Near‐infrared spectra of clinopyroxenes: Effects of calcium content and crystal structure

Abstract– Pyroxenes are among the most common minerals in the solar system and are ideally suited for remote geochemical analysis because of the sensitivity of their distinctive spectra to mineral composition. Fe²⁺ is responsible for the dominant pyroxene absorptions in the visible and near‐infrared, but substitutions of other cations such as Ca²⁺ change the crystal structure and site geometries and thus the crystal field splitting energies of the Fe cations. To define spectral systematics resulting from major pyroxene cations (Ca²⁺, Mg²⁺, and Fe²⁺), we focus on a suite of pyroxenes synthesized with only Ca²⁺, Mg²⁺, and Fe²⁺ in the two octahedral sites, specifically examining the effect of Ca²⁺ on pyroxene absorption bands. The modified Gaussian model is used to deconvolve pyroxene spectra into component bands that can then be linked directly to crystal field absorptions. In orthopyroxenes and low‐Ca clinopyroxenes, Ca²⁺‐content has a strong and predictable effect on the positions of the absorption bands. At a threshold of Wo₃₀, the crystal field environment stagnates and the M2 bands cease to change significantly as more Ca²⁺ is added. At Wo₅₀, when most of the M2 sites are filled by Ca²⁺, band positions do not change drastically, although the presence and strengths of the 1 and 2 μm bands are affected by even trace amounts of Fe²⁺ in the M2 site. It is thus apparent that next‐nearest neighbors and the distortions they impose on the pyroxene lattice affect the electronic states around the Fe²⁺ cations and control absorption band properties.     

Size Fractionation (Dissolved, Colloidal and Particulate) of Trace Metals in the Thur River, Switzerland

The distribution of some trace metals (Cu, Zn, Ni, Co,Fe, Mn) and of DOC over a particulate (> 1 m),a colloidal (size < 0.45 m and molecular weight > 10 kD) and an ultrafiltered fraction (< 10 kD)was determined at several sites on the Thur River,Switzerland, at various times of the year. Thecomplexation of Cu by strong ligands in theultrafiltrate and in the conventional filtrate (<0.45 m) was compared using a ligand-exchange/CSV method.The <0.45 m concentrations of Cu (from anaverage of 7 nM to 24 nM), Zn (<5–23 nM), Ni (5–13 nM),Co (1.5–3 nM) and Mn (7–92 nM)increased downstream. The major part of Cu, Zn, Niand Co usually occurred in the ultrafiltratefraction at all sites, whereas Fe and Mn were mostlyin the particulate fraction, under conditions of lowsuspended matter content (< 10 mg L^-1) in theriver. The percentage of metal in the colloidalfraction, with respect to the 0.45-m filtrate,decreased in the order: Cu (median 11%) > Zn Ni(median 5–6%) > Mn Co (median < 5%). DOCalso consisted mostly of molecules in the < 10 kDrange.Cu was strongly complexed by natural organic ligandsin all filtrate and ultrafiltrate samples. A largepart of the strong Cu binding ligands consisted ofcompounds in the < 10 kD range, but colloidalligands with similar properties also occurred. Cu wasdistributed among the dissolved and the colloidalligands, roughly in proportion to organic carbon.The colloidal fraction (as defined here) did notincrease in its proportional amount downstream and wasonly of limited significance in transporting traceelements in the Thur River under low discharge conditions.     

Volcanic ash forecast during the June 2011 Cordón Caulle eruption

We modelled the transport and deposition of ash from the June 2011 eruption from Cordón Caulle volcanic complex, Chile. The modelling strategy, currently under development at the Argentinean Naval Hydrographic Service and National Meteorological Service, couples the weather research and forecasting (WRF/ARW) meteorological model with the FALL3D ash dispersal model. The strategy uses volcanological inputs inferred from satellite imagery, eruption reports and preliminary grain-size data obtained during the first days of the eruption from an Argentinean ash sample collection network. In this sense, the results shown here can be regarded as a quasi-syn-eruptive forecast for the first 16 days of the eruption. Although this article describes the modelling process in the aftermath of the crisis, the strategy was implemented from the beginning of the eruption, and results were made available to the Buenos Aires Volcanic Ash Advisory Centers and other end users. The model predicts ash cloud trajectories, concentration of ash at relevant flight levels, expected deposit thickness and ash accumulation rates at relevant localities. Here, we validate the modelling strategy by comparing results with satellite retrievals and syn-eruptive ground deposit measurements. Results highlight the goodness of the combined WRF/ARW-FALL3D forecasting system and point out the usefulness of coupling both models for short-term forecast of volcanic ash clouds.     

Mixture of populations

A simple example simulating a mixture of two normal populations results in some important observations, nonnormality and nonsymmetry of the mixture conditional pdf, nonlinearity of the conditional mean as a function of the conditioning data, heteroscedasticity of the conditional variance and its nonmonotonicity as a function of distance of the unknown to the conditioning data. A comparison of the mixture statistics with those predicted by traditional models ignoring the mixture reveals the inadequacy and inappropriateness of these traditional approaches. A mixture of two multivariate normal populations is illustrated through the analytical expressions of its conditional distribution and moments.     

Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C₁–C₄, CO₂]). Molecular ratios of LMWHC (C₁/[C₂ + C₃] > 1000) and stable isotopic compositions of methane (δ¹³C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C₁/C₂₊ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C₁–C₄, CO₂]) relative to the other gas types and the virtual lack of ¹⁴C–CH₄ indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C₁–C₄, CO₂)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of ¹⁴C–CH₄ (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.     

Paleoecology and radiocarbon dating of the Pleistocene megafauna of the Brazilian Intertropical Region

During the Pleistocene a fauna composed of large (biomass > 44 kg) and giant mammals (biomass > 1000 kg) that are usually associated with open environments lived in the Brazilian Intertropical Region. We present here new information concerning the paleoecology and chronology of some species of this megafauna. Carbon isotope analyses were performed for a better understanding of the paleoecology of the species Eremotherium laurillardi (Lund, 1842), Notiomastodon platensis (Ameghino, 1888) and Toxodon platensis (Owen, 1849). The δ¹³C data allow attributing a generalist diet to these species, which varied according to the kind of habitat in which they lived. In more open habitats all species were grazers; in mixed habitats E. laurillardi and T. platensis were mixed feeders, and N. platensis was grazer; and in more closed habitats all species were mixed feeders.     

Procedure for the selection of runout model parameters from landslide back-analyses: application to the Metropolitan Area of San Salvador, El Salvador

The existing procedures for the selection of runout model parameters from back-analyses do not allow integrating different types of runout criteria and generally lack a systematic approach. A new method based on receiver operating characteristic (ROC) analyses and aimed at overcoming these limitations is herein proposed. The method consists of estimating discrete classifiers for every runout simulation associated with a set of model parameters. The set of parameters that yields the best prediction is selected using ROC metrics and space. The procedure is illustrated with the back-analyses of a rainfall-triggered debris flow that killed 300–500 people in the Metropolitan Area of San Salvador in 1982. The selected model parameters are used to estimate forward predictions for scenarios that correspond to different return periods. The proposed procedure may be useful in the assessment of areas potentially affected by landslides. In turn, this information can be used in the production or updating of land use plans and zonations, similar to that currently being carried out by the Office for Urban Planning of the Metropolitan Area of San Salvador in El Salvador.     

La theorie des deux magmas fondamentaux dans le volcanisme intracontinental et l'evolution geochimique des laves du Mont-Dore (France)

Résumé Les auteurs utilisent toutes les données chimiques, volcanologiques, chronologiques et tectonophysiques fournies pour un certain nombre de massif continentaux (Mont-Dore et autres). La synthèse de toutes ces études montre qu'il existe deux magmas continentaux indépendants: le magma basaltique venant du manteau (sima) et le magma rhyolitique fourni par la croûte supérieure (sial). Le mélange de ces deux magmas et l'action secondaire de la' gravité et de la pneumatolyse expliquent logiquement la totalité des phénomènes géochimiques des volcans continentaux.

---

The authors used all the chemical, volcanological, chronological and tectonophysical data supplied for a certain number of continental mountain massifs (Mont-Dore and others). The synthesis of these studies shows that there are two independent continental magmas: the basaltic magma coming from the mantle (sima) and the rhyolitic magma supplied by the upper crust (sial). The mixing of these two magmas, with the secondary action of gravity and pneumatolysis logically explains the totality of the geochemical phenomena in continental volcanoes.

---

Zusammenfassung Die Autoren benutzten alle chemischen, vulkanologischen, chronologischen und tektonisch-physikalischen Daten, die von einer bestimmten Anzahl von kontinentalen Massiven (Mont-Dore und andere) entnommen wurden.Das Ergebnis dieser Studien zeigt, daß es zwei voneinander unabhängige kontinentale Magmen gibt.Das basaltische Magma, vom Sima stammend, und das rhyolitische Magma aus der oberen Sial-Kruste. Die Vermischung dieser beiden Magmen und die zusätzliche Wirkung der Gravitation und Pneumatolyse erklären auf natürliche Weise die Gesamtheit der geochemischen Phänomene des kontinentalen Vulkanismus.

---

. , .

     

Mega-monsoon variability during the late Triassic: Re-assessing the role of orbital forcing in the deposition of playa sediments in the Germanic Basin

The formation of the supercontinent Pangaea during the Permo–Triassic gave rise to an extreme monsoonal climate (often termed ‘mega-monsoon’) that has been documented by numerous palaeo-records. However, considerable debate exists about the role of orbital forcing in causing humid intervals in an otherwise arid climate. To shed new light on the forcing of monsoonal variability in subtropical Pangaea, this study focuses on sediment facies and colour variability of playa and alluvial fan deposits in an outcrop from the late Carnian (ca 225 Ma) in the southern Germanic Basin, south-western Germany. The sediments were deposited against a background of increasingly arid conditions following the humid Carnian Pluvial Event (ca 234 to 232 Ma). The ca 2·4 Myr long sedimentary succession studied shows a tripartite long-term evolution, starting with a distal mud-flat facies deposited under arid conditions. This phase was followed by a highly variable playa-lake environment that documents more humid conditions and finally a regression of the playa-lake due to a return of arid conditions. The red–green (a*) and lightness (L*) records show that this long-term variability was overprinted by alternating wet/dry cycles driven by orbital precession and ca 405 kyr eccentricity, without significant influence of obliquity. The absence of obliquity in this record indicates that high-latitude forcing played only a minor role in the southern Germanic Basin during the late Carnian. This is different from the subsequent Norian when high-latitude signals became more pronounced, potentially related to the northward drift of the Germanic Basin. The recurring pattern of pluvial events during the late Triassic demonstrates that orbital forcing, in particular eccentricity, stimulated the occurrence and intensity of wet phases. It also highlights the possibility that the Carnian Pluvial Event, although most likely triggered by enhanced volcanic activity, may also have been modified by an orbital stimulus.