Water solubility in orthopyroxene

The solubility of water in pure enstatite was measured on samples synthesized at 1,100 °C and pressures to 100 kbar. Enstatite crystals were grown under water-saturated conditions from a stoichiometric mixture of high-purity SiO₂ and Mg(OH)₂. Water contents were calculated from polarized FTIR spectra measured on oriented single crystals. The water solubility in orthoenstatite increases with pressure to 867ᆷ ppm H₂O by weight at 75 kbar. At 100 kbar, in the stability field of high-clinoenstatite, a water solubility of 714ᆷ ppm was observed. The water solubility in enstatite at 1,100 °C can be described by the equation c_H2O=Af_H2O exp(-P(V/RT), where f_H2O is water fugacity, A=0.0204 ppm/bar and (V=12.3 cm³/mol. The infrared spectra of the hydrous enstatite crystals show a sharp, intense band at 3,363 cm^-1 and a broad, weaker band at 3,064 cm^-1. Both bands are strongly polarized parallel c. Most likely, pairs of protons attached to non-bridging oxygen atoms substitute for Mg²⁺. In order to investigate the effect of chemical impurities on water solubility in enstatite, an additional series of experiments was carried out with gels doped with Al, B, or Li as starting material. Whereas, the presence of Li and B had no detectable effect on water solubility, the addition of about 1 wt% Al₂O₃ increased water solubility in enstatite from 199 to 1,100 ppm at 1,100°C and 15 kbar. In the infrared spectra of these aluminous samples, additional bands occur in the range from 3,450 to 3,650 cm^-1. Similar bands are also observed in natural, aluminous orthopyroxenes and are most likely caused by protons coupled with Al according to the substitution of Al³⁺+H⁺ for Si⁴⁺. A series of hydrous annealing experiments on a natural, gem-quality aluminous enstatite from Tanzania yielded water solubilities generally consistent with the results from the synthetic model systems. The results presented here imply that pure enstatite has a similar storage capacity for water as olivine; however, aluminous orthopyroxenes in the mantle may dissolve much larger amounts of water comparable with the entire mass of the present hydrosphere. Moreover, the mechanism of aluminum substitution in orthopyroxenes, i.e., the distribution of Al between tetrahedral and octahedral sites, may be a potential probe of water fugacity.     

Wave velocities and attenuation of shaley sandstones as a function of pore pressure and partial saturation

We obtain the wave velocities and quality factors of clay‐bearing sandstones as a function of pore pressure, frequency and partial saturation. The model is based on a Biot‐type three‐phase theory that considers the coexistence of two solids (sand grains and clay particles) and a fluid mixture. Additional attenuation is described with the constant‐Q model and viscodynamic functions to model the high‐frequency behaviour. We apply a uniform gas/fluid mixing law that satisfies the Wood and Voigt averages at low and high frequencies, respectively. Pressure effects are accounted for by using an effective stress law. By fitting a permeability model of the Kozeny– Carman type to core data, the model is able to predict wave velocity and attenuation from seismic to ultrasonic frequencies, including the effects of partial saturation. Testing of the model with laboratory data shows good agreement between predictions and measurements.     

Use of Chemotaxonomy To Study the Influence of Benzalkonium Chloride on Bacterial Populations in Biodegradation Testing

Contradictory results are reported for the behaviour of quaternary ammonium compounds (QACs) in sewage treatment plants (STPs). QACs may sorb onto activated sludge. Only little information is available with respect to effects of QACs against bacteria in STPs. Only 5 to 15 % of bacteria present in sewage sludge can be detected by means of culture dependent microbiological methods. The shift of the bacterial populations due to effects of test compounds have not been studied up to now with culture independent methods. The microbial populations shift was studied in situ using culture independent chemotaxonomy profiling ubiquinones and polyamines. Additionally, toxic effects of QACs against bacteria present in the test vessels of the Zahn‐Wellens test (OECD 302 B) were assessed with a toxicity control in the test. The ubiquinone profiles representing changes in Gram‐negative populations mainly showed that the activated sludge was affected only in test vessels containing benzalkonium chloride. According to chemotaxonomy Acinetobacter or/and some members of Pseudomonas spp. have been selected by benzalkonium chloride after some adaptation period (8 to 12 days).     

Sediment yield and storage variations in the Négron River catchment (south western Parisian Basin,France) during the Holocene period

In the Négron River catchment area (162 km²), surface‐sediment stores are composed of periglacial calcareous ‘grèze’ (5 × 10⁶ t) and loess (21 × 10⁶ t), and Holocene alluvium (12·6 × 10⁶ t), peat (0·6 × 10⁶ t) and colluvium (18·5 × 10⁶ t). Seventy‐five per cent of the Holocene sediments is stored along the thalwegs. Present net sediment yield, calculated from solid discharge at the Négron outlet, is low (0·6 t km^?2 a^?1) due to the dominance of carbonate rocks in the catchment. Mean sediment yield during the Holocene period is 7·0 t km^?2 a^?1 from alluvium stores and 7·6 t km^?2 a^?1 from colluvium stores. Thus, the gross sediment yield during the Holocene period is about 18·7 t km^?2 a^?1 and the sediment delivery ratio 3 per cent. The yield considerably varies from one sub‐basin to another (3·9 to 24·5 t km^?2 a^?1) according to lithology: about 25 per cent and 50 per cent of initial stores of periglacial grèze and loess respectively were reworked during the Holocene period. Sediment yield has increased by a factor of 6 in the last 1000 years, due to the development of agriculture. The very high rate of sediment storage on the slope during that period (88 per cent of the yield) can be accounted for by the formation of cultivation steps (‘rideaux’). It is predicted that the current destruction of these steps will result in a sediment wave reaching the valley floors in the coming decades. Subboreal and Subatlantic sediments and pollen assemblages in the Taligny marsh, where one‐third of the alluvium is stored, show the predominant influence of human activity during these periods in the Négron catchment. Copyright © 2002 John Wiley & Sons, Ltd.     

Contrasting rifted margin styles south of Greenland: implications for mantle plume dynamics

We present new and reprocessed seismic reflection data from the area where the southeast and southwest Greenland margins intersected to form a triple junction south of Greenland in the early Tertiary. During breakup at 56 Ma, thick igneous crust was accreted along the entire 1300-km-long southeast Greenland margin from the Greenland Iceland Ridge to, and possibly 100 km beyond, the triple junction into the Labrador Sea. However, highly extended and thin crust 250 km to the west of the triple junction suggests that magmatically starved crustal formation occurred on the southwest Greenland margin at the same time. Thus, a transition from a volcanic to a non-volcanic margin over only 100–200 km is observed. Magmatism related to the impact of the Iceland plume below the North Atlantic around 61 Ma is known from central-west and southeast Greenland. The new seismic data also suggest the presence of a small volcanic plateau of similar age close to the triple junction. The extent of initial plume-related volcanism inferred from these observations is explained by a model of lateral flow of plume material that is guided by relief at the base of the lithosphere. Plume mantle is channelled to great distances provided that significant melting does not take place. Melting causes cooling and dehydration of the plume mantle. The associated viscosity increase acts against lateral flow and restricts plume material to its point of entry into an actively spreading rift. We further suggest that thick Archaean lithosphere blocked direct flow of plume material into the magma-starved southwest Greenland margin while the plume was free to flow into the central west and east Greenland margins. The model is consistent with a plume layer that is only moderately hotter, 100–200°C, than ambient mantle temperature, and has a thickness comparable to lithospheric thickness variations, 50–100 km. Lithospheric architecture, the timing of continental rifting and viscosity changes due to melting of the plume material are therefore critical parameters for understanding the distribution of magmatism.     

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).     

The BEAM-project: prediction and assessment of mixture toxicities in the aquatic environment

Freshwater and marine ecosystems are exposed to various multi-component mixtures of pollutants. Nevertheless, most ecotoxicological research and chemicals regulation focus on hazard and exposure assessment of individual substances only, the problem of chemical mixtures in the environment is ignored to a large extent. In contrast, the assessment of combination effects has a long tradition in pharmacology, where mixtures of chemicals are specifically designed to develop new products, e.g. human and veterinary drugs or agricultural and non-agricultural pesticides. In this area, two concepts are frequently used and are thought to describe fundamental relationships between single substance and mixture effects: Independent Action (Response Addition) and Concentration Addition. The question, to what extent these concepts may also be applied in an ecotoxicological and regulatory context may be considered a research topic of major importance, as the concepts would allow to make use of already existing single substance toxicity data for the predictive assessment of mixture toxicities. Two critical knowledge gaps are identified: (a) There is a lack of environmental realism, as a huge part of our current knowledge about the applicability of the concepts is restricted to artificial situations with respect to mixture composition or biological effect assessment. (b) The knowledge on what exactly is needed for using the concepts as tools for the predictive mixture toxicity assessment is insufficient. Both gaps seriously hamper the necessary, scientifically sound consideration of mixture toxicities in a regulatory context.In this paper, the two concepts will be briefly introduced, the necessity of considering the toxicities of chemical mixtures in the environment will be demonstrated and the applicability of Independent Action and Concentration Addition as tools for the prediction and assessment of mixture toxicities will be discussed. An overview of the specific aims and approaches of the BEAM project to fill in the identified knowledge gaps is given and first results are outlined.     

Asymmetric one‐storey elastic systems with non‐linear viscous and viscoelastic dampers: Simplified analysis and supplemental damping system design

Investigated is the accuracy in estimating the response of asymmetric one‐storey systems with non‐linear viscoelastic (VE) dampers by analysing the corresponding linear viscous system wherein all non‐linear VE dampers are replaced by their energy‐equivalent linear viscous dampers. The response of the corresponding linear viscous system is determined by response history analysis (RHA) and by response spectrum analysis (RSA) extended for non‐classically damped systems. The flexible and stiff edge deformations and plan rotation of the corresponding linear viscous system determined by the extended RSA procedure is shown to be sufficiently accurate for design applications with errors generally between 10 and 20%. Although similar accuracy is also shown for the ‘pseudo‐velocity’ of non‐linear VE dampers, the peak force of the non‐linear VE damper cannot be estimated directly from the peak damper force of the corresponding linear viscous system. A simple correction for damper force is proposed and shown to be accurate (with errors not exceeding 15%). For practical applications, an iterative linear analysis procedure is developed for determining the amplitude‐ and frequency‐dependent supplemental damping properties of the corresponding linear viscous system and for estimating the response of asymmetric one‐storey systems with non‐linear VE dampers from the earthquake design (or response) spectrum. Finally, a procedure is developed for designing non‐linear supplemental damping systems that satisfy given design criteria for a given design spectrum. Copyright © 2003 John Wiley & Sons, Ltd.     

Inelastic displacement ratios for evaluation of existing structures

Results of a detailed statistical study of constant relative strength inelastic displacement ratios to estimate maximum lateral inelastic displacement demands on existing structures from maximum lateral elastic displacement demands are presented. These ratios were computed for single‐degree‐of‐freedom systems with different levels of lateral strength normalized to the strength required to remain elastic when subjected to a relatively large ensemble of recorded earthquake ground motions. Three groups of soil conditions with shear wave velocities higher than 180m/s are considered. The influence of period of vibration, level of lateral yielding strength, site conditions, earthquake magnitude, distance to the source, and strain‐hardening ratio are evaluated and discussed. Mean inelastic displacement ratios and those associated with various percentiles are presented. A special emphasis is given to the dispersion of these ratios. It is concluded that distance to the source has a negligible influence on constant relative strength inelastic displacement ratios. However, for periods smaller than 1s earthquake magnitude and soil conditions have a moderate influence on these ratios. Strain hardening decreases maximum inelastic displacement at a fairly constant rate depending on the level of relative strength for periods of vibration longer than about 1.0s while it decreases maximum inelastic displacement non‐linearly as the period of vibration shortens and as the relative‐strength ratio increases for periods of vibration shorter than 1.0s. Finally, results from non‐linear regression analyses are presented that provide a simplified expression to be used to approximate mean inelastic displacement ratios during the evaluation of existing structures built on firm sites. Copyright © 2003 John Wiley & Sons, Ltd.     

On the circulation in the East Frisian Wadden Sea: numerical modeling and data analysis

 In this paper we use a combination of numerical modeling and data analysis to gain a better understanding of the major characteristics of the circulation in the East Frisian Wadden Sea. In particular, we concentrate on the asymmetry of the tidal wave and its modulation in the coastal area, which results in a complex pattern of responses to the sea-level forcing from the North Sea. The numerical simulations are based on the 3-D primitive equation General Estuarine Transport Model (GETM) with a horizontal resolution of 200 m and terrain-following vertical coordinates. The model is forced at its open boundaries with sea-level data from an operational model for the German Bight (German Hydrographic Office). The validation data for our model simulations include time series of tidal gauge data and surface currents measured at a pile in the back-barrier basin of the Island Langeoog, as well as several ADCP transects in the Accumer Ee tidal inlet. Circulation and turbulence characteristics are investigated for typical situations driven by spring and neap tides, and the analysis is focused on dominating temporal and spatial patterns. By investigating the response of five back-barrier basins with rather different morphologies to external forcing, an attempt is made to elucidate the dominating physical balances controlling the circulation in the individual sub-basins. It is demonstrated that the friction at the seabed tends to slow down the tidal signal in the shallow water. This leads to the establishment of flood dominance in the shallow sea north of the barrier islands. South of the islands, where the water volume of the channels at low tide is smaller than the tidal prism, the asymmetry of the tidal signal is shifted towards ebb dominance, a feature which is particularly pronounced at spring tide. At the northern open boundary, the tidal wave propagating from west to east generates a sea-level difference of ∼1 m along the boundary, and thereby triggers vigorous alongshore currents. The frictional control in the model is located in the inlets, as well as along the northern boundary. The correlation between velocity and turbulent kinetic energy tends to the establishment of a net southward transport, giving theoretical support to the observed accumulation of sediments on the intertidal flats. Weak turbulence along the northern shores of the barrier islands and the small magnitude of the residual currents there promote accumulation of suspended matter in these areas, although wave action will generally counteract this effect. Received: 29 May 2002 / Accepted: 26 September 2002 Responsible Editor: Jean-Marie Beckers Acknowledgements We are indebted to S. Dick for providing the data from the operational model of BSH and to B. Flemming for the useful discussions. The topography data and Fig. 1 have been prepared in cooperation with F. Meyer. Figure 2 has been prepared by G. Brink-Spalink. We also thank for the comments from an anonymous reviewer which helped to improve our paper.