Sulphide ore minerals:surface chemical properties

The surfaces of iron-containing sulphide minerals were oxidised by a range of inorganic oxidants, and the resultant surface alteration products studied using various spectroscopic techniques. The characterisation of surface oxidation is relevant to the alteration of ores in nature and their behaviour during flotation and leaching, of importance to the metallurgical industry. The sulphides investigated included pyrite (FeS2), hexagonal pyrrhotine (Fe9S10), monoclinic pyrrhotine (Fe7Se), violarite (FeNi2S4), pentlandite ((FeiNi)9Se), chalcopyrite (CuFeS2) and arsenopyrite (FeAsS). The surfaces were oxidised by various methods including acid (sulphuric), alkali (ammonium hydroxide), hydrogen peroxide, steam, electrochemical and air/oxygen (in a low-temperature (150ºC) furnace), The surfaces were examined using surface sensitive chemical spectroscopic methods including x-ray photoelectron spectroscopy (ms), Auger electron spectroscopy (LES) and conversion electron Mössbauer spectroscopy (CEKS). Physical characterisation of the surfaces was undertaken using scanning electron microscopy (SM), spectral reflectance measurements and optical microscopy. Bulk characterisation of the sulphide minerals was undertaken using x-ray diffraction and electron microprobe techniques. Observed phases suggested to form in most of the sulphide surfaces include Fe204, Fe1-x0, Fe202, Fe00H, Fe(OH)3, with iron II & III oxy-sulphates. The iron sulphides show variable extents of oxidation, indicating pyrite to be the most stable. Violarite shows stability to oxidation, suggested to result from both its stable spinel crystal structure, and from the rapid formation of sulphur at the surface protecting the sub-surface from further oxidation. The phenomenon of sub-surface enrichment (in metals), forming secondary sulphides, is exhibited by pentlandite and chalcopyrite, forming violarite and copper sulphides respectively. The consequences of this enrichment with regard to processing and leaching are discussed. Arsenopyrite, often a hindrance in ore processing, exhibits the formation of arsenic compounds at the surface, the dissolution of which is discussed in view of the possible environmental hazard caused by the local pollution of water systems. The results obtained allow a characterisation of the sulphides in terms of their relative stability to oxidation, and an order of stability of the sulphide surfaces is proposed. Models were constructed to explain the chemical compositions of the surfaces, and the inter-relationships between the phases determined at the surface and in the sub-surface. These were compared to the thermo-chemically predicted phases shown in Eh/pH and partial pressure diagrams! The results are discussed, both in terms of the mineralogy and geochemistry of natural ores, and the implications for extraction and processing of these ore minerals.

The sedimentology and diagenesis of Lower Permian (Rotliegend) sediments: (onshore U.K. and southern North Sea). Available in 2 volumes.

The thesis provides a comparative study of both sedimentology and diagenesis of Lower Permian (Rotliegend) strata, onshore and offshore U.K. (Southern North Sea). Onshore formations studied include the Bridgnorth, Penrith and Hopeman Sandstone, and are dominated by aeolian facies, with lesser amounts of interbedded fluvial sediments. Aeolian and fluvial strata in onshore basins typically grade laterally into alluvial fan breccias at basin margins. Onshore basins represent proximal examples of Rotliegend desert sediments. The Leman Sandstone Formation of the Ravenspurn area in the Southern North Sea displays a variety of facies indicative of a distal sedimentological setting; Aeolian, fluvial, sabkha, and playa lake sediments all being present. "Sheet-like" geometry of stratigraphical units within the Leman Sandstone, and alternation of fluvial and aeolian deposition was climatically controlled. Major first order bounding surfaces are laterally extensive and were produced by lacustrine transgression and regression from the north-west. Diagenesis within Permian strata was studied using standard petrographic microscopy, scanning electron microscopy, cold cathodo-Iuminescence, X-ray diffraction clay analysis, X-ray fluorescence spectroscopy, fluid inclusion microthermometry, and K-Ar dating of illites. The diagenesis of Permian sediments within onshore basins is remarkably similar, and a paragenetic sequence of early haematite, illitic clays, feldspar, kaolinite, quartz and late calcite is observed. In the Leman Sandstone formation, authigenic mineralogy is complex and includes early quartz, sulphates and dolomite, chlorite, kaolinite, late quartz, illite and siderite. Primary lithological variation, facies type, and the interdigitation and location of facies within a basin are important initial controls upon diagenesis. Subsequently, burial history, structure, the timing of gas emplacement, and the nature of sediments within underlying formations may also exersize significant controls upon diagenesis within Rotliegend strata.

Importance of syndecan-4 and syndecan -2 in osteoblast cell adhesion and survival mediated by a tissue transglutaminase-fibronectin complex

Tissue transglutaminase (TG2) has been identified as an important extracellular crosslinking enzyme involved in matrix turnover and in bone differentiation. Here we report a novel cell adhesion/survival mechanism in human osteoblasts (HOB) which requires association of FN bound TG2 with the cell surface heparan sulphates in a transamidase independent manner. This novel pathway not only enhances cell adhesion on FN but also mediates cell adhesion and survival in the presence of integrin competing RGD peptides. We investigate the involvement of cell surface receptors and their intracellular signalling molecules to further explore the pathway mediated by this novel TG-FN heterocomplex. We demonstrate by siRNA silencing the crucial importance of the cell surface heparan sulphate proteoglycans syndecan-2 and syndecan-4 in regulating the compensatory effect of TG-FN on osteoblast cell adhesion and actin cytoskeletal formation in the presence of RGD peptides. By use of immunoprecipitation and inhibitory peptides we show that syndecan-4 interacts with TG2 and demonstrate that syndecan-2 and the a5ß1 integrins, but not a4ß1 function as downstream modulators in this pathway. Using function blocking antibodies, we show activation of a5ß1 occurs by an inside out signalling mechanism involving activation and binding of protein kinase PKCa and phosphorylation of focal adhesion kinase (FAK) at Tyr861 and activation of ERK1/2.

Characterization of Transglutaminase 2 in macrophage clearance of apoptotic cells

Removal of dead or diseased cells is crucial feature of apoptosis for managing many biological processes such as tissue remodelling, tissue homeostasis and resolution and control of immune responses throughout life. Tissue transglutaminase (TG2) is a protein crosslinking enzyme that has been implicated in apoptotic cell clearance but also mediates many important cell functions including cell adhesion, migration and monocyte-macrophage differentiation. Cell surface-associated TG2 regulates cell adhesion and migration, via its association with receptors such as syndecan-4, ß1 and ß3 integrin. Whilst defective apoptotic cell clearance has been described in TG2-deficient mice, the precise extracellular role of TG2 in apoptotic cell clearance remains ill-defined. This thesis addresses macrophage TG2 in cell corpse clearance. TG2 expression (cytosolic and cell surface) in human macrophages was revealed and data demonstrate that loss of TG2 activity through the use of inhibitors of function, including cellimpermeable inhibitors significantly inhibit the ability of macrophages to clear apoptotic cells (AC). This includes reduced macrophage recruitment to and binding of apoptotic cells. Association studies reveal TG2-syndecan-4 interaction through heparan sulphate side chains, and knockdown of syndecan-4 reduces cell surface TG2 activity and apoptotic cell clearance. Furthermore, inhibition of TG2 activity reduces crosslinking of CD44, reported to augment AC clearance. Thus it defines for the first time a role for TG2 activity at the cell surface of human macrophages in multiple stages of AC clearance and proposed that TG2, in association with heparan sulphates, may exert its effect on AC clearance via crosslinking of CD44.

Transglutaminase 2 interacts with syndecan-4 and CD44 at the surface of human macrophages to promote removal of apoptotic cells

Tissue transglutaminase (TG2) is a multifunctional protein cross-linking enzyme that has been implicated in apoptotic cell clearance but is also important in many other cell functions including cell adhesion, migration and monocyte to macrophage differentiation. Cell surface-associated TG2 regulates cell adhesion and migration, via its association with receptors such as syndecan-4 and β1 and β3 integrins. Whilst defective apoptotic cell clearance has been described in TG2-deficient mice, the precise role of TG2 in apoptotic cell clearance remains ill-defined. Our work addresses the role of macrophage extracellular TG2 in apoptotic cell corpse clearance. Here we reveal TG2 expression and activity (cytosolic and cell surface) in human macrophages and demonstrate that inhibitors of protein crosslinking activity reduce macrophage clearance of dying cells. We show also that cell-impermeable TG2 inhibitors significantly inhibit the ability of macrophages to migrate and clear apoptotic cells through reduced macrophage recruitment to, and binding of, apoptotic cells. Association studies reveal TG2-syndecan-4 interaction through heparan sulphate side chains, and knockdown of syndecan-4 reduces cell surface TG2 activity and apoptotic cell clearance. Furthermore, inhibition of TG2 activity reduces crosslinking of CD44, reported to augment AC clearance. Thus our data define a role for TG2 activity at the surface of human macrophages in multiple stages of AC clearance and we propose that TG2, in association with heparan sulphates, may exert its effect on AC clearance via a mechanism involving the crosslinking of CD44.

Assessing hydrothermal liquefaction for the production of bio-oil and enhanced metal recovery from microalgae cultivated on acid mine drainage

The hydrothermal liquefaction(HTL) of algal biomass is a promising route to viable second generation biofuels. In this investigation HTL was assessed for the valorisation of algae used in the remediation of acid mine drainage (AMD). Initially the HTL process was evaluated using Arthrospira platensis (Spirulina) with additional metal sulphates to simulate metal remediation. Optimised conditions were then used to process a natural algal community (predominantly Chlamydomonas sp.) cultivated under two scenarios: high uptake and low uptake of metals from AMD. High metal concentrations appear to catalyse the conversion to bio-oil, and do not significantly affect the heteroatom content or higher heating value of the bio-oil produced. The associated metals were found to partition almost exclusively into the solid residue, favourable for potential metal recovery. High metal loadings also caused partitioning of phosphates from the aqueous phase to the solid phase, potentially compromising attempts to recycle process water as a growth supplement. HTL was therefore found to be a suitable method of processing algae used in AMD remediation, producing a crude oil suitable for upgrading into hydrocarbon fuels, an aqueous and gas stream suitable for supplementing the algal growth and the partitioning of most contaminant metals to the solid residue where they would be readily amenable for recovery and/or disposal.

Assessing hydrothermal liquefaction for the production of bio-oil and enhanced metal recovery from microalgae cultivated on acid mine drainage

The hydrothermal liquefaction(HTL) of algal biomass is a promising route to viable second generation biofuels. In this investigation HTL was assessed for the valorisation of algae used in the remediation of acid mine drainage (AMD). Initially the HTL process was evaluated using Arthrospira platensis (Spirulina) with additional metal sulphates to simulate metal remediation. Optimised conditions were then used to process a natural algal community (predominantly Chlamydomonas sp.) cultivated under two scenarios: high uptake and low uptake of metals from AMD. High metal concentrations appear to catalyse the conversion to bio-oil, and do not significantly affect the heteroatom content or higher heating value of the bio-oil produced. The associated metals were found to partition almost exclusively into the solid residue, favourable for potential metal recovery. High metal loadings also caused partitioning of phosphates from the aqueous phase to the solid phase, potentially compromising attempts to recycle process water as a growth supplement. HTL was therefore found to be a suitable method of processing algae used in AMD remediation, producing a crude oil suitable for upgrading into hydrocarbon fuels, an aqueous and gas stream suitable for supplementing the algal growth and the partitioning of most contaminant metals to the solid residue where they would be readily amenable for recovery and/or disposal.

Downstream processing of reverse osmosis brine: Characterisation of potential scaling compounds

Reverse osmosis (RO) brine produced at a full-scale coal seam gas (CSG) water treatment facility was characterized with spectroscopic and other analytical techniques. A number of potential scalants including silica, calcium, magnesium, sulphates and carbonates, all of which were present in dissolved and non-dissolved forms, were characterized. The presence of spherical particles with a size range of 10-1000nm and aggregates of 1-10 microns was confirmed by transmission electron microscopy (TEM). Those particulates contained the following metals in decreasing order: K, Si, Sr, Ca, B, Ba, Mg, P, and S. Characterization showed that nearly one-third of the total silicon in the brine was present in the particulates. Further, analysis of the RO brine suggested supersaturation and precipitation of metal carbonates and sulphates during the RO process should take place and could be responsible for subsequently capturing silica in the solid phase. However, the precipitation of crystalline carbonates and sulphates are complex. X-ray diffraction analysis did not confirm the presence of common calcium carbonates or sulphates but instead showed the presence of a suite of complex minerals, to which amorphous silica and/or silica rich compounds could have adhered. A filtration study showed that majority of the siliceous particles were less than 220nm in size, but could still be potentially captured using a low molecular weight ultrafiltration membrane. © 2015 Elsevier Ltd.

Avaliação do potencial anti-inflamatório, anticoagulante e hemorrágico de heparinóides presentes em "Artemia franciscana"

Heparan sulfate (HS) and Heparin (Hep) glycosaminoglycans (GAGs) are heterogeneous and highly charged polysaccharides. HS is structurally related to Hep but is much less substituted with sulfo groups than heparin and has a more varied structure (or sequence). Because of structural similiarities between these two polymers, they have been described together as heparinoids . Both chains bind a variety of proteins and mediate various physiologically important processes including, blood coagulation, cell adhesion and growth factor regulation. Heparinoids with structural characteristics similar to these described from HS and/or Hep from mammalian tissues have been isolated from different species of invertebrates, although only a few heparinoids from unusual sources have been characterized. The present study describes the presence of unusual heparinoids population from Artemia franciscana, isolated after proteolysis and fractionation by ion exchange resin and named, F-3.0M. The study model in vivo were hemostasis (rat tail scarification) and inflamatoty activity. The tests in vitro were used for coagulations assays (PT and APTT). The analyse of the heparinoids eluted with 3,0M NaCl showed electrophoretic migration in different buffer systems a single band with a behaviour intermediate between those of mammalian HEP and HS. The main products obtained from Artemia heparinoids after enzymatic degradation with heparitinases I and II from F. heparinum were N-sulphated disaccharides (∆U-GlcNS,6S/ ∆U,2S-GlcNS and ∆U-GlcNS) and N-acetylated disaccharides (∆U, GlcNAc). This heparinoid had a lower hemorrhagic effect (400μg/ml) when compared to unfractiionated heparins(25μg/ml).The results also suggest a negligible APTT activity of this heparinoid (62.2s). No action was observed on PT indicating that F-3.0M haven t action on the extrinsic pathway. The results showed that the fraction F- 3.0M have inhibitory effect on migration of leukocytes, 64.5% in the concentration of 10 μg/ml (P<0.001). The search for new heparin and/or heparan sulphates analogs devoid of anticoagulant activity is an atractive alternative and may open up a wide variety of new therapeutic applications

Chemical resistance of lime-based grouts for masonry strengthening

The stone masonry walls are present in many buildings and historical monuments, with undeniable asset value, but also in old buildings housing both in Portugal and in Europe. Most of these buildings in masonry are in certain cases in a high state of degradation needing urgent intervention. This requires the identification of deficiencies and the application of appropriate intervention techniques. One of the possible techniques for structural consolidation works of stone masonry walls is the injection of fluid mortars currently called grouts. The choice of grouts is very important with regard in particular to their chemical and physical properties. In this study, carried out under the Master of Chemical Engineering, two types of lime-based grouts were used, in order to evaluate and compare their chemical resistance due to the crystallization of soluble salts. One of the grouts is a pre-dosed blend commercially available, Mape-Antique I from company Mapei (CA), and the second grout is a mixture prepared in the laboratory (LB), comprising metakaolin, cement, hydrated lime, water and superplasticizer. With the purpose of evaluating the action of sulphates on these grouts, a series of samples underwent several wetting-drying cycles using two different temperatures, 20 °C and 50 °C. During the experiment it was determined the change of weight and compressive strength in the analyzed grouts, as well as the sulphate ion concentration and pH of the solution in which the samples were dipped. The commercial grout (CA) apparently has a greater chemical resistance to sulphates. However grout LB showed to have positive results in some parameters.

Influence of autogenous shrinkage on mass transport properties of concrete

La retracción autógena en el hormigón es el cambio volumétrico una vez iniciado su proceso de fraguado. Se desarrolla a edades muy tempranas debido a la retracción química y a la autodesecación. Éstos causan microfisuras en hormigones de alta resistencia y permiten el ingreso de agentes nocivos como dióxido de carbono, cloruros y sulfatos que deterioran al hormigón. A pesar de haber estudios de la retracción autógena, existe incertidumbre sobre su influencia en la durabilidad del hormigón. Por ello, el motivo del presente estudio es cuantificar y analizar el efecto de la retracción autógena en el hormigón usando tres pruebas de transporte: difusión de oxígeno, permeabilidad de oxígeno y absorción de agua. Dos métodos, para tres diferentes aglutinantes, fueron usados para determinar la mezcla control que produce menor retracción: utilizando SRA y realizando el curado en un cuarto de niebla. Posteriormente, los resultados de las pruebas de transporte entre la mezcla de control seleccionada y mezclas altamente afectadas por retracción autógena fueron comparados para diferentes aglutinantes. Resultados revelaron que muestras con SRA presentan menores retracciones autógenas y se sugiere que estas muestras sean consideradas de control. Se demostró que la retracción autógena afecta significativamente los coeficientes de transporte los cuales en un punto de vista de servicio pueden reducir la vida útil de cualquier estructura realizada con hormigón de alta resistencia. Esta investigación además confirmó que la mayor deformación autógena ocurre durante las dos primeras semanas; por lo tanto, se debe tomar cuidado suficiente en el curado.