Analysis of Re, Au, Pd, Pt and Rh in NIST Glass Certified Reference Materials and Natural Basalt Glasses by Laser Ablation ICP-MS

A new technique for the in situ analysis of Re, Au, Pd, Pt and Rh in natural basalt glass by laser ablation (LA)-ICP-MS is described. The method involves external calibration against NIST SRM 612/613 or 614/615 glass certified reference materials, internal standardisation using Ca, and ablation with a 200 μm wide beam spot and a pulsed laser repetition rate of 50 Hz. Under these conditions, sensitivities for Re, Au, Pd, Pt and Rh analyte ions are ˜ 5000 to 100,000 cps/μg g^-1. This is sufficient to make measurements precise to ˜ 10% at the 2-10 μg g^-1 level, which is well within the range of concentrations expected in many basalts. For LA-ICP-MS calibration and a demonstration of the accuracy of the technique, concentrations of Re, Au, Pd, Pt and Rh in the NIST SRM 610/611 (˜ 1 to 50 μg g^-1), 612/613 (˜ 1 to 7 μg g^-1), 614/615 (˜ 0.2 to 2 μg g^-1) and 616/617 (˜ 0.004 to 2 μg g^-1) glasses were determined by solution-nebulisation (SN)-ICP-MS. Using the 612/613 or 614/615 glasses as calibration standards, LA-ICP-MS measurements of these elements in the other NIST glasses fell within ˜ 15% of those determined by SN-ICP-MS. Replicate LA-ICP-MS analyses of the 612/613 and 614/615 glasses indicate that, apart from certain anomalous domains, the glasses are homogeneous for Re, Au, Pd, Pt and Rh to better than 3.5%. Two LA-ICP-MS analyses of natural, island-arc basalt glasses exhibit large fractionations of Re, Au and Pd relative to Pt and Rh, compared to the relative abundances in the primitive mantle.     

The normal grain growth behaviour of nominally pure calcitic aggregates

The normal grain growth behaviour of four different, but all nominally pure, calcite powders (99%+ analytic grade calcite, 99.7% chalk, 99.97% crushed Iceland Spar, 99.95%+ chelometric grade calcite) has been investigated as a function of temperature (550, 600, 650, 700 °C) and confining pressure (100, 190 MPa) under both “dry” and hydrostatic (P _fluid = P _total) conditions. The initial particle size of both the analytic grade and chelometric grade calcite was about 5 μm, and that of the chalk was about 3 μm, while the experiments on the Iceland Spar were conducted on powders of three different initial particle sizes (3.4, 7.5, 38.5 μm). On each material, at each pressure/temperature condition 6 to 15 experiments, equally spaced in log time from 15 minutes to 50 days, were conducted. Under dry conditions all four materials recrystallized to aggregates which contained less than 2% porosity and which had a grain size of between 4 and 20 μm (depending on the initial particle size). Subsequently the aggregates coarsened by normal grain growth, with the kinetics of the growth process being controlled by the rate at which the grain boundaries could drag the residual pores with them as they migrated. Under nominally identical conditions both the mechanism and rates of pore drag differed greatly for the different materials, implying that this process is highly sensitive to trace solute impurity concentrations. This sensitivity renders the task of providing a systematic account of dry calcite grain growth kinetics highly problematic. Under hydrostatic conditions all the powders followed the same normal grain growth kinetics in which the growth process was rate-controlled by diffusion through the pore fluid on the grain boundaries. An activation enthalpy of 162.6 kJ mol⁻¹ and an activation volume of 34.35 cm³ mol⁻¹ was obtained for this process. Received: 23 May 1996 / Accepted: 8 July 1997     

Are open fractures necessarily aligned with maximum horizontal stress?

Fluid flow in fractured rock is an increasingly central issue in recovering water and hydrocarbon supplies and geothermal energy, in predicting flow of pollutants underground, in engineering structures, and in understanding large-scale crustal behaviour. Conventional wisdom assumes that fluids prefer to flow along fractures oriented parallel or nearly parallel to modern-day maximum horizontal compressive stress, or S_Hmax. The reasoning is that these fractures have the lowest normal stresses across them and therefore provide the least resistance to flow. For example, this view governs how geophysicists design and interpret seismic experiments to probe fracture fluid pathways in the deep subsurface. Contrary to these widely held views, here we use core, stress measurement, and fluid flow data to show that S_Hmax does not necessarily coincide with the direction of open natural fractures in the subsurface (>3 km depth). Consequently, in situ stress direction cannot be considered to predict or control the direction of maximum permeability in rock. Where effective stress is compressive and fractures are expected to be closed, chemical alteration dictates location of open conduits, either preserving or destroying fracture flow pathways no matter their orientation.     

Lithium isotopes in the system Qz-Ms-fluid:An experimental study

The fractionation of lithium isotopes among quartz, muscovite, and a chloride-bearing aqueous fluid has been investigated experimentally at 400°-500°C and 50-100 MPa. Experiments were performed for 15-60 days in cold seal vessels with natural mineral specimens. Lithium was introduced primarily through the fluid, which also contained KCl and HCl. In most runs, the fluid was prepared with the L-SVEC standard (δ⁷Li = 0) and was 1 M in total chloride with K/Li/H = 100/10/1. In two experiments, a ⁶Li spike was employed. The experiments demonstrate that quartz and muscovite are susceptible to pronounced, rapid shifts in Li isotopic composition by diffusion through interaction with a Li-bearing fluid, particularly at 500°C. At 500°C, fractionation factors were determined to be Δ_{quartz-aqueous} ≅ +8 to + 12‰ and Δ_{muscovite-aqueous} ≅ +18 to + 20‰. An intermineral fractionation factor is given by Δ_{muscovite-quartz} ≈ +9‰. At 400°C, the results suggest Δ_{quartz-aqueous} ≈ +4 to + 6‰. The study provides evidence of systematic fractionation in lithium isotopes at the temperatures of some magmatic processes, such as those associated with porphyry-type ore systems and pegmatites.     

The age,origin, and volcanological significance of the Y-5 ash layer in the Mediterranean

The Y-5 ash is the most widespread layer in deep-sea sediments from the eastern Mediterranean. This ash layer was previously correlated with the Citara-Serrara tuff on Ischia Island and dated at approximately 25,000 yr B.P. New data on the glass chemistry of the Y-5 ash and pyroclastic deposits from the Neopolitan volcanic province suggest that the layer is correlative with the large-volume Campanian ignimbrite and not with the deposit from Ischia Island. The volume of the Y-5 ash is approximately 65 km³ which is comparable in magnitude to the volume of the Campanian ignimbrite. An interpolated age of approximately 38,000 yr B.P. is estimated based on sedimentation rates derived from δ¹⁸O stratigraphy. There is a discrepancy between this estimate and previously reported radiocarbon ages which range from 24,000 to 35,000 yr B.P. We propose that the “Campanian tuff ash layer” should be adopted as the full stratigraphic name for the Y-5 ash. The deep-sea ash layer is divisible into two units in proximal localities, probably correlating with two major phases of the eruption: plinian and ignimbrite.     

Linking gold mineralization to regional-scale drivers of mineral systems using in situ U–Pb geochronology and pyrite LA-ICP-MS element mapping

Proterozoic orogens commonly host a range of hydrothermal ores that form in diverse tectonic settings at different times. However, the link between mineralization and the regional-scale tectonothermal evolution of orogens is usually not well understood, especially in areas subject to multiple hydrothermal events.Regional-scale drivers for mineral systems vary between the different classes of hydrothermal ore, but all involve an energy source and a fluid pathway to focus mineralizing fluids into the upper crust. The Mount Olympus gold deposit in the Proterozoic Capricorn Orogen of Western Australia, was regarded as an orogenic gold deposit that formed at ca. 1738 Ma during the assembly of Proterozoic Australia. However,the trace element chemistry of the pyrite crystals closely resembles those of the Carlin deposits of Nevada,with rims that display solid solution gold accompanied by elevated As, Cu, Sb, Hg, and Tl, surrounding gold-poor cores. New SHRIMP UeP b dating of xenotime intergrown with auriferous pyrite and ore-stage alteration minerals provided a weighted mean~(207) Pb*/~(206) Pb* date of 1769 ± 5 Ma, interpreted as the age of gold mineralization. This was followed by two discrete episodes of hydrothermal alteration at 1727 ± 7 Ma and 1673 ± 8 Ma. The three ages are linked to multiple reactivation of the crustal-scale Nanjilgardy Fault during repeated episodes of intracratonic reworking. The regional-scale drivers for Carlin-like gold mineralization at Mount Olympus are related to a change in tectonic regime during the final stages of the intracratonic 1820 -1770 Ma Capricorn Orogeny. Our results suggest that substantial sized Carlin-like gold deposits can form in an intracratonic setting during regional-scale crustal reworking.     

Use of Rhodamine water tracer in the marshland upwelling system

Rhodamine water tracer (RWT) was used to characterize the migration of waste water within the saline subsurface of a marshland upwelling system (MUS), which is an alternative on-site waste water treatment system for coastal areas. Field tracer studies were performed to investigate the fresh waste water plume movement within the saline ground water. Pore velocities were calculated using first detection times and ranged from 0.68 to 10.7 x 10(-4) cm/sec for the loamy sandy soil matrix present at the site. Use of RWT in the field also allowed determination of main and preferential flowpaths. One- and two-dimensional laboratory experiments were performed using silica sand to investigate the interactions of the organically rich waste water with RWT within the zone surrounding the point of injection (one-dimensional) and the impact of background salinity on plume movement (two-dimensional). The results from these studies were used to help explain the field data. One-dimensional breakthrough curves revealed retardation factors for the RWT in the waste water mixture of 1.73 to 1.90. These results were similar to other researchers, indicating little interaction between the waste water and RWT. Variations in pore water salinity (5, 15, 25, and 35 ppt) were found to have a significant effect on pore water velocities of the fresh water plume (two-dimensional), indicating the need to incorporate background salinities into the design process for MUS.