Olive stones (OS) constitute a waste lignocellulosic material produced by the olive oil industry in great amounts, that currently is only used as a low-value energy source for industrial or domestic boilers. Having in view its full valorization, this work proposes and validates an integrated strategy aiming to obtain three different streams of sugars / lignin-derived compounds. Dilute acid hydrolysis was used to obtain a xylose-rich hydroysate that was chemically converted into furfural with a 48.7 % yield. The resulting acid-pretreated solid biomass that consisted mainly of lignin and cellulose, was subjected to a catalyzed ethanol-based organosolv delignification. Temperature, time, and sulphuric acid concentration were optimized in order to recover added-value lignin products and digestible cellulose. At the optimal conditions (190 ᵒC and 30 min), a 50 % delignification was reached, together with the highest enzymatic hydrolysis yields (190 g glucose/kg of OS). Phenolic compounds content in organosolv liquors reached 41.6 mg GAE/g OS. This extract presented an antioxidant capacity up to 10.9 mg TE/g OS. The pretreated solid fraction was used as a substrate for ethanol production by a pre-saccharification and simultaneous saccharification and fermentation process, enabling to obtain an ethanol concentration of 47 g/L, with a fermentation yield of 61.4 % of the theoretical maximum. Globally, from 100 kg of OS processed according to this experimental scheme, 6.9 kg of furfural, 6.2 kg of ethanol, 7.4 kg of lignin, and 4.2 kg of phenolics compounds can be obtained as main products, thus constituting a way of valorization of renewable material in a multiproduct biorefinery strategy.
A CuCrFeTiV high entropy alloy was prepared and irradiated with swift heavy ions in order to check its adequacy for use as a thermal barrier in future nuclear fusion reactors. The alloy was prepared from the elemental powders by ball milling, followed by consolidation by spark plasma sintering at 1178 K and 65 MPa. The samples were then irradiated at room temperature with 300 keV Ar⁺ ions with fluences in the 3 × 10¹⁵ to 3 × 10¹⁸ Ar⁺/cm² range to mimic neutron-induced damage accumulation during a duty cycle of a fusion reactor. Structural changes were investigated by X-ray diffraction, and scanning electron microscopy and scanning transmission electron microscopy, both coupled with X-ray energy dispersive spectroscopy. Surface irradiation damage was detected for high fluences (3 × 10¹⁸ Ar⁺/cm²) with formation of blisters of up to 1 μm in diameter. Cross-sectional scanning transmission electron microscopy showed the presence of intergranular cavities only in the sample irradiated with 3 × 10¹⁸ Ar⁺/cm², while all irradiation experiments produced intragranular nanometric-sized bubbles with increased density for higher Ar⁺ fluence. The Williamson-Hall method revealed a decrease in the average crystallite size and an increase in residual strain with increasing fluence, consistent with the formation of Ar⁺ bubbles at the irradiated surface.
A mineralogical study of Gonçalo lithium-bearing mica-rich pegmatite ore (Portugal) indicated that lepidolite occurs in coarse-grained textures, which allows an appreciable liberation of gangue minerals (quartz, k-feldspar, and albite) from lepidolite. However, the intergrowth of these gangue minerals results in uncomplicated liberation (i.e., inclusions). Taking advantage of this coarse gangue liberation, optical ore sorting through image analysis was attempted in order to predict the grades of different-sized fractions using a random comminution algorithm. The ore-sorting process allowed the production of a marketable Li pre-concentrate product for metallurgy. Moreover, this method also highlighted the possible valuation of the reject as low-Li-content quartz–feldspar mixtures for the ceramic industry (reduction in the temperature of porosity closing). Furthermore, a scaled approach of grinding and sieving allowed the formation of a lepidolite-rich fraction (>210 μm), which was processed using an electrostatic separator by varying key process parameters. The lepidolite and muscovite were separated to obtain a Li pre-concentrate assaying 3.5 % Li2O from a feed grade containing 1.8 % Li2O. Nevertheless, according to the zeta-potential measurements, the flotation test performed with the finer-sized fraction (–210 + 63 μm) showed that lepidolite flotation was optimised between pH 3 and 5. In this pH range, concentrates from the rougher stage assayed 4.2–4.5 % Li2O, corresponding to 87–95 % Li recovery. At pH > 5, the selectivity decreases, and SiO2 analysis suggests the flotation of quartz and other silicates rather than lepidolite. Feldspar/quartz flotation was also tested using lepidolite flotation rejects to promote the separation of feldspars from quartz and obtain products for ceramic applications.
The worldwide targets for carbon-neutral societies increased the penetration of distributed generation and storage. Smart cities now play a key role in achieving these targets by considering the alliances of their demand and supply assets as local citizen energy communities. These communities need to have enough weight to trade electricity in wholesale markets. Trading of electricity can be done in spot markets or by bilateral contracts involving customers and suppliers. This paper is devoted to bilateral contracting, which is modeled as a negotiation process involving an iterative exchange of offers and counter-offers. This article focuses on local citizen energy communities. Specifically, it presents team and single-agent negotiation models, where each member has its sets of strategies and tactics and also its decision model. Community agents are equipped with intra-team strategies and decision protocols. To evaluate the benefits of CECs, models of both coalition formation and management have been adapted. This paper also describes a case study on forward bilateral contracts, involving a retailer agent and three different types of citizen energy communities. The results demonstrate the benefits of CECs during the negotiation of private bilateral contracts of electricity. Furthermore, they also demonstrate that in the case of using a representative strategy, the selection of the mediator may be critical for achieving a good deal.
The present study shows a comparison between two sintering processes, microwave and conventional sintering, for the manufacture of NiTi porous specimens starting from powder mixtures of nickel and titanium hydrogenation–dehydrogenation (HDH) milled by mechanical alloying for a short time (25 min). The samples were sintered at 850 °C for 15 min and 120 min, respectively. Both samples exhibited porosity, and the pore size results are within the range of the human bone. The NiTi intermetallic compound (B2, R-phase, and B19′) was detected in both sintered samples through X-ray diffraction (XRD) and electron backscattering diffraction (EBSD) on scanning electron microscopic (SEM). Two-step phase transformation occurred in both sintering processes with cooling and heating, the latter occurring with an overlap of the peaks, according to the differential scanning calorimetry (DSC) results. From scanning electron microscopy/electron backscatter diffraction, the R-phase and B2/B19′ were detected in microwave and conventional sintering, respectively. The instrumented ultramicrohardness results show the highest elastic work values for the conventionally sintered sample. It was observed throughout this investigation that using mechanical alloying (MA) powders enabled, in both sintering processes, good results, such as intermetallic formation and densification in the range for biomedical applications.
The presence of inhibitor compounds in the culture medium can cause severe effects on the microorganisms cells. Brewery wastewaters present organic acids (acetic, propionic and butyric acids) which can severely affect yeast cells metabolism, when grown in pure cultures, although in mixed cultures they are able to develop. To understand the physiological changes on Rhodotorula toruloides (formerly Rhodosporidium toruloides) cells when fermenting in the presence of the organic acids present in brewery wastewater, pure and mixed cultures with the microalga Tetradesmus obliquus were performed in a synthetic medium containing the same organic acids concentrations that are present in brewery wastewater at pH 4 and 6. It was concluded that, at pH 4, the organic acids effects in the yeast cells were much more toxic than at pH 6. Moreover, mixed cultures can be an advantage over heterotrophic pure cultures as the microalga is able to contribute for the consumption of potential inhibitors for the yeast.
Organosolv pre-treatments aiming to selectively remove and depolymerise lignin and hemicellulose and yield an easily digestible cellulose fraction are one of the potential options for industrial implementation within the biorefinery concept. However, the use of high temperatures and/or high catalyst concentrations is still hindering its wide adoption. In this work, mild temperature organosolv processes (140 °C) that were either non-catalysed or catalysed with sulphuric or acetic acid were compared to standard similar conditions using ethanol-based organosolv for both wheat straw (WS) and eucalyptus wood residues (ERs) as agricultural and forestry-derived model raw materials, respectively. The experimental results demonstrated that high cellulose purities could be obtained for the catalysed ethanol-based processing of the WS, which resulted in high saccharification yields (>80%), conversely to the non-catalysed process, which only reached values close to 70%. For eucalyptus residues (ERs), the pulp yields obtained were lower than the values obtained for the WS, suggesting that the ERs were a more reactive material. Cellulose purity was higher than that obtained for the corresponding treatment for the WS, with the highest cellulose purity being obtained for the ethanol-based process catalysed with sulphuric acid. Both materials presented high lignin yield recovery in the liquid stream.
Climate change may increase water needs for irrigation in southern Europe competing with other water uses, such as hydropower, which may likely be impacted by lower precipitation. Climate change will also potentially affect the variability and availability of other renewable energy resources (solar and wind) and electricity consumption patterns. This work quantifies the effect of competition for water use between irrigation and hydropower in the future 2050 Portuguese carbon-neutral power sector under Representative Concentration Pathway 8.5 climate change projections. It uses the power system eTIMES_PT model to assess the combined effects of climate change impacts on irrigation, hydropower, wind and solar PV on the cost-optimal configuration of the power sector. eTIMES_PT is a linear optimisation model that satisfies electricity demand at a minimal power system costs. Results show that, by 2050, climate change can lead to an increase of demand for irrigation water up 12% in Tagus and 19% in Douro watersheds from 2005 values, with substantially higher values for Spring (up to 84%). Combining these supplementary water needs with the expected reduction in river runoff can lead to a decline in Summer and Spring hydropower capacity factors from half to three times below current values. By 2050, concurrent water uses under climate change can reduce hydropower generation by 26–56% less than historically observed, mainly in summer and spring. Higher solar PV, complemented with batteries’ electricity storage can offset the lower hydropower availability, but this will lead to higher electricity prices. Adequate transboundary water management agreements and reducing water losses in irrigation systems will play a key role in mitigating climate impacts in both agriculture and power sector.
The Sustainable Value methodology was used to compare and rank eight combinations of waste biomass types and conversion technologies on a common assessment basis to produce energy, energy vectors and advanced biofuels. The studied combinations included agricultural and agro-industrial residues, slurries and effluents, pulp and paper mill sludge, piggery effluents and organic fractions of municipal solid waste, to produce biodiesel by (trans)esterification, biogas by anaerobic digestion, ethanol by fermentation, hydrogen by dark fermentation, electricity and heat by combustion, biogas and synthesis gas by gasification, and bio-oils by pyrolysis or hydrothermal liquefaction. The numerator “Functional Performance” of the Sustainable Value indicator was estimated according to 14 criteria of process technology, material and energy inputs and outputs, and acceptance by the stakeholders. The performance of the technologies was classified based on the values of relative importance (φ) and level of satisfaction (S) attributed to each criterion. The gasification of residues from the olive-oil industry reached the highest “Functional Performance”, followed by anaerobic digestion of chestnut processing residues and pig-rearing effluents. The Sustainable Value denominator “Costs” depended mainly on the degree of maturity of the technologies, which penalised pyrolysis, hydrothermal liquefaction and dark fermentation. The final ranking of the Sustainable Value indicator was gasification > combustion > anaerobic digestion > (trans)esterification > pyrolysis and fermentation to ethanol > hydrothermal liquefaction > dark fermentation, respectively for the most adequate waste biomass types under study. Thermochemical conversions were mainly impacted by process and input criteria, while output and social acceptance criteria were more decisive for the biochemical conversions.
The Multi-scale Laboratories (MSL) are a network of European laboratories bringing together the scientific fields of analogue modeling, paleomagnetism, experimental rock and melt physics, geo- chemistry and microscopy. MSL is one of nine (see below) Thematic Core Services (TCS) of the European Plate Observing System (EPOS). The overarching goal of EPOS is to establish a compre- hensive multidisciplinary research platform for the Earth sciences in Europe. It aims at facilitating the integrated use of data, models, and facilities, from both existing and new distributed pan European Research Infrastructures, allowing open access and transparent use of data. The TCS MSL network allows researchers to collaborate with other labs and scientists. By becoming part of the rapidly growing TCS MSL network, new laboratories are offered a platform to showcase their research data output, laboratory equipment and information, and the opportunity to open laboratories to guest researchers through the Transnational Access (TNA) program. The EPOS Multi-scale laboratories offer researchers a fully operational data publication chain tailored to the specific needs of laboratory research, from a bespoke metadata editor, through dedi cated, (domainspecific) data repositories, to the MSL Portal showcasing these citable data publica- tions. During this process the data publications are assigned with digital object identidiers (DOI), published with open licenses (e.g. CC BY 4.0) and described with standardized and machine-read- able rich metadata (following the FAIR Principles to make research data Findable, Accessible, Interoperable and Reusable. The TCS MSL is currently working on linking these data publications to the EPOS Central Portal1, the main discovery and access point for European multi-disciplinary data, and on increasing the number of connected data repositories.
In this study, Rhodosporidium toruloides and Tetradesmus obliquus were used for lipid and carotenoid production in mixed cultures using primary brewery wastewater (PBWW) as a culture medium, supplemented with sugarcane molasses (SCM) as a carbon source and urea as a nitrogen source. To improve biomass, lipid, and carotenoid production by R. toruloides and T. obliquus mixed cultures, initial SCM concentrations ranging from 10 to 280 g L⁻¹ were tested. The medium that allowed higher lipid content (26.2% w/w dry cell weight (DCW)) and higher carotenoid productivity (10.47 µg L⁻¹ h⁻¹) was the PBWW medium supplemented with 100 g L⁻¹ of SCM and 2 g L⁻¹ of urea, which was further used in the fed-batch mixed cultivation performed in a 7-L bioreactor. A maximum biomass concentration of 58.6 g L⁻¹ and maximum lipid content of 31.2% w/w DCW were obtained in the fed-batch cultivation. PBWW supplemented with SCM was successfully used as a low-cost medium to produce lipids and carotenoids in a R. toruloides and T. obliquus mixed culture, with higher productivities than in pure cultures, which can significantly reduce the cost of the biofuels obtained.
In this work, new doped Nafion membranes for PEMFC are prepared by casting with 1 wt% loading of the prepared indazole- and condensed pyrazolebisphosphonic acids (AzBPs). The new membranes were analysed by ATR-FTIR spectroscopy and their morphology was examined by SEM. Membranes were evaluated for water uptake and ion exchange capacity (IEC), and their hydration number was estimated. The proton conduction properties of the modified membranes were evaluated by electrochemical impedance spectroscopy (EIS), at different temperatures (30, 40, 50 and 60 °C) and relative humidity (RH) (40, 60 and 80%). The proton conductivities of all membranes increase with increasing temperature and RH. Also, all new membranes doped with AzBPs exhibited higher proton conductivities than Nafion N-115, used as a reference and tested at the same experimental conditions, with values up to 1.5-fold. Results show that the incorporation of AzBPs dopants on Nafion membranes enhances the proton conduction throughout the modified membranes. The best proton conductivity was observed for membranes with AzBP1 as dopant, with a value of 94 mS cm-¹. These results indicate that the Nafion membranes doped with indazole- and condensed pyrazolebisphosphonic acids are a promising approach for new membranes for PEMFC with improved proton conductivity.
Market agents with renewable resources face amplified uncertainty when forecasting energy production to securely place bids in electricity markets. To deal with uncertainties, stochastic modelling has been applied to optimize the bidding strategy of these market agents. However, studies found in the literature usually focus on day-ahead and balancing markets, leaving aside intraday markets that could be used to correct bidding positions as uncertainty gets resolved. This paper proposes a multistage stochastic decision-aid algorithm based on linear programming to optimize the bidding strategy of market agents in three different electricity markets - day-ahead, intraday, and balance markets. The market agent represents a Virtual Power Plant with wind, solar PV, and storage technologies, and its participation in three electricity markets was compared to the participation in DA and BM markets only. Results show that participating in all three markets increased the profit achieved by the VPP agent by 10.1% while also decreasing the incurred imbalances by 63.8%. The results demonstrate that having accurate tools to deal with the multi-settlement framework of electricity markets while considering the uncertainties of daily operations is key to a successful integration of renewable energy resources into electricity markets and power systems.
Bluish-grey limestones have been extensively used as ornamental stones for decoration purposes in buildings, as well as in works of art, and accordingly, have been the target of intense exploration. In Portugal, the Jurassic limestone massif known as the Maciço Calcário Estremenho (MCE), has been the source of grey-coloured ornamental stones, namely the Azul Valverde (one of the most well-known bluish-grey limestones) and Atlantic Blue varieties, both of which may undergo colour changes in outdoor environments. In this sense, it is important to understand the sudden colour change from bluish-grey to yellow/beige in the same limestone block in a quarry, or even, what happens to the colour when polished limestone is placed outdoors. This study was undertaken using various techniques, namely XRF (X-ray fluorescence spectrometry), XRD (X-ray diffraction), SEM (scanning electron microscopy), DTA–TG (differential thermal analysis/thermogravimetry) and colourimetry. Synchrotron radiation was also used at the European Synchrotron Radiation Facility (ESRF, Grenoble, France) where XANES (X-ray Absorption Near Edge Structure) spectra at Fe K-edge were collected to ascertain the speciation state of Fe in different coloured zones of the limestone, previously checked by EDXRF (energy dispersive X-ray fluorescence). The presence of Fe2+ and Fe3+ are responsible for the greyish and yellow/brown colour, respectively. On the other hand, the UV radiation from the sun causes a quickened and severe bleaching/fading on the dark blue/grey polished limestone.
Algae have been consumed for millennia in several parts of the world as food, food supplements, and additives, due to their unique organoleptic properties and nutritional and health benefits. Algae are sustainable sources of proteins, minerals, and fiber, with well-balanced essential amino acids, pigments, and fatty acids, among other relevant metabolites for human nutrition. This review covers the historical consumption of algae in Europe, developments in the current European market, challenges when introducing new species to the market, bottlenecks in production technology, consumer acceptance, and legislation. The current algae species that are consumed and commercialized in Europe were investigated, according to their status under the European Union (EU) Novel Food legislation, along with the market perspectives in terms of the current research and development initiatives, while evaluating the interest and potential in the European market. The regular consumption of more than 150 algae species was identified, of which only 20% are approved under the EU Novel Food legislation, which demonstrates that the current legislation is not broad enough and requires an urgent update. Finally, the potential of the European algae market growth was indicated by the analysis of the trends in research, technological advances, and market initiatives to promote algae commercialization and consumption.
High-pressure pre-treatment followed by supercritical carbon dioxide (ScCO2) extraction (300 bar, 40 °C) was applied for the attainment of the lipophilic fraction of microalga Tetradesmus obliquus. The chemical profile of supercritical extracts of T. obliquus was analyzed by ultra-high-performance liquid chromatography–high-resolution mass spectrometry with electrospray ionization (UHPLC-ESI-HRMS). Moreover, the impact of ScCO2 on the microbiological and metal profile of the biomass was monitored. The application of the pre-treatment increased the extraction yield approximately three-fold compared to the control. In the obtained extracts (control and pre-treated extracts), the identified components belonged to triacylglyceroles, fatty acid derivatives, diacylglycerophosphocholines and diacylglycerophosphoserines, pigments, terpenes, and steroids. Triacylglycerols (65%) were the most dominant group of compounds in the control extract. The pre-treatment decreased the percentage of triacylglycerols to 2%, while the abundance of fatty acid derivatives was significantly increased (82%). In addition, the pre-treatment led to an increase in the percentages of carotenoids, terpenoids, and steroids. Furthermore, it was determined that ScCO2 extraction reduced the number of microorganisms in the biomass. Considering its microbiological and metal profiles, the biomass after ScCO2 can potentially be used as a safe and important source of organic compounds.
Energy crops are dedicated cultures directed for biofuels, electricity, and heat production. Due to their tolerance to contaminated lands, they can alleviate and remediate land pollution by the disposal of toxic elements and polymetallic agents. Moreover, these crops are suitable to be exploited in marginal soils (e.g., saline), and, therefore, the risk of land-use conflicts due to competition for food, feed, and fuel is reduced, contributing positively to economic growth, and bringing additional revenue to landowners. Therefore, further study and investment in R&D is required to link energy crops to the implementation of biorefineries. The main objective of this study is to present a review of the potential of selected energy crops for bioenergy and biofuels production, when cultivated in marginal/degraded/contaminated (MDC) soils (not competing with agriculture), contributing to avoiding Indirect Land Use Change (ILUC) burdens. The selected energy crops are Cynara cardunculus, Arundo donax, Cannabis sativa, Helianthus tuberosus, Linum usitatissimum, Miscanthus × giganteus, Sorghum bicolor, Panicum virgatum, Acacia dealbata, Pinus pinaster, Paulownia tomentosa, Populus alba, Populus nigra, Salix viminalis, and microalgae cultures. This article is useful for researchers or entrepreneurs who want to know what kind of crops can produce which biofuels in MDC soils.
Mannosylerythritol lipids (MELs) are biosurfactants with excellent biochemical properties and a wide range of potential applications. However, high production costs, low productivity and unsatisfactory scale-up production have hampered commercial adoption. Herein, we report for the first time the β-galactosidase production by Moesziomyces spp. from different sugars (D-galactose, D-glucose and D-lactose), with D-galactose being the best β-galactosidase inducer, with 11.2 and 63.1 IU/mgbiomass, for Moesziomyces aphidis 5535 T and Moesziomyces antarcticus 5048 T, respectively. The production of this enzyme allows to break down D-lactose and thus to produce MEL directly from D-lactose or cheese whey (a cheese industry by-product). Remarkably, when CW was used as sole media component (carbon and mineral source), in combination with waste frying oil, MEL productivities were very close (1.40 and 1.31 gMEL/L/day) to the ones obtained with optimized medium containing yeast extract (1.92 and 1.50 gMEL/gsusbtrate), both for M. antarcticus and M. aphidis. The low-cost, facile and efficient process which generates large amounts of MELs potentiates its industrialization. Supplementary information: The online version contains supplementary material available at 10.1007/s13399-022-02837-y.
Brewery wastewater (BWW) is an appealing low-cost substrate for the production of single cell oils by oleaginous microorganisms. However, it may contain inhibitor compounds that may affect the microbial metabolism. This work investigated, for the first time, the presence of potential inhibitor compounds in primary brewery wastewater (PBWW) and secondary brewery wastewater (SBWW) for the pure and mixed cultivation of the yeast Rhodosporidium toruloides NCYC 921 and the microalga Tetradesmus obliquus ACOI 204/07. Three organic acids (OrgAc) were identified in the brewery effluents (acetic, propionic and butyric acids). Yeast and microalga pure and mixed cultivations were performed in PBWW and SBWW in order to understand the behaviour of the microorganisms, individually and together. Flow cytometry (FC) was used to monitor each microbial population during the mixed cultivations, and to study the yeast and microalga cell viability throughout all cultivations. The yeast cells in pure cultures grown in both effluents were severely affected by the OrgAc presence confirmed by the cell stress results obtained by FC. However, in the mixed cultures, the yeast cells were able to develop, and the levels of stress conditions were considerably lower. Only in microalga pure and mixed cultures efficient OrgAc removal was observed.
Located in the Iberian pyrite belt, the Neves–Corvo mine is a world-class massive sulfide deposit and the largest operating mine in Portugal with underground mining down to 1000 m depth focused on massive and stockwork Cu, Zn, Pb rich ores. Gravimetric data have had a leading role in the discovery of the seven known deposits, together with time-domain electromagnetic (TEM) ground data. In this work, we present the results of a 3D constrained gravity inversion carried out with legacy ground gravity data. The 3D gravity inversions were carried out using an updated density database containing approximately 142,000 measurements. A recently constructed 3D geological model based on reprocessed 2D seismic reflection, 3D seismic, TEM and updated geology from detailed surface mapping and drill-hole data, was used to constrain the inversions. The results show multiple high-density anomalies that may indicate the presence of mineralization at depth. These anomalies were therefore cross-checked with holes previously drilled. Approximately 97% of more than 1000 available surface drill-holes located on or at a distance of less than 200 m from the high-density anomalies intersected mineralization. However, gravity anomalies have been drilled in the past and particularly dense black shales or rhyolitic/gabbroic rocks have been intersected. To increase the success of future drilling, gravimetric anomalies have been correlated spatially with high-conductivity TEM zones and strong-amplitude seismic reflections, because igneous rocks usually present weak-to-moderate conductivity and a massive column of black shales presents a seismic signature quite different from that of mineralization. We concluded that some of these locations represent high-quality targets to consider following up with drilling and further exploration.
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