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A novel impedance sensor for monitoring the thickness of undesired micrometric deposits on the surfaces of water pipes and tanks is presented. Coplanar 10 μm-spaced gold microelectrodes were fouled in controlled laboratory conditions and the influence of slime on impedance response was measured. Two different sets of experiments were conducted to form slime on the electrodes surface, addressing biofilm growth and calcium carbonate precipitation, respectively. Following the formation, the thickness of the slime was characterized by Atomic Force Microscopy. Experimental tests highlighted that the impedance response is linear with to the thickness of the slime in both cases, in a 2 μm to 10 μm range. Interestingly, the slope of the response (i.e. of the ionic resistance change vs. thickness) is opposite: a decrease in the case of biofilm (-0.6 Ω/μm where the conductivity of the extracellular matrix becomes dominant) and an increase (+1.4 Ω/μm) in the case of inorganic deposits. In conclusion, this simple and robust sensor provides an accurate and selective determination of slime, while fouling and cleaning up cycles have demonstrated the possibility of regeneration. The final goal for the microsensor, once coupled to an electronic system for data processing and transmission, is the installation along the inner surface of pipes and tanks for real-time remote monitoring of long-term formation of slime with sub-micrometric thickness resolution.

Hematite-based photoanodes were used for the photoelectrocatalysed batch oxidation of As(III) in water at pH 7 and 10. Tests were carried out at different As(III) initial concentrations, ranging from 150 μg/L to 30 mg/L. With no pre-treatments, an initial inactive period of 40–50 min was always observed at the beginning of every test. This initial inactive period is completely removed by a surface modification of surface active sites induced by a pre-polarisation at 800 mV (vs. Ag/AgCl). The water splitting active sites related to the Fe(III)-Fe(IV) redox couple were proved to be not active towards As(III) oxidation. The modifications induced by the anodic prepolarisation were deeply studied: no evidence of the formation of surface highly oxidised iron sites (Fe(V) or Fe(VI)) and/or of highly reactive oxygen vacant sites emerges from XPS analysis. Rather, all collected characterisation data support the conclusion that more reactive terminal oxygen species are necessary for As(III) oxydation. The As(III) abatement reaction was modelled by two subsequent first order kinetics in As(III), independently from the initial As(III) concentration: this behaviour was explained suggesting that the highly reactive sites, being formed after prepolarisation, are gradually depleted during the reaction. As this reaction was proved to be very sensitive to the presence of highly reactive iron sites, its utilisation as a probe reaction to study hematite photoanodes is suggested.

Homogeneous Surface Diffusion Model (HSDM) has been widely used to simulate the breakthrough of organic micropollutants in fixed-bed adsorbers, but its practical applicability in real-scale conditions is not fully established. In this study we proposed a validated methodology to support the assessment of full-scale GAC adsorbers, providing a sound framework for a sustainable management. Specifically, we predicted the breakthrough of volatile organic compounds by the HSDM applied to full-scale granular activated carbon (GAC) adsorbers treating a complex groundwater matrix. Isotherm and short bed adsorber (SBA) tests were conducted to obtain equilibrium and mass-transfer coefficients for two contaminants (chloroform and perchloroethylene, PCE) and two GACs. Isotherm data were well described by Freundlich and Langmuir models, showing that single-component isotherms can be also used in complex water matrices, indirectly taking into account competition phenomena into the estimated parameters. The fitting of SBA data by HSDM was effective for chloroform, while PCE results were not well described, indicating that the combination of isotherm and SBA experiments to estimate HSDM parameters is not always effective, but it can depend on the characteristics of the adsorbate. Breakthrough data from the monitoring of two full-scale adsorbers were finally used to validate HSDM parameters for chloroform: its breakthrough was effectively simulated, without introducing any competition effect in HSDM equations. The model well reproduced also the release of the contaminant (resulting in chromatographic effect) by considering the variation of its influent concentration over time.

Photoelectrocatalytic degradation of target molecules on nanotubular titanium dioxide (TiO 2 ) immobilized on meshed conductive substrate was assessed by measuring the photoelectrochemical response (i.e., generated photocurrent) as indicator of TiO 2 performance. Furthermore, a simple and reliable methodology for degradation modelling and laboratory reactor optimization has been proposed and validated. Nanotubular TiO 2 was grown by anodic oxidation of Ti wire meshes and characterized by ESEM and XRD. Immobilized TiO 2 on Ti wire mesh was used as photo-anode under UV irradiation (254 nm) and subjected to electrical polarization. The photocurrent was monitored in a three-electrode cell, by varying polarization voltage, TiO 2 electrode relative positioning to the UV source (distance), and concentration of a model azo dye compound (Reactive Red 243, RR243). Photoelectrochemical response was modelled as a function of operating parameters and guidelines for photoreactor configuration were identified. Optimized batch photoreactor configuration (1.8 L) was used for degrading a 25 mg L −1 RR243 aqueous solution, achieving 90% decolorization in 45 min and 60% mineralization in 100 min. Decolorization kinetics were effectively described by means of a modified Langmuir-Hinshelwood model based on experimentally measured photocurrents, accounting for the dynamic behaviour of the process due to the change in solution transmittance over time determined by the degradation of target compounds.

N-nitrosamines are a group of potent human carcinogens that can be formed during oxidative treatment of drinking water and wastewater. Many tertiary and quaternary amines present in consumer products (e.g., pharmaceuticals, personal care and household products) are known to be N-nitrosodimethylamine (NDMA) precursors during chloramination, but the formation of other N-nitrosamines has been rarely studied. This study investigates the specific and total N-nitrosamine (TONO) formation potential (FP) of various precursors from nitrogen-containing micropollutants (chlorhexidine, metformin, benzalkonium chloride and cetyltrimethylammonium chloride) and tertiary and quaternary model amines (trimethyl amine, N,N-dimethylbutyl amine, N,N-dimethylbenzyl amine and tetramethyl ammonium). All the studied nitrogenous micropollutants displayed quantifiable TONO FP, with molar yields in the range 0.04-11.92%. However, the observed TONO pools constituted mostly of uncharacterized species, not included in US-EPA 8270 N-nitrosamines standard mix. Only the quaternary ammonium compound benzalkonium chloride showed quantifiable NDMA FP (0.56% molar yield), however, explaining only a minor fraction of the observed TONO FP. The studied model amines showed molar NDMA yields from 0.10% (trimethyl amine) to 5.05% (N,N-dimethylbenzyl amine), very similar to the molar TONO yields. The comparison of the FPs of micropollutants and model compounds showed that the presence of electron donating functional groups (such as a benzyl group) in tertiary and quaternary amine precursors leads to a higher formation of NDMA and uncharacterized N-nitrosamines, respectively. LC-qTOF screening of a list of proposed N-nitrosamine structures has enabled to identify a novel N-nitrosamine (N-nitroso-N-methyldodecylamine) from the chloramination of benzalkonium chloride. This finding supports the hypothesis that different functional groups in quaternary amines can act as leaving groups during chloramination and form differing N-nitrosamine structures at significant yield. Molar TONO yields determined for micropollutants were finally validated under experimental conditions closer to real water matrices, confirming their representativeness also for lower concentration ranges. (C) 2018 Elsevier Ltd. All rights reserved.

The aim of this study was to evaluate the influence of the physical–chemical characteristics of wastewater on PAA decay, in multi-component solutions of inorganic and organic compounds (11 compounds in total) representative of secondary effluents of wastewater treatment plants, disinfected at various PAA concentrations (2–5 mg/L). Batch experiments were defined using the statistical method of the Design of Experiments (DoE) in order to evaluate the effect of each compound and their interaction on PAA decay. Results showed that the organics consumed immediately a considerable amount of PAA, independently from the initial PAA concentration, and consumption dropped rapidly to almost nil after 5 min, whereas PAA consumption due to the inorganics was slow, dependent on the initial PAA concentration and persisted until the end of the experiments (60 min). In detail, inorganics (such as reduced iron and orthophosphate) have shown to be the main drivers of the exponential decay: iron, particularly, has proved to directly consume PAA due to its catalysing capacity, whereas orthophosphate has shown to mainly interact with iron, acting as a chelating compound towards iron and consequently reducing the iron effect in consuming PAA. As for organics, proteins such as, casein and peptone, have been highlighted as the main cause of the initial PAA demand, probably due to the homolytic fission of PAA to generate peroxyl and hydroxyl radicals, which are known to have a high reactivity towards proteins. Finally, a model for predicting the residual PAA concentration was obtained and validated; uncertainty analysis was also performed by a series of Monte Carlo simulations to propagate input uncertainties to the model output.

The presence of antibiotic resistant bacteria (ARB) in wastewater was investigated and the role of wastewater treatment plants (WWTPs) in promoting or limiting antibiotic resistance was assessed. Escherichia coli (E. coli) and total heterotrophic bacteria (THB) resistance to ampicillin, chloramphenicol and tetracycline was monitored in three WWTPs located in Milan urban area (Italy), differing among them for the operating parameters of biological process, for the disinfection processes (based on sodium hypochlorite, UV radiation, peracetic acid) and for the discharge limits to be met. Wastewater was collected from three sampling points along the treatment sequence (WWTP influent, effluent from sand filtration, WWTP effluent). Antibiotic resistance to ampicillin was observed both for E. coli and for THB. Ampicillin resistant bacteria in the WWTP influents were 20–47% of E. coli and 16–25% of THB counts. A limited resistance to chloramphenicol was observed only for E. coli, while neither for E. coli nor for THB tetracycline resistance was observed. The biological treatment and sand filtration led to a decrease in the maximum percentage of ampicillin-resistant bacteria (20–29% for E. coli, 11–21% for THB). However, the conventionally adopted parameters did not seem adequate to support an interpretation of WWTP role in ARB spread. Peracetic acid was effective in selectively acting on antibiotic resistant THB, unlike UV radiation and sodium hypochlorite. The low counts of E. coli in WWTP final effluents in case of agricultural reuse did not allow to compare the effect of the different disinfection processes on antibiotic resistance.

Monitoring and management of drinking water distribution networks (DWDNs), including possible leaching from materials in contact with drinking water, have been stressed as crucial to avoid re-contamination of drinking water leading to a potential increase of human health risk. Recent scientific studies and regulations clearly highlighted the leaching of bisphenol A (BPA) from plastic materials used to renovate DWDNs pipelines as one of the major hazardous source, resulting in severe consequences for human health. In this study, lab migration tests were performed on three commercial epoxy resins, designed with the Design of Experiments (DoE) method in order to build a BPA migration model as a function of water chemical stability, evaluated as aggressivity index (AI), and residual chlorine concentration. Tests lasted about 170 days to account for both short and long-term leaching. BPA migration over time was well described by a combination of two 1st-order kinetic models with an initial peak of leaching, a decrease and, then, a second increase due to resins' deterioration. Initial BPA concentration in the contact water and BPA integral migration over time showed inverse proportionality with both chlorine concentration and AI values. However, measurements of free BPA content in epoxy resins proved that this is due to BPA transformation, not to a reduced leaching. The validated BPA migration model was combined with the hydraulic model of the DWDN in an urban area, through EPANET-MSX software. The model allowed to simulate the propagation of BPA in the DWDN, after the execution of a relining intervention, identifying the most vulnerable areas and permitting to customize a site-specific monitoring and intervention plan to minimize the health risk for final consumers.

A detailed computational fluid dynamics model is presented that integrates reactor hydrodynamics with advanced light models and UV-TiO2 advanced oxidation kinetics to yield the degradation of oxalic acid in a dispersed-phase photoreactor. Model predictions were first compared against experimental data obtained from the literature and subsequently used in a parametric study for investigating scale-up effects associated with both process and photoreactor variables. Investigated variables included: TiO2 concentration (5–400 mg L−1), initial oxalic acid concentration (0.9–32 mg L−1), lamp irradiance (100–10,000 W m−2), background fluid absorbance (0-30 m−1), reactor size (1/4-4 as relative scaling factor), lamp orientation (0-360°) and flowrate (2.5–10 m3 h−1). The analysis revealed that an optimum in oxalic acid degradation is observed when the TiO2 concentration was controlled in the 20–40 mg L−1 range (depending on lamp irradiance). While lamp orientation showed minimal impact, reactor size and flowrate emerged as key variables for photoreactor design. Moreover, an increase in initial oxalic acid concentration substantially reduced oxalic acid degradation performance observed at high loadings. Also, TiO2 activation and photoreactor degradation performance were impacted negatively by light competition with background fluid absorbance.

A computational fluid dynamic (CFD) model was developed to describe the process performance of a semi-batch annular TiO 2 –UV photoreactor in an Eulerian framework. The model accounted for the optical behaviour of titanium dioxide (TiO 2 ) suspensions, the flow distribution and the oxalic acid degradation in the reactor. The scattering component of the optical model, explicitly included in the CFD simulations using a TiO 2 -specific scattering phase function integrated in the radiative transfer equation, was calibrated using an optical goniometer by comparing simulated scattering light profiles against irradiance measurements collected for various TiO 2 concentrations and UV wavelengths and subsequently solved by the discrete ordinate (DO) radiation model. Several scattering phase functions were tested against the goniometric measurements confirming that the Henyey-Greenstein (HG) equation was the most appropriate angular distribution function at 254 and 355 nm, irrespective of the TiO 2 concentration. Using the calibrated HG function, a new approach for quantifying the absolute values of absorption and scattering coefficients in TiO 2 suspensions was proposed. It consists of iteratively solving, using the DO model, the radiative transfer equation for various combinations of absorption and scattering coefficients until the error between observed and predicted angular irradiance measurements is minimized. The accuracy of the optical parameters was verified with independent CFD simulations carried out for an annular photoreactor and already available in the literature. Predicted and simulated irradiance and oxalic acid degradation data were found to be in excellent agreement, confirming the considerable potential of the integrated modelling approach presented in this paper for the design, optimization and scale-up of photocatalytic technologies for water and wastewater treatment applications.

In recent years, the presence of micropollutants in drinking water has become an issue of growing global concern. Due to their low concentrations, monitoring databases are usually rich in censored data (e.g. samples with concentrations reported below the limit of quantification, LOQ) which are typically eliminated or replaced with a value arbitrarily chosen between 0 and LOQ. These conventional methods have some limitations and can lead to erroneous conclusions on: presence of micropollutants in the source water, treatment efficiencies, produced water quality and associated human health risk. In this work, an advanced approach, based on Maximum Likelihood Estimation method for left-censored data (MLELC), was applied on monitoring data of 19 contaminants (metals, volatile organic compounds, pesticides and perfluorinated compounds) in 5362 groundwater (GW) and 12,344 drinking water (DW) samples, collected from 2012 to 2017 in 28 drinking water treatment plants in an urbanized area. This study demonstrates the benefits of MLELC method, especially for high percentages of censored data. Data are used to build statistical distributions which can be effectively used for several applications, such as the time trend evaluation of GW micropollutant concentrations and the estimation of treatment removal efficiency, highlighting the adequacy or the need for an upgrade. Moreover, the MLELC method has been applied to assess the human health risk associated with micropollutants, indicating the high discrepancy in the estimations obtained with conventional methods, whose results do not follow precautionary or sustainability criteria.

It was investigated the feasibility of decolorization of an azo dye (DG 26) using a large scale nanotubular TiO 2 structured electrode in a laboratory photoelectrochemical reactor (0.8 L). Catalyst was grown by anodic oxidation directly on Ti surface and its microstructure and crystalline structure were characterized with SEM and XRD. TiO 2 /Ti photoactivity under different anodic polarization values was evaluated via photoelectrochemical tests. The nanostructured TiO 2 was used in a reactor as photo-anode under UV monochromatic irradiation (254 nm) and it was subjected to bias (+ 1.5 V vs. SCE). A comparison with photolysis and photocatalysis processes was carried out under the same operating conditions to evaluate the synergistic action of photocatalysis and TiO 2 /Ti electrochemical polarization. Electrophotocatalysis was proven to be more effective than photocatalysis in DG 26 decolorization. Catalyst polarization resulted in synergistic effect on process yields. The complete decolorization of a 40 mg/L solution of DG 26 was achieved in 24 h, without adding chemical reagents, and catalyst durability was demonstrated over 360 h tests. Therefore, the work done is challenging to prove that the process (irradiation + catalyst + polarization) is feasible and effectively up-grading to pilot and demonstrative scale applications after a fluid dynamics optimization of the photoreactor.