Climatic and anthropogenic influence on the stable isotope record from bulk carbonates and ostracodes in Lake Neuchatel, Switzerland, during the last two millennia

Lake Neuchatel is a medium sized, hard-water lake, lacking varved sediments, situated in the western Swiss Lowlands at the foot of the Jura Mountains. Stable isotope data (delta(18)O and delta(13)C) from both bulk carbonate and ostracode calcite in an 81 cm long, radiocarbon-dated sediment core represent the last 1500 years of Lake Neuchatel's environmental history. Comparison between this isotopic and other palaeolimnologic data (mineralogical, geochemical, palynological, etc.) helps to differentiate between anthropogenic and natural factors most recently affecting the lake. An increase in lacustrine productivity (450-650AD ca), inferred from the positive trend in delta(13)C values of bulk carbonate, is related to medieval forest clearances and the associated nutrient budget changes. A negative trend in both the bulk carbonate and ostracode calcite delta(18)O values between approximately 1300 and 1500AD, is tentatively interpreted as due to a cooling in mean air temperature at the transition from the Medieval Warm Period to the Little Ice Age. Negative trends in bulk carbonate delta(18)O and delta(13)C values through the uppermost sediments, which have no equivalent in ostracode calcite isotopic values, are concomitant with the recent onset of eutrophication in the lake. Isotopic disequilibrium during calcite precipitation, probably due to kinetic factors in periods of high productivity is postulated as the mechanism to explain the associated negative isotopic trends, although the effect of a shift of the calcite precipitation towards the warmer months cannot be excluded.

Oxidation of methane at the CH4/H2O-(CO2) transition zone in the external part of the Central Alps, Switzerland: Evidence from stable isotope investigations

With the aim of understanding the mechanisms that control the metamorphic transition from the CH4- to the H2O-(CO2)-dominated fluid zone in the Helvetic domain of the Central Alps of Switzerland, fluid inclusions in quartz, illite ``crystallinity'' index, vitrinite reflectance, and the stable isotope compositions of vein and whole rock minerals and fluids trapped in quartz were investigated along four cross-sections. Increasing temperature during prograde metamorphism led to the formation of dry gas by hydrocarbon cracking in the CH4-zone. Fluid immiscibility in the H2O-CH4-(CO2)-NaCl system resulted in cogenetic, CH4- and H2O-dominated fluid inclusions. In the CH4-zone, fluids were trapped at temperatures <= 270 +/- 5 degrees C. The end of the CH4-zone is markedby a sudden increase of CO2 content in the gas phase of fluid inclusions. At temperatures > 270 +/- 5 degrees C, in the H2O-zone, the total amount of volatiles within the fluid decreased below 1 mol% with no immiscibility. This resulted m total homogenization temperatures of H2O-(CO2-CH4)-NaCl inclusions below 180 degrees C. Hydrogen isotope compositions of methane in fluid inclusion have delta D values of less than -100 parts per thousand in the CH4-zone, typical for an origin through cracking of higher hydrocarbons, but where the methane has not equilibrated with the pore water. delta D values of fluid inclusion water are around -40 parts per thousand., in isotopic equilibrium with phyllosilicates of the whole rocks. Within the CH4 to H2O(CO2) transition zone, delta D(H2O) values in fluid inclusions decrease to -130 parts per thousand interpreted to reflect the contribution of deuterium depleted water from methane oxidation. In the H2O-zone, delta D(H2O) values increase again towards an average of -30 parts per thousand which is again consistent with isotopic equilibrium with host-rock phyllosilicates. delta C-13 values of methane in fluid inclusions from the CH4-zone are around -27 parts per thousand in isotopic equilibrium with calcite in veins and whole rocks. The delta C-13(CH4) values decrease to less than -35 parts per thousand at the transition to the H2O-zone and are no longer in equilibrium with the carbonates in the whole rocks. delta C-13 values of CO, are variable but too low to be in equilibrium with the wall rock fluids, compatible with a contribution of CO2 from closed system oxidation of methane. Differences in isotopic composition between host-rock and Alpine fissure carbonate are generally small, suggesting that the amount of CO2 produced by oxidation of methane was small compared to the C-budget in the rocks and local pore fluids were buffered by the wall rocks during precipitation of calcite within the fissures. (c) 2006 Elsevier B.V. All rights reserved.

Stable isotope (C, O, S) systematics of the mercury mineralization at Idrija, Slovenia: constraints on fluid source and alteration processes

The world-class Idrija mercury deposit (western Slovenia) is hosted by highly deformed Permocarboniferous to Middle Triassic sedimentary rocks within a complex tectonic structure at the transition between the External Dinarides and the Southern Alps. Concordant and discordant mineralization formed concomitant with Middle Triassic bimodal volcanism in an aborted rift. A multiple isotopic (C, O, S) investigation of host rocks and ore minerals was performed to put constraints on the source and composition of the fluid, and the hydrothermal alteration. The distributions of the delta(13)C and delta(18)O values of host and gangue carbonates are indicative of a fracture-controlled hydrothermal system, with locally high fluid-rock ratios. Quantitative modeling of the delta(13)C and delta(18)O covariation for host carbonates during temperature dependent fluid-rock interaction, and concomitant precipitation of void-filling dolomites points to a slightly acidic hydrothermal fluid (delta(13)Capproximate to-4parts per thousand and delta(18)Oapproximate to+10parts per thousand), which most likely evolved during isotopic exchange with carbonates under low fluid/rock ratios. The delta(34)S values of hydrothermal and sedimentary sulfur minerals were used to re-evaluate the previously proposed magmatic and evaporitic sulfur sources for the mineralization, and to assess the importance of other possible sulfur sources such as the contemporaneous seawater sulfate, sedimentary pyrite, and organic sulfur compounds. The delta(34)S values of the sulfides show a large variation at deposit down to hand-specimen scale. They range for cinnabar and pyrite from -19.1 to +22.8parts per thousand, and from -22.4 to +59.6parts per thousand, respectively, suggesting mixing of sulfur from different sources. The peak of delta(34)S values of cinnabar and pyrite close to 0parts per thousand is compatible with ore sulfur derived dominantly from a magmatic fluid and/or from hydrothermal leaching of basement rocks. The similar stratigraphic trends of the delta(34)S values of both cinnabar and pyrite suggest a minor contribution of sedimentary sulfur (pyrite and organic sulfur) to the ore formation. Some of the positive delta(34)S values are probably derived from thermochemical reduction of evaporitic and contemporaneous seawater sulfates.

Apparent stable-isotope heterogeneities in gangue carbonates of the Mississippi Valley-type Zn-Pb deposits of San-Vicente, Central Peru

The aim of the present communication is to emphasize that some variations of the measured delta(13)C and delta(18)O values are apparent, and due to analytical interferences caused by the presence of sulfur and organosulfur compounds in the analyzed carbonates. This is particularly relevant for isotopic studies on carbonate-hosted mineral deposits, where the nearly ubiquitous association of the host carbonates with organic matter and sulfides can certainly affect the metallogenetic interpretations. In this work two methods were used to overcome the disturbing effects of sulfides and organic matter: (1) sample pretreatment following the method proposed by Charef and Sheppard (1984), combining the oxidation of organic matter with sodium hypochlorite and trapping of the sulfur species with silver phosphate; and (2) laser-based microprobe extraction. Apparent isotopic variations in sparry dolomite from a single hand sample of zebra ore from the MVT Zn-Pb deposit, San Vicente, central Peru, are as large as 6 parts per thousand delta(13)C and 4 parts per thousand delta(18)O. These variations are reduced to several tenths of a per mil when the samples are pretreated. A careful examination of the effects of treatment with NaOCl and/or Ag3PO4 in relation to the concentration of sulfide inclusions indicates that the main disturbing effects for delta(13)C values are the presence of sulfur species and organic matter, whereas the delta(18)O values are mainly affected by the presence of sulfides. Fine- and medium-grained replacement carbonates from MVT and other sediment-hosted base metal deposits are potentially the most affected during isotope analysis, due to the common presence of organic matter and sulfides. Using in situ laser microprobe techniques, it is possible to determine isotopic variations at a sub-millimeter scale. Our results show that laser extraction analysis allows a more precise sampling of the carbonate minerals, and minimizes contamination of the sample with sulfides and to some extent with intergrown organic matter. However, there is an isotopic shift associated with the laser extraction technique, of the order of 0.5-1 parts per thousand for delta(13)C and delta(18)O values.

Multi-scale effects of nestling diet on breeding performance in a terrestrial top predator inferred from stable isotope analysis

Inter-individual diet variation within populations is likely to have important ecological and evolutionary implications. The diet-fitness relationships at the individual level and the emerging population processes are, however, poorly understood for most avian predators inhabiting complex terrestrial ecosystems. In this study, we use an isotopic approach to assess the trophic ecology of nestlings in a long-lived raptor, the Bonelli"s eagle Aquila fasciata, and investigate whether nestling dietary breath and main prey consumption can affect the species" reproductive performance at two spatial scales: territories within populations and populations over a large geographic area. At the territory level, those breeding pairs whose nestlings consumed similar diets to the overall population (i.e. moderate consumption of preferred prey, but complemented by alternative prey categories) or those disproportionally consuming preferred prey were more likely to fledge two chicks. An increase in the diet diversity, however, related negatively with productivity. The age and replacements of breeding pair members had also an influence on productivity, with more fledglings associated to adult pairs with few replacements, as expected in long-lived species. At the population level, mean productivity was higher in those population-years with lower dietary breadth and higher diet similarity among territories, which was related to an overall higher consumption of preferred prey. Thus, we revealed a correspondence in diet-fitness relationships at two spatial scales: territories and populations. We suggest that stable isotope analyses may be a powerful tool to monitor the diet of terrestrial avian predators on large spatio-temporal scales, which could serve to detect potential changes in the availability of those prey on which predators depend for breeding. We encourage ecologists and evolutionary and conservation biologists concerned with the multi-scale fitness consequences of inter-individual variation in resource use to employ similar stable isotope-based approaches, which can be successfully applied to complex ecosystems such as the Mediterranean.

Trophic structure in a seabird host-parasite food web: insights from stable isotope analyses

Ecological studies on food webs rarely include parasites, partly due to the complexity and dimensionality of host-parasite interaction networks. Multiple co-occurring parasites can show different feeding strategies and thus lead to complex and cryptic trophic relationships, which are often difficult to disentangle by traditional methods. We analyzed stable isotope ratios of C (13C/12C, δ13C) and N (15N/14N, δ15N) of host and ectoparasite tissues to investigate trophic structure in 4 co-occurring ectoparasites: three lice and one flea species, on two closely related and spatially segregated seabird hosts (Calonectris shearwaters). δ13C isotopic signatures confirmed feathers as the main food resource for the three lice species and blood for the flea species. All ectoparasite species showed a significant enrichment in δ15N relatively to the host tissue consumed (discrimination factors ranged from 2 to 5 depending on the species). Isotopic differences were consistent across multiple host-ectoparasite locations, despite of some geographic variability in baseline isotopic levels. Our findings illustrate the influence of both ectoparasite and host trophic ecology in the isotopic structuring of the Calonectris ectoparasite community. This study highlights the potential of stable isotope analyses in disentangling the nature and complexity of trophic relationships in symbiotic systems.

Combining stable isotope analyses and geolocation to reveal kittiwake migration

Determining migratory strategies of seabirds is still a major challenge due to their relative inaccessibility. Small geolocators are improving this knowledge, but not all birds can be tracked. Stable isotope ratios in feathers can help us to understand migration, but we still have insufficient baseline knowledge for linking feather signatures to movements amongst distinct water masses. To understand the migration strategies of kittiwakes Rissa tridactyla and the link between stable isotopes in feathers and the areas in which these were grown, we tracked 6 kittiwakes from Hornøya, Norway, with light level geolocators over 1 yr. Then we analysed the stable isotopes of carbon and nitrogen in their 1st and 7th primary feathers as well as in the 1st, 3rd, 5th, 7th and 10th primaries of 12 birds found freshly dead in the same breeding colony. After breeding, all tracked birds moved east of the Svalbard Archipelago and subsequently migrated to the Labrador Sea. Thereafter, birds showed individual variation in migration strategies: 3 travelled to the NE Atlantic, whereas the others remained in the Labrador Sea until the end of the wintering period. Changes in stable isotope signatures from the 1st to the 10th primary feathers corresponded well to the sequence of movements during migration and the area in which we inferred that each feather was grown. Thus, by combining information on moult patterns and tracking data, we demonstrate that stable isotope analysis of feathers can be used to trace migratory movements of seabirds.

Trophic versus geographic structure in stable isotope signatures of pelagic seabirds breeding in the northeast Atlantic

Feeding ecology and geographic location are 2 major factors influencing animal stable isotope signatures, but their relative contributions are poorly understood, which limits the usefulness of stable isotope analysis in the study of animal ecology. To improve our knowledge of the main sources of isotopic variability at sea, we determined δ15N and δ13C signatures in the first primary feather of adult birds from 11 Procellariiform species (n = 609) across 16 northeast Atlantic localities, from Cape Verde (20°N) to Iceland (60°N). Post-breeding areas (where the studied feather is thought to be grown) were determined using light-level geolocation for 6 of the 11 species. Isotopic variability was geographically unstructured within the mid-northeast Atlantic (Macaronesian archipelagos), but trophically structured according to species and regardless of the breeding location, presumably as a result of trophic segregation among species. Indeed, the interspecific isotopic overlap resulting from combining δ15N and δ13C signatures of seabirds was low, which suggests that most species exploited exclusive trophic resources consistently across their geographic range. Species breeding in north temperate regions (Iceland, Scotland and Northern Ireland) showed enriched δ15N compared to the same or similar species breeding in tropical and subtropical regions, suggesting some differences in baseline levels between these regions. The present study illustrates a noticeable trophic segregation of northeast Atlantic Procellariiformes. Our results show that the isotopic approach has limited applicability for the study of animal movements in the northeast Atlantic at a regional scale, but is potentially useful for the study of long-distance migrations between large marine systems

The impact of bioavailability limitations on microbial stable isotope fractionation in a multiphase system

Stable isotope fractionation analysis of contaminants is a promising method for assessing biodegradation of contaminants in natural systems. However, standard procedures to determine stable isotope fractionation factors, so far, neglect the influence of pollutant bioavailability on stable isotope fractionation. On a microscale, bioavailability may vary due to the spatio-temporal variability of local contaminant concentrations, limited effective diffusivities of the contaminants and cell densities, and thus, the pollutant supply might not meet the intrinsic degradation capacity of the microorganisms. The aim of this study was to demonstrate the effect of bioavailability on the apparent stable isotope fractionation, using a multiphase laboratory setup. The data gained show that the apparent isotope fractionation factors observed during biodegradation processes depend on the amount of biomass and/or the rate of toluene mass transfer from a second to the aqueous phase. They indicate that physico-chemical processes need to be taken into account when stable isotope fractionation analysis is used for the quantification of environmental contaminant degradation.

Comparative performance of the stable isotope signatures of carbon, nitrogen and oxygen in assessing early vigour and grain yield in durum wheat

The present paper studied the performance of the stable isotope signatures of carbon (δ13C), nitrogen (δ15N) and oxygen (δ18O) in plants when used to assess early vigour and grain yield (GY) in durum wheat growing under mild and moderate Mediterranean stress conditions. A collection of 114 recombinant inbred lines was grown under rainfed (RF) and supplementary irrigation (IR) conditions. Broad sense heritabilities (H2) for GY and harvest index (HI) were higher under RF conditions than under IR. Broad sense heritabilities for δ13C were always above 0·60, regardless of the plant part studied, with similar values for IR and RF trials. Some of the largest genetic correlations with GY were those shown by the δ13C content of the flag leaf blade and mature grains. Under both water treatments, mature grains showed the highest negative correlations between δ13C and GY across genotypes. Flag leaf δ13C was negatively correlated with GY only under RF conditions. The δ13C in seedlings was negatively correlated, under IR conditions only, with GY but also with early vigour. The sources of variation in early vigour were studied by stepwise analysis using the stable isotope signatures measured in seedlings. The δ13C was able to explain almost 0·20 of this variation under RF, but up to 0·30 under IR. In addition, nitrogen concentration in seedlings accounted for another 0·05 of variation, increasing the amount explained to 0·35. The sources of variation in GY were also studied through stable isotope signatures and biomass of different plant parts: δ13C was always the first parameter to appear in the models for both water conditions, explaining c. 0·20 of the variation. The second parameter (δ15N or N concentration of grain, or biomass at maturity) depended on the water conditions and the plant tissue being analysed. Oxygen isotope composition (δ18O) was only able to explain a small amount of the variation in GY. In this regard, despite the known and previously described value of δ13C as a tool in breeding, δ15N is confirmed as an additional tool in the present study. Oxygen isotope composition does not seem to offer any potential, at least under the conditions of the present study.

A compositional approach to stable isotope data analysis

Isotopic data are currently becoming an important source of information regarding sources, evolution and mixing processes of water in hydrogeologic systems. However, it is not clear how to treat with statistics the geochemical data and the isotopic data together. We propose to introduce the isotopic information as new parts, and apply compositional data analysis with the resulting increased composition. Results are equivalent to downscale the classical isotopic delta variables, because they are already relative (as needed in the compositional framework) and isotopic variations are almost always very small. This methodology is illustrated and tested with the study of the Llobregat River Basin (Barcelona, NE Spain), where it is shown that, though very small, isotopic variations comp lement geochemical principal components, and help in the better identification of pollution sources

Linking Canadian Harvested Juvenile American Black Ducks to Their Natal Areas Using Stable Isotope (δD, δ13C, and δ15N) Methods

Understanding source-sink dynamics of game birds is essential to harvest and habitat management but acquiring this information is often logistically and financially challenging using traditional methods of population surveys and banding studies. This is especially true for species such as the American Black Duck (Anas rubripes), which have low breeding densities and extensive breeding ranges that necessitate extensive surveys and banding programs across eastern North America. Despite this effort, the contribution of birds fledged from various landscapes and habitat types within specific breeding ranges to regional harvest is largely unknown but remains an important consideration in adaptive harvest management and targeted habitat conservation strategies. We investigated if stable isotope (δD, δ13C, δ15N) could augment our present understanding of connectivity between breeding and harvest areas and so provide information relevant to the two main management strategies for black ducks, harvest and habitat management. We obtained specimens from 200 hatch-year Black Duck wings submitted to the Canadian Wildlife Service Species Composition Survey. Samples were obtained from birds harvested in Western, Central, and Eastern breeding/harvest subregions to provide a sample representative of the range and harvest rate of birds harvested in Canada. We sampled only hatch-year birds to provide an unambiguous and direct link between production and harvest areas. Marine origins were assigned to 12%, 7%, and 5% of birds harvested in the Eastern, Central, and Western subregions, respectively. In contrast, 32%, 9%, and 5% of birds were assigned, respectively, to agricultural origins. All remaining birds were assigned to nonagricultural origins. We portrayed probability of origin using a combination of Bayesian statistical and GIS methods. Placement of most eastern birds was western Nova Scotia, eastern New Brunswick, Prince Edward Island, and southern Newfoundland. Agricultural birds from the Central region were consistent with the Saguenay region of Québec and the eastern claybelt with nonagricultural birds originating in the boreal. Western nonagricultural birds were associated with broad boreal origins from southern James Bay to Lake of the Woods and east to Cochrane, Ontario. Our work shows that the geographic origins, landscape, and habitat associations of hatch-year Black Ducks can be inferred using this technique and we recommend that a broad-scale isotopic study using a large sample of Canadian and US harvested birds be implemented to provide a continental perspective of source-sink population dynamics.