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Summary Serpentinites from the northern Vermont were examined for the distribution and abundance of As. XRD and electron microprobe showed the samples are composed of antigorite, chromite, magnetite, and carbonate minerals (magnesite, dolomite, calcite). The concentration in As when the samples were dissolved in H3PO4 was 10% of the concentration in As when the samples were dissolved in concentrated HF/HNO3, suggesting that As is mainly incorporated in the structure of antigorite. X-ray absorption near-edge structure spectra showed that the As is As(III) in the samples. Extended X-ray absorption fine structure spectra suggested that the As has a tetrahedral coordination and is located in the Si-site in serpentine.

Summary Serpentinites from the northern Vermont were examined for the distribution and abundance of As. XRD and electron microprobe showed the samples are composed of antigorite, chromite, magnetite, and carbonate minerals (magnesite, dolomite, calcite). The concentration in As when the samples were dissolved in H3PO4 was 10% of the concentration in As when the samples were dissolved in concentrated HF/HNO3, suggesting that As is mainly incorporated in the structure of antigorite. X-ray absorption near-edge structure spectra showed that the As is As(III) in the samples. Extended X-ray absorption fine structure spectra suggested that the As has a tetrahedral coordination and is located in the Si-site in serpentine.

Arsenic (As), Chromium (Cr), and Copper (Cu) are ubiquitous in soils as a result of anthropogenic and geogenic processes. The fate of As, Cr, and Cu in the environment is largely governed by their speciation, which is influenced by soil physiochemical properties. This study investigated the influence of soil physiochemical properties and landscape position on As, Cr, and Cu concentration and speciation in soils adjacent to Chromated Copper Arsenate (CCA) treated lumber fence posts. Concentration gradients showed elevated total As and Cu adjacent to the three fence posts, which decreased with increasing distance from the posts. In addition, As and Cu had higher concentrations in the surface soil samples than the subsoil samples possibly due to enhanced weathering of the CCA treated posts at the surface. Concentrations of As, Cr, and Cu were similar among the Maury and Donerail silt loam, however, they were closer to the background concentration in the Newark silt loam, a partially hydric soil, indicating mobility of the metals. Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy indicates As(V) is the predominate species which is principally coordinated with Fe and Al whereas, Cu(II) is coordinated with soil organic matter. Overall, the use of CCA treated lumber as a metal source can help determine how soil properties influence mobility and speciation of As, Cr, and Cu across the soil landscape.

Summary Serpentinites from the northern Vermont were examined for the distribution and abundance of As. XRD and electron microprobe showed the samples are composed of antigorite, chromite, magnetite, and carbonate minerals (magnesite, dolomite, calcite). The concentration in As when the samples were dissolved in H3PO4 was 10% of the concentration in As when the samples were dissolved in concentrated HF/HNO3, suggesting that As is mainly incorporated in the structure of antigorite. X-ray absorption near-edge structure spectra showed that the As is As(III) in the samples. Extended X-ray absorption fine structure spectra suggested that the As has a tetrahedral coordination and is located in the Si-site in serpentine.

Thesis (Ph. D.)--University of Washington, 1997. / Vita. Includes bibliographical references (p. [153]-167).

Thesis (Ph. D.)--University of Washington, 1998. / Vita. Includes bibliographical references (p. [225]-236).

Thesis (Ph. D.)--University of Washington, 1998. / Vita. Includes bibliographical references (p. [139]-145).

Orientadores: Gustavo Fernandes Lopes, Eduardo Granado Monteiro da Silva / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-14T22:47:18Z (GMT). No. of bitstreams: 1 Fabbris_GilbertoFernandesLopes_M.pdf: 3782519 bytes, checksum: d66cd36be4756310d108388eaef23b5e (MD5) Previous issue date: 2009 / Resumo: Materiais multiferróicos apresentam pelo menos duas propriedades ferróicas na mesma temperatura: (anti) ferroeletricidade, (anti) ferromagnetismo, ou ferroelasticidade. Esses materiais têm atraído grande atenção da comunidade científica nos últimos anos devido às suas potenciais aplicações e ao complexo acoplamento entre suas propriedades, o que ainda não é bem compreendido. Neste trabalho, nos concentramos nos materiais multiferróicos da família RMn2O5, que possuem estrutura ortorrômbica com grupo espacial Pbam. Nestes compostos, a transição antiferromagnética acontece a ~40K e a ferroelétrica em torno de 39K para todos os membros da família. A ferroeletricidade vista nesse material é incompatível com o centro de simetria existente no grupo espacial Pbam. Resultados de EXAFS para o composto TbMn2O5 existentes na literatura indicam uma distribuição bimodal de Tb-O na primeira camada de coordenação. Este desdobramento da primeira camada de coordenação independe da temperatura e indica uma possível variação do grupo espacial Pbam. Tais resultados nos motivaram a empreender o estudo da estrutura local da família RMn2O5 a fim de entendermos a correlação entre a estrutura local e a natureza do íon R. Medidas do espectro de XAFS como função da temperatura foram realizadas na linha XAFS2 do Laboratório Nacional de Luz Síncrotron (LNLS). Foram realizadas varreduras na borda K do Mn e em torno da borda L3 dos íons R (Bi, Gd, Pr, Tb). Os resultados para a borda do manganês em todos os compostos indicam que os poliedros de MnO são rígidos. Já na borda do íon R há comportamentos distintos. Enquanto no composto com bismuto observamos uma possível vibração rígida dos poliedros de MnO, para os outros compostos estudados identificamos uma distorção rígida desses poliedros. O comportamento distinto do composto com Bi, em relação aos demais membros da família, parece estar relacionado ao lone pair do bismuto / Abstract: Multiferroic materials present, at the same temperature, at least two of the so-called ferroic properties: (anti) ferroelectricity, (anti) ferromagnetism and ferroelasticity. They have attracted great attention in the last few years due to their potential applications as well as from the basic science point of view, given the intricate coupling between their physical properties, which remains poorly understood. In this work, we have focused on the study of the RMn2O5 family multiferroic materials. Their crystalline structure belongs to the Pbam orthorhombic space group, with an antiferromagnetic and ferroelectric phase transition temperatures below 40 K and 39K, respectively. Such ferroelectric phase is incompatible with the inversion center of symmetry in the Pbam space group. Recently published EXAFS results for TbM n2O5 revealed a first coordination shell with a bimodal Tb-O bond length distribution. Such bond length splitting is temperature-independent and may be related to a change of the Pbam space group. Such results were our main motivation to undertake a systematic study of the local structure of the RMn2O5 multiferroic family, aiming at a better understanding the correlation between the ion R and the local structure. Mn K-Edge and R-ion L3 Edge (R=Bi, Gd, Pr, Tb) temperature-dependent XAFS measurements were performed at the Brazilian Synchrotron Light Laboratory XAFS2 beam line. Results for the Mn K-edge in all studied compounds reveal the Mn-O coordination polyhedral are rigid. The R-ion results reveal distinct behaviours. For the R=Bi compound, we identified that low energy Mn-O rigid unit vibrational modes are likely to be operative. For the other compounds, we have identified a rigid distortion of the Mn-O polyhedra. The distinct behavior of the BiMn2O5 seems to be related to the Bi 6s2 lone pair / Mestrado / Física da Matéria Condensada / Mestre em Física