Lacustrine sediments provide geochemical evidence of environmental change during the last millennium in southeastern Brazil

A 172 cm-long sediment core was collected from a small pristine lake situated within a centripetal drainage basin in a tropical karst environment (Ribeira River valley, southeastern Brazil) in order to investigate the paleoenvironmental record provided by the lacustrine geochemistry. Sediments derived from erosion of the surrounding cambisoils contain quartz, kaolinite, mica, chlorite and goethite. Accelerator mass spectroscopy (AMS) (14)C dating provided the geochronological framework. Three major sedimentary units were identified based on the structure and color of the sediments: Unit III from 170 to 140 cm (1030 +/- 60-730 +/- 60 yr BP), Unit II from 140 to 90 cm (730 +/- 60-360 +/- 60 yr BP) and Unit I from 90 to 0 cm (360 +/- 60-0 yr BP). Results of major and trace element concentrations were analysed through multivariate statistical techniques. Factor analysis provided three factors accounting for 72.4% of the total variance. F1 and F2 have high positive loadings from K, Ba, Cs, Rb, Sr, Sc, Th, light rare earth element (LREE), Fe, Cr, Ti, Zr, Hf and Ta, and high negative loadings from Mg, Co, Cu, Zn, Br and loss on ignition (LOI). F3, with positive loadings from V and non-metals As and Sb, accounts for a low percentage (9.7%) of the total variance, being therefore of little interpretative use. The profile distribution of F1 scores reveals negative values in Units I and III, and positive values in Unit II, meaning that K, Ba, Cs, Rb, Sr, Sc, Th, LREE, Fe, Cr, Ti, Zr, Hf and Ta are relatively more concentrated in Unit II, and Mg, Co, Cu, Zn and Br are relatively more abundant in Units I and III. The observed fluctuations in the geochemical composition of the sediments are consistent with slight variations of the erosion intensity in the catchment area as a possible response to variations of climatic conditions during the last millennium. (c) 2009 Elsevier GmbH. All rights reserved.

Iron oxyhydroxide nanostructured in montmorillonite clays: Preparation and characterization

Akaganeite is a very rare iron oxyhydroxide in nature. It can be obtained by many synthetic routes, but thermohydrolysis is the most common method reported in the literature. In this work, akaganeite-like materials were prepared through the thermohydrolysis of FeCl(3)center dot 6H(2)O in water and suspensions containing clay minerals. X-ray diffractometry (XRD), Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM) data show that the clays determine the crystal phase and size of the iron oxyhydroxide crystals. According to XRD and FTIR data, beta-FeO(OH) (akaganeite) is the main metal oxyhydroxide phase. Considering the small basal spacing (d(0 0 1)) displacement observed when comparing the XRD patterns of pristine clays with the composites containing beta-FeO(OH), the iron oxyhydroxide should be mostly located on the basal and edge surfaces of the clay minerals. UV-Vis electronic absorption spectra indicate that the preferred phase of the iron oxyhydroxide is determined by the nature of the clay minerals. (C) 2010 Elsevier Inc. All rights reserved.

Photocatalytic decomposition of methylene blue via Fenton mechanisms by silicon wafer doped with Au and Cu: a theoretical and experimental study

In this work, we studied the photocatalytic and the structural aspects of silicon wafers doped with Au and Cu submitted to thermal treatment. The materials were obtained by deposition of metals on Si using the sputtering method followed by fast heating method. The photocatalyst materials were characterized by synchrotron-grazing incidence X-ray fluorescence, ultraviolet-visible spectroscopy, X-ray diffraction, and assays of H(2)O(2) degradation. The doping process decreases the optical band gap of materials and the doping with Au causes structural changes. The best photocatalytic activity was found for thermally treated material doped with Au. Theoretical calculations at density functional theory level are in agreement with the experimental data.

Variabilidade espacial de atributos mineralógicos de um latossolo sob diferentes formas do relevo: I - mineralogia da fração argila

A distribuição dos minerais da fração argila depende de condições pedoambientais específicas. O estudo das relações entre atributos desses minerais e locais específicos de sua ocorrência na paisagem torna-se importante para o entendimento das relações entre a mineralogia e os demais atributos do solo. Este trabalho teve como objetivo avaliar os atributos cristalográficos, as razões Gt/(Gt+Hm) e Ct/(Ct+Gb) dos minerais da fração argila (hematita, goethita, caulinita e gibbsita) e o padrão de distribuição espacial destes em um Latossolo Vermelho eutroférrico sob cultivo de cana-de-açúcar há mais de 30 anos, com colheita no sistema cana crua. As amostras de solo foram coletadas nos pontos de cruzamento de uma malha, georreferenciados, com intervalos regulares de 10 m, e dimensão de 100 x 100 m, na profundidade de 0,2-0,4 m, totalizando 119 pontos, em uma área de 1 ha. As amostras de solos foram analisadas quimicamente. Posteriormente, a fração argila foi submetida à difração de raios X. Foram feitas as análises estatísticas e geoestatísticas dos atributos cristalográficos dos minerais analisados. Mapas de krigagem foram realizados para a visualização da variabilidade espacial dos atributos. Todos os atributos estudados apresentaram dependência espacial, e os atributos mineralógicos apresentaram-se relacionados com variações das formas do relevo. A gibbsita apresentou o maior diâmetro médio do cristal (DMC) entre os minerais da fração argila estudados, e a goethita foi o mineral que apresentou a maior variação do DMC e da largura à meia altura. Os maiores valores do DMC da goethita, hematita e gibbsita foram encontrados no compartimento II, caracterizado por uma área côncavo-convexa.

Mineralogy of the clay fraction of Alfisols in two slope curvatures: III - spatial variability

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Mineralogy of the clay fraction of alfisols in two slope curvatures: IV - spatial correlation with physical properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Variabilidade espacial de atributos mineralógicos de um latossolo sob diferentes formas do relevo: II - correlação espacial entre mineralogia e agregados

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Caracterização mineralógica de Latossolos em diferentes feições do relevo na região de Jaboticabal, SP

Different surface land form expressed by the relief can cause variations in soil properties in different magnitudes, depending mainly on a specific location in the landscape. Therefore, the objective of this study was to make the mineralogical characterization of Oxisols in different relief forms in the region of Jaboticabal, SP. Three trenches were opened in the convex, linear and concave landforms, done morphological description of the soil horizons and collected soil samples for physical, chemical and mineralogical characterization. It was found that the oxidic mineralogy is dependent on the type of landform, with the dominance of goethite on the concave landform and hematite on the linear landform. The desferrific clay minerals exhibited dominance of gibbsite in the concave, compared to convex and linear landforms that were dominated by the kaolinitic mineralogy.

A história do intemperismo na Província Borborema Oriental, Nordeste do Brasil: implicações paleoclimáticas e tectônicas

Until some years ago, weathering geochronology was primarily based on the K-Ar and 40Ar/39Ar dating of supergene minerals. Recent advances in the analysis of supergene goethite by the (U-Th)/He method expanded the number of suitable minerals for such purpose, as well as the time of application for weathering geochronology. This study represents the first systematic approach in Brazil, combining both the 40Ar/39Ar e (U-Th)/He methodologies to improve the knowledge on the weathering and the age of nonfossiliferous sediments. Supported by geologic and geomorphologic correlations, we identified different types of weathering profiles occurring in the interior and coastal areas of northeastern Brazil. These profiles were correlated to main regional geomorphological domains: the Borborema Plateau , the Sertaneja Depression , and the Coastal Cuestas and Plains, and respective planation surfaces, which study is fundamental to understand the landscape evolution of the northern portion of the eastern Borborema Province. The depth and stratigraphic organization of the weathering profiles in each of the geomorphological domains permitted to establish that: (i) the profiles on the highlands that cap the Borborema Surface are deeper (up to 100 m) and can be considered as typical lateritic profiles; (ii) on the lowlands that form the Sertaneja Surface , the weathering profiles are shallow and poorly developed (2-5 m deep); (iii) the profiles along the coastal area are moderately developed (up to 25 m deep), and are characterized by thick saprolites and mottle zones. Aiming to establish the timing of the evolution of northeastern Brazil, we studied 29 weathering profiles representing distinct topographic levels of the Borborema Province, from the highlands to the coast, through the analysis of 248 grains of supergene manganese oxides using laser step-heating 40Ar/39Ar geochronology. Additionally, we applied the (U-Th)/He method in 20 weathering profiles, by dating 171 grains of supergene iron oxides and hydroxides. Geochronological results for 248 grains of manganese oxides analyzed by the 40Ar/39Ar method indicate that the weathering profiles in the study area record the history of weathering from the Oligocene to the Pleistocene, with ages in the order of 31.4 ± 1.0 Ma to 0.8 ± 0.4 Ma. Dating of 171 grains of goethite by the (U-Th)/He method yielded ages ranging from 43.2 ± 4.3 Ma to 0.8 ± 0.1 Ma, suggesting the weathering processes last from the Eocene to the Pleistocene. The precipitation of supergene goethite in this interval confirms the age of the weathering processes identified from the manganese oxides record. 105 goethite grains from 8 different occurrences of the Barreiras Formation were dated by the (U-Th)/He method. Five grains collected from the cement in the Barreiras Formation sandstones, in the Lagoa Salgada and Rio do Fogo coastal cuestas, yielded ages of 17.6 ± 1.8 Ma, 17.3 ± 1.7 Ma, 16.3 ± 1.6 Ma, 16.2 ± 1.6 Ma and 13.6 ± 1.4 Ma. Results of 69 goethite grains from authigenic pisoliths collected in 7 different localities also yielded concordant ages, varying from 17.8 ± 1.8 to 7.5 ± 0.8 Ma. Results obtained from 31 detrital grains are concordant in 3 distinct localities (Lagoa Salgada, Praia da Garças e Ponta Grossa); they vary in the range of 43.2 ± 4.3 to 21.6 ± 2.2 Ma, and indicate that the maximum age for the Barreiras Formation deposition is around 22 Ma. 40Ar/39Ar results for 15 manganese oxides grains associated with the Barreiras Formation weathering profiles, in 3 different localities, vary from 13.1 ± 0.9 to 7.7 ± 0.4 Ma, in the same range of ages obtained by the (U-Th)/He method. The systematic application of the 40Ar/39Ar and (U-Th)/He methods, respectively for manganese oxides and goethites, show that the Barreiras Formation sediments were already deposited since ca. 17 Ma, and that the weathering processes were active until ca. 7 Ma ago. The ages obtained from manganese oxides collected in the Cenozoic basalts (Macau Formation) also reveal a weathering history between 19 and 7 Ma, pointing to hot and humid conditions during most of the Miocene. 40Ar/39Ar ages yielded by manganese oxides associated with the Serra do Martins Formation vary from 14.1 ± 0.4 to 10.5 ± 0.3 Ma. On the other hand, (U-Th)/He ages from iron oxides/hydroxides collected in the Serra do Martins Formation mesas vary from 20.0 ± 2.0 to 5.5 ± 0.6 Ma, indicating that those sediments are older than 20 Ma. 40Ar/39Ar and (U-Th)/He results produced in this study are in agreement with paleoclimatic interpretations based on stable isotopes and clay index values measured in the Atlantic Ocean sediments, validating the use of weathering geochronology to investigate paleoclimatic variations. The direct dating of the Barreiras Formation permitted, for the first time, confident inferences on the age of the brittle deformation recorded by this sedimentary unit in the Rio Grande do Norte and Ceará states. The first event, syn-deposition, occurred during the early Miocene; an younger event, related to the post-depositional deformation of the Barreiras Formation, is associated with tectonic activity from the very early Miocene to the Holocene. In agreement with data from other areas, results obtained in this study reveal that the depth and complexity of the weathering profiles reflect the time of exposition of such areas to the weathering agents close to the surface. However, there is no clear relationship between ages vs. altitude. The depth and the stratigraphic organization of weathering profiles in northeastern Brazil, contrary to the southeastern Brazil pattern, do not vary toward the coast. In our study area, field observations reveal the presence of ancient, thick and complex lateritic profiles preserved in the sedimentary mesas on the Borborema Plateau, as younger, narrow and incipient ones occur in the dissected areas. Geochronological results obtained for these profiles yielded older ages on the high altitudes, and younger ages in the lowlands, suggesting the scarp retreatment is the most reliable model to explain the regional landscape evolution. However, in the coastal lowlands, the relatively older ages obtained indicate that more complexes processes were involved in the modeling of the local relief

Caracterização química e mineralógica da incrustação em rede de ferro fundido e potencial de recuperação da capacidade hidráulica

The purpose of this work was to characterize chemical and mineralogical the water supply networks and to assess the hydraulic recovery on high-degraded pipe. Thus, the resistance (by pitometric essays), chemical analyses (ICP-MS and ICP-ES), mineralogical analysis (petrographic thin sections, X-ray difractometry and scanning electronic microscopy), hardness (Mohs scale) and simulations for pipe's change and rehabilitations scenarios were investigated (from Scenario 1 to 4). The results showed that the high-degraded pipe had a limited recovery (from 3,9 to 14,0 m(0,367).s(-1)). The deposits were formed by oxide and hydroxide of iron (magnetite and goethite), which are materials of high hardness (6 on Mohs scale). The simulations indicated the required power ratio (C-i/C-1) around 86.00, 1.00 and 0.02% in relation to present scenario.

Red Mud from Brazil: Thermal Behavior and Physical Properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Simulação geoestatística na caracterização espacial de óxidos de ferro em diferentes pedoformas

Os minerais da fração argila, goethita e hematita, são óxidos de ferro (Fe) indicadores pedoambientais com grande influência nos atributos físicos e químicos do solo. O conhecimento dos padrões espaciais desses óxidos auxilia a compreensão das interrelações de causa e efeito com os atributos do solo. Nesse sentido, a qualidade das estimativas espaciais produzidas pode alterar os resultados obtidos e, por consequência, as interpretações dos padrões espaciais obtidos. O presente estudo teve o objetivo de avaliar o desempenho dos métodos geoestatísticos de estimativas (KO) e simulações sequenciais gaussianas (SSG) na caracterização espacial de teores de óxidos de Fe, goethita (Gt) e hematita (Hm), em uma pedoforma côncava e outra convexa. Foram coletadas 121 amostras de solos em cada pedoforma de um Argissolo em pontos com espaçamentos regulares de 10 m. Os teores de óxidos de Fe foram obtidos por meio de difração de raios-X. Os dados foram submetidos a análises geoestatísticas por meio da modelagem do variograma e posterior interpolação por KO e SSG. A KO não refletiu a verdadeira variabilidade dos óxidos de Fe, hematita e goethita, demonstrando ser inapropriada para a caracterização espacial dos teores dos óxidos de Fe. Assim, o uso da SSG é preferível à krigagem quando a manutenção dos altos e baixos valores nas estimativas espaciais é necessária. O desempenho dos métodos geoestatísticos foi influenciado pelas pedoformas. Os mapas E-type devem ser recomendados em vez de mapas de KO para os óxidos de Fe, por serem ricos em detalhes e práticos na definição de zonas homogêneas para o manejo localizado em frente de KO, sobretudo em pedoforma côncava.

Mineralogical characterization of clays used in the structural ceramic industry in west of S. Paulo State, Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Podzolization as a deferralitization process: a study of an Acrisol-Podzol sequence derived from Palaeozoic sandstones in the northern upper Amazon Basin

Morphological, geochemical and mineralogical studies were carried out in a representative soil catena of the low-elevation plateaux of the upper Amazon Basin to interpret the steps and mechanisms involved in the podzolization of low-activity clay soils. The soils are derived from Palaeozoic sandstones. They consist of Hydromorphic Podzols under tree savannah in the depressions of the plateaux and predominantly of Acrisols covered by evergreen forest elsewhere.Incipient podzolization in the uppermost Acrisols is related to the formation of organic-rich A and Bhs horizons slightly depleted in fine-size particles by both mechanical particle transfer and weathering. Weathering of secondary minerals by organic acids and formation of organo-metallic complexes act simultaneously over short distances. Their vertical transfer is limited. Selective dissolution of aluminous goethite, then gibbsite and finally kaolinite favour the preferential cheluviation of first Fe and secondly Al. The relatively small amount of organo-metallic complexes produced is related to the quartzitic parent materials, and the predominance of Al over Fe in the spodic horizons is due to the importance of gibbsite in these low-activity clay soils.Morphologically well-expressed podzols occur in strongly iron-depleted topsoils of the depression. Mechanical transfer and weathering of gibbsite and kaolinite by organic acids is enhanced and leads to residual accumulation of sands. Organo-metallic complexes are translocated in strongly permeable sandy horizons and impregnate at depth the macro-voids of embedded soil and saprolite materials to form the spodic Bs and 2BCs horizons. Mechanical transfer of black particulate organic compounds devoid of metals has occurred later within the sandy horizons of the podzols. Their vertical transfer has formed well-differentiated A and Bh horizons. Their lateral removal by groundwater favours the development of an albic E horizon. In an open and waterlogged environment, the general trend is therefore towards the removal of all the metals that have initially accumulated as a response to the ferralitization process and have temporarily been sequestrated in organic complexes in previous stages of soil podzolization.

Magnetic properties of acicular ultrafine iron particles

Magnetic properties of acicular (similar to60 and similar to200 nm) iron particles, obtained by reduction of alumina-coated goethite particles, are reported. X-ray diffraction and Mossbauer spectroscopy showed that the particles consist of a alpha-Fe core and a thin surface layer of maghemite. Magnetization data indicated an improvement of similar to28% in the saturation magnetization, coercive field, and squareness for particles with similar to60 nm. This magnetic property enhancement of the present particles, whose size is 40% smaller than those commercially available, could result in a similar decrease of the bit-size for higher density of magnetic media.