Benchmarking tertiary water treatments for the removal of micropollutants and pathogens based on operational and sustainability criteria

In a context of increasing water scarcity, it is essential to ensure an integrated watershed management, savings in the consumption of water as a finite resource and improve the performance of wastewater treatment plants to guarantee the quality of treated effluents. Therefore, advanced technologies for tertiary wastewater treatment have been widely studied in recent decades. These treatments have been reviewed over the years mainly providing comparisons from a technical perspective. However, there is a lack of a holistic evaluation considering environmental and economic aspects together with the aforementioned technical aspects. In this review, treatment alternatives for micropollutant and pathogen abatement have been identified based on technologies implemented on a large scale (ozonation, ultraviolet treatment, adsorption on activated carbon or membrane filtration) as well as those treatments in the process of implementation, such as electrochemical, Fenton-based or photocatalytic techniques. Thus, a systematic bibliographic search was performed considering works applying pilot and full-scale equipment, leaving lab-scale results out of the analysis. The description of each process allowed the identification of the technical feasibility, operating costs and associated environmental impacts, providing a comparative assessment that will help decision-making in the development and application of the different technologies. The benchmarking results reveal that the selected treatment should be chosen based on the source and specific pollutants present in the wastewater, as there is no single solution for the treatment of micropollutants and pathogens. In addition, recommendations are presented for the publication of reliable process-related data to facilitate comparison between different technologies and treatment scenarios.This research was supported by HP-NANOBIO (PID2019-111163RB-I00) and SPOTLIGHT (PDC2021-121540-I00) projects, granted by Spanish Ministry of Science and InnovationS

Modeling Dispersal of UV Filters in Estuaries

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Environmental Science & Technology, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see: http://dx.doi.org/10.1021/acs.est.8b03725Lagrangian ocean analysis, where virtual parcels of water are tracked through hydrodynamic fields, provides an increasingly popular framework to predict the dispersal of water parcels carrying particles and chemicals. We conduct the first direct test of Lagrangian predictions for emerging contaminants using (1) the latitude, longitude, depth, sampling date, and concentrations of UV filters in raft cultured mussel (Mytilus galloprovincialis) of the estuary Ria de Arousa, Spain (42.5°N, 8.9°W); (2) a hydrodynamic numerical model at 300 m spatial resolution; and (3) a Lagrangian dispersion scheme to trace polluted water parcels back to pollution sources. The expected dispersal distances (mean ± SD) are 2 ± 1 km and the expected dispersal times (mean ± SD) are 6 ± 2 h. Remarkably, the probability of dispersal of UV filters from potential sources to rafts decreases 5-fold over 5 km. In addition to predicting dispersal pathways and times, this study also provides a framework for quantitative investigations of concentrations of emerging contaminants and source apportionment using turbulent diffusion. In the coastline, the ranges of predicted concentrations of the UV-filters 4-methylbenzylidene-camphor, octocrylene, and benzophenone-4 are 3.2 × 10–4 to 0.023 ng/mL, 2.3 × 10–5 to 0.009 ng/mL, and 5.6 × 10–4 to 0.013 ng/mL, respectively. At the outfalls of urban wastewater treatment plants these respective ranges increase to 8.9 × 10–4 to 0.07 ng/mL, 6.2 × 10–5 to 0.027 ng/mL, and 1.6 × 10–3 to 0.040 ng/mL.This research is supported by the Spanish State Research Agency projects CTM2014-56628-C3-2-R, CTM2014-56628-C3-3-R, CTM2017-84763-C3-2-R, CTM2017-84763-C3-3-R, and CTM2017-90890-REDT (MINECO/AEI/FEDER, EU). This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation grant number NSF-OCE170005S

Electrochemical oxidation of lignin for the simultaneous production of bioadhesive precursors and value-added chemicals

Electrochemical oxidation of lignin has been widely regarded as a clean and reliable alternative to obtain value-added products from lignin, such as vanillin or guaiacol. This work aims to go one step beyond the production of low molecular weight molecules and explore the possibility of using lignin residues from electrochemical treatments in the context of biorefinery. To this end, a two-way valorization of lignin by electrochemical oxidation is proposed, in order to obtain a liquid phase enriched in low molecular weight organic oligomers and a solid phase of modified lignin to be used as bioadhesive precursor. Hydroxylation of lignin by electrochemical oxidation using boron-doped diamond (BDD) anodes was observed according to the FTIR and MALDI-TOF results, concluding that an applied current density of 10 mA cm−2 leads to promising modifications for the formulation of bioadhesives. Furthermore, NIPU bioadhesives with electrochemically modified lignin were successfully prepared and tested for use in particleboard panels, showing satisfactory mechanical properties, and thus paving the way for more environmentally friendly lignin modification procedures for the wood industryJJC acknowledges financial support from Galician Government though a postdoctoral fellowship (ED481B-2021/015). SG-R and GE predoctoral and postdoctoral fellowships (BES-2017-081677 and RYC-2018-024846-I, respectively) were funded by MCIN/AEI/10.13039/501100011033 and by “ESF Investing in your future”. JJC, SG-R, TAL-C, GE and MTM belong to the Galician Competitive Research Group (GRC) ED431C-2021/37. LERMAB is financed by the French Agence Nationale de la Recherche (ANR) as part of the laboratory of excellence (LABEX) ARBRE. The authors would also like to thank the use of the analytical facilities of IR-Raman Spectroscopy Unit and Mass Spectrometry Unit from RIAIDT-USC.S

Improving the sustainability of heterogeneous Fenton-based methods for micropollutant abatement by electrochemical coupling

Advanced oxidation processes such as Fenton reaction-based processes have attracted great interest in recent years as a promising alternative for the removal of persistent pollutants in wastewater. The use of nanocatalysts in advanced oxidation processes overcomes the limitations of homogeneous Fenton processes, where acidic pH values are required, and a large amount of sludge is generated after treatment. Aiming at maximizing the catalytic potential of the process, different configurations include coupling photocatalysis or electrochemistry to Fenton reactions. This manuscript presents a comparative environmental and economic analysis of different heterogeneous Fenton-based process using magnetic nanoparticles: Fenton, photo-Fenton, electro-Fenton and photoelectron-Fenton. These alternatives encompass not only different reaction conditions but also varying degradation kinetics, which control the treatment capability in each specific case. It is not only important to determine the technological feasibility of the proposal based on the removal performance of the target compounds, but also to identify the environmental profile of each configuration. In this regard, the Life Cycle Assessment methodology was applied considering a combination of primary and secondary data from process modeling. Moreover, and aiming towards the future large-scale implementation of the technology, an economic analysis of each configuration was also performed to provide a better understanding about the costs associated to the operation of Fenton-based wastewater treatmentsThis research was supported by HP-NANOBIO (PID2019-111163RB-I00), funded by Agencia Estatal de Investigación (AEI), and SPOTLIGHT (PDC2021-121540-I00) projects, funded by Agencia Estatal de Investigación (AEI) and European Union NextGenerationEU/PRTR. J.J.C. acknowledges Xunta de Galicia financial support through a postdoctoral fellowship (Grant reference ED481B-2021/015). S.E. and J.G.-R. predoctoral fellowships were funded by Agencia Estatal de Investigación (AEI) and by “ESF Investing in your future” (Grant references PRE2020-092074 and FPU19/004612, respectively). The authors belong to the Galician Competitive Research Group (GRC) ED432C-2021/37S

Exploiting the potential of supported magnetic nanomaterials as Fenton-Like catalysts for environmental applications

In recent years, the application of magnetic nanoparticles as alternative catalysts to conventional Fenton processes has been investigated for the removal of emerging pollutants in wastewater. While this type of catalyst reduces the release of iron hydroxides with the treated effluent, it also presents certain disadvantages, such as slower reaction kinetics associated with the availability of iron and mass transfer limitations. To overcome these drawbacks, the functionalization of the nanocatalyst surface through the addition of coatings such as polyacrylic acid (PAA) and their immobilization on a mesoporous silica matrix (SBA15) can be factors that improve the dispersion and stability of the nanoparticles. Under these premises, the performance of the nanoparticle coating and nanoparticle-mesoporous matrix binomials in the degradation of dyes as examples of recalcitrant compounds were evaluated. Based on the outcomes of dye degradation by the different functionalized nanocatalysts and nanocomposites, the nanoparticles embedded in a mesoporous matrix were applied for the removal of estrogens (E1, E2, EE2), accomplishing high removal percentages (above 90%) after the optimization of the operational variables. With the feasibility of their recovery in mind, the nanostructured materials represented a significant advantage as their magnetic character allows their separation for reuse in different successive sequential batch cyclesThis research was funded by HP-NANOBIO Project (PID2019-111163RB-I00) and MAGDEMON Project (PID2020-112626RB) granted by Spanish Ministry of Science and InnovationS

Magnetoelectric behavior in the complex CaMn7O12 perovskite

This is the accepted manuscript of the following article: Sánchez-Andújar, M., Yáñez-Vilar, S., Biskup, N., Castro-García, S., Mira, J., Rivas, J., & Señarís-Rodríguez, M. (2009). Magnetoelectric behavior in the complex CaMn7O12 perovskite. Journal Of Magnetism And Magnetic Materials, 321(11), 1739-1742. doi: 10.1016/j.jmmm.2009.02.018We report a magnetoelectric effect in the double perovskite CaMn7O12, that shows a complex magnetic behavior below 90 K with two magnetic phases coexisting (one ferrimagnetic and the other modulated). A second magnetic transition, associated with changes in the magnetic modulation and magnetic ordering coherence lengths of the two magnetic phases occurs at 50 K (TN2). A detailed structural characterization of this compound, that we have carried out by means of high-resolution X-ray powder diffraction, reveals an anisotropic thermal expansion of its lattice parameters at 50 K (TN2). In addition, our study of the complex permittivity of this sample as a function of temperature, frequency and magnetic field shows very interesting results below 90 K and specially below 50 K: the dielectric constant ε′r that was decreasing continuously on cooling experiences an upturn, and even more, on application of a magnetic field it shows a moderate magnetoelectric response. We attribute such dielectric behavior to the formation of electric dipoles by magnetostriction in this charge and spin ordered system, that are sensible to the presence of an external magnetic fieldThe authors are grateful from financial support for MEC (Spain) under project FEDER MAT 2007-66696 and Xunta de Galicia under project PGIDIT06PXB103298PR. S. Yáñez-Vilar want to thank to MEC of Spain for her FPI fellowship and M. Sánchez-Andújar acknowledges to Xunta de Galicia for support under program Parga PondalS

LED-driven photo-Fenton process for micropollutant removal by nanostructured magnetite anchored in mesoporous silica

The presence of organic micropollutants in water bodies represents a threat to living organisms and ecosystems due to their toxicological effects and recalcitrance in conventional wastewater treatments. In this context, the application of heterogeneous photo-Fenton based on magnetite nanoparticles supported on mesoporous silica (SBA15) is proposed to carry out the non-specific degradation of the model compounds ibuprofen, carbamazepine, hormones, bisphenol A and the dye ProcionRed®. The operating conditions (i.e., pH, catalyst load and hydrogen peroxide concentration) were optimized by Response Surface Methodology (RSM). The paramagnetic properties of the nanocatalysts allowed their repeated use in sequential batch operations with catalyst losses below 1%. The feasibility of the process was demonstrated as removal rates above 90% after twelve accomplished after twelve consecutive cycles. In addition, the contributions of different reactive oxygen species, mainly •OH, were analyzed together with the formation of by-products, achieving total mineralization values of 15% on averageThis research was supported by HP-NANOBIO [PID2019-111163RB-I00] and MAGDEMON [PID2020-112626RB] projects, funded by MCIN/AEI/10.13039/501100011033 and SPOTLIGHT [PDC2021-121540-I00] project, funded by MCIN/AEI/10.13039/501100011033 and European Union NextGenerationEU/PRTR. J.G.-R. thanks MCIN/AEI/10.13039/501100011033 for their FPU predoctoral fellowship [FPU19/00461] and J.J.C. thanks Xunta de Galicia for his postdoctoral fellowship [ED481B-2021/015]. The authors belong to the Galician Competitive Research Groups (GRC) ED431C-2021/16 and ED432C-2021/37, co-funded by FEDER (EU)S

2,3-Diarylxanthones as potential inhibitors of Arachidonic acid metabolic pathways

In response to an inflammatory stimulus, arachidonic acid (AA), the main polyunsaturated fatty acid present in the phospholipid layer of cell membranes, is released and metabolized to a series of eicosanoids. These bioactive lipid mediators of inflammation arise physiologically through the action of the enzymes 5-lipoxygenase (5-LOX) and cyclooxygenases (constitutive COX-1 and inducible COX-2). It is believed that dual inhibition of 5-LOX and COXs may have a higher beneficial impact in the treatment of inflammatory disorders rather than the inhibition of each enzyme. With this demand for new dual-acting anti-inflammatory agents, a range of 2,3-diarylxanthones were tested through their ability to interact in the AA metabolism. In vitro anti-inflammatory activity was evaluated through the inhibition of 5-LOX-catalyzed leukotriene B4 (LTB4) formation in human neutrophils and inhibition of COX-1- and COX-2-catalyzed prostaglandin E2 (PGE2) formation in human whole blood. The results showed that some of the studied arylxanthones were able to prevent LTB4 production in human neutrophils, in a concentration-dependent manner. The xanthone with a 2-catechol was the most active one (IC50 ∼ 9 μM). The more effective arylxanthones in preventing COX-1-catalyzed PGE2 production presented IC50 values from 1 to 7 μM, exhibiting a structural feature with at least one non-substituted aryl group. All the studied arylxanthones were ineffective to prevent the formation of PGE2 catalyzed by COX-2, up to the maximum concentration of 100 μM. The ability of the tested 2,3-diarylxanthones to interact with both 5-LOX and COX-1 pathways constitutes an important step in the research of novel dual-acting anti-inflammatory drugs.Sincere thanks are expressed to Faculdade de Farmácia da Universidade do Porto, Universidade de Aveiro, Instituto Politécnico de Bragança, Fundação para a Ciência e a Tecnologia (FCT, Portugal), Ministério da Educação e Ciência, European Union, FEDER, PT 2020, QREN, and COMPETE funding UCIBIO, REQUIMTE [(PT2020 UID/MULTI/04378/2013 - POCI/01/0145/FEDER/007728), (NORTE-01-0145-FEDER-000024), and (PTDC/QEQ-QAN/1742/2014 – POCI-01-0145- FEDER-016530)] and QOPNA (FCT UID/QUI/00062/2013) Research Units and also to the Portuguese National NMR Network (RNRMN). We gratefully acknowledge Graça Porto and the nursing staff of the Centro Hospitalar do Porto - Hospital de Santo António blood bank for the collaboration in the recruitment of blood donors involved in the present work.info:eu-repo/semantics/publishedVersio

Ozone membrane contactor to intensify gas/liquid mass transfer and contaminants of emerging concern oxidation

A tubular porous borosilicate membrane contactor was investigated for ozone gas/water mass transfer and the removal of contaminants of emerging concern (CECs) in water. Ozone gas/water contact occurs on the membrane shell-side, which is coated with a photocatalyst (TiO2-P25), as the ozone gas stream is fed from the lumen side and permeates through the pores generating micro-sized ozone bubbles uniformly delivered to the annular reaction zone where the contaminated water to be treated flows. Under continuous flow, water pH at 3.0 and temperature at 20 ºC, the volumetric mass transfer coefficient (KLa) ranged from 3.5 to 9.0 min−1 and improved with the increase of gas flow rate (QG, 1.5-fold from 0.15 to 1.0 Ndm3 min−1) and liquid flow rate (QL, 2.0-fold from 20 to 50 L h−1), due to enhanced turbulence on the membrane shell-side and annular zone. The mass transfer efficiency was more pronounced as the QG decreased and the QL increased, which is advantageous for large-scale applications. The main resistances to ozone transfer were in the water phase boundary layer (53–76%) and in the membrane (24–47%; kM = (1.14 ± 0.01) × 10−4 m s−1). For an ozone dose of 12 g m−3 and residence time of 3.9 s, removals ≥ 80% were achieved for 13 of 19 CECs spiked in demineralized water (each 10 µg L−1), demonstrating the applicability of this membrane contactor for ozonation treatment. Photocatalytic ozonation (O3/UVC/TiO2) did not significantly improve the treatment performance due to the low residence time inside the contactor.This work was financially supported by (i) Project NOR-WATER funded by INTERREG VA Spain-Portugal cooperation programme, Cross-Border North Portugal/Galizia Spain Cooperation Program (POCTEP), ref. 0725_NOR_WATER_1_P; (ii) National funds through the FCT/MCTES (PIDDAC), under the project PTDC/EAM-AMB/4702/2020 (OZONE4WATER); (iii) Project “Healthy Waters – Identification, Elimination, Social Awareness and Education of Water Chemical and Biological Micropollutants with Health and Environmental Implications”, with reference NORTE-01-0145-FEDER-000069, supported by Norte Portugal Regional Operational Programme (NORTE 2020), under the PORTUGAL 2020 Partnership Agreement, through the European Regional Development Fund (ERDF); and (iv) LA/P/0045/2020 (ALiCE), UIDB/50020/2020 and UIDP/50020/2020 (LSRE-LCM), and also UIDB/00511/2020 and UIDP/00511/2020 (LEPABE), funded by national funds through FCT/MCTES (PIDDAC). P. H. Presumido acknowledges FCT for his scholarship (SFRH/BD/138756/2018). Vítor J.P. Vilar acknowledges the FCT Individual Call to Scientific Employment Stimulus 2017 (CEECIND/01317/2017). The researchers from the University of Santiago de Compostela would also like to acknowledge funding provided by Xunta de Galicia (ED431C 2021/06), the Spanish Agencia Estatal de Investigación –MCIN/AEI/10.13039/501100011033 (ref. PID2020-117686RB-C32) and Banco Santander and Universidade de Santiago de Compostela for the sponsorship of “outstanding researcher contract” of R. Montes.S

Description of the annual reproductive cycle of wreckfish; Polyprion americanus, in captivity

Successful spontaneous reproduction and the production of viable offspring of wild fish in captivity can take some years of adaptation, and may also involve different environmental conditions, sex ratios and densities compared to natural populations. We followed the reproductive cycle of wreckfish Polyprion americanus—a late maturing, deep-sea benthic species—in captivity in three different broodstocks in Spain under natural photoperiod and temperature, and one broodstock in Greece under a constant temperature of 16 °C for two consecutive years, to describe the reproductive cycle of the species and the associated sex steroid hormone profiles. Oogenesis begun in the fall and post-vitellogenic oocytes of 1250 μm were present between March and June. Males were in spermiation condition and produced good-quality sperm throughout the year, regardless of the temperature profile to which they were exposed. Some females completed oogenesis, underwent oocyte maturation, and spawned spontaneously under both constant and fluctuating temperatures. The sex steroid hormones of both males and females followed the already-known profiles during fish gametogenesis, except for 17,20β-dihydroxy-progesterone, which did not seem to be related to either female or male maturation. The female reproductive dysfunctions that were identified included (a) the arrest of oogenesis at the cortical alveoli stage in certain females; (b) the failure to undergo oocyte maturation in others; and (c) the production of large percentages of unfertilized eggs from the females that spawned spontaneously. Our study suggests that reproduction in captivity is possible in wreckfish maintained under typical marine aquaculture conditions, but that reliable spawning and production of high-quality eggs may require some years of adaptation to captivity, before the reproductive dysfunctions will be overcome.Versión del edito