A great number of field measurements with different methods and instruments were conducted in attempts to develop a method for an optimal combination of various geochemical and geophysical methods in archaeological prospecting. The research presented in this thesis focuses on a study of how different anthropogenic changes in the ground can be detected by geochemical and geophysical mapping and how the results can be presented. A six-year pilot project, Svealand in Vendel and Viking periods (SIV), was the beginning of this work in which EM- measurements, gradiometer and GPR surveys together with phosphate mapping succeeded in detecting settlements, mainly from the Iron Age. During the project, a new field kit for soil phosphate analysis was also developed and patented. Another major project was the examination of the Kings’ Mounds in Old Uppsala where a multi method survey including two different slingrams, three different types of GPR equipments and two different gradiometers was used for detecting structures inside the mounds. The Thing Mound was interpreted not to be a burial mound. The layers indicated by the GPR survey are most probably natural glaciofluvial layers. At the Eastern Mound the measurements detected an excavation tunnel from 1846-47, some known old brick furnaces from the time of building of the church, the original esker surface and the central cairn. The survey also detected two linear structures from the mounds base to the top and a depression under the mound in the old esker. The linear structures were interpreted as possible boulder rows and the depression as a possible older burial preceding the construction of the mound. Other surveys with slingram and GPR were used to detect subsurface features at historical gardens and historical glass works. A number of surveys to detect older church remnants were also carried out. In a project at Arethousa, Greek Macedonia, slingram measurements pointed out possible subsurface stonewalls and a possible hearth, which were confirmed later by excavations. At Old Uppsala, Sweden a GPR survey was successfully used for detecting the older cathedral under the present church. The overall results led to a recommended concept of combined methods for archaeological prospecting, especially in northern Europe. Slingram measurements of both electrical and magnetic components combined with phosphate mapping and GPR surveys proved to be useful methods for such prospecting.

Summary: Throughout the world there are many places with a high concentration of arsenic in water. In the Czech Republic is such a place the area of Mokrsko, where arsenic in groundwater reaches the values, which are well above recommended limits for drinking water. On the studied locality arsenic is bound to secondary minerals containing iron; however, in the reducing conditions of the fluvial sediments arsenic is bound to newly-formed realgar accumulations associated with organic matter. Aim of this diploma thesis was to characterize realgar from this locality and try to determine the way and conditions of its origin. For the purpose of research, realgar and pore- water have been sampled, using lysimeters and rhizon samplers. Specimen of realgar was characterized by numerous standard techniques (XRD, SEM, TEM, chemical and isotopic composition). Water samples have been analysed for As, F and S species. Analysis of realgar using XRD, SEM and TEM techniques confirmed the presence of nanocrystalline realgar, forming clusters and needle like aggregates. Domination of divalent iron and reduced form of As3+ (4,3-7,3 mg/L) in similar concentrations has been observed within the pore- water samples. The concentration of dissolved sulfide was very low (cca 30 µg/L), on the other hand, content of sulphate was always...

A thesis submitted for the degree of Doctor of Philosophy in the Faculty of Science at the University of the Witwatersrand. / The present thesis is divided into three parts. The study described in Part I arose out of a request by the Chamber of Mines Mining Research Laboratory to the National Institute for Metallurgy to undertake a preliminary study of whether it would be feasible, in Witwatersrand conglomerates, to carry out rapid delimitation of areas rich in gold and/or uranium at the rock face, a procedure which would permit areas of rich ore to be removed selectively by means of the "rock-cutter". The approach adopted in this study was essentially geochemical, while conventional mineralogical techniques (macro-auto radiographs , thin section and polished section analyses) provided a control. The samples were drawn from the Vaal Reef at Hartebeestfontein and Zandpan and from the Ventersdorp Contact Reef at Venterspost, and were analysed quantitatively for gold, silver, uranium, pyrite, muscovite, pyrophyllite, chlorite, quartz, iron, potassium, nickel, titanium, zirconium and chromium. The intensity of the interrelationships between the elements and minerals analysed for was examined statistically by means of correlation covariance and factor analysis programmes written for an IBM 360/50 digital computer. A sympathetic relationship -- defined as significant positive correlation (with a correlation coefficient r> 0. 7) -- was found to exist between gold and uranium in both the Vaal Reef and Ventersdorp Contact Reef samples. These findings suggest that gold and uranium can be removed Simultaneously by means of the rock-cutter, and that radioactivity can be used as an indicator for on-site delimitation of areas rich in gold. In the course of the study described in Part I, it became evident that little detailed mineralogical work had ever been done on the phyllosilicates occurring in the Witwatersrand System. Accordingly, certain phyllosilicates from Witwatersrand conglomerate bands and other sources were examined in detail, this study being described in Part II of the present thesis. This study called for detailed chemical, optical, X-ray crystallographic, infra-red, differential thermal and thermogravimetric analyses, the results of which are presented. The findings were examined in the light of variolls classification schemes that have bep proposed for the phyllosilicates. This investigation revealed the need for a universally acceptable system of classification for the phyllosilicates, which should preferably be drawn up under the auspices of the International Mineralogical Association to avoid the confusion that exists at present. Part III of the present thesis is devoted to a discussion and description of various analytical techniques that had to be modified or developed to meet th8 requirements of the studies described in Parts I and II. The techniques described include: (1) An X-ray diffraction method which was developed for the quantitative analysis of pyrite, muscovite, pyrophyllite, chlorite and quartz in crushed ore from Witwatersrand conglomerates. This method makes use of novacul iie as an external standard and of binary mixtures as analytical standards, and had a mean absolute error of 1. 1 %. This method may be expanded to permit analysis of an n-component mixture. (2) A whole rock pressed powder technique of X-ray fluorescence analysis which was used for the quantitative determination of iron, potassium, nickel, titanium, zirconium and chromium. This method makes use of internstional rock standards as external standards. Six computer programmes used for the computation of the analytical results and in the statistical and crystallographic calculations are also presented in Part III. / AC2017

Cette thèse vise à évaluer l’impact du changement climatique sur la qualité des eaux du système karstique dans le Val d’Orléans. En 1er lieu, un bilan de la qualité géochimique de la Loire et de la Source du Bouillon a été réalisé : les isotopes stables et éléments majeurs ont révélé un mélange des eaux de Loire avec des eaux déjà présentes dans le karst ; la formation de calcite et d’hydroxydes de fer joue un rôle majeur sur le comportement des éléments traces dans le karst. Le bilan réalisé ensuite pour les produits phytosanitaires et pharmaceutiques montre que leur occurrence et comportement dans le karst varie suivant la molécule considérée, selon : son pouvoir d’adsorption au sol/sédiment, son taux de dégradation dans les stations d’épuration (pour les pharmaceutiques) et dans les eaux naturelles, les saisons et conditions climatiques, le mélange avec des eaux résiduelles karstiques plus ou moins chargées en produits que la Loire. Ces bilans géochimiques ont permis de fixer la qualité de l’eau souterraine pendant la durée de prélèvement. Le risque d’inversion de courant au niveau de rivières locales pouvant entraîner une dégradation de cette qualité, l’occurrence future de ces inversions de courant a été calculée : en reliant les inversions de courant et les résultats d’une désagrégation d’échelle d’un modèle climatique, il apparaît que le risque d’inversion de courant dans le Val d’Orléans diminuerait dans le futur. La qualité des eaux souterraines resterait alors semblable à celle exposée pendant cette thèse, sans mélanges avec l’eau de surface provenant des inversions, et par conséquent sans dégradation manifeste de la ressource en eau du Val d’Orléans. / The aim of this study is the impact of climate change on groundwater quality in the Val of Orléans (France). First, geochemical studies made on Loire River and related spring with isotopic composition and major elements revealed a mixing between Loire river water and older karst water in the aquifer. Calcite precipitation and Fe-Hydroxydes formation in the karst play a major role on the behaviour and fate of trace elements. Then, geochemical studies on contaminants like pesticids and pharmaceuticals showed that their occurrence and behaviour vary for each component, according to : the capacity of adsorption on soil/sediment, the degradation rate in waste water treatment plant (for pharmaceuticals) and in natural waters, seasons and climatic conditions, mixing of Loire river water with residual waters in the karst. These chemical investigations allowed us to fix the groundwater quality during our samplings. The threat of local river backflow in the karst system can lead to a degradation of its quality, so the future occurrence of backflow events in the Val was calculated : using a link between backflow events and results of a climatic model downscaling, we found that these events would decrease in frequency in the future. Thus groundwater quality would remain stable, without mixing with contaminated local freshwaters.

Les cryptokarsts de Beez (Namur, Belgique) se sont développés au dépens de calcaires dolomitiques viséens, à la faveur de drains constitués par les filons sulfurés Fe-Pb-Zn, sous une couverture composée de pélites gréseuses viséo-namuriennes et de sables oligocènes. À Khamouda (Kasserine, Tunisie), les poches karstiques se sont développées suivant la stratification sub-horizontale des calcaires sénoniens de la Formation Douleb à partir d'une faille normale les mettant au contact de la couverture sableuse miocène (Formation Béglia). Dans les deux sites, des paragenèses riches et complexes s'installent aux interfaces entre encaissant carbonaté et remplissages karstiques. Des argilites blanches, principalement composées de phases silico-alumineuses et alumineuses, ainsi que des croûtes ferrugineuses sont toujours présentes. À Beez, l'argilite est constituée d'halloysite et de gibbsite. À Khamouda, elle s'enrichit de phases zincifères plus rares, telles que la sauconite, ainsi que d'un phyllosilicate à 7 Å et d'un hydroxyde de zinc amorphe. Des sulfates sont également néoformés, notamment du gypse, dissout par la suite mais dont les croûtes ferrugineuses comportent encore des indices, ainsi que de la jarosite à Beez. D'un point de vue fondamental, les systèmes cryptokarstiques, qui opposent une barrière carbonatée à la migration de fluides acides, sont des structures privilégiées pour l'étude et la compréhension de la migration et la fixation des éléments chimiques dans le domaine supergène. Dans les deux cas, les fluides météoriques acquièrent leur acidité (pH ~2 à Beez et pH~4 à Khamouda) par lessivage de la couverture sédimentaire sus-jacente et notamment par oxydation des sulfures qu'elle contient (pyrite à Beez, pyrite et sphalérite à Khamouda). Les principaux éléments mobilisés à Beez sont Si et Al et dans une moindre mesure Fe, Mn et les Terres Rares ; tandis qu'à Khamouda, les principaux éléments mobilisés sont Si, Al et Zn, et dans une moindre mesure Fe, Pb et les Terre Rares. La neutralisation des fluides au contact du mur carbonaté conduit dans un premier temps à la formation de sulfates (gypse, jarosite) et d'oxy-hydroxydes de fer, puis d'halloysite et d'hydroxydes d'aluminium à partir de pH 4,8-5,4. À Khamouda, les phases zincifères ne se forment que plus tardivement (pH < ~9,5). Dans les deux cas étudiés, nous avons mis en évidence l’évolution de phases minérales depuis des gels silico-alumineux jusqu’à des minéraux bien cristallisés, tels que l’halloysite, ou moins bien organisés, tels que certains oxydes de manganèse à Beez. Dans les deux gîtes, le microfaciès tubulaire de l'halloysite, correspondant à une croissance fissurale, prédomine par rapport au faciès sphéroïdal se développant habituellement au sein des masses de gel ; ce qui suggère une fracturation répétée des masses de gels précurseurs. Nous avons également établi que ces gels continuent à incorporer des cations des solutions percolantes, notamment du manganèse à Beez. La difficulté majeure de l'étude des altérations cryptokarstiques réside dans la détermination des âges des phénomènes. L'âge des couvertures sédimentaires impliquées dans les poches karstiques donne une première approximation. Ainsi, la phase majeure d'altération à Beez est post-oligocène suivie d'une réactivation quaternaire ; tandis que l'altération est post-miocène à Khamouda. Le site de Beez propose un éventail de minéralisations pouvant faire l'objet de datations radiométriques. Ces datations "absolues" doivent constituer une priorité forte à l'avenir. __________________________________________________________________________________________________ Résumé en anglais : The cryptokarsts from Beez (Namur, Belgium) were settled in dolomitic Visean limestones, in which vertical Fe-Pb-Zn sulphides veins play an important role as karstic drains. The sedimentary cover is made up of Viseo-Namurian siliceous shales and Oligocene sands. The cryptokarsts from Khamouda (Kasserine, Tunisia) were found in Senonian limestones (Douleb Formation). They expand from a down fault, which has brought limestones into contact with Miocene sands (Béglia Formation), following the sub-horizontal stratification. In both sites, complex paragenesis settled at the limestone/karst-filling interface. White clays, principaly composed of Si-Al and Al phases, and ferruginous crusts are the main paragenesis. In Beez, the white clays are made up of halloysite and gibbsite, while in Khamouda, they are enriched with uncommon zinciferous phases as sauconite (Zn-smectite), a 7Å-phyllosilicate and an amorphous Zn­hydroxide. Sulphates have also been found, as imprints of gypsum crystals in both sites, and as jarosite in Beez. Acid fluids percolated in the overlying sedimentary cover (pH~2 in Beez and pH~4 in Khamouda). The acidity is due to the oxidation of some sulphides (pyrite in Beez; pyrite and sphalerite in Khamouda). Cryptokarsts basically play an important role in chemical elements mobilization and trapping processes. In Beez, Si and Al have mainly been mobilized. Fe, Mn and the Rare Earth Elements (REE) have been mobilized too. In Khamouda, the main mobilized elements are Si, Al and Zn. Fe, Pb and REE have been mobilized too. The acid fluids are neutralized at the limestone karst-wall. It leads first to the neogenesis of sulphates (as gypsum and jarosite) and iron oxi-hydroxides (pH < 4,8). Then, halloysite and Al-oxi-hydroxides are formed (from pH~4,8-5,4 upward). In Khamouda, zinciferous phases developed lately (from pH~9,5 upward). In both studied systems, we clearly show the development of mineral phases from a Si-Al gel to well-crystallized minerals, as halloysite, or badly organized minerals, as some Mn-oxides from Beez. In both deposits, tubular halloysite, which usually develops in cracks, is prominent in comparison to spheroidal halloysite, which usually growths in gel masses. It suggests an extreme fracturing of the gel masses. We established that these gel masses mix cations from the percolating solutions. The main difficulty in cryptokarstic environments is to determine ages of weathering processes, nevertheless the age of overlying deposits give an idea. Thus, the major weathering stage in Beez is post-Oligocene (followed by a Quaternary reactivation), while weathering in Khamouda is post-Miocene. The cryptokarsts from Beez contain several mineral phases, which could be dated with radiometric methods. This "absolute" dating has to be the next step.

<p>The complex nature and composition of regolith cover in Southern Africa is a major challenge to geochemical mapping for concealed mineralization. Some of the setbacks to successful geochemical exploration may be ascribed to the use of various partial extraction techniques,without a profound understanding of the regolith components and their composition. This investigation therefore focuses on the use of hydroxylamine partial extraction geochemistry for geochemical mapping in regolith over two contrasting environments viz / aeolian sand-calcrete regolith over Au mineralization at Amalia Blue Dot Mine in South Africa and lateritic regolith covering the Ni-Cu deposit at Kabanga Main and Luhuma in Tanzania. Regolith samples from the above areas were sieved and extracted with hydroxylamine hydrochloride solution and analyzed for multi-element by AAS and ICP-MS techniques. A stepwise optimization of the hydroxylamine extraction technique of samples from both areas was carried out and incorporated into the analytical programme (in a pilot study). Results of hydroxylamine partial extraction generally gave better anomaly contrast and reflection of bedrock mineralization than the conventional aqua regia techniques that were previously used in the region. The results however show that lateritic regolith may be best extracted using 0.25M hydroxylamine while 0.1M concentration appears most suitable for extraction of aeolian-calcrete regolith. The above results are corroborated by principal component analysis of the analytical data that show various element associations, e.g. with Fe-Mn oxides while others possibly belong to the loosely adsorbed or exchangeable group. The&nbsp / gochemical maps in the pilot study areas at Amalia, Kabanga and Luhuma show elevated element contents or clusters of anomalies of diverse elements associated with Fe-Mn oxides. Geochemical mapping at Kabanga with deeply concealed mineralization however shows variability of subdued element patterns over mineralized areas. Geochemical signatures associated with hydroxylamine hydrochloride partial leach are therefore characterized by a lower geochemical background than that using conventional aqua regia leach. This study leads recommending for further investigations into partial extraction of the exchangeable group of elements, possibly using ammonium acetate.</p>

Obsidian was a prized tool stone heavily exploited in the Greater Yellowstone Ecosystem throughout the pre-contact period. Fifteen geochemically distinct sources in this area were utilized on a regular basis consistently through time. A large dataset of sourced obsidian artifacts currently exists but has rarely been applied to specific archaeological problems for Yellowstone National Park, Wyoming.<p> This thesis provides a comprehensive list of obsidian sources important to the archaeology of Yellowstone and analyzes spatial and temporal trends of obsidian source selection. This study examines diagnostic tools produced by people during the Archaic period, focusing on the McKean complex (~5500-3000 BP) and Pelican Lake phase (3000-1600 BP). The potential for a cultural preference for obsidian source selection is discussed by applying landscape theory and ethnographic evidence to the examination of archaeological data.<p> A pattern of obsidian source exploitation as seen at the Osprey Beach site (representing the Cody Complex) has led to the development of a proposed annual round, typically applied to the entire pre-contact period in the Park. This large annual round, however, is determined to be unlikely and unnecessary by this author. Alternative local rounds to this model are proposed and supported by the evidence.<p> A clear preference for the Obsidian Cliff source (a National Historic Landmark) located in the northern end of the Park is shown in these results. This preference can be interpreted in both economic and cultural terms. Otherwise, no purely cultural preference for an obsidian source is supported. The exploitation of certain obsidian sources did not change significantly between the McKean and Pelican Lake cultures. However, a significantly different pattern of exploitation is seen when analyzed by geographical area. The results of this research suggest a more localized pattern of obsidian exploitation than previously thought, impacting interpretations of seasonality and travel routes in the Yellowstone area.

<p>A great number of field measurements with different methods and instruments were conducted in attempts to develop a method for an optimal combination of various geochemical and geophysical methods in archaeological prospecting. The research presented in this thesis focuses on a study of how different anthropogenic changes in the ground can be detected by geochemical and geophysical mapping and how the results can be presented.</p><p>A six-year pilot project, Svealand in Vendel and Viking periods (SIV), was the beginning of this work in which EM- measurements, gradiometer and GPR surveys together with phosphate mapping succeeded in detecting settlements, mainly from the Iron Age. During the project, a new field kit for soil phosphate analysis was also developed and patented.</p><p>Another major project was the examination of the Kings’ Mounds in Old Uppsala where a multi method survey including two different slingrams, three different types of GPR equipments and two different gradiometers was used for detecting structures inside the mounds. The Thing Mound was interpreted not to be a burial mound. The layers indicated by the GPR survey are most probably natural glaciofluvial layers. At the Eastern Mound the measurements detected an excavation tunnel from 1846-47, some known old brick furnaces from the time of building of the church, the original esker surface and the central cairn. The survey also detected two linear structures from the mounds base to the top and a depression under the mound in the old esker. The linear structures were interpreted as possible boulder rows and the depression as a possible older burial preceding the construction of the mound.</p><p>Other surveys with slingram and GPR were used to detect subsurface features at historical gardens and historical glass works. A number of surveys to detect older church remnants were also carried out. In a project at Arethousa, Greek Macedonia, slingram measurements pointed out possible subsurface stonewalls and a possible hearth, which were confirmed later by excavations. At Old Uppsala, Sweden a GPR survey was successfully used for detecting the older cathedral under the present church.</p><p>The overall results led to a recommended concept of combined methods for archaeological prospecting, especially in northern Europe. Slingram measurements of both electrical and magnetic components combined with phosphate mapping and GPR surveys proved to be useful methods for such prospecting.</p>

Studying the mean state and variability of past climate provides important insight into the dynamically coupled climate system, directly aiding projections of future climate. Reconstruction of past climate conditions can be achieved using geochemical proxies including the novel clumped isotope paleothermometer. In this thesis I use multiple proxies to study climate variability during the last glacial period and at the onset of Antarctic glaciation. Greenland ice cores record repeated millennial-scale fluctuations in climate during the last glacial period known as Dansgaard-Oeschger (DO) cycles. We measure 18O of bulk sediment and planktonic foraminifera (Neogloboquadrina Pachyderma) in sediment cores from the North Atlantic to investigate fluctuations in sediment properties on the timescale of DO cycles. We find evidence of episodic deposition of carbonate ice-rafted debris near Iceland. Integrating these observations with published data and modeling studies, we propose a new hypothesis to explain DO cycles. We suggest that a large ice shelf in the Nordic Seas acted in concert with sea ice to set the slow and fast timescales of DO cycles. The ice shelf was periodically removed by subsurface warming with the timescale of shelf regrowth setting the duration of each interstadial. We utilize the clumped isotope proxy to reconstruct the climate history during a key period of the Cenozoic - the onset of Antarctic glaciation. To facilitate this work, a new inlet is developed to streamline sample preparation and reduce sample size requirements. We decrease the required sample size from 5-8mg to 1-2mg per replicate, while still achieving external precision of 0.005-0.010o/oo, equivalent to previous methods. This new capability increases the range of possible applications for the clumped isotope paleothermometer, specifically in the field of paleoceanography. We apply the clumped isotope paleothermometer to thermocline-dwelling foraminifera (Subbotina angiporoides and Subbotina utilisindex) from the Southern Ocean core ODP689 across the Eocene-Oligocene transition. With the clumped isotope paleothermometer we separate the contributions of near- surface temperature change and ice sheet growth on the ~1o/oo increase in 18O observed in planktonic foraminifera from this site. We measure no change in temperature, and 0.8±0.2o/oo change in 18Osw, equivalent to 124-140% of the modern Antarctic ice sheet volume. / Earth and Planetary Sciences

<p>The complex nature and composition of regolith cover in Southern Africa is a major challenge to geochemical mapping for concealed mineralization. Some of the setbacks to successful geochemical exploration may be ascribed to the use of various partial extraction techniques,without a profound understanding of the regolith components and their composition. This investigation therefore focuses on the use of hydroxylamine partial extraction geochemistry for geochemical mapping in regolith over two contrasting environments viz / aeolian sand-calcrete regolith over Au mineralization at Amalia Blue Dot Mine in South Africa and lateritic regolith covering the Ni-Cu deposit at Kabanga Main and Luhuma in Tanzania. Regolith samples from the above areas were sieved and extracted with hydroxylamine hydrochloride solution and analyzed for multi-element by AAS and ICP-MS techniques. A stepwise optimization of the hydroxylamine extraction technique of samples from both areas was carried out and incorporated into the analytical programme (in a pilot study). Results of hydroxylamine partial extraction generally gave better anomaly contrast and reflection of bedrock mineralization than the conventional aqua regia techniques that were previously used in the region. The results however show that lateritic regolith may be best extracted using 0.25M hydroxylamine while 0.1M concentration appears most suitable for extraction of aeolian-calcrete regolith. The above results are corroborated by principal component analysis of the analytical data that show various element associations, e.g. with Fe-Mn oxides while others possibly belong to the loosely adsorbed or exchangeable group. The&nbsp / gochemical maps in the pilot study areas at Amalia, Kabanga and Luhuma show elevated element contents or clusters of anomalies of diverse elements associated with Fe-Mn oxides. Geochemical mapping at Kabanga with deeply concealed mineralization however shows variability of subdued element patterns over mineralized areas. Geochemical signatures associated with hydroxylamine hydrochloride partial leach are therefore characterized by a lower geochemical background than that using conventional aqua regia leach. This study leads recommending for further investigations into partial extraction of the exchangeable group of elements, possibly using ammonium acetate.</p>