Palaeogeography, Palaeoclimatology, Palaeoecology 416 (2014) 142–149

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Palaeogeography, Palaeoclimatology, Palaeoecology

journal homepage: www.elsevier.com/locate/palaeo

Strontium isotope analysis of curved tooth enamel surfaces by

laser-ablation multi-collector ICP-MS
P.J. Le Roux a,⁎, J.A. Lee-Thorp b, S.R. Copeland c,d, M. Sponheimer c, D.J. de Ruiter e
a
Dept. of Geological Sciences, University of Cape Town, Rondebosch, Cape Town 7700, South Africa
b
Research Laboratory for Archaeology, Oxford University, Oxford, UK
c
Dept. of Anthropology, University of Colorado Boulder, Boulder, CO, USA
d
Dept. of Human Evolution, Max Planck Institute for Evolutionary Anthropology, Leipzig, Germany
e
Dept. of Anthropology, Texas A&M University, College Station, TX, USA

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

Article history: Laser ablation multi-collector ICP-MS (LA-MC-ICP-MS) is increasingly applied to measure the strontium isotope
Received 14 February 2014 composition (87Sr/86Sr) of fossil or modern tooth samples in order to address questions about mobility. Recently,
Received in revised form 5 September 2014 concerns have been raised that an analytical bias due to instrumental isotopic mass fractionation might be
Accepted 9 September 2014
introduced when this method is used to sample across naturally curved tooth enamel surfaces.
Available online 16 September 2014
We address this concern by reanalyzing data that were originally produced using 750 μm linear LA-MC-ICP-MS
Keywords:
scans on the external, slightly curved surfaces of fossil hominin teeth (Australopithecus and Paranthropus) from
Strontium isotopes South Africa. By re-integrating the first and last 1/3 of the data along the original 750 μm linear scans, we
Laser ablation compared 87Sr/86Sr results produced by sections of each scan with varying degrees of laser focus. The results
Multi-collector inductively coupled plasma show no evidence of any analytical scatter between strontium isotope values for the different sections of the
mass spectrometry curved tooth surfaces and results for the different sections of each linear scan agree well within the precision
Enamel of the method (external 2σ ± 0.0004). Furthermore, each analytical session was bracketed by analysis of a curved
Teeth rodent (Otomys sp.) tooth in-house standard with up to ±100 μm vertical change along the 750 μm linear scan.
Long-term, average LA-MC-ICP-MS 87Sr/86Sr results for one such Otomys tooth standard (0.72989 ± 0.00029,
n = 71) agree well with the solution MC-ICP-MS analysis of the same tooth (0.72976 ± 0.00002). New LA-
MC-ICP-MS 87Sr/86Sr ratios, using both a 213 nm and solid-state 193 nm laser ablation system, for sets of
consecutive 750 μm linear scans along the curved, outer tooth enamel surface on another single Otomys tooth
in-house standard agree within ± 0.0004 regardless of progressively more extreme vertical change during
analysis (±10 μm to ±900 μm).
These results are similar to LA-MC-ICP-MS Sr isotope analyses, using the same instrumentation and
methodology, of an in-house, polished, flat clinopyroxene mineral standard (LA: 0.70482 ± 0.00029, n = 155;
solution: 0.70495 ± 0.00003).
We conclude that, provided the stable 86Sr/88Sr ratio is used in conjunction with the exponential law to
constantly correct for instrumental isotopic mass fractionation during acquisition, curved tooth enamel surfaces
represent no impediment to accurate LA-MC-ICP-MS strontium isotope analyses.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction studies. It therefore opens up possibilities for investigating an

The use of laser ablation multi-collector inductively coupled plasma
mass spectrometry (LA-MC-ICP-MS) to obtain the strontium isotope
composition of tooth enamel has become more widespread and accessi-
ble (e.g. Richards et al., 2008; Radloff et al., 2010; Copeland et al., 2011;
Balter et al., 2012; Moffat et al., 2012). This method can yield a relatively
large number of strontium isotope values for tooth enamel within a rel-
atively short timescale, with sufficient resolution for many bioecological
⁎ Corresponding author. Fax: +27 216503783.
E-mail address: petrus.leroux@uct.ac.za (P.J. Le Roux).
individual's movements or use of landscape during the period of miner-
alization of one or several teeth.
Doubts have been raised about the validity of its application, and
accuracy, when used to analyze curved tooth enamel surfaces (Balter
et al., 2012). These authors proposed that variations observed in 87Sr/
86
Sr values (as in Copeland et al., 2011) are analytical artifacts due to
variable laser focus during individual LA-MC-ICP-MS analysis of curved
outer tooth surfaces. We expect any analytical bias due to laser- or
plasma-induced instrumental mass fractionation to be continually
corrected during the data collection procedure through the use of the
internal, stable 86Sr/88Sr ratio and the exponential fractionation correc-
tion law (Dickin, 1995).

http://dx.doi.org/10.1016/j.palaeo.2014.09.007
0031-0182/© 2014 Elsevier B.V. All rights reserved.
 P.J. Le Roux et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 416 (2014) 142–149
Although this protocol was followed, we reassessed published LA-
MC-ICP-MS strontium isotope data on tooth enamel (Copeland et al.,
2011) for any possible curvature effects. Strontium isotope data obtain-
ed by the same LA-MC-ICP-MS method on variably curved rodent
(Otomys) tooth enamel surfaces, at 213 nm and 193 nm laser wave-
lengths, and flat clinopyroxene mineral surfaces are also presented
and discussed. This contribution therefore addresses the important
validity issue of in situ strontium isotope analysis of curved surfaces
for studies aiming to use strontium isotope compositions of tooth enam-
el to address questions such as migration and landscape use.
2. Background
2.1. LA-MC-ICP-MS strontium isotope analysis of curved surfaces
The concern raised by Balter et al. (2012) with regard to LA-MC-ICP-
MS strontium isotope analysis is that laser sampling carried out on
curved tooth enamel surfaces would inevitably lead to the sampling of
laser-unfocused areas during individual analyses. The result of ablation
becoming progressively more unfocused is the production of progres-
sively finer or coarser sized ablated particles, which in turn leads to var-
iation in instrumental isotopic mass fractionation during ionization and
artificially scattered isotopic ratios (Jackson and Günther, 2003). This
phenomenon is well-documented and discussed by Jackson and
Günther (2003). These authors examined the fundamental nature and
sources of isotope fractionation during LA-MC-ICP-MS analysis in gen-
eral, of which LA analysis of a curved surface is an example.
Instrumental isotopic mass fractionation occurs to various degrees
during analysis on all mass spectrometric instruments. There are three
algorithms which can be applied to correct isotope ratio measurements
for instrumental mass fractionation, the so-called linear, power or expo-
nential laws. Of these, the exponential law is most commonly applied in
MC-ICP-MS analysis. All three correction algorithms are dependent on
the difference between the known value of a stable isotope pair within
the isotope system of interest, and the actual fractionated ratio mea-
sured during the analysis. A correction factor is derived based on this
observed difference and applied using the exponential law to correct
the radiogenic, variable isotope ratio of interest for instrumental mass
fractionation (see discussion in for example Dickin, 1995).
It is therefore a particular problem for isotope systems with no inter-
nal, stable isotope pair which can be used in conjunction with the expo-
nential law to correct for instrumental mass fractionation, e.g. Li, B, or
Cu. In these cases, the standard approach is to bracket analyses of sam-
ples with unknown isotopic compositions with analyses of standards
with known, certified isotopic compositions. The measured difference
between the known and the measured, fractionated isotope ratios of
the bracketing standard analyses can then be used to correct the
same ratios measured in the standard-bracketed sample analyses. This
approach is dependent on stable and consistent instrumental isotopic
mass fractionation throughout the standard-bracketed analytical
period. Variable instrumental isotopic mass fractionation between the
standard analyses and sample analyses can be due to various factors,
for example differences in laser-surface coupling (e.g. le Roux, 2010)
or laser ablation along variably curved surfaces (e.g. Jackson and
Günther, 2003). The result in such cases is artificially scattered isotope
values derived for the samples analyses, as stated by Balter et al. (2012).
However, isotope systems like strontium and hafnium have internal,
stable isotope ratios (e.g. 86Sr/88Sr and 179Hf/177Hf) which are routinely
used to monitor and correct for instrumental isotopic mass fractionation
during solution or LA-MC-ICP-MS isotopic analysis (as in e.g. Radloff
et al., 2010; Copeland et al., 2011). Such continuous, internal correction
for instrumental isotopic mass fractionation during LA-MC-ICP-MS
analysis can effectively correct for all laser or plasma-source isotope
fractionation and yields accurate isotope ratio results as noted in
Jackson and Günther (2003).
143
The routine LA-MC-ICP-MS analytical method corrects strontium
isotope data from curved tooth surfaces for all known instrumental iso-
topic mass fractionation (e.g. Copeland et al., 2008). Nevertheless, in
order to interrogate this approach further, the raw, original data of the
published 87Sr/86Sr values for selected hominin teeth in Copeland
et al. (2011) are re-integrated.
Each original intra-tooth laser value in Copeland et al. (2011)
was determined with a 750 μm linear scan across a curved surface.
We selected a representative subset of analyses and re-integrated sub-
sections of each scan. This allows a comparison between the new 87Sr/
86
Sr values obtained for the first third (0–250 μm) and last third
(500–750 μm) of each scan with the original 87Sr/86Sr value obtained
from the entire 750 μm scan. This approach provides a comparison
between sections of a single analysis with different extents of vertical
change.
2.2. Quantified, variable vertical change during analysis of curved
enamel surface
New LA-MC-ICP-MS strontium isotope analyses with quantified,
variable vertical change were performed along the length of a single
Otomys rodent tooth. The extent of vertical change during each analysis
could be quantified, as well as the point of laser focus for each individual
linear line scan. As all other parameters remain constant, the resulting
87
Sr/86Sr isotope data should record any instrumental isotopic mass
fractionation induced by the laser ablation sampling operating progres-
sively more out of focus for different linear line scans. This experiment
was also repeated, using the same tooth and instrumentation, at a
shorter laser wavelength (193 nm versus the more common 213 nm)
to test whether observed analysis characteristics are unique to a par-
ticular laser ablation wavelength used.
3. Methods
3.1. Sampling of the fossil teeth
The original sampling methods of the hominin and other fossil fau-
nal teeth are described in detail in Copeland et al. (2011). To summarize
briefly, each tooth was sampled with a series of linear laser scans (from
4 to 15 for each of the hominin teeth) along the external surface of the
enamel (Fig. 1). Each intra-tooth linear scan was oriented with its long
axis (750 μm) perpendicular to the tooth growth axis. Although the
flattest possible well-preserved area of hominin tooth enamel surface
was chosen (excluding the occlusal surface) for sampling, the surfaces
are more curved than those of artificially sectioned samples, with esti-
mated divergence of up to ±50 μm vertical change along the 750 μm
linear scan (see photos in Fig. 1).
The new strontium isotope data presented here for sequential LA-
MC-ICP-MS analyses of a single Otomys rodent tooth followed the
same methodology as above, but with progressively more vertical
change during each line scan. The vertical laser focus position on the
tooth surface at the start and end points of a line scan was noted to
quantify the total vertical change during each scan. The laser focus for
the whole line scan was set at the appropriate vertical position for the
tooth surface to be in sharp laser focus in the middle of each line scan.
This procedure was used for the analyses employing both the 213 nm
and 193 nm laser ablation units.
3.2. Analytical methods
The analytical methods and protocols given below are also published
(see Copeland et al., 2008 for full description) and remained unchanged
during the acquisition of the LA-MC-ICP-MS strontium isotope data pre-
sented here, except for the use of the 193 nm laser unit where indicated.
A NewWave UP213 LA unit coupled to a NuPlasma HR MC-ICP-MS in-
strument, housed in the Department of Geological Sciences, University
144 P.J. Le Roux et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 416 (2014) 142–149

Fig. 1. Images of six fossil hominin teeth analyzed by LA-MC-ICP-MS for 87Sr/86Sr compositions (Copeland et al., 2011), along with original raw time resolved analysis (TRA) laser
ablation data for the first and last laser scans in each intra-tooth analysis sequence. TRA scans are labeled with the original 87Sr/86Sr value in the center, and the 87Sr/86Sr value obtained
by re-integrating the initial 1/3 and final 1/3 of the TRA data (doubled-headed arrows indicate approximate data used).
 P.J. Le Roux et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 416 (2014) 142–149 145

Fig. 1 (continued).

of Cape Town, South Africa, was used. All laser ablation analyses were
performed with helium as the sample chamber sweep gas, subsequently
mixed with argon using a y-connector prior to injection into the plasma.
The laser system was focused anew on the surface of the tooth before
each individual LA-MC-ICP-MS analysis, at the approximate mid-point
of the linear line scan. To remove any potential surface contamination,
a rapid pre-ablation laser sweep was performed along the path of
the analysis (250 μm spot size, 750 μm line length, 10 Hz repetition
rate, 50 μm s−1 translation rate, 0.25 mJ energy and 0.5 J cm−2 fluency)
removing ±2–5 μm of surface material. The actual laser ablation analy-
sis along this pre-cleaned line (200 μm spot size, 750 μm line length,
20 Hz repetition rate, 5 μm s− 1 translation rate, 1.35 mJ energy and
146 P.J. Le Roux et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 416 (2014) 142–149

4.35 J cm−2 fluency) removed a further 20–30 μm deep layer of materi-
al. A 30 s on-peak background gas composition was measured before
each analysis for subtraction from later signals measured during laser
ablation. Typical total Kr backgrounds were b 5 mV.
For some of the new strontium isotope data presented here
(Section 3.5) a NewWave UP193 LA unit was coupled to the exact
same MC-ICP-MS instrument, using the exact same tubing, instrument
settings and sample chamber insert containing the tooth being ana-
lyzed. The “cleaning” scan was performed with the maximum spot
size available on the UP193 system (125 μm spot size, 750 μm line
length, 10 Hz repetition rate, 50 μm s− 1 translation rate, irradiance
0.1 GW cm−2 and 0.25 J cm−2 fluency) and the “analysis” scan with a
100 μm laser spot (750 μm line length, 10 Hz repetition rate, 5 μm s−1
translation rate, irradiance 1.8 GW cm−2 and 5 J cm−2 fluency).
The LA-MC-ICP-MS strontium isotope analysis used the NuPlasma
Time Resolved Analysis software, which pools consecutive 0.2 s long
static measurements to build up a final value for each analysis. With
special importance to later discussion, each 0.2 s strontium isotope mea-
surement was individually and instantly corrected for instrumental
mass fractionation using the exponential law and a fractionation factor
based on the measured internal, stable 86Sr/88Sr ratio and the accepted
value of 0.1194.
3.3. Standards
LA-MC-ICP-MS data quality was monitored by analyzing a
bracketing standard at the start and end of each data collecting session.
Routine standards are either a modern rodent (Otomys sp.) incisor
when analyzing tooth enamel or a clinopyroxene mineral standard
used for geological applications. These in-house laser ablation standards
are well-characterized for isotopic homogeneity at the stated 2σ level,
low rubidium content, as well as for 87Sr/86Sr compositions by conven-
tional solution MC-ICP-MS referenced to the international Sr isotope
standard, SRM 987 (87Sr/86Sr 0.710255). Depending on the study, the
solution 87Sr/86Sr compositions for these in-house standards are either
the same teeth dissolved after laser ablation sampling (e.g. Copeland
et al., 2008; Radloff et al., 2010; Copeland et al., 2011) or in some current
studies the contralateral. The complete tooth is dissolved, enamel plus
dentine, for conventional solution MC-ICP-MS analysis to ensure the
resulting 87Sr/86Sr value is representative of all possible variability
present. Although initial test analyses are done, it must be noted that
our a priori assumption is that these in-house tooth standards have
homogeneous strontium isotope compositions. This assumption is
quite conservative given that these are, in fact, natural teeth and there-
fore could have some natural variation along their length.
Strontium isotope ratios of analyzed unknowns were therefore not
corrected to the bracketing in-house standard, but rather results from
an analytical session were only accepted when the 87Sr/86Sr ratios of
the bracketing in-house standard were within 0.001 of their solution
values.
LA-MC-ICP-MS strontium isotope data obtained using the same
instrumentation and protocols are presented for the in-house
clinopyroxene standard JJG1424 (see Class and le Roex, 2011).
3.4. Re-integrating previous LA-MC-ICP-MS data for this study
Two additional 87Sr/86Sr values are obtained for each LA-MC-ICP-MS
tooth analysis by integrating only the initial ~ 1/3 and separately the
final ~ 1/3 of the original time-series data. These 87Sr/86Sr values are
compared with each other, as well as with the original value from
Copeland et al. (2011), which was derived from the whole, 750 μm
laser ablation scan. Systematic changes between these 87Sr/86Sr values,
outside of the stated analytical precision of 2σ ±0.0004, might indicate
isotopic mass fractionation due to analysis of the curved tooth enamel
surfaces as proposed in Balter et al. (2012).
The subset of samples selected for re-integration of LA-MC-ICP-
MS strontium isotope data encompassed both Australopithecus and
Paranthropus M3 and canine tooth samples, large and small tooth
samples, and also tooth samples that we categorize as “less curved”
or “more curved” based on the tooth position (M3 versus C) and
lobe that was analyzed (see Table 1).
3.5. New 87Sr/86Sr data for LA-MC-ICP-MS analyses with variable
vertical change
Table 2 reports the results for two sets of LA-MC-ICP-MS strontium
isotope analyses performed, using either a 213 nm or 193 nm laser
ablation unit, along the outer curved enamel surface of a single Otomys

Table 1
Absolute offset of 87Sr/86Sr values based on re-integrated subsections of the 750 μm linear laser ablation scans (LA-MC-ICP-MS) on curved tooth surfaces versus the original values reported
(Copeland et al., 2011) for the whole linear scan. These re-integrated values are from the first (closest to the apex) linear laser scan in the sequence of intra-tooth scans completed per
tooth.

Australopithecus africanus Sizea Toothb Initial 1/3 87Sr/86Sr diff Final 1/3 87Sr/86Sr diff

Less curved Sts 3 ++ C +0.0003 −0.0001

Sts 48 − C — +0.0001
Sts 72 − M3 −0.0001 +0.0001
Sts 28 ++ M3 −0.0001 +0.0001
More curved Sts 54 − M3 — +0.0003
TM 1561 − M3 +0.0001 −0.0002
TM1518 + M3 +0.0002 +0.0001

Paranthropus robustus

Less curved SKX 241 −− C — —

SK 4 ++ C −0.0001 +0.0003
SK 38 ++ C — —
SK 87 ++ C −0.0001 —
SK 94 + C +0.0001 —
SK 22 + M3 — —
More curved SK 96 −− C +0.0001 −0.0001
SK 95 −− C −0.0001 —
SK 835 − M3 +0.0001 —
SK 836 ++ M3 — —
SK 92 − C −0.0001 —
a
Size: “++” = above the mean occlusal area for the hypodigm by N1 standard deviation (SD); “+” = above the mean by ≤1 SD; “−” = below the mean by ≤1 SD; “−−” = below
the mean by N1 SD (Copeland et al., 2011: Supplementary Table 1).
b
Tooth: permanent canine (C) or permanent third molar (M3) (Copeland et al., 2011: Supplementary Table 1).
 P.J. Le Roux et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 416 (2014) 142–149 147

Table 2
New 87Sr/86Sr isotope data for sequential LA-MC-ICP-MS analyses on a single Otomys rodent tooth (26-r52), obtained using either a 213 nm wavelength laser ablation unit or 193 nm
wavelength laser ablation unit. The extent of vertical change during each analysis, as well as the vertical focus level at the mid-scan point is recorded. Note that the published long-
term, external 2σ reproducibility of this method ±0.0004 (e.g. Copeland et al., 2008).

213 nm wavelength
87
Analysis # Sr/86Sr Δ87Sr/86Sra Δzb Focusc
(μm) (μm)

1 0.7202 −0.0003 +350 +230

2 0.7202 −0.0003 +160 +90
3 0.7203 −0.0002 −10 0
4 0.7205 +0.0001 −160 −100
5 0.7206 +0.0001 −350 −150
6 0.7207 +0.0002 −620 −190
7 0.7208 +0.0003 −900 −450
Average 0.7205 ± 0.0005 (2σ external)

193 nm wavelength
87
Analysis # Sr/86Sr Δ87Sr/86Sra Δzb Focusc

1 0.7206 −0.0003 +260 +160

2 0.7209 +0.0001 +180 +100
3 0.7207 −0.0001 +20 +10
4 0.7209 – −80 −30
5 0.7210 +0.0002 −260 −100
6 0.7208 −0.0001 −370 −210
7 0.7211 +0.0002 −700 −330
Average 0.7209 ± 0.0003 (2σ external)
a
Difference between 87Sr/86Sr value of analysis and average 87Sr/86Sr value for all seven analyses.
b
Extent of vertical change during 750 μm linear line scan relative to start point.
c
Vertical offset of laser focus at mid-point of linear line scan relative to start point.

rodent tooth (26-r52). The vertical change recorded during the linear
line scans in Table 2 ranges from 10 μm to 900 μm, significantly beyond
the approximately 50 μm (hominin teeth) to 100 μm (rodent teeth)
vertical change general observed in published studies like Copeland
et al. (2011) or Radloff et al. (2010). As stated above, systematic changes
between these 87Sr/86Sr values, outside of the stated analytical precision
of 2σ ±0.0004, might indicate artificial isotope ratio variability due to
analysis of the curved tooth enamel surfaces as proposed by Balter
et al. (2012).
4. Results and discussion
Fig. 1 shows images of six of the teeth listed in Table 1, with the laser
ablation tracks along the curved outer enamel surfaces visible. Also
shown are images of the raw time-resolved analysis (TRA) data collec-
tions during the first (closest to tooth cusp) and the final (closest
to tooth cervix) laser ablation scans on each specific tooth sample. It
is clear form Fig. 1 and Table 1 that in each case the re-integration
of raw strontium isotope data using only the first 1/3 or only the final
1/3 of the TRA data yield 87Sr/86Sr values which agree within the stated
2σ and also with the original 87Sr/86Sr value from Copeland et al. (2011)
obtained using the complete TRA data.
Therefore, no evidence exists of any artificial, analytical scatter be-
tween strontium isotope data for different sections of the curved tooth
surfaces analyzed.
Table 3
Comparison of laser ablation versus solution MC-ICP-MS strontium isotope values of
curved rodent (Otomys sp.) tooth and flat, polished clinopyroxene. Precision listed as 2σ,
with number of repeat laser ablation analyses indicated.
LA-MC-ICP-MS Solution MC-ICP-MS
87
Sr/86Sr 87
Sr/86Sr
26-to10z (Otomys tooth) 0.72989 0.72976
±0.00029 (n = 71) ±0.00002
JJG1424 (clinopyroxene) 0.70482 0.70495
±0.00029 (n = 155) ±0.00003
Each analytical session of the Copeland et al. (2011) study started
and ended with 750 μm long LA-MC-ICP-MS analyses of a curved
Otomys rodent tooth in-house standard, with up to ±100 μm vertical
change (Copeland et al., 2008). In Table 3, the 87Sr/86Sr results of numer-
ous LA-MC-ICP-MS analyses performed over N20 analytical sessions on
one such rodent tooth standard (26-to10z) average 0.72989 ± 0.00029
(external 2σ, n = 71). This average value is in good agreement with
conventional solution strontium isotope MC-ICP-MS data for the same
tooth (0.72976 ± 0.00002).
Similarly, results of laser ablation and solution MC-ICP-MS Sr isotope
analyses of the in-house, polished and perfectly flat clinopyroxene min-
eral standard agree well (LA: 0.70482 ± 0.00029, n = 155; solution:
0.70495 ± 0.00003). Therefore, using the exact same analytical instru-
mentation and methodology, there is no discernable difference in
terms of accuracy and precision between LA-MC-ICP-MS strontium iso-
tope results of analyses of the significantly curved rodent teeth versus
the perfectly flat, polished clinopyroxene mineral grains (see Fig. 2).
New LA-MC-ICP-MS strontium isotope analyses along the curved
outer surface of a single Otomys rodent tooth in-house standard (26-
r52) encountered variable vertical change during line scans (see
Table 2 and Fig. 3). Even though vertical change during a line scan
ranged from 10 to 900 μm, there was no significant difference in stron-
tium isotope values between analyses beyond the analytical precision of
2σ ±0.0004 of this method (Copeland et al., 2008). Although the values
for the 213 nm wavelength analysis series progressively increase, the
vertical change of the first and fifth analysis is the same in absolute
terms. Therefore this might be natural variability within the tooth and
within the analytical precision of this method. The strontium isotope
data for the 193 nm wavelength analyses are randomly distributed
around the average value, with no systematic increase or correlation
with absolute vertical change during the line scan.
No significant changes were observed in the total strontium signal
intensities or internal 2σ errors for the 87Sr/86Sr values of these analyses,
regardless of the extent of vertical change during individual linear line
scans. The total strontium signal voltages for the 213 nm wavelength
analyses were restricted to 2.2–2.5 V while for the 193 nm wavelength
analyses the range was 0.58–0.72. The internal 2σ errors for the 87Sr/
86
Sr values for the 213 nm wavelength analyses were ± 0.00005 and
148 P.J. Le Roux et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 416 (2014) 142–149
Fig. 2. Images of Otomys tooth used as bracketing LA-MC-ICP-MS strontium isotope stan-
dard (top) and clinopyroxene standard (bottom). Note the numerous laser ablation tracks
on both the curved tooth surface and the flat, polished mineral surfaces.
Fig. 3. Image of Otomys tooth standard analyzed using both 213 nm (200 μm spot size) and
193 nm (100 μm spot-size) wavelength laser ablation (linear line scans #1 and #7 in
Table 2 indicated). Note that the progressively larger vertical change during successive
linear laser ablation scans is reflected in changing width of the laser scan track from
narrow at the start (focused below the tooth surface) to wide at the end (focused above
the tooth surface).
for the 193 nm wavelength analyses ±0.0002, the difference between
these values is related to the lower total strontium signal voltage of
the 193 nm wavelength analyses.
Therefore, there is no discernable significant, systematic correlation
between an increase in vertical change during LA-MC-ICP-MS analysis
and any observable change in resulting strontium isotope values. This
is observed for analysis performed using both a 213 nm and 193 nm
wavelength laser ablation unit.
5. Conclusions
Instrumental isotopic mass fractionation is a reality in all multi-
collector inductively-coupled plasma-mass spectrometry isotope
measurements. There are different physical causes of instrumental
isotopic mass fractionation, and a number of approaches to monitor
and correct for this process. With respect to strontium isotope laser
ablation MC-ICP-MS analysis, it is known and shown here that
using the internal, stable 86Sr/88Sr ratio and the exponential fraction-
ation law, it is possible to correct for all instrumental isotopic mass
fractionation. This includes the production of variable, and changing,
ablation particle size populations when performing LA-MC-ICP-MS
analyses on the curved enamel surfaces of teeth samples.
This contribution showed that when analyzing the curved enamel
surface of hominin teeth, 87Sr/86Sr values obtained by re-integrating
only the first and last 1/3 of LA-MC-ICP-MS data are similar and agree
within the stated analytical precision (2σ ± 0.0004; Copeland et al.,
2008) with original values obtained using the complete analysis data.
There is no evidence of any artificial, analytical scatter between stron-
tium isotope data for different sections of the curved tooth surfaces
analyzed.
LA-MC-ICP-MS strontium isotope analyses of significantly curved
Otomys rodent teeth used as in-house standards, selected based on
strontium isotope homogeneity and low Rb content, agree well with so-
lution strontium isotope MC-ICP-MS data for the same teeth. Similar
agreement is found when using the same instrumentation and method-
ology for solution- and LA-MC-ICP-MS strontium isotope analyses of a
flat, polished clinopyroxene mineral standard. Therefore, there is no
discernable difference in terms of accuracy and precision between LA-
MC-ICP-MS strontium isotope results of analyses of these curved rodent
teeth used as in-house standards versus the perfectly flat clinopyroxene.
Additionally, new LA-MC-ICP-MS strontium isotope analyses
along the curved outer surface of a single Otomys rodent tooth in-
house standard encountered progressively more vertical change
during the line scan. Even though vertical change during a line scan
significantly exceeded that typical for such studies (± 100 μm versus
10–900 μm), there was no significant difference in strontium isotope
values between analyses. This was observed for analyses performed
using both a 213 nm and a 193 nm laser ablation unit.
Acknowledgments
This work is based on research supported in part by the National
Research Foundation of South Africa (UID: 85512). The Grantholder
acknowledges that opinions, findings and conclusions or recommen-
dations expressed in any publication generated by the NRF support-
ed research are that of the author(s), and that the NRF accepts no
liability whatsoever in this regard.
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