Browsing by Author "Duarte, Hugo"
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- Advancements in detection and mitigation strategies for Petroleum-Derived contaminants in aquatic environments: a comprehensive reviewPublication . Duarte, Hugo; Aliaño González, María José; Medronho, BrunoThe exponential increase in the production and transportation of petroleum-derived products observed in recent years has been driven by the escalating demand for energy, textiles, plastic-based materials, and other goods derived from petroleum. Consequently, there has been a corresponding rise in spills of these petroleum derivatives, particularly in water sources utilized for transportation or, occasionally, illegally utilized for tank cleaning or industrial equipment maintenance. Numerous researchers have proposed highly effective techniques for detecting these products, aiming to facilitate their cleanup or containment and thereby minimize environmental pollution. However, many of these techniques rely on the identification of individual compounds, which presents significant drawbacks, including complexity of handling, subjectivity, lengthy analysis times, infeasibility for in situ analysis, and high costs. In response, there has been a notable surge in the utilization of sensors or generalized profiling techniques serving as sensors to generate characteristic fingerprints of these products, thereby circumventing the aforementioned disadvantages. This review comprehensively examines the evolution of techniques employed for detecting petroleum-derived products in water samples, along with their associated advantages and disadvantages. Furthermore, the review examines current perspectives on methods for the removal and/or containment of these products from water sources, to minimize their environmental impact and the associated health repercussions on living organisms and ecosystems.
- Engineering novel phenolic foams with lignin extracted from pine wood residues via a new levulinic-acid assisted processPublication . Melro, Elodie; Duarte, Hugo; Antunes, Filipe E.; Valente, Artur J.M.; Romano, Anabela; Norgren, Magnus; Medronho, BrunoPhenolic foams are typically produced from phenolic resins, using phenol and formaldehyde precursors. Therefore, common phenolic foams are non-sustainable, comprising growing environmental, health, and economic concerns. In this work, lignin extracted from pine wood residues using a "green" levulinic acid-based solvent, was used to partially substitute non-sustainable phenol. The novel engineered foams were systematically compared to foams composed of different types of commercially available technical lignins. Different features were analyzed, such as foam density, microstructure (electron microscopy), surface hydrophilicity (contact angle), chemical grafting (infrared spectroscopy) and mechanical and thermal features. Overall, it was observed that up to 30 wt% of phenol can be substituted by the new type of lignin, without compromising the foam properties. This work provides a new insights on the development of novel lignin-based foams as a very promising sustainable and renewable alternative to petrol-based counterparts.
- From a new cellulose solvent to the cyclodextrin induced formation of hydrogelsPublication . Medronho, Bruno; Duarte, Hugo; Magalhaes, Solange; Alves, Luis; Valente, Artur J. M.; Romano, AnabelaA new efficient solvent for cellulose dissolution was developed based on the mixture of aqueous tetrabutylammonium hydroxide, TBAH(aq) and an organic co-solvent, dimethylsulfoxide (DMSO). Clear cellulose solutions were readily obtained at mild conditions in a few minutes. The viscoeleastic properties of the dopes formed are found to be dependent on the cellulose content and TBAH(aq)/DMSO ratio. Additionally, stiff hydrogels are formed when adding beta-cyclodextrin (beta-CD) to the cellulose dopes. The formation of a host-guest complex between the beta-CD and the tetrabutylammonium cations (TBA(+)), which presumably destabilizes the cellulose solution state triggering the hydrogel formation, is suggested as mechanism. The robust hydrogels formed have been characterized regarding their viscoelasticity, microscopic morphology and release properties. The kinetics and released amount of the TBA(+) from the cellulose gel matrixes are found to be strongly dependent on the balance between average pore diameter, surface area and free volume of the hydrogels. (C) 2017 Elsevier B.V. All rights reserved.
- Lignin-furanic rigid foams: Enhanced methylene blue removal capacity, recyclability, and flame retardancyPublication . Duarte, Hugo; Brás, João; Saoudi Hassani, El Mokhtar; Aliaño González, María José; Magalhães, Solange; Alves, Luís; Valente, Artur J. M.; Eivazi, Alireza; Norgren, Magnus; Romano, Anabela; Medronho, BrunoWorldwide, populations face issues related to water and energy consumption. Water scarcity has intensified globally, particularly in arid and semiarid regions. Projections indicate that by 2030, global water demand will rise by 50%, leading to critical shortages, further intensified by the impacts of climate change. Moreover, wastewater treatment needs further development, given the presence of persistent organic pollutants, such as dyes and pharmaceuticals. In addition, the continuous increase in energy demand and rising prices directly impact households and businesses, highlighting the importance of energy savings through effective building insulation. In this regard, tannin-furanic foams are recognized as promising sustainable foams due to their fire resistance, low thermal conductivity, and high water and chemical stability. In this study, tannin and lignin rigid foams were explored not only for their traditional applications but also as versatile materials suitable for wastewater treatment. Furthermore, a systematic approach demonstrates the complete replacement of the tannin-furan foam phenol source with two lignins that mainly differ in molecular weight and pH, as well as how these parameters affect the rigid foam structure and methylene blue (MB) removal capacity. Alkali-lignin-based foams exhibited notable MB adsorption capacity (220 mg g−1), with kinetic and equilibrium data analysis suggesting a multilayer adsorption process. The prepared foams demonstrated the ability to be recycled for at least five adsorption-desorption cycles and exhibited effective flame retardant properties. When exposed to a butane flame for 5 min, the foams did not release smoke or ignite, nor did they contribute to flame propagation, with the red glow dissipating only 20 s after flame exposure.
- On cellulose dissolution and aggregation in aqueous tetrabutylammonium hydroxidePublication . Gubitosi, Marta; Duarte, Hugo; Gentile, Luigi; Olsson, Ulf; Medronho, BrunoAqueous tetrabutylammonium hydroxide, TBAH(aq), has been found to dissolve cellulose and to be a potential solvent for chemical processing or fiber spinning. In this paper, we have investigated the dissolution state of cellulose in 40 wt % TBAH(aq) solvent, and present an extensive study of rheology, combined with static light and small-angle X-ray scattering, to correlate cellulose aggregation with changes in the rheological parameters. Two cellulose molecular weights are compared. Microcrystalline cellulose (MCC), with a degree of polymerization of ca. 260, and a dissolving pulp with an approximately ten times higher molecular weight. Scattering data demonstrate that cellulose is molecularly dissolved at lower cellulose concentrations, while aggregates are present when the concentration exceeds a certain value. The onset of the aggregate formation is marked by a pronounced increase in the scattering intensity at low q, shear thinning behavior and violation of the empirical Cox-Merz rule. Additionally, the SAXS data suggest the presence of a solvation shell enriched in TBA+ ions, compared to the bulk solvent. The results are consistent with the recent suggestion that while native cellulose I may still dissolve, solutions are, above a particular concentration, becoming supersaturated with respect to the more stable crystal form cellulose II.
- On the development of Phenol-Formaldehyde resins using a new type of lignin extracted from pine wood with a Levulinic-Acid based solventPublication . Melro, Elodie; Antunes, Filipe E.; Valente, Artur J. M.; Duarte, Hugo; Romano, A.; Medronho, BrunoResole resins have many applications, especially for foam production. However, the use of phenol, a key ingredient in resoles, has serious environmental and economic disadvantages. In this work, lignin extracted from pine wood using a “green” solvent, levulinic acid, was used to partially replace the non-sustainable phenol. The physicochemical properties of this novel resin were compared with resins composed of different types of commercial lignins. All resins were optimized to keep their free formaldehyde content below 1 wt%, by carefully adjusting the pH of the mixture. Substitution of phenol with lignin generally increases the viscosity of the resins, which is further increased with the lignin mass fraction. The addition of lignin decreases the kinetics of gelification of the resin. The type and amount of lignin also affect the thermal stability of the resins. It was possible to obtain resins with higher thermal stability than the standard phenol-formaldehyde resins without lignin. This work provides new insights regarding the development of lignin-based resoles as a very promising sustainable alternative to petrol-based resins.
- On the optimization of carob seed peel extraction using aqueous-based acidic systemsPublication . Medronho, Bruno; boutoub, Oumaima; Duarte, Hugo; Aliaño González, María José; Guerra, Rui; Brazio, António; Gonçalves, Sandra; Romano, AnabelaCarob fruit utilization remains limited, with most of their commercial value derived from locust bean gum, which is obtained from seed endosperm. Efficient extraction requires dehusking, which is traditionally performed under harsh conditions. This study aims to develop and optimize a milder, more sustainable dehusking method while preserving seed quality for industrial applications. Various aqueous-based solvents were tested, leading to the selection of metanesulfonic acid (CH4O3S). A Box-Behnken design with response surface methodology optimized the process, using husk removal efficiency as the response variable. The optimized conditions were 24.5 g of seeds treated in 50 mL of a solvent mixture (41% CH4O3S and 59% H2SO4) at 90 degrees C for 10 min, followed by washing by 5 min with water (87 mL). The treated seeds were analyzed using colorimetry assays and diffusive reflectance spectroscopy and benchmarked against both pristine and dehusked seeds from a local company. The resulting seeds remained morphologically intact and exhibited appealing color characteristics comparable to commercial samples. The optimized method ensured intact seed morphology and color characteristics comparable to commercial standards, offering a viable alternative to conventional H2SO4-based dehusking. Furthermore, this study also highlights for the first time the effectiveness of diffusive reflectance spectroscopy as a rapid and straightforward tool for assessing the dehusking process.
- On the valorization of Arbutus unedo L. Pomace: Polyphenol extraction and development of novel functional cookiesPublication . Duarte, Hugo; Carrera, Ceferino; Aliaño-González, M.J.; Gutiérrez-Escobar, Rocío; Jiménez-Hierro, María Jesús; Palma, Miguel; Galego, Ludovina; Romano, Anabela; Medronho, BrunoThe fruits of Arbutus unedo L. have a crimson colour and are enriched with remarkable concentrations of bioactive compounds such as anthocyanins and polyphenols. These fruits are commonly used in the production of a Portuguese Protected Geographical Indication distillate called “Aguardente de Medronho”. During this process, a solid pomace is generated and presently discarded without valuable applications. In this work, two strategies have been developed for the valorisation of A. unedo pomace. The first approach considers the extraction of polyphenols from this by-product through the optimization of an ultrasound-assisted method using a Box-Behnken design coupled with response surface methodology. The results indicate that the temperature and the percentage of methanol, along with their interaction, significantly influence the total concentration of polyphenols and the antioxidant activity of the extracts obtained. The optimal conditions identified consider the extraction of 0.5 g of sample with 20 mL of a solvent containing 74% MeOH (aq), at a pH of 4.8, maintained at 70 ◦C for 15 min. On the other hand, the second valorisation strategy considered the use of A. unedo pomace in the development of functional cookies. The incorporation of 15–20% pomace in the cookie formulation was well-received by consumers. This incorporation results in an intake of ca. 6.55 mg of polyphenols per gram of cookie consumed, accompanied by an antioxidant activity of 4.54 mg Trolox equivalents per gram of cookie consumed. Overall, these results encourage the employment of A. unedo pomace either as a reliable source of extracts enriched in polyphenols or as a nutraceutical active ingredient in functional cookies, thereby positively impacting human health.
- On the valorization of olive oil pomace: a sustainable approach for methylene blue removal from aqueous mediaPublication . saoudi hassani, el mokhtar; Duarte, Hugo; Brás, João; Taleb, Abdeslam; Taleb, Mustapha; Rais, Zakia; Eivazi, Alireza; Norgren, Magnus; Romano, Anabela; Medronho, BrunoCurrently, industrial water pollution represents a significant global challenge, with the potential to adversely impact human health and the integrity of ecosystems. The continuous increase in global consumption has resulted in an exponential rise in the use of dyes, which have become one of the major water pollutants, causing significant environmental impacts. In order to address these concerns, a number of wastewater treatment methods have been developed, with a particular focus on physicochemical approaches, such as adsorption. The objective of this study is to investigate the potential of a bio-based material derived from olive oil pomace (OOP) as an environmentally friendly bio-adsorbent for the removal of methylene blue (MB), a cationic dye commonly found in textile effluents. The biobased material was initially characterized by determining the point of zero charge (pHpzc) and using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). Subsequently, a comprehensive analysis was conducted, evaluating the impact of specific physicochemical parameters on MB adsorption, which included a thorough examination of the kinetic and thermodynamic aspects. The adsorption process was characterized using Langmuir, Freundlich, Brunauer-Emmett-Teller (BET), and Dubinin Radushkevich (D-R) isotherms. The results suggest that the equilibrium of adsorption is achieved within ca. 200 min, following pseudo-second-order kinetics. The optimal conditions, including adsorbent mass, temperature, bulk pH, and dye concentration, yielded a maximum adsorption capacity of ca. 93% (i.e., 428 mg g−1) for a pomace concentration of 450 mg L−1. The results suggest a monolayer adsorption process with preferential electrostatic interactions between the dye and the pomace adsorbent. This is supported by the application of Langmuir, BET, Freundlich, and D-R isotherm models. The thermodynamic analysis indicates that the adsorption process is spontaneous and exothermic. This work presents a sustainable solution for mitigating MB contamination in wastewater streams while simultaneously valorizing OOP, an agricultural by-product that presents risks to human health and the environment. In conclusion, this approach offers an innovative ecological alternative to synthetic adsorbents.
- Poly(butylene succinate)-based composites with technical and extracted lignins from wood residuesPublication . Melro, Elodie; Duarte, Hugo; Eivazi, Alireza; Costa, Carolina; Faleiro, Maria Leonor; Rosa Da Costa, Ana; Antunes, Filipe E.; Valente, Artur J. M.; Romano, Anabela; Norgren, Magnus; Medronho, BrunoPoly(butylene succinate) (PBS) has been drawing attention as a reliable biodegradable and sustainable alternative to synthetic petroleum-based polymers. In this study, PBS-lignin composites were developed using a recently extracted lignin (LA-lignin) from pine wood residues employing an innovative sustainable approach. These composites were systematically compared with PBS-based composites formed with commonly used technical lignins. The molecular weight of the lignins was evaluated, along with various structural and performance-related properties. The LA-lignin/PBS composites display a remarkably low water solubility (ca. < 2%), water uptake (ca. 100 degrees). Moreover, the rigidity and thermal stability of the LA-lignin-PBS composites were higher than those of the systems formed with technical lignins. Although all composites studied present remarkable antioxidant features, the novel LA-lignin-PBS systems stand out in terms of antiadhesion activity against both Gram-positive and Gram-negative bacteria. Overall, the systematic analysis performed in this work regarding the impact of various lignins on the formed PBS composites enables a better understanding of the essential structural and compositional lignin features for achieving biobased materials with superior properties.