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.     

Hafnium and neodymium isotopes in surface waters of the eastern Atlantic Ocean: Implications for sources and inputs of trace metals to the ocean

We present hafnium (Hf) and neodymium (Nd) isotopic compositions and concentrations in surface waters of the eastern Atlantic Ocean between the coast of Spain and South-Africa. These data are complemented by Hf and Nd isotopic and concentration data, as well as rare earth element (REE) concentrations, in Saharan dust.Hafnium concentrations range between a maximum of 0.52 pmol/kg in the area of the Canary Islands and a minimum value of 0.08 pmol/kg in the southern Angola Basin. Neodymium concentrations also show a local maximum in the area of the Canary Islands (26 pmol/kg) but are even higher between ∼20°N and ∼4°N reaching maximum concentrations of 35 pmol/kg. These elevated concentrations provide evidence of inputs from weathering of the Canary Islands and from the partial dissolution of dust from the Sahara/Sahel region. The inputs from ocean island weathering are also reflected in radiogenic Hf and Nd isotopes.The Hf isotopic compositions of dust samples themselves are highly variable, ranging between ε_Hf = −20 and −0.6. The combined Hf and Nd isotopic compositions of dust plot close to the “terrestrial array” during periods of appreciable dust load in the atmosphere. During low atmospheric dust loading combined Hf and Nd isotopic compositions similar to seawater are observed. Most of the variability can be explained in terms of variable degrees of zircon loss from the dust samples, which in turn is linked to sorting during atmospheric transport to the eastern Atlantic Ocean and possibly presorting by sedimentary redistribution on the continent. In addition, increasing relative proportions of radiogenic clay minerals with decreasing grain size may contribute to the radiogenic Hf isotopic compositions observed.While the Nd isotopic composition in the surface ocean reflects the Nd isotopic composition of the Saharan dust adjacent to the Sahara/Sahel region, the release of Hf from that dust appears to be incongruent and results in surface ocean Hf isotopic compositions which are ∼10 ε_Hf more radiogenic than the bulk dust. Radiogenic Hf appears to be released from clays and possibly from trace apatite. Rare earth element patterns of dust samples indicate the presence of apatite but provide no evidence for ferromanganese grain coatings, suggesting that such coatings are insignificant in the release of Hf and Nd from Saharan dust to the surface ocean.The Nd isotopic composition of the surface waters becomes less radiogenic south of the equator, most likely reflecting the release of Nd from Congo river sediments. The release of Hf from Saharan dust and the Congo river sediments, however, does not produce distinct Hf isotopic signatures in the surface ocean, implying that the mobile fraction of Hf integrated over large continental areas is isotopically uniform. The Hf isotopic uniformity in the surface ocean means that the limited variability in deep water isotopic compositions is consistent with a short deep water residence time and reflects homogenous continental inputs rather than efficient deep water homogenization.     

The constancy of galactic cosmic rays as recorded by cosmogenic nuclides in iron meteorites

We measured the He, Ne, and Ar isotopic concentrations and the ¹⁰Be, ²⁶Al, ³⁶Cl, and ⁴¹Ca concentrations in 56 iron meteorites of groups IIIAB, IIAB, IVA, IC, IIA, IIB, and one ungrouped. From ⁴¹Ca and ³⁶Cl data, we calculated terrestrial ages indistinguishable from zero for six samples, indicating recent falls, up to 562 ± 86 ka. Three of the studied meteorites are falls. The data for the other 47 irons confirm that terrestrial ages for iron meteorites can be as long as a few hundred thousand years even in relatively humid conditions. The ³⁶Cl‐³⁶Ar cosmic ray exposure (CRE) ages range from 4.3 ± 0.4 Ma to 652 ± 99 Ma. By including literature data, we established a consistent and reliable CRE age database for 67 iron meteorites. The high quality of the CRE ages enables us to study structures in the CRE age histogram more reliably. At first sight, the CRE age histogram shows peaks at about 400 and 630 Ma. After correction for pairing, the updated CRE age histogram comprises 41 individual samples and shows no indications of temporal periodicity, especially not if one considers each iron meteorite group separately. Our study contradicts the hypothesis of periodic GCR intensity variations (Shaviv 2002, 2003), confirming other studies indicating that there are no periodic structures in the CRE age histogram (e.g., Rahmstorf et al. 2004; Jahnke 2005). The data contradict the hypothesis that periodic GCR intensity variations might have triggered periodic Earth climate changes. The ³⁶Cl‐³⁶Ar CRE ages are on average 40% lower than the ⁴¹K‐K CRE ages (e.g., Voshage 1967). This offset can either be due to an offset in the ⁴¹K‐K dating system or due to a significantly lower GCR intensity in the time interval 195–656 Ma compared to the recent past. A 40% lower GCR intensity, however, would have increased the Earth temperature by up to 2 °C, which seems unrealistic and leaves an ill‐defined ⁴¹K‐K CRE age system the most likely explanation. Finally, we present new ²⁶Al/²¹Ne and ¹⁰Be/²¹Ne production rate ratios of 0.32 ± 0.01 and 0.44 ± 0.03, respectively.     

A cross-ecosystem comparison of spatial and temporal patterns of covariation in the recruitment of functionally analogous fish stocks

Temporal and spatial patterns of recruitment (R) and spawning stock biomass (S) variability were compared among functionally analogous species and similar feeding guilds from six marine ecosystems. Data were aggregated into four regions including the Gulf of Maine/Georges Bank, the Norwegian/Barents Seas, the eastern Bering Sea, and the Gulf of Alaska. Variability was characterized by calculating coefficients of variation and anomalies for three response variables: ln(R), ln(R/S), and stock–recruit model residuals. Patterns of synchrony and asynchrony in the response variables were examined among and between ecosystems, between- and within-ocean basins and among functionally analogous species groups using pair-wise correlation analysis corrected for within-time series autocorrelation, multivariate cross-correlation analyses and regime shift detectors. Time series trends in response variables showed consistent within basin similarities and consistent and coherent differences between the Atlantic and Pacific basin ecosystems. Regime shift detection algorithms identified two broad-scale regime shift time periods for the pelagic feeding guild (1972–1976 and 1999–2002) and possibly one for the benthic feeding guild (1999–2002). No spatial patterns in response variable coefficients of variation were observed. Results from multivariate cross-correlation analysis showed similar trends. The data suggest common external factors act in synchrony on stocks within ocean basins but temporal stock patterns, often of the same species or functional group, between basins change in opposition to each other. Basin-scale results (similar within but different between) suggest that the two geographically broad areas are connected by unknown mechanisms that, depending on the year, may influence the two basins in opposite ways. This work demonstrates that commonalities and synchronies in recruitment fluctuations can be found across geographically distant ecosystems but biophysical causes of the fluctuations remain difficult to identify.     

Differential Colonization of Roots of Rhizophora mangle by the Wood Boring Isopod Sphaeroma terebrans as a Mechanism to Increase Root Density

Abstract. The frequency of parasitism of free ending prop roots of the red mangrove, Rhizophora mangle, by the wood boring isopod Sphaeroma terebrans, increased with increasing distance of the endings to established roots. In a field experiment, in which isolated endings were, surrounded by wooden sticks, the endings were colonized by S. terebrans at a lower rate than control endings, thus indicating that the wooden structures in the vicinity of the ending tended to reduce colonization rate by S. terebrans. It is concluded that S. terebrans may cause mangrove root density to increase by colonizing peripheral endings more readily than endings which are near established roots.     

The Relation Between Humidity and Liquid Water Content in Fog: An Experimental Approach

Microphysical measurements of orographic fog were performed above a montane cloud forest in northeastern Taiwan (Chilan mountain site). The measured parameters include droplet size distribution (DSD), absolute humidity (AH), relative humidity (RH), air temperature, wind speed and direction, visibility, and solar short wave radiation. The scope of this work was to study the short term variations of DSD, temperature, and RH, with a temporal resolution of 3?Hz. The results show that orographic fog is randomly composed of various air volumes that are intrinsically rather homogeneous, but exhibit clear differences between each other with respect to their size, RH, LWC, and DSD. Three general types of air volumes have been identified via the recorded DSD. A statistical analysis of the characteristics of these volumes yielded large variabilities in persistence, RH, and LWC. Further, the data revealed an inverse relation between RH and LWC. In principle, this finding can be explained by the condensational growth theory for droplets containing soluble or insoluble material. Droplets with greater diameters can exist at lower ambient RH than smaller ones. However, condensational growth alone is not capable to explain the large observed differences in DSD and RH because the respective growth speeds are too slow to explain the observed phenomena. Other mechanisms play key roles as well. Possible processes leading to the large observed differences in RH and DSD include turbulence induced collision and coalescence, and heterogeneous mixing. More analyses including fog droplet chemistry and dynamic microphysical modeling are required to further study these processes. To our knowledge, this is the first experimental field observation of the anti-correlation between RH and LWC in fog.     

Changes in Venice Lagoon dynamics due to construction of mobile barriers

The MoSE project (construction of mobile barrier to safeguard the Lagoon of Venice) entails changes to the structure of the lagoon's inlets. This could have consequences for the areas near the inlets and for the dynamics of the lagoon ecosystem as a whole. In order to predict the effects of the proposed alterations on the hydrodynamics of the lagoon, a well-tested hydrodynamic-dispersion model was applied. Simulations were carried out considering both idealised and realistic tide and wind scenarios.     

On the occurrence and origin of anthropogenic radionuclides found in a fragment of the Chelyabinsk (LL5) meteorite

A piece of the 2013 Chelyabinsk meteorite was investigated for its content of anthropogenic radionuclides. In addition to traces of cesium‐137 that had been previously reported for this particular fragment, we found an unusually high amount of strontium‐90, which indicates that the source of this contamination was the Kyshtym accident (1957). A high Sr‐90/Cs‐137 activity ratio is characteristic for Kyshtym‐derived contaminations. Based on the cesium‐137 content in the soil from the finding site, it is estimated that the fragment was contaminated with soil particles in the milligram range upon impact. Investigation of the soil revealed very unusual ferromagnetic characteristics and an iron‐rich chemical composition. Mössbauer spectroscopy indicated the presence of steel components in this soil, suggesting that the investigated meteorite fragment was found in an industrial dumping site rather than natural soil.     

<Superscript>57</Superscript>Fe Mössbauer spectroscopy,X-ray single-crystal diffractometry,and electronic structure calculations on natural alexandrite

Natural alexandrite Al₂BeO₄:Cr from Malyshevo near Terem Tschanka, Sverdlovsk, Ural, Russia, has been characterized by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine oxidation state and location of iron. The sample contains 0.3 wt% of total iron oxide. The ⁵⁷Fe Mössbauer spectrum can be resolved into three doublets. Two of them with hyperfine parameters typical for octahedrally coordinated high-spin Fe³⁺ and Fe²⁺, respectively, are assigned to iron substituting for Al in the octahedral M2-site. The third doublet is attributed to Fe³⁺ in hematite. Electronic structure calculations in the local spin density approximation are in reasonable agreement with experimental data provided that expansion and/or distortion of the coordination octahedra are presumed upon iron substitution. The calculated hyperfine parameters of Fe³⁺ are almost identical for the M1 and M2 positions, but the calculated ligand-field splitting is by far too large for high-spin Fe³⁺ on M1.     

Stress anisotropy in natural debris flows during impacting a monitoring structure

Landslides - The frictional resistance of rock and debris is supposed to induce stress anisotropy in the unsteady, non-uniform flow of gravitational mass flows, including debris flows. Though...