Reclamation of boron from solid and liquid streams for fertilizer application.

Boron (B) is a crucial element for efficient plant growth and development; therefore, B-based fertilisers have been employed in agricultural applications. The need for B-based fertilisers for agricultural uses is continuously increasing as a result of the world's growing population. It is expected that the global market for B-based fertiliser will grow by around $6.3 billion by 2032; hence, demand for B sources will also increase. In addition to being used in fertiliser, B is also employed in the production of neodymium iron B (NdFeB) permanent magnets. The demand for NdFeB magnets is also continuously increasing. Hence, it is of the utmost importance to reclaim B from secondary resources due to the rising demand for B in a wide variety of applications. This review study addresses the recovery of B from various waste streams. The main focus is on the recovery of B from spent NdFeB magnets, borax sludge, and liquid streams such as brine water, seawater, sewage, industrial wastewater, and agricultural effluents. Different technologies for B recovery are discussed, such as sorption, solvent extraction, membrane processes, precipitation, and hydrometallurgical methods. Solvent extraction has been found to be a very effective approach for reclaiming B from spent NdFeB magnet waste and from liquid streams with high B concentration (>1-2 g/L). Further, the application of B-based fertiliser in agriculture application is reviewed. Challenges associated with B recovery from waste streams and future perspectives are also highlighted in this review.

Boron recovery from desalination seawater brines by selective ion exchange resins.

The European Union (EU) depends on third markets to supply many important raw materials. Increasing the circularity of critical raw materials within the EU is important not only from an environmental perspective, but also as a competitive advantage for the EU economy. In the case of boron, the EU's import dependency is about 100%. This work aims to evaluate the boron recovery from seawater desalination plants (SWDP) brines using ion-exchange resins in a circular economy approach. Commercial boron selective resins Purolite S108, DIAION CRB03 and CRB05 were tested and compared on batch and dynamic experiments. Thermodynamic and kinetic experiments were performed, and results were fitted by linear and non-linear models. After a comparison, results showed a good fit to the Langmuir isotherm and the pseudo-second order model, respectively, for all the commercial resins tested. The DIAION CRB03 resin presented higher sorption capacity and percentage of boron sorbed than the other resins and was selected as the best option for boron recovery from SWDP brine. Dynamic experiments in fixed bed column using DIAION CRB03 resulted in a sorption capacity of 13 mg/g of resin, a boron recovery of 98% and a concentration factor of 30, for an initial boron concentration of 50 mg/L. In addition, an economic analysis was carried out as a preliminary estimate of the revenues obtained from the production of boric acid from the brine produced by El Prat desalination plant.

Advanced Hybrid System for Ammonium Valorization as Liquid Fertilizer from Treated Urban Wastewaters: Validation of Natural Zeolites Pretreatment and Liquid-Liquid Membrane Contactors at Pilot Plant Scale.

This study evaluates a hybrid system combining zeolites as a sorption stage and a hollow fiber membrane contactor (HFMC) for ammonia (NH3) recovery from treated urban wastewater. Ion exchange with zeolites was selected as an advanced pretreatment and concentration step before the HFMC. The system was tested with wastewater treatment plant (WWTP) effluent (mainstream, 50 mg N-NH4/L) and anaerobic digestion centrates (sidestream, 600-800 mg N-NH4/L) from another WWTP. Natural zeolite, primarily clinoptilolite, demonstrated effective desorption of retained ammonium using a 2% NaOH solution in a closed-loop configuration, resulting in an ammonia-rich brine that enabled over 95% NH3 recovery using polypropylene HFMCs. A 1 m3/h demonstration plant processed both urban wastewaters, which were pretreated by ultrafiltration, removing over 90% of suspended solids and 60-65% of COD. The 2% NaOH regeneration brines (2.4-5.6 g N-NH4/L) were treated in a closed-loop HFMC pilot system, producing 10-15% N streams with potential use as liquid fertilizers. The resulting ammonium nitrate was free of heavy metals and organic micropollutants, making it suitable for use as liquid fertilizer. This comprehensive N management solution for urban wastewater applications can contribute to local economies while achieving reduced N discharge and circularity goals.

Removal of nitrate from groundwater by nano-scale zero-valent iron injection pulses in continuous-flow packed soil columns.

Injection of zero-valent iron nanoparticles (nZVI) into aquifers has gained increasing attention of researchers for in-situ treatment of NO3--contaminated groundwater. nZVI has proved efficient in chemically reducing NO3- and, according to recent research efforts, in supporting biological denitrification under favoured conditions. Given the scarce research on nZVI pulsed injection in continuous-flow systems, the objective of this study was to evaluate the effect of nZVI pulses on the removal of NO3- from groundwater in packed soil columns and, more particularly, to elucidate whether or not biotic NO3- removal processes were promoted by nZVI. Three identical columns were filled with aquifer soil samples and fed with the same nitrate polluted groundwater but operated under different conditions: (A) with application of nZVI pulses and biocide spiked in groundwater, (B) without application of nZVI pulses and (C) with application of nZVI pulses. Results showed that the application of nZVI (at 30 mg/L and 78 mg/L doses) resulted in an immediate and sharp removal of NO3- (88-94%), accompanied by an increase in pH (from 7.0 to 9.0-10.0), a drop in redox potential (Eh) (from +420 mV to <100 mV) and a release of Fe(II) and Total Organic Carbon (TOC) in the effluent (to 200 mg/L and 150-200 mg/L, respectively). The released TOC came from the organic polymer used as stabilizer of the nZVI particles. Comparison against the sterilized control column revealed that, under the experimental conditions, no biological denitrification developed and that the removal of NO3- was due to chemical reduction by nZVI. The main by-product of the NO3- removal was NH4+, which at the prevailing pH was partially converted to NH3, which dissipated from the aqueous solution resulting in a net removal of total dissolved N. A mass balance of Fe permitted to quantify the percentage of injected nZVI trapped in the column (>98%) and the NO3- retention capacity of the nZVI particles (13.2-85.5 mg NO3-/g nZVI).

Impact of Sidestream Pre-Treatment on Ammonia Recovery by Membrane Contactors: Experimental and Economic Evaluation.

Membrane contactor is a promising technology for ammonia recovery from the anaerobic digestion centrate. However, high suspended solids and dissolved organic matter concentrations can reduce the effectiveness of the technology. In this study, coagulation-flocculation (C/F) and aeration pre-treatments were evaluated to reduce chemical oxygen demand (COD), turbidity, suspended solids and alkalinity before the ammonia recovery stage using a membrane contactor. The mass transfer coefficient (Km) and total ammonia (TAN) recovery efficiency of the membrane contactor increased from 7.80 × 10-7 to 1.04 × 10-5 m/s and from 8 to 67%, respectively, after pre-treating the real sidestream centrate. The pre-treatment results showed that dosing aluminium sulphate (Al2(SO4)3) at 30 mg Al/L was the best strategy for the C/F process, providing COD, turbidity and TSS removal efficiencies of 50 ± 5, 95 ± 3 and 90 ± 4%, respectively. The aeration step reduced 51 ± 6% the HCO3- content and allowed reducing alkaline consumption by increasing the pH before the membrane contactor. The techno-economic evaluation showed that the combination of C/F, aeration and membrane contactor can be economically feasible for ammonia recovery. Overall, the results of this study demonstrate that C/F and aeration are simple and effective techniques to improve membrane contactor performance for nitrogen recovery from the anaerobic digestion centrate.

Ammonia Valorization by Liquid-Liquid Membrane Contactors for Liquid Fertilizers Production: Experimental Conditions Evaluation.

Liquid-liquid membrane contactors (LLMCs) were studied as a sustainable technology for ammonia recovery from wastewater. Ammonia can be valorized by LLMCs as a potential nutrient and produce liquid fertilizers. Thus, this work aims for the study of different experimental LLMC conditions to produce ammonium salts by an acid stripping stream. The experiments were conducted using two 3MTMLiqui-CellTM LLMC in a series, located in the vertical position and using HNO3 as the acid stripping solution. The flow rates for the feed and stripping sides were fixed during the tests, and two steps were conducted based on previous works. However, different experimental conditions were evaluated to determine its effect on the overall performance: (i) replacing the feed or stripping solution between the steps, (ii) the initial ammonia concentration of the feed solution, (iii) feed volume and (iv) feed temperature. The results demonstrated that better achievements were obtained replacing the acid stripping solution between steps, whereas the feed temperature did not substantially affect the overall performance. Additionally, a high initial ammonia concentration provided more ammonia recovery, although the concentration factor achieved was higher for the low initial ammonia concentration. Finally, a high feed volume afforded better results for the fertilizer side, whereas more NH3 recovery was achieved using less feed volume.

Recovery of Natural Polyphenols from Spinach and Orange By-Products by Pressure-Driven Membrane Processes.

Spinach and orange by-products are well recognized for their health benefits due to the presence of natural polyphenols with antioxidant activity. Therefore, the demand to produce functional products containing polyphenols recovered from vegetables and fruits has increased in the last decade. This work aims to use the integrated membrane process for the recovery of polyphenols from spinach and orange wastes, implemented on a laboratory scale. The clarification (microfiltration and ultrafiltration, i.e., MF and UF), pre-concentration (nanofiltration, NF), and concentration (reverse osmosis, RO) of the spinach and orange extracts were performed using membrane technology. Membrane experiments were carried out by collecting 1 mL of the permeate stream after increasing the flow rate in 1 mL/min steps. The separation and concentration factors were determined by HPLC-DAD in terms of total polyphenol content and by polyphenol families: hydroxybenzoic acids, hydroxycinnamic acids, and flavonoids. The results show that the transmembrane flux depended on the feed flow rate for MF, UF, NF, and RO techniques. For the spinach and orange matrices, MF (0.22 µm) could be used to remove suspended solids; UF membranes (30 kDa) for clarification; NF membranes (TFCS) to pre-concentrate; and RO membranes (XLE for spinach and BW30 for orange) to concentrate. A treatment sequence is proposed for the two extracts using a selective membrane train (UF, NF, and RO) to obtain polyphenol-rich streams for food, pharmaceutical, and cosmetic applications, and also to recover clean water streams.

A green approach to phenolic compounds recovery from olive mill and winery wastes.

The aim of this study was to evaluate the recovery of phenolic compounds from olive mill and winery wastes by conventional solid-liquid extraction (SLE) using water as the extraction solvent. The studied variables were extraction time (5-15 min), temperature (25-90 °C), solid-to-liquid ratio (1:10-1:100 (kg/L)), pH (3-10) and application of multiple extractions (1-3). The extraction efficiency was evaluated in terms of total phenolic content (TPC), determined by high performance liquid chromatography (HPLC-UV), but also from the recovery of some representative phenolic compounds. The optimized conditions were one extraction step, 10 min, 25 °C, 1:30 (kg/L), pH 5 for olive pomace, and one extraction step, 10 min, 70 °C, 1:100 (kg/L), pH 5 for winery residues. The extraction method is simple and suitable for scaling-up in industry, and the aqueous extracts are fully compatible with further purification schemes based on the use of membranes or resins. The optimized technique was applied to a set of different representative residues from olive mill and winery industries, to assess their suitability as sources for phenolic compounds recovery. The phenolic content in the extracts was evaluated by chromatographic analysis and by the Folin-Ciocalteu assay (FC). Furthermore, the antioxidant capacity was determined by 2,2-azinobis-3-etilbenzotiazolina-6-sulfonat (ABTS), 2,-diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing antioxidant power (FRAP) assays. Because of their high contents in phenolic compounds and great antioxidant capacity, olive pomace and lees filters were identified as especially suited sources for phenolic compounds recovery.

Recovery of Polyphenols from Agri-Food By-Products: The Olive Oil and Winery Industries Cases.

The production of olive oil and wine are two of the main agri-food economic activities in Southern Europe. They generate large amounts of solid and liquid wastes (e.g., olive pomace, olive mill wastewater, grape pomace, grape stems, wine lees, and wine processing wastewater) that represent a major environmental problem. Consequently, the management of these residues has become a big challenge for these industries, since they are harmful to the environment but rich in bioactive compounds, such as polyphenols. In recent years, the recovery of phenolic compounds has been proposed as a smart strategy for the valorization of these by-products, from a circular economy perspective. This review aims to provide a comprehensive description of the state of the art of techniques available for the analysis, extraction, and purification of polyphenols from the olive mill and winery residues. Thus, the integration and implementation of these techniques could provide a sustainable solution to the olive oil and winery sectors.

Integration of Nanofiltration and Reverse Osmosis Technologies in Polyphenols Recovery Schemes from Winery and Olive Mill Wastes by Aqueous-Based Processing.

More sustainable waste management in the winery and olive oil industries has become a major challenge. Therefore, waste valorization to obtain value-added products (e.g., polyphenols) is an efficient alternative that contributes to circular approaches and sustainable environmental protection. In this work, an integration scheme was purposed based on sustainable extraction and membrane separation processes, such as nanofiltration (NF) and reverse osmosis (RO), for the recovery of polyphenols from winery and olive mill wastes. Membrane processes were evaluated in a closed-loop system and with a flat-sheet membrane configuration (NF270, NF90, and Duracid as NF membranes, and BW30LE as RO membrane). The separation and concentration efficiency were evaluated in terms of the total polyphenol content (TPC), and by polyphenol families (hydroxybenzoic acids, hydroxycinnamic acids, and flavonoids), using high-performance liquid chromatography. The water trans-membrane flux was dependent on the trans-membrane pressure for the NF and RO processes. NF90 membrane rejected around 91% of TPC for the lees filters extracts while NF270 membrane rejected about 99% of TPC for the olive pomace extracts. Otherwise, RO membranes rejected more than 99.9% of TPC for both types of agri-food wastes. Hence, NF and RO techniques could be used to obtain polyphenol-rich streams, and clean water for reuse purposes.

Use of Membrane Technologies in Dairy Industry: An Overview.

The use of treatments of segregated process streams as a water source, as well as technical fluid reuse as a source of value-added recovery products, is an emerging direction of resource recovery in several applications. Apart from the desired final product obtained in agro-food industries, one of the challenges is the recovery or separation of intermediate and/or secondary metabolites with high-added-value compounds (e.g., whey protein). In this way, processes based on membranes, such as microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO), could be integrated to treat these agro-industrial streams, such as milk and cheese whey. Therefore, the industrial application of membrane technologies in some processing stages could be a solution, replacing traditional processes or adding them into existing treatments. Therefore, greater efficiency, yield enhancement, energy or capital expenditure reduction or even an increase in sustainability by producing less waste, as well as by-product recovery and valorization opportunities, could be possible, in line with industrial symbiosis and circular economy principles. The maturity of membrane technologies in the dairy industry was analyzed for the possible integration options of membrane processes in their filtration treatment. The reported studies and developments showed a wide window of possible applications for membrane technologies in dairy industry treatments. Therefore, the integration of membrane processes into traditional processing schemes is presented in this work. Overall, it could be highlighted that membrane providers and agro-industries will continue with a gradual implementation of membrane technology integration in the production processes, referring to the progress reported on both the scientific literature and industrial solutions commercialized.

Recovery of Added-Value Compounds from Orange and Spinach Processing Residues: Green Extraction of Phenolic Compounds and Evaluation of Antioxidant Activity.

Phenolic compounds recovery by mechanical stirring extraction (MSE) was studied from orange and spinach wastes using water as a solvent. The statistical analysis showed that the highest total polyphenol content (TPC) yield was obtained using 15 min, 70 °C, 1:100 (w/v) solid/solvent ratio and pH 4 for orange; and 5 min, 50 °C, 1:50 (w/v) solid/solvent ratio and pH 6 for spinach. Under these conditions, the TPC was 1 mg gallic acid equivalent (GAE) g-1 fresh weight (fw) and 0.8 mg GAE g-1 fw for orange and spinach, respectively. MSE substantially increased the phenolic compounds yields (1-fold for orange and 2-fold for spinach) compared with ultrasound-assisted extraction. Furthermore, the antioxidant activity of orange and spinach extracts was evaluated using DPPH, FRAP and ABTS. The obtained results pointed out that the evaluated orange and spinach residues provided extracts with antioxidant activity (2.27 mg TE g-1 and 0.04 mg TE g-1, respectively).

Polyphenols and their potential role to fight viral diseases: An overview.

Fruits, vegetables, spices, and herbs are a potential source of phenolic acids and polyphenols. These compounds are known as natural by-products or secondary metabolites of plants, which are present in the daily diet and provide important benefits to the human body such as antioxidant, anti-inflammatory, anticancer, anti-allergic, antihypertensive and antiviral properties, among others. Plentiful evidence has been provided on the great potential of polyphenols against different viruses that cause widespread health problems. As a result, this review focuses on the potential antiviral properties of some polyphenols and their action mechanism against various types of viruses such as coronaviruses, influenza, herpes simplex, dengue fever, and rotavirus, among others. Also, it is important to highlight the relationship between antiviral and antioxidant activities that can contribute to the protection of cells and tissues of the human body. The wide variety of action mechanisms of antiviral agents, such as polyphenols, against viral infections could be applied as a treatment or prevention strategy; but at the same time, antiviral polyphenols could be used to produce natural antiviral drugs. A recent example of an antiviral polyphenol application deals with the use of hesperidin extracted from Citrus sinensis. The action mechanism of hesperidin relies on its binding to the key entry or spike protein of SARS-CoV-2. Finally, the extraction, purification and recovery of polyphenols with potential antiviral activity, which are essential for virus replication and infection without side-effects, have been critically reviewed.

Olive Mill and Winery Wastes as Viable Sources of Bioactive Compounds: A Study on Polyphenols Recovery.

In this study, the recovery of polyphenols from olive oil mill and winery waste was investigated. The performance of ultrasound assisted extraction (UAE), microwave assisted extraction (MAE), and pressurized liquid extraction (PLE) was assessed using ethanol-water mixtures, which are compatible with food, nutraceutical, and cosmetic applications. The extraction efficiency from olive pomace and lees samples was evaluated in terms of total polyphenol content (TPC), determined by high performance liquid chromatography (HPLC) and Folin-Ciocalteu assay. The effect of solvent composition, temperature, and time was analyzed by response surface methodology. Ethanol:water 50:50 (v/v) was found to be a suitable solvent mixture for both kinds of samples and all three extraction techniques. The performance of the extraction techniques was evaluated, under optimal experimental conditions, with a set of different representative samples of residues from olive oil and wine production. Overall, the best extraction efficiency for olive pomace residues was provided by MAE (ethanol:water 50:50 (v/v), 90 °C, 5 min), and for wine residues by PLE (ethanol:water 50:50 (v/v), 100 °C, 5 min, 1 cycle). However, the results provided by UAE (ethanol:water 50:50 (v/v), 30 min) were also suitable. Considering not only extraction performance, but also investment and operational costs, UAE is proposed for a future scaling up evaluation. Regarding olive pomace as a source for natural phenolic antioxidants, olive variety and climatic conditions should be taken into account, since both influence TPC in the extracts, while for winery residues, lees from red wines are more suitable than those from white wines.