Terrestrial carbon-isotope records from coastal deposits (Algarve, Portugal): a tool for chemostratigraphic correlation on an intrabasinal and global scale

ABSTRACT The carbon-isotope signature of terrestrial organic matter (OM) offers a valuable tool to develop stratigraphic correlations for near-shore deposits. A mid-Cretaceous coastal succession of the western Algarve Basin, Portugal, displays a marked negative δ¹³C excursion ranging from − 21.2‰ to − 27.8‰ in the Early Aptian followed by two shifts towards higher values (up to − 19.3‰) during the Early and Late Aptian, respectively. The dominance of cuticle and leaf debris in the bulk OM fraction is confirmed by optical studies, Rock-Eval pyrolysis and by comparison with the δ¹³C signature of four different types of fossilized land-plant particles. Correlation of two terrestrial δ¹³C_bulk OM records from different study sites leads to a significant enhancement of the intrabasinal stratigraphic correlation within the Algarve Basin. Three prominent excursions in the Portuguese records can be correlated with existing δ¹³C curves from pelagic and terrestrial environments. The general carbon-isotope pattern is superimposed by small-scale fluctuations which can be explained by compositional variations within the OM.     

Phase transitions in the system CaCO<Subscript>3</Subscript> at high P and T determined by in situ vibrational spectroscopy in diamond anvil cells and first-principles simulations

The stability of the high-pressure CaCO₃ calcite (cc)-related polymorphs was studied in experiments that were performed in conventional diamond anvil cells (DAC) at room temperature as a function of pressure up to 30 GPa as well as in internally heated diamond anvil cells (DAC-HT) at pressures and temperatures up to 20 GPa and 800 K. To probe structural changes, we used Raman and FTIR spectroscopy. For the latter, we applied conventional and synchrotron mid-infrared as well as synchrotron far-infrared radiation. Within the cc-III stability field (2.2–15 GPa at room temperature, e.g., Catalli and Williams in Phys Chem Miner 32(5–6):412–417, 2005), we observed in the Raman spectra consistently three different spectral patterns: Two patterns at pressures below and above 3.3 GPa were already described in Pippinger et al. (Phys Chem Miner 42(1):29–43, 2015) and assigned to the phase transition of cc-IIIb to cc-III at 3.3 GPa. In addition, we observed a clear change between 5 and 6 GPa that is independent of the starting material and the pressure path and time path of the experiments. This apparent change in the spectral pattern is only visible in the low-frequency range of the Raman spectra—not in the infrared spectra. Complementary electronic structure calculations confirm the existence of three distinct stability regions of cc-III-type phases at pressures up to about 15 GPa. By combining experimental and simulation data, we interpret the transition at 5–6 GPa as a re-appearance of the cc-IIIb phase. In all types of experiments, we confirmed the transition from cc-IIIb to cc-VI at about 15 GPa at room temperature. We found that temperature stabilizes cc-VI to lower pressure. The reaction cc-IIIb to cc-VI has a negative slope of ?7.0 × 10^?3 GPa K^?1. Finally, we discuss the possibility of the dense cc-VI phase being more stable than aragonite at certain pressure and temperature conditions relevant to the Earth’s mantle.     

Oxygen isotope biogeochemistry of pore water sulfate in the deep biosphere: Dominance of isotope exchange reactions with ambient water during microbial sulfate reduction (ODP Site 1130)

Microbially mediated sulfate reduction affects the isotopic composition of dissolved and solid sulfur species in marine sediments. Experiments and field data show that the composition is also modified in the presence of sulfate-reducing microorganisms. This has been attributed either to a kinetic isotope effect during the reduction of sulfate to sulfite, cell-internal exchange reactions between enzymatically-activated sulfate (APS), and/or sulfite with cytoplasmic water. The isotopic fingerprint of these processes may be further modified by the cell-external reoxidation of sulfide to elemental sulfur, and the subsequent disproportionation to sulfide and sulfate or by the oxidation of sulfite to sulfate. Here we report values from interstitial water samples of ODP Leg 182 (Site 1130) and provide the mathematical framework to describe the oxygen isotope fractionation of sulfate during microbial sulfate reduction. We show that a purely kinetic model is unable to explain our data, and that the data are well explained by a model using oxygen isotope exchange reactions. We propose that the oxygen isotope exchange occurs between APS and cytoplasmic water, and/or between sulfite and adenosine monophosphate (AMP) during APS formation. Model calculations show that cell external reoxidation of reduced sulfur species would require up to 3000 mol/m³ of an oxidant at ODP Site 1130, which is incompatible with the sediment geochemical data. In addition, we show that the volumetric fluxes required to explain the observed data are on average 14 times higher than the volumetric sulfate reduction rates (SRR) obtained from inverse modeling of the porewater data. The ratio between the gross sulfate flux into the microbes and the net sulfate flux through the microbes is depth invariant, and independent of sulfide concentrations. This suggests that both fluxes are controlled by cell density and that cell-specific sulfate reduction rates remain constant with depth.     

Multi-proxy reconstruction of the Holocene vegetation and land use dynamics in the Julian Alps,north-west Slovenia

Small mountain lakes are natural archives for understanding long-term natural and anthropogenic impact on the environment. This study focused on long-term (last ca. 13 000 years) vegetation changes and sedimentary processes in the catchment area of Lake Planina pri jezeru (1430 m a.s.l.) by using mineralogical, geochemical and palynological methods. Palynological results suggest that regional vegetation between 12 900 and 11 700 cal a bp was a herbaceous–forest tundra (Pinus, Artemisia, Poaceae ). Climate warming at the beginning of the Holocene (ca. 11 700 cal a bp ) caused the transition from a wetland (Cyperaceae) to an eutrophic lake with alternating anoxic (pyrite) and oxic conditions (gypsum). In addition, the surrounding area became forested (Picea, Larix, Ulmus). Fagus expanded at 10 200 cal a bp and Abies at 8200 cal a bp. Between 7500 and 4300 cal a bp , human impact on the environment was barely noticeable and mostly limited to grazing. During 4300–430 cal a bp human impact became more evident and gradually increased. The greatest influence was observed from 430 cal a bp onwards, when excessive exploitation of the surrounding area (logging and grazing) severely eutrophicated the lake.     

Inventory of Glaciers in Mongolia,Derived from Landsat Imagery from 1989 to 2011

Glaciers in the Altai Mountains of Mongolia provide an estimated 11% of the total water resources within the country. Yet, their number and area in inconsistent. Using satellite imagery acquired from Landsat 4, 5, and 7, and SRTM digital elevation model (DEM) data, we present here an intuitive, robust, and inexpensive methodology to map the exposed ice of glaciers in the Altai Mountains for the period 1989 to 2011. The total glacierized area was 515 km² in 1989/1991, 428 km² in 1998/2001, and 372 km² in 2010/2011; it decreased by 17% from 1989/1991 to 1998/2001, 13% from 1998/2001 to 2010/2011, and 28% for the entire period 1989/1991 to 2010/2011. In analyzing a sub‐sample of 260 glaciers, 6% advanced, 11% were stable, and 83% receded from 1989 to 2011. The glacier dataset is available to the public free of charge at the Global Land Ice Measurements from Space (GLIMS) website.     

The Herschel-PACS photometer calibration

This paper provides an overview of the PACS photometer flux calibration concept, in particular for the principal observation mode, the scan map. The absolute flux calibration is tied to the photospheric models of five fiducial stellar standards (α Boo, α Cet, α Tau, β And, γ Dra). The data processing steps to arrive at a consistent and homogeneous calibration are outlined. In the current state the relative photometric accuracy is ～2 % in all bands. Starting from the present calibration status, the characterization and correction for instrumental effects affecting the relative calibration accuracy is described and an outlook for the final achievable calibration numbers is given. After including all the correction for the instrumental effects, the relative photometric calibration accuracy (repeatability) will be as good as 0.5 % in the blue and green band and 2 % in the red band. This excellent calibration starts to reveal possible inconsistencies between the models of the K-type and the M-type stellar calibrators. The absolute calibration accuracy is therefore mainly limited by the 5 % uncertainty of the celestial standard models in all three bands. The PACS bolometer response was extremely stable over the entire Herschel mission and a single, time-independent response calibration file is sufficient for the processing and calibration of the science observations. The dedicated measurements of the internal calibration sources were needed only to characterize secondary effects. No aging effects of the bolometer or the filters have been found. Also, we found no signs of filter leaks. The PACS photometric system is very well characterized with a constant energy spectrum νF _ν = λF _λ = const as a reference. Colour corrections for a wide range of sources SEDs are determined and tabulated.