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.     

Formation of iodo-trihalomethanes, iodo-haloacetic acids, and haloacetaldehydes during chlorination and chloramination of iodine containing waters in laboratory controlled reactions

Iodine containing disinfection by-products (I-DBPs) and haloacetaldehydes (HALs) are emerging disinfection by-product (DBP) classes of concern. The former due to its increased potential toxicity and the latter because it was found to be the third most relevant DBP class in mass in a U.S. nationwide drinking water study. These DBP classes have been scarcely investigated, and this work was performed to further explore their formation in drinking water under chlorination and chloramination scenarios. In order to do this, iodo-trihalomethanes (I-THMs), iodo-haloacetic acids (I-HAAs) and selected HALs (mono-HALs and di-HALs species, including iodoacetaldehyde) were investigated in DBP mixtures generated after chlorination and chloramination of different water matrices containing different levels of bromide and iodide in laboratory controlled reactions. Results confirmed the enhancement of I-DBP formation in the presence of monochloramine. While I-THMs and I-HAAs contributed almost equally to total I-DBP concentrations in chlorinated water, I-THMs contributed the most to total I-DBP levels in the case of chloraminated water. The most abundant and common I-THM species generated were bromochloroiodomethane, dichloroiodomethane, and chlorodiiodomethane. Iodoacetic acid and chloroiodoacetic acid contributed the most to the total I-HAA concentrations measured in the investigated disinfected water. As for the studied HALs, dihalogenated species were the compounds that predominantly formed under both investigated treatments.     

Chloramination of wastewater effluent: Toxicity and formation of disinfection byproducts

The reclamation and disinfection of waters impacted by human activities (e.g., wastewater effluent discharges) are of growing interest for various applications but has been associated with the formation of toxic nitrogenous disinfection byproducts (N-DBPs). Monochloramine used as an alternative disinfectant to chlorine can be an additional source of nitrogen in the formation of N-DBPs. Individual toxicity assays have been performed on many DBPs, but few studies have been conducted with complex mixtures such as wastewater effluents. In this work, we compared the cytotoxicity and genotoxicity of wastewater effluent organic matter (EfOM) before and after chloramination. The toxicity of chloraminated EfOM was significantly higher than the toxicity of raw EfOM, and the more hydrophobic fraction (HPO) isolated on XAD-8 resin was more toxic than the fraction isolated on XAD-4 resin. More DBPs were also isolated on the XAD-8 resin. N-DBPs (i.e., haloacetonitriles or haloacetamides) were responsible for the majority of the cytotoxicity estimated from DBP concentrations measured in the XAD-8 and XAD-4 fractions (99.4% and 78.5%, respectively). Measured DBPs accounted for minor proportions of total brominated and chlorinated products, which means that many unknown halogenated compounds were formed and can be responsible for a significant part of the toxicity. Other non-halogenated byproducts (e.g., nitrosamines) may contribute to the toxicity of chloraminated effluents as well.     

Effects of ultrasonication on the DBP formation and toxicity during chlorination of saline wastewater effluents

Chlorine disinfection of saline wastewater effluents rich in bromide and iodide forms relatively toxic brominated and iodinated disinfection byproducts (DBPs). Ultrasonication is a relatively new water treatment technology, and it is less sensitive to suspended solids in wastewaters. In this study, we examined the effects of ultrasonication (in terms of reactor type and combination mode with chlorination) on the DBP formation and toxicity in chlorinated primary and secondary saline wastewater effluents. Compared with the chlorinated wastewater effluent samples without ultrasonication, ultrasonic horn pretreatment of the wastewater effluent samples reduced the total organic halogen (TOX) levels in chlorination by ∼30%, but ultrasonic bath pretreatment of the wastewater samples did not significantly change the TOX levels in chlorination, which might be attributed to the higher energy utilization and decomposition extent of organic DBP precursors in the ultrasonic horn reactor. Moreover, the TOX levels in the chlorinated samples with ultrasonic horn pretreatment (USH–chlorination), simultaneous treatment (chlorination+USH) and subsequent treatment (chlorination–USH) were also significantly reduced, with the maximum TOX reductions occurring in the samples with ultrasonic horn pretreatment. A toxicity index was calculated by weighting and summing the levels of total organic chlorine, total organic bromine and total organic iodine in each treated sample. The calculated toxicity index values of the chlorinated wastewater effluent samples followed a descending rank order of “chlorination” > “chlorination+USH” > “chlorination–USH” > “USH–chlorination”, with the lowest toxicity occurring in the samples with ultrasonic horn pretreatment. Then, a developmental toxicity bioassay was conducted for each treated sample. The measured toxicity index values of the chlorinated wastewater samples followed the same descending rank order.     

Disinfection byproduct formation from algal organic matters after ozonation or ozone combined with activated carbon treatment with subsequent chlorination

Algal organic matter (AOM), including extracellular organic matter (EOM) and intracellular organic matter (IOM) from algal blooms, is widely accepted as essential precursors of disinfection byproducts (DBPs). This study evaluated the effect of ozonation or ozone combined with activated carbon (O₃-AC) treatment on characteristic alternation and DBP formation with subsequent chlorination of Chlorella sp.. The effects of pH and bromide concentration on DBP formation by ozonation or O₃-AC treatment were also investigated. Results showed that the potential formation of DBPs might be attributed to ozonation, but these DBP precursors could be further removed by activated carbon (AC) treatment. Moreover, the formation of target DBPs was controlled at acidic pH by alleviating the reactions between chlorine and AOM. Besides, the bromide substitution factor (BSF) value of trihalomethanes (THMs) from EOM and IOM remained constant after AC treatment. However, THM precursors could be significantly decreased by AC treatment. The above results indicated that O₃-AC was a feasible treatment method for algal-impacted water.     

Bioavailability of wastewater derived dissolved organic nitrogen to green microalgae Selenastrum capricornutum, Chlamydomonas reinhardtii, and Chlorella vulgaris with/without presence of bacteria

Effluent dissolved organic nitrogen (DON) is problematic in nutrient sensitive surface waters and needs to be reduced to meet demanding total dissolved nitrogen discharge limits. Bioavailable DON (ABDON) is a portion of DON utilized by algae or algae + bacteria,while biodegradable DON (BDON) is a portion of DON decomposable by bacteria. ABDON and BDON in a two-stage trickling filter (TF) wastewater treatment plant was evaluated using three different microalgal species, Selenastrum capricornutum, Chlamydomonas reinhardtii and Chlorella vulgaris and mixed cultured bacteria. Results showed that up to 80% of DON was bioavailable to algae or algae + bacteria inoculum while up to 60% of DON was biodegradable in all the samples. Results showed that C. reinhardtii and C. vulgaris can be used as a test species the same as S. capricornutum since there were no significant differences among these three algae species based on their ability to remove nitrogen species.