Chemical Geology 207 (2004) 135 – 145

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Apatite fission-track chronometry using laser ablation ICP-MS

Noriko Hasebe a,*, Jocelyn Barbarand b, Kym Jarvis c,
Andrew Carter a, Anthony J. Hurford a
a
Research School of Earth Sciences, University College and Birkbeck College, London WC1E 6BT, UK
b
Department des Sciences de la Terre, Université Paris Sud, France
c
NERC ICP-MS Facility, Kingston University, Surrey KT1 2EE, UK
Received 27 August 2003; accepted 13 January 2004

Abstract

Comparison is made of apatite fission-track (FT) ages measured by using conventional thermal neutron irradiation and Laser
Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) to determine sample uranium content. Spontaneous
track densities were determined on specified apatite grains from the Durango, Fish Canyon Tuff, and Mount Dromedary
Complex age standards. Neutron-induced track densities and ICP-MS uranium values were determined for the same specified
grains. Ages determined using the two approaches show reasonable consistency, indicating the possibility of routine fission-
track analysis using LA-ICP-MS. Uncertainties and assumptions in the LA-ICP-MS approach include the laser ablation of
chemically etched mineral surfaces, the suitability of reference materials for calibration, and the derivation of FT ages using the
alternatives of selection of a kf value or a revised zeta comparative approach. The use of LA-ICP-MS in FT chronometry would
dramatically increase the speed of analysis and hence sample throughput, as well as avoiding the need for neutron irradiation
and the production, transport and handling of radioactive samples. With the acknowledged dependency of FT annealing in
apatite on composition, such grain-by-grain, multi-element analysis could provide a more robust definition of the specific track
annealing characteristics of each apatite crystal.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Apatite; Fission-track chronometry; Laser ablation

1. Introduction variety of geological applications (see, e.g. Green et

1.1. Uranium measurement in conventional FT
method
Fission-track (FT) chronometry is widely used to
establish both age and thermal history in a wide
* Corresponding author. Present address: Institute of Nature and
Environment Technology, Kakuma-machi, Kanazawa, Ishikawa 920
1192, Japan.
al., 1989; Gallagher et al., 1994; Fitzgerald et al.,
1995; Carter, 1999; Kohn and Green, 2002). Conven-
tionally in the FT method, uranium concentration is
determined using a neutron activation technique to
induce fission in a proportion of 235U atoms, record-
ing the fission events in an external detector to give
essentially a map of uranium distribution (e.g.
Gleadow, 1981; Hurford and Green, 1982). A major
strength of this approach is that data are collected
from identical areas on individual grains and their
mirror-images in the detector, particularly important

0009-2541/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemgeo.2004.01.007
136 N. Hasebe et al. / Chemical Geology 207 (2004) 135–145
when analysing sedimentary samples where variable
provenance and/or mineral chemistry (including ura-
nium content) may result in grains having different
ages. However, this methodology contains a number
of uncertainties, including the absolute value of the
238
U spontaneous fission decay constant (kf) (Bigazzi,
1981), the efficiency of irradiation in terms of induc-
ing fission of 235U (Green and Hurford, 1984), and the
geometry factor which relates to registration of in-
duced fission tracks on an external detector (Gleadow
and Lovering, 1977). To overcome these issues, the
FT community adopted a system calibration based on
the comparison of sample measurement with the
analysis of standards whose ages are known—the zeta
calibration (Fleischer and Hart, 1972; Hurford, 1990;
Hurford and Green, 1983). Using the zeta approach
and common age standards has resulted in a unified
system of calibration which has been highly effective
over the last 12 years and has produced a wealth of
useful data in diverse geosciences applications.
Whilst zeta circumvents many of the technical
uncertainties, the quality of sample irradiation remains
a fundamental limitation on the quality of data. The
number of research reactors able to deliver suitable
levels of neutron thermalisation for FT analysis (Hur-
ford, 1990; Tagami and Nishimura, 1992) is limited
and recently environmental, safety and political pres-
sures have led to a number of suitable reactor facilities
closing. A consequence is that FT samples are having
to be sent across the globe for irradiation with the
ensuing real problems of loss, damage, disturbance
through customs inspection, longer turn-round times,
transport of modestly active samples and lack of direct
collaboration with reactor staff. With the surviving
research reactors getting older and a low probability
of replacement (especially with positions that give
suitable thermal/epithermal flux ratios), alternative
approaches to uranium determination merit serious
exploration.
1.2. Alternative method for uranium measurement
This study considers the suitability of Laser Abla-
tion-Inductively Coupled Plasma-Mass Spectrometry
(LA-ICP-MS) as a method for direct measurement of
uranium concentrations for determination of single-
grain fission-track ages. LA-ICP-MS has been used
widely to measure the chemical composition of small
amounts of solid samples in many fields (e.g. envi-
ronmental, geological, and archeological sciences).
The methodology does not require special sample
preparation such as sample dissolution and carbon
film coating, and is therefore time efficient. In the
earth sciences a wide range of elements including rare-
earths are routinely measured on a single-grain basis
(e.g. Jarvis and Williams, 1993; Odegard, 1999) to
study, for example, mineral growth process through
metamorphism (e.g. Rubatto, 2002) and the fractional
coefficient of target element (e.g. Ertel et al., 2001).
Initially, the use of ICP-MS methods for U – Pb geo-
chronology required zircon with uranium contents
generally >50 Ag/g (e.g. Hirata, 1997; Horn et al.,
2000). The method has now matured such that it offers
spatial resolutions down to f 10 Am, and for U – Pb
applications, permits rapid analyses ( f 30 ages/h)
with precision equivalent to that of the ion probe,
provided a f 40– 60 Am diameter ablated pit is used.
Importantly, high precision in situ isotopic analysis is
now possible with laser-ablation multi-collector ICP-
MS for U – Th isotopic compositions (e.g. Stirling et
al., 2000; Horn et al., 2000). Whereas zircon has been
the main focus of LA-ICP-MS geochronological stud-
ies, apatite has seen comparatively little research (e.g.
Kimura et al., 2000; Gleadow et al., 2002). One area
that has been briefly mentioned is the viability of using
LA-ICP-MS methods for uranium measurement for FT
analysis (e.g. conference abstracts by Cox et al., 2000;
Svojtka and Kosler, 2002). The aim of this study is to
build on these preliminary proposals and provide a
more complete assessment of the suitability of LA-
ICP-MS methods for uranium mapping in apatite, to
determine whether it is a viable alternative to the
neutron irradiation methods currently used in FT
analysis.
2. Experimental details
2.1. Conventional FT method
Aliquots of the apatite FT age standards from
Durango, Fish Canyon Tuff and Mount Dromedary
Complex (e.g. Hurford, 1990; Green, 1985) were
mounted in resin, polished and the spontaneous tracks
etched using standard techniques (Hurford et al.,
1999), before irradiation in close contact with low-
 N. Hasebe et al. / Chemical Geology 207 (2004) 135–145 137

uranium mica detectors in thermal neutron facility Table 2

4VGR of the reactor PLUTO, Harwell, UK (Cd ratio ICP-MS and laser operating conditions
for Au > 500). Tracks from the induced fission of 235U ICP-MS: instrument operating conditions
Instrument Thermo Elemental
were recorded in the external mica detectors. Glass
PlasmaQuad PQ2+ STE
dosimeters Corning CN5 ( f 12.2 Ag/g natural urani- Forward power 1.5 kW
um, Bellmans et al., 1995) or NIST 612 (37 Ag/g Reflected power <5 W
depleted uranium, Pearce et al., 1997) together with Plasma gas argon
detectors were included to monitor each irradiation. Coolant gas flow rate 14 l min 1
Carrier gas flow rate 0.975 l min 1
After irradiation, the mica external detectors from age
Auxiliary gas flow rate 1.5 l min 1
standards and dosimeters were etched in 48% HF acid
at 20 jC for 30 min and the track densities counted ICP-MS: data acquisition parameters
using a Zeiss Axioplan optical microscope with a Dwell time 100 As
100
dry objective and 1250x total magnification. Channels 20
Sweeps 100
Ten to fifteen grains were analysed for each apatite
Data acquisition time 5s
standard, the grain location and specific area counted Data acquisition mode scanning
being recorded on photomicrographs. Table 1 provides Isotopes measured 44
Ca, 232Th and 238
U
a summary of the FT analytical data.
Laser: operating conditions
Laser type CETAC LSX100 Nd:YAG
2.2. LA-ICP-MS
Wavelength 266 nm
Laser mode Q switched
Uranium measurements were carried out using Laser output energy 0.422 mJ
LA-ICP-MS on exactly the same grains of apatite Shot repetition rate 10 Hz
standards used in the FT analyses to permit direct Sampling scheme Zig-zag raster area f 50
50 Am
comparison of results. Analysis was made at the NERC
ICP-MS facility, Kingston University, using a Cetac
LSX-100 (wavelength 266 nm) laser with an energy of FT and LA-ICP-MS data from equivalent areas. ICP-
0.422 mJ measured as energy output from the laser MS and laser ablation operating parameters are given in
head. Scan speed was 10 Am/s with firing repetition rate Table 2. Ablated material was introduced into a VG
of 10 Hz and an ˜ 10A beam diameter. The analysis was Elemental PlasmaQuad 2+ STE, and 238U concentra-
carried out using the raster mode, i.e. ablation took tions were calibrated against NIST 610 and NIST 612
place in a zig-zag pattern. The space between lines of standard glasses (Pearce et al., 1997). Standards were
ablation was set to be 25 Am to avoid overlap of two measured every f 30 min using the same procedure as
adjacent trenches. For each grain the total ablated area for apatite to monitor the stability of the signal, together
was broadly equivalent to that counted for fission with the gas blanks. In total six datasets were provided
tracks (e.g. 50
50 Am), allowing direct comparison for a whole measurements. One dataset contains three

Table 1
Fission-track apatite ages calculated by conventional neutron irradiation and LA-ICP-MS methods
Apatite No. of qs, Ns qi, Ni Dosimeter qd, Nd P(v2), tconv, Ma tlaser, Ma U, ppm
sample grains 106 cm 2 106 cm 2 glass 106 cm 2 % ( F 1r) ( F 1r)
DUR 11 0.18 323 1.79 3153 CN5 1.65 1144 80 26.8 F 1.9 29.7 F 1.9 14.9
FCT 14 0.24 145 1.05 626 SRM612 0.943 1045 53 33.7 F 3.5 30.6 F 2.7 19.7
MDC 12 0.97 839 3.47 2990 SRM612 2.45 1356 0.02 106 F 6 94.6 F 4.5 28.4
DUR = Durango; FCT = Fish Canyon Tuff; MDC = Mount Dromedary Complex.
Ns,i,d = numbers of tracks counted for spontaneous, induced and dosimeter measurements; qs,i,d = densities of spontaneous, induced and
dosimeter tracks cm 2, tconv = fission track pooled  age calculated from pooled Ns and Ni for all grains counted using zeta values shown in
Table 2; P(v2) = probability of v2 for (n  1) degrees of freedom (Galbraith, 1981); U = average uranium content of all grains measured by LA-
ICP-MS; tlaser = weighted mean of grain ages calculated from individual Ns and 238U content measured by LA-ICP-MS.
138 N. Hasebe et al. / Chemical Geology 207 (2004) 135–145
measurements for each standard glass. Data reduction
was carried out in Microsoft Excel. 44Ca was used as an
internal standard using chemical data obtained previ-
ously (e.g. Jarvis and Williams, 1993; Barbarand et al.,
2003). Blank correction was performed prior to internal
standard correction. All samples and standards were
corrected for change in 44Ca throughout the run.
However, the gas blank was not internally standardised
in any way since it does not contain calcium. Corrected
integrals for NIST 610 and NIST 612 were used to
construct calibration lines which were forced through
the origin.
3. Measurement of uranium content
3.1. Induced FT method
The uranium concentration of each apatite grain
was determined by comparing its induced-track
density in an external detector with that of a
uranium dosimeter glass (also recorded in an ex-
ternal detector) using the equation:
qi A235dos g  REDdos
U¼  Udos   ð1Þ
qd A235 g  RED
where U = total uranium content of apatite (Ag/g),
qi = induced track density for an apatite grain mea-
sured in an external detector (cm 2), qd =induced
track density for the dosimeter glass measured in an
external detector (cm 2), Udos = the uranium content
of the dosimeter glass (Ag/g), A235dos = 235U abun-
dance in weight for the dosimeter glass (g/g),
A235 = 235U abundance in weight for the apatite (g/g),
g = geometry factor, necessary because tracks
recorded in the external detector have a 2k geometry
(originating from only one side of the observed
surface), whilst tracks in apatite have a 4k geometry
(coming from both sides of the viewed surface); equal
to 0.5 for the c-axis parallel apatite sections analysed
in this study. REDdos = a registration efficiency factor
for 235U induced tracks in the dosimeter glass (cm),
RED = a registration efficiency factor for 235U induced
tracks in the apatite (cm).
The probability of a FT intersecting the observed
surface is a function of two distances: (a) the distance
between the observed surface and a nucleus whose
fission produces an etchable, observable track; and (b)
the distance travelled by the fission fragment (Laslett et
al., 1982). Assuming no preferred orientation in the
fission process and no variation in distance travelled for
different spontaneous fission events, the probability
may be calculated from (Wagner and Van den haute,
1992):
the area of a part of the semi  sphere
representing track orientation in which
a track intersect an observed surface
Px ¼ ð2Þ
the area of the semi  sphere
representing all posible track orientation
Lx
¼
L
where Px = probability of a FT intersecting the ob-
served surface for a nucleus which is x Am away from
the observed surface, and L = distance travelled by a
fission fragment (Am).
Assuming the number of fission events (Dx) at x
Am away from the observed surface is homoge-
neous, the general registration efficiency R is calcu-
lated as
Z L
PxDxdx Z L
0
R¼2
Z L ¼2
Pxdr ¼ L ð3Þ
0
Dxdx
0
Therefore, RED can be estimated as half the in-
duced FT length in apatite ( f 7.9 Am after chemical
etching, Iwano and Danhara, 1998, see also Gleadow
et al., 1986) plus an unetchable track range (and
therefore invisible in apatite) which is visible if the
range is in the mica ( f 1.0 Am) (Iwano and Danhara,
1998). However, measurement of track lengths in
glass and the registration efficiency in an external
detector are less well studied. Accordingly we use a
factor of 1 for REDdos/RED as a first-order estimation of
U concentration by the induced FT method. Consid-
ering that the material exerts a major control on the
registration efficiency (e.g. the difference between
apatite and zircon is more than 30%), the real uranium
concentration might be much more (or less) than the
 N. Hasebe et al. / Chemical Geology 207 (2004) 135–145 139

estimated concentration derived using the ratio RED-

dos/RED. However, the relative relationship between 1
2
grains would be preserved. 3
4

Relative signal Intensity

Uncertainty of the measured uranium concentration 5
6
was calculated using the formation of Green (1981); all

ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
s   2
1 2 1
Uncertainty ¼ U þ ð4Þ
Ni Nd

where Ni = number of counted induced tracks recorded

in the apatite external detector, and Nd = number of
counted induced tracks recorded in the dosimeter
glass external detector.
0 100 200 300 400 500

3.2. LA-ICP-MS calibration and U content U238 content (µg/g)

Fig. 1. Relative LA-ICP-MS signal intensity of 238U for NIST610

Calibration of the LA-ICP-MS analyses was made and 612 standard glasses. Six sets of measurement were made
by measurement of 6 datasets on NIST 610 and 612 during the analyses with a calibration line obtained for each set
glasses interspaced with the apatite sample determi- based on triplicate measurements for each standard glass. Signal
nations. The weighted mean of 238U relative intensity intensity is relative figures after ablated volume correction using Ca-
was calculated from triplicate analysis for each stan- 44 intensity.
dard glass set after ablated volume correction using
Ca-44 intensity and CaO content, and compared
lysed by the FT method. Some apatite grains of the
against 238U concentration based on their published
Mount Dromedary standard did not give a suffi-
uranium concentrations (Pearce et al., 1997) and
ciently strong signal and therefore failed the accep-
isotopic ratio (235U: 0.24% in number of atoms;
tance criteria defined as being a sample signal
Carpenter and Reimer, 1974). Calibration lines (rela-
greater than three standard deviations of the blank.
tive signal intensity vs. 238U concentration) remained
The average uranium content for each sample is
stable within error throughout the measurements (Fig.
listed in Table 1.
1) and this enabled adoption of a mean calibration line
to calculate 238U concentration to within f 10% of
3.3. Comparison of uranium values
analytical error. Total uranium concentration of apa-
tites (Ag/g) was calculated from measured 238U con-
Fig. 2 plots uranium concentrations of apatite
tent (Ag/g) and natural isotope abundance ratio of
grains estimated from neutron-induced tracks and
uranium (235U: 0.72%/238U: 99.28% in number of
from LA-ICP-MS. The data for Durango apatite form
atoms, and 0.71% and 99.29% in weight), making the
a cluster because the analysed apatites are fragments
reasonable assumption of a natural 235U/238U ratio in
of a single large megacryst which has been crushed. In
all apatite samples. Therefore
the absence of zoning and between-grain variation,
238
U broadly similar uranium values would be expected for
U¼ 238 A
ð5Þ all fragments. The Fish Canyon Tuff data show a
broadly linear relationship between the two estimates
where U = sample total uranium content (Ag/g), of uranium. The data points are below the one-to-one
238
U = uranium-238 content (Ag/g) obtained from correlation line, uranium concentrations determined
LA-ICP-MS, and A238 = abundance of 238U in weight by induced-track density being underestimated rela-
(0.9929). tive to the LA-ICP-MS data. This could result from
Uranium concentrations were successfully mea- the approximation of REDdos in the induced FT ap-
sured by LA-ICP-MS on most apatite grains ana- proach, implying that REDdos should be larger when
140 N. Hasebe et al. / Chemical Geology 207 (2004) 135–145

broad cluster with no significant relationship between

the results from the two different approaches used to
determine uranium concentration.

4. Calculation of FT ages

Comparison of ages calculated for the same apatite

grains by both the conventional FT and LA-ICP-MS
approaches represents for chronometry a more useful
assessment of the utility of the new approach.

4.1. Conventional FT ages

Conventional FT ages were determined for each

Fig. 2. Uranium contents in Ag/g of individual apatite grains
determined by LA-ICP-MS and neutron-induced fission-track
density. Error on x-axis is F 10% assessed from reproducibility of
measurements on standard glasses. Error on y-axis is F 1 standard
error derived from track counts. Dur; Durango, FCT; Fish Canyon
Tuff, MDC; Mount Dromedary Complex.
compared to RED, which would be consistent with a
fission fragment travelling further in glass than in
apatite. The Mount Dromedary Complex data show a
apatite grain using the zeta approach (Hurford, 1990;
Hurford and Green, 1983) with data presented in
Table 1. The zeta calibration approach (Fleischer
and Hart, 1972; Hurford and Green, 1983) is a
consensus approach adopted by the FT community
to avoid absolute evaluation of neutron fluence and
selection of a value 238U spontaneous fission decay
constant kf (Hurford, 1990). By definition, the cali-
bration factor zeta must be determined for a dosimeter
glass by analysis of age standards. The zeta values of
319 F 9 for CN5 and 311 F 10 for SRM 612 used in
this study were derived from analysis of the apatite
age standards from Durango, Fish Canyon Tuff and

Table 3
Fission-track data for zeta calibration against apatite age standards
Apatite standard No. of grains qs, 106 cm 2 Ns qi, 106 cm 2 Ni qd, 106 cm 2 Nd fFr P(v2), %
CN5 dosimeter glass
DUR-1 11 0.20 299 1.89 2884 1.6508 1144 368 F 26 67
DUR-2 22 0.14 420 0.86 2632 1.3104 1453 301 F 18 15
FCT-1 20 0.19 252 1.37 1826 1.2996 1441 310 F 22 94
FCT-2 20 0.22 313 1.26 1809 1.1751 1303 274 F 18 99
MDC 21 0.86 1219 1.74 2452 1.1896 1319 336 F 15 0.5
Weighted mean f CN5 319 F 9

SRM 612 dosimeter glass

DUR-1 11 0.14 337 1.57 3847 2.4621 1365 292 F 19 14
DUR-2 11 0.12 254 1.57 3274 2.4621 1365 330 F 24 74
FCT-1 14 0.20 121 1.13 669 0.9425 1045 327 F 38 22
FCT-2 20 0.21 262 1.45 1824 1.2617 1399 307 F 22 27
MDC 10 0.92 375 3.50 1433 2.4459 1356 311 F 20 73
Weighted mean f SRM612 311 F 10
DUR = Durango; FCT = Fish Canyon Tuff; MDC = Mount Dromedary Complex.
Ns,i,d = numbers of tracks counted for spontaneous, induced and dosimeter measurements; qs,i,d = densities of spontaneous, induced and
dosimeter tracks cm 2; P(v2) probability of v2 for (n  1) degrees of freedom (Galbraith, 1981).
 N. Hasebe et al. / Chemical Geology 207 (2004) 135–145 141

the Mount Dromedary Complex (Table 3). However, Because we observe the number of fission decay
these original and multiple zeta calibration experi- events as a spontaneous track density, the equation is
ments were made on separate aliquots and were changed to:
completely independent of the analyses presented in
kf
this study. qs ¼ N238 ðekD t  1ÞRsp k ð7Þ
kD
4.2. LA-ICP-MS FT ages where qs = spontaneous FT density at the observed
surface (cm 2), Rsp = a registration factor by which
238
For the LA-ICP-MS approach, the FT age of each U in a unit volume would leave spontaneous
grain was calculated using an absolute approach tracks on an observed surface (cm), and k = a con-
which required selection of a kf value. Although there stant, which would be variable depending on exper-
is a diversity of values for kf, those direct determi- imental factors such as etching and observation
nations which are independent of absolute neutron conditions.
fluence measurement centre around 8.5
10  17 Here N238 (cm 3) is calculated using the content of
year 1. Of these analyses, we have chosen to use in uranium-238:
this study the precise value of (8.46 F 0.06)
10 17
year 1 (Spadavecchia and Hahn, 1967; Bigazzi, 238
U  106  d
N238 ¼ NA  ð8Þ
1981). M
The general age equation is
where NA = Avogadro’s number, 238U = uranium-238
kf content measured by LA-ICP-MS ( Ag/g), d = apatite
Dt ¼ N238 ðekD t  1Þ ð6Þ density (taken as 3.19 g/cm3), and M = the mass of
kD 238
U. Therefore,
where Dt = number of decay events of 238U during !
time t in a unit volume (cm 3), kf = 238U sponta- 1 qs kD M
t¼ ln 1 þ ð9Þ
neous fission decay constant (8.46
10 17 year 1 kD kf NA238 U106 dRsp k
Spadavecchia and Hahn, 1967), kD = 238U total
decay constant (1.55125
10 10 year 1 Jaffey et In this study we adopted as Rsp a half of the mean
al., 1971), N238 = current number of uranium-238 etchable spontaneous fission-track length in apatite
atoms in a unit volume (cm 3), and t = FT age from geologically rapidly cooled samples without
(years). subsequent thermal disturbance (i.e. unannealed): 7.5

Fig. 3. Single-grain FT apatite ages calculated by using 238U content determined by LA-ICP-MS plotted against FT ages determined by
conventional zeta age calibration. Continuous lines represent reference age of each apatite standard (e.g. Hurford, 1998). Error bars are F 1
standard error.
142 N. Hasebe et al. / Chemical Geology 207 (2004) 135–145
Am = 7.5
10 5 cm (Gleadow et al., 1986), and we
have set k as 1.
The error of a grain age is given by
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1
t þ d2 ð10Þ
Ns2
where Ns = the number of counted spontaneous tracks,
and d = uncertainties in uranium concentration (10% =
0.1).
The results are shown in Fig. 3 with the weighted
mean age for each sample listed in Table 1.
5. Discussion
These first results demonstrate that a LA-ICP-MS
approach to calculating a FT age is viable and offers
an alternative to reactor-based uranium determinations
and mapping. Although the age data produced in this
study are in reasonable agreement with conventional
FT results, several issues need to be resolved in order
to enhance the LA-ICP-MS approach.
5.1. Depth drilled by laser ablation
Firstly, the depth of the ablated trench, estimated in
this study to be 25 F 5 Am by microscopic observation
for most grains although occasionally deeper, needs
better control. In some cases the laser drilled com-
pletely through the smaller grains. The Durango
apatite tends to have shallower pits than other two
samples. The wide scatter of U contents and FT ages
for the MDC apatite (Figs. 2 and 3) could be
explained by the in-grain heterogeneity of U content,
up to a factor of f 4 between, for example, rim and
core of one grain (Kohn, unpublished data). The
variation in ablated depth between samples could be
caused by chemical composition which may change
the optical property and therefore alter the efficiency
of energy absorption. In addition, the spontaneous
track density could also change the ablation character-
istics of material. The aim of ablation is to determine
the uranium concentration of a volume equivalent to
that used to measure spontaneous fission-track densi-
ties. The spontaneous tracks counted on the observed
surface result from fission of uranium both from a
portion of the grain that has been polished away, and
from up to half the distance of a fission-track length
below the polished surface, in total a maximum depth
of f 10 Am. Since we cannot determine uranium
concentrations for the missing portion of the apatite,
we have to rely on data collected from the polished
grain. For the conventional FT method, neutron irra-
diation is used to induce fission forming new tracks
that register in an external detector. The tracks
recorded in the detector are produced by uranium up
to 10 Am (broadly half a fission-track length) below
the grain surface, an approach that assumes no sig-
nificant variation in uranium between the missing and
preserved portions of the apatite, i.e. zoning is unim-
portant over a 20 Am range.
A similar assumption must be made for LA-ICP-
MS analysis, with ablation to greater than half a FT
length sampling uranium in area not equivalent to that
used for FT measurements.
5.2. Etched FT density and laser ablation
LA-ICP-MS measurements were made on apatites
that had been etched to reveal the spontaneous track
densities. If etching removes U or Ca (which is
measured as the internal standard) selectively, the
calculated 238U content would be biased. Currently it
is unknown whether any such losses occur and the
potential significance of any such removal. Further-
more, the levels of etching may change the ablation
characteristics of apatite, whilst differences in the
numbers of etched tracks on an apatite surface may
affect the volume of material ablated and the particle
distribution introduced into the ICP potentially affect-
ing the ionising efficiency, although previous studies
on fractionation (Horn and Gunther, 2002) suggest this
to be unlikely. It is interesting that the apatite which
shows greatest variation in age is that from the Mount
Dromedary Complex (Fig. 3) which has the highest
spontaneous track density ( f 3.5
106 cm 2), sig-
nificantly greater than in the other two samples,
although the scatter is most probably caused by ura-
nium heterogeneity within a grain.
5.3. Age equation
The equation used in this study to calculate the
LA-ICP-MS ages gave reasonable results when
 N. Hasebe et al. / Chemical Geology 207 (2004) 135–145
compared with independent age data. However,
some of the constants in the age equation may
be poorly evaluated. The registration efficiency
(Rsp: equivalent to a half of spontaneous track
length) could vary F 3% according to chemical
composition (Barbarand et al., 2003) and affect
calculated ages by a similar amount. The apatite
density (d) also depends on its chemical compo-
sition and cell parameters, and varies F 1.5% (Bar-
barand, unpublished data), resulting in an additio
nal uncertainty in calculated age. However, such
factors are of minor importance when compared to
the present uncertainties of up to 10% in 238U
measurement.
The lack of an internationally agreed value for kf
remains a problem (Hurford, 1998 and references
therein). Published kf values range from 5 to 12
(10 17 year 1) (Bigazzi, 1981), the majority falling
within two groups which differ by f 15%; choice of
kf could cause this difference of up to 15% to
propagate into the age. Ideally, a consensus agree-
ment should be sought for a single value of kf to be
used in FT chronometry; this might be an easier task
than in the past where the complexity of neutron
fluence measurement was intimately associated in the
discussion. However, even if such a consensus was
reached, it would still be necessary to evaluate a
composite procedural value, the factor Q of Wagner
and Van den haute (1992), which encompasses
differences in etching, counting, microscope, obser-
vation and other experimental variation. An alterna-
tive comparative procedure, avoiding absolute
evaluation of kf, would be analogous to the zeta
approach in the conventional FT method (Hurford
and Green, 1983). A calibration factor (let us call it
epsilon, e) would include experimental differences in
etching and spontaneous track counting (k in the age
Eq. (9) above) and registration factor (Rsp) and
would be defined as:
qs kD M
e¼ 238
kf NA U106 dRsp K
which, when substituted into the age equation, gives:
 
1 qs
t¼ ln 1 þ e  238 ð11Þ
kD U significant advance for the FT method.
143
The factor e would be determined by analysis of age
standard sample, as with the present zeta calibration:
238
U
e¼ ðekD tstd  1Þ ð12Þ
qs
where tstd represents a reference age of the age
standard sample.
5.4. Reference material
The uncertainty in ICP-MS measurement of urani-
um concentration was estimated in this study as up to
f 10%, based on repeated measurements of NIST
standard glasses (Fig. 1). Consideration of the results
from the Durango apatite suggest that the real uncer-
tainty may be larger: despite being the crushed frag-
ments of a single large crystal, the dispersion of
Durango results exceeds the nominal 10% error bars
for LA-ICP-MS shown in Fig. 2. The source of this
additional apparent uncertainty in apatite measure-
ment may arise from a matrix effect: differences in
the behaviours between apatite and standard glasses
through ablation and ionisation processes. Reduced
errors may result from using a standard of similar
composition and ablation-transformation efficiency
(Odegard, 1999; Greenwood and Jarvis, 2002).
5.5. Multi-elemental analysis
In this study, we have measured only the 238U
concentration to obtain the largest gain from a small
amount of sample. However, an advantage of the LA-
ICP-MS lies in multi-element analysis. The annealing
behaviour of fission tracks in apatite is largely depen-
dent on crystal structure and elements substituted in
that structure such as Cl and rare earth elements
(Barbarand et al., 2003). The level of chlorine substi-
tution appears the most influential factor (Green et al.,
1985, 1986; Crowley et al., 1990; Donelick, 1993),
and thus determination of chlorine content may have
an important bearing on robust interpretation of apa-
tite FT data. Although chlorine measurement by ICP-
MS is difficult mainly because of poor ionization
efficiency (e.g. Tran et al., 2001), potentially it may
be possible to measure both uranium, chlorine and
rare earths at the same time. This would represent a
144 N. Hasebe et al. / Chemical Geology 207 (2004) 135–145
6. Conclusions
This study has demonstrated that LA-ICP-MS is a
viable alternative method for measuring uranium
content for apatite FT analysis. LA-ICP-MS analysis
appears to offer a fast and efficient way of acquiring
data with a level of precision comparable to the
current neutron-irradiation technique. However, be-
fore this method can be used routinely, several issues
need to be resolved. Firstly, assessment must be made
of any possible linkage between the level of etching
and spontaneous track density to degradation of
uranium ICP-MS measurement. This requires a better
understanding of how laser ablation works on etched
apatite surfaces. Secondly, consideration must be
given to adopting a consensus value for kf. Or we
could avoid kf by developing a comparative calibra-
tion approach analogous to zeta, linking analysis of
samples to that of standards. Thirdly, a more appro-
priate ICP-MS standard is required, of similar com-
position to apatite, to reduce uncertainties in analysis.
Acknowledgements
Noriko Hasebe’s stay at UCL was supported by
the Japanese Society of Promotion of Science 2000.
Jocelyn Barbarand was supported at UCL by a
Marie Curie fellowship of the European Community
programme Energy, Environment and Sustainable
Development under Contract No. ENK6-CT-1999-
50002. Analytically, the ICP-MS measurements at
the NERC Kingston University facility have been
enabled by grant ICP/179/1200. Fission-track stud-
ies at UCL are supported by NERC-JREI grant
NER/F/S/2000/00/165 ‘‘Defining low-temperature
thermal history in the Earth’s upper crust by U –
Th/He dating and fission-track analysis’’. We thank
Robin Clayton and Barry Kohn for comments on an
earlier draft. Jan Kosler and an anonymous reviewer
gave us helpful comments. [PD]
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