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No / Human migration is a hallmark of the species and there is significant interest in methods that can determine the past migrations of humans and associated fauna. We present a new method that utilizes collagen oxygen, carbon and nitrogen isotopes from histologically informed samples of cortical bone. The utility of this multi-isotopic, life history approach is demonstrated in migrating Dutch whalers, and both the possibilities and limitations of the method are described.

The potential of Arctica islandica, a long lived marine bivalve with a lifespan of over 300 years, to reconstruct a high resolution (sub-annual) climate record is explored in this thesis. Fluctuations in trace element and isotopic data from live-collected specimens from Irvine Bay, NW Scotland are compared to instrumental (particularly temperature) data. X-ray absorption spectroscopy data demonstrate the coordination state of Sr and Mg within the shell. These are consistent with models in which Sr substitutes ideally for Ca in aragonite, and Mg is bound predominantly to organic molecules. Sr/Ca incorporation may be influenced by changes in the crystal nucleation, propagation and growth rate as well as vital effects. However any effect of seawater temperature on Sr/Ca incorporation was obscured by these other factors. Mg concentration is not a linear function of a single environmental variable or organic content within the shell, indicating that Mg uptake is biologically mediated. Ba variation shows sporadic increases (of >500% above baseline) in both shells, the timing of which is similar between the prismatic layer and umbo region. The maxima are, however, not synchronous between the two shells analysed. The controls on Ba uptake require further research, but low Ba/Ca may reflect Ba/Ca concentrations within the seawater. Aliquots taken from cod otoliths show that micromilling has negligible effect on δ¹⁸O. The range of reconstructed temperature from δ¹⁸O profiles Arctica islandica shows good agreement with the sea surface temperature data from the nearby Millport marine station to within 2.1 °C. However, both the interannual and intra-annual variation appears to be sensitive to changes in temporal resolution resulting from changes in growth rates. Modelling of δ¹⁸O highlights dependence on changes in temporal resolution of the sampling, in addition to temperature and salinity. Results from the radiocarbon pilot study show that Arctica islandica is a suitable archive for changes in radiocarbon associated with anthropogenic ¹⁴C fluxes.

The volcanic Island of Fogo that is situated near the end of the southern island chain in the archipelago of Cape Verde is one of the most active oceanic volcanoes in the world. The purpose of this study was to investigate temporal variations in lavas from Fogo by using whole rock major and trace elements and describe trends in magmatic differentiation, melting systematics and mantle source compositions. Further, for the first time Fogo lavas have been investigated by using 18O isotopes, to test for crustal assimilation and source variations. The time span for this study includes one sample of unknown prehistoric age and then from 1799 and onward all eruptions including the most recent in 2014-2015 are covered. The Fogo lavas are mafic, alkali rich, porphyritic, basanite-tephrites dominated by clinopyroxene phenocrysts followed by olivine and opaque phases situated within glass and microcrystalline groundmass.  Fractional crystallization and phenocryst accumulation is important mechanisms for magmatic differentiation, and the best result from fractional crystallization modelling gave a crystallizing assemblage of 20.7 % clinopyroxene, 5.4 % olivine, 4.2 % Fe-Ti oxides and 0.8 % apatite. Temporal variations in MgO content reveal a trend that change from more evolved lavas in older historic eruptions, to more primitive compositions in lavas from the middle of the 19th century, back to more evolved compositions in recent eruptions. Oxygen isotopes of glass and microcrystalline groundmass vary within a normal upper mantle range (δ18O = 5.7±0.3 ‰) which rule out any significant crustal assimilation, and the variations observed for the oxygen isotopes are probably related to source variations as there are tendencies towards covariation with source lithology proxies. Trace element ratios together with high TiO2 contents indicate that pyroxenite is an important source lithology. The Fogo lavas are highly enriched in incompatible elements and utilizing a simple batch melting model suggests ~2-4 % degree of melt for most sampled eruptions. In addition, melting is occurring at high pressures in the presence of residual garnet as the REE are fractionated. Trace element ratios of Ce/Pb and Zr/Y in Fogo lavas are consistent with mixing of a HIMU-like and an EM 1-like mantle source. There are also indications of an increasing involvement of the EM 1-like source through time. Magma mixing is indicated by petrographic observations such as complex zonation patterns and the occurrence of rounded cores in euhedral clinopyroxenes, as well as inferred from a large scatter in certain trace element ratios. / Vulkanön Fogo som ligger nära änden av den sydvästra ökedjan i Kap Verdes skärgård är en av de mest aktiva vulkanerna i världen. Syften med denna studie var att undersöka den kemiska variationen i lava från Fogo över tid och koppla variationen till olika magmatiska processer i vulkanen. Lava från Fogo har dessutom i denna studie för första gången undersökts med hjälp av syreisotoper för att testa för inblandning av material från jordskorpan samt för variationer i manteln i jordens inre där lavan bildas. Denna studie omfattar en tid som sträcker sig från ett förhistoriskt icke tidsbestämt vulkanutbrott, samt från 1799 till och med det senaste utbrottet 2014-2015. Lava från Fogo i denna studie är basisk och relativt magnesiumrik samt rik på alkaliska ämnen och har en porfyrisk textur som innebär att större mineralkorn sitter inbäddade i en finkornig grundmassa. Detta är typiskt för ytliga vulkaniska bergarter som svalnat snabbt. Mineralsammansättningen i lavan domineras av silikatmineralen pyroxen följt av olivin tillsammans med vad som troligen är järn-titan oxider. Dessa mineraler sitter i en grundmassa som består av mikroskopiska mineralkristaller och av glas. Lavan från Fogo har spårämnen som tillsammans med en hög koncentration av titandioxid påvisar att pyroxenit smält i manteln där lavan producerats, till skillnad från peridotit som är vanligare förekommande. Lavan har producerats genom smältning i manteln under relativt högt tryck vilket är typiskt för den här typen av vulkanöar och är dessutom berikad i vissa spårämnen som beror på att bara en liten andel av manteln smält när lavan bildats. En enkel smältningsmodell beräknade att ca 2-4 % smältning av manteln kunde ge de observerade koncentrationerna av spårämnen. Öarna i Kap Verdes skärgård har en geografiskt varierande geokemisk karaktär som beror på att den underliggande manteln består av skilda mantelkomponenter med olika kemisk sammansättning. I lava från den södra ökedjan dit Fogo tillhör ingår en mantelkomponent som saknas i den övriga delen av skärgården. Spårämnen i lava från denna studie överensstämmer med en blandning av dessa mantelkomponenter, dessutom verkar det förekomma en tidsmässig variation av inblandning från respektive komponent. Det finns även bevis för att olika typer av magma blandats från t.ex. mikroskopistudier av mineraltexturer. Resultatet från de analyserade syreisotoperna visar på en variation inom vad som är normalt för övre delen av manteln (5,7 ± 0,3 ‰), vilket utesluter inblandning av större mängder material från jordskorpan. Den variation av syreisotoper som förekommer i lavan beror därför förmodligen på att manteln inte är enhetlig.

Thesis (PhD)--Stellenbosch University, 2013. / Please refer to full text to view abstract.

The iron apatite mineralizations of northern Sweden are mainly situated in supracrustal rocks and are thought to have formed during approximately the same time as the major plutonic suites in northern Sweden. In this thesis the Malmberget iron apatite ore deposit have been compared to the Kiruna iron apatite ore deposit to see whether the role of hydrothermal processes are different between the two ore districts. Also, since it has proven problematic to distinguish between the different mafic and ultramafic members of the major plutonic suites in northern Sweden (i.e. the Haparanda suite (1.94-1.85 Ga), the Perthite-monzonite suite (PMS) (1.87 Ga) and the Edefors suite (1.80-1.79 Ga)), a second goal is to trace the distribution and distinguish between these suites. Major elements, REE and trace elements have been studied along with polished sections from the ores and oxygen isotopes of magnetites from the ore districts to trace the ore formation process and separate between suites. All ore districts display a close similarity in geochemistry between host rocks and magnetites, especially regarding the REE pattern. Oxygen isotopes show that samples from the Kiruna district plot exclusively at positive δ18O-values with the majority of them at values < 1‰. Samples from the Malmberget district display δ18O-values either close to the igenous range or at slightly negative values. However, samples that display very low or negative δ18O-values show signs of either high temperature hydrothermal alteration, oxidation or crustal contamination. The δ18O composition along with textural observations from the polished sections and geochemistry, points towards a magmatic origin for these deposits. No apparent evidence has been found to support a primary ore formation by hydrothermal process in any of the districts studied. Regarding the suites, normalized spider plot patterns of REEs and trace elements served as a basis for subdivision into groups by similarities in key identification parameters. Several patterns are characterized by a pronounced Eu-trough while the middle- to HREEs display a rather flat trend, criteria that are related to rocks from the Haparanda suite, while samples with positive Eu-anomaly (Eu/Eu* > 1) and a nearly flat trend from La to Pr with a marked positive peak at Sr and generally less enriched in LILE, are consistent with the Edefors suite. Also, the Edefors suite generally display low concentrations of both Th and U but are somewhat enriched in Sr with relation to Pr. No distinct geochemical features could help to separate between the Haparanda and the PMS suites.

The characterization of natural climate variability is important in order to understand the climate response to natural forcings and to identify anthropogenic influences. The aim of this thesis is to reconstruct climate changes in the southwest of France, a region which is characterised by recurrent drought periods, where high resolution proxy records of the last millennia were lacking.The reconstruction is based on multiple proxies from two continental archives: speleothems and tree rings. Their combination can make use of the strengths of each archive while compensating their weaknesses. There are two principal objectives: first, to gain a better understanding of the climatic and non-climatic influences on each proxy; and second, to reconstruct drought periods in the past.The oxygen isotopic composition (δ18O) of speleothem fluid inclusions and tree ring cellulose is controlled to a large extent by the δ18O of precipitation, which can serve as a tracer of the atmospheric circulation. In order to interpret these proxies in terms of climate, it is necessary to understand how the climate signal becomes recorded in the proxy, and which processes modify the original signal during the formation of the archive.Measurements of δ18O in precipitation, cave drip water, and fluid inclusions in modern speleothem samples from Villars Cave demonstrated that the isotopic composition of cave drip water corresponds to the pluri-annual average precipitation. The speleothem fluid inclusions, in turn, preserve the isotopic composition of the drip water. Based on this calibration, it is possible to reconstruct drip water isotope variability using fluid inclusions in a more than 2000 year old stalagmite, which has been dated by laminae counting, as well as U-Th and 14C measurements. Changes in the cave environment, e.g. the vegetation cover, are indicated by other proxies from the same stalagmite (stable isotopes in calcite and trace element concentrations), but these changes do not seem to impact the fluid inclusion δ18O significantly.The isotopic composition of tree ring cellulose from Quercus spp. in the study area is strongly influenced by climate conditions during the summer. However, non-climatic influences on the isotopic composition of cellulose are identified. They are linked to the age of the trees and to site hydrology, and must be accounted for in the sampling and analytical procedures. Crossdated cores from living trees and timber wood in historic buildings near Angoulême are used to build an annually resolved chronology of cellulose δ18O. Significant correlations with meteorological data enable a calibration and a reconstruction of drought periods since 1360 AD.Lastly, this thesis explores a novel approach of integrating oxygen isotope records from speleothem fluid inclusions and tree ring cellulose from closely located sites to reconstruct both high- and low-frequency variability of droughts in the past.

L’étude de la composition isotopique de l’oxygène de l’émail des dents de vertébrésconstitue une méthode fiable de reconstitution des paléotempératures, grâce àl’interdépendance entre le δ18O de l’apatite des dents, le δ18O des fluides corporels, del’eau ingérée et la température du milieu. L’amélioration et la miniaturisation des techniquesanalytiques a permis d’augmenter la résolution du signal reconstitué, depuis les variations detempérature sur de grandes échelles de temps jusqu’aux variations saisonnières durant laformation de la dent. Cependant, ces variations du δ18O de la dent ne sont pas uniquementdépendantes des variations de température du milieu, mais peuvent également êtreaffectées par d’autres paramètres climatiques, comme la répartition des précipitations aucours de l’année, ou biologique, comme le mode de minéralisation de la dent, l’alimentation,la physiologie de l’animal ou des migrations.Les paramètres biologiques peuvent être estimés dans le cas de taxons possédantdes parents proches dans la faune actuelle. Par exemple, la connaissance des processus deformation et de minéralisation des dents de bovinés actuels permet d’interpréter le signalisotopique de l’oxygène enregistré dans les dents de bovinés fossiles. Ainsi, l’analyse dedents de Bison priscus provenant de l’aven de Coudoulous (Lot, France) a permis dereconstituer les variations saisonnières de température au cours de l’avant-dernier épisodeglaciaire (MIS 6) au Pléistocène moyen, lorsque la région servait de terrain de chasse àHomo neanderthalensis. Le climat était à cette époque plus froid de 4°C en moyenne, maisavec des saisons nettement plus contrastées. Ainsi, si les températures estivales étaientidentiques aux valeurs actuelles, les températures hivernales étaient plus basses de 6-7°C.En milieu marin, les variations saisonnières de température affectent uniquement leseaux de surface. Les plaques dentaires de myliobatidés, un groupe de raies pélagiquesvivant principalement entre 0 et 100 mètres de profondeur, sont un outil potentiel pourreconstituer la paléosaisonnalité. L’étude de plaques dentaires de Myliobatis et deRhinoptera actuels montre que la composition isotopique des dents de ces animauxenregistre des variations de température et de δ18O des eaux de surface. Ainsi, il est doncpossible de reconstituer les caractéristiques des masses d’eau traversées par l’animal. Cetoutil a également un intérêt paléoécologique car il permet de mettre en évidence d’éventuelscomportements migratoires, comme chez certains myliobatidés actuels. L’étude despécimens d’Aetomylaeus provenant du Pliocène de Montpellier (Hérault, France) montredes températures 5°C plus élevées par rapport aux v aleurs actuelles. / The oxygen isotopic composition of the vertebrate tooth enamel is a reliable proxy toreconstruct paleotemperatures based on the dependence of the δ18O of the tooth apatite onthe δ18O of body fluids, on the δ18O of the drinking water, and on the environmentaltemperature. The improvement and the miniaturization of the analytical procedures allowedincreasing the resolution of the reconstructed signal, from paleotemperature variations overgeological times to seasonal variations during the tooth growth. However seasonal variationsof the enamel δ18O do not only depend on temperature variations but can also be influencedby other climatic parameters such as rainfall distribution over the year, or by biological andecological parameters such as tooth mineralization process, diet, physiology or migratorypatterns.Biological parameters can be estimated based on the study of extant relatives inmodern faunas. For example, data on tooth formation and mineralization processes inmodern bovids allow a better understanding of the oxygen isotopic signal recorded in fossilbovid teeth. Thus reconstruction of seasonal variations of temperature during the penultimateglacial episode (MIS 6) has been made possible from the analysis of Bison priscus teethfrom the aven of Coudoulous (Lot, France). Climate was 4°C colder during the middlePleistocene when Europe was still Homo neanderthalensis hunting ground, and seasonswere more contrasted than today. Summer temperatures were similar to modern values, butwinter temperatures were 6-7°C colder.In marine environments, seasonal variations of temperature only affect surfacewaters. Myliobatids are pelagic rays living mostly between 0 and 100 m depth, thus theoxygen isotopic composition of myliobatid dental plates is a potential proxy to reconstruct thepaleoseasonality. The isotopic analysis of modern Myliobatis and Rhinoptera samplesconfirmed that variations of the sea-surface temperature (SST) and the δ18O of seawater arerecorded in the δ18O of myliobatid teeth. Thus it is possible to reconstruct the variations ofseawater temperature during a part of the animal’s life, but it also allows pointing outmigratory patterns in some myliobatid species. Reconstructions of seasonal variations ofSST during the middle Pliocene in Montpellier (Hérault, France) from the δ18O of myliobatiddental plates yielded paleotemperatures 5°C higher than modern values.

La caractérisation de la variabilité naturelle du climat est importante pour comprendre la réponse de celui-ci aux forçages naturels et pour identifier les influences anthropiques. L'objectif de cette thèse est de reconstituer les changements climatiques dans le sud-ouest de la France, une région qui se caractérise par des périodes de sécheresse récurrentes, où les reconstitutions millénaires basées sur des « proxies » à haute résolution font défaut.La reconstruction est basée sur plusieurs proxies dans deux archives continentales : les spéléothèmes et les cernes d'arbre. Leur combinaison permet de tirer avantage de leurs points forts tout en compensant leurs faiblesses. Il y a deux objectifs principaux : d’une part de mieux comprendre les influences climatiques et non climatiques qui s’exercent sur chaque proxy ; et, d'autre part, de reconstituer les périodes de sécheresse dans le passé.La composition isotopique en oxygène (δ18O) des inclusions fluides des spéléothèmes et de la cellulose des cernes d’arbre est contrôlée dans une large mesure par le δ18O des précipitations, qui peut servir de traceur de la circulation atmosphérique. Pour interpréter ces proxies en termes de climat, il est nécessaire de comprendre comment le signal climatique est enregistré dans le proxy, et quels processus modifient ce signal lors de la formation de l'archive.Les mesures de δ18O dans les précipitations, l'eau d’infiltration, et les inclusions fluides dans des échantillons de spéléothèmes modernes de la Grotte de Villars démontrent que la composition isotopique de l'eau d’infiltration dans la grotte correspond à une moyenne pluriannuelle des précipitations, et que les inclusions fluides des spéléothèmes préservent la composition isotopique de cette eau d’infiltration. Sur la base de cette calibration, il est possible de reconstituer les variations de la composition isotopique de l'eau d’infiltration à partir de celles des inclusions fluides d’une stalagmite vieille de plus de 2000 ans, datée par comptage de lamines, et par des mesures U-Th et 14C. Des changements dans l'environnement de la grotte, par exemple du couvert végétal, sont indiqués par d'autres proxies de la même stalagmite (les isotopes stables dans la calcite et les concentrations d'éléments traces), mais ces changements n'ont pas d'incidence significative sur le δ18O des inclusions fluides.La composition isotopique de la cellulose des cernes d'arbre de Quercus spp. dans la zone d'étude est fortement influencée par les conditions climatiques estivales. Cependant, des influences non-climatiques sur la composition isotopique de la cellulose sont identifiées ; elles sont liées à l'âge de l'arbre et à l'hydrologie du site, et doivent être prises en compte dans l'échantillonnage et dans les procédures analytiques. Grace à l’inter-datation de carottes d’arbres vivants et de poutre de bâtiments historiques des environs d'Angoulême, une chronologie de δ18O dans la cellulose à résolution annuelle a été établie. Des corrélations significatives avec les données météorologiques permettent une calibration des données isotopiques et une reconstruction des périodes de sécheresse depuis 1360 AD.Enfin, cette thèse explore une nouvelle approche intégrant les enregistrements isotopiques de l'oxygène dans les inclusions fluides des spéléothèmes et dans la cellulose des cernes d’arbre de sites proches pour reconstruire la variabilité à la fois haute et basse fréquence des sécheresses dans le passé. / The characterization of natural climate variability is important in order to understand the climate response to natural forcings and to identify anthropogenic influences. The aim of this thesis is to reconstruct climate changes in the southwest of France, a region which is characterised by recurrent drought periods, where high resolution proxy records of the last millennia were lacking.The reconstruction is based on multiple proxies from two continental archives: speleothems and tree rings. Their combination can make use of the strengths of each archive while compensating their weaknesses. There are two principal objectives: first, to gain a better understanding of the climatic and non-climatic influences on each proxy; and second, to reconstruct drought periods in the past.The oxygen isotopic composition (δ18O) of speleothem fluid inclusions and tree ring cellulose is controlled to a large extent by the δ18O of precipitation, which can serve as a tracer of the atmospheric circulation. In order to interpret these proxies in terms of climate, it is necessary to understand how the climate signal becomes recorded in the proxy, and which processes modify the original signal during the formation of the archive.Measurements of δ18O in precipitation, cave drip water, and fluid inclusions in modern speleothem samples from Villars Cave demonstrated that the isotopic composition of cave drip water corresponds to the pluri-annual average precipitation. The speleothem fluid inclusions, in turn, preserve the isotopic composition of the drip water. Based on this calibration, it is possible to reconstruct drip water isotope variability using fluid inclusions in a more than 2000 year old stalagmite, which has been dated by laminae counting, as well as U-Th and 14C measurements. Changes in the cave environment, e.g. the vegetation cover, are indicated by other proxies from the same stalagmite (stable isotopes in calcite and trace element concentrations), but these changes do not seem to impact the fluid inclusion δ18O significantly.The isotopic composition of tree ring cellulose from Quercus spp. in the study area is strongly influenced by climate conditions during the summer. However, non-climatic influences on the isotopic composition of cellulose are identified. They are linked to the age of the trees and to site hydrology, and must be accounted for in the sampling and analytical procedures. Crossdated cores from living trees and timber wood in historic buildings near Angoulême are used to build an annually resolved chronology of cellulose δ18O. Significant correlations with meteorological data enable a calibration and a reconstruction of drought periods since 1360 AD.Lastly, this thesis explores a novel approach of integrating oxygen isotope records from speleothem fluid inclusions and tree ring cellulose from closely located sites to reconstruct both high- and low-frequency variability of droughts in the past.