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.

Occurrence and Treatment of Antibiotic-Resistant Bacteria Present in Surface Water.

According to the World Health Organization, antibiotic resistance is one of the main threats to global health. The excessive use of several antibiotics has led to the widespread distribution of antibiotic-resistant bacteria and antibiotic resistance genes in various environment matrices, including surface water. In this study, total coliforms, Escherichia coli and enterococci, as well as total coliforms and Escherichia coli resistant to ciprofloxacin, levofloxacin, ampicillin, streptomycin, and imipenem, were monitored in several surface water sampling events. A hybrid reactor was used to test the efficiency of membrane filtration, direct photolysis (using UV-C light emitting diodes that emit light at 265 nm and UV-C low pressure mercury lamps that emit light at 254 nm), and the combination of both processes to ensure the retention and inactivation of total coliforms and Escherichia coli as well as antibiotic-resistant bacteria (total coliforms and Escherichia coli) present in river water at occurrence levels. The membranes used (unmodified silicon carbide membranes and the same membrane modified with a photocatalytic layer) effectively retained the target bacteria. Direct photolysis using low-pressure mercury lamps and light-emitting diode panels (emitting at 265 nm) achieved extremely high levels of inactivation of the target bacteria. The combined treatment (unmodified and modified photocatalytic surfaces in combination with UV-C and UV-A light sources) successfully retained the bacteria and treated the feed after 1 h of treatment. The hybrid treatment proposed is a promising approach to use as point-of-use treatment by isolated populations or when conventional systems and electricity fail due to natural disasters or war. Furthermore, the effective treatment obtained when the combined system was used with UV-A light sources indicates that the process may be a promising approach to guarantee water disinfection using natural sunlight.

Donnan Dialysis for Recovering Ammonium from Fermentation Solutions Rich in Volatile Fatty Acids.

For the production of polyhydroxyalkanoates (PHA) using nitrogen-rich feedstocks (e.g., protein-rich resources), the typical strategy of restricting cell growth as a means to enhance overall PHA productivity by nitrogen limitation is not applicable. In this case, a possible alternative to remove the nitrogen excess (NH4+/NH3) is by applying membrane separation processes. In the present study, the use of Donnan dialysis to separate ammonium ions from volatile fatty acids present in the media for the production of PHA was evaluated. Synthetic and real feed solutions were used, applying NaCl and HCl receiver solutions separated by commercial cation-exchange membranes. For this specific purpose, Fumasep and Ralex membranes showed better performance than Ionsep. Sorption of ammonium ions occurred in the Ralex membrane, thus intensifying the ammonium extraction. The separation performances with NaCl and HCl as receiver solutions were similar, despite sorption occurring in the Ralex membrane more intensely in the presence of NaCl. Higher volumetric flow rates, NaCl receiver concentrations, and volume ratios of feed:receiver solutions enhanced the degree of ammonium recovery. The application of an external electric potential difference to the two-compartment system did not significantly enhance the rate of ammonium appearance in the receiver solution. The results obtained using a real ammonium-containing solution after fermentation of cheese whey showed that Donnan dialysis can be successfully applied for ammonium recovery from such solutions.

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.

Recovery of Valuable Aromas from Sardine Cooking Wastewaters by Pervaporation with Fractionated Condensation: Matrix Effect and Model Validation.

Due to the lack of studies addressing the influence of real food matrices on integrated organophilic pervaporation/fractionated condensation processes, the present work analyses the impact of the real matrix of sardine cooking wastewaters on the fractionation of aromas. In a previous study, a thermodynamic/material balance model was developed to describe the integrated pervaporation-a fractionated condensation process of aroma recovery from model solutions that emulate seafood industry aqueous effluents, aiming to define the best conditions for off-flavour removal. This work assesses whether the previously developed mathematical model, validated only with model solutions, is also applicable in predicting the fractionation of aromas of different chemical families from real effluents (sardine cooking wastewaters), aiming for off-flavour removals. It was found that the food matrix does not influence substantial detrimental consequences on the model simulations, which validates and extends the applicability of the model.

Modelling of Fractionated Condensation for Off-Flavours Reduction from Red Wine Fermentation Headspace.

A mathematical model of fractionated condensation is proposed for predicting the recovery and fractionation of target aromas from red wine fermentation headspaces in order to remove off-flavours. The applicability of the model is assessed for two different alternative processes: fractionated condensation and vapour permeation-fractionated condensation. The aromas of the headspace of red wine fermentation are commonly lost through the fermenter venting system and are enhanced by the stripping effect of the produced CO2. To mimic the operating conditions during the red wine fermentation, all experiments were performed at 30 °C with a red wine model solution containing relevant red wine aromas, the cosolvent ethanol at representative concentrations, and CO2. Both studied processes allow for a good recovery of esters in the 2nd condenser, with over 80% of ethyl acetate and isoamyl acetate recovery when using vapour permeation-fractionated condensation and a recovery of 84-96% of all esters when using fractionated condensation. However, only the integrated process of vapour permeation-fractionated condensation achieves a significant decrease in the amount of ethyl phenols (off-flavours compounds) in the 1st condenser, above 50%, as expected due to the use of an organophilic membrane. The developed model was validated experimentally for the integrated process, proving to be a highly valuable tool for the prediction of aroma fractionation, aiming at the removal of off-flavours.

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.

A Study on Biofouling and Cleaning of Anion Exchange Membranes for Reverse Electrodialysis.

This study covers the modification, (bio)fouling characterization, use, and cleaning of commercial heterogeneous anion exchange membranes (AEMs) to evaluate their feasibility for reverse electrodialysis (RED) applications. A surface modification with poly (acrylic) acid resulted in an improved monovalent perm-selectivity (decreased sulfate membrane transport rate). Moreover, we evaluated the (bio)fouling potential of the membrane using sodium dodecyl sulfate (SDS), sodium dodecyl benzenesulfonate (SDBS), and Aeromonas hydrophila as model organic foulants and a biofoulant, respectively. A detailed characterization of the AEMs (water contact angle, ion exchange capacity (IEC), scanning electron microscopy (SEM), cyclic voltammetry (CV), and Fourier Transform Infrared (FTIR) spectra) was carried out, verifying that the presence of such foulants reduces IEC and the maximum current obtained by CV. However, only SDS and SDBS affected the contact angle values. Cleaning of the biofouled membranes using a sodium hypochlorite aqueous solution allows for (partially) recovering their initial properties. Furthermore, this work includes a fouling characterization using real surface and sea water matrixes, confirming the presence of several types of fouling microorganisms in natural streams. A lower adhesion of microorganisms (measured in terms of total bacteria counts) was observed for the modified membranes compared to the unmodified ones. Finally, we propose a cleaning strategy to mitigate biofouling in AEMs that could be easily applied in RED systems for an enhanced long-term process performance.

Osteochondrosis (Osteochondritis Dissecans) in Lusitano Horses: Prevalence and Characteristics.

Osteochondrosis (osteochondritis dissecans), OC(D), is an important joint disorder that has been studied through the years in different breeds but, to our knowledge, there are no reports of its prevalence in Lusitano horses. The aim of this study was to assess the prevalence of OC(D) in Lusitanos, define the characteristics of the disorder in this breed and compare with Spanish Purebred horses. This is a retrospective study that analysed the radiographs from the metacarpometatarsophalangeal, tarsocrural and femoropatellar joints that were taken in 302 Lusitano horses (1-12 years; obtained from 2007 until 2019). The classification of the radiographs for OC(D) was performed using a 0-4 scale and scored by three veterinarians. Radiographical evidence of OC(D) was diagnosed in 53.3% of the horses examined. Most of the findings were lesions of score 1 or 2 corresponding to flattening, (36.8%). The distal intermediate ridge of the tibia in the tarsocrural joint was the most affected predilection site (31.0%, n=187/604 joints assessed). Overall, the tarsocrural joints were more likely to be affected, followed by metatarso-metacarpophalangeal joints and finally the femoropatellar joints. The prevalence of horses with scores 3 or 4 (fragments) in any of the joints was 16.6%. A positive correlation was found between the scores of contralateral joints. We can conclude that the prevalence of OC(D) in Lusitano horses is similar to the prevalence in Spanish Purebred, but there is a lower percentage of fragmentation. The present phenotypic description can provide valuable information for further quantitative and molecular genetic studies.

Nanofiltration as an Efficient Tertiary Wastewater Treatment: Elimination of Total Bacteria and Antibiotic Resistance Genes from the Discharged Effluent of a Full-Scale Wastewater Treatment Plant.

Wastewater reuse for agricultural irrigation still raises important public health issues regarding its safety, due to the increasing presence of emerging contaminants, such as antibiotic resistant bacteria and genes, in the treated effluents. In this paper, the potential for a commercial Desal 5 DK nanofiltration membrane to be used as a tertiary treatment in the wastewater treatment plants for a more effective elimination of these pollutants from the produced effluents was assessed on laboratory scale, using a stainless steel cross-flow cell. The obtained results showed high concentrations of total bacteria and target carbapenem and (fluoro)quinolone resistance genes (blaKPC, blaOXA-48, blaNDM, blaIMP, blaVIM, qnrA, qnrB and qnrS) not only in the discharged, but also in the reused, effluent samples, which suggests that their use may not be entirely safe. Nevertheless, the applied nanofiltration treatment achieved removal rates superior to 98% for the total bacteria and 99.99% for all the target resistance genes present in both DNA and extracellular DNA fractions, with no significant differences for these microbiological parameters between the nanofiltered and the control tap water samples. Although additional studies are still needed to fully optimize the entire process, the use of nanofiltration membranes seems to be a promising solution to substantially increase the quality of the treated wastewater effluents.

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.