Open Access

Sm-Nd isotopic analysis of mixed standard solutions by multi-collector inductively coupled plasma mass spectrometry: evaluations on isobaric interference correction of Nd isotopic composition and external calibration of Sm/Nd ratio

  • Jong-Sik Ryu1,
  • Min Seok Choi1,
  • Youn-Joong Jeong1 and
  • Chang-sik Cheong1Email author
Journal of Analytical Science and Technology20134:8

DOI: 10.1186/2093-3371-4-8

Received: 12 March 2013

Accepted: 12 March 2013

Published: 18 April 2013



The Sm-Nd isotope system has long been used to provide information on the age and geochemical evolution of terrestrial rocks and extraterrestrial objects. Traditional thermal ionization mass spectrometry requires a refined chemical separation of Sm and Nd. Here, we present multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) Sm-Nd isotopic results for a series of mixed standard solutions with different Sm/Nd ratios to test the validity of isobaric interference corrections of Nd isotopic composition and external calibration of Sm/Nd inter-elemental ratio.


Reliable 143Nd/144Nd and 145Nd/144Nd ratios of the mixed solutions were obtained by using the exponential law and selected Sm isotopic compositions. The Sm/Nd ratios of the mixed solutions corrected by the standard bracketing method were consistent with the gravimetric values mostly within 1% difference.


This study provides a simple and high-throughput technique that can simultaneously measure Nd isotopic composition and Sm/Nd ratio without chemical separation between Sm and Nd.


Sm-Nd MC-ICP-MS Isobaric interference Isotopic composition Inter-elemental ratio


Sm and Nd are rare earth elements presenting in only small amounts in most rock-forming minerals. Sm and Nd each have seven naturally occurring isotopes (144Sm, 147Sm, 148Sm, 149Sm, 150Sm, 152Sm, 154Sm; 142Nd, 143Nd, 144Nd, 145Nd, 146Nd, 148Nd, 150Nd). One isotope of Sm (147Sm) decays by α-emission to one isotope of Nd (143Nd) with a half-life of 106 Ga (Lugmair & Marti 1978; Begemann et al. 2001). The Sm-Nd decay system has been efficiently used for determining the timing of major events occurred during the chemical evolution of planets and probing into the earth's interior (DePaolo 1988). The application of this system demands highly accurate Sm-Nd isotope data because its half-life is very long and natural variations in Sm/Nd inter-elemental ratio are typically quite limited.

Although the traditional thermal ionization mass spectrometry (TIMS) is still regarded as the benchmark technique for Sm-Nd isotopic measurement (Chu et al. 2009; Harvey & Baxter 2009; Ali & Srinivasan 2011), more recent multi collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) has also become a routine technique with high sample throughput and comparable precision to TIMS (Walder et al. 1993; Vance & Thirlwall 2002; Yang et al. 2010; Yang et al. 2011). The classic Sm-Nd isotope analysis requires a separation of two elements from the sample matrix by refined chemical procedures. Recently, however, it was reported that the 143Nd/144Nd ratio of geological samples could be measured accurately by MC-ICP-MS without Sm and Nd separation (Yang et al. 2010). This study further evaluates the validity of Nd isotopic and Sm/Nd elemental ratio measurements for a series of Sm + Nd mixed standard solutions by MC-ICP-MS technique, and revisited various sets of reported Sm isotopic composition.


The Sm-Nd isotopic analysis of this study was conducted by using a Neptune MC-ICP-MS installed at the Korea Basic Science Institute (KBSI) in Ochang. This double focusing high-resolution ICP-MS is equipped with eight movable Faraday collectors and one fixed axial channel where the ion beam intensities can be measured with either a Faraday collector or an ion counting electron multiplier. The Faraday collectors were statically set to simultaneously detect the required isotopes: 140Ce (L4), 142Nd (L3), 143Sm (L2), 144(Sm + Nd) (L1), 145Nd (axial), 146Nd (H1), 147Sm (H2), 148(Sm + Nd) (H3), and 149Sm (H4). The sensitivity on 145Nd was typically around 5 V/Nd ppm (1011Ω resistors) in a low-resolution mode. Details of the other operational parameters are summarized in Table 1.
Table 1

Instrumental setting and operational parameters

RF forward power

1200 W

RF reflected power

< 2 W

Cooling gas

15 L/min

Auxiliary gas

0.75 - 0.80 L/min

Sample gas

0.985 - 0.990 L/min


−2 kV


−0.654 kV

Acceleration voltage

10 kV

Interface cones


Spray chamber

Quartz dual cyclonic


ESI PFA MicroFlow

Sample uptake rate

100 μL/min

Instrumental resolution

ca. 400

Mass analyzer pressure

2.9 × 10-9 mbar

Measurement of Nd standard solutions

The basic performance of KBSI Neptune was tested by using the JNdi standard solution with Nd concentration of 100 μg/L. The mass bias was exponentially normalized to 146Nd/144Nd = 0.7219. One measurement consists of 9 blocks of 10 cycles with an integration time of 4.194 s. The average 143Nd/144Nd ratio was 0.512100 ± 0.000004 (n = 10, 2σ S.E.), in reasonable agreement with the recommended value (0.512115 ± 0.000007) (Tanaka et al. 2000).

The in-house Nd standard solution of 100 μg/L was prepared from the AccuTrace™ Nd Reference Standard (lot no. B9035110, plasma emission standard). It yielded an average 143Nd/144Nd ratio of 0.512204 ± 0.000005 (n = 9, 2σ S.E.) with the same analytical design as above (9 blocks of 10 cycles with an integration time of 4.194 s). Two diluted in-house Nd solutions of 50 and 10 μg/L also yielded comparable results of 143Nd/144Nd = 0.512212 ± 0.000006 (n = 5, 2σ S.E.) and 0.512207 ± 0.000004 (n = 5, 2σ S.E.), respectively.

Isobaric interference correction

The contribution of 144Sm imposed on the 144Nd peak should be carefully corrected for accurate determination of 143Nd/144Nd ratio. The first step of correction in this study was to calculate the Sm mass bias factor, β(Sm), for which the exponential law (Russel et al. 1978) was applied as the following.
β Sm = ln 147 Sm / 149 Sm true / 147 Sm / 149 Sm measured ÷ ln M 147 / M 149 ,

where M denotes the mass of the isotope.

The exponential law also yields an equation for (144Sm/149Sm)measured:
144 Sm / 149 Sm measured = 144 Sm / 149 Sm true × M 149 / M 144 β Sm
The 144Sm intensity was calculated as multiplying Eq (2) by measured 149Sm intensity. Then, 144Nd intensity was calculated by subtracting the 144Sm intensity from the intensity on mass 144 using the equation.
144 Nd measured = 144 Sm + Nd measured [ 149 Sm measured × 144 Sm / 149 Sm true × M 149 / M 144 β Sm ]

Finally, the 144Sm-corrected 143Nd/144Nd ratio was exponentially normalized to 146Nd/144Nd = 0.7219.

The Sm isotope ratios (147Sm/149Sm and 144Sm/149Sm) have not been uniformly reported. The following sets of reported Sm isotopic composition were evaluated in this study.
147 Sm / 149 Sm = 1.0868 Yang et al. 2010 , 1.0851 Wasserburg et al. 1981 , 1.06119 MCFarlane & McCulloch 2007 , 1.0847 Berglund & Wieser 2011
144 Sm / 149 Sm = 0.22332 Yang et al. 2010 , 0.22249 Wasserburg et al. 1981 , 0.2103 McFarlane & McCulloch 2007 , 0.22214 Berglund & Wieser 2011 ,
To evaluate these Sm isotopic compositions, the in-house Nd standard solution of 100 μg/L was doped with AccuTraceTM Sm Reference Standard (lot no. B8085072, plasma emission standard), in which the concentration ratio of Sm to Nd was 0.2041. As depicted in Figure 1, analytical results (7 measurements, 1 block of 20 cycles with an integration time of 4.194 s) of this solution were different according to the employed Sm isotopic compositions (Yang et al. 2010; Wasserburg et al. 1981; McFarlane & McCulloch 2007; Berglund & Wieser 2011). Sm isotopic compositions reported in (Yang et al. 2010; Wasserburg et al. 1981; McFarlane & McCulloch 2007) yielded the 143Nd/144Nd ratios comparable with the unspiked value, which were 0.512190 ± 0.000014 (2σ S.E.), 0.512195 ± 0.000014 (2σ S.E.), and 0.512194 ± 0.000014 (2σ S.E.), respectively.
Figure 1

The 143 Nd/ 144 Nd ratios of a Sm-doped Nd standard solution with 100 μg/L Nd and Sm/Nd of 0.2041. The isobaric interference was corrected using reported Sm isotopic compositions (9] Yang et al. 2010; 13] Wasserburg et al. 1981; 14 ] McFarlane & McCulloch 2007; 15 ] Berglund & Wieser 2011). Solid and dashed lines respectively represent an average measured 143Nd/144Nd ratio and 2σ S.D. of the unspiked Nd standard solution.

Sm isotopic compositions were iteratively solved to minimize the residual sum of squares between corrected 143Nd/144Nd ratio of Sm-doped Nd standard solution and the unspiked value using the Excel Solver. The result suggests that the ratios of 147Sm to 149Sm and 144Sm to 149Sm would be 1.0844 and 0.22233, respectively. Because these values are the closest to the recommended values in (Wasserburg et al. 1981), we hereafter use 1.0851 and 0.22249 as the (147Sm/149Sm)true and (144Sm/149Sm)true ratios for correcting mass fractionation of Sm and calculating its isobaric contribution to 144Nd.

The 143Nd/144Nd ratios of the Sm-doped Nd standard solutions with similar Sm/Nd ratio of around 0.20 but different Nd concentrations (200 and 50 μg/L) were 0.512195 ± 0.000022 and 0.512208 ± 0.000038, respectively, corroborating the validity of this correction design (Table 2). Furthermore, the corrected 145Nd/144Nd ratios of the mixed solutions were well consistent with a constant value of 0.348417 obtained by TIMS (Wasserburg et al. 1981). The correlation between β(Sm) and β(Nd) values indicates that the two factors are not identical and are roughly positively correlated with each other (β(Sm) = 0.516 × β(Nd)-0.997) (Figure 2).
Table 2

Nd isotope ratios of the Sm-doped Nd standard solutions with the Sm/Nd ratio of 0.2


Gravimetric Sm/Nd

143Nd/ 144Nd

2σ S.E.

145Nd/ 144Nd

2σ S.E.


100 μg/L Nd







200 μg/L Nd







50 μg/L Nd






Figure 2

The correlation between the Sm and Nd mass bias factors (β(Sm) and β(Nd)) measured for Sm-doped Nd standard solutions with the Sm/Nd ratio of 0.2041.
Figure 3

Comparisons of the measured and corrected 147 Sm/ 145 Nd ratios with gravimetric values.

We further analyzed a series of Sm-doped Nd standard solutions of 100 μg/L Nd with different Sm/Nd ratios (Sm/Nd = ca. 0.1, 0.3, 0.4, and 0.5) to test the validity of correction scheme described above. The results show that the correction protocol is reasonable (Table 3). However, there is a systematic increasing trend in the corrected 143Nd/144Nd ratio with increasing Sm/Nd ratios, implying that the mass bias may not be perfectly corrected by the exponential law for high-Sm/Nd (> 0.5) samples.
Table 3

Sm-Nd isotopic data of the Sm-doped Nd standard solutions of 100 μg/L Nd

143Nd/ 144Nd

2σ S.E.


147Sm/ 145Nd

Nd (μg/L)







































Calibration of Sm/Nd ratio

The instrumental mass bias on isotope measurements could be corrected by using either double-spike or standard bracketing methods. The latter method consists in interpolating the mass bias of an unknown sample between the biases inferred from two standard runs, one preceding and one following the sample analysis (Albarede & Beard 2004).

In order to correct the inter-elemental mass bias on the measurement, this study considered the Sm-doped Nd standard solution with the Sm/Nd of 0.2 as the bracketing standard and various mixed solutions with different Sm/Nd values (Sm/Nd = ca. 0.1, 0.3, 0.4, and 0.5) as unknown samples. During the measurements, the average correlation factor in the instrumental mass bias inferred from the standard runs was 0.943 ± 0.002 (n = 7, 2σ S.E.), which yielded consistent Sm/Nd ratios with gravimetric Sm/Nd values mostly within 1% difference (Table 3; Figure 3). This result indicates that the mass bias in the measurement of the Sm/Nd ratio can be reasonably corrected by the standard bracketing method.

The Nd concentrations of the mixed solutions were calculated based on the intensity of the bracketing standard of 100-101 μg/L. Calculated Nd concentrations were consistent with gravimetric values within 3% difference (Table 3).


We evaluated the capability of a Neptune MC-ICP-MS to obtain accurate Nd isotopic composition and Sm/Nd elemental ratio using a series of Sm + Nd mixed standard solutions with different Sm/Nd ratios. The isobaric interference correction using the exponential law and selected Sm isotopic composition yielded accurate 143Nd/144Nd and 145Nd/144Nd ratios for the mixed solutions, although there is a systematic increasing trend in the corrected 143Nd/144Nd ratios with increasing Sm/Nd ratios. The Sm/Nd ratios of the Sm-doped Nd standard solutions could be reliably calibrated by the standard bracketing method mostly within 1% difference from the gravimetric values. These results indicate that accurate Nd isotopic composition and Sm/Nd ratio can be simultaneously measured by a simple and high-throughput technique without chemical separation of Sm and Nd.



This study was supported by the KBSI grants (G33200 and C33710).

Authors’ Affiliations

Division of Earth and Environmental Sciences, Korea Basic Science Institute


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© Ryu et al.; licensee Springer. 2013

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