Synthesis Gas Generation by Chemical-Looping Reforming Using Ce-Based Oxygen Carriers Modified with Fe, Cu, and Mn Oxides

Chemical-looping reforming (CLR) is a technology that can be used for partial oxidation and steam reforming of hydrocarbon fuels. It involves the use of a metal oxide as an oxygen carrier, which transfers oxygen from combustion air to the fuel. Composite oxygen carriers of cerium oxide added with Fe, Cu, and Mn oxides were prepared by co-precipitation and investigated in a thermogravimetric analyzer and a fixed-bed reactor using methane as fuel and air as oxidizing gas. It was revealed that the addition of transition-metal oxides into cerium oxide can improve the reactivity of the Ce-based oxygen carrier. The three kinds of mixed oxides showed high CO and H-2 selectivity at above 800 degrees C. As for the Ce-Fe-O oxygen carrier, methane was converted to synthesis gas at a H-2/CO molar ratio close to 2:1 at a temperature of 800-900 degrees C; however, the methane thermolysis reaction was found on Ce-Cu-O and Ce-Mn-O oxygen carriers at 850-900 degrees C. Among the three kinds of oxygen carriers, Ce-Fe-O presented the best performance for methane CLR. On Ce-Fe-O oxygen carriers, the CO and H-2 selectivity decreased as the Fe content increased in the carrier particles. An optimal range of the Ce/Fe molar ratio is Ce/Fe > 1 for Ce-Fe-O oxygen carriers. Scanning electron microscopy (SEM) analysis revealed that the microstructure of the Ce-Fe-O oxides was not dramatically changed before and after 20 cyclic reactions. A small amount of Fe3C was found in the reacted Ce-Fe-O oxides by X-ray diffraction (XRD) analysis.

Mossbauer spectroscopy and chemical bonds in BaFe12O19 hexaferrite

Barium hexaferrite was synthesized by chemical co-precipitation. Its Mossbauer spectra were obtained. A semi-empirical model, based on the Phillips theory of bonding, has been developed for quantitative explanation of the Mossbauer isomer shifts of Fe ions in BaFe12O19 crystals. The results show that, using the relationship between isomer shifts and covalency, the site assignments in hexaferrites will be resolved easily. This paper provides a powerful tool for studying other members of the hexagonal ferrimagnetic oxides family.

Geochemistry, mineralogy, and chemical modeling of the acid crater lake of Kawah Ijen volcano, Indonesia

The Kawah Ijen volcano-with a record of phreatic eruptions-has its 1000 m wide crater filled with a lake that has existed for at least one century. At present, the lake waters are hot (T ≈ 37°C), strongly mineralized (TDS = 105 g/L) and extremely acidic (pH ≈ 0.4). By its volume, the Javanese lake is probably the largest accumulation in the world of such acidic waters. Mineralogy of the suspended solids within the lake waters suggests that concentrations of Si, Ca, Ti, and Ba are controlled by precipitation of silica, gypsum, anatase, and barite. Lake sediment is composed of chemical precipitates with composition similar to the suspended solids. Thermodynamic calculations predict that the lake waters have reached equilibrium with respect to α-cristobalite, barite, gypsum, anglesite, celestite, and amorphous silica, in agreement with the analytical observations. Significant concentrations of ferric iron suggest that the current lake waters are fairly oxidized. Sulfides are absent in the water column but are always present in the native S spherules that form porous aggregates which float on the lake. The presence of native S provides direct evidence of more reduced conditions at the lake floor where H2S is probably being injected into the lake. With progressive addition of H2S to the acid waters, native S, pyrite, and enargite are theoretically predicted to be saturated. Reactions between upward streaming H2S-bearing gases discharged by subaqueous fumaroles, and metals dissolved in the acidic waters could initiate precipitation of these sulfides. A model of direct absorption of hot magmatic gases into cool water accounts for the extreme acidity of the crater lake. Results show that strongly acidic, sulfate-rich solutions are formed under oxidizing conditions at high gas/water ratios. Reactions between the acidic fluids and the Ijen andesite were modeled to account for elevated cation concentrations in lake water. Current concentrations of conservative rockforming elements are produced by dissolution of approximately 60 g of andesite per kg of acid solution. Complete neutralization of the acid lake waters by reaction with the wallrock produces a theoretical alteration assemblage equivalent to that observed in volcano-hosted, acid-sulfate epithermal ore deposits. © 1994.

The effect of co-precipitation on cadmium(II) adsorption on hydrous aluminium(III) hydroxide in the presence of a range of chelates

The adsorption of cadmium(II) on freshly precipitated aluminium(III) hydroxide in the presence of a range of chelates has been investigated. By precipitating the metal, chelate and adsorbent together it is possible to change the pH variation of the metal-complex adsorption from anionic, ligand-like, binding to cationic binding. This is a general phenomenon and is explained by the formation of a ternary Al-O-Cd-L surface species. As a consequence of the preparation method, the pH edge is found to shift to lower pH values in the presence of the chelate which gives rise to an apparent increase in adsorption of Cd2+. This increase is, in general, most pronounced at [chelate] / [metal] > 1. Computer modelling shows that the observed trends result from the competition between Al-O-Cd-L and Al-L for the available aluminium( III) binding sites. The enhanced adsorption in the presence of phenylenediaminetetraacetate is anomalous since it is observed at a [ chelate] / [metal] approximate to 0.1 and cannot be interpreted by the simple competition model.

Linking watershed terrain and hydrology to soil chemical properties, microbial communities and impacts on soil organic C in a humid mid-latitude forested watershed

Understanding the response of humid mid-latitude forests to changes in precipitation, temperature, nutrient cycling, and disturbance is critical to improving our predictive understanding of changes in the surface-subsurface energy balance due to climate change. Mechanistic understanding of the effects of long-term and transient moisture conditions are needed to quantify
linkages between changing redox conditions, microbial activity, and soil mineral and nutrient interactions on C cycling and greenhouse gas releases. To illuminate relationships between the soil chemistry, microbial communities and organic C we established transects across hydraulic and topographic gradients in a small watershed with transient moisture conditions. Valley bottoms tend to be more frequently saturated than ridge tops and side slopes which generally are only saturated when shallow storm flow zones are active. Fifty shallow (~36”) soil cores were collected during timeframes representative of low CO2, soil winter conditions and high CO2, soil summer conditions. Cores were subdivided into 240 samples based on pedology and analyses of the geochemical (moisture content, metals, pH, Fe species, N, C, CEC, AEC) and microbial (16S rRNA gene
amplification with Illumina MiSeq sequencing) characteristics were conducted and correlated to watershed terrain and hydrology. To associate microbial metabolic activity with greenhouse gas emissions we installed 17 soil gas probes, collected gas samples for 16 months and analyzed them for CO2 and other fixed and greenhouse gasses. Parallel to the experimental efforts our data is being used to support hydrobiogeochemical process modeling by coupling the Community Land Model (CLM) with a subsurface process model (PFLOTRAN) to simulate processes and interactions from the molecular to watershed scales. Including above ground processes (biogeophysics, hydrology, and vegetation dynamics), CLM provides mechanistic water, energy, and organic matter inputs to the surface/subsurface models, in which coupled biogeochemical reaction
networks are used to improve the representation of below-ground processes. Preliminary results suggest that inclusion of above ground processes from CLM greatly improves the prediction of moisture response and water cycle at the watershed scale.

Origin, seasonality and chemical characteristics of rainwater in Aveiro

Este trabalho teve como objectivo caracterizar quimicamente a água da chuva recolhida na cidade de Aveiro, localizada a sudoeste da Europa, no período de Setembro de 2008 a Setembro de 2009. Para matrizes diluídas como a da água da chuva, as metodologias analíticas a utilizar para se conseguir uma rigorosa caracterização química são de grande importância e ainda não estão uniformizadas. Assim, para caracterizar a fracção orgânica, primeiramente foram comparadas duas metodologias de filtração (0.22 e 0.45 μm) e foram estudados dois procedimentos de preservação da água da chuva (refrigeração e congelação), utilizando a espectroscopia de fluorescência molecular. Além disso, foram comparados dois procedimentos de isolamento e extracção da matéria orgânica dissolvida (DOM) da água da chuva, baseados na sorção nos sorbentes DAX-8 e C-18, utilizando as espectroscopias de ultravioleta-visível e fluorescência molecular. Relativamente aos resultados das metodologias de filtração e preservação, é recomendada a filtração por 0.45 μm, assim como, as amostras de água da chuva deverão ser mantidas no escuro a 4ºC, no máximo até 4 dias, até às análises espectroscópicas. Relativamente à metodologia de isolamento e extracção da DOM, os resultados mostraram que o procedimento de isolamento baseado na C-18 extraiu a DOM que é representativa da matriz global, enquanto que o procedimento da DAX-8 extraiu preferencialmente a fracção do tipo húmico. Como no presente trabalho pretendíamos caracterizar a fracção do tipo húmico da DOM da água da chuva, foi escolhida a metodologia de isolamento e extracção baseada na sorção no sorvente DAX-8. Previamente ao isolamento e extracção da DOM da água da chuva, toda a fracção orgânica das amostras de água da chuva foi caracterizada pelas técnicas de ultravioleta-visível e de fluorescência molecular. As amostras mostraram características semelhantes às de outras águas naturais, e a água da chuva do Verão e Outono apresentou maior conteúdo da matéria orgânica dissolvida cromofórica que a do Inverno e Primavera. Posteriormente, a fracção do tipo húmico de algumas amostras de água da chuva, isolada e extraída pelo procedimento baseado na DAX-8, foi caracterizada utilizando as técnicas espectroscópicas de ultravioleta-visível, fluorescência molecular e ressonância magnética nuclear de protão. Todos os extractos continham uma mistura complexa de compostos hidroxilados e ácidos carboxílicos, com uma predominância da componente alifática e um baixo conteúdo da componente aromática. A fracção inorgânica da água da chuva foi caracterizada determinando a concentração das seguintes espécies iónicas: H+, NH4 +, Cl-, NO3 -, SO4 2-. Os resultados foram comparados com os obtidos na chuva colectada no mesmo local entre 1986-1989 e mostraram que de todos os iões determinados a concentração de NO3 - foi a única que aumentou (cerca do dobro) em 20 anos, tendo sido atribuído ao aumento de veículos e emissões industriais na área de amostragem. Durante o período de amostragem cerca de 80% da precipitação esteve associada a massas de ar oceânicas, enquanto a restante esteve relacionada com massas que tiveram uma influência antropogénica e terrestre. De um modo geral, para as fracções orgânica e inorgânica da água da chuva analisadas, o conteúdo químico foi menor para as amostras que estiveram associadas a massas de ar marítimas do que para as amostras que tiveram contribuições terrestres e antropogénicas.

Structural and chemical characterization of corals grown under present day and naturally elevated pCO2 conditions in Papua New Guinea - a window into the future

Dissertação de mestrado, Biologia Marinha, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2015

Physico-chemical controls on phosphorus cycling in two lowland streams. Part 1 - the water column

This paper investigates phosphorus (P) transport and transformation dynamics in two contrasting sub-catchments of the River Kennel, England. Samples were collected daily under baseflow and hourly under stormflow conditions using autosamplers for 2 years and analysed for a range of determinands (full P fractionation, suspended sediment (SS), cations, pH, alkalinity, temperature and oxygen). Concentrations of SRP, SUP, PP and SS were higher in the flashy River Enborne (means of 0.186, 0.071, 0.101 and 34 mg l(-1), respectively) than the groundwater-fed River Lambourn (0.079, 0.057, 0.028 and 9 mg l(-1), respectively). A seasonal trend in the daily P dataset was evident, with lower concentrations during intermediate flows and the spring (caused by a dilution effect and macrophyte uptake) than during baseflow conditions. However, in the hourly P dataset, highest concentrations were observed during storm events in the autumn and winter (reflecting higher scour with increased capacity to entrain particles). Storm events were more significant in contributing to the total P load in the River Enborne than the River Lambourn, especially during August to October, when dry antecedent conditions were observed in the catchment. Re-suspension of P-rich sediment that accumulated within the channel during summer low flows might account for these observations. It is suggested that a P-calcite co-precipitation mechanism was operating during summer in the River Lambourn, while adsorption by metal oxyhydroxide groups was an important mechanism controlling P fractionation in the River Enborne. The influence of flow conditions and channel storage/release mechanisms on P dynamics in these two lowland rivers is assessed. (C) 2004 Elsevier B.V. All rights reserved.

Physico-chemical controls on phosphorus cycling in two lowland streams. Part 2 - The sediment phase

This article investigates the temporal and spatial controls on sediment-phosphorus (P) dynamics in two contrasting sub-catchments of the River Kennet, England. Suspended sediment (collected under representative flow conditions) and size-fractionated bedload (collected weekly for one year) from the Rivers Lambourn and Enborne was analysed for a range of physico-chemical determinands. Total P concentrations were highest in the most mobile fractions of sediment: suspended sediment, fine silt and clay and organic matter (mean concentrations of 1758, 1548 and 1440 mug P g(-1) dry sediment, respectively). Correlation analysis showed significant relationships between total P and total iron (n = 110), total manganese (n = 110), organic matter (n = 110) and specific surface area (n = 28) in the Lambourn (r(2) 0.71, 0.68, 0.62 and 0.52, respectively) and between total P and total iron (n = 110), total manganese (n = 110) and organic matter (n = 110) in the Enborne (r(2) 0.74, 0.85 and 0.68, respectively). These data highlight the importance of metal oxyhydroxide adsorption of P on fine particulates and organic matter. However, high total P concentrations in the granule gravel and coarse sand size fraction during the summer period (mean concentration 228 mug P g(-1) dry sediment) also highlight the role of calcite co-precipitation on P dynamics in the Lambourn. P to cation ratios in Lambourn sediment indicated that fine silt and clay and granule gravel and coarse sand size fractions were potential sources of P release to the water column during specific periods of the summer and autumn. In the Enborne, however, only the granule gravel and coarse sand size fraction had high ratios and a slow, constant release of P was observed. In addition, scanning electron microscopy work confirmed the association of P with calcite in the Lambourn and P with iron on clay particles in the Enborne. The study highlighted the importance of the chemical and physical properties of the sediment in influencing the mechanisms controlling P storage and release within river channels. (C) 2004 Elsevier B.V. All rights reserved.

Chemical and aerosol characterisation of the troposphere over West Africa during the monsoon period as part of AMMA

During June, July and August 2006 five aircraft took part in a campaign over West Africa to observe the aerosol content and chemical composition of the troposphere and lower stratosphere as part of the African Monsoon Multidisciplinary Analysis (AMMA) project. These are the first such measurements in this region during the monsoon period. In addition to providing an overview of the tropospheric composition, this paper provides a description of the measurement strategy (flights performed, instrumental payloads, wing-tip to wing-tip comparisons) and points to some of the important findings discussed in more detail in other papers in this special issue. The ozone data exhibits an "S" shaped vertical profile which appears to result from significant losses in the lower troposphere due to rapid deposition to forested areas and photochemical destruction in the moist monsoon air, and convective uplift of ozone-poor air to the upper troposphere. This profile is disturbed, particularly in the south of the region, by the intrusions in the lower and middle troposphere of air from the southern hemisphere impacted by biomass burning. Comparisons with longer term data sets suggest the impact of these intrusions on West Africa in 2006 was greater than in other recent wet seasons. There is evidence for net photochemical production of ozone in these biomass burning plumes as well as in urban plumes, in particular that from Lagos, convective outflow in the upper troposphere and in boundary layer air affected by nitrogen oxide emissions from recently wetted soils. This latter effect, along with enhanced deposition to the forested areas, contributes to a latitudinal gradient of ozone in the lower troposphere. Biogenic volatile organic compounds are also important in defining the composition both for the boundary layer and upper tropospheric convective outflow. Mineral dust was found to be the most abundant and ubiquitous aerosol type in the atmosphere over Western Africa. Data collected within AMMA indicate that injection of dust to altitudes favourable for long-range transport (i.e. in the upper Sahelian planetary boundary layer) can occur behind the leading edge of mesoscale convective system (MCS) cold-pools. Research within AMMA also provides the first estimates of secondary organic aerosols across the West African Sahel and have shown that organic mass loadings vary between 0 and 2 μg m−3 with a median concentration of 1.07 μg m−3. The vertical distribution of nucleation mode particle concentrations reveals that significant and fairly strong particle formation events did occur for a considerable fraction of measurement time above 8 km (and only there). Very low concentrations were observed in general in the fresh outflow of active MCSs, likely as the result of efficient wet removal of aerosol particles due to heavy precipitation inside the convective cells of the MCSs. This wet removal initially affects all particle size ranges as clearly shown by all measurements in the vicinity of MCSs.

Protein precipitation behaviour of condensed tannins from Lotus pedunculatus and Trifolium repens with different mean degrees of polymerization

The precipitation of bovine serum albumin (BSA), lysozyme (LYS) and alfalfa leaf protein (ALF) by two large- and two medium-sized condensed tannin (CT) fractions of similar flavan-3-ol subunit composition is described. CT fractions isolated from white clover flowers and big trefoil leaves exhibited high purity profiles by 1D/2D NMR and purities >90% (determined by thiolysis). At pH 6.5, large CTs with a mean degree of polymerization (mDP) of ~18 exhibited similar protein precipitation behaviors and were significantly more effective than medium CTs (mDP ~9). Medium CTs exhibited similar capacities to precipitate ALF or BSA, but showed small but significant differences in their capacity to precipitate LYS. All CTs precipitated ALF more effectively than BSA or LYS. Aggregation of CT-protein complexes likely aided precipitation of ALF and BSA, but not LYS. This study, one of the first to use CTs of confirmed high purity, demonstrates that mDP of CTs influences protein precipitation efficacy.

Influence of neodymium ions on photocatalytic activity of TiO(2) synthesized by sol-gel and precipitation methods

Titanium dioxide with and without the addition of neodymium ions was prepared using sol-gel and precipitation methods. The resulting catalysts were characterized by thermal analysis, X-ray diffraction and BET specific surface area. Neodymium addition exerted a remarkable influence on the phase transition temperature and the surface properties of the TiO(2) matrix. TiO(2) samples synthesized by precipitation exhibit an exothermic event related from the amorphous to anatase phase transition at 510 degrees C, whereas in Nd-doped TiO(2) this transition occurred at 527 degrees C. A similar effect was observed in samples obtained using sol-gel method. The photocatalytic reactivity of the catalysts was evaluated by photodegradation of Remazol Black B (RB) under ultraviolet irradiation. Nd-doped TiO(2) showed enhanced photodegradation ability compared to undoped TiO(2) samples, independent of the method of synthesis. In samples obtained by sol-gel, RB decoloration was enhanced by 16% for TiO(2) doped with 0.5% neodymium ions. (C) 2010 Elsevier B.V. All rights reserved.

Thermal study and physico-chemical characterization of some functional properties of guava seeds protein isolate (Psidium guajava)

The guava seed protein isolate ( PI) was obtained from the protein precipitation belonging to the class of the gluteline (Ip 4.5). The conditions for the preparation of the PI were determined by both the solubility curve and simultaneous thermogravimetry-differential thermal analysis (TG-DTA): pH 11.5, absence of NaCl and whiteners and T=( 25 +/- 3) degrees C. Under these conditions a yield of 77.0 +/- 0.4%, protein content of 94.2 +/- 0.3, ashes 0.50 +/- 0.05% and thermal stability, T= 200 degrees C, were obtained. The TG-DTA curves and the PI emulsification capacity study showed the presence of hydrophobic microdomains at pH 11.5 and 3.0 suggesting a random coil protein conformation and, to pH 10.0, an open protein conformation. The capacity of emulsification (CE), in the absence of NaCl, was verified for: 1 - pH 3.0 and 8.5, using the IP extracted at pH 10.0 and 11.5, CE >= 343 +/- 5 g of emulsified oil/g of protein; 2 - pH 6.60 just for the PI obtained at pH 11.5, CE >= 140 +/- 8 g of emulsified oil/g of protein.

Effect of Iron II on Hydroxyapatite Dissolution and Precipitation in vitro

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)