No / Stable isotope analysis has provided crucial new insights into dietary change at the Neolithic transition in north-west Europe, indicating an unexpectedly sudden and radical shift from marine to terrestrial resources in coastal and island locations. Investigations of early Neolithic skeletal material from Sumburgh on Shetland, at the far-flung margins of the Neolithic world, suggest that this general pattern may mask significant subtle detail. Analysis of juvenile dentine reveals the consumption of marine foods on an occasional basis. This suggests that marine foods may have been consumed as a crucial supplementary resource in times of famine, when the newly introduced cereal crops failed to cope with the demanding climate of Shetland. This isotopic evidence is consistent with the presence of marine food debris in contemporary middens. The occasional and contingent nature of marine food consumption underlines how, even on Shetland, the shift from marine to terrestrial diet was a key element in the Neolithic transition.

Earth's near-surface environment sustains nearly all terrestrial life, yet this critical zone is threatened by the environmental migration of new and potentially harmful compounds produced to support a growing human population. Traditional transport equations often fail to capture the environmental behavior of these emerging contaminants due to issues such as flow heterogeneity. Thus, there is a need to better evaluate controls on pollutant partitioning in Earth's critical zone. Our first study investigated the transport and distribution of the neonicotinoid insecticide thiamethoxam (TMX) by growing TMX-coated corn seeds in coarse vs fine-textured soil columns maintained with versus without growing corn plants. Fine-textured soil transported TMX at concentrations that were two orders of magnitude higher than coarse-textured soil, due to preferential flow in the fine-textured soil columns and higher evapotranspiration (ET) concentrating more TMX in the coarse-textured soil. Living plants increased the concentration of TMX at depth, indicating that growing plants may drive preferential transport of neonicotinoids. For the second study we planted TMX-coated corn seeds and maintained field plots with and without viable crops (n = 3 plots per treatment), measuring TMX concentrations in three hydrological compartments (surface runoff, shallow lateral flow, and deep drainage) and soil. TMX was transported in the highest concentrations via surface runoff, while also showing continual migration within the subsurface throughout the growing season. Plants facilitated downward migration of TMX in soil yet restricted losses in drainage. For our final study, we used a simple isotope mixing method to evaluate how preferential flow alters the influence of compound chemical properties on solute transport. We applied deuterium-labeled rainfall to plots containing manure spiked with eight veterinary antibiotics with a range of mobility, and quantified transport to suction lysimeters (30 and 90 cm). We showed that low preferential flow (<20%) eliminates the influence of compound chemical properties and, contrary to conventional understanding, more preferential flow (~ >20%) amplifies these chemical controls, with more mobile compounds appearing in significantly higher concentrations than less mobiles ones. Altogether, we provide a refined understanding of solute partitioning in the critical zone necessary to improve process-based transport modeling. / Doctor of Philosophy / Earth’s near-surface environment sustains nearly all terrestrial life, yet this critical zone is threatened by the environmental migration of new and potentially harmful pollutants produced to support a growing human population. Additionally, traditional mathematical methods fail to accurately describe the behavior of these emerging pollutants in soils due to complex flow patterns. Thus, scientists need to better understand how these pollutants contaminate water bodies in the critical zone. We first conducted a greenhouse experiment to understand and measure the amount of the neonicotinoid insecticide thiamethoxam (TMX) that could move from coated corn seeds through the soil environment. Water draining from fine-textured soil had >100 times more TMX than water draining from course-textured soil, due to commonly occurring fractures/cracks in the finer-particle soil and more evaporation from soil and plant leaves sequestering TMX in the sandy soil. Growing plants amplified TMX movement through soil voids to lower depths. We then conducted a field study to determine how much TMX could move to the surrounding environment throughout the corn growing season. We found that plants aided in downward movement of TMX yet restricted total losses from the plot overall by removing soil water. Our third study investigated the degree to which chemical pollutant properties control movement of solutes when water flows preferentially through soil void space. Common dairy manure was spiked with eight pollutants ranging in chemical attraction to soil and was added to an agricultural field. After irrigation, we found that when total drainage water was less than 20% derived from preferential flow, chemical properties had a negligible effect on the amount of pollutant in draining soil water. Contrary to conventional understanding, when draining water contained more than 20% preferential flow, chemical properties had a strong influence on the amount of pollutant detected. Altogether, we provide new understanding of how solutes move though the critical zone. These findings are necessary to create mathematical tools that more accurately depict pollutant behavior below-ground.

No / Dietary ecology is one key to understanding the biology, lifeways, and evolutionary pathways of many animals. Determining the diets of long-extinct hominins, however, is a considerable challenge. Although archaeological evidence forms a pillar of our understand-ing of diet and subsistence in the more recent past, for early hominins, the most direct evidence is to be found inthe fossils themselves. Here we review the suite of emerging biochemical paleodietary tools based on stable isotopeand trace element archives within fossil calcified tissues.We critically assess their contribution to advancing our understanding of australopith, early Homo, and Neander-thal diets within the broader context of non-biogeochemical techniques for dietary reconstruction, such as mor-phology and dental microwear analysis. The most signifi-cant outcomes to date are the demonstration of hightrophic-level diets among Neanderthals and Late Pleistocene modern humans in Glacial Europe, and the persis-tent inclusion of C4 grass-related foods in the diets of Plio¿Pleistocene hominins in South Africa. Such studies clearly show the promise of biogeochemical techniques for testing hypotheses about the diets of early hominins.Nevertheless, we argue that more contextual data from modern ecosystem and experimental studies are needed if we are to fully realize their potential.

No / A number of charred surface residues, adhering to ceramic containers, were obtained from various coastal and inland sites in north-west Europe dating from the sixth to the fourth millennium cal bc. In order to investigate the use of these vessels and in particular to identify any marine products, the residues were subjected to carbon and nitrogen stable isotope analysis. Variation in carbon isotope ratios between different samples indicated that some vessels may have been used to process marine products. This analysis was corroborated by specific identification of aquatic products following structural and isotopic characterization of lipids extracted from selected samples.

Yes / A key goal for archaeozoology is to define and characterise pastoral farming strategies. In the last decade, some of the most innovative approaches for addressing these questions have centered on the mammalian dentition, including inter alia sequential sampling of stable isotopes, dental microwear analysis and the study of dental pathologies. It is when these techniques are integrated and combined with more traditional approaches, such as tooth eruption and wear, however, that their full potential is realised. In this article we demonstrate how such an integrated dental analysis combining isotopes, microwear, dental development, dental pathologies, tooth eruption and wear can be used to elucidate changing pastoral practices and their impacts on the landscape from the Iron Age and Viking-Late Norse periods in the North Atlantic islands, a period of significant socio-economic and cultural change in this region. Analysis focuses on two case study sites, Mine Howe, dating to the Atlantic Middle Iron Age (MIA) and the Earls’ Bu, one of the residences of the Orkney Earl’s from the 10th to 13/14th centuries AD. Each of the techniques applied to the sheep/goat and cattle dentition identifies clear differences between the two sites, in diet, in culling season, herd health and stress levels, all of which point to potential differences in underlying husbandry practices. These are related to wider socio-economic developments in Orkney at these periods, specifically increasing control of pastoral resources and economic production by North Atlantic elites in the MIA and the emergence of manorial estates in Late Norse/Early Medieval Scandinavia. / AHRC PhD studentships; British Academy Mid-Career Fellowship (2014-5)

Yes / This paper presents the results of interdisciplinary investigations of human remains, discovered in 2011 at the Early Iron Age cemetery at Zagorje ob Savi (Cesta Borisa l(jdrica) in Slovenia. The present study is a part of a larger isotopic and osteological investigation of Bronze/Iron Age (14th-4th centuries BC) skeletal assemblages from Croatia and Slovenia. The osteological analysis of the six individuals uncovered on this site indicates that they represent the remains of two adult males, two adult females and two infants of unknown sex. The results of carbon and nitrogen stable isotope analysis on the bone and dentine collagen extracted from these six individuals is strongly indicative of a terrestrial based diet, including animal-based protein (meat and/or dairy) and a mix of C3 and C4 plants.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2016-07-27T16:16:01Z No. of bitstreams: 1 MAIA 2016.pdf: 4239749 bytes, checksum: 3670e8f040c7e0ba5e1a4bba302867d4 (MD5) / Made available in DSpace on 2016-07-27T16:16:01Z (GMT). No. of bitstreams: 1 MAIA 2016.pdf: 4239749 bytes, checksum: 3670e8f040c7e0ba5e1a4bba302867d4 (MD5) / Conselho Nacional de DesenvolvimentO Científico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências - Geoquímica. Niterói, RJ / O sistema de circulação oceânica desempenha um importante papel na regulação e manutenção do clima no planeta. Uma vez que o Atlântico Equatorial representa o ponto de conexão entre o Atlântico Sul e Norte, estudos paleoceanográficos nesta área podem contribuir para o entendimento dos processos e fatores envolvidos nas variações climáticas ao longo do tempo geológico, principalmente durante o Quaternário. Dentro desse contexto, o presente estudo visou descrever elementos representativos da paleoprodutividade do Atlântico Equatorial Oeste no Pleistoceno tardio, por meio da análise de dados sedimentológicos e geoquímicos do testemunho sedimentar MD09-3243CQ coletado no talude da margem continental do nordeste do Brasil. A partir desse testemunho, foi recuperado o período entre 33.700 e 10.150 anos cal A.P., o qual foi dividido em seis fases principais, de acordo com a análise de agrupamento das frações granulométricas representativas do testemunho. As fases apresentaram características distintas em função de mudanças das condições paleoambientais, paleoceanográficas e da paleoprodutividade. O cenário do último glacial (Fase V), caracterizado pela alta produtividade carbonática e baixa produtividade orgânica (COT = 0,40 ± 0,12%; NT = 0,05 ± 0,01%; derivados de clorofila = 0,06 ± 0,04 SPDU; teor de carbonato = 51,04 ± 6,39%), foi gradualmente substituído por ambiente com certa influência terrígena em virtude do clima mais seco e maior erosão, como sugerido pela razão C/N e δ13C, que proporcionou o aumento da produtividade fitoplanctônica, e, assim, das concentrações de COT (0,90 ± 0,25%), NT (0,09 ±0,02%) e derivados de clorofila (0,12 ± 0,07 SPDU) durante o Último Máximo Glacial (Fase IV). No H1, por outro lado, foi observada uma redução abrupta das concentrações destas variáveis e da razão C/N, concomitante com o aumento do teor de carbonato, δ13C e δ15N, indicando uma produtividade estritamente marinha, com maior remineralização da matéria orgânica. Essas alterações na paleoprodutividade estão relacionadas ao enfraquecimento da AMOC e aumento da temperatura no Atlântico Equatorial durante o H1, que resultaram em um ambiente mais oligotrófico e com maior precipitação de carbonatos. O YD (Fase II) apresentou uma tendência oposta ao H1 e semelhante ao LGM. O tardiglacial (final da Fase II e Fase I), por sua vez, apresentou uma redução do COT, NT e derivados de clorofila de 1,21 ± 0,24%, 0,11 ± 0,02% e 0,27 ± 0,08 SPDU para 0,83 ± 0,06%, 0,08 ± 0,01% e 0,15 ± 0,05 SPDU, respectivamente, acompanhado de uma ligeira diminuição do C/N (de 10,98 ± 1,05 para 10,47 ± 0,59) e valores menos negativos de δ13C (-21,92 ± 1,26‰ para -20,31 ± 0,25‰). De uma forma geral, a relação entre a razão C/N e δ13C sugeriu a presença de matéria orgânica predominantemente marinha ao longo do testemunho, com alguns períodos com tendências terrígenas. A taxa de sedimentação foi relativamente baixa 0,013 ± 0,051 cm.ano-1, apresentando maiores valores nos primeiros 100 cm. Os resultados mostram que a paleoprodutividade nessa região foi influenciada pelas alternâncias de inputs terrestres e produção de carbonatos ao longo do Pleistoceno tardio / The ocean circulation system plays an important role in climate on Earth. Once the Equatorial Atlantic is the connection point between the South and North Atlantic, paleoceanographic studies in this area can contribute to the understanding of the processes and factors involved in climate variations over geological time, especially during the Quaternary. Within this context, The present study aimed to describe representative elements of the western equatorial Atlantic paleoproductivity during the Last Glacial through the sedimentological and geochemical analysis of sedimentary MD09-3243CQ core collected in the slope of the continental margin of northeastern Brazil. It was recovered the period between 33,700 and 10,150 years B.P., which was divided into six main phases, according to the cluster analysis of representative size fractions. Stages had different characteristics due to changes of paleoenvironmental conditions, paleoceanographic and paleoproductivity. The Last Glacial scenario (Phase V), characterized by high productivity and low carbonate marine primary productivity (TOC = 0.40 ± 0.12%; TN = 0.05 ± 0.01%, derived from chlorophyll = 0.06 0.04 ± SPDU; carbonate = 51.04 ± 6.39%) was gradually replaced by environmental influenced by terrigenous material because the drier climate and greater erosion, as suggested by the C/N ratio and δ13C that provided increased phytoplankton productivity, and thus the concentrations of TOC (0.90 ± 0.25%), TN (0.09 ± 0.02%) and derivatives of chlorophyll (0.12 ± 0.07 SPDU) during the Last Glacial Maximum (Phase IV). During H1, on the other hand, an abrupt reduction of the concentrations of these variables and the C/N ratio, concomitant with the increase in carbonate content, δ13C and δ15N was observed, indicating a strictly marine productivity with increased remineralization of organic matter. These changes in paleoproductivity are related to the weakening of AMOC and increase of temperature in the Equatorial Atlantic during H1, which resulted in a more oligotrophic environment and greater precipitation carbonates. The YD (Phase II) had an opposite trend to H1 and was similar to LGM. The Late Glacial (end of Phase II and Phase I), in turn, showed a reduction in TOC, TN and derivatives of chlorophyll 1.21 ± 0.24%, 0.11 ± 0.02%, and 0.27 ± 0.08 SPDU, to 0.83 ± 0.06%, 0.08 ± 0.01% and 0.15 ± 0.05 SPDU, respectively, accompanied by a slight decrease in the C/N (10.98 ± 1.05 to 10.47 ± 0.59) and less negative values of δ13C (-21.92 ± 1.26 ‰ to -20.31 ± 0.25 ‰). In general, the relation between the C/N ratio and δ13C suggested organic matter predominantly marine with some periods with terrigenous trends. The sedimentation rate was relatively low, 0.013 ± 0.051 cm.year-1, with higher values in the first 100 cm. The results show that paleoproductivity in the studied region was influenced by the alternation of terrigenous input and carbonate production during the Late Pleistocene

This study aims to integrate groundwater geochemistry and mathematical modeling to determine the dominant geochemical processes and groundwater residence time within the Wilcox aquifer in the northern Gulf Coastal Plain. Groundwater samples were collected and analyzed for major ion chemistry, stable isotopes (18O, 2H, and 13C), and radioisotope 36Cl content. Geochemical modeling enabled the identification of major sources and sinks of solutes in the aquifer. A two-dimensional, finite-difference, numerical model was used to determine the deep groundwater flow rate and transport of 36Cl in the aquifer. Major ion chemistry shows a chromatographic pattern along the flow path in which a gradual increase of Na+ and decrease of Ca2+ and Mg2+ is evident. The most plausible inverse models in the downgradient section of the aquifer indicate that oxidation of organic matter (OM), which may be associated with discontinuous lenses of lignite, and consequent release of CO2 sustain the reduction of Fe(III) (oxyhydr)oxides and sulfate and the dissolution of carbonate minerals (calcite and, in some instances, siderite). These processes, in turn, result in pyrite precipitation and exchange of Ca2+ for Na+ on clay-mineral surfaces. Models constrained with 13C are consistent with mole transfers between pairs of wells in close proximity, but not for the entire flow path. The observed range of δ13C of dissolved inorganic carbon (-7.3‰ to -12.4‰) is interpreted as a result of both oxidation of OM and dissolution of carbonates. Calculated values of 36Cl/Cl show an abrupt discontinuity between the upgradient and downgradient sections that was also observed in δ18O and δ2H data. The gradual enrichment of 18O and 2H along the flow path could be the result of diffusion. The distinct differences in δ18O and δ2H between the upgradient and downgradient Wilcox aquifer suggest that the latter preserves a paleoclimatic signal.

Food web structure is of underlying importance to ecological functions and processes. Whilst it is understood that a range of biotic and abiotic factors affect structure, relatively little is known of the role of biodiversity per se in structuring food webs. In this thesis I utilise novel multi-dimensional estimates of food web structure based on stable isotope ratios of nitrogen (δ15N) and carbon (δ13C) to quantify structural responses to changing community diversity. I additionally investigate methodological aspects of sample preparation and stable isotope quantifications of food chains. Using an arthropod prey-predator system, in chapter 2 I demonstrate that tissue selection and lipid extraction are important methodological procedures for deriving accurate δ15N and δ13C signatures. In chapter 3 I test the utility of δ15N to quantify food chain length, and δ13C to trace primary energy sources through to end consumers. Bayesian resampling of variance in sample means for plant and arthropod food chains produces robust isotopic estimates that match known food chain length well despite some error variance, and estimates of δ13C-range that trace trophic transfers. Chapter 4 represents a change in system from lab to field as I determine δ15N and δ13C signatures for plant and invertebrate species within three grassland communities representing a gradient of biodiversity. Quantifications of community bivariate isotopic space using isotopic metrics revealed that greater taxonomic richness increased both diversity of resource space exploited and overlap in resource space. These results therefore suggest that loss of diversity affected structure through altering relative patterns of niche partitioning in resource exploitation amongst community members. In chapter 5, I additionally find evidence that grassland management mediated changes in food web compartmental structure that were associated with differences in generalist invertebrate predator feeding habits. Taken together, these findings develop and demonstrate the utility of isotopic approaches to quantifying food web structure, and provide evidence of important mechanisms by which biodiversity affects food web structure. I conclude that the preservation of natural food web structure and trophic dynamics are further reasons for halting loss of biodiversity.

Testing ecological theory at macroecological scales may be useful for disentangling abiotic influences from anthropogenic disturbances, and thus provide insights into fundamental processes that structure ecological communities. In tropical coral reef systems, our understanding of community structure is limited to small-scale studies conducted in moderately degraded regions, while larger regional or ocean scale analyses have typically focused on identifying human drivers of reef degradation. In this thesis, my collaborators and I combined stable isotope specimens, underwater visual censuses, and remote sensing data from 43 Pacific islands and atolls in order to examine the relative roles of natural environmental variation and anthropogenic pressures in structuring coral reef fish and benthic communities. First, at unexploited sites on Kiritimati Atoll (Kiribati), isotope estimates indicated that trophic level increased with body size across species and individuals, while negative abundance ~ body size relationships (size spectra) revealed distinct energetic constraints between energy-competing carnivores and energy-sharing herbivores. After demonstrating size structuring of reef fish communities in the absence of humans, we then examined evidence for size-selective exploitation impacts on coral reefs across the Pacific Ocean. Size spectra 'steepened' as human population density increased and proximity to market center decreased, reflecting decreases in large-bodied fish abundance, biomass, turnover rate, and mean trophic level. Depletion of large fish abundances likely diminishes functions such as bioerosion by grazers and food chain connectivity by top predators, further degrading reef community resilience. Next, we considered the relative strengths of abiotic, biotic and anthropogenic influences in determining reef benthic state across spatial scales. We found that from fine (0.25 km2) to coarse (1,024 km2) grain scales the phase shift index (a multivariate metric of the relative cover of hard coral and macroalgal) was primarily predicted by local abiotic and bottom-up influences, such that coral-dominated reefs occurred in warm, productive regions at sites exposed to low wave energy, irrespective of grazing or human impacts. Our size- based analyses of reef fish communities revealed novel exploitation impacts at ocean-basin scales, and provide a foundation for delineating energetic pathways and feeding interactions in complex tropical food webs. Furthermore, we demonstrate that abiotic constraints underpin natural variation among fish and benthic communities of remote uninhabited reefs, emphasizing the importance of accounting for local environmental conditions when developing quantitative baselines for coral reef ecosystems. / Graduate / 0329