Zircon chronochemistry of high heat-producing granites in Queensland and Europe

High heat-producing granites (HHPGs) are reservoir rocks for enhanced geothermal systems (EGS), yet the origins of their anomalous chemistry remain poorly understood. To gain a better understanding of the characteristic distribution of elemental depletions and enrichments (focussing on U, Th & K) within granite suites of different heritage and tectonic setting, and the processes that lead to these enrichments, we are undertaking a systematic accessory-mineral chronochemical study of two suites of S- and I-type granites in northern Queensland, as well as two archetypal HHPGs in Cornwall, England (S-type) and Soultz-sous- Forêts, France (I-type). Novel zircon LA-ICP-MS chronochemical methods will later be underpinned by a systematic petrographic, scanning electron microscope (SEM), and electron microprobe (EPMA) study of all the REE-Y-Th-U-rich accessory minerals to fully characterise how the composition, textural distributions and associations change with rock chemistry between and among the suites. Preliminary results indicate that zircons with inherited ages do not have anomalously high U (>1000 ppm) & Th (>400 ppm) values (Ahrens, 1965). Instead, enrichment in these HPE is seen in zircons dated to around the time of magmatic emplacement. These results indicate that enrichment arose primarily through fractional crystallisation of the granitic magmas. Our results support the suggestion that a source pre-enriched in the HPEs does not appear to be fundamental for the formation of all HHPGs. Instead fractional crystallisation processes, and the accessory minerals formed in magmas of differing initial compositions, are the key controls on the levels of enrichment observed (e.g. Champion & Chappell, 1992; Chappell & Hine, 2006). One implication is that the most fractionated granites may not be the most enriched in the HPEs and therefore prospective to future EGS development.

Identification and elimination of a matrix-induced systematic error in LA–ICP–MS 206Pb/238U dating of zircon

Black et al. (2004) identified a systematic difference between LA–ICP–MS and TIMS measurements of 206Pb/238U in zircons, which they correlated with the incompatible trace element content of the zircon. We show that the offset between the LA–ICP–MS and TIMS measured 206Pb/238U correlates more strongly with the total radiogenic Pb than with any incompatible trace element. This suggests that the cause of the 206Pb/238U offset is related to differences in the radiation damage (alpha dose) between the reference and unknowns. We test this hypothesis in two ways. First, we show that there is a strong correlation between the difference in the LA–ICP–MS and TIMS measured 206Pb/238U and the difference in the alpha dose received by unknown and reference zircons. The LA–ICP–MS ages for the zircons we have dated can be as much as 5.1% younger than their TIMS age to 2.1% older, depending on whether the unknown or reference received the higher alpha dose. Second, we show that by annealing both reference and unknown zircons at 850 °C for 48 h in air we can eliminate the alpha-dose-induced differences in measured 206Pb/238U. This was achieved by analyzing six reference zircons a minimum of 16 times in two round robin experiments: the first consisting of unannealed zircons and the second of annealed grains. The maximum offset between the LA–ICP–MS and TIMS measured 206Pb/238U for the unannealed zircons was 2.3%, which reduced to 0.5% for the annealed grains, as predicted by within-session precision based on counting statistics. Annealing unknown zircons and references to the same state prior to analysis holds the promise of reducing the 3% external error for the measurement of 206Pb/238U of zircon by LA–ICP–MS, indicated by Klötzli et al. (2009), to better than 1%, but more analyses of annealed zircons by other laboratories are required to evaluate the true potential of the annealing method.

Tectonometamorphic evolution of the Åreskutan Nappe-Caledonian history revealed by SIMS U–Pb zircon geochronology

Secondary ionization mass spectrometry (SIMS) U–Pb dating of zircons from the Åreskutan Nappe in the central part of the Seve Nappe Complex of western central Jämtland provides new constraints on the timing of granulite–amphibolite-facies metamorphism and tectonic stacking of the nappe during the Caledonian orogeny. Peak-temperature metamorphism in garnet migmatites is constrained to c. 442 ± 4 Ma, very similar to the ages of leucogranites at 442 ± 3 and 441 ± 4 Ma. Within a migmatitic amphibolite, felsic segregations crystallized at 436 ± 2 Ma. Pegmatites, cross-cutting the dominant Caledonian foliation in the Nappe, yield 428 ± 4 and 430 ± 3 Ma ages. The detrital zircon cores in the migmatites and leucogranites provide evidence of Late Palaeoproterozoic, Mesoproterozoic to Early Neoproterozoic source terranes for the metasedimentary rocks. The formation of the ductile and hot Seve migmatites, with their inverted metamorphism and thinning towards the hinterland, can be explained by an extrusion model in which the allochthon stayed ductile for a period of at least 10 million years during cooling from peak-temperature metamorphism early in the Silurian. In our model, Baltica–Laurentia collision occurred in the Late Ordovician–earliest Silurian, with emplacement of the nappes far on to the Baltoscandian platform during the Silurian and early Devonian, Scandian Orogeny lasting until c. 390 Ma.

Low delta18O zircon grains in the Neoarchean Rum Jungle Complex, northern Australia: An indicator of emergent continental crust

The timing of widespread continental emergence is generally considered to have had a dramatic effect on the hydrological cycle, atmospheric conditions, and climate. New secondary ion mass spectrometry (SIMS) oxygen and laser-ablation–multicollector–inductively coupled plasma–mass spectrometry (LA-MC-ICP-MS) Lu-Hf isotopic results from dated zircon grains in the granitic Neoarchean Rum Jungle Complex provide a minimum time constraint on the emergence of continental crust above sea level for the North Australian craton. A 2535 ± 7 Ma monzogranite is characterized by magmatic zircon with slightly elevated δ18O (6.0‰–7.5‰ relative to Vienna standard mean ocean water [VSMOW]), consistent with some contribution to the magma from reworked supracrustal material. A supracrustal contribution to magma genesis is supported by the presence of metasedimentary rock enclaves, a large population of inherited zircon grains, and subchondritic zircon Hf (εHf = −6.6 to −4.1). A separate, distinct crustal source to the same magma is indicated by inherited zircon grains that are dominated by low δ18O values (2.5‰–4.8‰, n = 9 of 15) across a range of ages (3536–2598 Ma; εHf = −18.2 to +0.4). The low δ18O grains may be the product of one of two processes: (1) grain-scale diffusion of oxygen in zircon by exchange with a low δ18O magma or (2) several episodes of magmatic reworking of a Mesoarchean or older low δ18O source. Both scenarios require shallow crustal magmatism in emergent crust, to allow interaction with rocks altered by hydrothermal meteoric water in order to generate the low δ18O zircon. In the first scenario, assimilation of these altered rocks during Neoarchean magmatism generated low δ18O magma with which residual detrital zircons were able to exchange oxygen, while preserving their U-Pb systematics. In the second scenario, wholesale melting of the altered rocks occurred in several distinct events through the Mesoarchean, generating low δ18O magma from which zircon crystallized. Ultimately, in either scenario, the low δ18O zircons were entrained as inherited grains in a Neoarchean granite. The data suggest operation of a modern hydrological cycle by the Neoarchean and add to evidence for the increased emergence of continents by this time

Reduction In Metal-Mold Reactivity In Titanium Castings Through The Use Of Sodium Aluminate As Binder In Zircon Sand Molds

The present work is aimed at evaluating an alternative moulding system, namely, sodium aluminate bonded zircon sand mould and assess its suitability in relation to the much studied sodium silicate bonded zircon sand moulding system. It is described in the study presented here that with regard to metal - mould reaction, sodium aluminate bonded zircon sand mould system is a superior viable system as compared to sodium silicate bonded zircon moulding system at mould firing temperatures of 873 - 1473 K.

Thermal barrier coating application of zircon sand

Naturally occurring zircon sand was plasma spray coated on steel substrates previously coated with NiCrAlY bond coat. The coatings were characterized for their microstructure, chemical composition, thermal shock resistance, and the nature of structural phases present, The as-sprayed coatings consisted of t-ZrO2 (major phase), m-ZrO2, ZrSiO4 (minor phases), and amorphous SiO2. These coatings, when annealed at 1200 degrees C/1.44 x 10(4) s yielded a ZrSiO4 phase as a result of the reaction between ZrO2 and SiO2, Dramatic changes occurred in the characteristics of the coatings when a mixture of zircon sand and Y2O3 was plasma spray coated and annealed at 1400 degrees C/1.44 x 10(4) s, The t-ZrO2 phase was completely stabilized, and these coatings were found to have considerable potential for thermal barrier applications.

Metal mould reactions during casting of titanium in zircon sand moulds

Metal-mold reaction during Ti casting in zircon sand molds has been studied using scanning electron microscope, energy and wave length dispersive analysis of X-rays, X-ray diffraction, microhardness measurements, and chemical analysis. Experimental results suggest that oxides from the mold are not fully leached out by liquid Ti, but oxygen is preferentially transferred to liquid Ti, leaving behind metallic constituents in the mold as lower oxides or intermetallics of Ti. The electron microprobe analysis has revealed the depth profile of contaminants from the mold into the cast Ti metal. The elements Si, Zr and O were found to have diffused to a considerable distance within the Ti metals. A possible mechanism has now been evolved in regard to the reactions that occur during casting of Ti in zircon sand molds.

Zircon Sand--a Viable Alternative Moulding System for Titanium Castings

The experimental observations of casting titanium in sodium silicate bonded zircon sand mould are presented in this paper. Metal-mould reactions, in general, involved dissolution of oxides in liquid titanium resulting in contamination of the casting. Minimal metal-mould reactions occurred when titanium was cast in zircon sand mould containing about 7.5 wt% of ZrO2. It has been further shown that the metal-mould reaction is considerably reduced if moulds were fired at high temperatures (> 1273K). This ensured elimination of moisture from the mould and also resulted in some beneficial changes in the mould chemistry. The reduction in metal-mould reaction is reflected in the decrease in oxygen and hydrogen contamination and decrease in hardness. Thus microhardness profile and oxygen analysis seems to provide a good index for evaluation of severity of metal-mould reaction. The method has been demonstrated to be satisfactory for casting titanium components.

A Short Review on Lu-Hf Isotope System in Zircon: Implications for Crustal Evolution

Zircon has been recognized as the unaltered part of the Earth's history which preserves nearly 4 billion year record of earth's evolution. Zircon preserves igneous and metamorphic processes during its formation and remains unaffected by sedimentary processes and crustal recycling. U-Pb and Lu-Hf in zircon work as geochronometer and geochemical tracer respectively. Zircon provide valuable information about the source composition of the rocks and the intrinsic details of an unseen crust-mantle processes. The world wide data of U-Pb and Lu-Hf isotope systems in zircon reveal crustal evolution through geological history. Moreover, the U-Pb age pattern of zircons show distinct peaks attributed to preservation of crustal rocks or mountain building during supercontinent assembly. The histogram of continental crust preservation shows that nearly one-third of continental crust was formed during the Archean, almost 20% was formed during Paleoproterozoic and 14% in last 400 Ma.