Accurate determination of elements in silicate glass by nanosecond and femtosecond laser ablation ICP-MS at high spatial resolution

    Accurate determination of elements in silicate glass by nanosecond and femtosecond laser ablation ICP-MS at high spatial resolution Zhen Li, Zhaochu Hu, Yongsheng Liu, Shan Gao, Ming Li, Keqing Zong, Haihong Chen, Shenghong Hu PII: DOI: Reference:

S0009-2541(15)00032-7 doi: 10.1016/j.chemgeo.2015.02.004 CHEMGE 17482

To appear in:

Chemical Geology

Received date: Revised date: Accepted date:

30 June 2014 24 November 2014 5 February 2015

Please cite this article as: Li, Zhen, Hu, Zhaochu, Liu, Yongsheng, Gao, Shan, Li, Ming, Zong, Keqing, Chen, Haihong, Hu, Shenghong, Accurate determination of elements in silicate glass by nanosecond and femtosecond laser ablation ICP-MS at high spatial resolution, Chemical Geology (2015), doi: 10.1016/j.chemgeo.2015.02.004

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ACCEPTED MANUSCRIPT Accurate determination of elements in silicate glass by nanosecond and femtosecond laser ablation ICP-MS at high

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spatial resolution

Zhen Li, Zhaochu Hu *, Yongsheng Liu, Shan Gao, Ming Li, Keqing Zong, Haihong

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Chen, Shenghong Hu

State Key Laboratory of Geological Processes and Mineral Resources, Faculty of

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Earth Sciences, China University of Geosciences, Wuhan 430074, PR China.

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*Author to whom correspondence should be sent. E-mail: [email protected] Tel: 86 27 67885100, Fax: 86 27 67885096

Submitted to chemical Geology

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ACCEPTED MANUSCRIPT Abstract Despite the large number of successful applications of LA-ICP-MS, elemental

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fractionation remains the main limitation for many of its applications in the Earth

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sciences. This limitation is particularly notable for high spatial resolution analysis. Elemental fractionation and mass-load effect in silicate glasses NIST SRM 610 and GSE-1G were investigated by using 193 nm ArF excimer nanosecond (ns) laser and

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257 nm femtosecond (fs) laser ablation systems coupled to inductively coupled

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plasma mass spectrometry. Contrary to those observed in ns-LA-ICP-MS, the most elemental fractionation at the small spot sizes of 16–24 µm are lower than that at the

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large spot sizes of 44–60 µm in fs-LA-ICP-MS. The significantly different

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fractionation behavior of Li, Na, Si, K, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Cs and U

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between silicate glass materials NIST SRM 610 and GSE-1G observed in 193 nm excimer LA-ICP-MS are eliminated by using 257 nm fs-LA-ICP-MS at high spatial

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resolution. In addition, the mass load effect and matrix dependent mass load effect are also found to be reduced by using fs-LA-ICP-MS in comparison with ns-LA-ICP-MS. Except for Sb, Pb and Bi, the elemental fractionation is independent on the laser fluence chosen, which is irrespective of ns- or fs-LA-ICP-MS. In this study, a spot size of 24 µm was used to test the capabilities of LA-ICP-MS analysis at high spatial resolution. The agreement between our data and the reference values is better than 10% for most of the elements in MPI-DING, USGS, and NIST glasses by using fs-LA-ICP-MS. For ns laser ablation analysis, the accuracy is highly dependent on the calibration strategies used (conventional external calibration method or 100% oxide 2

ACCEPTED MANUSCRIPT normalization method) and the selected external reference materials (NIST SRM 610 or GSE-1G). The much less laser-induced elemental fractionation and matrix effect in

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fs-LA-ICP-MS in comparison with 193 nm excimer LA-ICP-MS make it more

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suitable for the analysis of silicate materials at high spatial resolution. Keywords: LA-ICP-MS; elemental fractionation; matrix effect; mass load effect;

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silicate materials; high spatial resolution analysis

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ACCEPTED MANUSCRIPT 1. Introduction Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) has

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become one of the most popular techniques for the in situ analysis of element and

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isotopic compositions for a wide variety of materials (Arrowsmith, 1987; Poitrasson et al., 2000; Jackson et al., 2004; Günther and Hattendorf, 2005; Košler, 2007; Sylvester, 2008; Russo et al., 2011; Orellana et al., 2013). Ever since the first

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feasibility studies were carried out during the 1980s (Gray, 1985; Arrowsmith, 1987),

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the performance characteristics of LA-ICP-MS have been strongly enhanced, principally with the use of ultraviolet (UV) wavelength LA systems (Günther and

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Hattendorf, 2005; Jochum et al., 2007). Among these different UV lasers, the 193 nm

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excimer laser was reported to be excellent for LA-ICP-MS because its laser pulse

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energy could be effectively absorbed by most materials and produce small-size particles that could be easily transported by the carrier gas and efficiently atomized

2003).

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and ionized in the ICP (Günther et al., 1997; Guillong et al., 2003; Hattendorf et al.,

193 nm excimer LA-ICP-MS has been successfully applied for the analysis of minerals and silicate glasses with non-matrix matched calibration (Günther et al., 1997; Gao et al., 2002; Resano et al., 2003; Günther and Hattendorf, 2005). Most of these reported element determinations in minerals and silicate glasses were focused on using large spot sizes of 40 to 120 μm. This is also true for many other UV-LA-ICP-MS analyses ( Kurosawa et al., 2006; Mertz-Kraus et al., 2009; Donohue et al., 2012). The major reason for large spot sizes is to improve sensitivity when the 4

ACCEPTED MANUSCRIPT samples were analyzed. The technological progress in ICP-MS instrumentation has led to the possibility

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of analysing craters of smaller diameter. In addition, spatially resolved analysis using

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a laser beam spot as small as possible is necessary for microanalysis applications, such as for the analysis of melt inclusions, dust aerosols and the zonations of minerals. Liu et al. (2010) reported simultaneous measurements of zircon U-Pb ages and trace

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elements by LA-ICP-MS at spot sizes of 16−32 μm by introducing N2 into the ICP to

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increase sensitivity. The obtained U-Pb ages were consistent with the preferred values within about 1% uncertainty (2σ) by external calibration against 91500. Whereas, the

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most trace elements for 91500 and relatively homogenous GJ-1 showed a systematic

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deviation of 10%–30% calibrated against NIST glasses using Si as an internal

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standard. The systematic deviation of REEs in carbonate pellets were also as high as 20% when calibrated against NIST SRM 610 with the use of Ca as an internal

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standard at a spot size of 32 μm (Chen et al., 2011). Hu et al. (2011) showed the effect of spot sizes on the determined 24 element concentrations in zircon GJ-1, GSE-1G and NIST SRM 612 using NIST SRM 610 as an external reference material and Si as internal standard. By changing the spot sizes from 16 μm to 60 μm, the determined element concentrations in zircon GJ-1 and GSE-1G were increased by 30% (Pb in zircon GJ-1 is an exception), and they were almost not effected in NIST SRM 612. The determined Pb concentration in carbonate MACS-1 calibrated with NIST SRM 612 varied from approximately 170 to 130 ppm with spot sizes varying from 25 μm to 110 μm for 193 nm laser measurements (Jochum et al., 2012). These results implied 5

ACCEPTED MANUSCRIPT that matrix dependent effects would significantly deteriorate the analysis results of LA-ICP-MS at high spatial resolution when matrix-matched calibration standards

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were not available. Therefore, how to reduce the matrix dependent fractionation is

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important for high spatial resolution analysis.

Many investigations suggest that a fs laser might be one of the best solutions to reduce the matrix effect and elemental fractionation in the ablation process (Russo et

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al., 2002; Fernández et al., 2007; Koch and Günther, 2007; Garcia et al., 2008;

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Shaheen et al., 2012). The LA process using a fs laser is significantly less thermal and leads to a shrinking of the heat-affected zone (Fernández et al., 2007). However, the

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applications of fs-lasers have mainly been concentrated on the fractionation behavior

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and the analysis of a few elements in conductors and semi-conductors (González et al.,

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2004; Liu et al., 2004; Koch et al., 2005; Bian et al., 2006; Garcia et al., 2008; Wiltsche and Günther, 2011). For example, Koch et al. (2005) studied the

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composition and fractionation properties of dielectric aerosols generated by near infrared (NIR) fs-LA of silicate glass. It had been found that for fluences larger than 5 J cm-2, the total Zn-, Ca-, Sr-, Ba-, and Pb-specific composition of these aerosols corresponded to that of the bulk material even though the composition of different aerosols was size-dependent. Bian et al. (2006) measured the major and minor concentrations of Zn and Cu in brass, aluminum, and silicate glass using NIR-fs-LA-ICP-MS. Their results indicated the possibility of non matrix-matched calibration if the fluence, depending on the matrix, was appropriately adjusted. Garcia et al. (2008) observed that the fractionation of a few elements in binary metallic and 6

ACCEPTED MANUSCRIPT semiconductor samples as well as multi-component glass samples occurred in the first laser shots particularly if the laser fluence was near the ablation threshold of the

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sample. The fractionation could be reduced by applying many low-fluence laser shots

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or one high-fluence laser shot only. In most cases, the fractionation could most likely be correlated with the respective ionization energies of the elements. There are only a few publications on multi-element analyses of silicate materials by using fs-LA,

reported

the

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matrix-dependent

fractionation

for

volatile

and

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(2014)

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especially for an UV-fs-LA (Jochum et al., 2014; Ohata et al., 2014). Jochum et al.

siderophile/chalcophile elements such as Pb and Zn with 200 nm fs laser compared to

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the 193 nm excimer laser and 213 Nd:YAG laser. The concentrations of 47 elements

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in twenty-two international synthetic silicate glass, geological glass, silicate mineral,

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phosphate and carbonate reference materials were successfully determined by using NIST SRM 610 as an external reference material at the spot size of 40–65 μm with

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spot analysis and line scan analysis. Ohata et al. (2014) demonstrated that middle ultraviolet (MUV) fs- and far ultraviolet (FUV) ns-LA-ICP-MS applying either Ca or Si as an internal standard resulted in only minor discrepancies of element concentrations at spot sizes of 60–90 μm. Glaus et al. (2010) observed the similar morphologies of silicate glass aerosols generated by ns- and fs-LA. They considered that fs-LA of silicate with non-matrix matched calibration would be limited because of a pronounced element separation into different particle size fractions. The aim of this study is to evaluate the matrix effect and elemental fractionation in the analysis of silicates by using the UV 193 nm ArF excimer LA-ICP-MS and the 7

ACCEPTED MANUSCRIPT advanced 257 nm fs-LA-ICP-MS at high spatial resolution. The widely used NIST SRM 610 and USGS new synthesis GSE-1G have been selected for studying the

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elemental fractionation and matrix effect. This is because they not only fulfill the need

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for different types of matrices due to different major element compositions, but also have sufficient levels of trace elements to provide adequate signals for calibrating the fractionation indexes. For the purposes of comparison, the MPI-DING, USGS and

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NIST reference glasses were also analyzed by ns- and fs-LA-ICP-MS with different

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calibration strategies at a high spatial resolution of 24 μm.

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2.1. Instrumentation

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2. Experimental

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Experiments were conducted on an Agilent 7500a ICP-MS (Agilent Technology, Tokyo, Japan) in combination with a 193 nm ArF excimer LA system (GeoLas 2005,

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Lambda Physik, Göttingen, Germany) and a 257 nm Yb fs-LA system (NWR-FemtoUC, USA) owned by the State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences (Wuhan). Details of the instrumental operating conditions and measurement parameters are summarized in Table 1. The excimer 193 nm laser is installed with an optical configuration producing a fairly flat-topped lateral energy distribution leading to pan-shaped ablation pits on the sample. The Yb fs-laser system has a Gaussian energy beam profile across its diameter. Helium was chosen as the ablation cell gas as it has been found to consistently enhance the signal 2- to 5-fold compared to argon gas with the 193 nm 8

ACCEPTED MANUSCRIPT excimer laser (Eggins et al., 1998a; Günther et al., 1999). The carrier and make-up gas flows were optimized by ablating NIST SRM 610 to obtain maximum signal intensity

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for La+, while keeping the ThO/Th ratio <0.3% and the U/Th ratio close to 1. Except

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for spot analysis, we also performed line scan analysis at a 10 µm/s speed applying crater diameters of 16–120 µm (193 nm excimer) and 16–60 µm (257 nm fs) to investigate a possible mass-loading effect. Due to the maximum crater diameter of 65

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µm in fs laser, a high mass is essential for investigating the mass-loading effect.

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Therefore, line scanning ablation (10 µm/s scan speed) at 44 and 60 µm crater diameters with a high repetition rate of 20 Hz were used in fs-LA-ICP-MS.

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Each LA-ICP-MS analysis incorporated an approximately 20 s background

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acquisition followed by 50 s data acquisition from the sample. All analyses were

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acquired using time resolved software. The off-line selection and integration of the background and analyte signals, and time-drift correction and quantitative calibration

2010).

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were conducted using an in-house program ICPMSDataCal (Liu et al., 2008; Liu et al.,

2.2. Samples The well characterized reference materials NIST SRM 610 and GSE-1G were used to study the elemental fractionation. To investigate the accuracies of 193 nm excimer LA-ICP-MS and 257 nm fs-LA-ICP-MS for high spatial resolution analysis, the following range of silicate glasses were selected in this study: MPI-DING reference glasses (KL2-G (basalt), ML3B-G (basalt), StHs6/80-G (andesite) and T1-G 9

ACCEPTED MANUSCRIPT (quartz-diorite)), USGS basaltic reference glasses (BCR-2G and BHVO-2G), synthetic USGS reference glasses (GSE-1G and GSD-1G) and synthetic NIST SRM

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soda-lime glasses (610 and 612). The working values are from Jochum et al. (2011)

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for NIST SRM 610–612, from Jochum et al. (2006) for the MPI-DING reference glasses and from the GeoReM database (http://georem.mpch-mainz.gwdg.de/) for the USGS basalt reference glasses and synthetic USGS reference glasses (Table 2). Prior

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to LA-ICP-MS analyses, all of the reference glasses were polished fairly smooth using

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2.3. Element fractionation index

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aluminum powder and cleaned in a 2% HNO3 bath with an ultrasonic washer.

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The elemental fractionation indexes were calculated based on Ca as internal

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standard. To simulate real application conditions, the elemental fractionation indexes were calculated by dividing the 50 s transient signals into two equal time intervals,

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instead of 240 s as reported in reference (Fryer et al., 1995). The ratios to calcium of the second 25 s interval were divided by the corresponding ratio of the first time interval, as described by Fryer et al. (1995). The elemental fractionation indexes are, therefore, a measure of the fractionation of each element relative to Ca, a value of 1 indicating no relative fractionation.

3. Results and discussion 3.1. Matrix induced elemental fractionation Fig. 1 shows the effect of changing crater diameters from 60 μm to 16 μm on the 10

ACCEPTED MANUSCRIPT calculated elemental fractionation index by using 193 nm excimer LA-ICP-MS and 257 nm fs-LA-ICP-MS. The laser fluence is 8.0 J/cm2 which is independent of crater

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diameter for 193 nm excimer laser. For 257 nm fs laser, the detected fluences are 2.90

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J/cm2, 3.14 J/cm2, 3.11 J/cm2 and 2.48 J/cm2 for spot sizes of 16 µm, 24 µm, 44 µm and 60 µm, respectively. As shown for NIST SRM 610 and GSE-1G in Fig. 1, the calculated elemental fractionation indexes (with respect to Ca) for 56 elements (Zn

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and Cd are exceptions) are very close to each other at the small spot sizes of 16–24

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µm, which are close to 1, and significantly increase for some elements after switching spot sizes from 24 µm to 44 µm and 60 µm in fs-LA-ICP-MS. This is contrary to the

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fractionation indexes observed in 193 nm excimer LA analysis (Fig. 1). Unlike in

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excimer LA system, there is no homogenizing lens in fs laser (NWR-FemtoUC). Thus,

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the increased elemental fractionation indexes with increasing crater diameter may be related to the heterogeneous distribution of the fs laser beam energy, which has a 140

Ce signal intensity as a function of the

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Gaussian distribution. Fig. 2 shows the

crater area for single hole ablation on NIST SRM 610 and GSE-1G by using 193 nm excimer LA-ICP-MS and fs-LA-ICP-MS. The excellent positive correlation between the crater area and the

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Ce signal intensity indicates that the distribution of energy

density of the laser beam is independent of the selected crater area for both 193 nm excimer laser and fs laser to a certain extent (Fig. 2). Therefore, the change of the fs laser beam energy distribution is unable to explain the observed phenomenon of the increased elemental fractionation indexes with increasing crater diameter. Further investigations are needed to reveal the exact mechanism behind this occurrence. It is 11

ACCEPTED MANUSCRIPT worth noting that the slopes of the

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Ce signal response curves are similar for both

NIST SRM 610 and GSE-1G when using fs-LA-ICP-MS. In contrast, they are

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significant different for 193 nm excimer LA-ICP-MS. This result suggests that the

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ablation behavior of the fs laser is more matrix-independent than that of the ns laser. For ns-LA-ICP-MS analysis, there are some significant differences between the calculated elemental fractionation indexes for Li, Na, Si, K, V, Cr, Mn, Fe, Co, Ni, Cu,

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Rb, Cs and U in NIST SRM 610 and GSE-1G at spot sizes of 16–24 µm. The

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calculated elemental fractionation indexes for these elements in GSE-1G are significantly increased by changing the spot sizes from 44 µm to 24 µm and 16 µm

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(Fig. 1b). However, they remain nearly constant at spot sizes of 24–60 µm in NIST

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SRM 610, and show only a slight increase at a spot size of 16 µm (Fig. 1a). The

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increased elemental fractionation indexes with decreasing crater diameter should be related to the increased depth/diameter ratio, which has been reported to have a

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significant effect on elemental fractionation (Mank and Mason, 1999). Loewen and Kent (2012) reported that the ablation rate for NIST SRM 610 glass was ~170 nm/pulse, whereas that was ~125 nm/pulse for more opaque GSE-1G at the same ablation conditions. Under our given laser ablation conditions, the ablation rate for NIST SRM 610 was approximately 180 nm/pulse, which is 1.5 times bigger than the ablation rate determined for more opaque GSE-1G (approximately 120 nm/pulse). Thus the depth/diameter ratio fails to explain the much less significant laser-induced elemental fractionation for these elements in NIST SRM 610. Further work on the elemental fractionation in the ns-LA-ICP-MS is needed to identify the specific 12

ACCEPTED MANUSCRIPT mechanisms. In contrast, these fractionation index differences between GSE-1G and NIST SRM 610 are eliminated by using fs-LA. The much less laser-induced elemental

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fractionation and matrix effect in fs-LA-ICP-MS in comparison with 193 nm excimer

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LA-ICP-MS make it more suitable for the analysis of silicate materials at high spatial resolution (Fig. 1). Zn and Cd are exceptions, whose elemental fractionation in fs-LA-ICP-MS are more serious than those in 193 nm excimer LA-ICP-MS. The

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calculated elemental fractionation indexes of Zn and Cd are in the range of 0.49–0.88

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at spot sizes of 16–24 µm on NIST SRM 610 and GSE-1G by fs-LA-ICP-MS while they are 0.88–0.98 for 193 nm excimer LA-ICP-MS (Fig. 1). Fig. 3 shows the change

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of the Zn/Ca ratios with time during single hole ablation of NIST SRM 610 and

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GSE-1G using spot sizes from 16 µm to 60 µm in fs-LA-ICP-MS. The Zn/Ca ratios

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are near similar at the beginning of ablation time (15 s) and then gradually disperse with time by the change of spot sizes from 16 µm to 24 µm to 60 µm (Fig. 3a and b).

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The significantly reduced Zn/Ca ratios with increasing ablation time at small spot sizes of 16–24 µm correspond with their low elemental fractionation indexes in Fig. 1. The highly volatile element Zn may remain in the gaseous state or be partitioned into the smaller particulates during LA process (Košler et al., 2005; Hirata and Miyazaki, 2007; D'Abzac et al., 2012), which could much more easily condense on or adhere to the ablation crater wall leading to the significant loss of Zn in the signal ratios at high depth to diameter ratios. Similar trends for elemental fractionation indexes for Zn and Cd by fs-LA of silicate glass NIST SRM 610 were previously reported by Koch et al. (2006) and Shaheen et al. (2008). Pb and Bi are other exceptions. The calculated 13

ACCEPTED MANUSCRIPT elemental fractionation indexes of Pb and Bi are close to 1 in NIST SRM 610 at spot sizes of 16–24 µm by using fs-LA-ICP-MS; however, they are 0.82–0.92 in GSE-1G.

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Therefore, there is significant matrix effect between NIST SRM 610 and GSE-1G for

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the analysis of Pb and Bi by using fs-LA-ICP-MS. Jochum et al. (2014) reported that the fractionation indexes for Pb are similar (both less than 1) at spot sizes of 12–25 µm by fs-LA of NIST SRM 610 and GSE-1G. The significant matrix dependent

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effects for Pb and Bi in fs-LA-ICP-MS between NIST SRM 610 and GSE-1G at high

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spatial resolution observed in this study contradict the result reported by Jochum et al. (2014). This could be due to the different LA systems used. Many studies have

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observed matrix dependent effects for volatile elements such as Pb and Zn in the

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LA-ICP-MS analysis of silicates (Jochum et al., 2007; Jochum et al., 2012). Glaus et

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al. (2010) proposed that this might be related to the melting effect produced by heat diffusion in the samples. The melting effect can be well restrained when the laser

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pulse duration falls below the thermal relaxation time of a few hundred femtoseconds (Koch and Günther, 2007). However, the opposite effects are observed in our fs-LA measurements, indicating that the heat diffusion may not be or at least may not be the only one explanation for the matrix effect in LA-ICP-MS.

3.2. Mass load effect The mass load of the ICP may have an effect on elemental fractionation in LA-ICP-MS (Kroslakova and Günther, 2007; Hu et al., 2011; Czas et al., 2012; Jochum et al., 2012). Kroslakova and Günther (2007) showed that an increase of the 14

ACCEPTED MANUSCRIPT mass load of the ICP by a factor of 16 (crater diameter from 30 to 120 µm) led to a decrease in certain intensity ratios (e.g., Cu/Ca) up to 25%. This effect is element

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dependent and most severe for elements with low boiling points (e.g., Cu, Zn, Ag, Cd

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and Pb). Fig. 4 shows the effect of changing spot sizes (16–120 µm) and laser repetition rates (8–20 Hz) on the normalized element (Cu, Zn, Rb, Sr, Ba and Pb)/Ca ratios in NIST SRM 610 and GSE-1G by using 193 nm excimer LA-ICP-MS and 257

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nm fs-LA-ICP-MS. To better compare the results between different elements, we

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normalized the element ratios for different crater sizes and frequencies to the 16 µm spot size measurement conditions for both LA systems. To eliminate the laser-induced

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elemental fractionation effect on element/Ca ratios, we adopted a line scanning

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ablation mode at a speed of 10 µm/s.

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In agreement with the observations by Kroslakova and Günther (2007), the ratios of Cu/Ca, Zn/Ca, Rb/Ca and Pb/Ca by 193 nm excimer LA of NIST SRM 610

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decrease gradually with increasing spot sizes from 16 µm to 120 µm (increasing mass load) (Fig. 4a). Unlike NIST SRM 610, the mass load induced matrix effects are negligible for GSE-1G at the small spot sizes of 16–32 µm, where the ratios of Cu/Ca, Zn/Ca, Rb/Ca and Pb/Ca are similar (Fig. 4b). In general, the decrease in these element/Ca ratios is less than 20% for an increase of the mass load by a factor of 56.3 (crater diameter from 16 to 120 µm). In great contrast, the Sr/Ca and Ba/Ca ratios are almost not effected by a change of the mass load in 193 nm excimer LA of both NIST SRM 610 and GSE-1G. These results demonstrate that the mass load effect is matrix dependent, which deteriorates the capabilities of 193 nm excimer LA-ICP-MS at high 15

ACCEPTED MANUSCRIPT spatial resolution analyses. In fs-LA analysis, the mass load effects for these elements are much smaller, and the mass load differences between NIST SRM 610 and

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GSE-1G are reduced.

3.3. Effect of the laser fluence

The characteristics of laser ablation and particle generation are strongly related to

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the energy deposited at the target surface (Diwakar et al., 2014). The fluence is often

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recognized as a major parameter affecting elemental fractionation when ns and fs pulses are used (Cromwell and Arrowsmith, 1995; Figg and Kahr, 1997; Mao et al.,

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1998; Bian et al., 2006; Koch et al., 2006; Garcia et al., 2008), and this phenomenon

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is emphasized when low fluences, especially close to the ablation threshold, are

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delivered to the sample. In Fig. 5, the effect of laser fluences on the calculated elemental fractionation indexes for 56 elements at a spot size of 24 µm in 193 nm

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excimer LA-ICP-MS and fs-LA-ICP-MS is shown. The discrepancies among the calculated elemental fractionation indexes are not significant under the selected laser fluence range (5.05–19.0 J/cm2 and 1.71–4.10 J/cm2 for ns- or fs-laser pulses, respectively) (Fig. 5). In the case of ns-LA-ICP-MS, the calculated fractionation indexes for Sb, Pb and Bi in NIST SRM 610 remain constant at these different laser fluences, whereas, they increase significantly with increasing laser fluences from 5.05 J/cm2 to 19.0 J/cm2 in GSE-1G (Fig. 5a and b). The calculated elemental fractionation indexes of these elements are closer to each other in NIST SRM 610 and GSE-1G at higher laser fluences (larger than 9.49 J/cm2), respectively (Fig. 5a and b). We 16

ACCEPTED MANUSCRIPT therefore recommend using high laser fluence to determine these elements in silicate materials when matrix-matched calibration standards are not available. For fs-LA

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measurements, the fractionation indexes of Zn and Cd are closer to 1 at high laser

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fluences (Fig. 5c and d); however, elemental fractionation is still significant. The differences in the fractionation indexes for Pb and Bi between NIST SRM 610 and GSE-1G are still significant at these different laser fluences. Thus, matrix-matched

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calibration standards are essential for accurate analysis of these elements in silicates

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by using fs-LA-ICP-MS.

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3.4. Calibration of trace elements by using external calibration

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The greatest strength of the LA-ICP-MS technique is its application to

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microsampling, in which extremely small pits are obtained. In this study, a spot size of 24 μm was used to test the capabilities of LA-ICP-MS analysis at high spatial

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resolution. We determined 48 element concentrations in MPI-DING glasses (KL2-G, ML3B-G, StHs6/80-G and T1-G), USGS basalt glasses (BCR-2G and BHVO-2G), USGS new synthetic glasses (GSD-1G and GSE-1G) and synthetic NIST SRM soda-lime glass NIST SRM 612 using NIST SRM 610 as an external reference material and Ca as an internal standard by 193 nm excimer LA-ICP-MS and 257 nm fs-LA-ICP-MS (Table 2). Fig. 6 shows the relative deviations of the determined average concentrations in these geological reference glasses in this study from the reference values. It can be seen from Fig. 6a that the relative deviations of the major elements (e.g., Na2O, Al2O3, SiO2, K2O, MnO and FeO) and some trace elements (e.g., 17

ACCEPTED MANUSCRIPT Li, V, Co, Ni, Cu, Zn, Ga, Rb, Cs and U) are usually consistently beyond 10% for most of the MPI-DING glasses, USGS basalt glasses and USGS new synthetic glasses

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with the use of 193 nm excimer LA-ICP-MS. Whereas, the results of most elements in

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NIST SRM 612 agree well with the reference values within 10% relative deviation. This can be well explained by the previous reported differences of the elemental fractionation indexes between NIST SRM 610 and GSE-1G at the spot size of 24 µm

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in 193 nm excimer LA-ICP-MS (Fig.1). These results suggest that GSE-1G and

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GSD-1G reference glasses are more suitable than NIST SRM 610 and NIST SRM 612 as external reference materials for natural silicate materials at high spatial resolution

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analysis. However, it should be noted that GSE-1G and GSD-1G have relatively high

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analytical uncertainties for some elements (e.g., Li, Be, B, P, Cr, Cu, Ga, Ta, W)

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(Jochum et al., 2005). More accurate calibration values of these elements in the GSE-1G and GSD-1G, especially from definitive methods, are needed. Geochemical

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applications using LA-ICP-MS often use NIST SRM 61X as external reference materials and naturally occurring elements of Si and Ca for internal standardization. To improve the accuracies of these elements in silicate materials when using NIST SRM 61X as external reference materials, the choice of Si for internal standardization in the analysis of these elements is recommended. For fs-LA analysis, the observed discrepancies in Fig. 6a disappear and the agreement between our data and the reference values is better than 10% for most of the elements in these geological reference glasses (Fig. 6b). The accuracies of the determined element concentrations for the MPI-DING glasses and USGS glasses 18

ACCEPTED MANUSCRIPT (basalt and synthetic) are significantly improved compared to the results obtained by 193 nm excimer LA-ICP-MS. Only several elements, such as Zn and Pb, show a

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system bias due to the matrix dependent fractionation. The concentrations of B are

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always higher than the reference values by a factor of ~20%–110% (Table 2), which could be partly attributed to the large uncertainty of the reference value of B in NIST SRM 610, as demonstrated by the high uncertainty of 16% (Jochum et al., 2011).

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Large relative deviations of other trace elements could potentially be due to

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heterogeneous element distribution (e.g., Cr for ML3B-G (Jochum et al., 2006)) and their abundances being close to low limit detection (e.g., Be, Cs, W). As shown in Fig.

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7, the RSD values of trace elements are plotted versus their concentrations at the spot

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size of 24 µm in fs-LA-ICP-MS. The data are obtained from 12 replicated analyses

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performed on different locations of the reference glasses. The analytical precision is less than 15% for most of these elements provided their concentrations are higher than

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1 µg g-1. There is a significant negative correlation between logarithmic concentration and logarithmic RSD, with correlation coefficients being -0.70. This expected trend of decreasing RSD with increasing concentration for these glasses indicates that the analytical precision follows counting statistics (Luo et al., 2007), and thus, most of the measurement uncertainty is analytical in origin and not due to chemical heterogeneities.

3.5. Determination of trace elements by 100% oxide normalization Since a summed-spectrum normalization calibration procedure to determine 19

ACCEPTED MANUSCRIPT elements in alloys by LA-ICP-MS was first explored by Leach and Hieftje (2002), a calibration method without applying internal standardization has been applied to

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analyse the major and trace elements of silicate glasses, silicate minerals, silicate

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whole-rocks, metal oxides and carbonate minerals (Halicz and Günther, 2004; Guillong et al., 2005; Liu et al., 2008; Liu et al., 2010; Chen et al., 2011; Li et al., 2011). This approach not only decreases costs and workload from determining the

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internal standard by an independent method (e.g., electron microprobe), but also

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expands the applications of LA-ICP-MS. By applying 100% oxide normalization and calibration using NIST SRM 610 reference material, we calibrated the same data

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obtained from 193 nm excimer LA-ICP-MS and fs-LA-ICP-MS spot analysis (24 μm)

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in the MPI-DING, USGS and NIST glasses (Fig. 8 and Table 2).

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The calculated element concentrations of Na2O, Al2O3, SiO2, MnO, FeO, Li, V, Co, Ni, Cu, Zn, Ga, Rb, Cs, U in MPI-DING and USGS glasses using 100% oxide

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normalization are in general agreement with the reference values within 10% when using 193 nm excimer LA-ICP-MS. Whereas, the calculated element concentrations of Sc, TiO2, Sr, Y, Zr, Hf, Th and REE in these glasses are lower than the reference values by approximately 10–40% (Fig. 8a and Table 2). A similar phenomenon has been observed by Liu et al. (2008) during 193 nm excimer LA-ICP-MS analysis, which has been attributed to the NIST SRM 610-specific matrix effect. To overcome this problem, Liu et al. (2008) suggested using multiple reference glasses (BCR-2G, BHVO-2G and BIR-1G) as reference materials for external calibration. It is apparent from Fig. 8b that the analytical results of these reference glasses 20

ACCEPTED MANUSCRIPT using 100% oxide normalization calibration strategy and NIST SRM 610 as an external reference material in fs-LA-ICP-MS lead to much more accurate results

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compared to the ns-LA analysis (Fig. 6a and 8a). Except for the several transition

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elements and those elements with concentrations close to detection limit, the determined values of most of the elements agree well with the reference values within 10% uncertainty. However, a system bias still exists for the element concentrations of

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Zn and Pb. This can be explained by the difference between their element

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fractionation behavior in NIST SRM 610 and GSE-1G (Fig. 1). For fs-LA-ICP-MS analysis, our results demonstrate that using NIST SRM 610 as an external reference

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material in combination with 100% oxide normalization calibration strategy is

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suitable for the multi-element analysis of natural silicate materials.

4. Conclusions

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Our results indicate that the significantly different fractionation behavior of Li, Na, Si, K, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Cs and U between silicate glass materials NIST SRM 610 and GSE-1G observed in 193 nm excimer LA-ICP-MS are eliminated by using 257 nm fs-LA-ICP-MS at high spatial resolution. However, Zn, Cd, Pb and Bi are exceptions because their matrix dependent effects in fs-LA-ICP-MS are much more serious than that in 193 nm excimer LA-ICP-MS. In comparison with ns-LA-ICP-MS, the mass load effect and matrix dependent mass load effect are also found to be reduced by using fs-LA-ICP-MS. For 193 nm excimer LA, NIST SRM 610 is an unsuitable external reference material for analyses of natural silicates due to 21

ACCEPTED MANUSCRIPT its much less significant laser-induced elemental fractionation for Li, Na, Si, K, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Cs and U compared to natural silicate materials at high

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spatial resolution analysis. This NIST SRM 610-specific matrix effect for these

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elements can be minimized by using Si as an internal standard for the determination of these elements or replacing NIST SRM 610 with GSE-1G as an external reference material. By using 257 nm fs-LA-ICP-MS, the NIST SRM 610-specific matrix effect

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disappears and NIST SRM 610 can be adopted as an ideal external reference material

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for the analysis of natural silicate materials. The determined values of most elements in MPI-DING and USGS glasses agree well with the reference values within 10%

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uncertainty at a spot size of 24 μm by using fs-LA-ICP-MS. The much smaller

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laser-induced elemental fractionation, matrix effect and mass load effect in

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fs-LA-ICP-MS compared with 193 nm excimer LA-ICP-MS make it more suitable for

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the analysis of silicate materials at high spatial resolution.

Acknowledgements We would like to thank Donald Dingwell and anonymous reviewers for their constructive comments. 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, 41073020, and 41173016), the Fundamental Research Funds for National Universities, the Program for New Century Excellent Talents in University (NCET-10-0754), the State Administration of the Foreign Experts Affairs of China (B07039), and the MOST Special Fund from the 22

ACCEPTED MANUSCRIPT State Key Laboratories of Geological Processes and Mineral Resources (Grant No.

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GPMR201106).

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Figure Captions 26

ACCEPTED MANUSCRIPT Fig. 1. Fractionation indexes for 56 elements with respect to Ca for the ablation of NIST SRM 610 (a) and GSE-1G (b) at spot sizes of 16–60 µm by using 193 nm

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excimer LA-ICP-MS and 257 nm fs-LA-ICP-MS. Error bars represent the standard

Fig. 2.

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deviation (1s) from 3 measurements.

Ce signal intensity as a function of crater area for single hole ablation on

NIST SRM 610 and GSE-1G by using 193 nm excimer LA-ICP-MS and 257 nm

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fs-LA-ICP-MS.

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Fig. 3. Variation of the Zn/Ca and Pb/Ca ratios with time during single spot ablation of NIST SRM 610 and GSE-1G at different spot sizes in 257 nm fs-LA-ICP-MS.

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Fig. 4. Element/Ca abundance ratios of six elements obtained from the investigation

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of NIST SRM 610 and GSE-1G by 193 nm excimer and 257 nm fs laser systems. For

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these experiments, different spot sizes, different frequencies, and line scan analysis have been chosen. These data are normalized to the 16 µm spot size measurements.

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Due to the maximum crater diameter of 65 µm in fs laser, a high mass is essential for investigating the mass-loading effect. Therefore, line scanning ablation (10 µm/s scan speed) at 44 and 60 µm crater diameters with a high repetition rate of 20 Hz were used in fs-LA-ICP-MS, which are represented by 90* and 120* on the x-axis, respectively. Error bars represent the standard deviation (1s) from 3 measurements. Fig. 5. Ca-normalized fractionation indexes determined for NIST SRM 610 and GSE-1G in 193 nm excimer LA-ICP-MS (a) (b) and 257 nm fs-LA-ICP-MS (c) (d) at three selected laser fluences, respectively. Fig. 6. Relative deviations of average concentrations in the reference glasses obtained 27

ACCEPTED MANUSCRIPT in this study from reference values calibrated against NIST SRM 610 and Ca internal standardization at the small spot size of 24 µm by using 193 nm excimer LA-CP-MS

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(a) and 257 nm fs-LA-CP-MS (b). The reference values of element concentrations are

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reference

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the

GeoReM

database

(http://georem.mpch-mainz.gwdg.de/) for USGS basalt reference glasses and

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synthetic USGS reference glasses.

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Fig. 7. Concentration versus relative standard deviation (RSD) for the determined elements obtained from fs-LA-ICP-MS spot analysis (24 µm) on different locations of

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the MPI-DING, USGS and NIST glasses (n = 12).

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Fig. 8. Relative deviations of average concentrations in the reference glasses obtained

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in this study from reference values calibrated against NIST SRM 610 and applying 100% oxide normalization at the small spot size of 24 µm in 193 nm excimer

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LA-CP-MS (a) and fs-LA-CP-MS (b).

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ICP-MS

Agilent 7500a

rf power Plasma gas flow rate Auxiliary gas flow rate Ion optic settings Sampling depth

1380 W 14.0 l min-1 1.0 l min-1 Typical 5.4 mm 7 Li, 9Be, 11B, 23Na, 25Mg, 27Al, 29 Si, 31P, 39K, 42Ca, 45Sc, 49Ti, 51 V, 52Cr, 55Mn, 57Fe, 59Co, 60 Ni, 65Cu, 66Zn, 71Ga, 72Ge, 75 As, 85Rb, 88Sr, 89Y, 90Zr, 93 Nb, 95Mo, 107Ag, 111Cd, 118 Sn, 121Sb, 133Cs, 137Ba, 139 La, 140Ce, 141Pr, 143Nd, 147 Sm, 151Eu, 157Gd, 159Tb, 163 Dy, 165Ho, 166Er, 169Tm, 173 Yb, 175Lu,179Hf, 181Ta, 182W, 208 Pb, 209Bi, 232Th, 238U 10 ms Dual

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Isotopes measured

Dwell time per isotope Detector mode

Yb:YAG femtosecond laser 257 nm 300 fs 3.14 J/cm2 16、24、32、44 and 60 µm

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Laser frequency Ablation cell gas Makeup gas

ArF excimer laser 193 nm 15 ns 8.0 J/cm2 16、24、32、44 、60、 90 and 120 µm 8 Hz Helium Argon

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Laser type Wavelength Pulse length Energy density Spot size

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MLB-3G

257 nm fs

A

B

A

B

193 nm excimer

Ref.1

A

B

6.72±0.49

6.09±0.51

5.34±0.42

5.58±0.35

5.1±0.5

5.74±0.67

4.97±0.53

1.33±0.36

1.21±0.33

0.87±0.32

0.91±0.34

0.88±0.34

1.09±0.59

0.95±0.51

B

3.75±0.74

3.4±0.7

3.44±1.44

3.62±1.53

2.73±0.28

5.44±1.69

4.70±1.45

Na2O

2.64±0.04

2.39±0.01

2.11±0.15

2.2±0.1

2.35±0.08

2.82±0.06

MgO

7.26±0.33

6.57±0.20

6.61±0.16

6.91±0.24

7.34±0.09

6.80±0.27

Al2O3

14.5±0.3

13.2±0.1

14.1±0.3

14.7±0.2

13.3±0.2

15.5±0.3

A

B

StHs6/80-G Ref.1

193 nm excimer A

B

257 nm fs A

B

Ref.1

4.36±0.47

4.51±0.51

4.5±0.4

25.2±0.8

21.4±0.7

21.2±0.8

21.0±0.9

0.66±0.34

0.68±0.35

0.62±0.14

2.69±0.93

2.30±0.83

1.41±1.47

1.40±1.46

1.2±0.1

5.19±1.57

5.39±1.72

2.5±0.6

16.2±1.7

13.8±1.7

16.3±4.6

16.1±4.4

11.8±1.3

2.44±0.01

2.18±0.08

2.25±0.05

2.40±0.06

5.47±0.15

4.65±0.03

4.57±0.15

4.52±0.12

4.44±0.14

5.89±0.13

5.99±0.15

6.19±0.19

6.59±0.08

1.94±0.04

1.65±0.02

1.75±0.05

1.73±0.04

1.97±0.04

13.4±0.1

14.6±0.3

15.1±0.3

13.6±0.2

20.2±0.4

17.2±0.1

18.9±0.7

18.7±0.2

17.8±0.2

MA N

Li Be

257 nm fs

US

193 nm excimer

CR

KL2-G Element

IP

T

Table 2a. Element concentrations for KL2-G, MLB-3G and StHs6/80-G obtained by 193 nm excimer LA-ICP-MS and 257 nm fs-LA-ICP-MS. Values are in units of μg g-1 except for major elements Na2O, MgO, Al2O3, SiO2, P2O5, K2O, CaO, TiO2, MnO, and FeO which are specified in weight percent (% m/m). Error bars represent the standard deviation (1s) from 12 measurements.

SiO2

59.0±1.2

53.5±0.3

48.4±2.1

50.5±0.8

50.3±0.3

63.4±1.6

50.3±2.4

51.9±1.1

51.4±0.6

76.8±2.1

65.4±0.3

63.8±2.5

63.2±0.4

63.7±0.5

P2O5

0.26±0.01

0.24±0.01

0.24±0.02

0.25±0.02

0.23±0.03

0.25±0.01

0.21±0.00

0.23±0.02

0.23±0.01

0.23±0.03

0.18±0.01

0.15±0.00

0.17±0.01

0.17±0.02

0.16±0.02

TE D

54.9±0.3

20.7±2.3

0.59±0.01

0.530±0.004

0.46±0.02

0.48±0.01

0.48±0.01

0.49±0.01

0.42±0.01

0.38±0.02

0.39±0.01

0.385±0.004

1.63±0.05

1.39±0.02

1.40±0.06

1.38±0.07

1.29±0.02

10.9±0.0

9.88±0.17

10.9±0.0

11.4±0.3

10.9±0.2

10.5±0.0

9.1±0.2

10.5±0.0

10.9±0.3

10.5±0.1

5.28±0.00

4.5±0.1

5.28±0.00

5.23±0.18

5.28±0.09

Sc

29.8±1.1

27.0±0.8

31.2±1.1

32.7±1.3

31.8±0.9

28.2±1.1

24.4±0.8

30.4±1.1

31.4±1.6

31.6±1.6

10.1±0.6

8.57±0.41

10.2±0.5

10.1±0.6

11.5±0.8

TiO2

2.53±0.08

2.29±0.08

2.53±0.05

2.64±0.08

2.56±0.09

2.12±0.04

1.84±0.07

2.07±0.05

2.14±0.07

2.13±0.09

0.71±0.02

0.60±0.01

0.69±0.02

0.68±0.01

0.70±0.02

V

348±11

316±5

312±12

326±5

309±38

326±8

283±1

282±12

292±6

268±23

97.4±2.7

82.9±0.5

85.5±3.3

84.6±2.4

90.3±6.7

Cr

316±19

286±12

265±8

277±10

294±27

192±20

166±15

150±8

155±5

177±23

8.82±7.81

7.47±6.60

13.3±3.3

13.2±3.3

16.9±3.3

MnO

0.19±0.01

0.170±0.005

0.160±0.004

0.170±0.003

0.17±0.01

0.20±0.01

0.180±0.005

0.170±0.004

0.170±0.003

0.17±0.01

0.084±0.002

0.071±0.001

0.073±0.003

0.072±0.002

0.076±0.004

FeO

12.2±0.4

11.0±0.4

10.0±0.3

10.5±0.3

10.7±0.1

13.1±0.6

11.4±0.4

10.2±0.3

10.6±0.4

10.9±0.1

4.98±0.24

4.24±0.25

4.11±0.17

4.08±0.14

4.37±0.07

Co

52.4±2.3

47.5±1.6

41.3±1.6

43.2±1.5

41.2±2.3

54.5±2.3

47.2±1.7

41.9±1.9

43.3±1.0

41.2±3.5

15.3±1.1

13.0±0.9

12.6±0.7

12.5±0.6

13.2±1.1

Ni

139±7

126±6

103±8

107±6

112±5

132±8

115±5

102±6

106±5

107±9

21.7±4.8

18.5±4.2

19.0±1.9

18.9±1.8

23.7±3.8

Cu

106±3

95.7±1.8

84.3±3.3

88.1±2.5

87.9±9.1

145±6

126±3

111±4

115±5

112±10

44.2±2.2

37.6±2.1

36.7±2.2

36.4±2.6

41.5±8.3

Zn

127±3

115±4

124±7

130±8

110±10

135±7

117±7

125±11

129±11

108±14

64.0±3.2

54.5±3.8

64.7±5.1

64.2±5.1

67±7

Ga

23.9±0.7

21.6±0.7

19.0±1.1

19.9±1.0

20.0±1.2

22.9±2.2

19.8±1.6

18.8±1.6

19.5±1.4

19.6±2.1

23.0±1.0

19.6±0.8

18.6±1.3

18.4±1.0

20.9±2.7

Rb

10.2±0.7

9.26±0.56

8.23±0.88

8.59±0.71

8.7±0.4

7.44±1.14

6.44±0.94

5.73±0.39

5.92±0.37

5.80±0.21

35.3±1.9

30.0±1.3

29.7±1.0

29.4±1.3

30.7±1.7

AC

CE P

K2O CaO

Sr

355±4

322±3

358±7

374±9

356±8

319±3

276±5

315±3

325±7

312±4

501±11

426±5

496±12

492±9

482±8

Y

22.9±0.8

20.7±0.8

24.7±0.5

25.8±0.8

25.4±1.1

22.2±1.3

19.3±1.4

23.1±0.8

23.9±1.1

23.9±0.7

10.7±0.7

9.08±0.61

11.9±0.8

11.8±0.9

11.4±0.4

Zr

142±6

128±6

150±4

157±3

152±5

110±5

95.1±3.8

124±4

128±6

122±3

115±9

97.6±7.9

122±6

121±5

118±3

39

ACCEPTED MANUSCRIPT

A

B

MLB-3G

257 nm fs A

B

193 nm excimer

Ref.1

A

B

257 nm fs

A

14.8±0.6

13.4±0.3

14.3±0.6

14.9±0.6

15.0±0.5

8.63±0.55

7.47±0.41

Cs

0.18±0.11

0.16±0.10

0.075±0.072

0.078±0.075

0.12±0.01

0.14±0.11

0.12±0.09

Ba

127±5

115±3

124±5

129±6

123±5

87.6±2.4

75.9±2.3

La

13.1±0.5

11.9±0.5

13.3±0.3

13.9±0.5

13.1±0.2

9.07±0.32

7.86±0.38

B

StHs6/80-G Ref.1

193 nm excimer

257 nm fs

A

B

A

B

Ref.1

8.38±0.37

8.65±0.36

8.61±0.22

6.68±0.44

5.68±0.35

6.63±0.58

6.57±0.57

6.94±0.25

0.15±0.08

0.16±0.09

0.14±0.01

2.26±0.42

1.93±0.35

1.71±0.18

1.70±0.19

1.75±0.11

81.2±3.3

83.9±3.4

80.1±2.2

339±6

289±6

307±6

304±11

298±9

9.02±0.48

9.32±0.42

8.99±0.13

11.8±0.7

10.0±0.4

12.1±0.7

11.9±0.4

12.0±0.3

MA N

Nb

US

193 nm excimer

CR

KL2-G Element

IP

T

Table 2a (continued). Element concentrations for KL2-G, MLB-3G and StHs6/80-G obtained by 193 nm excimer LA-ICP-MS and 257 nm fs-LA-ICP-MS. Values are in units of μg g-1 except for major elements Na2O, MgO, Al2O3, SiO2, P2O5, K2O, CaO, TiO2, MnO, and FeO which are specified in weight percent (% m/m). Error bars represent the standard deviation (1s) from 12 measurements.

Ce

33.3±1.3

30.1±0.9

32.2±1.1

33.7±1.5

32.4±0.7

24.0±0.9

20.8±0.7

23.0±0.7

23.7±0.9

23.1±0.3

26.6±1.1

22.6±0.5

26.3±1.0

26.0±1.1

26.1±0.7

Pr

4.54±0.24

4.11±0.18

4.57±0.20

4.78±0.20

4.6±0.1

3.31±0.18

2.87±0.15

3.35±0.20

3.46±0.22

3.43±0.06

3.26±0.33

2.78±0.32

3.38±0.24

3.35±0.26

3.20±0.06

20.9±2.4

18.9±2.1

21.0±0.9

21.9±0.9

21.6±0.4

15.8±1.3

16.3±1.1

16.8±1.3

16.7±0.2

12.7±1.0

10.8±0.9

13.0±1.4

12.9±1.6

13.0±0.3

5.43±0.74

4.92±0.69

5.85±0.51

6.11±0.55

5.54±0.09

4.53±0.46

3.92±0.33

13.7±1.3

4.17±0.50

4.31±0.55

4.75±0.07

3.07±0.57

2.62±0.51

3.17±0.55

3.14±0.51

2.78±0.05

2.02±0.15

1.83±0.16

2.01±0.12

2.10±0.14

1.92±0.04

1.83±0.11

1.58±0.09

1.62±0.18

1.67±0.17

1.67±0.02

1.08±0.15

0.92±0.11

0.97±0.36

0.96±0.34

0.95±0.02

5.46±0.57

4.94±0.51

5.91±0.64

6.18±0.71

5.92±0.20

4.43±1.26

3.83±1.05

5.11±0.72

5.29±0.82

5.26±0.23

2.08±0.64

1.76±0.51

3.23±0.60

3.20±0.61

2.59±0.09

Tb

0.95±0.17

0.86±0.15

0.88±0.09

0.92±0.09

0.89±0.03

0.71±0.13

0.62±0.13

0.83±0.11

0.86±0.12

0.80±0.02

0.38±0.12

0.33±0.10

0.36±0.11

0.35±0.11

0.37±0.01

Dy

4.94±0.24

4.48±0.27

5.23±0.30

5.46±0.29

5.22±0.12

4.43±0.85

3.84±0.75

4.69±0.61

4.84±0.62

4.84±0.07

1.91±0.44

1.63±0.39

2.31±0.59

2.28±0.57

2.22±0.06

Ho

0.92±0.09

0.83±0.08

0.99±0.07

1.03±0.08

0.96±0.02

0.84±0.14

0.72±0.11

0.89±0.11

0.92±0.13

0.91±0.02

0.47±0.13

0.40±0.11

0.46±0.13

0.46±0.12

0.42±0.01

Er

2.65±0.53

2.40±0.51

2.28±0.19

2.38±0.20

2.54±0.07

2.43±0.50

2.11±0.47

2.39±0.39

2.47±0.43

2.44±0.05

1.11±0.35

0.94±0.28

1.19±0.32

1.18±0.30

1.18±0.04

Tm

0.26±0.08

0.24±0.07

0.32±0.07

0.34±0.07

0.33±0.01

0.28±0.02

0.24±0.02

0.32±0.11

0.34±0.11

0.32±0.01

0.091±0.074

0.078±0.062

0.17±0.09

0.16±0.09

0.17±0.01

Yb

1.65±0.49

1.50±0.45

2.16±0.42

2.25±0.41

2.10±0.05

2.11±0.45

1.83±0.41

1.85±0.39

1.91±0.41

2.06±0.04

1.11±0.65

0.94±0.53

0.83±0.58

0.83±0.57

1.13±0.03

Lu

0.19±0.06

0.17±0.05

0.30±0.07

0.31±0.07

0.29±0.01

0.32±0.12

0.28±0.11

0.29±0.04

0.30±0.04

0.29±0.01

0.17±0.06

0.14±0.05

0.17±0.12

0.17±0.12

0.17±0.01

Hf

3.86±0.60

3.5±0.6

4.30±0.45

4.50±0.52

3.93±0.14

3.13±0.39

2.71±0.32

3.40±0.59

3.52±0.62

3.22±0.08

3.09±0.36

2.63±0.29

3.23±0.64

3.20±0.61

3.07±0.09

Ta

0.81±0.12

0.74±0.10

0.89±0.08

0.93±0.09

0.96±0.02

0.50±0.08

0.43±0.06

0.55±0.07

0.57±0.07

0.56±0.01

0.38±0.12

0.32±0.10

0.33±0.11

0.33±0.12

0.42±0.02

W

0.70±0.56

0.64±0.52

0.4±0.2

0.42±0.21

0.37±0.06

0.18±0.13

0.16±0.11

0.47±0.10

0.49±0.11

0.35±0.09

0.28±0.38

0.24±0.32

0.27±0.20

0.27±0.19

0.47±0.18

Pb

2.08±0.36

1.89±0.32

1.56±0.25

1.63±0.28

2.07±0.10

1.37±0.32

1.18±0.28

1.06±0.23

1.09±0.23

1.38±0.07

9.54±0.57

8.12±0.49

8.42±0.91

8.33±0.77

10.3±0.9

Th

0.92±0.13

0.84±0.12

1.01±0.12

1.05±0.13

1.02±0.03

0.59±0.17

0.51±0.15

0.52±0.08

0.54±0.08

0.55±0.01

2.18±0.26

1.85±0.20

2.34±0.37

2.32±0.35

2.28±0.07

U

0.64±0.06

0.58±0.05

0.53±0.11

0.56±0.11

0.55±0.02

0.43±0.06

0.38±0.05

0.42±0.11

0.43±0.12

0.44±0.02

1.21±0.20

1.03±0.17

1.02±0.18

1.01±0.17

1.01±0.04

CE P

Eu Gd

AC

TE D

Nd Sm

A=Calibrated against NIST SRM 610 and applying Ca internal standardization; B=Calibrated against NIST SRM 610 and applying 100% oxide normalization. 1

: Jochum et al. (2006); 2: the GeoReM database (http://georem.mpch-mainz.gwdg.de/); 3: Jochum et al. (2011).

40

ACCEPTED MANUSCRIPT

A

B

BCR-2G

257 nm fs A

B

193 nm excimer

Ref.1

A

B

257 nm fs

A

27.3±1.1

22.9±1.0

21.3±1.1

21.1±0.6

19.9±0.9

11.3±0.4

9.97±0.29

1.21±0.84

1.01±0.69

2.04±0.45

2.03±0.46

2.0±0.6

2.49±1.24

2.19±1.08

B

6.48±1.55

5.43±1.26

8.56±2.14

8.50±2.16

4.1±1.1

18.2±4.1

16.1±3.8

Na2O

3.83±0.09

3.21±0.02

3.07±0.17

3.04±0.09

3.13±0.09

3.80±0.08

MgO

3.71±0.09

3.11±0.06

3.37±0.09

3.34±0.04

3.75±0.04

3.38±0.07

Al2O3

19.2±0.3

16.1±0.1

18.4±0.6

18.2±0.2

17.1±0.2

14.8±0.3

B

BHVO-2G Ref.2

193 nm excimer

257 nm fs

A

B

A

B

Ref.2

9.23±1.00

9.17±0.87

9±1

5.2±0.5

4.62±0.46

4.48±0.32

4.55±0.33

4.4±0.8

2.33±0.79

2.32±0.81

2.3±0.4

1.14±0.23

1.01±0.20

1.06±0.44

1.07±0.44

1.3±0.2

9.07±2.13

9.01±2.06

6±1

6.37±0.96

5.66±0.86

5.06±1.56

5.13±1.57

3.36±0.04

3.14±0.20

3.12±0.14

3.23±0.07

2.62±0.02

2.33±0.01

2.09±0.06

2.12±0.08

2.4±0.1

2.99±0.04

3.21±0.06

3.19±0.06

3.56±0.09

7.11±0.06

6.32±0.06

6.63±0.13

6.74±0.16

7.13±0.02

13.1±0.1

14.2±0.4

14.2±0.5

13.4±0.4

14.8±0.0

13.2±0.1

14.4±0.4

14.6±0.3

13.6±0.1

MA N

Li Be

US

193 nm excimer

CR

T1-G Element

IP

T

Table 2b. Element concentrations for T1-G, BCR-2G and BHVO-2G obtained by 193 nm excimer LA-ICP-MS and 257 nm fs-LA-ICP-MS. Values are in units of μg g-1 except for major elements Na2O, MgO, Al2O3, SiO2, P2O5, K2O, CaO, TiO2, MnO, and FeO which are specified in weight percent (% m/m). Error bars represent the standard deviation (1s) from 12 measurements.

73.8±1.8

61.9±0.5

59.3±1.6

58.7±0.3

58.6±0.4

64.4±1.1

56.2±1.9

55.9±0.7

54.4±0.4

59.8±0.6

53.1±0.4

49.9±1.0

50.7±0.4

49.3±0.1

0.18±0.00

0.15±0.00

0.18±0.01

0.18±0.01

0.17±0.03

0.36±0.02

0.32±0.02

56.9±0.5

0.35±0.02

0.35±0.02

0.37±0.01

0.28±0.01

0.25±0.01

0.25±0.01

0.26±0.01

0.29±0.02

2.61±0.05

2.19±0.03

2.29±0.08

2.27±0.07

1.96±0.04

2.24±0.04

1.98±0.02

2.00±0.19

1.99±0.16

1.74±0.04

0.630±0.003

0.56±0.01

0.52±0.03

0.53±0.03

0.51±0.02

7.1±0.0

5.96±0.11

7.1±0.0

7.04±0.19

7.1±0.09

7.06±0.00

6.25±0.09

7.06±0.00

7.02±0.16

7.06±0.11

11.4±0.0

10.1±0.1

11.4±0.0

11.6±0.2

11.4±0.1

Sc

23.8±0.6

19.9±0.5

26.9±0.7

26.7±0.6

26.9±1.1

32.1±0.7

28.4±0.7

33.2±1.0

33±1

33±2

30.3±0.9

26.9±1.0

31.7±0.9

32.2±0.7

33±2

TiO2

0.74±0.01

0.62±0.02

0.74±0.02

0.73±0.01

0.76±0.02

2.28±0.03

2.01±0.02

2.22±0.05

2.21±0.05

2.27±0.04

2.72±0.03

2.41±0.01

2.65±0.05

2.69±0.04

2.79±0.02

V

216±5

181±2

187±11

185±6

190±11

470±14

416±10

433±11

431±12

425±18

352±5

313±4

315±8

320±7

308±19

Cr

14.2±4.7

11.9±4.0

15.1±2.9

14.9±2.8

20.9±2.0

17.5±5.3

15.5±4.5

17.3±1.8

17.2±2.1

17±2

317±14

282±13

273±12

277±11

293±12

MnO

0.150±0.004

0.130±0.001

0.13±0.01

0.130±0.003

0.13±0.01

0.220±0.004

0.190±0.003

0.200±0.004

0.200±0.003

0.19±0.01

0.190±0.003

0.170±0.002

0.170±0.003

0.170±0.003

0.17±0.03

FeO

7.72±0.53

6.48±0.45

6.18±0.35

6.12±0.23

6.44±0.06

14.2±0.8

12.5±0.7

11.6±0.4

11.6±0.5

12.4±0.3

12.6±0.8

11.2±0.6

10.2±0.3

10.4±0.2

11.3±0.1

Co

24.2±0.7

20.3±0.5

18.4±0.8

18.2±0.4

18.9±0.8

44.5±0.8

39.3±1.0

38.3±1.8

38.1±1.6

38±2

54.4±1.0

48.4±0.8

44.5±1.4

45.3±1.5

44±2

Ni

11.0±2.5

9.2±2.0

9.63±1.49

9.55±1.60

10.6±1.3

16.8±1.9

14.9±1.7

12.4±1.0

12.3±0.8

13±2

146±8

130±8

115±6

117±5

116±7

Cu

22.4±1.6

18.8±1.1

18.9±1.8

18.8±1.8

18.8±2.0

23.6±1.5

20.9±1.5

17.4±1.2

17.3±1.0

21±5

152±4

135±4

120±4

122±4

127±11

Zn

81.1±4.6

68.1±4.8

70.8±5.2

70.1±4.4

74±10

167±8

148±6

174±9

173±7

125±5

137±6

122±5

123±10

125±11

102±6

Ga

22.7±1.4

19.1±1.3

18.2±0.9

18.0±0.6

19.4±0.9

24.8±1.1

22.0±0.8

21.7±1.0

21.6±1.0

23±1

24.5±0.5

21.8±0.5

19.9±1.0

20.2±1.1

22±3

Rb

104±4

86.9±2.3

85±4

84.2±2.9

79.7±3.5

56.5±2.4

49.9±2.0

47.6±2.7

47.3±2.0

47.0±0.5

11.2±0.8

9.97±0.66

8.79±0.36

8.93±0.41

9.20±0.04 396±1

CE P

K2O CaO

AC

TE D

SiO2 P2O5

Sr

293±4

245±1

300±7

297±3

284±6

340±4

301±5

334±7

332±9

342±4

392±6

349±4

389±9

395±8

Y

22.0±0.4

18.4±0.6

24.7±0.8

24.5±0.5

23.9±0.8

30.6±0.7

27.1±0.6

32.9±0.9

32.7±1.0

35±3

22.4±0.7

19.9±0.6

23.1±0.7

23.4±0.7

26±2

Zr

134±6

112±5

158±4

157±2

144±4

169±7

150±5

178±4

177±5

184±15

151±5

134±5

161±5

164±4

170±7

41

ACCEPTED MANUSCRIPT

BCR-2G

257 nm fs

193 nm excimer

Ref.1

A

B

A

B

Nb

9.28±0.46

7.78±0.34

8.80±0.72

8.71±0.57

8.87±0.43

12.2±0.3

10.8±0.3

Cs

3.41±0.35

2.86±0.26

2.90±0.35

2.88±0.38

2.69±0.19

1.20±0.17

1.06±0.14

Ba

443±7

371±6

427±21

423±13

388±12

720±5

La

70.4±0.7

59.0±0.6

73.7±2.5

73.0±1.2

70.4±2.4

24.3±0.4

B

A

637±8

B

BHVO-2G Ref.2

193 nm excimer A

B

257 nm fs A

B

Ref.2

11.8±0.4

11.7±0.4

12.5±1.0

17.5±0.6

15.6±0.7

17.2±0.6

17.4±0.5

18.3±0.8

1.11±0.11

1.10±0.09

1.16±0.07

0.14±0.12

0.13±0.11

0.10±0.06

0.10±0.06

0.10±0.02

674±25

670±19

683±7

138±5

122±4

130±4

132±4

131±2

21.5±0.5

24.5±0.6

24.4±0.7

24.7±0.3

14.9±0.4

13.3±0.4

15.1±0.5

15.3±0.5

15.2±0.2

MA N

A

257 nm fs

US

193 nm excimer

CR

T1-G Element

IP

T

Table 2b (continued). Element concentrations for T1-G, BCR-2G and BHVO-2G obtained by 193 nm excimer LA-ICP-MS and 257 nm fs-LA-ICP-MS. Values are in units of μg g-1 except for major elements Na2O, MgO, Al2O3, SiO2, P2O5, K2O, CaO, TiO2, MnO, and FeO which are specified in weight percent (% m/m). Error bars represent the standard deviation (1s) from 12 measurements.

Ce

133±2

112±1

130±4

129±3

127±4

53.4±1.3

47.3±1.0

51.6±1.7

51.3±1.4

53.3±0.5

38.5±0.4

34.2±0.4

36.7±0.8

37.3±0.9

37.6±0.2

Pr

12.9±0.6

10.8±0.4

13.0±0.7

12.8±0.5

12.4±0.4

6.51±0.22

5.76±0.26

6.6±0.3

6.57±0.32

6.7±0.4

5.36±0.15

4.77±0.14

5.14±0.20

5.22±0.21

5.35±0.22

40.7±3.0

34.2±3.1

42.4±3.7

41.9±3.3

41.4±1.2

28.3±2.0

28.9±1.0

28.7±1.2

28.9±0.3

24.1±2.2

21.4±2.0

24.1±1.3

24.5±1.2

24.5±0.2

6.37±0.94

5.33±0.75

7.08±0.86

7.01±0.81

6.57±0.14

6.10±0.81

5.40±0.75

25.1±1.5

6.58±0.67

6.56±0.75

6.59±0.07

6.05±0.39

5.38±0.35

6.11±0.51

6.2±0.5

6.10±0.03

1.12±0.23

0.94±0.20

1.26±0.16

1.25±0.16

1.21±0.04

2.03±0.39

1.80±0.37

1.88±0.20

1.86±0.17

1.97±0.02

1.90±0.21

1.69±0.19

2.09±0.22

2.12±0.21

2.07±0.01

4.76±1.14

4.00±0.97

53.0±0.7

5.26±0.71

5.31±0.29

6.41±0.93

5.66±0.76

6.58±0.98

6.54±1.01

6.71±0.07

6.11±0.48

5.43±0.40

6.05±0.67

6.15±0.71

6.16±0.05

Tb

0.70±0.15

0.59±0.12

0.72±0.18

0.71±0.17

0.77±0.03

0.93±0.07

0.83±0.05

0.96±0.13

0.95±0.12

1.02±0.08

0.86±0.08

0.77±0.07

0.84±0.06

0.86±0.06

0.92±0.04

Dy

4.27±0.66

3.58±0.54

4.48±0.31

4.43±0.28

4.50±0.12

5.94±0.47

5.25±0.45

6.35±0.51

6.32±0.47

6.44±0.06

4.97±0.32

4.42±0.28

4.97±0.45

5.05±0.43

5.28±0.05

Ho

0.83±0.06

0.69±0.06

0.86±0.10

0.85±0.10

0.86±0.03

1.24±0.07

1.10±0.05

1.29±0.11

1.28±0.11

1.27±0.08

0.95±0.09

0.84±0.09

0.90±0.09

0.91±0.09

0.98±0.04

Er

2.36±0.30

1.98±0.28

2.84±0.35

2.82±0.38

2.49±0.08

3.53±0.39

3.12±0.36

3.78±0.33

3.76±0.34

3.70±0.04

2.52±0.30

2.24±0.26

2.43±0.28

2.47±0.29

2.56±0.02

Tm

0.38±0.08

0.32±0.06

0.35±0.07

0.35±0.07

0.35±0.02

0.44±0.05

0.39±0.04

0.51±0.06

0.51±0.06

0.51±0.04

0.34±0.06

0.30±0.05

0.30±0.06

0.30±0.06

0.34±0.02

Yb

2.24±0.44

1.88±0.35

2.39±0.87

2.38±0.88

2.38±0.08

3.17±0.42

2.81±0.39

3.23±0.44

3.21±0.43

3.39±0.03

1.56±0.38

1.38±0.33

1.89±0.31

1.92±0.32

2.01±0.02

Lu

0.33±0.04

0.28±0.03

0.37±0.08

0.36±0.07

0.35±0.01

0.52±0.10

0.46±0.10

0.51±0.07

0.51±0.07

0.503±0.005

0.18±0.09

0.16±0.08

0.29±0.07

0.29±0.07

0.279±0.003

Hf

3.43±0.40

2.88±0.30

3.96±0.81

3.92±0.82

3.88±0.15

4.64±0.33

4.10±0.29

4.97±0.46

4.94±0.44

4.84±0.28

4.24±0.41

3.77±0.36

4.37±0.45

4.43±0.42

4.32±0.18

Ta

0.45±0.05

0.38±0.04

0.43±0.10

0.42±0.10

0.46±0.02

0.69±0.04

0.61±0.04

0.72±0.08

0.72±0.08

0.78±0.06

0.95±0.12

0.85±0.11

1.06±0.07

1.08±0.07

1.15±0.10

W

0.56±0.38

0.47±0.32

0.60±0.24

0.59±0.23

0.69±0.12

0.71±0.09

0.63±0.08

0.49±0.20

0.49±0.20

0.50±0.07

0.26±0.27

0.23±0.24

0.16±0.09

0.16±0.09

0.23±0.04

Pb

10.5±0.6

8.77±0.45

7.31±0.99

7.23±0.88

11.6±1.5

9.03±0.61

7.98±0.45

9.67±0.65

9.61±0.55

11±1

2.09±0.26

1.86±0.23

1.48±0.14

1.50±0.14

1.7±0.2

Th

31.0±0.8

26.0±0.5

33.8±1.0

33.4±0.4

31.3±1

5.79±0.28

5.12±0.19

5.82±0.28

5.79±0.28

5.9±0.3

1.25±0.11

1.11±0.10

1.22±0.11

1.24±0.12

1.22±0.05

U

1.94±0.07

1.63±0.07

1.60±0.14

1.58±0.13

1.71±0.10

2.17±0.16

1.92±0.17

1.73±0.14

1.72±0.12

1.69±0.12

0.49±0.12

0.44±0.11

0.44±0.05

0.45±0.05

0.403±0.003

CE P

Eu Gd

AC

TE D

Nd Sm

A=Calibrated against NIST SRM 610 and applying Ca internal standardization; B=Calibrated against NIST SRM 610 and applying 100% oxide normalization. 1

: Jochum et al. (2006); 2: the GeoReM database (http://georem.mpch-mainz.gwdg.de/); 3: Jochum et al. (2011).

42

ACCEPTED MANUSCRIPT

GSD-1G

257 nm fs

A

B

A

B

193 nm excimer

Ref.3

A

B

40.2±0.7

40.2±0.6

41.1±2.3

40.5±1.9

40.2±1.3

51.2±1.6

45.2±0.9

40.5±1.6

40.5±1.6

40.4±2.0

39.9±2.0

37.5±1.5

44.3±3.3

39.1±3.0

B

38.8±2.3

38.8±2.2

41.6±3.7

41.1±3.1

34.3±1.7

69.7±2.2

61.5±1.4

13.7±0.1

13.7±0.1

13.9±0.6

13.7±0.4

13.7±0.3

4.21±0.08 3.46±0.03 15.1±0.2

Na2O MgO Al2O3

0.0095±0.0006 0.0095±0.0006 0.0096±0.0005 0.0095±0.0005 0.011±0.001 2.01±0.02

2±0

2.01±0.05

1.98±0.03

2.03±0.04

A

B

GSE-1G Ref.2

193 nm excimer A

257 nm fs

B

A

B

Ref.2

42.8±1.8

43±2

43±6

503±9

439±7

423±16

419±12

44.2±2.3

44.4±2.0

46±5

476±12

415±10

456±13

452±10

490±80

63.7±2.2

64.0±1.8

50±20

441±8

384±9

398±16

394±13

330±120

3.72±0.02

3.51±0.09

3.52±0.07

3.6±0.2

4.58±0.07

3.99±0.05

3.83±0.12

3.80±0.07

3.9±0.2

3.06±0.02

3.25±0.04

3.27±0.06

3.60±0.04

3.44±0.06

3.00±0.05

3.23±0.09

3.20±0.07

3.50±0.03

13.4±0.2

14.5±0.3

14.5±0.2

13.4±0.3

15.3±0.2

13.3±0.3

14.4±0.3

14.2±0.2

13.0±0.4

MA N

Li Be

257 nm fs

US

193 nm excimer

CR

NIST SRM 612 Element

IP

T

Table 2c. Element concentrations for NIST SRM 612, GSD-1G and GSE-1G obtained by 193 nm excimer LA-ICP-MS and 257 nm fs-LA-ICP-MS. Values are in units of μg g-1 except for major elements Na2O, MgO, Al2O3, SiO2, P2O5, K2O, CaO, TiO2, MnO, and FeO which are specified in weight percent (% m/m). Error bars represent the standard deviation (1s) from 12 measurements.

72.2±0.8

72.1±0.2

73.2±2.2

72.2±0.5

72.1±0.6

63.3±1.3

53.8±1.3

53.9±0.6

53.2±0.8

63.2±0.9

55.1±0.4

54.2±1.1

53.7±0.6

53.7±1.5

0.017±0.002

0.017±0.002

0.015±0.006

0.015±0.006

0.011±0.002

0.24±0.02

0.21±0.01

0.22±0.02

0.22±0.01

0.20±0.05

0.018±0.003

0.016±0.002

0.023±0.009

0.022±0.008

0.016±0.005

3.45±0.05

3.26±0.14

3.27±0.18

3.0±0.1

3.40±0.06

2.96±0.05

2.87±0.18

2.84±0.18

2.6±0.1

11.9±0.0

11.9±0.1

11.9±0.0

11.7±0.3

11.9±0.1

7.21±0.00

6.36±0.10

7.21±0.00

7.23±0.14

7.2±0.1

7.42±0.00

6.47±0.10

7.42±0.00

7.35±0.12

7.4±0.3

Sc

37.5±0.9

37.5±0.7

38.1±1.2

37.6±1.1

39.9±2.5

48.3±1.3

42.7±1.3

51.3±0.9

51.5±1.7

52±2

514±4

448±9

531±8

526±7

530±20

CE P

3.91±0.10

CaO

1.30±0.01

1.15±0.02

1.28±0.03

1.29±0.02

1.24±0.06

0.075±0.004

0.065±0.003

0.074±0.002

0.073±0.002

0.075±0.007

V

0.0073±0.0007 0.0073±0.0007 0.0067±0.0006 0.0067±0.0007 0.0073±0.0004 38.8±0.9

38.8±0.8

38.9±1.9

38.4±2.2

38.8±1.2

47±1

41.5±0.7

42.4±1.3

42.5±1.2

44±2

477±10

416±8

417±10

413±7

440±20

Cr

36.2±7.3

36.2±7.5

36.8±3.2

36.4±3.4

36.4±1.5

44.6±5.0

39.3±4.3

41.3±1.8

41.5±2.1

42±3

424±18

370±16

364±12

361±10

400±80

0.027±0.000

0.027±0.001

0.028±0.000

0.028±0.003

0.084±0.000

0.073±0.001

0.074±0.002

0.073±0.002

0.076±0.003

12.5±0.5

12.4±0.8

12.4±0.7

13.3±0.1

14.4±1.1

12.5±0.9

12.0±0.8

11.9±0.7

12.7±0.3

14.1±0.6

Co

34.5±0.5

34.4±0.5

34.7±1.0

34.2±0.9

AC

TiO2

0.0062±0.0008 0.0062±0.0008 0.0074±0.0007 0.0073±0.0007 0.0075±0.0003

TE D

SiO2 P2O5 K2O

55.9±0.4

430±60

35.5±1.0

45.7±1.4

40.3±1.4

39.2±1.3

39.4±1.0

40±2

449±6

391±4

377±10

374±8

380±20

Ni

41.7±3.0

41.7±3.3

39.6±2.6

39.1±2.8

38.8±0.2

71.6±3.2

63.2±2.5

58.5±3.3

58.7±3.5

58±4

525±9

457±13

427±11

423±5

440±30

Cu

39.9±0.8

39.9±0.6

36.6±1.8

36.1±1.9

37.8±1.5

47.9±2.1

42.3±2.0

39.7±1.6

39.9±1.6

42±2

440±7

383±6

381±11

377±10

380±40

Zn

41.6±1.3

41.6±1.4

35.7±2.6

35.2±2.2

39.1±1.7

59.3±3.2

52.4±2.9

64.8±2.7

65.1±2.9

54±2

491±6

428±4

613±36

607±35

460±10

Ga

37.2±1.5

37.2±1.3

36.5±1.5

36.0±1.4

36.9±1.5

63.5±1.6

56.1±1.9

55.7±1.3

55.9±1.5

54±7

594±13

518±5

534±15

529±11

490±70

Rb

31.2±0.8

31.2±0.8

31.7±1.1

31.3±1.0

31.4±0.4

45.2±1.9

39.9±1.2

37.6±1.6

37.8±1.9

37.3±0.4

444±2

387±6

367±16

364±13

356±4

Sr

78.3±1.7

78.3±1.5

78.4±1.8

77.4±2.3

78.4±0.2

70.9±1.4

62.6±0.9

69.6±1.3

69.8±1.8

69.4±0.7

463±2

404±6

456±7

452±7

447±5

Y

38.1±1.1

38.1±1.0

36.8±0.8

36.4±0.8

38.3±1.4

38.8±1.0

34.2±0.9

41.5±0.9

41.6±1.3

42±2

411±3

359±7

433±7

429±9

410±30

Zr

37.4±3.7

37.3±3.4

37.0±1.5

36.5±1.6

37.9±1.2

40.9±2.0

36.1±1.8

42.9±1.8

43.0±1.7

42±2

401±9

350±10

425±5

422±8

410±30

MnO

0.0050±0.0001 0.0050±0.0001 0.0051±0.0001 0.0050±0.0005 0.0050±0.0001 0.031±0.001

FeO

0.0039±0.0025 0.0039±0.0024 0.008±0.0023 0.0078±0.0022 0.0066±0.0003

43

ACCEPTED MANUSCRIPT

GSD-1G

257 nm fs A

B

Nb

38.6±0.6

38.6±0.3

38.1±1.1

37.6±0.8

Cs

41.7±1.1

41.7±1.2

41.8±2.0

41.3±1.5

Ba

40.9±2.1

40.9±2.3

39.2±1.6

La

36.2±0.6

36.2±0.7

Ce

38.8±0.4

Pr

Ref.3

A

B

38.9±2.1

46.3±1.2

40.9±1.0

42.7±1.8

36.9±0.4

32.6±0.4

38.7±1.7

39.3±0.9

73.0±3.2

64.5±2.4

34.9±0.6

34.4±0.7

36.0±0.7

38.8±0.6

38.8±0.4

38.9±1.2

38.4±1.2

38.4±0.7

37.9±0.9

37.8±0.6

37.5±1.0

37.0±0.8

A

B

GSE-1G Ref.2

193 nm excimer A

B

257 nm fs A

B

Ref.2

42.8±1.2

43.0±1.4

42±3

466±4

406±7

441±8

437±8

420±40

30.1±1.1

30.2±1.2

32±2

353±6

308±5

293±12

290±12

310±20

68.7±2.8

69.0±2.7

67±1

469±11

409±8

431±11

427±11

427±5

34.2±0.9

39.3±0.7

39.5±0.8

39.1±0.4

402±5

351±6

407±6

403±5

392±4

42.6±0.8

37.6±0.3

41.0±1.1

41.1±0.9

41.4±0.4

432±6

376±7

415±10

411±8

414±4

37.9±1.0

46.3±1.1

40.9±1.0

45.5±1.1

45.7±1.0

45±1

479±5

418±9

475±10

471±7

460±10

39.7±2.2

453±5

MA N

B

257 nm fs

35.1±2.1

35.1±2.0

35.4±2.0

35.0±2.3

35.5±0.7

44.9±1.8

44.7±1.8

44.9±2.0

44.7±0.5

460±11

401±15

459±13

454±12

38.4±1.4

38.4±1.3

36.5±1.4

36.1±1.4

37.7±0.8

47.2±1.8

41.7±2.1

47.8±1.4

48.0±1.2

47.8±0.5

497±10

433±12

506±12

502±11

488±5

Eu

35.4±0.5

35.4±0.7

35.1±0.8

34.7±0.9

35.6±0.8

40.3±0.6

35.6±0.8

41.0±1.3

41.2±1.0

41±2

417±4

363±8

419±8

415±6

410±20

Gd

36.8±2.9

36.8±2.7

36.1±1.4

35.7±1.5

37.3±0.9

47.8±1.2

42.2±1.7

50.1±1.5

50.3±1.1

50.7±0.5

509±8

444±12

533±11

528±8

514±6

Tb

36.9±0.6

36.9±0.3

35.4±1.0

34.9±0.4

37.6±1.1

45.4±0.7

40.1±0.8

47.8±1.0

48.0±1.8

47±2

486±6

424±8

508±8

503±9

480±20

Dy

35.4±0.7

35.4±0.8

34.8±1.2

34.3±1.2

35.5±0.7

49.3±0.8

43.6±1.2

52.0±1.6

52.2±2.3

51.2±0.5

522±12

455±17

548±8

543±10

524±6

Ho

37.4±0.7

37.4±0.4

36.3±0.8

35.8±0.7

38.3±0.8

47.8±1.0

42.3±1.3

50.0±0.6

50.2±1.3

49±2

502±7

438±12

529±10

524±8

501±8

Er

38.0±1.2

38.0±1.2

37.1±0.9

36.7±0.9

38.0±0.9

38.1±1.5

33.6±1.2

39.7±1.1

39.9±1.4

40.1±0.4

533±58

466±58

616±11

610±12

595±6

Tm

35.9±0.9

35.9±0.9

35.2±0.9

34.8±0.7

36.8±0.6

48.1±0.8

42.5±1.0

50.1±1.3

50.3±1.6

49±2

507±6

442±12

533±7

528±4

500±20

Yb

37.6±2.7

37.6±2.8

37.0±1.2

36.5±1.1

39.2±0.9

50.1±1.7

44.3±1.4

50.7±1.4

50.9±1.5

50.9±0.5

511±5

446±11

534±12

529±9

520±5

Lu

35.4±0.9

35.4±0.7

35.1±0.8

34.6±0.5

37.0±0.9

49.2±1.2

43.5±0.8

51.8±0.9

52.0±1.1

51.5±0.5

516±7

450±11

543±9

538±8

518±6

Hf

36.5±1.6

36.5±1.6

35.7±1.1

35.3±1.3

36.7±1.2

40.6±1.1

35.9±1.4

40.8±0.9

41±1

39±2

410±6

358±7

431±9

427±6

395±7

Ta

36.6±0.3

36.6±0.4

36.4±0.7

35.9±0.9

37.6±1.9

41.9±1.1

37.0±0.8

41.8±0.9

41.9±1.0

40±4

423±4

369±7

433±6

429±6

390±40

CE P

TE D

Nd Sm

AC

A

193 nm excimer

US

193 nm excimer

CR

NIST SRM 612 Element

IP

T

Table 2c (continued). Element concentrations for NIST SRM 612, GSD-1G and GSE-1G obtained by 193 nm excimer LA-ICP-MS and 257 nm fs-LA-ICP-MS. Values are in units of μg g-1 except for major elements Na2O, MgO, Al2O3, SiO2, P2O5, K2O, CaO, TiO2, MnO, and FeO which are specified in weight percent (% m/m). Error bars represent the standard deviation (1s) from 12 measurements.

W

37.9±2.5

37.9±2.3

37.4±1.6

36.9±1.2

38.0±1.1

47.4±1.2

41.8±1.0

40.3±2.0

40.5±2.1

43±4

476±4

415±7

408±14

404±12

430±50

Pb

39.6±1.0

39.6±0.9

34.6±1.4

34.2±1.3

38.6±0.2

54.0±1.5

47.6±0.6

46.4±1.2

46.6±0.8

50±2

402±5

350±9

386±17

382±14

378±12

Th

37.3±0.8

37.3±0.5

36.6±0.9

36.1±0.8

37.8±0.1

39.3±0.7

34.7±0.9

50.6±1.8

50.8±2.3

41±2

377±23

329±24

400±8

396±6

380±20

U

38.0±0.3

38.0±0.4

37.9±1.4

37.4±1.3

37.4±0.1

45.6±1.5

40.3±1.1

41.1±1.1

41.3±1.0

41±2

456±5

398±10

413±12

409±9

420±30

A=Calibrated against NIST SRM 610 and applying Ca internal standardization; B=Calibrated against NIST SRM 610 and applying 100% oxide normalization. 1

: Jochum et al. (2006); 2: the GeoReM database (http://georem.mpch-mainz.gwdg.de/); 3: Jochum et al. (2011).

44

ACCEPTED MANUSCRIPT

AC

CE P

TE

D

MA

NU

SC R

IP

T

Graphic abstract

45

ACCEPTED MANUSCRIPT Highlights ► High spatial resolution analysis is highly desirable for analyzing minerals.

IP

T

► Elemental fractionation is significant for ns-LA-ICP-MS analysis with high spatial

SC R

resolution.

►The NIST 610-specific matrix effect is reduced by fs-LA-ICP-MS. ►The mass load effect is small in fs-LA-ICP-MS.

NU

►The fs-LA-ICP-MS technique is especially suitable for high spatial resolution

AC

CE P

TE

D

MA

analysis.

46