Removal of pharmaceutically active compounds using low-pressure membrane processes

This is an Accepted Manuscript of an article published by Taylor & Francis in Desalination and water treatment on 2017, available online: http://doi.org/10.5004/dwt.2017.0449[EN] The increasing demand on water resources throughout the world has motivated researchers to seek new ways to obtain quality water increasing their interest in water reclamation. However, the presence of harmful organic chemicals such as pharmaceutically active compounds (PhACs) is a serious environmental concern. The objective of this study was to investigate the influence of the pH on the rejection of seven target PhACs (acetaminophen, caffeine, erythromycin, ibuprofen, naproxen, sulfamethoxazole, and trimethoprim) by different low-pressure membranes within the fine ultrafiltration (UF) and loose nanofiltration (NF) range. For this purpose, three ceramic membranes and a polyamide membrane were used for UF and NF experiments, respectively. Experimental results indicated that PhACs with negative charge were effectively rejected at basic conditions (< 75% for UF, < 90% for NF), improving both their hydrophilicity and solubility with increasing pH. Furthermore, high soluble PhACs with high pKa values showed low rejection values (similar to 15% for UF, similar to 30% for NF) and a pH-independent behaviour during low-pressure filtration experiments. Therefore, the use of low-pressure membranes could be considered as an appropriate and sustainable supplemental technique to remove PhACs in a wastewater treatment plant.The authors of this work wish to gratefully acknowledge the financial support from the Spanish Ministry of Economy and Competitiveness through the project CTM2013-42342-P.García-Ivars, J.; Iborra Clar, MI.; Massella, M.; Carbonell Alcaina, C.; Alcaina-Miranda, MI. (2017). Removal of pharmaceutically active compounds using low-pressure membrane processes. Desalination and Water Treatment. 69:252-260. https://doi.org/10.5004/dwt.2017.0449S2522606

Rejection of trace pharmaceutically active compounds present in municipal wastewaters using ceramic fine ultrafiltration membranes: Effect of feed solution pH and fouling phenomena

[EN] This study investigates the influence of feed solution pH and fouling on the rejection of ten selected pharmaceutically active compounds (PhACs) with different physicochemical characteristics (molecular weight, water solubility, log Kow, pKa, dipole moment, etc.) by three multichannel ceramic ultrafiltration membranes, ranging from 1 to 8 kDa, in order to improve their removal from water. For this purpose, the comparison between filtration of PhACs in deionised water (Feed I) and in real wastewater effluent (Feed II) was performed, demonstrating that the variation of pH and the formation of a foulant layer altered the separation mechanism and hence the rejection values of each PhAC varied. Higher rejections of most of the PhACs were higher at slightly alkaline pH, especially for anionic compounds in the filtration with real wastewater. In these conditions, flux decline was more severe. The formed fouling layer onto the hydrophilic membrane surface acted as a secondary barrier for separation with different properties like hydrophobicity and charge. Electrostatic interactions were the main separation mechanism in the filtration of PhACs in deionised water, while the hydrophobic/hydrophilic interactions played a crucial role in the filtration experiments with real wastewater effluent. Thus, the reported results indicated that the rejection of pharmaceutically active compounds was strongly pH-dependent, except for hydrophilic neutral compounds (acetaminophen and caffeine), which showed a pH-independent behaviour with low rejection values. (C) 2016 Elsevier B.V. All rights reserved.The authors of this work wish to gratefully acknowledge the financial support from the Spanish Ministry of Economy and Competitiveness through the project CTM2013-42342-P.García-Ivars, J.; Dura-Maria, J.; Moscardo-Carreño, C.; Carbonell Alcaina, C.; Alcaina-Miranda, MI.; Iborra Clar, MI. (2017). Rejection of trace pharmaceutically active compounds present in municipal wastewaters using ceramic fine ultrafiltration membranes: Effect of feed solution pH and fouling phenomena. Separation and Purification Technology. 175:58-71. https://doi.org/10.1016/j.seppur.2016.11.027S587117

Comparison between hydrophilic and hydrophobic metal nanoparticles on the phase separation phenomena during formation of asymmetric polyethersulphone membranes

Inorganic nanoparticles have been applied as additive in membrane synthesis for improving different properties from the base polymer such as hydrophilicity, fouling resistance or permselectivity. To investigate the changes caused by the presence of the inorganic nanoparticles in the formation of the membrane structure, two different metallic compounds with opposite hydrophilicity were used as additives: hydrophilic zinc oxide (ZnO) and hydrophobic tungsten disulphide (WS2). For this purpose, the effect of these metal nanoparticles at ultra-low concentrations (0.05 and 0.25 wt% metal nanoparticles/polymer ratio) in the preparation of flat-sheet membranes based on polyethersulphone (PES) by immersion-precipitation method was investigated. N-methyl-2-pyrrolidone (NMP) was used as solvent. The influence of both metal nanoparticles on the characteristics and permselective properties of PES membranes was studied with microscopic observations, contact angle measurements, and filtration experiments. Although the incorporation of metal nanoparticles could turn the system into thermodynamically unstable, the demixing process during formation of membranes was slightly delayed, suppressing the macrovoid formation (remarkably using WS2). Regardless the nature of the metal nanoparticles, results showed an overall improvement in membrane hydrophilicity and permselectivity by adding metal nanoparticles compared to the control PES membrane, demonstrating that the behaviour of both metal nanoparticles at ultra-low concentrations was very similar.García Ivars, J.; Iborra Clar, MI.; Alcaina Miranda, MI.; Van Der Bruggen, B. (2015). Comparison between hydrophilic and hydrophobic metal nanoparticles on the phase separation phenomena during formation of asymmetric polyethersulphone membranes. Journal of Membrane Science. 493:709-722. doi:10.1016/j.memsci.2015.07.009S70972249

Pharmaceutical compounds removal by adsorption with commercial and reused carbon coming from a drinking water treatment plant

[EN] The concern for the presence of pharmaceutical compounds in purified wastewater has grown in recent years. In this context, efficient and economically viable processes are required for their removal. In this study, adsorption was conducted to assess the removal of ibuprofen, caffeine, diazepam and acetaminophen, both as separated processes as in combination with a biological process in sequencing batch reactors. Removal efficiencies of these pharmaceutical active compounds were evaluated using two commercial activated carbons in granular and powder form and a discarded (after its use) activated carbon from a drinking water treatment plant. Concerning the biological treatment tests, simulated municipal wastewater was doped with 3¿mg/L of each pharmaceutical active compounds. Results showed that caffeine, acetaminophen and ibuprofen achieved excellent removal percentages, even without powder activated carbon addition (more than 94%); By contrast, whereas diazepam removal was low (lower than 50%); however, it was improved up to 68% with the powder activated carbon addition to the sequencing batch reactors. Regarding adsorption tests as separated process, ibuprofen was the pharmaceutical active compounds with the lowest removal percentage (around 50% for the granular activated carbon) and diazepam (around 80% for the granular activated carbon) was the compound with the maximum removal efficiency for the tested concentrations (between 0.5 and 3¿mg/L). Finally, results were very promising for the reused activated carbon since the removal efficiency of the pharmaceutical active compounds was higher than 90% (except for ibuprofen) when 0.5¿g/L of reused activated carbon was applied in powder form to solutions of 3¿mg/L of each pharmaceutical active compounds. In this way, a low cost activated carbon could be applied in wastewater treatment plants for pharmaceutical active compounds removal.This work has been carried out in the frame of the project IMIDTA/2017/73 granted to the company GECIVAL, S.L. by Instituto Valenciano de Competitividad Empresarial (IVACE) within the program for research and development projects for SMEs. This project has been co-financed (50%) by the operational program FEDER of Comunitat Valenciana 2014 2020.Lujan Facundo, MJ.; Iborra-Clar, MI.; Mendoza Roca, JA.; Alcaina-Miranda, MI. (2019). Pharmaceutical compounds removal by adsorption with commercial and reused carbon coming from a drinking water treatment plant. Journal of Cleaner Production. 238:1-9. https://doi.org/10.1016/j.jclepro.2019.117866S1923

Fabrication and characterization of organic pervaporation membranes to recover ethyl acetate of aqueous solutions

García Ivars, J.; Alcaina Miranda, MI.; Iborra Clar, MI.; Iborra Clar, A. (2012). Fabrication and characterization of organic pervaporation membranes to recover ethyl acetate of aqueous solutions. Procedia Engineering. 44:678-680. doi:10.1016/j.proeng.2012.08.527S6786804

Protein removal from waste brines generated during ham salting through acidification and centrifugation

[EN] The salting step in food processes implies the production of large quantities of waste brines, having high organic load, high conductivity, and other pollutants with high oxygen demand. Direct disposal of the residual brine implies salinization of soil and eutrophication of water. Since most of the organic load of the waste brines comes from proteins leaked from the salted product, precipitation of dissolved proteins by acidification and removal by centrifugation is an operation to be used in waste brine cleaning. The aim of this study is optimizing the conditions for carrying out the separation of proteins from waste brines generated in the pork ham salting operation, by studying the influence of pH, centrifugal force, and centrifugation time. Models for determining the removal of proteins depending on the pH, centrifugal force, and time were obtained. The results showed a high efficacy of the proposed treatment for removing proteins, suggesting that this method could be used for waste brine protein removal. The best pH value to be used in an industrial process seems to be 3, while the obtained results indicate that almost 90% of the proteins from the brine can be removed by acidification followed by centrifugation. A further protein removal from the brine should have to be achieved using filtrating techniques, which efficiency could be highly improved as a consequence of the previous treatment through acidification and centrifugation. Practical Application Waste brines from meat salting have high organic load and electrical conductivity. Proteins can be removed from the waste brine by acidification and centrifugation. The total protein removal can be up to 90% of the initial content of the waste brine. Protein removal is highly dependent on pH, centrifugation rate, and time.We would like to thank the Spanish Government (MCYT) and the EU (FEDER program) for the financial support of the project (AGL2004-05064-C02).Gutiérrez-Martínez, MDR.; Muñoz Guerrero, HP.; Alcaina-Miranda, MI.; Barat Baviera, JM. (2014). Protein removal from waste brines generated during ham salting through acidification and centrifugation. Journal of Food Science. 79(3):326-332. https://doi.org/10.1111/1750-3841.12373S32633279

Evolution of Membrane Performance During the Ultrafiltration of Reactive Black 5 Solutions: Effect of Feed Characteristics and Operating Pressure

[EN] In the present work, the feasibility of the ultrafiltration (UF) technology for the removal of a hazardous azo reactive dye, Reactive Black 5 (RB5), was studied. A tubular UF ceramic membrane was used to filter RB5 aqueous solutions. Solutions at different feed concentrations (50, 100, 500 mg/L) and temperatures (25, 30, 35, 40 °C) were tested in order to observe the influence of these two parameters on the evolution of permeate flux and dye rejection with operating time. Moreover, the effect of transmembrane pressure (TMP) was also studied by performing essays at different operating pressures (1, 2, 3, 4 bar). Additionally, membrane performance was also evaluated by means of the average permeate flux and the cumulative flux decline. The results showed that both the productivity and the permeate quality improved by increasing feed temperature and decreasing feed concentration. On the other hand, an increase in TMP led to an increase in permeate flux. However, in this case the flux decline was more pronounced and the retention of dye decreased. Finally, the relatively high dye rejections obtained are an indicator of the suitability of UF technology for the removal of RB5 from aqueous solutions as a pretreatment of other membrane processes to textile water reuse. Copyright © 2012, AIDIC Servizi S.r.l.This work was supported by the “Ministerio de Ciencia e Innovación” through the project ref. CTM2009-13048 and the “Ministerio de Educación” through the FPU grant ref. AP2009-3509.Alventosa De Lara, E.; Barredo Damas, S.; Alcaina Miranda, MI.; Iborra Clar, MI. (2012). Evolution of Membrane Performance During the Ultrafiltration of Reactive Black 5 Solutions: Effect of Feed Characteristics and Operating Pressure. Chemical Engineering Transactions. 29:1285-1290. https://doi.org/10.3303/CET1229215S128512902

Preparation of Sewage Sludge¿Based Activated Carbon for Hydrogen Sulphide Removal

[EN] The circular economy concept boosts the use of wastes as secondary raw materials in the EU renewable and sustainable framework. In wastewater treatment plants (WWTP), sludge is one of the most important wastes, and its management is being widely discussed in the last years. In this work, sewage sludge from WWTP was employed as raw material for producing activated carbon (AC) by physical-chemical activation. The prepared AC was subsequently tested for hydrogen sulphide removal in view of its further use in deodorization in a WWTP. The effects of the activation temperature and the chemical agent used (NaOH and KOH) during the activation process were studied. On the one hand, the characteristics of each AC fabricated were analysed in terms of BET (Brunauer-Emmett-Teller) surface area, pore and micropore volume, pore diameter, surface morphology and zeta potential. On the other hand, BET isotherms were also calculated. Finally, both the prepared AC and a commercial AC were tested for H2S removal from a gas stream. Results demonstrated that the optimum physical and chemical activation temperature was 600 degrees C and 1000 degrees C, respectively, and the best activated agent tested was KOH. The prepared AC showed excellent properties (specific surface area around 300 m(2)/g) for H2S removal, even better efficiencies than those achieved by the tested commercial AC.Lujan Facundo, MJ.; Iborra-Clar, MI.; Mendoza Roca, JA.; Alcaina-Miranda, MI.; Maciá, AM.; Lardin, C.; Pastor, L.... (2020). Preparation of Sewage Sludge¿Based Activated Carbon for Hydrogen Sulphide Removal. Water Air & Soil Pollution. 231(4):1-12. https://doi.org/10.1007/s11270-020-04518-wS1122314Andrade, S. N., Veloso, C. M., Fontan, R. C. I., Bonomo, R. C. F., Santos, L. S., Brito, M. J. P., & Diniz, G. A. (2018). 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Removal of pharmaceutical compounds commonly-found in wastewater through a hybrid biological and adsorption process

[EN] Nowadays, alternative options to conventional wastewater treatment should be studied due to rising concerns emerged by the presence of pharmaceuticals compounds (PhCs) in the aquatic environment. In this work, a combined system including biological treatment by activated sludge plus adsorption with activated carbon is proposed to remove three selected drugs (acetaminophen (ACT), caffeine (CAF) and ibuprofen (IBU)) in a concentration of 2 mg L-1 of each one. For it three sequencing batch reactors (SBR) were operated. SBR-B treated a synthetic wastewater (SWW) without target drugs and SBR-PhC and SBR-PhC + AC operated with SWW doped with the three drugs, adding into SBR-PhC + AC 1.5 g L-1 of a mesoporous granular activated carbon. Results showed that the hybrid system SBR-activated carbon produced an effluent free of PhCs, which in addition had higher quality than that achieved in a conventional activated sludge treatment in terms of lower COD, turbidity and SMP concentrations. On the other hand, five possible routes of removal for target drugs during the biological treatment were studied. Hydrolysis, oxidation and volatilization pathways were negligible after 6 h of reaction time. Adsorption mute only was significant for ACT, which was adsorbed completely after 5 h of reaction, while only 1.9% of CAF and 5.6% of IBU were adsorbed. IBU was the least biodegradable compound.This work was supported by Spanish grants AICO/2018/292 of the Generalitat Valenciana.Ferrer-Polonio, E.; Fernández-Navarro, J.; Iborra-Clar, MI.; Alcaina-Miranda, MI.; Mendoza Roca, JA. (2020). Removal of pharmaceutical compounds commonly-found in wastewater through a hybrid biological and adsorption process. Journal of Environmental Management. 263:1-8. https://doi.org/10.1016/j.jenvman.2020.110368S18263Al-Khazrajy, O. S. A., & Boxall, A. B. A. (2016). Impacts of compound properties and sediment characteristics on the sorption behaviour of pharmaceuticals in aquatic systems. 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C., & Amaral, M. C. S. (2019). Occurrence, fate and removal of pharmaceutically active compounds (PhACs) in water and wastewater treatment plants—A review. Journal of Water Process Engineering, 32, 100927. doi:10.1016/j.jwpe.2019.100927Desbiolles, F., Malleret, L., Tiliacos, C., Wong-Wah-Chung, P., & Laffont-Schwob, I. (2018). Occurrence and ecotoxicological assessment of pharmaceuticals: Is there a risk for the Mediterranean aquatic environment? Science of The Total Environment, 639, 1334-1348. doi:10.1016/j.scitotenv.2018.04.351Dong, X., Zhou, W., & He, S. (2013). Removal of anaerobic soluble microbial products in a biological activated carbon reactor. Journal of Environmental Sciences, 25(9), 1745-1753. doi:10.1016/s1001-0742(12)60224-1Fan, H., Li, J., Zhang, L., & Feng, L. (2014). Contribution of sludge adsorption and biodegradation to the removal of five pharmaceuticals in a submerged membrane bioreactor. 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Factors influencing the Ultrasound-enhaced cleaning process of an ultrafiltration ceramic membrane fouled by Reactive Dye Particles

This work was supported by the "Ministerio de Ciencia e Innovación" through the project ref. CTM2009-13048 and the "Ministerio de Educación" through the FPU grant ref. AP2009-3509.Alventosa De Lara, E.; Barredo Damas, S.; Alcaina Miranda, MI.; Iborra Clar, MI. (2012). Factors influencing the Ultrasound-enhaced cleaning process of an ultrafiltration ceramic membrane fouled by Reactive Dye Particles. Procedia Engineering. 44:1665-1667. doi:10.1016/j.proeng.2012.08.901S166516674