Thermal expansion and high-temperature P21/c–C2/c phase transition in clinopyroxene-type LiFeGe2O6 and comparison to NaFe(Si,Ge)2O6

A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) Å, β = 108.844(6)°, V = 442.75(16) ų, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the $(\bar{1}\,0\,1) A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) ?, β = 108.844(6)°, V = 442.75(16) ?³, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the ([`1] 0 1)(\bar{1}\,0\,1) plane, mostly along [0 1 0], and pure shear in the (0 1 0) plane due to the decrease of β. From comparison with silicate analogues, the germanate clinopyroxenes are more expansible, while the P2₁/c expands more than the C2/c phase. The evolution of Q ² (calculated as the normalized intensity of b-type reflections) with T in the framework of the Landau theory has been done using a standard expression for a first order phase transition. We observe a jump of Q ₀² = 0.538(2) at T _tr, with T _c of 481(7) K, b/a = −2,290 K, and c/a = 3,192 K, and thus far from being tri-critical point. A closely related composition (LiFe³⁺Si₂O₆) shows an equivalent phase transition at 228 K, which is very close to the tri-critical point and 561 K cooler. This result indicates that a change in the composition of tetrahedral sites can have dramatic effects on the P2₁/c ↔ C2/c displacive phase transition in clinopyroxenes. The major changes observed in the evolution of the crystal structure with T are observed in the M2 polyhedron, with a volume decrease by ca. 13.3%, compared to ca. 1.3% observed in the M1 polyhedron. The tetrahedra behave as rigid units with neither a significant change of volume at T > T _tr (<1‰), nor a change of tilting of the basal plane. No change in coordination is observed at T > T _tr in the M2 polyhedron, which remains sixfold coordinated although a strong deformation of this polyhedron is observed. This deformation is related to a strong change by 51.4° at T _tr of the kinking angle (O3–O3–O3 angle) of the B-chain of tetrahedra, which switches from O-rotated to S-rotated [from 143.3(5)° to 194.7(6)°]. The A-chain is S-rotated at T < T _tr [206.8(5)° at 703 K] and extends by 12° at the transition.     

Multiple mantle sources during island arc magmatism: U–Pb and Hf isotopic evidence from the Kohistan arc complex, Pakistan

ABSTRACT This paper presents high-precision U–Pb ages and initial Hf isotopic compositions of zircon from mafic to felsic rocks of the Kohistan Arc Complex, Pakistan. Three magmatic pulses tapping geochemically different reservoirs are distinguished. Partial melting of mantle with MORB-type isotopic characteristics generated 99–92-Ma-old magmas. Plutonism around 85 Ma tapped a more fertile mantle source, most likely consisting of a >600-Ma-old metasomatically enriched mantle, or of mantle contaminated by an old sedimentary component; 82-Ma-old felsic peraluminous dykes have MORB-type isotopic compositions considered to be inherited from remelting earlier magmas in the deep base of the arc. The isotopic results demonstrate several and rather rapid changes in melt source region during arc development. They also show that there was subordinate continental influence and negligible importance of slab components for the Hf budget during the generation of the Kohistan Arc Complex.     

C‐band SAR backscatter characteristics of Arctic sea and land ice during winter

Abstract

Synthetic Aperture Radar (SAR) data has become an important tool for studies of polar regions, due to high spatial resolution even during the polar night and under cloudy skies. We have studied the temporal variation of sea and land ice backscatter of twenty‐four SAR images from the European Remote Sensing satellite (ERS‐1) covering an area in Lady Ann Strait and Jones Sound, Nunavut, from January to March 1992. The presence of fast ice in Jones Sound and glaciers and ice caps on the surrounding islands provides an ideal setting for temporal backscatter studies of ice surfaces. Sample regions for eight different ice types were selected and the temporal backscatter variation was studied. The observed backscatter values for each ice type characterize the radar signatures of the ice surfaces. This time series of twenty‐four SAR images over a 3‐month period provides new insights into the degree of temporal variability of each surface. Ice caps exhibit the highest backscatter value of ‐3.9 dB with high temporal variability. Valley glacier ice backscatter values decrease with decreasing altitude, and are temporally the most stable, with standard deviations of 0.08–0.10 dB over the 90‐day period.

First‐year ice and lead ice show a negative trend in backscatter values in time and a positive correlation of up to 0.59 with air temperature over the 90‐day period. For first‐year ice and lead ice, episodes of large temperature fluctuations (±12°C) are associated with rapid changes in backscatter values (±2 dB). We attribute the backscatter increase to a temperature‐induced increase in brine volume at the base of the snow pack. Multi‐year ice, conglomerate ice and shore ice are relatively stable over the 3‐month period, with a backscatter variation of only a few dBs. An observed lag time of up to three days between backscatter increase/decrease and air temperature can be attributed to the insulation effect of the snow cover over sea ice. The net range of the backscatter values observed on the most temporally stable surface, valley glacier ice, of about 0.30 dB indicates that the ERS‐1 SAR instrument exceeds the 1 dB calibration accuracy specified for the Alaska SAR Facility processor for the three winter months.     

The Oxaya anticline (northern Chile): a buckle enhanced by river incision?

A prominent structure in the Western Escarpment of the Andes of northern Chile is the Oxaya anticline, dissected at the culmination by >1500 m deep valleys. The distribution of fault and fold structures indicates that the anticline could represent a simple buckle. Buckling thus appears to have accommodated crustal shortening in the plate overriding the subducting plate, between the trench and the Western Cordillera. Cross-cutting relationships between structures and dated strata indicated that the time interval of enhanced buckling coincides with the period when rates of valley formation were enhanced. We thus propose that the formation of this anticline was enhanced by fluvial incision, which is consistent with the results of published theoretical models.     

Nuclear and incommensurate magnetic structure of NaFeGe2O6 between 5?K and 298?K and new data on multiferroic NaFeSi2O6

The compound NaFeGe₂O₆ was grown synthetically as polycrystalline powder and as large single crystals suitable for X-ray and neutron-diffraction experiments to clarify the low temperature evolution of secondary structural parameters and to determine the low temperature magnetic spins structure. NaFeGe₂O₆ is isotypic to the clinopyroxene-type compound aegirine and adopts the typical HT-C2/c clinopyroxene structure down to 2.5?K. The Na-bearing M2 polyhedra were identified to show the largest volume expansion between 2.5?K and room temperature, while the GeO₄ tetrahedra behave as stiff units. Magnetic susceptibility measurements show a broad maximum around 33?K, which marks the onset of low-dimensional magnetic ordering. Below 12?K NaFeGe₂O₆ transforms to an incommensurately modulated magnetic spin state, with k?=?[0.323, 1.0, 0.080] and a helical order of spins within the M1-chains of FeO₆ octahedra. This is determined by neutron-diffraction experiments on a single crystal. Comparison of NaFeGe₂O₆ with NaFeSi₂O₆ is given and it is shown that the magnetic ordering in the latter compound, aegirine, also is complex and is best described by two different spin states, a commensurate one with C2??/c?? symmetry and an incommensurate one, best being described by a spin density wave, oriented within the (1 0 1) plane.     

Geomaterials related to photovoltaics: a nanostructured Fe-bearing kuramite,Cu<Subscript>3</Subscript>SnS<Subscript>4</Subscript>

The successful synthesis of nanoparticles of Fe-bearing kuramite, (Cu,Fe)₃SnS₄, is reported in this study. Nanocrystalline powders were obtained through a mild, environmentally friendly and scalable solvothermal approach, in a single run. The sample was the object of a multidisciplinary investigation, including X-ray diffraction and absorption, scanning electron microscopy and microanalysis, electron paramagnetic resonance, diffuse reflectance and Mössbauer spectroscopy as well as SQUID magnetometry. The nanoparticles consist of pure Fe-bearing kuramite, exhibiting tetragonal structure. The valence state of the metal cations was assessed to be Cu⁺, Sn⁴⁺ and Fe³⁺. The material presents a band gap value of 1.6 eV, which is fully compatible with solar cell applications. The uptake of Fe by nanokuramite opens a compositional field where the physical properties can be tuned. We thus foster the application of Fe-bearing nanokuramite for photovoltaics and energy storage purposes.     

Isotope paleontology: growth and composition of extant calcareous species

Isotope paleontology uses the isotopic composition of fossil remains of organisms to make inferences about the physical surroundings of growth of the organisms (especially temperature), and to obtain clues about life history and modes of growth. In calcareous fossils, oxygen isotopes are mainly used in the former, and carbon isotopes in the latter. However, since physical surroundings and organism response are intimately associated, both types of information are contained in each of the isotopic signals. To explore the potential of isotope paleontology, and to provide a basis for reconstruction, a broad range of extant organisms has been studied, taking the pioneering work of Epstein and associates as a starting point. Results are summarized for a representative sampling of these studies, with emphasis on work at the laboratories of the authors, from the mid-seventies to the present. The organisms considered are nannoplankton, benthic algae, planktonic and benthic deep-sea foraminifera, “larger” foraminifera, sponges, corals, bryozoans, polychaetes, arthropods, bivalves, gastropods, cephalopods, and vertebrates (fish otoliths). The survey broadly suggests that, regarding oxygen isotopes, materials tend to be precipitated close to equilibrium with the surrounding seawater (as postulated by Urey), and that for carbon isotopes disequilibrium is the rule. Life spans, growth rates, differential seasonal growth, and age of reproductive activity can be extracted under favorable circumstances from individual shells and skeletal parts. In detail, the interpretation of isotope records of individual shells is quite complicated, and simple models will fail to give satisfactory results in many or most cases.     

Possible flexural accommodation on the eastern edge of the Altiplano in relation to focussed erosion in the Rio La Paz drainage system

It has been proposed that erosional unloading by focused incision can be accommodated by flexural rebound, which in turn, potentially exerts a positive feedback on erosion. This paper presents morphometric data from the La Paz drainage basin in the Bolivian Andes to illustrate the effects of such a feedback mechanism between erosion and crustal bending. The Rio La Paz is a prominent system with the headwaters on the Altiplano and a trunk stream segment that cuts across the Cordillera Real thereby connecting large portions of the Altiplano with the Amazon Basin. The flexural feedback model explains why all drainages beyond the watershed disperse their waters to the Altiplano. It also provides an explanation for the presence of the highest peaks just next to the location where the La Paz River cuts into the bedrock across the Cordillera Real.     

Exhumation across the Indus Suture Zone: a record of back sliding of the hanging wall

The Kohistan Arc Complex is an integral part of the NW Himalayan collision system and is bounded by two major suture zones, the Indus Suture Zone (ISZ) and the Northern Suture in the south and north respectively. Fission‐track analyses on samples collected along the Indus River across the arcuated ISZ in the Besham region are presented here. The footwall yields zircon and apatite fission‐track (FT) ages of ∼23 Ma and ∼3.7 Ma respectively; the hanging wall ages range from 24 to 42 Ma for zircon and ∼10 Ma for apatite. Thus, the change in ISZ kinematics from thrusting to normal faulting was not later than Oligocene and normal faulting on this ISZ segment was still active at least into early Pliocene times. At this time normal faulting had already ended at other ISZ segments, but it was still (or again) active across the ISZ in the Besham region most likely as a local phenomenon caused by the growth of the Indus Syntaxis, a transverse antiform parallel to the Nanga Parbat Syntaxis.     

New estimates of rapid sea-floor spreading rates and the identification of young magnetic anomalies on the East Pacific rise, 6° and 11° S

Detailed surveys of the crest of the East Pacific Rise at 6° and 11°S form the basis for estimates of sea-floor spreading rates of 8.2 and 8.3 cm/yr, respectively. These estimates are significantly higher than previous ones of 6.5 to 7.5 cm/yr. The high quality of the magnetic profile at 6°S allows identification of shorter magnetic events such as the two Olduvai events of Cox. DSDP drill-hole data indicate that the present spreading rates have persisted throughout the Cenozoic.