A theoretical investigation of the relative stabilities of Fe-free clinozoisite and orthozoisite

 The relative stabilities of orthozoisite, Ca₂Al₃[O|OH|Si₂O₇|SiO₄], space group Pnma, and the monoclinic polymorph, clinozoisite, space group P2₁/m, have been investigated using calculations based on density functional theory. It is found that orthozoisite is more stable than clinozoisite by about 1 kJ mol⁻¹ at zero pressure in the athermal limit. The bulk moduli of the two polymorphs have been calculated to be B_ortho=117.5(1.7) GPa and B_clino=136(4) GPa. Received: 20 March 2000 / Accepted: 26 February 2001     

Thermodynamic properties of MgSiO3 perovskite derived from large scale molecular dynamics simulations

A molecular dynamics simulation study of MgSiO₃ has been performed using a large sample containing 4096 unit cells. Thermodynamic properties have been extracted using a semiclassical approximation to the correct quantum mechanical treatment, using the calculated density of states and the quantum harmonic formalism for thermodynamic functions. Simulations performed at different temperatures and volumes have given an estimate of the relative contributions due to thermal expansion (quasi-harmonic effects) and direct anharmonic interactions. Comparison of results for mean square atomic displacements with results on smaller samples have shown the limitations of smaller sample sizes.     

Inter-laboratory calibration of low-field magnetic and anhysteretic susceptibility measurements

Inter-laboratory and absolute calibrations of rock magnetic parameters are fundamental for grounding a rock magnetic database and for semi-quantitative estimates about the magnetic mineral assemblage of a natural sample. Even a dimensionless ratio, such as anhysteretic susceptibility normalized by magnetic susceptibility (K_a/K) may be biased by improper calibration of one or both of the two instruments used to measure K_a and K. In addition, the intensity of the anhysteretic remanent magnetization (ARM) of a given sample depends on the experimental process by which the remanence is imparted. We report an inter-laboratory calibration of these two key parameters, using two sets of artificial reference samples: a paramagnetic rare earth salt, Gd₂O₃ and a commercial “pozzolanico” cement containing oxidized magnetite with grain size of less than 0.1 μm according to hysteresis properties. Using Gd₂O₃ the 10 Kappabridges magnetic susceptibility meters (AGICO KLY-2 or KLY-3 models) tested prove to be cross-calibrated to within 1%. On the other hand, Kappabridges provide a low-field susceptibility value that is ca. 6% lower than the tabulated value for Gd₂O₃, while average high-field susceptibility values measured on a range of instruments are indistinguishable from the tabulated value. Therefore, we suggest that Kappabridge values should be multiplied by 1.06 to achieve absolute calibration. Bartington Instruments magnetic susceptibility meters with MS2B sensors produce values that are 2-13% lower than Kappabridge values, with a strong dependence on sample centering within the sensor. The K_a/K ratio of ca. 11, originally obtained on discrete cement samples with a 2G Enterprises superconducting rock magnetometer and a KLY-2, is consistent with reference parameters for magnetites of grain size <0.1 μm. On the other hand, K_a values from a 2G Enterprises magnetometer and K values from a Bartington Instruments MS2C loop sensor for u-channel and discrete cement samples, will produce average K_a/K values that are unrealistically high if not properly corrected for the nominal volume detected by the sensors for these instruments. Inter-laboratory measurements of K and K_a for standard paleomagnetic plastic cubes filled with cement indicate remarkable differences in the intensity of the newly produced ARMs (with a standard deviation of ca. 21%), that are significantly larger than the differences observed from the calibration of the different magnetometers employed in each laboratory. Differences in the alternating field decay rate are likely the major source of these variations, but cannot account for all the observed variability. With such large variations in experimental conditions, classical interpretation of a “King plot” of K_a versus K would imply significant differences in the determination of grain size of magnetite particles on the same material.     

Ground-Based and Airborne Measurements of Nonmethane Hydrocarbons in BERLIOZ: Analysis and Selected Results

During the Berlin Ozone Experiment BERLIOZ in July–August 1998 quasi-continuous measurements ofC₂–C₁₂ nonmethane hydrocarbons (NMHCs) were carried out at 10 sites in and around the city of Berlin using on-line gas-chromatographic systems (GCs) with a temporal resolution of 20–120 minutes. Additional airborne NMHCmeasurements were made using canister sampling on three aircraft and an on-line GC system on a fourth aircraft. The ground based data are analyzed to characterize the different sites and to identify the influence of emissions from Berlin on its surroundings. Benzene mixing ratios at the 4 rural sites were rather low (<0.5 ppbv). Berlin (and the surrounding highway ring) was identified as the main source of anthropogenic NMHCs at Eichstädt and Blossin, whilst other sources were important at the furthermost site Menz. The median toluene/benzene concentration ratio in Berlin was 2.3 ppbv/ppbv, agreeing well with measurements in other German cities. As expected, the ratios at the background sites decreased with increasing distance to Berlin and were usually around one or below. On 20 and 21 July, the three northwesterly sites were situated downwind of Berlin and thus were influenced by its emissions. Considering the distance between the sites and the windspeed, the city plume was observed at reasonable time scales, showing decreasing toluene/benzene ratios of 2.3, 1.6 and 1.3 with increasing distance from Berlin. Isoprene was the only biogenic NMHC measured at BERLIOZ. It was themost abundant compound at the background sites on the hotter days, dominating the local NMHC reactivity with averaged contributions to the total OH loss rate of 51% and 70% at Pabstthum and Blossin, respectively. Emissionratios (relative to CO and to the sum of analysed NMHCs) were derived from airborne measurements. The comparison with an emission inventory suggests traffic-related emissions to be the predominating source of the considered hydrocarbon species. Problems were identified with the emission inventory for propane, ethene and pentanes.     

Palynological and sequence stratigraphic analysis of the Napo Group in the Pungarayacu 30 well, Sub-Andean Zone, Ecuador

The study of palynomorphs and calcareous nannofossils from the Albian–Campanian Napo Group in the Pungarayacu 30 well in the Subandean Zone of Ecuador has led to a new biostratigraphic framework revealing the existence of several hiatuses for this area. The palynological and palynofacies data are used together with other fossils and lithological evidence to define a sequence stratigraphic framework. The distribution of palynomorphs and palynofacies indicates a strong terrestrial input for the lower part of the Napo Group (Napo Basal and Lower Napo formations). In the upper part (Middle and Upper Napo formations), terrestrial input is reduced and a restricted marine environment with several dysoxic–anoxic intervals can be inferred. The hydrocarbons present in the well studied have traditionally been regarded as locally sourced. However, several lines of evidence (TAS, Tmax and VR) prove the immature stage of the source rock in this borehole as well as in a larger area.     

Crystal field transitions in Co2[Al4Si5]O18 cordierite and CoAl2O4 spinel determined by neutron spectroscopy

Inelastic magnetic neutron scattering has been used to determine the energy of the ⁴ A ₂→⁴ T ₂ transition in CoAl₂O₄ spinel and the δ₁ transition in Co₂[Al₄Si₅]O₁₈ cordierite. The observed crystal field splitting in Co-spinel is 485 meV (3900 cm⁻¹), which corresponds to a crystal field stabilization energy of 56.2 kJmol⁻¹. The transition energy of the δ₁ transition in Co-cordierite has been determined to be 21 meV (170 cm⁻¹). The present data demonstrate that magnetic neutron scattering can be used to measure crystal field transitions at energies of interest in the study of 3d-containing silicates. It may be used to measure transition energies when the use of optical spectroscopy is inappropriate. Received: 30 January 1997 / Accepted: 5 July 1997     

Determination of radionuclides in water at uranium mining remediation – a comparison of analytical methods

The corporate purpose of Wismut GmbH is to decommission its former mining holdings and to rehabilitate the landscape and the environment. Sample taking and analysing the value of contaminants are necessary steps for the remediation of waste rock piles, the recycling of contaminated areas, controlled flooding of uranium mines. Main emphasis lies on the determination of heavy metals and radionuclides of natural decay chains of U‐238 and U‐235. Yearly about 60 000…70 000 determinations of radionuclides in waters were done. Facing this high output of determinations it is a permanent task for laboratory and quality management to ask: Are the results of different methods comparable to each other? Is there a preferred analytical technology? Which matrix influences exist? and What about the analytical costs? Answers to these important questions are given in this report. Summarizing our investigations done in the last few years it is possible to say that – by using different analytical methods the results of radionuclides in water samples (surface or groundwater) are comparable, – a not negligible influence of Ra‐223, Ra‐224 and Ra‐228 may exist by using the DIN 38404 C18 method to determine Ra‐226, – a preferred method cannot be defined, – the choice of the analytical method should include analytical questions (the sample matrix, the occurrence of other disturbing radionuclides, the necessary detection limit) and economical questions (costs, other parameters to be determined).