Zircon is the main mineral in the majority of igneous and metamorphic rocks with Zr as an essential structural constituent. It is a host for significant fractions of the whole-rock abundance of U, Th, Hf, and the REE (Sawka 1988, Bea 1996, O’Hara et al. 2001). These elements are important geochemically as process indicators or parent isotopes for age determination. The importance of zircon in crustal evolution studies is underscored by its predominant use in U-Th-Pb geochronology and investigations of the temporal evolution of both the crust and lithospheric mantle. In the past decade an increasing interest in the composition of zircon, trace-elements in particular, has been motivated by the effort to better constrain in situ microprobe-acquired isotopic ages. Electron-beam compositional imaging and isotope-ratio measurement by in situ beam techniques—and the micrometer-scale spatial resolution that is possible—has revealed in many cases that single zircon crystals contain a record of multiple geologic events. Such events can either be zircon-consuming, alteration, or zircon-forming and may be separated in time by millions or billions of years. In many cases, calculated zircon isotopic ages do not coincide with ages of geologic events determined from other minerals or from whole-rock analysis. To interpret the geologic validity and significance of multiple ages, and ages unsupported by independent analysis of other isotopic systems, has been the impetus for most past investigations of zircon composition. Some recent compositional investigations of zircon have not been directly related to geochronology, but to the ability of zircon to influence or record petrogenetic processes in igneous and metamorphic systems.

Sedimentary rocks may also contain a significant fraction of zircon. Although authigenic zircon has been reported (Saxena 1966, Baruah et al. 1995, Hower et al. 1999), it appears to be very rare and may in fact be related to …

/pdf/the-composition-of-zircon-and-igneous-and-metamorphic-1g2xfkpi4l.pdf

The Composition of Zircon and Igneous and Metamorphic Petrogenesis

The mineral zircon is extremely variable both in terms of external morphology and internal textures. These features reflect the geologic history of the mineral, especially the relevant episode(s) of magmatic or metamorphic crystallization (and recrystallization), strain imposed both by external forces and by internal volume expansion caused by metamictization, and chemical alteration. The paper presents a selection of both the most typical, but also of the less common, features seen in zircon, categorized according to the different geological processes responsible for their formation. The atlas is intended as a general guide for the interpretation of zircon characteristics, and of related isotopic data.

Zircon has become one of the most widely used minerals for the extraction of information on the prehistory and genesis of magmatic, metamorphic and sedimentary rocks. Much of the geological usefulness of zircon stems from its suitability as a geochronometer based on the decay of U (and Th) to Pb, but in addition it is also the major host of the radiogenic isotopic tracer Hf, and it is used to determine oxygen isotopic compositions and REE and other trace element abundances, all of which yield useful clues concerning the history of the host rock, and in some case, the parent rock in which the precursor zircon crystallized.

One of the major advantages of zircon is its ability to survive magmatic, metamorphic and erosional processes that destroy most other common minerals. Zircon-forming events tend to be preserved as distinct structural entities on a pre-existing zircon grain. Because of this ability, quite commonly zircon consists of distinct segments, each preserving a particular period of zircon-formation (or consumption). A long experience and modern instrumentation and techniques have provided the “zircon community” the means to image and interpret preserved textures, and hence to decipher the history and evolution of a rock. One …

Atlas of Zircon Textures

http://riceearthscience.org/wp-content/uploads/2015/09/Hoffman1988.pdf

Chemical differentiation of the Earth: the relationship between mantle, continental crust, and oceanic crust

We present the first finding of continental crust-derived Precambrian zircons in garnet/spinel pyroxenite veins within mantle xenoliths carried by the Neogene Hannuoba basalt in the central zone of the North China Craton (NCC). Petrological and geochemical features indicate that these mantle-derived composite xenoliths were formed by silicic melt^lherzolite interaction. The Precambrian zircon ages can be classified into three age groups of 2·4^2·5 Ga, 1·6^2·2 Ga and 0·6^1·2 Ga, coinciding with major geological events in the NCC. These Precambrian zircons fall in the field of continental granitoid rocks in plots of U/Yb vs Hf and Y. Their igneous-type REE patterns and metamorphic zircon type CL images indicate that they were not crystallized during melt^peridotite interaction and subsequent high-pressure metamorphism.The 2·5 Ga zircons have positive eHf(t) values (2·9^10·6), whereas the younger Precambrian zircons are dominated by negative eHf(t) values, indicating an ancient continental crustal origin.These observations suggest that the Precambrian zircons were xenocrysts that survived melting of recycled continental crustal rocks and were then injected with silicate melt into the host peridotite. In addition to the Precambrian zircons, igneous zircons of 315 3 Ma (2 ), 80^170 Ma and 48^64 Ma were separated from the garnet/spinel pyroxenite veins; these provide evidence for lower continental crust and oceanic crust recycling-induced multi-episodic melt^peridotite interactions in the central zone of the NCC. The combination of the positive eHf(t) values (2·91^24·6) of the 315 Ma zircons with the rare occurrence of 302^324 Ma subduction-related diorite^granite plutons in the northern margin of the NCC implies that the 315 Ma igneous zircons might record melt^peridotite interactions in the lithospheric mantle induced by Palaeo-Asian oceanic crust subduction. Igneous zircons of age 80^170 Ma generally coexist with the Precambrian metamorphic zircons and have lower Ce/Yb and Th/U ratios, higher U/Yb ratios and greater negative Eu anomalies.The eHf(t) values of these zircons vary greatly from ^47·6 to 24·6.The 170^110 Ma zircons are generally characterized by negative eHf(t) values, whereas the 110^100 Ma zircons have positive eHf(t) values.These observations suggest that melt^peridotite interactions at 80^170 Ma were induced by partial melting of recycled continental crust. The 48^64 Ma igneous zircons are characterized by negligible Ce anomalies, unusually high REE, U and Th contents, and positive eHf(t) values.These features imply that the melt^peridotite interactions at 48^64 Ma could be associated with a depleted mantle-derived carbonate melt or fluid.

Continental and Oceanic Crust Recycling-induced Melt^Peridotite Interactions in the Trans-North China Orogen: U^Pb Dating, Hf Isotopes and Trace Elements in Zircons from Mantle Xenoliths

Zircon trace element geochemistry: partitioning with garnet and the link between U–Pb ages and metamorphism

The models recognize that ZrSiO4, ZrTiO4,  and TiSiO4, but not ZrO2 or TiO2, are independently variable phase components in zircon. Accordingly, the equilibrium controlling the Zr content of rutile coexisting with zircon is ZrSiO4 = ZrO2 (in rutile) +  SiO2. The equilibrium controlling the Ti content of zircon is either ZrSiO4 + TiO2 = ZrTiO4 + SiO2 or TiO2 + SiO2 = TiSiO4, depending whether Ti substitutes for Si or Zr. The Zr content of rutile thus depends on the activity of SiO2
 $$(a_{\text{SiO}_{2}})$$
 as well as T, and the Ti content of zircon depends on $$a_{\text{SiO}_{2}}$$
  and 
 $$a_{\text{TiO}_{2}}$$
 as well as T. New and published experimental data confirm the predicted increase in the Zr content of rutile with decreasing $$a_{\text{SiO}_{2}},$$
 and unequivocally demonstrate that the Ti content of zircon increases with decreasing $$a_{\text{SiO}_{2}}$$
 . The substitution of Ti in zircon therefore is primarily for Si. Assuming a constant effect of P, unit $$a_{\text{ZrSiO}_{4}},$$
 and that $$a_{\text{ZrO}_{2}}$$
  and $$a_{\text{ZrTiO}_{4}}$$
 are proportional to ppm Zr in rutile and ppm Ti in zircon, [log(ppm Zr-in-rutile) + log
 $$a_{\text{SiO}_{2}}$$
 ] = A1 + B1/T(K) and  [log(ppm Ti-in-zircon) + log
 $$a_{\text{SiO}_{2}}$$
 − log
 $$a_{\text{TiO}_{2}}$$
 ] = A2 + B2/T, where the A and B are constants. The constants were derived from published and new data from experiments with $$a_{\text{SiO}_{2}}$$
 buffered by either quartz or zircon + zirconia, from experiments with $$a_{\text{SiO}_{2}}$$
 defined by the Zr content of rutile, and from well-characterized natural samples. Results are A1 = 7.420 ± 0.105;  B1 = −4,530 ± 111;  A2 = 5.711 ± 0.072;  B2 = −4,800 ± 86 with activity referenced to α-quartz and rutile at P and T of interest. The zircon thermometer may now be applied to rocks without quartz and/or rutile, and the rutile thermometer applied to rocks without quartz, provided that $$a_{\text{SiO}_{2}}$$
  and $$a_{\text{TiO}_{2}}$$
 are estimated. Maximum uncertainties introduced to zircon and rutile thermometry by unconstrained $$a_{\text{SiO}_{2}}$$
  and 
 $$a_{\text{TiO}_{2}}$$
 can be quantitatively assessed and are ≈60 to 70°C at 750°C. A preliminary assessment of the dependence of the two thermometers on P predicts that an uncertainty of ±1 GPa introduces an additional uncertainty at 750°C of ≈50°C for the Ti-in-zircon thermometer and of ≈70 to 80°C for the Zr-in-rutile thermometer.

New thermodynamic models and revised calibrations for the Ti-in-zircon and Zr-in-rutile thermometers

Zircon and rutile are common accessory minerals whose essential structural constituents, Zr, Ti, and Si can replace one another to a limited extent. Here we present the combined results of high pressure–temperature experiments and analyses of natural zircons and rutile crystals that reveal systematic changes with temperature in the uptake of Ti in zircon and Zr in rutile. Detailed calibrations of the temperature dependencies are presented as two geothermometers—Ti content of zircon and Zr content of rutile—that may find wide application in crustal petrology. Synthetic zircons were crystallized in the presence of rutile at 1–2 GPa and 1,025–1,450°C from both silicate melts and hydrothermal solutions, and the resulting crystals were analyzed for Ti by electron microprobe (EMP). To augment and extend the experimental results, zircons hosted by five natural rocks of well-constrained but diverse origin (0.7–3 GPa; 580–1,070°C) were analyzed for Ti, in most cases by ion microprobe (IMP). The combined experimental and natural results define a log-linear dependence of equilibrium Ti content (expressed in ppm by weight) upon reciprocal temperature:

 $$\log ({\text{Ti}}_{{{\text{zircon}}}}) = (6.01 \pm 0.03) - \frac{{5080 \pm 30}}{{T\;(\hbox{K})}}.$$
 In a strategy similar to that used for zircon, rutile crystals were grown in the presence of zircon and quartz (or hydrous silicic melt) at 1–1.4 GPa and 675–1,450°C and analyzed for Zr by EMP. The experimental results were complemented by EMP analyses of rutile grains from six natural rocks of diverse origin spanning 0.35–3 GPa and 470–1,070°C. The concentration of Zr (ppm by weight) in the synthetic and natural rutiles also varies in log-linear fashion with T
 −1:

 $$\log ({\text{Zr}}_{{{\text{rutile}}}}) = (7.36 \pm 0.10) - \frac{{4470 \pm 120}}{{T\;(\hbox{K})}}.$$
 The zircon and rutile calibrations are consistent with one another across both the synthetic and natural samples, and are relatively insensitive to changes in pressure, particularly in the case of Ti in zircon. Applied to natural zircons and rutiles of unknown provenance and/or growth conditions, the thermometers have the potential to return temperatures with an estimated uncertainty of ±10 ° or better in the case of zircon and ±20° or better in the case of rutile over most of the temperature range of interest (∼400–1,000°C). Estimates of relative temperature or changes in temperature (e.g., from zoning profiles in a single mineral grain) made with these thermometers are subject to analytical uncertainty only, which can be better than ±5° depending on Ti or Zr concentration (i.e., temperature), and also upon the analytical instrument (e.g., IMP or EMP) and operating conditions.

Crystallization thermometers for zircon and rutile

Pb diffusion in zircon

Ancient zircons from Western Australia9s Jack Hills preserve a record of conditions that prevailed on Earth not long after its formation. Widely considered to have been a uniquely violent period geodynamically, the Hadean Eon [4.5 to 4.0 billion years ago (Ga)] has recently been interpreted by some as far more benign—possibly even characterized by oceans like those of the present day. Knowledge of the crystallization temperatures of the Hadean zircons is key to this debate. A thermometer based on titanium content revealed that these zircons cluster strongly at ∼700°C, which is indistinguishable from temperatures of granitoid zircon growth today and strongly suggests a regulated mechanism producing zircon-bearing rocks during the Hadean. The temperatures substantiate the existence of wet, minimum-melting conditions within 200 million years of solar system formation. They further suggest that Earth had settled into a pattern of crust formation, erosion, and sediment recycling as early as 4.35 Ga.

https://science.sciencemag.org/content/sci/308/5723/841.full.pdf

E. B. Watson

Papers

New thermodynamic models and revised calibrations for the Ti-in-zircon and Zr-in-rutile thermometers

Crystallization thermometers for zircon and rutile

Pb diffusion in zircon

Zircon Thermometer Reveals Minimum Melting Conditions on Earliest Earth

Rutile saturation in magmas: implications for TiNbTa depletion in island-arc basalts