Simple and Sensitive Method for Synchronous Quantification of Regulated and Unregulated Priority Disinfection Byproducts in Drinking Water.

Due to their elevated concentrations in drinking water, compared to other emerging environmental contaminants, disinfection byproducts (DBPs) have become a global concern. To address this, we have created a simple and sensitive method for simultaneously measuring 9 classes of DBPs. Haloacetic acids (HAAs) and iodo-acetic acids (IAAs) are determined using silylation derivatization, replacing diazomethane or acidic methanol derivatization with a more environmentally friendly and simpler treatment process that also offers greater sensitivity. Mono-/di-haloacetaldehydes (mono-/di-HALs) are directly analyzed without derivatization, along with trihalomethanes (THMs), iodo-THMs, haloketones, haloacetonitriles, haloacetamides, and halonitromethanes. Of the 50 DBPs studied, recoveries for most were 70-130%, LOQs for most were 0.01-0.05 µg/L, and relative standard deviations were <30%. We subsequently applied this method to 13 home tap water samples. Total concentrations of 9 classes of DBPs were 39.6-79.2 µg/L, in which unregulated priority DBPs contributed 42% of total DBP concentrations and 97% of total calculated cytotoxicity, highlighting the importance of monitoring their presence in drinking water. Br-DBPs were the dominant contributors to total DBPs (54%) and total calculated cytotoxicity (92%). Nitrogenous DBPs contributed 25% of total DBPs while inducing 57% of total calculated cytotoxicity. HALs were the most important toxicity drivers (40%), particularly four mono-/di-HALs, which induced 28% of total calculated cytotoxicity. This simple and sensitive method allows the synchronous analysis of 9 classes of regulated and unregulated priority DBPs and overcomes the weaknesses of some other methods especially for HAAs/IAAs and mono-/di-HALs, providing a useful tool for research on regulated and unregulated priority DBPs.

Algae impacted drinking water: Does switching to chloramination produce safer drinking water?

Harmful algal (cyanobacterial) blooms (HABs) are increasing throughout the world. HABs can be a direct source of toxins in freshwater sources, and associated algal organic matter (AOM) can act as precursors for the formation of disinfection by-products (DBPs) in drinking water. This study investigated the impacts of algae on DBP formation using treatment with chloramine, which has become a popular disinfectant in the U.S. and in several other countries because it can significantly lower the levels of regulated DBPs formed. Controlled laboratory chloraminations were conducted using live field-collected algal biomass dominated by either Phormidium sp. or Microseira wollei (formerly known as Lyngbya wollei) collected from Lake Wateree and Lake Marion, SC. Sixty-six priority, unregulated or regulated DBPs were quantified using gas chromatography (GC)-mass spectrometry (MS). The presence of HAB-dominated microbial communities in source waters led to significant increases in more toxic nitrogen-containing DBPs (1.5-5 fold) relative to lake waters collected in HAB-free waters. Compared to chlorinated Phormidium-impacted waters, chloraminated waters yielded lower total DBP levels (up to 123 µg/L vs. 586 µg/L for low Br-/I- waters), but produced a greater number of brominated, iodinated, and mixed halogenated DBPs in high Br-/I- waters. Among the DBPs formed in Phormidium-impacted chloraminated waters, dichloroacetic acid, trichloromethane, chloroacetic acid, chloropropanone, and dichloroacetamide were dominant. For Microseira wollei-impacted chloraminated waters, total DBP concentrations ranged from 33 to 145 µg/L (approximately 3-5 times lower than chlorination), with dichloroacetic acid, dichloroacetamide, and trichloromethane dominant. Overall, chloramination significantly reduced calculated cytotoxicity and genotoxicity in low Br- and I- waters, but produced 1.3 fold higher calculated cytotoxicity (compared to chlorine) with high Br-/I- waters due to increased formation of more toxic iodo- and mixed halogenated DBPs.

Halocyclopentadienes: An Emerging Class of Toxic DBPs in Chlor(am)inated Drinking Water.

Although >700 disinfection by-products (DBPs) have been identified to date, most DBPs in drinking water are still unknown. Identifying unknown DBPs is an important step for improving drinking water quality because known DBPs do not fully account for the adverse health effects noted in epidemiologic studies. Using gas chromatography high-resolution mass spectrometry, six chloro- and bromo-halocyclopentadienes (HCPDs) were identified in chlorinated and chloraminated drinking water via non-target analysis; five HCPDs are reported for the first time as new alicyclic DBPs. Formation pathways were also proposed. Simulated disinfection experiments with Suwannee River natural organic matter (NOM) confirm that NOM is a precursor for these new DBPs. Further, HCPDs are more abundant in chlorinated drinking water (real and simulated) when compared to chloraminated drinking water due to the higher reactivity of chlorine. Of these new DBPs, 1,2,3,4,5,5-hexachloro-1,3-cyclopentadiene is approximately 100,000× more toxic (in vivo) than regulated trihalomethanes (THMs) and haloacetic acids (HAAs) and 20-2000× more toxic than halobenzoquinones, halophenols, and halogenated pyridinols using the available median lethal dose (LD50) and concentration for 50% of maximal effective concentration (EC50) of DBPs to aquatic organisms. The predicted bioconcentration factors of these HCPDs range from 384 to 3980, which are 2-3 orders of magnitude higher than those for regulated and priority DBPs (including THMs, HAAs, halobenzoquinones, haloacetonitriles, haloacetamides, halonitromethanes, haloacetaldehydes, iodo-THMs, and iodo-HAAs). Thus, HCPDs are an important emerging class of DBPs that should be studied to better understand their impact on drinking water quality and long-term human health exposure.

Do DBPs swim in salt water pools? Comparison of 60 DBPs formed by electrochemically generated chlorine vs. conventional chlorine.

Disinfectants are added to swimming pools to kill harmful pathogens. Although liquid chlorine (sodium hypochlorite) is the most commonly used disinfectant, alternative disinfection techniques like electrochemically generated mixed oxidants or electrochemically generated chlorine, often referred to as salt water pools, are growing in popularity. However, these disinfectants react with natural organic matter and anthropogenic contaminants introduced to the pool water by swimmers to form disinfection byproducts (DBPs). DBPs have been linked to several adverse health effects, such as bladder cancer, adverse birth outcomes, and asthma. In this study, we quantified 60 DBPs using gas chromatography-mass spectrometry and assessed the calculated cytotoxicity and genotoxicity of an indoor community swimming pool before and after switching to a salt water pool with electrochemically generated chlorine. Interestingly, the total DBPs increased by 15% upon implementation of the salt water pool, but the calculated cytotoxicity and genotoxicity decreased by 45% and 15%, respectively. Predominant DBP classes formed were haloacetic acids, with trichloroacetic acid and dichloroacetic acid contributing 57% of the average total DBPs formed. Haloacetonitriles, haloacetic acids, and haloacetaldehydes were the primary drivers of calculated cytotoxicity, and haloacetic acids were the primary driver of calculated genotoxicity. Diiodoacetic acid, a highly toxic iodinated DBP, is reported for the first time in swimming pool water. Bromide impurities in sodium chloride used to electrochemically generate chlorine led to a 73% increase in brominated DBPs, primarily driven by bromochloroacetic acid. This study presents the most extensive DBP study to-date for salt water pools.

How well does XAD resin extraction recover halogenated disinfection byproducts for comprehensive identification and toxicity testing?

Halogenated disinfection byproducts (DBPs) are an unintended consequence of drinking water disinfection, and can have significant toxicity. XAD resins are commonly used to extract and enrich trace levels of DBPs for comprehensive, nontarget identification of DBPs and also for in vitro toxicity studies. However, XAD resin recoveries for complete classes of halogenated DBPs have not been evaluated, particularly for low, environmentally relevant levels (ng/L to low µg/L). Thus, it is not known whether levels of DBPs or the toxicity of drinking water might be underestimated. In this study, DAX-8/XAD-2 layered resins were evaluated, considering both adsorption and elution from the resins, for extracting 66 DBPs from water. Results demonstrate that among the 7 classes of DBPs investigated, trihalomethanes (THMs), including iodo-THMs, were the most efficiently adsorbed, with recovery of most THMs ranging from 50%-96%, followed by halonitromethanes (40%-90%). The adsorption ability of XAD resins for haloacetonitriles, haloacetamides, and haloacetaldehydes was highly dependent on the individual species. The adsorption capacity of XAD resins for haloacetic acids was lower (5%-48%), even after adjusting to pH 1 before extraction. Recovery efficiency for most DBPs was comparable with their adsorption, as most were eluted effectively from XAD resins by ethyl acetate. DBP polarity and molecular weight were the two most important factors that determine their recovery. Recovery of trichloromethane, iodoacetic acid, chloro- and iodo-acetonitrile, and chloroacetamide were among the lowest, which could lead to underestimation of toxicity, particularly for iodoacetic acid and iodo-acetonitrile, which are highly toxic.

A balancing act: Optimizing free chlorine contact time to minimize iodo-DBPs, NDMA, and regulated DBPs in chloraminated drinking water.

Many drinking water treatment plants in the U.S. have switched from chlorination to chloramination to lower levels of regulated trihalomethane (THM) and haloacetic acid (HAA) disinfection byproducts (DBPs) in drinking water and meet the current regulations. However, chloramination can also produce other highly toxic/carcinogenic, unregulated DBPs: iodo-acids, iodo-THMs, and N-nitrosodimethylamine (NDMA). In practice, chloramines are generated by the addition of chlorine with ammonia, and plants use varying amounts of free chlorine contact time prior to ammonia addition to effectively kill pathogens and meet DBP regulations. However, iodo-DBPs and nitrosamines are generally not considered in this balancing of free chlorine contact time. The goal of our work was to determine whether an optimal free chlorine contact time could be established in which iodo-DBPs and NDMA could be minimized, while keeping regulated THMs and HAAs below their regulatory limits. The effect of free chlorine contact time was evaluated for the formation of six iodo-trihalomethanes (iodo-THMs), six iodo-acids, and NDMA during the chloramination of drinking water. Ten different free chlorine contact times were examined for two source waters with different dissolved organic carbon (DOC) and bromide/iodide. For the low DOC water at pH 7 and 8, an optimized free chlorine contact time of up to 1 h could control regulated THMs and HAAs, as well as iodo-DBPs and NDMA. For the high DOC water, a free chlorine contact time of 5 min could control iodo-DBPs and NDMA at both pHs, but the regulated DBPs could exceed the regulations at pH 7.

Microseira wollei and Phormidium algae more than doubles DBP concentrations and calculated toxicity in drinking water.

Warm weather and excess nutrients from agricultural runoff trigger harmful algal blooms, which can affect drinking water safety due to the presence of algal toxins and the formation of disinfection by-products (DBPs) during drinking water treatment. In this study, 66 priority, unregulated and regulated DBPs were quantified in chlorinated controlled laboratory reactions of harmful algae Microseira wollei (formerly known as Lyngbya wollei) and Phormidium using gas chromatography (GC)-mass spectrometry (MS). Live algae samples collected from algae-impacted lakes in South Carolina were chlorinated in both ultrapure water and real source waters containing natural organic matter. DBPs were also measured in finished water from a real drinking water plant impacted by a Microseira bloom. Results show that the presence of Microseira and Phormidium more than doubles total concentrations of DBPs formed by chlorination, with levels up to 586 µg/L formed in natural lake waters. Toxic nitrogen-containing DBPs also more than doubled in concentration, with levels up to 36.1, 3.6, and 37.9 µg/L for haloacetamides, halonitromethanes, and haloacetonitriles, respectively. In ultrapure water, DBPs also formed up to 314 µg/L when algae was chlorinated, demonstrating their ability to serve as direct precursors for these DBPs. When environmentally relevant levels of bromide and iodide were added to chlorination reactions, total DBPs increased 144, 51, and 24% for drinking water reservoir, Lake Marion and Lake Wateree Microseira respectively and 29% for Phormidium. Iodo-DBPs, bromochloroiodomethane, chloroiodoacetic acid, bromoiodoacetic acid, and diiodoacetic acid were observed in finished water from a drinking water plant impacted by Microseira, and bromochloroiodomethane and dibromoiodomethane were observed in chlorinated ultrapure water containing algae, bromide, and iodide. Notably, total calculated cytotoxicity tripled in Microseira-impacted waters and doubled for Phormidium-impacted waters. Calculated genotoxicity doubled for Microseira-impacted waters and more than doubled in Phormidium-impacted waters. Haloacetonitriles were major drivers of calculated cytotoxicity in algae-impacted waters, while haloacetic acids were major drivers of calculated genotoxicity in algae-impacted waters. These results provide the most extensive assessment of DBPs formed from chlorination of algae-impacted waters and highlight potential impacts to drinking water and human health. Results from this study are particularly applicable to drinking water treatment plants that employ pre-chlorination, which can cause the release of algal organic matter (AOM) precursors to form DBPs.

Are Disinfection Byproducts (DBPs) Formed in My Cup of Tea? Regulated, Priority, and Unknown DBPs.

Globally, tea is the second most consumed nonalcoholic beverage next to drinking water and is an important pathway of disinfection byproduct (DBP) exposure. When boiled tap water is used to brew tea, residual chlorine can produce DBPs by the reaction of chlorine with tea compounds. In this study, 60 regulated and priority DBPs were measured in Twinings green tea, Earl Grey tea, and Lipton tea that was brewed using tap water or simulated tap water (nanopure water with chlorine). In many cases, measured DBP levels in tea were lower than in the tap water itself due to volatilization and sorption onto tea leaves. DBPs formed by the reaction of residual chlorine with tea precursors contributed ∼12% of total DBPs in real tap water brewed tea, with the remaining 88% introduced by the tap water itself. Of that 12%, dichloroacetic acid, trichloroacetic acid, and chloroform were the only contributing DBPs. Total organic halogen in tea nearly doubled relative to tap water, with 96% of the halogenated DBPs unknown. Much of this unknown total organic halogen (TOX) may be high-molecular-weight haloaromatic compounds, formed by the reaction of chlorine with polyphenols present in tea leaves. The identification of 15 haloaromatic DBPs using gas chromatography-high-resolution mass spectrometry indicates that this may be the case. Further studies on the identity and formation of these aromatic DBPs should be conducted since haloaromatic DBPs can have significant toxicity.