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Isotopes in the landscape : carbon and nitrogen isotopes of domestic animals and their application to the archaeology of the Upper and Middle Thames Valley in the Neolithic to Roman periodsHamilton, Julie January 2015 (has links)
This thesis deals with the development of farming landscapes in the Thames Valley from the Neolithic to the Roman period (4000 BCE - 410 CE). The focus is on the major domestic animal species, cattle, sheep and pig, and their roles in the agroecosystem, traced using carbon and nitrogen isotope ratios measured in collagen. The large dataset of faunal isotope values from a limited area, obtained from sites with extensive archaeological and environmental information, allowed a thorough characterisation of variability in isotope values, within and between species, sites, archaeological periods, and landscape regions. Isotope ratios in a flock of modern sheep showed less variability than archaeological assemblages. Linear mixed models were used to analyse variation in isotope values in 1490 archaeological samples from 23 sites. The pattern of change over time differed for cattle, sheep and pig, reflecting both wide-scale environmental change and changes in animal management. d13C values of cattle and pigs reflected the loss of primary closed-canopy woodland. Pig management changed from an emphasis on woodland resources to a closer association with settlement and consumption of anthropogenic waste. Herbivore d15N values probably reflect variations in the intensity of pasture use and association with arable farming. Climatic cooling since the post-glacial thermal maximum cannot explain these varied trajectories of change. Variation between sites in faunal isotope values was related to landscape regions. Faunal isotope values at individual sites were useful in site interpretation in the context of other evidence. The trend in pig and cattle δ13C values with time was widely found in the UK, as expected if it represents forest clearance. In the Neolithic, cattle management was similar to the UK at central and eastern European Neolithic sites, but pig management was different. Patterns of faunal isotope values and their changes over time, analysed in the context of archaeological and environmental information, can contribute to the interpretation of sites, and give a unique perspective on changes in farming practice and their effects on the landscape.
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Fruits of the forest : human stable isotope ecology and rainforest adaptations in Late Pleistocene and Holocene Sri LankaRoberts, Patrick January 2016 (has links)
Despite ecological, anthropological, and archaeological debate surrounding their desirability as habitats for human occupation, tropical rainforests have received relatively little attention in discussions of Homo sapiens' Pleistocene dispersal. Sri Lanka has yielded some of the earliest dated fossil and material culture evidence (c. 38-35,000 cal. years BP) for our species in a modern rainforest context beyond Africa. Nevertheless, assertions in Sri Lanka, and elsewhere, regarding early human rainforest reliance have been largely based on coarse or 'off-site' palaeoenvironmental records, and the overall role of these environments in human subsistence strategies has remained uncertain. This study applies stable carbon and oxygen isotope analysis to Sri Lankan human fossil, and associated faunal, tooth enamel dated to between 36-29,000 and 3,000 cal. years BP, in order to directly test human rainforest resource reliance, reconstruct a stable isotope ecology, and develop 'on-site' palaeoenvironmental records for Late Pleistocene-Holocene Sri Lankan rainforest foragers. Stable carbon and oxygen isotope analysis of modern Sri Lankan primates, and stable carbon, oxygen, and nitrogen isotope analysis of modern plant samples from the Polonnaruwa Nature Sanctuary, are also performed to investigate the ecology of Sri Lankan primates on which Late Pleistocene-Holocene forager subsistence strategies were focused. The results demonstrate that Homo sapiens relied on rainforest resources in Sri Lanka from c. 36-29,000 cal. years BP until the Iron Age c. 3 cal. years BP, even when open environments, and their corresponding resources, were available. This remains the case through periods of evident environmental change at the Last Glacial Maximum and even upon the arrival of agriculture in the island's tropical forests. The primate stable isotope data prove difficult to interpret as ecological niche separation in the absence of observation data. Nonetheless, humans were evidently able to not only use but also rapidly specialise in the exploitation of South Asia's rainforests.
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Transition from the late Roman period to the early Anglo-Saxon period in the Upper Thames Valley based on stable isotopesSakai, Yurika January 2017 (has links)
Following the argument of cultural change between the Romano-British and Anglo-Saxon periods in Britain, the purpose of this thesis is to find evidence of change in human diet and animal husbandry in the Upper Thames Valley across this boundary. Research questions are set to find differences in human diet, animal diet, and birth seasonality of herbivores at Horcott, a site showing human activity in both periods. Stable carbon and nitrogen isotope measurements on collagen from humans and livestock animals and enamel carbonate extracted from herbivores were analysed. Results showed changes in the diets of cattle, sheep/goats, pigs, and human, and birth seasonality of cattle and sheep/goats. These changes were argued to have been caused by differences in the intensity of fertilising crop fields, the amount of animal protein fed to adult pigs, the amount of non-local food in human diet, and the significance and purpose of livestock rearing and the preference of dairy products. The outcome of this thesis enhances the understanding of: a) the strategy and the amount of human effort put into crop cultivation and livestock management; b) the availability and preference of food for humans depending on the period; and c) the site-dependent differences in the extent of change in the course of transition between the Romano-British and Anglo-Saxon periods. This thesis demonstrates the importance of animal data in order to discuss human diet, and the advantage of modelling enamel carbonate sequential data when analysing worn and shortened teeth.
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USE OF STABLE ISOTOPES TO INFER FORAGING NICHE IN TWO MARINE TURTLE SPECIES: CHELONIA MYDAS AND ERETMOCHELYS IMBRICATAUnknown Date (has links)
Stable isotope analysis is a powerful tool that can be used to describe a population’s foraging niche by identifying basal resource use, trophic feeding levels, environmental stability, seasonal ecological variation, important shifts in life history, ontogenetic shifts, intraspecific habitat use, and population dynamics. Describing these relationships in endangered marine turtle populations and their critical foraging grounds is essential for determining informed management decisions. This study systematically describes the foraging niche of hawksbills Eretmochelys imbricata, and green turtles, Chelonia mydas in Buck Island Reef National Monument, U.S. Virgin Islands, a critical habitat for nesting and foraging. It assesses the relationships within and between the species in terms of overlap, annual and seasonal variation, and life history and feeding strategies within the community. Most importantly it describes these relationships with metrics that can be used in global comparisons or to measure change in local conditions. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2020. / FAU Electronic Theses and Dissertations Collection
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Strontium, Lead, and Oxygen Isotopic Signatures of Mid-Miocene Silicic Volcanism in Eastern OregonHess, Emily Nancy 09 December 2014 (has links)
Widespread, mid-Miocene rhyolite volcanism of eastern Oregon that are coeval or slightly postdate flood basalts of the Columbia River Basalt Province allows for mapping crustal domains using radiogenic and stable isotopes. Rhyolites are thought to be derived in large part by partial melting of the crust and thus yield direct information on the composition of the crust. Silicic volcanism is expressed in the form of numerous domes and tuffs exposed over a wide area (~300 km in N-S dimension and ~200 km in E-W dimension) west of the presumed craton boundary, which runs parallel but mostly east of the Oregon-Idaho state border as delineated by geophysical characteristics and isotopic transitions, including the 87Sr/86Sri = 0.7060 line (MSL) and 87Sr/86Sri = 0.7040 (CSL).
87Sr/86Sri of twenty-seven silicic units are variable and some are high. Sr isotopic ratios are inconsistent with the location of the traditional MSL and CSL boundaries. A primary control on the 87Sr/86Sri isotope variations may reflect changes in the crustal make-up of Paleozoic accreted terranes of a particular area rather than arising from a westward-dipping decollement that moved cratonic lithosphere below accreted terranes in eastern Oregon. A secondary control on observed isotopic ratios may be related to the amount and composition of basalt involved in the generation of rhyolites. This could lead to higher or lower 87Sr/86Sri relative to the surrounding crust because de facto coeval mafic magmas of the Columbia River Basalt Group have a wide range of Sr isotopic signatures.
While Pb isotope data is incomplete for all samples of this study, the available data indicate a significant range in Pb isotopes. Yet, data of individual regions tend to plot close to one another relative to the entire data distribution. Comparison of samples from this study in a more regional view indicates the samples generally fall within the previously defined lead isotope boundaries of the main-phase Columbia River Basalt Group lavas.
[lowercase delta]¹⁸O values range from below 2 parts per thousand to above 9 parts per thousand. In addition, there is a crude trend of rhyolites having lower [lowercase delta]¹⁸O and more radiogenic ⁸⁷Sr/⁸⁶Sr[subscript i] ratios. The lowest oxygen ratios (< 2 parts per thousand) are found in rhyolites ~80 km west of the cratonic margin, potentially reflecting remelting or assimilation of hydrothermally altered crust. Low [lowercase delta]¹⁸O of selected rhyolite flows cannot be explained by remelting of Cretaceous plutons of the Idaho Batholith and appear irreconcilable with remelting of altered silicic rocks at centers of multiple, confocal caldera cycles- both processes that have been proposed to explain low [lowercase delta]¹⁸O of rhyolites of the Snake River Plain-Yellowstone area.
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Olive oil or lard?: distinguishing plant oils from animal fats in the archeological record of the eastern Mediterranean using gas chromatography/combustion/isotope ratio mass spectrometrySteele, V. J., Stern, B., Stott, A. W. January 2010 (has links)
Distinguishing animal fats from plant oils in archaeological residues is not straightforward. Characteristic plant sterols, such as beta-sitosterol, are often missing in archaeological samples and specific biomarkers do not exist for most plant fats. Identification is usually based on a range of characteristics such as fatty acid ratios, all of which indicate that a plant oil may be present, none of which uniquely distinguish plant oils from other fats. Degradation and dissolution during burial alter fatty acid ratios and remove short-chain fatty acids, resulting in degraded plant oils with similar fatty acid profiles to other degraded fats. Compound-specific stable isotope analysis of delta(13)C(18:0) and delta(13)C(16:0), carried out by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS), has provided a means of distinguishing fish oils, dairy fats, ruminant and non-ruminant adipose fats, but plant oils are rarely included in these analyses. For modern plant oils where C(18:1) is abundant, delta(13)C(18:1) and delta(13)C(16:0) are usually measured. These results cannot be compared with archaeological data or data from other modern reference fats where delta(13)C(18:0) and delta(13)C(16:0) are measured, as C(18:0) and C(18:1) are formed by different processes resulting in different isotopic values. Eight samples of six modern plant oils were saponified, releasing sufficient C(18:0) to measure the isotopic values, which were plotted against delta(13)C(16:0). The isotopic values for these oils, with one exception, formed a tight cluster between ruminant and non-ruminant animal fats. This result complicates the interpretation of mixed fatty residues in geographical areas where both animal fats and plant oils were in use.
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Mobilita lidských populací na konci doby kamenné / Mobility of human populations at the end of the Stone AgeČERVINKA, Pavel January 2017 (has links)
The presented work entitled "Mobility of Human Populations at the End of the Stone Age" describes, generalizes, summarizes and subsequently evaluates the factors of migratory tendencies in prehistory - for the period of Neolithic over Eneolithic to Early Bronze Age. Emphasis is placed on the clarification of all interdisciplinary issues. Further on a detailed description of individual processes and archaeological approaches to them. As a basis for my own research, a database of data impacted by articles based on the study of strontium isotopes was created. In the next steps, the database was processed using statistical tools and its outputs were contingency tabletables and charts. Spatial assessment and their contexts were conducted in the GIS (Geographic Information System).
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Neolithic Anatolia and Central Europe : disentangling enviromental impacts from diet isotope studiesBudd, Chelsea January 2015 (has links)
The aim of this thesis was to reconstruct dietary choices for Neolithic populations in Anatolia and Poland using stable isotope analysis, and to examine the extent to which local environmental factors in these regions affected the isotope values recorded from skeletal collagen. In total 278 new δ13C and δ15N values were obtained from human and animal bone collagen for this project (161 from the site of Oslonki 1, 59 from Barçin Höyük, and 58 from the site of Aktopraklik). From an environmental perspective, the multi-level statistical modelling highlighted a clear relationship with δ13C and δ15N and moisture availability, which was most evident through the proxy of mean annual precipitation (MAP). The modelling highlighted a 0.4‰ decrease in d13C for every 100mm decrease of MAP, and a 0.5‰ decrease in d15N for every 100mm decrease between sites. The δ13C and δ15N values for the North-West Anatolian sites are the first dietary isotopic studies for the Neolithic period in the region. The values are largely commensurate with the dietary isotope studies from Neolithic sites located on the Central Anatolian plateau, with the caveat that the North-West sites perhaps had a greater reliance on herbivore protein (instead of plant protein) than their plateau counterparts. The dietary reconstruction of Oslonki 1 uncovered a rather unexpected outcome - namely that status exerted a degree of control over human diet. If this is indeed true it will be the earliest evidence in Europe of a distinct relationship between the socioeconomic status and diet of an individual.
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Subduction dynamics at the middle America trench : new constraints from swath bathymetry, multichannel seismic data, and ¹⁰BeKelly, Robyn K January 2003 (has links)
Thesis (Ph. D.)--Joint Program in Oceanography/Applied Ocean Science and Engineering (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences, and the Woods Hole Oceanographic Institution), September 2003. / Includes bibliographical references. / The cosmogenic radionuclide ¹⁰Be is a unique tracer of shallow sediment subduction in volcanic arcs. The range in ¹⁰Be enrichment in the Central American Volcanic Arc between Guatemala and Costa Rica is not controlled by variations in ¹⁰Be concentrations in subducting sediment seaward of the Middle America Trench. Sedimentary ¹⁰Be is correlated negatively with ¹⁴³ND/¹⁴⁴Nd, illustrating that ¹⁰Be concentrations varied both between and within cores due to mixing between terrigenous clay and volcanic ash endmember components. This mixing behavior was determined to be a function of grain size controls on ¹⁰Be concentrations. A negative correlation of bulk sedimentary ¹⁰Be concentrations with median grain size and a positive correlation with the proportion of the sediment grains that were <32 [mu]m in diameter demonstrated that high concentrations of ¹⁰Be in fine-grained, terrigenous sediments were diluted by larger grained volcanogenic material. The sharp decrease in ¹⁰Be enrichment in the Central American Volcanic Arc between southeastern Nicaragua and northwestern Costa Rica correlates with changes in fault structure in the subducting Cocos plate. Offshore of Nicaragua, extensional faults associated with plate bending have throw equal to or greater than the overlying subducting sediment thickness. These faults enable efficient subduction of the entire sediment package by preventing relocation of the d6collement within the downgoing sediments. / (cont.) Offshore of Costa Rica, the reduction of fault relief results in basement faults that do not penetrate the overlying sediment. A conceptual model is proposed in which the absence of significant basement roughness allows the d6collement to descend into the subducting sediment column, leading to subsequent underplating and therefore removal of the bulk of the sediment layer that contains ¹⁰Be. Basement fault relief was linearly related to plate curvature and trench depth. The systematic shoaling of the plate from southeastern Nicaragua to northwestern Costa Rica is not explained by changes in plate age for this region. Instead, it is hypothesized that the flexural shape of the plate offshore of southeastern Nicaragua and northwestern Costa Rica represents a lateral response to a buoyant load caused by the thick crust and elevated thermal regime in the Cocos plate offshore of southeastern Costa Rica. / by Robyn K. Kelly. / Ph.D.
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Methodischer Beitrag zur Prozessidentifikation von Umsetzungsprozessen des Stickstoffs in belasteten Grundwasserleitern mittels stabiler IsotopeStock, Patricia 12 May 2022 (has links)
Diese Arbeit leistet einen methodischen Beitrag zur Identifizierung von Umsetzungsprozessen der Stickstoffverbindungen Ammonium und Nitrat in belasteten Grundwasserleitern mittels der Analytik der Isotopenverhältnisse N-15 bzw. O-18. Es existieren bereits verschiedene Präparationsmethoden, jedoch sind diese teilweise arbeits- oder zeitaufwändig und damit mit erheblichen Kosten verbunden. Für eine breitere Anwendbarkeit in den Umweltwissenschaften wurden im Rahmen dieser Arbeit zwei vereinfachte Methoden für die N-15 bzw. O-18 Stabilisotopenanalytik von Ammonium und Nitrat in Wässern erarbeitet. Zum einen wurde eine Fällungsmethode mit Natriumtetraphenylborat für die Probenvorbereitung der N-15 Isotopenanalyse für Ammonium weiterentwickelt, getestet und validiert. Bisher existierten keine Studien zur Anwendbarkeit dieser Methode auf die Analyse ammoniumhaltiger Wasserproben. Daher wurde die Methode in dieser Arbeit für die Anwendbarkeit auf Wasserproben optimiert, insbesondere auf natürliche Grundwasserproben. Zum anderen wurde eine gängige Aufbereitungsmethode für gelöstes Nitrat weiterentwickelt. Dabei wurden die Vorbereitungs- und Arbeitszeit der Denitrifizierermethode verkürzt, ohne die Genauigkeit der Messung negativ zu beeinflussen. Zu diesem Zweck wurden zwei bestehende Varianten der Methode miteinander kombiniert und modifiziert. Als Eignungsprüfung der Methoden zur Prozessidentifikation erfolgte eine exemplarische Feldstudie. Als Modellstandort diente ein Untersuchungsgebiet im Südosten Berlins. Der Grundwasserleiter des Standortes ist u. a. durch eine massive Kontamination von Ammonium gekennzeichnet. Im Untersuchungsgebiet wurde das sogenannte BIOXWAND-Verfahren entwickelt und zur Sanierung auf den Grundwasserleiter angewandt. Dabei handelt es sich um ein in-situ-Verfahren, wobei eine direkte Injektion von Sauerstoff in den Grundwasserleiter erfolgt um Nitrifikation zu begünstigen. Für die isotopengestützte Prozessidentifikation wurden im Rahmen dieser Arbeit von 2016 bis 2019 zweimal jährlich Grundwasserproben aus dem BIOXWAND-Anstrom und dem BIOXWAND-Abstrom entnommen und mit den erarbeiteten Präparationsmethoden aufbereitet und analysiert. Zur Prozessidentifikation wurde ein analytisches Modell erstellt.
Bei der vorliegenden kumulativen Dissertation handelt es sich um eine verkürzte Darstellung der Forschungsergebnisse. Die ausführlichen Ergebnisse wurden bereits in der Fachzeitschrift 'Rapid Communications in Mass Spectrometry' veröffentlicht.:VERZEICHNIS DER TABELLEN ................................................................................ 9
VERZEICHNIS DER ABBILDUNGEN ....................................................................... 10
VERZEICHNIS DER ANHÄNGE .............................................................................. 11
VERZEICHNIS DER SYMBOLE UND ABKÜRZUNGEN ............................................. 12
1 EINLEITUNG UND MOTIVATION ....................................................................... 14
2 ZIELSETZUNG UND KONZEPT ............................................................................ 16
3 THEORETISCHE EINFÜHRUNG .......................................................................... 18
3.1 Stickstoff in der Umwelt ........................................................................................ 18
3.2 Ammonium und Nitrat im Stickstoffkreislauf ........................................................... 18
3.3 Einflussfaktoren auf die Prozesse des Stickstoffkreislaufs ....................................... 21
3.4 Isotopenanalytik in den Umweltwissenschaften ...................................................... 22
3.4.1 Definition stabiler Isotope ................................................................................................... 22
3.4.2 Isotopieeffekte und Fraktionierung .................................................................................... 24
3.4.3 Delta-Notation ....................................................................................................................... 25
3.4.4 Fraktionierungs- und Anreicherungsfaktor ....................................................................... 28
3.5 Analyse stabiler Isotope mittels Isotopenverhältnis-Massenspektrometrie ................. 29
3.5.1 Allgemeine Informationen ................................................................................................... 29
3.5.2 Massenspektrometer ............................................................................................................ 29
3.5.3 Analyse stabiler Isotope mittels Elementaranalysator-Isotopenverhältnis-Massenspektrometrie-Kopplung (EA-IRMS) ...................................................................... 31
3.5.4 Analyse stabiler Isotope mittels GasBench II – IRMS ..................................................... 33
3.6 Ammonium und Nitrat im Kontext stabiler Isotope .................................................. 34
4 PROBENAUFBEREITUNGSMETHODEN ............................................................... 37
4.1 Bedeutung der Probenaufbereitung ....................................................................... 37
4.2 Probenaufbereitung für die δ15N-Isotopenanalyse von gelöstem NH4+ ....................... 37
4.2.1 Destillationsmethode ............................................................................................................ 37
4.2.2 Quecksilberfällung ................................................................................................................ 37
4.2.3 Diffusionsmethode ................................................................................................................ 38
4.2.4 Kationenaustausch................................................................................................................ 39
4.2.5 Fällung von Ammonium mittels Tetraphenylborat ........................................................... 39
4.2.6 Weitere Methoden ................................................................................................................ 40
4.3 Zusammenfassung der Probenaufbereitungsmethoden für die δ15N-Isotopenanalyse von gelöstem NH4+ ............................................................................................... 40
4.4 Probenaufbereitung für die δ15N- und δ18O-Isotopenanalyse von gelöstem NO3− ........ 41
4.4.1 Reduktionsmethoden ........................................................................................................... 41
4.4.2 Denitrifizierermethode ......................................................................................................... 41
4.4.3 Silbernitratfällung.................................................................................................................. 42
4.4.4 Bariumnitratfällung ............................................................................................................... 43
4.5 Zusammenfassung der Probenaufbereitungsmethoden für die δ15N- und δ18O-Isotopenanalyse von gelöstem NO3- ....................................................................... 43
5 ÜBERBLICK DER DURCHGEFÜHRTEN STUDIEN ................................................ 44
5.1 δ15N-Analyse von Ammonium in gefriergetrockneten, natürlichen Grundwasserproben durch Fällung mit Natriumtetraphenylborat ............................................................ 44
5.2 Weiterführende Optimierung der Denitrifizierermethode für die schnelle 15N und 18O-Analyse von Nitrat in natürlichen Wasserproben ..................................................... 44
5.3 Beispielhafte Identifizierung von Nitrifikation und Sorptionsprozessen von Ammonium als Feldstudie ...................................................................................................... 45
6 DISKUSSION UND AUSBLICK ............................................................................ 47
7 DANKSAGUNG ................................................................................................... 50
8 LITERATURVERZEICHNIS ................................................................................. 51
ANHANG ............................................................................................................... 61 / This thesis provides a method to identify the transformation of the nitrogen species ammonium and nitrate in polluted aquifers by analyzing the isotope ratios N-15 and O-18. Various preparation methods already exist, but are either labor intensive or time consuming and are therefore related with considerable costs. To achieve a broader applicability in environmental sciences, two simplified methods for the N-15 and O-18 stable isotope analysis of ammonium and nitrate in water were developed in this thesis. On the one hand, a precipitation method using sodium tetraphenylborate for the sample preparation of the N-15 isotope analysis for ammonium was modified, tested and validated. So far no studies could verify the applicability of this method for analysis of water samples containing ammonium. Therefore, the method was optimized for applicability to water samples, especially natural groundwater samples within this thesis. On the other hand, a common processing method for dissolved nitrate was optimized. The preparation and working time of the denitrification method was shortened without negatively affecting the accuracy of the measurement. For this purpose, two existing variants of the method were combined and modified. Furthermore, an exemplary field study was carried out to test the suitability of the preparation methods for process identification. A study area southeast of Berlin (Germany) containing an aquifer massively contaminated with ammonium served as a model location. Inside the area, the so-called BIOXWAND process, an in-situ process whereby oxygen is injected directly into the aquifer to promote nitrification, was developed and applied to the aquifer in terms of remediation. For isotope-based process identification, groundwater samples were taken twice a year from 2016 to 2019 from the BIOXWAND inflow and outflow and analyzed using the preparation methods developed. An analytical model was created for process identification.:VERZEICHNIS DER TABELLEN ................................................................................ 9
VERZEICHNIS DER ABBILDUNGEN ....................................................................... 10
VERZEICHNIS DER ANHÄNGE .............................................................................. 11
VERZEICHNIS DER SYMBOLE UND ABKÜRZUNGEN ............................................. 12
1 EINLEITUNG UND MOTIVATION ....................................................................... 14
2 ZIELSETZUNG UND KONZEPT ............................................................................ 16
3 THEORETISCHE EINFÜHRUNG .......................................................................... 18
3.1 Stickstoff in der Umwelt ........................................................................................ 18
3.2 Ammonium und Nitrat im Stickstoffkreislauf ........................................................... 18
3.3 Einflussfaktoren auf die Prozesse des Stickstoffkreislaufs ....................................... 21
3.4 Isotopenanalytik in den Umweltwissenschaften ...................................................... 22
3.4.1 Definition stabiler Isotope ................................................................................................... 22
3.4.2 Isotopieeffekte und Fraktionierung .................................................................................... 24
3.4.3 Delta-Notation ....................................................................................................................... 25
3.4.4 Fraktionierungs- und Anreicherungsfaktor ....................................................................... 28
3.5 Analyse stabiler Isotope mittels Isotopenverhältnis-Massenspektrometrie ................. 29
3.5.1 Allgemeine Informationen ................................................................................................... 29
3.5.2 Massenspektrometer ............................................................................................................ 29
3.5.3 Analyse stabiler Isotope mittels Elementaranalysator-Isotopenverhältnis-Massenspektrometrie-Kopplung (EA-IRMS) ...................................................................... 31
3.5.4 Analyse stabiler Isotope mittels GasBench II – IRMS ..................................................... 33
3.6 Ammonium und Nitrat im Kontext stabiler Isotope .................................................. 34
4 PROBENAUFBEREITUNGSMETHODEN ............................................................... 37
4.1 Bedeutung der Probenaufbereitung ....................................................................... 37
4.2 Probenaufbereitung für die δ15N-Isotopenanalyse von gelöstem NH4+ ....................... 37
4.2.1 Destillationsmethode ............................................................................................................ 37
4.2.2 Quecksilberfällung ................................................................................................................ 37
4.2.3 Diffusionsmethode ................................................................................................................ 38
4.2.4 Kationenaustausch................................................................................................................ 39
4.2.5 Fällung von Ammonium mittels Tetraphenylborat ........................................................... 39
4.2.6 Weitere Methoden ................................................................................................................ 40
4.3 Zusammenfassung der Probenaufbereitungsmethoden für die δ15N-Isotopenanalyse von gelöstem NH4+ ............................................................................................... 40
4.4 Probenaufbereitung für die δ15N- und δ18O-Isotopenanalyse von gelöstem NO3− ........ 41
4.4.1 Reduktionsmethoden ........................................................................................................... 41
4.4.2 Denitrifizierermethode ......................................................................................................... 41
4.4.3 Silbernitratfällung.................................................................................................................. 42
4.4.4 Bariumnitratfällung ............................................................................................................... 43
4.5 Zusammenfassung der Probenaufbereitungsmethoden für die δ15N- und δ18O-Isotopenanalyse von gelöstem NO3- ....................................................................... 43
5 ÜBERBLICK DER DURCHGEFÜHRTEN STUDIEN ................................................ 44
5.1 δ15N-Analyse von Ammonium in gefriergetrockneten, natürlichen Grundwasserproben durch Fällung mit Natriumtetraphenylborat ............................................................ 44
5.2 Weiterführende Optimierung der Denitrifizierermethode für die schnelle 15N und 18O-Analyse von Nitrat in natürlichen Wasserproben ..................................................... 44
5.3 Beispielhafte Identifizierung von Nitrifikation und Sorptionsprozessen von Ammonium als Feldstudie ...................................................................................................... 45
6 DISKUSSION UND AUSBLICK ............................................................................ 47
7 DANKSAGUNG ................................................................................................... 50
8 LITERATURVERZEICHNIS ................................................................................. 51
ANHANG ............................................................................................................... 61
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