Enhanced iron gettering by short, optimized low-temperature annealing after phosphorus emitter diffusion for industrial silicon solar cell processing

The introduction of a low-temperature (LT) tail after P emitter diffusion was shown to lead to considerable improvements in electron lifetime and solar cell performance by different researchers. So far, the drawback of the investigated extended gettering treatments has been the lack of knowledge about optimum annealing times and temperatures and the important increase in processing time. In this manuscript, we calculate optimum annealing temperatures of Fe-contaminated Si wafers for different annealing durations. Subsequently, it is shown theoretically and experimentally that a relatively short LT tail of 15 min can lead to a significant reduction of interstitial Fe and an increase in electron lifetime. Finally, we calculate the potential improvement of solar cell efficiency when such a short-tail extended P diffusion gettering is included in an industrial fabrication process.

Bioavailability and extraction of heavy metals from contaminated soil by Atriplex halimus

Pot experiments were performed to evaluate the phytoremediation capacity of plants of Atriplex halimus grown in contaminated mine soils and to investigate the effects of organic amendments on the metal bioavailability and uptake of these metals by plants. Soil samples collected from abandoned mine sites north of Madrid (Spain) were mixed with 0, 30 and 60 Mg ha?1 of two organic amendments, with different pH and nutrients content: pine-bark compost and horse- and sheep-manure compost. The increasing soil organic matter content and pH by the application of manure amendment reduced metal bioavailability in soil stabilising them. The proportion of Cu in the most bioavailable fractions (sum of the water-soluble, exchangeable, acid-soluble and Fe?Mn oxides fractions) decreased with the addition of 60 Mg ha?1 of manure from 62% to 52% in one of the soils studied and from 50% to 30% in the other. This amendment also reduced Zn proportion in water-soluble and exchangeable fractions from 17% to 13% in one of the soils. Manure decreased metal concentrations in shoots of A. halimus, from 97 to 35 mg kg?1 of Cu, from 211 to 98 mg kg?1 of Zn and from 1.4 to 0.6 mg kg?1 of Cd. In these treatments there was a higher plant growth due to the lower metal toxicity and the improvement of nutrients content in soil. This higher growth resulted in a higher total metal accumulation in plant biomass and therefore in a greater amount of metals removed from soil, so manure could be useful for phytoextraction purposes. This amendment increased metal accumulation in shoots from 37 to 138 mg pot?1 of Cu, from 299 to 445 mg pot?1 of Zn and from 1.8 to 3.7 mg pot?1 of Cd. Pine bark amendment did not significantly alter metal availability and its uptake by plants. Plants of A. halimus managed to reduce total Zn concentration in one of the soils from 146 to 130 mg kg?1, but its phytoextraction capacity was insufficient to remediate contaminated soils in the short-to-medium term. However, A. halimus could be, in combination with manure amendment, appropriate for the phytostabilization of metals in mine soils.

Bioaccessibility of metals and human health risk assessment in community urban gardens

Pseudo-total (i.e. aqua regia extractable) and gastric-bioaccessible (i.e. glycine + HCl extractable) concentrations of Ca, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn were determined in a total of 48 samples collected from six community urban gardens of different characteristics in the city of Madrid (Spain). Calcium carbonate appears to be the soil property that determines the bioaccessibility of a majority of those elements, and the lack of influence of organic matter, pH and texture can be explained by their low levels in the samples (organic matter) or their narrow range of variation (pH and texture). A conservative risk assessment with bioaccessible concentrations in two scenarios, i.e. adult urban farmers and children playing in urban gardens, revealed acceptable levels of risk, but with large differences between urban gardens depending on their history of land use and their proximity to busy areas in the city center. Only in a worst-case scenario in which children who use urban gardens as recreational areas also eat the produce grown in them would the risk exceed the limits of acceptability

Availability and uptake of trace elements in a forage rotation under conservation and plough tillage

After 14 years under conventional plough tillage (CT) or conservation minimum tillage (MT), the soil available Al, Fe, Mn, Cu and Zn (0-5, 5-15 and 15-30 cm layers) and their plant uptake were evaluated during two years in a ryegrass-maize forage rotation in NW Spain (t emperate-humid region). The three-way ANOVA showed that trace element concentrations in soil were mainly influenced by sampling date, followed by soil depth and tillage system (35-73 %, 7-58 % and 3- 11 % of variance explained, respectively). Excepting for Fe (CT) and Al (CT and MT), the elemental concentrations decreased with depth, the stratification being stronger under MT. For soil available Al, Fe, Mn and Cu, the concentrations were higher in CT than in MT (5-15 and 15-30 cm layers) or were not affected by tillage system (0-5 cm). In contrast, the available Zn contents were higher in MT than CT at the soil surface and did not differ in deeper layers. The concentration of Al, Fe and Cu in crops were not influenced by tillage system, which explain 22 % of Mn variance in maize (CT > MT in the more humid year) and 18 % of Zn variance in ryegrass (MT > CT in both years). However, in the summer crop (maize) the concentrations of Fe, Mn and Zn tended to be higher in MT than in CT under drought conditions, while the opposite was true in the year without water limitation. Therefore, under the studied conditions of climate, soil, tillage and crop rotation, little influence of tillage system on crop nutritive value would be expected. To minimize the potential deficiency of Zn (maize) and Cu (maize and ryegrass) on crop yields the inclusion of these micro-nutrients in fertilization schedule is reco mmended, as well as liming to alleviate Al toxicity on maize crops.

The extended environment of mononuclear metal centers in protein structures

The objectives of this and the following paper are to identify commonalities and disparities of the extended environment of mononuclear metal sites centering on Cu, Fe, Mn, and Zn. The extended environment of a metal site within a protein embodies at least three layers: the metal core, the ligand group, and the second shell, which is defined here to consist of all residues distant less than 3.5 Å from some ligand of the metal core. The ligands and second-shell residues can be characterized in terms of polarity, hydrophobicity, secondary structures, solvent accessibility, hydrogen-bonding interactions, and membership in statistically significant residue clusters of different kinds. Findings include the following: (i) Both histidine ligands of type I copper ions exclusively attach the Nδ1 nitrogen of the histidine imidazole ring to the metal, whereas histidine ligands for all mononuclear iron ions and nearly all type II copper ions are ligated via the Nɛ2 nitrogen. By contrast, multinuclear copper centers are coordinated predominantly by histidine Nɛ2, whereas diiron histidine contacts are predominantly Nδ1. Explanations in terms of steric differences between Nδ1 and Nɛ2 are considered. (ii) Except for blue copper (type I), the second-shell composition favors polar residues. (iii) For blue copper, the second shell generally contains multiple methionine residues, which are elements of a statistically significant histidine–cysteine–methionine cluster. Almost half of the second shell of blue copper consists of solvent-accessible residues, putatively facilitating electron transfer. (iv) Mononuclear copper atoms are never found with acidic carboxylate ligands, whereas single Mn2+ ion ligands are predominantly acidic and the second shell tends to be mostly buried. (v) The extended environment of mononuclear Fe sites often is associated with histidine–tyrosine or histidine–acidic clusters.

Paleoproterozoic snowball Earth: Extreme climatic and geochemical global change and its biological consequences

Geological, geophysical, and geochemical data support a theory that Earth experienced several intervals of intense, global glaciation (“snowball Earth” conditions) during Precambrian time. This snowball model predicts that postglacial, greenhouse-induced warming would lead to the deposition of banded iron formations and cap carbonates. Although global glaciation would have drastically curtailed biological productivity, melting of the oceanic ice would also have induced a cyanobacterial bloom, leading to an oxygen spike in the euphotic zone and to the oxidative precipitation of iron and manganese. A Paleoproterozoic snowball Earth at 2.4 Giga-annum before present (Ga) immediately precedes the Kalahari Manganese Field in southern Africa, suggesting that this rapid and massive change in global climate was responsible for its deposition. As large quantities of O2 are needed to precipitate this Mn, photosystem II and oxygen radical protection mechanisms must have evolved before 2.4 Ga. This geochemical event may have triggered a compensatory evolutionary branching in the Fe/Mn superoxide dismutase enzyme, providing a Paleoproterozoic calibration point for studies of molecular evolution.

Plasma Spectroscopic Techniques Applied to Biological and Environmental Matrices

The purpose of this research was to apply the use of direct ablation plasma spectroscopic techniques, including spark-induced breakdown spectroscopy (SIBS) and laser-induced breakdown spectroscopy (LIBS), to a variety of environmental matrices. These were applied to two different analytical problems. SIBS instrumentation was adapted in order to develop a fieldable monitor for the measurement of carbon in soil. SIBS spectra in the 200 nm to 400 nm region of several soils were collected, and the neutral carbon line (247.85 nm) was compared to total carbon concentration determined by standard dry combustion analysis. Additionally, Fe and Si were evaluated in a multivariate model in order to determine their impacts on the model's predictive power for total carbon concentrations. The results indicate that SIBS is a viable method to quantify total carbon levels in soils; obtaining a good correlation between measured and predicated carbon in soils. These results indicate that multivariate analysis can be used to construct a calibration model for SIBS soil spectra, and SIBS is a promising method for the determination of total soil carbon. SIBS was also applied to the study of biological warfare agent simulants. Elemental compositions (determined independently) of bioaerosol samples were compared to the SIBS atomic (Ca, Al, Fe and Si) and molecular (CN, N2 and OH) emission signals. Results indicate a linear relationship between the temporally integrated emission strength and the concentration of the associated element. Finally, LIBS signals of hematite were analyzed under low pressures of pure CO2 and compared with signals acquired with a mixture of CO2, N2 and Ar, which is representative of the Martian atmosphere. This research was in response to the potential use of LIBS instrumentation on the Martian surface and to the challenges associated with these measurements. Changes in Ca, Fe and Al lineshapes observed in the LIBS spectra at different gas compositions and pressures were studied. It was observed that the size of the plasma formed on the hematite changed in a non-linear way as a function of decreasing pressure in a CO2 atmosphere and a simulated Martian atmosphere.

Discussing the physical meaning of the absorption feature at 2.1 keV in 4U 1538–52

High resolution X-ray spectroscopy is a powerful tool for studying the nature of the matter surrounding the neutron star in X-ray binaries and its interaction between the stellar wind and the compact object. In particular, absorption features in their spectra could reveal the presence of atmospheres of the neutron star or their magnetic field strength. Here we present an investigation of the absorption feature at 2.1 keV in the X-ray spectrum of the high mass X-ray binary 4U 1538–52 based on our previous analysis of the XMM-Newton data. We study various possible origins and discuss the different physical scenarios in order to explain this feature. A likely interpretation is that the feature is associated with atomic transitions in an O/Ne neutron star atmosphere or of hydrogen and helium like Fe or Si ions formed in the stellar wind of the donor.

Estudios experimentales y teóricos de materiales y su optimización para uso como electrodos de baterías de ión-litio.

El presente proyecto se enmarca en el contexto del desarrollo de vectores de energía, particularmente aquellos destinados a almacenar la energía captada desde fuentes alternativas y sustentables, como son las energías eólica y solar, entre otras. Uno de los vectores de energía actualmente más importante lo constituyen las baterías de ión-Litio, las que por sus características de pequeño tamaño, alta densidad de energía y potencia, y larga ciclabilidad, son ampliamente utilizadas para alimentar todos los dispositivos electrónicos de pequeño tamaño (teléfonos móviles, notebooks, etc.). Este tipo de batería es, hasta el momento, la única que puede satisfacer la demanda de voltaje e intensidad de corriente, junto con bajo peso y volumen, del motor de un vehículo eléctrico, por lo que se espera un gran crecimiento de su demanda cuando comience la consolidación del mercado de este tipo de vehículos. Sin embargo, esto sólo será posible con importantes mejoras en los materiales activos que componen ambos electrodos, ánodo y cátodo, y/o con el desarrollo de nuevos materiales activos, que incrementen aun más la densidad de energía almacenada en dichas batería. En la Universidad Nacional de Córdoba hemos constituido un grupo de trabajo abocado a la investigación y desarrollo de materiales activos para ser utilizados como electrodos en este tipo de baterías, un área de investigación que concentra cada vez más la atención de científicos y tecnólogos en todo el mundo, particularmente, de países líderes del sector de electrónica y automotriz. Entre los objetivos del proyecto se pueden mencionar la intención de desarrollar capacidades científicas y técnicas en aspectos de investigación básica y tecnológica de sistemas electroquímicos de almacenamiento de energía, mediante la instalación de un laboratorio de síntesis, caracterización, investigación y ensayo de materiales activos para electrodos de baterías de ión-Litio. Específicamente, se llevará adelante la preparación y estudio electroquímico de materiales de ánodo en base a diferentes tipos de carbonos, de diferentes compuestos de titanatos de metales alcalinos, y de materiales de cátodo en base a diferentes tipos de compuestos de espinelas de fosfato de M-Litio, donde M puede ser Fe, Mn, Ni, Co o mezclas, y el ensayo posterior de celdas prototipo. La metodología de trabajo a aplicar es la del estado-del-arte a nivel mundial, que consiste en las etapas de síntesis, caracterización y estudio de funcionamiento de diferentes tipos de materiales activos para electrodos (ánodo o cátodo) de baterías de ión-Litio. Los procesos de síntesis comprenderán métodos por vía seca desde precursores adecuados (tratamientos térmicos) o por vía húmeda (hidrotermal, sol-gel). La caracterización física, química, estructural y morfológica abarcará la aplicación de técnicas de análisis de área específica y porosidad por método BET, microscopías SEM y TEM, análisis químico EDX, difracción de rayos X, espectroscopías XPS y Raman, y RMN, entre otras. Los estudios electroquímicos se llevarán a cabo utilizando técnicas potenciodinámicas, de multipulsos de potencial, galvanostáticas a diferentes densidades de corriente, espectroscopía de impedancia electroquímica y de ciclados de carga/descarga. Con la ejecución del proyecto se espera obtener materiales activos para electrodos de baterías de ión-Litio que cumplan con características tales como: alta capacidad de carga, adecuada densidad de potencia, alto grado de ciclabilidad, alto grado de seguridad, alta resistencia al envejecimiento, tanto estático como dinámico, y bajo costo del material. Teniendo en cuenta la inminente crisis en la producción mundial de combustibles fósiles líquidos, la necesidad de mudar la tecnología de vehículos actuales a la de vehículos eléctricos, y la disponibilidad nacional de recursos minerales de litio, la importancia del proyecto es directa para avanzar hacia un desarrollo tecnológico regional propio e independiente.

Geochemistry of basalts from ODP Leg 49, North Atlantic Ocean

The geochemistry of basalts recovered from seven sites in the North Atlantic is described with particular reference to minor elements. Three sites (407, 408, and 409) along the same mantle flow line, transverse to the Reykjanes Ridge at about 63°N, provide information on the composition of basalts erupted over a 34-m.y. interval between 2.3 and 36 m.y. ago. At Site 410, at 45°N, penetration into 10 m.y.-old crust west of the ridge axis permits comparisons with young basalts dredged from the median valley at 45°N. Three sites in the FAMOUS area at about 36°N provided material from very young (1 m.y.) basaltic crust (Site 411), and material to test the geochemical coherence of basalts of different ages (1.5 and 3.5 m.y.) on either side of a fracture zone (Sites 412 and 413). These sites complement earlier data from dredged and drilled sites (Leg 37) in the FAMOUS area. At Site 407, four geochemically distinct basalt units occur, with different normative and rare-earth element (REE) characteristics, and there is a clear correlation with magnetic stratigraphy. Yet there is a remarkable consistency in incompatible element ratios between these units, indicating derivation from an essentially similar mantle source. The basalts from the younger sites, 408 and 409, show a similar range of normative and REE variation, but incompatible element ratios are identical to those at Site 407, indicating that basalts at all three sites were produced from a mantle source which was geochemically relatively uniform. Rare-earth differences between the basalts can be interpreted in terms of variations in the degree and depth of partial melting causing HREE (+Y) retention in the source, although there may be some inter-site differences with respect to REE. A similar picture is presented at 45°N. Apparently a range of tholeiitic, transitional, and alkalic basalts were being erupted 10 m.y. ago, which have almost identical geochemical characteristics to those recently erupted in the median valley at 45°N. Incompatible element ratios are markedly different from those recorded at the Reykjanes Ridge. Basalts recovered from the FAMOUS sites are geochemically similar to previous samples recovered from the FAMOUS area, and their incompatible element ratios are similar, but not identical, to those at 45°N. However, total trace element levels are consistently lower than in 45°N basalts, which might imply smaller degrees of partial melting and/or greater depths of magma generation at 45°N, or higher trace element levels in the mantle source at 45°N. Few of the basalts recovered on Leg 49 have the geochemical characteristics of typical "MORB" (e.g., Nazca Plate, Leg 34). The data strongly support models invoking geochemical inhomogeneity in the source regions of basalts produced at the Mid-Atlantic Ridge. However, the data also introduce an additional time factor into such models and demonstrate the uniformity of the mantle source at a particular ridge sector (over periods in excess of 30 m.y.), while emphasizing the marked differences along the ridge. Mixing models invoking "depleted" and "enriched" mantle sources would seem to be inadequate to account for the observed variations.

Oxygen microprofiles and porewater chemistry in sediments of the Skagerrak

Sediment porewater oxygen profiles were measured with micro and needle electrodes in sediment cores of 27 stations in the Skagerrak (northeastern North Sea). Oxygen penetration depth ranged from 3 to 20 mm depth. Fluxes estimated from the oxygen gradients varied from 3 to 18 mmol m**-2 d**-1. Oxygen penetration and flux depend on water depth, but possibly more on the hydrological conditions, related to the import of fresh organic matter by primary production in the water column. Oxygen fluxes were not related to the total organic carbon (TOC) content of the sediments. Stations in the eastern part of the Skagerrak showed high burial rates of TOC. At 6 stations porewater chemistry of Fe, Mn and NO3- was strongly associated with the oxygen distribution. The average relative contribution of terminal electron acceptors to carbon mineralisation was estimated at 85% for O2, 0.5% for Mn, 4.5% for [NO3]3-, 1% for Fe and 9% for [SO4]2-. At one station the occurrence of exceptionally high solid manganese oxyhydroxides was probably related to an active internal manganese cycle.

Lithologic, mineral, chemical and isotopic compositions of altered rocks with increasing distance across the eastern flank of the Juan de Fuca Ridge, ODP Leg 168 data

During ODP Leg 168, 10 sites were drilled across the eastern flank of the Juan de Fuca Ridge (JdFR), to examine the conditions of fluid-rock interaction in three distinct hydrothermal regimes (referred to as the Hydrothermal Transition (HT), Buried Basement (BB) and Rough Basement (RB) transects), extending over a ~120 km linear transect perpendicular to the spreading ridge. This was carried out in an attempt to constrain the conditions and processes that control the location, style and magnitude of low temperature (<150°C) fluid-rock interaction within this setting. This paper presents new data on the petrology, mineral chemistry and whole rock strontium and oxygen isotopic compositions of basalts from the eastern flank of the JdFR, in order to investigate the extent, style and sequence of low-temperature hydrothermal alteration and to establish how the hydrothermal regime evolved with time. Throughout the flank, a progressive sequence of low-temperature hydrothermal alteration has been identified, marked by changes in the dominant secondary mineral assemblage, changing from: chlorite+chlorite/smectite; to iron oyxhydroxide+celadonite; to saponite+/-pyrite; culminating at present with Ca- to CaMg(+/-Fe,Mn)-carbonate. The changes in secondary mineralogy have been used to infer a series of systematic shifts in the conditions of alteration that occurred as the basement moved off-axis and was progressively buried by sediment. In general, hydrothermal alteration of the uppermost oceanic crust commenced under open, oxidative conditions, with interaction between unmodified to slightly modified seawater and basaltic crust, to a regime in which circulation of a strongly modified seawater-derived fluid was more restricted, and alteration occurred under non-oxidative conditions. Across the flank, petrological observations and microprobe analyses indicate that the observed ranges in secondary mineral composition are directly related to changes in the geochemical and textural characteristics of the basement, as well as to interaction between fluids and phases from the four stages of alteration. This is suggestive of an increase in fluid-rock increased with time. Whole rock 87Sr/86Sr and d18O analyses of basalts from across the eastern flank of the JdFR reinforce petrological observations, with 87Sr/86Sr and d18O values slightly elevated above accepted pristine MORB values for this region. These results are consistent with an increase in the amount of fluid-rock interaction with time. Across the flank, enrichment in the 87Sr/86Sr and d18O relative to MORB, is influenced by a number of factors, including: local and regional variations in the crustal lithology and structure; the age of the crust; the extent of bulk rock alteration; and theoretically, the relative abundance of different isotopically-enriched secondary mineral phases in the crust.