Contrib Mineral Petrol (2001) 141: 53±65

DOI 10.1007/s004100000202

Thorsten Geisler á Marcus Ulonska á Helmut Schleicher

Robert T. Pidgeon á Wilhelm van Bronswijk

Leaching and differential recrystallization of metamict zircon

under experimental hydrothermal conditions

Received: 8 June 2000 / Accepted: 14 September 2000 / Published online: 1 March 2001
Ó Springer-Verlag 2001

Abstract We report results of hydrothermal experiments that recrystallization in the reaction rims was catalyzed
on four alluvial zircons from Sri Lanka, which cover a by water in®ltration and ion exchange and prevented
wide range of radiation damage, at 450 °C and 1.3 kbar significant congruent zircon dissolution under the given
for 744 h with 2 M CaCl2 solution as reactive ¯uid. After experimental conditions. Previous zircon studies have
the hydrothermal treatment, the most metamict samples shown that (1) a transgressive morphology, (2) a reduced
show micrometer-thick reaction rims, which surround Th±U ratio, and (3) an enhanced CL emission are also
apparently unreacted zircon, as revealed by cathodolu- characteristics of rims in zircons from high-grade
minescence (CL) and Nomarski differential interference metamorphic rocks. Based on these similarities between
contrast (NDIC) images. These rims have sharp, curved, natural and experimentally produced rims, it is sug-
and transgressive boundaries with unreacted zircon and gested that leaching-catalyzed recrystallization is an
are, in some cases, spread out along cracks. The thick- important alteration process in zircon under wet geo-
ness of reaction rims increases with increasing cumu- logical conditions and can account for many complex
lated a-dosage of the starting materials. The reaction core-rim structures found in natural zircons. Further-
rims are strongly enriched in Ca (up to 7000 ppm) and a more, the strong enrichment of Ca in the reaction rims
water species and depleted in radiogenic Pb, Zr, and Si, supports previous assumptions that high Ca concentra-
as revealed by electron microprobe analyses. A signi®- tions in natural zircons are of secondary origin. It is
cant Th loss from the reaction rims was detected in the suggested that lower U±Pb concordia intercept ages
case of the most metamict sample, whereas U remained obtained from single-phase zircons with high Ca
in the structure. FT-infrared spectrometry and X-ray contents date a leaching event.
diffraction measurements revealed that the bulk run
products were recrystallized. Using micro-Raman
spectrometry, we were able to demonstrate that di€er- Introduction
ential recrystallization took place. The reaction rims
are strongly recrystallized, whereas the unreacted grain It is well known from numerous U±Pb isotopic studies
interiors underwent only minor recrystallization. that multi-grain fractions and single zircon grains fre-
Recrystallization of the rims is accompanied by an quently yield discordant U±Pb ages. A number of
enhancement of the integral CL intensity. It is suggested mechanisms have been proposed, which explain U±Pb
discordance generally in terms of Pb loss (cf. review of
Gebauer and GruÈnenfelder 1979; Mezger and Krogstad
T. Geisler (&) á M. Ulonska á H. Schleicher 1997). A significant factor in these models is the pro-
Mineralogisch-Petrographisches gressive damage of the zircon lattice caused by time-
Institut der UniversitaÈt Hamburg, Grindelallee 48,
20146 Hamburg, Germany integrated radiation ¯ux, which increasingly changes the
E-mail: t.geisler-wierwille@t-online.de susceptibility of zircon to alteration and open system
E-mail: thorsten.geisler@mineralogie.uni-hamburg.de behavior under various geological conditions (e.g., Silver
R. T. Pidgeon and Deutsch 1963; Krogh and Davis 1973; Medenbach
School of Applied Geology, Curtin University of Technology, 1976; Geisler and Schleicher 2000a). However, examples
GPO Box U 1987, Perth 6845, WA, Australia have also been reported where Pb loss from zircon was
W. van Bronswijk largely independent of radiation damage (e.g., Pidgeon
School of Applied Chemistry, Curtin University of Technology, 1992; Schaltegger et al. 1999; Vavra et al. 1999). Nev-
GPO Box U 1987, Perth 6845, WA, Australia ertheless, the effect of radiation damage on the magni-
Editorial responsibility: J. Hoefs tude of U±Pb discordance was demonstrated by a series
54

of hydrothermal experiments (Pidgeon et al. 1966, 1973, that the results of these experiments have important
1995; Hansen and Friderichsen 1989; Sinha et al. 1992; implications for the interpretation of complex core±rim
Levchenkov et al. 1998; Rizvanova et al. 1996, 2000). structures often found in metamorphically overprinted
The results of these experiments demonstrated the real- zircons and for the interpretation of U±Pb ages obtained
ity of episodic Pb loss and additionally showed that from these zircons.
under some circumstances U can be removed from zir-
con. The degree of Pb loss was seen to depend on the
metamict state of the original zircon, the nature of the Sample selection
environmental solution, the temperature and pressure,
and duration of the hydrothermal experiment. However, Alluvial, gem-type zircons from Sri Lanka were selected
details of the mechanisms and the kinetics of Pb (and U) as starting materials for the experimental study because
loss from zircon are still not known, which opens previous investigations have shown that they (1) contain
possibilities for further experimentation. insignificant amounts of Ca (e.g., Murakami et al. 1991),
Previous experimental studies were mainly performed (2) show no signs of alteration, (3) suffered a wide range
on heterogeneous, multi-grain samples and experimental of radiation damage because of highly variable U and
products were investigated using techniques that require Th contents (e.g., Holland and Gottfried 1955; Mura-
one or more grains for an analysis. Furthermore, none kami et al. 1991), (4) can occur as large homogeneous
of these experimental studies was designed to study in crystals with little zoning (Pidgeon et al. 1994; Pidgeon
detail the behavior of elements other than U and Pb 1997).
during ¯uid±crystal interaction. The potential to ad- After optical investigations and density measure-
vance our understanding by further experimentation is ments, we selected four Sri Lankan zircons (Z9, Z10,
provided by micro-analytical and imagery techniques, Z11, and Z16), obtained from the Mineralogical Muse-
which can monitor changes in the crystal structure and um of the University of Hamburg, as starting materials
elemental concentration within individual zircon grains for the experiments. These samples contained <40 ppm
on a micrometer-scale. These techniques have been used Ca (Table. 1) and also covered a wide range of radiation
in the present experimental program, which was de- damage as characterized by X-ray diffraction analysis,
signed to investigate the ability of zircon to accommo- FT-infrared and micro-Raman spectroscopy, their
date significant amounts of non-formula elements like density, and by their cumulative a-dosage (Figs. 3,4,5,
Ca, Al, Fe, and Mn (cf. review of Speer 1980), which do Tables 1 and 2). Cathodoluminescence images of small
not ®t into the crystal lattice according to Goldschmidt's fragments of the zircons show no heterogeneity. How-
rules. This is basic to understanding open system be- ever, sample Z10 shows distinct peak splitting in the
havior of the metamict zircon structure in hydrothermal X-ray diffraction spectrum, suggesting the existence
environments. of a crystalline zircon ``phase'', which forms part of the
The present work investigates the potential for Ca to otherwise heavily metamict starting grain (Fig. 4A). The
be incorporated into metamict zircon through crystal± re®ned unit-cell parameters of this zircon ``phase'' indi-
¯uid interaction. The choice of Ca by using a 2 M CaCl2 cate that it is well crystalline (Table 2). However, an
solution for initial experimentation was suggested by analytical survey across the half the grain using the
reports of Ca contents of several thousand ppm in nat- electron microprobe (EMP) revealed no area containing
ural zircons (cf. Speer 1980) and by the similarity in ion <2300 ppm U and 1500 ppm Th. Furthermore, infrared
size and charge between Ca2+(1.20 AÊ) and Pb2+(1.29 AÊ). powder spectra from another aliquot of this sample did
Experimental studies with solutions containing isotop- not indicate a crystalline zircon ``phase'' (Fig. 4). The
ically enriched Pb show that Pb from the hydrothermal origin of this ``phase'' remains unknown. However, its
environment can enter the zircon at the same time apparent existence does not affect any of our con-
radiogenic Pb is being lost (Pidgeon et al. 1995). clusions.
Furthermore, a systematic relationship between Ca
content, U±Th±Pb discordance and the cumulated
a-dosage in zircons as reported by Geisler and Schleicher Experimental details
(2000a) demonstrate the ability of metamict zircon to
incorporate Ca at the same time as losing radiogenic Pb. Hydrothermal treatment
The initial experiments were carried out at 450 °C and
1.3 kbar for 1 month. They are part of a more com- Zircon samples were crushed to powder in an agate mortar. About
prehensive experimental program, which is now in pro- 10±20 mg of the zircon powder was placed in a gold capsule along
with a 2 M CaCl2 solution prepared from pure CaCl2 and distilled
gress. The choice of the initial experimental parameters H2O. The gold capsules ± which were 50 mm in length and 3 mm in
was a compromise between the wish to enhance the diameter ± were sealed by welding with a gas ¯ame while cooling in
kinetics of leaching reactions, including a possible Ca ice-cold water. All experiments were carried out in standard cold-
in®ltration, and the fact that recrystallization of me- seal hydrothermal pressure vessels at 1.3 kbar and a temperature of
450 °C. The temperature and pressure were monitored during the
tamict zircon under hydrothermal conditions compete experiment and were held constant within ‹2 °C and ‹0.05 kbar,
with leaching reactions (Pidgeon et al. 1995; Rizvanova respectively. The accuracy of the temperature measurements was
et al. 1996, 2000; Levchenkov et al. 1998). We will show ‹3 °C. The duration of all runs was 744 h. At the end of the
Table 1 Average composition of starting materials and experimental run products as determined by electron probe. Errors represent the empirical 2r standard deviation of the given
mean obtained from n measurements. The total counting times for a single spot location on run products were: Zr: 50 s; Si: 100 s; Hf, P, Y, Yb, Ca, and Al: 200 s; Pb: 1000 s; U: 500 s;
Th: 600 s, and a tenth of these values for the starting material. A homogeneous zircon from Sri Lanka (SL-Z1) was used as standard for the U, Th and Pb determination (cf. Geisler-
Wierwille 1999; Geisler and Schleicher 2000b). The internal 2r errors for a single spot analysis on the run products were typically 20% at 200 ppm Pb, and 2% for U and Th at
concentrations of 2000 and 1000 ppm, respectively

Starting materials Run products

Unreacted cores Reaction rims

Sample Z11 Z16 Z9 Z10 Z9 Z10 Z9 Z10

(n=10) (n=14) (n=15) (n=14) (n=3) (n=4) (n=5)a (n=6)
ZrO2 (wt%) 67.39‹0.24 66.39‹0.30 65.72‹0.24 66.51‹0.34 65.89‹0.67 66.69‹0.24 64.86‹0.37 65.08‹0.35
SiO2 31.94‹0.08 31.44‹0.08 31.27‹0.18 31.56‹0.16 31.51‹0.36 31.50‹0.23 30.98‹0.17 30.87‹0.28
HfO2 0.36‹0.04 1.35‹0.02 1.65‹0.02 0.93‹0.02 1.62‹0.02 0.96‹0.02 1.60‹0.03 0.94‹0.01
H2Ob 0.41‹0.27 0.40‹0.32 0.57‹0.57 0.26‹0.71 0.15‹0.47 0.10‹0.38 1.11‹0.27 1.58‹0.52
P (ppm) 83‹24 262‹26 742‹148 140‹50 640‹29 55‹40 557‹41 38‹11
Y <85 693‹82 1724‹68 1425‹266 1849‹130 1548‹201 1704‹82 1469‹58
Yb <95 246‹64 527‹40 325‹80 613‹88 375‹26 614‹79 358‹35
U 252‹40 1385‹40 2233‹139 2589‹76 2436‹118 2414‹263 2449‹107 2468‹355
Th 114‹20 585‹26 517‹24 1631‹28 613‹85 1685‹58 515‹77 1495‹41
Pb <50 117‹32 176‹30 225‹30 213‹23 219‹28 83‹72 78‹21
Ca 36‹30 <20 29‹26 <20 141‹127 62‹68 4415‹1719 5753‹1319
Al <25 <25 <25 <25 <25 <25 438‹493 125‹150
Age (Ma)c <1050 510‹130 500‹130 500‹120 550‹40 510‹50 190‹190 220‹100
D (a/mg)d +0.08 +0.08 +0.28 +0.16 ± ± ± ±
0.55 )0.10 3.02 )0.34 4.68 )0.58 5.88 )0.68
a
Three analyses were excluded because extremely low totals indicate that Araldite resin was within the analyzed volume (see Fig. 3B)
b
The H2O content was estimated from the difference of the analytical total
c
The age represent the chemical U±Th±total Pb age obtained from the U, Th and Pb concentration through the equation given in Suzuki and Adachi (1991)
d
The a-dosage, D, was calculated for an age of 570 Ma (Gottfried et al. 1956). The upper error limit was estimated using the error of the U and Th concentration and the lower error
limit additionally includes an assumed error of the age of 30 Ma. This was done because recent U±Pb age data have shown that the age of 570 Ma should be considered as maximum age
for Sri Lankan zircons (e.g., Geisler-Wierwille 1999; Geisler, unpublished data)

55
56

Table 2 Density and re®ned

lattice parameters for starting Sample Starting materials Run products
materials and run products.
Density a0 c0 a0 c0
Errors are given at the 2r level
(g/cm3) (AÊ) (AÊ) (AÊ) (AÊ)

Z11 4.60‹0.04 6.608‹0.004 5.985‹0.008 6.602‹0.004 5.970‹0.007

Z16 4.46‹0.03 6.665‹0.012 6.062‹0.018 6.640‹0.014 6.042‹0.020
Z9 4.27‹0.03 6.673‹0.023 6.097‹0.051 6.619‹0.003 5.994‹0.005
Z10a 4.24‹0.03 6.679‹0.022 6.098‹0.041 6.616‹0.004 5.992‹0.006
6.605‹0.012 6.014‹0.023
a
The italicized values represent re®ned lattice parameters for a second, well crystalline zircon ``phase''
(see text for more details and Fig. 5A)

experiments the bombs were quenched in air to room temperature description of analytical strategy and more details of the analytical
and the gold capsules were weighed to check for leakage, carefully conditions are described elsewhere (Geisler-Wierwille 1999; Geisler
opened and ®nally washed out with distilled H2O. and Schleicher 2000a, 2000b).
The analytical work on experimental run products was com-
plicated by the fact that only thin reaction rims were developed
Electron microprobe analysis around hydrothermally treated grains (cf. Fig. 1). The smallest rim,
which could be measured by EMP under the chosen conditions,
Chemical analyses of the starting material and the experimental run was limited by a beam diameter of 1.5±2.0 lm as estimated from
products and X-ray scanning images were obtained with a Cameca Eq. (13.25) in Reed (1993). We thus had to carefully assess the
CX724 automated electron microprobe (EMP) equipped with three effect of following sources of unsystematic errors:
wavelength dispersive-type spectrometers at the Department of
Mineralogy and Petrography of the University of Hamburg. The 1. The obvious surface roughness could induce errors in the
major elements Zr and Si, as well as a set of minor and trace absorption correction.
elements (Hf, Y, P, Ca, Al, U, Th, Pb, and Yb), were measured 2. Because of the small thickness of the reaction rims, the
simultaneously. To obtain a high signal to noise ratio for trace embedding Araldite resin could be within the analyzed volume,
element analyses the operating conditions were 25 keV accelerating which would cause low analytical totals.
voltage at 100 nA beam current. Further details of the analytical 3. The ¯uorescence correction may not be accurate when analyzing
precision and detection limits are given in Table 1. A detailed areas near a phase boundary (``¯uorescence uncertainty'').

Fig. 1A±D Nomarski di€er-

entiation interference contrast
(NDIC) images; E±G cathodo-
luminescence (CL) images of
hydrothermally treated grains.
H A Ca±Ka X-ray scanning
image of a hydrothermally
treated grain, which is also
imaged in G and I with
the CL and NDIC technique,
respectively
 57

In order to avoid or at least to reduce these errors, we located single grain of sample Z10 in Fig. 1G, H, I. The NDIC
the analytical spots on deeper penetrated, convex reaction rims or technique allows imaging surface relief as little as
at grain corners, which show a ¯at surface in Nomarski differential
interference contrast (NDIC) images. However, three analyses 50 nm (Nomarski and Weill 1954) and is routinely
from sample Z9 have very low totals, which may indicate that used by us to check the quality of the polished zircon
Araldite was within the analyzed volume (marked in Fig. 3B). surface prior to trace element analysis by EMP. The
These were excluded from the mean values given in Table 1. Cal- NDIC images clearly reveal that a reaction front has
culations show that the ``¯uorescence uncertainty'' may have
caused an over-correction of the Si- and P±Ka line intensities for
progressed towards the grain centers of the most me-
spot locations at the boundary to the Araldite resin by maximal tamict sample Z9 and Z10 during the hydrothermal
0.7%. However, the ¯uorescence uncertainty on the M-lines of U, treatment, resulting in the formation of thick reaction
Th, and Pb intensity is negligible. rims of a different hardness (Fig. 1A±C). The reaction
rims have sharply curved phase boundaries with unre-
X-ray diffraction analysis acted zircon (in the following simply referred to as
cores), and in some cases, spread out along cracks
Powdered aliquots of all four samples used for the experiments (Fig. 1C). The external morphology of the grains was
were scanned with Cu±Ka radiation from 5 to 70° 2h using a not changed through the experiment, indicating that
Philips X'Pert automated diffractometer at the Department of
Mineralogy and Petrography of the University of Hamburg. The surface dissolution was insignificant. No reaction rims
operating conditions were 50 keV accelerating voltage at 30 nA were detected around grains of the less metamict sample
tube current. The instrument was calibrated using quartz as ex- Z16 using the NDIC technique. However, thin reaction
ternal standard, which did not permit the control of sample height rims (1 lm) are visible in CL images (Fig. 1E). The
effects on the 2h Bragg positions. However, re®ned lattice constants
of all four samples using the program of Holland and Redfern reaction rims of samples Z9, Z10, and Z16 are charac-
(1997) agree well with previously published data (Murakami et al. terized by bright CL emission whereas the unreacted
1991; Woodhead et al. 1991a) when plotting the lattice constants as cores generate the same weak luminescence as the
a function of the cumulated a-dosage as determined by EMP an- starting material (Fig. 1E, F, H). Neither the NDIC nor
alyses (not shown). Each identi®able zircon peak pro®le was ®tted
individually by using a Lorenzian and Pearson VII function for the
the CL technique revealed any hint of a reaction rim
Bragg peak and the diffuse scattering component, respectively, as around grains of the crystalline sample Z11 (Fig. 1D).
proposed by Murakami et al. (1991). Aliquots of all four samples To investigate the dependence of the thickness of the
were re-analyzed after hydrothermal treatment to record any reaction rims on the degree of metamictization, we
structural changes through the hydrothermal treatment. measured the thickness on a number of CL and NDIC
images on straight grain edges. The measured median
FTIR spectrometry thickness', bracketed by the observed maximum and
minimum values, are plotted on Fig. 2 as a function of
Infrared spectra were recorded with a Perkin±Elmer Spectrum 2000 the a-dosage of the starting material. The wide variation
FTIR spectrometer at the Technical University of Hamburg-Har-
burg over the range of 300±5000 cm±1 and with a resolution of in thickness is interpreted to be the result of sample
4 cm±1. For the FTIR powder analyses, new ®nely ground pow- properties like variations in the radiation damage of
ders were prepared from pieces of all four samples. About 2±3 mg individual grains and/or an anisotropic reaction behav-
of the sample powder was pressed in pellets together with 300 mg ior. However, some variation may be attributed to dif-
of KBr. Aliquots of sample Z9 and Z10 were re-analyzed after the
hydrothermal treatment.
®culties in identifying the real phase boundaries in the
images and to non-angular cuts between the rim/core

Micro-Raman spectrometry

Raman spectra of the starting materials and the run products of

sample Z10 were collected with an ISA LabRam dispersive Raman
spectrometer using the 514.5 nm line of an Ar+ laser with a beam
power of 4.5 mW at the Curtin University of Technology. The
scattered Raman light was analyzed with a charge-coupled device
(CCD) array detector after being dispersed by a grating of
1800 grooves per mm. A 100´ objective [numerical aperture
(NA)=0.9] was used on a BX-40 microscope. With this objective,
the lateral spot size of the laser beam was 1 lm. The spectral slit
was 100 lm and the resolution was 2 cm±1.

Results

Development of reaction rims

X-ray scanning, Nomarski differential interference con-

trast (NDIC) and cathodoluminescence images (CL) of Fig. 2 The thickness of the reaction rims as a function of the
hydrothermally treated grains are shown in Fig. 1. A cumulated a-dosage. The curve (stippled line) was estimated by eye
direct link of all three imaging techniques is given for a and we assign no mathematical significance to it
58

interface and the polished surface, which could result in indicated by reduced chemical U±Th±total Pb ages
overestimates of the thickness. Despite these limitations, (Fig. 3A). In contrast, EMP analyses of the unreacted
Fig. 2 clearly demonstrates that the thickness varies cores of both samples did not reveal any chemical al-
systematically with the a-dosage of the starting material. teration. The disturbance of U±Th±total Pb ages of re-
action rims is correlated with the Ca contents (Fig. 3A).
Most of the disturbance can be attributed to a severe
loss of Pb (Table 1). However, reaction rims of sample
Ion-exchange and the disturbance of the
Z10 also lost a significant amount of Th. The Th loss has
U±Th±Pb system
been veri®ed by comparing the overall mean Th con-
centration of reaction rims with those of the starting
The reaction rims of grains from sample Z9 and Z10 are
material and by comparing Th concentrations of the rim
strongly enriched in Ca, which is well documented by the
and the core of single grains (Table 1; Fig. 3C). In
X-ray scanning images (Fig. 1H) and quantitative EMP
analysis (Table 1), proving that intensive ion exchange
took place. In addition to the enrichment of Ca, the
Fig. 3A±E Electron microprobe data from the starting materials,
reaction rims of both samples are depleted in Zr and Si the unreacted cores and the reaction rims plotted in different
(Fig. 3B, Table 1). It was not possible to quantitatively diagrams. Analysis obtained from the same grain are marked with
analyze the small reaction rim around grains from the same number in C and D. The chemical U±Th±total Pb ages in
sample Z16, which are smaller than the estimated EMP A were calculated from the U, Th and Pb concentration through
the equation given by Suzuki and Adachi (1991). A zero U±Th±
beam width (see preceding section). An important result total Pb age means the Pb content was below the detection limit.
is that the U±Th±Pb system of the reaction rims of Error bars represent the 2r analytical uncertainty. Curves in E were
sample Z9 and Z10 were significantly disturbed as ®tted by eye for clarity only
 59

contrast, no loss of U could be detected from reaction strained crystalline zircon domains and recrystallization
rims of this sample. In the case of reaction rims of of amorphous domains. The IR bands of both samples ±
sample Z9, however, neither Th nor U loss was detected representing internal bending and stretching modes of
(Fig. 3D, Table 1). the SiO4 tetrahedron as well as external vibration modes
The reaction rims are furthermore enriched in a water (e.g., Woodhead et al. 1991a) ± are weaker and broader
species, which was estimated by the difference of the compared with those of well-crystalline zircon (e.g.,
analytical total from 100% and expressed as H2O (Ta- sample Z11). Sample Z10 appears to be more recrys-
ble 1). No significant amounts of elements other than the tallized than sample Z9 (Fig. 4B).
analyzed ones could be detected in the starting materials, In Fig. 5, the (200) diffraction peak of the starting
which could have been lost during the treatment and material of sample Z9, Z10, and Z16 is compared with
therefore could account for the observed analytical def- that of the experimental run products. In the untreated
icit. Furthermore, spectral scans do not detect any sig- samples Z9 and Z16, the overall pro®le results from the
nificant amount of chlorine in the reaction rims. Thus, superposition of two single pro®les (Fig. 5A). The pro®le
we conclude that the difference between the calculated at the lowest 2h angle can be attributed to crystalline but
H2O content of the reaction rims and of the unreacted strained domains with a high point defect density,
cores and the starting materials is significant because this whereas the second diffraction pro®le at the higher 2h
difference is greater than the sum of the empirical 2r angle is attributed to diffuse scattering from the amor-
error of the individual mean estimates (Table 1). phous matrix (e.g., Murakami et al. 1991). The di€rac-
A surprising result is that some reaction rims of tion pro®le of sample Z10 additionally contains the
sample Z9 and Z10 show an enrichment of Al, which is diffraction contribution of undamaged, crystalline areas
correlated with the Ca enrichment (Fig. 3E). The Al±Ca as discussed above. Sharp Bragg peaks were observed
trends of both samples differ from each other. However, for sample Z10 and Z9 after the hydrothermal treat-
the overall mean Al content in the rims is not signi®- ment, indicating the intensive growth of crystalline
cantly higher than in the starting material (Table 1). The domains, whereas the XRD spectrum of the hydro-
source of the Al3+ is uncertain. A possible explanation thermally treated sample Z16 at ®rst glance does not
would be the dissolution of Al-rich coatings on fractures show significant signs of recrystallization (Fig. 5B).
(e.g., kaolinite) within the uncrushed zircon samples. However, the peak pro®le results from the superposition
of three pro®les, indicating the formation of a new
``phase'' of higher crystallinity (Fig. 5B). Sample heter-
Differential recrystallization ogeneity can be excluded as the cause for this difference
because the same zircon powder was measured prior to
Powder FTIR spectra of experimental run products of and after the experiment.
sample Z9 and Z10 reveal that both samples were re- The apparent differences in recrystallization behavior
crystallized during the hydrothermal experiment (Fig. 4). of sample Z9, Z10, and Z16, as determined by XRD and
In the following, we use ``recrystallization'' as a purely IR bulk powder technique, can be understood when
descriptive term to describe structural recovery, which considering the nature and the extent of the reaction
includes point defect recombination, i.e., recovery of rims. Difference in the hardness of rims and cores as

Fig. 4A,B FTIR powder spec-

tra. A Starting materials; B ex-
perimental run products
60

Fig. 5A,B Deconvolution (solid

lines) of the measured (200)
X-ray diffraction pro®le (open
circles). A Starting materials;
B experimental run products

revealed by the NDIC technique indicates that di€er- The strongly enhanced integral CL emission of the
ential recrystallization has taken place; given the known reaction rims around grains from sample Z9 and Z16 is
difference in the hardness between crystalline and me- taken as evidence that these rims have also been re-
tamict zircon (Speer 1980; Chakoumakos et al. 1991). crystallized. Variations in the CL intensity within single
To obtain detailed information on the disorder-to-order grains usually have been interpreted to re¯ect variations
transition within single grains, we performed micro- in the concentration of luminescence-activating ions
Raman measurements on four experimentally treated such as Dy3+ and Sm3+ (e.g., Remond et al. 1992;
grains from sample Z10 (see Nasdala et al. 1996). Ra- Hanchar and Miller 1993). However, since the reaction
man spectra of the reaction rims and cores of four grains rims contain similar amounts of these rare earth ions ±
from sample Z10 are compared in Fig. 6 with spectra or if leaching occurred, a lesser amount ± we interpret
from untreated grains and a spectrum from the crystal- the enhanced CL intensity to be the result of recrystal-
line sample Z11. It is evident that the intensities of the lization associated with the in¯ux of Ca and water. The
Raman shift bands of the reaction rims, resulting from effect of point defect concentration on the CL intensity
internal and external vibrations of the SiO4 tetrahedron has recently been demonstrated in CL studies on Nd:
(e.g., Dawson et al. 1971), are significant higher than YAG crystals, which were amorphized with a neon ion
those of the starting material. Within the latter spectra, beam (Peto et al. 1997; Townsend et al. 1999). In these
the Raman shift bands are strongly broadened and weak arti®cially damaged crystals the CL intensity is reduced
to absent. Although the main Raman shift bands of by 1000 times when compared with the CL intensity
zircon can be identi®ed, the spectra from the reaction generated in undamaged crystals. Also, Rizvanova et al.
rims still do not resemble that of a crystalline zircon (1996, 2000) reported a change in the CL emission of
(inset diagram in Fig. 6). A stronger and more intense metamict zircon grains, which recrystallized during
m3(SiO4) band as well as a smoothed background indi- hydrothermal treatment with 2 M Na2CO3 solution.
cate that also the unreacted cores are slightly recrystal- In the light of these results, the most intense contri-
lized in comparison with the untreated zircon sample. bution to the overall (200) peak pro®le in Fig. 5B of the
Recrystallization of the unreacted cores is further indi- hydrothermally treated samples Z9 and Z16 can be as-
cated by a significant shift in the phonon frequency signed to the crystalline reaction rims, whereas the
(Fig. 6) and a reduction of the measured full width at the pro®les at lower 2h angle most probably originate from
half maximum of the m3(SiO4) band (18±22 cm±1 com- still strongly strained crystalline domains within the
pared with 30±35 cm±1 of the untreated sample). cores. In the case of sample Z16, the diffuse scattering
 61

Discussion

Leaching-catalyzed recrystallization

Diffusion studies have shown that true lattice diffusion of

cations in crystalline zircon is very slow under ambient
temperature conditions (e.g., Cherniak et al. 1997; Lee
et al. 1997). However, the presence of a high concentra-
tion of Ca2+ in the reaction rims indicates large-scale ion
exchange. Fast diffusion pathways are required allowing
diffusion of reactant and product atoms to and from the
deeply penetrated reaction fronts. Although a water
species was not detected directly, our water estimations by
EMP indicate that the reaction between ¯uid and me-
tamict zircon involves the permeation of hydrogen and/or
possibly molecular water in combination with intensive
ion exchange. Petit et al. (1989) demonstrated that the
rates of hydrogen in®ltration in arti®cially damaged sili-
cate structures in hydrothermal environments are en-
hanced compared with crystalline silicates. The following
structural features probably control the initial rate of
water permeation and ion exchange in metamict zircon
and account for the observed systematic relationship
between rim thickness and cumulated a-dosage:

1. The degree of macroscopic swelling of metamict zir-

con, which resulted from both accumulated point
defects and amorphous regions (e.g., Murakami et al.
1991; Weber 1993).
Fig. 6 Micro-Raman spectra of the reaction rims and unreacted 2. The spatial distribution of crystalline and amorphous
cores of hydrothermally treated grains from sample Z10 compared domains within the metamict network.
with spectra of the starting material and a spectrum of the 3. The recoil track density. Recoil tracks that intersect
crystalline sample Z11 (inset) the surface provide high-mobility pathways and per-
mit ion exchange to penetrate deeper into the interior
of the radiation damaged structure (e.g., Fleischer
component from amorphous regions within the cores is 1980).
also still detectable in the run product. Because the
grains are enclosed completely by the reaction rims this As shown by micro-Raman spectroscopy and indi-
can be explained by absorption of the primary as well as rectly by XRD analysis the reaction rims exhibit a higher
the diffracted and scattered X-rays in the reaction rims. degree of structural order than the unreacted cores and
The magnitude of this effect varies with the thickness of the starting material. Our current interpretation is that
the reaction layer according to the Beer±Lambert law, the high mobility of network forming ions within the re-
i.e., it is the highest for sample Z10 and has only a minor action rims probably resulted from the increasing con-
effect for sample Z16. It is thus concluded that the re- centration of water species in the leached rim and possibly
®ned lattice parameter of sample Z9 and Z10 describe from the necessity to completely reorganize the structure
the lattice dimension of the reaction rim, which ± in to eliminate non-bridging oxygens. It is important to note
agreement with the results from the Raman measure- that the in®ltration of water did not stabilize the metamict
ments ± is still larger than that of crystalline zircon state, but had the opposite effect. We conclude that
(Tab. 2). The peak splitting observed for the experi- leaching reactions catalyzed recrystallization and that
mental run products of sample Z16 is further evidence recrystallization was the ®nal rate-controlling process.
that recrystallized reaction rims are also present in the After recrystallization was activated, it competed with
run products of this sample. The strong overlap of all leaching reactions like hydration and ion exchange, and
three peaks of sample Z16, however, complicates the may have prevented significant congruent dissolution.
deconvolution of the composite pro®les at higher 2h Recrystallization in the reaction rims is not a simple
angles and, hence, does not allow a separate re®nement recovery of the original zircon structure because it in-
of the lattice constants. The re®ned cell parameters given volves the formation of a new, water- and Ca-rich zircon
in Tab. 2 therefore represent the mean of both reaction phase. Significant amounts of Ca2+ and water were re-
rims and unreacted cores. tained within the newly formed crystalline structure
62

because of the strong chemical potential gradient be- decreased (Pidgeon et al. 1966, 1973, 1995; Sinha et al.
tween zircon and reactive ¯uid. The Al3+ enrichment in 1992; Rizvanova et al. 1996, 2000; Levchenkov et al.
the reaction rims indicates that Al3+ behaves similar to 1998). All these workers have suggested that recrystal-
Ca2+ during zircon±¯uid interactions as suggested by lization of metamict zircon plays an important role in
previous studies on natural zircons (Medenbach 1976; causing the decrease in the Pb (and U) loss rate with
Geisler-Wierwille 1999; Geisler and Schleicher 2000a). time. Pidgeon et al. (1995) monitored the change of the
Possible charge-compensating substitution mechanisms powder X-ray diffraction intensity of the (200) peak,
(neglecting the loss of small quantities of Pb2+ and I(200), with increasing duration of the experiment. In
Th4+ and the gain of Al3+) are as follows: their experiments on a fully X-ray amorphous zircon
from Sri Lanka, the I(200) vs. time curves closely
Ca ‡2H‡ $ Zr4‡
 2‡   
…1†
resemble the Pb loss vs. time curves of the same set of
and the hydrogrossular substitution experiments. The reaction kinetics in these experiments
h i can be explained by our present experimental observa-
‰4…OH† Š $ …SiO4 †4 : …2† tion that an open system rim, bounded internally by a
reaction front, develops around metamict zircon sub-
The substitution of Eq. (1) is analogous to the sub-
jected to hydrothermal conditions. Pidgeon et al. (1995)
stitution
have shown that the I(200) vs. time curves depend not
M ‡H‡ $ Zr4‡ ;
 3‡   
…3† only on the temperature, but also on the composition of
the reactive solution. This indicates that the nature of
which probably control the charge compensation for the environmental solution is a major factor controlling
the incorporation of rare earth elements in zircon not only the solubility of U, Th, and Pb, and thus their
(Woodhead et al. 1991b). It is noteworthy that the ability to be leached from the zircon structure, but also
substitution represented by Eq. (2) was found to be the kinetics of rim formation and recrystallization. In
highly effective in zircons, which were synthesized in a experiments in pure water, only minor increase of I(200)
¯uorine-rich, hydrothermal environment, where up to and no Pb (or U) loss was observed by Pidgeon et al.
80% of (SiO4)4± were replaced by (OH, F)± (Caruba et (1995) after 11 h at 500 °C whereas experiments with 2 M
al. 1985). NaCl and HCl solutions under the same conditions
So far, we have only discussed recrystallization of the again revealed significant loss of Pb (and U) and a
reaction rims. However, as indicated by the Raman concurrent significant increase of I(200). Rizvanova et al.
spectra, the unreacted cores of grains of sample Z10 were (1996, 2000) demonstrated that hydrothermal treatment
also slightly recrystallized. This is somewhat surprising of metamict zircon with sodium carbonate solution at
when considering the relative low temperature used in the temperatures of 400 °C resulted in the congruent disso-
experiments and previous annealing experiments in air, lution of zircon and the precipitation of baddeleyite (and
with which we have to compare annealing effects in the a Zr±Na-silicate phase) without the formation of a
apparently unreacted cores. These experiments have sharply bounded reaction rim. XRD measurements
shown that temperatures in excess of 700±800 °C are showed, however, that the bulk zircon grains were re-
needed to start recrystallization of metamict zircon (e.g., crystallized. This observation is important because it
Vance and Anderson 1972; Murakami et al. 1991; Weber implies that dissolution of metamict zircon is faster than
1993; Colombo et al 1999; Meldrum et al. 2000). A recrystallization in carbonate solution. Hansen and
conceivable explanation for this discrepancy would be Friderichsen (1989) observed significant leaching of Pb
that lattice diffusion of hydrogen into the metamict and U from non-metamict zircon through Ca-enriched
grains across the rim/core boundary also catalyzed re- natural brine water at a temperature of 180 °C, sug-
crystallization within the apparently unreacted cores. gesting that small quantities of dissolved ions like Ca2+
This interpretation is in agreement with results from can have a profound effect on leaching kinetics. How-
studies on arti®cially amorphized SrTiO3 and silicon, ever, because a multi-grain fraction was used, it remains
which showed that hydrogen ions have a strong effect questionable whether the Pb and U loss actually
on the recrystallization kinetics of these phases (e.g., occurred from non-metamict zircon or from minor
McCallum et al. 1990; Godet et al. 1995). However, metamict zones, which were not detected in the multi-
further studies are necessary to prove this interpretation. grain starting material. Further research is in progress to
study in detail the dependence of the ¯uid chemistry on
the kinetics of rim formation.
Comparison with previous experimental studies
on zircon±¯uid interaction
Implication for zircon geochronology
Previous hydrothermal experimental studies on zircon±
¯uid interaction have shown that metamict zircon Leaching and recrystallization in natural zircons
treated with aqueous solutions under hydrothermal
conditions initially lost Pb rapidly (and in some cases Numerous studies on the internal morphology of various
U), whereas with increasing duration the Pb loss rate growth zones in natural zircon revealed the existence
 63

of transgressively inwards-penetrating rims, which trun- with the exception of Al, we still have no experimental
cate older growth zones within the crystal (e.g., Black et proof for this suggestion. One could argue that leaching
al. 1986; Pidgeon 1992; Pidgeon et al. 1998; Vavra et al. of radiogenic Pb could be charge-compensated by hy-
1996, 1999; Schaltegger et al. 1999). These rims (in the drogen alone. However, diffusion of hydrogen into the
following abbreviated tr rims) were interpreted to be the structure would possibly at ®rst stabilize radiogenic Pb
result of crystal±¯uid interaction and recrystallization because H+ could act as a charge-compensating species
under the in¯uence of aggressive solutions (e.g., Pidgeon for Pb2+, which results from the decay of U4+ (Watson
et al. 1998; Vavra et al. 1996, 1999; Schaltegger et al. et al. 1997). It is thus suggested that lower intercept ages
1999). It is striking that the inwards penetrating mor- on the U±Pb concordia obtained from single-phase zir-
phology of experimentally produced reaction rims re- cons (e.g., by ion microprobe) that contain a high con-
semble the morphology of tr rims in natural zircons centration of non-formula elements can be interpreted to
(Fig. 2). Besides this morphological characteristic, a date a leaching event. Although attempts are made to
common observation is that tr rims are depleted in U and avoid analyzing these altered areas, it could be impor-
Th and have a lower Th±U ratio with respect to typical tant to precisely de®ne lower intercept ages from these
values of magmatic zircon (Pidgeon et al. 1998; Vavra regions because they re¯ect ¯uid interaction, which
et al. 1996, 1999; Schaltegger et al. 1999). This indicates should have a geological meaning. Because the kinetics
that Th was preferentially lost during the proposed of leaching (and recrystallization) and its dependence on
leaching event; an effect that may be mainly controlled the composition of the ¯uid is not known, it is still
by the solubility of U and Th in the reactive ¯uid (see questionable whether radiogenic Pb could be leached
Keppler and Wyllie 1990). A more important common by weathering from metamict zircon as previously
characteristic of natural and experimental rims, however, suggested (Stern et al. 1966; Black 1987).
is a relatively enhanced integral CL intensity. All these
similarities between natural and experimentally pro- Acknowledgements Many thanks go to B. Cornelisen for her help
throughout the microprobe work, P. Stutz for preparing polished
duced rims suggest that leaching-catalyzed recrystalliza- grain sections, K.-H. Klaska for helping with the experiments, and
tion is an important alteration process in zircon under J. Ludwig for carrying out XRD measurements. We gratefully
wet geological conditions and can account for complex acknowledge P. Chapman and F. Tralau for their support
core±rim structures found in many metamorphically throughout the work on the micro-Raman and FTIR spectrometer,
respectively. We further acknowledge J. SchluÈter from the Miner-
overprinted zircons. The fact that ion probe U±Pb ana- alogical Museum of the University of Hamburg for providing the
lyses of tr rims of zircons from amphibolite to granulite samples used in this study. We appreciate the constructive com-
facies rocks yielded ages that post-date the time of ments of U. Schaltegger and an anonymous reviewer, which helped
metamorphism or zircon formation by only a few million to improve the ®nal manuscript. This work was ®nancially
years indicates that leaching of U, Th, and Pb can occur supported by the German Research Foundation (DFG), project
GE 1094/1-1.
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