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A combination of straw filtration and nanofiltration was investigated for the first time as a sustainable approach aimed at valorizing olive mill wastewaters (OMWs) within a circular economy strategy. Ground straw filters with different granulometry (120, 250 and 500 µm) were tested in the first step to clarify the raw wastewater. The 500 µm filter offered the best performance due to a lower exposed surface of the filtering fibers and a shorter filtering time, allowing us to reduce about 70% of the chemical oxygen demand (COD) of the raw wastewater. Three different commercial membranes in a flat-sheet configuration with a molecular weight cut-off (MWCO) in the range 150-500 Da were tested to fractionate the clarified wastewater according to a dead-end configuration. Among the investigated membranes, a polymeric membrane of 500 Da (NFA-12A) exhibited the highest productivity in selected operating conditions (steady-state values of 11.4 L/m2 h at 20 bar and 24 ± 2 °C). In addition, flux decays for this membrane were lower than the other two tested membranes, indicating a lower propensity to fouling phenomena. Higher rejections towards total polyphenols and total antioxidant activity (TAA) (76.6% and 73.2%, respectively) were also observed for this membrane. Flavanols and hydroxycinnamic acids were retained by more than 99%. The combination of straw filtration and NF with the NFA-12A membrane allowed us to reduce the COD of raw OMWs up to 97.6%. The retentate fraction of this membrane exhibited a TAA of 18.9 ± 0.7 mM Trolox, supporting its propensity for the development of innovative formulations of interest in food and nutraceutical applications.
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Osmotic distillation (OD) was implemented at laboratory scale to concentrate a red fruit juice produced from a blend of blood orange, prickly pear, and pomegranate juice. The raw juice was clarified by microfiltration and then concentrated by using an OD plant equipped with a hollow fiber membrane contactor. The clarified juice was recirculated on the shell side of the membrane module, while calcium chloride dehydrate solutions, used as extraction brine, were recirculated on the lumen side in a counter-current mode. The influence of different process parameters, such as brine concentration (20, 40, and 60% w/w), juice flow rate (0.3, 2.0, and 3.7 L min-1), and brine flow rate (0.3, 2.0, and 3.7 L min-1) on the performance of the OD process in terms of evaporation flux and increase in juice concentration, was investigated according to the response surface methodology (RSM). From the regression analysis, the evaporation flux and juice concentration rate were expressed with quadratic equations of juice and brine flow rates, as well as the brine concentration. The desirability function approach was applied to analyse the regression model equations in order to maximize the evaporation flux and juice concentration rate. The optimal operating conditions were found to be 3.32 L min-1 brine flow rate, 3.32 L min-1 juice flow rate, and an initial brine concentration of 60% w/w. Under these conditions, the average evaporation flux and the increase in the soluble solid content of the juice resulted in 0.41 kg m-2 h-1 and 12.0 °Brix, respectively. Experimental data on evaporation flux and juice concentration, obtained in optimized operating conditions, resulted in good agreement with the predicted values of the regression model.
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Membrane-based processes are increasingly used to clarify and concentrate thermo-sensitive fruit juices and plant extracts as alternatives to conventional processes. This work aimed to evaluate the quality of red fruit juices clarified and concentrated by an integrated membrane process with special regard to the preservation of valuable compounds. A red fruit juice obtained from a blend of pomegranate, cactus pear, and red orange juices of Sicilian origin was clarified by microfiltration (MF) and then pre-concentrated up to 33 °Brix by nanofiltration (NF). The pre-concentrated juice was finally concentrated by osmotic distillation (OD) up to 50 and 60 °Brix. Samples of clarified, pre-concentrated, and concentrated juice were analyzed for their physico-chemical composition and in terms of the antioxidant activity and inhibitory activity against α-amylase and lipase. The results clearly confirmed the assumption of a mild fruit juice processing method, allowing us to preserve the original nutritional and functional properties of the fresh juice. In particular, the OD retentate at 60 °Brix resulted the most active sample against pancreatic lipase and α-amylase inhibitory activity with IC50 values of 44.36 and 214.65 µg/mL, respectively.
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Sucos de Frutas e Vegetais , Frutas , Frutas/química , Destilação/métodos , alfa-Amilases , Lipase/análiseRESUMO
Partial removal of sugars in fruit juices without compromising their biofunctional properties represents a significant technological challenge. The current study was aimed at evaluating the separation of sugars from phenolic compounds in apple juice by using three different spiral-wound nanofiltration (NF) membranes with a molecular weight cut-off (MWCO) in the range of 200-500 Da. A combination of diafiltration and batch concentration processes was investigated to produce apple juice with reduced sugar content and improved health properties thanks to the preservation and concentration of phenolic compounds. For all selected membranes, permeate flux and recovery rate of glucose, fructose, and phenolic compounds, in both diafiltration and concentration processes, were evaluated. The concentration factor of target compounds as a function of the volume reduction factor (VRF) as well as the amount of adsorbed compound on the membrane surface from mass balance analysis were also evaluated. Among the investigated membranes a thin-film composite membrane with an MWCO of 200-300 Da provided the best results in terms of the preservation of phenolic compounds in the selected operating conditions. More than 70% of phenolic compounds were recovered in the retentate stream while the content of sugars was reduced by about 60%.
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The purification of phycocyanin (PC) from Spirulina generally involves a combination of different techniques. Here, we report the results on PC yields from a combined aqueous extraction-ultrafiltration (UF) process of a strain of Arthrospira maxima cultivated in a farm devoted to producing PC with food-grade purity. Samples optimized from different biomass/solvent ratios were purified by using a polyethersulphone (PES) membrane with a molecular weight cut-off (MWCO) of 20 kDa. The UF system was operated at 2.0 ± 0.1 bar and at 24 ± 2 °C up to a volume concentration factor (VCF) of 5. A diafiltration (DF) process was conducted after UF in order to increase the PC recovery in the retentate. Samples were collected during both UF and DF processes in order to evaluate membrane productivity and PC purity. The average permeate fluxes of about 14.4 L/m2h were measured in the selected operating conditions and more than 96% of PC was rejected by the UF membrane independently ofthe extraction yields and times. The concentration of PC in the final retentate was 1.17 mg/mL; this confirmed the observed rejection and the final VCF of the process (about 5-fold when compared to the concentration of PC in the crude extract). In addition, the combination of UF and diafiltration allowed the removal of about 91.7% of the DNA from the crude extract, thereby improving the purity of the phycocyanin in the retentate fraction.
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Tacle is a citrus variety which recently gained further interest due to its antioxidant and biological properties. This study suggests using Nuclear Magnetic Resonance (NMR) imaging to characterize Tacle juice's metabolic composition as it is intimately linked to its quality. First, polar and apolar solvent systems were used to identify a significant fraction of the Tacle metabolome. Furthermore, the antioxidant capacity and the total content of flavonoids, polyphenols and ß-carotene in the juice were investigated with UV-Visible spectroscopy. Tacle juice was clarified and fractionated by ultrafiltration (UF) and nanofiltration (NF) membranes in order to recover and purify its bioactive principles. Finally, the second part of this work sheds light on the spectrophotometric assays and 1H-NMR spectra of fractions coming from membrane operations coupled with a multivariate data analysis technique, PCA, to explore the impact of UF and NF processes on the metabolic profile of the juice.
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Olive mill wastewater (OMW), generated as a by-product of olive oil production, is considered one of the most polluting effluents produced by the agro-food industry, due to its high concentration of organic matter and nutrients. However, OMW is rich in several polyphenols, representing compounds with remarkable biological properties. This study aimed to analyze the chemical profile as well as the antioxidant and anti-obesity properties of concentrated fractions obtained from microfiltered OMW treated by direct contact membrane distillation (DCMD). Ultra-high performance liquid chromatography (UHPLC) analyses were applied to quantify some phenols selected as phytochemical markers. Moreover, α-Amylase, α-glucosidase, and lipase inhibitory activity were investigated together with the antioxidant activity by means of assays, namely ß-carotene bleaching, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic) acid (ABTS) diammonium salts, 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay, and Ferric Reducing Activity Power (FRAP) tests. MD retentate-which has content of about five times greater of hydroxytyrosol and verbascoside and about 7 times greater of oleuropein than the feed-was more active as an antioxidant in all applied assays. Of interest is the result obtained in the DPPH test (an inhibitory concentration 50% (IC50) of 9.8 µg/mL in comparison to the feed (IC50 of 97.2 µg/mL)) and in the ABTS assay (an IC50 of 0.4 µg/mL in comparison to the feed (IC50 of 1.2 µg/mL)).
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Destilação , Olea/química , Fenóis , Compostos Fitoquímicos , Águas Residuárias/química , Fenóis/química , Fenóis/isolamento & purificação , Compostos Fitoquímicos/química , Compostos Fitoquímicos/isolamento & purificaçãoRESUMO
In this work, a membrane-based process for the purification and concentration of antioxidant compounds from aqueous Goji (Lycium barbarum L.) berry extracts was investigated. The aqueous extract was previously clarified with hollow fiber ultrafiltration (UF) membranes in order to remove suspended solids and ß-carotene and to produce a clarified extract enriched in phenolic compounds. Then, three UF flat sheet polyamide membranes with a molecular weight cut-off (MWCO) in the range 1000-3500 Da were tested to purify and concentrate phenolic compounds from the clarified extract. The effect of MWCO and transmembrane pressure (TMP) on the performance of selected membranes in terms of productivity and selectivity towards total dissolved solids (TDS), total phenolic compounds (TPC), total carbohydrates (TC) and total antioxidant activity (TAA) was evaluated. Experimental results indicated that the 2500 Da membrane exhibited a lower fouling index, higher cleaning efficiency, lower rejection towards carbohydrates (lower than 30%) and higher rejection towards phenolic compounds (higher than 50%) in comparison to the other investigated membranes. The inclusion of a diafiltration process in the treatment of the clarified extract with this membrane in a spiral-wound configuration improved the concentration of sugar compounds in the permeate stream and increased the purification of phenolic compounds in the retentate fraction.
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Lycium/química , Membranas Artificiais , Fenóis/análise , Fenóis/isolamento & purificação , Extratos Vegetais/química , Ultrafiltração/métodosRESUMO
The valorisation of food wastes is a challenging opportunity for the green, sustainable, and competitive development of industry. The recovery of phenols contributes to the sustainability of olive waste sector, reducing its environmental impact and promoting the development of innovative formulations of interest for pharmaceutical, nutraceutical, and cosmeceutical applications. In this work, olive mill wastewater was treated through a combination of microfiltration (MF), nanofiltration (NF), and reverse osmosis (RO) in a sequential design to produce polyphenol-enriched fractions that have been investigated for their chemical profile using ultra-high-performance liquid chromatography (UHPLC), and their potential antioxidant, hypolipidemic, and hypoglycaemic activities. RO retentate exhibited the highest content of hydroxytyrosol, tyrosol, oleuropein, verbascoside, vanillic acid, and luteolin. In particular, a content of hydroxytyrosol of 1522.2 mg/L, about five times higher than the MF feed, was found. RO retentate was the most active extract in all in vitro tests. Interestingly, this fraction showed a 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic) acid (ABTS) radicals scavenging activity with an IC50 value of 6.9 µg/mL and a potential inhibition of lipid peroxidation evaluated by the ß-carotene bleaching test with IC50 values of 25.1 µg/mL after 30 min of incubation. Moreover, RO retentate inhibited α-amylase and α-glucosidase with IC50 values of 65.3 and 66.2 µg/mL, respectively.
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Pomegranate (Punica granatum L.) juice is well recognized for its high content of phytochemicals with proven health-promoting effects. Conventional processing techniques including clarification with fining agents, pasteurization and thermal concentration have significant influences on bioactive compounds and antioxidant activity of the juice. The growing consumers demand for high-quality pomegranate juice as well as the industrial interest for the production of functional foods, nutraceuticals, and cosmetics from its bioactive compounds have promoted the interest for minimal processing technologies. In this context, membrane-based operations represent an innovative approach to improve the overall quality of pomegranate juice production. This review focuses on the recent advances and developments related to the application of membrane technology in pomegranate juice processing. Conventional pressure-driven membrane operations and innovative membrane operations, such as osmotic distillation and pervaporation, are discussed in relation to their potential in juice clarification, fractionation, concentration and aroma recovery. Their implementation in integrated systems offer new opportunities to improve the healthiness and quality of the juice as well as to recover, purify and concentrate bioactive compounds for the formulation of functional ingredients.
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Goji (Lycium barbarum L.) leaves and fruits have been described as a valuable source of bioactive compounds with a great potential for the development of health-promoting formulations. The present study aimed to evaluate the potential of a sustainable process for the recovery of phenolic compounds from Goji leaves through a combination of aqueous extraction and membrane-based operations. Water was used as a safe, cheap, and non-hazardous extraction solvent, and parameters of extraction of dried Goji leaves were optimized in order to maximize the yield of polyphenols, total soluble solids (TSS), and total antioxidants simultaneously. The aqueous extract was clarified by ultrafiltration and then processed with three flat-sheet polyethersulphone (PES) membranes with molecular weight cut-off (MWCO) values in the range of 0.3-4.0 kDa, in order to remove sugar compounds from polyphenols and improve the antioxidant activity of the produced fractions. Among the selected membranes, a 1 kDa membrane exhibited the best performance in terms of purification of polyphenols from the clarified aqueous extract. The rejection by this membrane of TSS and total carbohydrates was in the range of 15.8-25.3%, and was decreased by increasing the volume reduction factor (VRF). On the other hand, the retention values for total polyphenols and total antioxidant activity (TAA) were in the range of 73-80%, and were increased by increasing the VRF.
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Antioxidantes/isolamento & purificação , Lycium/química , Fenóis/isolamento & purificação , Extratos Vegetais/isolamento & purificação , Folhas de Planta/química , Polímeros/química , Sulfonas/química , Antioxidantes/química , Antioxidantes/farmacologia , Benzotiazóis/antagonistas & inibidores , Fenóis/química , Fenóis/farmacologia , Extratos Vegetais/química , Extratos Vegetais/farmacologia , Ácidos Sulfônicos/antagonistas & inibidores , Água/químicaRESUMO
Polyamide commercial membranes in flat-sheet configuration and with molecular weight cut-off (MWCO) in the range of ultrafiltration (UF) to nanofiltration (NF) were tested for the recovery of phenolic compounds from clarified olive mill solid waste (OMSW) aqueous extracts. The performance of selected membranes was evaluated in terms of productivity (permeate flux) and selectivity towards biologically active compounds (such as phenolic compounds, flavanols, and hydroxycinnamic acids derivatives) and total antioxidant activity (TAA) as a function of transmembrane pressure (TMP). NF membranes produced higher permeate fluxes and a lower fouling index in comparison with UF membranes. Retention of bioactive compounds was also significantly higher for NF membranes than for UF membranes. In particular, membranes with MWCO in the range 150-500 Da showed rejection towards flavanols and hydroxycinnamic acid derivatives of about 100%. On the other hand, the rejection towards TAA and total polyphenols was of about 90% and 72%, respectively. Therefore, NF retentate fractions appear of practical interest for the production of food additives and food supplements due to their high antioxidant activity.
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In this work, the use of polymeric ultrafiltration and nanofiltration membranes was investigated in order to recover glycyrrhizin and phenolic compounds from licorice wastewaters. Filtration experiments were performed on a laboratory scale using four polyamide thin-film composite membranes (GK, GH, GE, and DK, from GE Osmonics) with different molecular weight cut-offs (from 150 to 3500 Da). The permeate flux and retention values of glycyrrhizin, the total polyphenols, the caffeic acid, the total carbohydrate, and the total antioxidant activity as a function of the transmembrane pressure (TMP) and weight reduction factor (WRF) were evaluated. In selected operating conditions, the membrane productivity decreased in the order of GK > DK > GH > GE, with a similar trend to that of water permeability. Glycyrrhizin was totally rejected by selected membranes, independently of TMP and WRF. For the other antioxidant compounds, the retention values increased by increasing both of the parameters. According to the experimental results, a combination of membranes in a sequential design was proposed as a viable approach to produce concentrated fractions enriched in bioactive compounds and purified water from licorice wastewater.
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Glycyrrhiza/química , Ácido Glicirrízico/isolamento & purificação , Membranas Artificiais , Fenóis/isolamento & purificação , Águas Residuárias/química , Ácido Glicirrízico/análise , Fenóis/análise , Ultrafiltração , Fluxo de TrabalhoRESUMO
Polyvinylidenefluoride (PVDF) hollow fiber membranes prepared in laboratory through the inversion phase method were characterized and used to clarify an aqueous extract from red wine lees. Steady-state permeate fluxes of 53 kg/m2h were obtained in the treatment of the aqueous extract in selected operating conditions. Suspended solids were completely retained by the hollow fiber membranes while bioactive compounds, including polyphenols, anthocyanins, and resveratrol were recovered in the permeate stream. The clarified stream was then fractionated by nanofiltration (NF). Three different commercial membranes, in flat-sheet configuration (NP010 and NP030 from Microdyn-Nadir, MPF36 from Koch Membrane Systems), were selected and tested for their productivity and selectivity towards sugars and bioactive compounds, including phenolic compounds, anthocyanins, and resveratrol. All selected membranes showed high retention towards anthocyanins (higher than 93%). Therefore, they were considered suitable to concentrate anthocyanins from clarified wine lees extracts at low temperature. On the other hand, NF permeate streams resulted enriched in phenolic compounds and resveratrol. Among the selected membranes, the MPF36 exhibited the lowest retention towards resveratrol (10%) and polyphenols (26.3%) and the best separation factor between these compounds and anthocyanins.
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To date, according to the latest literature inputs, membranes-based technologies (microfiltration, ultrafiltration and nanofiltration) have demonstrated to meet the recovery of biologically active compounds, mainly phenolic compounds and their derivatives, from agro-food products and by-products. The goal of this paper is to provide a critical overview of the on ongoing development works aimed at improving the separation, fractionation and concentration of phenolic compounds and their derivatives from their original sources. The literature data are analyzed and discussed in relation to separation processes, molecule properties, membrane characteristics and key factors affecting the performance of such technologies. Technological advances and improvements over conventional technologies, as well as critical aspects to be further investigated are highlighted and discussed. Finally, a critical outlook about the current status for a large-scale application and the role of these processes from an environmental viewpoint is provided.
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Tecnologia de Alimentos , Membranas Artificiais , Fenóis , Ultrafiltração , Fracionamento Químico , Análise de Alimentos , Tecnologia de Alimentos/métodos , Tecnologia de Alimentos/tendências , Fenóis/isolamento & purificaçãoRESUMO
An integrated membrane process for the treatment of wastewaters from a flue gas desulfurization (FGD) plant was implemented on a laboratory scale to reduce their salt content and to produce a water stream to be recycled in the power industry. The process is based on a preliminary pretreatment of FGD wastewaters, which includes chemical softening and ultrafiltration (UF) to remove Ca2+ and Mg2+ ions as well as organic compounds. The pretreated wastewaters were submitted to a reverse osmosis (RO) step to separate salts from water. The RO retentate was finally submitted to a membrane distillation (MD) step to extract more water, thus increasing the total water recovery factor while producing a high-purity permeate stream. The performance of RO and MD membranes was evaluated by calculating salts rejection, permeate flux, fouling index, and water recovery. The investigated integrated system allowed a total recovery factor of about 94% to be reached, with a consequent reduction of the volume of FGD wastewater to be disposed, and an MD permeate stream with an electrical conductivity of 80 µS/cm, able to be reused in the power plant, with a saving in fresh water demand.
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For the first time the chemical profile, physico-chemical parameters, inhibition of carbohydrate hydrolysing enzymes associated with type 2 diabetes, and radical scavenging properties of Sambucus nigra L. (elderberry) juice treated by nanofiltration (NF) were investigated. Three commercial NF membranes with different molecular weight cut-off (MWCO) (400 and 1000 Da) and polymeric material (composite fluoro-polymer and polyethersulphone) were tested. According to HPLC analyses, most part of bioactive compounds were retained by the NF membranes producing a retentate fraction of interest for the production of functional foods. The NP030 membrane, a polyethersulphone membrane with a MWCO of 400 Da, exhibited the highest rejection towards phenolic compounds when compared with the other selected membranes. Accordingly, the produced retentate fractions exhibited the highest radical scavenging activity.
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Filtração/instrumentação , Manipulação de Alimentos/métodos , Sucos de Frutas e Vegetais , Membranas Artificiais , Sambucus nigra/química , Antioxidantes/farmacologia , Cromatografia Líquida de Alta Pressão , Filtração/métodos , Manipulação de Alimentos/instrumentação , Sucos de Frutas e Vegetais/análise , Inibidores de Glicosídeo Hidrolases/farmacologia , Peso Molecular , Permeabilidade , Polímeros/química , Sulfonas/química , alfa-Amilases/antagonistas & inibidoresRESUMO
Pressure-driven membrane-based technologies represent a valid approach to reduce the environmental pollution of several agro-food by-products. Recently, in relation to the major interest for natural compounds with biological activities, their use has been also addressed to the recovery, separation and fractionation of phenolic compounds from such by-products. In particular, tight ultrafiltration (UF) and nanolfiltration (NF) membranes have been recognized for their capability to recover phenolic compounds from several types of agro-food by-products. The separation capability of these membranes, as well as their productivity, depends on multiple factors such as membrane material, molecular weight cut-off (MWCO) and operating conditions (e.g., pressure, temperature, feed flow rate, volume reduction factor, etc.). This paper aims at providing a critical overview of the influence of these parameters on the recovery of phenolic compounds from agro-food by-products by using tight UF and NF membranes. The literature data are analyzed and discussed in relation to separation processes, molecule properties, membrane characteristics and other phenomena occurring in the process. Current extraction methodologies of phenolic compounds from raw materials are also introduced in order to drive the implementation of integrated systems for the production of actractive phenolic formulations of potential interest as food antioxidants.
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Membranas Artificiais , Nanotecnologia , Polifenóis , Ultrafiltração , Alimentos , Análise de Alimentos , Estrutura Molecular , Polifenóis/análise , Polifenóis/química , Ultrafiltração/métodosRESUMO
Press liquors are typical by-products of the citrus juice processing characterized by a high content of organic compounds and associated problems of environmental impact, which imply high treatment costs. However, these wastes contain a great number of health promoting substances, including fibers, carotenoids and phenolic compounds (mainly flavonoids), whose recovery against waste-destruction technologies is very attractive for new business opportunities. In this work, the clarification of orange press liquor by using microfiltration (MF) membranes is studied as a preliminary step to obtain a permeate stream enriched in antioxidant compounds which can be further processed to produce extracts of nutraceutical and/or pharmaceutical interest. MF poly(vinylidene fluoride) (PVDF) hollow fibers were prepared by the dry/wet spinning technique. A series of fibers was produced from the same polymeric dope, in order to investigate the effect of selected spinning parameters, i.e., bore fluid composition and flowrate, on their properties. The morphology of the produced fibers was analyzed by Scanning Electron Microscopy (SEM). Fibers were further characterized for their mechanical properties, porosity, bubble point, pore size distribution and pure water permeability (PWP). Some of the produced fibers exhibited high permeability (pure water permeability ~530 L/m²·h·bar), coupled to good mechanical resistance and pore size in the range of MF membranes. These fibers were selected and used for the clarification of press liquor from orange peel processing. In optimized operating conditions, the selected fibers produced steady-state fluxes of about 41 L/m²·h with rejections towards polyphenols and total antioxidant activity of 4.1% and 1.4%, respectively.
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Commercial nanofiltration (NF) membranes in spiral-wound configuration (NP030 from Microdyn Nadir and Desal DK from GE Water & Process Technologies) were used in a sequential design in order to produce a separated fraction of phenolic and sugar compounds from an aqueous artichoke extract. For both membranes, the effect of transmembrane pressure (TMP) on the permeation flux was evaluated. In optimized conditions of TMP, the NP030 membrane exhibited high rejections of apigenin, cynarin and chlorogenic acid (higher than 85%); on the other hand, very low rejections of fructose, glucose and sucrose (lower than 4%) were measured. Starting from an extract with a total antioxidant activity (TAA) of 5.28 mM trolox a retentate fraction with a TAA of 47.75 mM trolox was obtained. The NF permeate from the NP030 membrane was processed with the Desal DK membrane in optimized conditions of TMP producing a permeate stream free of phenolic and sugar compounds. Accordingly, as most part of phenolic compounds was removed in the first NF step, the concentration of sugar compounds in the NF retentate had much higher results than that of phenolic compounds.