OH incorporation in nearly pure MgAl2O4 natural and synthetic spinels

Four nearly pure MgAl₂O₄ spinels, of both natural and synthetic occurrence, have been studied by means of X-ray single crystal diffraction and FTIR spectroscopy in order to detect their potential OH content. Absorption bands that can be assigned to OH incorporated in the spinel structure were only observed in spectra of a non-stoichiometric synthetic sample. The absorption intensity of two bands occurring at 3350 and 3548 cm⁻¹ indicate an OH content of 90 ppm H₂O. Based on correlations of OH vibrational frequencies and O-H?O distances, the observed absorption bands correspond to O-H?O distances of 2.77 and 2.99 Å, respectively, which is close to the values obtained by the structure refinements for ^VIO-O_unsh (2.825 Å) and ^IVO-O (3.001 Å). This indicates that one probable local position for hydrogen incorporation is the oxygens coordinating a vacant tetrahedral site. The present spectra demonstrate that the detection limit for OH in Fe-free spinels is in the range 10-20 ppm H₂O. However, at appreciable Fe²⁺ levels, the detection of OH bands becomes hampered due to overlap with strong absorption bands caused by electronic d-d transitions in Fe²⁺ in the tetrahedral position.     

The dynamics of wave induced ship motions in shallow water

The analytical method developed by Svendsen (1968) for a forced heave motion is extended to the general problem of wave induced heave, roll and sway motions of a long ship at a depth of water which is only slightly larger than the draught of the ship. This corresponds, for example, to the situation of a fully loaded ship in a harbour area.After linearization of the problem, the water motion is considered for each of the three individual motions and for the wave reflection-transmission problem for a fixed ship. The ensuing results for the forces on the ship are then synthesized to form the equations of motion, which are presented with all coefficients given, including mooring forces.Analytical and numerical results are given for the three components of motion, for the associated resonance frequencies, and for the hydrodynamic masses and moments of inertia. Finally, the assumptions used are analyzed and evaluated by comparison with measurements and with other results for a special case.     

4-tert-octylphenol and 17beta-estradiol applied by feeding to flounder Platichthys flesus: induction of vitellogenin and accumulation in tissues

In order to simulate a possible natural administration route of xenoestrogens male flounder Platichthys flesus were exposed via the diet to the alkylphenol 4-tert-octylphenol. Treatment with 4-tert-octylphenol (10, 50 and 100 mg OP kg(-1) BW) or 17beta-estradiol (0.05 mg kg(-1) BW) every second day during a period of 11 days resulted in a significant increase in plasma vitellogenin (Vtg) concentrations. The induction of Vtg was greatest in the fish receiving 50 mg OP kg-' BW. A significant accumulation of 4-tert-octylphenol was found in liver and muscle tissue of the OP treated groups. The tissue concentrations of 4-tert-octylphenol and the plasma vitellogenin concentration were positively correlated. The results show that 4-tert-octylphenol accumulates in liver and muscles of flounder P. flesus, and exerts estrogenic effects such as vitellogenin induction.     

Parameter sensitivity of three Kalman filter schemes for assimilation of water levels in shelf sea models

In applications of data assimilation algorithms, a number of poorly known assimilation parameters usually need to be specified. Hence, the documented success of data assimilation methodologies must rely on a moderate sensitivity to these parameters. This contribution presents a parameter sensitivity study of three well known Kalman filter approaches for the assimilation of water levels in a three dimensional hydrodynamic modelling system. The filters considered are the ensemble Kalman filter (EnKF), the reduced rank square root Kalman filter (RRSQRT) and the steady Kalman filter. A sensitivity analysis of key parameters in the schemes is undertaken for a setup in an idealised bay. The sensitivity of the resulting root mean square error (RMSE) is shown to be low to moderate. Hence the schemes are robust within an acceptable range and their application even with misspecified parameters is to be encouraged in this perspective. However, the predicted uncertainty of the assimilation results are sensitive to the parameters and hence must be applied with care. The sensitivity study further demonstrates the effectiveness of the steady Kalman filter in the given system as well as the great impact of assimilating even very few measurements.     

The petroleum generation potential and effective oil window of humic coals related to coal composition and age

A worldwide data set of more than 500 humic coals from the major coal-forming geological periods has been used to analyse the evolution in the remaining (Hydrogen Index, HI) and total (Quality Index, QI) generation potentials with increasing thermal maturity and the ‘effective oil window’ (‘oil expulsion window’). All samples describe HI and QI bands that are broad at low maturities and that gradually narrow with increasing maturity. The oil generation potential is completely exhausted at a vitrinite reflectance of 2.0–2.2%R_o or T_max of 500–510 °C. The initial large variation in the generation potential is related to the original depositional conditions, particularly the degree of marine influence and the formation of hydrogen-enriched vitrinite, as suggested by increased sulphur and hydrogen contents. During initial thermal maturation the HI increases to a maximum value, HI_max. Similarly, QI increases to a maximum value, QI_max. This increase in HI and QI is related to the formation of an additional generation potential in the coal structure. The decline in QI with further maturation is indicating onset of initial oil expulsion, which precedes efficient expulsion. Liquid petroleum generation from humic coals is thus a complex, three-phase process: (i) onset of petroleum generation, (ii) petroleum build-up in the coal, and (iii) initial oil expulsion followed by efficient oil expulsion (corresponding to the effective oil window). Efficient oil expulsion is indicated by a decline in the Bitumen Index (BI) when plotted against vitrinite reflectance or T_max. This means that in humic coals the vitrinite reflectance or T_max values at which onset of petroleum generation occurs cannot be used to establish the start of the effective oil window. The start of the effective oil window occurs within the vitrinite reflectance range 0.85–1.05%R_o or T_max range 440–455 °C and the oil window extends to 1.5–2.0%R_o or 470–510 °C. For general use, an effective oil window is proposed to occur from 0.85 to 1.7%R_o or from 440 to 490 °C. Specific ranges for HI_max and the effective oil window can be defined for Cenozoic, Jurassic, Permian, and Carboniferous coals. Cenozoic coals reach the highest HI_max values (220–370 mg HC/g TOC), and for the most oil-prone Cenozoic coals the effective oil window may possibly range from 0.65 to 2.0%R_o or 430 to 510 °C. In contrast, the most oil-prone Jurassic, Permian and Carboniferous coals reach the expulsion threshold at a vitrinite reflectance of 0.85–0.9%R_o or T_max of 440–445 °C.     

Small-Mammal Data on Early and Middle Holocene Climates and Biotic Communities in the Bonneville Basin, USA

Archaeological investigations in Camels Back Cave, western Utah, recovered a series of small-mammal bone assemblages from stratified deposits dating between ca. 12,000 and 500 ¹⁴C yr B.P. The cave's early Holocene fauna includes a number of species adapted to montane or mesic habitats containing grasses and/or sagebrush (e.g., Lepus townsendii, Marmota flaviventris, Reithrodontomys megalotis, and Brachylagus idahoensis) which suggest that the region was relatively cool and moist until after 8800 ¹⁴C yr B.P. Between ca. 8600 and 8100 ¹⁴C yr B.P. these mammals became locally extinct, taxonomic diversity declined, and there was an increase in species well-adapted to xeric, low-elevation habitats, including ground squirrels, Lepus californicus and Neotoma lepida. The early small-mammal record from Camels Back Cave is similar to the 11,300–6000 ¹⁴C yr B.P. mammalian sequence from Homestead Cave, northwestern Utah, and provides corroborative data on Bonneville Basin paleoenvironments and mammalian responses to middle Holocene desertification.     

Methodology for construction, calibration and validation of a national hydrological model for Denmark

An integrated groundwater/surface water hydrological model with a 1 km² grid has been constructed for Denmark covering 43,000 km². The model is composed of a relatively simple root zone component for estimating the net precipitation, a comprehensive three-dimensional groundwater component for estimating recharge to and hydraulic heads in different geological layers, and a river component for streamflow routing and calculating stream–aquifer interaction. The model was constructed on the basis of the MIKE SHE code and by utilising comprehensive national databases on geology, soil, topography, river systems, climate and hydrology. The present paper describes the modelling process for the 7330 km² island of Sjælland with emphasis on the problems experienced in combining the classical paradigms of groundwater modelling, such as inverse modelling of steady-state conditions, and catchment modelling, focussing on dynamic conditions and discharge simulation. Three model versions with different assumptions on input data and parameter values were required until the performance of the final, according to pre-defined accuracy criteria, model was evaluated as being satisfactory. The paper highlights the methodological issues related to establishment of performance criteria, parameterisation and assessment of parameter values from field data, calibration and validation test schemes. Most of the parameter values were assessed directly from field data, while about 10 ‘free’ parameters were subject to calibration using a combination of inverse steady-state groundwater modelling and manual trial-and-error dynamic groundwater/surface water modelling. Emphasising the importance of tests against independent data, the validation schemes included combinations of split-sample tests (another period) and proxy-basin tests (another area).