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The use of vegetable oils to produce biodiesel raises several sustainability issues, namely the fuel/food conflict. The high cost of vegetable oils and an expensive homogeneous base catalyzed process encourages the search for alternative raw materials and more efficient production processes. Biodiesel from beef tallow, a non-edible fat, was produced by methanolysis over calcium based heterogeneous catalyst. The catalyst was prepared by calcination of scallop shells at 800 ​°C. To overcome the undesired effect of the tallow acidity (3.9 mgKOH/gfat), mixtures of tallow and soybean oil (SBO) (0.6 mgKOH/gfat) were processed and alcohol co-solvents (isopropanol, 1-propanol, and isobutanol) and biodiesel itself, as a solvent, were used to improve the miscibility of the reaction mixture. Processing of neat tallow promotes an important decay of the catalytic activity due to the partial neutralization of the basic catalyst. Co-processing mixtures of tallow/SBO allowed minimizing the acidity effect. Alcohol co-solvents harmed the biodiesel yield due to competitive adsorption of alcohols with methanol on catalyst active sites but protected the catalyst against adsorption of the reaction mixture species. Biodiesel used as a solvent had an almost null effect on the esterification reaction yield, thus showing the absence of mass transfer limitation. Co-processing low-grade fat with vegetable oil seems to be a feasible strategy to process low-grade fats using basic heterogeneous catalysts, thus contributing to improving the sustainability of biodiesel production.

The on-board identification of ore minerals during a cruise is often postponed until long after the cruise is over. During the M127 cruise, 21 cores with deep-seafloor sediments were recovered in the Trans-Atlantic Geotraverse (TAG) field along the Mid Atlantic Ridge (MAR). Sediments were analyzed on-board for physicochemical properties such as lightness (L*), pH and Eh. Selected samples were studied for mineral composition by X-ray powder diffraction (XRD). Based on XRD data, sediment samples were separated into high-, low- and non-carbonated. Removal of carbonates is a common technique in mineralogical studies in which HCl is used as the extraction agent. In the present study, sequential extraction was performed with sodium acetate buffer (pH 5.0) to remove carbonates. The ratio between the highest calcite XRD reflection in the original samples (Iorig) vs its XRD-reflection in samples after their treatment with the buffer (Itreat) was used as a quantitative parameter of calcite removal, as well as to identify minor minerals in carbonated samples (when Iorig/Itreat &gt, 24). It was found that the lightness parameter (L*) showed a positive correlation with calcite XRD reflection in selected TAG samples, and this could be applied to the preliminary on-board determination of extraction steps with acetate buffer (pH 5.0) in carbonated sediment samples. The most abundant minerals detected in carbonated samples were quartz and Al- and Fe-rich clays. Other silicates were also detected (e.g., calcic plagioclase, montmorillonite, nontronite). In non-carbonated samples, Fe oxides and hydroxides (goethite and hematite, respectively) were detected. Pyrite was the dominant hydrothermal mineral and Cu sulfides (chalcopyrite, covellite) and hydrothermal Mn oxides (birnessite and todorokite) were mineral phases identified in few samples, whereas paratacamite was detected in the top 20 cm of the core. The present study demonstrates that portable XRD analysis makes it possible to characterize mineralogy at cored sites, in particular in both low- and high-carbonated samples, before the end of most cruises, thus enabling the quick modification of exploration strategies in light of new information as it becomes available in near-real time.

22 páginas.-- 6 figuras.-- 115 referencias.-- Additional Supporting Information may be found in the online version of this article: http://dx.doi.org/10.1111/sed.12431, Subsurface granitic environments are scarce and poorly investigated. A multi‐disciplinary approach was used to characterize the abundant moonmilk deposits and associated microbial communities coating the granite walls of the 16th Century Paranhos spring water tunnel in Porto city (north‐west Portugal). It is possible that this study is the first record of moonmilk in an urban subsurface granitic environment. The morphology and texture, mineralogical composition, stable isotope composition and microbial diversity of moonmilk deposits have been studied to infer the processes of moonmilk formation. These whitish secondary mineral deposits are composed of very fine needle‐fibre calcite crystals with different morphologies and density. Calcified filaments of fungal hyphae or bacteria were distinguished by field emission scanning electron microscopy. Stable isotope analysis revealed a meteoric origin of the needle‐fibre calcite, with an important contribution of atmospheric CO2, soil respiration and urn:x-wiley:00370746:media:sed12431:sed12431-math-0001 from weathering of Ca‐bearing minerals. The DNA‐based analyses revealed the presence of micro‐organisms related to urban contamination, including Actinobacteria, mainly represented by Pseudonocardia hispaniensis, Thaumarchaeota and Ascomycota, dominated by Cladosporium. This microbial composition is consistent with groundwater pollution and contamination sources of the overlying urban area, including garages, petrol stations and wastewater pipeline leakage, showing that the Paranhos tunnel is greatly perturbed by anthropogenic activities. Whether the identified micro‐organisms are involved in the formation of the needle‐fibre calcite or not is difficult to demonstrate, but this study evidenced both abiotic and biogenic genesis for the calcite moonmilk in this subsurface granitic environment., The authors acknowledge the Spanish Ministry of Economy, Industry and Competitiveness (MINEICO, project CGL2011-2569) and the Portuguese Foundation for Science and Technology, FCT (UID/GEO/04035/2013, UID/ECI/04028/2013, PEst-OE/CTE/UI0098/2011) and the LABCARGA| ISEP re-equipment program (IPP-ISEP|PAD’2007/ 08) for financial support. AZM thanks MINEICO for the ‘Juan de la Cierva – Incorporación’ postdoctoral contract (IJCI-2014-20443). PMMS thanks the Spanish Ministry of Science and Innovation for his contract associated with the ‘Research Programme in Technologies for the Assessment and Conservation of Cultural Heritage’ (TCP CSD2007-0005

The recovery of lithium from hard rock minerals has received increased attention given the high demand for this element. Therefore, this study optimized an innovative process, which does not require a high-temperature calcination step, for lithium extraction from lepidolite. Mechanical activation and acid digestion were suggested as crucial process parameters, and experimental design and response-surface methodology were applied to model and optimize the proposed lithium extraction process. The promoting effect of amorphization and the formation of lithium sulfate hydrate on lithium extraction yield were assessed. Several factor combinations led to extraction yields that exceeded 90%, indicating that the proposed process is an effective approach for lithium recovery. info:eu-repo/semantics/publishedVersion

Black crusts on different substrates (carbonate and silicate stones, cement-based mortar and carbonate detrital deposits) in urban environments were characterized microscopically by analysing their morphologies and compositions. The objective of this article is to study the interaction between the substrate and the crust and the influence of the environmental conditions on the crust development. On the one hand, the internal structure and morphology of each sample were evaluated with stereo and scanning electron microscopies. On the other hand, the black crust composition was accessed by X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy in backscattered electron mode combined with energy dispersive x-ray spectroscopy. The results of these analytical techniques provided interesting information about the composition and the mineralogical phases present in the collected black crusts. In most of the cases, gypsum was detected as the main component exhibiting different habits. Calcite was also detected in all the evaluated gypsum black crusts; its presence was attributed to different origins. The substrate-crust interaction was also evaluated, contributing to distinguish different crust development processes in relation to the substrate. In carbonate substrates (limestones, mortar and carbonate detrital deposits), it was detected a continuous diffuse boundary related to the replacement of Ca-carbonate by Ca-sulphate, while this boundary was significantly more defined for the granitic stone. This study shows that the substrate, the presence of different construction materials, (e.g. mortars), the motor exhaust particulate substances and the concentrations of atmospheric pollutants, the marine influence as well as biological or other anthropogenic compounds are decisive factors in the development of the black crust. Some ideas about the establishment of conservation strategies are also shown.

Mechanical activation in order to improve lithium recovery from a lepidolite ore concentrate was investigated. The concentrate was mechanically activated using different milling times and the effect on the resulting products was evaluated by X-ray powder diffraction, FTIR spectroscopy, TG-DTG analysis, SEM and particle size analysis by laser diffraction. The mechanical activation leads to lepidolite amorphization and concomitant improvement of the reactivity by sulfuric acid digestion and water leaching. About 85% of Li recovery was achieved when the concentrate was activated for 15 min and afterwards digested at 165 °C, during 4 h, using an acid/concentrate ratio of 650 g/kg. Li recoveries above 70% were reached even using digestion temperatures lower than 100 °C. However, to increase recovery, temperatures over 140 °C are more suitable. Results obtained showed that is possible to apply a low temperature technology for recovering Li from hard rock minerals, using mechanical activation.

Calcium diglyceroxide (CaD) was used as the catalyst for biodiesel production through oil methanolysis. It was evaluated its catalytic behavior, its air expo- sure tolerance, and the Ca leaching. CaD catalyst was synthesized from food waste scallop shell derived CaO (obtained by calcination at 900 °C) by contacting with a mixture of equal volumes of glycerin and methanol at 65 °C for 2 h. The CaO obtained by calcination of scallop shell was used as reference catalyst. In standard reaction conditions (2.5 h, methanol reflux temperature, 5 wt% (oil basis) catalyst loading, and methanol:oil = 12:1 moral ratio), CaD presented lower catalytic activity than CaO (FAME yield of 92% against 99%, respectively). 24 h repined CaD presented improved catalytic behavior probably due to the formation of surface Ca −OH groups, achieving 96% of FAME yield. Thermogravimetry (TG) data showed that inorganic residue was larger for biodiesel than for glycerin, being CaD catalyst more soluble than CaO. Data showed that CaD is unstable under reaction conditions, suffering leaching, but the absence of Matter Organic Non-Glycerol (MONG) in the glycerin phase allows to neglect the homogeneous contribution of the leached catalyst. CaD formation during reaction contributes to FAME contamination with Ca and promotes catalyst deactivation thus being an undesired occurrence.

Milled municipal solid waste incinerator bottom ash was used as a precursor in the production of alkali-activated mortars with recycled concrete aggregates as a sand substitute. Fly ash was used as control precursor and sodium hydroxide as an alkaline activator. Different thermal curing regimens were used: 24 h in ambient conditions; 24 h/70 °C; 48 h/70 °C; and 24 h/90 °C. Mechanical and durability-related performances were evaluated (i.e. flexural and compressive strength, modulus of elasticity, ultrasonic pulse velocity, carbonation, capillary water absorption, and shrinkage). The reaction between metallic aluminium from municipal solid waste incinerator bottom ash and OH− ions produced hydrogen gas, causing expansion, porosity increase and thus decline in performance. Low stability in high relative humidity settings due to leaching of highly soluble compounds was also observed. A further decline in performance was observed in mixes containing recycled aggregates. Alkali activated municipal solid waste incinerator bottom ash presented fast carbonation but also a considerable strength enhancement.

The lithium extraction from a lepidolite concentrate using roasting, followed by water leaching, was studied. Several alternative additives were initially tested. The use of sodium and calcium sulfates as additives was evaluated in more detail. The influence of some process variables, namely the roasting time, roasting temperature and the additive/concentrate mass ratio, was studied applying a design of experiments. The lithium extraction was modelled and the fitted and validated model was used to optimize the process response. The increase in the additive/concentrate mass ratio, roasting time and temperature seems to result in solid state reactions and transformations that lead to phase, morphological and particle size distribution modifications, which were assessed by XRPD, SEM, and particle size analyses. In this process, lithium sodium sulfate formation constitutes a crucial step enabling the Li water leaching. High lithium extractions were estimated for several combinations of factors. At 850...

Stone coatings, biological colonization, efflorescence and detachments are frequent on granitic surfaces of our cultural heritage infrastructure. In order to find the different origins for each deterioration form, this paper studies and compares several coatings, efflorescence and flakes found on granitic surfaces of bridges from different ages built in the same area (Ourense in NW Iberian Peninsula at 90 km from the sea) under the same environmental and traffic conditions. The most recent bridge was the New Bridge built in the beginning of 20th century and the oldest one was the Roman Bridge with the 1st century AD foundations but its current structure was built in 17th century. The New Bridge has exhibited a greater variety of deterioration forms such as black crusts, carbonate crusts, efflorescence and biological colonization. On the Roman Bridge, black crusts, efflorescence to a greater extent, and flakes associated with salt crystallization processes have been identified. Scanning electron microscopy with energy dispersive X-ray spectroscopy, X-ray diffraction and Fourier transform infrared (FTIR) spectroscopy studies were carried out in order to establish their composition, and optical and electronic microscopies and X-ray microtomography were used to study their morphologies. As a result, anthropogenic factors (industrial activities, traffic pollution and fertilizers) are considered to be the main contributors to crusts, efflorescence and flake formation on both studied substrates (granite ashlars and mortars). To a lesser extent, natural factors (marine influence and bird droppings) should be taken into account.

Lithium extraction from hard-rock ores has regained importance due to the increased demand for this metal to supply the growing battery market. Therefore, several studies have been focused on the lithium extraction from ores, however, leaching and purification steps are sparsely studied. Thus, the objective of this study was to evaluate the main factors affecting the water leaching step and the subsequent purification operations for lithium recovery from a lepidolite concentrate, which was processed by mechanical activation and sulphuric acid digestion. In the leaching step, among the variables studied, only one, the leaching temperature, showed a significant effect on the lithium extraction, taking into account the range of values tested. Thus, the recommended operating value for the leaching time and the L/S ratio is the minimum, while for the leaching temperature is 50°C. After optimizing the leaching operation, the purification of the leachate, by neutralization, was thoroughly performed by efficient removal of impurities (Fe, Al, Mn and Ca), allowing to obtain lithium carbonate as final product, as well as other relevant by-products, such as rubidium and potassium alums. info:eu-repo/semantics/publishedVersion

9 páginas.-- 3 figuras.-- 2 tablas.-- 83 referencias.-- Selected paper from the XVI Latin-American Congress on Chromatography (XVICOLACRO) and the 9th National Meeting on Chromatography (9ENC), 5–9 January 2016, Lisbon, Portugal., This study comprises an innovative approach based on the combination of chromatography (analytical pyrolysis and pyrolysis compound-specific isotope analysis (Py-CSIA)), light stable isotopes, microscopy and mineralogy analyses to characterize the internal layering of coralloid speleothems from the Ana Heva lava tube in Easter Island (Chile). This multidisciplinary proxy showed that the speleothems consist of banded siliceous materials of low crystallinity with different mineralogical compositions and a significant contribution of organic carbon. Opal-A constitutes the outermost grey layer of the coralloids, whereas calcite and amorphous Mg hydrate silicate are the major components of the inner whitish and honey-brown layers, respectively. The differences found in the mineralogical, elemental, molecular and isotopic composition of these distinct coloured layers are related to environmental changes during speleothem development. Stable isotopes and analytical pyrolysis suggested alterations in the water regime, pointing to wetter conditions during the formation of the Ca-rich layer and a possible increase in the amount of water dripping into the cave. The trend observed for δN values suggested an increase in the average temperature over time, which is consistent with the so-called climate warming during the Holocene. The pyrolysis compound-specific isotope analysis of each speleothem layer showed a similar trend with the bulk δC values pointing to the appropriateness of direct Py-CSIA in paleoenvironmental studies. The δC values for n-alkanes reinforced the occurrence of a drastic environmental change, indicating that the outermost Opal layer was developed under drier and more arid environmental conditions., A.Z. Miller acknowledges the support from the Marie Curie Intra-European Fellowship of the European Commission’s 7th Framework Programme (PIEF-GA-2012-328689). The Spanish Ministry of Economy and Competitiveness (MINECO, project CGL2013-41674-P) and the FEDER Funds are acknowledged for the financial support. N.T. Jiménez-Morillo thanks the MINECO for funding his pre-doctoral FPI fellowship (BES-2013-062573).

Cellulose acetate (CA)–silver (Ag) nanocomposite asymmetric membranes were prepared via the wet-phase inversion method by dispersing polyvinylpirrolydone-protected Ag nanoparticles in the membrane casting solutions of different compositions. Silver nanoparticles were synthesized ex situ and added to the casting solution as a concentrated aqueous colloidal dispersion. The effects of the dispersion addition on the structure and on the selective permeation properties of the membranes were studied by comparing the nanocomposites with the silver-free materials. The casting solution composition played an important role in the adequate dispersion of the silver nanoparticles in the membrane. Incorporation of nanoscale silver and the final silver content resulted in structural changes leading to an increase in the hydraulic permeability and molecular weight cut-off of the nanocomposite membranes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41796.

The development of polymer-calcium phosphate composite scaffolds with tailored architectures and properties has great potential for bone regeneration. Herein, we aimed to improve the functional performance of brittle ceramic scaffolds by developing a promising biopolymer-ceramic network. For this purpose, two strategies, namely, direct printing of a powder composition consisting of a 60:40 mixture of α/β-tricalcium phosphate (TCP) powder and alginate powder or vacuum infiltration of printed TCP scaffolds with an alginate solution, were tracked. Results of structural characterization revealed that the scaffolds printed with 2.5 wt% alginate-modified TCP powders presented a uniformly distributed and interfusing alginate TCP network. Mechanical results indicated a significant increase in strength, energy to failure and reliability of powder-modified scaffolds with an alginate content in the educts of 2.5 wt% when compared to pure TCP, as well as to TCP scaffolds containing 5 wt% or 7.5 wt% in the educts, in both dry and wet states. Culture of human osteoblast cells on these scaffolds also demonstrated a great improvement of cell proliferation and cell viability. While in the case of powder-mixed alginate TCP scaffolds, isolated alginate gels were formed between the calcium phosphate crystals, the vacuum-infiltration strategy resulted in the covering of the surface and internal pores of the TCP scaffold with a thin alginate film. Furthermore, the prediction of the scaffolds' critical fracture conditions under more complex stress states by the applied Mohr fracture criterion confirmed the potential of the powder-modified scaffolds with 2.5 wt% alginate in the educts as structural biomaterial for bone tissue engineering.

Sherds representative of the three Portuguese faience production centers of the 17th century – Lisbon, Coimbra and Vila Nova were studied with the use of mostly non-invasive spectroscopies, namely: ground state diffuse reflectance absorption (GSDR), micro-Raman, Fourier-transform infrared (FT-IR) and proton induced X-ray (PIXE) or X-ray fluorescence emission (XRF). X-ray diffraction (XRD) experiments were also performed. The obtained results evidence a clear similarity in the pastes of the pottery produced Vila Nova and some of the ceramic pastes from Lisbon, in accordance with documental sources that described the use of Lisbon clays by Vila Nova potters, at least since mid 17th century. Quartz and Gehlenite are the main components of the Lisbon’s pastes, but differences between the ceramic pastes were detected pointing out to the use of several clay sources. The spectroscopic trend exhibited Coimbra’s pottery is remarkably different, Quartz and Diopside being the major components of these pastes, enabling one to well define a pattern for these ceramic bodies. The blue pigment from the Lisbon samples is a cobalt oxide that exists in the silicate glassy matrix, which enables the formation of detectable cobalt silicate microcrystals in most productions of the second half of the 17th century. No micro-Raman cobalt blue signature could be detected in the Vila Nova and Coimbra blue glazes. This is in accordance with the lower kiln temperatures in these two production centers and with Co 2+ ions dispersed in the silicate matrix. In all cases the white glaze is obtained with the use of tin oxide. Hausmannite was detected as the manganese oxide mineral used to produce the purple glaze (wine color “vinoso”) in Lisbon.

11 páginas.-- 8 figuras.-- 1 tabla.-- 33 referencias, Coralloid-type speleothems were recorded on the ceiling of the Ana Heva lava tube in Easter Island (Chile). These speleothems were morphologically, geochemically and mineralogically characterized using a wide variety of microscopy and analytical techniques. They consist dominantly of amorphous Mg silicate and opal-A. Field emission scanning electron microscopy revealed a variety of filamentous and bacillary bacteria on the surface of the Ana Heva coralloid speleothems, including silicified filamentous microorganisms. Among them, intriguing reticulated filaments resemble those filaments documented earlier in limestone caves and lava tubes. The identification of silicified microorganisms on the coralloid speleothems from the Ana Heva lava tube suggests a possible role of these microorganisms in silica deposition. © 2014 Copyright Taylor and Francis Group, LLC., This research was partially financed by Portuguese Funds through FCT- Fundaçao para a Ciencia e a Tecnologia (PEst-OE/CTE/UI0098/2011) and also by the Spanish Ministry of Science and Innovation (Project CGL2011–2569). This work was supported by FCT grant to AZM (SFRH/BPD/63836/2009).