Mössbauer studies of iron silicate spinel at high pressure

We have measured in situ Mössbauer transmission spectra of iron silicate spinel (γ-Fe₂SiO₄) in a diamond anvil cell at room temperature and pressures up to 16 GPa. The observed spectra show a doublet characteristic of the paramagnetic state. The isomer shift and quadrupole splitting at atmospheric pressure are 1.10 and 2.63 mm/s, respectively, which are smaller than those of fayalite (α-Fe₂SiO₄). Both the isomer shift and quadrupole splitting decrease linearly with pressure with slope of ?0.003(1) and ?0.020(1) mm/sec · GPa, respectively. This simple linear trend suggests that no electronic or polymorphic transitions occur under 16 GPa except for those due to the small and continuous changes of volume and local symmetry under pressure. On the basis of a crystalline field calculation, the negative pressure derivative of the quadrupole splitting is associated with a trend towards an ideal cubic symmetry of the oxygen sublattice.     

Sampling for Purgeable Organic Compounds Using Positive-Displacement Piston and Centrifugal Submersible Pumps: A Comparative Study

Positive-displacement piston pumps that minimize sample agitation have no apparent advantage over centrifugal submersible pumps when used to collect ground water samples for analysis of low concentrations of purge-able organic compounds. Analytical uncertainties inherent in laboratory environments appear to influence analytical results of low-concentration purgeable organic compound samples more than either pump type or sampling team. Centrifugal submersible pumps are at least equally efficient as positive-displacement piston pumps in the recovery of carbon tetrachloride, 1,1,1-trichloroethane, trichloroethylene, and chloroform after sampling and analytical influences are made constant.     

Cation ordering of orthopyroxenes from the Skaergaard Intrusion: implications for the subsolidus cooling rates and permeabilities

 We have determined the quenched cation ordering states of five orthopyroxene crystals collected from the marginal border group and the lower zone a and b of the Skaergaard intrusion, and modeled these data to retrieve their closure temperatures (T _c) of Fe–Mg ordering and cooling rates. According to existing thermal models for the Skaergaard pluton, conductive cooling dominated the high and low temperature regimes, which were separated by an intermediate temperature regime in which the cooling was controlled primarily by convective fluid circulation. The cooling rates retrieved from the quenched cation ordering states of the orthopyroxene crystals strictly apply to temperatures around the closure temperatures of the ordering states, ∼340–400^° C, which fall at the transition from convective to the lower temperature conductive cooling. The cooling rates obtained from the cation ordering states of orthopyroxene vary from ∼1 to 270 K/ka. These results agree well with a thermal model calculated using an assumed average permeability of 10^-12 cm² for the pluton, but not completely with a model calculated on the basis of an average permeability of 10^-13 cm², although both values produced shifts of δ¹⁸O that are comparable to those observed in the pluton. Received: 27 February 1995/Accepted: 20 July 1995     

Measurements of solar occulation: the error in a naive retrieval if the constituent's concentration changes

The stratospheric concentrations of many minor constituents change rapidly at sunrise or sunset. If this happens, there is an inherent error when retrieving the vertical profiles of the constituents from measurements of their absorption of sunlight. For retrievals of NO at sunset the error can be estimated from in-situ measurements alone, without appeal to a model of stratospheric photochemistry. Below 20 km this error can approach 100% so that the retrieved NO is zero. But at 40 km, and at 25 km when the absorption is strong and Lorentzian, it can be less than 20%. Precise calculations of the error, even if small, require model calculations of the sunset and sunrise changes. With a model, we have calculated the error for NO, NO₂, OH and ClO.     

Deriving rules from activity diary data: A learning algorithm and results of computer experiments

 Activity-based models consider travel as a derived demand from the activities households need to conduct in space and time. Over the last 15 years, computational or rule-based models of activity scheduling have gained increasing interest in time-geography and transportation research. This paper argues that a lack of techniques for deriving rules from empirical data hinders the further development of rule-based systems in this area. To overcome this problem, this paper develops and tests an algorithm for inductively deriving rules from activity-diary data. The decision table formalism is used to exhaustively represent the theoretically possible decision rules that individuals may use in sequencing a given set of activities. Actual activity patterns of individuals are supplied to the system as examples. In an incremental learning process, the system progressively improves on the selection of rules used for reproducing the examples. Computer experiments based on simulated data are performed to fine-tune rule selection and rule value update functions. The results suggest that the system is effective and fairly robust for parameter settings. It is concluded, therefore, that the proposed approach opens up possibilities to derive empirically tested rule-based models of activity scheduling. Follow-up research will be concerned with testing the system on empirical data. Received: 31 January 2001 / Accepted: 13 September 2001     

On the sensitivity of mesoscale models to surface-layer parameterization constants

The Colorado State University standard mesoscale model is used to evaluate the sensitivity of one-dimensional (1D) and two-dimensional (2D) fields to differences in surface-layer parameterization constants. Such differences reflect the range in the published values of the von Karman constant, Monin-Obukhov stability functions and the temperature roughness length at the surface. The sensitivity of 1D boundary-layer structure, and 2D sea-breeze intensity, is generally less than that found in published comparisons related to turbulence closure schemes generally.