Application of catalytic ozonation using Y zeolite in the elimination of pharmaceuticals in effluents from municipal wastewater treatment plants.

Catalytic ozonation using faujasite-type Y zeolite with two different SiO2/Al2O3 molar ratios (60 and 12) was evaluated for the first time in the removal of 25 pharmaceutical compounds (PhCs) present in real effluents from two municipal wastewater treatment plants both located in the Mediterranean coast of Spain. Additionally, control experiments including adsorption and direct ozonation, were conducted to better understand the fundamental aspects of the different individual systems in wastewater samples. Commercial zeolites were used in sodium form (NaY). The results showed that the simultaneous use of ozone and NaY zeolites significantly improved the micropollutants degradation rate, able to degrade 95 % of the total mixture of PhCs within the early 9 min using the zeolite NaY-12 (24.4 mg O3 L-1 consumed), while 12 min of reaction with the zeolite NaY-60 (31 mg O3 L-1 consumed). In the case of individual experiments, ozonation removed 95 % of the total mixture of PhCs after 25 min (46.2 mg O3 L-1 consumed), while the direct adsorption, after 60 min of contact time, eliminated 30 % and 44 % using the NaY-12 and NaY-60 zeolites, respectively. Results showed that the Brønsted acid sites seemed to play an important role in the effectiveness of the treatment with ozone. Finally, the environmental assessment showed that the total risk quotients of pharmaceuticals were reduced between 87 %-99 % after ozonation in the presence of NaY-60 and NaY-12 zeolites. The results of this study demonstrate that catalytic ozonation using NaY zeolites as catalysts is a promising alternative for micropollutant elimination in real-world wastewater matrices.

Systematic analysis of the scientific-technological production on the use of the UV, H2O2, and/or Cl2 systems in the elimination of bacteria and associated antibiotic resistance genes.

This study presents a systematic review of the scientific and technological production related to the use of systems based on UV, H2O2, and Cl2 for the elimination of antibiotic-resistant bacteria (ARB) and genes associated with antibiotic resistance (ARGs). Using the Pro Know-C (Knowledge Development Process-Constructivist) methodology, a portfolio was created and analyzed that includes 19 articles and 18 patents published between 2011 and 2022. The results show a greater scientific-technological production in UV irradiation systems (8 articles and 5 patents) and the binary combination UV/H2O2 (9 articles and 4 patents). It was emphasized that UV irradiation alone focuses mainly on the removal of ARB, while the addition of H2O2 or Cl2, either individually or in binary combinations with UV, enhances the removal of ARB and ARG. The need for further research on the UV/H2O2/Cl2 system is emphasized, as gaps in the scientific-technological production of this system (0 articles and 2 patents), especially in its electrochemically assisted implementation, have been identified. Despite the gaps identified, there are promising prospects for the use of combined electrochemically assisted UV/H2O2/Cl2 disinfection systems. This is demonstrated by the effective removal of a wide range of contaminants, including ARB, fungi, and viruses, as well as microorganisms resistant to conventional disinfectants, while reducing the formation of toxic by-products.

Ozonation using a stainless-steel membrane contactor: Gas-liquid mass transfer and pharmaceuticals removal from secondary-treated municipal wastewater.

A tubular porous stainless steel membrane contactor was characterized in terms of ozone-water mass transport, as well as its application in removing 23 pharmaceuticals (PhACs) detected in the secondary-treated municipal wastewater, under continuous mode operation. The volumetric mass transfer coefficient (KLa) was evaluated based on liquid flow rate, gas flow rate, and ozone gas concentration. The KLa values were substantially improved with an increment in liquid flow rate (1.6 times from 30 to 70 dm3 h-1) and gas flow rate (3.6 times from 0.30 to 0.85 Ndm3 min-1) due to the improved mixing in the gas-liquid interface. For the lowest liquid flow rate (30 dm3 h-1), the water phase boundary layer (82%) exhibited the major ozone transfer resistance, but it became almost comparable with membrane resistance for the highest liquid flow rate (70 dm3 h-1). Additionally, the influence of the specific ozone dose (0.39, 0.53, and 0.69 g O3 g DOC-1) and ozone inlet gas concentration ( [Formula: see text]  = 27, 80, and 134 g Nm-3) were investigated in the elimination of 23 PhACs found in secondary-treated municipal wastewater. An ozone dose of 0.69 g O3 g DOC-1 and residence time of 60 s resulted in the removal of 12 out of the 23 compounds over 80%, while 17 compounds were abated above 60%. The elimination of PhACs was strongly correlated with kinetic reaction constants values with ozone and hydroxyl radicals (kO3 and kHO•), leading to a characteristic elimination pattern for each group of contaminants. This study demonstrates the high potential of membrane contactors as an appealing alternative for ozone-driven wastewater treatment.

Unraveling kinetic and synergistic effects during ultrasound-enhanced carbocatalysis for water remediation as a function of ultrasonic frequency.

The ability of the ultrasound (US) combined with peroxymonosulfate (PMS), and a carbonaceous material (BC) was evaluated in the degradation of a model pollutant (acetaminophen, ACE). The US/BC/PMS system was compared with other possible systems (US, oxidation by PMS, BC adsorption, BC/PMS, US/PMS, and US/BC. The effect of the ultrasonic frequency (40, 375, and 1135 kHz) on the kinetics and synergy of the ACE removal was evaluated. In the US system, kinetics was favored at 375 kHz due to the increased production of hydroxyl radicals (HO•), but this did not improve in the US/PMS and US/BC systems. However, synergistic and antagonistic effects were observed at the low and high frequencies where the production of radicals is less efficient but there is an activation of PMS through mechanical effects. US/BC/PMS at 40 kHz was the most efficient system obtaining ∼95% ACE removal (40 µM) in the first 10 min of treatment, and high synergy (S = 10.30). This was promoted by disaggregation of the carbonaceous material, increasing the availability of catalytic sites where PMS is activated. The coexistence of free-radical and non-radical pathways was analyzed. Singlet oxygen (1O2) played the dominant role in degradation, while HO• and sulfate radicals (SO4•-), scarcely generated at low frequency, play a minimum role. Performance in hospital wastewater (HWW), urine, and seawater (SW) evidenced the competition of organic matter by BC active sites and reactive species and the removal enhancement when Cl- is present. Besides, toxicity decreased by ∼20% after treatment, being the system effective after three cycles of reuse.

Rice husk-based pyrogenic carbonaceous material efficiently promoted peroxymonosulfate activation toward the non-radical pathway for the degradation of pharmaceuticals in water.

Pristine pyrogenic carbonaceous material (BRH) obtained from rice husk and modified with FeCl3 (BRH-FeCl3) were prepared and explored as carbocatalysts for the activation of peroxymonosulfate (PMS) to degrade a model pharmaceutical (acetaminophen, ACE) in water. The BRH-FeCl3/PMS system removed the pharmaceutical faster than the BRH/PMS. This is explained because in BRH-FeCl3, compared to BRH, the modification (iron played a role as a structuring agent mainly) increased the average pore diameter and the presence of functional groups such as -COO-, -Si-O-, or oxygen vacancies, which allowed to remove the pollutant through an adsorption process and significant carbocatalytic degradation. BRH-FeCl3 was reusable during four cycles and had a higher efficiency for activating PMS than another inorganic peroxide (peroxydisulfate, PDS). The effects of BRH-FeCl3 and PMS concentrations were evaluated and optimized through an experimental design, maximizing the ACE degradation. In the optimized system, a non-radical pathway (i.e., the action of singlet oxygen, from the interaction of PMS with defects and/or -COO-/-Si-O- moieties on the BRH-FeCl3) was found. The BRH-FeCl3/PMS system generated only one primary degradation product that was more susceptible to biodegradation and less active against living organisms than ACE. Also, the BRH-FeCl3/PMS system induced partial removals of chemical oxygen demand and dissolved organic carbon. Furthermore, the carbocatalytic system eliminated ACE in a wide pH range and in simulated urine, having a low-moderate electric energy consumption, indicating the feasibility of the carbocatalytic process to treat water polluted with pharmaceuticals.

Enantioselective Biomimetic Structures Inspired by Oxi-Dase-Type Metalloenzymes, Utilizing Polynuclear Compounds Containing Copper (II) and Manganese (II) Ions as Building Blocks.

This study focuses on developing and evaluating two novel enantioselective biomimetic models for the active centers of oxidases (ascorbate oxidase and catalase). These models aim to serve as alternatives to enzymes, which often have limited action and a delicate nature. For the ascorbate oxidase (AO) model (compound 1), two enantiomers, S,S(+)cpse and R,R(-)cpse, were combined in a crystalline structure, resulting in a racemic compound. The analysis of their magnetic properties and electrochemical behavior revealed electronic transfer between six metal centers. Compound 1 effectively catalyzed the oxidation of ascorbic to dehydroascorbic acid, showing a 45.5% yield for the racemic form. This was notably higher than the enantiopure compounds synthesized previously and tested in the current report, which exhibited yields of 32% and 28% for the S,S(+)cpse and R,R(-)cpse enantiomers, respectively. This outcome highlights the influence of electronic interactions between metal ions in the racemic compound compared to pure enantiomers. On the other hand, for the catalase model (compound 2), both the compound and its enantiomer displayed polymeric properties and dimeric behavior in the solid and solution states, respectively. Compound 2 proved to be effective in catalyzing the oxidation of hydrogen peroxide to oxygen with a yield of 64.7%. In contrast, its enantiomer (with R,R(-)cpse) achieved only a 27% yield. This further validates the functional nature of the prepared biomimetic models for oxidases. This research underscores the importance of understanding and designing biomimetic models of metalloenzyme active centers for both biological and industrial applications. These models show promising potential as viable alternatives to natural enzymes in various processes.

Systematic study of the synergistic and kinetics effects on the removal of contaminants of emerging concern from water by ultrasound in the presence of diverse oxidants.

The enhancement of the ultrasound system by adding diverse oxidants to remove a model contaminant (acetaminophen, ACE) in water was investigated. Different parameters were evaluated to study their effect on both the degradation kinetics and the synergy of the combination. The variables studied were the ultrasonic frequency (575, 858, and 1135 kHz), type of oxidant (hydrogen peroxide, sodium peroxydisulfate (or persulfate, PDS), and potassium peroxymonosulfate (PMS)), ACE concentration (4, 8, and 40 µM), and oxidant concentration (0.01, 0.1, 1, and 5 mM). Particular interest was placed on synergistic effects, implying that one process (or both) is activated by the other to lead to greater efficiency. Interestingly, the parameters that led to the higher synergistic effects did not always lead to the most favorable degradation kinetics. An increase in ACE removal of 20% was obtained using the highest frequency studied (1135 kHz), PMS 0.1 mM, and the highest concentration of ACE (40 µM). The intensification of degradation was mainly due to the ability of ultrasound to activate oxidants and produce extra hydroxyl radicals (HO•) or sulfate radicals (SO4•-). Under these conditions, treatment of ACE spiked into seawater, hospital wastewater, and urine was performed. The hospital wastewater matrix inhibited ACE degradation slightly, while the urine components inhibited the pollutant degradation completely. The inhibition was mainly attributed to the competing organic matter in the effluents for the sono-generated radical species. On the contrary, the removal of ACE in seawater was significantly intensified due to "salting out" effects and the production of the strong oxidant HOCl from the reaction of chloride ions with PMS.

Impact of sonication power on the degradation of paracetamol under single- and dual-frequency ultrasound.

The effects of sonication power on the ultrasonic cavitation and sonochemistry as well as the degradation of paracetamol were studied and compared for single- and dual-frequency sonoreactors. For the single-frequency sonication, a 500 kHz plate transducer was employed, with three different calorimetric powers of 8.4, 16.7 and 27.9±3.9 W. For the dual-frequency sonication, the plate transducer was perpendicularly coupled with a low-frequency 20 kHz ultrasonic horn, and three calorimetric powers of 27.9, 33.4, 44.6±3.9 W were studied. At all the studied powers, dual-frequency sonication led to a synergistic effect in the degradation of paracetamol, though varying the power of the horn did not affect the degradation rate. A comparison of the degradation data versus the yield of oxidants as well as the overall intensities of sonoluminescence and sonochemiluminescence suggested the degradation is by the action of oxidants near the surface of the bubbles as the major reaction mechanism. Despite the enhancement observed for the degradation, dual-frequency sonication had no significant effect on the yield of either of the oxidants, regardless of the applied power to the horn. In contrast, dual-frequency sonication decreased the overall sonoluminescence and sonochemiluminescence intensities at all powers studied, suggesting that the application of dual-frequency sonication reduces the size of cavitation bubbles. Normal distribution function analysis confirmed dual-frequency sonication resulted in smaller sonoluminescing bubbles, hence the reduction in the sonoluminescence intensity. The increase in degradation rate under DFUS is attributed to the increase in the transfer of paracetamol from the bulk towards the bubbles. As a result, the availability of the pollutant molecules in the vicinity of the bubbles to react with HO• would increase and consequently, the degradation rate would enhance under DFUS.

Materials Based on Co, Cu, and Cr as Activators of PMS for Degrading a Representative Antibiotic-The Strategy for Utilization in Water Treatment and Warnings on Metal Leaching.

A chromate of copper and cobalt (Φy) was synthesized and characterized. Φy activated peroxymonosulfate (PMS) to degrade ciprofloxacin (CIP) in water. The Φy/PMS combination showed a high degrading capability toward CIP (~100% elimination in 15 min). However, Φy leached cobalt (1.6 mg L-1), limiting its use for water treatment. To avoid leaching, Φy was calcinated, forming a mixed metal oxide (MMO). In the combination of MMO/PMS, no metals leached, the CIP adsorption was low (<20%), and the action of SO4•- dominated, leading to a synergistic effect on pollutant elimination (>95% after 15 min of treatment). MMO/PMS promoted the opening and oxidation of the piperazyl ring, plus the hydroxylation of the quinolone moiety on CIP, which potentially decreased the biological activity. After three reuse cycles, the MMO still presented with a high activation of PMS toward CIP degradation (90% in 15 min of action). Additionally, the CIP degradation by the MMO/PMS system in simulated hospital wastewater was close to that obtained in distilled water. This work provides relevant information on the stability of Co-, Cu-, and Cr-based materials under interaction with PMS and the strategies to obtain a proper catalyst to degrade CIP.

Searching for pharmaceutically active products and metabolites in environmental waters of Peru by HRMS-based screening: Proposal for future monitoring and environmental risk assessment.

The presence of pharmaceutical active products (PhACs) in the aquatic environment is a matter of current concern, and there is an increasing trend to include these compounds in water quality monitoring programs and environmental risk assessments. Several studies have reported the presence of PhACs in environmental waters worldwide, but only a few studies have focused on Latin American countries. Thus, available information on the occurrence of parent pharmaceuticals, especially their metabolites, is very scarce. Peru is one of the less monitored countries in terms of contaminants of emerging concern (CECs) in waters, and only one study has been found, which was focused on the quantification of selected PhACs in urban wastewater and surface water. The aim of this work is to complement the previous data reported on PhACs in the aquatic environment by application of a wide-scope high-resolution (HRMS)-based screening, making use of target and suspect approaches. In the present work, 30 pharmaceuticals, drugs or other compounds (sweeteners, UV filters, etc.) and 21 metabolites have been identified, with antibiotics (and metabolites) being the most prevalent compounds. The use of liquid chromatography (LC) coupled to ion mobility-HRMS allowed the tentative identification of parent compounds and metabolites, for which the analytical reference standard was not available, with a high level of confidence in their identification. Based on the results obtained, a strategy for the monitoring of PhACs and relevant metabolites in environmental waters from Peru and for subsequent risk assessment is proposed. Our data will also help to focus future studies to evaluate the removal efficiency of wastewater treatment plants and the impact of treated water in receiving water bodies.

Solid state pelletizing for the synthesis of new Bi-doped strontium molybdate and its development as a photocatalytic precursor for Rhodamine B degradation.

At present, climate change, urbanization and globalization are the main factors that affect water quality, the primary vehicle for the translocation and permanence of emerging pollutants, resulting in a danger to human health and the environment. The scheelite-type compounds have been investigated owing to their interesting photocatalytic properties in water purification trough the removal of different organic and inorganic pollutants. In this article a method solid state for doping of bismuth(III) in systems Sr1-3xBi2xΦxMoO4 with (0 ≤ x ≤ 0.225) were obtained and, likewise its pelletizing process. Subsequently, these new materials were spectroscopically characterized with photocatalytic properties and finally is describe its development as oxidant against Rhodamine B. This work can be used for the synthesis of new Bi-doped strontium molybdates, which the best photochemical properties are chosen and, in turn, it is experimentally shown how can favor its absorption in the visible region. These electronic properties can be used in near studies, for to compressive the role of bismuth(III) in sheelite as photocatalyst and, to implement its use in the degradation of persistent pollutants that affect the world's water resources.•The doping of bismuth(III) for systems Sr1-3xBi2xΦxMoO4 modified the GAP absorption and this catalytic properties using this new solid state method.•The degradation of Rhodamine B for systems Sr1-3xBi2xΦxMoO4 as case study using of this methodology allows multiple applications associated with climate change such as: the degradation of emerging pollutants and the sensitization of semiconductors with solar claims.•The role of bismuth(III) in these systems can be harnessed to design similar materials with photocatalytic properties.

Inactivation of Giardia intestinalis cysts in water using a sonochemical method based on mid-high-frequency waves.

Giardia intestinalis is a pollutant of food and water, resistant to conventional disinfection treatments and its elimination requires effective methods action. Herein, mid-high-frequency ultrasound (375 kHz), which produces HO• and H2O2, was used as an alternative method of treatment to inactivate Giardia intestinalis cysts in water. The effect of ultrasound power (4.0, 11.2, 24.4 W) on the sonogeneration of radicals was tested, showing that 24.4 W was the condition most favorable to treat the parasite. The viability of the protozoan cysts was evaluated using the immunofluorescence technique and vital stains, showing this protocol was useful to quantify the parasite. The sonochemical method (at 375 kHz and 24.4 W) was applied at different treatment times (10, 20, and 40 min). A significant decrease in the protozoan concentration (reduction of 52.4% of viable cysts) was observed after 20 min of treatment. However, the extension of treatment time up to 40 min did not increase the inactivation. Disinfecting action was associated with attacks on the Giardia intestinalis cyst by sonogenerated HO• and H2O2 (which may induce structural damage, even the cell lysis). For future work is recommended to test combinations with UVC or Fenton process to enhance the inactivating action of this method.•Mid-high-frequency ultrasound produces HO• and H2O2 profitable to inactivate Giardia intestinalis.•Immunofluorescence technique and vital stains allowed us to quantify the parasite viability.•Giardia intestinalis cysts concentration decreased by 52.4% after only 20 min of sonication.

Methods involved in the treatment of four representative pharmaceuticals in hospital wastewater using sonochemical and biological processes.

A primary pollution source by pharmaceuticals is hospital wastewater (HWW). Herein, the methods involved in the action of a biological system (BS, aerobic activated sludge) or a sonochemical treatment (US, 375 kHz and 30.8 W), for degrading four relevant pharmaceuticals (azithromycin, ciprofloxacin, paracetamol, and valsartan) in HWW, are shown. Before treatment of HWW, the correct performance of BS was assessed using glucose as a reference substance, monitoring oxygen consumption, and organic carbon removal. Meanwhile, for US, a preliminary test using ciprofloxacin in distilled water was carried out. The determination of risk quotients (RQ) and theoretical analyses about reactive moieties on these target substances are also presented. For both, the degradation of the pharmaceuticals and the calculation of RQ, analyses were performed by LC-MS/MS. The BS action decreased the concentration of paracetamol and valsartan by ∼96 and 86%, respectively. However, a poor action on azithromycin (2% removal) was found, whereas ciprofloxacin concentration increased ∼20%; leading to an RQ value of 1.61 (high risk) for the pharmaceuticals mixture. The analyses using a biodegradation pathway predictor (EAWAG-BDD methodology) revealed that the amide group on paracetamol and alkyl moieties on valsartan could experience aerobic biotransformations. In turn, US action decreased the concentration of the four pharmaceuticals (removals > 60% for azithromycin, ciprofloxacin, and paracetamol), diminishing the environmental risk (RQ: 0.51 for the target pharmaceuticals mixture). Atomic charge analyses (based on the electronegativity equalization method) were performed, showing that the amino-sugar on azithromycin; piperazyl ring, and double bond close to the two carbonyls on ciprofloxacin, acetamide group on paracetamol, and the alkyl moieties bonded to the amide group of valsartan are the most susceptible moieties to attacks by sonogenerated radicals. The LC-MS/MS analytical methodology, RQ calculations, and theoretical analyses allowed for determining the degrading performance of BS and US toward the target pollutants in HWW.•Biological and sonochemical treatments as useful methods for degrading 4 representative pharmaceuticals are presented.•Sonochemical treatment had higher degrading action than the biological one on the target pharmaceuticals.•Methodologies for risk environmental calculation and identification of moieties on the pharmaceuticals susceptible to radical attacks are shown.

Possibilities and Limitations of the Sono-Fenton Process Using Mid-High-Frequency Ultrasound for the Degradation of Organic Pollutants.

Mid-high-frequency ultrasound (200-1000 kHz) eliminates organic pollutants and also generates H2O2. To take advantage of H2O2, iron species can be added, generating a hybrid sono-Fenton process (sF). This paper presents the possibilities and limitations of sF. Heterogeneous (a natural mineral) and homogeneous (Fe2+ and Fe3+ ions) iron sources were considered. Acetaminophen, ciprofloxacin, and methyl orange were the target organic pollutants. Ultrasound alone induced the pollutants degradation, and the dual competing role of the natural mineral (0.02-0.20 g L-1) meant that it had no significant effects on the elimination of pollutants. In contrast, both Fe2+ and Fe3+ ions enhanced the pollutants' degradation, and the elimination using Fe2+ was better because of its higher reactivity toward H2O2. However, the enhancement decreased at high Fe2+ concentrations (e.g., 5 mg L-1) because of scavenger effects. The Fe2+ addition significantly accelerated the elimination of acetaminophen and methyl orange. For ciprofloxacin, at short treatment times, the degradation was enhanced, but the pollutant complexation with Fe3+ that came from the Fenton reaction caused degradation to stop. Additionally, sF did not decrease the antimicrobial activity associated with ciprofloxacin, whereas ultrasound alone did. Therefore, the chemical structure of the pollutant plays a crucial role in the feasibility of the sF process.

A fundamental study on the degradation of paracetamol under single- and dual-frequency ultrasound.

The degradation of paracetamol, a widely found emerging pharmaceutical contaminant, was investigated under a wide range of single-frequency and dual-frequency ultrasonic irradiations. For single-frequency ultrasonic irradiation, plate transducers of 22, 98, 200, 300, 400, 500, 760, 850, 1000, and 2000 kHz were employed and for dual-frequency ultrasonic irradiation, the plate transducers were coupled with a 20 kHz ultrasonic horn in opposing configuration. The sonochemical activity was quantified using two dosimetry methods to measure the yield of HO• and H2O2 separately, as well as sonochemiluminescence measurement. Moreover, the severity of the bubble collapses as well as the spatial and size distribution of the cavitation bubbles were evaluated via sonoluminescence measurement. The paracetamol degradation rate was maximised at 850 kHz, in both single and dual-frequency ultrasonic irradiation. A synergistic index higher than 1 was observed for all degrading frequencies (200 - 1000 kHz) under dual-frequency ultrasound irradiation, showing the capability of dual-frequency system for enhancing pollutant degradation. A comparison of the results of degradation, dosimetry, and sonoluminescence intensity measurement revealed the stronger dependency of the degradation on the yield of HO• for both single and dual-frequency systems, which confirms degradation by HO• as the main removal mechanism. However, an enhanced degradation for frequencies higher than 500 kHz was observed despite a lower HO• yield, which could be attributed to the improved mass transfer of hydrophilic compounds at higher frequencies. The sonoluminescence intensity measurements showed that applying dual-frequency ultrasonic irradiation for 200 and 400 kHz made the bubbles larger and less uniform in size, with a portion of which not contributing to the yield of reactive oxidant species, whereas for the rest of the frequencies, dual-frequency ultrasound irradiation made the cavitation bubbles smaller and more uniform, resulting in a linear correlation between the overall sonoluminescence intensity and the yield of reactive oxidant species.

Concern levels of beta-lactamase-producing Gram-negative bacilli in hospital wastewater: hotspot of antimicrobial resistance in Latin-America.

Hospital wastewater (HWW) discharges are among the main sources of antibiotic-resistant bacteria. This study detected a high frequency of beta-lactamase-producing Gram-negative Bacilli in HWW of different geographical regions of Colombia, even in the presence of the wastewater treatment plant, highlighting the importance of regulating these environments in developing countries.

Manganese Dioxide Nanoparticles Prepared by Laser Ablation as Materials with Interesting Electronic, Electrochemical, and Disinfecting Properties in Both Colloidal Suspensions and Deposited on Fluorine-Doped Tin Oxide.

Nanoparticles (NPs) of α-MnO2 have high applicability in photoelectrochemical, heterogeneous photocatalysis, optical switching, and disinfection processes. To widen this panorama about MnO2 NPs, the formation of this material by laser ablation and deposition by dip-coating on fluorine-doped tin oxide (FTO), were considered in this study. The optical, spectroscopic, electrochemical characterization, and the evaluation of the antimicrobial activity, plus the photocatalytic response, were measured herein in colloidal media and deposited. For the deposition of NPs on FTO sheet, an anode is produced with a pseudocapacitive behavior, and 2.82 eV of band gap (GAP) in comparison with colloidal NPs for a value of 3.84 eV. Both colloidal suspension and deposited NPs have intrinsic antibacterial activity against two representative microorganisms (E. coli and S. aureus), and this biological activity was significantly enhanced in the presence of UVA light, indicating photocatalytic activity of the material. Thus, both the colloidal suspension and deposited NPs can act as disinfecting agents themselves or via light activation. However, an antibacterial behavior different for E. coli and S. aureus was observed, in function of the aggregation state, obtaining total E. coli disinfection at 30 min for deposited samples on FTO.

Instantaneous Wave-Free Ratio for the Assessment of Intermediate Left Main Coronary Artery Stenosis: Correlations With Fractional Flow Reserve/Intravascular Ultrasound and Prognostic Implications: The iLITRO-EPIC07 Study.

BACKGROUND: There is little information available on agreement between fractional flow reserve (FFR) and instantaneous wave-free ratio (iFR) in left main coronary artery (LMCA) intermediate stenosis. Besides, several meta-analyses support the use of FFR to guide LMCA revascularization, but limited information is available on iFR in this setting. Our aims were to establish the concordance between FFR and iFR in intermediate LMCA lesions, to evaluate with intravascular ultrasound (IVUS) in cases of FFR/iFR discordance, and to prospectively validate the safety of deferring revascularization based on a hybrid decision-making strategy combining iFR and IVUS. METHODS: Prospective, observational, multicenter registry with 300 consecutive patients with intermediate LMCA stenosis who underwent FFR and iFR and, in case of discordance, IVUS and minimal lumen area measurements. Primary clinical end point was a composite of cardiovascular death, LMCA lesion-related nonfatal myocardial infarction, or unplanned LMCA revascularization. RESULTS: FFR and iFR had an agreement of 80% (both positive in 67 and both negative in 167 patients); in case of disagreement (31 FFR+/iFR- and 29 FFR-/iFR+) minimal lumen area was ≥6 mm2 in 8.7% of patients with FFR+ and 14.6% with iFR+. Among the 300 patients, 105 (35%) underwent revascularization and 181 (60%) were deferred according to iFR and IVUS. At a median follow-up of 20 months, major adverse cardiac events incidence was 8.3% in the defer group and 13.3% in the revascularization group (hazard ratio, 0.71 [95% CI 0.30-1.72]; P=0.45). CONCLUSIONS: In patients with intermediate LMCA stenosis, a physiology-guided treatment decision is feasible either with FFR or iFR with moderate concordance between both indices. In case of disagreement, the use of IVUS may be useful to indicate revascularization. Deferral of revascularization based on iFR appears to be safe in terms of major adverse cardiac events. REGISTRATION: URL: https://www. CLINICALTRIALS: gov; Unique identifier: NCT03767621.

Biochar from palm fiber wastes as an activator of different oxidants for the elimination of pharmaceuticals from diverse classes in aqueous samples.

Biochar (BP) obtained from palm fiber wastes was combined with H2O2, peroxymonosulfate (PMS), or persulfate (PDS) to treat valsartan, acetaminophen, and cephalexin in water. BP activated PMS and PDS but no H2O2. Computational calculations indicated that interactions of PMS and PDS with BP are more favored than those with HP. The highest synergistic effect was obtained for the removal of valsartan by BP + PMS. This carbocatalytic process was optimized, evaluating the effects of pH, BP dose, and peroxymonosulfate concentration, and minimizing the oxidant quantity to decrease costs and environmental impacts of the process. SO4•-, HO•, 1O2, and O2•- were the agents involved in the degradation of the pharmaceuticals. The reusability of BP was tested, showing that the carbocatalytic process removed ∼80% of target pollutants after 120 min of treatment even at the fourth reuse cycle. Also, the process decreased the phytotoxicity of the treated sample. Simulated hospital wastewater was treated and its components induced competing effects, but the system achieved the target pharmaceuticals removal in this matrix. Additionally, the analysis of environmental impact using a life cycle assessment unraveled that the carbocatalytic process had a carbon footprint of 2.87 Kg CO2-Eq, with the biochar preparation (which involves the use of ZnCl2 and electric energy consumption) as the main hotspot in the process.

High-frequency ultrasound processes as alternative methods for degrading meropenem antibiotic in water.

ß-lactam, more specifically carbapenems, are antibiotics used as last resort pharmaceuticals to deal with infections. Despite the medical relevance, they are considered contaminants of emerging concern in water because of their recalcitrance to conventional systems in the municipal wastewater treatment plants. This work aimed to show alternative methods based on the use of high-frequency ultrasound (200-1000 kHz) at a laboratory scale to degrade meropenem (a representative carbapenem antibiotic) in water. The ability of the sonochemical method alone to eliminate meropenem was tested initially. Then, the improvements of degradation by the addition of ferrous iron, or Fe (II) plus UVA light (sono-Fenton, or sono-photo-Fenton methods) were assessed. Finally, the effect of the best ultrasound-based method on the removal of biological activity of meropenem was determined. • Three high-frequency ultrasound processes were applied to degrade meropenem in water. • Sono-photo-Fenton degraded 67% of imipenem at 60 min of treatment and decreased significantly H2O2 accumulation. • Antimicrobial activity was removed after only 30 min of sono-photo-Fenton action.