Zircon as a Monitor

of Crustal Growth
Cathodoluminescence
imaging of zircon
reveals several stages
of growth.
Erik E. Scherer1, Martin J. Whitehouse2 and Carsten Münker 3

Z
ircon has long played a key role in crustal evolution studies as the pre- secondary ion mass spectrometry
(SIMS) and laser-ablation induc-
eminent U–Pb geochronometer. Recent advances in analytical capabilities
tively coupled plasma – mass spec-
now permit investigations of complex grains at high spatial resolution, trometry (LA–ICP–MS) have made
where the goal is to link zircon ages to other petrographic and geochemical it possible to determine U–Pb ages
with a high spatial resolution (typ-
information. Zircon can provide time-stamped ‘snapshots’ of hafnium and
ically ≤25 μm spots for SIMS). Com-
oxygen isotope signatures of magmas throughout Earth’s history, even at the bined, these tools have revolu-
scale of individual growth zones within a single grain. This information is an tionised zircon dating. Within a
invaluable help to geochemists trying to distinguish magmatic events that single grain for example, imaging
may identify two or more growth
added new, mantle-derived material to the continental crust from those zones, which then can be individ-
that merely recycled existing crust. ually dated in situ. Growth zones,
however, sometimes differ in age
KEYWORDS: crustal evolution, early Earth, zircon, U–Pb age, hafnium isotopes by over a billion years! Reliable
assignment of these ages to specific
geologic events requires unlocking
INTRODUCTION
of more than just the U–Th–Pb geochronometers, and
At present, new crust forms by the extraction of melts from again, modern analytical methods provide the key. With
the convecting mantle and emplacement of these melts detailed in situ analysis of trace elements and oxygen iso-
into – or on top of – pre-existing crust. Rigid and buoyant, topes, researchers can now evaluate the geochronology and
the continental crust floats, protected from recycling back constrain age interpretations in terms of igneous or meta-
into the mantle. But what was the nature of Earth’s first morphic petrogenesis. In addition, hafnium (Hf) isotope
crust? How have crust-making and recycling mechanisms analysis of U–Pb-dated zircon can reveal the relative contri-
changed as a function of a cooling Earth? Has the volume butions of juvenile (directly mantle-derived) crust versus
of continental crust been more or less constant or has it recycled continental crust, making zircon a ‘one-stop shop’
gradually increased over time? Geochemical clues locked for assessing crustal evolution.
away within ancient grains of zircon are essential to answering
these questions.
ZIRCON AND CRUSTAL EVOLUTION
Zircon is perhaps the most versatile chronometer available
to the modern geologist. During formation, zircon incorpo-
The Challenge of Dating Earth’s Oldest Rocks
rates modest amounts of uranium (U) and thorium (Th) Zircon geochronology is essential for the reconstruction of
into its crystal structure, but excludes lead (Pb). Over time, crustal growth history, providing magmatic protolith ages
however, steady decay of U and Th causes accumulation of with a precision of a few million years. Major break-
radiogenic Pb, providing the basis for accurate and precise throughs include the identification of the oldest zircon
determination of a zircon’s isotopic age. What makes zircon grains on Earth (e.g. Compston and Pidgeon 1986), which
unique among geochronometers is its robustness: it is a predate Earth’s oldest rocks by several hundred million
hard, refractory mineral that can remain intact even if its years. However, interpreting ages of complex zircon grains
host rock is metamorphosed, melted, or mechanically is not always straightforward, as illustrated by the ongoing
weathered away. Furthermore, diffusion rates within zircon debate over the age of the dominant early Archean
for many elements are extremely low, so this mineral com- tonalite–trondhjemite–granodiorite (TTG) Amîtsoq gneisses
monly retains age and other isotopic information even of southern West Greenland. Of the limited exposures of
when exposed to magmatic temperatures. early Archean rocks on Earth, these are among the best pre-
served (Nutman 2006). They potentially carry intact iso-
Improvements in imaging techniques over the last two topic and trace element information that can place con-
decades have led to a fuller appreciation of the internal straints on the earliest evolution of the Earth’s crust and
complexity of zircon. Contemporaneous developments in mantle. Many pioneering studies were performed without
the benefit of the detailed imaging of internal structure by
cathodoluminescence (CL) or backscattered electrons,
1 Institut für Mineralogie, Universität Münster, which today is considered an essential part of any SIMS or
48149 Münster, Germany LA–ICP–MS work on zircon. Lacking this information, the
2 Laboratory for Isotope Geology, Swedish Museum of Natural History, wide-ranging spectra of U–Pb ages were interpreted by
SE-104 05 Stockholm, Sweden attributing the oldest age to the magmatic protolith and
3 Mineralogisch-Petrologisches Institut, Universität Bonn, younger ages to variable degrees of later loss of radiogenic Pb.
53115 Bonn, Germany

ELEMENTS, VOL. 3, PP. 19–24 19 F EBRUARY 2007

In some cases, ages of low-Th/U zones within zircon were
inferred to date metamorphism. For the Amîtsoq gneisses of
the Godthåbsfjord region, the picture that emerged from
the early SIMS analyses was one of magmatic growth at ≥3.8
Ga, with metamorphism at ~3.65 Ga and ~2.7 Ga. Some of
the first SIMS studies to be guided by detailed CL imaging
(e.g. Whitehouse et al. 1999) showed that many zircon crys-
tals were far more complexly zoned than previously appre-
ciated. An example from the island of Angisorsuaq (FIG. 1)
has four distinct growth phases. Interestingly, all grains
have thick rims characterised by oscillatory zoning and ele-
vated Th/U, features generally considered to be traits of mag-
matic zircon. These ~3.65 Ga rims may be interpreted to
date magmatism, with the older (≥3.8 Ga) cores represent-
ing zircon inherited from older crust that contributed to the
3.65 Ga magma. This interpretation contrasts with the
earlier, non-image-guided approach and illustrates a poten-
tial pitfall in dating complex Archean zircon crystals:
inheritance.
Zircon saturation models (e.g. Watson and Harrison 1983)
have been used to predict whether magmas should contain
inherited zircon. The assumed high magmatic temperature
(≥900°C) of many TTG gneisses coupled with their low Zr
concentration appears to preclude survival of inherited zir-
con: it should dissolve. The oldest U–Pb age obtained would
then be expected to date the magmatic protolith. With
respect to the Amîtsoq gneisses, this argument was used to
assign the ~3.8 Ga age of zircon cores to the intrusion of a
TTG gneiss sheet that was claimed to constrain the age of
ancient, possibly supracrustal, rocks (Mojzsis and Harrison
2002). Some field observations, however, suggest that the
TTG rock is no older than ~3.65 Ga (e.g. Whitehouse and
Fedo 2003). Bearing these observations in mind, White-
FIGURE 1 Zircon from the island of Angisorsuaq, West Greenland,
showing four distinct growth phases identified in CL imaging
(right). Transmitted light imaging (left) reveals at most two of these phases.
ELEMENTS
house and Kamber (2005) reported SIMS geochronology
and rare earth element (REE) data, revealing marked heavy
REE depletion in the 3.65 Ga rims and in some of the 2.7 Ga
overgrowths. These patterns were interpreted to indicate
early Archean partial melting of a garnet-bearing tonalite
(the presumed source of the ~3.8 Ga cores) under granulite
facies conditions, with possibly another episode of late
Archean partial melting. This example illustrates that simple
application of zircon solubility arguments may be inappro-
priate in cases of partial melting, where the melt reservoir
cannot be considered effectively infinite and zircon might
be shielded from melt by enclosing minerals. Dissolution
kinetics may also play an important role in preserving
inherited zircon.
Debate over the ages of the TTG gneisses in West Greenland
remains unresolved, but the quality of the U–Pb dating
itself is generally not to blame. Rather, the key issue is
determining which zircon domains date the emplacement
of their magmatic host rock, which ones are inherited from
older rocks, and which ones formed during younger meta-
morphism. In the broader context of applying zircon to
crustal evolution studies, assigning accurate magmatic ages
is crucial for interpreting whole-rock isotope data.
TYING GEOCHRONOLOGY TO
THE GEOCHEMICAL ROCK RECORD
The Sm–Nd System
Determining formation ages of continental crust may be
accomplished in part by Nd isotope studies of ancient rocks.
Due to alpha decay of 147Sm to 143Nd, the 143Nd/144Nd of
all rocks increases with time at a rate proportional to the
rock’s Sm/Nd value. During mantle melting, Nd fractionates
20 F EBRUARY 2007
more strongly than Sm into the melts that leave the mantle
and form new crust. This crust will thus have lower – and
the residual mantle higher – Sm/Nd values than the origi-
nal mantle, so the 143Nd/144Nd of these reservoirs will
diverge slowly over time. Because subsequent magmas added
to the crust tap these reservoirs to various degrees, the range
in initial 143Nd/144Nd values recorded by crustal rocks also
increases over time. (“Initial” refers to 143Nd/144Nd values cor-
rected for the accumulation of radiogenic 143Nd to give the
value the magma had when it first crystallized.) Calculation
of initial ratios requires knowledge of the Sm/Nd value and
age of the sample. Substantial heterogeneity among initial
143Nd/144Nd values of Earth’s oldest rocks would suggest
that a major differentiation event, perhaps extraction of
crust from the mantle, had occurred within the first few
hundred million years of Earth’s history. Indeed, studies of
Sm–Nd in early Archean rocks, one of which we discuss
below, initially appeared to have found just that.
The four-billion-year-old Acasta gneisses (Northwest Terri-
tories, Canada) may be the oldest relatively intact terrestrial
rocks yet discovered. Initial attempts to use these unique
samples to constrain the nature of the early Archean man-
tle applied 4.0 Ga zircon ages directly to whole-rock Sm–Nd
systematics. It was concluded that a surprisingly large range
of initial 143Nd/144Nd values already existed in the early
Archean (Bowring and Housh 1995). However, the initial
Nd isotope data reported in that study were critically
re-examined in terms of subsequent disturbance of the
whole-rock Sm–Nd system. The issue was not the zircon
ages themselves, but whether these ages could be used to cal-
culate valid initial Nd isotope ratios. This is probably not
possible because the Sm–Nd systematics in these rocks
appear to have been disturbed or reset up to 600 Myr after
zircon crystallization (Moorbath et al. 1997). Interestingly,
the isotopic memory of zircon survived relatively unscathed
during the thermal or fluid events that affected the Sm–Nd
systems of the whole rocks, demonstrating zircon’s robustness.
To the good fortune of geochemists, these tough and readily
dated zircons grains also happen to incorporate ~1 wt% Hf
into their crystal structure, thereby providing a powerful
isotopic tool for elucidating crustal growth processes using
the lutetium-176–hafnium-176 decay system.
The Lu–Hf System
The beta decay of 176Lu to 176Hf has a half-life of ~37 billion
years (e.g. Scherer et al. 2001). The Lu–Hf system was first
exploited as a geochemical tracer in the early 1980s (Patch-
ett and Tatsumoto 1980), but analytical difficulties
restricted its use. In the mid-1990s, however, the advent of
multiple collector (MC) ICP–MS enabled routine and rapid
acquisition of Lu–Hf data for nanogram amounts of these
elements, and the widespread application of this system to
geological and cosmochemical problems blossomed. With
respect to refractory elements such as Sm, Nd, Lu, and Hf,
Earth is assumed to have the same composition as that of
the chondritic uniform reservoir (CHUR) defined by undif-
ferentiated meteorites. Because these elements remained in
the silicate portion of Earth (i.e. bulk silicate Earth or BSE)
during early core segregation, the BSE is expected to have
the same Lu/Hf and Sm/Nd values as CHUR. The behaviour
of the Lu–Hf system during melting is analogous to that of
the Sm–Nd system, with the daughter element Hf fraction-
ating into the melt to a higher degree than the parent ele-
ment Lu. Fractionation of Lu/Hf among Earth’s silicate
reservoirs will, over time, lead to significant variation in
176Hf/177Hf. Thus Lu–Hf can be used in the same manner as
Sm–Nd to monitor the degree of isotopic heterogeneity of
Earth’s silicate reservoirs, but with several key advantages.
Thanks to their remarkable durability, detrital and
ELEMENTS
xenocrystic zircon grains reach further back into Earth’s
history (4.3–4.4 Ga; e.g. Wilde et al. 2001) than the oldest
intact whole rocks, which are ‘only’ about 4 billion years
old. Furthermore, much of the Hf in crustal rocks resides in
zircon, which has very low Lu/Hf and thus a present-day
176Hf/177Hf that is close to its initial value. In addition,
Lu–Hf in zircon is apparently more resistant to disturbance
than Sm–Nd in whole rocks, and therefore has the potential
to decipher the crustal growth history of highly metamor-
phosed terranes.
Measurement of Hf Isotopes in Zircon
Measurement of hafnium isotope ratios in zircon first
evolved from thermal-ionisation mass spectrometry (TIMS)
of multigrain fractions to routine solution MC–ICP–MS
analysis of single grains (e.g. Amelin et al. 1999). When
entire grains are dissolved, however, features such as
growth zones of different age, metamict or altered domains,
and inclusions of other minerals are all analysed together,
possibly yielding spurious results. The LA–MC–ICP–MS
technique has provided a means to separately measure the
Hf isotope compositions of different growth phases of single
zircon grains in situ (Thirlwall and Walder 1995), and a spa-
tial resolution of ~50–100 μm can now be achieved. This
resolution comes at a cost, however. Laser Hf analyses are
less precise than those made by solution MC–ICP–MS, and
they require major corrections for interferences of 176Yb
and 176Lu on 176Hf. Nevertheless, accuracy and precision of
better than one part per 104 have been achieved recently for
laser 176Hf/177Hf analyses (Woodhead et al. 2004). The ability
to acquire both a U–Pb age and Lu–Hf data from a single
growth zone within a grain of zircon vastly improves the
chances of successfully linking these two systems.
Hf Isotope Systematics as a
Tracer of Crust–Mantle Evolution
To illustrate how the Hf isotope composition of zircon
sheds light on Earth’s early differentiation history, we con-
sider a simple differentiation scenario in FIG. 2A, in which
crust is extracted from the BSE by melting at point 1, leav-
ing behind a complementary depleted mantle (DM) reser-
voir. Because Hf fractionates more strongly into melts than
Lu, the crust will have a lower Lu/Hf value than the BSE,
whereas the Lu/Hf value of the depleted mantle will be
higher. Over time, the isotopic compositions of the crust
and DM diverge to lower and higher 176Hf/177Hf values,
respectively. By convention, Hf isotope compositions are
expressed as deviations (in parts per 104) from that of
CHUR, whose Lu/Hf and 176Hf/177Hf values are assumed to
represent those of the BSE. The notation for these devia-
tions at some time t in the past is εHf(t). FIGURE 2B shows the
same reservoir trends in terms of εHf(t) versus time. In our
discussion about zircon below, t is the crystallization age, so
εHf(t) represents the zircon’s initial Hf isotope composition.
Although the calculated initial 176Hf/177Hf value of a zircon
is relatively insensitive to age, its εHf(t) is age dependent
because the 176Hf/177Hf value of the CHUR reference
evolves significantly over time. Therefore a εHf(t) value cal-
culated using the 207Pb/206Pb age of a discordant zircon
might not accurately represent the zircon’s initial Hf iso-
tope composition because the 207Pb/206Pb age is only a min-
imum age. The least discordant zircon therefore provides
the most robust initial εHf(t) values.
A plot of εHf(t) versus crystallization age for Archean and
Hadean zircon grains (FIG. 3) yields valuable information
about Earth’s early silicate differentiation. First, the transi-
tion from uniform to heterogeneous εHf(t) with time marks
the onset of major silicate differentiation in the early Earth.
Second, the slopes of crust and DM trends are proportional
21 F EBRUARY 2007

A had to separate from BSE even earlier, perhaps >4.5 Ga, to
B
FIGURE 2 (A) Hypothetical evolution of 176Hf/177Hf versus time for
the bulk silicate Earth (BSE), depleted mantle (DM), two
crustal reservoirs, and zircon. (B) The same reservoirs plotted as εHf(t)
versus time. The U–Pb age of a zircon dates its crystallization (3); the
Lu–Hf residence age estimates the time elapsed since the crustal domain
hosting the zircon was extracted from the depleted mantle (2). See text.
to the time-integrated Lu/Hf of the crustal and DM reser-
voirs; this fact can be used to evaluate how exchange
between these reservoirs has balanced continued crust
extraction and mantle depletion over time. For example, a
dip in the DM trajectory may signal large-scale recycling of
crust back into the mantle. Finally, it is also possible to
determine whether crustal samples were formed by melting
DM, old crust, or combinations of both. In the latter case,
rocks of the same age from the same locality would form
vertical arrays in FIGURE 3.
Detrital zircon grains from the Jack Hills, Western Australia,
comprise the oldest intact pieces of the geological record
yet found. These zircon data, represented by the blue sym-
bols on the right side of FIGURE 3, show that there was
already substantial Hf isotope heterogeneity by ~4.3 Ga. For
such a large range of εHf values to develop in a planet built
from isotopically homogeneous starting materials, distinct
low- and high-Lu/Hf reservoirs, schematically shown in
FIG. 3 as crust and depleted mantle, must have already sep-
arated from the BSE by ~4.4 Ga.
Considering first just the data of Amelin et al. (1999; open
blue symbols), we see that the oldest zircon grains
(4.07–4.14 Ga) plot well below the BSE reference. This could
happen if some crust was extracted from an early primitive
mantle by at least 4.3 Ga (Amelin et al. 2000; Scherer et al.
2001). We call this material crust because it must have been
isolated from the convecting mantle for at least 200 Myr to
develop its distinctive isotopic signature, yet it had to
remain accessible as the source of the zircon’s host magmas.
The ~4.3 Ga crust-formation age (read by tracing back along
the upper edge of the crust arrow to BSE) assumes a felsic
ELEMENTS
crust. A more mafic crust with higher Lu/Hf would have
explain the Hf compositions of the ~4.1 Ga zircon. The
Amelin et al. (1999) data, though hinting that crust-form-
ing processes got off to a very early start, show no evidence
of a complementary depleted mantle reservoir. One expla-
nation for this is that the volume of crust extracted (or that
remained isolated) from the mantle was small. Preservation
issues aside, a piece of crust the size of a soccer ball could
evolve along the same εHf(t) path as a continent, but
extracting so little crust would not deplete the mantle sig-
nificantly. The data of Harrison et al. (2005), which include
extremely high, positive initial εHf values, at first sight seem
to complete the picture by providing evidence for a strongly
depleted mantle before 4.4 Ga, thus allowing the existence
of a significant volume of crust at that time. Not much is
known about that first crust except that it was the source of
the magmas in which the Jack Hills zircon grains crystal-
lized. Chemical and isotopic clues in these grains are being
used to infer the mechanisms responsible for generating
those later magmas.
Citing the Hf data for the Jack Hills zircon grains, together
with their mildly elevated 18O/16O values indicative of low-
temperature interactions with water, low estimated crystal-
lization temperatures, and inclusions of quartz, Harrison et
al. (2005) boldly proposed that a continental environment
produced by modern-style plate tectonics had existed at 4.4
or even 4.5 Ga. Other workers interpret available data dif-
ferently, suggesting that while some granitic crust existed by
4.4 Ga, the first oceans, continents, and water-laid sedi-
ments came later, at 4.2 Ga or 4.3 Ga at the earliest (Cavosie
et al. 2005). Coogan and Hinton (2006) noted that some
features of the Jack Hills zircon grains, namely their crystal-
lization temperatures, light REE concentrations, and elevated
18O/16O signatures, do not necessarily require the existence
of continental crust and abundant liquid water. According
to these authors, the available data do not exclude the pos-
sibility that the zircon grains originated by differentiation
within a basaltic crust. When applying very stringent crite-
ria to filter out Jack Hills zircon grains that have disturbed
isotope systematics, Nemchin et al. (2006) find no evidence
of elevated 18O/16O, suggesting that perhaps the early Earth
wasn’t so wet and cool after all.
It should be noted that the calculated εHf(t) values of
ancient zircon grains and the interpretations based on them
hinge on the accuracy and precision of the 176Lu decay con-
stant (λ176Lu) and the 176Lu/177Hf and 176Hf/177Hf values of
CHUR. For low-Lu/Hf samples such as zircon, these three
parameters primarily affect the position of the BSE reference
(where εHf = 0) with respect to the data. This reference
divides positive εHf(t) values, which characterise melts
extracted from old, depleted mantle, from negative values,
which are typical of rocks formed by melting old crust. The
effect of λ176Lu on the BSE reference line is illustrated in
FIGURE 3, where the same data are plotted using both the
value that was widely used in earlier Hf isotope literature
(inset) and the recently revised value of 1.87×10-11yr-1 (e.g.
Scherer et al. 2001). Using the new value shifts the εHf(t) of
early Archean and Hadean zircon downward by an average
of 3 ε-units. Turning now to CHUR parameters, those for
Sm–Nd were reasonably well established early on, whereas
those for Lu–Hf are proving harder to pin down because of
the surprising degree of heterogeneity among – and within
– the supposedly primitive chondrite meteorites (see review
by Patchett et al. 2004). Nevertheless, the differences
among possible CHUR parameters discussed by Patchett et
al. (2004) would affect the εHf(t) of Jack Hills zircon grains
by less than 0.7 ε-units. While both the λ176Lu and CHUR
values affect the details of the Hf tale told by the oldest
22 F EBRUARY 2007
 FIGURE 3 Earth’s early differentiation history constrained by the
εHf(t) of Archean and Hadean zircon. Hypothetical evolu-
tion trends for depleted mantle (DM) and (proto?) crust with a typical
176Lu/177Hf value of 0.009 are shown. The CHUR parameters of Blichert-
Toft and Albarède (1997) are used. The data imply substantial crust for-
mation by ~4.3 Ga. Inset shows data calculated using the previously
used λ176Lu value, which would allow a more recent separation of the
first stable crust from the BSE, but the positive εHf(t) values still suggest
very early mantle depletion. Data sources: Pettingill and Patchett
(1981); Vervoort et al. (1996); Vervoort and Blichert-Toft (1999);
Amelin et al. (1999, 2000); Halpin et al. (2005); Harrison et al. (2005).
zircon grains, the main theme doesn’t change: very soon
after Earth formed, its silicate portion differentiated into
long-lived, isolated reservoirs, including a depleted mantle
and crust. This is also consistent with the 142Nd excesses
observed in all accessible terrestrial samples relative to
chondrites (Boyet and Carlson 2005). The extra 142Nd was
produced by the decay of short-lived 146Sm (half-life = 103
Myr) before the latter had effectively decayed to extinction
by ~4 Ga. On the basis of 142Nd excesses coupled with other
isotopic constraints, it was concluded from such studies
that major silicate differentiation occurred within 200 Myr,
and perhaps even within 40 Myr, after the birth of the solar
system.
Sediments and Crustal Growth – Combined
U–Pb, Lu–Hf, and O Isotope Measurements
in Detrital Zircon
Sediments – samples of eroded continental crust – provide
valuable insights into crustal growth processes. Sediment-
based crustal growth studies previously focused on Sm–Nd
analyses of bulk sediments to derive average crustal resi-
dence ages (e.g. Allègre and Rousseau 1984). Methods of
identifying individual sediment sources were long restricted
to dating detrital mica (K–Ar) and zircon (U–Pb). Unfortu-
nately, K–Ar systematics in mica are prone to metamorphic
ELEMENTS
overprints, and the U–Pb age spectra of detrital zircon from
different crustal domains are sometimes similar. In such
cases, combined Lu–Hf and U–Pb studies of detrital zircon
allow the distinction between grains that have the same
crystallization age but formed in crustal domains that had
separated from the mantle at different times. This is accom-
plished using Lu–Hf crustal residence ages determined for
the individual grains (FIG. 2). An assumed typical
176Lu/177Hf value for felsic continental crust is used to trace
the evolution of the crustal source back in time from the
initial 176Hf/177Hf value of zircon (point 3) to its intersection
with the DM curve (point 2). This approach has been applied
to numerous sedimentary systems, including currently active
river systems (e.g. Bodet and Schärer 2000) and crust-
derived granites and gneisses (e.g. Andersen et al. 2002).
When applied to sediments, such residence ages do not cor-
respond to actual crust-forming events if the sediments
represent mixtures of crustal domains that were extracted
from the mantle at different times. Such mixing occurs dur-
ing sedimentary reworking, e.g. via erosion of multiple
domains and re-deposition of the bulk sediment. Zircon
formed by melting such sediment will have Hf isotope com-
positions representing mixtures of the various crustal
domains involved, and its crustal residence ages will not
necessarily correspond to real crust-formation events. Oxy-
gen isotope analyses, in conjunction with Lu–Hf and U–Pb
measurements, can be used to determine whether a zircon’s
host magma was derived from reworked sediments. This
approach was recently applied to detrital zircon suites from
the Lachlan fold belt in Australia (Kemp et al. 2006). In this
study, some detrital zircon grains displayed higher 18O/16O
values than those expected for zircon in equilibrium with
mantle-derived magma. This suggests that the host magma
of these grains was derived from recycled crust that had
undergone low-temperature alteration in a wet environment.
Oxygen isotopes thus provide a means of ‘weeding out’ zircon
grains that might give spurious crustal residence ages.
23 F EBRUARY 2007
SUMMARY AND OUTLOOK
No longer just a geochronometer, zircon now doubles as a
detailed archive of the growth and recycling history of
Earth’s crust. Our view back into geological time has been
greatly expanded because a precious few Hadean zircon
grains were tough enough to survive the erosion of the
Earth’s oldest crust. The Hf isotope signature of Hadean zir-
con grains leaves little doubt that major mantle differentia-
tion occurred at ≥4.3 Ga, producing crustal material that
remained intact for >300 Myr. Other geochemical indicators
(e.g. oxygen isotopes, thermometry, trace element patterns,
and mineral inclusions) in the oldest zircon grains have
been used to infer the composition of the first crust and the
processes by which it formed. These issues are the subject of
lively debate, with interpretations ranging widely from a
hot, dry, moon-like scenario to one where full-blown, modern-
style plate tectonics, complete with oceans and felsic conti-
nental crust, was set in motion as early as 4.5 Ga. Further
progress in this area will require a deeper understanding of
complexly zoned zircon grains so that their primary age,
isotope characteristics, and chemical features may be accu-
rately linked and interpreted. The continued evolution of in
situ analytical methods will prove essential to this endeavour.
ACKNOWLEDGMENTS
We thank Frank Tomaschek for stimulating discussions on
the inner workings of zircon, as well as reviewers Chris
Hawkesworth, Matt Horstwood, Tony Kemp, and Ian Par-
sons, and guest editors Simon Harley and Nigel Kelly for
their constructive comments and suggestions. 

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