Temporal Variations of Chlorinated Solvents in Abstraction Wells

Data obtained during an organic water quality survey of abstraction (pumping) wells in the Triassic Sandstone Aquifer of Birmingham (U.K.) indicate that there are important variations of chlorinated solvent concentrations with time. Short-term observation of solvent concentrations with elapsed pumping time indicates widely differing well responses; such observations are important in establishing good sampling protocols. Long-term monitoring indicates that solvent concentrations, particularly trichloroethene, are often stable with time. When large solvent variations do occur, these are shown to be due to the variation in the abstraction history of the well or significant migration of solvent plumes during the monitoring period. The latter effect is particularly exemplified by rising trends in 1,1,1-trichlroethane concentrations. The changes observed in solvent concentrations during long-term monitoring of the Birmingham Aquifer are slow to occur, but often large.     

Nickeliferous sulfides in xenoliths,olivine megacrysts and basaltic glass

The composition of olivine and nickeliferous sulfide inclusions from a selection of mafic and ultramafre rocks, xenoliths and megacrysts, including picritic basalts from Kilauea Volcano, Hawaii, kimberlite from Fayette County, Pennsylvania, and megacrysts from Mount Shasta, California are compared with the mean experimental value of the distribution coefficient for Ni/Fe exchange (K_D3=32). Only nine of the forty five olivipe/bulk-sulfide pairs investigated have compositions consistent with equilibration at high temperature, yielding calculated K_D3 values in the range 22 to 41. The remaining pairs have calculated K_D3 values which range from 0 to 19. Bulk-sulfides in disequilibrated assem-blages are consistently depleted in nickel and within both indivudual associations and individual petrographic sections they exhibit a wide variation in NiS content. The bulk copper contents of olivine-and groundmass-hosted sulfides from Kilauea Volcano range from 0.5 to 43 at%, and samples from the Kilauea Iki lava lake are more Fe-and Cu-rich and generally have lower K_D3 values than those from the eruption itself. As with magmatic Ni–Cu sulfide deposits, most nickeliferous sulfide inclusions in mantle-related rocks and xenoliths and in volcanic rocks do not have pristine early-magmatic bulk compositions, and it would seem to be premature to attribute these sulfides solely to either a mantle or an early-magnatic origin.     

Chemistry of alkali extraction of brown coals—I. Kinetics, characterisation and implications to coalification

Three Australian brown coals have been separated into humin and humic acid fractions and studied by high resolution solid state ¹³C NMR spectroscopy and Fourier transform IR spectroscopy. The aromatic rings of the humic acids are highly substituted showing that extensive cross linking must have occurred during formation from wood lignin and tannin. However, the humins contain more aliphatic carbon and hydrogen than the corresponding humic acids. This shows that little cross linking has occurred with other components of the brown coal such as resins, waxes cutin and algal detritus, and cross linking has not rendered the aromatics alkali insoluble. The kinetics of extraction are complex and not simple first order. This is reflected in the chemical composition of the humic acid which is extraction temperature dependent. We also observed that there is a conversion of aromatic carbon to aliphatic carbon and gas during extraction, probably by alkaline oxidation, resulting in ring opening. A range of suitable model compounds have been studied to confirm this finding. Such a mechanism may account for the modification of lignin in oxidising environments such as those occurring in the initial stages of coalification (lignite or brown coal formation) and in soils.     

Large-scale floodplain modelling

A two-dimensional horizontal finite element numerical model (RMA-2) was applied to a 24 km river channel-floodplain reach in West Germany. Initial results indicate that finite element schemes may successfully estimate inundation in large-scale floodplain applications. Potentially, the resulting detailed velocity vector distributions and identification of inundation zones throughout storm events could provide an insight into the present day sedimentary environment on the floodplain.     

Complete chemical analyses of metamorphic hornblendes: implications for normalizations,calculated H2O activities,and thermobarometry

Twenty-two hornblendes separated from amphibolites and granulites of the Grenville Orogen of Ontario have been quantitatively analyzed for major and minor elements by electron microprobe, for FeO/Fe₂O₃ by wet chemistry, and for H₂O by manometric measurement as H₂. Hornblende formulae were calculated on the basis of 24O+OH+Cl+F. Most samples are magnesio-hornblendes, ferroan pargasitic hornblendes and ferroan hastingsitic hornblendes, with weight fractions of Fe³⁺/(Fe²⁺+Fe³⁺) ranging from 0.15 to 0.50. An oxy-amphibole component of 0–25 mol%, with an average value of 17 mol%, is obtained for these complete analyses. When compared with structural formulae determined solely from microprobe data, normalization based on 13=Si+Ti+Al+Fe+Mn+Mg cations provides the best approximation to hornblende formulae calculated from the complete analyses. Less satisfactory agreement is obtained from a normalization scheme based on 15=Si+Ti+Al+Fe+Mn+Mg+Ca, while worst agreement is obtained from normalization to 23 oxygens assuming all Fe is Fe²⁺. No normalization scheme based on microprobe data alone consistently replicates the measured FeO, Fe₂O₃, and H₂O; accurate determination of these values requires complete chemical analysies. Ionic solution models previously have been proposed to evaluate the activity of Ca₂Mg₅Si₈ O₂₂(OH)₂(a _Trem) in hornblende for use in equilibria that constrain the activity of H₂O (a _{H 2}O) in igneous and metamorphic rocks. Application of ionic models to typical hornblendes produces low a _Trem (usually<0.01), consequetly yielding extremely low a _{H 2}O. If an oxy-amphibole component is present, the calculated a _Trem and H₂O is further reduced. An oxy-amphibole component of 25% reduces the calculated H₂O activity and that of any hydroxyl-amphibole component by 50% below that calculated with simplified assumptions regarding X _OH in the hydroxyl site (i.e., X _OH=1, or X _OH=1–X _Cl–X _f). Thus, methods of amphibole normalizations appear to have a substantial effect on calculated amphibole and H₂O activites. Before quantitative hornblende thermobarometry can be calibrated and applied, the amounts of FeO, Fe₂O₃ and H₂O must be measured in order to fully characterize hornblende solid solutions.Contribution No. 478 from the Mineralogical Laboratory, University of Michigan     

An equation of state for carbon dioxide valid from zero to extreme pressures

A new form of equation of state is described with application to carbon dioxide from 215 K to T>2000 K and from zero pressure to more than 10⁵ bar (10 GPa). The equation was calibrated using properties predicted by existing formulations at low to moderate PT conditions, original experimental PVT data at higher pressures, corresponding states comparisons at higher temperatures and using shock compression data at still higher PTs. Extensive comparisons illustrating the correlation of our new EOS with available phase equilibria and volumetric data are provided. Fugacities of carbon dioxide at high pressures and temperatures predicted using our EOS are in agreement with mineral equilibria calculated from internally consistent thermodynamic data for minerals.     

Hydrodynamic coefficients of a monolithic circular offshore structure

Expressions for both the rectilinear and rotational inertial and damping coefficients for a circular monolithic tower of uniform radius are derived. The analysis matches the fluid velocity, derived from potential theory, with the structural velocity in sway. That is, the motions of the tower are assumed to be in a vertical plane. The analysis is then applied to a tower composed of (lumped-mass) elements, where the expressions for the added-mass and damping coefficients are shown to be functions of wave number. The added-mass is shown to be a product of two wave systems: a travelling wave system, which is responsible for the radiation damping, and a standing wave system, called the evanescent system, which is attached to the structure. The added-mass of the evanescent system is negative for small wave numbers, while that of the travelling waves is positive. The negative sign simply means that the inertial force of the evanescent waves is 180° out of phase with that of the travelling system. Furthermore, it is shown that the contributions of the two wave systems to the total added-mass of the structure counteract each other, resulting in a total added-mass which varies gradually with the wave number. Finally, the analysis is applied to an experiment, and results of the analysis and the experiment are found to agree rather well.     

Response of jointed arches to earthquake excitation

An efficient method for accurately modelling the gradual opening and closing of joints in two-dimensional slabs and arches has been devised. The method is used in computing the earthquake response of an arch which is a representative horizontal cross-section of a concrete arch dam. Responses of the arch with and without joints are compared to assess the effect of joint opening. An extension to three-dimensional arch dams is proposed.