Impact of combining chlorine dioxide and chlorine on DBP formation in simulated indoor swimming pools

The main objective of this study was to assess the combined use of chlorine dioxide (ClO2) and chlorine (Cl2) on the speciation and kinetics of disinfection by-product (DBP) formation in swimming pools using synthetic pool waters prepared with a body fluid analog (BFA) and/or fresh natural water. At 1:25 (mass ratio) of ClO2 to Cl2, there was no significant reduction in the formation of trihalomethanes (THMs) and haloacetic acids (HAAs) for both BFA solution and natural water compared to the application of Cl2 alone. When the mass ratio of ClO2 to Cl2 increased to 1:1, substantial decreases in both THMs and HAAs were observed in the natural water, while there was almost no change of DBP formations in the BFA solution. Haloacetonitriles and halonitromethanes levels in both water matrices remained similar. In the presence of bromide, the overall DBP formation increased in both BFA solution and natural water. For the DBP formation kinetics, after 72 hr of contact time, very low formation of THMs and HAAs was observed for the use of ClO2 only. Compared to Cl2 control, however, applying the 1:1 mixture of ClO2/Cl2 reduced THMs by > 60% and HAAs by > 50%. Chlorite was maintained below 1.0 mg/L, while the formation of chlorate significantly increased over the reaction time. Finally, in a bench-scale indoor pool experiment, applying ClO2 and Cl2 simultaneously produced less THMs compared to Cl2 control and kept chlorite at < 0.4 mg/L, while HAAs and chlorate accumulated over 4-week operation period.     

Formation of regulated and unregulated disinfection byproducts during chlorination and chloramination: Roles of dissolved organic matter type, bromide, and iodide

Algal blooms and wastewater effluents can introduce algal organic matter (AOM) and effluent organic matter (EfOM) into surface waters, respectively. In this study, the impact of bromide and iodide on the formation of halogenated disinfection byproducts (DBPs) during chlorination and chloramination from various types of dissolved organic matter (DOM, e.g., natural organic matter (NOM), AOM, and EfOM) were investigated based on the data collected from literature. In general, higher formation of trihalomethanes (THMs) and haloacetic acids (HAAs) was observed in NOM than AOM and EfOM, indicating high reactivities of phenolic moieties with both chlorine and monochloramine. The formation of haloacetaldehydes (HALs), haloacetonitriles (HANs) and haloacetamides (HAMs) was much lower than THMs and HAAs. Increasing initial bromide concentrations increased the formation of THMs, HAAs, HANs, and HAMs, but not HALs. Bromine substitution factor (BSF) values of DBPs formed in chlorination decreased as specific ultraviolet absorbance (SUVA) increased. AOM favored the formation of iodinated THMs (I-THMs) during chloramination using preformed chloramines and chlorination-chloramination processes. Increasing prechlorination time can reduce the I-THM concentrations because of the conversion of iodide to iodate, but this increased the formation of chlorinated and brominated DBPs. In an analogous way, iodine substitution factor (ISF) values of I-THMs formed in chloramination decreased as SUVA values of DOM increased. Compared to chlorination, the formation of noniodinated DBPs is low in chloramination.     

Isolation and fractionation of natural organic matter: evaluation of reverse osmosis performance and impact of fractionation parameters

Dissolved organic matter (DOM) from three surface waters was isolated using reverse osmosis (RO) and subsequently fractionated using resin adsorption chromatography (RAC). Efficacy of RO was evaluated by closing mass balances for dissolved organic carbon (DOC). RAC was evaluated by investigating the effect of column operational parameters (column capacity factor, k', and solute initial concentration, C0) on DOM fractionation and subsequent disinfection by-product formation. Efficacy of RO was dependent on both isolation conditions and source water characteristics. In general, RO more effectively isolated DOM in high specific ultraviolet absorbance (SUVA254) water than low SUVA254 water, and showed higher DOM recovery at ambient pH (approximately 7) than at low pH (approximately 4). The fractionation of the isolated DOM indicated that the relative amount of the hydrophobic fraction decreased with increasing k', thus affecting the overall distribution of DOM. However, the distribution of DOM fractions was not influenced by varying C0 up to 150 mg l(-1) at k' of 15. The effect of k' on the formation and speciation of trihalomethanes (THM) and haloacetic acids (HAA) was not significant up to k' of 30.     

Influence of drought and municipal sewage effluents on the baseflow water chemistry of an upper piedmont river

The Reedy River in South Carolina is affected by the urban area of Greenville, the third most populous city in the state, and by the effluents from two large-scale municipal wastewater treatment plants (WWTPs) located on the river. Riverine water chemistry was characterized using grab samples collected annually under spring season baseflow conditions. During the 4-year time period associated with this study, climatic variations included two severe drought spring seasons (2001 and 2002), one above-normal precipitation spring season (2003), and one below-normal precipitation spring season (2004). The influence of drought and human activities on the baseflow chemistry of the river was evaluated by comparing concentrations of dissolved anions, total metals, and other important water chemistry parameters for these different years. Concentrations of copper and zinc, common non-point source contaminants related to urban activities, were not substantially elevated in the river within the urban area under baseflow conditions when compared with headwater and tributary samples. In contrast, nitrate concentrations increased from 1.2–1.6 mg/l up to 2.6–2.9 mg/l through the urban stream reach. Concentrations of other major anions (e.g., sulfate, nitrate) also increased along the reach, suggesting that the river receives continuous inputs of these species from within the urban area. The highest concentrations of major cations and anions typically were observed immediately downstream from the two WWTP effluent discharge locations. Attenuation of nitrate downstream from the WWTPs did not always track chloride changes, suggesting that nitrate concentrations were being controlled by biochemical processes in addition to physical processes. The relative trends in decreasing nitrate concentrations with downstream distance appeared to depend on drought versus non-drought conditions, with biological processes presumably serving as a more important control during non-drought spring seasons.     

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.     

Effect of activated sludge treatment on the formation of Nnitrosamines under different chloramination conditions

Municipal wastewater discharge is considered as one of the main sources of N-nitrosamine precursors which can impact the qualities of downstream source waters and reclaimed wastewaters for potable reuse. NNitrosamine precursors can be removed to various degrees during biological wastewater treatment (e.g., the activated sludge (AS) process). So far, little is known about the impact of the AS process on N-nitrosamine formation under practical disinfection condition (e.g., uniform formation condition (UFC)). In this study, N-nitrosamine UFC from selected model compounds, sewage components (i.e., blackwaters and greywaters) and sewage samples were comprehensively investigated during batch AS treatment tests. NNitrosodimethylamine (NDMA) formation from the tested precursor compounds (i.e., trimethylamine (TMA) and sumatriptan (SMTR)) under UFC chloramination decreased mostly after 6 or 24 hr treatment with different types of AS (i.e., domestic rural AS, domestic urban AS, and textile AS), and the reductions in NDMA UFC were comparable to their NDMA formation potential (FP) reductions. In urine and feces blackwaters, NDMA UFC increased after 6 or 24 hr treatment with the domestic (i.e., rural and urban) AS, while NDMA FP decreased substantially. The increases in NDMA UFC after AS treatment was presumably attributed to the removal of bulk organic matters (e.g., dissolved organic carbon (DOC)) which favored NDMA formation under UFC. On the other hand, in laundry greywaters having relatively abundant DOC, N-nitrosamine UFC was less affected by DOC removal before or after AS treatment, but decreased to similar degrees with N-nitrosamine FP. In sewage samples collected from wastewater treatment plants, N-nitrosamines UFC tended to increase or remain constant during AS treatment, despite the decreases in their FPs. These results suggest that biological wastewater treatment (e.g., the AS process) may not effectively reduce N-nitrosamine formation (e.g., measured under UFC) partially because the concurrent removal of bulk organic matters (e.g., DOC) favored N-nitrosamine formation in s econdary effluents.