U–Th–Pb monazite dating and the timing of arc–continent collision in East Timor

The Timor Orogen represents one of the youngest arc–continent collisions exposed on the Earth. It has the potential to provide some of the key parameters about how this style of orogeny evolves. However, the metamorphic age of the highest-grade rocks formed in the collision remains controversial. Using U–Th–Pb dating of monazite from amphibolite-grade sillimanite and garnet-bearing schists we show the peak metamorphism occurred at 5.5–4.7 Ma. The young age of the monazite and the presence of significant amounts of common Pb required the development of a new protocol to simultaneously account for the ²³⁰Th disequilibrium and the ²⁰⁷Pb common Pb correction. The new estimate of metamorphic age is consistent with the estimates based on plate reconstructions for the initiation of arc–continent collision in East Timor. The metamorphic event is a result of this collision.     

Origin of complex zoning in olivine from diverse,diamondiferous kimberlites and tectonic settings: Ekati (Canada), Alto Paranaiba (Brazil) and Kaalvallei (South Africa)

Olivine in kimberlites can provide unique insights into magma petrogenesis, because it is the most abundant xenocrystic phase and a stable magmatic product over most of the liquid line of descent. In this study we examined the petrography and chemistry of olivine in kimberlites from different tectonic settings, including the Slave craton, Canada (Ekati: Grizzly, Koala), the Brasilia mobile belt (Limpeza-18, Tres Ranchos-04), and the Kaapvaal craton, South Africa (Kaalvallei: Samada, New Robinson). Olivine cores display a wide range of compositions (e.g., Mg# = 78–95). The similarity in olivine composition, resorption of core zones and inclusions of mantle-derived phases, indicates that most olivine cores originated from the disaggregation of mantle peridotites, including kimberlite-metasomatised lithologies (i.e. sheared lherzolites and megacrysts). Olivine rims typically show a restricted range of Mg#, with decreasing Ni and increasing Mn and Ca contents, a characteristic of kimberlitic olivine worldwide. The rims host inclusions of groundmass minerals, which implies crystallisation just before and/or during emplacement. There is a direct correlation between olivine rim composition and groundmass mineralogy, whereby high Mg/Fe rims are associated with carbonate-rich kimberlites, and lower Mg/Fe rims are correlated with increased phlogopite and Fe-bearing oxide mineral abundances. There are no differences in olivine composition between explosive (Grizzly) and hypabyssal (Koala) kimberlites. Olivine in kimberlites also displays transitional zones and less common internal zones, between cores and rims. The diffuse transitional zones exhibit intermediate compositions between cores and rims, attributed to partial re-equilibration of xenocrystic cores with the ascending kimberlite melt. In contrast, internal zones form discrete layers with resorbed margins and restricted Mg# values, but variable Ni, Mn and Ca concentrations, which indicates a discrete crystallization event from precursor kimberlite melts at mantle depths. Overall, olivine exhibits broadly analogous zoning in kimberlites worldwide. Variable compositions for individual zones relate to different parental melt compositions rather than variations in tectonic setting or emplacement mechanism.

     

Geochemistry and provenance of the Turquoise Bluff Slate,northeastern Tasmania: tectonic significance

The Ordovician Turquoise Bluff Slate in northeastern Tasmania is a 2?km-thick sequence of deep-marine siliceous black slates. It is dominated by meta-siltstones with bimodal grainsize distributions typical of turbidite T_E-1 and T_E-2 facies. The slates have high SiO₂ indicating they are hemipelagites. The high Ba and V indicate they were deposited in an anoxic environment associated with high oceanic productivity. All these features are common in muddy turbidites. U–Th–Pb dating of detrital monazite and authigenic xenotime in the slates supports previous evidence that the dominant cleavage, in this unit, formed during the Benambran Orogeny. The whole-rock composition of the slates is similar to black slates in the Adaminaby Group, NSW. A review of Paleozoic whole-rock compositions from the Lachlan Orogen confirms they all have trace element contents similar to average Australian shale. However, there are subtle differences in composition. The Turquoise Bluff Slate and other Mathinna Supergroup rocks from the Eastern Tasmania Terrane have higher average Cr content than similar age turbidites from Victoria and NSW. This probably reflects a small contribution from Tasmania Cambrian ultramafic rocks in the provenance. If this were correct, northeastern Tasmania was closer to western Tasmania in the Paleozoic than other provinces of the Lachlan Orogen, southeastern Australia. Other subtle features of the whole-rock composition of Paleozoic sedimentary rocks from the Lachlan Orogen indicate it may be possible to recognise provincial variations in composition that will provide new constraints on tectonic models of southeastern Australia.     

Diversity of primary CL textures in quartz from porphyry environments: implication for origin of quartz eyes

Porphyry-style mineralization is related to the intrusion and crystallization of small stocks, which can be of different compositions (from intermediate to felsic) and can intrude into different host rocks (from magmatic to sedimentary). We used cathodoluminescence and electron probe microanalysis to study the internal textures of more than 300 quartz eyes from six porphyry deposits, Panguna (Papua New Guinea), Far Southeast porphyry (Philippines), Batu Hijau (Indonesia), Antapaccay (Peru), Rio Blanco (Chile) and Climax (USA). Significant diversity of the internal textures in quartz eyes was revealed, sometimes even within a single sample. Quartz grains with Ti-rich cores surrounded by Ti-poor mantles were found next to the grains showing the opposite Ti distribution or only slight Ti fluctuations.We propose that diversity of the internal patterns in quartz eyes can actually reflect in situ crystallization history, and that prolonged crystallization after magma emplacement under conditions of continuous cooling can account for the observed features of internal textures. Formation of quartz eyes begins at high temperatures with crystallization of high titanium Quartz 1, which as the melt becomes more and more evolved and cooler, is overgrown by low Ti Quartz 2. Subsequent fluid exsolution brings about dramatic change in the melt composition: OH ^? , alkalis and other Cl-complexed elements partition into the fluid phase, whereas Ti stays in the melt, contributing to a rapid increase in Ti activity. Separation of the fluid and its further cooling causes disequilibrium in the system, and the Quartz 2 becomes partially resorbed. Exsolution of the fluid gradually builds up the pressure until it exceeds the yield strength of the host rocks and they then fracture. This pressure release most likely triggers crystallization of Quartz 3, which is higher in Ti than Quartz 2 because Ti activity in the melt is higher and pressure of crystallization is lower. As a result of the reaction between the exsolved fluid and quartz a new phase, a so called ‘heavy fluid’ forms. From this phase Quartz 4 crystallizes. This phase has extremely high metal-carrying capacity, and may give a rise to mineralizing fluids. Finally, on the brink of the subsolidus stage, groundmass quartz crystallizes. Prolonged crystallization under conditions of continuous cooling accounts better for the diversity of CL textures than crystallization in different parts of a deep magma chamber. It is also in a better agreement with the existing model for formation of porphyry-style deposits.     

Investigation of the Ablation Behaviour of Andradite-Grossular Garnets and Rutile with Implications for U-Pb Geochronology

U-Pb dating of andradite-grossular garnet (grandite) and rutile by LA-ICP-MS can be used to constrain various metamorphic, metasomatic and igneous geological processes. In this study, we examine and compare the impact of different analytical conditions (fluence, pulse width, laser beam size and ablation frequency) on the ablation crater morphology, ablation rates, down-hole fractionation and U-Pb ages of grandite and rutile samples of different compositions. The shapes of grandite ablation craters suggest the mineral ablates by classical evaporation with significant melting that cannot be eliminated even at fluences just above the ablation threshold. Grandite garnets with higher andradite proportions have faster ablation rates. The overall low U contents of grandite require using large laser beam sizes to obtain acceptable precision of U-Pb ages. At such conditions and crater depths < 10 μm, fluences of 2.1 and 3.5 J cm^-2, laser pulse width of 5 ns and 20 ns, and ablation frequencies between 3.5 and 6.5 Hz, obtain similar and reproducible ages when the proportion of grossular is < 35%. Rutile ablation crater morphology shows evidence of melt splashing and thermal stress cracking. They have significant crater bottom features, which increase in relief with lower fluences and a higher number of laser shots, indicating the features are probably energy-related and making higher fluences, such as 5 J cm^-2, necessary for uniform ablation when using 193 nm excimer lasers. The slow ablation rate at low fluences and then steep increase at around 2.0 J cm^-2 suggests a transition in the ablation mechanism from exfoliation to classical vaporisation. Crater bottom features and other ablation behaviour vary between samples, which could be related to their difference in colour. Although the down-hole fractionation patterns of the samples are similar at 5 J cm^-2, the U-Pb ages of some samples vary significantly with different analytical conditions and/or measurement sessions, particularly when using laser beam sizes of 30 μm, suggesting differences in mass bias and more variable ablation behaviour. A laser beam size of at least 60 μm is recommended for reproducible U-Pb dating of rutile.     

STDGL3, a Reference Material for Analysis of Sulfide Minerals by Laser Ablation ICP-MS: An Assessment of Matrix Effects and the Impact of Laser Wavelengths and Pulse Widths

A new reference material, STDGL3, for the calibration of in situ analyses of sulfide minerals by LA-ICP-MS has been developed and characterised. It represents a lithium-borate-based glass containing a mixture of Zn- and Fe-sulfide concentrates doped with several chalcophile elements as well as Zr, Gd, Hf and Ta required for assessing common interferences on Ag, Au and Pt. STDGL3 has a wider range of elements and a better homogeneity compared with existing reference materials for LA-ICP-MS analysis of sulfides. Compositional variations for most elements are below 3% RSD, below 5% RSD for Ag, Au and Pt, and below 7% RSD for Se, when performing spot analyses with a 50 μm beam size. Its preparation recipe is reproducible allowing for multiple batches to be made. Use of STDGL3 significantly improves accuracy of sulfide mineral analysis by LA-ICP-MS when compared with use of other available reference materials. Performance of STDGL3 was evaluated using several different laser systems. No significant change was observed between 193 nm ArF excimer lasers with 5 and 20 ns pulse widths, but use of 213 and 248 nm lasers displays more systematic differences, especially when analysing galena. Correction coefficients are needed for some elements (Zn and Cd in particular) when analysing sulfide minerals using STDGL3 as a calibration reference material.     

Textural evolution of perovskite in the Afrikanda alkaline–ultramafic complex,Kola Peninsula,Russia

Perovskite is a common accessory mineral in a variety of mafic and ultramafic rocks, but perovskite deposits are rare and studies of perovskite ore deposits are correspondingly scarce. Perovskite is a key rock-forming mineral and reaches exceptionally high concentrations in olivinites, diverse clinopyroxenites and silicocarbonatites in the Afrikanda alkaline–ultramafic complex (Kola Peninsula, NW Russia). Across these lithologies, we classify perovskite into three types (T1–T3) based on crystal morphology, inclusion abundance, composition, and zonation. Perovskite in olivinites and some clinopyroxenites is represented by fine-grained, equigranular, monomineralic clusters and networks (T1). In contrast, perovskite in other clinopyroxenites and some silicocarbonatites has fine- to coarse-grained interlocked (T2) and massive (T3) textures. Electron backscatter diffraction reveals that some T1 and T2 perovskite grains in the olivinites and clinopyroxenites are composed of multiple subgrains and may represent stages of crystal rotation, coalescence and amalgamation. We propose that in the olivinites and clinopyroxenites, these processes result in the transformation of clusters and networks of fine-grained perovskite crystals (T1) to mosaics of more coarse-grained (T2) and massive perovskite (T3). This interpretation suggests that sub-solidus processes can lead to the development of coarse-grained and massive perovskite. A combination of characteristic features identified in the Afrikanda perovskite (equigranular crystal mosaics, interlocked irregular-shaped grains, and massive zones) is observed in other oxide ore deposits, particularly in layered intrusions of chromitites and intrusion-hosted magnetite deposits and suggests that the same amalgamation processes may be responsible for some of the coarse-grained and massive textures observed in oxide deposits worldwide.     

Nickel-rich metasomatism of the lithospheric mantle by pre-kimberlitic alkali-S–Cl-rich C–O–H fluids

Metasomatism of the lithospheric mantle sometimes produces unusual assemblages containing native metals and alloys, which provide important insight into metasomatic processes in the mantle. In this study, we describe the metasomatic enrichment of a refractory harzburgite xenolith in Ni, Fe and, to a lesser extent, Cu, Co, As and Sb. The xenolith (XM1/422) derives from the Bultfontein kimberlite (Kimberley, South Africa) and hosts Ni mineralisation that includes native nickel (Ni_84.5-98.0), heazlewoodite (Ni₃S₂) and Ni-rich silicates (e.g. up to 37.5 wt % NiO in olivine, and 22.4 wt % NiO in phlogopite). The presence of several mineral phases enriched in alkali and volatile species (e.g. phlogopite, phosphates, carbonates, chlorides, djerfisherite) indicates that the transition metal cations were likely introduced during metasomatism by alkali-rich C–O–H fluids or alkali-carbonate melts. It is postulated that sulphide breakdown and fluid reaction with refractory mantle rocks contributed to the fluid’s enrichment in Ni and other metallic cations. The Ni-rich assemblages of xenolith XM1/422 show local chemical disequilibrium, and modelling of the Ni diffusion profiles adjacent to olivine-native nickel and olivine-heazlewoodite grain boundaries, suggests a close temporal relationship between Ni-rich metasomatism and subsequent entrainment by the kimberlite magma. However, metal-rich metasomatism has also been observed in other lithospheric mantle domains, including orogenic peridotitic massifs and the suboceanic mantle; regions unaffected by kimberlite magmatsim. As micro-scale occurrences of metallic phases are easily overlooked, it is possible that metal-rich metasomatism is more widespread in the Earth’s mantle than previously recognised.     

New Olivine Reference Material for In Situ Microanalysis

A new olivine reference material – MongOL Sh11‐2 – for in situ analysis has been prepared from the central portion of a large (20 × 20 × 10 cm) mantle peridotite xenolith from a ~ 0.5 My old basaltic breccia at Shavaryn‐Tsaram, Tariat region, central Mongolia. The xenolith is a fertile mantle lherzolite with minimal signs of alteration. Approximately 10 g of 0.5–2 mm gem quality olivine fragments were separated under binocular microscope and analysed by EPMA, LA‐ICP‐MS, SIMS and bulk analytical methods (ID‐ICP‐MS for Mg and Fe, XRF, ICP‐MS) for major, minor and trace elements at six institutions world‐wide. The results show that the olivine fragments are sufficiently homogeneous with respect to major (Mg, Fe, Si), minor and trace elements. Significant inhomogeneity was revealed only for phosphorus (homogeneity index of 12.4), whereas Li, Na, Al, Sc, Ti and Cr show minor inhomogeneity (homogeneity index of 1–2). The presence of some mineral and fluid‐melt micro‐inclusions may be responsible for the inconsistency in mass fractions obtained by in situ and bulk analytical methods for Al, Cu, Sr, Zr, Ga, Dy and Ho. Here we report reference and information values for twenty‐seven major, minor and trace elements.