A new approach to single shot laser ablation - Department of ...

PAPER www.rsc.org/jaas | Journal of Analytical Atomic Spectrometry
A new approach to single shot laser ablation analysis and its application to
in situ Pb/U geochronology
J. M. Cottle,* ab M. S. A. Horstwood b and R. R. Parrish b
Received 8th December 2008, Accepted 9th July 2009
First published as an Advance Article on the web 30th July 2009
DOI: 10.1039/b821899d
A novel approach to laser ablation Pb/U geochronology is presented that allows accurate
determination of isotope ratios from a single pulse of a 193 nm laser. Data are acquired using a low
volume ablation cell that facilitates: (1) production of a high density particle stream; and (2) a short
( 0.5 s) sample washout time. Isotope ratios from an individual laser pulse are calculated by
integrating the baseline-subtracted total number of counts for the entire pulse and assigning an internal
uncertainty based on counting statistics. This ‘total signal integration’ method eliminates the effects of
differing detector response times, particularly in multi-collector-inductively coupled plasma-mass
spectrometry (MC-ICP-MS), providing an alternative means to quantify transient signals. Data from
reference zircons indicate that it is possible to consistently measure 206 Pb/ 238 U and 207 Pb/ 206 Pb ratios
with external reproducibilities of 2% and 2.8% (2SD) respectively, using a similar amount of material to
standard static ablation protocols. Decreasing sample consumption to 14 ng zircon ( 75% less
than the ‘normal’ ablated mass) results in only a modest increase in the uncertainty to 5% on the
206 Pb/ 238 U ratio. By analysing consecutive laser pulses from the same ablation site, isotopic depth
profiles can be generated with a depth resolution of 0.1 mm pulse 1 . This technique offers a new
opportunity to identify complexities within accessory minerals that were previously beyond the
spatial resolution of laser based geochronology methods.
Introduction
Continued developments in laser ablation-inductively coupled
plasma mass spectrometry (LA-ICP-MS) over the past decade
(e.g. use of shorter wavelength lasers and more sensitive mass
spectrometers) have facilitated the production of ever more
precise and accurate U(-Th)-Pb age determinations from
a variety of accessory phase minerals. Alongside improvements
in precision, a fundamental goal of laser ablation geochronology
is to increase the spatial resolution with which analyses can be
performed; thereby decreasing the amount of sample consumed
and ultimately leading to avoidance of mixing micron-scale
complexities during analysis. This objective has largely been
addressed by using smaller ablation spot sizes and/or shorter
acquisition times. However, for the most part, analyses are
carried out using continuous pulsing of the laser at relatively high
repetition rates (>5 Hz) and a static or dynamic ablation
protocol (see e.g. Kosler 1 and Simonetti et al. 2 for reviews).
Because the signal generated by the laser ablation process is
generally transient, acquisition methods typically acquire data
from ablations lasting up to several tens of seconds, with the
minimum length of the analysis being largely determined by
the precision required on the least abundant isotope of interest
( 207 Pb in the case of U(-Th)-Pb geochronology). Continuous
a Department of Earth Science, University of California, Santa Barbara,
CA, 93106, USA. E-mail: cottle@geol.ucsb.edu; Fax: +1 805-893-2314;
Tel: +1 805-893-3471
b NERC Isotope Geosciences Laboratory, British Geological Survey,
Kingsley Dunham Centre, Keyworth, UK NG12 5GG; Fax: +44 (0) 115
936 3302; Tel: +44 (0) 115 936 3037
pulsing of the laser introduces a time-dependent elemental fractionation
with increasing crater depth 3 and although this can be
corrected 4 its minimisation is an important step to achieving the
goals outlined above.
An alternative approach to multi-second analyses is to obtain
information from the shortest time-interval possible, i.e. on the
single laser pulse scale. Several workers have experimented with
single laser pulses for a range of applications including time-offlight
mass spectrometry (TOF-MS) 5 and quantification of fast
transient signals. 6,7 Although this work met with some considerable
success, these workers highlighted several issues with
single shot analysis including poor reproducibility of shot-toshot
laser irradiance, 5 issues of spectral skew on single collector
ICP-MS 6 and potentially large deviations in the inter-element 7
and isotopic ratio(s) with successive laser pulses.
Therefore, despite the potential illustrated by this work there
have been few attempts to rigorously quantify isotope or interelement
ratios from single pulse spectra and assess their potential
application to U(-Th)-Pb geochronology and the earth sciences
generally. In this contribution we present a new method for
obtaining accurate isotopic data from single laser pulses that
seeks to minimise sample destruction whilst maximising the
spatial resolution of the analyses. This relatively straight forward
technique involves mounting crystals on double-sided sticky tape
and ablating the outer surface of the grains using single pulses of
a laser beam with a view to targeting the thin magmatic and
metamorphic zircon rims often seen on zircons. The material is
then analysed using multi-collector-inductively coupled plasma
mass spectrometry (MC-ICP-MS). We demonstrate, with data
from reference zircons, that this method is capable of producing
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accurate ages with comparable uncertainties to conventional
static spot analyses whilst consuming only two-thirds, and
potentially as little as 10%, of the material. Case studies from
complex natural zircons highlight the geologic utility of this
approach for obtaining reliable ages from age domains in
accessory phases that are otherwise beyond the limit of static
spot protocols. Finally, the potential for this method to generate
age depth profiles is considered.
Instrumentation
Pb/U isotope data were collected using a Nu Instruments’
Nu-Plasma HR MC-ICP-MS at the Natural Environment
Research Council Isotope Geosciences Laboratory (NIGL) UK.
The detection system in this instrument comprises 12 Faraday
cups and three ETP discrete dynode electron multipliers.
Analytical set-up and operating conditions are summarised in
Table 1. Faraday detectors equipped with 10 11 ohm resistors were
used to measure 238 U, 235 U, 205 Tl, 203 Tl and 202 Hg whilst 207 Pb,
206 Pb, and 204 X (where X represents the isotopes of Pb and Hg)
were measured on ion counters. 202 Hg was used to correct for
the 204 Hg isobaric interference on 204 Pb assuming a 204 Hg/ 202 Hg
natural isotopic composition of 0.22988, adjusted for mass bias
assuming 205 Tl/ 203 Tl ¼ 2.38925.
A Tl- 235 U solution was simultaneously aspirated into the
plasma via a Nu Instruments’ DSN-100 desolvating nebuliser to
correct for instrumental mass bias and to monitor plasma
induced inter-elemental fractionation. The Tl- 235 U solution was
also used to determine ion counter gain prior to analysis by
measuring the isotope pair of 205 Tl- 203 Tl first in Faraday cups
then by peak switching the 205 Tl through the three ion counters.
Total gain variation is usually

Fig. 1 Scanning electron microscope (SEM) secondary electron images
of ablation craters in the Himalayan zircon analysed during this
study. In both cases the laser settings used were 35 mm spot diameter
and 2.4 J cm 2 . (a) Twenty pulses equating to a final depth of 3 mm;
(b) from left to right: 5 ( 0.8 mm deep), 10 ( 1.5 mm deep), and
30 (final depth of 3 mm) pulses respectively.
followed by an ‘on-peak’ zero (OPZ). These were subtracted
on-line from the raw counts to give an OPZ baseline-subtracted
isotope intensity, apart from the continuously aspirated 203 Tl,
205 Tl and 235 U peaks which only had the ESA zero subtracted. A
dead-time correction was applied to isotopes measured on ion
counters using dead-time values of 7, 6 and 9 ns for IC0, IC1 and
IC2 respectively. A correction for the time-response delay (Tau)
of the Faraday detectors was made using the Nu Instruments
software. 204 Hg- 204 Pb interference correction, Tl correction for Pb
mass bias, initial Tl-U mass bias correction for Pb/U and final
Pb/U normalisation to the reference material were all carried out
off-line using an Excel spreadsheet.
Fig. 3(a) illustrates a time-resolved isotope trace for a single
pulse analysis (35 mm spot diameter, 2.4 J cm 3 fluence, and
1 Hz repetition rate) of Plesovice zircon. After the laser is fired
(at t ¼ 0 s) there is a delay of 1.2 s until a signal is registered by
the electron multipliers, representing the travel time of material
from the site of ablation to the plasma. Both Faraday and
multiplier signals rise at a similar rate but it is evident that the
time taken for the Faraday to reach its peak signal intensity is
delayed by 0.2 s relative to the multipliers.
Assuming that ionisation of the material and response of the
ion counting detector is instantaneous it is possible to make some
observations regarding the timing and nature of material flux to
the plasma. From Fig. 3(a) it is evident that material is being
transported to the plasma over an interval of 1.4 s (period of
1.2 and 2.6 s on Fig. 3(a)). The form of the signal profile can be
taken as reflecting the shape of the pulse of ablated material with
respect to its mass, assuming all particles are ionised and
contribute to the signal profile equivalently. The profile is near
symmetrical suggesting a near symmetrical mass of material
arriving at the plasma. The loss of symmetry exhibited in the
period between 2.1–2.6 s indicates a tail of particles after the
main pulse. The cell geometry and set-up therefore appear to
produce a largely symmetrical pulse of material with a small tail
of particles constituting a minimum washout time of 0.5 s.
Interestingly, the signal profile for the Faraday detector exhibits
a similar shape following the asymptotic shape of the ion counter
profile as the signal decays. This suggests that the input Faraday
Tau corrections are not limiting in this instance. The Faraday
Tau corrections were pre-determined for each collector and
applied on-line using the Nu Plasma instrument control software.
This involves determining the response for each collector
on removal of a >3 V ion beam and applying an arithmetic
correction to achieve a remnant ion signal of

Fig. 3 (a) Time-resolved profile for a single laser pulse analysis of Plesovice reference zircon. Note the apparent 0.2 s time-lag between intensities
recorded by the electron multipliers ( 206Pb and 207Pb) versus the Faraday detector ( 238U). This time-delay results from using a Faraday detector equipped
with a 1011 ohm resistor. A single intensity for each isotope (and therefore a single isotopic ratio) for each pulse is calculated by summing the total
number of counts for each isotope over the period 0.8–3.0 s. Uncertainties for each isotopic ratio are calculated through counting statistics. (b) The
207 206 206 238 207 206 Pb/ Pb and Pb/ U ratios were also calculated using a 200 ms integration interval. Also plotted for comparison are the ‘mean’ measured Pb/ Pb
and 206Pb/ 238U ratios from 20 40 s spot ablations run during the same analytical session.
multi-second static or dynamic ablations include: (1) producing
ratios of the mean intensities for each isotope measured multiple
times over a selected time-interval (e.g. Quadrupole ICP-MS) or
(2) calculating isotopic ratios on an integration-by-integration
basis (e.g. MC-ICP-MS). Applying either method to a single
pulse, such as that in Fig. 3(a), will yield erroneous results as
demonstrated by Fig. 3(b). Fig. 3(b) plots the 207 Pb/ 206 Pb and
206 Pb/ 238 U ratios calculated using each 200 ms integration
interval. Also plotted for comparison are the ‘mean’ measured
207 Pb/ 206 Pb and 206 Pb/ 238 U ratios from twenty 40 s spot ablations
run during the same analytical session. Fig. 3(b) reveals that
207 Pb/ 206 Pb ratios calculated from any 200 ms integration during
the period 1.4–2.0 s are accurate relative to the mean measured
multi-second ‘normal’ ablations, reflecting the simultaneous
response of the multipliers. In contrast, individual 206 Pb/ 238 U
ratios deviate consistently relative to this mean, largely as a result
of the time-offset between the signal intensities of the Faraday
and the multipliers and the variable nature of the ablation signal.
Because of the potential inaccuracies in calculating ratios by
these methods we use an alternative method, integrating the
whole of each pulse. This technique uses the time-resolved
analysis mode software on the mass spectrometer, to sum the
total number of baseline-subtracted counts for each isotope from
baseline-to-baseline on either side of the pulse (in this case 0.8 s to
3.0 s). By summing the total number of counts for each isotope
we eliminate the time-offset and decay (Tau) effects of the
Faraday detector relative to the ion counter, because as long as
the total signals for each isotope are integrated from before-shot
baseline to after-shot baseline there will be no systematic offset of
the resulting isotopic ratios.
Uncertainties for each isotope ratio were calculated by
assigning the limiting uncertainty based on counting statistics for
the smallest ion beam of the isotope pair in question (e.g. that for
207 Pb in the case of the 207 Pb/ 206 Pb ratio) propagated with the
standard deviation of this ratio for the ablation reference material
(as outlined by Horstwood 12 ). Because the 207 Pb isotope
yields the lowest intensity, its measurement uncertainty
dominates the uncertainty budget for the 207 Pb/ 206 Pb ratio of any
single pulse analysis.
Reference zircon data
We performed two separate experiments using the 91500
zircon, 13 treated as an ‘unknown’ or secondary reference material,
normalised to Plesovice zircon 14 as the primary reference
material. The aim of these experiments was to investigate the
precision and accuracy of this approach for geochronology
studies. In the first experiment we collected data from
30 consecutive pulses at the same ablation site (Fig. 4). The first
1358 | J. Anal. At. Spectrom., 2009, 24, 1355–1363 This journal is ª The Royal Society of Chemistry 2009

Fig. 4 Plots of 30 consecutive baseline-subtracted 206 Pb/ 238 U (A) and
207 Pb/ 206 Pb (B) ratios for two reference zircons (91500 and Plesovice).
Note that the first three ratios are inaccurate due to a significant
component of surface common-lead.
three pulses were discarded from both ‘reference’ and ‘unknown’
due to high surface common-lead.
The internal data point uncertainties on the measured
207 Pb/ 206 Pb and 206 Pb/ 238 U ratios for an individual pulse of ‘91500’
zircon are 2 and 2.8% (2s) respectively. The shot-to-shot or
‘within run’ reproducibility of the measured 207 Pb/ 206 Pb
and 206 Pb/ 238 U ratios is 3.6 and 3.2% (2s) respectively for
91500 (Fig. 4). The fractionation index of the measured
206 Pb/ 238 U ratio with increasing pulse number, calculated as the
mean ratio of the second half of the run relative to that of the first
half, 3 is 1.017 0.028 (2SD) for 91500 and 1.005 0.026 (2SD)
for Plesovice (Fig. 4(a)). Rejecting the first three analyses of
91500 yields a weighted mean 206 Pb/ 238 U age of 1070 6.0 Ma
(mean square weighted deviates (MSWD) ¼ 1.2) (Fig. 5(a))
in reasonable agreement with the published 206 Pb/ 238 U age of
1062.4 0.4 Ma. 13 During this experiment material was excavated
at a rate of 0.15 mm pulse 1 for a spot diameter of 50 mm,
yielding a total volume of material ablated for 30 pulses of
8836 mm 3 (calculated by measuring the pit depth with an SEM).
This equates to 41 ng zircon, 0.61 pg total ablated Pb (assuming
a specific gravity of 4.65 g cm 3 15 and 14.8 ppm Pb in 91500 13 ).
For comparison, at NIGL the standard ablation protocol
employs a 30 mm spot diameter, a duration of 40 s (including
grow-in and washout time) and comprises 200 pulses (at 5 Hz)
ablating down to 16 mm. 8,12 This results in a total ablated volume
of 11 310 mm 3 , and consumption of 53 ng zircon, 0.78 pg Pb
(for 91500). For similar LA-MC-ICP-MS set-ups, spot sizes and
ablation durations, Simonetti et al. (40 mm spot, 15 mm pit
depth) 2 utilise 1.3 pg total Pb per analysis of 91500 zircon whilst
Simonetti et al. 16 (40 mm spot 5 mm pit depth) utilise 0.43 pg total
Pb per analysis of 91500. A run of 30 consecutive single pulses
Fig. 5 Pb/U concordia diagrams for: (a) 30 consecutive 1 Hz pulses; and
(b)–(d) three different groups of 10 1 Hz pulses for 91500 zircon,
normalised to Plesovice analysed using the same conditions. The uncertainties
also include uncertainties related to the external reproducibility
of the primary reference material.
using the ablation conditions stated here, therefore consumes
around the same amount of material as standard spot ablation
protocols regularly employed by the geochronology community.
In the second experiment we obtained ten consecutive pulses
from a single ablation site and repeated this in three different
locations on the same crystal of ‘91500’ zircon. Again rejecting
the first three pulses from each site, we obtained weighted mean
206 Pb/ 238 U ages of: 1066 11 Ma (Fig. 5(b)), 1070 11 Ma
(Fig. 5(c)) and 1058 18 Ma (Fig. 5(d)) respectively, all with
MSWD values close to unity. The uncertainties on these analyses
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are larger than for the 30-pulse experiment since each represents
3 less data and the weighted mean calculation is dependent on
the square root of n. Nevertheless, they are consistently within
uncertainty of the accepted age. The total volume of ablated
material for each ten-pulse run is 2945 mm 3 (13.7 ng zircon,
0.2 pg Pb), indicating that approximately 75% less material is
consumed relative to our standard ablation protocol. Of particular
note is that each pulse of the laser produces isotope ratios
that are consistently accurate, within the defined uncertainty
ellipse whilst consuming only 1.4 ng of zircon ( 20 fg Pb)
therefore allowing interpretation of a pulse-to-pulse change in
isotope ratio as indicative of depth related changes in composition.
This is around half the material used by the small-spot
multiple-shot approach of Johnston et al. 17 which used 3ng
zircon and ablated down 4 mm. Sensitivities for this latter
approach are quoted as 2270 cps ppm 1 ng 1 U and (by calculation)
1350 cps ppm 1 ng 1 206 Pb. Equivalent sensitivities
described here are six times higher at 13 835 cps ppm 1 ng 1 U
and 8050 cps ppm 1 ng 1 206 Pb (assuming 950 ppm U and
50 ppm Pb in Plesovice). This difference is likely the result of the
better transportation dynamics of the low volume ablation
chamber utilised in this approach. Using half the material
therefore still allows a three-fold improvement of the signal/noise
ratio compared to the Johnston et al. 17 approach but sacrifices
two-dimensional resolution (35–50 mm vs. 14 mm) for greater
resolution in the third-dimension (0.15 mm vs. 4 mm). This is
important for resolving the existence of thin metamorphic rims
on zircons, the target of our study, which might otherwise be
missed. Clearly, however, there is scope to utilise a combination
of these two approaches to obtain data of equivalent quality on
sectioned polished representative cathodoluminescence (CL)imaged
zircons using ablation spots smaller than stated here but
shallower than stated in Johnston et al. 17 Since the data quality
will be governed by counting statistics, an ablation, of equivalent
volume to that described here for the 50 mm one-pulse approach
using our set-up, would be expected to yield data of equivalent
quality in an ablation pit of dimensions 20 mm wide 1 mm deep
( 1.5 ng zircon) and would require only 6 pulses (depending on
whether the accumulation of count rate was a purely linear
effect). Experiments to optimise this approach for the application
of dating complexly zoned zircon phases in a similar way to that
shown in Johnston et al., 17 whilst still maintaining a depth
resolution of 100 km then rapidly exhumed during the early stages of the
Fig. 6 CL-images of zircons from (a) KV16 and (b) BK14. Both contain
thin rims surrounded by inherited cores that are too small to analyse by
conventional in situ techniques.
Himalayan orogeny. For a full background to this sample the
reader is referred to Parrish et al. (and references therein). 18
Three single grain zircon fractions from KV16 were analysed
by isotope dilution-thermal-ionisation mass spectrometry (ID-
TIMS). They yield a linear discordia trajectory with intercepts of
45.5 6.6 Ma and 350 150 Ma (MSWD ¼ 0.4, 2s) (Fig. 7(a)).
These data were interpreted by Parrish et al. 18 as being consistent
with a mixture of Palaeozoic zircon (from the granitoid protolith)
and Tertiary overgrowths. The depth resolution capability
of the single pulse technique offers an ideal opportunity to
establish the age of these ‘Tertiary overgrowths’ (Fig. 6(a)) with
greater precision than the ID-TIMS analyses and thereby further
refine the timing and duration of high pressure metamorphism
and subsequent exhumation of these rocks.
We selected several zircon crystals from the same bulk separate
from which the ID-TIMS fractions were picked, and mounted
them on double-sided sticky tape. Ten consecutive single pulse
ablations were made on four randomly selected crystals. The spot
size (50 mm) and laser fluence ( 2.5 J cm 2 ) were optimised to
give good signal strength at a repetition rate of 1 Hz. These
settings equated to a drill rate of 0.13 mm pulse 1 (as measured
by SEM). As with the reference zircons described above, the first
three pulses were discarded because they were dominated by
common-lead. Whilst the majority of the remaining analyses are
concordant, the presence of several sub-concordant points is
interpreted to reflect a small amount of residual common-lead in
these analyses. Pooling the data yields a weighted mean
206 Pb/ 238 U age of 47.2 0.5 Ma (2SD, MSWD ¼ 1.6, n ¼ 27)
(Fig. 7(c)). This age is consistent with 46.4 0.9 Ma allanite from
the same rock 16 as well as 46.4 0.1 Ma zircon from a mafic
eclogite enclosed within the gneiss, validating the geologic
significance of the age and our methodology.
As a second example, BK14 is an augen gneiss from the
Greater Himalayan Series of north-central Bhutan (the geologic
context of this sample is given by Parrish et al.). 19 Five single and
one multi-grain zircon fractions were analysed by ID-TIMS.
1360 | J. Anal. At. Spectrom., 2009, 24, 1355–1363 This journal is ª The Royal Society of Chemistry 2009

Fig. 7 (a) Pb/U concordia diagram for ID-TIMS zircon data for granitic
gneiss KV16 from Kaghan Valley, Northern Pakistan, re-plotted with
permission from ref. 18. Copyright 2006, Geological Society of America.
(b) Pb/ 238 U concordia diagram for 27 single pulse analyses from four
KV16 zircon crystals. (c) 206 Pb/ 238 U ages for the same data in (c).
They yielded a linear discordia trajectory with intercepts of
72 41 Ma and 514 3 Ma (MSWD ¼ 0.45) (inset to
Fig. 8(a)). 19 The upper intercept can be confidently interpreted in
terms of a Cambrian granitoid protolith age, consistent with
numerous other augen gneisses throughout the Himalayas. In
contrast, the lower intercept age is extremely difficult to interpret.
The fact that it yields a ‘non-zero’ age raises at least two
possibilities: (1) there has been a significant amount of radiogenic
Fig. 8 (a) Pb/U concordia diagram of ID-TIMS zircon data from
orthogneiss BK14. (b) Pb/U concordia diagram for 14 consecutive single
pulses from a single BK14 zircon. (c) and (d) 206 Pb/ 238 U age depth profiles
for two zircon crystals from BK14.
lead loss, and/or (2) that new zircon growth occurred during the
Himalayan orogenesis (i.e. at

of material consumed and precision achieved, nevertheless it
demonstrates that by using the single pulse method it is possible
to extract geologically meaningful age information from
domains as thin as 1 mm in zoned accessory phases.
Summary
The method presented here represents a significant departure
from previous LA-ICP-MS Pb/U acquisition protocols. Standard
procedures employ continuous pulsing of the laser at higher
frequencies and a multi-second analysis period. In contrast, our
data demonstrate that it is possible to extract isotope data from
single pulses of a laser with uncertainties useful for Pb/U
geochronology. Within a single pulse profile, integration-byintegration
isotopic and inter-element ratios are inaccurate when
measured on disparate detectors, largely as a result of differing
detector response and decay times. This can be overcome by
employing a total signal integration method that sums the
intensities of each isotope for the entire pulse duration and
calculates a single intensity for each analyte. Isotope ratios and
resulting ages obtained from reference zircons are consistently
within the uncertainty of published values validating our total
signal integration approach.
Pooling 30 single pulse analyses produces total uncertainties
that are comparable to data from a multi-second smaller spot
analysis. It is possible to reduce sample consumption to 75% less
material than ‘normal’, with the resulting 2 loss in precision,
balanced by the benefit of minimal sample destruction.
For a 30 pulse analysis the Pb/U fractionation with increasing
pulse number (which equals depth) is in the order of 1.7% and
0.5% for 91500 and Plesovice reference zircons respectively. This
contrasts with 8% fractionation during normal 40 s static
ablations at 25–50 mm spot diameter, 2–3 J cm 2 fluence at 5 Hz
repetition rate (equating to 200 pulses/analysis, e.g. ref. 12).
This is attributed to the low crater depth/diameter aspect
ratio of

Acknowledgements
The Natural Environment Research Council is thanked for
providing support to NIGL which allowed support of J.M.C. as
an NIGL Isotope Apprentice and the development of this
application. Simon Chenery and three anonymous reviewers are
thanked greatly for helping improve the manuscript through
their constructive reviews.
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