Synergy between polyaniline and OMt clay mineral in Langmuir-Blodgett films for the simultaneous detection of traces of metal ions

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

Prospecção mineral de alvos potenciais à ocorrência de enriquecimento supergênico de níquel no Greenstone belt do Morro do Ferro

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Macromineral requirements in male and female Saanen goats

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

Determination of trace elements in bovine semen samples by inductively coupled plasma mass spectrometry and data mining techniques for identification of bovine class

The reproductive performance of cattle may be influenced by several factors, but mineral imbalances are crucial in terms of direct effects on reproduction. Several studies have shown that elements such as calcium, copper, iron, magnesium, selenium, and zinc are essential for reproduction and can prevent oxidative stress. However, toxic elements such as lead, nickel, and arsenic can have adverse effects on reproduction. In this paper, we applied a simple and fast method of multi-element analysis to bovine semen samples from Zebu and European classes used in reproduction programs and artificial insemination. Samples were analyzed by inductively coupled plasma spectrometry (ICP-MS) using aqueous medium calibration and the samples were diluted in a proportion of 1:50 in a solution containing 0.01% (vol/vol) Triton X-100 and 0.5% (vol/vol) nitric acid. Rhodium, iridium, and yttrium were used as the internal standards for ICP-MS analysis. To develop a reliable method of tracing the class of bovine semen, we used data mining techniques that make it possible to classify unknown samples after checking the differentiation of known-class samples. Based on the determination of 15 elements in 41 samples of bovine semen, 3 machine-learning tools for classification were applied to determine cattle class. Our results demonstrate the potential of support vector machine (SVM), multilayer perceptron (MLP), and random forest (RF) chemometric tools to identify cattle class. Moreover, the selection tools made it possible to reduce the number of chemical elements needed from 15 to just 8.

Crystallization conditions and controls on trace element residence in the main minerals from the Pedra Branca Syenite, Brazil: An electron microprobe and LA-ICPMS study

Major and trace-element microanalyses of the main minerals from the 610 Ma Pedra Branca Syenite, southeast Brazil, allow inferences on intensive parameters of magmatic crystallization and on the partition of trace-elements among these minerals, with important implications for the petrogenetic evolution of the pluton. Two main syenite types make up the pluton, a quartz-free syenite with tabular alkali feldspar (laminated silica-saturated syenite, LSS, with Na-rich augite + phlogopite + hematite + magnetite + titanite + apatite) and a quartz-bearing syenite (laminated silica-oversaturated syenite, LSO, with scarce corroded plagioclase plus diopside + biotite +/- hornblende + ilmenite magnetite +/- titanite + apatite). Both types share a remarkable enrichment in incompatible elements as K, Ba, Sr, P and LREE. Apatite saturation temperatures of similar to 1060-1090 degrees C are the best estimates of liquidus, whereas the pressure of emplacement, based on Al-in-hornblende barometry, is estimated as 3.3 to 4.8 khan Although both units crystallized under oxidizing conditions, oxygen fugacity was probably higher in LSS, as shown by higher mg# of the mafic minerals and higher hematite contents in Hem-Ilm(ss). In contrast with the Ca-bearing alkali-feldspar from LSO, which hosts most of the whole-rock Sr and Pb, virtually Ca-free alkali-feldspar from LSS hosts similar to 50% of whole-rock Sr and similar to 80% of Pb, the remainder of these elements being shared by apatite, pyroxene and titanite. This contrast reflects a strong crystal-chemical control, whereby a higher proportion of an element with similar ratio and charge (Ca2+) enhances the residence of Sr and Pb in the M-site of alkali feldspar. The more alkaline character of the LSS magma is inferred to have inhibited zircon saturation; Zr + Hf remained in solution until late in the crystallization, and were mostly accommodated in the structure of Ca-Na pyroxene and titanite, which are one order of magnitude richer in these elements compared to the same minerals in LSO, where most of Zr and Hf are inferred to reside in zircon. The REE, Th and U reside mostly in titanite and apatite; D(REE)Tit/Ap raises steadily from 1 to 6 from La to Tb then remains constant up to Lu in the LSO sample; these values are about half as much in the LSS sample, where lower contents of incompatible elements in titanite are attributed to its greater modal abundance and earlier crystallization. (C) 2012 Elsevier B.V. All rights reserved.

Retrieval of trace gases vertical profile in the lower atmosphere combining. Differential Optical Absorption Spectroscopy with radiative transfer models

The motivation for the work presented in this thesis is to retrieve profile information for the atmospheric trace constituents nitrogen dioxide (NO2) and ozone (O3) in the lower troposphere from remote sensing measurements. The remote sensing technique used, referred to as Multiple AXis Differential Optical Absorption Spectroscopy (MAX-DOAS), is a recent technique that represents a significant advance on the well-established DOAS, especially for what it concerns the study of tropospheric trace consituents. NO2 is an important trace gas in the lower troposphere due to the fact that it is involved in the production of tropospheric ozone; ozone and nitrogen dioxide are key factors in determining the quality of air with consequences, for example, on human health and the growth of vegetation. To understand the NO2 and ozone chemistry in more detail not only the concentrations at ground but also the acquisition of the vertical distribution is necessary. In fact, the budget of nitrogen oxides and ozone in the atmosphere is determined both by local emissions and non-local chemical and dynamical processes (i.e. diffusion and transport at various scales) that greatly impact on their vertical and temporal distribution: thus a tool to resolve the vertical profile information is really important. Useful measurement techniques for atmospheric trace species should fulfill at least two main requirements. First, they must be sufficiently sensitive to detect the species under consideration at their ambient concentration levels. Second, they must be specific, which means that the results of the measurement of a particular species must be neither positively nor negatively influenced by any other trace species simultaneously present in the probed volume of air. Air monitoring by spectroscopic techniques has proven to be a very useful tool to fulfill these desirable requirements as well as a number of other important properties. During the last decades, many such instruments have been developed which are based on the absorption properties of the constituents in various regions of the electromagnetic spectrum, ranging from the far infrared to the ultraviolet. Among them, Differential Optical Absorption Spectroscopy (DOAS) has played an important role. DOAS is an established remote sensing technique for atmospheric trace gases probing, which identifies and quantifies the trace gases in the atmosphere taking advantage of their molecular absorption structures in the near UV and visible wavelengths of the electromagnetic spectrum (from 0.25 μm to 0.75 μm). Passive DOAS, in particular, can detect the presence of a trace gas in terms of its integrated concentration over the atmospheric path from the sun to the receiver (the so called slant column density). The receiver can be located at ground, as well as on board an aircraft or a satellite platform. Passive DOAS has, therefore, a flexible measurement configuration that allows multiple applications. The ability to properly interpret passive DOAS measurements of atmospheric constituents depends crucially on how well the optical path of light collected by the system is understood. This is because the final product of DOAS is the concentration of a particular species integrated along the path that radiation covers in the atmosphere. This path is not known a priori and can only be evaluated by Radiative Transfer Models (RTMs). These models are used to calculate the so called vertical column density of a given trace gas, which is obtained by dividing the measured slant column density to the so called air mass factor, which is used to quantify the enhancement of the light path length within the absorber layers. In the case of the standard DOAS set-up, in which radiation is collected along the vertical direction (zenith-sky DOAS), calculations of the air mass factor have been made using “simple” single scattering radiative transfer models. This configuration has its highest sensitivity in the stratosphere, in particular during twilight. This is the result of the large enhancement in stratospheric light path at dawn and dusk combined with a relatively short tropospheric path. In order to increase the sensitivity of the instrument towards tropospheric signals, measurements with the telescope pointing the horizon (offaxis DOAS) have to be performed. In this circumstances, the light path in the lower layers can become very long and necessitate the use of radiative transfer models including multiple scattering, the full treatment of atmospheric sphericity and refraction. In this thesis, a recent development in the well-established DOAS technique is described, referred to as Multiple AXis Differential Optical Absorption Spectroscopy (MAX-DOAS). The MAX-DOAS consists in the simultaneous use of several off-axis directions near the horizon: using this configuration, not only the sensitivity to tropospheric trace gases is greatly improved, but vertical profile information can also be retrieved by combining the simultaneous off-axis measurements with sophisticated RTM calculations and inversion techniques. In particular there is a need for a RTM which is capable of dealing with all the processes intervening along the light path, supporting all DOAS geometries used, and treating multiple scattering events with varying phase functions involved. To achieve these multiple goals a statistical approach based on the Monte Carlo technique should be used. A Monte Carlo RTM generates an ensemble of random photon paths between the light source and the detector, and uses these paths to reconstruct a remote sensing measurement. Within the present study, the Monte Carlo radiative transfer model PROMSAR (PROcessing of Multi-Scattered Atmospheric Radiation) has been developed and used to correctly interpret the slant column densities obtained from MAX-DOAS measurements. In order to derive the vertical concentration profile of a trace gas from its slant column measurement, the AMF is only one part in the quantitative retrieval process. One indispensable requirement is a robust approach to invert the measurements and obtain the unknown concentrations, the air mass factors being known. For this purpose, in the present thesis, we have used the Chahine relaxation method. Ground-based Multiple AXis DOAS, combined with appropriate radiative transfer models and inversion techniques, is a promising tool for atmospheric studies in the lower troposphere and boundary layer, including the retrieval of profile information with a good degree of vertical resolution. This thesis has presented an application of this powerful comprehensive tool for the study of a preserved natural Mediterranean area (the Castel Porziano Estate, located 20 km South-West of Rome) where pollution is transported from remote sources. Application of this tool in densely populated or industrial areas is beginning to look particularly fruitful and represents an important subject for future studies.

Constraints on mantle melting from major and trace element systematics in residual abyssal peridotites

ZusammenfassungDie Bildung von mittelozeanischen Rückenbasalten (MORB) ist einer der wichtigsten Stoffflüsse der Erde. Jährlich wird entlang der 75.000 km langen mittelozeanischen Rücken mehr als 20 km3 neue magmatische Kruste gebildet, das sind etwa 90 Prozent der globalen Magmenproduktion. Obwohl ozeanische Rücken und MORB zu den am meisten untersuchten geologischen Themenbereichen gehören, existieren weiterhin einige Streit-fragen. Zu den wichtigsten zählt die Rolle von geodynamischen Rahmenbedingungen, wie etwa Divergenzrate oder die Nähe zu Hotspots oder Transformstörungen, sowie der absolute Aufschmelzgrad, oder die Tiefe, in der die Aufschmelzung unter den Rücken beginnt. Diese Dissertation widmet sich diesen Themen auf der Basis von Haupt- und Spurenelementzusammensetzungen in Mineralen ozeanischer Mantelgesteine.Geochemische Charakteristika von MORB deuten darauf hin, dass der ozeanische Mantel im Stabilitätsfeld von Granatperidotit zu schmelzen beginnt. Neuere Experimente zeigen jedoch, dass die schweren Seltenerdelemente (SEE) kompatibel im Klinopyroxen (Cpx) sind. Aufgrund dieser granatähnlichen Eigenschaft von Cpx wird Granat nicht mehr zur Erklärung der MORB Daten benötigt, wodurch sich der Beginn der Aufschmelzung zu geringeren Drucken verschiebt. Aus diesem Grund ist es wichtig zu überprüfen, ob diese Hypothese mit Daten von abyssalen Peridotiten in Einklang zu bringen ist. Diese am Ozeanboden aufgeschlossenen Mantelfragmente stellen die Residuen des Aufschmelz-prozesses dar, und ihr Mineralchemismus enthält Information über die Bildungs-bedingungen der Magmen. Haupt- und Spurenelementzusammensetzungen von Peridotit-proben des Zentralindischen Rückens (CIR) wurden mit Mikrosonde und Ionensonde bestimmt, und mit veröffentlichten Daten verglichen. Cpx der CIR Peridotite weisen niedrige Verhältnisse von mittleren zu schweren SEE und hohe absolute Konzentrationen der schweren SEE auf. Aufschmelzmodelle eines Spinellperidotits unter Anwendung von üblichen, inkompatiblen Verteilungskoeffizienten (Kd's) können die gemessenen Fraktionierungen von mittleren zu schweren SEE nicht reproduzieren. Die Anwendung der neuen Kd's, die kompatibles Verhalten der schweren SEE im Cpx vorhersagen, ergibt zwar bessere Resultate, kann jedoch nicht die am stärksten fraktionierten Proben erklären. Darüber hinaus werden sehr hohe Aufschmelzgrade benötigt, was nicht mit Hauptelementdaten in Einklang zu bringen ist. Niedrige (~3-5%) Aufschmelzgrade im Stabilitätsfeld von Granatperidotit, gefolgt von weiterer Aufschmelzung von Spinellperidotit kann jedoch die Beobachtungen weitgehend erklären. Aus diesem Grund muss Granat weiterhin als wichtige Phase bei der Genese von MORB betrachtet werden (Kapitel 1).Eine weitere Hürde zum quantitativen Verständnis von Aufschmelzprozessen unter mittelozeanischen Rücken ist die fehlende Korrelation zwischen Haupt- und Spuren-elementen in residuellen abyssalen Peridotiten. Das Cr/(Cr+Al) Verhältnis (Cr#) in Spinell wird im Allgemeinen als guter qualitativer Indikator für den Aufschmelzgrad betrachtet. Die Mineralchemie der CIR Peridotite und publizierte Daten von anderen abyssalen Peridotiten zeigen, dass die schweren SEE sehr gut (r2 ~ 0.9) mit Cr# der koexistierenden Spinelle korreliert. Die Auswertung dieser Korrelation ergibt einen quantitativen Aufschmelz-indikator für Residuen, welcher auf dem Spinellchemismus basiert. Damit kann der Schmelzgrad als Funktion von Cr# in Spinell ausgedrückt werden: F = 0.10×ln(Cr#) + 0.24 (Hellebrand et al., Nature, in review; Kapitel 2). Die Anwendung dieses Indikators auf Mantelproben, für die keine Ionensondendaten verfügbar sind, ermöglicht es, geochemische und geophysikalischen Daten zu verbinden. Aus geodynamischer Perspektive ist der Gakkel Rücken im Arktischen Ozean von großer Bedeutung für das Verständnis von Aufschmelzprozessen, da er weltweit die niedrigste Divergenzrate aufweist und große Transformstörungen fehlen. Publizierte Basaltdaten deuten auf einen extrem niedrigen Aufschmelzgrad hin, was mit globalen Korrelationen im Einklang steht. Stark alterierte Mantelperidotite einer Lokalität entlang des kaum beprobten Gakkel Rückens wurden deshalb auf Primärminerale untersucht. Nur in einer Probe sind oxidierte Spinellpseudomorphosen mit Spuren primärer Spinelle erhalten geblieben. Ihre Cr# ist signifikant höher als die einiger Peridotite von schneller divergierenden Rücken und ihr Schmelzgrad ist damit höher als aufgrund der Basaltzusammensetzungen vermutet. Der unter Anwendung des oben erwähnten Indikators ermittelte Schmelzgrad ermöglicht die Berechnung der Krustenmächtigkeit am Gakkel Rücken. Diese ist wesentlich größer als die aus Schweredaten ermittelte Mächtigkeit, oder die aus der globalen Korrelation zwischen Divergenzrate und mittels Seismik erhaltene Krustendicke. Dieses unerwartete Ergebnis kann möglicherweise auf kompositionelle Heterogenitäten bei niedrigen Schmelzgraden, oder auf eine insgesamt größere Verarmung des Mantels unter dem Gakkel Rücken zurückgeführt werden (Hellebrand et al., Chem.Geol., in review; Kapitel 3).Zusätzliche Informationen zur Modellierung und Analytik sind im Anhang A-C aufgeführt

Study of the interactions of Neptunium with humic substances and the clay mineral montmorillonite by direct and non direct speciation methods

For the safety assessment of radioactive waste, the possibility of radionuclide migration has to be considered. Since Np (and also Th due to the long-lived 232-Th) will be responsible for the greatest amount of radioactivity one million years after discharge from the reactor, its (im)-mobilization in the geosphere is of great importance. Furthermore, the chemistry of Np(V) is quite similar (but not identical) to the chemistry of Pu(V). Three species of neptunium may be found in the near field of the waste disposal, but pentavalent neptunium is the most abundant species under a wide range of natural conditions. Within this work, the interaction of Np(V) with the clay mineral montmorillonite and melanodins (as model substances for humic acids) was studied. The sorption of neptunium onto gibbsite, a model clay for montmorillonite, was also investigated. The sorption of neptunium onto γ-alumina and montmorillonite was studied in a parallel doctoral work by S. Dierking. Neptunium is only found in ultra trace amounts in the environment. Therefore, sensitive and specific methods are needed for its determination. The sorption was determined by γ spectroscopy and LSC for the whole concentration range studied. In addition the combination of these techniques with ultrafiltration allowed the study of Np(V) complexation with melanoidins. Regrettably, the available speciation methods (e.g. CE-ICP-MS and EXAFS) are not capable to detect the environmentally relevant neptunium concentrations. Therefore, a combination of batch experiments and speciation analyses was performed. Further, the preparation of hybrid clay-based materials (HCM) montmorillonitemelanoidins for sorption studies was achieved. The formation of hybrid materials begins in the interlayers of the montmorillonite, and then the organic material spreads over the surface of the mineral. The sorption of Np onto HCM was studied at the environmentally relevant concentrations and the results obtained were compared with those predicted by the linear additive model by Samadfam. The sorption of neptunium onto gibbsite was studied in batch experiments and the sorption maximum determined at pH~8.5. The sorption isotherm pointed to the presence of strong and weak sorption sites in gibbsite. The Np speciation was studied by using EXAFS, which showed that the sorbed species was Np(V). The influence of M42 type melanodins on the sorption of Np(V) onto montmorillonite was also investigated at pH 7. The sorption of the melanoidins was affected by the order in which the components were added and by ionic strength. The sorption of Np was affected by ionic strength, pointing to outer sphere sorption, whereas the presence of increasing amounts of melanoidins had little influence on Np sorption.

Effects of carbonation on the mineral composition of cement kiln dust

Due to their relatively high calcium oxide content, industrial mineral oxide wastes are potential candidates for mineral sequestration of carbon dioxide (CO2). Cement kiln dust (CKD), a byproduct of cement manufacturing contains 20-60% CaO making it a possible candidate for CO2 sequestration. In this study, three types of CKD are characterized, before and after carbonation, using environmental scanning electron microscopy and energy dispersive x-ray microanalysis to determine the mineralogical and morphological changes occurring due to carbonation. The reactants, products, and precipitation mechanisms were investigated to enhance understanding of the governing processes and allow better utilization of CKD for CO2 sequestration. The results of multiple independent analyses confirmed the formation of CaCO3 during carbonation. Examinations of the reaction pathways found that CaO and calcium hydroxide (Ca(OH)2) were the major reactants. Three types of CaCO3 precipitation mechanisms were observed: (1) diffusion of CO2 into Ca(OH)2 particles causing precipitation in the pores of the particle and the growth of a CaCO3 ring from the outside inward, (2) precipitation onto existing particles, and (3) precipitation from aqueous solution. The growth of a CaCO3 ring on the outside of a particle may slow further diffusion of CO2 into a particle slowing iv the overall sequestration rate. Additionally, changes caused by carbonation in the solubility of trace metals were studied by mixing pre- and post-carbonated CKD with water and analyzing the solution using inductively coupled plasma mass spectrometry. Decreases in the leaching of chromium, lead, and copper were observed, and is an incentive for use of CKD for CO2 sequestration. Equilibrium modeling using PHREEQC confirmed that CaO and Ca(OH)2 would carbonate readily and form CaCO3.

REE and Hf distribution among mineral phases in the CV-CK clan : a way to explain present-day Hf isotopic variations in chondrites

Chondrites are among the most primitive objects in the Solar System and constitute the main building blocks of telluric planets. Among the radiochronometers currently used for dating geological events, Sm–Nd and Lu–Hf are both composed of refractory, lithophile element. They are thought to behave similarly as the parent elements (Sm and Lu) are generally less incompatible than the daughter elements (Nd and Hf) during geological processes. As such, their respective average isotopic compositions for the solar system should be well defined by the average of chondrites, called Chondritic Uniform Reservoir (CHUR). However, while the Sm–Nd isotopic system shows an actual spread of less than 4% in the average chondritic record, the Lu–Hf system shows a larger variation range of 28% [Bouvier A., Vervoort J. D. and Patchett P. J. (2008) The Lu–Hf and Sm–Nd isotopic composition of CHUR: Constraints from unequilibrated chondrites and implications for the bulk composition of terrestrial planets. Earth Planet. Sci. Lett.273, 48–57]. To better understand the contrast between Sm–Nd and Lu–Hf systems, the REE and Hf distribution among mineral phases during metamorphism of Karoonda (CK) and Vigarano-type (CV) carbonaceous chondrites has been examined. Mineral modes were determined from elemental mapping on a set of five CK chondrites (from types 3–6) and one CV3 chondrite. Trace-element patterns are obtained for the first time in all the chondrite-forming minerals of a given class (CK chondrites) as well as one CV3 sample. This study reveals that REE are distributed among both phosphates and silicates. Only 30–50% of Sm and Nd are stored in phosphates (at least in chondrites types 3–5); as such, they are not mobilized during early stages of metamorphism. The remaining fraction of Sm and Nd is distributed among the same mineral phases; these elements are therefore not decoupled during metamorphism. Of the whole-rock total of Lu, the fraction held in phosphate decreases significantly as the degree of metamorphism increases (30% for types 3 and 4, less than 5% in type 6). In contrast to Lu, Hf is mainly hosted by silicates with little contribution from phosphates throughout the CK metamorphic sequence. A significant part of Sm and Nd are stored in phosphates in types 3–5, and these elements behave similarly during CK chondrite metamorphism. That explains the robustness of the Sm/Nd ratios in chondrites through metamorphism, and the slight discrepancies observed in the present-day isotopic Nd values in chondrites. On the contrary, Lu and Hf are borne by several different minerals and consequently they are redistributed during metamorphism–induced recrystallization. The Lu/Hf ratios are therefore significantly disturbed during chondrites metamorphism, leading to the high discrepancies observed in present-day Hf isotopic values in chondrites.

Fluid-related inclusions in Alpine high-pressure peridotite reveal trace element recycling during subduction-zone dehydration of serpentinized mantle (Cima di Gagnone, Swiss Alps).

Serpentinites release at sub-arc depths volatiles and several fluid-mobile trace elements found in arc magmas. Constraining element uptake in these rocks and defining the trace element composition of fluids released upon serpentinite dehydration can improve our understanding of mass transfer across subduction zones and to volcanic arcs. The eclogite-facies garnet metaperidotite and chlorite harzburgite bodies embedded in paragneiss of the subduction melange from Cima di Gagnone derive from serpentinized peridotite protoliths and are unique examples of ultramafic rocks that experienced subduction metasomatism and devolatilization. In these rocks, metamorphic olivine and garnet trap polyphase inclusions representing the fluid released during high-pressure breakdown of antigorite and chlorite. Combining major element mapping and laser-ablation ICP-MS bulk inclusion analysis, we characterize the mineral content of polyphase inclusions and quantify the fluid composition. Silicates, Cl-bearing phases, sulphides, carbonates, and oxides document post-entrapment mineral growth in the inclusions starting immediately after fluid entrapment. Compositional data reveal the presence of two different fluid types. The first (type A) records a fluid prominently enriched in fluid-mobile elements, with Cl, Cs, Pb, As, Sb concentrations up to 10(3) PM (primitive mantle), similar to 10(2) PM Tit Ba, while Rb, B, Sr, Li, U concentrations are of the order of 10(1) PM, and alkalis are similar to 2 PM. The second fluid (type B) has considerably lower fluid-mobile element enrichments, but its enrichment patterns are comparable to type A fluid. Our data reveal multistage fluid uptake in these peridotite bodies, including selective element enrichment during seafloor alteration, followed by fluid-rock interaction along with subduction metamorphism in the plate interface melange. Here, infiltration of sediment-equilibrated fluid produced significant enrichment of the serpentinites in As, Sb, B, Pb, an enriched trace element pattern that was then transferred to the fluid released at greater depth upon serpentine dehydration (type A fluid). The type B fluid hosted by garnet may record the composition of the chlorite breakdown fluid released at even greater depth. The Gagnone study-case demonstrates that serpentinized peridotites acquire water and fluid-mobile elements during ocean floor hydration and through exchange with sediment-equilibrated fluids in the early subduction stages. Subsequent antigorite devolatilization at subarc depths delivers aqueous fluids to the mantle wedge that can be prominently enriched in sediment-derived components, potentially triggering arc magmatism without the need of concomitant dehydration/melting of metasediments or altered oceanic crust.