Spectroscopy of comet P/Schaumasse

Column density profiles for CN, C₃, C₂ and NH have been determined from a long-slit CCD spectrum of periodic comet P/Schaumasse (1992x). Comparisons of these profiles with Haser models indicate that the ratios of the CN, C₃ and C₂ production rates are typical for a short-period comet. Although the scale lengths for NH and its parent species are uncertain, the results indicate that the production rate for NH is much greater than for either C₂ or CN.     

SHRIMP U–Pb ages of diagenetic and hydrothermal xenotime from the Archaean Witwatersrand Supergroup of South Africa

SHRIMP dating of xenotime overgrowths on detrital zircon grains can constrain maximum durations since diagenesis and therefore provide minimum dates of sediment deposition. Thus, xenotime dating has significant economic application to Precambrian sediment-hosted ore deposits, such as Witwatersrand Au–U, for which there are no precise depositional ages. The growth history of xenotime in the Witwatersrand Supergroup is texturally complex, with several phases evident. The oldest authigenic xenotime ²⁰⁷Pb/²⁰⁶Pb age obtained in sandstone underlying the Vaal Reef is 2764 ± 5 Myr (1 σ), and most likely represents a mixture of diagenetic and hydrothermal growth. Nevertheless, this represents the oldest authigenic mineral age yet recorded in the sequence and provides a minimum age of deposition. Other xenotime data record a spread of ages that correspond to numerous post-diagenetic thermotectonic events (including a Ventersdorp event at ≈ 2720 Ma) up to the ≈2020 Ma Vredefort event.     

Revisiting the magnification of type Ia supernovae with SDSS

We cross-correlate the sample of type Ia supernovae from Riess A. G. et al. with the SDSS DR2 photometric galaxy catalogue. In contrast to recent work, we find no detectable correlation between supernova magnitude and galaxy overdensity on scales ranging between 1 and 10 arcmin. Our results are in accord with theoretical expectations for gravitational lensing of supernovae by large-scale structure. Future supernova surveys such as SNAP will be capable of detecting unambiguously the predicted lensing signal.     

The structure and dynamics of 2-dimensional fluids in swelling clays

The interlayer pores of swelling 2:1 clays provide an ideal 2-dimensional environment in which to study confined fluids. In this paper we discuss our understanding of the structure and dynamics of interlayer fluid species in expanded clays, based primarily on the outcome of recent molecular modelling and neutron scattering studies. Counterion solvation is compared with that measured in bulk solutions, and at a local level the cation-oxygen coordination is found to be remarkably similar in these two environments. However, for the monovalent ions the contribution to the first coordination shell from the clay surfaces increases with counterion radius. This gives rise to inner-sphere (surface) complexes in the case of potassium and caesium. In this context, the location of the negative clay surface charge (i.e. arising from octahedral or tetrahedral substitution) is also found to be of major importance. Divalent cations, such as calcium, eagerly solvate to form outer-sphere complexes. These complexes are able to pin adjacent clay layers together, and thereby prevent colloidal swelling. Confined water molecules form hydrogen bonds to each other and to the clays' surfaces. In this way their local environment relaxes to close to the bulk water structure within two molecular layers of the clay surface. Finally, we discuss the way in which the simple organic molecules methane, methanol and ethylene glycol behave in the interlayer region of hydrated clays. Quasi-elastic neutron scattering of isotopically labelled interlayer CH₃OD and (CH₂OD)₂ in deuterated clay allows us to measure the diffusion of the CH₃- and CH₂-groups in both clay and liquid environments. We find that in both the one-layer methanol solvates and the two-layer glycol solvates the diffusion of the most mobile organic molecules is close to that in the bulk solution.     

Method of Data Reduction and Uncertainty Estimation for Platinum-Group Element Data Using Inductively Coupled Plasma-Mass Spectrometry

A data reduction method is described for determining platinum-group element (PGE) abundances by inductively coupled plasma-mass spectrometry (ICP-MS) using external calibration or the method of standard addition. Gravimetric measurement of volumes, the analysis of reference materials and the use of procedural blanks were all used to minimise systematic errors. Internal standards were used to correct for instrument drift. A linear least squares regression model was used to calculate concentrations from drift-corrected counts per second (cps). Furthermore, mathematical manipulations also contribute to the uncertainty estimates of a procedure. Typical uncertainty estimate calculations for ICP-MS data manipulations involve: (1) Carrying standard deviations from the raw cps through the data reduction or (2) calculating a standard deviation from multiple final concentration calculations. It is demonstrated that method 2 may underestimate the uncertainty estimate of the calculated data. Methods 1 and 2 do not typically include an uncertainty estimate component from a regression model. As such models contribute to the uncertainty estimates affecting the calculated data, an uncertainty estimate component from the regression must be included in any final error calculations. Confidence intervals are used to account for uncertainty estimates from the regression model. These confidence intervals are simpler to calculate than uncertainty estimates from method 1, for example. The data reduction and uncertainty estimation method described here addresses problems of reporting PGE data from an article in the literature and addresses both precision and accuracy. The method can be applied to any analytical technique where drift corrections or regression models are used.     

Tracking recent recovery from eutrophication in a high arctic lake (Meretta Lake, Cornwallis Island, Nunavut, Canada) using fossil diatom assemblages

Meretta Lake (Resolute Bay, Cornwallis Island, Nunavut, Canada) is a high arctic lake that received raw sewage for almost 50 years from the Canadian Department of Transport Base. The lake was sampled from 1968–72 during the International Biological Programme, as part of the Char Lake Project. As the number of users at the Transport Base declined throughout the 1990s, so too did the lake's nutrient levels, and Meretta Lake is now classified as oligotrophic. A previous diatom-based paleolimnological study revealed marked species assemblage shifts coincident with sewage inputs beginning in the late 1940s; however, because the core was taken at a time when nutrient levels were still relatively high (i.e., 1993), the diatom record did not yet track any signs of recovery. In this present study, we examined fossil diatom assemblages from a sediment core taken in 2001. Our results indicate a shift to the pre-impact diatom assemblages in the most recent sediments, indicating that the paleolimnological record is tracking the decreased nutrient inputs to this high arctic lake, and confirms that no significant lags exist in these largely ice-covered lakes.     

A Reappraisal of Rb, Y, Zr, Pb and Th Values in Geochemical Reference Material BHVO-1

The geochemical reference material BHVO-1 was analysed by a variety of techniques over a six year period. These techniques included inductively coupled plasma-mass spectrometry and atomic emission spectroscopy (ICP-MS and ICP-AES, respectively), laser ablation ICP-MS and spark source mass spectroscopy. Inconsistencies between the published consensus values reported by Gladney and Roelandts (1988, Geostandards Newsletter) and the results of our study are noted for Rb, Y, Zr, Pb and Th. The values reported here for Rb, Y, Zr and Pb are generally lower, while Th is higher than the consensus value. This is not an analytical artefact unique to the University of Notre Dame ICP-MS facility, as most of the BHVO-1 analyses reported over the last ten to twenty years are in agreement with our results. We propose new consensus values for each of these elements as follows: Rb = 9.3 ± 0.2 μg g-1 (compared to 11 ± 2 μg g-1), Y = 24.4 ± 1.3 μg g-1 (compared to 27.6 ± 1.7 μg g-1), Zr = 172 ± 10 μg g-1 (compared to 179 ± 21 μg g-1), Pb = 2.2 ± 0.2 μg g-1 (compared to 2.6 ± 0.9 μg g-1) and Th = 1.22 ± 0.02 μg g-1 (compared to 1.08 ± 0.15 μg g-1).     

Surface structure effects on direct reduction of iron oxides by Shewanella oneidensis

The atomic and electronic structure of mineral surfaces affects many environmentally important processes such as adsorption phenomena. They are however rarely considered relevant to dissimilatory bacterial reduction of iron and manganese minerals. In this regard, surface area and thermodynamics are more commonly considered. Here we take a first step towards understanding the nature of the influence of mineral surface structure upon the rate of electron transfer from Shewanella oneidensis strain MR-1 outer membrane proteins to the mineral surface and the subsequent effect upon cell “activity.” Cell accumulation has been used as a proxy for cell activity at three iron oxide single crystal faces; hematite (001), magnetite (111) and magnetite (100). Clear differences in cell accumulation at, and release from the surfaces are observed, with significantly more cells accumulating at hematite (001) compared to either magnetite face whilst relatively more cells are released into the overlying aqueous phase from the two magnetite faces than hematite. Modeling of the electron transfer process to the different mineral surfaces from a decaheme (protoporphyrin rings containing a central hexacoordinate iron atom), outer membrane-bound cytochrome of S. oneidensis has been accomplished by employing both Marcus and ab initio density functional theories. The resultant model of electron transfer to the three oxide faces predicts that over the entire range of expected electron transfer distances the highest electron transfer rates occur at the hematite (001) surface, mirroring the observed cell accumulation data. Electron transfer rates to either of the two magnetite surfaces are slower, with magnetite (111) slower than hematite (001) by approximately two orders of magnitude. A lack of knowledge regarding the structural details of the heme-mineral interface, especially in regards to atomic distances and relative orientations of hemes and surface iron atoms and the conformation of the protein envelope, precludes a more thorough analysis. However, the results of the modeling concur with the empirical observation that mineral surface structure has a clear influence on mineral surface-associated cell activity. Thus surface structure effects must be accounted for in future studies of cell-mineral interactions.     

Characterisation of Memory Effects and Development of an Effective Wash Protocol for the Measurement of Petrogenetically Critical Trace Elements in Geological Samples by ICP-MS

High sensitivity and low detection limits would seem to make inductively coupled plasma-mass spectrometry (ICP-MS) an ideal analytical tool for determining low (sub-μg g^-1) concentrations of the rare earth elements (REE), Y, Zr, Nb, Hf, Ta, Sn, W, Mo, Th, and U in most mafic materials (e.g. Hall and Plant 1992). However, the generally "sticky" nature exhibited by most of the high field strength elements (HFSEs: Zr, Nb, Hf, Ta, Th and U) as well as Sn, W and Mo can result in spurious results due to memory effects transmitted between unknowns and calibration samples. This, in turn, can seriously compromise the sensitivity, accuracy, and precision of ICP-MS analyses for these elements in geological materials. Data resulting from analyses with poor accuracy and precision can lead to erroneous interpretation and misleading petrogenetic modelling. To resolve this problem, we propose an effective wash protocol for these critical trace elements.