abstract: Migrations, past and present, fundamentally influence human interaction, community building, and social evolution. Studies of contemporary migrations demonstrate that the form and intensity of interaction migrants maintain between homeland and host communities shape social dynamics, innovations, and identities. This dissertation applies a contemporary theoretical framework and biogeochemical analyses to elucidate the scale, processes, and impacts of migration in the hinterland of the pre-Hispanic Tiwanaku polity (ca. AD 500-1100). Social diversity is examined by reconstructing the migration histories and dietary choices of individuals interred at the Tiwanaku-affiliated site of Omo M10 in the Moquegua Valley of southern Peru. Radiogenic strontium and stable oxygen isotope data from human dental and skeletal elements are used to characterize intra- and inter-individual paleomobility patterns at Omo M10. When contextualized with archaeological evidence, these data reveal multigenerational interaction through migration between communities in the highland Tiwanaku heartland and at Omo M10. The observed greater mobility of females and juveniles at Omo M10 indicates that women and families played an essential role in maintaining social relationships and persistent cultural continuity in Moquegua Tiwanaku life. Contact with the highlands waned over time as disruption in the urban highland centers likely weakened ties to peripheral lowland communities. Stable carbon and nitrogen data from human dental and skeletal elements are employed to estimate intra- and inter-individual paleodietary patterns. Results indicate diet at Omo M10 varied depending on an individual’s community affiliation, sex, age, and level of mobility; diet broadly changed over time with shifting levels of interaction with highland Tiwanaku communities. Intra-individual biogeochemical analyses of migration and diet at Omo M10 contribute a nuanced perspective on the diverse experiences of multigenerational colonists on the periphery of the Tiwanaku polity. / Dissertation/Thesis / Doctoral Dissertation Anthropology 2019

The upper Homerian Mulde Event was a mass extinction that devastated graptolite diversity and occurred before and during the onset of a major perturbation to the global carbon cycle recorded as a double-peaked positive carbon isotope excursion (CIE). Whereas the Mulde Event and associated CIE are well-documented globally, changes in global sea level associated with the Mulde Event have only been investigated in detail in the West Midlands, England and Gotland, Sweden. A critical step toward understanding both the drivers and results of global climatic change during the Mulde Event is to constrain changes in eustasy. This study integrates carbon isotope chemostratigraphy and conodont biostratigraphy of Homerian strata in Tennessee, Indiana, and Ohio in an effort to determine if a global type-1 sequence boundary is recorded within the ascending limb of the Mulde CIE, and to produce a high-resolution chronostratigraphic framework for Homerian strata in the midcontinent USA. Six sections, two from each state, were measured and described. Five were sampled for carbon isotope chemostratigraphy, and one for conodont biostratigraphy. All sections from Tennessee and Indiana evidently contain the Mulde CIE, whereas the sections from Ohio are less clear due to the truncation of upper Homerian strata. These data demonstrate that a sequence boundary identified herein in Indiana and Tennessee is the same sequence boundary that occurred during the ascending limb of the Mulde Excursion in the West Midlands and Gotland.

Thesis (M.Sc. (Chemistry)) -- University of Limpopo, 2019. / The concept of sustainable energy development is one of the crucial topics of the 21st century. It has evolved into a guiding principle for a liveable future world where human needs are met while maintaining balance with the environment. In this regard, hydrogen technology is a promising alternative energy source since it does not produce undesirable greenhouse gas (CO2). In order to place hydrogen energy into practical applications, there are certain problems that need to be addressed, these include the efficient production and storage of hydrogen. Currently, hydrogen is mostly produced from conventional processes such as steam reforming of fossil fuels, gasification and water splitting (photo/electrochemical and thermochemical). Among these methods, electrochemical water splitting is identified as a noble process to produce clean hydrogen gas and monitor all processes through hydrogen evolution reactions (HER). The entire HER processes are sluggish in nature and cathodic electrocatalysts are utilised to accelerate the process. Hence, in this work, we present highly active graphene oxide/metal organic framework (GO/MOF) and palladium (Pd) supported GO/MOF electrocatalysts for HER. GO/MOF was prepared through impregnation method of MOF and GO, whereas Pd@GO/MOF composite was synthesised using electroless Pd deposition on GO and followed by impregnation method of direct mixing of Pd@GO and MOF. The structural, morphological and electrochemical properties of the synthesised materials (GO/MOF and Pd@GO/MOF) were characterised by X-ray diffraction (XRD), Fourier transform infrared (FTIR), simultaneous thermogravimetric analysis (STA), scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS), high resolution transmission electron microscopy/Energy dispersive x-ray spectroscopy/selected area electron diffraction (HRTEM/EDX/SAED) and cyclic voltammetry (CV). XRD, FTIR, TGA and DSC results revealed the presence of GO on MOF confirming the formation of composites. The SEM/EDS and HRTEM/EDX/SAED results confirmed the presence of octahedral structure of MOF in the Pd@GO sheet-like structure, elemental composition and crystallinity of the synthesised materials. Furthermore, the electrocatalytic efficiency of GO/MOF and Pd@GO/MOF composites on HER was studied using three important parameters (exchange current density, Tafel slope and charge transfer coefficient) calculated from Tafel analysis. The GO/MOF and Pd@GO/MOF composites showed excellent HER activity at 0.45 mol.L-1 H2SO4 withexchange current densities of 25.12 A.m-2 and 24.5 A.m-2, Tafel slopes of 116 mV/dec and 123 mV/dec, and transfer coefficients of 0.49 and 0.52, respectively. These observed results are consistent with theory, thus suggesting the Volmer reaction as the limiting mechanism at high concentration. However, at low concentration both composites showed an increase in the Tafel slope and transfer coefficient, suggesting the reaction order of Volmer reaction coupled with either Heyrovsky or Tafel reaction. The proposed reaction order was further supported by slope of logarithm of current as a function of pH and Pourbaix diagram. The composites demonstrated the enhancement turnover frequency (TOF) values in this order MOF <GO/MOF <Pd@GO/MOF. The large TOF value of 7.81 mol H2.s-1 in the case of Pd@GO/MOF was due the H2 spillover effect as a result of the presence of Pd nanoparticles. The fabricated composites displayed high activity, good stability and excellent tolerance to the crossover effect, which may be used as a promising catalyst in electrochemical hydrogen production and storage technology via hydrogen evolution reaction.

This study gives the details about several experiments done in Eugene Mallove Laboratory for New Energy Research. Three experiments are presented and discussed in detail with different type of microscopes and mass spectrometry techniques. Also inspired by work done by Rolison and O'Grady [1], the other part of this study presents the variation of isotopic abundance after experiments on palladium cathode immersed in a heavy water electrolyte. This original inspiring paper has been published through proceedings of the first edition of International Conference on Cold Fusion held in Washington D.C. in 1989. In other words, both works provides similar evidence of an isotopic variation before and after low energy nuclear experiments. By measuring the variation in isotopic concentration, before and after electrolysis, these measurements provide insight for how the low energy nuclear phenomenon occurs. Scanning electron microscopes are used in the first part to provide high resolution, high magnification images of the electrodes. They show the morphology the topology of the cathode after experiment. An energy dispersive mass spectrometer is used to provide elemental composition of the cathode and provide a second independent measurement of elemental composition of the cathode. The presented isotopic measurements are made with a secondary ion mass spectrometer. [1]: D. Rolison & W. O'Grady - Mass/Charge Anomalies in Pd after electrochemical loading with deuterium - Section 10 in Proceedings: EPRI-NSF Workshop on Anomalous Effects in Deuterided Metals - (October 16-18, 1989) Washington, D.C.

Forensic anthropologists increasingly use chemical isotope analysis in the investigation of unidentified human remains, as biochemical georeferencing continually improves with the development of modern reference data of known origins. Isotope variations in trace elements such as strontium (Sr) and lead (Pb) in human teeth are some of the most useful indicators of past domicile in archaeological research and thus have high potential for modern, forensic applications. In this study, high-precision lead isotope analysis was conducted on 63 modern human teeth, which were previously analyzed for strontium isotopes. The results present new lead isotope data for the following countries: United States (n=34), Colombia (n=9), Haiti (n=5), Cape Verde (n=3), Morocco (n=2), El Salvador (n=2), Guatemala (n=2), Honduras (n=2), Jamaica (n=1), Dominican Republic (n=1), Albania (n=1), and United Kingdom (n=1). In addition, the lead and strontium isotope data of 23 modern human teeth from individuals born in Holland, eight teeth from individuals born in Bulgaria, and 26 teeth from individuals born in the U.S. are extracted from the literature to supplement the data analysis. Exploratory data analysis, nonparametric Kruskal-Wallis tests, and one-way analysis of variance (Scheffe post hoc) are conducted using IBM SPSS® Statistics 24 to test for regional variation. Several trends are observed in the lead isotope data that may be relevant to modern forensic contexts involving unidentified human remains: Individuals from the northeast U.S. have relatively distinct 208Pb/204Pb, 207Pb/204Pb, and 206Pb/204Pb ratios when compared to individuals from the rest of the U.S. European and American individuals can be easily distinguished from each other using 208Pb/204Pb, 207Pb/204Pb, and 206Pb/204Pb ratios. Central American individuals have significantly lower 87Sr/86Sr ratios than North American individuals, and these groups can be easily distinguished using lead versus strontium scatterplots. Colombian individuals have significantly lower 87Sr/86Sr ratios than North American individuals, and these groups can be easily distinguished using lead versus strontium scatterplots. Caribbean individuals have significantly lower 87Sr/86Sr isotope ratios than individuals from the northeast U.S., and these groups can be easily distinguished using lead versus strontium scatterplots.

The issue of granite petrogenesis plays a key role in our overall understanding of the growth and differentiation of continents, as well as in our ability to unravel the tectonic histories of orogenic belts. Granites are ubiquitous magmatic products found in almost all tectonic settings: oceanic and continental rifts (i.e., plagiogranites - extreme basalt differentiates), active continental margins (e.g,. the granitic batholiths of central and southern Andes), continent-continent collision zones (e.g., the orogenic batholiths of the Himalayas, Western Anatolia), post-collisional settings (e.g., the Variscan provinces of Europe), complex within-plates settings (e.g., Limmo massif, Afar, Ethiopia). Furthermore, granitoids are characterized by considerable petrological and geochemical heterogeneity, as they can form from a vast array of sources: sediments (e.g., pelites, arkoses, psammites), metamorphic rocks (e.g., (mica)schists, gneisses, etc.), and igneous rocks (e.g. andesites, dacites, tonalites, etc.). Aside from fertile sources (i.e., protoliths), granite petrogenesis is dependent upon two critical parameters: temperature (to promote melting of the protoliths) and water availability - either as freely available aqueous solutions/vapors (e.g., water input in subduction zones); or water released via dehydration melting of hydrous minerals (e.g., micas, amphiboles). The presence of water in protoliths depresses the melting temperature of mineral components and provides the environment for redistribution of chemical components. Understanding the origins of granitic rocks presents unique challenges, given that in many of the tectonic settings where granites are encountered, it is clear that their modes of formation can involve a spectrum of igneous and metamorphic processes that are not readily accessible for examination, either through the study of modern environments or via analogy to "classical" localities. The petrogenesis and emplacement of granites in post-collisional tectonic settings is one of the thornier challenges, as these rocks appear to be derived via thermal and magmatic processes within highly deformed and compositionally diverse continental crust for which we lack a clear understanding. A number of unconventional and difficult-to-test mechanisms have been posited to drive crustal heating, melting, and subsequent pluton post-collisional emplacement. Although large volumes of granitic magmas have been emplaced in post-collisional settings, the complexities of the processes active in such settings make it challenging to put forward testable models that effectively combine available geochemical, petrologic, and geophysical data. Models for granite genesis away from plate margins (by means of crustal thickening, thermal blanketing, and internal heating from radioactive decay of 40K, 230Th, 235U, and 238U; delamination of the crustal lithosphere and juxtaposition of hot mantle melts at the base of the crust; underplating of mantle melts; or slab brake-off and upwelling of mantle melts) have been successfully applied in comparatively young orogenic regions, such as the Himalayas, the Carpathians, and Turkey. These models have proven challenging to employ in older orogenic belts, given their sometimes intricate tectonic and metamorphic histories, and the loss of pertinent evidence due to the effects of post-emplacement tectonic reworking, and often extensive alteration and erosion. A series of ancient but fresh, age-correlative granitic plutons are exposed in Alpine nappes on the flanks of the Carpathians Mountains in southwestern Romania. These granites, all mapped as intruding the Neoproterozoic basement of the Danubian tectonic terrane, were emplaced during the post-collisional stages of two world-scale orogenies: an older, Pan-African event (~600 Ma) and a younger, Variscan event (~330- 280 Ma). My dissertation is focused on the study of late Variscan post-collisional plutons and associated sub-volcanic dykes, as they are tremendous tools for understanding and quantifying the mantle-crust interaction in post-collisional environments and the overall evolution of the continental crust during the Variscan orogeny. Originally believed to be Proterozoic in age, zircon U/Pb dating showed that the plutons are much younger (Chapter 1 - Post-collisional Late Variscan magmatism in the Danubian domain (South Carpathians, Romania) documented by zircon U/Pb LA-ICP-MS) and correspond to the latest stages of the Variscan orogeny, as recorded elsewhere in the European Variscan provinces. The granitic plutons are relatively small and are generally concordant with the structures preserved by the country rocks. The extraordinary petrological and geochemical heterogeneities, even at pluton scale (Chapter 2 - Petrology and geochemistry of the Late Variscan post-collisional Furătura granitic pluton South. Carpathian Mts. (Romania)) argue against unique protoliths and simple evolutionary processes (e.g., closed-system fractional crystallization; anatexis). Trace elemental data for the Furătura pluton shows that the melts were formed in equilibrium with a garnet-amphibole restite, under pressure-temperature conditions deeper than the plagioclase stability field, implying that the melting took place at depths in excess of 40 km in the continental crust. Stable and radiogenic isotope data suggest that a protolith was of (possibly enriched) mantle affinities, and that the melts were subsequently contaminated in various degrees by deep crustal lithologies. In comparison, other post-collisional Variscan plutons from the Danubian domain (Chapter 4 - The role of the continental crust and lithospheric mantle in Variscan post-collisional magmatism - insights from Muntele Mic, Ogradena, Cherbelezu, Sfârdinu, and Culmea Cernei plutons (Romanian Southern Carpathians)) have trace elemental compositions that suggest they were formed at different levels in the crust, under P-T conditions corresponding to both garnet-amphibole and plagioclase stability fields. Some of the plutons lack mantle geochemical signatures and their isotopic compositions are indicative of substantial involvement of both lower- and upper-crustal rocks in their formation and subsequent evolution. On the other hand, plutons emplaced during the same time interval and most likely in close geographical proximity have trace elemental and isotopic compositions indicating strong input from previously enriched mantle components which experienced various degrees of assimilation fractionation-crystallization and/or assimilation of continental crust material during their evolution. This variability in both protoliths and processes responsible for the formation of the granites, coupled with the presence of mantle signatures in late-orogenic post-collisional melts are strong evidence to support delamination as means of providing both the mantle-derived input and energy required for generation of granitoids in the crust. The pronounced variation in petrological and chemical compositions of synchronous plutons suggests that delamination in the Danubian domain was not a single, large scale event that affected the entire crust, but rather a collection of disparate, spatially and chronologically limited event, that affected the Variscan crust during the latest stages of the orogeny. This hypothesis is further tested on a series of sub-volcanic dykes (the Motru Dyke Swarm) crosscutting the entire Danubian basement (Chapter 3 - Post-collisional magmatism associated with Variscan orogeny in the Danubian Domain (Romanian Southern Carpathians): the Motru Dyke Swarm). Initially, the emplacement age of these dykes was assumed as "pre-Silurian" but our mapping has showed that they intrude components of the Danubian domain that shared a documented common history not earlier than the Carboniferous. Furthermore, the dykes are in intrusive relationship with two of the Danubian Variscan plutons, thus arguing for an early Permian emplacement age. Geochemical data show extraordinary heterogeneities in the dykes' composition and record both mantle and crust involvement in their formation. The dykes were emplaced at much shallower depths in the crust, as compared with the granitic plutons. Still, their isotopic compositions clearly indicate that they sampled both lower- and upper-crustal compositions during their evolution. This means that after the crustal thickening episodes that define continent-continent collisions, during the latest stages of the Variscan orogeny, the crust became progressively thinner, as a way to compensate for its metastable state. Thinning of the crust is greatly favored by delamination of the lithosphere. A delamination event, which usually postdates the cessation of continental collision or prolonged crustal shortening, involves the geologically rapid foundering of negatively buoyant lithosphere comprised of mantle and (potentially) lower crust into underlying hotter and less dense asthenosphere. Such a process will remove the lithospheric mantle (and potentially segments of the lower crust) along pre-existing lineaments or mechanical flaws, and juxtapose hot upwelling asthenosphere against the base of the crust, leading to partial melting. Field, petrological, and geochemical data presented in my dissertation document pronounced variations in the overall composition of synchronous plutons and dykes, and further suggest that delamination in the Danubian domain was an active process. This bears great importance in our understanding of the evolution of the crust and argues that mantle-crust interactions are responsible for the generation of continental crust even in the latest stages of an orogen.

The Louisiana (LA) shelf is chronically affected by seasonal hypoxia that has been shown to be spatially expanding and growing progressively more severe. Hypoxic conditions on the shelf have been closely linked to the large quantities of nutrients delivered to the Gulf of Mexico via the Mississippi River. Multiple geochemical proxies on a suite of sediment cores from the LA shelf provide a record of environmental change that parallels the onset of hypoxic conditions over the last century and prior to anthropogenic influences. The sedimentary record for the last century shows a shift from terrestrial to algal sources to the sediments, as well as a trend of increasingly enriched nitrogen isotopes, which is probably caused by a combination of large amounts of denitrification, either within the Mississippi watershed or on the continental shelf, increased primary productivity, compounded with relatively minor increases of enriched nitrogen source inputs. The current chronic hypoxia, especially since the early 1970's, is exacerbated by anthropogenic nutrient loading from the Mississippi River basin, but other processes must be responsible in the past. In the historic record, several episodic low-oxygen events are defined by forminiferal assemblages and shifts in the geochemical records. Geochemistry of three sediment cores from the Louisiana (LA) shelf indicates that these historic events are likely caused by increased inputs of terrestrially-derived organic matter during peaks in Mississippi River discharge. These results suggest that low-oxygen conditions may be a natural, aperiodic phenomenon on the LA shelf, and that the current seasonally severe hypoxia resulted from the excess anthropogenic nutrient input.

The study involved the investigation of ancient dental enamel derived from former inhabitants of Pacific Islands: a population whose movements were necessarily more restricted than their mainland counterparts. Lead and strontium isotope analysis of human teeth were undertaken using TIMS and MC-LAM-ICPMS. Exposure information was obtained from elemental concentrations of lead and strontium using LAM-ICPMS, GFAAS and ASV. Isotopic measurements of lead within the dental enamel of these individuals suggest that the dominant source of biogenic lead exposure in these and other pre-metallurgical societies derived from the local water supply. Data from these ancient populations are compared with measurements made on ‘moderns’ based at Broken Hill, NSW, as well as from other UK-based post Iron Age populations. Results of this study indicate that the concentration of ancient lead within crystalline dental enamel in both ancient and modern populations can in certain circumstances be approximately the same, even when the degree of lead exposure is very high. The study proposes reasons for the discrepancies between these results and those obtained in previous studies, as well as discusses the implications of these analytical results for future studies in lead exposure in human populations. / Doctor of Philosophy (PhD)

At present several groups are analysing quasar absorption spectra to search for variation of the fine structure constant, alpha, across space and time. These studies compare the wavelengths of several transitions observed in the absorption clouds with those seen in the laboratory, and interpret anomalies as variation in alpha. One group has already presented evidence that alpha may have been smaller at an early epoch. Other groups using different telescopes see no variation. These studies use the ???many-multiplet??? method, which relies on the utilisation of many transitions in many ions to enhance the size of the effects and remove sources of systematic error. While this method offers an order-of-magnitude improvement in sensitivity over the previously used alkali-doublet method, the alpha-dependence (relativistic shift) of every transition used in the analysis must be calculated ab initio. In this thesis we present a method for the precise calculation of relativistic shifts, based on an energy calculation involving combination of the configuration interaction method and many-body perturbation theory. The many-multiplet method also introduces a potential systematic error: if the relative isotope abundances of the absorbers differ from terrestrial abundances then there can be spurious shifts in the measured wavelengths, which may be incorrectly interpreted as variation of alpha. A ???conspiracy??? of several isotopic abundances may provide an alternative explanation for the observed spectral anomalies. To account for these systematic errors we need accurate values of the isotope shift. We calculate these shifts using the finite-field method to reduce the problem to that of an energy calculation, which in turn is done using the same method used for the relativistic shift. We present the results of our calculations for a variety of atoms and ions seen in quasar absorption spectra. The results of this research should allow astrophysicists to measure isotope abundances in the absorbers directly. This can provide a test for models of nuclear reactions in stars and supernovae, and of the chemical evolution of the Universe. Our calculations can also be used in conjunction with measurements to extract changes in nuclear charge radii between isotopes.

<p>The technique of ESR-dosimetry and strategies for investigation of new materials as in regard to their applicability as ESR-dosimeters for radiotherapy has been reviewed. As an example six salts of formic and lactic acid has been evaluated. The applicability of the dosimeter has been judged by evaluating the tissue equivalence, radical yield, radical stability, spectral suitability, optimal readout parameters, dose response and sensitivity of the dosimetric system. Dependence of material characteristics and influence parameters has been analysed.</p><p>The reviewed methods have been successfully used for evaluation of the new materials. Lithium formate has been shown to be a good candidate relative to the state of the art dosimeter of alanine. Using optimal readout parameters lithium formate has been shown to be nine times as sensitive but even at moderate settings lithium formate is more sensitive. The results for lithium formate are in accordance to those of previous studies. The signal intensity of sodium formate has also proved to be high but unfortunately the signal fades rapidly.</p><p>Two new methods have been proposed as synthesis of the reviewed methods. The first allows flexible, effective and objective baseline correction of the ESR-spectrum. The second deals with dose response measurement by linear regression of the entire spectrum and was found to be successful in separating the spectral peaks of the induced radicals from the background signal.</p>