Insight into the chemical transformation and organic release of polyurethane microplastics during chlorination.

The ubiquitous occurrence of microplastics in water and wastewater is a growing concern. In this study, the chemical transformation and organic release of virgin and UV-aged thermoplastic polyurethane (TPU) polymers during chlorination were investigated. As compared to virgin TPU polymer, the UV-aged TPU polymer exhibited high chlorine reactivity with noticeable destruction on its surface functional groups after chlorination, which could be ascribed to the UV-induced activation of hard segment of TPU backbone and increased contact area. The concentrations of leached organics increased by 1.6-fold with obviously high abundances of low-molecular-weight components. Additives, monomers, compounds relating to TPU chain extension, and their chlorination byproducts contributed to the increased organic release. Meanwhile, the formation of chloroform, haloacetic acids, trichloroacetaldehyde, and dichloroacetonitrile increased by 3.8-, 1.7-, 4.9-, and 2.4-fold, respectively. Two additives and six chlorination byproducts in leachate from chlorinated UV-aged TPU were predicted as highly toxic, e.g., butyl octyl phthalate, palmitic acid, 2,6-di-tert-butyl-1,4-benzoquinone, and chlorinated aniline. Evaluated by human hepatocarcinoma cells, the 50% lethal concentration factor of organics released from chlorinated UV-aged TPU was approximately 10% of that from its virgin counterpart, indicating a substantially increased level of cytotoxicity. This study highlights that the release of additives and chlorination byproducts from the chemical transformation of UV-aged microplastics during chlorination may be of potentially toxic concern.

Effects of organic additives on spectroscopic and molecular-level features of photo-induced dissolved organic matter from microplastics.

The environmental occurrence and impact of dissolved organic matter leached from microplastics (MP-DOM) has been the subject of increased research interest. Commercial plastics, which typically contain additives, are subject to natural weathering processes and can eventually lose their additives. However, the effects of organic additives in commercial microplastics (MPs) on the release of MP-DOM under UV irradiation remain poorly understood. In this study, four polymer MPs (polyethylene; PE, polypropylene; PP, polystyrene; PS, polyvinylchloride; PVC) and four commercial MPs, including a PE zip bag, a PP facial mask, a PVC sheet, Styrofoam, were subjected to leaching under UV irradiation, and the MP-DOM was characterized using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and fluorescence excitation emission matrix-parallel factor analysis (EEM-PARAFAC). Although UV light promoted the leaching of MP-DOM from both MP groups, the amount released was more pronounced for the polymer MPs than for the commercial MPs. The commercial MP-DOM was characterized by a prominent protein/phenol-like component (C1), while a humic-like component (C2) prevailed in the polymer MPs. FT-ICR-MS identified a higher number of unique molecular formulas for the commercial than for the polymer MP-DOM. The unique molecular formulas of commercial MP-DOM included known organic additives and other breakdown products, while the polymer MP-DOM featured more pronounced unsaturated carbon structures in its identified unique formulas. Several molecular-level parameters showed significant correlations with fluorescence properties, such as CHO formulas (%) with C1 and condensed aromatic structure (CAS-like, %) with C2, suggesting the potential application of fluorescent components as an optical descriptor for the complex molecular-level composition. This study also revealed the possible high environmental reactivity of both polymer MPs and fully weathered plastics due to the unsaturated structures generated in sunlit environments.

Removal of halides from drinking water: technological achievements in the past ten years and research needs.

Disinfection is an essential process for drinking water supplies resulting in the formation of unintended disinfection by-products (DBPs), many of which are potentially toxic and are known as the possible or probable human carcinogens. As of now, 100+ DBPs were characterized while about 600+ others can be formed in the supply water. To protect the human health, many regulatory agencies have set the guideline values for several DBPs. Removal of halide ions and natural organic matter prior to disinfection is an important step to reduce DBPs, and the associated exposure and risks. To date, many publications have reported various methods for halide removal from drinking water. The most review about halide removal technologies, associated challenges, and future research needs was published in 2012. Since then, a number of studies have been published on different methods of halide removal techniques. This paper aims to review the state of research on halide removal techniques focusing on the development during the past 10 years (2012-2021). The techniques were clustered into six major groups: adsorption, ion exchange, coagulation, advanced oxidation, membrane separation, and combined techniques. The progress on these groups of technologies, their advantages, and limitations were examined, and the future research directions to produce the safe drinking water were identified.

Impact of biological wastewater treatment on the reactivity of N-Nitrosodimethylamine precursors.

N-Nitrosodimethylamine (NDMA) is a probable human carcinogen which forms during chloramination of wastewater-impacted drinking waters. Municipal wastewater effluents are considered as major sources of NDMA precursors affecting downstream water quality. To evaluate the deactivation mechanisms and efficiencies of NDMA precursors during secondary treatment with the activated sludge (AS) process, NDMA formation potentials (FPs) of selected model precursor compounds and sewage components (i.e., blackwaters and greywaters) were monitored in batch AS treatment tests. After 24-h incubation with four different types of AS (i.e., domestic rural, domestic urban, textile and lab-grown AS), NDMA FP of trimethylamine (TMA) and minocycline (MNCL) decreased by 77-100%, while there was only 29-46% reduction in NDMA FP of sumatriptan (SMTR). The reduction in NDMA FP associated with ranitidine (RNTD) varied between 34% and 87%. The decrease in NDMA FP of RNTD depended on the AS type, hydraulic retention time (HRT) and solids retention time (SRT). The domestic AS (rural and urban) achieved higher decreases in NDMA FPs of the tested model precursors than the textile AS or lab-grown AS. Increasing the HRT or SRT enhanced NDMA FP decrease for RNTD. Among different processes tested (i.e., biodegradation, biosorption and volatilization), biosorption was the major mechanism responsible for the NDMA FP decrease of RNTD, MNCL and SMTR, while biodegradation was the major NDMA FP reduction mechanism for TMA. The reduction in NDMA FP of RNTD via biodegradation depended on the AS activity which may vary with sampling seasons and SRT. NDMA FPs in all tested sewage components (i.e., blackwaters and greywaters) decreased after 24-h AS treatment. Urine in blackwater was the predominant (i.e., >90%) contributor to NDMA FP in domestic sewage and AS-treated effluents.

Removal of N-nitrosodimethylamine precursors by cation exchange resin: The effects of pH and calcium.

Cation exchange resins have proved to be efficient in removing precursors of N-nitrosodimethylamine (NDMA). NDMA is a probable human carcinogen with a calculated lifetime cancer risk of 10-6 at 0.7 ng/L in drinking water. This paper investigated the effect of pH and calcium levels on the removal of NDMA precursors using a cation exchange resin. At pH 5 and 7, 30-50% of NDMA precursors, measured by formation potentials (FPs) changes before and after the treatment, were removed by Plus resin. However, increases in NDMA FPs were observed after the treatment at pH 10 indicating that NDMA precursors were released from the resin. NDMA FPs removals in samples containing 15 and 115 mg/L Ca2+ were 40% and -10% after the ion exchange treatments at pH 7, respectively. It was found that in the presence of high concentration of calcium only one out of four cation exchange resins released NDMA precursors (probably due to manufacturing impurities). Also, the release of NDMA precursors depended on the calcium concentration and the contact time of the resin with the solution containing calcium. Nonetheless, NDMA precursors release from the resin subsided significantly with increasing the number of regeneration cycles of the resin.

The role of chloramine species in NDMA formation.

N-nitrosodimethylamine (NDMA), a probable human carcinogen disinfection by-product, has been detected in chloraminated drinking water systems. Understanding its formation over time is important to control NDMA levels in distribution systems. The main objectives of this study were to investigate the role of chloramine species (i.e., monochloramine and dichloramine); and the factors such as pH, sulfate, and natural organic matter (NOM) influencing the formation of NDMA. Five NDMA precursors (i.e., dimethylamine (DMA), trimethylamine (TMA), N,N-dimethylisopropylamine (DMiPA), N,N-dimethylbenzylamine (DMBzA), and ranitidine (RNTD)) were carefully selected based on their chemical structures and exposed to varying ratios of monochloramine and dichloramine. All amine precursors reacted relatively fast to form NDMA and reached their maximum NDMA yields within 24 h in the presence of excess levels of chloramines (both mono- and dichloramine) or excess levels of dichloramine conditions (with limited monochloramine). When the formation of dichloramine was suppressed (i.e., only monochloramine existed in the system) over the 5 day contact time, NDMA formation from DMA, TMA, and DMiPA was drastically reduced (∼0%). Under monochloramine abundant conditions, however, DMBzA and RNTD showed 40% and 90% NDMA conversions at the end of 5 day contact time, respectively, with slow formation rates, indicating that while these amine precursors react preferentially with dichloramine to form NDMA, they can also react with monochloramine in the absence of dichloramine. NOM and pH influenced dichloramine levels that affected NDMA yields. NOM had an adverse effect on NDMA formation as it created a competition with NDMA precursors for dichloramine. Sulfate did not increase the NDMA formation from the two selected NDMA precursors. pH played a key role as it influenced both chloramine speciation and protonation state of amine precursors and the highest NDMA formation was observed at the pH range where dichloramine and deprotonated amines coexisted. In selected natural water and wastewater samples, dichloramine led to the formation of more NDMA than monochloramine.

Removal of both N-nitrosodimethylamine and trihalomethanes precursors in a single treatment using ion exchange resins.

Drinking water utilities are relying more than ever on water sources impacted by wastewater effluents. Disinfection/oxidation of these waters during water treatment may lead to the formation of several disinfection by-products, including the probable human carcinogen N-nitrosodimethylamine (NDMA) and the regulated trihalomethanes (THMs). In this study, the potential of ion exchange resins to control both NDMA and THMs precursors in a single treatment is presented. Two ion exchange resins were examined, a cation exchange resin (Plus) to target NDMA precursors and an anion exchange resin (MIEX) for THMs precursors control. We applied the resins, individually and combined, in the treatment of surface and wastewater effluent samples. The treatment with both resins removed simultaneously NDMA (43-85%) and THMs (39-65%) precursors. However, no removal of NDMA precursors was observed in the surface water with low initial NDMA FP (14 ng/L). The removals of NDMA FP and THMs FP with Plus and MIEX resins applied alone were (49-90%) and (41-69%), respectively. These results suggest no interaction between the resins, and thus the feasibility of effectively controlling NDMA and THMs precursors concomitantly. Additionally, the effects of the wastewater impact and the natural attenuation of precursors were studied. The results showed that neither the wastewater content nor the attenuation of the precursor affected the removals of NDMA and THMs precursors. Finally, experiments using a wastewater effluent sample showed that an increase in the calcium concentration resulted in a reduction in the removal of NDMA precursors of about 50%.

Wildfire altering terrestrial precursors of disinfection byproducts in forest detritus.

Wildfire occurrence and intensity are increasing worldwide causing severe disturbances to forest watersheds used for potable water supply. The effects of wildfire on drinking water quality are not well understood, especially in terms of terrestrial dissolved organic matter (DOM) and DOM-associated formation of disinfection byproducts (DBP). As the forest floor layer is a major source of terrestrial DOM, we investigated characteristics and DBP formation of water extractable organic matter (WEOM) from the 0-5 cm depth of nonburned detritus (control) and burned detritus with black ash (moderate severity) and white ash (high severity) associated with the 2013 Rim Fire in California. Spectroscopic results suggested that the aromaticity of WEOM followed white ash > control > black ash and fluorescence region II (excitation 220-250 nm; emission 330-380 nm) of the emission-excitation-matrix was identified as a potential burn severity indicator. Compared to the control, WEOM from white and black ashes had lower reactivity in forming trihalomethanes (55%-of-control) and haloacetic acids (67%-of-control), but higher reactivity in forming the more carcinogenic haloacetonitrile after chlorination (244%-of-control) and N-nitrosodimethylamine after chloramination (229%-of-control). There was no change in reactivity for chloral hydrate formation, while WEOM from black ash showed a higher reactivity for haloketone formation (150%-of-control). Because wildfire consumed a large portion of organic matter from the detritus layer, there was lower water extractable organic carbon (27%-of-control) and organic nitrogen (19%-of-control) yields in ashes. Consequently, the wildfire caused an overall reduction in water extractable terrestrial DBP precursor yield from detritus materials.

The effect of pre-oxidation on NDMA formation and the influence of pH.

N-nitrosodimethylamine (NDMA), a probable human carcinogen, is a disinfection by-product that has been detected in chloraminated drinking water systems. Pre-oxidation of the NDMA precursors prior to chloramination can be a viable approach for water utilities to control the NDMA levels. This study examined the effects of (i) commonly used oxidants (i.e., chlorine, chlorine dioxide and ozone) in water treatment, (ii) oxidant concentration and contact time (CT), and (iii) pre-oxidation pH on the formation of NDMA from subsequent chloramination. Fifteen model precursors with NDMA molar yields ranging from approximately 0.1%-90% were examined. Pre-chlorination reduced NDMA formation from most precursors by 10%-50% except quaternary amine polymers (i.e., PolyDADMAC, PolyACRYL, PolyAMINE). Pre-oxidation with chlorine dioxide and ozone achieved the same or higher deactivation of NDMA precursors (e.g., ranitidine) while increasing NDMA formation for some other precursors (e.g., daminozid). The increases with chlorine dioxide exposure were attributed to the release of oxidation products with dimethylamine (DMA) moiety, which may form more NDMA upon chloramination than the unoxidizied parent compound. On the other hand, chlorine dioxide was effective, if a precursors NDMA yield were higher than DMA. The ozone-triggered increases could be related to direct NDMA formation from DMA which are released by ozonation of amines with DMA moiety, amides or hydrazines. However, hydroxyl radicals formed from the decomposition of ozone would be also involved in decomposition of formed NDMA, reducing the overall NDMA levels at longer contact times. pH conditions influenced significantly the effectiveness of deactivation of precursors depending on the type of precursor and oxidant used.

Formation mechanism of NDMA from ranitidine, trimethylamine, and other tertiary amines during chloramination: a computational study.

Chloramination of drinking waters has been associated with N-nitrosodimethylamine (NDMA) formation as a disinfection byproduct. NDMA is classified as a probable carcinogen and thus its formation during chloramination has recently become the focus of considerable research interest. In this study, the formation mechanisms of NDMA from ranitidine and trimethylamine (TMA), as models of tertiary amines, during chloramination were investigated by using density functional theory (DFT). A new four-step formation pathway of NDMA was proposed involving nucleophilic substitution by chloramine, oxidation, and dehydration followed by nitrosation. The results suggested that nitrosation reaction is the rate-limiting step and determines the NDMA yield for tertiary amines. When 45 other tertiary amines were examined, the proposed mechanism was found to be more applicable to aromatic tertiary amines, and there may be still some additional factors or pathways that need to be considered for aliphatic tertiary amines. The heterolytic ONN(Me)2-R(+) bond dissociation energy to release NDMA and carbocation R(+) was found to be a criterion for evaluating the reactivity of aromatic tertiary amines. A structure-activity study indicates that tertiary amines with benzyl, aromatic heterocyclic ring, and diene-substituted methenyl adjacent to the DMA moiety are potentially significant NDMA precursors. The findings of this study are helpful for understanding NDMA formation mechanism and predicting NDMA yield of a precursor.

The roles of tertiary amine structure, background organic matter and chloramine species on NDMA formation.

N-nitrosodimethylamine (NDMA), a probable human carcinogen, is a disinfection by-product that has been detected in chloraminated and chlorinated drinking waters and wastewaters. Formation mechanisms and precursors of NDMA are still not well understood. The main objectives of this study were to systematically investigate (i) the effect of tertiary amine structure, (ii) the effect of background natural organic matter (NOM), and (iii) the roles of mono vs. dichloramine species on the NDMA formation. Dimethylamine (DMA) and 20 different tertiary aliphatic and aromatic amines were carefully examined based on their functional groups attached to the basic DMA structure. The wide range (0.02-83.9%) of observed NDMA yields indicated the importance of the structure of tertiary amines, and both stability and electron distribution of the leaving group of tertiary amines on NDMA formation. DMA associated with branched alkyl groups or benzyl like structures having only one carbon between the ring and DMA structure consistently gave higher NDMA yields. Compounds with electron withdrawing groups (EWG) reacted preferentially with monochloramine, whereas compounds with electron donating group (EDG) showed tendency to react with dichloramine to form NDMA. When the selected amines were present in NOM solutions, NDMA formation increased for compounds with EWG while decreased for compounds with EDG. This impact was attributed to the competitions between NOM and amines for chloramine species. The results provided additional information to the commonly accepted mechanism for NDMA formation including chloramine species reacting with tertiary amines and the role of the leaving group on overall NDMA conversion.

The effects of pH, bromide and nitrite on halonitromethane and trihalomethane formation from amino acids and amino sugars.

In this study, the effects of pH, bromide and nitrite on the formation of halonitromethanes (HNMs) and trihalomethanes (THMs) from eight amino acids (glycine, alanine, serine, cysteine, aspartic acid, glutamic acid, lysine and histidine) and four amino sugars (glucosamine, galactosamine, N-acetylglucosamine and N-acetylneuraminic acid) were examined for chlorination and ozonation followed by chlorination. During ozonation-chlorination, two amino acids, glycine and lysine, exhibited distinctly higher HNM formation than the other compounds. The formation of HNMs was higher at pH 8 than 6. Glycine and lysine also produced higher levels of THMs than the other compounds at pH 8. The presence of nitrite resulted in an increase in HNM formation. The presence of bromide increased the HNM formation, especially brominated HNM species. Bromine incorporation factors of trihalogenated HNMs were higher than those of THMs. For chlorination alone, HNM levels were about the detection limit (4 nM or 0.7 µg L(-1)) at pH 6 and 8, and in the presence of bromide or nitrite. Amino acids and amino sugars tested, except glycine and lysine, showed relatively low levels of THM (~15 µg L(-1)) formation.

Trichloroethylene adsorption by fibrous and granular activated carbons: aqueous phase, gas phase, and water vapor adsorption studies.

The important adsorption components involved in the removal of trichloroethylene (TCE) by fibrous and granular activated carbons from aqueous solutions were systematically examined. Namely, adsorption of TCE itself (i.e., TCE vapor isotherms), water molecules (i.e., water vapor isotherms), and TCE in water (i.e., TCE aqueous phase isotherms) were studied, side-by-side, using 20 well-characterized surface-modified activated carbons. The results showed that TCE molecular size and geometry, activated carbon surface hydrophilicity, pore volume, and pore size distribution in micropores control adsorption of TCE at relatively dilute aqueous solutions. TCE adsorption increased as the carbon surface hydrophilicity decreased and the pore volume in micropores of less than 10 A, especially in the 5-8 A range, increased. TCE molecules appeared to access deep regions of carbon micropores due to their flat geometry. The results indicated that characteristics of both adsorbate (i.e., the molecular structure, size, and geometry) and activated carbon (surface hydrophilicity, pore volume, and pore size distribution of micropores) control adsorption of synthetic organic compounds from water and wastewaters. The important micropore size region for a target compound adsorption depends on its size and geometry.

Performance of a hybrid reverse osmosis-constructed wetland treatment system for brackish oil field produced water.

Using constructed wetlands, produced waters from oil fields (i.e., waters that have been in contact with oil in situ) can be treated to enhance water quality for irrigation purposes, or subsequent discharge to receiving aquatic systems. In produced water containing elevated levels of salt (i.e., brackish-produced waters), the ability to decrease the conductivity of the produced water may influence potential reuse of the water for irrigation purposes. The objectives of this research were (1) to determine the efficacy of a pilot-scale hybrid reverse osmosis (RO)-constructed wetland system for treatment and reuse of produced waters from an oil field, and (2) to assess the quality of treated water in terms of physicochemical characteristics and toxicity influencing reuse of the water for irrigation or other designated uses. Specifically, the performance of the hybrid treatment system was examined in terms of outflow water conductivity, total dissolved solids (TDS), and toxicity using Ceriodaphnia dubia and Pimephales promelas in 7-day static/renewal exposure tests. Prior to treatment, significant mortality was observed for C. dubia and P. promelas exposed for 7 days to 6.25% untreated produced water. Following treatment through the hybrid system, no significant mortality was observed in C. dubia or P. promelas exposed to 100% treated produced water when compared to the control organisms. The pilot-scale RO-constructed wetland system effectively decreased conductivity by 95% and TDS by 94% in the brackish produced water tested in this study. Following treatment, the produced water was suitable for irrigation or discharge to surface waters. Therefore, hybrid RO-constructed wetland treatment systems present a viable alternative for treatment and reuse of produced waters from oil fields.