Nanoscale Pathway of Modern Dolomite Formation in a Shallow, Alkaline Lake.

Dolomite [CaMg(CO3)2] formation under Earth surface conditions is considered largely inhibited, yet protodolomite (with a composition similar to dolomite but lacking cation ordering), and in some cases also dolomite, was documented in modern shallow marine and lacustrine, evaporative environments. Authigenic carbonate mud from Lake Neusiedl, a shallow, episodically evaporative lake in Austria consists mainly of Mg-calcite with zoning of Mg-rich and Mg-poor regions in µm-sized crystals. Within the Mg-rich regions, high-resolution transmission electron microscopy revealed < 5-nm-sized domains with dolomitic ordering, i.e., alternating lattice planes of Ca and Mg, in coherent orientation with the surrounding protodolomite. The calcite with less abundant Mg does not show such domains but is characterized by pitted surfaces and voids as a sign of dissolution. These observations suggest that protodolomite may overgrow Mg-calcite as a result of the changing chemistry of the lake water. During this process, oscillating concentrations (in particular of Mg and Ca) at the recrystallization front may have induced dissolution of Mg-calcite and growth of nanoscale domains of dolomite, which subsequently became incorporated as ordered domains in coherent orientation within less ordered regions. It is suggested that this crystallization pathway is capable of overcoming, at least at the nanoscale, the kinetic barrier to dolomite formation.

Moraines in the Austrian Alps record repeated phases of glacier stabilization through the Late Glacial and the Early Holocene.

Climate is currently warming due to anthropogenic impact on the Earth's atmosphere. To better understand the processes and feedbacks within the climate system that underlie this accelerating warming trend, it is useful to examine past periods of abrupt climate change that were driven by natural forcings. Glaciers provide an excellent natural laboratory for reconstructing the climate of the past as they respond sensitively to climate oscillations. Therefore, we study glacier systems and their behavior during the transition from colder to warmer climate phases, focusing on the period between 15 and 10 ka. Using a combination of geomorphological mapping and beryllium-10 surface exposure dating, we reconstruct ice extents in two glaciated valleys of the Silvretta Massif in the Austrian Alps. The mountain glacier record shows that general deglaciation after the Last Glacial Maximum (LGM) was repeatedly interrupted by glacier stabilization or readvance, perhaps during the Oldest Dryas to Bølling transition (landform age: 14.4 ± 1.0 ka) and certainly during the Younger Dryas (YD; 12.9-11.7 ka) and the Early Holocene (EH; 12-10 ka). The oldest landform age indicates a lateral ice margin that postdates the 'Gschnitz' stadial (ca. 17-16 ka) and predates the YD. It shows that local inner-alpine glaciers were more extensive until the onset of the Bølling warm phase (ca. 14.6 ka), or possibly even into the Bølling than during the subsequent YD. The second age group, ca. 80 m below the (pre-)Bølling ice margin, indicates glacier extents during the YD cold phase and captures the spatial and temporal fine structure of glacier retreat during this period. The ice surface lowered approximately 50-60 m through the YD, which is indicative of milder climate conditions at the end of the YD compared to its beginning. Finally, the third age group falls into a period of more substantial warming, the YD-EH transition, and shows discontinuous glacier retreat during the glacial to interglacial transition. The new geochronologies synthesized with pre-existing moraine records from the Silvretta Massif evidence multiple cold phases that punctuated the general post-LGM warming trend and illustrate the sensitive response of Silvretta glaciers to abrupt climate oscillations in the past.

Nannofossil biostratigraphy, strontium and carbon isotope stratigraphy, cyclostratigraphy and an astronomically calibrated duration of the Late Campanian Radotruncana calcarata Zone.

A section from the southern (Austro-Alpine Northern Calcareous Alps) margin of the Penninic Ocean in the NW Tethys realm of Late Campanian age is investigated stratigraphically. Plankton foraminifer and nannofossil biostratigraphy designate the presence of the Globotruncana ventricosa Zone and the Radotruncana (Globotruncanita) calcarata Zone, and standard nannofossil zones CC21-UC15cTP and CC22ab-UC15deTP. The combination of carbon isotope stratigraphy, strontium isotopes, and cyclostratigraphy allows a detailed chronostratigraphic correlation. Periodicity was obtained by power spectral analysis, sinusoidal regression, and Morlet wavelets. The duration of the calcarata Total Range Zone is calculated by orbital cyclicity expressed in thickness data of limestone-marl rhythmites and stable carbon isotope data. Precessional, obliquity, and short and long eccentricity cycles are identified and give an extent of c. 806 kyr for the zone. Mean sediment accumulation rates are as low as 1.99 cm/kyr and correspond well to sediment accumulation rates in similar settings. We further discuss chronostratigraphic implications of our data.

The effect of tidal forcing on biogeochemical processes in intertidal salt marsh sediments.

BACKGROUND: Early diagenetic processes involved in natural organic matter (NOM) oxidation in marine sediments have been for the most part characterized after collecting sediment cores and extracting porewaters. These techniques have proven useful for deep-sea sediments where biogeochemical processes are limited to aerobic respiration, denitrification, and manganese reduction and span over several centimeters. In coastal marine sediments, however, the concentration of NOM is so high that the spatial resolution needed to characterize these processes cannot be achieved with conventional sampling techniques. In addition, coastal sediments are influenced by tidal forcing that likely affects the processes involved in carbon oxidation. RESULTS: In this study, we used in situ voltammetry to determine the role of tidal forcing on early diagenetic processes in intertidal salt marsh sediments. We compare ex situ measurements collected seasonally, in situ profiling measurements, and in situ time series collected at several depths in the sediment during tidal cycles at two distinct stations, a small perennial creek and a mud flat. Our results indicate that the tides coupled to the salt marsh topography drastically influence the distribution of redox geochemical species and may be responsible for local differences noted year-round in the same sediments. Monitoring wells deployed to observe the effects of the tides on the vertical component of porewater transport reveal that creek sediments, because of their confinements, are exposed to much higher hydrostatic pressure gradients than mud flats. CONCLUSION: Our study indicates that iron reduction can be sustained in intertidal creek sediments by a combination of physical forcing and chemical oxidation, while intertidal mud flat sediments are mainly subject to sulfate reduction. These processes likely allow microbial iron reduction to be an important terminal electron accepting process in intertidal coastal sediments.

Scanning electrochemical microscopy imaging of rhodochrosite dissolution using gold amalgam microelectrodes.

Gold/mercury amalgam (Au/Hg) microelectrodes with a diameter of 25 microm were developed for the detection of environmentally relevant analytes such as manganese and iron by scanning electrochemical microscopy (SECM), and applied to investigate the controlled dissolution of manganese carbonate (MnCO(3); rhodochrosite) in acidic conditions. Characterization of the amalgam electrode geometry via approach curves recorded during SECM experiments revealed Au/Hg microelectrodes with sphere cap geometry. Quantitative determination of Mn(2+) has been achieved by calibration of the Au/Hg microelectrode in bulk solution experiments. Subsequent SECM imaging experiments confirm the applicability of amalgam microelectrodes for imaging of Mn(2+) production during dissolution of MnCO(3) at pH 3.9. This study confirms feasibility and provides the fundamental basis of SECM imaging with amalgam microelectrodes to address biogeochemically relevant questions.