Analysis of the nano-surface of a modified glassy carbon electrode by pseudo phase plane method

This paper presents the Pseudo phase plane (PPP) method for detecting the existence of a nanofilm on the nitroazobenzene-modified glassy carbon electrode (NAB-GC) system. This modified electrode systems and nitroazobenze-nanofilm were prepared by the electrochemical reduction of diazonium salt of NAB at the glassy carbon electrodes (GCE) in nonaqueous media. The IR spectra of the bare glassy carbon electrodes (GCE), the NAB-GC electrode system and the organic NAB film were recorded. The IR data of the bare GC, NAB-GC and NAB film were categorized into five series consisting of FILM1, GC-NAB1, GC1; FILM2, GC-NAB2, GC2; FILM3, GC-NAB3, GC3 and FILM4, GC-NAB4, GC4 respectively. The PPP approach was applied to each group of the data of unmodified and modified electrode systems with nanofilm. The results provided by PPP method show the existence of the NAB film on the modified GC electrode.

Characterization approach to modified glassy carbon electrode-nanofilm system within multidimensional scaling

The aim of this work is to characterize the nanofilm consisting of the benzoic acid-modified glassy carbon (GC) electrode system through multidimensional scaling space analysis. The surface modification is based on the electrochemical reaction between the GC electrode and benzoic acid-diazonium salt (BA-DAS). As a result, the nonofilms regarding the benzoic acid-glassy carbon (BA-GC) electrode surface was obtained. For the analysis of the naonfilm of BC-GC electrode system, the IR spectra of the modified BA-GC electrode surface, GC surface and BA-DAS were recorded in the spectral range of 599.84 – 3996.34 [cm–1]. The IR data vectors of the above three forms were processed by the using the multidimensional scaling space approach to demonstrate the existence of a nanofilm on the modified BA-GC electrode system. Two- and three-dimensional MDS profiles obtained by application of multidimensional scaling approach to the data sets {CG1,...,CG10}, {BA-GC1,...,BA-GC10} and {FILM1,...,FILM10} allow a good recognition of the nanofilm on the modified glassy carbon (GC) electrode system.

Sensitive bi-enzymatic biosensor based on polyphenoloxidases–gold nanoparticles–chitosan hybrid film–graphene doped carbon paste electrode for carbamates detection

A bi-enzymatic biosensor (LACC–TYR–AuNPs–CS/GPE) for carbamates was prepared in a single step by electrodeposition of a hybrid film onto a graphene doped carbon paste electrode (GPE). Graphene and the gold nanoparticles (AuNPs) were morphologically characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, dynamic light scattering and laser Doppler velocimetry. The electrodeposited hybrid film was composed of laccase (LACC), tyrosinase (TYR) and AuNPs entrapped in a chitosan (CS) polymeric matrix. Experimental parameters, namely graphene redox state, AuNPs:CS ratio, enzymes concentration, pH and inhibition time were evaluated. LACC–TYR–AuNPs–CS/GPE exhibited an improved Michaelis–Menten kinetic constant (26.9 ± 0.5 M) when compared with LACC–AuNPs–CS/GPE (37.8 ± 0.2 M) and TYR–AuNPs–CS/GPE (52.3 ± 0.4 M). Using 4-aminophenol as substrate at pH 5.5, the device presented wide linear ranges, low detection limits (1.68×10− 9 ± 1.18×10− 10 – 2.15×10− 7 ± 3.41×10− 9 M), high accuracy, sensitivity (1.13×106 ± 8.11×104 – 2.19×108 ± 2.51×107 %inhibition M− 1), repeatability (1.2–5.8% RSD), reproducibility (3.2–6.5% RSD) and stability (ca. twenty days) to determine carbaryl, formetanate hydrochloride, propoxur and ziram in citrus fruits based on their inhibitory capacity on the polyphenoloxidases activity. Recoveries at two fortified levels ranged from 93.8 ± 0.3% (lemon) to 97.8 ± 0.3% (orange). Glucose, citric acid and ascorbic acid do not interfere significantly in the electroanalysis. The proposed electroanalytical procedure can be a promising tool for food safety control.

Characterization of molecular damage induced by UV photons and carbon ions on biomimetic heterostructures

The study of the effect of radiation on living tissues is a rather complex task to address mainly because they are made of a set of complex functional biological structures and interfaces. Particularly if one is looking for where damage is taking place in a first stage and what are the underlying reaction mechanisms. In this work a new approach is addressed to study the effect of radiation by making use of well identified molecular hetero-structures samples which mimic the biological environment. These were obtained by assembling onto a solid support deoxyribonucleic acid (DNA) and phospholipids together with a soft water-containing polyelectrolyte precursor in layered structures and by producing lipid layers at liquid/air interface with DNA as subphase. The effects of both ultraviolet (UV) radiation and carbon ions beams were systematically investigated in these heterostructures, namely damage on DNA by means vacuum ultraviolet (VUV), infrared (IR), X-Ray Photoelectron (XPS) and impedance spectroscopy. Experimental results revealed that UV affects furanose, PO2-, thymines, cytosines and adenines groups. The XPS spectrometry carried out on the samples allowed validate the VUV and IR results and to conclude that ionized phosphate groups, surrounded by the sodium counterions, congregate hydration water molecules which play a role of UV protection. The ac electrical conductivity measurements revealed that the DNA electrical conduction is arising from DNA chain electron hopping between base-pairs and phosphate groups, with the hopping distance equal to the distance between DNA base-pairs and is strongly dependent on UV radiation exposure, due loss of phosphate groups. Characterization of DNA samples exposed to a 4 keV C3+ ions beam revealed also carbon-oxygen bonds break, phosphate groups damage and formation of new species. Results from radiation induced damage carried out on biomimetic heterostructures having different compositions revealed that damage is dependent on sample composition, with respect to functional targeted groups and extent of damage. Conversely, LbL films of 1,2-dipalmitoyl-sn-Glycero-3-[Phospho-rac-(1-glycerol)] (Sodium Salt) (DPPG) liposomes, alternated with poly(allylamine hydrochloride) (PAH) revealed to be unaffected, even by prolonged UV irradiation exposure, in the absence of water molecules. However, DPPG molecules were damaged by the UV radiation in presence of water with cleavage of C-O, C=O and –PO2- bonds. Finally, the study of DNA interaction with the ionic lipids at liquid/air interfaces revealed that electrical charge of the lipid influences the interaction of phospholipid with DNA. In the presence of DNA in the subphase, the effects from UV irrladiation were seen to be smaller, which means that ionic products from biomolecules degradation stabilize the intact DPPG molecules. This mechanism may explain why UV irradiation does not cause immediate cell collapse, thus providing time for the cellular machinery to repair elements damaged by UV.

Anatomy of contaminated aquifers of an industrial site: insights from the stable isotope compositions of waters and dissolved inorganic carbon

The hydrogen and oxygen isotopes of water and the carbon isotope composition of dissolved inorganic carbon (DIC) from different aquifers at an industrial site, highly contaminated by organic pollutants representing residues of the former gas production, have been used as natural tracers to characterize the hydrologic system. On the basis of their stable isotope compositions as well as the seasonal variations, different groups of waters (precipitation, surface waters, groundwaters and mineral waters) as well as seasonably variable processes of mixing between these waters can clearly be distinguished. In addition, reservoir effects and infiltration rates can be estimated. In the northern part of the site an influence of uprising mineral waters within the Quaternary aquifers, presumably along a fault zone, can be recognized. Marginal infiltration from the Neckar River in the cast and surface water infiltration adjacent to a steep hill on the western edge of the site with an infiltration rate of about one month can also be resolved through the seasonal variation. Quaternary aquifers closer to the centre of the site show no seasonal variations, except for one borehole close to a former mill channel and another borehole adjacent to a rain water channel. Distinct carbon isotope compositions and concentrations of DIC for these different groups of waters reflect variable influence of different components of the natural carbon cycle: dissolution of marine carbonates in the mineral waters, biogenic, soil-derived CO2 in ground- and surface waters, as well as additional influence of atmospheric CO2 for the surface waters. Many Quaternary aquifer waters have, however, distinctly lower delta(13)C(DIC) values and higher DIC concentrations compared to those expected for natural waters. Given the location of contaminated groundwaters at this site but also in the industrially well-developed valley outside of this site, the most likely source for the low C-13(DIC) values is a biodegradation of anthropogenic organic substances, in particular the tar oils at the site.

Carbon dioxide in scree slope deposits: A pathway from atmosphere to pedogenic carbonate

A continuum of carbon, from atmospheric CO2 to secondary calcium carbonate, has been studied in a soil associ- ated with scree slope deposits in the Jura Mountains of Switzerland. This approach is based on former studies conducted in other environments. This C continuum includes atmospheric CO2, soil organic matter (SOM), soil CO2, dissolved inorganic carbon (DIC) in soil solutions, and secondary pedogenic carbonate. Soil parameters (pCO2, temperature, pH, Cmin and Corg contents), soil solution chemistry, and isotopic compositions of soil CO2, DIC, carbonate and soil organic matter (δ13CCO2, δ13CDIC, δ13Ccar and δ13CSOM values) have been monitored at different depths (from 20 to 140 cm) over one year. Results demonstrated that the carbon source in secondary carbonate (mainly needle fiber calcite) is related to the dissolved inorganic carbon, which is strongly dependent on soil respiration. The heterotrophic respiration, rather than the limestone parent material, seems to control the pedogenic carbon cycle. The correlation of δ13Corg values with Rock-Eval HI and OI indices demonstrates that, in a soil associated to scree slope deposits, the main process responsible for 13C-enrichment in SOM is related to bac- terial oxidative decarboxylation. Finally, precipitation of secondary calcium carbonate is enhanced by changes in soil pCO2 associated to the convective movement of air masses induced by temperature gradients (heat pump effect) in the highly porous scree slope deposits. The exportation of soil C-leachates from systems such as the one studied in this paper could partially explain the "gap in the European carbon budget" reported by recent studies.

Risk determinants of acute mountain sickness in trekkers in the Nepali Himalaya: a 24-year follow-up.

OBJECTIVE: Exposure to altitude may lead to acute mountain sickness (AMS) in nonacclimatized individuals. We surveyed AMS prevalence and potential risk factors in trekkers crossing a 5400-m pass in Nepal and compared the results with those of 2 similar studies conducted 12 and 24 years earlier. METHODS: In April 2010, 500 surveys were distributed to English-speaking trekkers at 3500 m on their way to 5400 m, of which 332 (66%) surveys were returned complete. Acute mountain sickness was quantified with the Lake Louise Scoring System (LLSS, cutoff ≥3 and ≥5) and the Environmental Statistical Questionnaire III AMS-C score (ESQ-III, cutoff ≥0.7). We surveyed demographics, body mass index (BMI), smoking habit, rate of ascent, awareness of AMS, and acetazolamide use. RESULTS: Prevalence of AMS was 22%, 23%, and 48% (ESQ-III ≥0.7, LLSS ≥5, and LLSS ≥3, respectively) lower when compared with earlier studies. Risk factors for AMS were younger age, female sex, higher BMI, and smoking habit. Forty-two percent had elementary knowledge about the risk and prevention of AMS. Forty-four percent used acetazolamide. Trekkers took longer to climb from 3500 to 5400 m than in earlier studies. CONCLUSIONS: Prevalence of AMS continued to decline over a period of 24 years, likely as a result of slower ascent and increased use of acetazolamide. The AMS risk factors of younger age, female sex, and high BMI are consistent with prior studies. Awareness of risk and prevention of AMS remains low, indicating an opportunity to better educate trekkers and potentially further reduce AMS prevalence.

Middle and Late Jurassic carbon stable-isotope stratigraphy and radiolarite sedimentation of the Umbria-Marche basin (Central Italy)

A continuous carbon isotope curve from Middle-Upper Jurassic pelagic carbonate rocks was acquired from two sections in the southern part of the Umbria-Marche Apennines in central Italy. At the Colle Bertone section (Terni) and the Terminilletto section (Rieti), the Upper Toarcian to Bajocian Calcari e Marne a Posidonia Formation and the Aalenian to Kimmeridgian Calcari e Marne a Posidonia and Calcari Diasprigni formations were sampled, respectively. Biostratigraphy in both sections is based on rich assemblages of calcareous nannofossils and radiolarians, as well as some ammonites found in the upper Toarcian-Bajocian interval. Both sections revealed a relative minimum of delta(13)C(PDB) close to + 2 parts per thousand in the Aalenian and a maximum around 3.5 parts per thousand in early Bajocian, associated with an increase in visible chert. In basinal sections in Umbria-Marche, this interval includes the very cherry base of the Calcari Diasprigni Formation (e.g. at Valdorbia) or the chert-rich uppermost portion of the Calcari a Posidonia (e.g at Bosso). In the Terminilletto section, the Bajocian-early Barthonian interval shows a gradual decrease in delta(13)C(PDB) values and a low around 2.3 parts per thousand. This part of the section is characterised by more than 40 m of almost chart-free limestones and correlates with a recurrence of limestone-rich facies in basinal sections at Valdorbia. A double peak with values of delta(13)C(PDB) around + 3 parts per thousand was observed in the Callovian and Oxfordian, constrained by well preserved radiolarian faunas. The maxima lie in the Callovian and the middle Oxfordian, and the minimum between the two peaks should be near the Callovian/Oxfordian boundary. In the Terminilletto section, visible chert increases together with delta(13)C(PDB) values from the middle Bathonian and reaches peak values in the Callovian-Oxfordian. In basinal sections in Umbria-Marche, a sharp increase in visible chert is observed at this level within the Calcari Diasprigni. A drop of delta(13)C values towards + 2 parts per thousand occurs in the Kimmeridgian and coincides with a decrease of visible chert in outcrop. The observed delta(13)C positive anomalies during the early Bajocian and the Callovian-Oxfordian may record changes in global climate towards warmer, more humid periods characterised by increased nutrient mobilisation and increased carbon burial. High biosiliceous (radiolarians, siliceous sponges) productivity and preservation appear to coincide with the delta(13)C positive anomalies, when the production of platform carbonates was subdued and ceased in many areas, with a drastic reduction of periplatform ooze input in many Tethyan basins. The carbon and silica cycles appear to be linked through global warming and increased continental weathering. Hydrothermal events related to extensive rifting and/or accelerated oceanic spreading may be the endogenic driving force that created a perturbation of the exogenic system (excess CO2 into the atmosphere and greenhouse conditions) reflected by the positive delta(13)C shifts and biosiliceous episodes.

Geological transect across the Northwestern Himalaya in eastern Ladakh and Lahul (A model for the continental collision of India and Asia)

The detailed geological mapping and structural study of a complete transect across the northwestern Himalaya allow to describe the tectonic evolution of the north Indian continental margin during the Tethys ocean opening and the Himalayan Orogeny. The Late Paleozoic Tethys rifting is associated with several tectonomagmatic events. In Upper Lahul and SE Zanskar, this extensional phase is recorded by Lower Carboniferous synsedimentary transtensional faults, a Lower Permian stratigraphic unconformity, a Lower Permian granitic intrusion and middle Permian basaltic extrusions (Panjal Traps). In eastern Ladakh, a Permian listric normal fault is also related to this phase. The scarcity of synsedimentary faults and the gradual increase of the Permian syn-rift sediment thickness towards the NE suggest a flexural type margin. The collision of India and Asia is characterized by a succession of contrasting orogenic phases. South of the Suture Zone, the initiation of the SW vergent Nyimaling-Tsarap Nappe corresponds to an early phase of continental underthrusting. To the S, in Lahul, an opposite underthrusting within the Indian plate is recorded by the NE vergent Tandi Syncline. This structure is associated with the newly defined Shikar Beh Nappe, now partly eroded, which is responsible for the high grade (amphibolite facies) regional metamorphism of South Lahul. The main thrusting of the Nyimaling-Tsarap Nappe followed the formation of the Shikar Beh Nappe. The Nyimaling-Tsarap Nappe developed by ductile shear of the upper part of the subducted Indian continental margin and is responsible for the progressive regional metamorphism of SE Zanskar, reaching amphibolite facies below the frontal part of the nappe, near Sarchu. In Upper Lahul, the frontal parts of the Nyimaling-Tsarap and Shikar Beh nappes are separated by a zone of low grade metamorphic rocks (pumpellyite-actinolite facies to lower greenschist facies). At high structural level, the Nyimaling-Tsarap Nappe is characterized by imbricate structures, which grade into a large ductile shear zone with depth. The related crustal shortening is about 87 km. The root zone and the frontal part of this nappe have been subsequently affected by two zones of dextral transpression and underthrusting: the Nyimaling Shear Zone and the Sarchu Shear Zone. These shear zones are interpreted as consequences of the counterclockwise rotation of the continental underthrusting direction of India relative to Asia, which occurred some 45 and 36 Ma ago, according to plate tectonic models. Later, a phase of NE vergent `'backfolding'' developed on these two zones of dextral transpression, creating isoclinal folds in SE Zanskar and more open folds in the Nyimaling Dome and in the Indus Molasse sediments. During a late stage of the Himalayan Orogeny, the frontal part of the Nyimaling-Tsarap Nappe underwent an extension of about 15 km. This phase is represented by two types of structures, responsible for the tectonic unroofing of the amphibolite facies rocks of the Sarchu area: the Sarchu high angle Normal Fault, cutting a first set of low angle normal faults, which have been created by reactivation of older thrust planes related to the Nyimaling-Tsarap Nappe.

Trophic dynamics in the northern Humboldt Current system: insights from stable isotopes and stomach content analyses

The northern Humboldt Current system (NHCS) off Peru is one of the most productive world marine regions. It represents less than 0.1% of the world ocean surface but presently sustains about 10% of the world fish catch, with the Peruvian anchovy or anchoveta Engraulis ringens as emblematic fish resource. Compared with other eastern boundary upwelling systems, the higher fish productivity of the NHCS cannot be explained by a corresponding higher primary productivity. On another hand, the NHCS is the region where El Niño, and climate variability in general, is most notable. Also, surface oxygenated waters overlie an intense and extremely shallow Oxygen Minimum Zone (OMZ). In this context, the main objective of this study is to better understand the trophic flows in the NHCS using both stomach content and stable isotope analyses. The study focuses on a variety of organisms from low trophic levels such as zooplankton to top predators (seabirds and fur seals). The approach combines both long-term and specific studies on emblematic species such as anchoveta, and sardine Sardinops sagax and a more inclusive analysis considering the 'global' food web in the recent years (2008 – 2012) using stable isotope analysis. Revisiting anchovy and sardine we show that whereas phytoplankton largely dominated anchoveta and sardine diets in terms of numerical abundance, the carbon content of prey items indicated that zooplankton was by far the most important dietary component. Indeed for anchovy euphausiids contributed 67.5% of dietary carbon, followed by copepods (26.3%). Selecting the largest prey, the euphausiids, provide an energetic advantage for anchoveta in its ecosystem where oxygen depletion imposes strong metabolic constrain to pelagic fish. Sardine feed on smaller zooplankton than do anchoveta, with sardine diet consisting of smaller copepods and fewer euphausiids than anchoveta diet. Hence, trophic competition between sardine and anchovy in the northern Humboldt Current system is minimized by their partitioning of the zooplankton food resource based on prey size, as has been reported in other systems. These results suggest an ecological role for pelagic fish that challenges previous understanding of their position in the foodweb (zooplanktophagous instead of phytophagous), the functioning and the trophic models of the NHCS. Finally to obtain a more comprehensive vision of the relative trophic position of NHCS main components we used stable isotope analyses. For that purpose we analyzed the δ13C and δ15N stable isotope values of thirteen taxonomic categories collected off Peru from 2008 - 2011, i.e., zooplankton, fish, squids and air-breathing top predators. The δ15N isotope signature was strongly impacted by the species, the body length and the latitude. Along the Peruvian coast, the OMZ get more intense and shallow south of ~7.5ºS impacting the baseline nitrogen stable isotopes. Employing a linear mixed-effects modelling approach taking into account the latitudinal and body length effects, we provide a new vision of the relative trophic position of key ecosystem components. Also we confirm stomach content-based results on anchoveta Engraulis ringens and highlight the potential remarkable importance of an often neglected ecosystem component, the squat lobster Pleuroncodes monodon. Indeed, our results support the hypothesis according to which this species forage to some extent on fish eggs and larvae and can thus predate on the first life stages of exploited species. However, the δ13C values of these two species suggest that anchoveta and squat lobster do not exactly share the same habitat. This would potentially reduce some direct competition and/or predation.

Redox index of soil carbon stability

As an alternative to the relatively complex and expensive spectroscopic methods, the redox properties of humic acids, determined by potentiometric titrations, have been used to evaluate the stability of soil organic C. The objective of the present study was to establish a Redox Index of C Stability (RICS) and to correlate it with some properties of the humic acids extracted from different modal soils in Brazil (distinct weathering stages or management) to facilitate system comparison. The RICS was efficient for soil comparison and variations were comparable to those of the chemical and spectroscopic methods used for humic acid characterization. The values of soil pH, point of zero salt effect, sum of bases, exchangeable Ca content, weathering index, as well as the humic acid O/C ratio, quinone and semiquinone free radical contents, aromatic C and fluorescence intensity were closely related with the RICS. The RICS was higher in less weathered soils, with more active clays and higher fertility. The RICS values of soils under long-term sugarcane management were ranked in decreasing order: unburned, burned with vinasse, burned without vinasse.

Geology of the NW Indian Himalaya

This review paper deals with the geology of the NW Indian Himalaya situated in the states of Jammu and Kashmir, Himachal Pradesh and Garhwal. The models and mechanisms discussed, concerning the tectonic and metamorphic history of the Himalayan range, are based on a new compilation of a geological map and cross sections, as well as on paleomagnetic, stratigraphic, petrologic, structural, metamorphic, thermobarometric and radiometric data. The protolith of the Himalayan range, the North Indian flexural passive margin of the Neo-Tethys ocean, consists of a Lower Proterozoic basement, intruded by 1.8-1.9 Ga bimodal magmatites, overlain by a horizontally stratified sequence of Upper Proterozoic to Paleocene sediments, intruded by 470-500 Ma old Ordovician mainly peraluminous s-type granites, Carboniferous tholeiitic to alkaline basalts and intruded and overlain by Permian tholeiitic continental flood basalts. No elements of the Archaen crystalline basement of the South Indian shield have been identified in the Himalayan range. Deformation of the Himalayan accretionary wedge resulted from the continental collision of India and Asia beginning some 65-55 Ma ago, after the NE-directed underthrusting of the Neo-Tethys oceanic crust below Asia and the formation of the Andean-type 103-50 (-41) Ma old Ladakh batholith to the north of the Indus Suture. Cylindrical in geometry, the Himalayan range consists, from NE to SW, from older to younger tectonic elements, of the following zones: 1) The 25 km wide Ladakh batholith and the Asian mantle wedge form the backstop of the growing Himalayan accretionary wedge. 2) The Indus Suture zone is composed of obducted slices of the oceanic crust, island arcs, like the Dras arc, overlain by Late Cretaceous fore arc basin sediments and the mainly Paleocene to Early Eocene and Miocene epi-sutural intra-continental Indus molasse. 3) The Late Paleocene to Eocene North Himalayan nappe stack, up to 40 km thick prior to erosion, consists of Upper Proterozoic to Paleocene rocks, with the eclogitic and coesite bearing Tso Morari gneiss nappe at its base. It includes a branch of the Central Himalayan detachment, the 22-18 Ma old Zanskar Shear zone that is intruded and dated by the 22 Ma Gumburanjun leucogranite; it reactivates the frontal thrusts of the SW-verging North Himalayan nappes. 4) The late Eocene-Miocene SW-directed High Himalayan or ``Crystalline'' nappe comprises Upper Proterozoic to Mesozoic sediments and Ordovician granites, identical to those of the North Himalayan nappes. The Main Central thrust at its base was created in a zone of Eocene to Early Oligocene anatexis by ductile detachment of the subducted Indian crust, below the pre-existing 25-35 km thick NE-directed Shikar Beh and SW-directed North Himalayan nappe stacks. 5) The late Miocene Lesser Himalayan thrust with the Main Boundary Thrust at its base consists of early Proterozoic to Cambrian rocks intruded by 1.8-1.9 Ga bimodal magmatites. The Subhimalaya is a thrust wedge of Himalayan fore deep basin sediments, composed of the Early Eocene marine Subathu marls and sandstones as well as the up to 8'000 m-thick Miocene to recent Ganga molasse, a coarsening upwards sequence of shales, sandstones and conglomerates. The active frontal thrust is covered by the sediments of the Indus-Ganga plains.

Controls on ostracod valve geochemistry: Part 2. Carbon and oxygen isotope compositions

The stable carbon and oxygen isotope compositions of fossil ostracods are powerful tools to estimate past environmental and climatic conditions. The basis for such interpretations is that the calcite of the valves reflects the isotopic composition of water and its temperature of formation. However, calcite of ostracods is known not to form in isotopic equilibrium with water and different species may have different offsets from inorganic precipitates of calcite formed under the same conditions. To estimate the fractionation during ostracod valve calcification, the oxygen and carbon isotope compositions of 15 species living in Lake Geneva were related to their autoecology and the environmental parameters measured during their growth. The results indicate that: (1) Oxygen isotope fractionation is similar for all species of Candoninae with an enrichment in 18O of more than 30/00 relative to equilibrium values for inorganic calcite. Oxygen isotope fractionation for Cytheroidea is less discriminative relative to the heavy oxygen, with enrichments in 18O for these species of 1.7 to 2.30/00. Oxygen isotope fractionations for Cyprididae are in-between those of Candoninae and Cytheroidea. The difference in oxygen isotope fractionation between ostracods and inorganic calcite has been interpreted as resulting from a vital effect. (2) Comparison with previous work suggests that oxygen isotope fractionation may depend on the total and relative ion content of water. (3) Carbon isotope compositions of ostracod valves are generally in equilibrium with DIC. The specimens' δ13C values are mainly controlled by seasonal variations in δ13CDIC of bottom water or variation thereof in sediment pore water. (4) Incomplete valve calcification has an effect on carbon and oxygen isotope compositions of ostracod valves. Preferential incorporation of at the beginning of valve calcification may explain this effect. (5) Results presented here as well as results from synthetic carbonate growth indicate that different growth rates or low pH within the calcification site cannot be the cause of oxygen isotope 'vital effects' in ostracods. Two mechanisms that might enrich the 18O of ostracod valves are deprotonation of that may also contribute to valve calcification, and effects comparable to salt effects with high concentrations of Ca and/or Mg within the calcification site that may also cause a higher temperature dependency of oxygen isotope fractionation.

Combination of carbon isotope ratio with hydrogen isotope ratio determinations in sports drug testing.

Carbon isotope ratio (CIR) analysis has been routinely and successfully applied to doping control analysis for many years to uncover the misuse of endogenous steroids such as testosterone. Over the years, several challenges and limitations of this approach became apparent, e.g., the influence of inadequate chromatographic separation on CIR values or the emergence of steroid preparations comprising identical CIRs as endogenous steroids. While the latter has been addressed recently by the implementation of hydrogen isotope ratios (HIR), an improved sample preparation for CIR avoiding co-eluting compounds is presented herein together with newly established reference values of those endogenous steroids being relevant for doping controls. From the fraction of glucuronidated steroids 5β-pregnane-3α,20α-diol, 5α-androst-16-en-3α-ol, 3α-Hydroxy-5β-androstane-11,17-dione, 3α-hydroxy-5α-androstan-17-one (ANDRO), 3α-hydroxy-5β-androstan-17-one (ETIO), 3β-hydroxy-androst-5-en-17-one (DHEA), 5α- and 5β-androstane-3α,17β-diol (5aDIOL and 5bDIOL), 17β-hydroxy-androst-4-en-3-one and 17α-hydroxy-androst-4-en-3-one were included. In addition, sulfate conjugates of ANDRO, ETIO, DHEA, 3β-hydroxy-5α-androstan-17-one plus 17α- and androst-5-ene-3β,17β-diol were considered and analyzed after acidic solvolysis. The results obtained for the reference population encompassing n = 67 males and females confirmed earlier findings regarding factors influencing endogenous CIR. Variations in sample preparation influenced CIR measurements especially for 5aDIOL and 5bDIOL, the most valuable steroidal analytes for the detection of testosterone misuse. Earlier investigations on the HIR of the same reference population enabled the evaluation of combined measurements of CIR and HIR and its usefulness regarding both steroid metabolism studies and doping control analysis. The combination of both stable isotopes would allow for lower reference limits providing the same statistical power and certainty to distinguish between the endo- or exogenous origin of a urinary steroid.

Shallow-platform palaeoenvironmental conditions recorded in deep-shelf sediments: C and stable isotopes in Upper Jurassic sections of southern Germany (Oxfordian-Kimmeridgian)

A high-resolution carbon and oxygen isotope analysis of Late Oxfordian-Early Kimmeridgian deep-shelf sediments of southern Germany is combined with investigation of nannofossil assemblage composition and sedimentological interpretations in order to evaluate the impact of regional palaeoenvironmental conditions on isotopic composition of carbonates. This study suggests that carbonate mud was essentially derived from the Jura shallow platform environments and also that the isotopic signature of carbonates deposited in the Swabian Alb deep shelf indirectly expresses the palaeoenvironmental evolution of the platform. Short-term fluctuations in delta(13) C and delta(18)O are probably controlled by changes in salinity (fresh-water input versus evaporation) in platform environments. Long-term fluctuations in carbon and oxygen isotope record throughout the Late Oxfordian-Early Kimmeridgian result from the interplay of increasing temperature and decreasing humidity, which both control the trophic level. Changes from mesotrophic to oligotrophic conditions in platform environments and in the deep-shelf surface waters are inferred. During the Late Oxfordian (Bimammatum Subzone to Planula Zone), the delta(13)C curve displays a positive shift of about 1 parts per thousand, which is comparable in intensity to global perturbations of the carbon cycle. This evident isotopic shift has not been documented yet in other basinal settings. It can be reasonably explained by local palaeoenvironmental changes on the Jura platform (salinity, temperature, and nutrient availability) that controlled platform carbonate production, and the geochemistry of overlying waters. However, increasing carbonate production on the Jura platform and related positive delta(13)C shifts recorded in the Swabian Alb deep shelf are the regional signatures of climatic changes affecting other palaeogeographical domains of Europe in which the carbonate production increased throughout the Late Oxfordian. (C) 2002 Elsevier Science B.V. All rights reserved.