Electrochemical treatment of a graphitic forging lubricant effluent: The effect of chloride concentration and current density

The graphite removal and the chemical oxygen demand (COD) reduction by the electrochemical treatment of an effluent containing a lubricant (oil in water emulsion with graphite) was investigated. The electrochemical cell used a pair of aluminum plates. Since the effluent conductivity was very low, NaCl was used as supporting electrolyte and different current densities as well as different distance between the electrodes were applied. In lower current densities, higher chloride concentrations implied in smaller COD values. The same behavior was observed when electrode distance was decreased. All the tested conditions presented significant graphite removal and COD reductions larger than 94%GKN Driveline Brazil is gratefully acknowledged for all the financial support and material given to the execution of this paper. Also, Capes, FAPERGS, CNPq, and Cyted are thanked for their financial support.Borsa, MB.; Jungblut, R.; Pérez-Herranz, V.; Müller, L.; Moura Bernardes, A.; Bergmann, C. (2016). Electrochemical treatment of a graphitic forging lubricant effluent: The effect of chloride concentration and current density. Separation Science and Technology. 51(1):126-134. doi:10.1080/01496395.2015.1086799S12613451

Evaluation of mass transfer behaviour of sulfamethoxazole species at ion–exchange membranes by chronopotentiometry for electrodialytic processes

Funding Information: The authors gratefully acknowledge the financial support given by Ministerio de Universidades de España (European Union – Next Generation EU) and CNPq (grant numbers 408282/2018-5 and 117290/2021-1). This study was also financed by Grant RTI2018-101341-B-C21 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe”. Publisher Copyright: © 2023 The Author(s)In recent years, electrodialysis has been often considered as an appropriate method to treat industrial and/or municipal wastewater containing pharmaceutically active compounds. However, the scarcity of information on the ion transport mechanisms through the membranes, especially concerning occurrence of possible sorption phenomena, has limited the process implementation in practice. The present work aims to evaluate, by chronopotentiometry, the transport of sulfamethoxazole (SMX) through a cation- (CEM) and anion-exchange membrane (AEM) using synthetic solutions at different concentrations (0.001–0.1 g/L) and pH conditions (1.6 for CEM and 9 for AEM). The dominant mechanism of mass transfer under overlimiting current conditions at each membrane/solution system was determined. The potential drop profile measured during and after application of current pulses, as well as the transition times obtained from the curves, showed that sorption occurs at/in both membranes, especially for the AEM. Besides, this phenomenon was reversible for the CEM and irreversible for the AEM under the conditions evaluated herein. The chronopotentiograms of the AEM showed that the intense occurrence of water dissociation with the most diluted solution caused chemical equilibrium shifts in the membrane/electrolyte system, leading to formation of neutral SMX species that can impair the electrodialysis performance. The results obtained are useful for optimizing the electrodialytic treatment of SMX-containing solutions as well as of other compounds with similar physicochemical properties.publishersversionpublishe

Electrodialysis for the tertiary treatment of municipal wastewater: Efficiency of ion removal and ageing of ion exchange membranes

[EN] Electrodialysis was applied as a tertiary treatment for effluents from a Brazilian sewage treatment plant, and the results are discussed in terms of membrane ageing and process efficiency. Current-voltage analysis and electrodialysis (ED) treatment were performed in a bench cell. The treatment was discontinuously carried out for 930 h within one year. During the experiments, samples were collected for evaluation, and the pH, conductivity and ion concentration were monitored. Thermogravimetric analyses of the membrane were also performed. A reduction in electrical conductivity and the high ion percentage extraction demonstrated the efficiency of the ED treatment, confirming the possibility of using ED as a tertiary treatment for sewage. ED showed 100% effectiveness in terms of meeting the quality standards established by Brazilian legislation on the discharge of effluents. Additionally, important corrosive (Cl-) and encrusting ions (Ca-2 +/- and Mg-2 +/- ) that limit certain industrial uses of water were satisfactorily removed, giving the treated effluent a suitable quality for industrial purposes. The treatment did not suffer harmful fouling effects in terms of ion extraction in the membrane ageing study, indicating the possibility of long-term treatment without requiring cleaning for the membranes; however, this needs to be validated by scaling up the process.The authorswish to thank the Municipality of Novo Hamburgo-RS, COMUSA (water and sewerage services to Novo Hamburgo), in partnership (No. 0004/2013) with Feevale University, and financial support from FAPERGS, FINEP-TECSANTA - Produtos e Processos: Desenvolvimento e aplicacao de tecnologias limpas ao saneamento ambiental (Grant Number 0113031300/ref.: 1099/13), CAPES, CNPq (Grant number 170283/2017-8), SCIT and BNDES (Brazil).Rodrigues Gally, C.; Benvenuti, T.; Da Trinidade, CDM.; Siqueira Rodrigues, MA.; Zoppas Ferreira, J.; Pérez-Herranz, V.; Moura Bernardes, A. (2018). Electrodialysis for the tertiary treatment of municipal wastewater: Efficiency of ion removal and ageing of ion exchange membranes. Journal of Environmental Chemical Engineering. 6(5):5855-5869. https://doi.org/10.1016/j.jece.2018.07.052S585558696

Antibiotics mineralization by electrochemical and UV-based hybrid processes: evaluation of the synergistic effect

[EN] Antibiotics are not efficiently removed in conventional wastewater treatments. In fact, different advanced oxidation process (AOPs), including ozone, peroxide, UV radiation, among others, are being investigated in the elimination of microcontaminants. Most of AOPs proved to be efficient on the degradation of antibiotics, but the mineralization is on the one hand not evaluated or on the other hand not high. At this work, the UV-based hybrid process, namely Photo-assisted electrochemical oxidation (PEO), was applied, aiming the mineralization of microcontaminants such as the antibiotics Amoxicillin (AMX), Norfloxacin (NOR) and Azithromycin (AZI). The influence of the individual contributions of electrochemical oxidation (EO) and the UV-base processes on the hybrid process (PEO) was analysed. Results showed that AMX and NOR presented higher mineralization rate under direct photolysis than AZI due to the high absorption of UV radiation. For the EO processes, a low mineralization was found for all antibiotics, what was associated to a mass-transport limitation related to the low concentration of contaminants (200 ¿g/L). Besides that, an increase in mineralization was found, when heterogeneous photocatalysis and EO are compared, due to the influence of UV radiation, which overcomes the mass-transport limitations. Although the UV-based processes control the reaction pathway that leads to mineralization, the best results to mineralize the antibiotics were achieved by PEO hybrid process. This can be explained by the synergistic effect of the processes that constitute them. A higher mineralization was achieved, which is an important and useful finding to avoid the discharge of microcontaminants in the environment.The authors thank CAPES project number DGPU-2015/7595/14-0, CNPq, FAPERGS, Cyted and FINEP for the financial support.Da Silva, SW.; Heberle, AN.; Santos, AP.; Rodrigues, M.; Valentín Pérez-Herranz; Bernardes, A. (2018). Antibiotics mineralization by electrochemical and UV-based hybrid processes: evaluation of the synergistic effect. Environmental Technology. https://doi.org/10.1080/09593330.2018.1478453SKummerer, K. (2003). Significance of antibiotics in the environment. Journal of Antimicrobial Chemotherapy, 52(1), 5-7. doi:10.1093/jac/dkg293Dı́az-Cruz, M. S., López de Alda, M. J., & Barceló, D. (2003). Environmental behavior and analysis of veterinary and human drugs in soils, sediments and sludge. TrAC Trends in Analytical Chemistry, 22(6), 340-351. doi:10.1016/s0165-9936(03)00603-4De Carvalho RN, Ceriani L, Ippolito A, et al. Development of the first Watch List under the Environmental Quality Standards Directive, in, European Commission, 2015.Riaz, L., Mahmood, T., Khalid, A., Rashid, A., Ahmed Siddique, M. B., Kamal, A., & Coyne, M. S. (2018). Fluoroquinolones (FQs) in the environment: A review on their abundance, sorption and toxicity in soil. Chemosphere, 191, 704-720. doi:10.1016/j.chemosphere.2017.10.092Hirte, K., Seiwert, B., Schüürmann, G., & Reemtsma, T. (2016). New hydrolysis products of the beta-lactam antibiotic amoxicillin, their pH-dependent formation and search in municipal wastewater. Water Research, 88, 880-888. doi:10.1016/j.watres.2015.11.028D. Barcelo, J. Bennett, editors. Antibiotic Resistance in the Environment. Sci Total Environ; 2015.Larsen, T. A., Lienert, J., Joss, A., & Siegrist, H. (2004). How to avoid pharmaceuticals in the aquatic environment. Journal of Biotechnology, 113(1-3), 295-304. doi:10.1016/j.jbiotec.2004.03.033Barbosa, M. O., Moreira, N. F. F., Ribeiro, A. R., Pereira, M. F. R., & Silva, A. M. T. (2016). Occurrence and removal of organic micropollutants: An overview of the watch list of EU Decision 2015/495. Water Research, 94, 257-279. doi:10.1016/j.watres.2016.02.047Niu, J., Zhang, L., Li, Y., Zhao, J., Lv, S., & Xiao, K. (2013). Effects of environmental factors on sulfamethoxazole photodegradation under simulated sunlight irradiation: Kinetics and mechanism. Journal of Environmental Sciences, 25(6), 1098-1106. doi:10.1016/s1001-0742(12)60167-3Wan, Z., Hu, J., & Wang, J. (2016). Removal of sulfamethazine antibiotics using Ce Fe-graphene nanocomposite as catalyst by Fenton-like process. Journal of Environmental Management, 182, 284-291. doi:10.1016/j.jenvman.2016.07.088Marcelino, R. B. P., Leão, M. M. D., Lago, R. M., & Amorim, C. C. (2017). Multistage ozone and biological treatment system for real wastewater containing antibiotics. Journal of Environmental Management, 195, 110-116. doi:10.1016/j.jenvman.2016.04.041Zhu, L., Santiago-Schübel, B., Xiao, H., Hollert, H., & Kueppers, S. (2016). Electrochemical oxidation of fluoroquinolone antibiotics: Mechanism, residual antibacterial activity and toxicity change. Water Research, 102, 52-62. doi:10.1016/j.watres.2016.06.005Choudhry, G. G., & Webster, G. R. B. (1987). Environmental photochemistry of polychlorinated dibenzofurans (PCDFs) and dibenzo‐p‐dioxins (PCDDs): A review. Toxicological & Environmental Chemistry, 14(1-2), 43-61. doi:10.1080/02772248709357193Juretic, D., Kusic, H., Koprivanac, N., & Loncaric Bozic, A. (2012). Photooxidation of benzene-structured compounds: Influence of substituent type on degradation kinetic and sum water parameters. Water Research, 46(9), 3074-3084. doi:10.1016/j.watres.2012.03.014Yuan, F., Hu, C., Hu, X., Qu, J., & Yang, M. (2009). Degradation of selected pharmaceuticals in aqueous solution with UV and UV/H2O2. Water Research, 43(6), 1766-1774. doi:10.1016/j.watres.2009.01.008Kim, I., Yamashita, N., & Tanaka, H. (2009). Performance of UV and UV/H2O2 processes for the removal of pharmaceuticals detected in secondary effluent of a sewage treatment plant in Japan. Journal of Hazardous Materials, 166(2-3), 1134-1140. doi:10.1016/j.jhazmat.2008.12.020Da Silva, S. W., Viegas, C., Ferreira, J. Z., Rodrigues, M. A. S., & Bernardes, A. M. (2016). The effect of the UV photon flux on the photoelectrocatalytic degradation of endocrine-disrupting alkylphenolic chemicals. Environmental Science and Pollution Research, 23(19), 19237-19245. doi:10.1007/s11356-016-7121-3Konstantinou, I. K., & Albanis, T. A. (2004). TiO2-assisted photocatalytic degradation of azo dyes in aqueous solution: kinetic and mechanistic investigations. Applied Catalysis B: Environmental, 49(1), 1-14. doi:10.1016/j.apcatb.2003.11.010Rivera-Utrilla, J., Sánchez-Polo, M., Ferro-García, M. Á., Prados-Joya, G., & Ocampo-Pérez, R. (2013). Pharmaceuticals as emerging contaminants and their removal from water. A review. Chemosphere, 93(7), 1268-1287. doi:10.1016/j.chemosphere.2013.07.059Kapałka, A., Fóti, G., & Comninellis, C. (2009). The importance of electrode material in environmental electrochemistry. Electrochimica Acta, 54(7), 2018-2023. doi:10.1016/j.electacta.2008.06.045Kapałka, A., Lanova, B., Baltruschat, H., Fóti, G., & Comninellis, C. (2008). Electrochemically induced mineralization of organics by molecular oxygen on boron-doped diamond electrode. Electrochemistry Communications, 10(9), 1215-1218. doi:10.1016/j.elecom.2008.06.005Einaga, Y., Foord, J. S., & Swain, G. M. (2014). Diamond electrodes: Diversity and maturity. MRS Bulletin, 39(6), 525-532. doi:10.1557/mrs.2014.94Fóti, G., Mousty, C., Reid, V., & Comninellis, C. (1998). Characterization of DSA type electrodes prepared by rapid thermal decomposition of the metal precursor. Electrochimica Acta, 44(5), 813-818. doi:10.1016/s0013-4686(98)00240-0Trasatti, S. (2000). Electrocatalysis: understanding the success of DSA®. Electrochimica Acta, 45(15-16), 2377-2385. doi:10.1016/s0013-4686(00)00338-8Pelegrini, R., Peralta-Zamora, P., de Andrade, A. R., Reyes, J., & Durán, N. (1999). Electrochemically assisted photocatalytic degradation of reactive dyes. Applied Catalysis B: Environmental, 22(2), 83-90. doi:10.1016/s0926-3373(99)00037-5Pinhedo, L., Pelegrini, R., Bertazzoli, R., & Motheo, A. J. (2005). Photoelectrochemical degradation of humic acid on a (TiO2)0.7(RuO2)0.3 dimensionally stable anode. Applied Catalysis B: Environmental, 57(2), 75-81. doi:10.1016/j.apcatb.2004.10.006Batchu, S. R., Panditi, V. R., O’Shea, K. E., & Gardinali, P. R. (2014). Photodegradation of antibiotics under simulated solar radiation: Implications for their environmental fate. Science of The Total Environment, 470-471, 299-310. doi:10.1016/j.scitotenv.2013.09.057Gonçalves, A. G., Órfão, J. J. M., & Pereira, M. F. R. (2014). Ozonation of erythromycin over carbon materials and ceria dispersed on carbon materials. Chemical Engineering Journal, 250, 366-376. doi:10.1016/j.cej.2014.04.012Liu, P., Zhang, H., Feng, Y., Yang, F., & Zhang, J. (2014). Removal of trace antibiotics from wastewater: A systematic study of nanofiltration combined with ozone-based advanced oxidation processes. Chemical Engineering Journal, 240, 211-220. doi:10.1016/j.cej.2013.11.057Bolton, J. R., Bircher, K. G., Tumas, W., & Tolman, C. A. (2001). Figures-of-merit for the technical development and application of advanced oxidation technologies for both electric- and solar-driven systems (IUPAC Technical Report). Pure and Applied Chemistry, 73(4), 627-637. doi:10.1351/pac200173040627Li, G., Zhu, M., Chen, J., Li, Y., & Zhang, X. (2011). Production and contribution of hydroxyl radicals between the DSA anode and water interface. Journal of Environmental Sciences, 23(5), 744-748. doi:10.1016/s1001-0742(10)60470-6Panizza, M., & Cerisola, G. (2009). Direct And Mediated Anodic Oxidation of Organic Pollutants. Chemical Reviews, 109(12), 6541-6569. doi:10.1021/cr9001319Niu, X.-Z., Busetti, F., Langsa, M., & Croué, J.-P. (2016). Roles of singlet oxygen and dissolved organic matter in self-sensitized photo-oxidation of antibiotic norfloxacin under sunlight irradiation. Water Research, 106, 214-222. doi:10.1016/j.watres.2016.10.002Hartmann, J., Bartels, P., Mau, U., Witter, M., Tümpling, W. v., Hofmann, J., & Nietzschmann, E. (2008). Degradation of the drug diclofenac in water by sonolysis in presence of catalysts. Chemosphere, 70(3), 453-461. doi:10.1016/j.chemosphere.2007.06.063Martínez-Huitle, C. A., Rodrigo, M. A., Sirés, I., & Scialdone, O. (2015). Single and Coupled Electrochemical Processes and Reactors for the Abatement of Organic Water Pollutants: A Critical Review. Chemical Reviews, 115(24), 13362-13407. doi:10.1021/acs.chemrev.5b00361Ohtani, B. (2010). Photocatalysis A to Z—What we know and what we do not know in a scientific sense. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 11(4), 157-178. doi:10.1016/j.jphotochemrev.2011.02.001Chong, M. N., Jin, B., Chow, C. W. 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Membrane Separation Process in Wastewater and Water Purification

The current scenario of increasing water scarcity and degradation of water bodies has led to the development of processes and technologies that provide more suitable treatment for both water and wastewater [...

Uso do processo de sulfatação para recuperação de metais em lodos provenientes da indústria galvânica

Este artigo apresenta o estudo da recuperação de metais provenientes de lodos galvânicos (LG) gerados por indústrias de semi-jóias, através do processo conhecido como sulfatação seletiva. Os metais que foram alvos deste estudo são ouro e prata, devido a seu valor agregado, e os metais mais abundantes neste resíduo, como o cobre, níquel e zinco. A pirita, enxofre e sulfato ferroso foram usados como agentes sulfatantes. Os ensaios realizados para caracterização do lodo galvânico foram fluorescência de raios x, absorção atômica e o percentual de água livre. O lodo galvânico apresentou em sua composição um alto teor de cobre, aproximadamente 73% (base seca), enquanto ouro e prata apresentaram respectivamente 0,017% e 0,1% em base seca. Após a caracterização, o LG foi misturado aos agentes sulfatantes e levado ao forno, por 90 minutos e temperatura de 550◦C, para avaliação de qual agente sulfatante e qual proporção LG/agente sulfatante apresenta melhores resultados na recuperação dos metais em solução. Após a etapa do forno, o resíduo foi solubilizado com água por 15 min. A configuração que apresentou os melhores resultados, no que diz respeito à recuperação de metais em solução, foi 1/ 0,4 LG/ enxofre, com aproximadamente 70% de recuperação de prata, 70% de recuperação de cobre e de zinco e 50% de níquel. O ouro não pode ser recuperado através deste processo sendo necessária sua lixiviação com agentes mais específicos como cianeto e tiossulfato

Characterization of an anion-exchange membrane subjected to phosphate and sulfate separation by electrodialysis at overlimiting current density condition

[EN] The structural degradation of an anion-exchange membrane used on the separation of phosphate from sulfate ions at overlimiting current density conditions was investigated. To this, the chemical structure changes, apparent counterion transport number, limiting current density, the apparent fraction of surface conductive regions, degree of hydrophobicity, membrane resistance and conductivity, morphology and thermal degradation profile were studied for the original and used samples of the anion-exchange membrane. The results showed that the degradation of the membrane fixed ion groups and structural polymer backbone affected the ionic transport conditions, reducing its apparent permselectivity and fraction of conductive regions. Also, the increase in the hydrophobicity degree together with the formation of cavities observed in the membrane surface may be responsible for the alteration of membrane conductivity, leading to a higher limiting current density value and a decrease in the plateau length.The authors are grateful for the research grant funded by Coordenac ao de Aperfeicoamento de Pessoal de Nivel Superior -CAPES/Brazil (88882.345780/2010-01). The financial support of the Brazilian funding agencies Conselho Nacional de Desenvolvimento Cientifico e Tecnologico -CNPq/Brazil, Fundacao de Amparo a Pesquisa do Estado do Rio Grande do Sul FAPERGS/Brazil, Financiadora de Estudos e Projetos -FINEP/Brazil, and from the Ibero-American Program on Science and Technology for Development (CYTED) are also acknowledged. Moreover, this project was founded by CNPq (CNPq/BRICS-STI-2-442229/2017-8), RFBR (No. 18-58-80031), DST (DST/IMRCD/BRICS/PC2/From waste to resources/2018 (G)), NSFC (51861145313), NRF (No: 116020)Rotta, EH.; Marder, L.; Pérez-Herranz, V.; Moura Bernardes, A. (2021). Characterization of an anion-exchange membrane subjected to phosphate and sulfate separation by electrodialysis at overlimiting current density condition. Journal of Membrane Science. 635:1-9. https://doi.org/10.1016/j.memsci.2021.1195101963