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Zircon

Tiny but Timely LEFT: Zircon grain (400 m)


crystallized from a 530 Ma
high-temperature partial
melt, Prydz Bay,
Simon L. Harley and Nigel M. Kelly* Antarctica. PHOTOMICRO-
GRAPH (CROSSED POLARIZERS)
BY NIGEL KELLY

W
here would Earth science be without zircon? Tiny crystals of zircon in the crust, zircon potentially con-
tains a record, in its oxygen isotope
occur in many rocks, and because their atomic structure remains
composition, of the role of low-
stable over very long periods of geological time, they are able to temperature versus high-tempera-
provide a picture of the early history of the Earth and of the evolution of the ture processes in defining the char-
acter of source regions for melts
crust and mantle. Zircon has long been recognized as the best geochronometer
(Valley 2003). Measurements of
using the radioactive decay of uranium to lead. Recent developments in analytical the U, Th and He contents of zircon
techniques, using small-diameter laser, ion and electron beams, high-precision can be used to infer the rates at
mass spectrometry and a variety of microscopic imaging methods, allow us to which recently active landscapes
developed and the times at which
obtain the ages of tiny volumes of complex crystals that record stages in their the exposed rocks cooled to near-
long growth history. Coupled measurements of the isotopes of oxygen and surface temperatures. Finally, zircon
hafnium provide a mineralogical window into the separation of the Earths offers significant potential as a
phase into which the highly
crust from the mantle and the temperature and character of processes involved
radioactive isotopic products of
in crustal evolution. Zircon is being used to unravel ever more complex nuclear reactions may be intro-
geological systems, presenting exciting opportunities for research on this duced in order to evaluate their
impact on mineral structures (e.g.
remarkable mineral.
Hanchar and van Westrenen 2007).
KEYWORDS: zircon, geochronology, continental crust, UPb, Hf, trace elements
Central to all of these applications
is the behaviour of zircon in com-
INTRODUCTION plex Earth systems. Thanks to impor-
tant developments in secondary ion mass spectrometry
Zircon, ZrSiO4, is a mineral of singular importance in Earth
(SIMS), laser- ablation induced coupled plasma mass spec-
science. Its widespread use in geochronology, based on the
trometry (LA-ICPMS) and low-blank thermal-ionisation mass
decay of uranium (U) to lead (Pb), has established it as
spectrometry (TIMS), we are now able to accurately and pre-
Earths timekeeper. Thus, zircon records the ages of hall-
cisely measure a battery of useful trace element and isotopic
mark events in Earth history, including its earliest evolution,
signatures in zircon. The interpretation of these isotopic
the oldest sediments, extinction episodes, mountain-building
and compositional data in terms of ages, isotopic reservoirs
events, and supercontinent construction and dispersal
and processes requires the careful and systematic integra-
(Rubatto and Hermann 2007 this issue; Harley et al. 2007
tion of microanalysis with petrology and mineral charac-
this issue).
terisation.
Recent developments in microanalysis have extended the
This issue of Elements focuses on the advances in our under-
range of Earth problems that can be addressed using zircon.
standing of zircon and highlights the gaps in our knowl-
As a phase enriched in hafnium (Hf) compared to radioac-
edge that have emerged from in situ isotopic, chemical,
tive lutetium (Lu), zircon retains a strong fingerprint of the
spectroscopic and microtextural studies on zircon formed at
isotopic character of the sources of the magmatic rocks in
high and low temperatures. The systems range from melt-
which it crystallizes, evidence that is critical for models of
bearing ultrahigh-temperature metamorphic environments
formation and growth of continental crust (Scherer et al.
(Harley et al. 2007) and ultrahigh-pressure metamorphic
2007 this issue). As a phase that can accommodate significant
environments (Rubatto and Hermann 2007) to lower-
amounts of temperature- or process-sensitive trace elements,
temperature hydrothermal environments in which zircon
including the rare earth elements (REE, or lanthanides),
behaviour may be dictated by its response to aggressive flu-
yttrium (Y) and titanium (Ti), zircon can also provide com-
ids (Geisler et al. 2007). Understanding the processes that
pelling chemical evidence for the mineralmeltfluid
operate in each environment is critical to the interpretation
processes operating during crust formation and maturation,
of zircon age data and the hafnium isotope information
hydrothermal alteration and diagenesis (Hanchar and van
used to infer continental growth rates and earliest Earth his-
Westrenen 2007 this issue; Harley et al. 2007; Geisler et al.
tory (Scherer et al. 2007). The importance of this under-
2007 this issue). Despite the ravages of cycling through and
standing is highlighted by new experiments and models
relating to the partitioning of trace elements among zircon,
melts and fluids and to the dissolutionreprecipitation of
* Grant Institute of Earth Science, The University of Edinburgh
Edinburgh EH9 3JW, United Kingdom zircon in fluids (Hanchar and van Westrenen 2007; Geisler
E-mail: Simon.Harley@ed.ac.uk et al. 2007).
Nigel.Kelly@ed.ac.uk

ELEMENTS, VOL. 3, PP. 1318 13 F EBRUARY 2007


There is still much to learn about zircon and its behaviour.
Zircon cannot be treated simply as a passive safehouse of
stored isotopic and chemical information but must instead
be interpreted carefully, in its petrological, mineralogical
and geological contexts, and in the light of all possible lines
of evidence. Zircon has been a wonderful servant in our
quest to unravel the history of the Earth but has much more
to offer as we unlock the secrets of its chemical and physical
responses to Earth processes.

WHAT IS ZIRCON ANYWAY?


Zircon is a tetragonal orthosilicate mineral in which iso-
lated SiO4 tetrahedra are linked through sharing their edges
and corners with intervening ZrO8 dodecahedra (FIG. 1).
These ZrO8 dodecahedra share edges to form zigzag chains
along the b axis, whereas along the c axis, edges are shared
with the SiO4 tetrahedra to produce chains with alternating
SiO4 and ZrO8 polyhedra. These sets of chains are separated
by channels or voids that are unoccupied in pure zircon.
However, in natural zircon, these channels may contain
interstitial impurities at parts per million (ppm) to tens of
ppm levels (Hoskin et al. 2000; Hanchar et al. 2001). The
c-axis chains are important in controlling the anisotropic
physical properties of zircon and its common prismatic
habit. The effect of Zr4+Si4+ repulsion on the symmetry of
the cation sites in zircon is considerable. First, the SiO4
tetrahedra are elongated by 13% along the c axis compared FIGURE 2 A view of the zircon structure projected from the a axis,
stripped of the cross-linking shortened ZrO4 tetrahedra to
with their size along the a axis. Second, the ZrO8 polyhedra highlight the chains of edge-sharing, alternating SiO4ZrO4 tetrahedra
resolve into two interpenetrating ZrO4 tetrahedra (FIG. 1). parallel to the c axis (after Finch and Hanchar 2003). SiO4 tetrahedra are
One type of tetrahedron has longer ZrO bond lengths coloured yellow, and elongated ZrO4 tetrahedra blue.
(0.227 nm) parallel to the c axis and can be visualised as
forming elongate chains by sharing two of its edges with
the alternating SiO4 tetrahedra (FIG. 2). The other type of The overall structure of zircon is relatively open, with unoc-
ZrO4 tetrahedron has shorter ZrO bond lengths (0.213 nm) cupied space represented by the channels parallel to the
and shares its four corners with SiO4 tetrahedra. Further c axis and the void volumes bounded by SiO4 and ZrO8
details of the crystal structure of zircon are presented in the polyhedra, as shown in FIGURE 1. This structure results in
excellent review by Finch and Hanchar (2003). zircons moderately high density, 4.66 g cm-3, and also con-
tributes significantly to its very low absolute thermal
expansion and compressibility and to the anisotropy of
these parameters. Most of the small amount of volume
expansion in zircon, about 0.6% from room temperature to
its stability limit of 1690C, is accommodated along the c
axis by increase in the ZrO bond length. Although pure
zircon is highly incompressible, it is anisotropic in its com-
pressibility because the ZrO bonds parallel to the c axis are
able to shorten preferentially. These properties make pure
zircon or zircon with low contents of trace elements
extremely resistant to physical modification related to
changes in pressure or temperature, and render it an excel-
lent refractory mineral that is potentially useful for storage
of radioactive and toxic isotopes provided they have suit-
able ionic radii.

WHAT IS ZIRCON GOOD FOR?


Even with its underlying structural beauty, zircon would be
of little interest to most Earth scientists if it were just plain
ZrSiO4. However, the simplicity of zircons chemical for-
mula belies its great scope for chemical diversity at the trace
to minor element level. An indication of the variety of uses
of zircon is provided in TABLE 1. Since most cations in zircon
have very low diffusivity, many of zircons chemical signa-
tures are preserved either from the time of its formation or
from the last significant geological process to have acted on
and modified its chemistry (Cherniak and Watson 2003).
FIGURE 1 A view of the zircon structure projected from the a axis
onto the plane defined by the b and c axes (after Finch Zircon can incorporate many elements, e.g. P, Sc, Nb, Hf, Ti,
and Hanchar 2003). SiO4 tetrahedra are coloured yellow, and ZrO8 U, Th and REE, in trace (up to thousands of ppm) or minor
dodecahedra are in shades of blue. One dodecahedron is unshaded to (up to 3 wt%) amounts. These elements are incorporated
reveal its sub-structure consisting of two distorted ZrO4 tetrahedra. The
elongated ZrO4 tetrahedra share upper and lower edges with the SiO4
through a number of single-site and coupled-cation substi-
tetrahedra. tution mechanisms (Hoskin and Schaltegger 2003). The pri-

ELEMENTS 14 F EBRUARY 2007


TABLE 1 KEY CHEMICAL FEATURES OF ZIRCON AND THEIR APPLICATIONS

Chemical/physical Substitutions/
Key applications Comments
property other points to note
A concordia diagram can be used to evaluate the isotopes
U and Th
of U and their Pb decay products. Th/U ratios, used in the
U up to 5000 ppm (U4+, Th4+) = Si4+ UPb geochronology
past to distinguish magmatic from metamorphic and
Th up to 1000 ppm
hydrothermal zircon, must be treated with caution.
Determination of exhumation and Low-temperature chronometry is based on the closure of
Formed by decay
He landscape development rates using zircon to He loss. This method gives an age related to the
of U and Th
UThHe thermochronometry time the zircon cooled through ~40C.
Investigation of crustal residency and 176Lu decays to 176Hf. High Hf/Lu in zircon means its ratio
Hf
HfO2 mostly <3 wt% Hf4+ = Si4+ continental growth; crustal versus mantle of 176Hf/177Hf changes very little with time, so it can be
sources of magmas in which zircon formed used to infer sources by reference to an Earth model.
Ti is maximised when zircon is in equilibrium with rutile.
Ti Ti thermometry can yield T of zircon crystallization, which
Ti up to 120 ppm Ti4+ = Si4+ Ti in zircon thermometry
usually occurs late in the cooling of a magma, or T of
metamorphic zircon growth with rutile.
Y and REE Reconstruction of magmatic histories; Requires extensive knowledge of trace element partitioning
Y mostly <5000 ppm (Y3+, REE3+)P5+ = Zr4+Si4+ fingerprinting of magma sources; among zircon, melts and competitor minerals over a range
Total REE <2500 ppm tuning of ages to mineral reactions of P, T, composition and oxygen fugacity conditions.

Fingerprinting the contribution of Significant fractionation of 18O from 16O occurs at low T.
O isotope composition sediments and crust to the sources of Variations in 18O/16O isotopic composition of zircon are
magmas; examining crustal recycling used to determine the role of sources that have been
affected by low-T fractionation.

mary controls on the substitutions are the ionic radii of the zircon formation and by competition between zircon and
substituting cations compared with Zr4+ and Si4+ cations. other minerals in which some of these elements may be
Substitutions that minimise strain effects on either or both more compatible (Hanchar and van Westrenen 2007;
sites will be favoured. The crystal-chemical limitations are Harley et al. 2007). REE and Y contents will be affected also
that Zr4+ in 8-fold co-ordination has an ionic radius of by the operation of other coupled substitutions and by the
0.084 nm and Si4+ in tetrahedral co-ordination an ionic requirement to charge-balance additional cations, such as
radius of 0.026 nm. On this basis it has been suggested that Mg, Fe, Ca and Al, that may be incorporated on the inter-
(OH)4 can replace SiO4. There can be considerable substitu- stitial sites described above (Hoskin et al. 2000; Geisler et al.
tion of Hf4+ (ionic radius = 0.083 nm) on the 8-fold Zr4+ site, 2007). Compilations of zircon from high- and low-temper-
and a solid solution towards the mineral hafnon (HfSiO4) ature geological environments and formed through a vari-
exists. Zircon generally contains considerable HfO2 ety of processes show that Y contents generally range
(TABLE 1), which is central to its utility as an indicator of between 10 and 5000 ppm and total REE typically between
crustal residence and growth via Hf isotope analysis 100 and 2500 ppm (e.g. Hoskin and Schaltegger 2003).
(Hawkesworth and Kemp 2006; Scherer et al. 2007). U4+ Considerable discussion has arisen as to the use of REE pat-
(8-fold ionic radius 0.10 nm), Th4+ (0.105 nm) and Ti4+ terns and abundances as discriminants of the provenance of
(0.074 nm) can also be accommodated, generally at much detrital zircon populations (Hoskin and Ireland 2000) and,
lower abundance levels, on this site. Although U can reach in the case of zircon xenocrysts, of source-rock lithologies
wt% levels, its concentration is usually less than 5000 ppm, (Belousova et al. 2002). Considerations surrounding these
while the abundances of Th (<1000 ppm) and Ti (<120 ppm) and other uses of zircon REE data are explored further by
are lower still. The incorporation of Ti into zircon, particu- Hanchar and van Westrenen (2007).
larly if it has formed in equilibrium with rutile and quartz,
is temperature sensitive and provides the basis for a new zir- The cation substitutions mentioned above often lead to the
con geothermometer (Watson et al. 2006). This may be production of spectacular internal textures in zircon that
used, with caution, to determine the temperature of crys- may be interpreted in terms of growth histories and diffu-
tallization of magmas, migmatites and zirconrutile assem- sionreaction or dissolutionreprecipitation processes.
These features, for example oscillatory and sector zoning,
blages in metamorphic rocks. Because of its 8-fold ionic
can be imaged using cathodoluminescence (CL), backscat-
radius of 0.129 nm, Pb2+ is not incorporated into growing
tered electron imagery and a variety of other techniques
zircon crystals at more than ppb levels under most condi-
(e.g. forescatter imagery, Nomarski interference imagery,
tions, which is crucial to geochronology.
infrared spectrometry, atomic force microscopy, Raman
The most important coupled substitution involving both spectroscopy). Yet another of the many remarkable proper-
the Zr4+ and Si4+ sites in zircon is that commonly referred ties of zircon is that it often contains negligible amounts of
to as the xenotime substitution. This substitution (TABLE 1) cations that suppress its cathodoluminescence response,
involves Y and REE substituting for Zr and charge-balancing and so it can be imaged to very high resolution using CL. In
P5+ (4-fold ionic radius = 0.029 nm) substituting for Si, addition, most of the substitutions involve replacement of
which would ultimately produce xenotime, (Y,REE)PO4. the lower mass elements Zr and Si by much heavier ele-
Scandium (Sc3+, with an ionic radius of 0.087 nm) also sub- ments (U, Th, REE, Hf), resulting in major shifts in average
stitutes for Zr, in quantities up to 250 ppm, in a similar cou- atomic mass, which are well imaged by changes in backscat-
pled substitution. In principle the heavy trivalent REE, with tered electron intensity.
their smaller ionic radii (e.g. 8-fold Lu3+ = 0.0977 nm), Y3+
At this point it is worth recalling that zircon is an orthosil-
(8-fold ionic radius 0.1019 nm) and tetravalent Ce4+ (8-fold
icate mineral, with the Zr and Si cations and their substi-
ionic radius 0.097 nm) are closer to Zr4+ and so will be more
tutes bound to oxygen anions in tetrahedral and 8-fold
favourably incorporated in the zircon structure (i.e. they are
co-ordination. Given the slow diffusivities inferred and doc-
more compatible) than the larger light trivalent REE (e.g.
umented for oxygen in zircon (Cherniak and Watson 2003;
La3+ = 0.116 nm). However, the absolute and relative abun-
dances of the REE and Y in zircon will be influenced by Valley 2003), it is likely that magmatic zircon can preserve
their abundances and availability in the environments of an oxygen isotope composition that was in equilibrium
with the magma from which it crystallized. In confirmation

ELEMENTS 15 F EBRUARY 2007


of this, magmatic zircon grains with inherited xenocrystic of the zircon grains from any one of the three clocks, by
cores have in several cases been shown to have distinctive measuring the appropriate isotopic ratio and solving for
18O/16O isotopic compositions (expressed as 18O in per mil time using the relevant exponential equation. We can go
units, , relative to the Vienna Standard Mean Ocean further and obtain three age estimates if we measure all
Water VSMOW), interpreted as reflecting differences in three isotopic ratios. In an ideal closed system, the three age
the isotopic compositions of the magmas in which they estimates would agree within the errors of measurement.
formed. Given that mantle-derived zircon has a 18O value However, in real zircon grains, we cannot assume that Th
of +5.5, and that O isotopes are significantly fractionated and U are equally closed to post-crystallization effects. It is
at low temperatures to produce potential crustal source also essential to correct for any Pb initially present prior to
rocks (e.g. sediments) with much higher oxygen isotope the accumulation of radiogenic Pb in the grain, as this
ratios (i.e. 18O values of +12 to +14), the 18O values of inherited Pb would lead to erroneously old age estimates.
granitoid zircon may be used to trace the involvement of Yet another of the wonderful features of crystallizing zircon
older, chemically evolved crust in magma genesis (Valley is that it can only incorporate negligible amounts of ambient
2003). In other words, the oxygen isotope ratio of zircon Pb into its structure. Nearly all of the Pb in zircon is pro-
can be used to discriminate between new, mantle-derived duced by U and Th decay so corrections for inherited Pb
crust and crust that has been reworked (Valley 2003). This are in most instances very small relative to the amounts of
approach is even more powerful when combined with zir- true radiogenic Pb* present in the grains. Inherited (or
con UPb age data and Hf isotope information on the same common) Pb can be corrected for by analysing non-
analysed grains (e.g. Hawkesworth and Kemp 2006) These radiogenic 204Pb, where present in the zircon, and then sub-
considerations highlight the importance of zircon as a tracting the 206Pb and 207Pb that would be associated with
geochronometer, the principles of which will be explained this 204Pb at a chosen reference age the common Pb
in the remaining section of this introduction. correction.

The usual approach to zircon geochronology is to consider


BACK TO BASICS: the UPb system alone, as there is no natural non-nuclear
ZIRCON UPB GEOCHRONOLOGY means of fractionating 235U from 238U. In addition, as the
The potential of zircon as a mineral geochronometer was modern-day ratio of 235U/238U is well known (1/137.88),
recognised by Holmes (1911), amongst others, well before the need to actually analyse very low abundances of 235U is
the isotopes of Pb could be measured and long before 235U obviated [i.e. 207Pb*/235U = 137.88(206Pb*/238U)]. Instead of
was identified as the second radioactive isotope of uranium. solving the 235U and 238U decay systems separately, we can
It is now known that there are three distinct radioactive plot mutually compatible sets of daughter/parent ratios,
decay series involving the parent isotopes 238U, 235U and 207Pb*/235U and 206Pb*/238U, that would evolve in the zircon
232Th, which produce as their final daughter products the grains as time elapses since their formation (i.e. as they age).
isotopes 206Pb, 207Pb and 208Pb, respectively. Each of these This is the basis of the concordia diagram (FIG. 3; Wetherill
decay processes involves several intermediate steps and 1956). As this article is being written, we are celebrating the
short-lived intermediate isotopes. For example, the decay of 50th anniversary of this elegant graphical device, which has
238U to 206Pb occurs via a chain of intervening alpha-decay opened the door to the systematic assessment of zircon and
steps (liberating 4He -particles) coupled with beta-decay other accessory mineral UPb isotopic data.
steps (releasing a -particle and transforming a neutron to a
The concordia curve itself is the locus of the mutually com-
proton). These steps yield short-lived isotopes that decay in
patible or concordant 207Pb*/235U and 206Pb*/238U ratios,
seconds, years, decades or hundreds of thousands of years.
both of which increase outwards from the origin as the time
However, because the final step in the decay series is many
since zircon crystallization passes by. At time zero, when
orders of magnitude slower than the earlier steps, the whole
decay process can be mathematically described by a single
decay equation relating the number of ultimate parent
atoms remaining (e.g. 238U) and the number of final radi-
ogenic daughter atoms (e.g. 206Pb*) to time:
238t
206Pb*/238U = e 1 (1)
where e is the exponential function, t is time, and is the
decay constant specific to this decay scheme, i.e. 238 =
1.55125e-10. 206Pb* refers to the radiogenic 206Pb accumu-
lated in the crystal as a result of the decay of 238U. In the
case of 238U, it takes approximately 4468 million years for
half the 238U initially present in the grain to decay to 206Pb
this is the half-life, which again is characteristic of the spe-
cific decay scheme. Similar expressions can be formulated
for 207Pb* produced from the decay of 235U and 208Pb* pro-
duced from 232Th, with 235 = 9.8485e-10 and 232 = 4.9475e-11.
The half-life of 235U is 704 million years and that of 232Th
about 14 billion years.

In the following we will consider the case of a suite of zircon


grains formed at a single time, perhaps through crystalliza-
tion of a felsic magma. Through the incorporation of U and
Th at the time of growth, in every zircon grain there will, in FIGURE 3 Concordia diagram. Note that the axes are the ratios
effect, be three different clocks ticking away, each at its of the radiogenic daughter Pb isotopes divided by their
characteristic rate. By virtue of the half-lives noted above, respective parent U isotope. The concordia curve traces out the com-
235U decays about 7 times faster than 238U does, while 232Th patible ratios as they develop with time elapsed since the moment the
clocks are set in newly formed zircon, and is annotated with this time
decays even more slowly. In principle, we could find the age elapsed, or age. Lines a and b show the evolution of the compatible
ratios in 1000 and 3000 Ma zircon respectively (see text).

ELEMENTS 16 F EBRUARY 2007


the zircon forms, there is no radiogenic Pb* in the zircon. A
Some 1000 million years later, these ratios have increased to
1.6777 and 0.1678, respectively (FIG. 3, line a), because the
two types of radiogenic Pb have accumulated through
decay of their respective parent U isotope. So, if we sampled
a rock formed 1000 Ma ago and analysed its zircon grains,
we would, ideally, expect them to preserve these
207Pb*/235U and 206Pb*/238U ratios and hence lie on the

concordia curve at the point corresponding to 1000 Ma. By


the same logic, if we analysed zircon grains from an undis-
turbed rock that is now 3000 Ma old, we would expect the
207Pb*/235U and 206Pb*/238U ratios to have evolved to

18.1988 and 0.5926, respectively (FIG. 3 line b). These are


concordant zircon grains: the two Pb*/U ratios as measured
in the grains correspond to the same age (time elapsed), and
the position along concordia is a direct measure of age. The
individual analysis points plot as elongated ellipses or poly-
hedra because the two ratios, and hence their errors, are
strongly correlated.

The elegance of the concordia diagram is that it also allows


you to investigate and evaluate zircon Pb*/U analyses that
B
do not lie on concordia. In such cases, where the ages deter-
mined from the 207Pb*/235U and 206Pb*/238U ratios do not
agree, the zircon grains are said to be discordant. They are
normally discordant if they lie below the concordia curve,
which is the usual type of discordancy, and are termed
reverse discordant if the analyses lie above the concordia
curve (i.e. at a higher 206Pb*/238U for a given 207Pb*/235U ratio).

An example of the former situation is illustrated on the con-


cordia diagrams of FIGURE 4. In this case discordant zircon
Pb*/U analyses have been generated through the superposition
of a second, real, geological event on a suite of zircon grains
some 3000 million years after they initially formed. This
event not only formed new zircon crystals, possibly with
distinctive morphologies and trace element signatures, but
also caused variable loss (without any Pb isotope fractiona-
tion) of the previously accumulated radiogenic Pb from
domains in the older zircon grains (FIG. 4A). Whatever the
precise mechanism causing this Pb loss (e.g. Geisler et al.
2007), the large ionic radius of Pb2+ renders it susceptible to
removal from the old zircon grains.
FIGURE 4 Concordia diagram and episodic Pb loss. Variable loss of
FIGURE 4B illustrates the effect on the concordia diagram if Pb from older zircon grains, arising because of the effects
the zircon grains plotted in FIG. 4A evolve for a further 1000 of a second event, produces a discordia between the older formation
million years. All grains will now have accumulated radi- age (now 4000 Ma) and the age of the second event (1000 Ma).
ogenic Pb* over this 1000 million years, so that those newly
formed in the second event will be concordant at 1000 Ma
of cores and overgrowths in such cases may yield concor-
(FIG. 4B). If all the radiogenic Pb* accumulated up to the
dant populations that define the ages of the growth/modi-
time of the second event was lost from the first-generation
fication events, but even with careful microtextural control,
zircon grains, then these would be completely reset, and all
it is not uncommon to find that some zircon populations
memory of the antiquity of these 4000 Ma old grains would
define discordia.
be lost; they too would record ages of 1000 Ma. Alternatively,
and more typically, the loss of Pb in these old zircon grains Complex UPb isotopic data can be interpreted and utilised
is only partial or confined to spaced microdomains. In this to gain insights into Earth history, but only in concert with
case a series of discordant analyses may result, spread out complementary chemical and isotopic information, which
along a discordia (FIG. 4B) that intersects the concordia at includes the REE, Ti, Hf isotopes and O isotopes, briefly
two points: an upper (older) intercept giving the formation alluded to above and listed in TABLE 1. A number of these
age of the zircon grains 4000 Ma in this case and a lower key signatures of zircon behaviour and the processes involved
intercept giving an age of 1000 Ma, in accord with the in zircon modification and recrystallization are considered
newly formed grains. in the articles that follow.
The case described above is an idealised example of episodic
Pb loss, which is a major cause of discordant zircon popu- ACKNOWLEDGMENTS
lations. Nevertheless, it serves to illustrate how the concordia We thank the editors of Elements for providing us with this
diagram can be read to reveal several pieces of geologically forum for presenting some of the current developments in
useful information. As will be shown in the articles that fol- zircon research. In particular, we thank Ian Parsons and
low, we now are very aware through microanalytical and Pierrette Tremblay for their tireless editorial and organisa-
mictotextural studies that many zircon grains (especially in tional work on our behalf. We also thank all contributors
metamorphic rocks, but also in granites) preserve more and reviewers, without which this issue would not have
than one period of growth or grain modification. Analysis been possible. .

ELEMENTS 17 F EBRUARY 2007


GLOSSARY
Accessory mineral A mineral that represents <1% of the modal pro- LA-ICPMS (laser-ablation inductively coupled plasma mass
portion of the minerals in a rock. These minerals are commonly (but spectrometry) A microanalytical method that employs a focused
not in all cases) enriched in trace elements important for the interpre- laser beam to ablate material from samples. The ejected matter is
tation of rock history. ionised using a plasma before being passed through to a mass spec-
Backscattered electron imaging A technique in which the high- trometer.
energy electrons produced by elastic collision of an incident electron Monazite A phosphate mineral rich in light rare earth elements (LREE)
beam with the electron cone of a sample atom are imaged using a and commonly Th, based on the general formula (La,Ce,Th)PO4. It
detector within an SEM. The yield of backscattered electrons is pro- incorporates appreciable U and Y (up to several weight %) through
portional to the number of sample electrons, therefore offering the coupled substitutions.
potential to image chemical zoning within a target sample.
Orogenesis Mountain building resulting from thickening of the crust
BSE (bulk silicate Earth) What is left after subtracting the core from and lithosphere through collision of continents and/or accretion of
the bulk Earth composition; also referred to as primitive mantle. microcontinents or island arcs to a continent at the end of a Wilson
Cathodoluminescence (CL) Light emitted from minerals during bom- Cycle.
bardment by an electron beam, typically imaged using a detector fit- Supracrustal rocks Sedimentary or volcanic rocks formed at or near
ted to a scanning electron microscope or an optical microscope. Lumi- Earths surface. Those found today in ancient portions of continents
nescence within minerals is enhanced by particular elements (e.g. Dy) were buried and metamorphosed before being exposed by uplift and
but is potentially suppressed by other elements (e.g. U, Th, Fe) or erosion. They provide important clues (e.g. basalt pillows, cross bed-
defects in the crystal structure. Zoning observed in CL images there- ding) about ancient depositional environments and contain the only
fore reflects chemical variations within individual crystals. records of early life.
CHUR (chondritic uniform reservoir) CHURs characteristics are PT paths When rock masses are buried deep in the Earths crust, the
derived from meteorite studies. The BSE and CHUR reservoirs are paths along which they move can be described in terms of the
assumed to have identical ratios of refractory lithophile elements (e.g. changes in pressure (depth) and temperature. The relationship
Lu/Hf, Sm/Nd). between pressure and temperature over the time span of the meta-
Concordance Agreement of ages obtained by the 238U206Pb and morphism reflects the tectonic history of the rocks in question.
235U207Pb chronometers. Recrystallization A general term used to refer to in situ modification
Depleted Mantle Mantle that has had melt extracted from it. Some or change in the character, and potentially the chemistry, of a mineral
elements fractionate more strongly into the melt phase. As a result, the or rock. Recrystallization may be partial or total, and may involve dis-
depleted mantles Lu/Hf and Sm/Nd values are higher than those of BSE. tinct processes such as reactiondiffusion or replacement, and coupled
dissolutionreprecipitation.
Discordance Disagreement between 238U206Pb and 235U207Pb ages.
This commonly results from the partial loss of radiogenic Pb by a zir- SIMS (secondary ion mass spectrometry) Also referred to as an ion
con during alteration or heating and recrystallization. For recent Pb microprobe or microscope, SIMS measures the chemical or isotopic
loss, the ratio of the Pb daughter isotopes may be used to calculate a composition of small sample volumes by focusing a beam of high-
207Pb/206Pb age, which may still date zircon crystallization. If the Pb energy primary ions onto a polished sample surface, ablating atoms
loss is ancient, the 207Pb/206Pb age is only a minimum crystallization age. and molecules, and generating secondary ions that are analysed by
mass spectrometry. The high spatial resolution offered by SIMS (com-
ID-TIMS (isotope-dilution thermal-ionisation mass spectrometry) monly <30 m wide and <1 m deep during analysis of geological
A method of isotopic analysis in which an isotopic tracer is added to materials) allows in situ analysis of geological materials. The method is
a dissolved sample (e.g. zircon) to make a homogeneous isotopic mixture, relatively non-destructive, allowing multiple analyses to be performed
the isotopic composition of which is analysed using TIMS. This tech- within single grains or zones within grains, but has lower analytical
nique is currently the form of isotopic measurement with the highest precision than ID-TIMS.
precision, but it requires complete dissolution of part of or whole grains.
Zoning Variation in chemical composition among different domains
Inheritance The presence of older zircon grains in an igneous or meta- within a single crystal. The geometry of zoning patterns preserved in
morphic rock that did not crystallize from that rocks parent magma. crystals may give insights into the processes that led to the formation
The inherited zircon grains may have been incorporated into a magma of new crystals or the alteration of previously existing grains. For exam-
through the partial melting of a pre-existing zircon-bearing rock or through ple, oscillatory zoning (regular, finely spaced, circular zoning patterns)
assimilation of zircon-bearing country rocks during magma ascent. is commonly preserved in magmatic zircon crystals and reflects fluctu-
ating trace element concentrations in the parent magma.

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ELEMENTS 18 F EBRUARY 2007

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