IR characteristics of hydrotalcite-like compounds

The infrared spectra of well characterized hydrotalcite-like compounds with M ²⁺/M ³⁺= 2/1 and M ²⁺/M ³⁺=3/1 chemical ratios indicate that octahedral cation ordering is only present for the 2/1 composition. For M ²⁺/M ³⁺ ratios greater than 2/1, the octahedral sheets are disordered although local cation order can be present through cation segregation. The order-disorder characteristics of these compounds can be explained by the total cation charge around any hydroxyl which cannot exceed seven units nor be lower than six. In addition, the infrared spectra suggest that the interlayer anions are symmetrically perturbed, the electrostatic interaction being greater for the 2/1 compositions.     

A study for improving precipitation occurrences modelling with a Markov chain

Daily precipitation occurrences and their monthly wet-days' sums of precipitation-measuring stations in Greece are modelled with a Markov chain. The order of the chain is taken to be seasonally varying in accordance with the precipitation station's meteorological conditions and geographical location. The modelling efficiency of the Markov chain is significantly improved when it is conjunctively used with a second-order autoregressive stochastic model fitted on the monthly wet-days' sums.     

Electron microprobe dating of monazite from high-T shear zones in the São José de Campestre Massif, NE Brazil

The easternmost domain of the Borborema Province, northeastern Brazil, presents widespread, extensional-related high-temperature metamorphism during the Brasiliano (=Pan-African) orogeny. This event reached the upper amphibolite to granulite facies and provoked generalized migmatization of Proterozoic metapelitic rocks of the Seridó Group and tonalitic to granodioritic orthogneisses of the Archean to Paleoproterozoic basement. We report new geochronological data based on electron microprobe dating of monazite from metapelitic migmatite and leuconorite within the high-T shear zones that make up the eastern continuation of the huge E–W Patos shear belt. These data were also constrained by using the Sm–Nd isotopic systematic on garnet from a syntectonic alkaline granite and two garnet-bearing leucosomes. The results suggest an age of about 578 to 574 Ma for the peak of the widespread high-T metamorphism. This event is best recorded by Sm–Nd garnet-whole rock ages. The U–Th–Pb isotopes on monazite of the metapelitic migmatite show a younger thermal event at 553 ± 10 Ma. When compared to the Sm–Nd garnet-whole rock ages, the U–Th–Pb electron probe monazite ages seem to record an event of slightly lower temperatures after the peak of the high-T metamorphism. This may reflect the difference in the isotopic behavior of the geochronological methods employed. Otherwise, the U–Th–Pb ages on monazites could indicate an event not yet very well defined. In anyway, this paper reveals the partial or even complete re-opening and resetting of the U–Th–Pb isotopic system produced by the action of low-T Ca-rich fluid.     

High-temperature single-crystal neutron diffraction study of natural chondrodite

The H-atom environment in a Tilly Foster chondrodite was analyzed using single-crystal neutron-diffraction data collected at 500, 700 and 900 K and previously published low temperature data collected at 10, 100 and 300 K on the same crystal (Mg_4.64Fe_0.28Mn_0.014Ti_0.023(Si_1.01O₄)₂F_1.16(OH)_0.84; Friedrich et al. in Am Mineral 86:981–989, 2001). The full mean square displacement matrix Σ of the O–H pair was determined from the temperature dependence of the anisotropic displacement parameters, enabling a proper correction of the O–H bond for thermal vibration without assumptions about the correlation of O and H movements. The results show that the perpendicular O–H motions in chondrodite are intermediate between the riding and the independent motion models. The corrected O–H bond lengths do not change with temperature whereas the corrected H···F distances show an increase of ~0.02 Å with temperature, as do the Mg–O distances. This result shows that spectroscopic observations on the strength of the covalent O–H bond cannot be interpreted unambiguously in terms of a corresponding behaviour of the associated H···O/F hydrogen bond.     

Fractionation of carbon isotopes in biosynthesis of fatty acids by a piezophilic bacterium Moritella japonica strain DSK1

We examined stable carbon isotope fractionation in biosynthesis of fatty acids of a piezophilic bacterium Moritella japonica strain DSK1. The bacterium was grown to stationary phase at pressures of 0.1, 10, 20, and 50 MPa in media prepared using sterile-filtered natural seawater supplied with glucose as the sole carbon source. Strain DSK1 synthesized typical bacterial fatty acids (C_14-19 saturated, monounsaturated, and cyclopropane fatty acids) as well as long-chain polyunsaturated fatty acids (PUFA) (20:6ω3). Bacterial cell biomass and individual fatty acids exhibited consistent pressure-dependent carbon isotope fractionations relative to glucose. The observed Δδ_FA-glucose (−1.0‰ to −11.9‰) at 0.1 MPa was comparable to or slightly higher than fractionations reported in surface bacteria. However, bulk biomass and fatty acids became more depleted in ¹³C with pressure. Average carbon isotope fractionation (Δδ_FA-glucose) at high pressures was much higher than that for surface bacteria: −15.7‰, −15.3‰, and −18.3‰ at 10, 20, and 50 MPa, respectively. PUFA were more ¹³C depleted than saturated and monounsaturated fatty acids at all pressures. The observed isotope effects may be ascribed to the kinetics of enzymatic reactions that are affected by hydrostatic pressure and to biosynthetic pathways that are different for short-chain and long-chain fatty acids. A simple quantitative calculation suggests that in situ piezophilic bacterial contribution of polyunsaturated fatty acids to marine sediments is nearly two orders of magnitude higher than that of marine phytoplankton and that the carbon isotope imprint of piezophilic bacteria can override that of surface phytoplankton. Our results have important implications for marine biogeochemistry. Depleted fatty acids reported in marine sediments and the water column may be derived simply from piezophilic bacteria resynthesis of organic matter, not from bacterial utilization of a ¹³C-depleted carbon source (i.e., methane). The interpretation of carbon isotope signatures of marine lipids must be based on principles derived from piezophilic bacteria.     

Geochemical Responses to a Major Transgression in Giant African Lakes

Bulk organic matter (OM) in sediments that accumulated in Lakes Victoria, Albert and Tanganyika during the major transgression that transformed these basins from a desiccated or lowstand condition at the time of the Last Glacial Maximum to highstand with overflow in the terminal Pleistocene and early Holocene, show some striking compositional trends. Sediment OM content (TOC) and Rock-Eval Hydrogen Index (HI) both rise markedly, reflecting increasing primary productivity during the transgression and enhanced conditions for the preservation of labile OM, In Lake Victoria rising sedimentary sulphur content tracks the change in HI. Over the same time interval in all three lakes, δ¹³C_OM shows a falling trend of 5–8‰ . Nitrogen isotopic and C/N trends are, in contrast, more variable. Relatively high δ¹⁵N values at an early stage in the transgression may reflect isotopic effects associated with ammonia loss from an alkaline waterbody, while high δ¹⁵N later in the transgression was probably due to periods when stratification-related denitrification had a particularly strong impact upon the lakes' N cycle. The observed changes are attributed to the influence of the landscape drowned during the transgression upon the nutrient budget of the lake, a rise in river-supplied nutrients as the climate became wetter, and an increasing tendency to stable chemical stratification as the water column deepened. In the case of δ¹³C, additional contributory factors were changes in the amount and isotopic composition of river-supplied dissolved inorganic carbon (DIC) as runoff and soil–moisture turnover rates increased, and the replacement of a C4-grassland dominated flora by mixed woodland-grassland and forest with a significant presence of C3 plants. Distinct geochemical changes are also apparent in Lakes Victoria and Albert sediments at the end of the transgression which are consistent with a reduction in nutrient loading. In the case of N this resulted in biological N fixation becoming a major part of the lakes' N cycle, Some of the observed geochemical variations may be generally applicable as proxy indicators of major transgressions in large lakes. IDEAL Contribution No. 152.     

Assessment of the Enhanced Geothermal System Resource Base of the United States

This paper describes an assessment of the enhanced geothermal system (EGS) resource base of the conterminous United States, using constructed temperature at depth maps. The temperature at depth maps were computed from 3 to 10 km, for every km. The methodology is described. Factors included are sediment thickness, thermal conductivity variations, distribution of the radioactive heat generation and surface temperature based on several geologic models of the upper 10 km of the crust. EGS systems are extended in this paper to include coproduced geothermal energy, and geopressured resources. A table is provided that summarizes the resource base estimates for all components of the EGS geothermal resource. By far, the conduction-dominated components of EGS represent the largest component of the U.S. resource. Nonetheless, the coproduced resources and geopressured resources are large and significant targets for short and intermediate term development. There is a huge resource base between the depths of 3 and 8 km, where the temperature reaches 150–250°C. Even if only 2% of the conventional EGS resource is developed, the energy recovered would be equivalent to roughly 2,500 times the annual consumption of primary energy in the U.S. in 2006. Temperatures above 150°C at those depths are more common in the active tectonic regions of the western conterminous U.S., but are not confined to those areas. In the central and eastern U.S. there are identified areas of moderate size that are of reasonable grade and probably small areas of much higher grade than predicted by this analyses. However because of the regional (the grid size is 5′ × 5′) scale of this study such potentially promising sites remain to be identified. Several possible scenarios for EGS development are discussed. The most promising and least costly may to be developments in abandoned or shut-in oil and gas fields, where the temperatures are high enough. Because thousands of wells are already drilled in those locations, the cost of producing energy from such fields could be significantly lowered. In addition many hydrocarbon fields are producing large amounts of co-produced water, which is necessary for geothermal development. Although sustainability is not addressed in this study, the resource is so large that in at least some scenarios of development the geothermal resource is sustainable for long periods of time.