Cathodoluminescence (CL) and electron paramagnetic resonance (EPR) studies of clay minerals

Summary ?Sheet silicates of the serpentine–kaolin-group (serpentine, kaolinite, dickite, nacrite, halloysite), the talc–pyrophyllite-group (talc, pyrophyllite), the smectite-group (montmorillonite), and illite (as a mineral of the mica-group) were investigated to obtain information concerning their cathodoluminescence behaviour. The study included analyses by cathodoluminescence (CL microscopy and spectroscopy), electron paramagnetic resonance (EPR), X-Ray diffraction (XRD), scanning electron microscopy (SEM) and trace element analysis. In general, all dioctahedral clay minerals exhibit a visible CL. Kaolinite, dickite, nacrite and pyrophyllite have a characteristic deep blue CL, whereas halloysite emission is in the greenish-blue region. On the contrary, the trioctahedral minerals (serpentine, talc) and illite do not show visible CL. The characteristic blue CL is caused by an intense emission band around 400 nm (double peak with two maxima at 375 and 410 nm). EPR measurements indicate that this blue emission can be related to radiation induced defect centres (RID), which occur as electron holes trapped on apical oxygens (Si–O centre) or located at the Al–O–Al group (Al substituting Si in the tetrahedron). Additional CL emission bands were detected at 580 nm in halloysite and kaolinite, and between 700 and 800 nm in kaolinite, dickite, nacrite and pyrophyllite. Time-resolved spectral CL measurements show typical luminescence kinetics for the different clay minerals, which enable differentiation between the various dioctahedral minerals (e.g. kaolinite and dickite), even in thin section. Received December 3, 2001; revised version accepted February 27, 2002     

Elemental and isotopic fractionation of Type B CAI-like liquids by evaporation

Vacuum evaporation experiments with Type B CAI-like starting compositions were carried out at temperatures of 1600, 1700, 1800, and 1900 °C to determine the evaporation kinetics and evaporation coefficients of silicon and magnesium as a function of temperature as well as the kinetic isotope fractionation factor for magnesium. The vacuum evaporation kinetics of silicon and magnesium are well characterized by a relation of the form J = J_oe^−E/RT with J_o = 4.17 × 10⁷ mol cm⁻² s⁻¹, E = 576 ± 36 kJ mol⁻¹ for magnesium, J_o = 3.81 × 10⁶ mol cm⁻² s⁻¹, E = 551 ± 63 kJ mol⁻¹ for silicon. These rates only apply to evaporation into vacuum whereas the actual Type B CAIs were almost certainly surrounded by a finite pressure of a hydrogen-dominated gas. A more general formulation for the evaporation kinetics of silicon and magnesium from a Type B CAI-like liquid that applies equally to vacuum and conditions of finite hydrogen pressure involves combining our determinations of the evaporation coefficients for these elements as a function of temperature (γ = γ₀e^−E/RT with γ₀ = 25.3, E = 92 ± 37 kJ mol⁻¹ for γ_Si; γ₀ = 143, E = 121 ± 53 kJ mol⁻¹ for γ_Mg) with a thermodynamic model for the saturation vapor pressures of Mg and SiO over the condensed phase. High-precision determinations of the magnesium isotopic composition of the evaporation residues from samples of different size and different evaporation temperature were made using a multicollector inductively coupled plasma mass spectrometer. The kinetic isotopic fractionation factors derived from this data set show that there is a distinct temperature effect, such that the isotopic fractionation for a given amount of magnesium evaporated is smaller at lower temperature. We did not find any significant change in the isotope fractionation factor related to sample size, which we interpret to mean that recondensation and finite chemical diffusion in the melt did not affect the isotopic fractionations. Extrapolating the magnesium kinetic isotope fractionations factors from the temperature range of our experiments to temperatures corresponding to partially molten Type B CAI compositions (1250-1400 °C) results in a value of α_Mg ≈ 0.991, which is significantly different from the commonly used value of .     

Managing Groundwater to Ensure Ecosystem Function

Groundwater is a critical resource not only for human communities but also for many terrestrial, riparian, and aquatic ecosystems and species. Yet groundwater planning and management decisions frequently ignore or inadequately address the needs of these natural systems. As a consequence, ecosystems dependent on groundwater have been threatened, degraded, or eliminated, especially in arid regions. There is growing acknowledgment that governmental protections for these ecological resources are necessary, but current legal, regulatory and voluntary provisions are often inadequate. Groundwater management premised on “safe yield,” which aims to balance human withdrawals with natural recharge rates, typically provides little to no consideration for water needed by ecosystems. Alternatively, the “sustainable yield” concept aims to integrate social, economic and environmental needs for groundwater, but the complexity of groundwater systems creates substantial uncertainty about the impact that current or future groundwater withdrawals will have on ecosystems. Regardless of the legal or regulatory framework, guidance is needed to help ensure environmental water needs will be met, especially in the face of pressure to increase human uses of groundwater resources. In this paper, we describe minimum provisions for planning, managing, and monitoring groundwater that collectively can lower the risk of harm to groundwater-dependent ecosystems and species, with a special emphasis on arid systems, where ecosystems and species may be especially reliant upon and sensitive to groundwater dynamics.     

Paleoclimatic and archeological implications of Pleistocene and Holocene environments in Azraq, Jordan

Wetlands are a key archive for paleoclimatic and archeological work, particularly in arid regions, as they provide a focus for human occupation and preserve environmental information. The sedimentary record from 'Ayn Qasiyya, a spring site on the edge of the Azraq Qa, provides a well-dated sequence through the last glacial–interglacial transition (LGIT) allowing environmental changes in the present-day Jordanian desert to be investigated robustly through this time period for the first time. Results show that the wettest period at the site preceded the last glacial maximum, which itself was characterised by marsh formation and a significant Early Epipaleolithic occupation. A sedimentary hiatus between 16 and 10.5 ka suggests a period of drought in the region although seasonal rains and surface waters still allowed seasonal occupation of the Azraq region. Archeological evidence suggests that conditions had improved by the Late Epipaleolithic, about the time of the North Atlantic Younger Dryas. The changes between wet and dry conditions at the site show similarities to patterns in the eastern Mediterranean and in Arabia suggesting the Jordan interior was influenced by changes in both these regions through the LGIT climatic transition.     

Io’s atmosphere: Constraints on sublimation support from density variations on seasonal timescales using NASA IRTF/TEXES observations from 2001 to 2010

We present an analysis of 19 μm spectra of Io’s SO₂ atmosphere from the TEXES mid-infrared high spectral resolution spectrograph on NASA’s Infrared Telescope Facility, incorporating new data taken between January 2005 and June 2010 and a re-analysis of earlier data taken from November 2001 to January 2004. This is the longest set of contiguous observations of Io’s atmosphere using the same instrument and technique thus far. We have fitted all 16 detected blended absorption lines of the ν₂ SO₂ vibrational band to retrieve the subsolar values of SO₂ column abundance and the gas kinetic temperature. By incorporating an existing model of Io’s surface temperatures and atmosphere, we retrieve sub-solar column densities from the disk-integrated data. Spectra from all years are best fit by atmospheric temperatures <150 K. Best-fit gas kinetic temperatures on the anti-Jupiter hemisphere, where SO₂ gas abundance is highest, are low and stable, with a mean of 108 (±18) K. The sub-solar SO₂ column density between longitudes of 90–220° varies from a low of 0.61 (±0.145) × 10^?17 cm^?2, near aphelion in 2004, to a high of 1.51 (±0.215) × 10¹⁷ cm^?2 in 2010 when Jupiter was approaching its early 2011 perihelion. No correlation in the gas temperature was seen with the increasing SO₂ column densities outside the errors.Assuming that any volcanic component of the atmosphere is constant with time, the correlation of increasing SO₂ abundance with decreasing heliocentric distance provides good evidence that the atmosphere is at least partially supported by frost sublimation. The SO₂ frost thermal inertias and albedos that fit the variation in atmospheric density best are between 150–1250 W m^?2 s^?1/2 K^?1 and 0.613–0.425 respectively. Photometric evidence favors albedos near the upper end of this range, corresponding to thermal inertias near the lower end. This relatively low frost thermal inertia produces larger amplitude seasonal variations than are observed, which in turn implies a substantial additional volcanic atmospheric component to moderate the amplitude of the seasonal variations of the total atmosphere on the anti-Jupiter hemisphere. The seasonal thermal inertia we measure is unique both because it refers exclusively to the SO₂ frost surface component, and also because it refers to relatively deep subsurface layers (few meters) due to the timescales of many years, while previous studies have determined thermal inertias at shallower levels (few centimeters), relevant for timescales of ～2 h (eclipse) or ～2 days (diurnal curves).     

Investigating the redox sensitivity of para-toluenesulfonamide (p-TSA) in groundwater

The groundwater downstream of a former sewage irrigation farm in Berlin is contaminated with ammonium (NH₄ ⁺) and para-toluenesulfonamide (p-TSA), besides other anthropogenic pollutants. In the field, in situ removal of NH₄ ⁺ by gaseous oxygen (O₂) and air injection is currently being tested. A laboratory column experiment using aquifer material and groundwater from the site was performed to determine whether this remediation technology is also feasible to reduce high p-TSA concentrations in the anoxic groundwater. First, the column was operated under anoxic conditions. Later, compressed air was introduced into the system to simulate oxic conditions. Samples were collected from the column outlet before and after the addition of compressed air. The experiment revealed that whereas p-TSA was not removed under anoxic conditions, it was almost fully eliminated under oxic conditions. Results were modelled using a transient one-dimensional solute transport model. The degradation rate constants for p-TSA increased from 2.8E−06 to 7.5E−05 s^–1 as a result of microbial adaption to the change of redox conditions. Results show that O₂ injection into an anoxic aquifer is a successful strategy for p-TSA remediation.     

Large wood budget and transport dynamics on a large river using radio telemetry

Despite the abundance of large wood (LW) river studies there is still a lack of understanding of LW transport dynamics on large low gradient rivers. This study used 290 radio frequency identification tagged (RFID) LW and 54 metal (aluminum) tagged LW, to quantify the percent of in‐channel LW that moves per year and what variables play a role in LW transport dynamics. Aluminum tags were installed and monitored on LW in‐transit during the rising limb of a flood, the mean distance traveled by those pieces during the week was 13.3 river kilometers (km) with a maximum distance of 72 km. RFID tagged LW moved a mean of 11.9 km/yr with a maximum observed at 101.1 km/yr. Approximately 41% of LW low on the bank moves per year. The high rate of transport and distance traveled is likely due to the lack of interaction between LW floating in the channel and the channel boundaries, caused primarily by the width of the channel relative to length of the LW. Approximately 80% of the RFID tags moved past a fixed reader during the highest 20% of river stage per year. LW transport and logjam dynamics are complicated at high flows as pieces form temporary jams that continually expand and contract. Unlike most other studies, key members that create a logjam were defined more by stability than jam size or channel/hydrologic conditions. Finally, using an existing geomorphic database for the river, and data from this study, we were able to develop a comprehensive LW budget showing that 5% of the in‐channel LW population turns over each year (input from mass wasting and fluvial erosion equals burial, decomposition, and export out of system) and another 16% of the population moving within the system. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.     

Silicon isotopic fractionation of CAI-like vacuum evaporation residues

Calcium-, aluminum-rich inclusions (CAIs) are often enriched in the heavy isotopes of magnesium and silicon relative to bulk solar system materials. It is likely that these isotopic enrichments resulted from evaporative mass loss of magnesium and silicon from early solar system condensates while they were molten during one or more high-temperature reheating events. Quantitative interpretation of these enrichments requires laboratory determinations of the evaporation kinetics and associated isotopic fractionation effects for these elements. The experimental data for the kinetics of evaporation of magnesium and silicon and the evaporative isotopic fractionation of magnesium is reasonably complete for Type B CAI liquids (Richter F. M., Davis A. M., Ebel D. S., and Hashimoto A. (2002) Elemental and isotopic fractionation of Type B CAIs: experiments, theoretical considerations, and constraints on their thermal evolution. Geochim. Cosmochim. Acta66, 521-540; Richter F. M., Janney P. E., Mendybaev R. A., Davis A. M., and Wadhwa M. (2007a) Elemental and isotopic fractionation of Type B CAI-like liquids by evaporation. Geochim. Cosmochim. Acta71, 5544-5564.). However, the isotopic fractionation factor for silicon evaporating from such liquids has not been as extensively studied. Here we report new ion microprobe silicon isotopic measurements of residual glass from partial evaporation of Type B CAI liquids into vacuum. The silicon isotopic fractionation is reported as a kinetic fractionation factor, α_Si, corresponding to the ratio of the silicon isotopic composition of the evaporation flux to that of the residual silicate liquid. For CAI-like melts, we find that α_Si = 0.98985 ± 0.00044 (2σ) for ²⁹Si/²⁸Si with no resolvable variation with temperature over the temperature range of the experiments, 1600-1900 °C. This value is different from what has been reported for evaporation of liquid Mg₂SiO₄ (Davis A. M., Hashimoto A., Clayton R. N., and Mayeda T. K. (1990) Isotope mass fractionation during evaporation of Mg₂SiO₄. Nature347, 655-658.) and of a melt with CI chondritic proportions of the major elements (Wang J., Davis A. M., Clayton R. N., Mayeda T. K., and Hashimoto A. (2001) Chemical and isotopic fractionation during the evaporation of the FeO-MgO-SiO₂-CaO-Al₂O₃-TiO₂-REE melt system. Geochim. Cosmochim. Acta65, 479-494.). There appears to be some compositional control on α_Si, whereas no compositional effects have been reported for α_Mg. We use the values of α_Si and α_Mg, to calculate the chemical compositions of the unevaporated precursors of a number of isotopically fractionated CAIs from CV chondrites whose chemical compositions and magnesium and silicon isotopic compositions have been previously measured.     

Zur Auswertung astronomischer Aufnahmen mit dem automatischen Flächenphotometer

By measuring astronomical plates point by point by a microdensitometer information of very high redundancy is provided together with considerable noise due to the grains of the emulsion. In order to get astronomically relevant parameters the signal has to be separated from this noise and the data should be compressed. A chain of processing steps is described and analysed the crucial part of which being a variable twodimensional filter. This filter fits automatically its own band width to the incoming signal and reduces the number of data considerably (up to a factor of about 100). It is based on a modified HAAR transform and can be implemented easily on a relatively small processor working on line with the microdensitometer. The optimal separation of the noise is accomplished by a further variable digital filter (twodimensional KALMAN filter performed on an universal computer) the band width of which is also steered by the HAAR filter. The stars and galaxies in a larger field of the plate are picked up in the domain of the HAAR transform. Finally, the astronomically relevant parameters (coordinates and brightness of stars; furthermore diameter, axial ratio, position angle, perturbation, bright core et al. for galaxies) are obtained from the expansion of the intensity distribution into potential moments. The method is applicable e.g. to the determination of the brightness or colour distribution in a single galaxy or to the photometry of all stars and galaxies in a large part of the plate. The star photometry is obtained by integrating the intensity distribution of each object, if the characteristic curve of the plate is known from a calibration wedge copied onto the plate. Then no photoelectric sequency across the whole brightness range under consideration is needed besides of the zero point of the magnitude scale.