Raman and infrared spectroscopic study of turquoise minerals

Raman and infrared spectra of three well-defined turquoise samples, CuAl6(PO4)4(OH)8·4H2O, from Lavender Pit, Bisbee, Cochise county, Arizona; Kouroudaiko mine, Faleme river, Senegal and Lynch Station, Virginia were studied, interpreted and compared. Observed Raman and infrared bands were assigned to the stretching and bending vibrations of phosphate tetrahedra, water molecules and hydroxyl ions. Approximate O–H⋯O hydrogen bond lengths were inferred from the Raman and infrared spectra. No Raman and infrared bands attributable to the stretching and bending vibrations of (PO3OH)2− units were observed.

Characteristics and alteration origins of matrix minerals in volcaniclastic kimberlite of the Muskox pipe (Nunavut, Canada)

The matrix of volcaniclastic kimberlite (VK) from the Muskox pipe (Northern Slave Province, Nunavut, Canada) is interpreted to represent an overprint of an original clastic matrix. Muskox VK is subdivided into three different matrix mineral assemblages that reflect differences in the proportions of original primary matrix constituents, temperature of formation and nature of the altering fluids. Using whole rock X-ray fluorescence (XRF), whole rock X-ray diffraction (XRD), microprobe analyses, back-scatter electron (BSE) imaging, petrography and core logging, we find that most matrix minerals (serpentine, phlogopite, chlorite, saponite, monticellite, Fe-Ti oxides and calcite) lack either primary igneous or primary clastic textures. The mineralogy and textures are most consistent with formation through alteration overprinting of an original clastic matrix that form by retrograde reactions as the deposit cools, or, in the case of calcite, by precipitation from Ca-bearing fluids into a secondary porosity. The first mineral assemblage consists largely of serpentine, phlogopite, calcite, Fe-Ti oxides and monticellite and occurs in VK with relatively fresh framework clasts. Alteration reactions, driven by deuteric fluids derived from the juvenile constituents, promote the crystallisation of minerals that indicate relatively high temperatures of formation (> 400 °C). Lower-temperature minerals are not present because permeability was occluded before the deposit cooled to low temperatures, thus shielding the facies from further interaction with fluids. The other two matrix mineral assemblages consist largely of serpentine, phlogopite, calcite, +/- diopside, and +/- chlorite. They form in VK that contains more country rock, which may have caused the deposit to be cooler upon emplacement. Most framework components are completely altered, suggesting that larger volumes of fluids drove the alteration reactions. These fluids were likely of meteoric provenance and became heated by the volcaniclastic debris when they percolated into the VK infill. Most alteration reactions ceased at temperatures > 200 °C, as indicated by the absence or paucity of lower-temperature phases in most samples, such as saponite. Recognition that Muskox VK contains an original clastic matrix is a necessary first step for evaluating the textural configuration, which is important for reconstructing the physical processes responsible for the formation of the deposit.

Geochronological (U–Pb, U–Th–total Pb, Sm–Nd) and geochemical (REE, 87Sr/86Sr, δ18O, δ13C) tracing of intraplate tectonism and associated fluid flow in the Warburton Basin, Australia

The Warburton Basin of central Australia has experienced a complex tectonic and fluid-flow history, resulting in the formation of various authigenic minerals. Geochemical and geochronological analyses were undertaken on vein carbonates from core samples of clastic sediments. Results were then integrated with zircon U–Pb dating and uraninite U–Th–total Pb dating from the underlying granite. Stable and radiogenic isotopes (δ18O, Sr and εNd), as well as trace element data of carbonate veins indicate that >200 °C basinal fluids of evolved meteoric origin circulated through the Warburton Basin. Almost coincidental ages of these carbonates (Sm–Nd; 432 ± 12 Ma) with primary zircon (421 ± 3.8 Ma) and uraninite (407 ± 16 Ma) ages from the granitic intrusion point towards a substantial period of active tectonism and an elevated thermal regime during the mid Silurian. We hypothesise that such a thermal regime may have resulted from extensional tectonism and concomitant magmatic activity following regional orogenesis. This study shows that the combined application of geochemical and geochronological analyses of both primary and secondary species may constrain the timing of tectonomagmatic events and associated fluid flow in intraplate sedimentary basins. Furthermore, this work suggests that the Sm–Nd-isotopic system is surprisingly robust and can record geologically meaningful age data from hydrothermal mineral species.

Postglacial Early Permian (late Sakmarian-early Artinskian) shallow-marine carbonate deposition along a 2000 km transect from Timor to west Australia

Late Sakmarian to early Artinskian (Early Permian) carbonate deposition was widespread in the marine intracratonic rift basins that extended into the interior of Eastern Gondwana from Timor in the north to the northern Perth Basin in the south. These basins spanned about 20° of paleolatitude (approximately 35°S to 55°S). This study describes the type section of the Maubisse Limestone in Timor-Leste, and compares this unit with carbonate sections in the Canning Basin (Nura Nura Member of the Poole Sandstone), the Southern Carnarvon Basin (Callytharra Formation) and the northern Perth Basin (Fossil Cliff Member of the Holmwood Shale). The carbonate units have no glacial influence and formed part of a major depositional cycle that, in the southern basins, overlies glacially influenced strata and lies a short distance below mudstone containing marine fossils and scattered dropstones (perhaps indicative of sea ice). In the south marine conditions became more restricted and were replaced by coal measures at the top of the depositional sequence. In the north, the carbonate deposits are possibly bryozoan–crinoidal mounds; whereas in the southern basins they form laterally continuous relatively thin beds, deposited on a very low-gradient seafloor, at the tops of shale–limestone parasequences that thicken upward in parasequence sets. All marine deposition within the sequence took place under very shallow (inner neritic) conditions, and the limestones have similar grain composition. Bryozoan and crinoidal debris dominate the grain assemblages and brachiopod shell fragments, foraminifera and ostracod valves are usually common. Tubiphytes ranged as far south as the Southern Carnarvon Basin, albeit rarely, but is more common to the north. Gastropod and bivalve shell debris, echinoid spines, solitary rugose corals and trilobite carapace elements are rare. The uniformity of the grain assemblage and the lack of tropical elements such as larger fusulinid foraminifera, colonial corals or dasycladacean algae indicate temperate marine conditions with only a small increase in temperature to the north. The depositional cycle containing the studied carbonate deposits represents a warmer phase than the preceding glacially influenced Asselian to early Sakmarian interval and the subsequent cool phase of the “mid” Artinskian that is followed by significant warming during the late Artinskian–early Kungurian. The timing of cooler and warmer intervals in the west Australian basins seems out-of-phase with the eastern Australian succession, but this may be a problem of chronostratigraphic miscorrelation due to endemic faunas and palynofloras.

Inhibition by poly(acrylic acid) and morphological changes in calcium carbonate and calcium carbonate/calcium sulfate crystallization on silica fibers

An intrinsic exposed core optical fiber sensor (IECOFS) made from fused silica was used to monitor the crystallization of calcium carbonate (CaCO3) and CaCO3/calcium sulfate (CaSO4) composite at 100 and 120 °C in the absence and presence of low-molar-mass (Mn ≤ 2000) poly(acrylic acid) (PAA) with different end groups. The IECOFS responded only to deposition and growth processes on the fiber surface rather than changes occurring in the bulk of the solution. Hexyl isobutyrate-terminated PAA (Mn = 1400) and hexadecyl isobutyrate-terminated PAA (Mn = 1700) were the most effective species in preventing CaCO3 deposition. Phase transformation from vaterite to aragonite/calcite decreased with increasing hydrophobicity of the PAA end group. Low-molar-mass PAA at 10 ppm showed very significant inhibition of CaCO3/CaSO4 composite formation for all end groups investigated.