A model for the viscosity of rhyolite as a function of H2O-content and pressure: A calibration based on centrifuge piston cylinder experiments

The Newtonian viscosity of synthetic rhyolitic liquids with 0.15-5.24 wt% dissolved water was determined in the interval between 580 and 1640 °C and pressures of 1 atm and 5-25 kbar. Measurements were performed by combining static and accelerated (up to 1000g) falling sphere experiments on water-bearing samples, with high temperature concentric cylinder experiments on 0.15 wt% H₂O melts. These methods allowed viscosity determinations between 10² and 10⁷ Pa s, and cover the complete range of naturally occurring magmatic temperatures, pressures, and H₂O-contents for rhyolites.Our viscosity data, combined with those from previous studies, were modeled by an expression based on the empirical Vogel-Fulcher-Tammann equation, which describes viscosities and derivative properties (glass transition temperature T_g, fragility m, and activation volume of viscous flow Va) of silicic liquids as a function of P-T-X_(H2O). The fitted expressions do not account for composition-dependent parameters other than X_(H2O) and reproduce the entire viscosity database for silicic liquids to within 3.0% average relative error on log η (i.e. std. error of estimate of 0.26 log units).The results yield the expected strong decrease of viscosity with temperature and water content, but show variable pressure dependencies. Viscosity results to be strongly affected by pressure at low pressures; an effect amplified at low temperatures and water contents. Fragility, as a measure for the deviation from Arrhenian behavior, decreases with H₂O-content but is insensitive to pressure. Activation volumes are always largely negative (e.g., less than −10 cm³/mol) and increase strongly with H₂O-content. Variations in melt structure that may account for the observed property variations are discussed.     

Analysis of the probability distribution of the late Pleistocene climatic record implications for model validation

Some statistical properties of the late Pleistocene climatic changes, as inferred from the analysis of the Probability Density Function (PDF) of the deep-sea ¹⁸O record, are discussed. Estimates of the probability distribution of the SPECMAP record seem to reveal a bimodal character over the last 600 000 years BP, with a transition to a unimodal distribution for a longer time interval. Based on knowledge of the accuracy of the measurements, we try to remove the arbitrariness of such estimates, and by employing a number of different estimators we show that the major features observed are not affected by the particular method used. Possible dynamic interpretations are discussed. The abruptness of many transitions between the two modes and their symmetric occurrence seem to be significant features of the past climatic changes, which should be reproduced by climate models. The distribution of this indicator is then used to compare the performances of two climate models. Various statistical tests are employed and it is shown that, for a proper determination of the physical significance of such tests, information about the accuracy and reliability of the data must be included. For example, the comparison of two generalized isotopic curves, independently developed, shows a correlation coefficient of the order of 70%; therefore any account of the variance of any particular target curve beyond this level cannot be considered significant. These types of analyses suggest how the standard data evaluation and model validation techniques can be improved when discussing the essential features of observed and simulated dynamical systems.     

One dimensional aperture synthesis observations at 2.8 cm of the brightness distribution over the solar equator

The brightness distribution of the equatorial region of the Sun has been investigated at 2.8 cm with an east-west resolution of 16.1, for the following days: 30 June, 1 July, 3 July and 4 July, 1972. The results confirm the existence of very intense cores inside active regions with typical sizes of the order of 10–30 and brightness temperatures in the range of 10⁵ K, with possible peaks up to 6 × 10⁶ K. The relationship of these features to the H structure is also discussed.     

Estimation of daily stream water temperatures with a Bayesian regression approach

Stream water temperature plays a significant role in aquatic ecosystems where it controls many important biological and physical processes. Reliable estimates of water temperature at the daily time step are critical in managing water resources. We developed a parsimonious piecewise Bayesian model for estimating daily stream water temperatures that account for temporal autocorrelation and both linear and nonlinear relationships with air temperature and discharge. The model was tested at 8 climatically different basins of the USA and at 34 sites within the mountainous Boise River Basin (Idaho, USA). The results show that the proposed model is robust with an average root mean square error of 1.25 °C and Nash–Sutcliffe coefficient of 0.92 over a 2‐year period. Our approach can be used to predict historic daily stream water temperatures in any location using observed daily stream temperature and regional air temperature data.     

In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite,FeOH(SO<Subscript>4</Subscript>)·5H<Subscript>2</Subscript>O

The thermal dehydration process of fibroferrite, FeOH(SO₄)·5H₂O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO₄)·4H₂O, appearing at about 80 °C due to release of one interstitial H₂O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.     

Using a regional numerical weather prediction model for GNSS positioning over Brazil

The global navigation satellite system (GNSS) can provide centimeter positioning accuracy at low costs. However, in order to obtain the desired high accuracy, it is necessary to use high-quality atmospheric models. We focus on the troposphere, which is an important topic of research in Brazil where the tropospheric characteristics are unique, both spatially and temporally. There are dry regions, which lie mainly in the central part of the country. However, the most interesting area for the investigation of tropospheric models is the wet region which is located in the Amazon forest. This region substantially affects the variability of humidity over other regions of Brazil. It provides a large quantity of water vapor through the humidity convergence zone, especially for the southeast region. The interconnection and large fluxes of water vapor can generate serious deficiencies in tropospheric modeling. The CPTEC/INPE (Center for Weather Forecasting and Climate Studies/Brazilian Institute for Space Research) has been providing since July 2012 a numerical weather prediction (NWP) model for South America, known as Eta. It has yield excellent results in weather prediction but has not been used in GNSS positioning. This NWP model was evaluated in precise point positioning (PPP) and network-based positioning. Concerning PPP, the best positioning results were obtained for the station SAGA, located in Amazon region. Using the NWP model, the 3D RMS are less than 10 cm for all 24 h of data, whereas the values reach approximately 60 cm for the Hopfield model. For network-based positioning, the best results were obtained mainly when the tropospheric characteristics are critical, in which case an improvement of up to 7.2 % was obtained in 3D RMS using NWP models.     

Analysis of stratigraphical sequences at Cocina Cave (Spain) using rare earth elements geochemistry

This study investigates the stratigraphical sequence of Cocina Cave (Spain) employing and testing for the first time the capability of rare earth elements as markers of human activities in caves. Located in Dos Aguas (Valencian Community, Spain), Cocina Cave is characterized by the presence of several Holocene archaeological deposits from the final Mesolithic to the present day and is a pivotal site for understanding the socio-ecological dynamics of the last hunter-gatherer inhabitants of the Iberian Peninsula and the transition to pastoral and agricultural economies in the Western Mediterranean. However, the identification of strata from particular time-periods in the cave is often difficult due to the homogeneity of layers, the poor archaeological record in some strata and the presence of severe disturbance phenomena. The methodological approach of this study consisted of cross-referencing rare earth elements and other chemical markers with the archaeological stratigraphical interpretation, in an attempt to not only support the identification of the anthropic contribution to the formation of Cocina Cave strata, but also to characterize and confirm different natural and occupational episodes, particularly those associated with hunter-gatherer, early agriculturalist, and shepherd activities. Sediments were collected from different excavation areas and analysed for major elements, trace elements, rare earth elements (REE), soil organic matter (SOM) amounts and pH. Multivariate statistics were employed to group samples according to their elemental profile, and these were then compared to the archaeological temporal interpretation. The obtained results showed that REE amount and fractionation geochemical processes were regulated by carbonates, phosphates and pH. The use of REE as markers was particularly useful as their concentrations and their calculated ratios and anomaly distributions were demonstrated to be highly consistent with the archaeological stratigraphical interpretation.     

Groundwater resource degradation in coastal plains: The example of the Cecina area (Tuscany – Central Italy)

The paper describes the degradation of the groundwater resources in the Cecina area, where seawater intrusion, B contamination and NO₃ pollution are all affecting the heavily exploited Pleistocene aquifer. Over-pumping has brought water levels to about 0 m.a.s.l. as far as about 7 km from the shore line, thereby promoting the seawater intrusion. The intrusion, which is characterized by cation exchange phenomena and Ca–Cl type waters, enters the plain mostly through the shallower horizons. The saline front, which advanced from 0.5 to 1 km in 4 a, has by now reached the foot of the hills to the east of the town, where it is also affecting wells of the local aqueduct. Boron contamination, linked to past discharge of industrial waste transported downstream by the river, reached concentrations as high as 3.5 mg/L in the mid-1980s. Although a decreasing trend is now under way, B content is still close to 1 mg/L. The presence of high NO₃, which, together with the seawater intrusion, represents a major issue for groundwater management in the area, is linked to the widespread utilization of fertilizers. Nitrate concentration, which reaches a maximum of about 300 mg/L in the shallow aquifer horizons and then decreases rather regularly with depth, is strongly influenced by precipitation. However, irrigation also contributes significantly to transporting the NO₃ contamination to depth, as clearly shown by δ¹⁸O data. The severe decline in the quality of the groundwater resource in the Cecina area is further compounded by an overall decrease in water availability in the region of Tuscany, as evidenced by long-term monitoring of precipitation and fluvial discharge.