference values to
within 5%. An energy density of 18 J/cm2 produced the best
analytical results (Figs. 5e and 5f). MC-ICP-MS signal intensity values using this energy density were between those using
13 and 22 J/cm2, but the relative error of Pb isotopic ratios (e.g.,
208
Pb/206Pb) using 13 J/cm2 is 2.1 times higher than that using 18
J/cm2, and 2.3 times that using 22 J/cm2 (Figs. 6e and 6f).
Therefore, to intensify the signal strength and optimize acquisition of elemental contents and Pb isotope ratios, we set the energy
97
density at 18 J/cm2, with an ablation spot size of 160 μm, and an
ablation frequency of 15 Hz. The Ca was applied as internal standard for trace elemental concentration analysis instead of Si due to
the fraction index among Si, Ca and trace elements. Previous studies showed that the elemental fractionation of Ca is closer to other
trace elements than Si (Gaboardi and Humayun, 2009).
2.3 Simultaneous Analysis Results for Major and Trace
Elements and Pb Isotopes
2.3.1 Major and trace element contents
The reference silicate glasses are analyzed using NIST 610
and GSE-1G as external standards. Using different chemical
property silicate glasses as the external standards would obtain
2.171
208
Pb/ 207Pb
2.170
2.169
2.168
2.167
2.166
206
Pb/ 204Pb
2.165
2.164
17.08
17.07
17.06
17.05
17.04
17.03
17.02
17.01
17.00
10 Hz
15 Hz
(a)
(c)
(e)
(b)
(d)
(f)
20 Hz
90 μm
120 μm
160 μm
13 J/cm 2
18 J/cm 2
22 J/cm 2
Figure 6. Effect of different laser ablation conditions (frequency (a), (b), spot size (c), (d), energy density (e), (f)) on in situ measurements of Pb isotope compositions (NIST 610): cases of 208Pb/207Pb and 206Pb/204Pb.
(a)
RE (%)
100
80
60
40
20
0
-20
-40
-60
-80
-100
100
80
60
40
20
0
-20
-40
-60
-80
-100
RE (%)
(b)
NIST610
NIST612
GSD-1G
GSE-1G
CGSG-1G
CGSG-2G
CGSG-4G
CGSG-5G
Li Na Al P Ca Ti Cr Fe Ni Zn Ge Sr Zr Cs La Pr Sm Gd Dy Er Yb Hf W Th
Be Mg Si K Sc V Mn Co Cu Ga Rb Y Nb Ba Ce Nd Eu Tb Ho Tm Lu Ta Pb U
Figure 7. Relative error (RE%) of major and trace element concentrations in the reference silicate glasses using GSE-1G (a) and NIST 610 (b) as external
standards.
Mengning Dai, Zhi’an Bao, Kaiyun Chen, Chunlei Zong and Honglin Yuan
98
needs to be confirmed by further chemical analysis. The relative errors of Tm and Lu are >30%, which is significant due to
their low contents in CGSG standards (0.13 μg/g and 0.12 μg/g,
respectively). Generally, the GSE-1G external standard produces more reliable analytical data for major and trace elements,
whereas both NIST 610 and GSE-1G are recommended if only
analyzing trace element contents (Kimura and Chang, 2012).
the different calibrated values for the major and trace elements
analysis. Because the Fe content of NIST 610 cannot be compared with those in natural samples (0.006 6 wt.%), when this
was used as the external standard, the relative error in Fe content for all other samples is larger than 15% and <2% for Cr,
Ga, Ge, Zr, Nb, as well as elements in small quantities. When
GSE-1G is taken as the external standard, Fe content for all
other samples is <2%, except NIST 610 and 612 (relative error
of Fe in NIST 612 is out of range, as shown in Fig. 7), and the
relative error for Cr, Ga and Ge is >10%. The high relative
errors for Cr of some preferred glasses could be caused by the
low Cr elemental concentration in those samples. The relative
error of Ga and Ge in the two methods, using different external
standards, are both >10%, indicating that the reference value of
these two elements in CGSG standards may be lower, which
2.3.2
Analytical results of Pb isotopes
Pb isotope results using LA-MC-ICP-MS and preferred
values using femtosecond laser ablation (fsLA-MC-ICP-MS)
are given in Table 2 and Fig. 8. All analytical results match the
preferred values well to within 2 s analytical uncertainty. For
standards with high Pb contents, such as CGSG-2G, GSE-1G,
and NIST 610, the relative error of 208Pb/206Pb is within 0.03%,
Table 2 Comparison of Pb isotopic ratios of the reference glass materials in this study and previous references
Sample name
208
Pb/
206
2SD
207
Pb/
206
Pb
2SD
208
Pb/
204
Pb
2SD
207
Pb/
204
Pb
2SD
206
Pb/
204
Pb
2SD
Pb
Analysis
References
method
CGSG-1G
2.082 6
0.001 8
0.840 97
0.000 64
38.771
0.071
15.655
0.028
18.616
0.034
NIST 610_std
~32.6 μg/g Pb
2.082 9
0.001 2
0.840 92
0.000 60
38.772
0.093
15.654
0.039
18.613
0.051
GSE-1G_std
Ref.
2.083 3
0.000 1
0.841 14
0.000 04
38.795
0.008
15.664
0.003
18.624
0.004
fsLA-MC-ICP-MS
CGSG-2G
2.160 4
0.000 5
0.895 26
0.000 30
37.537
0.006
15.557
0.004
17.376
0.005
NIST 610_std
~138 μg/g Pb
2.160 5
0.000 4
0.895 37
0.000 26
37.515
0.039
15.548
0.019
17.365
0.018
GSE-1G_std
Ref.
2.160 9
0.000 0
0.895 59
0.000 02
37.526
0.003
15.553
0.001
17.366
0.001
fsLA-MC-ICP-MS
CGSG-4G
2.127 1
0.000 9
0.869 21
0.000 35
38.142
0.035
15.585
0.016
17.929
0.018
NIST 610_std
~47 μg/g Pb
2.126 7
0.001 2
0.869 13
0.000 50
38.109
0.018
15.574
0.007
17.920
0.013
GSE-1G_std
Ref.
2.127 0
0.000 1
0.869 30
0.000 03
38.126
0.008
15.582
0.003
17.926
0.004
fsLA-MC-ICP-MS
CGSG-5G
2.139 2
0.001 7
0.881 61
0.000 74
37.686
0.067
15.531
0.030
17.618
0.043
NIST 610_std
~20.8 μg/g Pb
2.137 0
0.002 9
0.880 46
0.002 25
37.596
0.108
15.490
0.067
17.597
0.053
GSE-1G_std
Ref.
2.139 9
0.000 1
0.882 03
0.000 05
37.727
0.016
15.548
0.006
17.627
0.007
fsLA-MC-ICP-MS
GSD-1G
1.986 8
0.000 5
0.804 31
0.000 23
38.859
0.040
15.732
0.015
19.561
0.024
NIST 610_std
~50 μg/g Pb
1.987 4
0.001 3
0.804 53
0.000 58
38.863
0.085
15.733
0.037
19.557
0.044
GSE-1G_std
Ref.
1.987 1
0.000 5
0.804 18
0.000 10
38.908
0.009
15.745
0.002
19.579
0.004
Ref.
GSE-1G
1.964 0
0.000 5
0.791 96
0.000 12
39.101
0.028
15.768
0.011
19.910
0.012
NIST 610_std
~378 μg/g Pb
1.964 6
0.000 5
0.792 30
0.000 14
39.141
0.025
15.785
0.010
19.923
0.011
GSE-1G_std
Ref.
1.964 6
0.000 1
0.792 32
0.000 02
39.145
0.003
15.787
0.001
19.925
0.002
fsLA-MC-ICP-MS
NIST 610
2.169 4
0.000 3
0.909 86
0.000 09
36.991
0.009
15.515
0.004
17.052
0.004
NIST 610_std
~426 μg/g Pb
2.168 8
0.000 5
0.909 89
0.000 15
36.988
0.017
15.518
0.006
17.055
0.006
GSE-1G_std
Ref.
2.169 4
0.000 1
0.909 86
0.000 05
36.991
0.005
15.515
0.002
17.052
0.002
TIMS
NIST 612
2.163 9
0.000 5
0.907 16
0.000 29
37.005
0.043
15.514
0.024
17.102
0.022
NIST 610_std
~38.57 μg/g Pb
2.163 2
0.001 7
0.907 00
0.000 85
37.016
0.077
15.519
0.036
17.114
0.046
GSE-1G_std
Ref.
2.164 7
0.000 4
0.907 30
0.000 10
37.005
0.010
15.511
0.003
17.095
0.002
Ref.
Chen et al.
(2014)
Chen et al.
(2014)
Chen et al.
(2014)
Chen et al.
(2014)
Jochum et
al. (2011)
Chen et al.
(2014)
Baker et
al. (2004)
Jochum
and Stoll
(2008)
Ref. Data from references.
Simultaneous Measurement of Major, Trace Elements and Pb Isotopes in Silicate Glasses
99
20.5
20.5
206
206
Pb/ 204Pb
Pb/ 204Pb
GSE-1G
GSE-1G
GSD-1G
CGSG-1G
18.5
CGSG-4G
CGSG-5G
17.5
19.5
Reference values
Reference values
19.5
CGSG-2G
17.5
18.5
Obtained values
19.5
NIST612
CGSG-2G
NIST610
16.5
16.5
20.5
17.5
(b)
18.5
Obtained values
19.5
20.5
16.0
16.0
207
207
204
Pb/ Pb
15.8
GSD-1G
CGSG-1G
15.6
CGSG-5G
NIST610
15.4
204
Pb/ Pb
15.8
GSE-1G
Reference values
Reference values
CGSG-4G
CGSG-5G
(a)
NIST610
16.5
16.5
CGSG-1G
18.5
17.5
NIST612
GSD-1G
CGSG-4G
CGSG-2G
NIST612
GSE-1G
GSD-1G
CGSG-1G
15.6
CGSG-5G
NIST610
15.4
CGSG-4G
CGSG-2G
NIST612
15.2
15.2
(c)
15.0
15.0
15.2
15.4
15.6
Obtained values
15.8
(d)
15.0
15.0
16.0
15.4
15.6
Obtained values
15.8
16.0
39.5
39.5
208
204
Pb/ Pb
CGSG-1G
CGSG-4G
CGSG-5G
CGSG-2G
NIST612
NIST610
36.5
36.5
GSE-1G
GSD-1G
38.5
37.5
204
Pb/ Pb
GSE-1G
37.5
38.5
Obtained values
CGSG-1G
Reference values
208
Reference values
15.2
38.5
CGSG-4G
CGSG-5G
37.5
CGSG-2G
NIST612
NIST610
(e)
39.5
GSD-1G
36.5
36.5
37.5
38.5
Obtained values
(f)
39.5
Figure 8. Comparison between the measured and preferred Pb isotopic compositions of the reference silicate glasses (Figs. 8a, 8c and 8e using NIST 610 as the
external standard, Figs. 8b, 8d and 8f using GSE-1G as the external standard).
while the relative error is 0.17% (e.g., 208Pb/206Pb) for those of
Pb contents lower than 50 ppm (e.g., Pb in CGSG-5G, 20.8
μg/g). Higher relative error is caused by the low signal intensities of Pb isotopes in CGSG-5G. The beam intensities of 208Pb
and 204Pb are 150 and 4 mV, respectively.
The data were collected in two independent analytical sessions. The instrumental sensitivities of session using GSE-1G
as external standard is slightly lower than that using NIST 610
as external standard. And another possible reason is the analytical uncertainties of the two standards since the Pb content of
GSE-1G (378 ppm) is lower than that of NIST 610 (426 ppm).
3
CONCLUSION
A new method for in situ analysis of major, trace elements,
and Pb isotopes has been presented, combining laser ablation
quadrupole (LA-Q-ICP-MS) and multi-collector inductively
coupled plasma mass spectrometry (MC-ICP-MS) for silicate
glasses. To acquire accurate, simultaneous analytical results of
major elements, trace elements and Pb isotopic ratios, we set
the aerosol distribution ratio at 1 : 9. An energy density of 18
J/cm2, an ablation frequency of 15–20 Hz, and a spot size of
160 µm were determined as the optimum conditions. Under
these conditions, with the exception Cr, Ga, and Ge, trace ele-
100
Mengning Dai, Zhi’an Bao, Kaiyun Chen, Chunlei Zong and Honglin Yuan
ment contents generally matched the preferred values within
5%. With Pb contents >20 μg/g, the precision for 208Pb/206Pb,
207
Pb/206Pb, 208Pb/204Pb, 207Pb/204Pb, and 206Pb/204Pb was better
than 0.17%, 0.074%, 6.7%, 3.0%, and 4.3%, respectively. For
samples with lower Pb contents, it may be necessary to enhance
the sensitivity of the instrument.
ACKNOWLEDGMENTS
This study was supported by the National Natural Science
Foundation of China (Nos. 41427804, 41421002, 41373004),
the Beijing SHRIMP Center Open Foundation, the Program for
Changjiang Scholars and Innovative Research Team in China
Universities (No. IRT1281), and the MOST Research Foundation from the State Key Laboratory of Continental Dynamics,
Northwest University, Xi’an, China (Nos. BJ08132-1,
201210006). The final publication is available at Springer via
http://dx.doi.org/10.1007/s12583-017-0742-8.
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