Microalgal Bioassays as a Test of Pesticide Photodegradation Efficiency in Water

Xunta de Galicia; XUGA 10307A9

Preparation, Characterization and Testing of a Bulky Non-supported Photocatalyst for Water Pollution Abatement

Financiado para publicación en acceso aberto: Universidade da Coruña/CISUG[Abstract] An innovative bulky photocatalyst for water decontamination has been developed. The semiconductor (TiO2) is homogeneously distributed in an aggregating material through the whole piece. This design prevents the activity reduction usually observed in supported catalysts due to the loss of the photoactive layer, and facilitates its recovery for an easy reuse, which is a recurrent problem dealing with nanoparticles. The photocatalyst combines the excellent properties of TiO2 with those of a natural clay, which serves as binder, slows down the phase transition of anatase to rutile upon calcination, and has a synergetic function. The photocatalyst has been prepared in the form of small pellets with an Ecuadorian clay and TiO2 in the commercial form of P25 by evenly dry mixing, forming a paste with water, and subsequent extrusion, drying and calcination at 600 °C. The photodegradation of phenol, as a model pollutant, has been achieved by using this aggregate material in a flow reactor with artificial UVA-Vis radiation, and reused without any significant loss of activity. The photocatalyst showed an optimum activity at a 40% clay / 60% P25 ratio, while higher calcination temperatures had a negative effect on its performance.This research has received funds from the Spanish Ministerio de Ciencia e Innovación [Project PID2021-127898OB-I00], and the regional government Xunta de Galicia [GPC project ED431B 2020/52], to finance a contract to DRR. Funding for open access charge: Universidade da Coruña/CISUG. DRR also acknowledges UDC for a Margarita Salas contract and SDA acknowledges UTPL for financial support for pursuing PhD studies at UDCXunta de Galicia; ED431B 2020/5

Mechanical Stability Is Key for Large-Scale Implementation of Photocatalytic Surface-Attached Film Technologies in Water Treatment

[Abstract] Replacement of classical tertiary water treatment by chemical-free sunlight-driven photocatalytic units has been often proposed. Photocatalysts are required to be cost-effective, inert, chemically stable, reusable, and easy to separate and also that they are mechanically stable. The effect of mechanical stress on a photoactive TiO2 layer, and on its effectivity for degradation of phenol as a model pollutant, has been studied during photocatalytic water treatment using NUV–vis light. Sol–gel (SG) and liquid phase deposition (LPD) methods have been used to coat spherical glass beads with the photocatalyst (TiO2). Physicochemical characterization of coated glass beads has been performed by N2 adsorption–desorption isotherms, SEM, EDXS, and AFM. Phenol photocatalyzed degradation was carried out both in stirred batch and flow reactors irradiated with a medium-pressure Hg-vapor lamp (λ > 350 nm). Phenol concentration was determined by HPLC, and its photoproducts were identified using HPLC/MS. In the stirred batch reactor, all LPD-coated glass beads displayed higher catalytic activity than SG-coated ones, which increased with calcination temperature, 700°C being the most efficient temperature. Preliminary etching of the glass beads surface yielded dissimilar results; whereas, phenol photodegradation with SG-coated etched glass beads is twice faster than with unetched SG ones, the rate reduces to one-third using LPD etched instead of unetched LPD glass beads. Phenol photodegradation using LPD is similar both in stirred batch and flow reactors, despite the latter uses a lower catalyst load. LPD-etched catalyst was recovered and reused in the stirred batch reactor; its activity reduced sharply after the first use, and it also lost activity in successive runs, ca. 10% of activity after each “use and recover” cycle. In the flow reactor, activity loss after the first experiment and recycling (ca. 30%) was much larger than in the following runs, where the activity remained rather constant through several cycles. LPD is more adequate than SG for TiO2 immobilization onto glass beads, and their calcination at 700°C leads to relatively strong and reactive photocatalytic films. Still, TiO2-coated glass beads exhibited very low photoactivity compared to TiO2-P25 nanoparticles, though their separation is much easier and almost costless. The durability of the catalytic layer increases when using a flow reactor, with the pollutant solution flowing in a laminar regime through the photocatalyst bed. In this way, the abrasion of the photocatalytic surface is largely reduced and its photoactivity is better maintained.This research was partially supported by the Group React! and funded by the Ministerio de Economía y Competitividad (Spain, Project CTQ2015-71238-R MINECO/FEDER), and by the regional government of the Xunta de Galicia (Spain, Project GPC ED431B 2020/52)Xunta de Galicia; ED431B 2020/5

Combining Constructed Wetlands and UV Photolysis for the Advanced Removal of Organic Matter, Nitrogen, and Emerging Pollutants from Wastewater

This article belongs to the Special Issue Recent Advances in Technologies for Water and Wastewater Treatment[Abstract] This study reports the performance of a three-step lab-scale system including a hybrid digester (HD), a vertical flow (VF) constructed wetland, and a photodegradation (PD) lamp, with two different arrangements regarding the position of the recirculation point. In addition to total suspended solids (TSS), chemical oxygen demand (COD), and nitrogen compounds, removal of the following pollutants was investigated: paracetamol (ACE), ofloxacin (OFL), caffeine (CAF), ketoprofen (KET), ibuprofen (IBU), clofibric acid (ACB), bisphenol A (BPA), and sotalol (SOT). An excellent performance of HD was achieved on the elimination of TSS (82.2 ± 18.5% on average) and COD (63.9 ± 4.1%). TSS and COD removal increased to 91.2 ± 0.4% and 83.4 ± 2.9%, respectively, for the combined HD–VF system. Ammonia removal was 57.0 ± 7.8% in the VF unit while significant denitrification occurred in the HD. The overall HD–VF–PD system achieved mean removals of 100% for OFL, KET, SOT, and IBU, 98 ± 2% for ACE, 87 ± 8% for CAF, 81 ± 38% for ACB and 26 ± 9% for BPA. The removal of ACE, OFL, CAF, and IBU was mostly by biodegradation in the HD and VF units while the PD unit was responsible for the removal of KET, ACB, and SOT.This research is part of the project CTQ2015-71238-R (MINECO/FEDER, funded by the Spanish Ministerio de Economía y Competitividad), the project TED2021-132667B-I00 funded by MCIN/AEI/10.13039/501100011033 and by the European Union NextGenerationEU/PRTR, and projects GPC ED431B 2020/52 and GPC ED431B 2019/44 (funded by the Xunta de Galicia)Xunta de Galicia; ED431B 2020/52Xunta de Galicia; ED431B 2019/4

Improved Photocatalyzed Degradation of Phenol, as a Model Pollutant, over Metal-Impregnated Nanosized TiO₂

[Abstract] Photocatalyzed degradation of phenol in aqueous solution over surface impregnated TiO₂ (M = Cu, Cr, V) under UV-Vis (366 nm) and UV (254 nm) irradiation is described. Nanosized photocatalyts were prepared from TiO₂-P25 by wet impregnation, and characterized by X-ray diffraction, X-ray fluorescence, transmission electron microscopy, UV-Vis diffuse reflectance spectroscopy, Raman spectroscopy, and adsorption studies. No oxide phases of the metal dopants were found, although their presence in the TiO₂-P25 lattice induces tensile strain in Cu-impregnated TiO₂-P25, whereas compressive strain in Cr- and V-impregnated TiO₂-P25. Experimental evidences support chemical and mechanical stability of the photocatalysts. Type IV N₂ adsorption–desorption isotherms, with a small H3 loop near the maximum relative pressure were observed. Metal surface impregnated photocatalysts are mesoporous with a similar surface roughness, and a narrow pore distribution around ca. 25 Å. They were chemically stable, showing no metal lixiviation. Their photocatalytic activity was followed by UV-Vis spectroscopy and HPLC–UV. A first order kinetic model appropriately fitted the experimental data. The fastest phenol degradation was obtained with M (0.1%)/TiO₂-P25, the reactivity order being Cu > V >> Cr > TiO₂-P25 under 366 nm irradiation, while TiO₂-P25 > Cu > V > Cr, when using 254 nm radiation. TOC removal under 366 nm irradiation for 300 min showed almost quantitative mineralization for all tested materials, while 254 nm irradiation for 60 min led to maximal TOC removal (ca. 30%). Photoproducts and intermediate photoproducts were identified by HPLC–MS, and appropriate reaction pathways are proposed. The energy efficiency of the process was analysed, showing UV lamps are superior to UVA lamps, and that the efficiency of the surface impregnated catalyst varies in the order Cu > V > Cr.This research was partially supported by the Group of Chemical Reactivity & Photoreactivity at University and funded by the Spanish Ministerio de Economía y Competitividad through project CTQ2015-71238-R (MINECO/FEDER), and the regional government Xunta de Galicia (Project Grupo Potencial Crecemento (GPC) ED431B 2017/59), respectivelyXunta de Galicia; ED431B 2017/5

Cobalt Impregnation on Titania Photocatalysts Enhances Vis Phenol Photodegradation

This article belongs to the Special Issue Advanced Catalysts for Energy and Environmental Applications[Abstract] One of the main challenges of photocatalysis is to find a stable and effective photocatalyst, that is active and effective under sunlight. Here, we discuss the photocatalytic degradation of phenol as a model pollutant in aqueous solution using NUV-Vis (>366 nm) and UV (254 nm) in the presence of TiO2-P25 impregnated with different concentrations of Co (0.1%, 0.3%, 0.5%, and 1%). The modification of the surface of the photocatalyst was performed by wet impregnation, and the obtained solids were characterized using X-ray diffraction, XPS, SEM, EDS, TEM, N2 physisorption, Raman and UV-Vis DRS, which revealed the structural and morphological stability of the modified material. BET isotherms are type IV, with slit-shaped pores formed by nonrigid aggregate particles and no pore networks and a small H3 loop near the maximum relative pressure. The doped samples show increased crystallite sizes and a lower band gap, extending visible light harvesting. All prepared catalysts showed band gaps in the interval 2.3–2.5 eV. The photocatalytic degradation of aqueous phenol over TiO2-P25 and Co(X%)/TiO2 was monitored using UV-Vis spectrophotometry: Co(0.1%)/TiO2 being the most effective with NUV-Vis irradiation. TOC analysis showed ca. 96% TOC removal with NUV-Vis radiation, while only 23% removal under UV radiation.This research received support through grant TED2021-132667B-I00, funded by the EU NextGenerationEU/PRTR through project MCIN/AEI/10.13039/501100011033. Financial support was also provided by the regional government Xunta de Galicia through project GPC/ED431B 2020/52. S.B. thanks the KA-107 grant received from the EU through the Erasmus+ program for a research stay at UDCXunta de Galicia; ED431B 2020/5

Degradation of 2-mercaptobenzothizaole in microbial electrolysis cells: Intermediates, toxicity, and microbial communities

[EN] The compound 2-mercaptobenzothizaole (MBT) has been frequently detected in wastewater and surface water and is a potential threat to both aquatic organisms and human health (its mutagenic potential has been demonstrated). This study investigated the degradation routes of MBT in the anode of a microbial electrolysis cell (MEC) and the involved microbial communities. The results indicated that graphene-modified anodes promoted the presence of more enriched, developed, and specific communities compared to bare anodes. Moreover, consecutive additions of the OH substituent to the benzene ring of MBT were only detected in the reactor equipped with the graphene-treated electrode. Both phenomena, together with the application of an external voltage, may be related to the larger reduction of biotoxicity observed in the MEC equipped with graphene-modified anodes (46.2 eqtox∙m−3 to 27.9 eqtox∙m−3).SIThis research was possible thanks to the financial support by ‘Consejería de Educación de la Junta de Castilla y León’ (ref: LE320P18), a project co-financed by FEDER funds. R. M. Alonso thanks the University of León for the predoctoral contract. M. Canle acknowledges financial support from the Ministerio de Economía y Competitividad (Spain) through project CTQ2015-71238-R (MINECO/FEDER), and regional government Xunta de Galicia (project GPC ED431B 2017/59), respectively

Face-Fusion of Icosahedral Boron Hydride Increases Affinity to γ‐Cyclodextrin: closo,closo‐[B₂₁H₁₈]⁻ as an Anion with Very Low Free Energy of Dehydration

[Abstract] The supramolecular recognition of closo,closo‐[B₂₁H₁₈]⁻ by cyclodextrins (CDs) has been studied in aqueous solution by isothermal titration calorimetry and nuclear magnetic resonance spectroscopy. These solution studies follow up on previous mass‐spectrometric measurements and computations, which indicated the formation and stability of CD ⋅ B₂₁H₁₈⁻ complexes in the gas phase. The thermodynamic signature of solution‐phase binding is exceptional, the association constant for the γ‐CD complex with B₂₁H₁₈⁻ reaches 1.8×10⁶ M⁻¹, which is on the same order of magnitude as the so far highest observed value for the complex between γ‐CD and a metallacarborane. The nature of the intermolecular interaction is also examined by quantum‐mechanical computational protocols. These suggest that the desolvation penalty, which is particularly low for the B₂₁H₁₈⁻ anion, is the decisive factor for its high binding strength. The results further suggest that the elliptical macropolyhedral boron hydride is another example of a CD binder, whose extraordinary binding affinity is driven by the chaotropic effect, which describes the intrinsic affinity of large polarizable and weakly solvated chaotropic anions to hydrophobic cavities and surfaces in aqueous solution.K.I.A. and W.M.N. are grateful to the DFG for grant NA-686/8 within the priority program SPP 1807 “Control of London Dispersion Interactions in Molecular Chemistry”. J.H., J.F., and D.H. thank the Czech Science Foundation (grant number 17-08045S) and M.I.F.P., M.C.L, and J.A.S.L. thank the regional government Xunta de Galicia for financial support (Project Grupo Potencial Crecemento -GPC- ED431B 2017/59). J.M.O.-E. acknowledges financial support from the Spanish MICINN through project CTQ2018-094644-B-C22German Research Foundation; NA‐686/8Czech Science Foundation; 17‐08045SXunta de Galicia; ED431B 2017/5

Removal of Emerging Pollutants by a 3-Step System: Hybrid Digester, Vertical Flow Constructed Wetland and Photodegradation Post-treatments

Financiado para publicación en acceso aberto: Universidade da Coruña/CISUG[Abstract] The removal of emerging pollutants from municipal wastewater was studied for the first time using a three-step pilot-scale system: 1) hybrid digester (HD) as first step, 2) subsurface vertical flow constructed wetland (VF) as second step, and 3) photodegradation (PD) unit as third step or post-treatment. The HD and VF units were built and operated in series with effluent recirculation at pilot scale. For the PD post-treatment, three alternatives were studied at lab-scale, i) UVC irradiation at 254 nm (0.5 h exposure time), ii) UVA irradiation at 365 nm using a TiO2-based photocatalyst and iii) sunlight irradiation using a TiO2-based photocatalyst, the last two for 1 and 2 h. Alternative iii) was also tested at pilot-scale. Degradation of nine compounds was evaluated: acetaminophen (ACE), caffeine (CAF), carbamazepine (CBZ), ketoprofen (KET), ibuprofen (IBU), diclofenac (DCL), clofibric acid (ACB), bisphenol A (BPA), and sotalol (SOT). Overall, the HD-VF-UVC system completely removed (>99.5 %) ACE, CAF, KET, IBU, DCL and ACB, and to a lesser extent SOT (98 %), BPA (83 %) and CBZ (51 %). On the other hand, the HD-VF-UVA/TiO2 system (at 2 h) achieved >99.5 % removal of ACE, CAF, KET, IBU and DCL while ACB, BPA, CBZ and SOT were degraded by 83 %, 81 %, 78 % and 68 %, respectively. Working also at 2 h of exposure time, in summer conditions, the HD-VF-Sol/TiO2 system achieved >99.5 % removal of ACE, CAF, KET, IBU, DCL and ACB, and to a minor extent BPA (80 %), SOT (74 %) and CBZ (69 %). Similar results, although slightly lower for SOT (60 %) and CBZ (59 %), were obtained in the pilot sunlight plus TiO2 catalyst unit. However, the use of sunlight irradiation with a TiO2-based photocatalyst clearly showed lower removal efficiency in autumn conditions (i.e., 47 % SOT, 31 % CBZ).This research was funded by the Spanish Ministerio de Economía y Competitividad through project CTQ2015-71238-R (MINECO/FEDER), and the Xunta de Galicia (project GPC ED431B 2020/52 and project GPC ED431B 2019/44), respectively. Funding for open access charge: Universidade da Coruña/CISUGXunta de Galicia; GPC ED431B 2020/52Xunta de Galicia; GPC ED431B 2019/4

A theoretical study on the mechanism of the base-promoted decomposition of N-chloro,N-methylethanolamine

The first step of the base-promoted decomposition of N-chloro,N-methylethanolamine in aqueous solution (CH3N(Cl)CH2CH2OH + HO- →imine + Cl- + H2O (+ CH2O)→amine + aldehyde) is investigated at the MP2/6-31++G(d,p) computing level. Solvation is included by using both a microsolvated model, in which two explicit water molecules simulate the specific solvent effects, and a hybrid cluster-continuum model, by applying a polarized continuum on the previous results, to account for the bulk effect of the solvent. Four alternative pathways (bimolecular fragmentation, Hofmann, Zaitsev and intramolecular eliminations) are possible for the rate-limiting step of this base-promoted decomposition. These reactive processes are bimolecular asynchronous concerted reactions. The common feature of the four pathways is the proton transfer to HO- being more advanced than all other molecular events, whereas imine formation is delayed. Non-reactive cyclic arrangements involving one of the explicit water molecules are found at transition structures of Hofmann and Zaitsev eliminations, such water molecule acting both as H+ donor and acceptor. Although MP2 calculations misjudge the absolute activation Gibbs free energy values, this computational level adequately predicts the enhancement in the decomposition rate due to the presence of the -OH grou