Pyrogenic carbon-promoted haloacetic acid decarboxylation to trihalomethanes in drinking water

Abstract

Drinking water disinfection by chlorination or chloramination can result in the formation of disinfection byproducts (DBPs) such as haloacetic acids (HAAs) and trihalomethanes (THMs). Pyrogenic carbonaceous matter (PCM), such as activated carbon (AC), is commonly used as an ostensibly inert adsorbent to remove HAAs from water. HAA degradation has been mainly attributed to biological factors. This study, for the first time, revealed that abiotic HAA degradation in the presence of PCM could be important under water treatment conditions. Specifically, we observed complete destruction of Br₃AA, a model HAA, in the presence of powder AC at pH 7 within 30 min. To understand the role of PCM and the reaction mechanism, we performed a systematic study using a suite of HAAs and various PCM types. We found that PCM significantly accelerated the transformation of three HAAs (Br₃AA, BrCl₂AA, Br₂ClAA) at pH 7. Product characterization indicated an approximately 1:1 HAA molar transformation into their respective THMs following a decarboxylation pathway with PCM. The Br₃AA activation energy (E_a) was measured by kinetic experiments at 15-45 °C with and without a model PCM, wherein a significant decrease in E_a from 25.7 ± 3.2 to 13.6 ± 2.2 kcal•mol^-1 was observed. We further demonstrated that oxygenated functional groups on PCM (e.g., -COOH) can accelerate HAA decarboxylation using synthesized polymers to resemble PCM. Density functional theory simulations were performed to determine the enthalpy of activation (ΔH^‡) for Br₃AA decarboxylation with H₃O⁺ and formic acid (HCOOH). The presence of HCOOH significantly lowered the overall ΔH^‡ value for Br₃AA decarboxylation, supporting the hypothesis that -COOH catalyzes the C-C bond breaking in Br₃AA. Overall, our study demonstrated the importance of a previously overlooked abiotic reaction pathway, where HAAs can be quickly converted to THMs with PCM under water treatment relevant conditions. These findings have substantial implications for DBP mitigation in water quality control, particularly for potable water reuse or pre-chlorinated water that allow direct contact between HAAs and AC during filtration as well as PAC fines traveling with finished water in water distribution systems. As such, the volatilization and relative low toxicity of volatile THMs may be considered as a detoxification process to mitigate adverse DBP effects in drinking water, thereby lowering potential health risks to consumers.

Keywords: Decarboxylation; Density functional theory; Disinfection byproducts; Haloacetic acids; Pyrogenic carbonaceous matter; Trihalomethanes.