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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
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
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