Aplicació de la termoquimiolisi - cromatografia de gasos - espectrometria de masses a l'estudi de la matèria orgànica del sòl

Estudi realitzat a partir d’una estada a la Université de Poitiers, França, entre 2007 i 2009. El treball s'ha centrat en dues activitats bàsiques. El treball realitzat s’ha centrat en dues activitats bàsiques. D’una banda, la posada a punt d'un protocol de fraccionament de la matèria orgànica del sòl, per extraccions successives amb solvents alcalins després d'una seqüència de pretractaments al sòl: cap pretractament, atac amb àcid (per destruir els carbonats), atac amb ditionit (per reduir els òxids de Fe i Al i facilitar l'extracció de la matèria orgànica associada a aquests compostos). El protocol dóna una visió de conjunt de la situació de la matèria orgànica del sòl, combinant aspectes físics (protecció, precipitació, oclusió per carbonats) i químics (grau d'humificació). D’altra banda, l'aprenentatge de la tècnica de termoquimiolisi-cromatografia de gasos-espectrometria de masses. Aquest era l'objectiu de l'estada a Poitiers, al qual hem donat prioritat. Ens hem centrat en l'estudi de fraccions físiques (densimètriques) obtingudes en estudis anteriors sobre sòls forestals. Les fraccions considerades són: fracció lleugera (FL), tres fraccions ocluïdes (OC1, OC2 i OC3) i fracció densa (FD). L’aplicació de la termoquimiolisi permet de caracteritzar diversos grups de substàncies, de les quals ens hem centrat en alguns indicadors bioquímics: àcids grasos, alcohols, diàcids, productes fenòlics i altres productes aromàtics, derivats de carbohidrats. L’estudi de conjunt d’aquests productes indica que és a les fraccions ocluïdes (que solen ser minoritàries a tots els horitzons) on la matèria orgànica d’origen microbià és dominant, mentre que a les fraccions lleugera (FL) i densa (FD) la matèria orgànica d’origen vegetal sembla dominant. Es preveu aplicar aquesta tècnica a l’estudi de les fraccions obtingudes a la primera part del treball, actualment congelades i a l’espera de ser processades.

Compositional analysis of archaeological glasses

At CoDaWork'03 we presented work on the analysis of archaeological glass composi-tional data. Such data typically consist of geochemical compositions involving 10-12variables and approximates completely compositional data if the main component, sil-ica, is included. We suggested that what has been termed `crude' principal componentanalysis (PCA) of standardized data often identi ed interpretable pattern in the datamore readily than analyses based on log-ratio transformed data (LRA). The funda-mental problem is that, in LRA, minor oxides with high relative variation, that maynot be structure carrying, can dominate an analysis and obscure pattern associatedwith variables present at higher absolute levels. We investigate this further using sub-compositional data relating to archaeological glasses found on Israeli sites. A simplemodel for glass-making is that it is based on a `recipe' consisting of two `ingredients',sand and a source of soda. Our analysis focuses on the sub-composition of componentsassociated with the sand source. A `crude' PCA of standardized data shows two clearcompositional groups that can be interpreted in terms of di erent recipes being used atdi erent periods, reected in absolute di erences in the composition. LRA analysis canbe undertaken either by normalizing the data or de ning a `residual'. In either case,after some `tuning', these groups are recovered. The results from the normalized LRAare di erently interpreted as showing that the source of sand used to make the glassdi ered. These results are complementary. One relates to the recipe used. The otherrelates to the composition (and presumed sources) of one of the ingredients. It seemsto be axiomatic in some expositions of LRA that statistical analysis of compositionaldata should focus on relative variation via the use of ratios. Our analysis suggests thatabsolute di erences can also be informative

Studies in stoichiometry with compositional data

Geochemical data that is derived from the whole or partial analysis of various geologic materialsrepresent a composition of mineralogies or solute species. Minerals are composed of structuredrelationships between cations and anions which, through atomic and molecular forces, keep the elementsbound in specific configurations. The chemical compositions of minerals have specific relationships thatare governed by these molecular controls. In the case of olivine, there is a well-defined relationshipbetween Mn-Fe-Mg with Si. Balances between the principal elements defining olivine composition andother significant constituents in the composition (Al, Ti) have been defined, resulting in a near-linearrelationship between the logarithmic relative proportion of Si versus (MgMnFe) and Mg versus (MnFe),which is typically described but poorly illustrated in the simplex.The present contribution corresponds to ongoing research, which attempts to relate stoichiometry andgeochemical data using compositional geometry. We describe here the approach by which stoichiometricrelationships based on mineralogical constraints can be accounted for in the space of simplicialcoordinates using olivines as an example. Further examples for other mineral types (plagioclases andmore complex minerals such as clays) are needed. Issues that remain to be dealt with include thereduction of a bulk chemical composition of a rock comprised of several minerals from which appropriatebalances can be used to describe the composition in a realistic mineralogical framework. The overallobjective of our research is to answer the question: In the cases where the mineralogy is unknown, arethere suitable proxies that can be substituted?Kew words: Aitchison geometry, balances, mineral composition, oxides

Oxidation of silicon: further tests for the interfacial silicon emission model

The classical description of Si oxidation given by Deal and Grove has well-known limitations for thin oxides (below 200 Ã). Among the large number of alternative models published so far, the interfacial emission model has shown the greatest ability to fit the experimental oxidation curves. It relies on the assumption that during oxidation Si interstitials are emitted to the oxide to release strain and that the accumulation of these interstitials near the interface reduces the reaction rate there. The resulting set of differential equations makes it possible to model diverse oxidation experiments. In this paper, we have compared its predictions with two sets of experiments: (1) the pressure dependence for subatmospheric oxygen pressure and (2) the enhancement of the oxidation rate after annealing in inert atmosphere. The result is not satisfactory and raises serious doubts about the model’s correctness

Reversible ferromagnetic switching in ZnO:(Co,Mn) powders

We report here on the magnetic properties of ZnO:Mn- and ZnO:Co-doped nanoparticles. We have found that the ferromagnetism of ZnO:Mn can be switched on and off by consecutive low-temperature annealings in O2 and N2, respectively, while the opposite phenomenology was observed for ZnO:Co. These results suggest that different defects (presumably n-type for ZnO:Co and p-type for ZnO:Mn) are required to induce a ferromagnetic coupling in each case. We will argue that ferromagnetism is likely to be restricted to a very thin, nanometric layer at the grain surface. These findings reveal and give insight into the dramatic relevance of surface effects to the occurrence of ferromagnetism in ZnO-doped oxides.

Ophiolite-related ultramafic rocks (Serpentinites) in the Caribbean region: a review of their occurrence, composition, origin, emplacements and Ni-Laterite soil formation

Ultramafic rocks, mainly serpentinized peridotites of mantle origin, are mostly associated with the ophiolites of Mesozoic age that occur in belts along three of the margins of the Caribbean plate. The most extensive exposures are in Cuba. The ultramafic-mafic association (ophiolites) were formed and emplaced in several different tectonic environments. Mineralogical studies of the ultramafic rocks and the chemistry of the associated mafic rocks indicate that most of the ultramafic-mafic associations in both the northern and southern margins of the plate were formed in arc-related environments. There is little mantle peridotite exposed in the ophiolitic associations of the west coast of Central America, in the south Caribbean in Curacao and in the Andean belts in Colombia. In these occurrences the chemistry and age of the mafic rocks indicates that this association is mainly part of the 89 Ma Caribbean plateau province. The age of the mantle peridotites and associated ophiolites is probably mainly late Jurassic or Early Cretaceous. Emplacement of the ophiolites possibly began in the Early Cretaceous in Hispaniola and Puerto Rico, but most emplacement took place in the Late Cretaceous to Eocene (e.g. Cuba). Along the northern South America plate margin, in the Caribbean mountain belt, emplacement was by major thrusting and probably was not completed until the Oligocene or even the early Miocene. Caribbean mantle peridotites, before serpentinization, were mainly harzburgites, but dunites and lherzolites are also present. In detail, the mineralogical and chemical composition varies even within one ultramafic body, reflecting melting processes and peridotite/melt interaction in the upper mantle. At least for the northern Caribbean, uplift (postemplacement tectonics) exposed the ultramafic massifs as a land surface to effective laterization in the beginning of the Miocene. Tectonic factors, determining the uplift, exposing the peridotites to weathering varied. In the northern Caribbean, in Guatemala, Jamaica, and Hispaniola, uplift occurred as a result of transpresional movement along pre-existing major faults. In Cuba, uplift occurred on a regional scale, determined by isostatic adjustment. In the south Caribbean, uplift of the Cordillera de la Costa and Serrania del Interior exposing the peridotites, also appears to be related to strike-slip movement along the El Pilar fault system. In the Caribbean, Ni-laterite deposits are currently being mined in the central Dominican Republic, eastern Cuba, northern Venezuela and northwest Colombia. Although apparently formed over ultramafic rocks of similar composition and under similar climatic conditions, the composition of the lateritic soils varies. Factors that probably determined these differences in laterite composition are geomorphology, topography, drainage and tectonics. According to the mineralogy of principal ore-bearing phases, Dominican Ni-laterite deposits are classified as the hydrous silicate-type. The main Ni-bearing minerals are hydrated Mg-Ni silicates (serpentine and ¿garnierite¿) occurring deeper in the profile (saprolite horizon). In contrast, in the deposits of eastern Cuba, the Ni and Cooccurs mainly in the limonite zone composed of Fe hydroxides and oxides as the dominant mineralogy in the upper part of the profile, and are classified as the oxide-type.

X-ray photoelectron spectroscopy analysis of ion¿beam¿induced oxidation of GaAs and AlGaAs

The oxidation of GaAs and AlGaAs targets subjected to O2+ bombardment has been analyzed, using in situ x¿ray photoelectron spectroscopy, as a function of time until steady state is reached. The oxides formed by the O2+ bombardment have been characterized in terms of composition and binding energy. A strong energy and angular dependence for the oxidation of As relative to Ga is found. Low energies as well as near normal angles of incidence favor the oxidation of As. The difference between Ga and As can be explained in terms of the formation enthalpy for the oxide and the excess supply of oxygen. In an AlGaAs target the Al is very quickly completely oxidized irrespective of the experimental conditions. The steady state composition of the altered layers show in all cases a preferential removal of As.

Modifications in the Si valence band after ion-beam-induced oxidation

The changes undergone by the Si surface after oxygen bombardment have special interest for acquiring a good understanding of the Si+-ion emission during secondary ion mass spectrometry (SIMS) analysis. For this reason a detailed investigation on the stoichiometry of the builtup surface oxides has been carried out using in situ x-ray photoemission spectroscopy (XPS). The XPS analysis of the Si 2p core level indicates a strong presence of suboxide chemical states when bombarding at angles of incidence larger than 30°. In this work a special emphasis on the analysis and interpretation of the valence band region was made. Since the surface stoichiometry or degree of oxidation varies with the angle of incidence, the respective valence band structures also differ. A comparison with experimentally measured and theoretically derived Si valence band and SiO2 valence band suggests that the new valence bands are formed by a combination of these two. This arises from the fact that Si¿Si bonds are present on the Si¿suboxide molecules, and therefore the corresponding 3p-3p Si-like subband, which extends towards the Si Fermi level, forms the top of the respective new valence bands. Small variations in intensity and energy position for this subband have drastic implications on the intensity of the Si+-ion emission during sputtering in SIMS measurements. A model combining chemically enhanced emission and resonant tunneling effects is suggested for the variations observed in ion emission during O+2 bombardment for Si targets.

Strain-induced stabilization of new magnetic spinel structures in epitaxial oxide heterostructures.

We report here on the growth of NiFe2O4 epitaxial thin films of different thickness (3 nm ¿ t ¿ 32 nm) on single crystalline substrates having spinel (MgAl2O4) or perovskite (SrTiO3) structure. Ultrathin films, grown on any of those substrates, display a huge enhancement of the saturation magnetization: we will show that partial cationic inversion may account for this enhancement, although we will argue that suppression of antiparallel collinear spin alignment due to size-effects cannot be excluded. Besides, for thicker films, the magnetization of films on MAO is found to be similar to that of bulk ferrite; in contrast, the magnetization of films on STO is substantially lower than bulk. We discuss on the possible mechanisms leading to this remarkable difference of magnetization.

Epitaxial growth of biferroic YMnO3(0001) on platinum electrodes

Epitaxial films of the biferroic YMnO3 (YMO) oxide have been grown on platinum-coated SrTiO3(1 1 1) and Al2O3(0 0 0 1) substrates. The platinum electrodes, (1 1 1) oriented, are templates for the epitaxy of the hexagonal phase of YMO with a (0 0 0 1) out-of-plane orientation, which is of interest as this is the polarization direction of YMO. X-ray diffractometry indicates the presence of two crystal domains, 60° rotated in-plane, in the Pt(1 1 1) layers which subsequently are transferred on the upperlaying YMO. Cross-section analysis by high-resolution transmission electron microscopy (HRTEM) of YMnO3/Pt/SrTiO3(1 1 1) shows high-quality epitaxy and sharp interfaces across the structure in the observed region. We present a detailed study of the epitaxial growth of the hexagonal YMO on the electrodes.

Gas sensing properties of catalytically modified WO3 with copper and vanadium for NH3 detection

Ammonia gas detection by pure and catalytically modified WO3 based gas sensor was analysed. The sensor response of pure WO3 to NH3 was not only rather low but also presented an abnormal behaviour, probably due to the unselective oxidation of ammonia to NOx. Copper and vanadium were introduced in different concentrations and the resulting material was annealed at different temperatures in order to improve the sensing properties for NH3 detection. The introduction of copper and vanadium as catalytic additives improved the response to NH3 and also eliminated the abnormal behaviour. Possible mechanisms of NH3 reaction over these materials are discussed. Sensor responses to other gases like NO2 or CO and the interference of humidity on ammonia detection were also analysed so as to choose the best sensing element.

Enhanced electron-electron correlations in nanometric epitaxial SrRuO3 epitaxial films

Epitaxial and fully strained SrRuO3 thin films have been grown on SrTiO3(100). At initial stages the growth mode is three-dimensional- (3D-)like, leading to a finger-shaped structure aligned with the substrate steps and that eventually evolves into a 2D step-flow growth. We study the impact that the defect structure associated with this unique growth mode transition has on the electronic properties of the films. Detailed analysis of the transport properties of nanometric films reveals that microstructural disorder promotes a shortening of the carrier mean free path. Remarkably enough, at low temperatures, this results in a reinforcement of quantum corrections to the conductivity as predicted by recent models of disordered, strongly correlated electronic systems. This finding may provide a simple explanation for the commonly observed¿in conducting oxides-resistivity minima at low temperature. Simultaneously, the ferromagnetic transition occurring at about 140 K, becomes broader as film thickness decreases down to nanometric range. The relevance of these results for the understanding of the electronic properties of disordered electronic systems and for the technological applications of SrRuO3¿and other ferromagnetic and metallic oxides¿is stressed.

Spin filtering through ferromagnetic BiMnO3 tunnel barriers

We report on experiments of spin filtering through ultrathin single-crystal layers of the insulating and ferromagnetic oxide BiMnO3 (BMO). The spin polarization of the electrons tunneling from a gold electrode through BMO is analyzed with a counterelectrode of the half-metallic oxide La2/3Sr1/3MnO3 (LSMO). At 3 K we find a 50% change of the tunnel resistances according to whether the magnetizations of BMO and LSMO are parallel or opposite. This effect corresponds to a spin-filtering efficiency of up to 22%. Our results thus show the potential of complex ferromagnetic insulating oxides for spin filtering and injection.

Influence of RF power on the properties of sputtered ZnO:Al thin films

Transparent conducting, aluminium doped zinc oxide thin films (ZnO:Al) were deposited by radio frequency (RF) magnetron sputtering. The RF power was varied from 60 to 350Wwhereas the substrate temperature was kept at 160 °C. The structural, electrical and optical properties of the as-deposited films were found to be influenced by the deposition power. The X-ray diffraction analysis showed that all the films have a strong preferred orientation along the [001] direction. The crystallite size was varied from 14 to 36 nm, however no significant change was observed in the case of lattice constant. The optical band gap varied in the range 3.44-3.58 eV. The lowest resistivity of 1.2×10 -3Vcm was shown by the films deposited at 250 W. The mobility of the films was found to increase with the deposition power.

Transparent conducting thin films by the co-sputtering of ZnO-ITO targets

Transparent and conductive Zn-In-Sn-O (ZITO) amorphous thin films have been deposited at room temperature by the rf magnetron co-sputtering of ITO and ZnO targets. Co-sputtering gives the possibility to deposit multicomponent oxide thin films with different compositions by varying the power to one of the targets. In order to make ZITO films with different Zn content, a constant rf power of 50 W was used for the ITO target, where as the rf power to ZnO target was varied from 25 W to 150 W. The as deposited films showed an increase in Zn content ratio from 17 to 67 % as the power to ZnO target was increased from 25 to 150 W. The structural, electrical and optical properties of the as deposited films are reported. The films showed an average transmittance over 80% in the visible wavelength range. The electrical resistivity and optical band gap of the ZITO films were found to depend on the Zn content in the film. The ZITO films deposited at room temperature with lower Zn content ratios showed better optical transmission and electrical properties compared to ITO film.