The crystal and magnetic structure of Li-aegirine LiFe3+Si2O6: a temperature-dependent study

Single crystals of Li-aegirine LiFe³⁺Si₂O₆ were synthesized at 1573?K and 3?GPa, and a polycrystalline sample suitable for neutron diffraction was produced by ceramic sintering at 1223?K. LiFe³⁺Si₂O₆ is monoclinic, space group C2/c, a=9.6641(2)?Å, b= 8.6612(3)?Å, c=5.2924(2)?Å, β=110.12(1)^° at 300?K as refined from powder neutron data. At 229?K Li-aegirine undergoes a phase transition from C2/c to P2₁ /c. This is indicated by strong discontinuities in the temperature variation of the lattice parameters, especially for the monoclinic angle β and by the appearance of Bragg reflections (hkl) with h+k≠2n. In the low-temperature form two non-equivalent Si-sites with 〈SiA–O〉=1.622?Å and 〈SiB–O〉=1.624?Å at 100?K are present. The bridging angles of the SiO₄ tetrahedra O3–O3–O3 are 192.55(8)° and 160.02(9)° at 100?K in the two independent tetrahedral chains in space group P2₁ /c, whereas it is 180.83(9)° at 300?K in the high-temperature C2/c phase, i.e. the chains are nearly fully expanded. Upon the phase transition the Li-coordination changes from six to five. At 100?K four Li–O bond lengths lie within 2.072(4)–2.172(3)?Å, the fifth Li–O bond length is 2.356(4)?Å, whereas the Li–O3?A bond lengths amount to 2.796(4)?Å. From ⁵⁷Fe Mössbauer spectroscopic measurements between 80 and 500?K the structural phase transition is characterized by a small discontinuity of the quadrupole splitting. Temperature-dependent neutron powder diffraction experiments show first occurrence of magnetic reflections at 16.5?K in good agreement with the point of inflection in the temperature-dependent magnetization of LiFe³⁺Si₂O₆. Distinct preordering phenomena can be observed up to 35?K. At the magnetic phase transition the unit cell parameters exhibit a pronounced magneto-striction of the lattice. Below T _N Li-aegirine shows a collinear antiferromagnetic structure. From our neutron powder diffraction experiments we extract a collinear antiferromagnetic spin arrangement within the a–c plane.     

Combined L1/L2 Kalman filter-based tracking scheme for weak signal environments

A Kalman filter-based method combining the energy of both L1 C/A and L2C GPS signals in a combined tracking loop method to enhance performance under adverse conditions is developed. Standard tracking methods and the ionospheric effect on GPS signals are reviewed and compared to a new Kalman filter that simultaneously estimates delay, phase and total electron content by combining L1 C/A and L2C code and phase discriminator outputs. The new filter is tested and compared to standard methods for tracking L1 C/A and L2C using both simulated and real data. The new method is found to have improved sensitivity of 3 dB compared to standard L1 tracking and 4.5 dB compared to standard L2C tracking while at the same time providing an accurate estimate of the total electron content along the signal path.     

Experiments on the ocean sequestration of fossil fuel CO2: pH measurements and hydrate formation

We have carried out a series of in situ experiments to investigate the formation of a CO₂ hydrate (CO₂:5.75 H₂O) for the purpose of evaluating scenarios for ocean fossil fuel CO₂ disposal with a solid hydrate as the sequestered form. The experiments were carried out with a remotely operated vehicle in Monterey Bay at a depth of 619 m. pH measurements made in close proximity to the hydrate–seawater interface showed a wide range of values, depending upon the method of injection and the surface area of the hydrate formed. Rapid injection of liquid CO₂ into an inverted beaker to form a flocculant mass of hydrate resulted in pH initially as low as 4.5 within a few centimeters of the interface, decaying slowly over 1–2 h towards normal seawater values as dense CO₂ rich brine drained from the hydrate mass. In a second experiment, slower injection of the liquid CO₂ to produce a simple two-layer system with a near planar interface of liquid CO₂ with a thin hydrate film yielded pH values indistinguishable from the in situ ocean background level of 7.6. Both field and laboratory results now show that the dissolution rate of a mass of CO₂ hydrate in seawater is slow but finite.     

Cave bear occupation in Schwabenreith Cave,Austria, during the early last glacial: constraints from 230Th/U‐dated speleothems

The cave bear was a prominent member of the Upper Pleistocene fauna in Eurasia. While breakthroughs were recently achieved with respect to its phylogeny using ancient DNA techniques, it is still challenging to date cave bear fossils beyond the radiocarbon age range. Without an accurate and precise chronological framework, however, key questions regarding the palaeoecology cannot be addressed, such as the extent to which large climate swings during the last glacial affected the habitat and possibly even conditioned the final extinction of this mammal. Key to constraining the age of cave bear fossils older than the lower limit of radiocarbon dating is to date interlayered speleothems using ²³⁰Th/U. Here we report new results from one such site in the Eastern European Alps (Schwabenreith Cave), which yielded the highest density of bones of cave bear (Ursus spelaeus eremus). Although dating of the flowstones overlying this fossiliferous succession was partly compromised by diagenetic alteration, the ²³⁰Th/U dates indicate that the bear hibernated in this cave after about 113 ka and before about 109 ka. This time interval coincides with the equivalent of Greenland Stadial 25, suggesting possible climate control on the cave bear's habitat and behaviour. © 2019 The Authors. Journal of Quaternary Science Published by John Wiley & Sons Ltd     

Monitoring GOCE gradiometer calibration parameters using accelerometer and star sensor data: methodology and first results

The Gravity field and steady-state Ocean Circulation Explorer (GOCE) satellite, launched on 17 March 2009, is designed to measure the Earth’s mean gravity field with unprecedented accuracy at spatial resolutions down to 100?km. The accurate calibration of the gravity gradiometer on-board GOCE is of utmost importance for achieving the mission goals. ESA’s baseline method for the calibration uses star sensor and accelerometer data of a dedicated calibration procedure, which is executed every 2?months. In this paper, we describe a method for monitoring the evolution of calibration parameter during that time. The method works with star sensor and accelerometer data and does not require gravity field models, which distinguishes it from other existing methods. We present time series of calibration parameters estimated from GOCE data from 1 November 2009 to 17 May 2010. The time series confirm drifts in the calibration parameters that are present in the results of other methods, including ESA’s baseline method. Although these drifts are very small, they degrade the gravity gradients, leading to the conclusion that the calibration parameters of the ESA’s baseline method need to be linearly interpolated. Further, we find a correction of ?36 × 10^?6 for one calibration parameter (in-line differential scale factor of the cross-track gradiometer arm), which improves the gravity gradient performance. The results are validated by investigating the trace of the calibrated gravity gradients and comparing calibrated gravity gradients with reference gradients computed along the GOCE orbit using the ITG-Grace-2010s gravity field model.     

The impact of salinity on the Mg/Ca and Sr/Ca ratio in the benthic foraminifera Ammonia tepida: Results from culture experiments

Over the last decade, sea surface temperature (SST) reconstructed from the Mg/Ca ratio of foraminiferal calcite has increasingly been used, in combination with the δ¹⁸O signal measured on the same material, to calculate the δ¹⁸O_w, a proxy for sea surface salinity (SSS). A number of studies, however, have shown that the Mg/Ca ratio is also sensitive to other parameters, such as pH or , and salinity. To increase the reliability of foraminiferal Mg/Ca ratios as temperature proxies, these effects should be quantified in isolation. Individuals of the benthic foraminifera Ammonia tepida were cultured at three different salinities (20, 33 and 40 psu) and two temperatures (10-15 °C). The Mg/Ca and Sr/Ca ratios of newly formed calcite were analyzed by Laser Ablation ICP-MS and demonstrate that the Mg concentration in A. tepida is overall relatively low (mean value per experimental condition between 0.5 and 1.3 mmol/mol) when compared to other foraminiferal species, Sr being similar to other foraminiferal species. The Mg and Sr incorporation are both enhanced with increasing temperatures. However, the temperature dependency for Sr disappears when the distribution factor D_Sr is plotted as a function of calcite saturation state (Ω). This suggests that a kinetic process related to Ω is responsible for the observed dependency of Sr incorporation on sea water temperature. The inferred relative increase in D_Mg per unit salinity is 2.8% at 10 °C and 3.3% at 15 °C, for the salinity interval 20-40 psu. This implies that a salinity increase of 2 psu results in enhanced Mg incorporation equivalent to 1 °C temperature increase. The D_Sr increase per unit salinity is 0.8% at 10 °C and 1.3% at 15 °C, for the salinity interval 20-40 psu.     

Interstitial flow through preferential flow paths in the hyporheic zone of the Oberer Seebach,Austria

We investigated interstitial flow velocities in the Oberer Seebach, Austria, with NaCl tracer injections at a sediment depth of 30 cm to estimate the hydraulic conditions experienced by invertebrates inhabiting the hyporheic zone. Flow velocity measured with tracers is taken as travel time of the water along a straight line between injection and sampling points, although the water flows around sediment particles, and thus travels a somewhat longer distance. From sections of stream sediment in which the interstitial spaces were replaced by concrete, we estimated that this difference amounts, on average, to 27% and used this factor to correct the results of our velocity measurements. Corrected interstitial water velocities ranged from 0.01 to 1.32 cm s^-1 and were independent of surface discharge. We also studied spatial flow patterns in the bed sediments with long-term tracer injections. The three-dimensional distribution of tracer concentrations 24 hours after the start of the injection indicated that interstitial water preferentially flows in a complex network of areas of high hydraulic connectivity. Reynolds numbers for flow in the hyporheic pore space ranged from 0.1 to 489, implying that the flow environment varies from laminar up to the zone of transition to turbulent flow. Therefore, invertebrates may have a size-related active choice of areas where either friction drag or pressure drag predominates. The consequence of flow patterns, such as those observed in our study, is that small-scale variability of hydraulic conditions may be an important determinant of the patchy invertebrate distribution in bed sediments.     

Late Holocene to Recent aragonite-cemented transgressive lag deposits in the Abu Dhabi lagoon and intertidal sabkha

Modern cemented intervals (beachrock, firmgrounds to hardgrounds and concretionary layers) form in the lagoon and intertidal sabkha of Abu Dhabi. Seafloor lithification actively occurs in open, current-swept channels in low-lying areas between ooid shoals, in the intertidal zone of the middle lagoon, some centimetres beneath the inner lagoonal seafloor (i.e. within the sediment column) and at the sediment surface the intertidal sabkha. The concept of ‘concretionary sub-hardgrounds’, i.e. laminar cementation of sediments formed within the sediment column beneath the shallow redox boundary, is introduced and discussed. Based on calibrated radiocarbon ages, seafloor lithification commenced during the Middle to Late Holocene (ca 9000 cal yr bp ), and proceeds to the present-day. Lithification occurs in the context of the actualistic relative sea-level rise shifting the coastline landward across the extremely low-angle carbonate ramp. The cemented intervals are interpreted as parasequence boundaries in the sense of ‘marine flooding surfaces’, but in most cases the sedimentary cover overlying the transgressive surface has not yet been deposited. Aragonite, (micritic) calcite and, less commonly, gypsum cements lithify the firmground/hardground intervals. Cements are described and placed into context with their depositional and marine diagenetic environments and characterized by means of scanning electron microscope petrography, cathodoluminescence microscopy and Raman spectroscopy. The morphology of aragonitic cements changes from needle-shaped forms in lithified decapod burrows of the outer lagoon ooidal shoals to complex columnar, lath and platy crystals in the inner lagoon. Precipitation experiments provide first tentative evidence for the parameters that induce changes in aragonite cement morphology. Data shown here shed light on ancient, formerly aragonite-cemented seafloors, now altered to diagenetic calcites, but also document the complexity of highly dynamic near coastal depositional environments.