Competition and cooperation between antiferrodistortive and ferroelectric instabilities in the model perovskite SrTiO₃

We use density functional theory to explore the interplay between octahedral rotations and ferroelectricity in the model compound SrTiO3. We find that over the experimentally relevant range octahedral rotations suppress ferroelectricity as is generally assumed in the literature. Somewhat surprisingly, we observe that at larger angles the previously weakened ferroelectric instability strengthens significantly. By analyzing geometry changes, energetics, force constants and charges, we explain the mechanisms behind this transition from competition to cooperation with increasing octahedral rotation angle.

From pink to blue and back to pink again: changing the Co( ii ) ligation in a two-dimensional coordination network upon desolvation

Heating of a pink two-dimensional Co(II) coordination network {[Co2(μ2-OH2)(bdc)2(S-nia)2(H2O)(dmf)]·2(dmf)·(H2O)}n (1) built from 1,4-benzenedicarboxylic acid (H2bdc) residues and thionicotinamide (S-nia) ligands initiates a single-crystal-to-single-crystal transition accompanied by removal of both coordinated and co-crystallized solvents. In the dry blue form, [Co(bdc)(S-nia)]n (dry_1), the Co(II) centers changed from an octahedral to a square pyramidal configuration.

Submaximal cardiopulmonary thresholds on a robotics-assisted tilt table, a cycle and a treadmill: a comparative analysis

BACKGROUND: The robotics-assisted tilt table (RATT), including actuators for tilting and cyclical leg movement, is used for rehabilitation of severely disabled neurological patients. Following further engineering development of the system, i.e. the addition of force sensors and visual bio-feedback, patients can actively participate in exercise testing and training on the device. Peak cardiopulmonary performance parameters were previously investigated, but it also important to compare submaximal parameters with standard devices. The aim of this study was to evaluate the feasibility of the RATT for estimation of submaximal exercise thresholds by comparison with a cycle ergometer and a treadmill. METHODS: 17 healthy subjects randomly performed six maximal individualized incremental exercise tests, with two tests on each of the three exercise modalities. The ventilatory anaerobic threshold (VAT) and respiratory compensation point (RCP) were determined from breath-by-breath data. RESULTS: VAT and RCP on the RATT were lower than the cycle ergometer and the treadmill: oxygen uptake (V'O2) at VAT was [mean (SD)] 1.2 (0.3), 1.5 (0.4) and 1.6 (0.5) L/min, respectively (p < 0.001); V'O2 at RCP was 1.7 (0.4), 2.3 (0.8) and 2.6 (0.9) L/min, respectively (p = 0.001). High correlations for VAT and RCP were found between the RATT vs the cycle ergometer and RATT vs the treadmill (R on the range 0.69-0.80). VAT and RCP demonstrated excellent test-retest reliability for all three devices (ICC from 0.81 to 0.98). Mean differences between the test and retest values on each device were close to zero. The ventilatory equivalent for O2 at VAT for the RATT and cycle ergometer were similar and both were higher than the treadmill. The ventilatory equivalent for CO2 at RCP was similar for all devices. Ventilatory equivalent parameters demonstrated fair-to-excellent reliability and repeatability. CONCLUSIONS: It is feasible to use the RATT for estimation of submaximal exercise thresholds: VAT and RCP on the RATT were lower than the cycle ergometer and the treadmill, but there were high correlations between the RATT vs the cycle ergometer and vs the treadmill. Repeatability and test-retest reliability of all submaximal threshold parameters from the RATT were comparable to those of standard devices.

Inclination-dependent changes of the critical shoulder angle significantly influence superior glenohumeral joint stability.

BACKGROUND The critical shoulder angle combines the acromion index and glenoid inclination and has potential to discriminate between shoulders at risk for rotator cuff tear or osteoarthritis and those that are asymptomatic. However, its biomechanics, and particularly the role of the glenoid inclination, are not yet fully understood. METHODS A shoulder simulator was used to analyze the independent influence of glenoid inclination during abduction from 0 to 60°. Spindle motors transferred tension forces by a cable-pulley on human cadaveric humeri. A six-degree-of-freedom force transducer was mounted directly behind the polyethylene glenoid to measure shear and compressive joint reaction force and calculate the instability ratio (ratio of shear and compressive joint reaction force) with the different force ratios of the deltoid and supraspinatus muscles (2:1 and 1:1). A stepwise change in the inclination by 5° increments allowed simulation of a critical shoulder angle range of 20° to 45°. FINDINGS Tilting the glenoid to cranial (increasing the critical shoulder angle) increases the shear joint reaction force and therefore the instability ratio. A balanced force ratio (1:1) between the deltoid and the supraspinatus allowed larger critical shoulder angles before cranial subluxation occurred than did the deltoid-dominant ratio (2:1). INTERPRETATION Glenoid inclination-dependent changes of the critical shoulder angle have a significant impact on superior glenohumeral joint stability. The increased compensatory activity of the rotator cuff to keep the humeral head centered may lead to mechanical overload and could explain the clinically observed association between large angles and degenerative rotator cuff tears.

UHP Metamorphism Documented in Ti-chondrodite- and Ti-clinohumite-bearing Serpentinized Ultramafic Rocks from Chinese Southwestern Tianshan

The southwestern Tianshan (China) metamorphic belt records high-pressure (HP) to ultrahigh-pressure (UHP) conditions corresponding to a cold oceanic subduction-zone setting. Serpentinites enclosing retrogressed eclogite and rodingite occur as lenses within metapelites in the UHP unit, which also hosts coesite-bearing eclogites. Based on the petrology and petrography of these serpentinites, five events are recognized: (1) formation of a wehrlite–harzburgite–dunite association in the mantle; (2) retrograde metamorphism and partial hydration during exhumation of the mantle rocks close to the seafloor; (3) oceanic metamorphism leading to the first serpentinization and rodingitization; (4) UHP metamorphism during subduction; (5) retrograde metamorphism during exhumation together with a second serpentinization. The peak metamorphic mineral assemblage of the serpentinized wehrlite comprises Ti-chondrodite + olivine + antigorite + chlorite + magnetite + brucite. A computed pseudosection for this serpentinized wehrlite shows that the Al content in antigorite is mostly sensititive to temperature but can also be used to constrain pressure. The average XAl = 0·204 ± 0·026 of antigorite (XAl = Al (a.p.f.u.)/8, where Al is in atoms per formula unit for a structural formula M48T34O85(OH)62, and M and T are octahedral and tetrahedral sites, respectively) included in Ti-chondrodite and average XAl = 0·203 ± 0·019 of antigorite in the matrix result in a well-constrained peak metamorphic temperature of 510–530°C. Peak pressures are less precisely constrained at 37 ± 7 kbar. The Tianshan serpentinites thus record UHP metamorphic conditions and represent the deepest subducted serpentinites discovered so far. The retrograde evolution occurs within the stability field of brucite + antigorite + olivine + chlorite and formation of Ti-clinohumite at the expense of Ti-chondrodite has been observed, suggesting isothermal decompression. The resulting P–T path is in excellent agreement with the metamorphic evolution of country rocks, indicating that the UHP unit in Tianshan was subducted and exhumed as a coherent block. To refine the metamorphic path of the ultramafic rocks, we have investigated the stability fields of Ti-chondrodite and Ti-clinohumite using piston-cylinder experiments. A total of 11 experiments were conducted at 25–55 kbar and 600–750°C in a F-free natural system. Combined with previous experiments and information from natural rocks we constructed a petrogenetic grid for the stability of Ti-chondrodite and Ti-clinohumite in F-free peridotite compositions. The formation of Ti-chondrodite in serpentinites requires a minimum pressure of about 26 kbar, whereas in Ti-rich systems it can form at considerably lower pressures. A key finding is that at UHP conditions, F-free Ti-chondrodite or Ti-clinohumite breaks down in the presence of orthopyroxene between 700 and 750°C, at temperatures that are significantly lower than those of the terminal breakdown reactions of these humite minerals. These breakdown reactions are an additional source of fluid during prograde subduction of serpentinites.

The Effect of Increasing Intracranial Pressure on Ocular Vestibular-Evoked Myogenic Potential Frequency Tuning.

OBJECTIVE Ocular vestibular-evoked myogenic potentials (oVEMPs) represent extraocular muscle activity in response to vestibular stimulation. The authors sought to investigate whether posture-induced increase of the intracranial pressure (ICP) modulated oVEMP frequency tuning, that is, the amplitude ratio between 500-Hz and 1000-Hz stimuli. DESIGN Ten healthy subjects were enrolled in this study. The subjects were positioned in the horizontal plane (0 degree) and in a 30-degree head-downwards position to elevate the ICP. In both positions, oVEMPs were recorded using 500-Hz and 1000-Hz air-conducted tone bursts. RESULTS When tilting the subject from the horizontal plane to the 30-degree head-down position, oVEMP amplitudes in response to 500-Hz tone bursts distinctly decreased (3.40 μV versus 2.06 μV; p < 0.001), whereas amplitudes to 1000 Hz were only slightly diminished (2.74 μV versus 2.48 μV; p = 0.251). Correspondingly, the 500/1000-Hz amplitude ratio significantly decreased when tilting the subjects from 0- to 30-degree inclination (1.59 versus 1.05; p = 0.029). Latencies were not modulated by head-down position. CONCLUSIONS Increasing ICP systematically alters oVEMPs in terms of absolute amplitudes and frequency tuning characteristics. oVEMPs are therefore in principle suited for noninvasive ICP monitoring.

Geochemistry and petrology of ODP Leg 121 basalts

Basement lavas from Sites 756, 757, and 758 on Ninetyeast Ridge are tholeiitic basalts. Lavas from Sites 756 and 757 appear to be subaerial eruptives, but the lowermost flows from Hole 758A are pillow lavas. In contrast to the compositional variation during the waning stages of Hawaiian volcanism, no alkalic lavas have been recovered from Ninetyeast Ridge and highly evolved lavas were recovered from only one of seven drill sites (DSDP Site 214). All lavas from Site 758 have relatively high MgO contents (8-10 wt%), and they are less evolved than lavas from Sites 756 and 757. Although abundances of alkali metals in these Ninetyeast Ridge basalts were significantly modified by postmagmatic alteration, abundances of other elements reflect magmatic processes. At Site 757 most of the lavas are Plagioclase cumulates, but lava compositions require two compositionally distinct, AhCb-rich parental magmas, perhaps segregated at relatively low mantle pressures. In addition, at both Sites 756 and 758 more than one compositionally distinct parental magma is required. The compositions of these Ninetyeast Ridge lavas, especially those from Site 758, require a source component with a depleted composition; specifically, the abundance ratios Th/Ta, Th/La, Ba/Nb, Ba/La, and La/Ce in these lavas are generally less than the ratios inferred for primitive mantle. Lavas from Ninetyeast Ridge and the Kerguelen Archipelago have very different chondrite-normalized REE patterns, with lower light REE/heavy REE (LREE/HREE) ratios in lavas from Ninetyeast Ridge. However, lavas from Sites 757 and 758 have Pb isotope ratios that overlap with the field defined by lavas from the Kerguelen Archipelago (Weis and Frey, this volume). Therefore, these Ninetyeast Ridge lavas contain more of a component that is relatively depleted in LREE and other highly incompatible elements, but have similar amounts of the component that controls radiogenic Pb isotopes. A model involving mixing between components related to a depleted source and an enriched plume source has been proposed for the oldest Kerguelen Archipelago basalts and Ninetyeast Ridge lavas. Although the incompatible element characteristics of the Ninetyeast Ridge lavas are intermediate between depleted MORB and Kerguelen Archipelago basalts, these data are not consistent with a simple two-component mixing process. A more complex model is required.

Analysis of biogenic magnetite nanoparticles

Cobalt doped magnetite (CoxFe3-xO4) nanoparticles have been produced through the microbial reduction of cobalt-iron oxyhydroxide by the bacterium Geobacter sulfurreducens. The materials produced, as measured by SQUID, x-ray magnetic circular dichroism, Mössbauer spectroscopy, etc., show dramatic increases in coercivity with increasing cobalt content without a major decrease in overall saturation magnetization. Structural and magnetization analyses reveal a reduction in particle size to <4 nm at the highest Co content, combined with an increase in the effective anisotropy of the magnetic nanoparticles. The potential use of these biogenic nanoparticles in aqueous suspensions for magnetic hyperthermia applications is demonstrated. Further analysis of the distribution of cations within the ferrite spinel indicates that the cobalt is predominantly incorporated in octahedral coordination, achieved by the substitution of Fe2+ site with Co2+, with up to 17 per cent Co substituted into tetrahedral sites.

Sedimentology and mineralogy of surface sediments from the Chilean continental margin

The regional patterns of texture and composition of modern continental slope and pelagic sediments off Chile between 25°S and 43°S reflect the latitudinal segmentation of geological, morphological, and climatic features of the continental hinterland. Grain-size characteristics are controlled by the grain-size of source rocks, the weathering regime, and mode of sediment input (eolian off northern Chile vs fluvial further south). Bulk-mineral assemblages reveal a low grade of maturity. Regional variations are governed by the source-rock composition of the different geological terranes and the relative source-rock contribution of the Coastal Range and Andes, as controlled by the continental hydrology. The relative abundance of clay minerals is also predominantly influenced by the source-rock composition and partly by continental smectite neoformation. Latitudinal variations of illite crystallinities along the Chilean continental slope (and west of the Peru-Chile trench) clearly reflect modifications of the weathering regime which correspond to the strong climatic zonation of Chile.

Distribution, genesis and age of the Schlagwasser breccia (Warstein anticline, Rhenish massif)

The name "Schlagwasser breccia" is a synopsis of several debris flows in the Warstein area, which can be derived from the Warstein carbonate platform and the Scharfenberg reef. Though only locally developed, the breccia is important for the understanding of paleogeography and sedimentology in the Eastern Sauerland. Considering this breccia some gravitational-resedimentary slide movements between a high, consisting of reef carbonates, and a basin with flinz beds can be pointed out. From the uppermost Middle Devonian to the lowermost Lower Carboniferous several slides yielded the sedimentary components building up the 30 to 50 m thick polymict breccia. Some breccias were redeposited repeatedly as can be verified by different conodont maxima in single samples. Supplying area was the western part of the Warstein high, from which the slide masses glided off to the East and Southeast, more seldom to the West and Westsouthwest. All conodont zones from the upper Middle Devonian up to the lowermost Carboniferous could be identified in the Schlagwasser breccia. Therefore, an uninterrupted continuous sedimentation must have been prevalent in the supplying area; today this area nearly is denuded of flinz beds and cephalopod limestones. The slide masses spread transgressively to the East up to a substratum consisting of different units as massive limestone, flinz beds and cephalopod limestone; they are overlapped by Hangenberg beds, alum schists and siliceous rocks of the Lower Carboniferous. Parts of the substratum were transported during the progress of the slide masses. Proximal and distal parts of the flow masses can be distinguished by the diameter of the pebbles. Graded bedding and banking structures are marked only rarely. Way of transport was up to 3 km. Differently aged slide masses do not always overlap, but are placed side by side, too. Usually the slide masses do not spread out upon a greater area during sedimentation, but form closely limited debris flows. Synsedimentary fracturing and tilting of the reef platform, epirogenetic movements and seaquakes caused the slides. The entire formation period of the breccia includes about 20 millions of years. The longevity of the events points to solid paleomorphological situations around the eastern margin of the carbonate platform.

Geochemistry on smectites in sediment cores CRP-1 and CRP-2 from the Ross Sea, Antarctica

TEM (transmission electron microscopy) observations and microanalyses on smectite microparticles in the sediments of the CRP-2A core were carried out to determine their origin (authigenic or detrital) and the source rocks. Smectites are dioctahedral and are Fe-rich members of the nontronite-beidellite series. They generally display both flaky and hairy shapes, but no large compositional difference between the two forms was observed. Flaky smectites are detrital while hairy smectites probably formed in situ through the reorganisation of previous flaky particles. The source rocks for smectites are probably represented by the McMurdo Volcanic Group to the south, but also by the Ferrar Dolerites and Kirkpatrick Basalts in the Transantarctic Mountains. CRP-2A smectites are Fe and Mg richer than those of the coeval or not coeval levels of the CIROS-I, DSDP 270 and 274 cores. The average compositions of smectite in CRP-1 and CRP-2A cores show a downcore trend toward more alluminiferous terms, which might reflect the increase of the chemical weathering processes on the continent.

Composition of phyllosilicates from hydrothermally altered basalts of DSDP Hole 83-504B, Costa Rica Rift, Pacific Ocean

Phyllosilicates occurring as replacements of olivine, clinopyroxene and interstitial materials and as veins or fracture-fillings in hydrothermally altered basalts from DSDP Hole 504B, Leg 83 have been studied using transmission and analytical electron microscopy. The parageneses of phyllosilicates generally change systematically with depth and with the degree of alteration, which in turn is related to permeability of basalts. Saponite and some mixed-layer chlorite/smectite are the dominant phyllosilicates at the top of the transition zone. Chlorite, corrensite, and mixed-layer chlorite/corrensite occur mainly in the lower transition zone and upper levels of the sheeted dike zone. Chlorite, talc, and mixed-layer talc/chlorite are the major phyllosilicates in the sheeted dike zone, although replacement of talc or olivine by saponite is observed. The phyllosilicates consist of parallel or subparallel discrete packets of coherent layers with packet thicknesses generally ranging from < 100 A to a few hundred A. The packets of saponite layers are much smaller or less well defined than those of chlorite, corrensite and talc, indicating poorer crystallinity of saponite. By contrast, chlorite and talc from the lower transition zone and the sheeted dike zone occur in packets up to thousands of A thick. The Si/(Si + A1) ratio of these trioctahedral phyllosilicates increases and Fe/(Fe + Mg) decreases in the order chlorite, corrensite, saponite, and talc. These relations reflect optimal solid solution consistent with minimum misfit of articulated octahedral and tetrahedral sheets. Variations in composition of hydrothermal fluids and precursor minerals, especially in Si/(Si+A1) and Fe/(Fe+Mg) ratios, are thus important factors in controlling the parageneses of phyllosilicates. The phyllosilicates are generally well crystallized discrete phases, rather than mixed-layered phases, where they have been affected by relatively high fluid/rock ratios as in high-permeability basalts, in veins, or areas adjacent to veins. Intense alteration in basalts with high permeability (indicating high fluid/rock ratios) is characterized by pervasive albitization and zeolitization. Minimal alteration in the basalts without significant albitization and zeolitization is characterized by the occurrence of saponite ± mixed-layer chlorite/smectite in the low-temperature alteration zone, and mixed-layer chlorite/corrensite or mixed-layer talc/chlorite in the high-temperature alteration zone. Textural non-equilibrium for phyllosilicates is represented by mixed layering and poorly defined packets of partially incoherent layers. The approach to textural equilibrium was controlled largely by the availability of fluid or permeability.

Geochemistry of low-temperatuer altered basalts of ODP Hole 136-843B

The mineralogy and chemistry of altered basalts and the stable isotopic compositions of secondary vein carbonates were studied in cores from Ocean Drilling Program Hole 843B, located in 95-Ma crust of the Hawaiian Arch. Millimeter- to centimeter-sized dark alteration halos around veins are 5%-15% altered to celadonite and Fe-oxyhydroxides, plus minor saponite and calcite. Adjacent gray host rocks are about 15% altered to saponite and calcite. The dark halos are enriched in H2O+, CO2, FeT, K2O, MnO, and Fe3+/FeT and depleted in SiO2, Al2O3, MgO, and TiO2 relative to gray host rocks. Brown alteration halos occur around veins where veins are more abundant, and are similar to dark halos, but contain more Fe-oxyhydroxides and exhibit greater Fe2O3T contents and higher Fe3+/FeT. Stable isotopic compositions of vein carbonates are consistent with their precipitation from seawater at temperatures of 5°-40°C. Crosscutting relationships of veins and zoned vein and vesicle fillings reveal a sequence of secondary mineral formation and alteration conditions. Celadonite and Fe-oxyhydroxides formed and dark alteration halos developed relatively early, under oxidizing conditions at low temperatures (<50°C). Saponite formed later at lower seawater/rock ratios and under more reducing conditions. Calcite and pyrite formed last in veins and vesicles from more evolved, seawaterderived fluids at temperatures of 5°-40°C. A second stage of celadonite, with compositions distinct from the early celadonite, also occurred relatively late (within the "calcite stage"), and may be related to refracturing of the crust and introduction of less-evolved seawater solutions into the rocks. Trends to higher K2O contents are attributed to alteration, but high K/Ti, Ba, and Zr contents indicate the presence of enriched or transitional MORB. CO2 contents of Pacific ODP cores exhibit a general increase with age suggesting progressive fixation of CO2 as calcite in the crust, but this could be complicated by local heterogeneities in fracturing and calcite formation in the crust.