Volatile Disinfection By-products Research Articles

Mammalian Cell Genotoxicity of Potable Reuse and Conventional Drinking Waters.

Potable reuse water is increasingly part of the water supply portfolio for municipalities facing water shortages, and toxicity assays can be useful for evaluating potable reuse water quality. We examined the Chinese hamster ovary cell acute direct genotoxicity of potable reuse waters contributed by disinfection byproducts (DBPs) and anthropogenic contaminants and used the local conventional drinking waters as benchmarks for evaluating potable reuse water quality. Our results showed that treatment trains based on reverse osmosis (RO) were more effective than RO-free treatment trains for reducing the genotoxicity of influent wastewaters. RO-treated reuse waters were less genotoxic than the local tap water derived from surface water, whereas reuse waters not treated by RO were similarly genotoxic as the local drinking waters when frequent replacement of granular activated carbon limited contaminant breakthrough. The genotoxicity contributed by nonvolatile, uncharacterized DBPs and anthropogenic contaminants accounted for ≥73% of the total genotoxicity. The (semi)volatile DBPs of current research interest contributed 2-27% toward the total genotoxicity, with unregulated DBPs being more important genotoxicity drivers than regulated DBPs. Our results underscore the need to look beyond known, (semi)volatile DBPs and the importance of determining whole water toxicity when assessing the quality of disinfected waters.

Adsorption, boiling or membrane filtration for disinfection by-product removal: How to make our drinking water safer?

Disinfection by-products (DBPs) generated in drinking water have become a global concern due to their potential harm to human health. Nevertheless, there are few studies about different point-of-use water treatments in household drinking water. The study aims to compare the effectiveness of three point-of-use water treatments: adsorption, boiling, and membrane filtration. The experimental results showed that the initial average concentration of volatile DBPs and non-volatile DBPs for tap water were 63.71 μg/L and 6.33 μg/L. The removal efficiency of DBPs for adsorption which were 75.6 % (the filter volumes from 0 L to 20 L) and 45.4 % (the filter volumes from 20 L to 50 L) during the service life of the filter element (50 L). Boiling had a high removal efficiency for volatile DBPs like trihalomethanes (THMs), haloacetaldehydes (HALs), haloacetonitriles (HANs), and haloketones (HKs) (90.5 %, 100 %, 100 %, and 100 %, respectively). However, boiling had a low removal efficiency which was 15 % in removing non-volatile DBPs like haloacetic acids (HAAs). Membrane filtration had a middle removal efficiency for THMs, HAAs, HALs, HKs, and HANs (45.3 %, 75.2 %, 46.5 %, 47.6 %, and 100 %, respectively). Through analysis of the correlation between dissolved organic matter (DOM) removal efficacy and DBP removal efficiency, it was found that the strongest correlation was observed between UV254 and DBP removal efficiency. Boiling showed a lower estimated cytotoxicity of DBPs compared to adsorption and membrane filtration. Cancer risk assessment of DBPs was below the specified risk range for three point-of-use water treatments. This study provides a reference for choosing point-of-use water treatments in household drinking water.

Removal and transformation of disinfection by-products in water during boiling treatment

Disinfection by-products (DBPs) remain an ongoing issue because of their widespread occurrence and toxicity. Boiling is the most popular household water treatment method and can effectively remove some DBPs. However, the transformation behavior of DBPs during boiling is still unclear, and the key contributors to toxicity have not been identified. In this study, the changes in the concentrations of DBPs in the single-DBP systems and the multi-DBP systems during boiling were monitored, and in-depth discussions on the removal and transformation of DBPs in both systems were carried out. The results showed that boiling was effective in removing volatile DBPs (over 90% for TCAL, TCAN, and DCAN, and over 60% for TCM), but ineffective for non-volatile DBPs (around 20% for TCAA and below 10% for DCAA and MCAA). By hydrolysis and decarboxylation, the transformation occurred among DBPs, i.e., 55% TCAL to TCM, followed by 23% DCAN to DCAA, 22% TCAN to TCAA, and 10% TCAA to TCM. The transformations were found to be significantly influenced by other co-existing DBPs. In multi-DBP systems, the transformations of DCAN to DCAA and TCAN to TCAA were both promoted, while the transformation of TCAN to TCAA was inhibited. Transformation and volatilization are the two processes responsible for DBP removal. Toxicity estimates indicated that boiling was effective in reducing the toxicity of DBPs and improving the safety of the water, despite the interconversion of DBPs in drinking water during boiling. This study emphasized the importance of studying the interconversion behaviors of DBPs in drinking water during boiling and provided practical information for end-use drinking water safety.

Enhanced coagulation and oxidation by the Mn(VII)-Fe(III)/peroxymonosulfate process: Performance and mechanisms

To improve the performance of the conventional coagulation process, a permanganate (Mn(VII)) pre-oxidation combined with Fe(III)/peroxymonosulfate (PMS) coagulation process (Mn(VII)-Fe(III)/PMS) that can significantly improve the removal of dissolved organic carbon (DOC), turbidity, and micropollutants is proposed in this study. Compared with conventional Fe(III) coagulation, the Mn(VII)-Fe(III)/PMS process can also significantly enhance the removal of iohexol and sulfamethoxazole in raw water. During this process, the primary reduction product, Mn(IV), after Mn(VII) pre-oxidation was adsorbed on the floc surfaces and involved in the Fe(III)/PMS process. The natural organic matter (NOM) in raw water mediated the redox cycle of iron. The synergistic effect of NOM, Fe, and Mn facilitated the redox cycle of Mn(III)/Mn(IV) and Fe(III)/Fe(II) to promote the activation of PMS. The sulfate radical (SO4•−) played an important role in the degradation of micropollutants. The formation potential of the detected volatile disinfection by-product (DBP) during the subsequent chlorination was reduced by 21.9% after the Mn(VII)-Fe(III)/PMS process. This study demonstrated the promising application of the Mn(VII)-Fe(III)/PMS process for coagulation and micropollutant control and illustrated the reaction mechanism. This study provides guidance for improving conventional drinking water treatment processes.

Long-Term Monitoring of Water and Air Quality at an Indoor Pool Facility during Modifications of Water Treatment

Previous research has shown that volatile disinfection byproducts (DBPs) can adversely affect the human respiratory system. As a result, swimming pool water treatment processes can play important roles in governing water and air quality. Thus, it was hypothesized that water and air quality in a swimming pool facility can be improved by renewing or enhancing one or more components of water treatment. This study is designed to identify and quantify changes in water and air quality that are associated with changes in water treatment at an indoor chlorinated swimming pool facility. Reductions in aqueous trichloramine (NCl3) concentration were observed following the use of secondary oxidizer with its activator. This inclusion also resulted in significant decreases in the concentrations of cyanogen chloride (CNCl) in pool water. The concentration of urea, a compound that is common in swimming pools and that functions as an important precursor to NCl3 formation, as well as a marker compound for the introduction of contaminants by swimmers, was also reduced after the addition of the activator. Concentrations of gas-phase NCl3 did not decrease after the treatment processes were changed. The collection of long-term water and air quality measurements also allowed for an assessment of the effects of bather load on water and air quality. In general, the concentrations of urea (an NCl3 precursor), liquid-phase NCl3, and gas-phase NCl3 all increased during periods of high swimmer number.

Cumulative impact of swimmers on pool water quality: A full-scale study revealing seasonal and daily variabilities of disinfection by-products

Swimming pool water is continuously disinfected to control microbial safety. However, the disinfection processes also generate disinfection by-products (DBPs) that are created by the reaction between a disinfectant and organic matter. In this study, the water quality of two indoor pools with different characteristics was monitored at full scale. To assess the cumulative impact of swimmers, pools water quality was monitored for long term (2 months), after complete water renewal in pools. The daily impact of swimmers on water quality was also estimated by intensively sampling water quality during one high attendance day. Samples were analyzed for DBPs (Trihalomethanes-THMs, Haloacetic acids-HAAs, chlorites and chlorates) and their precursors (total organic carbon-TOC, UV 254 nm, water temperature, pH, free and total chlorine). Results showed that swimmers had a clear impact on the levels of organic matter indicators (TOC and UV 254 nm) and total nitrogen, whose variabilities were associated with the swimmers attendance. The highest levels of DBPs (THMs and HAAs) were detected in the pools during periods of maximum attendance and when there was a higher ratio of swimmers to pool-water volume. THM levels were also found to be influenced by parameters associated with pool operations (water temperature, water renewal, disinfection). Most notably HAAs accumulated in both pools due to their low volatility. Further studies should include nitrogenous DBPs, given their important toxicity, and should assess the impact of water quality and ventilation on the presence of volatile DBPs in air.

Disinfection Byproduct Recovery during Extraction and Concentration in Preparation for Chemical Analyses or Toxicity Assays.

Over 700 disinfection byproducts (DBPs) have been identified, but they account for only ∼30% of total organic halogen (TOX). Extracting disinfected water is necessary to assess the overall toxicity of both known and unknown DBPs. Commonly used DBP extraction methods include liquid-liquid extraction (LLE) and solid-phase extraction (SPE), which may use either XAD resins or other polymeric sorbents. With few exceptions, DBP recoveries have not been quantified. We compared recoveries by LLE, XAD resins, and a mixture of Phenomenex Sepra SPE sorbents (hereafter SPE) for (semi-)volatile DBPs and nonvolatile model compounds at the 1-L scale. We scaled up the three methods to extract DBPs in 10 L of chlorinated creek waters. For (semi-)volatile DBPs, XAD resulted in lower recoveries than LLE and SPE at both 1- and 10-L scales. At the 10-L scale, recovery of certain trihalomethanes and trihalogenated haloacetic acids by XAD was negligible, while recovery of other (semi-)volatile DBPs extracted by XAD (<30%) was lower than by SPE or LLE (30-60%). TOX recovery at the 10-L scale was generally similar by the three extraction methods. The low TOX recovery (<30%) indicates that the toxicity assessed by bioassays predominantly reflects the contribution of the nonvolatile, hydrophobic fraction of DBPs.

Antiviral drug Umifenovir (Arbidol) in municipal wastewater during the COVID-19 pandemic: Estimated levels and transformation

An indole derivative umifenovir (Arbidol) is one of the most widely used antiviral drugs for the prevention and treatment of COVID-19 and some other viral infections. The purpose of the present study was to shed light on the transformation processes of umifenovir in municipal wastewater, including disinfection with active chlorine, as well as to assess the levels of the antiviral drug and its metabolites entering and accumulating in natural reservoirs under conditions of the SARS-CoV-2 pandemic. The combination of high-performance liquid chromatography with electrospray ionization high-resolution mass-spectrometry and inductively coupled plasma mass spectrometry was used for tentative identification and quantification of umifenovir and its transformation products in model reaction mixtures and real samples of wastewater, river water, biological sludge and bottom sediments taken at the wastewater treatment plant in Arkhangelsk, a large cultural and industrial center at the Russian North. Laboratory experiments allowed identifying fifteen bromine-containing transformation products, forming at the initial stages of the chlorination and fourteen classic volatile and semi volatile disinfection by-products with bromoform as the dominant one. Chlorinated derivatives are only the minor disinfection by-products forming by substitution of alkylamine group in the aromatic ring. The schemes of umifenovir transformation in reactions with dissolved oxygen and sodium hypochlorite are proposed. Two established primary transformation products formed by oxidation of the thioether group to sulfoxide and elimination of thiophenol were detected in noticeable concentrations in the wastewater together with their precursor. The level of umifenovir reached 1.3 mg kg−1 in the sludge and municipal wastewater treat contained 1 μg L−1 of that drug, while its removal during biological wastewater treatment was about 40%. Pronounced accumulation of umifenovir and its transformation products in biological sludge and bottom sediments of natural reservoirs may be a source of the future secondary pollution of the environment.

Monitoring and Statistical Analysis of Formation of Organochlorine and Organobromine Compounds in Drinking Water of Different Water Intakes.

The main drawback of drinking water chlorination involves the formation of quite hazardous disinfection by-products (DBPs), represented mainly by halogenated species. Based on the authors’ monitoring data since 2002, the prevalence of chlorine over bromine in the composition of volatile DBPs was shown for the drinking water in Ufa (Russia). However, the situation was completely reversed in the case of semi-volatile DBPs. The principal goal of the present study involved rationalization of the results of the long-term monitoring. Gas chromatography–mass spectrometry (GC-MS) was used for the qualitative and quantitative analysis of volatile DBPs. Identification of semi-volatile compounds was carried out with GC-MS, while gas chromatography with an atomic emission detector (GC-AED) was used for their quantification. A significant contribution of oxygen to the composition of semi-volatile compounds proves the decisive role of the dissolved organic matter oxidative destructive processes. Statistical analysis revealed notable linear correlations for trihalomethane and haloacetic acid formation vs. chlorine dose. On the contrary, halogenated semi-volatile products do not demonstrate any correlations with the water quality parameters or chlorine dose. Principal component analysis (PCA) placed them into separate groups. The results allow for proposing that formation of the organohalogenated species involved the fast penetration of bromine into the humic matter molecules and, further, their oxidative destruction by active chlorine.

Assessment of UV combined with free chlorine for removal of valsartan acid from water samples

Valsartan acid (VALA) is a persistent and mobile pollutant, ubiquitously distributed in the aquatic environment. Herein, we assessed the efficiency of UV/free chlorine for the removal of this pollutant. Degradation experiments were performed using different water samples, considering several pH values and concentrations of inorganic anions. Time-course of VALA was measured by injection of different reaction time aliquots in a liquid chromatography (LC) triple quadrupole (QqQ) mass spectrometry (MS) system, whilst the study of potential transformation products (TPs) was evaluated by LC combined with a hybrid quadrupole time-of-flight (QTOF) MS system. Formation of volatile disinfection by-products (DBPs) was investigated by gas chromatography (GC) with TOF-MS detection. Compared to free chlorine treatment and UV photolysis, the combination of both parameters significantly enhanced the degradability of VALA. At neutral pH, UV/free chlorine was also more effective than UV/H2O2 to remove VALA from spiked water solutions. Three TPs of VALA were tentatively identified by LC-QTOF-MS, although only one was stable in the UV/free chlorine media. As regards volatile DBPs, the formation of chloroform, dichloroacetonitrile, di- and trichloroacetic acid was noticed. The mass yield of DBPs formation from VALA varied from 0.3% (dichloroacetonitrile) to 1.1% (chloroform). The efficiency of UV/free chlorine was first investigated in spiked solutions with increasing complexities: ultrapure, river and treated wastewater. Thereafter, the feasibility of reducing VALA levels in polluted river water was demonstrated.

Non-volatile disinfection byproducts are far more toxic to mammalian cells than volatile byproducts

Water is often chlorinated to protect public health, but chlorination causes harmful disinfection byproducts to form. Currently available in vitro assays generally determine non-volatile disinfection byproduct (NVDBP) toxicities because of the limitation of pretreatments used, but chemical analyses and regulations are focused on volatile disinfection byproducts (VDBPs) such as trihalomethanes. The gap of VDBP toxicities have been of concern for some time. In this study, we extracted VDBPs from two chlorinated effluent organic matters and one chlorinated natural organic matter, using a helium aeration–liquid nitrogen condensation system, and systematically assessed the VDBP and NVDBP toxicities to mammalian cells. VDBPs accounted for 10%–20% of the total organic halogen concentrations in three chlorinated water samples. VDBPs were much less cytotoxic, caused fewer DNA double-strand breaks, induced less reactive oxygen species and DNA/RNA oxidative damage marker of 8-hydroxyl(deoxy)guanosine in cells than did NVDBPs. Moreover, by collecting the VDBPs, toxicity measurement of the full range of DBPs was achieved. Cytotoxicity, reactive oxygen species and 8-hydroxyl(deoxy)guanosine levels were significantly higher for cells exposed to the mixture of VDBPs and NVDBPs than only NVDBPs, but not by large percentages (20%–30% for cytotoxicity), suggesting NVDBPs mainly contributed to the toxicity of chlorinated water. Our study suggested that future research should focus more on NVDBP toxicity and identifying toxicity drivers from NVDBPs.

Volatile DBPs contributed marginally to the developmental toxicity of drinking water DBP mixtures against Platynereis dumerilii

Halogenated disinfection byproducts (DBPs) are formed during chlorine disinfection of drinking water. The complicated natural organic matter in source water causes the formation of an even more complicated mixture of DBPs. To evaluate the toxicity of a DBP mixture in a disinfected water sample, the sample needs to be pretreated in order to attain an observable acute adverse effect in the toxicity test. During sample pretreatment, volatile DBPs including trihalomethanes, haloacetonitriles and haloketones may be lost, which could affect the toxicity evaluation of the DBP mixture. In this study, we intentionally prepared “concentrated” simulated drinking water samples, which contained sufficiently high levels of volatile and nonvolatile DBPs and thus enabled directly evaluating the toxicity of the DBP mixtures without sample pretreatment. Specifically, the natural organic matter and bromide concentrations and the chlorine dose in the concentrated water samples were 250 times higher than those in a typical drinking water sample. Each concentrated water sample was divided into two aliquots, and one of them was nitrogen sparged to eliminate volatile DBPs; then, both aliquots were used directly in a well-established developmental toxicity test. No significant difference (p > 0.10) was found between the developmental toxicity indexes of each concentrated water sample without and with nitrogen sparging, indicating that the contribution of volatile DBPs to the developmental toxicity of the DBP mixture might be marginal. A reasonable interpretation is that nonvolatile halogenated DBPs (especially the aromatic ones) in the DBP mixture could be the major developmental toxicity contributor that warrants more attention.

+Chlorination by-products in indoor swimming pools: Development of a pilot pool unit and impact of operating parameters

Chlorine addition in swimming pools ensures the microbiological quality of the water and the bathers’ safety. However, water chlorination is associated with disinfection byproducts (DBP) formation and adverse health effects. The impact of operating parameters and innovative water treatment systems on DBPs levels has been reported in several studies, but sampling campaign in real pools remain difficult to carry out, mainly due to unexpected attendance variations. This study presents the development of a pilot pool plant allowing to perform experiments under controlled and reproducible conditions. Bathers inputs were simulated both for the organic load and for the mechanical agitation of water. Two sampling campaigns were performed during the building of the pilot, before and after the hall was closed. Key operating parameters such as chlorine dose, water temperature and attendance were controlled and monitored. DBP levels in the pilot plant were representative of French indoor swimming pools and the impact of bathers’ activity was visible on volatile DBPs. Furthermore, correlations could be stated between operating parameters and DBP levels. Stripping effectively reduced volatile DBP concentrations in water. Moreover, energy consumption data, which are usually very scarce in experimental studies, showed the influence of heat pump consumption on the global energy consumption.

Are workers on board vessels involved with chemicals from treated ballast water sufficiently protected? – A decadal perspective and risk assessment

Ballast Water Managements Systems (BWMS) installed on vessels may use Active Substances (AS) to inactivate organisms. This paper provides new insights in the global issue of noxious Disinfection By-Products (DBP) produced with primarily oxidant-based BWMS, and the risk assessment for workers, including port State control officers, while performing tasks on a vessel that involve exposure to treated ballast water. The Joint Group of Experts on the Scientific Aspects of Marine Environmental Protection – Ballast Water Working Group (GESAMP-BWWG) plays a role in the certification process of BWMS that make use of AS evaluating potential negative effects. All BWMS that passed GESAMP-BWWG Final Approval until mid 2019 were analyzed providing an overview of chemicals in the treated ballast water before and after neutralization. The ballast tank cleaning scenario, the sampling scenario, and the ballast tank inspection scenario all showed elevated human health risks using the Derived Minimal Effect Levels approach. The most critical exposure occurs in the ballast tank cleaning scenario through the inhalation of volatile DBP, such as tribromomethane. This substance may cause acute effects such as headache, dizziness and also has carcinogenic properties. The two risk reducing options available in the GESAMP-BWWG Tier 2 calculations were compared, one being mitigation measures such as protective gloves and coveralls, the other option is taking into account a time correction factor. The results showed that the trihalomethanes in air are most problematic, however, there is a possibility that the calculated values may be overestimated as generally worst case assumptions were used.

Impact of Different Combinations of Water Treatment Processes on the Concentration of Disinfection Byproducts and Their Precursors in Swimming Pool Water.

To mitigate microbial activity in swimming pools and to ensure hygienic safety for bathers, pool systems have a recirculating water system ensuring continuous water treatment and disinfection by chlorination. A major drawback associated with the use of chlorine as disinfectant is its potential to react with precursor substances present in pool water to form harmful disinfection byproducts (DBPs). In this study, different combinations of conventional and advanced treatment processes were applied to lower the concentration of DBPs and their precursors in pool water by using a pilot-scale swimming pool model operated under reproducible and fully controlled conditions. The quality of the pool water was determined after stationary concentrations of dissolved organic carbon (DOC) were reached. The relative removal of DOC (Δc cin-1) across the considered treatment trains ranged between 0.1 ± 2.9% and 7.70 ± 4.5%, where conventional water treatment (coagulation and sand filtration combined with granular activated carbon (GAC) filtration) was revealed to be the most effective. Microbial processes in the deeper, chlorine-free regions of the GAC filter have been found to play an important role in the degradation of organic substances. Almost all treatment combinations were capable of removing trihalomethanes to some degree and trichloramine and dichloroacetonitrile almost completely. However, the results demonstrated that effective removal of DBPs across the treatment train does not necessarily result in low DBP concentrations in the basin of a pool. This raises the importance of the DBP formation potential of the organic precursors, which has been shown to depend strongly on the treatment concept applied. Irrespective of the filtration technique employed, treatment combinations employing UV irradiation as a second treatment step revealed higher concentrations of volatile DBPs in the pool compared to those employing GAC filtration as a second treatment step. In the particular case of trichloramine, results confirm that its removal across the treatment train is not a feasible mitigation strategy because it cannot compensate for the fast formation in the basin.

Analysis of chlorination by‐products in swimming pool water by membrane introduction mass spectrometry – Influence of water physicochemical parameters

RationaleChlorine reacts in swimming pools with several compounds released by bathers to form disinfection by‐products (DBPs). Epidemiological studies have shown adverse effects on health associated with the exposure to DBPs present in indoor swimming pool atmosphere. DBPs analyses require the use of multiple techniques depending on the targeted molecules. The measurement process itself is challenging due to the low stability of several compounds and the lack of specificity of certain methods. The Membrane Introduction Mass Spectrometry (MIMS) technique provides a solution to these problems by specific and sensitive in situ measurement of DBPs. This study investigates the effect of analytical conditions on quantification of DBPs and assesses the relevance of using MIMS for reliable analysis under typical swimming pool operating conditions.MethodsMIMS is based on the simultaneous permeation of the selected compounds from the air or water samples through a polydimethylsiloxane (PDMS) membrane. DBPs are identified and quantified with a quadrupole analyzer after electron ionization. Limits of quantification (LOQs) of five DBPs are determined to assess the sensitivity of the system. Moreover, signal changes are monitored while varying physicochemical parameters such as temperature, pH and ionic strength.ResultsThe mass spectra obtained for individual molecules show that the simultaneous measurement of trihalomethanes (THMs) and chloramines requires the monitoring of several ions and mathematical corrections of the signal. The pH and ionic strength of the solution do not significantly influence the determination of THMs. On the contrary, the temperature and hydraulics at the membrane interface must be controlled for accurate determination of DBPs.ConclusionsResults confirm that MIMS is a promising technology for the simultaneous quantification of volatile DBPs in both water and air of swimming pools. However, operating conditions such as membrane temperature should be treated with great care in order to avoid interferences.

Modelling the concentration of chloroform in the air of a Norwegian swimming pool facility-A repeated measures study

Certain volatile disinfection by-products (DBPs) off-gassing from pool water can cause eye and skin irritations, respiratory problems, and even cancer. No guidelines or recommendations concerning DBPs in the air exist in Norway. Traditionally, ventilation strategies in indoor swimming pools are based on reducing condensation on the windows rather than ensuring proper air quality in the users' breathing zone.A total of 93 air samples of airborne concentrations of trihalomethanes (THMs) were collected via stationary sampling. We investigated the distribution of total THM (tTHM) 0.05 m and 0.60 m above the water surface at six different locations in the poolroom and the covariation between the water and air quality parameters. Based on a linear mixed effects model, the most important determinants in terms of predicting the air concentration of CHCl3 were height above water surface, air changes of fresh air per hour, concentration of combined chlorine in the water, relative humidity (RH) and day of the week. Approximately 36% of the total variability could be attributed to these variables; hence, to reduce the average exposure in the poolroom, hazard control should focus on these variables. Based on the identified predictor variables, the supplied air should be controlled based on water quality in addition to the traditional control censors for RH and air temperature used in the ventilation system of Norwegian swimming facilities.

Chlorotyrosines versus Volatile Byproducts from Chlorine Disinfection during Washing of Spinach and Lettuce.

Following the Food Safety Modernization Act of 2011 in the U.S., guidelines for disinfection washes in food packaging facilities are under consideration to control pathogen risks. However, disinfectant exposures may need optimization because the high concentrations of chlorine disinfectant promote the formation of high levels of disinfection byproducts (DBPs). When chlorine doses up through the 200 mg/L as Cl2 range relevant to the current practice were applied to spinach and lettuce, significant DBP formation was observed, even within 5 min at 7 °C. Concentrations of volatile chlorinated DBPs in washwater were far higher than typically observed in disinfected drinking water (e.g., 350 μg/L 1,1-dichloropropanone). However, these DBPs partitioned to the aqueous phase and so represent a greater concern for the disposal or reuse of washwater than for consumer exposure via food. The volatile DBPs represent the low-yield, final products of chlorination reactions with multiple biomolecular precursors. The initial, high-yield transformation products of such reactions may represent a greater concern for consumer exposure because they remain bound within the biopolymers in food and would be liberated during digestion. Using protein-bound tyrosine as an example precursor, the concentrations of the initial 3-chlorotyrosine and 3,5-dichlorotyrosine transformation products from this one precursor in the leaf phase were comparable to, and, in the case of some lettuces, exceeded, the aggregate aqueous concentration of volatile DBPs formed from multiple precursors. Chlorotyrosine formation increased when spinach was shredded due to the greater accessibility of chlorine to proteins in the leaf interiors. The cytotoxicity of chlorotyrosines to Chinese hamster ovary cells was higher than any of the trihalomethanes regulated in drinking water.

Facile fabrication of MIL-96 as coating fiber for solid-phase microextraction of trihalomethanes and halonitromethanes in water samples

Trihalomethanes (THMs) and halonitromethanes are the two most dominant categories of volatile disinfection by-products that pose considerable public health concerns. The pretreatment and determination methods of THMs in low concentrations, particularly trichloronitromethane (TCNM), have always been the focus of researchers. Metal-organic frameworks, which are effective adsorbents, have considerable potential for solid-phase microextraction (SPME) because of their tuned pore structure, large surface area, and high thermal and chemical stabilities. In this study, MIL-96 was successfully fabricated and developed as a coating fiber for SPME of THMs and TCNM in water samples. Several extraction parameters (i.e., extraction temperature, extraction time, stirring rate, pH, and ionic strength) and desorption parameters (i.e., temperature and time) were investigated and optimized in detail. Ionic strength, extraction temperature, and pH/desorption temperature were identified as key factors that affected the SPME efficiencies of THMs and TCNM. The developed method under optimal conditions obtained wide linearity (0.02–50 µg/L), low limits of detection (0.0030–0.0110 µg/L), and high enrichment factors (81–1181) for detecting THMs and TCNM. The spiked recoveries (1 and 10 µg/L) and relative standard deviations ranged from 81.0% to 109.9% and from 3.92% to 10.10%. Notably, the developed SPME method could overcome thermal degradation and showed excellent performance for TCNM. These results indicated the applicability of MIL-96 as coating fiber.

Bioanalytical assessment of adaptive stress responses in drinking water: A predictive tool to differentiate between micropollutants and disinfection by-products

Drinking water can contain low levels of micropollutants, as well as disinfection by-products (DBPs) that form from the reaction of disinfectants with organic and inorganic matter in water. Due to the complex mixture of trace chemicals in drinking water, targeted chemical analysis alone is not sufficient for monitoring. The current study aimed to apply in vitro bioassays indicative of adaptive stress responses to monitor the toxicological profiles and the formation of DBPs in three drinking water distribution systems in France. Bioanalysis was complemented with chemical analysis of forty DBPs. All water samples were active in the oxidative stress response assay, but only after considerable sample enrichment. As both micropollutants in source water and DBPs formed during treatment can contribute to the effect, the bioanalytical equivalent concentration (BEQ) approach was applied for the first time to determine the contribution of DBPs, with DBPs found to contribute between 17 and 58% of the oxidative stress response. Further, the BEQ approach was also used to assess the contribution of volatile DBPs to the observed effect, with detected volatile DBPs found to have only a minor contribution as compared to the measured effects of the non-volatile chemicals enriched by solid-phase extraction. The observed effects in the distribution systems were below any level of concern, quantifiable only at high enrichment and not different from bottled mineral water. Integrating bioanalytical tools and the BEQ mixture model for monitoring drinking water quality is an additional assurance that chemical monitoring is not overlooking any unknown chemicals or transformation products and can help to ensure chemically safe drinking water.