Monitoring iohexol and its transformation products as evidence of reclaimed water irrigation input to contiguous waterbodies.

Irrigation with reclaimed water alleviates water supply shortages, but excess application often results in impairment of contiguous waterbodies. This project investigated the potential use of iohexol, an iodinated contrast media used in medical imaging, together with its bio- and phototransformation products as unique reconnaissance markers of reclaimed water irrigation intrusion at three golf courses within the state of Florida. Inter-facility iohexol concentrations measured in reclaimed waters ranged over ~2 orders of magnitude while observed intra-facility seasonal differences were ≤1 order of magnitude. A ~50 % reduction in iohexol was observed post-disinfection for reclaimed water facilities utilizing UV light while none was observed with use of chlorine. Iohexol biotransformation products were observed to decline or shift to lower molecular weight compounds when exposed to UV light but not during disinfection using chlorine. Iohexol biotransformation products were observed in most of the samples but were more prevalent in samples collected during the dry season. Much fewer iohexol phototransformation products were observed in chlorinated reclaimed water, and they were only observed in UV light irradiated reclaimed water when the pre-disinfectant iohexol concentration was ≥5000 ng/L or from solar exposure of reclaimed water spiked with 10 µM of iohexol. For the Hillsborough golf course overlaying an aquifer, the groundwater did not contain iohexol or phototransformation products but did contain biotransformation products. It is not known if these biotransformation products are from active or historical intrusion. The additional presence of sucralose in the aquifer suggests that intrusion has occurred within the past 3 years. This study demonstrates three crucial points in attempting to utilize iohexol to denote reclaimed water intrusion from irrigation overapplication: (1) interpretable results are obtained when iohexol concentrations in the reclaimed water employed for irrigation are ≥1000 ng/L, with higher concentrations in the range of ≥5000 ng/L better able to meet analytical sensitivity requirements after further dilution or degradation in the environment; (2) it is beneficial to assess iohexol transformation products in tandem with iohexol monitoring to account for environmental transformations of iohexol during storage and transport to the receiving water of concern; and (3) inclusion of monitoring for sucralose, an artificial sweetener ubiquitous in wastewater sources that is comparatively stable in the environment, can aid in interpretating whether reclaimed water intrusion based on identification of iohexol and transformation products in the receiving water is attributable to historic or ongoing irrigation overapplications.

Combining Nontargeted Analysis with Computer-Based Hazard Comparison Approaches to Support Prioritization of Unregulated Organic Contaminants in Biosolids.

Biosolids are a byproduct of wastewater treatment that can be beneficially applied to agricultural land as a fertilizer. While U.S. regulations limit metals and pathogens in biosolids intended for land applications, no organic contaminants are currently regulated. Novel techniques can aid in detection, evaluation, and prioritization of biosolid-associated organic contaminants (BOCs). For example, nontargeted analysis (NTA) can detect a broad range of chemicals, producing data sets representing thousands of measured analytes that can be combined with computational toxicological tools to support human and ecological hazard assessment and prioritization. We combined NTA with a computer-based tool from the U.S. EPA, the Cheminformatics Hazard Comparison Module (HCM), to identify and prioritize BOCs present in U.S. and Canadian biosolids (n = 16). Four-hundred fifty-one features were detected in at least 80% of samples, with identities of 92 compounds confirmed or assigned probable structures. These compounds were primarily categorized as endogenous compounds, pharmaceuticals, industrial chemicals, and fragrances. Examples of top prioritized compounds were p-cresol and chlorophene, based on human health end points, and fludioxonil and triclocarban, based on ecological health end points. Combining NTA results with hazard comparison data allowed us to prioritize compounds to be included in future studies of the environmental fate and transport of BOCs.

(Non)targeted Chemical Analysis and Risk Assessment of Organic Contaminants in Darkibor Kale Grown at Rural and Urban Farms.

This study investigated the presence and human hazards associated with pesticides and other anthropogenic chemicals identified in kale grown in urban and rural environments. Pesticides and related compounds (i.e., surfactants and metabolites) in kale samples were evaluated using a nontargeted data acquisition for targeted analysis method which utilized a pesticide mixture containing >1,000 compounds for suspect screening and quantification. We modeled population-level exposures and assessed noncancer hazards to DEET, piperonyl butoxide, prometon, secbumeton, terbumeton, and spinosyn A using nationally representative estimates of kale consumption across life stages in the US. Our findings indicate even sensitive populations (e.g., pregnant women and children) are not likely to experience hazards from these select compounds were they to consume kale from this study. However, a strictly nontargeted chemical analytical approach identified a total of 1,822 features across all samples, and principal component analysis revealed that the kale chemical composition may have been impacted by agricultural growing practices and environmental factors. Confidence level 2 compounds that were ≥5 times more abundant in the urban samples than in rural samples (p < 0.05) included chemicals categorized as "flavoring and nutrients" and "surfactants" in the EPA's Chemicals and Products Database. Using the US-EPA's Cheminformatics Hazard Module, we identified that many of the nontarget compounds have predicted toxicity scores of "very high" for several end points related to human health. These aspects would have been overlooked using traditional targeted analysis methods, although more information is needed to ascertain whether the compounds identified through nontargeted analysis are of environmental or human health concern. As such, our approach enabled the identification of potentially hazardous compounds that, based on their hazard assessment score, merit follow-up investigations.

Extracting Structural Information from Physicochemical Property Measurements Using Machine Learning─A New Approach for Structure Elucidation in Non-targeted Analysis.

Non-targeted analysis (NTA) has made critical contributions in the fields of environmental chemistry and environmental health. One critical bottleneck is the lack of available analytical standards for most chemicals in the environment. Our study aims to explore a novel approach that integrates measurements of equilibrium partition ratios between organic solvents and water (KSW) to predictions of molecular structures. These properties can be used as a fingerprint, which with the help of a machine learning algorithm can be converted into a series of functional groups (RDKit fragments), which can be used to search chemical databases. We conducted partitioning experiments using a chemical mixture containing 185 chemicals in 10 different organic solvents and water. Both a liquid chromatography quadrupole time-of-flight mass spectrometer (LC-QTOF MS) and a LC-Orbitrap MS were used to assess the feasibility of the experimental method and the accuracy of the algorithm at predicting the correct functional groups. The two methods showed differences in log KSW with the QTOF method showing a mean absolute error (MAE) of 0.22 and the Orbitrap method 0.33. The differences also culminated into errors in the predictions of RDKit fragments with the MAE for the QTOF method being 0.23 and for the Orbitrap method being 0.31. Our approach presents a new angle in structure elucidation for NTA and showed promise in assisting with compound identification.

Bacteria exposed to antiviral drugs develop antibiotic cross-resistance and unique resistance profiles.

Antiviral drugs are used globally as treatment and prophylaxis for long-term and acute viral infections. Even though antivirals also have been shown to have off-target effects on bacterial growth, the potential contributions of antivirals to antimicrobial resistance remains unknown. Herein we explored the ability of different classes of antiviral drugs to induce antimicrobial resistance. Our results establish the previously unrecognized capacity of antivirals to broadly alter the phenotypic antimicrobial resistance profiles of both gram-negative and gram-positive bacteria Escherichia coli and Bacillus cereus. Bacteria exposed to antivirals including zidovudine, dolutegravir and raltegravir developed cross-resistance to commonly used antibiotics including trimethoprim, tetracycline, clarithromycin, erythromycin, and amoxicillin. Whole genome sequencing of antiviral-resistant E. coli isolates revealed numerous unique single base pair mutations, as well as multi-base pair insertions and deletions, in genes with known and suspected roles in antimicrobial resistance including those coding for multidrug efflux pumps, carbohydrate transport, and cellular metabolism. The observed phenotypic changes coupled with genotypic results indicate that bacteria exposed to antiviral drugs with antibacterial properties in vitro can develop multiple resistance mutations that confer cross-resistance to antibiotics. Our findings underscore the potential contribution of wide scale usage of antiviral drugs to the development and spread of antimicrobial resistance in humans and the environment.

Non-targeted analysis (NTA) and suspect screening analysis (SSA): a review of examining the chemical exposome.

Non-targeted analysis (NTA) and suspect screening analysis (SSA) are powerful techniques that rely on high-resolution mass spectrometry (HRMS) and computational tools to detect and identify unknown or suspected chemicals in the exposome. Fully understanding the chemical exposome requires characterization of both environmental media and human specimens. As such, we conducted a review to examine the use of different NTA and SSA methods in various exposure media and human samples, including the results and chemicals detected. The literature review was conducted by searching literature databases, such as PubMed and Web of Science, for keywords, such as "non-targeted analysis", "suspect screening analysis" and the exposure media. Sources of human exposure to environmental chemicals discussed in this review include water, air, soil/sediment, dust, and food and consumer products. The use of NTA for exposure discovery in human biospecimen is also reviewed. The chemical space that has been captured using NTA varies by media analyzed and analytical platform. In each media the chemicals that were frequently detected using NTA were: per- and polyfluoroalkyl substances (PFAS) and pharmaceuticals in water, pesticides and polyaromatic hydrocarbons (PAHs) in soil and sediment, volatile and semi-volatile organic compounds in air, flame retardants in dust, plasticizers in consumer products, and plasticizers, pesticides, and halogenated compounds in human samples. Some studies reviewed herein used both liquid chromatography (LC) and gas chromatography (GC) HRMS to increase the detected chemical space (16%); however, the majority (51%) only used LC-HRMS and fewer used GC-HRMS (32%). Finally, we identify knowledge and technology gaps that must be overcome to fully assess potential chemical exposures using NTA. Understanding the chemical space is essential to identifying and prioritizing gaps in our understanding of exposure sources and prior exposures. IMPACT STATEMENT: This review examines the results and chemicals detected by analyzing exposure media and human samples using high-resolution mass spectrometry based non-targeted analysis (NTA) and suspect screening analysis (SSA).

Optimization of a method for collecting infant and toddler urine for non-target analysis using cotton pads and commercially available disposable diapers.

BACKGROUND: Urine is an abundant and useful medium for measuring biomarkers related to chemical exposures in infants and children. Identification of novel biomarkers is greatly enhanced with non-targeted analysis (NTA), a powerful methodology for broad chemical analysis of environmental and biological specimens. However, collecting urine in non-toilet trained children presents many challenges, and contamination from specimen collection can impact NTA results. OBJECTIVES: We optimized a caregiver-driven method for collecting urine from infants and children using cotton pads and commercially available disposable diapers for NTA and demonstrate its applicability to various children biomonitoring studies. METHODS: Experiments were first performed to evaluate the effects of processing method (i.e., centrifuge vs. syringe), storage temperature, and diaper brand on recovery of urine absorbed to cotton pads. Caregivers of 11 children (<2 years) used and retained diapers (with cotton pads) to collect their child's urine for 24 h. Specimens were analyzed via a NTA method implementing an exclusion list of ions related to contamination from collection materials. RESULTS: Centrifuging cotton pads through a small-pore membrane, compared to a manual syringe method, and storing diapers at 4 °C, compared to room temperature, resulted in larger volumes of recovered sample. This method was successfully implemented to recover urine from cotton pads collected in the field; between 5-9 diapers were collected per child in 24 h, and the total mean volume of urine recovered was 44.7 (range 26.7-71.1) mL. NTA yielded a list of compounds present in urine and/or stool that may hold promise as biomarkers of chemical exposures from a variety of sources. IMPACT STATEMENT: Infant and children urine is a valuable matrix for studies of the early life exposome, in that numerous biological markers of exposure and outcome can be derived from a single analysis. Depending on the nature of the exposure study, it may be the case that a simple collection method that can be facilitated by caregivers of young children is desirable, especially when time-integrated samples or large volumes of urine are needed. We describe the process for development and results of an optimized method for urine collection and analysis using commercially available diapers and non-target analysis.

Implementing a suspect screening method to assess occupational chemical exposures among US-based hairdressers serving an ethnically diverse clientele: a pilot study.

BACKGROUND: There are over 700,000 hairdressers in the United States, and it is estimated that >90% are female and 31% are Black or Hispanic/Latina. Racial and ethnic minorities in this workforce may be exposed to a unique mixture of potentially hazardous chemicals from products used and services provided. However, previous biomonitoring studies of hairdressers target a narrow list of compounds and few studies have investigated exposures among minority hairdressers. OBJECTIVE: To assess occupational chemical exposures in a sample of US-based Black and Latina hairdressers serving an ethnically diverse clientele by analyzing urine specimens with a suspect screening method. METHODS: Post-shift urine samples were collected from a sample of US female hairdressers (n = 23) and office workers (n = 17) and analyzed via reverse-phase liquid chromatography coupled to high-resolution mass spectrometry. Detected compounds were filtered based on peak area differences between groups and matching with a suspect screening list. When possible, compound identities were confirmed with reference standards. Possible exposure sources were evaluated for detected compounds. RESULTS: The developed workflow allowed for the detection of 24 compounds with median peak areas ≥2x greater among hairdressers compared to office workers. Product use categories (PUCs) and harmonized functional uses were searched for these compounds, including confirmed compounds methylparaben, ethylparaben, propylparaben, and 2-naphthol. Most product use categories were associated with "personal use" and included 11 different "hair styling and care" product types (e.g., hair conditioner, hair relaxer). Functional uses for compounds without associated PUCs included fragrance, hair and skin conditioning, hair dyeing, and UV stabilizer. SIGNIFICANCE: Our suspect screening approach detected several compounds not previously reported in biomonitoring studies of hairdressers. These results will help guide future studies to improve characterization of occupational chemical exposures in this workforce and inform exposure and risk mitigation strategies to reduce potential associated work-related health disparities.

Assessing the fate of antibiotics and agrochemicals during anaerobic digestion of animal manure.

Antibiotics and pesticides are used extensively by the livestock industry. Agricultural chemicals can pose potential human and environmental health risks due to their toxicity and through their contributions to antimicrobial resistance, and strategies to reduce their emission into the environment are urgently needed. Anaerobic digestion (AD) is a sustainable technology for manure management that produces biogas while also providing an opportunity to degrade agricultural chemicals that are present in manure. While the effects of selected chemicals on biogas production have been investigated previously, little is known about chemical transformations during AD. Using lab-scale AD batch reactors containing dairy manure, degradation kinetics and transformation products (TPs) were investigated for twenty compounds that are likely to be present in manure management systems and that we hypothesized would transform during AD. Digestate samples were extracted using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method and analyzed using liquid chromatography - high-resolution mass spectrometry. Eleven of the tested chemicals degraded, leading to the formation of 47 TPs. Three compounds degraded abiotically only, two degraded biotically only, and six degraded both abiotically and biotically. These results suggest that in addition to renewable energy generation, AD contributes to the degradation of chemical contaminants present in agricultural waste streams. However, the potential toxic effects of TPs require further investigation.

Comparative investigation of PFAS adsorption onto activated carbon and anion exchange resins during long-term operation of a pilot treatment plant.

Widespread contamination of groundwater with per- and polyfluoroalkyl substances (PFAS) has required drinking water producers to quickly adopt practical and efficacious treatments to limit human exposure and deleterious health outcomes. This pilot-scale study comparatively investigated PFAS adsorption behaviors in granular activated carbon (GAC) and two strong-base gel anion exchange resin (AER) columns operated in parallel over a 441-day period to treat contaminated groundwater dominated by short-chain perfluorocarboxylic acids (PFCA). Highly-resolved breakthrough profiles of homologous series of 2-8 CF2 PFCA and perfluorosulfonic acids (PFSA), including ultrashort-chain compounds and branched isomers, were measured to elucidate adsorption trends. Sample ports at intermediate bed depths could predict 50% breakthrough of compounds on an accelerated basis, but lower empty bed contact times led to conservative estimates of initial breakthrough. Homologous PFAS series displayed linear (GAC) and log-linear (AER) relationships between chain-length and breakthrough, independent of initial concentration. AERs generally outperformed GAC on a normalized bed volume basis, and this advantage widened with increasing PFAS chain-length. As designed, all treatments would have short full-scale service times (≤142 days for GAC; ≤61 days for AERs) before initial breakthrough of short-chain (2-4 CF2) PFCA. However, AER displayed far longer breakthrough times for PFSA compared to GAC (>3× treatment time), and breakthrough was not observed for PFSA with >4 CF2 in AERs. GAC had a finite molar adsorption capacity for total PFAS, leading to a stoichiometric replacement of short-chain PFCA by PFSA and longer-chain PFCA over time. AERs quickly reached a finite adsorption capacity for PFCA, but they showed substantially greater selectivity for PFSA whose capacity was not reached within the duration of the pilot. Breakthrough characteristics of keto- and unsaturated-PFSA, identified in the groundwater by suspect screening, were also evaluated in absence of reference standards. Modified PFAS structures (branched, keto-, unsaturated-) broke through faster than linear and unmodified perfluorinated structures with equal degrees of fluorination, and the effects were more pronounced in GAC compared to AERs. The results highlight that the design of robust PFAS treatment systems should consider facets beyond current PFAS targets including operational complexities and impacts of unregulated and unmonitored co-contaminants.

Chlorination of para-substituted phenols: Formation of α, ß-unsaturated C4-dialdehydes and C4-dicarboxylic acids.

Despite the widespread occurrence of phenols in anthropogenic and natural compounds, their fate in reactions with hypochlorous acid (HOCl), one of the most common water treatment disinfectants, remains incompletely understood. To close this knowledge gap, this study investigated the formation of disinfection by-products (DBPs) in the reaction of free chlorine with seven para-substituted phenols. Based on the chemical structures of the DBPs and the reaction mechanisms leading to their formation, the DBPs were categorized into four groups: chlorophenols, coupling products, substituent reaction products, and ring cleavage products. In contrast to previous studies that investigated the formation of early-stage chlorophenols, the primary focus of this study was on the elucidation of novel ring cleavage products, in particular α, ß-unsaturated C4-dialdehydes, and C4-dicarboxylic acids, which, for the first time, were identified and quantified in this study. The molar yields of 2-butene-1,4-dial (BDA), one of the identified α, ß-unsaturated C4-dialdehydes, varied among the different phenolic compounds, reaching a maximum value of 10.4% for bisphenol S. Molar yields of 2-chloromaleic acid (Cl-MA), one of the identified C4-dicarboxylic acids, reached a maximum value of 30.5% for 4-hydroxy-phenylacetic acid under given conditions. 2,4,6-trichlorophenol (TCP) was shown to be an important intermediate of the parent phenols and the C4-ring cleavage products. Based on the temporal trends of α, ß-unsaturated C4-dialdehydes and C4-dicarboxylic acids, their formation is likely attributable to two separate ring cleavage pathways. Based on the obtained results, an overall transformation pathway for the reaction of para-substituted phenols with free chlorine leading to the formation of novel C4 ring cleavage products was proposed.

Adaptation of selected models for describing competitive per- and polyfluoroalkyl substances breakthrough curves in groundwater treated by granular activated carbon.

Granular activated carbon (GAC) has proven to be a successful technology for per- and polyfluoroalkyl substances (PFAS) removal from contaminated drinking water supplies. Proper design of GAC treatment relies upon characterization of media service-life, which can change significantly depending on the PFAS contamination, treatment media, and water quality, and is often determined by fitting descriptive models to breakthrough curves. However, while common descriptive breakthrough models are favored for their ease-of-use, they have a significant shortcoming in that they are not able to properly fit PFAS desorption in competitive sorption scenarios. The present work adapts three common descriptive models to fit competitive PFAS breakthrough curves from a GAC pilot study. The adapted and original models were fit to the experimental breakthrough curves for 12 common PFAS and evaluated using adjusted R2 and reduced χ2 values. This study found that the novel adaptation of the common descriptive models successfully accounted for desorption of PFAS compounds from the GAC, accurately describing increased exposure risks due to elevated effluent levels during desorption without significantly increasing the complexity of implementing the models.

Characterizing the Chemical Landscape in Commercial E-Cigarette Liquids and Aerosols by Liquid Chromatography-High-Resolution Mass Spectrometry.

The surge in electronic cigarette (e-cig) use in recent years has raised questions on chemical exposures that may result from vaping. Previous studies have focused on measuring known toxicants, particularly those present in traditional cigarettes, while fewer have investigated unknown compounds and transformation products formed during the vaping process in these diverse and constantly evolving products. The primary aim of this work was to apply liquid chromatography-high-resolution mass spectrometry (LC-HRMS) and chemical fingerprinting techniques for the characterization of e-liquids and aerosols from a selection of popular e-cig products. We conducted nontarget and quantitative analyses of tobacco-flavored e-liquids and aerosols generated using four popular e-cig products: one disposable, two pod, and one tank/mod. Aerosols were collected using a condensation device and analyzed in solution alongside e-liquids by LC-HRMS. The number of compounds detected increased from e-liquids to aerosols in three of four commercial products, as did the proportion of condensed-hydrocarbon-like compounds, associated with combustion. Kendrick mass defect analysis suggested that some of the additional compounds detected in aerosols belonged to homologous series resulting from decomposition of high-molecular-weight compounds during vaping. Lipids in inhalable aerosols have been associated with severe respiratory effects, and lipid-like compounds were observed in aerosols as well as e-liquids analyzed. Six potentially hazardous additives and contaminants, including the industrial chemical tributylphosphine oxide and the stimulant caffeine, were identified and quantified in the e-cig liquids and aerosols analyzed. The obtained findings demonstrate the potential of nontarget LC-HRMS to identify previously unknown compounds and compound classes in e-cig liquids and aerosols, which is critical for the assessment of chemical exposures resulting from vaping.

Aqueous ozonation of furans: Kinetics and transformation mechanisms leading to the formation of α,ß-unsaturated dicarbonyl compounds.

Despite the widespread occurrence of furan moieties in synthetic and natural compounds, their fate in aqueous ozonation has not been investigated in detail. Reaction rate constants of seven commonly used furans with ozone were measured and ranged from kO3 = 8.5 × 104 to 3.2 × 106 M-1 s-1, depending on the type and position of furan ring substituents. Transformation product analysis of the reaction of furans with ozone focusing on the formation of toxic organic electrophiles using a novel amino acid reactivity assay revealed the formation of α,ß-unsaturated dicarbonyl compounds, 2-butene-1,4-dial (BDA) and its substituted analogues (BDA-Rs). Their formation can be attributed to ozone attack at the reactive α-C position leading to furan ring opening. The molar yields of α,ß-unsaturated dicarbonyl compounds varied with the applied ozone concentration reaching maximum values of 7% for 2-furoic acid. The identified α,ß-unsaturated dicarbonyls are well-known toxicophores that are also formed by enzymatic oxidation of furans in the human body. In addition to providing data on kinetics, transformation product analysis and proposed reaction mechanisms for the ozonation of furans, this study raises concern about the presence of α,ß-unsaturated dicarbonyl compounds in water treatment and the resulting effects on human and environmental health.

Ozonation products of zidovudine and thymidine in oxidative water treatment.

Ozonation is an advanced treatment technology that is increasingly used for the removal of organic micropollutants from wastewater and drinking water. However, reaction of organic compounds with ozone can also result in the formation of toxic transformation products. In the present study, the degradation of the antiviral drug zidovudine during ozonation was investigated. To obtain further insights into the reaction mechanisms and pathways, results of zidovudine were compared with the transformation of the naturally occurring derivative thymidine. Kinetic experiments were accompanied by elucidation of formed transformation products using lab-scale batch experiments and subsequent liquid chromatography - high resolution mass spectrometry (LC-HRMS) analysis. Degradation rate constants for zidovudine with ozone in the presence of t-BuOH as radical scavenger varied between 2.8 ∙ 104 M-1 s-1 (pH 7) and 3.2 ∙ 104 M-1 s-1 (pH 3). The structural difference of zidovudine to thymidine is the exchange of the OH-moiety by the azide function at position 3'. In contrast to inorganic azide, no reaction with ozone was observed for the organic bound azide. In total, nine transformation products (TPs) were identified for both zidovudine and thymidine. Their formation can be attributed to the attack of ozone at the C-C-double bond of the pyrimidine-base. As a result of rearrangements, the primary ozonide decomposed in three pathways forming two different TPs, including hydroperoxide TPs. Rearrangement reactions followed by hydrolysis and subsequent release of H2O2 further revealed a cascade of TPs containing amide moieties. In addition, a formyl amide riboside and a urea riboside were identified as TPs indicating that oxidations of amide groups occur during ozonation processes.

Enhanced Treatment of Municipal Wastewater Effluents by Fe-TAML/H2O2: Efficiency of Micropollutant Abatement.

Combining iron with a tetraamido-macrocyclic ligand (Fe-TAML) as a catalyst and with hydrogen peroxide (H2O2) as the bulk oxidant is a process that has been suggested for the oxidative abatement of micropollutants during water treatment. In this study, the reactivity of the Fe-TAML/H2O2 system was evaluated by investigating the degradation of a group of electron-rich organic model compounds with different functional groups in a secondary wastewater effluent. Phenolic compounds and a polyaromatic ether are quickly and substantially abated by Fe-TAML/H2O2 in a wastewater effluent. For tertiary amines, a moderate rate of abatement was observed. Primary and secondary amines, aromatic ethers, aromatic aldehydes, and olefins are oxidized too slowly in the investigated Fe-TAML/H2O2 systems to be significantly abated in a secondary wastewater effluent. Trichlorophenol is readily oxidized to chloromaleic acid and chlorofumaric acid, which support a one-electron transfer reaction as the initial step of the reaction between Fe-TAML/H2O2 and the target compound. Fe-TAML/H2O2 does not oxidize bromide to hypobromous acid; however, iodide is oxidized to hypoiodous acid, and as a consequence, the H2O2 consumption is accelerated by a catalytic reaction in iodide-containing water. Overall, Fe-TAML/H2O2 is a rather selective oxidant, which makes it an interesting system for the abatement of electron-rich phenolic-type pollutants.

Reactivity-directed analysis - a novel approach for the identification of toxic organic electrophiles in drinking water.

Drinking water consumption results in exposure to complex mixtures of organic chemicals, including natural and anthropogenic chemicals and compounds formed during drinking water treatment such as disinfection by-products. The complexity of drinking water contaminant mixtures has hindered efforts to assess associated health impacts. Existing approaches focus primarily on individual chemicals and/or the evaluation of mixtures, without providing information about the chemicals causing the toxic effect. Thus, there is a need for the development of novel strategies to evaluate chemical mixtures and provide insights into the species responsible for the observed toxic effects. This critical review introduces the application of a novel approach called Reactivity-Directed Analysis (RDA) to assess and identify organic electrophiles, the largest group of known environmental toxicants. In contrast to existing in vivo and in vitro approaches, RDA utilizes in chemico methodologies that investigate the reaction of organic electrophiles with nucleophilic biomolecules, including proteins and DNA. This review summarizes the existing knowledge about the presence of electrophiles in drinking water, with a particular focus on their formation in oxidative treatment systems with ozone, advanced oxidation processes, and UV light, as well as disinfectants such as chlorine, chloramines and chlorine dioxide. This summary is followed by an overview of existing RDA approaches and their application for the assessment of aqueous environmental matrices, with an emphasis on drinking water. RDA can be applied beyond drinking water, however, to evaluate source waters and wastewater for human and environmental health risks. Finally, future research demands for the detection and identification of electrophiles in drinking water via RDA are outlined.

Formation and Fate of Carbonyls in Potable Water Reuse Systems.

Low molecular weight, uncharged compounds have been the subject of considerable study at advanced treatment plants employed for potable water reuse. However, previously identified compounds only account for a small fraction of the total dissolved organic carbon remaining after reverse osmosis treatment. Uncharged carbonyl compounds (e.g., aldehydes and ketones) formed during oxidation have rarely been monitored in potable water reuse systems. To determine the relative importance of these compounds to final product water quality, samples were collected from six potable water reuse facilities and one conventional drinking water treatment plant. Saturated carbonyl compounds (e.g., formaldehyde, acetone) and α,ß-unsaturated aldehydes (e.g., acrolein, crotonaldehyde) were quantified with a sensitive new analytical method. Relatively high concentrations of carbonyls (i.e., above 7 µM) were observed after ozonation of wastewater effluent. Biological filtration reduced concentrations of carbonyls by over 90%. Rejection of the carbonyls during reverse osmosis was correlated with molecular weight, with concentrations decreasing by 33% to 58%. Transformation of carbonyls resulted in decreases in concentration of 10% to 90% during advanced oxidation, with observed decreases consistent with rate constants for reactions of the compounds with hydroxyl radicals. Overall, carbonyl compounds accounted for 19% to 38% of the dissolved organic carbon in reverse osmosis-treated water.