Water in silicate glasses

The speciation of water in a variety of hydrous silicate glasses, including simple and rhyolitic compositions, synthesized over a range of experimental conditions with up to 11 weight percent water has been determined using infrared spectroscopy. This technique has been calibrated with a series of standard glasses and provides a precise and accurate method for determining the concentrations of molecular water and hydroxyl groups in these glasses.

For all the compositions studied, most of the water is dissolved as hydroxyl groups at total water contents less than 3-4 weight percent; at higher total water contents, molecular water becomes the dominant species. For total water contents above 3-4 weight percent, the amount of water dissolved as hydroxyl groups is approximately constant at about 2 weight percent and additional water is incorporated as molecular water. Although there are small but measurable differences in the ratio of molecular water to hydroxyl groups at a given total water content among these silicate glasses, the speciation of water is similar over this range of composition. The trends in the concentrations of the H-bearing species in the hydrous glasses included in this study are similar to those observed in other silicate glasses using either infrared or NMR spectroscopy.

The effects of pressure and temperature on the speciation of water in albitic glasses have been investigated. The ratio of molecular water to hydroxyl groups at a given total water content is independent of the pressure and temperature of equilibration for albitic glasses synthesized in rapidly quenching piston cylinder apparatus at temperatures greater than 1000°C and pressures greater than 8 kbar. For hydrous glasses quenched from melts cooled at slower rates (i.e., in internally heated or in air-quench cold seal pressure vessels), there is an increase in the ratio of molecular water to hydroxyl group content that probably reflects reequilibration of the melt to lower temperatures during slow cooling.

Molecular water and hydroxyl group concentrations in glasses provide information on the dissolution mechanisms of water in silicate liquids. Several mixing models involving homogeneous equilibria of the form H_2O + O = 20H among melt species have been explored for albitic melts. These models can account for the measured species concentrations if the effects of non-ideal behavior or mixing of polymerized units are included, or by allowing for the presence of several different types of anhydrous species.

A thermodynamic model for hydrous albitic melts has been developed based on the assumption that the activity of water in the melt is equal to the mole fraction of molecular water determined by infrared spectroscopy. This model can account for the position of the watersaturated solidus of crystalline albite, the pressure and temperature dependence of the solubility of water in albitic melt, and the volumes of hydrous albitic melts. To the extent that it is successful, this approach provides a direct link between measured species concentrations in hydrous albitic glasses and the macroscopic thermodynamic properties of the albite-water system.

The approach taken in modelling the thermodynamics of hydrous albitic melts has been generalized to other silicate compositions. Spectroscopic measurements of species concentrations in rhyolitic and simple silicate glasses quenched from melts equilibrated with water vapor provide important constraints on the thermodynamic properties of these melt-water systems. In particular, the assumption that the activity of water is equal to the mole fraction of molecular water has been tested in detail and shown to be a valid approximation for a range of hydrous silicate melts and the partial molar volume of water in these systems has been constrained. Thus, the results of this study provide a useful thermodynamic description of hydrous melts that can be readily applied to other melt-water systems for which spectroscopic measurements of the H-bearing species are available.

Reconstructing Past Depositional and Diagenetic Processes through Quantitative Stratigraphic Analysis of the Martian Sedimentary Rock Record

High-resolution orbital and in situ observations acquired of the Martian surface during the past two decades provide the opportunity to study the rock record of Mars at an unprecedented level of detail. This dissertation consists of four studies whose common goal is to establish new standards for the quantitative analysis of visible and near-infrared data from the surface of Mars. Through the compilation of global image inventories, application of stratigraphic and sedimentologic statistical methods, and use of laboratory analogs, this dissertation provides insight into the history of past depositional and diagenetic processes on Mars. The first study presents a global inventory of stratified deposits observed in images from the High Resolution Image Science Experiment (HiRISE) camera on-board the Mars Reconnaissance Orbiter. This work uses the widespread coverage of high-resolution orbital images to make global-scale observations about the processes controlling sediment transport and deposition on Mars. The next chapter presents a study of bed thickness distributions in Martian sedimentary deposits, showing how statistical methods can be used to establish quantitative criteria for evaluating the depositional history of stratified deposits observed in orbital images. The third study tests the ability of spectral mixing models to obtain quantitative mineral abundances from near-infrared reflectance spectra of clay and sulfate mixtures in the laboratory for application to the analysis of orbital spectra of sedimentary deposits on Mars. The final study employs a statistical analysis of the size, shape, and distribution of nodules observed by the Mars Science Laboratory Curiosity rover team in the Sheepbed mudstone at Yellowknife Bay in Gale crater. This analysis is used to evaluate hypotheses for nodule formation and to gain insight into the diagenetic history of an ancient habitable environment on Mars.

Determinação da viscosidade de misturas assimétricas em alta pressão usando regras de mistura

O conhecimento de propriedades de transporte de misturas a diferentes pressões e temperaturas é importante em projetos, operação, controle e otimização de processos industriais. Nestes processos, frequentemente, o fluido é uma mistura binária ou multicomponente de hidrocarbonetos, como fluidos de petróleo. Propriedades experimentais de misturas, especialmente, a viscosidade absoluta como função de temperatura e pressão, podem fornecer importantes informações sobre o comportamento do fluido em diferentes composições e são usadas no desenvolvimento de modelos e correlações e na caracterização de misturas complexas. Diversas regras de mistura têm sido propostas na literatura para cálculo de viscosidade de misturas. Estas regras de mistura preveem o comportamento da mistura à pressão atmosférica usando propriedades dos componentes puros. Porém, em diversas aplicações é necessário estimar a viscosidade de misturas a altas pressões. Neste estudo, foram avaliadas regras de mistura comumente usadas como Refutas, Fator de Mistura, Índice de Mistura, Grunberg e Nissan, Kendall-Monroe e Eyring bem como Aditividade Molar, usando dados de viscosidade experimental de misturas em altas pressões. Inicialmente, foram realizadas medidas de viscosidade absoluta para a mistura altamente assimétrica de ciclohexano e n-hexadecano na faixa de temperatura entre (318,15 a 413,15) K e pressões até 62,053 MPa e, para este sistema, um modelo foi proposto para cálculo dos componentes puros para dada temperatura e pressão. Além disso, dados experimentais de viscosidade de trinta misturas cujos componentes diferem em forma, tamanho ou flexibilidade foram selecionados na literatura e modelados empregando-se regras de mistura. As viscosidades das misturas foram estimadas a partir de dados de viscosidade experimental dos componentes puros medidos nas mesmas temperaturas e pressões. A altas pressões, Refutas, Fator de Mistura e Índice de Mistura apresentaram os melhores resultados para todos os sistemas estudados. Mesmo para moléculas bastante assimétricas, Refutas, Fator de Mistura e Índice de Mistura podem ser usados.

Studies of noble gases in meteorites and in the earth

The isotopic and elemental abundances of noble gases in the solar system are investigated, using simple mixing models and mass-spectrometric measurements of the noble gases in meteorites and terrestrial rocks and minerals.

Primordial neon is modeled by two isotopically distinct components from the interstellar gas and dust. Neon from the gas dominates solar neon, which contains about ten times more ²⁰Ne than ²²Ne. Neon from the dust is represented in meteorites by neon-E, with ²⁰Ne/²²Ne less than 0.6. Isotopic variations in meteorites require neon from both dust and gas to be present. Mixing dust and gas without neon loss generates linear correlation lines on three-isotope and composition-concentration diagrams. A model for solar wind implantation predicts small deviations from linear mixing, due to preferential sputtering of the lighter neon isotopes.

Neon in meteorites consists of galactic cosmic ray spallation neon and at least two primordial components, neon-E and neon-S. Neon was measured in several meteorites to investigate these end- members. Cosmogenic neon produced from sodium is found to be strongly enriched in ²²Ne. Neon measurements on sodium-rich samples must be interpreted with care so not to confuse this source of ²²Ne with neon-E, which is also rich in ²²Ne.

Neon data for the carbonaceous chondrite Mokoia show that the end member composition of neon-Si in meteorites is ²⁰Ne/²²Ne = 13.7, the same as the present solar wind. The solar wind composition evidently has remained constant since before the compaction of Mokoia.

Ca, Al-rich inclusions from the Allende meteorite were examined for correlation between neon-E and oxygen or magnesium isotopic anomalies. ²²Ne and ³⁶Ar enrichments found in some inclusions are attributed to cosmic- ray-induced reactions on Na and Cl, not to a primordial component. Neon-E is not detectably enriched in Allende.

Measurements were made to determine the noble gas contents of various terrestrial rocks and minerals, and to investigate the cycling of noble gases between different terrestrial reservoirs. Beryl crystals contain a characteristic suite of magmatic gases including nucleogenic ²¹Ne and ²²Ne from (α,n) reactions, radiogenic ⁴⁰Ar, and fissiogenic ^131-136Xe from the decay of K and U in the continental crust. Significant concentrations of atmospheric noble gases are also present in beryl.

Both juvenile and atmospheric noble gases are found in rocks from the Skaergaard intrusion. The ratio ⁴⁰Ar/³⁶Ar (corrected for in situ decay of ⁴⁰K) correlates with δ¹⁸O in plagioclase. Atmospheric argon has been introduced into samples that have experienced oxygen-isotope exchange with circulating meteoric hydrothermal fluids. Unexchanged samples contain juvenile argon with ⁴⁰Ar/³⁶Ar greater than 6000 that was trapped from the Skaergaard magma.

Juvenile and atmospheric gases have been measured in the glassy rims of mid-ocean ridge (MOR) pillow basalts. Evidence is presented that three samples contain excess radiogenic ¹²⁹Xe and fission xenon, in addition to the excess radiogenic ⁴⁰Ar found in all samples. These juvenile gases are being outgassed from the upper-mantle source region of the MOR magma. No isotopic evidence has been found here for juvenile primordial noble gases accompanying the juvenile radiogenic gases in the MOR glasses. Large argon isotopic variations in a single specimen provide a clear indication of the late-stage addition of atmospheric argon, probably from seawater.

The Skaergaard data demonstrate that atmospheric noble gases dissolved in ground water can be transferred into crustal rocks. Subduction of oceanic crust altered by seawater can transport atmospheric noble gases into the upper mantle. A substantial portion of the noble gases in mantle derived rocks may represent subducted gases, not a primordial component as is often assumed.

Petrogênese das rochas máficas alcalinas do litoral entre São Sebastião (SP) e Parati (RJ)

Lamprófiros e diabásios alcalinos afloram no litoral dos estados de São Paulo e Rio de Janeiro e integram o Enxame de Diques da Serra do Mar (EDSM). Essas rochas ocorrem sob a forma de diques e intrudem o Orógeno Ribeira, de idade Neoproterozóica/Cambro-Ordoviciana, inserindo-se no contexto geodinâmico de abertura do Oceano Atlântico Sul durante o Cretáceo Superior. Essas intrusões são subverticais e orientam-se preferencialmente a NE-SW, seguindo a estruturação das rochas encaixantes. Os lamprófiros são classificados como monchiquitos e camptonitos e exibem, respectivamente, textura hipocristalina e holocristalina. Apresentam também textura panidiomórfica, fenocristais de clinopiroxênio e olivina, imersos em matriz formada essencialmente por esses mesmos minerais, além de biotita, kaersutita e minerais opacos. O camptonito apresenta ainda plagioclásio na matriz. Os diabásios alcalinos são hipocristalinos a holocristalinos, equigranulares a inequigranulares, com fenocristais de olivina e/ou clinopiroxênio e/ou plagioclásio, em uma matriz composta essencialmente por esses minerais. As rochas estudadas caracterizam séries alcalinas miaskíticas, com os lamprófiros sendo tanto sódicos, potássicos e ultrapotássicos e os diabásios alcalinos como predominantemente sódicos. Modelagens petrogenéticas envolvendo possíveis processos evolutivos mostram que é improvável que os lamprófiros sejam cogenéticos por processos evolutivos envolvendo tanto cristalização fracionada, com ou sem assimilação concomitante, quanto hibridização. O mesmo ocorre para os diabásios alcalinos. A discriminação de fontes mantélicas foi feita com base nos teores de elementos traços de amostras representativas de líquidos parentais e indica que esse magmatismo alcalino está relacionado a fontes lherzolíticas com fusão parcial na zona de estabilidade do espinélio, isto é, a poucas profundidades. Os dados litogeoquímicos e isotópicos do sistema Sr-Nd das rochas estudadas sugerem tanto o envolvimento de fontes férteis, associadas ao manto sublitosférico, quanto de fontes enriquecidas, relacionadas ao manto litosférico subcontinental. Modelagens de mistura binária revelam que a petrogênese dos lamprófiros e diabásios alcalinos envolveu uma grande participação de um componente fértil misturado com contribuições menores de um componente enriquecido. Idades TDM (760-557 Ma) obtidas sugerem remobilização do manto litosférico no Neoproterozóico, talvez relacionadas à subducção da Placa São Francisco preteritamente à colisão do Orógeno Ribeira. Altas razões CaO/Al2O3 para os líquidos lamprofíricos menos evoluídos, altos teores de Zr, correlações negativas Zr/Hf e Ti/Eu e associação com carbonatitos indicam condições metassomáticas de alto CO2/H2O. Em escala local, modelos geodinâmicos baseados na astenosfera não isotérmica parecem mais aplicáveis. No entanto, modelos geodinâmicos baseados na astenosfera isotérmica (com o envolvimento de plumas) parecem mais indicados num contexto regional, considerando-se outras províncias alcalinas contemporâneas e correlatas.

Spatial and temporal variability in the relative contribution of king mackerel (Scomberomorus cavalla) stocks to winter mixed fisheries off South Florida

King mackerel (Scomberomorus cavalla) are ecologically and economically important scombrids that inhabit U.S. waters of the Gulf of Mexico (GOM) and Atlantic Ocean (Atlantic). Separate migratory groups, or stocks, migrate from eastern GOM and southeastern U.S. Atlantic to south Florida waters where the stocks mix during winter. Currently, all winter landings from a management-defined south Florida mixing zone are attributed to the GOM stock. In this study, the stock composition of winter landings across three south Florida sampling zones was estimated by using stock-specific otolith morphological variables and Fourier harmonics. The mean accuracies of the jackknifed classifications from stepwise linear discriminant function analysis of otolith shape variables ranged from 66−76% for sex-specific models. Estimates of the contribution of the Atlantic stock to winter landings, derived from maximum likelihood stock mixing models, indicated the contribution was highest off southeastern Florida (as high as 82.8% for females in winter 2001−02) and lowest off southwestern Florida (as low as 14.5% for females in winter 2002−03). Overall, results provided evidence that the Atlantic stock contributes a certain, and perhaps a significant (i.e., ≥50%), percentage of landings taken in the management-defined winter mixing zone off south Florida, and the practice of assigning all winter mixing zone landings to the GOM stock should

Size-related shifts in reliance on benthic and pelagic food webs by lake anchovy

This paper reports large variations in stable carbon and nitrogen isotope ratios of lake anchovy (Coilia ectenes taihuensis) from Lake Chaohu, China. The lake anchovy exhibited a significant C-13- and N-15- enrichment in relation to increasing fish length, and the isotopic compositions of small lake anchovy (<= 130 mm) were significantly more enriched than those of large lake anchovy (> 130 mm). The significant differences in the isotopic compositions of small and large lake anchovy suggested that their assimilated diets differed over a period of time and reflected the size-related diet shift of this fish. Bellamya aeruginosa and Corbicula fluminea were used to establish the baseline carbon signal of benthic and pelagic food webs, and these data were used to parameterize a 2-source mixing model to estimate in consumers the contribution of carbon derived from benthic versus pelagic food webs. Mixing models showed that small lake anchovy derived only 37% of their carbon from benthic food web, indicating increased reliance on pelagic prey, whereas benthic prey contributed 71% of large lake anchovy diet, suggesting greater use of benthic sources. These data indicate that there was a change in lake anchovy feeding strategy related to their size, suggesting a role in dynamic coupling between pelagic and benthic food chains. The trophic position of small lake anchovy averaged 3.0, indicating a zooplankton-based diet, compared with 3.6 in large lake anchovy, indicative of an increase in piscivorous diet. Overlap in the isotopic compositions of small and large lake anchovy probably indicated that these fish occasionally shared common diets, as suggested by stomach content studies, and/or resulted from the differences in the rate of isotopic turnover depending on differences in growth rate and metabolic turnover between small and large anchovy during diet shift from pelagic to benthic food webs. This study presents the contributions of benthic and pelagic food webs supporting lake anchovy and indicates that the intraspecific isotopic dynamic should be considered when applying stable isotope analyses to infer trophic interactions in aquatic ecosystems.

Analysis of diets of upland buzzards using stable carbon and nitrogen isotopes

We measured the stable carbon and nitrogen isotope ratios for muscles of the upland buzzards (Buteo hemilasius) and their potential food sources, plateau pikas (Ochotona curzoniae), Qinghai voles (Lasiopodomys fuscus), plateau zokors (Myospalax fontanierii), and several passerine bird species at the alpine meadow in Maduo county, Guoluo prefecture of Qinghai province, People's Republic of China, to provide diet information of upland buzzards, highlighting different diet composition of upland buzzards exposed to different locations. The results demonstrated that stable carbon isotope ratios of upland buzzards, passerine birds, plateau pikas, plateau zokors, and Qinghai voles were -24.42 +/- 0.25parts per thousand, -22.89 +/- 1.48parts per thousand, -25.30 +/- 1.47parts per thousand, -25.78 +/- 0.22parts per thousand, and -25.41 +/- 0.01parts per thousand, respectively, and stable nitrogen isotope ratios were 7.89 +/- 0.38parts per thousand, 8.37 +/- 2.05parts per thousand, 5.83 +/- 1.10parts per thousand, 5.23 +/- 0.34parts per thousand, and 8.86 +/- 0.06parts per thousand, respectively. Fractionation of stable carbon and nitrogen isotope ratios between upland buzzards and their food were 1.03parts per thousand and 2.11parts per thousand, respectively. Based on mass balance principle of stable isotopes and the Euclidean distance mixing model, upland buzzards depended mainly on plateau pikas as food (74.56%). Plateau zokors, Qinghai voles, and passerine birds only contributed a small proportion (25.44%) to diets of upland buzzards. The results were closely accordant with analyses of stomach contents and food pellets, which firmly supported the feasibility of using stable carbon and nitrogen isotope ratios to investigate diet information of upland buzzards. Another study based on stable carbon isotopes showed that upland buzzards living in the Haibei prefecture (another prefecture located in the southeast Qinghai province) mainly preyed on passerine birds (64.96% or more) as food supply. We were alarmed by the preliminary results that widespread poisoning activities of small mammals could reshape the food composition of upland buzzards, influencing the stability and sustainability of the alpine meadow. Bio-control on rodent pests should be carried out rather than the chemical measures.

Do non-native invasive fish support elevated lamprey populations?

Summary
1: Managing populations of predators and their prey to achieve conservation or resource management goals is usually technically challenging and frequently socially controversial. This is true even in the simplest ecosystems but can be made much worse when predator–prey relationships are in?uenced by complex interactions, such as biological invasions, population trends or animal movements.
2: Lough Neagh in Northern Ireland is a European stronghold for pollan Coregonus autumnalis, a coregonine ?sh and for river lampreyLampetra ?uviatilis, which feeds parasitically as an adult. Both species are of high conservation importance. Lampreys are known to consume pollan but detailed knowledge of their interactions is scant. While pollan is well known to be a landlocked species in Ireland, the life cycle of normally anadromous river lamprey in Lough Neagh has been unclear. The Lough is also a highly perturbed ecosystem, supporting several invasive, non-native ?sh species that have the potential to in?uence lamprey–pollan interactions.
3: We applied stable isotope techniques to resolve both the movement patterns of lamprey and trophic interactions in this complex community. Recognizing that stable isotope studies are often hampered by high-levels of variability and uncertainty in the systems of interest, we employed novel Bayesian mixing models, which incorporate variability and uncertainty.
4: Stable isotope analyses identi?ed troutSalmo trutta and non-native breamAbramis brama as the main items in lamprey diet. Pollan only represented a major food source for lamprey between May and July.
5: Stable isotope ratios of carbon in tissues from 71 adult lamprey showed no evidence of marine carbon sources, strongly suggesting that Lough Neagh is host to a highly unusual, nonanadromous freshwater population. This ?nding marks out the Lough’s lamprey population as of particular scienti?c interest and enhances the conservation signi?cance of this feature of the Lough.
6: Synthesis and applications.Our Bayesian isotopic mixing models illustrate an unusual pattern of animal movement, enhancing conservation interest in an already threatened population. We have also revealed a complex relationship between lamprey and their food species that is suggestive of hyperpredation, whereby non-native species may sustain high lamprey populations that may in turn be detrimental to native pollan.Long-term conservation of lamprey and pollan in this system is likely to require management intervention, but in light of this exceptional complexity, no simple management options are currently supported. Conservation plans will require better characterization ofpopulation-level interactions and simulation modelling of interventions. More generally, our study demonstrates the importance of considering a full range of possible trophic interactions, particularly in complex ecosystems, and highlights Bayesian isotopic mixing models as powerful tools in resolving trophic relationships.
Key-words: Bayesian, conservation dilemma, Coregonus autumnalis, hyperpredation, Lampetra ?uviatilis, pollan, potamodromous, River lamprey, stable isotope analysis in R, stable isotope

Towards a better understanding of the nature and contribution of the interflow to catchment dynamics.

A detailed understanding of flow and contaminant transfer along each of the key hydrological pathways within a catchment is critical for designing and implementing cost effective Programmes of Measures under the Water
Framework Directive.
The Contaminant Movement along Pathways Project (’The Pathways Project’) is an Irish, EPA STRIVE funded, large multi-disciplinary project which is focussed on understanding and modelling flow and attenuation along each of these pathways for the purposes of developing a catchment management tool. The tool will be used by EPA and RBD catchment managers to assess and manage the impacts of diffuse contamination on stream aquatic ecology. Four main contaminants of interest — nitrogen, phosphorus, sediment and pathogens — are being
investigated in four instrumented test catchments. In addition to the usual hydrological and water chemistry/quality parameters typically captured in catchment studies, field measurements at the test catchments include ecological
sampling, sediment dynamics, soil moisture dynamics, and groundwater levels and chemistry/quality, both during and between significant rainfall events. Spatial and temporal sampling of waters directly from the pathways of
interest is also being carried out.
Sixty-five percent of Ireland is underlain by poorly productive aquifers. In these hydrogeological settings, the main pathways delivering flow to streams are overland flow, interflow and shallow bedrock flow. Little is
known about the interflow pathway and its relative importance in delivery of flow and contaminants to the streams. Interflow can occur in both the topsoil and subsoil, and may include unsaturated matrix flow, bypass or macropore
flow, saturated flow in locally perched water tables and artificial field drainage.
Results to date from the test catchment experiments show that artificial field drains play an important role in the delivery of interflow to these streams, during and between rainfall events when antecedent conditions are
favourable. Hydrochemical mixing models, using silica and SAC254 (the absorbance of UV light at a wavelength of 254 nm which is a proxy for dissolved organic matter) as tracers, show that drain flow is an important end
member contributing to the stream and that proportionally, its contribution is relatively high.
Results from the study also demonstrate that waters originating from one pathway often mix with the waters from another, and are subsequently delivered to the stream at rates, and with chemical/quality characteristics,
that are not typical of either pathway. For example, pre-event shallow groundwater not far from the catchment divide comes up to the surface as rejected recharge during rainfall events and is rapidly delivered to the stream
via overland flow and/or artificial land drainage, bringing with it higher nitrate than would often be expected from a quickflow pathway contribution. This is contrary to the assumption often made in catchment studies that the
deeper hydrological pathways have slower response times in stream hydrographs during a rainfall event, and it emphasizes that it is critical to have a strong three-dimensional conceptual model as the basis for the interpretation
of catchment data.

A Factor analysis of hidrochemical composition of Llobregat river basin

Hydrogeological research usually includes some statistical studies devised to elucidate mean background state, characterise relationships among different hydrochemical parameters, and show the influence of human activities. These goals are achieved either by means of a statistical approach or by mixing models between end-members. Compositional data analysis has proved to be effective with the first approach, but there is no commonly accepted solution to the end-member problem in a compositional framework. We present here a possible solution based on factor analysis of compositions illustrated with a case study. We find two factors on the compositional bi-plot fitting two non-centered orthogonal axes to the most representative variables. Each one of these axes defines a subcomposition, grouping those variables that lay nearest to it. With each subcomposition a log-contrast is computed and rewritten as an equilibrium equation. These two factors can be interpreted as the isometric log-ratio coordinates (ilr) of three hidden components, that can be plotted in a ternary diagram. These hidden components might be interpreted as end-members. We have analysed 14 molarities in 31 sampling stations all along the Llobregat River and its tributaries, with a monthly measure during two years. We have obtained a bi-plot with a 57% of explained total variance, from which we have extracted two factors: factor G, reflecting geological background enhanced by potash mining; and factor A, essentially controlled by urban and/or farming wastewater. Graphical representation of these two factors allows us to identify three extreme samples, corresponding to pristine waters, potash mining influence and urban sewage influence. To confirm this, we have available analysis of diffused and widespread point sources identified in the area: springs, potash mining lixiviates, sewage, and fertilisers. Each one of these sources shows a clear link with one of the extreme samples, except fertilisers due to the heterogeneity of their composition. This approach is a useful tool to distinguish end-members, and characterise them, an issue generally difficult to solve. It is worth note that the end-member composition cannot be fully estimated but only characterised through log-ratio relationships among components. Moreover, the influence of each endmember in a given sample must be evaluated in relative terms of the other samples. These limitations are intrinsic to the relative nature of compositional data

Stable Isotope Analysis Reveals That Agricultural Habitat Provides an Important Dietary Component for Nonbreeding Dunlin

Although shorebirds spending the winter in temperate areas frequently use estuarine and supratidal (upland) feeding habitats, the relative contribution of each habitat to individual diets has not been directly quantified. We quantified the proportional use that Calidris alpina pacifica (Dunlin) made of estuarine vs. terrestrial farmland resources on the Fraser River Delta, British Columbia, using stable isotope analysis (δ13C, δ15N) of blood from 268 Dunlin over four winters, 1997 through 2000. We tested for individual, age, sex, morphological, seasonal, and weather-related differences in dietary sources. Based on single- (δ13C) and dual-isotope mixing models, the agricultural habitat contributed approximately 38% of Dunlin diet averaged over four winters, with the balance from intertidal flats. However, there was a wide variation among individuals in the extent of agricultural feeding, ranging from about 1% to 95% of diet. Younger birds had a significantly higher terrestrial contribution to diet (43%) than did adults (35%). We estimated that 6% of adults and 13% of juveniles were obtaining at least 75% of their diet from terrestrial sources. The isotope data provided no evidence for sex or overall body size effects on the proportion of diet that is terrestrial in origin. The use of agricultural habitat by Dunlin peaked in early January. Adult Dunlin obtained a greater proportion of their diet terrestrially during periods of lower temperatures and high precipitation, whereas no such relationship existed for juveniles. Seasonal variation in the use of agricultural habitat suggests that it is used more during energetically stressful periods. The terrestrial farmland zone appears to be consistently important as a habitat for juveniles, but for adults it may provide an alternative feeding site used as a buffer against starvation during periods of extreme weather. Loss or reduction of agricultural habitat adjacent to estuaries may negatively impact shorebird fitness, with juveniles disproportionately affected.