M. John M. Duke

Spectroscopy of the cation distribution in the schorlomite species of garnet

Abstract A homogeneous megacryst of schorlomite was investigated to determine the valence states of Fe and Ti and the crystallographic sites occupied by these elements. The chemical composition of the specimen was analyzed by electron microprobe, wet-chemical analysis, FTlR, and INAA. The results from X-ray absorption near-edge structure spectroscopy (XANES) are consistent with exclusively Ti4+ occupying the octahedral site only. The tetrahedral site is deficient in Si and the results of low-temperature 57Fe Mossbauer spectroscopy indicate that the remainder of the site is occupied by Fe3+ and substantial Fe2+. A spin-allowed intensified crystal-field transition of [4]Fe2+ is present in the near-infrared spectrum. The optical absorption spectrum is dominated by an intense band centered at 500 nm with a full width of 8000 cm-1 at half maximum peak height; this band is assigned to an Fe2+-Ti4+ intervalence charge transfer transition between ,[4]Fe2+ and [6]Ti. The cation site occupancies in this specimen of schorlomite can be expressed by the following formula: {Ca2.866Mg0.800Na0.038Mn0.019}Σ3.003 [Ti4+1.058Fe3+0.631 Al0.137Fe2+0.057 Mg0.055Zr0.039V3+0.014Mn0.013] Σ2.004 - (Si2.348Fe3+0.339Fe2+0.311 [4H]0.005)Σ3.003O12.

Dust is the dominant source of "heavy metals" to peat moss (Sphagnum fuscum) in the bogs of the Athabasca Bituminous Sands region of northern Alberta.

Sphagnum fuscum was collected from twenty-five ombrotrophic (rain-fed) peat bogs surrounding open pit mines and upgrading facilities of Athabasca Bituminous Sands (ABS) in northern Alberta (AB) in order to assess the extent of atmospheric contamination by trace elements. As a control, this moss species was also collected at a bog near Utikuma (UTK) in an undeveloped part of AB and 264km SW of the ABS region. For comparison, this moss was also collected in central AB, in the vicinity of the City of Edmonton which is approximately 500km to the south of the ABS region, from the Wagner Wetland which is 22km W of the City, from Seba Beach (ca. 90km W) and from Elk Island National Park (ca. 45km E). All of the moss samples were digested and trace elements concentrations determined using ICP-SMS at a commercial laboratory, with selected samples also analyzed using instrumental neutron activation analysis at the University of Alberta. The mosses from the ABS region yielded lower concentrations of Ag, As, Bi, Cd, Cu, Pb, Sb, Tl, and Zn compared to the moss from the Edmonton area. Concentrations of Ni and Mo in the mosses were comparable in these two regions, but V was more abundant in the ABS samples. Compared with the surface vegetation of eight peat cores collected in recent years from British Columbia, Ontario, Quebec and New Brunswick, the mean concentrations of Ag, As, Bi, Cd, Cu, Mo, Ni, Pb, Sb, Tl and Zn in the mosses from the ABS region are generally much lower. In fact, the concentrations of these trace elements in the samples from the ABS region are comparable to the corresponding values in forest moss from remote regions of central and northern Norway. Lithophile element concentrations (Ba, Be, Ga, Ge, Li, Sc, Th, Ti, Zr) explain most of the variation in trace metal concentrations in the moss samples. The mean concentrations of Th and Zr are greatest in the moss samples from the ABS region, reflecting dust inputs to the bogs from open pit mines, aggregate quarries, and gravel roads. Linear regressions of V, Ni, and Mo (elements enriched in bitumen) versus Sc (a conservative, lithophile element) show excellent correlations in the mosses from the ABS region, but this is true also of Ag, Pb, Sb and Tl: thus, most of the variation in the trace metal concentrations can be explained simply by the abundance of dust particles on the plants of this region. Unlike the moss samples from the ABS region and from UTK where Pb/Sc ratios resemble those of crustal rocks, the moss samples from the other regions studied yielded much greater Pb/Sc ratios implying significant anthropogenic Pb contributions at these other sites.

Evaluating the applicability of portable-XRF for the characterization of Hokkaido Obsidian sources: a comparison with INAA, ICP-MS and EPMA

Abstract As a result of the limited application of portable X-ray fluorescence (pXRF) in archaeological research in Japan it is necessary to compare this technique to proven, laboratory-based, analytical techniques. In this study instrumental neutron activation analysis, inductively-coupled plasma mass spectrometry, and electron probe microanalysis are used to validate pXRF and determine the overall suitability of this technique for archaeological obsidian provenance studies in Hokkaido, northern Japan. Furthermore, the results of this study are compared to previously published data to assess reproducibility and compatibility. This study demonstrates the reliability of pXRF for the rapid characterization of Hokkaido obsidian while contributing to the ongoing evaluation of the applicability of “off-the-shelf” pXRF to obsidian provenance research in archaeology.

Practical reactor production of 41Ar from argon clathrate

The radionuclide 41Ar has many ideal properties as a gas flow tracer. However, the modest cross-section of 40Ar for thermal neutron activation makes preparation of suitable activities of 41Ar technically difficult particularly for low flux reactors. Argon can however be trapped in a molecular complex called a clathrate that can then be irradiated. We prepared argon clathrate and explored its irradiation and stability characteristics. Argon clathrate can be used to provide gigabecquerel quantities of 41Ar even with low power reactors.

Uncertainty in analyte mass for samples containing small numbers of particles.

A sampling equation was derived that relates the standard deviation in analyte mass to the number of particles in the sample, the fractions of the different types of particles in the mixture and the masses and analyte concentrations of the individual particles. The equation, which is applicable to samples containing any number of particles, was verified by sampling and analysis of two cereal grain mixtures for manganese, potassium, chlorine and magnesium, and by Monte Carlo computer simulation. Comparison of the sampling precision of analyte mass with the analytical measurement precision was also studied, and it was shown that use of the equation allows the calculation of the minimum number of particles required to hold the sampling relative standard deviation to that of the analytical measurement.