TiO2 exsolution from garnet by open-system precipitation: evidence from crystallographic and shape preferred orientation of rutile inclusions

We investigated rutile needles with a clear shape preferred orientation in garnet from (ultra) high-pressure metapelites from the Kimi Complex of the Greek Rhodope by electron microprobe, electron backscatter diffraction and TEM techniques. A definite though complex crystallographic orientation relationship between the garnet host and rutile was identified in that Rt[001] is either parallel to Grt<111> or describes cones with opening angle 27.6° around Grt<111>. Each Rt[001] small circle representing a cone on the pole figure displays six maxima in the density plots. This evidence together with microchemical observations in TEM, when compared to various possible mechanisms of formation, corroborates a precipitate origin. A review of exchange vectors for Ti substitution in garnet indicates that rutile formation from garnet cannot occur in a closed system. It requires that components are exchanged between the garnet interior and the rock matrix by solid-state diffusion, a process we refer to as “open-system precipitation” (OSP). The kinetically most feasible reaction of this type will dominate the overall process. The perhaps most efficient reaction involves internal oxidation of Fe²⁺ to Fe³⁺ and transfer from the dodecahedral to the octahedral site just vacated by $ {\text{Ti}}^{ 4+ }: 6\,{\text{M}}^{ 2+ }_{ 3} {\text{TiAl}}\left[ {{\text{AlSi}}_{ 2} } \right]{\text{O}}_{ 1 2} + 6\,{\text{M}}^{ 2+ }_{ 2, 5} {\text{TiAlSi}}_{ 3} {\text{O}}_{ 1 2} = 10\,{\text{M}}^{ 2+ }_{ 3.0} {\text{Al}}_{ 1. 8} {\text{Fe}}_{0. 2} {\text{Si}}_{ 3} {\text{O}}_{ 1 2} + {\text{M}}^{2+} + 2 {\text{e}}^{-} + 1 2\,{\text{TiO}}_{ 2} . $ OSP is likely to occur at conditions where the transition of natural systems to open-system behaviour becomes apparent, as in the granulite and high-temperature eclogite facies.     

Hydrodynamics and sediment dynamics in the German Bight. A focus on observations and numerical modelling in the East Frisian Wadden Sea

This work deals with analysis of hydrographic observations and results of numerical simulations. The data base includes acoustic Doppler current profilers (ADCP) observations, continuous measurements on data stations and satellite data originating from the medium resolution imaging spectrometer (MERIS) onboard the European Space Agency (ESA) satellite ENVISAT with a spatial resolution of 300 m. Numerical simulations use nested models with horizontal resolutions ranging from 1 km in the German Bight to 200 m in the East Frisian Wadden Sea coupled with a suspended matter transport model. Modern satellite observations have now a comparable horizontal resolution with high-resolution numerical model of the entire area of the East Frisian Wadden Sea allowing to describe and validate new and so far unknown patterns of sediment distribution. The two data sets are consistent and reveal an oscillatory behaviour of sediment pools to the north of the back-barrier basins and clear propagation patterns of tidally driven suspended particulate matter outflow into the North Sea. The good agreement between observations and simulations is convincing evidence that the model simulates the basic dynamics and sediment transport processes, which motivates its further use in hindcasting, as well as in the initial steps towards forecasting circulation and sediment dynamics in the coastal zone.     

Modelling blue and green water resources availability in Iran

Knowledge of the internal renewable water resources of a country is strategic information which is needed for long‐term planning of a nation's water and food security, among many other needs. New modelling tools allow this quantification with high spatial and temporal resolution. In this study we used the program Soil and Water Assessment Tool (SWAT) in combination with the Sequential Uncertainty Fitting program (SUFI‐2) to calibrate and validate a hydrologic model of Iran based on river discharges and wheat yield, taking into consideration dam operations and irrigation practices. Uncertainty analyses were also performed to assess the model performance. The results were quite satisfactory for most of the rivers across the country. We quantified all components of the water balance including blue water flow (water yield plus deep aquifer recharge), green water flow (actual and potential evapotranspiration) and green water storage (soil moisture) at sub‐basin level with monthly time‐steps. The spatially aggregated water resources and simulated yield compared well with the existing data. The study period was 1990–2002 for calibration and 1980–1989 for validation. The results show that irrigation practices have a significant impact on the water balances of the provinces with irrigated agriculture. Concerning the staple food crop in the country, 55% of irrigated wheat and 57% of rain‐fed wheat are produced every year in water‐scarce regions. The vulnerable situation of water resources availability has serious implications for the country's food security, and the looming impact of climate change could only worsen the situation. This study provides a strong basis for further studies concerning the water and food security and the water resources management strategies in the country and a unified approach for the analysis of blue and green water in other arid and semi‐arid countries. Copyright © 2008 John Wiley & Sons, Ltd.     

Towards continuous long-term measurements of suspended particulate matter (SPM) in turbid coastal waters

The dynamics of sediment transport in the East Frisian Wadden Sea are important for the coastal zone and for ecosystem functioning. The tidal inlets between the East Frisian islands connect the back-barrier intertidal flats to the North Sea. Here, concentrations of suspended particulate matter (SPM) in the water column are highly variable, depending on weather conditions and tides. In order to estimate the nature and quantity of sediment transport, in situ measurements were carried out at a Time Series Station in the tidal inlet between the islands of Spiekeroog and Langeoog. This study shows the suitability of multispectral transmissometry (MST) for obtaining long-term SPM measurements with high resolution. The comparability of this technique to the standard filter method and the laser diffraction method [laser in situ scattering and transmissometry (LISST)] is demonstrated. In addition, the Junge coefficients derived from both MST and LISST measurements are compared. A time series of SPM data covering nearly 4 months is presented. As a major result, the data reveal that a single storm surge can have less impact on SPM dynamics than longer-lasting gales. This high-resolution long-term data set is very valuable for modelling suspended matter flux. It also provides background information for studying the influence of SPM dynamics on coastal sediments.     

Node-centered finite volume discretizations for the numerical simulation of multiphase flow in heterogeneous porous media

Three node-centered finite volume discretizations for multiphase porous media flow are presented and compared. By combination of these methods two additional discretization methods are generated. The ability of these schemes to describe flows at textural interfaces of different geologic formations is investigated. It was found that models with nonzero-entry pressures for the capillary pressure-saturation relationship in conjunction with the Box discretization may give rise to spurious oscillations for flows around low permeable lenses. Furthermore, the applicability and sensitivity of the discretization methods with regard to the used computational grids is discussed. The schemes are used for the numerical study of two-phase flow in porous media with zones of different material properties. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ionic conductivity in gem-quality single-crystal alkali feldspar from the Eifel: temperature,orientation and composition dependence

We measured the ion conductivity of single-crystal alkali feldspar originating from two different locations in the Eifel/Germany, named Volkesfeld and Rockeskyller sanidine and having potassium site fractions \(C_\mathrm{K}\) of 0.83 and 0.71, respectively. The dc conductivities resulting from electrochemical impedance spectroscopy over the temperature range of 300–900 \(^{\circ }\hbox {C}\) show a weak composition dependence but pronounced differences between the b-direction [\(\perp (010)\)] and \(c^{*}\)-direction [\(\perp (001)\)] of the monoclinic feldspar structure. Conductivity activation energies obtained from the observed linear Arrhenius plots are close to 1.2 eV in all cases, which is closely similar to the activation energies of the \(^{22}\mathrm{Na}\) tracer diffusivity in the same crystals. Taking into account literature data on K tracer diffusion and diffusion correlation effects, the present results point to a predominance of the interstitialcy mechanism over the vacancy mechanism in mass and charge transport on the alkali sublattice in potassium-rich alkali feldspar.     

Redistribution of HFSE elements during rutile replacement by titanite

Titanite growth at the expense of rutile during retrograde hydration of eclogite into amphibolite is a common phenomenon. We investigated an amphibolite sample from the Tromsø eclogite facies terrain in Northern Norway to gain insight into the trace element distribution between rutile and titanite during incomplete resorption of the rutile by titanite. Patchy compositional zoning of Al, Ti, and F in titanite relates to the presence of a fluid with variable Ti/Al and/or F during its growth. Laser ablation ICP–MS and electron microprobe data for high field strength elements (HFSE: Nb, Zr, Ta, and Hf) of rutile resorbed by titanite indicate a pronounced enrichment of these elements in the rim of a large single rutile crystal (~8 mm) and a systematic decrease towards uniform HFSE contents in the large core. HFSE contents of smaller rutile grains (~0.5 mm) and rutile inclusions (<100 μm) in the titanite overgrowth are similar or higher than in the rims of large rutile crystals. Element profiles from the rim inward demonstrate that HFSE enrichment in rutile is controlled by diffusion. HFSE ratios in diffusion-altered rutile show systematic variations compared with the uniform core composition of the large rutile. Modelling of Zr and Nb diffusion in rutile indicates that diffusion coefficients in rutile in fluid-dominated natural systems must be considerably higher than those determined experimentally at 1 bar in dry systems. Variations of HFSE contents in the newly formed titanite show no systematic spatial distribution. HFSE ratios in titanite and the rims of rutile are different, indicating different solid/fluid distribution coefficients in these minerals. Element fractionation by diffusion into the relict rutile and during fluid-mediated growth of new titanite could substantially change the HFSE budget of these minerals and could affect their use for geochemical tracing and other applications, such as Zr-based geothermobarometry.     

The Late Precambrian Timna igneous complex, Southern Israel: Evidence for comagmatic-type sanukitoid monzodiorite and alkali granite magma

New data from a geochemical, geochronological and isotopic study of the Late Precambrian Timna igneous complex suggest the formation of alkali granites from a LIL-enriched, mantle derived, sanukitoid-type monzodiorite (a silica oversaturated rock with Mg# >60). These data also provide new insights into the petrology, timing and regional tectonic control of the transition from the calc-alkaline to the alkaline magmatic activity in the northern Arabian-Nubian Shield (ANS) during the Late Precambrian.

The Timna alkali granite was formed by fractional crystallization from the monzodioritic magma in a quasi-stratified magmatic cell which formed 610 Ma ago in the 625 Ma old calc-alkaline, porphyritic granite crust. These monzodiorites are mantle-derived, as demonstrated by their high Mg# (63), Cr (230 ppm), and Ni (120 ppm). They are characterized by initial ⁸⁷Sr/⁸⁶Sr of 0.7034, ε-Nd (610 Ma) = +3.4, and are enriched in K₂O (2.9%), Sr (840 ppm), Ba (1290 ppm) and LREE [(La/Lu)_n= 10–25]. The chemical characteristics and REE patterns of the monzodiorites and andesitic dykes of Timna are very similar to Dokhan andesites from northeastern Egypt and the Archean sanukitoids from Canada. The isotopic, geochemical and geochronologic data all indicate that Timna monzodiorites are comagmatic with the alkali granite. The alkali granite is a typical post-orogenic, borderline A-type granite. It is enriched in potassium (K₂O=4.68–6.64%), has a negative europium anomaly (Eu/Eu^*=0.058–0.38) and ε-Nd (610 Ma) of +3.9. The calc-alkaline granite is a typical I-type granite with a small positive europium anomaly (Eu/Eu^*=1.02–1.16). Its age and the Sr, Nd and Pb isotopic characteristics with ε-Nd (625 Ma) of +5.6 to +5.9 are significantly different from these of the alkali granite and monzodiorites, and indicate little interaction with the monzodiorite during the formation of the alkali granite.

The alkali granites are correlative with the post-collisional extensional granites in Jordan and Egypt while the porphyritic granites can be correlated with the late orogenic types. Crustal thickening associated with orogenic compression resulted in crustal anatexis to form the I-type granitic rocks, whereas crustal thinning associated with extension allowed LIL-enriched mantle melts to rise very near to the surface, where space was available for these to pond and fractionate to alkali granite.     

Noble gas composition of the solar wind as collected by the Genesis mission

We present the elemental and isotopic composition of noble gases in the bulk solar wind collected by the NASA Genesis sample return mission. He, Ne, and Ar were analyzed in diamond-like carbon on a silicon substrate (DOS) and ^84,86Kr and ^129,132Xe in silicon targets by UV laser ablation noble gas mass spectrometry. Solar wind noble gases are quantitatively retained in DOS and with exception of He also in Si as shown by a stepwise heating experiment on a flown DOS target and analyses on other bulk solar wind collector materials. Solar wind data presented here are absolutely calibrated and the error of the standard gas composition is included in stated uncertainties. The isotopic composition of the light noble gases in the bulk solar wind is as follows: ³He/⁴He: (4.64 ± 0.09) × 10⁻⁴, ²⁰Ne/²²Ne: 13.78 ± 0.03, ²¹Ne/²²Ne: 0.0329 ± 0.0001, ³⁶Ar/³⁸Ar 5.47 ± 0.01. The elemental composition is: ⁴He/²⁰Ne: 656 ± 5, and ²⁰Ne/³⁶Ar 42.1 ± 0.3. Genesis provided the first Kr and Xe data on the contemporary bulk solar wind. The preliminary isotope and elemental composition is: ⁸⁶Kr/⁸⁴Kr: 0.302 ± 0.003, ¹²⁹Xe/¹³²Xe: 1.05 ± 0.02, ³⁶Ar/⁸⁴Kr 2390 ± 150, and ⁸⁴Kr/¹³²Xe 9.5 ± 1.0. The ³He/⁴He and the ⁴He/²⁰Ne ratios in the Genesis DOS target are the highest solar wind values measured in exposed natural and artificial targets. The isotopic composition of the other noble gases and the Kr/Xe ratio obtained in this work agree with data from lunar samples containing “young” (∼100 Ma) solar wind, indicating that solar wind composition has not changed within at least the last 100 Ma. Genesis could provide in many cases more precise data on solar wind composition than any previous experiment. Because of the controlled exposure conditions, Genesis data are also less prone to unrecognized systematic errors than, e.g., lunar sample analyses. The solar wind is the most authentic sample of the solar composition of noble gases, however, the derivation of solar noble gas abundances and isotopic composition using solar wind data requires a better understanding of fractionation processes acting upon solar wind formation.