Lithos 184–187 (2014) 155–166

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Lithos
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U–Th–Pb dating of collision in the external Alpine domains

(Urseren zone, Switzerland) using low temperature allanite
and monazite
Emilie Janots a,⁎, Daniela Rubatto b
a
Univ Grenoble 1, ISTerre, 38041 Grenoble, France
b
Research School of Earth Sciences, ANU, Canberra, Australia

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

Article history: Dating metamorphism in external domains of orogenic belts is a challenging task due to the few chronometers
Received 9 March 2013 available and common inheritance or disturbance of the isotopic systems at low-temperature metamorphic con-
Accepted 30 October 2013 ditions. In the external domains of the Central Alps (Urseren zone), the occurrence of distinct populations of
Available online 6 November 2013
monazite and allanite in one single outcrop offers a unique chance to evaluate the potential of these two REE-
minerals to date successive metamorphic stages within a collisional cycle. The studied outcrop (locality of
Keywords:
Monazite
Garvera) exposes Mesozoic metasediments that were metamorphosed under greenschist facies conditions
Allanite (T b 450 °C). Under these conditions, REE-mineral grains (or domains) are typically small (~5–50 μm), and in
U–Th–Pb dating this case also occur as porphyroblast in pelites at the contact with carbonate layers or veins (allanite grains
Collision N 200 μm). Based on the texture and mineral assemblages, REE-mineral growth conditions were attributed to
Swiss Alps be detrital (Mnz1), syn-kinematic (Mnz2 and Aln1), post-kinematic at the thermal peak (Aln2) and retrograde
during late-stage deformation (Mnz3). To constrain temporally the successive crystallisation conditions, REE-
minerals have been dated using SHRIMP ion microprobe. U–Th–Pb analyses show that the Alpine REE-
minerals have a high Th/U and while most of the 206Pb is non-radiogenic (f206 that can reach up to 99% for
allanite), Th–Pb ages can be obtained using 206Pbc-corrected Th–Pb isochron. The age of different generations
of allanite and monazite constrains the timing of successive collisional stages: for the prograde accretion at
22.5 ± 1.5 Ma (Mnz1 and Aln1), thermal peak at 19.3 ± 2.0 Ma (Aln2) and late stage hydrothermal veining
at 13.6 ± 1.4 Ma (Mnz3). These novel geochronological data confirm the regional diachroneity through the Cen-
tral Alps with younger ages (burial, thermal peak and exhumation) toward the external domains. The similarity
between metamorphic ages of samples taken in the Urseren zone and the nearby crystalline massifs suggests that
the metasedimentary cover of the Urseren zone remained closely juxtaposed to the external crystalline basement
during the Alpine collision cycle. The monazite age of the late stage vein testifies for active tectonic deformation
at 13.6 ± 1.5 Ma, which likely played a crucial control on the exhumation of the external massifs in the Middle
Miocene.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction isotopic resetting in robust minerals (e.g. zircon). In the external

In the external portion of mountain belts, deformation and meta-
morphism occur in the terminal stages of the collision cycle. Timing of
cooling and exhumation of the external domains is robustly assessed
by thermochronological studies. In contrast, absolute ages of early
tectonometamorphic stages are challenging to determine (e.g. Clauer
and Chaudhuri, 1999; Foster et al., 2004; Rasmussen et al., 2001) as
this requires chronometers with isotopic signature that are unaffected
by inheritance or disturbance after metamorphic crystallisation. Few
chronometers respect these criteria under low temperature metamor-
phic conditions, which inhibit mineral crystallisation (e.g. garnet) or
⁎ Corresponding author.
E-mail address: emilie.janots@ujf-grenoble.fr (E. Janots).
portions of orogenic belts, which are typically at or below greenschist
facies conditions, metamorphic ages have been consistently obtained
by Ar–Ar or Rb–Sr dating methods on mineral separates (mica, amphi-
bole) or bulk–rock fraction. Resulting ages are commonly ambiguous
and subject to controversies (e.g. Kelley, 2002; Rolland et al., 2009) be-
cause of uncertainties in closure temperatures, isotopic resetting or
disequilibrium.
Increasingly, U–Th–Pb minerals formed at low temperature condi-
tions are used to date low temperature tectonometamorphic events
(T b 500–550 °C). Robustness of the U–Th–Pb isotopic system resides
in its three decay-chains that allow the independent evaluation of pos-
sible isotopic inheritance of resetting after mineral crystallisation. Fur-
thermore, U–Th–Pb chronometers have high closure temperatures
(Cherniak et al., 2004; Gardes et al., 2006) and, low grade metamorphic

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http://dx.doi.org/10.1016/j.lithos.2013.10.036
156 E. Janots, D. Rubatto / Lithos 184–187 (2014) 155–166
rocks, consistently record the timing of crystallisation rather than
cooling temperature. However the major limitation is the limited
reactivity of U–Pb minerals at low temperatures. Amongst the most
common REE-minerals, monazite has long been applied to date meta-
morphic rocks with conditions higher than amphibolite facies condi-
tions (Parrish, 1990). During progressive metamorphism, in most rock
types detrital monazite reacts to form allanite at or close to sub-
greenschist facies conditions (Gasser et al., 2012; Janots et al., 2008;
Rasmussen and Muhling, 2009; Wing et al., 2003). With increasing
metamorphism, allanite reacts to form metamorphic monazite at or
close to amphibolite facies conditions (Gasser et al., 2012; Janots et al.,
2008; Krenn et al., 2008, 2012; Smith and Barreiro, 1990; Tomkins and
Pattison, 2007; Wing et al., 2003; Yang and Pattison, 2006). These suc-
cessive metamorphic reactions lead to the disappearance of detrital
monazite (and a resetting of the U–Th–Pb inherited signature),
explaining why monazite, unlike zircon, most commonly records the
age of metamorphism. At low-grade metamorphic conditions, monazite
has long been assumed to be chemically inert, implying that its isotopic
signature reflects the inherited ages of detrital grain (Parrish, 1990). Re-
cent systematic application of micro-imaging combined with in-situ
dating techniques revealed that, if monazite occurs as detrital grain, it
can also (re)crystallise under low-grade temperature conditions at
T b 400 °C (Del Rio et al., 2009; Finger et al., 2002; Janots et al., 2006,
2008; Krenn and Finger, 2007; Rasmussen and Muhling, 2007, 2009;
Rasmussen et al., 2001; Wing et al., 2003). Low grade metamorphic
monazite commonly occurs as small grains or domains (typically
~10 μm), which require to be dated with in-situ techniques.
Allanite is also an excellent candidate to record low temperature
metamorphic stages. In comparison to monazite, allanite usually con-
tains lower Th and U, and can incorporate a significant amount of com-
mon Pb. This explains why routine analyses of in-situ allanite dating
have not been achieved until recently (e.g. Catlos et al., 2000; Darling
et al., 2012; Gregory et al., 2007). Pioneer allanite dating has been re-
vealed to be successful in dating metamorphic events in rocks of various
metamorphic conditions including high temperature (Gregory et al.,
2012; Kim et al., 2009) and high pressure conditions (Gabudianu
Radulescu et al., 2009; Rubatto et al., 2011). This latest chronometer re-
mains relatively unexplored for greenschist-facies rocks that are typical
of external domains (Cenki-Tok et al., 2013; Janots et al., 2009).
Geochronology of REE-mineral is also powerful because REE-
mineral can form at variable metamorphic conditions by distinct
reactions and can therefore record successive metamorphic stages
(e.g. Gregory et al., 2012; Rubatto et al., 2006, 2011). In metamorphic
rocks, REE-mineral zoning is rather the rule than the exception. Compo-
sitional domains preserve the memory of successive growth and in-situ
dating of these domains brings constraints on the timing of the interme-
diate equilibration stages in the course of metamorphism. One remark-
able example was obtained by dating allanite zoning in the Sesia Zone
(Rubatto et al., 2011): it revealed an early subduction stage that was
otherwise overprint during a second subduction episode. Another alter-
native to derive several ages of a metamorphic history consists in com-
bining monazite and allanite dating. When the two minerals coexist, the
combination of their ages is powerful because they date distinct
tectonometamorphic stages, which can potentially be assessed based
on textural or compositional evidences. For example, combining allanite
and monazite dating gave one unique way to retrieve the ages of pro-
grade metamorphism and thermal peak, and to deduce the correspond-
ing heating rate of the Alpine collision in the northern part of the
Lepontine domain (Janots et al., 2009).
In one single outcrop of the external domains of the Central Alps
(locality of Garvera, Urseren zone, Switzerland), Janots et al. (2011)
documented 5 coexisting populations of REE-minerals depending on
the deformation and physicochemical conditions of the samples. This
variety of REE-minerals offers one exceptional opportunity to assess
the power of REE-mineral to date successive metamorphic stages in
low grade rocks of external massifs. The Central Alps are excellent for
such a case study because they are one of the best known terranes in
terms of tectonic, metamorphic and geochronological characterizations.
In the present study, the REE-minerals of the Garvera outcrop were
dated using the SHRIMP ion microprobe. The resulting dataset is
discussed in terms of analytical resolution and age interpretation in
the Alpine regional context.
2. Geological context and sample
The Central Alps (Fig. 1), located in southern Switzerland, are the re-
sult of the Tertiary subduction of the Paleo Tethys ocean followed by the
collision between the Eurasian and African (Apulia) plates (e.g. Pfiffner
et al., 2000; Schmid et al., 1996). In the Central Alps, the succession of
the metamorphic assemblages along the North–south transect indicates
a sequence typical of Barrovian metamorphic gradient (Fig. 1). The in-
ternal domain, also known as the Lepontine domain, underwent condi-
tions ranging from upper-greenschist facies at the contact with the
external massifs of the Aar and Gotthard (northern steep belt, Engi
et al., 1995; Todd and Engi, 1997), up to partial melting and amphibolite
facies conditions at the contact with the Southern Alps along the
Insubric Line (Berger et al., 2005, 2008; Engi et al., 1995; Frey and
Ferreiro Mählmann, 1999). This Barrovian metamorphism sequence is
attributed to the stacking of crustal units during the Alpine collision
(Berger et al., 2011; Bousquet et al., 2008; Engi et al., 2001). In the
Lepontine domain, early subduction stages are evidenced by rare
Eocene eclogite relics (Brouwer et al., 2005; Gebauer, 1999; Hermann
et al., 2006) or samples with bimodal P–T paths with high pressure
peak followed by thermal heating during decompression (Bousquet
et al., 2008). No high-pressure evidence is found in the external Aar
and Gotthard massifs, which surround the unit investigated in this
study. In these external massifs, metamorphic pressure conditions of
3–4 kbars were estimated from fluid inclusion thermobarometry in
quartz veins (Mullis, 1996). The structural position of these quartz
veins crosscutting the main foliation indicates however a late-stage ret-
rograde fluid. In the crystalline basement of the Aar and Gotthard mas-
sifs, Alpine metamorphic reequilibration is in fact commonly restricted
to vein or shear zone and Alpine metamorphic conditions are best
estimated in metasediments from the Urseren zone, a thin band
of Mesozoic sedimentary cover wedged between the crystalline
external massifs (Fig. 1). There, chlorite–chloritoid assemblages attest
greenschist facies conditions (Frey and Wiedeland, 1975). In the studied
outcrop (Garvera, Urseren zone), temperatures of 400–450 °C
have been repeatedly obtained using chlorite–chloritoid and calcite–
dolomite thermometres and Raman spectrometry on carbonaceous ma-
terial (Janots et al., 2008; Livi et al., 2002).
3. Methods
3.1. REE-mineral identification
REE-minerals were identified in polished thin sections with optical
microscopy and with back-scattered electron images acquired with an
electron microprobe (EMP, JEOL JXA8200, University of Bern). Quantita-
tive compositions of the REE-minerals were obtained by EMP and LA-
ICP-MS analyses; analytical protocol and mineral compositions are pre-
sented in Janots et al. (2011).
3.2. Sample preparation for SHRIMP II dating
REE-minerals with a size of b50 μm were dated in-situ in thin sec-
tion (Mnz1, Mnz2, Aln1 and Mnz3), while allanite porphyroblasts
were dated as grain separates (Aln2). Grain separation was obtained
by sample disaggregation using high voltage pulsed power discharges
(SELFRAG, Bern) followed by separation in heavy liquids and magnetic
separation. Although allanite porphyroblasts (Aln2) contain abundant
inclusions, the euhedral morphology of allanite is preserved after rock
 E. Janots, D. Rubatto / Lithos 184–187 (2014) 155–166
Switzerland
a ssif
A ar M
Lepontine domain
in
Ky-
LEGEND
Helvetic nappes
External basement
massifs
Penninic Bündnerschiefer
and Ophiolite
Fig. 1. Tectonic map of the central Alps in Switzerland showing the Garvera locality and the mineral isograds related to the Barrovian metamorphism.
fragmentation. Grain and thin sections were mounted in epoxy resin
with the standards and polished to expose the standard centres. Back-
scattered electron images (JEOL JSM-6610, Australian National Univer-
sity) of grains were acquired prior to SHRIMP analysis. Allanite dating
was indistinctly done in the different compositional domains. Beam
spot was preferentially localized in mineral domains free of inclusions.
3.3. SHRIMP II protocol
Thin sections and epoxy mounts of grain separates were analysed for
U, Th and Pb using a sensitive high resolution ion microprobe (SHRIMP
II) at the Australian National University in Canberra. Instrumental con-
ditions and data acquisition were generally as described by Williams
(1998). The primary oxygen beam was focused to a spot of 10 and
30 μm in diameter for monazite and allanite, respectively. The young
age, the low content in U and Th in the targets and the reduced spot
size for monazite implied a particularly low radiogenic Pb content and
this had some analytical consequence: (i) error due to counting statis-
tics are particularly high, (ii) any contamination from initial Pb is ampli-
fied, and (iii) energy filtering for monazite analysis was not applied to
not further reduce the signal. For allanite separates (Aln2), analysis du-
plicates further indicate the good reproducibility of the dataset (indicat-
ed by “+” in Tables 3 and 4).
157
-in
Ctd
Garvera
tth ard
Go
St-in
Insubric Line
LC
Penninic basement
Austroalpine basement
South Alpine basement
Tertiary Granitoid
25 km
N
The measured isotopic ratios were standardised to a matrix-
matched reference material: monazite 44069 from USGS (Aleinikoff
et al., 2006) and two allanite standards, Tara and Bona (417 and
30.1 Ma; Gregory et al., 2007; von Blanckenburg, 1992; respectively).
The calibration error within a single session was 1.5% for monazite
and 2% (2 sigma) for allanite, which was propagated to single analyses.
Tara was used as main allanite standard whereas Bona was analysed as
secondary standard and returned ages within 1% of the reference TIMS
value (von Blanckenburg, 1992).
Data evaluation and age calculation were done using the software
Squid 2 and Isoplot/Ex (Ludwig, 2003), respectively. Average ages are
quoted at 95% confidence level (c.l.).
Two additional tests were done to evaluate the potential matrix ef-
fect due to the difference in composition between the Tara standard
and the analysed allanite samples. (1) The sample/standard ratio in
Th + LREE composition is between 0.6 and 0.9; our preliminary data
suggest that significant matrix effects occur when the Th + REE
sample/standard ratio is less than ~ 0.3. For Fe, another element that
has been related to matrix effects in SIMS analysis, the ratio between
sample and standard is 0.60–1.15, reasonably close to unity. (2) The
ln(ThO/Th) of the samples is reasonably close and partly overlapping
with that of the Tara standard. The ln(ThO/Th) is at the base of the cal-
ibration for SHRIMP analysis and used to correct for difference in
158 E. Janots, D. Rubatto / Lithos 184–187 (2014) 155–166
ionization and extraction efficiency between different species. Similar
values for standard and unknowns are necessary for a robust
standardisation.
3.4. Common Pb correction
Estimation of the initial Pb fraction is not trivial, especially
for allanite that incorporates Pb in its structure, and can have an initial
Pb composition containing a radiogenic component (Romer and
Siegesmund, 2003). Initial Pb correction for individual analysis was
based on the measured ratio 207Pb/206Pbmeas and assuming concordance
in the U-Pb systematics (Williams, 1998). This approach was preferred
over correction using the non-radiogenic isotope due to its inferior pre-
cision in measuring 204Pb and a possible isobaric interference (see also
Gregory et al., 2007). Fractions of initial 206Pb (f206) was calculated as
followed:
  
207 206 207 206 207 206 207 206
ƒ 206 ¼ Pb= Pbmeas − Pb= Pbrad = Pb= Pbc − Pb= Pbrad
with 207Pb/206Pbrad being the expected radiogenic ratio at the
crystallisation age, and 207Pb/206Pbc the common Pb composition pre-
dicted by the model of Stacey and Kramers (1975) at the same age.
Th–Pb ages were calculated following the method of Gregory et al.
(2007), where the 208Pb–232Th isochron is normalized to common
206
Pb (estimated from ƒ206) instead of non-radiogenic 204Pb (see
Gregory et al. (2007) for further details and calculation of errors on
f206 and f208). This method is particularly robust, any inference on
the composition of the initial Pb has no bearing on the calculated age:
variations in the 207Pb/206Pbcom will only affect the 208Pb/206Pb intercept
but not the slope of the isochron, i.e. the age calculated. For allanite
isochrons, the initial 208Pb/206Pb intercept is significantly higher
(2.08–2.09) than the predicted values by Stacey and Kramers (1975)
at ages between 10 and 30 Ma, i.e. 208Pb/206Pbcom of 2.0659–2.0673.
Conventionally, Th–Pb ages are obtained by weighted average of
corrected individual Th–Pb data. The fraction of initial 208Pb is then
given by:
    chloritoid. Allanite can be zoned in REE (La and Nd) and Th (Janots
208 206 208 206
ƒ208 ¼ Pb= Pbc  ƒ206 = Pb= Pbmeas
with 208Pb/206Pbc being the common Pb composition predicted by the
model of Stacey and Kramers (1975). In the case of allanite, where initial
208
Pb/206Pb is higher (2.08–2.09) than the values predicted by the
model of Stacey and Kramers (1975), f208 is underestimated and the
corresponding age will be overestimated. In worst case (Aln2 in sample
Ga06), there is a 10 Ma difference between the Th–Pb ages calculated
using the predicted common Pb value (29.9 ± 2.5 Ma) and Th–Pb iso-
chron age (19.3 ± 2.4 Ma), with the latter being more accurate. For
monazite (in samples Ga02 and Ga06), the initial composition is com-
patible with common Pb composition, and Th–Pb isochron ages will
overlap with weighted average obtained using individual spot analyses
(corrected using common Pb composition predicted by the model of
Stacey and Kramers (1975)). In order to avoid possible confusion, single
corrected Th–Pb ages are not presented in the Tables (but can be calcu-
lated based on the present dataset).
4. Results
In the Garvera locality, 13 samples were collected a few metres
apart. The investigated samples are pelitic to marly metasediments,
with typical mineral assemblages of greenschist facies conditions
(e.g. chlorite–chloritoid–white mica). Two samples contain veins,
attesting to fluid/rocks interactions. Sample Ga04 corresponds to a
quartz–carbonate vein occurring as boudin in the foliation, while
sample Ga02 is a metapelite crosscut by a late-stage quartz vein.
Morphology, texture, zoning, mineral association and composition of
the five REE-mineral populations (Mnz1, Mnz2, Mnz3, Aln1 and Aln2)
were cautiously described and documented in Janots et al. (2011). The
most important features are recalled here (Fig. 2) in combination with
the novel geochronological dataset determined in this study. All the
studied minerals contain very low radiogenic proportion (f206 presented
in Tables). Except for Mnz3 (f206 = 41–94%), ages could not be deter-
mined from the U–Pb dataset (f206 N 84%). With high Th concentrations
(see Tables for Th/U values), and thus a stronger radiogenic 208Pb com-
ponent (f208, see Tables), REE-minerals were successfully dated using
the 206Pbc-normalized Th–Pb isochron described in Gregory et al.
(2007).
Mnz1 and Mnz2 are found in the metamarl Ga06. Monazite occurs in
most of the pelitic layers as elongated grains that are oriented parallel
with the foliation. Monazite grains are usually tiny (b 10 μm), but few
grains reach 100 μm in length. In BSE mode, monazite shows a strong
 zoning with a round brighter core separated from the darker rim by
abundant quartz inclusions (Fig. 3a). EMP dating of monazite core yields
Variscan ages indicating that monazite cores (Mnz1) are relics of detri-
ð1Þ
tal grain (Janots et al., 2011). In the rim (Mnz2), Pb content is systemat-
ically below the detection limit, attesting to Alpine age. Due to the few
grains with a diameter N 20 μm, only 4 grains could be analysed in-situ
with the SHRIMP. In total 7 analyses were achieved in these grains
(Table 1), two of them giving intermediate ages between Variscan and
Alpine ages. The Th–Pb isochron for the youngest group of dates yields
a monazite age of 22.3 ± 2.3 Ma (MSWD = 1.1; Fig. 4a).
Syn-kinematic allanite grains (Aln1) are found in 10 of the 13 stud-
ied samples. The grains are generally tiny (b10 μm), except for the
metapelite MF482 where grains (or aggregates) can reach up to
100 μm in length (Fig. 3b). Owing to mineral size, dating was only
achieved in sample MF482, which is a metapelite containing quartz,
chlorite, white mica, calcite and chloritoid and minor rutile, apatite
and allanite. Allanite grains are preferentially located as clusters in
two layers of the thin section, where they occur as euhedral grains
with abundant quartz inclusions. Elongated grains are found parallel
to the foliation (Fig. 3b), while the basal sections are surrounded by
symmetrical pressure shadows. Allanite can be found as inclusions in
chloritoid porphyroblasts or sharing straight grain boundaries with
ð2Þ et al., 2008, 2011), but the distinct domains are too small to be dated in-
dividually (typically b10 μm large). EMP results indicate that Th and U
contents are typically ~ 1000–1200 ppm and b100–200 ppm, respec-
tively. A high amount of initial Pb in Aln1 is revealed by the EMP analy-
ses that give Pb concentrations above the detection limit (N 100 ppm)
and confirmed by SHRIMP U–Th–Pb isotopic data (Table 2, f206 N 97%).
The slightly more radiogenic Th–Pb systems (f208 89–96%) returned
analyses that define an isochron with an age of 22.7 ± 2.0 Ma
(MSWD = 1.5; Fig. 4b).
Post-kinematic allanite (Aln2) is found in samples Ga06 and Ga04. In
both samples, allanite occurs as euhedral porphyroblasts overgrowing
the main foliation and containing abundant inclusions, mainly of Fe-
oxide. In the three studied thin sections of the metamarl Ga06, allanite
is rare and was found only in carbonate-poor layer with green biotite.
This allanite contains 1000 ppm of Th, U below EMP detection limit
and 900 ppm of Pb. Although only a few grains were observed in thin
section (Fig. 3c), allanite porphyroblasts were successfully separated
and dated (Table 3). 206Pbc normalized Th–Pb isochron yields an age
of 19.3 ± 2.4 Ma (MSWD = 1.20; Fig. 4c). Sample Ga04 is a quartz–
carbonate vein separated from its adjacent wall-rock by a thin chlorite
selvage. Within the vein, a few grains of submicrometric REE-minerals
(monazite, xenotime and REE-carbonate) were identified. On the
other hand, the wall-rock shows abundant allanite porphyroblasts over-
growing the oxide-rich foliation made of quartz, mica and Fe-oxide.
Post-kinematic apatite and chloritoid porphyroblasts are also found in
the wall-rock. Allanite is commonly euhedral (up to 500 μm in length),
but some grains are broken and resorbed at the contact with late quartz
 E. Janots, D. Rubatto / Lithos 184–187 (2014) 155–166
Time (relative) Ga06
Mnz1 Mnz2
Syn-kinematic
Prograde accretion
Post-kinematic
thermal peak Aln2
Late-stage retrograde
hydrothermalism
Fig. 2. Schematic summary of the REE-minerals dated. The relative crystallisation sequence is deduced from microstructural observations.
Modified from Janots et al. (2011).
veins. Allanite has Th concentrations of ~3000 ppm, U commonly below
EMP detection limit, and Pb at ~400 ppm. Allanite porphyroblasts in the
whole rock were successfully concentrated as mineral separate for fur-
ther U–Th–Pb SHRIMP dating (Fig. 3d). In BSE, some allanite grains
show a brighter rim (Fig. 3d), but the two domains were indistinctly
dated in this study. Similarly to samples MF482 and Ga06, the analyses
have extreme proportion of initial Pb (ƒ206 N 0.99; Table 4), and define a
206
Pbc normalized Th–Pb isochron that yields a particularly imprecise
age of 19.4 ± 3.6 Ma (MSWD = 1.2; Fig. 4d).
The pelitic sample Ga02 contains few millimetric interconnected
quartz-veins that crosscut the foliation composed of quartz, mica, chlo-
rite and chloritoid. Remarkably, the quartz veins contain no other min-
eral than monazite crystals, referred as “Mnz3” (Fig. 3e). Although few
grains can reach up to 40–50 μm, most of the grains are b 20 μm.
Mnz3 is sub‐euhedral and homogeneous in composition (Fig. 3f); previ-
ous LA-ICP-MS measurements gave Pb ~ 3–8 ppm, U ~ 85–135 ppm
and Th ~ 210–1654 ppm (Janots et al., 2011). SHRIMP measurements
of these small (b20 μm) Mnz3 grains were performed in-situ directly
in the thin section. The 206Pbc normalized Th–Pb isochron yields an
age of 13.6 ± 1.4 Ma (MSWD = 0.55; Fig. 4e). This age is independent-
ly confirmed by U–Pb linear regression in the Tera–Wasserburg diagram
(11.0 ± 1.9 Ma; MSWD = 2.0; Fig. 4f).
Although xenotime has been observed in almost all samples, it was
invariably too small for SHRIMP dating.
5. Discussion
5.1. U–Th–Pb age determination in Alpine REE-minerals
Dating Alpine REE-minerals in metamorphic rocks at or below
greenschist facies conditions is analytically challenging. Under these
physicochemical conditions, REE-mineral grains or domains are com-
monly with a b 10 μm size that is below or at minimum spatial resolu-
tion even for micro-beam techniques. Over the 13 studied samples,
only 4 samples show (few) grains with a diameter N10 μm. In sample
Ga02, monazite grain size is typically ~ 5–20 μm, but the location of
the grains within a quartz-vein facilitates analysis and limits possible
isotopic contamination by the neighbouring phases as quartz does not
contain any appreciable U, Th or Pb.
159
MF482 Ga04 Ga02
Aln1
Aln2
Mnz3
Another obstacle of U–Th–Pb dating resides in the low concentration
of radiogenic Pb that had time to accumulate since the Alpine minerals
crystallised. It has been successively reported that low-temperature mon-
azite has relatively low Th content, typically below 2 wt.% (e.g. Janots
et al., 2008, 2011; Rasmussen and Muhling, 2007, 2009). In line with
these results, EMP and LA-ICP-MS analyses of the studied REE-minerals
show that both Th and U concentrations are low in Mnz2, Aln1, Aln2
and Mnz3 (dataset partly presented in Janots et al., 2011): Th is typically
within 100s to 1000s ppm, and U concentrations are close to or below de-
tection limit (b100 ppm). These low concentrations, attributed to the
physicochemical conditions of crystallisation (P, T, redox and ligands), ex-
plain the remarkably low radiogenic Pb fraction measured in the investi-
gated REE-minerals. As allanite and monazite preferentially favour Th
incorporation over U (e.g. Barth et al., 1994; Schärer, 1984), the U–Pb iso-
topic system is more strongly affected by low radiogenic Pb and common
Pb contamination than the Th–Pb isotopic system.
In the studied REE-minerals, Th/U is high (23–235 in Aln1; Table 2)
to remarkably high (up to 1360 in Aln2 and N2500 in Mnz2;
Tables 1, 3, 4). In allanite, initial 206Pb and 207Pb (expressed as fraction
over total measured Pb: f206 and f207, respectively) dominate the Pb sig-
nal (N99%; Tables 2–4) and it is impossible to determine U–Pb allanite
ages. Similarly, U–Pb isotopic systems are also dominated by initial Pb
in Mnz2 (f206 N 88%; Table 1) and Mnz3 (f206 = 41–96%; Table 5). Al-
though initial Pb is generally negligible in monazite (Montel et al.,
1996; Williams et al., 2007), it has been found to be present in altered
and hydrothermal monazite (e.g. Didier et al., 2013; Janots et al.,
2012; Seydoux-Guillaume et al., 2003, 2012), low temperature mona-
zite (Del Rio et al., 2009) or S-rich monazite (Krenn et al., 2011). Here,
the significant proportions of initial Pb in REE-minerals are attributed
to the unfavourable combination of young age, low Th and U contents,
mineral inclusions (in Aln2), small size of monazite with increased
possibility of sampling Pb-rich fractures and/or grain boundaries
during analysis. With lower Th/U ratio (1.7–50.8, Table 5) and more
variable f206 (Table 5), the U–Pb analyses of Mnz3 define a reasonable
regression in a Tera–Wasserburg diagram to give an age at
11.0 ± 1.9 Ma (MSWD = 2.0).
For “young” LREE-minerals, the Th–Pb systematics is usually more
robust than the U–Pb systematics for age determination (e.g. Gregory
et al., 2012; Janots et al., 2012; Schärer, 1984), although the U–Pb data
are required for estimating the proportion of initial 208Pb (f208, see
160 E. Janots, D. Rubatto / Lithos 184–187 (2014) 155–166

a) Sample Ga-06 b) Sample MF482

Aln
1
n z2 Al
M n1

1
nz
M

20 µm Aln 50 µm
1

c) Sample Ga-06 d) Sample Ga-04

Aln
2
Aln2

50 µm 50 µm

e) Sample Ga-02 f) Sample Ga-02

Mnz3

Qtz Mnz3
-vei
n

500 µm 2 µm

Fig. 3. BSE images of REE-minerals: (a) zoned monazite with a bright rounded core (Mnz1) surrounded by a darker rim (Mnz2) that is oriented parallel to the foliation; (b) syn-kinematic
Aln1 crystals; (c) post-kinematic Aln2 euhedral crystal overgrowing the main foliation; (d) post-kinematic Aln2 grain separate; (e) Mnz3 grains found in the late-stage quartz vein cross-
cutting the main foliation and (f) euhedral Mnz3 grain.

Methods). However, uncertainty on the composition of initial Pb will isochron enables robust age determination even for weakly radiogenic
have a significant impact on the calculation of f208 and thus on individ- materials and provides an independent control on the isotopic compo-
ually corrected Th–Pb ages. Alternatively, 206Pbc normalized Th–Pb sition of the initial Pb (Gregory et al., 2007). Although this Th–Pb

Table 1
SHRIMP II U–Th–Pb analyses of Mnz2 in sample Ga06.
204
Spot name Th/U Pb/206Pb 1σ 207
Pb/206Pb 1σ 208
Pb/206Pb 1σ 206
Pb/238U 1σ 208
Pb/232Th 1σ f206 f208 232
Th/206Pbc 1σ 208
Pb/206Pbc 1σ
% % % % % % % % %

Mnz2
Ga6-3C 1831 0.044 13 0.817 2.4 8.54 1.9 0.28 18 0.00131 4.8 97 24 6687 5.3 8.76 1.9
Ga6-2B 2038 0.062 17 0.745 3.4 19.4 2.6 0.12 17 0.00115 3.1 88 9 19,124 4.0 21.9 2.6
Ga6-2C 911 0.046 17 0.748 2.9 9.68 5.2 0.13 13 0.00136 1.5 89 19 8045 6.8 10.9 5.9
Ga6-1 1177 0.054 19 0.860 3.5 7.33 5.9 0.25 27 0.00156 3.2 100 29 4576 5.5 7.13 5.2
Ga6-3 2553 0.045 15 0.789 9.7 16.3 2.0 0.20 14 0.00128 1.5 94 12 13,587 2.5 17.3 2.0

Mnz1
Ga6-2 13 0.0011 19 0.0643 1.2 2.71 0.44 0.0525 2.1 0.0107 2.9 2.3 2
Ga6-4 31 0.0029 18 0.0904 1.9 7.99 0.64 0.0438 1.5 0.0113 1.5 5.6 1

f206 and f208 are the fraction of 206Pbcom and 208Pbcom calculated assuming common Pb composition predicted by Stacey and Kramers (1975).
 E. Janots, D. Rubatto / Lithos 184–187 (2014) 155–166 161

26 a) Ga06 Mnz2 2.34 b) MF482 Aln1

22 2.30

208Pb/206Pbc
208Pb/206Pbc
18 2.26

14 2.22

10 2.18

Age= 22.3±2.3 Ma
6 2.14 Age= 22.7±2.0 Ma
Initial 208Pb/206Pbc= 1.8±1.1
Initial 208Pb/206Pbc= 2.0871±0.0099
MSWD= 1.1; N= 5
MSWD= 1.5; N= 19
2 2.10
0 4000 12000 20000 0 40 80 120 160 200
232Th/206Pbc 232Th/206Pbc

2.18 2.18
c) Ga06 Aln2 d) Ga04 Aln2
2.16

2.14

208Pb/206Pbc
208Pb/206Pbc

2.14

2.12
2.10

Age= 19.3±2.4 Ma 2.10 Age= 19.4±3.6 Ma

Initial 208Pb/206Pbc= 2.0842±0.0026 Initial 208Pb/206Pbc= 2.0844±0.0089
MSWD= 1.20; N= 17 MSWD= 1.2; N= 24
2.06 2.08
0 20 40 60 80 10 30 50 70 90
232Th/206Pbc 232Th/206Pbc

e) Ga02 Mnz3 f) Ga02 Mnz3 Intercept age at 11.0 ±1.9

20 0.9 MSWD= 2.0; N= 20
Total207Pb/206Pb

16
0.7
208Pb/206Pbc

12
0.5
8

0.3
4 Age= 13.6±1.4 Ma
Initial 208Pb/206Pbc= 2.04±0.13
MSWD= 0.55; N= 20
0 0.1
0 10000 20000 30000 0 100 200 300 400 500
232Th/206Pbc Total238U/206Pb

Fig. 4. 206Pbc normalized Th–Pb isochron of: (a) syn-kinematic Mnz2 in sample Ga06; (b) syn-kinematic Aln1 in sample MF482; (c) post-kinematic Aln2 in sample Ga06; (d) post-
kinematic Aln2 in sample Ga04; (e) late-stage hydrothermal Mnz3 in sample Ga02. For comparison, a Tera–Wasserburg diagram plotting total U–Pb isotopic ratios of Mnz3 is presented
in (f). Data ellipses represent 2σ errors. See text for details on the isochron calculation.

isochron was originally designed for allanite with significant radiogenic
Pb contribution, it appears in fact extremely attractive to obtain Th–Pb
ages of minerals with low radiogenic 208Pb content. In our study, Th–
Pb analyses of allanite and monazite define a statistically sound iso-
chron (MSWD of 1.2–1.5 and 0.55–1.1 in allanite and monazite, respec-
tively). This demonstrates the robustness of the Th–Pb isochron ages,
with no evidences of significant isotopic disturbance after mineral
crystallisation (by Th, U or Pb mobilization; e.g. Seydoux-Guillaume
et al., 2002, 2012). With low proportions of radiogenic Pb, allanite Th–
Pb data yield a precise lower intercept, i.e. estimate of initial Pb
composition. The obtained initial 208Pb/206Pb is systematically higher
(around 2.08–2.09; Fig. 4) than 208Pb/206Pb values predicted by models
(2.0659–2.0673 between 10 and 30 Ma). This discrepancy has critical
implications on individual Th–Pb allanite analyses: corrections using
model common Pb composition will give older ages than the Th–Pb iso-
chron (up to 10 Ma difference). Where there is no independent control
on the initial Pb composition (as compared in Cenki-Tok et al., 2013),
Gregory et al.'s (2007) isochron is in fact the only method to determine
Th–Pb ages for minerals with high initial Pb proportion (see Methods).
With higher proportions of radiogenic Pb (higher 208Pb/206Pb and 232Th/
162 E. Janots, D. Rubatto / Lithos 184–187 (2014) 155–166

Table 2
SHRIMP II U–Th–Pb analyses of Aln1 in sample MF482.
204
Spot name Th/U Pb/206Pb 1σ 207
Pb/206Pb 1σ 208
Pb/206Pb 1σ 206
Pb/238U 1σ 208
Pb/232Th 1σ % f206 f208 232
Th/206Pbc 1σ 208
Pb/206Pbc 1σ
% % % % % % % %

MF482-25.1 40 0.0519 1.2 0.8264 0.22 2.169 0.23 0.382 2.7 0.0207 2.7 99 94 106.0 2.7 2.20 0.23
MF482-25.2 34 0.0522 1.1 0.8165 0.21 2.138 0.21 0.390 2.6 0.0245 2.9 97 94 89.6 2.9 2.20 0.21
MF482-25.3 42 0.0535 1.2 0.8249 0.23 2.160 0.23 0.427 2.7 0.0220 2.0 98 94 99.5 2.0 2.19 0.23
MF482-25.4 67 0.0525 1.1 0.8225 0.22 2.159 0.22 0.770 2.9 0.0247 2.4 98 94 89.1 2.4 2.20 0.22
MF482-25.5 44 0.0536 1.2 0.8203 0.23 2.151 0.23 0.508 2.7 0.0248 2.6 98 94 88.7 2.6 2.20 0.23
MF482-25.6 94 0.0535 1.2 0.8231 0.23 2.169 0.23 0.928 2.9 0.0214 2.0 98 94 103.1 2.0 2.21 0.23
MF482-25.7 67 0.0541 1.3 0.8257 0.29 2.164 0.26 0.693 3.0 0.0223 2.0 99 94 98.5 2.0 2.20 0.26
MF482-25.8 43 0.0535 1.3 0.8256 0.25 2.151 0.25 0.489 2.8 0.0243 2.0 99 95 89.7 2.0 2.18 0.25
MF-482-25.9 108 0.0528 1.3 0.8243 0.25 2.191 0.25 0.951 3.3 0.0193 3.7 98 93 115.5 3.7 2.23 0.25
MF482-25.10 42 0.0527 1.4 0.8245 0.26 2.139 0.26 0.517 10.3 0.0262 2.0 98 95 83.0 2.1 2.17 0.26
MF482-25.11 44 0.0533 1.2 0.8225 0.24 2.175 0.23 0.383 2.8 0.0190 2.3 98 93 116.4 2.3 2.22 0.23
MF482-25.12 79 0.0538 2.1 0.8256 0.24 2.155 0.24 0.864 3.1 0.0235 2.0 99 95 93.2 2.0 2.19 0.24
MF482-22 235 0.0531 1.2 0.8263 0.23 2.279 0.23 1.217 3.6 0.0118 2.0 99 89 195.4 2.0 2.31 0.23
MF482-23 104 0.0527 1.2 0.8281 0.24 2.185 0.23 0.920 3.2 0.0194 2.0 99 94 113.9 2.0 2.21 0.23
MF482-19.1 116 0.0537 1.2 0.8225 0.42 2.163 0.37 1.137 3.4 0.0211 2.0 98 94 104.3 2.0 2.20 0.37
MF482-19.2 125 0.0524 1.3 0.8266 0.25 2.162 0.25 1.246 3.5 0.0216 2.0 99 94 101.7 2.0 2.19 0.25
MF482-19.3 23 0.0522 1.3 0.8218 0.24 2.115 0.25 0.350 2.7 0.0324 2.0 98 96 66.5 2.0 2.16 0.25
MF482-4 54 0.0528 1.1 0.8258 0.21 2.119 0.22 1.041 3.1 0.0411 2.0 99 96 52.2 2.0 2.15 0.22
MF482-2 24 0.0529 1.6 0.8170 0.59 2.115 0.31 0.349 2.8 0.0312 2.0 97 95 69.5 2.1 2.17 0.31

f206 and f208 are the fraction of 206Pbcom and 208Pbcom calculated assuming common Pb composition predicted by Stacey and Kramers (1975).

206
Pb; Fig. 4), Th–Pb datasets of monazite give initial 208Pb/206Pb values
(1.8 ± 1.1 and 2.04 ± 0.13 in Mnz2 and Mnz3, respectively; Fig. 4) that
are in good agreement with model 208Pb/206Pb (2.0659–2.0673 be-
tween 10 and 30 Ma) and isochron Th–Pb ages overlap with weighted
averages obtained using corrected individual Th–Pb analyses.
Despite the high proportion of initial Pb in the REE-minerals studied
here, the statistically sound Th–Pb isochron and the good agreement of
ages obtained using Th–Pb and U–Pb systematics (e.g. Th–Pb isochron
and Tera–Wasserburg diagram for Mnz3, Fig. 4f) demonstrate the ro-
bustness of the ages presented. We reinforce the fact that in allanite
grains with high Th/U and high initial Pb fraction, 206Pbc normalized
Th–Pb isochron is the only method for age determination and provides
an independent control on the isotopic composition of the initial Pb.
5.2. REE-mineral age interpretation
In the absence of major tectonic discontinuities in the Garvera litho-
logical sequence, all the studied samples are taken to have undergone
similar P–T and tectonic evolutions. Consequently, the difference in
the ages obtained by the different REE-minerals attest to distinct equil-
ibration conditions during the course of metamorphism, namely differ-
ent metamorphic stages. Along the N–S geotransect of the Central Alps
(Janots et al., 2008), monazite–allanite sequence respects the evolution
described in other studies (e.g. Wing et al., 2003). Monazite occurs in
low-grade metamorphic rocks and disappears to form allanite at condi-
tions close to greenschist facies conditions. In the Garvera outcrop
(greenschist facies conditions), most samples (12 over 13) contain ef-
fectively allanite as LREE-mineral, although monazite was found in
two samples (Ga02 and Ga06). Five populations of REE-minerals are
recognized and their relative crystallisation timing can be deduced
from textural positions only (Fig. 2). This timing has been confirmed
here and specified using in-situ U–Th–Pb geochronology.
The first population of REE-mineral corresponds to detrital monazite
(Mnz1), which is preserved as relict cores of zoned monazite only in
sample Ga06. EMP data indicate Variscan ages (Janots et al., 2011).
Two populations show syn-kinematic texture: Mnz2 and Aln1. Mnz2
surrounds Mnz1 and corresponds to elongated rim parallel to the
foliation, indicating that Mnz2 formed during the main deformation
stage, likely by pressure solution processes in the presence of fluids
(e.g. Harlov et al., 2011; Hetherington et al., 2010; Seydoux-Guillaume
et al., 2002; Williams et al., 2011). Aln1 is found as elongated grains par-
allel to the foliation or prismatic section with pressure shadows. Aln1 is
in contact with chloritoid indicating that it grew conjointly at T close to
the thermal peak (Frey and Wiedeland, 1975) during the main

Table 3
SHRIMP II U–Th–Pb analyses of Aln2 in sample Ga06.
204
Spot name Th/U Pb/206Pb 1σ 207
Pb/206Pb 1σ 208
Pb/206Pb 1σ 206
Pb/238U 1σ 208
Pb/232Th 1σ f206 f208 232
Th/206Pbc 1σ 208
Pb/206Pbc 1σ
% % % % % % % % %

Ga6-1 1360 0.0528 0.75 0.8303 0.17 2.075 0.17 74.3 4.5 0.113 2.0 99 99 18.5 2.0 2.093 0.17
Ga6-2 285 0.0533 0.70 0.8296 0.16 2.075 0.16 26.4 4.5 0.192 2.0 99 99 10.1 2.1 2.094 0.16
Ga6-3 135 0.0544 1.3 0.8334 0.28 2.111 0.27 3.51 4.5 0.055 2.0 100 97 3.16 2.0 2.094 0.27
Ga6-3+ 118 0.0538 0.91 0.8337 0.20 2.114 0.19 3.03 8.7 0.054 2.0 100 97 3.03 2.1 2.085 0.19
Ga6-4 398 0.0534 0.75 0.8323 0.17 2.082 0.17 39.3 4.5 0.206 2.0 99 99 50.3 2.1 2.126 0.17
Ga6-5 27 0.0525 1.2 0.8346 0.26 2.088 0.26 2.67 4.5 0.207 2.0 100 99 14.4 2.0 2.100 0.26
Ga6-6 163 0.0533 1.3 0.8319 0.27 2.112 0.27 3.26 4.5 0.042 2.0 99 97 32.3 2.1 2.113 0.27
Ga6-6A 189 0.0532 1.2 0.8349 0.26 2.135 0.25 3.52 4.5 0.040 2.0 100 97 7.24 2.0 2.096 0.25
Ga6-7 634 0.0533 0.77 0.8304 0.17 2.083 0.17 44.3 4.5 0.146 2.0 99 98 39.0 2.0 2.123 0.17
Ga6-8 613 0.0525 0.77 0.8326 0.17 2.081 0.17 66.7 4.5 0.226 2.0 99 99 54.0 2.1 2.140 0.17
Ga6-9 253 0.0549 1.3 0.8385 0.28 2.153 0.27 3.94 4.5 0.033 2.0 100 96 7.96 2.0 2.087 0.27
Ga6-10 119 0.0530 1.2 0.8358 0.26 2.110 0.26 3.70 4.5 0.066 2.0 100 98 17.6 2.0 2.103 0.26
Ga6-11 212 0.0531 0.79 0.8330 0.17 2.077 0.18 26.8 4.5 0.262 2.0 99 99 10.2 2.0 2.094 0.18
Ga6-12 615 0.0527 0.75 0.8320 0.17 2.083 0.17 85.5 4.5 0.290 2.0 99 99 64.1 2.1 2.149 0.17
Ga6-12A 474 0.0536 0.67 0.8309 0.15 2.077 0.15 151 4.5 0.663 2.0 99 99 9.25 2.0 2.092 0.15
Ga6-12A+ 428 0.0524 0.50 0.8321 0.11 2.072 0.11 142 14 0.688 2.1 99 99 38.6 2.1 2.121 0.11
Ga6-13 598 0.0528 0.72 0.8280 0.16 2.079 0.16 34.3 4.5 0.119 2.0 99 98 10.9 2.0 2.094 0.16

f206 and f208 are the fraction of 206Pbcom and 208Pbcom calculated assuming common Pb composition predicted by Stacey and Kramers (1975).
 E. Janots, D. Rubatto / Lithos 184–187 (2014) 155–166 163

Table 4
SHRIMP II U–Th–Pb analyses of Aln2 in sample Ga04.
204
Spot name Th/U Pb/206Pb 1σ 207
Pb/206Pb 1σ 208
Pb/206Pb 1σ 206
Pb/238U 1σ 208
Pb/232Th 1σ f206 f208 232
Th/206Pbc 1σ 208
Pb/206Pbc 1σ
% % % % % % % % %

Ga4-1 191 0.0544 1.2 0.841 0.25 2.130 0.25 3.89 4.5 0.0435 2.0 100 98 49.0 2.1 2.13 0.25
Ga4-2 115 0.0539 1.5 0.832 0.32 2.103 0.31 3.31 4.5 0.0605 2.0 99 98 34.8 2.1 2.10 0.31
Ga4-3 137 0.0533 1.2 0.834 0.25 2.122 0.25 2.72 4.5 0.0422 2.0 100 97 50.2 2.1 2.12 0.25
Ga4-4 193 0.0550 1.2 0.831 0.27 2.129 0.27 3.25 4.5 0.0359 2.0 99 96 59.3 2.1 2.13 0.27
Ga4-5 197 0.0537 1.4 0.832 0.29 2.100 0.29 5.58 4.5 0.0595 2.0 99 98 35.3 2.1 2.10 0.29
Ga4-6 171 0.0534 1.2 0.835 0.26 2.129 0.25 3.44 4.5 0.0428 2.0 100 97 49.7 2.1 2.13 0.25
Ga4-7 195 0.0541 1.2 0.836 0.25 2.123 0.25 4.58 4.5 0.0497 2.0 100 97 42.7 2.1 2.12 0.25
Ga4-8 256 0.0534 1.3 0.836 0.27 2.131 0.27 4.55 4.5 0.0379 2.0 100 97 56.2 2.1 2.13 0.27
Ga4-8B 213 0.0536 1.4 0.834 0.29 2.122 0.29 5.96 4.5 0.0593 2.0 100 97 35.8 2.1 2.12 0.29
Ga4-9 184 0.0536 1.2 0.835 0.26 2.120 0.26 3.75 4.5 0.0434 2.0 100 97 48.9 2.1 2.12 0.26
Ga4-10 207 0.0536 1.2 0.834 0.25 2.136 0.25 3.47 4.5 0.0359 2.0 100 96 59.5 2.1 2.14 0.25
Ga4-11 157 0.0535 1.4 0.831 0.29 2.120 0.29 3.10 4.5 0.0420 2.0 99 97 50.5 2.1 2.12 0.29
Ga4-12 90 0.0534 1.1 0.835 0.24 2.105 0.24 3.56 4.5 0.0832 2.0 100 98 25.3 2.1 2.10 0.24
Ga4-13 78 0.0543 1.2 0.834 0.26 2.101 0.25 3.63 4.5 0.0973 2.0 100 98 21.6 2.1 2.10 0.25
Ga4-14 222 0.0542 1.2 0.838 0.25 2.142 0.25 3.53 4.5 0.0340 2.0 100 97 63.1 2.1 2.14 0.25
Ga4-15 149 0.0540 1.3 0.829 0.28 2.130 0.27 2.44 4.5 0.0348 2.0 99 96 61.1 2.1 2.13 0.27
Ga4-16 282 0.0533 1.1 0.832 0.24 2.142 0.24 4.12 4.5 0.0313 2.0 99 96 68.5 2.1 2.14 0.24
Ga4-17 76 0.0552 1.2 0.835 0.26 2.129 0.25 1.36 4.5 0.0380 2.0 100 97 56.1 2.1 2.13 0.25
Ga4-18 146 0.0544 1.2 0.837 0.26 2.120 0.25 4.41 4.5 0.0640 2.0 100 98 33.1 2.1 2.12 0.25
Ga4-1+ 205 0.0528 0.78 0.832 0.17 2.125 0.16 3.97 5.4 0.0412 2.0 99 97 51.6 2.0 2.12 0.16
Ga4-2+ 174 0.0538 0.97 0.836 0.37 2.113 0.20 4.50 5.8 0.0546 2.0 100 98 38.7 2.0 2.11 0.20
Ga4-3+ 156 0.0528 0.88 0.833 0.19 2.131 0.18 2.94 5.3 0.0402 2.0 99 96 53.0 2.0 2.13 0.18
Ga4-7+ 200 0.0540 0.83 0.835 0.18 2.121 0.18 4.69 5.8 0.0497 2.0 100 97 42.7 2.0 2.12 0.18
Ga4-11+ 169 0.0539 0.90 0.832 0.20 2.117 0.19 3.12 5.5 0.0391 2.0 99 97 54.1 2.0 2.12 0.19

f206 and f208 are the fraction of 206Pbcom and 208Pbcom calculated assuming common Pb composition predicted by Stacey and Kramers (1975).

deformation event. Mnz2 age at 22.3 ± 2.3 Ma is undistinguishable from
that of Aln1 at 22.7 ± 2.0 Ma. Aln2 is post-kinematic (porphyroblast
overgrowing the foliation) and its association with post-kinematic
chloritoid or biotite suggests growth conditions at the thermal peak
(probably in the presence of fluids; Janots et al., 2011). Because of the mi-
crostructure, Aln2 ages (19.3 ± 2.4 Ma and 19.3 ± 3.6 Ma) are
interpreted as dating a static stage posterior to the main deformation
stage. Due to the relatively large errors on the ages, Aln2 ages overlap
with that of Mnz2 and Aln1, which also grew close from the thermal
peak. Based on the textural relationships, REE-minerals are interpreted
to date the same protracted tectonometamorphic event that started dur-
ing the prograde accretion (Mnz2 and Aln1) and ended during thermal
relaxation at P–T conditions close to the thermal peak (Aln2). In the
Lepontine domain, this stage is attributed to the Barrovian overprint for
which isograds cut across the structures related to the stacking of the
different units during initial compression (e.g. Bousquet et al., 2008;
Engi et al., 1995). Mnz3 is found in quartz vein crosscutting the foliation
indicating that it grew from a late-stage fluid during retrogression. Similar
late-stage veins are also found in sample Ga04, where they cut across
Aln2, indicating that this last stage vein postdates Aln2 crystallisation.
Th–Pb dating of Mnz3 yields the youngest age of 13.6 ± 1.4 Ma for this
retrograde hydrothermal growth.
5.3. Tectonometamorphic evolution in the external domains of the Central
Alps
The new U–Th–Pb dataset dramatically increases the age constraints
in a tectonic unit that was lacking such data with respect to the adjacent
Lepontine dome and the external massifs (Aar and Gotthard). The ages
of prograde accretion, thermal peak and retrograde exhumation

Table 5
SHRIMP II U–Th–Pb isotopic ratio of Mnz3 (sample Ga02).
204
Spot name Th/U Pb/206Pb 1σ 207
Pb/206Pb 1σ 208
Pb/206Pb 1σ 206
Pb/238U 1σ 208
Pb/232Th 1σ f206 f208 232
Th/206Pbc 1σ 208
Pb/206Pbc 1σ
% % % % % % % % %

Ga2-2 4.4 0.044 21 0.464 4.8 1.80 3.7 0.0040 17 0.00162 1.9 53 61 480 13.3 2.3 10.6
Ga2-3 5.3 0.049 21 0.679 4.5 1.92 3.7 0.0124 5.0 0.00449 2.2 80 86 2100 12.3 3.4 9.6
Ga2-4 4.2 0.029 27 0.485 4.9 1.74 6.8 0.0039 3.2 0.00162 7.3 56 66 1930 10.0 3.1 6.8
Ga2-5 1.3 0.041 27 0.641 5.3 1.57 6.9 0.0061 34 0.00764 3.7 75 99 270 8.3 2.1 5.6
Ga2-6 1.7 0.057 22 0.619 9.9 1.69 4.2 0.0068 4.2 0.00658 3.3 72 89 400 18.3 2.4 15.6
Ga2-7 3.2 0.038 21 0.726 3.8 1.99 3.2 0.0155 3.7 0.0048 11 86 89 340 14.3 2.3 11.6
Ga2-8 6.5 0.039 24 0.571 4.7 1.71 3.7 0.0066 4.1 0.00358 2.7 66 80 1050 16.3 2.8 13.6
Ga2-9 1.7 0.045 25 0.666 5.2 1.87 4.3 0.0086 20 0.00957 2.5 78 87 800 9.3 2.5 6.6
Ga2-10 14.9 0.126 15 0.554 4.9 3.52 3.5 0.0037 3.3 0.00087 1.7 64 38 530 11.3 2.4 8.6
Ga2-11 10.7 0.052 25 0.615 6.2 2.37 4.6 0.0100 4.0 0.00220 5.6 72 63 1500 7.3 3.3 4.6
Ga2-12 2.3 0.014 45 0.511 6.1 1.66 4.6 0.0038 20 0.00270 2.6 59 73 360 17.3 2.3 14.6
Ga2-13 17.3 0.017 45 0.35 15.3 4.26 4.3 0.0037 22 0.00091 7.8 38 19 12,300 8.8 11.1 4.3
Ga2-14 26.8 0.041 18 0.775 2.9 3.06 5.4 0.0151 3.8 0.00173 6.1 92 62 1920 8.1 3.3 5.4
Ga2-15 16.4 0.13 39 0.804 3.6 2.36 3.1 0.021 21 0.00309 7.9 96 84 6280 10.3 5.5 7.6
Ga2-16 50.8 0.036 28 0.450 6.2 8.33 6.0 0.0042 26 0.00069 4.5 51 13 23,600 7.5 16.3 6.0
Ga2-17 5.1 0.041 19 0.747 3.7 2.10 3.1 0.0143 3.8 0.00590 5.4 89 87 250 19.3 2.4 16.6
Ga2-18 10.5 0.048 13 0.790 2.4 2.14 2.0 0.0327 4.0 0.00666 5.8 94 91 720 15.3 2.6 12.6
Ga2-19 7.3 0.043 29 0.370 7.5 2.25 4.8 0.0033 21 0.00103 2.0 41 38 5360 5.2 5.5 4.8
Ga2-20 10.1 0.032 21 0.573 7.0 2.40 2.9 0.0071 21 0.0017 13 67 57 2130 13.2 3.6 2.9
Ga2-21 12.3 0.044 20 0.617 4.1 2.34 3.1 0.0102 4.2 0.00195 1.9 72 64 1660 3.6 3.2 3.1

f206 and f208 are the fraction of 206Pbcom and 208Pbcom calculated assuming common Pb composition predicted by Stacey and Kramers (1975).
164 E. Janots, D. Rubatto / Lithos 184–187 (2014) 155–166

EOCENE
Aar Urseren Northern Southern
Massif Zone * Steep Belt Steep Belt Tectonometamorphic stage
35
Prograde accretion

OLIGOCENE
30 Metamorphic Peak
5) 6) Retrograde exhumation

25

8)
20 1)
9) 10) Chronometers
6)
MIOCENE

2)
7) 7) U-Pb Zircon
15
3) z 4)
z 11) U-Th-Pb Allanite
U-Th-Pb Monazite
10 z
a 3) 6) a 11) Ar-Ar or K-Ar muscovite
Ar-Ar or K-Ar biotite
5 a
QUAT PLIO

6)
Fission track apatite a
Fission track zircon z
0
Ma

Central Alps
N S
0 Upper crustal basement
Ma
-10 European lower crust

TAC
Si
Aa Go Luc Helvetic sedimentary cover

Lev Penninic sedimentary cover

-50
Bergell intrusion

underplating
IL
Southern Alps
Upper crustal basement

Lower crust
[km]
0 50 km

Fig. 5. Schematic N–S cross-section of the Central Alps (modified from Schmid et al., 1996) with a synthesis of published ages of metamorphism; timing of prograde accretion, metamor-
phic peak and retrograde exhumation are distinguished. Geochronological data from: (1) Rolland et al. (2009), (2) Dempster (1986), (3) Glotzbach et al. (2010), Michalski and Soom
(1990), (4) Janots et al. (2012), (5) Wiederkehr et al. (2009), (6) Janots et al. (2009), (7): Allaz et al. (2011), (8) Berger et al. (2009) and Engi et al. (1995), (9) Rubatto et al. (2009)
(10) Gregory et al. (2012), (11): Hurford (1986). Abbreviations of tectonic units are Aa: Aar, Go: Gotthard, Luc: Lucomagno, Lev: Leventina, Si: Simano, Ma: Maggia, IL: Insubric Line
and TAC: tectonic accretion channel (Engi et al., 2001).

through the Central Alps are compiled in Fig. 5. Such compilation is
based on the comparison and interpretation of a vast geochronological
dataset developed over more than 50 years (e.g. Hunziker et al.,
1992). For metamorphic ages, we have preferred to compile robust
in-situ U–Th–Pb ages. One challenge of such compilation is to inter-
pret the crystallisation timing of U–Th–Pb chronometer that de-
pends on the whole-rock composition and the P–T path of the
dated sample. For example, while monazite Th–Pb ages constrain
thermal metamorphic peak in the northern Lepontine domain, the
same mineral records prograde accretion and retrograde exhuma-
tion in the Urseren zone. At lower metamorphic grade (T b 550 °C),
we compared our dataset with Ar–Ar ages, which can be also ambig-
uous to interpret because they can either be cooling or crystallisation
age (e.g. Allaz et al., 2011).
Based on this age compilation, the new geochronological dataset con-
firms a North–south diachronism across the Lepontine dome, with youn-
ger ages found toward the North, in line with previous studies (Engi et al.,
1995; Hunziker et al., 1992; Janots et al., 2009). Th–Pb ages at 21–24 Ma
of the syn-kinematic REE-minerals (average of Mnz2 and Aln1 ages at
22.5 ± 1.5 Ma) indicate that the accretion of the Urseren zone postdates
that of the internal units. In the external massifs, there is no evidence of
high pressure mineral assemblages and the main deformation stage
dated at 21–24 Ma is thus attributed to the nappe stacking phase during
Alpine collision. This Th–Pb age is consistent with an Ar–Ar age of
21.1 ± 0.2 Ma measured on biotite from a shear zone of the Aar massif
(Rolland et al., 2009). This suggests that the Aar massif with its para-
autochton cover of the Urseren zone were accreted contemporaneously.
In this external domain accretion occurred later than in the Lepontine
units, where the main deformation phase is dated at 29–32 Ma from
allanite in-situ dating (Janots et al., 2009) and 26–35 Ma using Ar–Ar dat-
ing on mica (Wiederkehr et al., 2009).
In the Central Alps, metamorphic equilibration (thermal peak) at-
tributed to the Barrovian overprint is dated from 19–18 Ma in the
north (Allaz et al., 2011; Janots et al., 2009) to 30–20 Ma in the south
of the Lepontine dome (Berger et al., 2009; Engi et al., 1995; Gregory
et al., 2012; Rubatto et al., 2011). The Aln2 age of 17–21 Ma (average
of the two samples = 19.3 ± 2.0 Ma) extends the young Miocene
age for the metamorphic peak to the external domains of the Central
Alps. It is similar to that obtained in the Helvetic nappes in the northern
Lepontine dome and also consistent, although slightly older, with K–Ar
ages of 16–18 Ma obtained in the Aar massif and the Urseren zone
(review in Hunziker et al., 1992). The slight difference between K–Ar
and Th–Pb dating may be explained by Ar-loss due to diffusion or
recrystallisation during exhumation.
In the Aar and Gotthard massifs, fission track or (U–Th)/He data in-
dicate a nearly constant exhumation of ~0.5 km/Ma since Middle Mio-
cene with faster rates of exhumation in the order of ~0.7 km/Ma from
16 to 14 Ma (Glotzbach et al., 2010). In the Urseren zone, Mnz3 age at
 E. Janots, D. Rubatto / Lithos 184–187 (2014) 155–166
13.6 ± 1.4 Ma is similar to the zircon fission track ages obtained in the
Aar massif (Glotzbach et al., 2010), confirming that Mnz3 formed during
the exhumation of the Urseren zone, at temperatures probably close to
the annealing temperature of zircon fission track (~250 °C). Mnz3 age is
also consistent with the Ar–Ar phengite ages of 13.8–12.2 Ma obtained
in late-mylonite of the Aar massif (Rolland et al., 2009) and with in-situ
Th–Pb ages of 13.5–15.5 Ma obtained on hydrothermal monazite crys-
tals found in clefts of the Aar and Gotthard massifs (Janots et al.,
2012). The systematic occurrence of 12–16 Ma ages for tectonic struc-
tures such as mylonite, cleft and veins, argues for an intensive tectonic
activity, which may have accounted for the accelerated exhumation
rates at that time (~ 0.7 km/Ma from 16 to 14 Ma, Glotzbach et al.,
2010).
6. Conclusions and perspectives
This study demonstrates how powerful the geochronology of REE-
minerals is in determining collision timing in low-temperature
metamorphic rocks of external massifs. In the metasediments studied,
U–Th–Pb isotopic dating of the distinct REE-mineral populations brings
novel geochronological constraints on the tectonometamorphic evolu-
tion in the external domains of the Central Alps. While grains are tiny
(except for allanite observed close to carbonate-rich veins or layers)
and contain low proportions of radiogenic Pb, robust Th–Pb ages have
been determined from 206Pbc normalized Th–Pb isochron. The entire
Th–Pb dataset can be reduced to three distinct successive metamorphic
events: 21–24 Ma for prograde accretion, 17–21 Ma for subsequent
thermal peak and 13.6 ± 1.4 Ma for late-stage hydrothermal activity.
The similarities between these ages from the cover units with those pre-
viously obtained for the crystalline basements (Ar–Ar ages on mica and
Th–Pb ages on cleft monazite), suggest for a close tectonometamorphic
evolution of basement and cover through the collisional cycle. Hydro-
thermal monazite can be a reliable recorder of late deformation events
that could complete the thermochronological dataset and help to date
the mobility of fluids during tectonic activity and exhumation (Berger
et al., 2013; Janots et al., 2012).
Acknowledgements
This research project was supported by the CNRS (projects INSU
2010–2011) and the University Joseph Fourier (action BQR 2011). The
paper has been greatly improved by the critical and constructive com-
ments of Antonio Langone and an anonymous reviewer, supervised by
the editor Marco Scambelluri. We are grateful to Nathaniel Findling
for his assistance with the SEM and thin section cuts; S. Brechbühl and
V. Jacob for their excellent polished sections; J. Allaz for his help on
the field and with the figures. This paper benefited from numerous fruit-
ful discussions with A. Berger, E. Gnos and M. Engi.
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