Molecular and isotopic characterization of biomarkers in the Frick Swiss Jura sediments: A palaeoenvironmental reconstruction on the northern Tethys margin

Molecular and stable carbon isotope compositions of source-specific hydrocarbons have been used to reconstruct palaeoenvironmental conditions during deposition of the Middle Hettangian to Upper Sinemurian sediments on the northern epicontinental Tethys margin, Frick Swiss Jura. Increasing algal, cyanobacterial and phytoplanktonic (i.e., dinoflagellate) contributions associated with the C-13-enrichment of cyanobacteria derivatives (i.e., hopanes and monomethylalkanes) suggest enhanced primary productivity upsection. This is related to the C-13-enrichment of dissolved CO2 in the upper layers and the progressive increase of depth and oxygenation of the water column. In the Middle Hettangian shallow-water environments (lagoon), the occurrence of green sulfur bacteria (Chlorobiaceae) derivatives indicates that the lower part of the water column was strictly anoxic and rich in H2S. Since these bacteria require very low light intensity to grow, these euxinic conditions may be extended up to the photic zone, allowing for anaerobic photosynthesis. Light penetration depth is most likely reduced by high productivity and/or turbidity in the photic zone. In these sediments, C-13-depleted hopanoids (-39.5 parts per thousand) are most likely associated with phototrophic purple sulfur bacteria utilizing isotopically light organic carbon at the base of the aerobic zone. These purple sulfur bacteria may have consumed the H2S used by Chlorobiaceae in the deeper layers and thus, sustained the algae and cyanobacteria productivity in the upper layers. The C-13-depleted carbonate (-13.3 parts per thousand) may be partially related to the anaerobic oxidation of the organic matter during bacterial sulfate-reduction. (c) 2006 Elsevier Ltd. All rights reserved.

Chemical and carbon isotopic evolution of hydrocarbons during prograde metamorphism from 100°C to 550°C: Case study in the Liassic black shale formation of Central Swiss Alps

Hydrocarbon distributions and stable isotope ratios of carbonates (delta(13)C(car), delta(18)O(car)), kerogen (delta(13)C(ker)), extractable organic matter (delta(13)C(EOM)) and individual hydrocarbons of Liassic black shale samples from a prograde metamorphic sequence in the Swiss Alps were used to identify the major organic reactions with increasing metamorphic grade. The studied samples range from the diagenetic zone (< 100 degrees C) to amphibolite facies (similar to 550 degrees C). The samples within the diagenetic zones (< 100 and 150 degrees C) are characterized by the dominance of C-< 20 n-alkanes, suggesting an origin related with marine and/or bacterial inputs. The metamorphic samples (200 to 550 degrees C) have distributions significantly dominated by C-12 and C-13 n-alkanes, C-14, C-16 and C-18 n-alkylcyclopentanes and to a lesser extend C-15, C-17 and C-21 n-alkylcyclohexanes. The progressive C-13-enrichment (up to 3.9 parts per thousand) with metamorphism of the C-> 17 n-alkanes suggests the occurrence of cracking reactions of high molecular weight compounds. The isotopically heavier (up to 5.6 parts per thousand) C-< 17 n-alkanes in metamorphic samples are likely originated by thermal degradation of long-chain homologous with preferential release of isotopically light C-1 and C-2 radicals. The dominance of specific even C-number n-alkylcyclopentanes suggests an origin related to direct cyclization mechanism (without decarboxylation step) of algal or bacterial fatty acids occurring in reducing aqueous metamorphic fluid conditions. The regular increase of the concentrations of n-alkylcycloalkanes vs. C-> 13 n-alkanes with metamorphism suggests progressive thermal release of kerogen-linked fatty acid precursors and degradation of n-alkanes. Changes of the steroid and terpenoid distributions are clearly related to increasing metamorphic temperatures. The absence of 18 alpha(H)-22,29,30-trisnorneohopane (Ts), the occurrence of 17 beta(H)-trisnorhopane, 17 beta(H), 21 alpha(H)-hopanes in the C-29 to C-31 range and 5 alpha(H),14 alpha(H),17 alpha(H)-20R C-27, C-29 steranes in the low diagenetic samples (< 100 degrees C) are characteristic of immature bitumens. The higher thermal stress within the upper diagenetic zone (150 degrees C) is marked by the presence of Ts, the disappearance of 17 beta(H)-trisnorhopane and thermodynamic equilibrium of the 22S/(22S + 22R) homohopane ratios. The increase of the alpha alpha alpha-sterane 20S/(20S + 20R) and 20R beta beta/(beta beta + alpha alpha) ratios (from 0.0 to 0.55 and from 0.0 to 0.40, respectively) in the upper diagenetic zone indicates the occurrence of isomerization reactions already at < 150 degrees C. However, the isomerization at C-20 (R -> S) reaches thermodynamic equilibrium values already at the upper diagenesis (similar to 150 degrees C) whereas the epimerisation at C-14 and C-17 (alpha alpha ->beta beta) arrives to constant values in the lower anchizone (similar to 200 degrees C). The ratios Ts vs. 17 alpha(H)-22,29,30-trisnorneohopane [(Ts/(Ts + Tm)] and 18 alpha(H)-30-norneohopane (C29Ts) vs. 17 alpha(H),21 beta(H)-30-norhopane [C29Ts/(C29Ts + C-29)] increase until the medium anchizone (200 to 250 degrees C) from 0.0 to 0.96 and from 0.0 to 0.44, respectively. An opposite trend owards lower values is observed in the higher metamorphic samples. The occurrence of specific hydrocarbons (e.g., n-alkylcyclopentanes, cadalene, hydrogenated aromatic compounds) in metamorphic samples points to kerogen degradation reactions most probably occurring in the presence of water and under reducing conditions. The changes of hydrocarbon distributions and carbon isotopic compositions of n-alkanes related to metamorphism suggest that the organic geochemistry may help to evaluate the lowest grades of prograde metamorphism. Copyright (c) 2005 Elsevier Ltd.

Rare earth elements and stable isotope geochemistry (δ13C and δ18O) of phosphorite deposits in the Gafsa Basin, Tunisia

Rare earth elements (REE) and stable isotope compositions (delta C-13 and delta O-18) of shark teeth and phosphatic coprolites were analyzed from the Lower Maastrichtian layers of the El Haria Formation and two sequences of the Paleocene-Eocene (P/E) Chouabine Formation in the Gafsa Basin (south western of Tunisia) in order to trace the sedimentological, climatic and oceanographic conditions. The REE chemistry and their distribution in the two archives are the same for each of the studied layers indicating that the coprolites and shark teeth experienced the same early diagenetic environments. However major differences occur between the Maastrichtian and the P/E reflecting changes in the depositional conditions. The Early Maastrichtian burial environment tended to be more anoxic with REE derived from reduced FeO. While in the P/E the REE patterns mimic the modern oxic-suboxic seawater, the REE source from remineralisation of organic coating could have more significance. The oxygen isotope compositions of the structural phosphates (delta O-18(PO4)) indicate a stable and warm climate during both studied time intervals. A small offset (-0.4 parts per thousand) in the delta O-18 value between the coprolites and shark teeth show minor thermal gradient between bottom and surface water. The pronounced negative shift of 34%. in delta C-13 values recorded in the upper part of the Chouabine Formation was ascribed to the Paleocene-Eocene boundary. At the same time the lack of negative change in the delta O-18 is explained by the semi-closed situation of the Gafsa Basin, which situation also played an important role in the evolution of the organic matters in the sediment resulting in the exceptional low delta C-13 values. (C) 2008 Elsevier B.V. All rights reserved.

Correlating the end-Triassic mass extinction and flood basalt volcanism at the 100 ka level

New high-precision U/Pb geochronology from volcanic ashes shows that the Triassic-Jurassic boundary and end-Triassic biological crisis from two independent marine stratigraphic sections correlate with the onset of terrestrial flood volcanism in the Central Atlantic Magmatic Province to <150 ka. This narrows the correlation between volcanism and mass extinction by an order of magnitude for any such catastrophe in Earth history. We also show that a concomitant drop and rise in sea level and negative delta C-13 spike in the very latest Triassic occurred locally in <290 ka. Such rapid sea-level fluctuations on a global scale require that global cooling and glaciation were closely associated with the end-Triassic extinction and potentially driven by Central Atlantic Magmatic Province volcanism.

The Early Toarcian anoxia, a synchronous event in the Western Tethys? An approach by quantitative biochronology (Unitary Associations), applied on calcareous nannofossils

During the Early Toarcian, major paleoenvironnemental and paleoceanographical changes occurred, leading to an oceanic anoxic event (OAE) and to a perturbation of the carbon isotope cycle. Although the standard biochronology of the Lower Jurassic is essentially based upon ammonites, in recent years biostratigraphy based on calcareous nannofossils and dinoflagellate cysts is increasingly used to date Jurassic rocks. However, the precise dating and correlation of the Early Toarcian OAE, and of the associated delta C-13 anomaly in different settings of the western Tethys, are still partly problematic, and it is still unclear whether these events are synchronous or not. In order to allow more accurate correlations of the organic rich levels recorded in the Lower Toarcian OAE, this account proposes a new biozonation based on a quantitative biochronology approach, the Unitary Associations (UA), applied to calcareous nannofossils. This study represents the first attempt to apply the UA method to Jurassic nannofossils. The study incorporates eighteen sections distributed across western Tethys and ranging from the Pliensbachian to Aalenian, comprising 1220 samples and 72 calcareous nannofossil taxa. The BioGraph [Savary, J., Guex, J., 1999. Discrete biochronological scales and unitary associations: description of the Biograph Computer program. Memoires de Geologie de Lausanne 34, 282 pp] and UA-Graph (Copyright Hammer O., Guex and Savary, 2002) softwares provide a discrete biochronological framework based upon multi-taxa concurrent range zones in the different sections. The optimized dataset generates nine UAs using the co-occurrences of 56 taxa. These UAs are grouped into six Unitary Association Zones (UA-Z), which constitute a robust biostratigraphic synthesis of all the observed or deduced biostratigraphic relationships between the analysed taxa. The UA zonation proposed here is compared to ``classic'' calcareous nannofossil biozonations, which are commonly used for the southern and the northern sides of Tethys. The biostratigraphic resolution of the UA-Zones varies from one nannofossil subzone or part of it to several subzones, and can be related to the pattern of calcareous nannoplankton originations and extinctions during the studied time interval. The Late Pliensbachian - Early Toarcian interval (corresponding to the UA-Z II) represents a major step in the Jurassic nannoplankton radiation. The recognized UA-Zones are also compared to the carbon isotopic negative excursion and TOC maximum in five sections of central Italy, Germany and England, with the aim of providing a more reliable correlation tool for the Early Toarcian OAE, and of the associated isotopic anomaly, between the southern and northern part of western Tethys. The results of this work show that the TOC maximum and delta C-13 negative excursion correspond to the upper part of the UA-Z II (i.e., UA 3) in the sections analysed. This suggests that the Early Toarcian OAE was a synchronous event within the western Tethys. (c) 2006 Elsevier B.V. All rights reserved.

Modelling changes in stable isotope compositions of minerals during net transfer reactions in a contact aureole: Wollastonite growth at the northern Hunter Mountain Batholith (Death Valley National Park, USA)

One of the world's largest wollastonite deposits was formed at the contact of the northern Hunter Mountain Batholith (California, USA) in Paleozoic sediments. Wollastonite occurs as zones of variable thickness surrounding layers or nodules of quartzite in limestones. A minimum formation temperature of 650 degrees C is estimated from isolated periclase-bearing lenses in that area. Contact metamorphism of siliceous carbonates has produced mineral assemblages that are consistent with heterogeneous, and partly limited infiltration of water-rich fluids, compatible with O-18/O-16 and C-13/C-12 isotopic patterns recorded in carbonates. Oxygen isotope compositions of wollastonites in the study area may also not require infiltration of large quantities of externally-derived fluids that were out of equilibrium with the rocks. 8180 values of wollastonite are high (14.8 parts per thousand to 25.0 parts per thousand; median: 19.7 parts per thousand) and close to those of the host limestone (19.7 parts per thousand to 28 parts per thousand; median: 24.9 parts per thousand) and quartz (18.0 parts per thousand. to 29.1 parts per thousand; median: 22.6 parts per thousand). Isotopic disequilibrium exists at quartz/wollastonite and wollastonite/calcite boundaries. Therefore, classical batch/Rayleigh fractionation models based on reactant and product equilibrium are not applicable to the wollastonite rims. An approach that relies on local instantaneous mass balance for the reactants, based on the wollastonite-forming reaction is suggested as an alternative way to model wollastonite reaction rims. This model reproduces many of the measured delta O-18 values of wollastonite reaction rims of the current study to within +/- 1 parts per thousand, even though the wollastonite compositions vary by almost 10 parts per thousand. (C) 2011 Elsevier B.V. All rights reserved.

Bitumens in the late Variscan hydrothermal vein-type uranium deposit of Pribram, Czech Republic: Sources, radiation-induced alteration, and relation to mineralization

The late Variscan (275-278 Ma) Pribram uranium deposit is one of the largest known accumulations of uraniferous bitumens in hydrothermal veins. The deposit extends along the northwestern boundary of the Central Bohemian pluton (345-335 Ma) with low-grade metamorphosed Late Proterozoic and unmetamorphosed Cambrian rocks. From a net uranium production of 41,742 metric tons (t), more than 6,000 t were extracted from bitumen-uraninite ores during 43 years of exploration and mining. Three morphological varieties of solid bitumen are recognized: globular, asphaltlike, and cokelike. While the globular bitumen is uranium free, the other two types are uraniferous. The amount of bitumen in ore veins gradually decreases toward the contact with the plutonic body and increases with depth. Two types of bitumen microtextures are recognized using high-resolution transmission electron microscopy: amorphous and microporous, the former being less common in uraniferous samples. A lower Raman peak area ratio (1,360/1,575 cm(-1)) in mineralized bitumens (0.9) compared with uranium-free samples (2.0) indicates a lower degree of microtextural organization in the latter The H/C and O/C atomic ratios in uranium-free bitumens (0.9-1.1 and 0.09, respectively) are higher than those in mineralized samples (H/C = 0.3-0.8, O/C = 0.03-0.09). The chloroform extractable matter yield is Very low in uranium-free bitumens (0.30-0.35% of the total organic carbon,TOC) and decreases with uranium content increase. The extracted solid uraniferous bitumen infrared spectra show depletion in aliphatic CH2 and CH3 groups compared to uranium-free samples. The concentration of oxygen-bearing functional groups relative to aromatic bonds in the IR spectra of uranium-free and mineralized bitumen, however, do not differ significantly. C-13 NMR confirmed than the aromaticity of a uraniferous sample is higher (F-ar = 0.61) than in the uranium-free bitumen (F-ar = 0.51). Pyrolysates from uraniferous and nonuraniferous bitumens do not differ significantly, being predominantly cresol, alkylphenols, alkylbenzenes, and alkylnaphthalenes. The liquid pyrolysate yield decreases significantly with increasing uranium content. The delta(13)C Values of bulk uranium-free bitumens and low-grade uraniferous, asphaltlike bitumens range from -43.6 to 52.3 per mil. High-grade, cokelike, uraniferous bitumens are more C-13 depleted (54.5 to -58.4 parts per thousand). In contrast to the very light isotopic ratios of the high-grade uraniferous cokelike bitumen bulk carbon, the individual n-alkanes and isoprenoids (pristane and phytane) extracted from the same sample are significantly C-13 enriched. The isotopic composition of the C13-24 n-alkanes extracted from the high-grade uraniferous sample (delta(13)C = -28.0 to 32.6 parts per thousand) are heavier compared with the same compounds in a uranium-free sample (delta(13)C = 31.9 to 33.8 parts per thousand). It is proposed that the bitumen source was the isotopically light (delta(13)C = 35.8 to 30.2 parts per thousand) organic matter of the Upper Proterozoic host rocks that were pyrolyzed during intrusion of the Central Bohemian pluton. The C-13- depleted pyrolysates were mobilized from the innermost part of the contact-metamorphic aureole, accumulated in structural traps in less thermally influenced parts of the sedimentary complex and were later extracted by hydrothermal fluids. Bitumens at the Pribram deposit are younger than the main part of the uranium mineralization and were formed through water-washing and radiation-induced polymerization of both the gaseous and liquid pyrolysates. Direct evidence for pyrolysate reduction of uranium in the hydrothermal system is difficult to obtain as the chemical composition of the original organic fluid phase was modified during water-washing and radiolytic alteration. However, indirect evidence-e.g., higher O/C atomic ratios in uranium-free bitumens (0.1) relative to the Upper Proterozoic source rocks (0.02-0.05), isotopically very light carbon in associated whewellite (delta(13)C = 31.7 to -28.4 parts per thousand), and the striking absence of bitumens in the pre-uranium, hematite stage of the mineralization-indicates that oxidation of organic fluids may have contributed to lowering of aO(2) and uraninite precipitation.

Fluid flow through the sedimentary cover in northern Switzerland recorded by calcite-celestite veins (Oftringen borehole, Olten)

Abundant veins filled by calcite, celestite and pyrite were found in the core of a 719 m deep borehole drilled in Oftringen near Olten, located in the north-western Molasse basin, close to the thrust of the Folded Jura. Host rocks are calcareous marl, argillaceous limestone and limestone of the Dogger and Malm. The delta O-18 values of vein calcite are lower than in host rock carbonate and, together with microthermometric data from fluid inclusions in vein calcite, indicate precipitation from a seawater-dominated fluid at average temperatures of 56-68A degrees C. Such temperatures were reached at the time of maximum burial of the sedimentary pile in the late Miocene. The depth profile of delta C-13 and Sr-87/Sr-86 values and Sr content of both whole-rock carbonate and vein calcite show marked trends towards negative delta C-13, high Sr-87/Sr-86, and low Sr content in the uppermost 50-150 m of the Jurassic profile (upper Oxfordian). The Sr-87/Sr-86 of vein minerals is generally higher than that of host rock carbonate, up to very high values corresponding to Burdigalian seawater (Upper Marine Molasse, Miocene), which represents the last marine incursion in the region. No evidence for internally derived radiogenic Sr (clay minerals) has been found and so an external source is required. S and O isotope composition of vein celestite and pyrite can be explained by bacterial reduction of Miocene seawater sulphate. The available data set suggests the vein mineralization precipitated from descending Burdigalian seawater and not from a fluid originating in the underlying Triassic evaporites.

The Toarcian in the Subbetic basin (southern Spain): Bio-events (ammonite and calcareous nannofossils) and carbon-isotope stratigraphy

A detailed carbon-isotope stratigraphic study for the uppermost Pliensbachian lowermost Aalenian interval in the Median Subbetic palaeogeographic domain (External zones of the Betic Cordillera, southern Spain) has been carried out. During the Early Jurassic, the Median Subbetic, which represents a typical basin of the Hispanic Corridor connecting the Tethys and the Eastern Pacific, was located in the westernmost Tethys. The analyzed sections encompass the entire Toarcian stage as represented in the southern Iberian palaeomargin. Rocks are mainly rhythmic sequences of grey marls and marly limestones containing a rich ammonite fauna, nannofossils, and benthic foraminifers-all these provide an accurate biostratigraphic control. The lower and upper Toarcian boundaries are well represented in some of these sections and therefore represent optimal sites to link the carbon-isotope curves to ammonite zones, and to nannofossil events. delta C-13 values of bulk carbonates from the different localities of the Subbetic basin have similar variations from the uppermost Pliensbachian to the lowermost Aalenian, suggesting changes in the original DIC carbon isotope composition along the Hispanic corridor. The transition from Pliensbachian to Toarcian is marked by increasing delta C-13 values from similar to 12 to 2.0 parts per thousand, interrupted in the Serpentinum Zone by a negative shift concomitant with the Toarcian oceanic anoxic event (T-OAE), with the major ammonite extinction event of the Toarcian, and an important turnover of calcareous nannoplankton. The negative shift observed in the Serpentinum Zone confirms the global perturbation of the carbon cycling documented along the Tethys and the palaeo-Pacific in organic material and in marine carbonates. However, the amplitude of the negative excursion (similar to - 1.5 parts per thousand) is not compatible with an isotopic homogeneous seawater DIC and/or CO2 atmospheric reservoirs. The interval from the middle to the top of the Toarcian delta C-13 shows relatively constant values, minor ammonite turnovers, and is associated with increasing diversity of calcareous nannoplankton. (c) 2012 Elsevier B.V. All rights reserved.

Characterization of cocoa butter and cocoa butter equivalents by bulk and molecular carbon isotope analyses: Implications for vegetable fat quantification in chocolate

The fatty acids from cocoa butters of different origins, varieties, and suppliers and a number of cocoa butter equivalents (Illexao 30-61, Illexao 30-71, Illexao 30-96, Choclin, Coberine, Chocosine-Illipe, Chocosine-Shea, Shokao, Akomax, Akonord, and Ertina) were investigated by bulk stable carbon isotope analysis and compound specific isotope analysis. The interpretation is based on principal component analysis combining the fatty acid concentrations and the bulk and molecular isotopic data. The scatterplot of the two first principal components allowed detection of the addition of vegetable fats to cocoa butters. Enrichment in heavy carbon isotope (C-13) of the bulk cocoa butter and of the individual fatty acids is related to mixing with other vegetable fats and possibly to thermally or oxidatively induced degradation during processing (e.g., drying and roasting of the cocoa beans or deodorization of the pressed fat) or storage. The feasibility of the analytical approach for authenticity assessment is discussed.

Characterization of olive oil by carbon isotope analysis of individual fatty acids: Implications for authentication

The fatty acids of olive oils of distinct quality grade from the most important European Union (EU) producer countries were chemically and isotopically characterized. The analytical approach utilized combined capillary column gas chromatography-mass spectrometry (GC/MS) and the novel technique of compound-specific isotope analysis (CSIA) through gas chromatography coupled to a stable isotope ratio mass spectrometer (IRMS) via a combustion (C) interface (GC/C/IRMS). This approach provides further insights into the control of the purity and geographical origin of oils sold as cold-pressed extra virgin olive oil with certified origin appellation. The results indicate that substantial enrichment in heavy carbon isotope (C-13) of the bulk oil and of individual fatty acids are related to (1) a thermally induced degradation due to deodorization or steam washing of the olive oils and (2) the potential blend with refined olive oil or other vegetable oils. The interpretation of the data is based on principal component analysis of the fatty acids concentrations and isotopic data (delta(13)C(oil), delta(13)C(16:0), delta(13)C(18:1)) and on the delta(13)C(16:0) vs delta(13)C(18:1) covariations. The differences in the delta(13)C values of palmitic and oleic acids are discussed in terms of biosynthesis of these acids in the plant tissue and admixture of distinct oils.

Deep thiopental anesthesia alters steady-state glucose homeostasis but not the neurochemical profile of rat cortex.

Barbiturates are regularly used as an anesthetic for animal experimentation and clinical procedures and are frequently provided with solubilizing compounds, such as ethanol and propylene glycol, which have been reported to affect brain function and, in the case of (1)H NMR experiments, originate undesired resonances in spectra affecting the quantification. As an alternative, thiopental can be administrated without any solubilizing agents. The aim of the study was to investigate the effect of deep thiopental anesthesia on the neurochemical profile consisting of 19 metabolites and on glucose transport kinetics in vivo in rat cortex compared with alpha-chloralose using localized (1)H NMR spectroscopy. Thiopental was devoid of effects on the neurochemical profile, except for the elevated glucose at a given plasma glucose level resulting from thiopental-induced depression of glucose consumption at isoelectrical condition. Over the entire range of plasma glucose levels, steady-state glucose concentrations were increased on average by 48% +/- 8%, implying that an effect of deep thiopental anesthesia on the transport rate relative to cerebral glucose consumption ratio was increased by 47% +/- 8% compared with light alpha-chloralose-anesthetized rats. We conclude that the thiopental-induced isoelectrical condition in rat cortex significantly affected glucose contents by depressing brain metabolism, which remained substantial at isoelectricity.

Assignment strategies for large proteins by magic-angle spinning NMR: the 21-kDa disulfide-bond-forming enzyme DsbA.

We present strategies for chemical shift assignments of large proteins by magic-angle spinning solid-state NMR, using the 21-kDa disulfide-bond-forming enzyme DsbA as prototype. Previous studies have demonstrated that complete de novo assignments are possible for proteins up to approximately 17 kDa, and partial assignments have been performed for several larger proteins. Here we show that combinations of isotopic labeling strategies, high field correlation spectroscopy, and three-dimensional (3D) and four-dimensional (4D) backbone correlation experiments yield highly confident assignments for more than 90% of backbone resonances in DsbA. Samples were prepared as nanocrystalline precipitates by a dialysis procedure, resulting in heterogeneous linewidths below 0.2 ppm. Thus, high magnetic fields, selective decoupling pulse sequences, and sparse isotopic labeling all improved spectral resolution. Assignments by amino acid type were facilitated by particular combinations of pulse sequences and isotopic labeling; for example, transferred echo double resonance experiments enhanced sensitivity for Pro and Gly residues; [2-(13)C]glycerol labeling clarified Val, Ile, and Leu assignments; in-phase anti-phase correlation spectra enabled interpretation of otherwise crowded Glx/Asx side-chain regions; and 3D NCACX experiments on [2-(13)C]glycerol samples provided unique sets of aromatic (Phe, Tyr, and Trp) correlations. Together with high-sensitivity CANCOCA 4D experiments and CANCOCX 3D experiments, unambiguous backbone walks could be performed throughout the majority of the sequence. At 189 residues, DsbA represents the largest monomeric unit for which essentially complete solid-state NMR assignments have so far been achieved. These results will facilitate studies of nanocrystalline DsbA structure and dynamics and will enable analysis of its 41-kDa covalent complex with the membrane protein DsbB, for which we demonstrate a high-resolution two-dimensional (13)C-(13)C spectrum.

Deep thiopental anesthesia alters steady-state glucose homeostasis but not the neurochemical profile of rat cortex.

Barbiturates are regularly used as an anesthetic for animal experimentation and clinical procedures and are frequently provided with solubilizing compounds, such as ethanol and propylene glycol, which have been reported to affect brain function and, in the case of (1)H NMR experiments, originate undesired resonances in spectra affecting the quantification. As an alternative, thiopental can be administrated without any solubilizing agents. The aim of the study was to investigate the effect of deep thiopental anesthesia on the neurochemical profile consisting of 19 metabolites and on glucose transport kinetics in vivo in rat cortex compared with alpha-chloralose using localized (1)H NMR spectroscopy. Thiopental was devoid of effects on the neurochemical profile, except for the elevated glucose at a given plasma glucose level resulting from thiopental-induced depression of glucose consumption at isoelectrical condition. Over the entire range of plasma glucose levels, steady-state glucose concentrations were increased on average by 48% +/- 8%, implying that an effect of deep thiopental anesthesia on the transport rate relative to cerebral glucose consumption ratio was increased by 47% +/- 8% compared with light alpha-chloralose-anesthetized rats. We conclude that the thiopental-induced isoelectrical condition in rat cortex significantly affected glucose contents by depressing brain metabolism, which remained substantial at isoelectricity.

Geochronological constraints on post-extinction recovery of the ammonoids and carbon cycle perturbations during the Early Jurassic

This paper presents the first quantitative study of the Early Jurassic recovery of ammonoids after the end-Triassic mass extinction based on detailed U-Pb ID-TIMS (isotope dilution thermal ionization mass spectrometry) geochronology from ash bed zircons placed within a clear phylogenetical and biochronological framework at the subzonal and species level. This study was triggered by the discovery of a rich Peruvian succession of ammonites, deposited concomitantly with an unusually large number of ash beds. Two major phases of rediversification are observed during the Psiloceras spelae and Angulaticeras zones that correspond to positive peaks in the delta C-13(org) curve, providing a possible link between biodiversity and the global carbon cycle. In the case of the post-extinction recovery, the development of the earliest Hettangian ammonites occurs within the genus Psiloceras, which begins with the occurrence of P. spelae and then explodes into worldwide development of smooth psiloceratids of the Psiloceras planorbis group s.l. This rapid biodiversification likely occurred less than 100 ka after the end-Triassic crisis; the genus Psiloceras occupied all the possible ecological niches worldwide, from the Pacific deep waters to the NW European shallow deposits and also in some rare Tethyan occurrences like at Germig in Tibet. This global dispersion allowed the differentiation of the group in several major phyla, the Schlotheimiidae, Discamphiceratinae, Arietitidae and Lytocerataceae, which were the roots of all other Jurassic and Cretaceous ammonites. (C) 2012 Elsevier B.V. All rights reserved.