The effect of Ca-Tschermaks component on trace element partitioning between clinopyroxene and silicate melt

We have studied the influence of Ca-Tschermaks (Calcium Tschermaks or CaTs) content of clinopyroxene on the partitioning of trace elements between this phase and silicate melt at fixed temperature and pressure. Ion probe analyses of experiments carried out in the system Na₂O–CaO–MgO–Al₂O₃–SiO₂, at 0.1 MPa and 1218°C, produced crystal-melt partition coefficients (D) of 36 trace elements (Li, Cl, Sc, Ti, V, Cr, Fe, Co, Ge, Sr, Y, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta and W), for clinopyroxene compositions between 10 and 32 mol% CaTs. Partition coefficients for 2+ to 5+ cations show, for each charge, a near parabolic dependence of log D on ionic radius of the substituting cation, for partitioning into both the M1 and M2 sites of clinopyroxene. Fitting the results to the elastic strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal-melt partition coefficients from elastic moduli. Nature 372, 452–454] we obtain results for the strain-free partition coefficients of theoretical cations (D₀), with site radius r₀, and for the site's Young's Modulus (E).

In agreement with earlier data our results show that increasing ^ivAl concentration in cpx is matched by increasing D, E_M1, E_M2 and D₀ for tri-, tetra- and pentavalent cations. The degree of fractionation between chemically similar elements (i.e. Ta/Nb, Zr/Hf) also increases. In contrast, D values for mono-, di- and hexavalent cations decrease with increasing ^ivAl in the cpx. The large suite of trace elements used has allowed us to study the effects of cation charge on D₀, r₀ and E. We have found that D₀ and r₀ decrease with increasing cation charge, e.g. r₀=0.66 Å for 4+ cations and 0.59 Å for 5+ cations substituting into M1. Values of E_M1 and E_M2 increase with cation charge as well as with increasing ^ivAl content. The increase in E_M2 is linear and close to the trend set by Hazen and Finger [Hazen, R.M., Finger, L.W., 1979. Bulk modulus-volume relationship for cation–anion polyhedra. J. Geophys. Res. 84 (10) 6723–6728] for oxides. E_M1 values are much higher and do not fit the trend predicted by the Hazen and Finger relationship.     

New aromatic biomarkers and possible maturity indicators found in New Albany Shale extracts

Aromatic hydrocarbons from benzene extracts of New Albany Shale were characterized. A biomarker that has a molecular weight of 546 and a structural configuration consistent with that of an alkyl-aromatic hydrocarbon (C₄₀H₆₆) was tentatively identified. It was found that the relative concentrations of the biomarker are indicative of differing levels of thermal maturity of the shale organic matter. A 40-carbon bicyclic carotenoid (C₄₀H₄₈) is proposed as the geochemical precursor of this biomarker. Thermal maturity of the shale organic matter can also be differentiated by observing differences in “fingerprints” as obtained by field-ionization mass spectrometry on the aromatic hydrocarbon fraction. Using this technique, we found that the more mature shale samples from southeastern Illinois contain more low molecular weight extractable aromatic hydrocarbons and the less mature shale samples from northwestern Illinois contain more high molecular weight extractable aromatic hydrocarbons. It was demonstrated that field-ionization and tandem mass spectrometric techniques through fingerprint and individual compound identification, are useful for shale aromatic hydrocarbon fraction characterization and for thermal maturation interpretation.     

Modification of a Parametrization of Shallow Convection in the Grey Zone Using a Mesoscale Model

In current operational numerical weather prediction models, the effect of shallow convection is parametrized. The grey zone of shallow convection is found between the horizontal resolutions of mesoscale numerical models (2–3 km) and large-eddy simulations (10–100 m or finer). At these horizontal scales the shallow convection is to some extent explicitly resolved by the model. The shallow-convection parametrization is still needed, but has to be regulated according to the model horizontal resolution. Here the behaviour of the non-hydrostatic mesoscale numerical weather prediction model Application of Research to Operations at Mesoscale is examined in the grey zone and a new scale-adaptive surface closure of its shallow-convection parametrization, dependent on horizontal resolution, is defined based on large-eddy simulation. The new closure is tested on a series of numerical experiments and validated on a 15-day-long real case period. Its impact on the development of deep convection is examined in detail. The idealized simulations show promising results, as the mean profiles of the subgrid and resolved turbulence change in the desired way. Based on the real case tests our modification has a low impact on model performance, but is part of a set of upgrades of the current parametrization that is aimed to treat the shallow convection grey zone.     

The allocation of rights to public forests in Tasmania: a geographical critique

Change in spatial economies, industrial technologies and societal attitudes can make long-established systems of resource allocation inefficient. Through a detailed examination of the procedures by which publicly owned forest has been allocated in Tasmania, this paper illustrates spatial, economic and other inefficiencies that have become embedded in the concession system. Analysis shows that the long-term costs of transporting timber to processing sites could be significantly reduced by rationalization of concession boundaries. Recommendations are also made that would produce more efficient use of forest resources. Inter alia, the paper illustrates the vulnerability of peripheral economies to big business enterprises.     

Full waveform inversion of field sonar returns for a visco-acousticEarth; a comparison of linearized and fully nonlinear methods

The techniques of linearized least squares inversion (LLSI) and simulated annealing (SA) are both used to invert a series of synthetic and real normal-incidence, geo-acoustic sonar returns for estimates of impedance versus two-way travel time in the top several meters of ocean floor sediment. The objective is to determine the better (faster, more accurate) method for inverting this class of data. LLSI uses an over parameterized earth, i.e., one composed of layers whose thickness corresponds to a travel time equal to the sample interval. This makes the inverse problem quite large, but also makes it nearly linear. SA uses a more efficient parameterization, one whose layers have variable thickness as well as variable impedance. Because of the relatively narrow frequency band (~1 octave at 20 dB down from the peak) the time domain signal is oscillatory and inversion for layer thickness is nonlinear. Results show greater time efficiency in solving the large linear problem (LLSI) than in solving the small nonlinear problem (SA). However, in both cases almost all of the waveform energy was modeled, indicating that essentially all the information in the data had been successfully recovered. The inversions are applied to 10-20 kHz field data acquired offshore Florida, and several techniques are employed to enhance the effectiveness of each inversion method     

AIDS NORTH AND SOUTH: DIFFUSION PATTERNS OF A GLOBAL EPIDEMIC AND A RESEARCH AGENDA FOR GEOGRAPHERS *

Apart from the tragic certainty of death which accompanies AIDS everywhere, the means of its transmission, the spatial patterns of its diffusion, and the groups at highest risk of infection vary considerably among world regions. This paper reviews the disease and its transmission, then proposes three models of AIDS diffusion to assess the implications of the epidemic on various regions. AIDS North, of North America and western Europe, is urban based and primarily confined to homosexuals and IV drug abusers. AIDS South, in central Africa and the Caribbean, is spreading from cities into rural regions and affects primarily heterosexuals. The third, an AIDS North/South hybrid, is postulated as a model of diffusion of the disease in other Third World regions. The final section addresses the potential contribution of geographic research to policy-makers in attempting to cope with the diffusion of AIDS and in curbing the epidemic's advance.     

BiSON performance

Since 1981 we have been operating the Birmingham Solar-Oscillations Network (BiSON), a global network of resonant-scattering spectrometers, observing the low-l solar p modes. Here we discuss historical developments, culminating in the establishment of a 6-station network in 1992 September, and the subsequent performance of that network. The data record of each station from 1992 to 1994 has been analysed in terms of weather and equipment breakdowns. Our early experience suggests that the best long-term coverage possible with a 6-station network is limited in practice to about 80%, which falls short of previous predictions.     

Ferric iron in mantle-derived garnets

The oxidation state of a mantle assemblage may be defined by heterogeneous reactions between oxygen and iron-bearing minerals. In spinel lherzolites, the presence of Fe³⁺ in spinel allows use of the assemblage olivine-orthopyroxene-spinel to define f _{O 2} at fixed T and P. As a first step towards establishing an analogous reaction for garnet lherzolites, garnets from mantle-derived xenoliths from South Africa and the USSR have been analyzed with ⁵⁷Fe Mössbauer spectroscopy at 298 and 77K to determine Fe³⁺/Fe²⁺ and the coordination state of iron. Garnets from South African alkremites (pyrope+Mg-spinel) and eclogites, as well as garnet-spinel and low-temperature garnet lherzolites from both South Afica and the USSR, have Fe³⁺/Fe<0.07. In contrast, garnets from high-temperature garnet lherzolites from within the Kaapvaal craton of South Africa have Fe³⁺/Fe>0.10. Ferric iron is octahedrally coordinated, and ferrous iron is present in the dodecahedral site in all samples. The occurrence of significant Fe³⁺ in these garnets necessitates caution in the use of geothermometers and geobarometers that are applied to mantle samples. For example, the presence of 12% of the Fe as Fe³⁺ in garnets can increase temperatures calculated from existing Fe/Mg geothermometers by>200°C. The concomitant increase in pressures calculated from geobarometers that use the Al content in orthopyroxene coexisting with garnet are 10–15 kbar. Results of calculations based on heterogeneous equilibria between garnet, olivine, and pyroxene are consistent with the derivation of the peridotite samples from source regions that are relatively oxidized, between the f _{O 2} of the FMQ (quartz-fayalite-magnetite) buffer and that of the WM buffer. No samples yield values of f _{O 2} as reduced as IW (iron-wüstite buffer).