Drinking Water Matrices Research Articles

Current Challenges in Monitoring Low Contaminant Levels of Per- and Polyfluoroalkyl Substances in Water Matrices in the Field.

The Environmental Protection Agency (EPA) of the United States recently released the first-ever federal regulation on per- and polyfluoroalkyl substances (PFASs) for drinking water. While this represents an important landmark, it also brings about compliance challenges to the stakeholders in the drinking water industry as well as concerns to the general public. In this work, we address some of the most important challenges associated with measuring low concentrations of PFASs in drinking water in the field in real drinking water matrices. First, we review the "continuous monitoring for compliance" process laid out by the EPA and some of the associated hurdles. The process requires measuring, with some frequency, low concentrations (e.g., below 2 ppt or 2 ng/L) of targeted PFASs, in the presence of many other co-contaminants and in various conditions. Currently, this task can only (and it is expected to) be accomplished using specific protocols that rely on expensive, specialized, and laboratory-scale instrumentation, which adds time and increases cost. To potentially reduce the burden, portable, high-fidelity, low-cost, real-time PFAS sensors are desirable; however, the path to commercialization of some of the most promising technologies is confronted with many challenges, as well, and they are still at infant stages. Here, we provide insights related to those challenges based on results from ab initio and machine learning studies. These challenges are mainly due to the large amount and diversity of PFAS molecules and their multifunctional behaviors that depend strongly on the conditions of the media. The impetus of this work is to present relevant and timely insights to researchers and developers to accelerate the development of suitable PFAS monitoring systems. In addition, this work attempts to provide water system stakeholders, technicians, and even regulators guidelines to improve their strategies, which could ultimately translate in better services to the public.

For the occurrence of PPCPs from source to tap: A novel approach modified in terms of sample preservation and SPE cartridge to monitor PPCPs in our water supply

BackgroundThe ongoing infusion of pharmaceutical and personal care products (PPCPs) into ecosystems sustains a perpetual life cycle and leads to multi-generational exposures. Limited understanding of their environmental impact and their intrinsic ability to induce physiological effect in humans, even at low doses, pose great risks to human health. Few scholarly works have conducted systematic research into the occurrence of PPCPs within potable water systems. Concurrently, the associated monitoring techniques have not been comprehensively examined with regards to the specific nature of drinking water, namely whether the significant presence of disinfectants may influence the detection of PPCPs. ResultsA modified approach in terms of detailed investigation of sample preservation and optimization of an in-lab fabricated solid phase extraction (SPE) cartridge filled with DVB-VP and PS-DVB sorbent was proposed. Favorable methodological parameters were achieved, with correlation coefficients spanning from 0.9866 to 0.9998. The LODs of the PPCPs fluctuated from 0.001 to 2 μg L−1, while the LOQs varied from 0.002 to 5 μg L−1. The analysis of spiked samples disclosed a methodological precision of 2.31–9.86 % and a recovery of 52.4–119 %. We utilized the established method for analyzing 14 water samples of three categories (source water, finished water and tap water) from five centralized water supply plants. A total of 24 categories encompassing 72 PPCPs were detected, with the concentrations of PPCPs manifested a marked decrease from source water to finished water and finally to tap water. SignificanceOur research meticulously examined the enhancement and purification effects of widely used commercial SPE cartridges and suggested the use of in-lab fabricated SPE cartridges packed with DVB-VP and PS-DVB adsorbents. We also conducted a systematic evaluation of the need to incorporate ascorbic acid and sodium thiosulfate as preservatives for PPCP measurement, in consideration of the unique characteristics of drinking water matrices, specifically, the significant concentration levels of disinfectants. Furthermore, the proposed method was effectively employed to study the presence of PPCPs in source water, finished water, and tap water collected from centralized water supply plants.

A validated reverse-phase LC-MS/MS method for the analysis of haloacetic acids in drinking water: supporting the transition from HAA5 to HAA9

ABSTRACT Haloacetic acids (HAAs) are potentially toxic by-products formed from interactions between organic matter and chlorine during disinfection of drinking water, with brominated HAAs forming when bromide is present. Some countries require monitoring of drinking water for five HAAs, but there is increasing health concern related to the more toxic brominated HAAs and monitoring of nine HAAs (HAA9) is becoming more widespread. However, existing methods of analysis for HAA9 are often sub-optimal, involving complex derivatisation steps and/or long analytical run times. This article presents an improved methodology utilising reverse-phase liquid chromatography mass spectrometry (LC-MS/MS) for which sample preparation involves simple pH adjustment and the analytical run takes 10 min. The efficacy of the method was demonstrated by a full validation across four drinking water matrices with good sensitivity (<0.8 μg/L), precision (<7%), and bias (<10%) observed. A direct comparison using real water samples was performed against the widely used existing gas chromatography method. The new LC-MS/MS method was significantly quicker and easier and demonstrated improved performance in terms of accuracy and precision. This has implications for understanding the risk posed by HAAs in chlorinated water by eliminating the possible historical under-estimates of the levels of the more toxic brominated compounds.

Perchlorate and chlorate assessment in drinking water in northern Chilean cities

Perchlorate and chlorate are endocrine disruptors considered emerging contaminants (ECs). Both oxyanions are commonly associated with anthropogenic contamination from fertilizers, pesticides, explosives, and disinfection byproducts. However, the soils of the Atacama Desert are the most extensive natural reservoirs of perchlorate in the world, compromising drinking water sources in northern Chile. Field campaigns were carried (2014–2018) to assess the presence of these ECs in the water supply networks of twelve Chilean cities. Additionally, the occurrence of perchlorate, chlorate and other anions typically observed in drinking water matrices of the Atacama Desert (i.e., nitrate, chloride, sulfate) was evaluated using a Spearman correlation analysis to determine predictors for perchlorate and chlorate. High concentrations of perchlorate (up to 114.48 μg L−1) and chlorate (up to 9650 μg L−1) were found in three northern cities. Spatial heterogeneities were observed in the physicochemical properties and anion concentrations of the water supply network. Spearman correlation analysis indicated that nitrate, chloride, and sulfate were not useful predictors for the presence of perchlorate and chlorate in drinking water in Chile. Hence, this study highlights the need to establish systematic monitoring, regulation, and treatment for these EC of drinking water sources in northern Chilean cities for public health protection.

Is adsorption onto activated carbon a feasible drinking water treatment option for persistent and mobile substances?

Persistent and mobile (PM) substances among the organic micropollutants have gained increasing interest since their inherent properties enable them to enrich in water cycles. This study set out to investigate the potential of adsorption onto activated carbon as a drinking water treatment option for 19 PM candidates in batch experiments in a drinking water matrix using a microporous and a mesoporous activated carbon. Overall, adsorption of PM candidates proved to be very variable and the extent of removal could not be directly related to molecular properties. At an activated carbon dose of 10 mg/L and 48 h contact time, five (out of 19) substances were readily removed (≥ 80%), among them N-(3-(dimethylamino)-propyl)methacrylamide, which was investigated for the first time. For five other substances, no or negligible removal (< 20%) was observed, including 2-methyl-2-propene-1-sulfonic acid and 4‑hydroxy-1-(2-hydroxyethyl)-2,2,6,6,-tetramethylpiperidine. For the former, current state of the art adsorption processes may pose a sufficient barrier. Additionally, substance specific surrogate correlations between removals and UVA254 abatements were established to provide a cheap and fast estimate for PM candidate elimination. Adsorption onto activated carbon could contribute significantly to PM substance elimination as part of multi barrier approaches, but assessments for individual substances still require clarification, as demonstrated for the investigated PM candidates.

Peroxymonosulfate activated by composite ceramic membrane for the removal of pharmaceuticals and personal care products (PPCPs) mixture: Insights of catalytic and noncatalytic oxidation

A composite manganese-based catalytic ceramic membrane (Mn-CCM) was developed by a solid-state sintering method, and its effectiveness toward activation of peroxymonosulfate (PMS) for the degradation of 11 pharmaceutical and personal care products (PPCPs) mixture was tested. The optimized Mn-CCMs/PMS system showed remarkable degradation efficiencies for PPCPs mixture with total removal >90% in ultrapure water, river water and natural organic matter (NOM) solution. The Mn-CCMs/PMS system showed the contribution of different phenomena in PPCPs removal in the order of catalytic oxidation (54.7%, Mn-CCMs/PMS) > noncatalytic oxidation (42.3%, PMS oxidation) > adsorption (3.0%, by Mn-CCMs). The singlet oxygen (1O2) was the dominant reactive oxygen specie for the degradation of PPCPs in all water matrices proved by the quenching experiments and electro-paramagnetic resonance (EPR) spectroscopy. The extraordinary stability of Mn-CCMs for the activation of PMS has been noted in terms of repeatability experiments for PPCPs degradation with fewer leaching of Mn (1.9 to 3.6 µg/L). Mineralization was achieved in the range of 28–65% for different water matrices. The toxicity of the PPCPs mixture was reduced by 85.9%. The Mn-CCMs/PMS system showed a reduction (25–100%) in precursors of different carbon- and nitrogen-based disinfection by-products. This study found the Mn-CCMs/PMS system as a feasible purification unit for removing trace concentrations of PPCPs (ng/L) in real drinking water matrices.

Development of multi-residue gas chromatography coupled with mass spectrometry methodologies for the measurement of 15 chemically different disinfection by-products (DBPs) of emerging concern in drinking water from two different Portuguese water treatment plants.

In water treatment plants (WTPs), chemical agents, such as chlorine and ozone, might react with organic matter and anthropogenic contaminants, forming a high diversity of disinfection by-products (DBPs). Due to the potential toxicological effects, the identification of unregulated DBPs (UR-DBPs) is critical to help water managers in the selection of effective water treatment processes, contributing to improving water safety plans. Given the limited validated analytical methods to detect UR-DBPs, here we developed new multi-residue gas chromatography coupled with mass spectrometry methodologies for the detection and quantification of 15 UR-DBPs, including aldehydes, haloketones (HKs), nitrosamines and alcohols, in drinking water matrices. Solid-phase extraction (SPE), for the nitrosamine group, and solid-phase micro extraction (SPME), for the remaining DBPs, were used as sample preparation methods. The developed methodologies allowed the quantification of target UR-DBPs at trace concentration levels (ng L-1), with method quantification limits (MQLs) ranging from 14.4 ng L-1 to 26.0 ng L-1 (SPE-GC-MS) and 2.3 ng L-1 and 1596 ng L-1 (SPME-GC-MS). The methods were applied to different drinking water matrices, considering distinct delivery points of EPAL - Empresa Portuguesa das Águas Livres WTPs. Overall, the aldehyde group, represented by decanal, nonanal and 2-ethylheaxanal, showed the highest occurrence, followed by HKs and nitrosamines. The results of this study suggested that the formation of these UR-DBPs should be further monitored in WTPs.

Per‐ and polyfluoroalkyl substances removal with granular activated carbon and a specialty adsorbent: A case study

AbstractRemoval of per‐ and polyfluoroalkyl substances (PFAS) from water sources is of significant interest as many states have established limits. Three granular activated carbons (GACs) and a clay‐based adsorbent, Fluoro‐sorb® 200 (FS200), were tested using rapid small scale column tests (RSSCTs) to compare relative performance of the media for PFAS removal. FS200 effluent was below detection for all PFAS except PFHxA at 300,000 bed volumes (BVs). The three GACs performed similarly except for PFBS and PFHxA. FS200 showed higher BVs to breakthrough, required a significantly shorter empty bed contact time, and had higher hydraulic loading rate, translating into a smaller footprint than GAC. This work provides important contributions to the water treatment literature, including RSSCT evaluation of FS200 media and media life comparison of GAC and FS200 in drinking water matrices with low PFAS and organic carbon concentrations.Article Impact StatementUtilities needing PFAS treatment will benefit from the testing methodology and results.

Assessment of microplastic sampling and extraction methods for drinking waters

To date, no standardized methods have been proposed for conducting microplastic analyses in treated drinking waters, resulting in challenges associated with direct comparisons among studies. This study compares known methods for collecting and extracting microplastics from drinking waters: an in-laboratory (in-lab) filtration method and an in-line filtration method (i.e., water filtered on-site without an intermediate storage and/or transportation step). In-lab methods have been the predominant method for sample collection in drinking water matrices, and in-line methods are emerging due to the potential to sample large volumes of water on site and minimize contamination from airborne particles, but the two methods have yet to be directly compared using real samples. In response, this study evaluates both methods in terms of recovering spiked reference microplastics, collecting microplastics from tap water samples using the same water volume, and quantifying the removal of microplastics through a full-scale ultrafiltration system. In-line filtration was shown to have higher recoveries for all the reference microplastics examined (+37 % for PVC fragments, +23 % for PET fragments, +22 % for nylon fibers and +7 % for PET fibers) and a greater potential to reduce microplastic contamination. It also resulted in lower standard deviations for total microplastic counts in the tap water and UF influent and effluent samples. The filtration capacity of the proposed in-line filtration method could exceed 350 L of treated water, but this is highly dependent on the water quality. This study therefore supports the use of in-line filtration methods towards the standardization of microplastic collection procedures in drinking water.

Evaluation of DNA extraction yield from a chlorinated drinking water distribution system.

Desalination technology based on Reverse Osmosis (RO) membrane filtration has been resorted to provide high-quality drinking water. RO produced drinking water is characterized by a low bacterial cell concentration. Monitoring microbial quality and ensuring membrane-treated water safety has taken advantage of the rapid development of DNA-based techniques. However, the DNA extraction process from RO-based drinking water samples needs to be evaluated regarding the biomass amount (filtration volume) and residual disinfectant such as chlorine, as it can affect the DNA yield. We assessed the DNA recovery applied in drinking water microbiome studies as a function of (i) different filtration volumes, (ii) presence and absence of residual chlorine, and (iii) the addition of a known Escherichia coli concentration into the (sterile and non-sterile, chlorinated and dechlorinated) tap water prior filtration, and directly onto the (0.2 μm pore size, 47 mm diameter) mixed ester cellulose membrane filters without and after tap water filtration. Our findings demonstrated that the co-occurrence of residual chlorine and low biomass/cell density water samples (RO-treated water with a total cell concentration ranging between 2.47 × 102–1.5 × 103 cells/mL) failed to provide sufficient DNA quantity (below the threshold concentration required for sequencing-based procedures) irrespective of filtration volumes used (4, 20, 40, 60 L) and even after performing dechlorination. After exposure to tap water containing residual chlorine (0.2 mg/L), we observed a significant reduction of E. coli cell concentration and the degradation of its DNA (DNA yield was below detection limit) at a lower disinfectant level compared to what was previously reported, indicating that free-living bacteria and their DNA present in the drinking water are subject to the same conditions. The membrane spiking experiment confirmed no significant impact from any potential inhibitors (e.g. organic/inorganic components) present in the drinking water matrix on DNA extraction yield. We found that very low DNA content is likely to be the norm in chlorinated drinking water that gives hindsight to its limitation in providing robust results for any downstream molecular analyses for microbiome surveys. We advise that measurement of DNA yield is a necessary first step in chlorinated drinking water distribution systems (DWDSs) before conducting any downstream omics analyses such as amplicon sequencing to avoid inaccurate interpretations of results based on very low DNA content. This study expands a substantial source of bias in using DNA-based methods for low biomass samples typical in chlorinated DWDSs. Suggestions are provided for DNA-based research in drinking water with residual disinfectant.

Development and optimization of analytical methods for the detection of 18 taste and odor compounds in drinking water utilities

Taste and odor (T&O) issues have been a major concern among drinking water utilities as source waters are becoming increasingly vulnerable to compounds released during algal blooms as well as non-algal compounds. While most of the literature focuses on the two most common T&O compounds – 2-MIB and geosmin, there are other compounds that have the potential to cause T&O events. The aim of this study was to develop an advanced analytical method using solid phase microextraction (SPME) and gas chromatography-tandem mass spectrometry (GC-MS/MS) to identify 18 T&O compounds belonging to various odor classes. The developed method was optimized for the 18 analytes and implemented to determine the holding time of the compounds in raw and treated (distribution system point-of-entry or PoE) drinking water matrices. Compounds belonging to certain classes such as pyrazines and anisoles were found to be “stable” (< 30% loss) in all tested waters for up to two weeks, while aldehydes, ketones, esters and alkyl sulfides showed > 30% loss within 96 h in raw water. Preservation of samples at low pH (< 2) using hydrochloric acid increased the holding times and reduced losses within 96 h for aldehydes, ketones and esters. The paper also discusses the occurrence of these compounds with water utilities from the Midwest and Eastern US during the summer months. The study detected eight T&O compounds - 2-MIB, geosmin, β-cyclocitral, β-ionone, hexanal, indole, dimethyl disulfide and dimethyl trisulfide. While five compounds were detected above their threshold concentrations in the raw water, two of them (2-MIB and geosmin) were detected above threshold in the PoE samples.

Superparamagnetic nanoadsorbents for the removal of trace As(III) in drinking water

A series of novel zeolitic imidazolate framework (ZIF) decorated superparamagnetic graphene oxide hybrid nanoadsorbents were synthesized, characterized, and tested for their As(III) adsorbed amount in simulated drinking water. The three composite nanomaterials are based each on three isostructural and water stable ZIFs, (C-1 based on ZIF-8, C-2 based on ZIF-67, and C-3 based on ZIF-Zn/Co). The composite nanomaterials and there parent materials were characterized through pXRD, TEM, FTIR, BET and magnetometry methods (SQUID), and were tested as adsorbents in a representative drinking water matrix containing arsenite (As(III)) at an initial trace concentration (realistic in some natural drinking water sources) of 35 µg/L. The nanoadsorbents were magnetically captured and removed after adsorption in batch conditions. Out of the three composites, C-2 shows the highest As(III) adsorbed amount at an initial concentration of 35 µg/L (q0) of 202 µg/g, followed by C-3 with 102 µg/g and C-1 with 82 µg/g.

Determination of free chlorine based on ion chromatography\u2014application of glycine as a selective scavenger

Free available chlorine (FAC) is the most widely used chemical for disinfection and in secondary disinfection; a minimum chlorine residual must be present in the distribution system. FAC can also be formed as an impurity in ClO2 production as well as a secondary oxidant in the ClO2 application, which has to be monitored. In this study, a new method is developed based on the reaction of FAC with glycine in which the amine group selectively scavenges FAC and the N-chloroglycine formed can be measured by ion chromatography with conductivity detector (IC-CD). Utilizing IC for N-chloroglycine measurement allows this method to be incorporated into routine monitoring of drinking water anions. For improving the sensitivity, IC was coupled with post-column reaction and UV detection (IC-PCR-UV), which was based on iodide oxidation by N-chloroglycine resulting in triiodide. The method performance was quantified by comparison of the results with the N,N-diethyl-p-phenylenediamine (DPD) method due to the unavailability of an N-chloroglycine standard. The N-chloroglycine method showed limits of quantification (LOQ) of 24 μg L−1 Cl2 and 13 μg L−1 Cl2 for IC-CD and IC-PCR-UV, respectively. These values were lower than those of DPD achieved in this research and in ultrapure water. Measurement of FAC in the drinking water matrix showed comparable robustness and sensitivity with statistically equivalent concentration that translated to recoveries of 102% for IC-CD and 105% for IC-PCR-UV. Repeatability and reproducibility performance were enhanced in the order of DPD, IC-CD, and IC-PCR-UV. Measurement of intrinsic FAC in the ClO2 application revealed that the N-chloroglycine method performed considerably better in such a system where different oxidant species (ClO2, FAC, chlorite, etc.) were present.

Sonophotocatalytic degradation of sodium diclofenac using low power ultrasound and micro sized TiO2.

The nonsteroidal anti-inflammatory drug sodium diclofenac (DC) is an emerging water pollutant which resists conventional wastewater treatments. Here the sonophotocatalytic degradation of DC was carried out using micrometric TiO2 (both pristine and Ag-decorated), UV-A irradiation and 20kHz pulsed ultrasound. Sonophotocatalytic tests were compared with photolysis, sonolysis, sonophotolysis, sonocatalysis and photocatalysis data performed in the same conditions. A synergy index of over 2 was determined for tests with pristine TiO2, while values close to 1.3 were observed for Ag-TiO2. Reaction intermediates were studied by HPLC-MS, showing degradation mechanisms activated by hydroxyl radicals. Similar pathways were identified for photocatalytic and sonophotocatalytic tests, although the latter led to more oxidized compounds. Different reactor configurations (static and dynamic set ups) were studied. Sequential and simultaneous application of UV light and ultrasound led to similar performance. The role of water matrix was investigated using ultrapure and drinking water, showing marked detrimental effects of electrolytes on the DC degradation. Overall, the combined treatment proved more efficient than photocatalysis alone especially in demanding working conditions, like in drinking water matrices.

Sustainable synthesis of zinc oxide nanoparticles for photocatalytic degradation of organic pollutant and generation of hydroxyl radical

Abstract Herein, a sustainable and reproducible method for the preparation of zinc oxide nanoparticles (ZnO) and their application in photocatalytic degradation of organic pollutant is reported. The ZnO nanoparticles were prepared by combusting a mixture of highly porous sawdust and zinc nitrate hexahydrate at 600 °C in a tube furnace. The porous morphology of the sawdust mediated the formation of ZnO nanoparticles by preventing their growth to the macroscopic size. Four different ZnO nanoparticles samples [ZnO-n, where n = 1–4] were prepared by varying the ratio of sawdust and zinc nitrate salt to obtain the best-performing ZnO nanoparticles. The average size of the ZnO nanoparticles was found to be ~ 23 nm, measured from TEM image. The ZnO-4 and ZnO-2 degraded ~ 95% methyl orange (MO) in deionized and simulated fresh drinking water matrices after 42 min of ultraviolet (UV-B) light irradiation. The ZnO-2 and ZnO-4 catalyzed degradation of MO in deionized and fresh drinking water matrices were found to be about 24 and 27 times faster compared to the ZnO-control. The ability of ZnO-n towards the generation of hydroxyl radicals (•OH) was studied by the terephthalic acid fluorescence tests. Additionally, the reproducibility of the synthesis methodology and the cyclic stability of the as prepared ZnO-n was thoroughly studied. Finally, it was found that the ZnO nanoparticles, prepared in this study, leached less amount of zinc in water compared to the commercial ZnO; which indicated its better safety and sustainability in regard to the photocatalytic water treatment.

Online monitoring and control of drinking water corrosion potential at a full-scale plant

Abstract To mitigate pipe and water quality degradation in distribution, treatment targets were established to continuously control the corrosion potential of drinking water towards cement, lead and iron materials at a 225 MLD surface water treatment plant. Indicators were identified to estimate the corrosion potential of water for each of the 3 materials: the Langelier Saturation Index (LSI) for cement, pH for lead and a novel corrosion index for iron. Linear Polarization Resistance (LPR) probes equipped with cast iron and lead electrodes provided direct and continuous measurements of actual lead and iron corrosion rates for finished water. Corrosion control was achieved by adjustments to caustic soda doses. The set-point for finished water pH was determined with a site-specific algorithm using online values for temperature, pH, and conductivity as surrogate for calcium and alkalinity. Over the 7 months of implementation, measured iron corrosion rates were maintained well below the established threshold of 50 μm/year. Lead corrosion rates varied from 20 to 40 μm/year with higher levels occurring when pH dropped below 7.5. The full-scale experience validated a treatment strategy and demonstrated the feasibility of using LPR probes for online monitoring of corrosion potential on drinking water matrices.

Towards the revision of the drinking water directive 98/83/EC. Development of a direct injection ion chromatographic-tandem mass spectrometric method for the monitoring of fifteen common and emerging disinfection by-products along the drinking water supply chain

According to the recent proposal released by the European Commission for the revision of the 98/83/EC Directive, water suppliers will be requested to monitor the nine bromine- and chlorine congeners of haloacetic acids, HAAs, as well as the oxyhalides chlorite and chlorate, as disinfection by-products (DBPs) originated during the potabilization process.In this work, we propose a direct-injection method based on ion chromatography and mass spectrometric detection for the determination of the mentioned DBPs as well as bromate (already included in the 98/83/EC), implemented also for the following emerging HAAs monoiodo-, chloroiodo- and diiodo-acetic acids. The method was optimized to include the fifteen compounds in the same analytical run, tuning the chromatographic (column and gradient) and detection conditions (suppression current, transitions, RF lens settings and collision energies). To avoid matrix effect and to manage the instrumental conditions, optimization was performed directly in drinking water matrix. The method quantitation limits satisfy the new limits imposed by the future directive and range from 0.08 μg/L (monobromoacetic acid) to 0.34 μg/L (trichloroacetic acid). The performance of the method was checked along different strategic sampling points of three potabilization plants serving the city of Turin (Italy), including intermediate treatments and finished waters. Recovery was checked according to the ±30% limit of acceptability set by EPA regulations. The effect of disproportionate concentrations of chlorite and chlorate in respect to HAAs on HAA signals was studied; this aspect is underestimated in literature. The method is routinely applied by the potabilization plant of the city of Turin to confirm the effectiveness of all control measures in abstraction, treatment, distribution and storage. This study represents the first example in Italy of development and use of a cutting-edge technique for HAAs analysis along the potabilization processes.

Aqueous chlorination of sulfamethazine and sulfamethoxypyridazine: Kinetics and transformation products identification.

Sulfonamides (SNs) are synthetic antimicrobial agents. These substances are continually introduced into the environment, and they may spread and maintain bacterial resistance in the different compartments. The chlorination of 2 SNs, namely, sulfamethazine (SMT) and sulfamethoxypyridazine (SMP), was investigated to study their reactivity with chlorine at typical concentrations for water treatment conditions. Experiments conducted in purified water show an acceleration of SMT and SMP degradation of a factor 1.5 by comparison to drinking water matrix. This difference is due to pH variation and competitive reactions between SNs and mineral and organic compounds, with chlorine in drinking water. In the presence of an excess of chlorine (6.7μmol·L-1 ) in ultrapure water at pH7.2, second-order degradation rate constants were equal to 4.5×102 M-1 ·s-1 and 5.2×102 M-1 ·s-1 for SMT and SMP, respectively. The structures of transformation products were investigated by liquid chromatography tandem mass spectrometry analyses with equimolar concentrations between chlorine and SNs. SO2 elimination, cyclization, and electrophilic substitutions were the main pathways of by-products formation. Moreover, the toxicity of the proposed structures was predicted by using toxicity estimation software tool program. The results indicated that most by-products may present developmental toxicity.

Photocatalytic removal of hexavalent chromium by newly designed and highly reductive TiO2 nanocrystals

Hexavalent chromium Cr(VI), a highly toxic oxyanion, widely occurs in drinking water supplies. This study designed and synthesized a new type of highly reductive TiO2 nanocrystals for photochemical Cr(VI) removal, via the thermal hydrolysis of TiCl4 in the presence of diethylene glycol (DEG). Surface analyses and hydroxyl radical measurements suggested that DEG was chemically bonded on TiO2 surface that resulted in an internal hole-scavenging effect and a high electron-releasing capacity, making it advantageous to conventional TiO2 materials. Upon UV irradiation, the synthesized TiO2 photocatalyst exhibited fast Cr(VI) reduction kinetics in diverse water chemical conditions. Fast elimination of Cr(VI) was achieved on a time scale of seconds in drinking water matrices. The removal of Cr(VI) by reductive TiO2 exhibited a three-stage kinetic behavior: an initial fast-reaction phase, a lag phase resulting from surface precipitation of Cr(OH)3(s), and a final reaction phase due to surface regeneration from oxidation-reduction induced ripening process. The lag phase disappeared in acidic conditions that prevented the formation of Cr(OH)3(s). The catalyst exhibited extremely high electron-releasing capacity that can be reused for multiple cycles of Cr(VI) removal in drinking water treatment.

Tests of a novel sensor for α-spectrometry in drinking water matrices

The technical innovation of boron-doped diamond on top of a silicon layer as alpha nuclide measurement device offers promising advances, since the energy-resolved measurement takes place in-situ in water without matrix separation. Several experiments were performed to detect disturbance factors by investigating the yield of 241Am in the presence of main or minor drinking water elements. The results show that an activity was detected by the sensor in any case. Generally, the yields were higher with NaNO3 as electrolyte than with Na2SO4, due to speciation and higher hydrogen formation. A reduced yield was observed for nitrate as electrolyte and maximum concentrations of Ca, Mg, PO4, and F in drinking water. The generally high standard deviation of the measurement, which is mainly due to hydrogen evolution, mass attenuation, and surface site occupation, does not allow for an exact determination of a present α-contamination. However, a significant aqueous alpha activity can be detected.