Chemical Geology 386 (2014) 22–30

Contents lists available at ScienceDirect

Chemical Geology
journal homepage: www.elsevier.com/locate/chemgeo

Determination of boron isotope compositions of geological materials by

laser ablation MC-ICP-MS using newly designed high sensitivity skimmer
and sample cones
Lin Lin a, Zhaochu Hu a,⁎, Lu Yang b, Wen Zhang a, Yongsheng Liu a, Shan Gao a, Shenghong Hu a
a
State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, China
b
Measurement Science and Standards, National Research Council Canada, Ottawa, Ontario K1A 0R6, Canada

a r t i c l e i n f o a b s t r a c t

Article history: The effects of addition of nitrogen gas with use of three different combinations of sample and skimmer cones on
Received 17 December 2013 the performance of LA-MC-ICP-MS for in situ B isotope ratio measurements were investigated in detail. Com-
Received in revised form 22 July 2014 pared to the standard arrangement (H skimmer cone + standard sample cone), sensitivities of B isotopes
Accepted 1 August 2014
were improved by a factor of 2.4 and 3.8 with use of X skimmer cone + standard sampler cone and the X skim-
Available online 10 August 2014
mer cone + Jet sample cone, respectively. The best within-run precision (2 s) of 11B/10B was approximately
Editor: David R. Hilton 50 ppm for B4 reference material (B content = 31,400 μg/g) with use of X skimmer cone + Jet sample cone. It
was found that different cone combinations had significant effects on the instrument mass bias, but had little
Keywords: effect on the precisions of B isotope ratios. Addition of nitrogen (2–4 ml/min) in the central channel gas did
Boron isotopes not improve the sensitivity of B. However, significant wider ion axial distribution profile and more stable
Laser ablation mass-bias for B isotope ratios were evident. Under selected optimum conditions, good agreements between
MC-ICP-MS the measured δ11B values and the reference values were obtained for the international reference minerals (B4,
Nitrogen Dravite, Elbaite, IMMRB1 and Schorl), the NIST SRM 610–612 synthetic soda-lime glasses and the MPI-DING
Signal enhancement
glasses (GOR-128-G, GOR-132-G, and StHs6/80). It was found that for low-B containing (11 ppm and 31 ppm)
Reference materials
materials, the precisions (2 s) of 11B/10B can be improved by a factor of 2–10 by using the newly designed
X-skimmer cone and Jet sample cone, compared to that of using the standard cones. The international reference
mineral Danburite (δ11B of −14.92 ± 6.77 2SD, n = 32) showed a significant non-uniformity of B isotope ratio
distribution. Our first boron isotopic results from standards GSD-1G (δ11B: 11.92 ± 1.03, n = 30), GSE-1G (δ11B:
1.63 ± 0.32, n = 30), GP-4 (δ11B: −5.85 ± 1.01, n = 40) and DD-1 (δ11B: −13.21 ± 0.56, n = 35) showed these
materials were fairly homogeneous in boron isotope ratios, making them as good candidates as reference mate-
rials. The proposed LA-MC-ICPMS method is suitable for the direct determination of B isotope ratio in a variety of
geological materials.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction in boric minerals in vaporized continental lakes and some tourmalines,

whereas, positive values occur in brine of salty lakes and vaporized
Boron is a volatile element, consisting of two stable isotopes (10B and seawater (Palmer, 1991; Aggarwal and Palmer, 1995). The δ11B value
11
B) with 19.9 % and 80.1% relative abundances, respectively. Due to its of modern seawater is constantly at +39.5‰, and is in a range of −10
high relative mass difference, about 10%, the two isotopes of B are to +2.5‰ in the primary mantle (Spivack and Edmond, 1987; Palmer,
strongly fractionated in nature, which is commonly illustrated using 1991; Ishikawa and Nakamura, 1992; Smith et al., 1995; Jiang et al.,
the δ-notation: 1997).
The light element B and its isotopic composition have been well
    
11 11 10 11 10 proved to be useful in diverse fields of geosciences, such as the compo-
δ B½‰ ¼ B= B = B= B −1  1000
sample standard sition of the mantle and meteorites (Chaussidon and Marty, 1995;
Chaussidon et al., 1997; Chaussidon and Robert, 1998), the composi-
δ11B [‰] values can vary dramatically from −37 to +58‰ in nature tional alteration of the oceanic crust and MORB magmas (Vengosh
(Palmer, 1991; Aggarwal and Palmer, 1995). Negative δ11B values occur et al., 1991; Williams et al., 2001; Kobayashi et al., 2004), defining sub-
duction zones processes (Ishikawa and Nakamura, 1992), and chemical
⁎ Corresponding author. Tel.: +86 27 61055600; fax: +86 27 67885096. palaeo-oceanography (Hemming and Hanson, 1992; Hemming et al.,
E-mail address: zchu@vip.sina.com (Z. Hu). 1998; Lécuyer et al., 2002; Rollion-Bard et al., 2003; Simon et al.,

http://dx.doi.org/10.1016/j.chemgeo.2014.08.001
0009-2541/© 2014 Elsevier B.V. All rights reserved.
 L. Lin et al. / Chemical Geology 386 (2014) 22–30 23

Table 1 are capable of B isotope ratio measurements in low B containing sam-

Typical LA-MC-ICP-MS operating conditions. ples. The first in situ B isotope ratio measurements was carried out by
Instrument settings le Roux et al. (2004) using laser ablation MC-ICP-MS and ion counting
Reflected forward power 1280 W detectors. Data obtained with Faraday detectors on NIST 610 and B4
Plasma Ar gas flow rate 16.0 l/min tourmaline show high precision (down to 0.08‰, 2σ) and accuracy
Auxiliary Ar gas flow rate 1.00 l/min
(Tiepolo et al., 2006). In contrast, B isotope ratio measured in the glass
Ar makeup gas flow rate 0.50–1.5 l/min
Lens settings Typical samples (GOR-128-G, GOR-132-G, StHs6/80-G) using multiple ion
Data acquisition parameters counting shows significantly higher standard deviations (3.2–6.4‰, 2σ)
Scan type Static (Tiepolo et al., 2006).
Faraday cup configuration L3 and H3
Unfortunately, natural samples usually contain low levels of B
Signal integration time 0.131 s
Number of integrations 1
(below 100 ppm) with an exception of a few minerals where B is a
Cycles/blocks 300/1 major constituent such as tourmaline (Chaussidon and Marty, 1995).
GeoLas 2005 laser ablation system To improve the precision and accuracy of in situ B isotope analysis of
Ablation cell gas (Helium) 0.6 l/min low-B containing samples and to apply the technique to small or isoto-
Spot sizes 44–90 μm
pically heterogeneous samples, a higher analytical sensitivity is re-
Fluence 5.3 J/cm2
Repetition rate 8 Hz quired. To obtain the desired precision and accuracy, a large spot size,
Scan mode Single spot analysis a high laser ablation repetition rate and/or a high energy density of
laser ablation are often adopted for LA-ICP-MS analysis. However,
such approaches increase the amount of consumed sample and the
2006; Foster, 2008; Kasemann et al., 2009). Moreover, because of B is chance of element fractionation during laser ablation, and are therefore
relatively highly soluble in moderate-to high temperature (≥ 100 °C) not suitable for high spatial/depth resolution analysis. Thus, it would be
aqueous fluids, B mobilization is expected in all magmatic, geothermal ideal to increase the analytical sensitivity of the MC-ICP-MS instrument
and hydrothermal environments where fluids are involved (Leeman instead.
and Sisson, 1996). In the quest to enhance the analytical capabilities, addition of gases
Accurate and precise methodologies are desired for the determina- and solvents (e.g., N2, H2, methane, methanol, and water) into one of
tion of B isotope ratio in various sample matrices. Several analytical the three gas flows of ICP have been studied with LA-ICP-MS (Durrant,
techniques for the determination of B isotopes have been reported. 1994; Guillong and Heinrich, 2007; Fliegel et al., 2011; Liu et al.,
Thermal ionization mass spectrometry (TIMS) is the most precise (typ- 2014). Nitrogen is one of the most popular gases used in LA-ICP-MS to
ical 2σ precision is 0.16–0.7‰) and commonly used approach to date improve sensitivity and stability. The addition of N2 has been successful-
(Vengosh et al., 1989; Hemming and Hanson, 1992; Swihart, 1996; ly used to improve the precision and accuracy of in situ Hf isotope mi-
Wei et al., 2014). Secondary ion mass spectrometry (SIMS) even with croanalysis of zircon using LA-MC-ICP-MS (Iizuka and Hirata, 2005;
single collector was reported to have its capability of producing high Hu et al., 2012). Alternatively, different design and construction of the
quality δ11B data (typical 2σ precision is 1.2–4‰) (Chaussidon and sample and skimmer cones were reported to significantly change the
Albarède, 1992; Gurenko et al., 2005). Despite poorer precision com- analytical sensitivity and instrumental mass fractionation behavior. A
pared to TIMS, SIMS has the advantages of simpler sample preparation number of studies have investigated the effects of sample and skimmer
and high spatial resolution. Similar to TIMS, MC-ICP-MS can provide cone geometry and interface pump configuration on the ion extraction
high precision and accuracy measurements (precision around 0.25‰, efficiency and mass fractionation behavior in ICP-MS and MC-ICP-MS
2σ) for B isotope ratio (Foster, 2008). When coupled to a laser ablation (Grain et al., 1988; Niu and Houk, 1996; Jarvis et al., 1998; Zahran
system, MC-ICP-MS equipped with Faraday detectors requires several et al., 2003; Bouman et al., 2009; Brenner et al., 2009; Newman et al.,
hundred ppm B in a sample to achieve high precision 11B/10B ratio mea- 2009; le Roux, 2010; Yang et al., 2011; Huang et al., 2012; Newman,
surements (le Roux et al., 2004; Tiepolo et al., 2006; Bouman et al., 2012; Cottle et al., 2013). For example, through a series of modifications
2009; Fietzke et al., 2010). On the other hand, ion counting detectors to the geometry of the sampler and skimmer cones, the pumping

Table 2
A list of fifteen reference materials studied.

Sample name Description Reference

B4 Tourmaline Black, from the Rosina pegmatite dyke hosted in the monzogranite of Tonarini et al. (2003);
San Piero in Campo, Elba Island Dyar et al. (2001)
Dravite #108796 NaMg3Al6(BO3)3Si6O18(OH)4 Black, from Madagascar. Probably an eluvial crystal from a granitic pegmatite Dyar et al. (2001)
Elbaite #98144 Na(Li,Al)3Al6(BO3)3Si6O18(OH)4 Dark olive green, crystal from a gem pocket in a granitic pegmatite in Dyar et al. (2001)
Minas Gerais, Brazil
Danburite #115089 CaB2Si2O8 Colorless, from Pb–Zn–Cu–Ag veins and limestone replacement ore bodies at Dyar et al. (2001)
the La Bufa Mine, Charcas, San Luis Potosi, Mexico
Schorl #112566 NaFe3Al6(BO3)3Si6O18(OH)4 Black, from a granitic pegmatite, Alto Ligonha, Zambezia Province, Mozambique Dyar et al. (2001)
IMR RB1 Tourmaline Black, from a granitic pegmatite, Shandong Province, China Hou et al. (2010)
GOR132-G Komatiite glass Prepared at the Bayerisches Geoinstitut, Bayreuth, from Gorgona Island Jochum et al. (2000);
Jochum et al. (2006)
GOR128-G Komatiite glass Prepared at the Bayerisches Geoinstitut, Bayreuth, from Gorgona Island Jochum et al. (2000);
Jochum et al. (2006)
StHs6/80 Andesite ash glass Prepared at the Bayerisches Geoinstitut, Bayreuth, from St. Helens eruption Jochum et al. (2000);
Jochum et al. (2006)
NIST SRM 610 Synthesized Si–Na–Ca–Al-oxide glass Produced by the U.S., National Institute of Standards and Technology Pearce et al. (1997)
NIST SRM 612 Synthesized Si–Na–Ca–Al-oxide glass Produced by the U.S., National Institute of Standards and Technology Pearce et al. (1997)
DD-01 Tourmaline Black, from a granitic pegmatite, Shandong Province, China This study
GSD-1G Synthesized glass Produced by the USGS in Denver, Colorado, USA Guillong et al. (2005)
GSE-1G Synthesized glass Produced by the USGS in Denver, Colorado, USA Guillong et al. (2005)
GP-4 Carbonate pellet Produced by the USGS
24 L. Lin et al. / Chemical Geology 386 (2014) 22–30

10
configuration and the source, the sensitivity of the Nu Instruments Nu Standard + H
Plasma HR MC-ICP-MS system is improved by 80–125% in solution Standard + X
mode and 70–95% in laser-ablation mode (Cottle et al., 2013). Com- Jex + X
8
pared to the standard arrangement (H skimmer cone + standard

intensity [V]
sample cone), the signal sensitivity of Hf was improved by a factor of
1.4 and 2.5, respectively, with using the X skimmer cone + standard 6
sampler cone, and the X skimmer cone + Jet sample cone in Thermo
Scientific NEPTUNE Plus (Hu et al., 2012). It is worth noting that the ef- 4

11B
fects of the geometry and structure of the cones on signal intensity are
usually element specific (Bouman et al., 2009; Newman et al., 2009;
Newman, 2012; Cottle et al., 2013). In addition, it has been reported 2
that the skimmer geometry and material may also influence the inten-
sity of polyatomic ion (Weyer and Schwieters, 2003; Zahran et al.,
0
2003; Ferguson and Houk, 2006). 0.5 0.75 1 1.25 1.5
In this study, we systematically investigated the effects of three Makeup Gas flow rate [l/min]
different cone combinations, namely a standard sample cone + H
skimmer cone, a standard sample cone + X skimmer cone and a Jet Fig. 1. The integrated average signal intensity of 11B from tourmaline standard B4 using a
sample cone + X skimmer cone, with or without addition of nitrogen spot size of 44 μm as a function of makeup gas flow rate for the three different sample and
on the performance of LA-MC-ICP-MS (Thermo Scientific NEPTUNE skimmer cone combinations. a: standard sample cone + H skimmer cone (Standard + H);
b: standard sample cone + X skimmer cone (Standard + X); c: Jet sample cone + X skim-
Plus) for the in situ B isotope analysis of zircon, with the purpose of
mer cone (Jet + X).
achieving high sensitivity and more stable mass-bias in B isotope ratio
measurements.

2. Experimental
3
2.1. Instrumentation and acqusition Standard + H (a)
N2 = 0
All measurements were performed on a NEPTUNE Plus MC-ICP-MS N2 = 2
(Thermo Fisher Scientific, Germany) connected to a Geolas 2005 excimer 2 N2 = 4
ArF laser ablation system (Lambda Physik, Göttingen, Germany) at the
state Key Laboratory of Geological Processes and Mineral Resources,
China University of Geosciences in Wuhan. Typical operating conditions
and measurement parameters are summarized in Table 1. NEPTUNE Plus 1
is a double focusing multi-collector ICP-MS equipped with seven ion
counters, eight motorized Faraday cups and one fixed central Faraday
cup that can be equipped with an ion counter. The maximum distance
0
between the outmost cup positions corresponds to a relative mass (b)
8 Standard + X
range of ~17%. The NEPTUNE Plus is an update of the Thermo Scientific
NEPTUNE MC-ICP-MS platform. Among the new features include the
use of a large dry interface pump (max. 130 m3/h pumping speed) and
intensity [V]

6
the newly designed X skimmer cone and Jet sample cone (Bouman
et al., 2009). Three different combinations of sampler and skimmer
cones were used in this study, including a H skimmer cone + standard 4
sample cone, a X skimmer cone + standard sample cone and a X skim-
11B

mer cone + Jet sample cone. 2

The Geolas 2005 laser ablation system consists of a COMPexPro102
ArF excimer laser (wavelength of 193 nm; maximum energy of
200 mJ) and a MicroLas optical system. Its optical configuration allows 0
for the selection of a constant fluence that is independent of the crater Jet + X (c)
diameters. The energy density used in this study was 5.3 J/cm2. The 8
laser was operated in single spot mode with a repetition rate of 8 Hz
and a spot size from 44 to 90 μm in diameter. Helium was used as the 6
carrier gas within the ablation cell and was merged with argon (makeup
gas) after the ablation cell. As demonstrated by previous studies (Eggins
4
et al., 1998; Günther and Heinrich, 1999), a 2- to 5-fold signal enhance-
ment was consistently achieved in helium than in argon gas for the
2
193 nm laser. A simple Y junction downstream from the sample cell
was used to add small amounts of nitrogen to the argon makeup gas
flow (Hu et al., 2008). The additional nitrogen gas flow was controlled 0
0.5 0.75 1 1.25 1.5
by a mass flow controller (Aalborg DFC 26 mass flow controller) in a
range of up to 50 ml/min. Prior to the acquisition of MC-ICP-MS signal, Makeup Gas flow rate [l/min]
the addition of N2 gas was increased to the desired values (2 ml/min or
Fig. 2. The integrated average signal intensity of 11B from tourmaline standard B4 using a
4 ml/min) over approximately 10 min. The B ion distribution profiles
spot size of 44 μm as a function of makeup gas flow rate for the three different sample and
were acquired by scanning the ICP torch horizontally between 0.4 mm skimmer cone combinations in both normal and nitrogen (N2 = 2–4 ml/min) modes.
and 1.8 mm across the sampler orifice. Movement was performed a: standard sample cone + H skimmer cone (Standard + H); b: standard sample
using the software controlled motorized translation stage of the cone + X skimmer cone (Standard + X); c: Jet sample cone + X skimmer cone (Jet + X).
 L. Lin et al. / Chemical Geology 386 (2014) 22–30 25

MC-65ICP-MS. The vertical profiles were recorded at fourteen different observed under both the X skimmer cone and standard sample cone
sampling depths, between − 1.0 mm and 5.0 mm. Signals for 10B and mode and the X skimmer cone and Jet sample cone combination
11
B were simultaneously collected using the L3 and H3 Faraday Cups. (Fig. 2b and c), respectively. It is also evident that signal intensity of
11
Each measurement consisted of 15 s of acquisition of the background B decreased with the addition of nitrogen for all three combinations
signal followed by 25 s of ablation signal acquisition. Faraday cup pre- of cones. For the combination of a standard sample cone and H skimmer
amplifier gains were calibrated daily. cone, the maximum B signal intensity was suppressed by about 30–60%
with addition of 2–4 ml/min nitrogen. In contrast, such suppression was
2.2. Samples and standards only about 10–20% for the combination of a Jet sample cone and X skim-
mer cone. Conflicting observations were reported in studies using N2 for
Two types of external standards were used in this study: Soda-lime the purpose of enhancement of signal sensitivity. Durrant (1994) first
glass SRM (NIST 610) and IAEA B4. The certified reference materials reported that addition of about 12% N2 to the cell gas increased the Ce
NIST 610 used in the study are synthesized Si–Na–Ca–Al-oxide glasses and Th signal sensitivities by a factor of 2–3 in LA-ICP-MS. Nesbitt
produced by the U.S., National Institute of Standards and Technology et al. (1997) also reported enhanced sensitivities of heavy mass ele-
(Pearce et al., 1997; Rocholl et al., 1997). The trace B concentrations ments by about a factor of 10 (N100 amu) by addition of small amount
are about 356.5 ppm in these reference glasses (Pearce et al., 1997;
Rocholl et al., 1997). The sample IAEA B4 is tourmaline, coming from
the Rosina pegmatite dyke hosted in the monzog ranite of San Piero in
Campo, Elba Island (Gonfiantini and Tonarini, 2003; Tonarini et al., 4.70
2003; Jochum and Stoll, 2008). It has a mean B concentration of (a) Standard + H
31,400 ppm with a determined mean δ11B value of − 8.62 ± 0.17‰
(2σ) on milled material and a mean δ11B value of − 8.85 ± 0.33‰ 4.65 N2 = 0
(2σ) on fragments, using positive TIMS. N2 = 2
A range of minerals were selected for analyses in this study: synthet- N2 = 4
4.60
ic NIST SRM soda-lime glasses (610, 612), synthetic USGS reference
glasses (GSE-1G, GSD-1G), MPI-DING glasses GOR128-G (komatiite),
GOR132-G (komatiite) and StHs6/80-G (andesite), tourmaline refer- 4.55
ence materials B4, Dravite, Elbaite, Danburite and Schorl and marine
carbonate (GP-4) (Table 2). In addition an in-house natural tourmaline
sample (DD-1) was tested as a potential standard. As a result of this 4.50
work this tourmaline sample of DD-1 was identified as a candidate
boron isotope reference material for laser ablation studies. DD-1 is a
hydrothermal vein tourmaline from a granitic pegmatite, Shandong
province, northwest China.
.5 (b) 0. 75 1 1. 25 + X 1.
Standard
4.70

3. Results and discussion 4.65

/ 10B Ratio

3.1. Effects of different cone combinations on signal intensity 4.60

There are three different sets of sampler and skimmer cones avail- 4.55
11B

able for use in NEPTUNE and NEPTUNE Plus MC-ICP-MS instruments,

which differ in their external/internal angle and geometry at the tip 4.50
(Bouman et al., 2009; Newman, 2012). It was reported that using mod-
4.45
ified cone geometries can enhance the analytical sensitivity (Bouman
et al., 2009; Huang et al., 2012; Newman, 2012). In this study as
shown in Fig. 1, signal enhancements of approximately 2.4- and
3.8-folds were observed for B isotopes with use of X skimmer cone in
0. 5 (c) 0. 75 1 1. 25
Jet +X 1..
combination with the standard sample cone and the Jet sample cone, re- 4.80
spectively, compared to that of using standard cones. It should be noted
that the optimum makeup gas flow rate shifted to a lower makeup gas
flow rate by approximately 0.15 l/min relative to the standard sample 4.70
cone mode when the Jet sample cone was used (Fig. 1). This is due to
the increased height of the Jet sample cone in comparison with the stan-
4.60
dard sample cone, which makes the Jet sample cone tip more close to
the torch (Hu et al., 2012).
4.50
3.2. Effect of addition of N2 on signal intensity

The intensity of 11B from B4 reference standard as a function of 4.40

makeup gas flow rate for the three different sample and skimmer 0.5 0.75 1 1.25 1.5
cone combinations in both the normal and nitrogen (2–4 ml/min) Makeup gas flow rate [l/min]
modes was studied. Results are presented in Fig. 2. Clearly, the optimum
Ar gas flow shifted to lower flow rate when N2 gas was added under Fig. 3. Effect of makeup gas flow rate on the 11B/10B ratio for the three different sample and
skimmer cone combinations (a: standard sample cone + H skimmer cone (Standard + H);
three different sample and skimmer cone combinations. Approximate
b: standard sample cone + X skimmer cone (Standard + X); c: Jet sample cone + X skim-
0.15 l/min shift was observed for each 2 ml/min increase in the nitro- mer cone (Jet + X)) from tourmaline standard B4. The vertical lines show the optimum
gen gas flow rate under H skimmer cone and standard sample cone makeup gas flow rates for normal and nitrogen (N2 = 2–4 ml/min) modes that yielded
combination mode (Fig. 2a). Slightly small shift of 0.10 l/min was maximum signal intensity for B.
26 L. Lin et al. / Chemical Geology 386 (2014) 22–30

Fig. 4. Radial and axial intensity distributions for 11B signal intensities in both normal and nitrogen (N2 = 2–4 ml/min) modes from tourmaline standard B4. This contour plot was
produced by using software SigmaPlot 10.0.

of N2 (0.4 ml/min) into the carrier gas in LA-ICP-MS, whereas signal in-
tensities of the low mass elements were suppressed by about a factor of
10. Hu et al. (2008) reported increased sensitivities for most of the 65
elements investigated by a factor of 2–3 with addition of 5–10 ml/min
nitrogen to the central channel gas in LA-ICP-MS. Shaheen and Fryer
(2010) also reported enhancements in intensities of Pb and Tl by a factor
of 3–4 when nitrogen was mixed with Ar carrier gas. However, Guillong
and Heinrich (2007) reported almost no sensitivity enhancement with
addition of nitrogen (1–10 ml/min) in their investigation. Results pre-
sented here suggest that the effect of the addition of nitrogen on signal
intensity in LA-MC-ICP-MS is cone specific.
3.3. Effect of addition of N2 on B isotope ratio
Similarly, the 11B/10B ratio in B4 reference standard as a function of
makeup gas flow rate for the three different sample and skimmer
cone combinations in both normal and nitrogen (2–4 ml/min) modes
was studied, shown in Fig. 3. Clearly with different gas flow of N2, 11B/
10
B ratio changed with the makeup gas flow rate for all three different
combinations of cones. When using the standard cone and H cone, the
11 10
B/ B ratio decreased as makeup gas increased from 0.5 l/min to
flow rate resulting maximum sensitivity (e.g., 1.17 l/min without N2)
under different amount of N2, then increased to a sub-maximum as
makeup gas continue increased to 1.4 l/min. It was noted that as N2 gas
increased the 11B/10B ratio decreased more slowly. For standard and
X cones, 11B/10B ratio generally decreased to lowest points and then
leveled out as makeup gas increased in the tested range. For Jet +
X cone combination, 11B/10B ratio decreased with a couple of sub-
maximums as makeup gas increased. Overall, 11B/10B ratio decreased
relatively smaller when using Jet + X cone combination (Fig. 3c)
compared to other two combinations (Fig. 3a and b), favoring the
isotope ratio measurements. This observation maybe due to the jet
cone design which is different from the standard cone, having bigger
orifice and deeper depth from the base to the tip. Fontaine et al.
(2009) has proposed a promising approach to stabilize the mass
bias by measuring at elevated carrier gas flow rate in Nu Plasma
MC-ICP-MS. However, as indicated in Fig. 3, this method only
works when using the standard cone and H cone combination in
NEPTUNE Plus MC-ICP-MS. Results presented in this study clearly
demonstrated that the design of sample and skimmer cone geometry
and the addition of nitrogen have significant effects on mass bias and
mass-bias stability.

Fig. 5. Radial and axial distributions for 11B/10B ratios in both normal and nitrogen (N2 = 2–4 ml/min) modes obtained from tourmaline standard B4.
 L. Lin et al. / Chemical Geology 386 (2014) 22–30 27

10
3.4. Effect of addition of N2 on spatial profiles of B ion distributions
Jet+X
Sample+X
Similar to previous studies (Wang et al., 2006; Hu et al., 2008), the Sample+H
effect of addition of N2 on the spatial (including axial and radial) distri-

RSE of 11B/10B (‰)

bution of B isotope intensity was investigated with use of Jet and X cones 1
and B4 reference standard. 11B intensity was monitored by changing
torch position from 0.4 mm to 1.8 mm for x-pos and − 1.0 mm to
5.0 mm for z-pos with fourteen different sampling depths. Other param-
eters for LA-MC-ICPMS were remained same during these experiments 0.1
in order to obtain accurate data. Results are presented in Fig. 4. Without
addition of N2 gas, it is evident that the B intensities were relatively con-
centrated in the center of the plasma and shape of the profile was quite
symmetric. When N2 gas increased the distribution of 11B intensities 0.01
in the plasma were expanded. As shown in Fig. 4, when adding 0 2 4 6 8
2 ml/min N2, the spatial profile of B ion distribution was elongated, Intensity [V]
but the center of the channel was not significantly expanded wider. In
addition, 11B intensity in the center position in the ion contour was Fig. 6. The relationship between the 11B signal intensity and the precision of 11B/10B (1σ)
slightly decreased (lighter color). When N2 increased to 4 ml/min, the for in situ B isotope ratio measurements.
spatial profile of B was also elongated with more significant decrease
in 11B intensity (lighter color). This observation maybe due to B element 11 10
B/ B ratio, larger spot size can be used. Unfortunately, this approach
is an easily ionized element, through the addition of small amount of
is at the expense of spatial resolution. Alternatively, the increase of ana-
nitrogen to increase plasma temperature do not increase its ionization
lytical sensitivity of MC-ICP-MS instrument itself by using high sensitiv-
efficiency. As total B ions in the plasma remain constant, the expansion
ity skimmer and sample cones can be an attractive approach for 11B/10B
of spatial profile of B ion distribution would result in decreased intensity
ratio measurements in low B containing materials such as the MPI-DING
and therefore decreased sensitivity for B measurements.
glass samples GOR128-G, GOR132-G and StHs6/80-G (only 0.05–0.2 V
for 11B intensity even with a large spot size of 90 μm). As illustrated in
3.5. Effect of addition of N2 on 11B/10B ratio distributions in the plasma
Fig. 1, the use of the newly designed X skimmer cone and Jet sample
cone led to a signal enhancement factor of 3.8 for 11B, relative to the
The effect of addition of N2 on 11B/10B ratio distribution in the plasma
use of the H skimmer cone and standard sample cone. This sensitivity
is presented in Fig. 5. The red boxes in Fig. 5 represent the regions with
high concentrations of B ions (N5 V for 11B). It is evident, with the addi-
tion of N2, 11B/10B ratio increased significantly (the color gradually 1
becomes deeper). It is worth noting that the stable area of 11B/10B B4
ratio in the plasma was increased by a factor of 2.5 in axis with addition
Jet + X
of N2 gas. Average measured 11B/10B ratios calculated from high 11B
Standard + X
intensities N 5 V were used to calculate their relative standard deviations
Standard + H
from B4 reference value. Values of 13.5 ± 1.2%, 13.9 ± 0.9% and 14.4 ± 0.1
0.6% (2SD) were obtained for additions of 0, 2 and 4 ml/min N2 gas
respectively. This observation indicates that addition of N2 gas leads to
slightly increased instrument mass discrimination for B. However, mea-
sured 11B/10B ratios were more stable with addition of N2 gas and there-
fore resulted in better precision of B ratio measurements. Mass bias can
be easily corrected by using the recommend value in reference material
RSE of 11B/10B (‰)

with standard-sample bracketing mass bias correction model. There- NIST 610
fore, Jet and X cone combination with addition of 4 ml/min N2 was 1
chosen for all subsequent experiments.

3.6. Intensity vs. precision 0.1

In general, the precision of the isotope ratio measurements is corre-

lated to its signal sensitivity. The signal intensity verse relative standard
error (RSE) of 11B/10B ratio obtained in the above experiments was plot-
ted and shown in Fig. 6. Clearly, low RSEs were associated with high NIST 612
intensity measurements, and were not related to the combinations of
10
cones. Fig. 7 shows the effect of changing laser ablation spot size on
the calculated relative standard error (RSE) of 11B/10B ratio in tourma-
line standard B4, NIST SRM 610 and NIST SRM 612. Clearly, better rela-
tive standard error (RSEs) of 11B/10B were obtained for X skimmer 1
cone + Jet sample cone, and the X skimmer cone + standard sampler
cone using a same spot size compared to that of the standard skimmer
cone + H sample cone. This improvement is more significant with use 0.1
of smaller spot size in low B containing materials NIST SRM 612. For 16 24 32 44 60 90 120
example, the use of the newly designed X skimmer cone and Jet sample Spot Size (µm)
cone led to a precision improvement factor of 10 for 11B/10B ratio with a
spot size of 16 μm in NIST SRM 612 relative to the use of the H skimmer Fig. 7. Effect of changing laser ablation spot size on the calculated relative standard error
cone and standard sample cone. To improve measurement precision of (RSE) of 11B/10B ratio in NIST SRM 610, NIST SRM 612 and tourmaline standard B4.
28 L. Lin et al. / Chemical Geology 386 (2014) 22–30

improvement leads to improvement of by a factor of 2–10 in the preci-
sions (2 s) of 11B/10B in low B (11 ppm and 31 ppm) containing materials
(GOR128-G, GOR132-G, StHs6/80). Therefore, to achieve lowest RSDs,
especially for low-B samples like MPI-DING glass series, it is best to
use Jet cone and X cone combination.
Our first B isotopic results for DD-1 (δ11B: − 13.21 ± 0.56, n = 35),
GSE-1G (δ11B: 1.63 ± 0.32, n = 30), GSD-1G (δ11B: 11.92 ± 1.03,
n = 30), GP-4 (δ11B: − 5.85 ± 1.01, n = 40) were very consistent,
respectively (Fig. 8), indicating these materials are homogeneous in
B isotopes and are good candidates as B isotope standards.

3.7. Results for standard reference materials

Based on above studies, Jet and X cone combination with addition of
4 ml/min N2 were therefore chosen for 11B/10B ratio measurements in
several reference materials. Results obtained for δ11B are summarized
in Table 3 and Fig. 8 for fifteen samples. For the determination of B
isotope ratio using LA-MC-ICP-MS, different LA spot size was used,
depending on the B concentration. The tourmalines (B4, Danburite,
Dravite, Elbaite, Schorl, IMM RB1 and DD-1) were measured using a
spot size of 44 μm, and the MPI-DING glass samples, the NIST SRM
610–612, GSD-1, GSE-1 and GP-4 were measured using a spot size of
90 μm. Depends on the number of measurements (n = 23–71), the
total measurement time for each sample is in a range of 920 to 2840 s.
The δ11B values are calculated by normalizing the measured 11B/10B
ratio to the mean of the NIST SRM 610 11B/10B ratios measured before
and after the sample. The determined mean values of δ11B obtained
here covered a range from − 12.47 to 13.85‰. The determined δ11B
values of tourmalines B4 (− 8.41 ± 0.43, n = 53), Dravite (− 6.51 ±
0.33, n = 38), Elbaite (− 10.66 ± 0.26, n = 33) and Schorl
(−12.47 ± 0.31, n = 26) are in excellent agreement with the published
data by Tiepolo et al. (2006) and Dyar et al. (2001). Whereas, reference
material Danburite (δ11B: −14.92 ± 6.77, n = 32) shows a significantly
non-uniformity distribution for B isotope ratio (Fig. 8). In addition,
results show that δ11B values for the MPI-DING glasses GOR-128-G
(13.85 ± 2.09, n = 71), GOR-132-G (8.94 ± 2.79, n = 67) and StHs6/
80-G (−3.63 ± 2.68, n = 41), NIST SRM 610 and NIST SRM 612 are in
excellent agreement with the δ11B values obtained by N-TIMS. Previous
study by Tiepolo et al. (2006) reported δ11B values for the MPI-DING
glasses GOR-128-G (13.5 ± 3.2, n = 8), GOR-132-G (6.8 ± 6, n = 9)
and StHs6/80-G (− 4.3 ± 4.8, n = 9), within-run precisions of 3.2 to
6.4‰ (2σ) using multiple ion counting detectors in LA-MC-ICP-MS. Pre-
cisions obtained in this study using Faraday detectors are significantly
better (1 to 2-fold) than those reported by Tiepolo et al. (2006) using
ion counting detectors. Excellent agreements between the measured
11 /10
B B ratios by LA-MC-ICP-MS and reference values by p-TIMS for
these reference materials confirm the accuracy of the proposed method.
4. Conclusions
The effects of addition N2 gas with use of three different sample and
skimmer cone combinations on the performance of laser ablation MC-
ICP-MS for the in situ B isotope ratio measurements were investigated
in detail. The isotope ratio variations as a function of carrier gas flow
rate and sampling depth were evident, similar to those observed by
other research groups using MC-ICP-MS (Andrén et al., 2004; Fontaine
et al., 2009). Different sample and skimmer cone combinations had
significant effects on the analytical sensitivity and mass bias in laser
ablation MC-ICP-MS. Compared to the standard arrangement, the use
of the newly designed X skimmer cone and Jet sample cone improved
the signal intensity of 11B by a factor of 3.8. Although the addition of
N2 gas in the central channel gas did not improve B signal intensity,
but mass-bias stability of measured 11B/10B ratio was significantly
enhanced. The determined 11B/10B isotope ratios in nine different refer-
ence materials using X skimmer cone and Jet sample cone with
4 ml/min N2 are in good agreement with the literature values. The
proposed method is suitable to obtain reliable in situ B isotope data in
geological samples, especially for low B content materials.
Acknowledgments
We would like to thank David R. Hilton and two anonymous
reviewers for their constructive comments and Vijayakumar
Venkataraman for overseeing the editorial process. We also thank
Klaus Peter Jochum for providing MPI-DING reference glasses. This
research is supported by the National Nature Science Foundation of
China (Grants 41273030, 41322023, 41373026, and 41173016), the
Fundamental Research Funds for National Universities, the CERS-China
Equipment and Education Resources System (CERS-1-81), the State
Administration of the Foreign Experts Affairs of China (B07039), and
the MOST Special Fund from the State Key Laboratories of Geological
Processes and Mineral Resources (Grant No. GPMR201106).

Table 3
Results of the determined δ11B values in fifteen reference materials.

B concentration δ11B Ref. (by N-TIMS) Ref. (by ion counting detectors
(μg/g) (2SD) (2σ) in LA-MC-ICP-MS) (2σ)

IAEA B4 31,400 −8.41 ± 0.43(n = 53) −8.71 ± 0.18a

NIST 610 356.5 0.02 ± 0.47(n = 42) −0.16 ± 0.21b
NIST 612 35 0.041 ± 1.5(n = 47) −0.29 ± 0.37b
IMR RB1 32,430 −13.01 ± 0.35 (n = 23) −12.22 ± 1.10c
GOR132-G 17.8 8.94 ± 2.79(n = 67) 7.11 ± 0.97d 6.8 ± 6f
GOR128-G 22.7 13.85 ± 2.09(n = 71) 13.55 ± 0.21d 13.5 ± 3.2f
StHs6/80-G 11.6 −3.63 ± 2.68(n = 41) −4.48 ± 0.29d −4.3 ± 4.8f
Dravite 32,457 −6.51 ± 0.33(n = 38) −6.6 ± 0.10e
Elbaite 26,085 −10.66 ± 0.26(n = 33) −10.5 ± 0.20e
Danburite 90,200 −14.92 ± 6.77(n = 32) −18.7 ± 1.50e
Schorl 35,828 −12.47 ± 0.31(n = 26) −12.5 ± 0.05e
DD-01 34,330 −13.21 ± 0.56(n = 35)
GSD-1G 50 12.41 ± 1.94(n = 40)
GSE-1G 330 1.63 ± 0.32(n = 30)
GP-4 55 −5.85 ± 1.01(n = 40)
a
The reference values were taken from Tonarini et al. (2003).
b
The reference values were taken from le Roux et al. (2004).
c
The reference values were taken from Hou et al. (2010).
d
The reference values were taken from Rosner and Meixner (2004).
e
The reference values were taken from Dyar et al. (2001).
f
The reference values were taken from Tiepolo et al. (2006).
 L. Lin et al. / Chemical Geology 386 (2014) 22–30
Fig. 8. The determined δ11B values of fifteen reference materials. The horizontal dash line and gray area in each panel represent the determined average δ11B value and its 2σ error in the
present study, respectively. The thick horizontal lines represent the recommended values of these reference materials.
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