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.     

Comparison of source rock geochemistry of selected rocks from the Schei Point group and Ringnes formation, Sverdrup basin, arctic Canada

Organic-rich from the Schei Point group (middle to late Triassic in age) and the Ringnes formation (late Jurassic) from the Sverdrup basin of the Canadian arctic archipelago have been geochemically evaluated for source rock characterization. Most samples from the Schei Point group are organic-rich (> 2% TOC and are considered as immature to mature oil-prone source rocks [kerogen types I, I–II (IIA) and II (IIA)]. These kerogen types contain abundant AOM1, AOM2 and alginite (Tasmanales, Nostocopsis, Leiosphaeridia, acritarch and dinoflagellate) with variable amounts of vitrinite, inertinite and exinite. Samples from the Ringnes formation contain dominant vitrinite and inertinite with partially oxidized AOM2, alginite and exinite forming mostly immature to mature condensate- and gas-prone source rocks [kerogen type II–III (IIB), III and a few II (IIA)]. Schei Point samples contain higher bitumen extract, saturate hydrocarbons and saturate/ aromatic ratio than the Ringnes samples. Triterpane and sterane (dominant C₃₀) distribution patterns and stable carbon isotope of bitumen and kerogen suggest that the analyzed samples from the Schei Point group are at the onset of oil generation and contain a mixture of sapropelic (algal) and minor terrestrial humic organic matter. Sterane carbon number distributions in the Ringnes formation also suggest a mixed algal and terrestrial organic matter type. There are some variations in hopane carbon number distributions, but these are apparently a function of thermal maturity rather than significant genetic differences among samples. Pyrolysis-gas chromatography/mass spectrometry of the two samples with similar maturity shows that the Schei Point sample generates three times more pyrolyzate than the Ringnes sample. Both samples have a dominant aliphatic character, although the Ringnes sample contains phenol and an aromaticity that is higher than that of the Schei Point sample.     

Redetermination of the transformation enthalpies of the xanthoconite–proustite, pyrostilpnite–pyrargyrite and trechmannite–smithite phase transitions

 We report here refined values of the transformation enthalpy for xanthoconite to proustite (54.81 kJ/mol) and pyrostilpnite to pyrargyrite (40.32 kJ/mol). Additionally, the enthalpy for the transformation of trechmannite to smithite (5.82 kJ/mol) has been determined. The refinement was possible by taking into account a previously unknown dependence of electrochemical signals on the amount of substance undergoing the reduction process. Received December 21, 1995/Revised, accepted June 29, 1996     

ELNES spectroscopy of mixed Si coordination minerals

 Si K- and L-edge ELNES spectroscopy and multiple-scattering (MS) calculations are used to examine mixed Si coordination compounds varying in Si^VI:Si^IV ratio. As in previous studies, the edges are influenced mainly by silicon coordination (tetrahedral vs. octahedral), as supported by the MS calculations. We demonstrate two methods semi-quantitatively to extract the value of Si^VI/(Si^VI+Si^IV): (1) A linear relationship between the L_2,3-L₁ splitting and Si^VI/(Si^VI+Si^IV) is observed, (2) a fitting method based on the coaddition of reference tetrahedral and octahedral Si spectra is applied to both Si K- and L-edge ELNES spectra. Received: February 10, 1997 / Revised, accepted: May 23, 1997     

Analysis of DNAPL infiltration in a medium with a low-permeable lens

In this paper we study the infiltration of DNAPL in a porous medium containing a single low-permeable lens. Our aim is to determine whether or not DNAPL infiltrates into the lens. A key role is played by the capillary pressure: DNAPL cannot infiltrate into the lens unless the capillary pressure exceeds the entry pressure of the lens. In the model this is reflected by an interface condition, the extended capillary pressure condition. To derive analytical approximations we first consider a steady-state DNAPL plume in a homogeneous medium. This results in an estimate of the DNAPL plume width as a function of depth, and an asymptotic solution for small saturations. Assuming that the extent of the lens is much larger than the width of the unperturbed DNAPL plume in the homogeneous medium, we derive an explicit criterion for DNAPL infiltration into the lens in terms of a critical inflow rate. A numerical algorithm is presented in which the extended capillary pressure condition is incorporated. The numerical and analytical results show good qualitative agreement. This revised version was published online in August 2006 with corrections to the Cover Date.     

An auto-biographical approach to understanding migration: the case of Hong Kong emigrants

Summary This paper seeks to make a methodological contribution by evaluating the autobiographical approach and its application to migration research. The migration act is seen as a manifestation of an individual's identity. This is moulded by many social influences over an individual's lifecourse. The paper explores the realm of practical consciousness (Giddens 1984) using a biographical approach in an attempt to identify the values underpinning the intentions of professional emigrants from Hong Kong.