Ab-initio structure, energy and stable Cr isotopes equilibrium fractionation of some geochemically relevant H-O-Cr-Cl complexes

Twelve Cr(III) molecules and six Cr(VI) molecules of geochemical interest in the system Cr-H-O-Cl were investigated by ab initio Density Functional Theory in the aim of determining stationary state geometries, electronic energies and vibrational properties. The vibrational analysis conducted on the ⁵⁰Cr, ⁵²Cr, ⁵³Cr and ⁵⁴Cr isotopomers indicates important separative effects which result in mass spectrometric measurable fractionation factors in a wide thermal range. The effect of the central cation on the computed vibrational modes is interpreted in terms of Redlich’s product rule with the introduction of an isotopic ergodicity factor related to the effect of bulk molecular masses and momenta of inertia about the principal rotational axes. After the initial gas phase optimization, some relevant molecules were subjected to the effects of reaction field through Onsager’s Model, Tomasi’s continuum Model and Conductor-like Screening Model procedures. Structures and vibrational properties prove in all cases not to be severely affected by solvation, although the effect of the reaction field is to reduce somewhat the isotopic fractionation in Cr(III)-Cr(VI) aqueous redox equilibria, with respect to the gaseous state. Some of the computed separative effects are applicable to geochemical investigations.     

Chemical and tectonic controls on the formation of sparry magnesite deposits — the deposits of the northern Greywacke Zone (Austria)

The sparry magnesite deposits of the northern Greywacke Zone are situated at the base of thrust sheets. Model calculations and natural examples suggest that an inverse temperature gradient can only be established at the base of a thrust sheet if thrusting is so rapid as to be geologically unrealistic. Independently of this thrusting induces a fluid flow from the lower units to the front of the moving thrust sheet. Stability data of magnesite and dolomite in contact with fluids with different Ca/(Ca+Mg) ratios suggest that this tectonically induced fluid flow produce magnesite from preexisting dolomite by metasomatism.

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Zusammenfassung Die Spatmagnesitvorkommen der Nördlichen Grauwackenzone liegen innerhalb von Deckengrenzen. Modellberechnungen zeigen, daß ein inverser Temperaturgradient sich nur dann an der Basis von Decken einstellen kann, wenn die Überschiebungsgeschwindigkeit so groß wird, daß sie geologisch unglaubwürdig ist. Deckenüberschiebungen erzeugen aber in jedem Fall in der überschobenen Einheit einen zur Deckenfront hin gerichteten Fluidstrom. Eine Betrachtung der Stabilitätsdaten für Magnesit und Dolomit im Gleichgewicht mit einer fluiden Phase mit unterschiedlichen Ca/(Ca+Mg)-Verhältnissen zeigt, daß durch einen solchen Fluidstrom metasomatisch Magnesit aus Dolomit gebildet werden kann.

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Résumé Les dépôts de magnésite spathique de la Grauwacken Zone septentrionale sont situés à la base d'unités charriées. Un calcul de modélisation et des exemples naturels montrent qu'un gradient inverse de température ne peut s'établir à la base d'une unité charriée qu'à la condition d'admettre une vitesse de charriage tellement élevée qu'elle est irréaliste. D'autre part, le phénomene de charriage induit un déplacement de fluide depuis les unités inférieures vers le front de la nappe. Les données relatives aux conditions de stabilité de la magnésite et de la dolomite en présence de fluides de divers rapports Ca/Ca+Mg permettent de déduire que le flux ainsi engendré par la tectonique peut engendrer la magnésite par métasomatose à partir de dolomite préexistante.

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Fault plane processes and mesoscopic structure of a strong-type seismogenic fault in tonalites (Adamello batholith, Southern Alps)

The Gole Larghe Fault is an exhumed paleoseismic fault crosscutting the Adamello tonalites (Italian Southern Alps). Ambient conditions of faulting were 9–11 km in depth and 250–300 °C. In the study area the fault accommodates 1100 m of dextral strike-slip over a fault thickness of 550 m. Displacement is partitioned into three hierarchically different sets of discrete subparallel cataclastic horizons (faults_1–2–3). Fault displacement is in the range of few centimeters (faults₃) to a maximum of a few tens of meters in major faults₁. Faults_1–2 nucleated on pre-existing joints, whereas faults₃ are newly generated fractures produced during slip along faults_1–2. Each fault within the Gole Larghe Fault records the same evolution with development of indurated cataclasites precursory to pseudotachylyte production. Pseudotachylytes are usually generated at the host rock/cataclasite boundary and within cataclasites the mean clast size decreases getting closer to pseudotachylyte fault veins. Pseudotachylytes and cataclasites have a similar chemical composition which is enriched in Loss On Ignition, K, Rb, Ba, U and Fe³⁺ compared to host rock.We envision two models for the evolution of the Gole Larghe Fault. In both models synkinematic fluid–rock interaction along a fault causes fault hardening by precipitation of abundant K-feldspar+epidote (and minor chlorite) in the cataclasite matrix conducive to final production of pseudotachylyte. In the first model, induration occurs progressively by differential precipitation related to fabric evolution in cataclasites. In the second model, induration occurs abruptly dependent on the development of full connectivity within the fault network and to fluid reservoir. Whatever the model, the Gole Larghe Fault represents a strong fault, where hardening processes resulted in a low displacement/fault thickness ratio and contrast with many mature weak faults where localized repeated seismic slip along the same weak horizons yields high displacement/fault thickness ratios.     

Guidelines for the good practice of surface wave analysis: a product of the InterPACIFIC project

Surface wave methods gained in the past decades a primary role in many seismic projects. Specifically, they are often used to retrieve a 1D shear wave velocity model or to estimate the V_S,30 at a site. The complexity of the interpretation process and the variety of possible approaches to surface wave analysis make it very hard to set a fixed standard to assure quality and reliability of the results. The present guidelines provide practical information on the acquisition and analysis of surface wave data by giving some basic principles and specific suggestions related to the most common situations. They are primarily targeted to non-expert users approaching surface wave testing, but can be useful to specialists in the field as a general reference. The guidelines are based on the experience gained within the InterPACIFIC project and on the expertise of the participants in acquisition and analysis of surface wave data.     

Biomorphological scaling laws from convectively accelerated streams

Worldwide convectively accelerated streams flowing in downstream-narrowing river sections show that riverbed vegetation growing on alluvial sediment bars gradually disappears, forming a front beyond which vegetation is absent. We revise a recently proposed analytical model able to predict the expected longitudinal position of the vegetation front. The model was developed considering the steady state approximation of 1-D ecomorphodynamics equations. While the model was tested against flume experiments, its extension and application to the field is not trivial as it requires the definition of proper scaling laws governing the observed phenomenon. In this work, we present a procedure to calculate vegetation parameters and flow magnitude governing the equilibrium at the reach scale between hydromorphological and biological components in rivers with converging boundaries. We collected from worldwide rivers data of section topography, hydrogeomorphological and riparian vegetation characteristics to perform a statistical analysis aimed to validate the proposed procedure. Results are presented in the form of scaling laws correlating biological parameters of growth and decay from different vegetation species to flood return period and duration, respectively. Such relationships demonstrate the existence of underlying selective processes determining the riparian vegetation both in terms of species and cover. We interpret the selection of vegetation species from ecomorphodynamic processes occurring in convectively accelerated streams as the orchestrated dynamic action of flow, sediment and vegetation characteristics. © 2019 John Wiley & Sons, Ltd.     

Origin of mud in turbidites and hybrid event beds: Insight from ponded mudstone caps of the Castagnola turbidite system (north-west Italy)

The partitioning of different grain-size classes in gravity flow deposits is one of the key characteristics used to infer depositional processes. Turbidites have relatively clean sandstones with most of their clay deposited as part of a mudstone cap or as a distal mudstone layer, whereas sand-bearing debrites commonly comprise mixtures of sand grains and interstitial clay; hybrid event beds develop alternations of clean and dirty (clay-rich) sandstones in varying proportions. Analysis of co-genetic mudstone caps in terms of thickness and composition is a novel approach that can provide new insight into gravity flow depositional processes. Bed thickness data from the ponded Castagnola system show that turbidites contain more clay overall than do hybrid event beds. The Castagnola system is characterized by deposits of two very different petrographic types. Thanks to this duality, analyses of sandstone and mudstone composition allow inference of which proportion of the clay in each of the deposit types was acquired en route. In combination with standard sedimentological observations the new data allow insight into the likely characteristics of their parent flows. Clean turbidites were deposited by lower concentration, long duration, erosive, muddy turbidity currents which were more efficient at fractionating clay particles away from their basal layer. Hybrid event beds were deposited by shorter duration, higher-concentration, less-erosive sandier flows which were less efficient at clay fractionation. The results are consistent with data from other turbidite systems (for example, Marnoso-arenacea). The approach represents a new method to infer the controls on the degree of clay partitioning in gravity flow deposits.     

Seasonal variations of exposure biomarkers, oxidative stress responses and cell damage in the clams, Tapes philippinarum, and mussels, Mytilus galloprovincialis, from Adriatic sea

This work investigated the natural variability of several biomarkers in Tapes philippinarum and Mytilus galloprovincialis, sampled from Northern Adriatic where these organisms are important sentinel species for future environmental impact assessment. Levels of metallothioneins, peroxisomal enzymes and acetylcholinesterase, showed a significant seasonality and marked differences between clams and mussels. Among antioxidant enzymes, catalase and GST decreased during the warmer period, the latter enzyme activity resulting particularly high in clams. The total oxyradical scavenging capacity toward peroxyl radicals decreased in mussels from winter to summer, indicating a prooxidant challenge due to higher seawater temperature and intensity of light irradiance. Lysosomal membrane stability did not exhibit significant seasonal variations, while some variations were observed for DNA damages. Overall results indicated a significant influence of seasonal variability on several biomarkers and species-specific differences which should be considered to discriminate the appearance of anthropogenic disturbance.     

CYP1B1 knockdown does not alter synergistic developmental toxicity of polycyclic aromatic hydrocarbons in zebrafish (Danio rerio)

Polycyclic aromatic hydrocarbons (PAHs) are contaminants increasing in the environment largely due to burning of fossil fuels. Our previous work identified a synergistic toxicity interaction in zebrafish embryos occurring when PAHs that are agonists for the aryl hydrocarbon receptor (AHR) co-occur with PAHs that are CYP1A inhibitors. This toxicity is mediated by the AHR2, and morpholino knockdown of CYP1A exacerbated toxicity. This study tested two hypotheses: (1) in the absence of functional CYP1A, metabolism of PAHs is shunted towards CYP1B1, which has been shown in mammals to produce more reactive metabolites of PAHs; alternatively, (2) CYP1B1 serves a protective role similar to CYP1A. We used a morpholino approach to knockdown CYP1B1 alone and in co-knockdown with CYP1A to determine whether we could alter deformities caused by synergistic toxicity of PAHs. CYP1B1 knockdown was not different from non-injected controls; nor were CYP1B1+CYP1A co-knockdown deformities different from CYP1A knockdown alone. These data suggest that CYP1B1 is not a significant factor in causing synergistic toxicity of PAHs, nor, in contrast to CYP1A, in providing protection.     

Timescales and dynamics of the formation of a thermocline

In a state of equilibrium, the constraint of a balanced heat budget for the ocean strongly influences the depth of the tropical thermocline because that depth controls the rate at which the ocean absorbs heat from the atmosphere. Thus, an increase in the oceanic heat loss in high latitudes results in a shoaling of the equatorial thermocline so that the heat gain also increases. How does the ocean adjust to such a new equilibrium state after an abrupt change in the heat flux in high latitudes? The adjustment of the wind-driven circulation of the upper ocean is shown to involve two timescales. The first is the familiar adiabatic wave-adjustment time associated with the horizontal redistribution of warm water above the thermocline in shallow water models. (This is essentially the time it takes Rossby and Kelvin waves to propagate from the disturbed extra-equatorial region to the equator.) The second adjustment-time is associated with the diabatic processes that come into play once the waves from higher latitudes modify the thermal structure in low latitudes and hence the flux of heat into the ocean; it is the timescale on which the ocean recovers a balanced heat budget. The identification of this timescale is the main result of this paper.Through a series of simulations of an idealized ocean basin, we identify the diabatic timescale and argue that it is determined by the strength of the upwelling and the intensity of the air–sea heatfluxes. By simulating the formation of a thermocline from isothermal conditions, we are able to relate this timescale to other relevant timescales such as that associated with diffusive processes and the adiabatic timescale invoked by Gu and Philander [Gu, D., Philander, S.G.H., 1997. Interdecadal climate fluctuations that depend on exchanges between the tropics and extra-topics. Science 275, 805–807].