SECO Tools manufactures tool inserts for all types of metal cutting machining. (Ti,W)C is a common raw material used in the production. At arrival, the material (Ti,W)C is always analyzed. Titanium has previously been analysed with x-ray fluorescence spectrometry, but as the calibration has previously been performed with two different types of titanium (rutile and metallic titanium), the results has differed. Because of that, this thesis project has been devoted to analyze titanium, to find the best titanium compound for producing standards. The work has been performed using literature studies and many experiments in the laboratories at SECO Tools inFagersta,Sweden. This project has included about ten working weeks. In this report the analysis methods of x-ray fluorescence spectrometry and spectrophotometry is described, as the methods has been used in the experiments. A big problem that was discovered during this project was the big standard deviation of results for the method used for analysing titanium with x-ray fluorescence. Because of that, much time of this project has been devoted to experiments trying to reduce the standard deviation between the samples, as this is vital to performing a reliable calibration. A variety of experiments has been performed without reducing the standard deviation between the samples to below 0.2 % -units for the (Ti, W) C-samples.

This dissertation consists of three articles that develop and implement geoarchaeological approaches to the study of hominin biogeography in the Greek islands, a region that may have played a key role during the initial peopling of southeastern Europe in the Middle to Late Pleistocene (770 – 13 ka). The first article addresses the need to find Palaeolithic sites in the Greek islands by reviewing geoarchaeologically informed archaeological surveys that prioritize deposits – Pleistocene sediments and soils – on mainland Greece. I operationalize and implement a four-phase approach for future deposit-centered surveys in the islands. I conclude that future surveys should target geomorphic settings conducive to paleosol preservation, such as in near-shore coastal areas (e.g., uplifted hillslopes and actively eroding alluvial fans) marked by paleo-sea-level-indicators (sea notches, marine terraces, and aeolianites), as well as sediment depo-centers (e.g., internally drained basins) in non-coastal geomorphic settings. The second article develops and employs a multiscalar geoarchaeological approach for investigating and interpreting complex hillslope formation processes at the newly excavated Palaeolithic site of Stelida, located on the island of Naxos, Greece. Here, I integrate traditional geoarchaeological methods (lithostratigraphy, pedostratigraphy, allostratigraphy) with microarchaeological techniques, such as thin-section soil micromorphology and portable x-ray fluorescence spectroscopy (pXRF) to separate sediments and soils aiding in the construction of a stratigraphic framework for Stelida.The third article further develops the method of integrating pXRF and soil micromorphology applied at the site-specific scale. In this article, I developed an Exploratory Spatial Data Analysis (ESDA) method for visualizing geochemistry-facies relationships through the application of pXRF to a resin-impregnated block sample preserving an Archaic (seventh century BCE) ash midden (eschara) from the site of Kalopodi, Greece.This dissertation addresses a primary research effort in Greece’s Aegean Basin (Greek islands): the search for and study of Palaeolithic archaeology dating to Middle and Late Pleistocene. Geoarchaeologically informed research designs, such as deposit-centered surveys in open-air environments, can increase Palaeolithic site inventories for the region by focusing on finding geomorphic settings conducive to paleosol preservation. Moreover, the multi-scalar geoarchaeological approaches here, which integrate sedimentology, pedology, micromorphology, and geochemistry, provide an effective approach for the identification and compositional (mineralogic and geochemical) study of paleosols within those settings.

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The aim of this master's thesis has been to develop and optimize the method of UV- photochemical vapor generation of cadmium volatile compounds for atomic fluorescence spectrometry. Two configurations with different materials wrapped around the low-pressure mercury vapor lamp were tested. I experimentally determined optimal conditions for both systems; the optimalized parametres included selection of photochemical reagent and its concentration, flow rate of liquids and gases, and the lenghth of the reaction coil. After finding the optimal parametres I determined the figures of merit of the method. I found from the measured data that UV-photoreactor with the quartz capillary provided lower limits of detection and thus was more suitable for generation of cadmium volatile compounds. With this arrangement and using the ferrous sulphate heptahydrate as the chemical modifier I obtained limit of detection 2,0 µg·l-1 , limit of determination 7,0 µg·l-1 , linear dynamic rate LOD-50 µg·l-1 and repeatibility 0,35 %. I also carried out the interference study in my thesis and determined the generation effeciency of cadmium volatile compounds. The interference study shows the influence of mineral acids (HCl, H2SO4, HNO3), their salts (NaNO2, NaNO3) and transition metals (Co, Ni, Cu). Based on literature review I also...

Diss. (sammanfattning) Stockholm : Karol. inst., 2003. / Härtill 8 uppsatser.

For studies using lake sediments as a medium, understanding factors governing sediment distribution and properties is crucial for making accurate interpretations and conclusions. General lake sedimentation theory is however mainly based on larger lakes and systems, potentially leading to biased sampling and data interpretation when applied on a smaller system. In a paper published in 2008, Rippey et al. evaluated the fit of some general sedimentation theories on element distribution in the sediments of Kassjön (63°55´ N, 20°01´ E), northern Sweden. This small boreal lake reoccurs in the scientific literature, largely from paleolimnological studies on varved sediments in the lake, making the understanding of its sediment properties highly relevant. As part of a wider geochemical study on the lake, this paper scrutinizes the findings of Rippey et al. (2008) by using updated bathymetry and geochemical analyses, to provide further insight on sedimentation in Kassjön. Element composition, analysed with X-ray fluorescence spectrometry, and dry weight was obtained from sediment samples at 40 sites. Depth at sampling sites, together with catchment morphometry and previous bathymetry, was used to improve the bathymetric understanding. Kassjön was found to have a less steep bathymetry than previously assumed, with distribution of sediment geochemistry and dry weight showing heterogeneity differing from that expected of general sedimentation theories only. These results indicate that previous findings on sedimentation in Kassjön might be too simplistic, and that small-lake sedimentation is influenced by factors not included in general sedimentation models. Caution is therefore advised when e.g. interpreting the environmental record in lake sediments.

The aim of the Diploma thesis is to consider an influence of soil management (rotation of crops on arable land and grassland) to quantity and quality of humic substances. These properties are depended not only upon way of soil management, but also upon climatic effects, such are rainfall, temperature, elevation above sea-level, level of underground water and content of clay. Significantly influenced factors are content and form of organic carbon which is very tightly bonded to humic substances. In this work the humic acids content and properties progression was studied in given time period. Also the effect of crop rotations to changes of physical and chemical properties of humic acids in soil environment was observed. Diploma thesis was realized in co-operation with Mendel University in Brno, which supplied elaborating samples. Studied soil samples were taken from humus horizon Cambisol modal Vatín during years 1999–2006, always in autumn. Individual samples were characterized by available analytical methods, which are generally used in humic substances research area. They are especially fluorescence spectrometry, UV-VIS and infrared spectrometry and acid-base and conductometric titrations.

Methods were developed for the determination of methylmercury in natural waters and sediments based on steam distillation and aqueous phase ethylation followed by gas chromatography-atomic fluorescence spectrometry. The methods were shown to be free from measurable artefactual methylation of inorganic mercury and offered improved sample throughput over existing methods. Improvements were made to existing methods for the determination of total mercury in biota, sediments and natural waters and dissolved mercury species in natural waters. These methods were applied to the study of mercury cycling in two remote field sites. The cycling of mercury species was studied in Lake Murray in Western Province, Papua New Guinea, which has been historically noted as a region of high mercury concentrations in fish. Concentrations of methylmercury and total mercury in the water column were found to be variable and consistent with non-contaminated lake systems. Concentrations of methylmercury and total mercury in the sediments were also found to be low, except for in the south of the lake, which was influenced by an intermittent supply of water and sediments with elevated mercury concentrations from the Strickland River. Methylmercury concentrations in the sediments were generally higher in the backwater areas due to littoral processes. The low concentrations of methylmercury in the sediments and waters were inconsistent with other systems previously studied in the northern hemisphere, showing a link between high mercury concentrations in fish and high concentrations of methylmercury in waters or sediments. Therefore, the biota of Lake Murray were studied in order to account for the differences between this and other systems. A study was conducted of the stable isotope ratios of carbon and nitrogen in biota from Lake Murray to elucidate key food-web interactions. This study revealed that the dominant carbon source for fish in the lake is plankton, although algae and macrophytes may also be involved in the food-web. The methylmercury bioaccumulation factors between trophic levels were similar to those measured in temperate systems of the northern hemisphere. The high concentrations of methylmercury, observed in piscivorous fish, were shown to be a consequence of the complex food-web and the number of trophic levels in the food-chains. The cycling of mercury species was studied in Lake Gordon and Lake Pedder in southwest Tasmania, which has recently been identified as being in a region of high mercury concentrations in trout and eels. The concentrations of total mercury were found to be reasonably uniform in the waters of both lakes, spatially and temporally. The concentrations of methylmercury in the waters were seasonally variable, and were consistently lower in Lake Pedder than in Lake Gordon. Dilution of methylmercury concentrations by precipitation direct to the lake surface, probably accounts for the most of the difference in methylmercury concentrations between the lakes. Owing to the long residence time of water in Lake Gordon, this reservoir mixes inputs of water with varying methylmercury concentrations. Concentrations of total mercury and methylmercury in submerged soils were low and depth profiles of mercury species in the water column did not show evidence of a gradient of mercury concentrations due to releases from the sediments. The concentrations of methylmercury observed in the water column are consistent with the concentrations observed in the fish. A budget of the mercury inputs and outputs to Lake Gordon showed that in-lake processes and sources in the catchment areas both contributed significantly to the concentrations of methylmercury in the lake. The methylation of mercury in Lake Gordon appeared to mainly occur in the surface waters (< 10 m) and was not consistent with processes leading to the methylation of mercury at the oxic/anoxic boundary observed in seepage lakes in Wisconsin. The concentrations of total mercury and methylmercury in bogs in the catchment areas of Lakes Gordon and Pedder, were high and governed by the concentration of organic matter in the sediments. The processes involved in the supply of mercury species from the Lake Gordon and Lake Pedder catchments appear to be similar to those in drainage lakes in the temperate and boreal regions of the northern hemisphere. The formation of the Lake Gordon and Lake Pedder reservoirs appears to have had little impact on the mean annual concentrations of methylmercury released to the downstream environment.

Imitation of archeological artifacts or replacing the authentic ones with fake replicates is a universal problem / it is particularly important in Turkey for historical metal objects. Traditionally used visual inspection methods alone are not sufficient for the solution of contemporary problems. In this study, chemical characterization has been used to determine the differences between the authentic and fake objects. The non-destructive analyses were carried out by Portable X-ray Fluorescence Spectrometry (P-XRF). Silver Roman Coins (27 B.C. to 244 A.D.) were the objects handled in this research. In particular the concentrations of Zr, Pt, Pb and Bi were used for differentiation / it has been observed that the concentrations have different trends in the authentic and fake silver coins. In authentic coins the average Pb concentration was found to be 0.77%, while this value was 0.055% for the fake ones. Bi could be determined in 86% of the authentic coins while it could not be detected in any fake coin. It has been generally observed that the silver and copper concentrations could not be utilized in authenticity tests. Another approach was the use of Line Scanning Electron Microscopy-Energy Dispersive X-Ray Fluorescence Spectrometry (LSEM-EDX). Using LSEM-EDX technique, it was observed that the concentration changes near the interface between the matrix and the copper-rich locations exhibits difference behaviors for the authentic and fake objects. This difference is originated by the fact that a newly formed copper amalgam contains copper-rich phases while with extended time concentration changes at interfaces become more gradual or not detectable. Pearson correlation was used in order to elucidate the relations between the element concentrations determined by P-XRF. In order to see whether the authentic and silver fake coins can form separate groups, dendograms have been constructed utilizing SPSS 16.0 software and Euclidian Square Distance method. It has been observed that the authentic and fake coins can be successfully grouped when the proper statistical choices are used. It has been observed that these groups have significant differences using t-test. The selected and used technology is proposed for use by museums and entities keeping archaeological collections in order to prevent forgeries.

ABSTRACT DIFFERENTIATION AND CLASSIFICATION OF COUNTERFEIT AND REAL COINS BY APPLYING STATISTICAL METHODS Tansel, I&ccedil / ten M.Sc, Archaeometry Graduate Program Supervisor : Assist. Prof. Dr. Zeynep Isil Kalaylioglu Co-Supervisor : Prof. Dr. Sahinde Demirci June 2012, 105 pages In this study, forty coins which were obtained from Museum of Anatolian Civilizations (MAC) in Ankara were investigated. Some of those coins were real (twenty two coins) and the remaining ones (eighteen coins) were fake coins. Forty coins were Greek coins which were dated back to middle of the fifth century BCE and reign of Alexander the Great (323 &ndash / 336 BCE). The major aims of this study can be summarized as follow