Photodegradation of halogenated organic disinfection by-products: Decomposition and reformation.

In this study, the photodegradation of 33 different DBPs (trihalomethanes, haloacetic acids, haloacetaldehydes, and haloacetonitriles) and TOX with low pressure UV light and the subsequent reformation of DBPs with chlorine and monochloramine were investigated. Results indicated that photodegradation followed the order of TOI > TOBr > TOCl, and treated surface water with low SUVA254 background did not impact the photodegradation of highly UV susceptible DBPs such as triiodomethane (TIM), diiodobromomethane (DIBM), tribromomethane (TBM). The mass balance results of chloride, bromide and iodide showed that the main photodegradation mechanism of TOBr and TOI was dehalogenation supported by halide releases (i.e., Cl-, Br- and/or I- ion). In addition, the photodegradation removal effect was higher, when brominated DBPs formation was high. Although low pressure UV light effectively removed halogenated organic DBPs, subsequent use of disinfectants (Cl2 and NH2Cl) reformed photodegraded DBPs, and the overall DBPs concentrations were increased, which suggested that the released Br- and I- ions will reform DBPs in distribution systems, with oxidants present or added (e.g., booster chlorination) in distribution systems. This study showed that although UV photodegradation will reduce halogenated organic DBPs in distribution systems, especially more toxic iodinated and brominated DBPs, it will be a more effective technology towards the end of the distribution system or a point of entry solution rather than in distribution system with post-disinfection and residence time.

Effect of prescribed fires on the export of dissolved organic matter, precursors of disinfection by-products, and water treatability.

In this study, we report for the first time the effect of prescribed fires on the export of dissolved organic matter (DOM) and precursors of disinfectant by-products (DBPs) from periodically (every 2-3 years) and seasonally (i.e., dormant and growing) burned forest fuel materials (i.e., live vegetation, woody debris, and detritus [litter and duff]) and treatability of its rainwater leachate. Periodically applied (every 2-3 years for 40 years) prescribed fires decreased total fuel load (62±10%), primarily detrital mass (75±2%). However, functional groups (i.e., phenolic compounds, proteins, carbohydrates, aromatic [1-ring], polycyclic aromatic hydrocarbons [PAHs], and lipids) attached to DOM of ground solid materials did not change significantly. Outside rainwater leaching (from forest fuel materials) experiments showed that the leaching capacity of dissolved organic carbon (DOC) from burned litter samples decreased by 40±20% regardless of burning season when compared to unburned litter samples. The leaching of total dissolved nitrogen (TDN), dissolved organic nitrogen (DON), ammonium (NH4+), and reactive phosphorus (PO43-) from burned materials decreased between 40 and 70% when compared to unburned materials. Also, DOM composition was affected by prescribed fire, which partially consumed humic-like substances based on fluorescence analyses. Thus, periodically applied prescribed fires also resulted in a reduction of trihalomethane (THM) (42±23%) and haloacetic acid (HAA) (42±20%) formation potentials (FPs), while DOC normalized reactivity of THM and HAA FPs did not change significantly. Additionally, the leaching of N-nitrosodimethylamine (NDMA) precursors, bromide ion (Br-), and selected elements (K, Ca, Mg, Mn, Fe, S, Na, B, and Al) were not significantly affected by prescribed fires. Finally, coagulant (i.e., alum and ferric) dose requirements and coagulation efficiencies were similar (i.e., removal of DOC, precursors of THMs and HAAs were 52-56%, 69-70%, 78-79%, respectively) in unburned and pre-burned leachate samples.

Activated carbon and organic matter characteristics impact the adsorption of DBP precursors when chlorine is added prior to GAC contactors.

Pre-chlorination (i.e. dosing chlorine prior to granular activated carbon (GAC) contactors) was recently introduced as a promising method to reduce the formation of disinfection byproducts (DBPs). However, our understanding on the effect of natural organic matter (NOM) and GAC characteristics on pre-chlorination efficiency is still elusive. Thus, we have designed this systematic study to investigate the effects of GAC characteristics (i.e. surface area, pore size, and surface charge) on the subsequent reduction of DBP formation using five well-characterized adsorbents with three different NOM under three initial Br- concentrations. The results revealed that the adsorption of halogenated DBPs precursors mostly occurs in the mesoporous region (i.e. 2 nm < pore size <50 nm) of the adsorbents. Subsequently, pre-chlorination before treatment with HD3000 (i.e. GAC with the highest mesoporous surface area) decreased the formation of DBPs by 58%. Furthermore, oxidation of GAC increased the surface acidity and negatively impacted the adsorption of halogenated DBP precursors, which suggests basic GACs as promising adsorbents when applying pre-chlorination. In addition, experiments with different NOM showed that pre-chlorination was effective with higher aromatic NOM (i.e. high specific ultraviolet absorbance (SUVA254)). However, pre-chlorination of NOM with low SUVA254 has decreased the adsorption of some DBP precursors which resulted in increased formations of haloacetic acid (HAA) and total organic halogen (TOX). Also, experiments with effluent organic matter (EfOM) showed that pre-chlorination did not increase the adsorption of DBP precursors in low SUVA254 wastewater effluents. Besides, increasing initial Br- concentration increased the formation of brominated DBPs (Br-DBPs) and the adsorbed Br-DBP precursors. This study gives in-depth understanding of the mechanisms, advantages, and limitations of pre-chlorination as a potential method to control DBPs formation.

Two years of post-wildfire impacts on dissolved organic matter, nitrogen, and precursors of disinfection by-products in California stream waters.

We investigated the effects of two California wildfires (Rocky and Wragg Fires, 2015) compared to an unburned reference watershed on water quality, dissolved organic matter (DOM), and precursors of disinfection by-products (DBPs) for two years' post-fire. The two burned watersheds both experienced wildfires but differed in the proportion of burned watershed areas. Burned watersheds showed rapid water quality degradation from elevated levels of turbidity, color, and suspended solids, with greater degradation in the more extensively burned watershed. During the first year's initial flushes, concentrations of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), ammonium (NH4+/NH3), and specific ultraviolet absorbance (SUVA254) were significantly higher (67 ± 40%, 418 ± 125%, 192 ± 120%, and 31 ± 17%, respectively) in the more extensively burned watershed compared to the reference watershed. These elevated values gradually declined and finally returned to levels like the reference watershed in the second year. Nitrate concentrations were near detection limits (0.01 mg-N/L) in the first year but showed a large increase in fire-impacted streams during the second rainy season, possibly due to delayed nitrification. Changes in DOM composition, especially during the initial storm events, indicated that fires can attenuate humic-like and soluble microbial by-product-like (SMP) DOM while increasing the proportion of fulvic-like, tryptophan-like, and tyrosine-like compounds. Elevated bromide (Br-) concentrations (up to 8.7 µM]) caused a shift in speciation of trihalomethanes (THMs) and haloacetic acids (HAAs) to brominated species for extended periods (up to 2 years). Wildfire also resulted in elevated concentrations of N-nitrosodimethylamine (NDMA) precursors. Such changes in THM, HAA, and NDMA precursors following wildfires pose a potential treatability challenge for drinking water treatment, but the effects are relatively short-term (≤1 year).

Effect of bromide on NDMA formation during chloramination of model precursor compounds and natural waters.

In this work, we investigated the effect of bromide ion (Br-) on NDMA formation using model precursor compounds, wastewater effluents and surface waters. Previous studies showed that Br- reacts with chloramines and forms bromochloramine, a reactive compound responsible for NDMA formation enhancement. Some limitations of those studies were the highest Br- concentrations used, and the limited number of precursors considered. Here, we observed enhancement of NDMA formation from most of the model precursor compounds within the Br- range (0-1000 µg/L) but this effect was suppressed in the presence of NOM. Also, NDMA formation was favored at pH 8 in the presence of Br- compared to pH 6. Nevertheless, Br- suppressed NDMA formation in wastewater effluent samples at low monochloramine doses while no effects were observed in surface waters.

Selective removal of bromide and iodide from natural waters using a novel AgCl-SPAC composite at environmentally relevant conditions.

The removal of bromide (Br-) and iodide (I-) from source waters mitigates the formation of brominated and iodinated disinfection by-products (DBPs), which are more toxic than their chlorinated analogues. In this study, we report on our recently developed environmental-friendly method for the preparation of novel silver chloride/superfine activated carbon composite (AgCl-SPAC) to rapidly and selectively remove Br- and I- from surface waters. The material characteristics were tracked, before and after treatment, using scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), X-ray diffraction (XRD), and X-ray photoelectron spectra (XPS) spectroscopies. The results showed very fast removal kinetics of Br- and I- by AgCl-SPAC with equilibrium times at 150 s and <10 s, respectively (i.e., 2-3 orders of magnitudes faster than previously tested Ag-based composites). In addition, AgCl-SPAC was evaluated under eight different Cl- concentrations up to 400 mg/L and exhibited high removal efficiencies for I- (i.e., >90% at all tested conditions) and Br- (i.e, >80% at Cl- = 0.5-200 mg/L, and 60-75% at extreme Cl- conditions = 300-400 mg/L). Unlike previous Ag-based composites, AgCl-SPAC performance was not affected by elevated concentrations of two types of natural organic matter (2-16 mg-NOM/L). The superior performance was further confirmed in four different surface waters and one groundwater. After the removal of Br- and I- from all waters by AgCl-SPAC, the subsequent DBPs formation (trihalomethanes, haloacetic acids, and haloacetonitriles), total organic halogens (TOX), bromine substitution factor (BSF), and calculated cytotoxicity under the uniform formation conditions (UFC) decreased significantly. Overall, this novel composite represents a promising alternative approach, to be integrated continuously or seasonally, for controlling the formation of brominated and/or iodinated DBPs at water treatment plants.