Hydroxytyrosol recovery from olive pomace: a simple process using olive mill industrial equipment and membrane technology.

In this work, pilot-scale nanofiltration was used to obtain aqueous solutions rich in hydroxytyrosol and tyrosol from olive oil by-products. A large-scale simple process involving olive mill standard machinery (blender and decanter) was used for the olive pomace pre-treatment with water. The aqueous extract was then directly fed to a nanofiltration unit and concentrated by reverse osmosis. Final concentration factors ranged between 7 and 9 for hydroxytyrosol and between 4 and 7 for tyrosol. The final aqueous solution, obtained as retentate stream of reverse osmosis, was highly concentrated in hydroxytyrosol and tyrosol and their concentrations remained stable over at least 14 months.

Antineoplastic drugs in urban wastewater: Occurrence, nanofiltration treatment and toxicity screening.

Antineoplastic drugs are pharmaceuticals that have been raising concerns among the scientific community due to: (i) their increasing prescription in the fight against the disease of the twentieth century (cancer); (ii) their recalcitrance to conventional wastewater treatments; (iii) their poor environmental biodegradability; and (iv) their potential risk to any eukaryotic organism. This emerges the urgency in finding solutions to mitigate the entrance and accumulation of these hazardous chemicals in the environment. Advanced oxidation processes (AOPs) have been taken into consideration to improve the degradation of antineoplastic drugs in wastewater treatment plants (WWTPs), but the formation of by-products that are more toxic or exhibit a different toxicity profile than the parent drug is frequently reported. This work evaluates the performance of a nanofiltration pilot unit, equipped with a Desal 5DK membrane, in the treatment of real WWTP effluents contaminated (without spiking) with eleven pharmaceuticals, five of which were never studied before. Average removals of 68 ± 23% were achieved for the eleven compounds, with decreasing risks from feed to permeate for aquatic organisms from receiving waterbodies (with the exception of cyclophosphamide, for which a high risk was estimated in the permeate). Aditionally, no significative impact on the growth and germination of three different seeds (Lepidium sativum, Sinapis alba, and Sorghum saccharatum) were determined for permeate matrix in comparison to the control.

Development and Implementation of MBR Monitoring: Use of 2D Fluorescence Spectroscopy.

The monitoring of a membrane bioreactor (MBR) requires the assessment of both biological and membrane performance. Additionally, the development of membrane fouling and the requirements for frequent membrane cleaning are still major concerns during MBR operation, requiring tight monitoring and system characterization. Transmembrane pressure is usually monitored online and allows following the evolution of membrane performance. However, it does not allow distinguishing the fouling mechanisms occurring in the system or predicting the future behavior of the membrane. The assessment of the biological medium requires manual sampling, and the analyses involve several steps that are labor-intensive, with low temporal resolution, preventing real-time monitoring. Two-dimensional fluorescence spectroscopy is a comprehensive technique, able to assess the system status at real-time without disturbing the biological system. It provides large sets of data (system fingerprints) from which meaningful information can be extracted. Nevertheless, mathematical data analysis (such as machine learning) is essential to properly extract the information contained in fluorescence spectra and correlate it with operating and performance parameters. The potential of 2D fluorescence spectroscopy as a process monitoring tool for MBRs is, therefore, discussed in the present work in view of the actual knowledge and the authors' own experience in this field.

Design of Enzyme Loaded W/O Emulsions by Direct Membrane Emulsification for CO2 Capture.

Membrane-based gas separation is a promising unit operation in a low-carbon economy due to its simplicity, ease of operation, reduced energy consumption and portability. A methodology is proposed to immobilise enzymes in stable water-in-oil (W/O) emulsions produced by direct membrane emulsification systems and thereafter impregnated them in the pores of a membrane producing emulsion-based supported liquid membranes. The selected case-study was for biogas (CO2 and CH4) purification. Upon initial CO2 sorption studies, corn oil was chosen as a low-cost and non-toxic bulk phase (oil phase). The emulsions were prepared with Nadir® UP150 P flat-sheet polymeric membranes. The optimised emulsions consisted of 2% Tween 80 (w/w) in corn oil as the continuous phase and 0.5 g.L-1 carbonic anhydrase enzyme with 5% PEG 300 (w/w) in aqueous solution as the dispersed phase. These emulsions were impregnated onto a porous hydrophobic PVDF membrane to prepare a supported liquid membrane for gas separation. Lastly, gas permeability studies indicated that the permeability of CO2 increased by ~15% and that of CH4 decreased by ~60% when compared to the membrane without carbonic anhydrase. Thus, a proof-of-concept for enhancement of CO2 capture using emulsion-based supported liquid membrane was established.

Comparative Analysis of Bio-Vanillin Recovery from Bioconversion Media Using Pervaporation and Vacuum Distillation.

The increasing demand for natural products has led to biotechnological vanillin production, which requires the recovery of vanillin (and vanillyl alcohol at trace concentrations, as in botanical vanillin) from the bioconversion broth, free from potential contaminants: the substrate and metabolites of bioconversion. This work discusses the recovery and fractionation of bio-vanillin, from a bioconversion broth, by pervaporation and by vacuum distillation, coupled with fractionated condensation. The objective was to recover vanillin free of potential contaminants, with maximised fluxes and selectivity for vanillin against water and minimised energy consumption per mass of vanillin recovered. In vacuum distillation fractionated condensation, adding several consecutive water pulses to the feed increased the percentage of recovered vanillin. In pervaporation-fractionated condensation and vacuum distillation-fractionated condensation processes, it was possible to recover vanillin and traces of vanillyl alcohol without the presence of potential contaminants. Vacuum distillation-experiments presented higher vanillin fluxes than pervaporation fractionated condensation experiments, 2.7 ± 0.1 g·m-2 h-1 and 1.19 ± 0.01 g·m-2 h-1, respectively. However, pervaporation fractionated condensation assures a selectivity of vanillin against water of 4.5 on the pervaporation step (acting as a preconcentration step) and vacuum distillation fractionated condensation requires a higher energy consumption per mass of vanillin recovered when compared with pervaporation- fractionated condensation, 2727 KWh kgVAN-1 at 85 °C and 1361 KWh kgVAN-1 at 75 °C, respectively.

Protein Attachment Mechanism for Improved Functionalization of Affinity Monolith Chromatography (AMC).

This work aims at understanding the attachment mechanisms and stability of proteins on a chromatography medium to develop more efficient functionalization methodologies, which can be exploited in affinity chromatography. In particular, the study was focused on the understanding of the attachment mechanisms of bovine serum albumin (BSA), used as a ligand model, and protein G on novel amine-modified alumina monoliths as a stationary phase. Protein G was used to develop a column for antibody purification. The results showed that, at lower protein concentrations (i.e., 0.5 to 1.0 mg·mL-1), protein attachment follows a 1st-order kinetics compatible with the presence of covalent binding between the monolith and the protein. At higher protein concentrations (i.e., up to 10 mg·mL-1), the data preferably fit a 2nd-order kinetics. Such a change reflects a different mechanism in the protein attachment which, at higher concentrations, seems to be governed by physical adsorption resulting in a multilayered protein formation, due to the presence of ligand aggregates. The threshold condition for the prevalence of physical adsorption of BSA was found at a concentration higher than 1.0 mg·mL-1. Based on this result, protein concentrations of 0.7 and 1.0 mg·mL-1 were used for the functionalization of monoliths with protein G, allowing a maximum attachment of 1.43 mg of protein G/g of monolith. This column was then used for IgG binding-elution experiments, which resulted in an antibody attachment of 73.5% and, subsequently, elution of 86%, in acidic conditions. This proved the potential of the amine-functionalized monoliths for application in affinity chromatography.

Nannochloropsis sp. Biorefinery: Recovery of Soluble Protein by Membrane Ultrafiltration/Diafiltration.

This work proposes a way to maximize the potential of a Nannochloropsis sp. biorefinery process, through membrane technology, producing an extract enriched in soluble proteins, free from the insoluble protein fraction, with a low lipid content and eliminating the colored chlorophyll-a. This procedure, following the principles of a circular economy approach, allows for the valorization of a stream from the biorefining of Nannochloropsis sp. that, otherwise, would be considered a residue without commercial value. The process proposed minimizes fouling phenomena at the membrane surface, making it possible to achieve high permeate fluxes, thus reducing the need for membrane cleaning and, therefore, contributing to an extended membrane lifetime. Supernatant obtained after centrifugation of a suspension of ruptured Nannochloropsis sp. cells was processed by ultrafiltration using a membrane with a cut-off of 100 kDa MWCO. Two different operating approaches were evaluated-controlled transmembrane pressure and controlled permeate flux-under concentration and diafiltration modes. Ultrafiltration operated in a diafiltration mode, under controlled permeate flux conditions, led to the highest soluble protein recovery (78%) with the highest constant permeate flux (12 L·m-2·h-1) and low membrane fouling.

Nitrate Removal by Donnan Dialysis and Anion-Exchange Membrane Bioreactor Using Upcycled End-of-Life Reverse Osmosis Membranes.

This work explores the application of Reverse Osmosis (RO) upcycled membranes, as Anion Exchange Membranes (AEMs) in Donnan Dialysis (DD) and related processes, such as the Ion Exchange Membrane Bioreactor (IEMB), for the removal of nitrate from contaminated water, to meet drinking water standards. Such upcycled membranes might be manufactured at a lower price than commercial AEMs, while their utilization reinforces the commitment to a circular economy transition. In an effort to gain a better understanding of such AEMs, confocal µ-Raman spectroscopy was employed, to assess the distribution of the ion-exchange sites through the thickness of the prepared membranes, and 2D fluorescence spectroscopy, to evaluate alterations in the membranes caused by fouling and chemical cleaning The best performing membrane reached a 56% average nitrate removal within 24 h in the DD and IEMB systems, with the latter furthermore allowing for simultaneous elimination of the pollutant by biological denitrification, thus avoiding its discharge into the environment. Overall, this work validates the technical feasibility of using RO upcycled AEMs in DD and IEMB processes for nitrate removal. This membrane recycling concept might also find applications for the removal and/or recovery of other target negatively charged species.

Overview of Membrane Science and Technology in Portugal.

Membrane research in Portugal is aligned with global concerns and expectations for sustainable social development, thus progressively focusing on the use of natural resources and renewable energy. This review begins by addressing the pioneer work on membrane science and technology in Portugal by the research groups of Instituto Superior Técnico-Universidade de Lisboa (IST), NOVA School of Science and Technology-Universidade Nova de Lisboa (FCT NOVA) and Faculdade de Engenharia-Universidade do Porto (FEUP) aiming to provide an historical perspective on the topic. Then, an overview of the trends and challenges in membrane processes and materials, mostly in the last five years, involving Portuguese researchers, is presented as a contribution to a more sustainable water-energy-material-food nexus.

Perspectives of fluorescence spectroscopy for online monitoring in microalgae industry.

Microalgae industrial production is viewed as a solution for alternative production of nutraceuticals, cosmetics, biofertilizers, and biopolymers. Throughout the years, several technological advances have been implemented, increasing the competitiveness of microalgae industry. However, online monitoring and real-time process control of a microalgae production factory still require further development. In this mini-review, non-destructive tools for online monitoring of cellular agriculture applications are described. Still, the focus is on the use of fluorescence spectroscopy to monitor several parameters (cell concentration, pigments, and lipids) in the microalgae industry. The development presented makes it the most promising solution for monitoring up-and downstream processes, different biological parameters simultaneously, and different microalgae species. The improvements needed for industrial application of this technology are also discussed.

Predicting the concentration of hazardous phenolic compounds in refinery wastewater-a multivariate data analysis approach.

The present study focused on the methodology for identification of the wastewater stream that presents the highest phenolic impact at a large oil refinery. As a case-study, the oil refinery, Petrogal S.A., in Sines, Portugal, was selected. Firstly, stripped sour water from the cracking complex was identified as the most relevant wastewater stream concerning phenolic emission. Secondly, multivariate data analysis was used, through projection to latent structures (PLS) regression, to find existing correlations between process parameters and phenols content in stripped sour water. The models developed allowed the prediction of phenols concentration with predictive errors down to 20.16 mg/L (corresponding to 8.2% average error), depending on the complexity of the correlation used, and R2 values as high as 0.85. Models were based in input parameters related to fluid catalytic crackers (FCC) feedstock quality, crudemix and steam injected in the catalyst stripper. The studied data analysis approach showed to be useful as a tool to predict the phenolic content in stripped sour water. Such prediction would help improve the wastewater management system, especially the units responsible for phenol degradation. The methodology shown in this work can be used in other refineries containing catalytic cracking complexes, providing a tool which allows the online prediction of phenols in stripped sour water and the identification of the most relevant process parameters. An optimised system at any refinery leads to an improvement in the wastewater quality and costs associated with pollutant discharge; thus, the development of monitoring online tools, as proposed in this work, is essential.

Degradation of Neonicotinoids and Caffeine from Surface Water by Photolysis.

Along with rapid social development, the use of insecticides and caffeine-containing products increases, a trend that is also reflected in the composition of surface waters. This study is focused on the phototreatment of a surface water containing three neonicotinoids (imidacloprid, thiamethoxam, and clothianidin) and caffeine. Firstly, the radiation absorption of the target pollutants and the effect of the water matrix components were evaluated. It was observed that the maximum absorption peaks appear at wavelengths ranging from 246 to 274 nm, and that the water matrix did not affect the efficiency of the removal of the target pollutants. It was found that the insecticides were efficiently removed after a very short exposure to UV irradiation, while the addition of hydrogen peroxide was needed for an efficient caffeine depletion. The electrical energy per order was estimated, being the lowest energy required (9.5 kWh m-3 order-1) for the depletion of thiamethoxan by indirect photolysis, and a concentration of hydrogen peroxide of 5 mg dm-3. Finally, a preliminary evaluation on the formation of by-products reveals that these compounds play a key role in the evolution of the ecotoxicity of the samples, and that the application of direct photolysis reduces the concentration of these intermediates.

From Black Box to Machine Learning: A Journey through Membrane Process Modelling.

Membrane processes are complex systems, often comprising several physicochemical phenomena, as well as biological reactions, depending on the systems studied. Therefore, process modelling is a requirement to simulate (and predict) process and membrane performance, to infer about optimal process conditions, to assess fouling development, and ultimately, for process monitoring and control. Despite the actual dissemination of terms such as Machine Learning, the use of such computational tools to model membrane processes was regarded by many in the past as not useful from a scientific point-of-view, not contributing to the understanding of the phenomena involved. Despite the controversy, in the last 25 years, data driven, non-mechanistic modelling is being applied to describe different membrane processes and in the development of new modelling and monitoring approaches. Thus, this work aims at providing a personal perspective of the use of non-mechanistic modelling in membrane processes, reviewing the evolution supported in our own experience, gained as research group working in the field of membrane processes. Additionally, some guidelines are provided for the application of advanced mathematical tools to model membrane processes.

Detection of anticancer drugs in wastewater effluents: Grab versus passive sampling.

The occurrence of six anticancer drugs was evaluated in wastewater effluents. Several grab samples from wastewater effluent were collected throughout a year. Capecitabine, cyclophosphamide and ifosfamide were detected at concentrations ranging from 8 to 46 ng·L-1. Capecitabine was detected in all the sampling events whereas cyclophosphamide and ifosfamide were detected less frequently. Additionally, the suitability of using pharmaceutical-polar organic chemical integrative samplers (POCIS) to monitor the target drugs in wastewater effluents was assessed. Capecitabine, ifosfamide and cyclophosphamide were detected with POCIS and showed a linear uptake over 15 days. The sampling rates, determined in situ, were used to estimate time-weighted average concentrations. A good correlation was found between the concentration of capecitabine detected with POCIS deployed during five days (32 ± 1 ng·L-1) and the average concentrations obtained in grab samples. The use of passive samplers has advantages over grab samples: easier analysis, less time and costs associated with the analytical method. Passive samplers also provide a time-weighted information about the concentration of pollutants in the aquatic environment. However, information may be lost when the concentration of the target compounds in wastewater effluents is low and the passive samplers are deployed for a short time.

Block Copolymer-Based Magnetic Mixed Matrix Membranes-Effect of Magnetic Field on Protein Permeation and Membrane Fouling.

In this study, we report the impact of the magnetic field on protein permeability through magnetic-responsive, block copolymer, nanocomposite membranes with hydrophilic and hydrophobic characters. The hydrophilic nanocomposite membranes were composed of spherical polymeric nanoparticles (NPs) synthesized through polymerization-induced self-assembly (PISA) with iron oxide NPs coated with quaternized poly(2-dimethylamino)ethyl methacrylate. The hydrophobic nanocomposite membranes were prepared via nonsolvent-induced phase separation (NIPS) containing poly (methacrylic acid) and meso-2,3-dimercaptosuccinic acid-coated superparamagnetic nanoparticles (SPNPs). The permeation experiments were carried out using bovine serum albumin (BSA) as the model solute, in the absence of the magnetic field and under permanent and cyclic magnetic field conditions OFF/ON (strategy 1) and ON/OFF (strategy 2). It was observed that the magnetic field led to a lower reduction in the permeate fluxes of magnetic-responsive membranes during BSA permeation, regardless of the magnetic field strategy used, than that obtained in the absence of the magnetic field. Nevertheless, a comparative analysis of the effect caused by the two cyclic magnetic field strategies showed that strategy 2 allowed for a lower reduction of the original permeate fluxes during BSA permeation and higher protein sieving coefficients. Overall, these novel magneto-responsive block copolymer nanocomposite membranes proved to be competent in mitigating biofouling phenomena in bioseparation processes.

Feeding strategies to optimize vanillin production by Amycolatopsis sp. ATCC 39116.

The growing consumer demand for natural products led to an increasing interest in vanillin production by biotechnological routes. In this work, the biotechnological vanillin production by Amycolatopsis sp. ATCC 39116 is studied using ferulic acid as precursor, aiming to achieve maximized vanillin productivities. During biotech-vanillin production, the effects of glucose, vanillin and ferulic acid concentrations in the broth proved to be relevant for vanillin productivity. Concerning glucose, its presence in the broth during the production phase avoids vanillin conversion to vanillic acid and, consequently, increases vanillin production. To avoid the accumulation of vanillin up to a toxic concentration level, a multiple-pulse-feeding strategy is implemented, with intercalated vanillin removal from the broth and biomass recovery. This strategy turned out fruitful, leading to 0.46 g L-1 h-1 volumetric productivity of vanillin of and a production yield of 0.69 gvanillin gferulic acid-1, which are among the highest values reported in the literature for non-modified bacteria.

Stability of Polymeric Membranes to UV Exposure before and after Coating with TiO2 Nanoparticles.

The combination of photocatalysis and membrane filtration in a single reactor has been proposed, since the photocatalytic treatment may degrade the pollutants retained by the membrane and reduce fouling. However, polymeric membranes can be susceptible to degradation by UV radiation and free radicals. In the present study, five commercial polymeric membranes were exposed to ultraviolet (UV) radiation before and after applying a sol-gel coating with TiO2 nanoparticles. Membrane stability was characterized by changes in hydrophilicity as well as analysis of soluble substances and nanoparticles detached into the aqueous medium, and by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), and energy-dispersive X-ray spectrometry (EDS) for structural, morphological, and elemental distribution analysis, respectively. The TiO2 coating conferred photocatalytic properties to the membranes and protected them during 6 h of UV radiation exposures, reducing or eliminating chemical and morphological changes, and in some cases, improving their mechanical resistance. A selected commercial nanofiltration membrane was coated with TiO2 and used in a hybrid reactor with a low-pressure UV lamp, promoting photocatalysis coupled with cross-flow filtration in order to remove 17α-ethinylestradiol spiked into an aqueous matrix, achieving an efficiency close to 100% after 180 min of combined filtration and photocatalysis, and almost 80% after 90 min.

Tannery Effluent Treatment by Nanofiltration, Reverse Osmosis and Chitosan Modified Membranes.

The objective of this work is to develop an appropriate technology for environmentally sound membrane-based purification of a tannery effluent assuring, simultaneously, the recovery of chromium, considered as the most hazardous inorganic water pollutant extensively used in leather tanning. A comparison between the permeate fluxes obtained during treatment of a synthetic tannery effluent through nanofiltration (NF270 and NF90 membranes) and reverse osmosis (BW30 and SW30) membranes was first performed. Then, a dedicated polymeric membrane was prepared by coating chitosan (cs) on a polyethersulfone (PES) microfiltration membrane (cs-PES MFO22) support. The resulting membrane was characterized by Fourier Transforms Infrared Spectroscopy Attenuated Total Reflectance (FTIR-ATR), Emission Scanning Electronic Microscopy (SEM) to confirm the process of surface modification and cross-linking of chitosan with glutaraldehyde. This membrane was found to be highly effective for chromium removal (>99%), which was more than eight times higher in reference to monovalent cations (e.g., Na+ and K+) and more than six times higher in reference to the divalent cations (Mg2+ and Ca2+) studied. The reverse osmosis permeate conforms to local Algerian regulations regarding being discharged directly into the natural environment (in this case, Reghaia Lake) or into urban sewers linked to wastewater biological treatment stations. While the SW30 membrane proved to be the most effective for purification of the tannery effluent, the chitosan modified membrane proved to be appropriate for recovery of chromium from the reverse osmosis concentrate.

Development of bioactive films based on chitosan and Cynara cardunculus leaves extracts for wound dressings.

The development of natural based, effective and protective wound dressings associated to local treatment applied on chronic wounds, represents a major challenge nowadays. In this work chitosan-based films were prepared with different concentrations of ethanolic ultrasound assisted extracts from Cynara cardunculus leaves (EtPUAE). The physico-chemical film properties revealed that extract incorporation influences the volumetric swelling capacity and mechanical properties of the films, leading to materials with a lower fluid absorption capacity and more fragile. However, no impact was detected on the thermal properties of the films, as well as on their dense structure characterized by Scanning Electronic Microscopy (SEM) analysis. Biological screening of chitosan-based films show that chitosan with a 1% (w/w) and a 5% (w/w) EtPUAE loading did not induce cytotoxicity on normal human skin fibroblasts (Bj5-ta cell line), mainly attributed to cynaropicrin (extract key active compound) present in the film below its IC50 value. Nevertheless, chitosan-based films with 5% (w/w) EtPUAE presented an interesting anti-inflammatory activity. Bj5-ta cells stimulated with liposaccharides (LPS), presented a reduction of 86% on IL-6 cytokine levels, after exposure to chitosan with 5% EtPUAE film extract. The results obtained in this study open up the possibility of successfully using chitosan films doped with EtPUAE for development of chronic wound dressings, with the advantage of using naturally-sourced materials with anti-inflammatory activity.

A corrosion evaluation of mild carbon steel in reclaimed refinery stripped sour water.

Reclaiming water for cooling systems in oil refineries has been strongly encouraged over the past years for decreasing the large consumption of fresh water, thus contributing to the efficient use of this valuable resource. In a recent study [Journal of Environmental Management 261 (2020) 110229], some of the authors studied the retention of phenols in refinery wastewater through reverse osmosis (RO) and found rejections of up to 98% of phenols and 99% of both chemical oxygen demand (COD) and total organic carbon (TOC). The permeates complied with the quality standards for make-up water in cooling processes. A missing aspect, important for the water to be used in the oil and gas industry, was the level of corrosivity of the new permeates. In this work the corrosion of mild carbon steel in the permeates and in the original cooling tower make-up water was studied by electrochemical techniques. The corrosion rate of steel in the permeates in aerated conditions was lower (between 0.053 ± 0.006 and 0.123 ± 0.011 mm year-1) than in the make-up water (0.167 ± 0.030 mm year-1), confirming their suitability for replacing make-up water in the cooling towers. The low corrosion of carbon steel was attributed to the low conductivity and absence of oxidizing species in the fluids, compared to fresh water.