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Immobilised TiO 2 nanotube (TiO 2 -NT) electrodes were grown via electrochemical anodisation in an aqueous solution containing fluoride ions at 10, 20 and 30 V. The photocatalytic (PC) and photoelectrocatalytic (PEC) activity of TiO 2 -NTs electrodes in the oxidation of methanol and the inactivation of bacteria and fungi was studied in different chloride salts electrolytes. Low concentrations of electrochemically generated oxidising species, such as free chlorine, were measured in experiments at pH 8.5 and +1 V of applied potential. Increasing the anodising potential results in longer nanotubes with higher photoactivity. The TiO 2 -NT electrode anodised at 30 V (TiO 2 -NT30V) generates free chlorine with an average concentration of 0.03 mg·L -1 upon illumination with UV-A at +1 V of potential bias. This concentration was enough to achieve 99.99 % of inactivation of a 10 6  CFU·mL -1 Gram-negative bacteria (Escherichia coli) in <3 min and Gram-positive bacteria (Enterococcus faecalis) after 7 min, whereas fungi (Candida albicans) required 15 min. The low production of chlorine was found to have a big impact on the bacteria and fungi inactivation even in not favourable chlorine generation conditions. An in situ investigation of the most influential parameters in the inactivation of some microorganisms with PEC and NT30V electrode has been done. It was found that free chlorine production increases with the length of TiO 2 -NT, with Cl - concentration up to 15 mmol·L -1 and with the application of potential bias. TiO 2 -NT30V photoanode has been demonstrated to produce active chlorine at levels compatible with the water disinfection process, suggesting that the present method could be considered a promising alternative for in situ chlorine-based disinfection., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

The increase in efficiency achieved by UV LED devices has led to a compelling increase in research reports on UV LED water treatment for consumption in the past few years. This paper presents an in-depth review based on recent studies on the suitability and performance of UV LED-driven processes for water disinfection. The effect of different UV wavelengths and their combinations was analysed for the inactivation of various microorganisms and the inhibition of repair mechanisms. Whereas 265 nm UVC LED present a higher DNA damaging potential, 280 nm radiation is reported to repress photoreactivation and dark repair. No synergistic effects have been proved to exist when coupling UVB + UVC whereas sequential UVA-UVC radiation seemed to enhance inactivation. Benefits of pulsed over continuous radiation in terms of germicidal effects and energy consumption were also analysed, but with inconclusive results. However, pulsed radiation may be promising for improving thermal management. As a challenge, the use of UV LED sources introduces significant inhomogeneities in the light distribution, pushing for the development of adequate simulation methods to ensure that the minimum target dose required for the target microbes is achieved. Concerning energy consumption, selecting the optimal wavelength of the UV LED needs a compromise between the quantum efficiency of the process and the electricity-to-photon conversion. The expected development of the UV LED industry in the next few years points to UVC LED as a promising technology for water disinfection at a large scale that could be competitive in the market in the near future., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

The availability of protein standards and methods for their characterization, quantification, and purity assessment are currently a bottleneck in absolute quantitative proteomics. In this work, we introduce an absolute quantitative analytical strategy based on ICP-MS sulfur detection that uses sulfate as generic standard to quantify and certify the mass purity of protein standards. The methodology combines capillary chromatographic separation with parallel detection with ICP-MS and ESI-MS to determine proteoforms concentration and identity, respectively. The workability of the methodology was demonstrated using recombinant human cytokine standards IP-10 and Flt3L (2 batches), which are relevant biomarkers for carcinoma or inflammatory diseases. Every key factor (transport efficiency, column recovery, signal stability and internal standard suitability) was taken into account and certified BSA standard was used as quality control for validation purposes. Protein quantification values and resulting mass purity certification of IP-10 and one batch of Flt3L were very high (100 and 86%, respectively). Lower mass purity obtained for another batch of Flt3L (<70%) concurred with the finding of significant proteoforms resulted from oxidation processes as observed by parallel ESI-MS., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Jorge Ruiz Encinar reports financial support was provided by Spanish Ministry of Science and Innovation. Jorge Ruiz Encinar reports financial support was provided by Principality of Asturias. Sara Escudero Cernuda reports financial support was provided by Principality of Asturias. Francisco Calderon Celis reports financial support was provided by Principality of Asturias., (Copyright © 2023 Elsevier B.V. All rights reserved.)

It is accepted that Microplastic (MP) biofilms accumulates antibiotic-resistant bacteria (ARB) and antibiotic-resistant genes (ARGs) in water. ARB/ARGs and MPs are emerging pollutants of concern due to various associated health risks. The objective of this study was to 1) investigate the ARB community in a pilot-scale wastewater treatment plant (WWTP) effluent, 2) to study and visualize the ARB/ARGs in MP biofilm grown in WWTP effluent and tap water, and 3) to analyze microplastic adherent ARB/ARGs in the biofilm and planktonic ARB/ARGs in the filtrate under controlled conditions. Results indicated the dominance of Pseudomonas, Aeromonas, and Bacillus among isolated ARB in WWTP effluent. Representative resistance strains were incubated in 300 mL water containing commercial polystyrene beads of 300550 μm diameter (MP) in a series of batch experiments. Microbiological, molecular, and microscopic analyses were performed by enumeration, 16srRNA, real-time polymerase chain reaction (qPCR), and Field Emission-Scanning Electron Microscopy (FEG-SEM) techniques. The analyzed viable ARB indicated an increasing trend in MP biofilms between days 3 and 5. It further decreased on days 7 and 9. The prevalence of ARB in the filtrate and MP biofilm varied as a function of time and TOC level, while no significant impacts were observed for minor temperature variation, low antibiotic pressure, and increased MP mass with few exceptions. Relative abundance of ARGs (vanA, sul1) and integron integrase gene (intl1) in MP biofilm were significantly different across different TOC levels, time, and antibiotic pressure. ARGs and intl1 were detected in the MP biofilm in tap water and WWTP effluent on day 30., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Solar water disinfection (SODIS) is a simple, inexpensive and sustainable Household Water Treatment (HWT) that is appropriate for low-income countries or emergency situations. Usually, SODIS involves solar exposure of water contained in transparent polyethylene terephthalate (PET) bottles for a minimum of 6 h. Sunlight, especially UVB radiation, has been demonstrated to photoinactivate bacteria, viruses and protozoa. In this work, an in-depth study of the optical and mechanical properties, weathering and production prices of polymeric materials has been carried out to identify potential candidate materials for manufacturing SODIS devices. Three materials were ruled out (polystyrene (PS), polyvinyl chloride (PVC) and polyethylene (PE)) and four materials were initially selected for study: polymethylmethacrylate (PMMA), polypropylene (PP), polycarbonate (PC) and polyethylene terephthalate (PET). These plastics transmit sufficient solar radiation to kill waterborne pathogens with production costs compensated by their durability under solar exposure. A predictive model has been developed to quantitatively estimate the radiation available for SODIS inside the device as a function of the material and thickness. This tool has two applications: to evaluate design parameters such as thickness, and to estimate experimental requirements such as solar exposure time. In this work, this model evaluated scenarios involving different plastic materials, device thicknesses, and pathogens (Escherichia coli bacterium, MS2 virus and Cryptosporidium parvum protozoon). The developed Solar UV Calculator model is freely available and can be also applied to other customized materials and conditions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

This research reports for the first time the full-scale application of different homogeneous Advanced Oxidation Processes (AOPs) (H 2 O 2 /UV-C, PMS/UV-C and PMS/Fe(II)/UV-C) for the removal of antibiotics (ABs) and antibiotic resistance genes (ARGs) from wastewater effluent at Estiviel wastewater treatment plant (WWTP) (Toledo, Spain). AOPs based on the photolytic decomposition of H 2 O 2 and peroxymonosulfate tested at low dosages (0.05-0.5 mM) and with very low UV-C contact time (4-18 s) demonstrated to be more efficient than UV-C radiation alone on the removal of the analyzed ABs. PMS (0.5 mM) combined with UV-C (7 s contact time) was the most efficient treatment in terms of AB removal: 7 out of 10 ABs detected in the wastewater were removed more efficiently than using the other oxidants. In terms of ARGs removal efficiency, UV-C alone seemed the most efficient treatment, although H 2 O 2 /UV-C, PMS/UV-C and PMS/Fe(II)/UV-C were supposed to generate higher concentrations of free radicals. The results show that treatments with the highest removal of ABs and ARGs did not coincide, which could be attributed to the competition between DNA and oxidants in the absorption of UV photons, reducing the direct photolysis of the DNA. Whereas the photolytic ABs removal is improved by the generation of hydroxyl and sulfate radicals, the opposite behavior occurs in the case of ARGs. These results suggest that a compromise between ABs and ARGs removal must be achieved in order to optimize wastewater treatment processes., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Background: The undercarboxylated form of osteocalcin (ucOC) is an emerging marker of cardiovascular disease. It is unknown if ucOC in related to common cardiovascular risk markers in children. In offspring of families with and without metabolic syndrome (MetS+ and MetS- families), we assessed whether ucOC was related to a continuous metabolic syndrome score (MetS score) and to carotid intima-media thickness (cIMT)., Methods: ucOC and total OC, MetS score and cIMT were assessed in 203 asymptomatic prepubertal children (age 7.6 ± 0.1 yr; 49% girls), of whom 99 were from MetS+ families., Results: In children from MetS+ families, percent ucOC was higher than in children from MetS- families (p < 0.01). In offspring from MetS+ families, higher ucOC and especially higher percent ucOC was independently associated with both the MetS score and cIMT (both p ≤ 0.01)., Conclusions: The undercarboxylated form of OC is related to common cardiovascular risk markers in children at risk for cardiovascular disease., (Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.)

The development of efficient bioassays is a necessary step for cost-effective environmental monitoring and evaluation of novel decontamination technologies. Marine Vibrio fischeri kits have demonstrated to be extremely sensitive but lack of ecological relevance, especially when assessing impacts on freshwater higher organisms. A novel riparian are fern spore microbioassay could merge higher ecological relevance and reduced costs. The aim of this work is the comparative evaluation of the V. fischeri and fern spore bioassays for the follow up of detoxification processes of water contaminated with cyanide and phenol by advanced oxidation technologies, using heterogeneous photocatalysis as example. In both cases, EC(50) values differed significantly for V. fischeri commercial kit, V. fischeri lab cultures and Polystichum setiferum fern spores (1.9, 16 and 101 mg cyanide L(-1) and 27.0, 49.3 and 1440 mg phenol L(-1), respectively). Whereas V. fischeri bioassays are extremely sensitive and dilution series must be prepared, toxicant solutions can be directly applied to spores. Spore microbioassay was also useful in the follow up of photoxidation processes of cyanide and phenol, also reflecting the formation of intermediate degradation by-products even more toxic than phenol. We conclude that this new microbioassay is a promising cost-effective tool for the follow up of decontamination processes., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Around a quarter of Friedreich ataxia (FA) patients, despite being homozygous for GAA expansion within the FRDA gene, show atypical presentations. Our aim is to describe the case of three brothers with long-term follow-up suffering from late onset FA manifested with spastic ataxia. The three patients belong to a family with occipital dysplasia (OD) and Chiari I malformation previously reported by us. We have carried out serial examinations since 1977. Electrophysiological and neuroimaging studies, and molecular genetic analyses of hereditary ataxias are available in all three patients. Onset of symptoms occurred between 25 and 35 years. The clinical picture consisted of progressive spastic gait, truncal and limb ataxia, dysarthria, nystagmus, hyperreflexia with knee and ankle clonus and extensor plantar response, and mild hypopallesthesia. Ages at present vary between 50 and 59. One patient is wheelchair-bound but the other two are able to walk with support. Leaving OD aside, skeletal anomalies are not prominent. All three patients showed cardiomyopathy. MR imaging revealed atrophy of the cerebellum and spinal cord. Motor and sensory nerve conduction velocities were normal. Central conduction time of both motor and sensory pathways was delayed or unobtainable. All three patients were homozygous for the GAA expansion, the smaller expanded allele ranging between 131 and 156 repeats. Four heterozygotic carriers were detected among non-ataxic relatives including one with OD; furthermore, an asymptomatic OD patient showed normal genotype. We conclude that adult onset spastic ataxia is a distinctive FA phenotype associated with minimal GAA expansion. This phenotype represents a new cause of selective distal degeneration of central sensory axons. The present concurrence of OD and FA reflects coincidental cosegregation of two different inherited disorders.