Stable isotopic evidence for Middle Pleistocene environmental change from a loess‐paleosol sequence: Kärlich,Germany

Loess‐paleosol sequences are important terrestrial archives of palaeoenvironmental change. Such sequences are rich in pedogenic carbonate, the oxygen and carbon isotopic values of which can provide important palaeoenvironmental information. Although some studies have pioneered the use of O and C isotopes in loess‐paleosol sequences, they are not routinely used as palaeoclimate proxies. In this study we analysed the sedimentology, micromorphology, geochronology and isotopic geochemistry of a Middle Pleistocene loess‐paleosol section, located at Kärlich, Germany. The section studied correlates with the Elsterian glacial (MIS 12) and Holsteinian interglacial (MIS 11). Embedded tephra layers yielded ⁴⁰Ar/³⁹Ar ages of 466±3 ka, 447±1 ka and 361±3 ka. The sedimentology and micromorphology of the sequence record a shift from accretionary loess accumulation (MIS 12) to prolonged pedogenesis at a stable land surface (MIS 11). Soil carbonate δ¹⁸O values record an enrichment of ～3‰ during the accumulation of the loess, reaching peak values comparable with those found in the MIS 11 soil. The δ¹⁸O signal is interpreted as reflecting temperature, highlighting the potential of δ¹⁸O analysis of European loess soil carbonates as a means of reconstructing palaeotemperature history.     

A Tortonian onset for the Algerian margin inversion: Evidence from low‐temperature thermochronology

In North Africa, the Algerian margin is made of basement blocks that drifted away from the European margin, namely the Kabylia, and docked to the African continental crust in the Early Miocene. This young margin is now inverted, as dated Miocene (17 Ma) granites outcrop alongshore, evidencing kilometre‐scale exhumation since their emplacement. Age of inversion is actually unknown, although Pliocene is often considered in the offshore domain. To decipher the exhumation history of the margin between 17 and 5 Ma, we performed a coupled apatite fission track (AFT) and (U–Th–Sm)/He (AHe) study in the Cap Bougaroun Miocene granite. AFT dates range between 7 ± 1 and 10 ± 1 Ma, and mean AHe dates between 8 ± 2 and 10 ± 1 Ma. These data evidence rapid and multi‐kilometre exhumation during Tortonian times. This event cannot be related to slab break‐off but instead to the onset of margin inversion that has since developed as an in‐sequence north‐verging deforming prism.     

A statistical�Cdynamical scheme for reconstructing ocean forcing in the Atlantic. Part I: weather regimes as predictors for ocean surface variables

The links between the observed variability of the surface ocean variables estimated from reanalysis and the overlying atmosphere decomposed in classes of large-scale atmospheric circulation via clustering are investigated over the Atlantic from 1958 to 2002. Daily 500?hPa geopotential height and 1,000?hPa wind anomaly maps are classified following a weather-typing approach to describe the North Atlantic and tropical Atlantic atmospheric dynamics, respectively. The algorithm yields patterns that correspond in the extratropics to the well-known North Atlantic-Europe weather regimes (NAE-WR) accounting for the barotropic dynamics, and in the tropics to wind classes (T-WC) representing the alteration of the trades. 10-m wind and 2-m temperature (T2) anomaly composites derived from regime/wind class occurrence are indicative of strong relationships between daily large-scale atmospheric circulation and ocean surface over the entire Atlantic basin. High temporal correlation values are obtained basin-wide at low frequency between the observed fields and their reconstruction by multiple linear regressions with the frequencies of occurrence of both NAE-WR and T-WC used as sole predictors. Additional multiple linear regressions also emphasize the importance of accounting for the strength of the daily anomalous atmospheric circulation estimated by the combined distances to all regimes centroids in order to reproduce the daily to interannual variability of the Atlantic ocean. We show that for most of the North Atlantic basin the occurrence of NAE-WR generally sets the sign of the ocean surface anomaly for a given day, and that the inter-regime distances are valuable predictors for the magnitude of that anomaly. Finally, we provide evidence that a large fraction of the low-frequency trends in the Atlantic observed at the surface over the last 50?years can be traced back, except for T2, to changes in occurrence of tropical and extratropical weather classes. All together, our findings are encouraging for the prospects of basin-scale ocean dynamical downscaling using a weather-typing approach to reconstruct forcing fields for high resolution ocean models (Part II) from coarse resolution climate models.     

Cyclic spattering,seismic tremor,and surface fluctuation within a perched lava channel,Kīlauea Volcano

In late 2007, a perched lava channel, built up to 45 m above the preexisting surface, developed during the ongoing eruption near Pu‘u ‘Ō‘ō cone on Kīlauea Volcano’s east rift zone. The lava channel was segmented into four pools extending over a total of 1.4 km. From late October to mid-December, a cyclic behavior, consisting of steady lava level rise terminated by vigorous spattering and an abrupt drop in lava level, was commonly observed in pool 1. We use geologic observations, video, time-lapse camera images, and seismicity to characterize and understand this cyclic behavior. Spattering episodes occurred at intervals of 40–100 min during peak activity and involved small (5–10-m-high) fountains limited to the margins of the pool. Most spattering episodes had fountains which migrated downchannel. Each spattering episode was associated with a rapid lava level drop of about 1 m, which was concurrent with a conspicuous cigar-shaped tremor burst with peak frequencies of 4–5 Hz. We interpret this cyclic behavior to be gas pistoning, and this is the first documented instance of gas pistoning in lava well away from the deeper conduit. Our observations and data indicate that the gas pistoning was driven by gas accumulation beneath the visco-elastic component of the surface crust, contrary to other studies which attribute similar behavior to the periodic rise of gas slugs. The gas piston events typically had a gas mass of about 2,500 kg (similar to the explosions at Stromboli), with gas accumulation and release rates of about 1.1 and 5.7 kg s⁻¹, respectively. The time-averaged gas output rate of the gas pistoning events accounted for about 1–2% of the total gas output rate of the east rift zone eruption.     

Production of n-alkyl lipids in living plants and implications for the geologic past

Leaf waxes (i.e., n-alkyl lipids or n-alkanes) are land-plant biomarkers widely used to reconstruct changes in climate and the carbon isotopic composition of the atmosphere. There is little information available, however, on how the production of leaf waxes by different kinds of plants might influence the abundance and isotopic composition of n-alkanes in sedimentary archives. This lack of information increases uncertainty in interpreting n-alkyl lipid abundance and δ¹³C signals in ancient settings. We provide here n-alkyl abundance distributions and carbon isotope fractionation data for deciduous and evergreen angiosperm and gymnosperm leaves from 46 tree species, representing 24 families. n-Alkane abundances are significantly higher in angiosperms than gymnosperms; many of the gymnosperm species investigated did not produce any n-alkanes. On average, deciduous angiosperms produce 200 times more n-alkanes than deciduous gymnosperms. Although differences between angiosperms and gymnosperms dominate the variance in n-alkane abundance, leaf life-span is also important, with higher n-alkane abundances in longer-lived leaves. n-Alkanol abundances covary with n-alkanes, but n-alkanoic acids have similar abundances across all plant groups. Isotopic fractionation between leaf tissue and individual alkanes (ε_lipid) varies by as much as 10‰ among different chain lengths. Overall, ε_lipid values are slightly lower (−4.5‰) for angiosperm than for gymnosperm (−2.5‰) n-alkanes. Angiosperms commonly express slightly higher Δ_leaf (photosynthetic discrimination) relative to gymnosperms under similar growth conditions. As a result, angiosperm n-alkanes are expected to be generally 3-5‰ more depleted in ¹³C relative to gymnosperm alkanes for the same locality. Differences in n-alkane production indicate the biomarker record will largely (but not exclusively) reflect angiosperms if both groups were present, and also that evergreen plants will likely be overrepresented compared with deciduous ones. We apply our modern lipid abundance patterns and ε_lipid results to constrain the magnitude of the carbon isotope excursion (CIE) at the onset of the Paleocene-Eocene Thermal Maximum (55.8 Ma). When Bighorn Basin (WY) sediment n-alkanes are interpreted in context of floral changes and modern n-alkane production estimates for angiosperms and gymnosperms, the CIE is greater in magnitude (−5.6‰) by ∼1‰ compared to previous estimates that do not take into account n-alkane production.     

Chlorins in mid-Cretaceous black shales of the Demerara Rise: The oldest known occurrence

Liquid chromatography, multi-stage mass spectrometry (LC-MSⁿ) of acetone extracts confirms the presence of mesochlorophyllone in the mid-Cretaceous black shales of Demerara Rise. This finding represents molecular confirmation of the oldest primary chlorins in the geologic record and is evidence for a chlorophyll a source for bicycloalkanoporphyrins in the Demerara Rise black shales.     

V oxidation state in Fe–Ti oxides by high-energy resolution fluorescence-detected X-ray absorption spectroscopy

The oxidation state of vanadium in natural and synthetic Fe–Ti oxides is determined using high-energy resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS). Eleven natural magnetite-bearing samples from a borehole of the Main Magnetite Layer of the Bushveld Complex (South Africa), five synthetic Fe oxide samples, and three natural hematite-bearing samples from Dharwar supergroup (India) are investigated. V K edge spectra were recorded on the ID26 beamline at the European Synchrotron Radiation Facility (Grenoble, France), and the pre-edge features were used to determine the local environment and oxidation state of vanadium. In the case of the magnetite samples (natural and synthetic), we show that vanadium is incorporated in the octahedral site of the spinel structure under two oxidation states: +III and +IV. The variations of the pre-edge area are interpreted as various proportions in V³⁺ and V⁴⁺ (between 9.5 and 16.3% of V⁴⁺), V³⁺ being the main oxidation state. In particular, the variations of the V⁴⁺/V³⁺ ratio along the profile of the Main Magnetite Layer seem to follow the crystallization sequence of the layer. In the case of the hematite samples from India, the pre-edge features indicate that vanadium is substituted to Fe and mainly incorporated as V⁴⁺ (between 40 and 72% of V⁴⁺). We also demonstrate the potentiality of HERFD-XAS for mineralogical studies, since it can filter out the unwanted fluorescence and give better resolved spectra than conventional XAS.     

Multi‐Element Determination of Trace Elements in Natural Water Reference Materials by ICP‐SFMS after Tm Addition and Iron Co‐precipitation

We report on an improved method for determining trace element abundances in seawater and other natural waters. The analytical procedure involves co‐precipitation on iron hydroxides after addition of a Tm spike, and measurement by inductively coupled plasma‐sector field mass spectrometry (ICP‐SFMS). The validity of the method was assessed through a series of co‐precipitation experiments, using ultra‐diluted solutions of a certified rock reference material (BIR‐1). Results obtained for four natural water reference materials (NASS‐5, CASS‐4, SLEW‐3, SLRS‐4) are in agreement with published working values for rare earth elements, yttrium, vanadium and, when available, for hafnium, zirconium, thorium and scandium. A set of proposed values with uncertainties typically better than 8% RSD is proposed for Hf, Zr and Th.     

Development of a refinement criterion for adaptive mesh refinement in steam-assisted gravity drainage simulation

Steam-assisted gravity drainage (SAGD) is an enhanced oil recovery process for heavy oils and bitumens. Numerical simulations of this thermal process allow us to estimate the retrievable volume of oil and to evaluate the benefits of the project. As there exists a thin flow interface (compared to the reservoir dimensions), SAGD simulations are sensitive to the grid size. Thus, to obtain precise forecasts of oil production, very small-sized cells have to be used, which leads to prohibitive CPU times. To reduce these computation times, one can use an adaptive mesh refinement technique, which will only refine the grid in the interface area and use coarser cells outside. To this end, in this work, we introduce new refinement criteria, which are based on the work achieved in Kröner and Ohlberger (Math Comput 69(229):25–39, 2000) on a posteriori error estimators for finite volume schemes for hyperbolic equations. Through numerical experiments, we show that they enable us to decrease in a significant way the number of cells (and then CPU times) while maintaining a good accuracy in the results.