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Made available in DSpace on 2014-10-09T12:54:08Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:09:21Z (GMT). No. of bitstreams: 1 12434.pdf: 5335647 bytes, checksum: a56abda29440b5de525348eee5d618da (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Quimica, Universidade de Sao Paulo - IQ/USP

Ever since the development of farming humans have been implicitly linked with the landscape. Influences include the manipulation of natural environments by woodland clearance, field developments and animal husbandry. Development can also be determined by the identification and distribution of soils developed and modified by the addition of organic and inorganic components. Anthropogenic or amended soils have been identified in many forms across north west Europe that retain distinctive physical and chemical indications of historical agrarian and settlement history. This thesis researched the on-site distribution of anthropogenic and amended soils across different landuse areas and identified and quantified a range of black carbonised particles in order to investigate their role in the soils ability to retain high elemental concentrations of manuring and elements associated with domestic activity and industrial processes. Three sites in contrasting environments were chosen for analysis; in Fair Isle, the Netherlands and Ireland on the basis of an excellent agararian and settlement history and previous analysis of anthropogenic soils. The fieldwork results showed extremly deep plaggen soils in the Netherlands but considerably shallower horizons of amended arable soils on Fair Isle and in Ireland contrary to previous analysis. There was however, clear evidence of a reduction in anthropogenic and amended soils with increased distance from the farm centres as a result of less manuring. The soil pH, organic matter, particle size, magnetic susceptibility and bulk elemental analysis results showed unexpected increases in the amended soils of Fair Isle and Ireland and reflected a similar manuring process. In the Netherlands the deep plaggen soils had very low results reflecting modern arable farming. The micromorphology results illustrated distinctive characteristics associated with localised manuring techniques. On Fair Isle and in Ireland the main organic manuring material was peat and burnt peat, whereas in the Netherlands the plaggen soils were predominantly composed of meadowland and heathland turf. At all three sites there was a large number of black carbonised and black amorphous inclusions and point counting and image analysis results showed a decrease with depth and distance from settlement nucleii mirroring the fieldwork observations. The elemental analysis conducted has proved to be an extremly useful tool for the identification of various forms of black carbon and for identifying the provenance of high elemental concentrations. The oxygen:carbon ratios confirmed the origins of organic components used in the development of the amended and anthropogenic soils and the elemental analysis showed that at each site over 80% of visually unidentifiable amorphous black carbon particles were heavily decomposed carbonised inclusions. Overall the elemental concentrations within the black carbonised particles was very low but this reflected the elemental results found in the bulk soils and the inclusions contained higher concentrations of P, Ca, K, Fe and Al and considerably lower concentrations of elements associated with domestic activity or industry Zn, Cu, Ba, Cr, As and Pb.

Laser Ablation - Inductively Coupled Plasma - Mass Spectrometry (LA-ICP-MS) is a powerful analytical technique for the direct elemental analysis of solid samples, with spatial resolution down to a few microns However, calibration remains the limiting factor in obtaining quantitative analysis by LA-ICP-MS for a wide range of sample types. No universal method exists as yet and the ones that are currently used tend to employ matrix-matched solid standards Matrix-matched solid standards are not available for many types of sample, such as polymers, biological materials, fluid inclusions, etc The need for a universal method of calibration that involves standards that are easy to prepare and suitable for any type of sample is required. Additional to matrix-matching, internal standards are widely used in LA-ICP-MS for quantitative analyses The internal standard compensates for the different ablation yields from the sample and the standard and for the laser shot to shot variation. Given that the use of an internal standard is required to obtain reliable results, the need for matrix-matching might be regarded as questionable This project has focused on the development and application of a new method of calibration for LA-ICP-MS. It involves the use of aqueous standards whose absorption characteristics are modified by the addition of a chromophore to the solution. Additives were selected for ablation with KrF excimer, and Nd.YAG lasers The influence of the additive concentration on the ablation yield was investigated for different laser energies. Response curves were obtained showing that as the additive concentration was increased, less energy was required to ablate the modified standard solutions efficiently. A general procedure was then defined for the preparation and use of the modified standard solutions for a given sample. The new method of calibration was used for the quantitative analysis of different sample types· low density polyethylene (LDPE), polyketone (PK), polyethylene thin film as well as gels contained in the thin film, and stainless steel. Investigations were carried out on the mechanism of ablation of the modified standard solutions. It appeared that the ablation proceeded by a three-step process leading ultimately to nebulisation of the bulk liquid.

Made available in DSpace on 2014-10-09T12:28:20Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:38Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:44:36Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:57:37Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:28:44Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:57:15Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP