Changes in Zn speciation during soil formation from Zn-rich limestones

In order to better understand the long-term speciation and fractionation of Zn in soils, we investigated three soils naturally enriched in Zn (237–864 mg/kg Zn) from the weathering of Zn-rich limestones (40–207 mg/kg Zn) using extended X-ray absorption fine structure (EXAFS) spectroscopy and sequential extractions. The analysis of bulk EXAFS spectra by linear combination fitting (LCF) indicated that Zn in the oolitic limestones was mainly present as Zn-containing calcite (at site Dornach), Zn-containing goethite (Gurnigel) and Zn-containing goethite and sphalerite (Liestal). Correspondingly, extraction of the powdered rocks with 1 M NH₄-acetate at pH 6.0 mobilized only minor fractions of Zn from the Gurnigel and Liestal limestones (<30%), but most Zn from the Dornach rock (81%). In the Dornach soil, part of the Zn released from the dissolving limestone was subsequently incorporated into pedogenic hydroxy-interlayered vermiculite (Zn-HIV, 30%) and Zn-containing kaolinite (30%) and adsorbed or complexed by soil organic and inorganic components (40%). The Gurnigel and Liestal soils contained substantial amounts of Zn-containing goethite (50%) stemming from the parent rock, smaller amounts (20%) of Zn-containing kaolinite (and possibly Zn-HIV), as well as adsorbed or complexed Zn-species (30%). In the soil from Liestal, sphalerite was only found in trace amounts, indicating its dissolution during soil formation. In sequential extractions, large percentages of Zn (55–85%) were extracted in recalcitrant extraction steps, confirming that Zn-HIV, Zn-containing kaolinite and Zn-containing goethite are highly resistant to weathering. These Zn-bearing phases thus represent long-term hosts for Zn in soils over thousands of years. The capability of these phases to immobilize Zn in heavily contaminated soils may however be limited by their uptake capacity (especially HIV and kaolinite) or their abundance in soil.     

Reconnaissance par sismique réfraction de la décompression et de l’instabilite des falaises vives du Bessin (Normandie,France)

Résumé

Les falaises normandes du Bessin (France) sont constituées par une succession de formations calcaires et marneuses. De nombreux mouvements de terrain, parfois de grande ampleur, affectent périodiquement ces falaises. La faible résistance mécanique des marnes, mise en évidence lors de l’étude du récent glissement du Bouffay de 1981, a dû être favorisée par un fluage associé à la décompression des calcaires sus-jacents suivant un type de déformation qui peut être observé dans un mouvement quaternaire fossilisé (vallon du Pisseau). Grâce à une reconnaissance systématique de la zone décomprimée par la petite sismique réfraction, des relations simples sont établies, permettant d’évaluer le volume décomprimé â partir des caractéristiques géométriques et lithologiques de la falaise. Ce volume semble définir l’enveloppe à l’intérieur de laquelle les mouvements sont susceptibles d’intervenir.     

Empirical determination of diffusion coefficients and geospeedometry

Geospeedometry allows to estimate the cooling rate (s_init) of metamorphic rocks at the beginning of the cooling history using diffusion data. But the choice of a diffusion activation energy (E) and a preexponential factor (D₀) from experimental results can be difficult. We propose a method to obtain E directly from the rock itself by studying the variation of the average concentration of elements or isotopes (〈C〉) as a function of mineral grain size (d). An appropriate value of D₀ can then be estimated using an existing compensation rule, a linear relationship between log D₀ and E. Consequently, uncertainties on s_init are markedly reduced. All parameters of this analytical model and their sensitivity on s_init can be estimated from 〈C〉 of the mineral grains under study. As a test we apply our model to a study by Edwards and Valley (1998)**** on ¹⁸O/¹⁶O fractionation between diopside and calcite in Adirondacks marbles, and find a cooling rate in agreement with previous works, without choosing experimental values for E and D₀.     

Warm‐temperate,marine, carbonate sedimentation in an Early Miocene,tide‐influenced,incised valley; Provence,south‐east France

The Saumane‐Venasque compound palaeovalley succession accumulated in a strongly tide‐influenced embayment or estuary. Warm‐temperate normal marine to brackish conditions led to deposition of extensive cross‐bedded biofragmental calcarenites. Echinoids, bryozoans, coralline algae, barnacles and benthic foraminifera were produced in seagrass meadows, on rocky substrates colonized by macroalgae and within subaqueous dune fields. There are two sequences, S1 and S2, the first of which contains three high‐frequency sequences (S1a, S1b and S1c). Sequence 1 is largely confined to the palaeovalley with its upper part covering interfluves. Each of these has a similar upward succession of deposits that includes: (i) a basal erosional surface that is bored and glauconitized; (ii) a discontinuous lagoonal lime mudstone or wackestone; (iii) a thin conglomerate generated by tidal ravinement; (iv) a transgressive systems tract series of cross‐bedded calcarenites; (v) a maximum flooding interval of argillaceous, muddy quartzose, open‐marine limestones; and (vi) a thin highstand systems tract of fine‐grained calcarenite. Tidal currents during stages S1a, S1b and S1c were accentuated by the constricted valley topography, whereas basin‐scale factors enhanced tidal currents during the deposition of S2. The upper part of the succession in all but S1c has been removed by later erosion. There is an overall upward temporal change with quartz, barnacles, encrusting corallines and epifaunal echinoids decreasing but bryozoans, articulated corallines and infaunal echinoids increasing. This trend is interpreted to be the result of changing oceanographic conditions as the valley was filled, bathymetric relief was reduced, rocky substrates were replaced as carbonate factories by seagrass meadows and subaqueous dunes, and the setting became progressively less confined and more open marine. These limestones are characteristic of a suite of similar cool‐water calcareous sand bodies in environments with little siliciclastic or fresh water input during times of high‐amplitude sea‐level change wherein complex inboard antecedent topography was flooded by a rising ocean.     

Deciphering petrogenic processes using Pb isotope ratios from time-series samples at Bezymianny and Klyuchevskoy volcanoes,Central Kamchatka Depression

The Klyuchevskoy group of volcanoes in the Kamchatka arc erupts compositionally diverse magmas (high-Mg basalts to dacites) over small spatial scales. New high-precision Pb isotope data from modern juvenile (1956–present) erupted products and hosted enclaves and xenoliths from Bezymianny volcano reveal that Bezymianny and Klyuchevskoy volcanoes, separated by only 9 km, undergo varying degrees of crustal processing through independent crustal columns. Lead isotope compositions of Klyuchevskoy basalts–basaltic andesites are more radiogenic than Bezymianny andesites (²⁰⁸Pb/²⁰⁴Pb = 37.850–37.903, ²⁰⁷Pb/²⁰⁴Pb = 15.468–15.480, and ²⁰⁶Pb/²⁰⁴Pb = 18.249–18.278 at Bezymianny; ²⁰⁸Pb/²⁰⁴Pb = 37.907–37.949, ²⁰⁷Pb/²⁰⁴Pb = 15.478–15.487, and ²⁰⁶Pb/²⁰⁴Pb = 18.289–18.305 at Klyuchevskoy). A mid-crustal xenolith with a crystallization pressure of 5.2 ± 0.6 kbars inferred from two-pyroxene geobarometry and basaltic andesite enclaves from Bezymianny record less radiogenic Pb isotope compositions than their host magmas. Hence, assimilation of such lithologies in the middle or lower crust can explain the Pb isotope data in Bezymianny andesites, although a component of magma mixing with less radiogenic mafic recharge magmas and possible mantle heterogeneity cannot be excluded. Lead isotope compositions for the Klyuchevskoy Group are less radiogenic than other arc segments (Karymsky—Eastern Volcanic Zone; Shiveluch—Northern Central Kamchatka Depression), which indicate increased lower-crustal assimilation beneath the Klyuchevskoy Group. Decadal timescale Pb isotope variations at Klyuchevskoy demonstrate rapid changes in the magnitude of assimilation at a volcanic center. Lead isotope data coupled with trace element data reflect the influence of crustal processes on magma compositions even in thin mafic volcanic arcs.     

Cumulating processes at the crust-mantle transition zone inferred from Permian mafic-ultramafic xenoliths (Puy Beaunit,France)

Ultramafic and mafic xenoliths of magmatic origin, sampled in the Beaunit vent (northern French Massif Central), derive from the Permian (257 Ma) Beaunit layered complex (BLC) that was emplaced at the crust-mantle transition zone (∼1 GPa). These plutonic xenoliths are linked to a single fractional crystallisation process in four steps: peridotitic cumulates; websteritic cumulates; Al-rich mafic cumulates (plagioclase, pyroxenes, garnet, amphibole and spinel) and finally low-Al mafic cumulates. This sequence of cumulates can be related to the compositional evolution of hydrous Mg basaltic magma that evolved to high-Al basalt and finally to andesitic basalt. Sr and Nd isotopic compositions confirm the co-genetic character of the various magmatic xenoliths and argue for an enriched upper mantle source comparable to present mantle wedges above subduction zones. LILE, LREE and Pb enrichment are a common feature of all xenoliths and argue for an enriched sub-alkaline transitional parental magma. The existence of a Permian magma chamber at 30 km depth suggests that the low-velocity zone observed locally beneath the Moho probably does not represent an anomalous mantle but rather a sequence of mafic/ultramafic cumulates with densities close to those of mantle rocks.     

Mid-Holocene to present-day evolution of the Indian monsoon in transient global simulations

The low-frequency evolution of Indian rainfall mean-state and associated interannual-to-decadal variability is discussed for the last 6000 years from a multi-configuration ensemble of fully coupled global transient simulations. This period is marked by a shift of Indian Summer Monsoon Rainfall (ISMR) distribution towards drier conditions, including extremes, and a contraction of the rainy season. The drying is larger in simulations with higher horizontal resolution of the atmosphere and revised land surface hydrology. Vegetation–climate interactions and the way runoff is routed to ocean modulate the timing of the monsoon onset but have negligible effects on the evolution of seasonal rainfall amounts in our modeling framework in which carbon cycling is always active. This drying trend is accompanied by changes in ISMR interannual-to-decadal variability decreasing over north and south India but increasing over central India (20°–25° N). The ISMR interannual-to-decadal variability is decomposed into six physically consistent regimes using a clustering technique to further characterize its changes and associated teleconnections. From 6 to 3.8 kyr bp, the century-to-century modulations in the frequency of occurrence associated to the regimes are asynchronous between the simulations. Orbitally-driven trends can only be detected for two regimes over the whole 6–0 kyr bp period. These two regimes reflect increased influence of ENSO on both ISMR and Indian Ocean Dipole as the inter-hemispheric energy gradient weakens. Severe long-term droughts are also shown to be a combination of long-term drying and internally generated low-frequency modulations of the interannual-to-decadal variability.

     

Experimental study of dense pyroclastic density currents using sustained,gas-fluidized granular flows

Submarine lava flow morphology is commonly used to estimate relative flow velocity, but the effects of crystallinity and viscosity are rarely considered. We use digital petrography and quantitative textural analysis techniques to determine the crystallinity of submarine basaltic lava flows, using a set of samples from previously mapped lava flow fields at the hotspot-affected Galápagos Spreading Center. Crystallinity measurements were incorporated into predictive models of suspension rheology to characterize lava flow consistency and rheology. Petrologic data were integrated to estimate bulk lava viscosity. We compared the crystallinity and viscosity of each sample with its flow morphology to determine their respective roles in submarine lava emplacement dynamics. We find no correlation between crystallinity, bulk viscosity, and lava morphology, implying that flow advance rate is the primary control on submarine lava morphology. However, we show systematic variations in crystal size and shape distribution among pillows, lobates, and sheets, suggesting that these parameters are important indicators of eruption processes. Finally, we compared the characteristics of lavas from two different sampling sites with contrasting long-term magma supply rates. Differences between lavas from each study site illustrate the significant effect of magma supply on the physical properties of the oceanic upper crust.