Effect of coexisting manganese ion on the formation of haloacetic acids during chlorination.

Haloacetic acids (HAAs) are a group of disinfection by-products formed by the reaction of dissolved organic matter (DOM) in source water and disinfectants in the drinking water treatment process. The formation of HAAs is known to be affected by several factors (e.g., pH, temperature, concentration, and DOM components in source water). However, the effects of coexisting substances, such as metal ions, on HAA formation are not well understood. In this study, HAA formation potentials (FPs) of model compounds of DOM and environmental waters in the presence or absence of manganese ion upon chlorination were compared. The results of experiments with model compounds of DOM showed that manganese ion promoted the formation of HAA from citric acid, trans-aconitic acid, and cis-aconitic acid. Even for a manganese concentration of less than 50 µg/L, which is the standard value of manganese in drinking water in the USA, EU, and Japan, manganese had great influence on the dichloroacetic acid FPs of these compounds. However, the manganese ion did not enhance the HAAFPs of the environmental waters tested. Nevertheless, manganese may have an effect on HAAFPs of environmental waters collected at the occurrence of an unusual growth of microorganisms, such as algal bloom.

Predicting formation of haloacetic acids by chlorination of organic compounds using machine-learning-assisted quantitative structure-activity relationships.

The presence of disinfection byproducts (DBPs) in drinking water is a major public health concern, and an effective strategy to limit the formation of these DBPs is to prevent their precursors. In silico prediction from chemical structure would allow rapid identification of precursors and could be used as a prescreening tool to prioritize testing. We present models using machine learning algorithms (i.e., support vector regressor, random forest regressor, and multilayer perceptron regressor) and chemical descriptors as features to predict the formation of haloacetic acids (HAAs). A robust model with good predictivity (i.e., leave-one-out cross-validated Q2 > 0.5) to predict the formation of trichloroacetic acid (TCAA) was developed using a random forest regressor. The number of aromatic bonds, hydrophilicity, and electrotopological descriptors related to electrostatic interactions and the atomic distribution of electronegativity were identified as important predictors of TCAA formation potentials (FPs). However, the prediction of dichloroacetic acid was less accurate, which is congruent with the presence of different types of precursors exhibiting distinct mechanisms. This study demonstrates that nonlinear combinations of general chemical descriptors can adequately estimate HAAFPs, and we hope that our study can be used to predict precursors of other disinfection byproducts based on chemical structures using a similar workflow.

Effect of biodegradation on haloacetic acid formation potentials of anthropogenic compounds during chlorination.

During drinking water treatment processes, anthropogenic compounds act as important precursors of disinfection by-products such as haloacetic acids (HAAs). Several transformations in these precursors occur prior to the disinfection stage, such as partial biodegradation. We hypothesized that this partial biodegradation of anthropogenic compounds potentially affects their HAA formation potentials (HAAFPs). In this study, the HAAFPs of 51 anthropogenic compounds after short-term contact (less than 1 h) and long-term contact (24 h) with activated sludge were compared. Considerable changes were observed particularly in trichloroacetic acid (TCAA) formation potentials (FPs) of phenols, demonstrating that biodegradation should be considered in investigations of potential precursors of HAAs. Phenols with low HAAFPs, such as hydroquinone, show higher HAAFPs after biodegradation, but HAAFPs of most phenols and anilines decreased after biodegradation. Thus, biodegradation will most likely have a positive impact on water quality from the standpoint of HAAFP reduction. For most aliphatic compounds, changes in HAAFP were negligible, but the dichloroacetic acid (DCAA) FP of acrylic acid largely increased. This study illustrates that biodegradation may have a large effect on the HAAFPs of anthropogenic compounds.

Formation of chlorinated haloacetic acids by chlorination of low molecular weight compounds listed on pollutant release and transfer registers (PRTRs).

Anthropogenic compounds accidentally released to the environment could be important precursors of disinfection byproducts (DBPs) in drinking water treatment processes. In this study, the haloacetic acid formation potentials (HAAFPs) of 155 anthropogenic compounds listed on the Japanese pollutant release and transfer register (PRTR) system were evaluated. The results showed that phenolic and aromatic amine compounds were important HAA precursors, and chlorinated phenols showed high HAAFPs (>400 µg/mgC). Moreover, trichlorfon and ethyl chloroacetate (HAAFP of 104.9 and 602.3 µg/mgC, respectively) were also important HAA precursors because of their ability to undergo hydrolysis. Although most anthropogenic compounds with high HAAFPs showed high chlorine consumptions, no clear correlation between HAAFPs and chlorine consumptions was found in this study. In addition, the quantitative structure-activity relationship (QSAR) approach was a useful tool for predicting the chlorine consumption of organic compounds but was not effective for predicting HAAFPs based on the information currently available. A scenario study assuming a hypothetical accidental release predicted that the release of 3,4-dichloroaniline (HAAFP of 407.6 µg/mgC) would lead to a violation of the current drinking water quality standards for HAAs in Japan.