Polymorphic phase transition in Superhydrous Phase B

We synthesized superhydrous phase B (shy-B) at 22 GPa and two different temperatures: 1200°C (LT) and 1400°C (HT) using a multi-anvil apparatus. The samples were investigated by transmission electron microscopy (TEM), single crystal X-ray diffraction, Raman and IR spectroscopy. The IR spectra were collected on polycrystalline thin-films and single crystals using synchrotron radiation, as well as a conventional IR source at ambient conditions and in situ at various pressures (up to 15 GPa) and temperatures (down to −180°C). Our studies show that shy-B exists in two polymorphic forms. As expected from crystal chemistry, the LT polymorph crystallizes in a lower symmetry space group (Pnn2), whereas the HT polymorph assumes a higher symmetry space group (Pnnm). TEM shows that both modifications consist of nearly perfect crystals with almost no lattice defects or inclusions of additional phases. IR spectra taken on polycrystalline thin films exhibit just one symmetric OH band and 29 lattice modes for the HT polymorph in contrast to two intense but asymmetric OH stretching bands and at least 48 lattice modes for the LT sample. The IR spectra differ not only in the number of bands, but also in the response of the bands to changes in pressure. The pressure derivatives for the IR bands are higher for the HT polymorph indicating that the high symmetry form is more compressible than the low symmetry form. Polarized, low-temperature single-crystal IR spectra indicate that in the LT-polymorph extensive ordering occurs not only at the Mg sites but also at the hydrogen sites.     

GPS monitoring of vertical ground motion in northern Ardenne–Eifel: five campaigns (1999–2003) of the HARD project

We present the HARD project of GPS monitoring of vertical ground motion in NE Ardenne and Eifel (western Europe). Its main purposes are to get a better insight into the present-day rates of vertical ground motion in intraplate settings and to identify the various causes of these motions. Since 1999, we have carried out yearly campaigns of simultaneous GPS measurements at 12 sites situated so as to sample the different tectonic subunits of the study area and especially to record potential displacements across the seismogenic Hockai fault zone. Five campaigns (1999–2003) have been processed currently. Key issues of the data processing with the Gamit software are discussed and first results are presented. Though temporally consistent in many cases, the obtained vertical motion rates are spatially highly variable. They are also much too high (several mm/year) to support a tectonic interpretation, and a long-term influence of groundwater level variations is proposed to account for the observed motions. This influence should be distinguished from seasonal variations and from inter-survey variations linked to the varying degree of soil and subsoil drying off during the successive spring surveys.     

Effect of melt composition on the partitioning of trace elements between titanite and silicate melt

Isobaric and isothermal experiments were performed to investigate the effect of melt composition on the partitioning of trace elements between titanite (CaTiSiO₅) and a range of different silicate melts. Titanite-melt partition coefficients for 18 trace elements were determined by secondary ion mass spectrometry (SIMS) analyses of experimental run products. The partition coefficients for the rare earth elements and for Th, Nb, and Ta reveal a strong influence of melt composition on partition coefficients, whereas partition coefficients for other studied monovalent, divalent and most quadrivalent (i.e., Zr, Hf) cations are not significantly affected by melt composition. The present data show that the influence of melt composition may not be neglected when modelling trace element partitioning.It is argued that it is mainly the change of coordination number and the regularity of the coordination space of trace elements in the melt structure that controls partition coefficients in our experiments. Furthermore, our data also show that the substitution mechanism by which trace elements are incorporated into titanite crystals may be of additional importance in this context.     

Partitioning of trace elements between rutile and silicate melts: Implications for subduction zones

Mineral/melt trace element partition coefficients were determined for rutile (TiO₂) for a large number of trace elements (Zr, Hf, Nb, Ta, V, Co, Cu, Zn, Sr, REE, Cr, Sb, W, U, Th). Whilst the high field strength elements (Zr, Hf, Nb, Ta) are compatible in rutile, other studied trace elements are incompatible (Sr, Th, REE). In all experiments we found D_Ta > D_Nb, D_Hf > D_Zr and D_U > D_Th. Partition coefficients for some polyvalent elements (Sb, W, and Co) were sensitive to oxygen fugacity. Melt composition exerts a strong influence on HFSE partition coefficients. With increasing polymerization of the melt, rutile/melt partition coefficients for the high field strength elements Zr, Hf, Nb and Ta increase about an order of magnitude. However, D_Nb/D_Ta and D_Hf/D_Zr are not significantly affected by melt composition. Because D_U ? D_Th, partial melting of rutile-bearing eclogite in subducted lithosphere may cause excesses of ²³⁰Th over ²³⁸U in some island arc lavas, whereas dehydration of subducted lithosphere may cause excesses of ²³⁸U over ²³⁰Th. From our partitioning results we infer partition coefficients for protactinium (Pa) which we predict to be much lower than previously anticipated. Contrary to previous studies, our data imply that rutile should not significantly influence observed ²³¹Pa-²³⁵U disequilibria in certain volcanic rocks.     

Arsenic mobility in the ambient sulfidic environment: Sorption of arsenic(V) and arsenic(III) onto disordered mackinawite

Arsenate, As(V), sorption onto synthetic iron(II) monosulfide, disordered mackinawite (FeS), is fast. As(V) sorption decreases above the point of zero surface charge of FeS and follows the pH-dependent concentration of positively charged surface species. No redox reaction is observed between the As(V) ions and the mineral surface over the time span of the experiments. This observation shows that As(V) dominantly forms an outer-sphere complex at the surface of mackinawite. Arsenite, As(III), sorption is not strongly pH-dependent and can be expressed by a Freundlich isotherm. Sorption is fast, although slower than that of As(V). As(III) also forms an outer-sphere complex at the surface of mackinawite. In agreement with previous spectroscopic studies, complexation at low As(V) and As(III) concentration occurs preferentially at the mono-coordinated sulfide edge sites. The K_d (L g⁻¹) values obtained from linear fits to the isotherm data are ∼9 for As(V) and ∼2 for As(III). Stronger sorption of As(V) than As(III), and thus a higher As(III) mobility, may be reflected in natural anoxic sulfidic waters when disordered mackinawite controls arsenic mobility.     

Modeling the impact of microbial activity on redox dynamics in porous media

The present study investigates the interaction between microbial growth and activity and the redox dynamics in natural porous media. The impact the transport regime has on this interaction is also addressed. Expressions for microbial growth are incorporated into a geochemical reaction network linking redox reaction rates to the activity of the microorganisms. A flexible simulation environment, the Biogeochemical Reaction Network Simulator (BRNS) is used for this purpose. Two reactive transport applications relevant to fields of contaminant hydrology and early diagenesis are simulated with the BRNS. Model results are evaluated based on a comparison with comprehensive datasets on the biodegradation of lactate in a sand column experiment and on the distribution of redox-sensitive chemical species in marine sediments of the Skagerrak, Denmark. It is shown that, despite quite different transport regimes, the geomicrobiological model performs equally well in the reproduction of measured chemical species distribution for both applications. This result emphasizes the broad applicability of the proposed approach. Our simulations support that the competitive behavior between various microbial groups is a process controlling the development of redox stratified environments. Furthermore, it is also shown that the transport regime is a key controlling factor for the degree of spatial correlation between microbial biomass distributions and redox reaction rates. Although all our simulations yield a pronounced stratification of the redox processes in the system, the biomass distribution is related to the associated reaction rates only in case of the advection controlled column experiment. In the early diagenetic application, mixing due to bioturbation is the dominant transport process for particulate matter, hence leading to fairly homogeneous distribution of bacterial biomasses which are unrelated to the spatial distribution of redox reaction rates. This homogeneous biomass distribution combined with the 1G carbon degradation model approach might explain why the steady state concentration profiles in such systems can be reproduced by diagenetic models without explicit representation of microbial growth.     

Experimental characterization of the impact of temperature and humidity on the breakdown of soil water repellency in sandy soils and composts

Soil water repellency is a widespread phenomenon with the capacity to alter hydrological and geomorphological processes. Water repellency decays with time, and the consequences are only of concern during the timescale at which the water repellency persists. This study aimed to characterize the influence of temperature and humidity on the breakdown of water repellency. Apparent contact angle measurements were carried out on samples consisting of sand treated with stearic acid as well as naturally repellent dune sands and composts. Temperature and humidity were controlled using a cooled incubator and a purpose designed enclosed box in which humidity could be raised or lowered. Results showed the contact angle of the stearic‐acid‐treated sands decayed with time and that there was a significant increase with stearic acid concentration. For all samples, the decay in apparent contact angle could be described with a continuous breakdown model. The stearic‐acid‐treated sands showed a significant increase in contact angle with relative humidity at a temperature of 10 and 20 °C. These differences diminished with increasing temperature. Similar results were seen for the dune sands and composts. Despite the influence of temperature and humidity on contact angles, there was no significant change in the rate at which the contact angle decayed in any sample. Absolute humidity was found to provide a more relevant indicator than relative humidity when assessing the influence of humidity on repellency over a range of temperatures. The contact angle initially increased with absolute humidity before plateauing owing to the confounding effect of temperature. Copyright © 2014 John Wiley & Sons, Ltd.     

Characterisation of hydroclimatological trends and variability in the Lake Naivasha basin,Kenya

Recent hydro‐climatological trends and variability characteristics were investigated for the Lake Naivasha basin with the aim of understanding the changes in water balance components and their evolution over the past 50 years. Using a Bayesian change point analysis and modified Mann–Kendall tests, time series of annual mean, maximum, minimum, and seasonal precipitation and flow, as well as annual mean lake volumes, were analysed for the period 1960–2010 to uncover possible abrupt shifts and gradual trends. Double cumulative curve analysis was used to investigate the changes in hydrological response attributable to either human influence or climatic variability. The results indicate a significant decline in lake volumes at a mean rate of 9.35 × 10⁶ m³ year^?1. Most of the river gauging stations showed no evidence of trends in the annual mean and maximum flows as well as seasonal flows. Annual minimum flows, however, showed abrupt shifts and significant (upward/downward) trends at the main outlet stations. Precipitation in the basin showed no evidence of abrupt shifts, but a few stations showed gradual decline. The observed changes in precipitation could not explain the decline in both minimum flows and lake volumes. The findings show no evidence of any impact of climate change for the Lake Naivasha basin over the past 50 years. This implies that other factors, such as changes in land cover and infrastructure development, have been responsible for the observed changes in streamflow and lake volumes. Copyright © 2015 John Wiley & Sons, Ltd.     

Towards more systematic perceptual model development: a case study using 3 Luxembourgish catchments

The synthesis of experimental understanding of catchment behaviour and its translation into qualitative perceptual models is an important objective of hydrological sciences. We explore this challenge by examining the cumulative understanding of the hydrology of three experimental catchments and how it evolves through the application of different investigation techniques. The case study considers the Huewelerbach, Weierbach and Wollefsbach headwater catchments of the Attert basin in Luxembourg. Subsurface investigations including bore holes and pits, analysis of soil samples and Electrical Resistivity Tomography measurements are presented and discussed. Streamflow and tracer data are used to gain further insights into the streamflow dynamics of the catchments, using end‐member mixing analysis and hydrograph separation based on dissolved silica and electrical conductivity. We show that the streamflow generating processes in all three catchments are controlled primarily by the subsolum and underlying bedrock. In the Huewelerbach, the permeable sandstone formation supports a stable groundwater component with little seasonality, which reaches the stream through a series of sources at the contact zone with the impermeable marls formation. In the Weierbach, the schist formation is relatively impermeable and supports a ‘fill and spill’‐type of flow mechanism; during wet conditions, it produces a delayed response dominated by pre‐event water. In the Wollefsbach, the impermeable marls formation is responsible for a saturation‐excess runoff generating process, producing a fast and highly seasonal response dominated by event water. The distinct streamflow generating processes of the three catchments are represented qualitatively using perceptual models. The perceptual models are in turn translated into quantitative conceptual models, which simulate the hydrological processes using networks of connected reservoirs and transfer functions. More generally, the paper illustrates the evolution of perceptual models based on experimental fieldwork data, the translation of perceptual models into conceptual models and the value of different types of data for processes understanding and model representation. Copyright © 2014 John Wiley & Sons, Ltd.