Insights into cation exchange selectivity of a natural clinoptilolite by means of dielectric relaxation spectroscopy

Purified natural clinoptilolite from the Tasajeras deposit, Cuba, and some of its metal exchanged forms are studied, at the dehydrated state, by means of dielectric relaxation spectroscopy (DRS) using two different modus operandi: complex impedance spectroscopy and dielectric dynamic thermal analysis. Data analysis yields the determination of the extra-framework cation (EFC) population into the various possible crystallographic sites of the zeolitic framework as well as of the activation energy characterizing the localized hopping mechanism of EFC. First, it is shown that the DRS responses obtained here match well with the previous reported data, which were previously localized EFCs in positions close to M1 and M2 sites when the clinoptilolite is modified to almost homoionic form. From this outcome, it can be concluded that all EFCs are in the same crystallographic situation regarding solvation or, in other terms, that no steric effect can be taken into account to explain cationic selectivity. Second, based on the assumption that the activation energy for EFC hopping is directly connected to the EFC/framework interaction and on simple thermodynamics consideration, we show this interaction does not govern the EFC exchange reaction. So, it is emphasized that EFC/H₂O interaction is the key factor for cation exchange selectivity.     

Characterization of contact properties in biocemented sand using 3D X-ray micro-tomography

The mechanical efficiency of the biocementation process is directly related to the microstructural properties of the biocemented sand, such as the volume fraction of calcite, its distribution within the pore space (localized at the contact between grains, over the grain surfaces) and the contact properties: coordination number, contact surface area, contacts orientation and types of contact. In the present work, all these micromechanical properties are computed, for the first time, from 3D images obtained by X-ray tomography of intact biocemented sand samples. The evolution of all these properties with respect to the volume fraction of calcite is analyzed and compared between each other (from untreated sand to highly cemented sand). Whatever the volume fraction of calcite, it is shown that the precipitation of the calcite is localized at the contacts between grains. These results are confirmed by comparing our numerical results with analytical estimates assuming that the granular medium is made of periodic simple cubic arrangements of grains and by considering two extreme cases of precipitation: (1) The calcite is localized at the contact, and (2) the grains are covered by a uniform layer of calcite. In overall, the obtained results show that a small percentage of calcite is sufficient to get a large amount of cohesive contacts.

     

Late glacial vegetation and climate oscillations on the southeastern Tibetan Plateau inferred from the Lake Naleng pollen profile

We present a late glacial pollen record (17,700 to 8500 cal yr BP) from a Lake Naleng sediment core. Lake Naleng is located on the southeastern Tibetan Plateau (31.10°N 99.75°E, 4200 m) along the upper tree-line. Variations in the summer monsoon are evident from shifts in vegetation that correspond to late glacial climate trends from other monsoon-sensitive regions. Alpine steppe was recorded between 17,700 and 14,800 cal yr BP, indicating low effective moisture at the study site. Expansion of alpine meadows followed by advances in the position of tree-line around Lake Naleng suggest that climate became warmer and wetter between ∼ 14,800 and 12,500 cal yr BP, probably representing an enhancement of the Asian monsoon. Climatic cooling and reduced effective moisture are inferred from multivariate analysis and the upward retreat of tree-line between ∼ 12,500 and 11,700 cal yr BP. The timing and nature of these shifts to warm, wet and then cold, dry climatic conditions suggest that they correspond to the Bølling/Allerød and Younger Dryas intervals. Abies-Betula forests, representing warm and moist conditions, spread during the early Holocene.     

Maps of the natural environment''s potential in West Germany and Norway as an aid for mineral resources management and protection

Mattig, U., 1990. Maps of the natural environment's potential in West Germany and Norway as an aid for mineral resources management and protection. Eng. Geol., 29: 321–331.

The applied geosciences are of increasing importance for finding an answer to many current problems in spatial management and environmental protection.

Based on the problem of an intelligent use of the geopotential, the paper deals with the achievement and optimization of an appropriate concept for designing geoscientific maps of the natural environment's potential, relevant to areal planning, by comparing a densely populated country like Germany and a more sparsely populated country like Norway. The study carried out is following the example of a map for reserve areas for mineral resources/near surface raw materials—sand and gravel—which enables a comparison and an assessment of the translation of information, relevant to land-use planning, in both countries.

The appropriateness of the interpretation of geoscientific information is ensured by drafting a comprehensive, clearly arranged cartographic presentation, for which uniform and comparable methods, criteria and standards will be developed. The basic concepts of areal planning have to be simple, distinct, adaptable and capable of development. They should enable the geoscientist to contribute his complex and expert knowledge to decisions of regional planning and spatial management.     

Eddy covariance measurements of carbon dioxide,latent and sensible energy fluxes above a meadow on a mountain slope

Carbon dioxide, latent and sensible heat fluxes were measured by means of the eddy covariance method above a mountain meadow situated on a steep slope in the Stubai Valley in Austria, based on the hypothesis that, due to the low canopy height, measurements can be made in the shallow equilibrium layer where the wind field exhibits characteristics akin to level terrain. In order to test the validity of this hypothesis and to identify effects of complex terrain in the turbulence measurements, data were subjected to a rigorous testing procedure using a series of quality control measures established for surface-layer flows. The resulting high quality dataset comprised 36% of the original observations, the substantial reduction being mainly due to a change in surface roughness and associated fetch limitations in the wind sector dominating during nighttime and transition periods. The validity of the high quality dataset was further assessed by two independent tests: (i) a comparison with the net ecosystem carbon dioxide exchange measured by means of ecosystem chambers, and (ii) the ability of the eddy covariance measurements to close the energy balance. The net ecosystem CO₂ exchange measured by the eddy covariance method agreed reasonably well with ecosystem chamber measurements. The assessment of the energy balance closure showed that there was no significant difference in the correspondence between the meadow on the slope and another one situated on flat ground at the bottom of the Stubai Valley, available energy being underestimated by 28% and 29%, respectively. We thus conclude that, appropriate quality control provided, the eddy covariance measurements made above a mountain meadow on a steep slope are of similar quality as compared to flat terrain.     

A first approach to calculate BIOCLIM variables and climate zones for Antarctica

Theoretical and Applied Climatology - For testing the hypothesis that macroclimatological factors determine the occurrence, biodiversity, and species specificity of both symbiotic partners of...     

Bioturbation, short-lived radioisotopes, and the tracer-dependence of biodiffusion coefficients

Bioturbation refers to the mixing of sediment particles resulting from benthic faunal activity. It is the dominant particle mixing process in most marine sediments and exerts an important control on diagenetic processes. In models, bioturbation is usually treated as a diffusive process where the biodiffusion coefficient (D_b) characterizes the biological mixing intensity. Biodiffusion coefficients are classically computed by fitting a diffusive model to vertical profiles of particle-bound radioisotopes. One peculiar observation is tracer-dependence: D_b values from short-lived tracers tend to be larger than those obtained from long-lived tracers from the same site. Recent theoretical work, based on random walk theory and Lattice Automaton Bioturbation Simulations (LABS), has suggested that this tracer-dependence is simply a model artifact and has concluded that the biodiffusion model is not applicable to the short observational time scales associated with short-lived radioisotopes. Here we have compiled a global dataset of D_b values obtained from different radiotracers to assess tracer-dependence from a data perspective. Tracer-dependence is significant in low-mixing environments like slope and deep-sea sediments, but is not present in intensely mixed coastal areas. Tracer-dependence is absent when the number of mixing events is larger than 20, or the potential length scale is greater than 0.5 cm. Roughly this comes down to tracer-derived D_b values greater than 2 cm² yr⁻¹. This condition is met for 68%, 50%, and 8% of published D_b values obtained from coastal, continental slope, and abyssal environments, respectively. These results show that short-lived radioisotopes are suitable to quantify biodiffusion mixing in sedimentary environments featuring intense bioturbation.     

Driving forces of mid-Holocene vegetation shifts on the upper Tibetan Plateau,with emphasis on changes in atmospheric CO2 concentrations

Numerous pollen records across the upper Tibetan Plateau indicate that in the early part of the mid-Holocene, Kobresia-rich high-alpine meadows invaded areas formerly dominated by alpine steppe vegetation rich in Artemisia. We examine climate, land-use, and CO₂ concentration changes as potential drivers for this marked vegetation change. The climatic implications of these vegetational shifts are explored by applying a newly developed pollen-based moisture-balance transfer-function to fossil pollen spectra from Koucha Lake on the north-eastern Tibetan Plateau (34.0°N; 97.2°E; 4540 m a.s.l.) and Xuguo Lake on the central Tibetan Plateau (31.97°N; 90.3°E; 4595 m a.s.l.), both located in the meadow-steppe transition zone. Reconstructed moisture-balances were markedly reduced (by ～150–180 mm) during the early mid-Holocene compared to the late-Holocene. These findings contradict most other records from the Indian monsoonal realm and also most non-pollen records from the Tibetan Plateau that indicate a rather wet early- and mid-Holocene. The extent and timing of anthropogenic land-use involving grazing by large herbivores on the upper Tibetan Plateau and its possible impacts on high-alpine vegetation are still mostly unknown due to the lack of relevant archaeological evidence. Arguments against a mainly anthropogenic origin of Kobresia high-alpine meadows are the discovery of the widespread expansion of obviously ‘natural’ Kobresia meadows on the south-eastern Tibetan Plateau during the Lateglacial period indicating the natural origin of this vegetation type and the lack of any concurrence between modern human-driven vegetation shifts and the mid-Holocene compositional changes. Vegetation types are known to respond to atmospheric CO₂ concentration changes, at least on glacial–interglacial scales. This assumption is confirmed by our sensitivity study where we model Tibetan vegetation at different CO₂ concentrations of 375 (present-day), 260 (early Holocene), and 650 ppm (future scenario) using the BIOME4 global vegetation model. Previous experimental studies confirm that vegetation growing on dry and high sites is particularly sensitive to CO₂ changes. Here we propose that the replacement of drought-resistant alpine steppes (that are well adapted to low CO₂ concentrations) by mesic Kobresia meadows can, at least, be partly interpreted as a response to the increase of CO₂ concentration since 7000 years ago due to fertilization and water-saving effects. Our hypothesis is corroborated by former CO₂ fertilization experiments performed on various dry grasslands and by the strong recent expansion of high-alpine meadows documented by remote sensing studies in response to recent CO₂ increases.     

Sedimentary DNA versus morphology in the analysis of diatom-environment relationships

The Arctic treeline ecotone is characterised by a steep vegetation gradient from arctic tundra to northern taiga forests, which is thought to influence the water chemistry of thermokarst lakes in this region. Environmentally sensitive diatoms respond to such ecological changes in terms of variation in diatom diversity and richness, which so far has only been documented by microscopic surveys. We applied next-generation sequencing to analyse the diatom composition of lake sediment DNA extracted from 32 lakes across the treeline in the Khatanga region, Siberia, using a short fragment of the rbcL chloroplast gene as a genetic barcode. We compared diatom richness and diversity obtained from the genetic approach with diatom counts from traditional microscopic analysis. Both datasets were employed to investigate diversity and relationships with environmental variables, using ordination methods. After effective filtering of the raw data, the two methods gave similar results for diatom richness and composition at the genus level (DNA 12 taxa; morphology 19 taxa), even though there was a much higher absolute number of sequences obtained per genetic sample (median 50,278), compared with microscopic counts (median 426). Dissolved organic carbon explained the highest percentage of variance in both datasets (14.2 % DNA; 18.7 % morphology), reflecting the compositional turnover of diatom assemblages along the tundra-taiga transition. Differences between the two approaches are mostly a consequence of the filtering process of genetic data and limitations of genetic references in the database, which restricted the determination of genetically identified sequence types to the genus level. The morphological approach, however, allowed identifications mostly to species level, which permits better ecological interpretation of the diatom data. Nevertheless, because of a rapidly increasing reference database, the genetic approach with sediment DNA will, in the future, enable reliable investigations of diatom composition from lake sediments that will have potential applications in both paleoecology and environmental monitoring.