Nine per- and polyfluoroalkyl substances (PFASs), including six perfluoroalkyl carboxylic acids (PFCAs) and three perfluoroalkyl sulfonic acids (PFSAs), were tested to find their adsorption selectivity from surface water and the feasibility of the powder activated carbon (PAC) process between the perchlorination and coagulation processes by operating parameters such as mixing intensity, dosage, contact time, initial pH, and concentration of perchlorination. The removal efficiency of four types of PAC revealed that the coal-based activated carbon was clearly advanced for all of the PFASs, and the thermal regenerated PAC did not exhibit a significant reduction in adsorption capacity. The longer carbon chain or the higher molecular weight (MW) obtained a higher adsorption capacity and the MW exhibited a more proportional relationship with the removal efficiency than the carbon chain number, regardless of the PFCA and PFSA species. Approximately 80% and 90% equilibria were accomplished within 60 and 120 min for the long chain carbon PFAS, respectively, while for the short chain PFAS, 240 min was required to reach 85% equilibrium. The effect of mixing intensity (rpm) was not considered for the removal of the PFAS, although it was relatively influenced in the short PFAS species. Due to the surface charge of the PAC and the properties of protonation of the PFASs, the acid condition increased the PFASs’ adsorption capacity. The prechlorination decreased the removal efficiency, and the reduction rate was more significantly influenced for the short chain PFAS than for the long chain PFAS.
The influence of the characteristics of natural organic matter (NOM) on disinfection by-product formation was investigated for Maeri raw water, located in downstream of Nakdong river and Hoedong reservoir at Busan in Korea. The NOM was chlorinated and analyzed for trihalomethanes (THMs), 5 haloacetic acids (HAA-5) and total organic halide (TOX). Aromatic contents determined by specific UV absorbance at 254 nm (SUVA) correlated well with THMs, HAA-5 and TOX formation for the NOM in the Maeri raw water and Hoedong reservoir. Especially, THMFP/ DOC showed better correlation with SUVA than HAAFP-5/DOC and TOXFP/DOC with SUVA. Chloroform formation showed good correlation with SUVA for Maeri raw water, but poor correlation with SUVA for the Hoedong raw water. In addition, TCAA formation potential showed good correlation with SUVA for both raw waters. In contrast, a lack of correlation was observed for DCAA formation for both raw waters. THM formation per unit DOC concentration was 70.2-81.1% and 18.9-29.8% for hydrophobic and hydrophilic organic matter in the Maeri raw water, respectively, in which the hydrophobic organic matter had much higher THM formation. In contrast, HAA-5 formation per unit DOC concentration varied seasonally for Maeri raw water. THM formation in the Maeri raw water had a good correlations with SUVA regardless of the ratio of hydrophobic and hydrophilic fraction, and THM formation per unit DOC concentration was higher for the order of humic acid>fulvic acid>hydrophilic organic matter. HAA-5 formation per unit DOC concentration for the hydrophilic organic matter was about 30 µg per mg DOC regardless of SUVA values, but HAA-5 formation per unit DOC concentration for the hydrophobic organic matter was proportionally increased with increasing SUVA values. However, the HAA-5 formation per mg DOC was the highest for the hydrophilic organic matter.
Transformation
of atenolol (ATN), a micropollutant containing a secondary (2°)
amine moiety, can be significantly enhanced in water treatment with
sequential and combined use of chlorine and UV (chlorine/UV) through
photolysis of the N–Cl bond. This study investigated the transformation
kinetics, products, and mechanisms of the amine moiety of ATN in chlorine/UV
(254 nm). The fluence-based, photolysis rate constant for N–Cl
ATN was 2.0 × 10–3 cm2/mJ. Transformation
products (TPs) with primary (1°) amines were mainly produced,
but TPs with 2° and 3° amines were also formed, on the basis
of liquid chromatography (LC)/quadrupole-time-of-flight/mass spectrometry
and LC/UV analyses. The amine-containing TPs could be further transformed
in chlorine/UV (with residual chlorine in post UV) via formation and
photolysis of new N–Cl bonds. Photolysis of N–Cl 1°
amine TPs produced ammonia as a major product. These data could be
explained by a reaction mechanism in which the N–Cl bond was
cleaved by UV, forming aminyl radicals that were transformed via 1,2-hydrogen
shift, β-scission, intramolecular addition, and 1,2-alkyl shift.
Among these, the 1,2-alkyl shift is newly discovered in this study.
Despite enhanced transformation, only partial mineralization of the
ATN’s amine moiety was expected, even under chlorine/UV advanced
oxidation process conditions. Overall, the kinetic and mechanistic
information from this study can be useful for predicting the transformation
of amine moieties by chlorine/UV water treatment.
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