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Titanite from various rocks of the Karkonosze granitoid pluton (South-Eastern Poland) was studied, in order to evaluate its precision in recording magma evolution processes. The rocks are of lamprophyric, dioritic, granodioritic and granitic composition, including hybrid structures such as microgranular magmatic enclaves and composite dykes. Based on textures, chemistry and Zr-in-titanite geothermometry, titanites can be divided into magmatic and post-magmatic populations. Late- to post-magmatic titanite is present in almost all rock types, especially in the most evolved ones (where magmatic titanite is absent) and can be characterized by low trace element and high Al and F contents. Magmatic titanite crystallized in temperatures between 610 and 870 °C, after apatite and relatively simultaneously with amphibole and zircon. Titanite from lamprophyre exhibits compositional features typical of titanites formed in mafic rocks: low Al and F, high Ti4+/(Al + Fe3+), LREE (light rare earth elemet)-enriched chondrite-normalized REE patterns, low Y/Zr, Nb/Zr, Lu/Hf, high (Ce + Nd)/Y, Th/U and Zr. Titanite from hybrid rocks inherited these characteristics, indicating major contribution of the mantle-derived magma especially during early stages of magmatic evolution. Titanite compositional variations, as well as a wide range of crystallization temperatures in hybrid granodiorites point to prolonged crystallization from distinct magma domains of variable mafic versus felsic melt proportions. The extent of compositional variations decreases through subsequent stages of magmatic evolution, and titanite with the least contribution of the mafic component is characterized by higher total REE, Al and F contents, lower Ti4+/(Al + Fe3+), (Ce + Nd)/Y and Th/U ratios, LREE-depleted chondrite-normalized REE patterns and higher Y/Zr, Nb/Zr and Lu/Hf ratios. Titanite composition from the intermediate and late stage hybrids bears signature of decreasing amount of the mafic melt and higher degree of its evolution, however, the exact distinction between the former and the latter is very limited. [ABSTRACT FROM AUTHOR]

In this paper, zonation patterns of trace elements in fluorapatite are discussed that were visualized using four analytical techniques, namely back-scattered electrons (BSE) and cathodoluminescence (CL) imaging, electron probe micro-analysis (EPMA), and micro-proton-induced X-ray/gamma ray emission (μPIXE/μPIGE) mapping. Each method demonstrates the in-grain compositional variations in a slightly different way. Both BSE and CL provide qualitative data, and the internal textures are displayed in most detail. Additionally, CL points to specific elements enriched in certain growth zones. Qualitative EPMA maps show detailed zonation patterns for specific elements (with high spatial resolution), which are in general correspondence with the patterns observed in BSE and CL images. The μPIXE/μPIGE maps are fully quantitative and the detection limits are relatively low compared to EPMA mapping. In present spot measurements μPIXE demonstrates lower detection limits than EPMA, however, the latter could be considerably improved by extending the acquisition times. There is no significant overlap of REE (rare earth elements) peaks in the acquired μPIXE energy spectra, however, when multiple REEs are present with sufficiently high concentrations, peak deconvolution may pose some difficulties. Spatial resolution of μPIXE/μPIGE images is not sufficiently high to reflect minor textural features, which also result from the greater interaction depth of the proton beam. However, major growth zones are distinguishable. Even though each method has their advantages and limitations, when applied together, they provide an almost complete characterization of compositional variability in trace-element-bearing minerals. [ABSTRACT FROM AUTHOR]

An alkali feldspar megacryst from a protomylonite has been studied using laser ablation-ICP-mass spectrometry combined with cathodoluminescence imaging, Raman spectroscopy, and electron probe microanalysis. The aim was to determine the original (magmatic) geochemical pattern of the crystal and the changes introduced by protomylonitization. Digital concentration-distribution models, derivative gradient models, and fractal statistics, e.g., Hurst-exponent values are used in a novel way to reveal subtle changes in the trace-element composition of the feldspar. Formation of the crystal is reflected in a slightly chaotic trace-element (Ba, Sr, and Rb) distribution pattern that is more or less characterized by continuous development from a fairly homogeneous environment. Derivative gradient models demonstrate a microdomain pattern. Fractal statistics show that element behavior was changeable, with Ba and Sr always more persistent (continuing) and Rb always less persistent, with the latter showing a tendency to migrate. The variations in the Hurst exponent are, however, too large to be explained by magmatic differentiation alone. The observed element behavior may be explained by structural changes revealed by Raman spectroscopy and CL. In high-strain domains, T-O-T modes become stronger for Si-O-Al than Al-O-Al linkages. Increasing amounts of Al-O-Al defects are demonstrated by cathodoluminescence. Both may result from small-distance diffusion creep, making the crystal geochemical pattern slightly patchy. In turn, the marginal part of the megacryst has a mosaic of randomly orientated, newly crystallized K-feldspars. The re-growth is confirmed by trace-element distribution patterns and fractal statistics which identify an abrupt change in the transformation environment. The novel set of tools used in this study reveals a complicated history of megacryst formation and transformation that otherwise would be difficult to unravel and decipher. [ABSTRACT FROM AUTHOR]

Growth and regrowth textures, trace element and oxygen isotope compositions, and water content or species have been studied in alkali feldspars from the late Archaean Closepet igneous bodies. Feldspar crystals grew from mixed magmas that are characterized by a high degree of homogenization. The 3D depiction of trace element distribution indicates that the crystallization process was followed by interaction with fluids. The magmatic system involved in feldspar formation shows non-linear dynamics. The interaction with fluids is also deterministic, but in contrast to magmatic crystallization, it shows an increasing persistency in element behaviour. The degree of persistency of the element activities in both processes has been calculated using the Hurst exponent. The recrystallization (regrowth) process induced by fluids proceeded along crystal fractures and cleavages, causing selective enrichment in large ion lithophile elements (light rare earth elements), Pb, Y, and in various water species. It did not change the feldspar oxygen isotope signature. In turn, the incorporation of hydrogen species into feldspar domains reduced Al–O−–Al defect densities in the structure, decreasing their luminescence. Water speciation shows persistent behaviour during heating, the process being reversible at least up to 600°C. Carbonate crystals with a mantle isotope signature are associated with the re-equilibrated feldspar domains. The feldspar compositions, the abundance of water species in them and the refractory nature of the residuum after heating, the unchanged oxygen isotopes and the mantle signature of co-precipitated carbonates testify that the observed recrystallization has taken place at temperatures above 600°C with H2O–CO2 fertile, mantle-derived fluids. The paper draws special attention to some methodological aspects of the problem. The multi-method approach used here (major element, trace element and isotope geochemistry, infra-red, cathodoluminescence, 3D depiction of geochemical data and fractal statistics) may help to recognize and separate the various processes throughout the alteration history of the pluton. [ABSTRACT FROM AUTHOR]

The aim of this paper is to determine the composition and age of high-temperature (HT) hydrothermal fluids in Closepet granites (Dharwar craton, India). The magmatic origin of the Neoarchaean Closepet batholith has been recognized and dated many times, whereas a HT fluid system, strong evidence for which has been partly investigated, has never been dated. Titanite was chosen for a geochemical study on its pristine and altered domains to illustrate the fluid composition; the domains were dated to recognize the timing of fluid activity. Titanite presents distinct trace element enrichments in non-altered domains and strong depletions in trace elements in marginal, irregular, patchy zones. The high total rare earth element (REE) concentrations and the marked negative Eu anomalies suggest crystallization from a residual melt. The negative Eu anomalies diminish progressively in the REE patterns of altered parts and become positive. Trace element ratios (Nb/Ta, Y/Ho, and U/Th) indicate fluid-crystal interactions. Strong U/Th fractionation might be linked to the presence of CO 2 and Cl−. Zr-in-titanite thermometry yields a crystallization/recrystallization temperature of ~700 °C for both magmatic and altered domains. The titanite factor Ti+4/(Al+3 + Fe+3) reveals an affinity with significant mantle input to the fluid system. Pristine and altered titanite domains have been successfully dated by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Reversely discordant apparent ages suggest interaction with fluids, which modified the Pb composition of the magmatic titanite. The oldest semi-concordant analyses of titanite cores indicate an age of approximately 2500 Ma, which we interpret as the minimum age of magmatic titanite crystallization. Narrow dark rims of titanite with considerably lower Th/U ratios form a more coherent group of analyses defining an upper concordia intercept age of 2345 ± 0.016 Ma, interpreted as the best estimate for the time of complete titanite resetting associated with the metasomatic event. The HT fluid system appears to have remained active into the Palaeoproterozoic. Confirmation by dating that the tested fluids belonged to the Archaean hydrothermal system gives us information about this system at the time, but the information that it worked at least until the Palaeoproterozoic provides additional valuable information about the hydrothermal systems during the Neoarchaean-Palaeoproterozoic transition. [Display omitted] • Sustained HT fluid of mantle-crust origin operating in the Neoarchaean granite • First Neoarchaean fluids system dating using pristine/altered titanite domains • Indication of the extension of the fluids activity timing to the Palaeoproterozoic • Unique and relevant processes in the Neoarchaean - Palaeoproterozoic transition [ABSTRACT FROM AUTHOR]