Theoretical investigation of atomic and electronic structures of Ga(2)O(3)(ZnO)(6)

Transparent conducting oxides (TCO) are widely used in technological applications ranging from photovoltaics to thin-film transparent field-effect transistors. In this work we report a first-principles investigation, based on density-functional theory, of the atomic and electronic properties of Ga(2)O(3)(ZnO)(6) (GZO(6)), which is a promising candidate to be used as host oxide for wide band gap TCO applications. We identify a low-energy configuration for the coherent distribution of the Ga and Zn atoms in the cation positions within the experimentally reported orthorhombic GZO(6) structure. Four Ga atoms are located in four-fold sites, while the remaining 12 Ga atoms in the unit cell form four shared Ga agglomerates (a motif of four atoms). The Zn atoms are distributed in the remaining cation sites with effective coordination numbers from 3.90 to 4.50. Furthermore, we identify the natural formation of twin-boundaries in GZO(6), which can explain the zigzag modulations observed experimentally by high-resolution transmission electron microscopy in GZO(n) (n=9). Due to the intrinsic twin-boundary formation, polarity inversion in the ZnO tetrahedrons is present which is facilitated by the formation of the Ga agglomerates. Our analysis shows that the formation of fourfold Ga sites and Ga agglomerates are stabilized by the electronic octet rule, while the distribution of Ga atoms and the formation of the twin-boundary help alleviate excess strain. Finally we identify that the electronic properties of GZO(6) are essentially determined by the electronic properties of ZnO, i.e., there are slight changes in the band gap and optical absorption properties.

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in sediments from Hong Kong

Concentrations of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in 14 sediment samples collected from four sites in the Mai Po Marshes Nature Reserve (within a RAMSAR Site) and from another six sites in Victoria Harbour and along the Hong Kong coastline. Elevated levels of PCDDs, and particularly OCDD, were detectable in all samples collected from the Mai Po Marshes and five of the six sites. In contrast to PCDDs, PCDFs were mainly found in sediment samples collected from industrial areas (Kwun Tong and To Kwa Wan) in Victoria Harbour. PCDD/F levels and congener profiles in the samples from the Mai Po Marshes Nature Reserve in particular show strong similarities to those reported in studies which have attributed similar elevated PCDD concentrations to nonanthropogenic PCDD sources. (C) 2002 Elsevier Science Ltd. All rights reserved.

Transformation processes, pathways, and possible sources of distinctive polychlorinated dibenzo-p-dioxin signatures in sink environments

In recent years, studies on environmental samples with unusual dibenzo-p-dioxin (PCDD) congener profiles were reported from a range of countries. These profiles, characterized by a dominance of octachlorinated dibenzodioxin (OCDD) and relatively low in dibenzofuran (PCDF) concentrations, could not be attributed to known sources or formation processes. In the present study, the processes that result in these unusual profiles were assessed using the concentrations and isomer signatures of PCDDs from dated estuarine sediment cores in Queensland, Australia. Increases in relative concentrations of lower chlorinated PODS and a relative decrease of OCDD were correlated with time of sediment deposition. Preferred lateral, anaerobic dechlorination of OCDD represents a likely pathway for these changes. In Queensland sediments, these transformations result in a distinct dominance of isomers fully chlorinated in the 1,4,6,9-positions (1,4-patterns), and similar 1,4-patterns were observed in sediments from elsewhere. Consequently, these environmental samples may not reflect the signatures of the original source, and a reevaluation of source inputs was undertaken. Natural formation of PCDDs, which has previously been suggested, is discussed; however, based on the present results and literature comparisons, we propose an alternative scenario. This scenario hypothesizes that an anthropogenic PCDD precursor input (e.g. pentachlorophenol) results in the contamination. These results and hypothesis imply further investigations are warrented into possible anthropogenic sources in areas where natural PCDD formation has been suggested.

Investigations into the PCDD contamination of topsoil, river sediments and kaolinite clay in Queensland, Australia

Recent findings of elevated PCDDs from an unknown source in the coastal marine environment of Queensland, Australia has instigated further investigations into the distribution of, and environments associated with the PCDD contamination. This study presents data for OCDD concentrations in the coastal, mountainous and inland environment of Queensland. Additionally, full 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofuran (PCDD/F) profiles from different land-use types and environments in the coastal region were analysed. Distinct east-west gradients were detected in topsoil collected from various bushland regions with elevated OCDD concentrations confined to the coastal region. However, PCDD/F results from topsoil and river sediments collected in the Queensland coastal region suggest that elevated OCDD concentrations cannot be attributed to any of the environments, land-use or industry types investigated. PCDD/F congener profiles from select samples were remarkably similar to those previously described in marine sediments collected along the entire Queensland coastline. In addition, kaolinite clay samples from Queensland exhibited elevated OCDD concentrations, and PCDD/F profiles in these samples were similar to those detected in kaolinite clays elsewhere. Natural formation processes have been hypothesised as the source of elevated PCDDs in Queensland and other locations, where similar PCDD/F profiles and the general lack of anthropogenic sources are evident. This study presents additional data supporting this hypothesis and provides further information that may assist in the identification of the processes involved in the natural formation of PCDDs. (C) 2002 Elsevier Science Ltd. All rights reserved.

Microbial respiration with chlorine oxyanions: diversity and physiological and biochemical properties of chlorate- and perchlorate-reducing microorganisms

Chlorine oxyanions are valuable electron acceptors for microorganisms. Recent findings have shed light on the natural formation of chlorine oxyanions in the environment. These suggest a permanent introduction of respective compounds on Earth, long before their anthropogenic manufacture. Microorganisms that are able to grow by the reduction of chlorate and perchlorate are affiliated with phylogenetically diverse lineages, spanning from the Proteobacteria to the Firmicutes and archaeal microorganisms. Microbial reduction of chlorine oxyanions can be found in diverse environments and different environmental conditions (temperature, salinities, pH). It commonly involves the enzymes perchlorate reductase (Pcr) or chlorate reductase (Clr) and chlorite dismutase (Cld). Horizontal gene transfer seems to play an important role for the acquisition of functional genes. Novel and efficient Clds were isolated from microorganisms incapable of growing on chlorine oxyanions. Archaea seem to use a periplasmic Nar-type reductase (pNar) for perchlorate reduction and lack a functional Cld. Chlorite is possibly eliminated by alternative (abiotic) reactions. This was already demonstrated for Archaeoglobus fulgidus, which uses reduced sulfur compounds to detoxify chlorite. A broad biochemical diversity of the trait, its environmental dispersal, and the occurrence of relevant enzymes in diverse lineages may indicate early adaptations of life toward chlorine oxyanions on Earth.

Biosynthesis of panaxynol and panaxydol in Panax ginseng

The natural formation of the bioactive C17-polyacetylenes (−)-(R)-panaxynol and panaxydol was analyzed by 13C-labeling experiments. For this purpose, plants of Panax ginseng were supplied with 13CO2 under field conditions or, alternatively, sterile root cultures of P. ginseng were supplemented with [U-13C6]glucose. The polyynes were isolated from the labeled roots or hairy root cultures, respectively, and analyzed by quantitative NMR spectroscopy. The same mixtures of eight doubly 13C-labeled isotopologues and one single labeled isotopologue were observed in the C17-polyacetylenes obtained from the two experiments. The polyketide-type labeling pattern is in line with the biosynthetic origin of the compounds via decarboxylation of fatty acids, probably of crepenynic acid. The 13C-study now provides experimental evidence for the biosynthesis of panaxynol and related polyacetylenes in P. ginseng under in planta conditions as well as in root cultures. The data also show that 13CO2 experiments under field conditions are useful to elucidate the biosynthetic pathways of metabolites, including those from roots.

Biosynthesis of panaxynol and panaxydol in Panax ginseng

The natural formation of the bioactive C17-polyacetylenes (−)-(R)-panaxynol and panaxydol was analyzed by 13C-labeling experiments. For this purpose, plants of Panax ginseng were supplied with 13CO2 under field conditions or, alternatively, sterile root cultures of P. ginseng were supplemented with [U-13C6]glucose. The polyynes were isolated from the labeled roots or hairy root cultures, respectively, and analyzed by quantitative NMR spectroscopy. The same mixtures of eight doubly 13C-labeled isotopologues and one single labeled isotopologue were observed in the C17-polyacetylenes obtained from the two experiments. The polyketide-type labeling pattern is in line with the biosynthetic origin of the compounds via decarboxylation of fatty acids, probably of crepenynic acid. The 13C-study now provides experimental evidence for the biosynthesis of panaxynol and related polyacetylenes in P. ginseng under in planta conditions as well as in root cultures. The data also show that 13CO2 experiments under field conditions are useful to elucidate the biosynthetic pathways of metabolites, including those from roots.

Evaluación geoecológica de los paisajes del Departamento Minas (Provincia de Neuquén), para el estudio de la degradación de la tierra

Las sociedades en su afán de aprovechar los recursos naturales que la tierra le provee, han ido transformando permanentemente el medio que habitamos, generando una crisis ambiental que es tema de preocupación y permanente discusión en organismos, foros y conferencias relacionados con el cuidado y protección del medio ambiente. En las regiones áridas y semiáridas uno de los problemas ambientales más comunes es la degradación de tierras por efecto del sobrepastoreo. La tercera parte de la superficie terrestre del planeta es árida y semiárida y en ella los procesos de desertización se han intensificado en los últimos decenios. Según la Convención de las Naciones Unidas de lucha contra la Desertificación (CNULD), este problema amenaza al 40 por ciento aproximadamente, de la masa terrestre de nuestro planeta. Más de 1000 millones de personas en alrededor de 100 países están afectadas directamente por la desertificación o corren peligro de estarlo (CNULD, 2003), estimándose que "la pérdida de ingresos en las áreas afectadas alcanza a unos 42.000 millones de dólares". Argentina en general y la Patagonia en particular, no son ajenas a esta situación. La Secretaría de Recursos Naturales y Medio Ambiente Humano (1996), calcula que aproximadamente el 75 por ciento de nuestro territorio nacional se encuentra afectado por crecientes condiciones de aridez y en la Patagonia, el 90 por ciento de la superficie (unos 780.000 km2) presenta signos de degradación. De esta superficie, un 30 por ciento, está bajo procesos erosivos eólicos e hídricos severos o graves con tendencia a agravarse. Teniendo en cuenta esta situación, esta tesis tiene como propósito aplicar las concepciones metodológicas de la geoecología de los paisajes en el Departamento Minas (Provincia de Neuquén), con vistas a estudiar la estructura y funcionamiento de los paisajes, herramienta fundamental para comprender el fenómeno de la degradación de la tierra. El objetivo central de este trabajo consiste en estudiar la degradación de los paisajes de este lugar a partir de los preceptos de la geoecología, con apoyo de los Sistemas de Información Geográfica y la teledetección, estableciendo índices diagnósticos que reflejen la interacción e interdependencia entre los componentes naturales y sociales del paisaje. El estudio de los paisajes brinda la posibilidad de integrar transdisciplinariamente los conocimientos y percepciones de la diversidad geoecológica y socioeconómica desde una perspectiva dinámica. Mediante este análisis se puede arribar al conocimiento de las formas de ocupación y conservación de los recursos naturales procurando la protección de la oferta ecológica a largo plazo. El paisaje geográfico o geosistema se concibe como "un sistema espacio-temporal, complejo y abierto, que se origina y evoluciona justamente en la interfase naturaleza-sociedad, en un constante estado de intercambio de energía, materia e información, donde su estructura, funcionamiento, dinámica y evolución reflejan la interacción entre los componentes naturales (abióticos y bióticos), técnico-económicos y socio-culturales (Mateo, J. 1991; Salinas. E. 1991y 1997). Se trata de una formación socio-natural que constituye una categoría científica y como tal, será adoptada en este trabajo.

Evaluación geoecológica de los paisajes del Departamento Minas (Provincia de Neuquén), para el estudio de la degradación de la tierra

Las sociedades en su afán de aprovechar los recursos naturales que la tierra le provee, han ido transformando permanentemente el medio que habitamos, generando una crisis ambiental que es tema de preocupación y permanente discusión en organismos, foros y conferencias relacionados con el cuidado y protección del medio ambiente. En las regiones áridas y semiáridas uno de los problemas ambientales más comunes es la degradación de tierras por efecto del sobrepastoreo. La tercera parte de la superficie terrestre del planeta es árida y semiárida y en ella los procesos de desertización se han intensificado en los últimos decenios. Según la Convención de las Naciones Unidas de lucha contra la Desertificación (CNULD), este problema amenaza al 40 por ciento aproximadamente, de la masa terrestre de nuestro planeta. Más de 1000 millones de personas en alrededor de 100 países están afectadas directamente por la desertificación o corren peligro de estarlo (CNULD, 2003), estimándose que "la pérdida de ingresos en las áreas afectadas alcanza a unos 42.000 millones de dólares". Argentina en general y la Patagonia en particular, no son ajenas a esta situación. La Secretaría de Recursos Naturales y Medio Ambiente Humano (1996), calcula que aproximadamente el 75 por ciento de nuestro territorio nacional se encuentra afectado por crecientes condiciones de aridez y en la Patagonia, el 90 por ciento de la superficie (unos 780.000 km2) presenta signos de degradación. De esta superficie, un 30 por ciento, está bajo procesos erosivos eólicos e hídricos severos o graves con tendencia a agravarse. Teniendo en cuenta esta situación, esta tesis tiene como propósito aplicar las concepciones metodológicas de la geoecología de los paisajes en el Departamento Minas (Provincia de Neuquén), con vistas a estudiar la estructura y funcionamiento de los paisajes, herramienta fundamental para comprender el fenómeno de la degradación de la tierra. El objetivo central de este trabajo consiste en estudiar la degradación de los paisajes de este lugar a partir de los preceptos de la geoecología, con apoyo de los Sistemas de Información Geográfica y la teledetección, estableciendo índices diagnósticos que reflejen la interacción e interdependencia entre los componentes naturales y sociales del paisaje. El estudio de los paisajes brinda la posibilidad de integrar transdisciplinariamente los conocimientos y percepciones de la diversidad geoecológica y socioeconómica desde una perspectiva dinámica. Mediante este análisis se puede arribar al conocimiento de las formas de ocupación y conservación de los recursos naturales procurando la protección de la oferta ecológica a largo plazo. El paisaje geográfico o geosistema se concibe como "un sistema espacio-temporal, complejo y abierto, que se origina y evoluciona justamente en la interfase naturaleza-sociedad, en un constante estado de intercambio de energía, materia e información, donde su estructura, funcionamiento, dinámica y evolución reflejan la interacción entre los componentes naturales (abióticos y bióticos), técnico-económicos y socio-culturales (Mateo, J. 1991; Salinas. E. 1991y 1997). Se trata de una formación socio-natural que constituye una categoría científica y como tal, será adoptada en este trabajo.

Evaluación geoecológica de los paisajes del Departamento Minas (Provincia de Neuquén), para el estudio de la degradación de la tierra

Las sociedades en su afán de aprovechar los recursos naturales que la tierra le provee, han ido transformando permanentemente el medio que habitamos, generando una crisis ambiental que es tema de preocupación y permanente discusión en organismos, foros y conferencias relacionados con el cuidado y protección del medio ambiente. En las regiones áridas y semiáridas uno de los problemas ambientales más comunes es la degradación de tierras por efecto del sobrepastoreo. La tercera parte de la superficie terrestre del planeta es árida y semiárida y en ella los procesos de desertización se han intensificado en los últimos decenios. Según la Convención de las Naciones Unidas de lucha contra la Desertificación (CNULD), este problema amenaza al 40 por ciento aproximadamente, de la masa terrestre de nuestro planeta. Más de 1000 millones de personas en alrededor de 100 países están afectadas directamente por la desertificación o corren peligro de estarlo (CNULD, 2003), estimándose que "la pérdida de ingresos en las áreas afectadas alcanza a unos 42.000 millones de dólares". Argentina en general y la Patagonia en particular, no son ajenas a esta situación. La Secretaría de Recursos Naturales y Medio Ambiente Humano (1996), calcula que aproximadamente el 75 por ciento de nuestro territorio nacional se encuentra afectado por crecientes condiciones de aridez y en la Patagonia, el 90 por ciento de la superficie (unos 780.000 km2) presenta signos de degradación. De esta superficie, un 30 por ciento, está bajo procesos erosivos eólicos e hídricos severos o graves con tendencia a agravarse. Teniendo en cuenta esta situación, esta tesis tiene como propósito aplicar las concepciones metodológicas de la geoecología de los paisajes en el Departamento Minas (Provincia de Neuquén), con vistas a estudiar la estructura y funcionamiento de los paisajes, herramienta fundamental para comprender el fenómeno de la degradación de la tierra. El objetivo central de este trabajo consiste en estudiar la degradación de los paisajes de este lugar a partir de los preceptos de la geoecología, con apoyo de los Sistemas de Información Geográfica y la teledetección, estableciendo índices diagnósticos que reflejen la interacción e interdependencia entre los componentes naturales y sociales del paisaje. El estudio de los paisajes brinda la posibilidad de integrar transdisciplinariamente los conocimientos y percepciones de la diversidad geoecológica y socioeconómica desde una perspectiva dinámica. Mediante este análisis se puede arribar al conocimiento de las formas de ocupación y conservación de los recursos naturales procurando la protección de la oferta ecológica a largo plazo. El paisaje geográfico o geosistema se concibe como "un sistema espacio-temporal, complejo y abierto, que se origina y evoluciona justamente en la interfase naturaleza-sociedad, en un constante estado de intercambio de energía, materia e información, donde su estructura, funcionamiento, dinámica y evolución reflejan la interacción entre los componentes naturales (abióticos y bióticos), técnico-económicos y socio-culturales (Mateo, J. 1991; Salinas. E. 1991y 1997). Se trata de una formación socio-natural que constituye una categoría científica y como tal, será adoptada en este trabajo.

Uppermost Limit, Extent, and Fluctuations of the Timberline and Treeline Ecocline in the Swiss Central Alps during the past 11,500 Years

Pollen and macrofossils were analyzed at two sites above today's treeline (or tree limit) in the Swiss Central Alps (Gouillé Loéré, 2503 m a.s.l., and Lengi Egga, 2557 m a.s.l.) to test two contrasting hypotheses about the natural formation of timberline (the upper limit of closed forest) in the Alps. Our results revealed that Pinus cembra--Larix decidua forests near timberline were rather closed between 9000 and 2500 B.C. (9600-4000 ¹⁴C yr BP), when timberline fluctuations occurred within a belt 100-150 m above today's tree limit. The treeline ecocline above timberline was characterized by the mixed occurrence of tree, shrub, dwarf-shrub, and herbaceous species, but it did not encompass more than 100-150 altitudinal meters. The uppermost limit reached by timberline and treeline during the Holocene was ca. 2420 and 2530 m, respectively, i.e., about 120 to 180 m higher than today. Between 3500 and 2500 B.C. (4700-4000 ¹⁴C yr BP) timberline progressively sank by about 300 m, while treeline was lowered only ca. 100 m. This change led to an enlargement of the treeline-ecocline belt (by ca. 300 m) after 2500 B.C. (4000 ¹⁴C yr BP). Above the treeline ecocline, natural meadows dominated by dwarf shrubs (e.g., Salix herbacea) and herbaceous species (e.g., Helianthemum, Taraxacum, Potentialla, Leontodon t., Cerastium alpinum t., Cirsium spinosissimum, Silene exscapa t., and Saxifraga stellaris) have been present since at least 11,000 cal yr ago. In these meadows tree and tall shrub species (>0.5 m) never played a major role. These results support the conventional hypothesis of a narrow ecocline with rather sharp upper timberline and treeline boundaries and imply that today's treeless alpine communities in the Alps are close to a natural stage. Pollen (percentages and influx), stomata, and charcoal data may be useful for determining whether or not a site was treeless. Nevertheless, a reliable and detailed record of past local vegetation near and above timberline is best achieved through the inclusion of macrofossil analysis.

Influence of crust formation under natural rain on physical attributes of soils with different textures

One of the main negative anthropic effects on soil is the formation of crusts, resulting in soil degradation. This process of physical origin reduces soil water infiltration, causing increased runoff and consequently soil losses, water erosion and/or soil degradation. The study and monitoring of soil crusts is important for soil management and conservation, mainly in tropical regions where research is insufficient to explain how soil crusts are formed and how they evolve. The purpose of this study was to monitor these processes on soils with different particle size distributions. Soil crusts on a sandy/sandy loam Argissolo Vermelho-Amarelo (Typic Hapludult), sandy loam Latossolo Vermelho-Amarelo (Typic Hapludox) and a clayey Nitossolo Vermelho eutroférrico (Rhodic Kandiudalf) were monitored. The soil was sampled and data collected after 0, 3, 5 and 10 rain storms with intensities above 25 mm h-1, from December 2008 to May 2009. Soil chemical and particle size distribution analysis were performed. The changes caused by rainfall were monitored by determining the soil roughness, hydraulic conductivity and soil water retention curves and by micromorphological analysis. Reduced soil roughness and crust formation were observed for all soils during the monitored rainfall events. However, contrary to what was expected according to the literature, crust formation was not always accompanied by reductions in total porosity, hydraulic conductivity and soil water retention.

Natural resources, redistribution and Human capital formation

How do resource booms affect human capital accumulation? We exploit time and spatial variation generated by the commodity boom across local governments in Peru to measure the effect of natural resources on human capital formation. We explore the effect of both mining production and tax revenues on test scores, finding a substantial and statistically significant effect for the latter. Transfers to local governments from mining tax revenues are linked to an increase in math test scores of around 0.23 standard deviations. We find that the hiring of permanent teachers as well as the increases in parental employment and improvements in health outcomes of adults and children are plausible mechanisms for such large effect on learning. These findings suggest that redistributive policies could facilitate the accumulation of human capital in resource abundant developing countries as a way to avoid the natural resources curse.

Fidelity of molluscan assemblages from the touro passo formation (pleistocene-holocene), southern brazil: taphonomy as a tool for discovering natural baselines for freshwater communities

This study is the first assessment of mollusk fossil assemblages relative to the compositional fidelity of modern mollusk living and death assemblages. It also shows that the sedimentary record can provide information on the original, non-human-impacted, freshwater malacofauna biodiversity, based on Late Pleistocene shells. The fossil mollusk assemblage from the Touro Passo Formation (Pleistocene-Holocene) was compared to living and death assemblages of the Touro Passo River, southern Brazil, revealing little resemblance between fossil and live-dead species composition. Although the living and death assemblages agree closely in richness, species composition, and species relative abundances (both proportional and rank), the fossil assemblage differs significantly from both modern assemblages in most of these measures. The fossil assemblage is dominated by the native endemic corbiculid bivalve Cyanocyclas limosa and the gastropod Heleobia aff. bertoniana. These are absent in the living assemblages, and both living and death assemblages are dominated by the alien Asiatic corbiculid C. fluminea, which is absent in the fossil assemblage. The fossil assemblage also contains, overall, a higher proportional abundance of relatively thick-shelled species, suggesting a genuine bias against the thinner- and smaller-shelled species. Our results suggest that contemporary environmental changes, such as the introduction of some alien freshwater mollusk species, together with post-burial taphonomic processes, are the main factors leading to the poor fidelity of the fossil assemblage studied. Hence, the taxonomic composition of the Late Pleistocene mollusks from the Touro Passo Formation probably would show greater similarity to present-day assemblages wherever the mollusk biodiversity is not disturbed by human activities.