Interpreting main features of the differential absorbance spectra of chlorinated natural organic matter: Comparison of the experimental and theoretical spectra of model compounds. (15th October 2020)

• Record Type: Journal Article
• Authors: Chen, Bingya; Zhang, Chenyang; Zhao, Yanmei; Wang, Dongsheng; Korshin, Gregory V.; Ni, Jinren; Yan, Mingquan
• Is Part Of: Water research. Volume 185(2020)
• Publication Date: 2020-10-15
• Subjects: Chlorination -- Differential absorbance spectra -- Disinfection byproducts -- Electronic transition -- Natural organic matter -- Frontier molecular orbital theory; Water -- Pollution -- Research -- Periodicals; 363.7394
• DOI: 10.1016/j.watres.2020.116206
• Languages: English
• ISSNs: 0043-1354

Abstract

Highlights: Six Gaussian bands comprise differential absorbance spectra of all examined waters. Bands A1-A4 in the spectra of chlorinated compounds show dependence of conjugation. Spectral parameters from long wavelength have high correlation with DBPs formation. Abstract: This study compared chlorination-induced changes of the properties of natural organic matter (NOM) represented by standard humic substances and NOM present in pristine and anthropogenically-affect reservoirs, rivers, groundwater and seawater. The chlorination-induced changes of NOM properties were quantified using the differential absorbance spectra (DAS) which were processed via numeric deconvolution. Six Gaussian bands were found to comprise the DAS of all examined waters. These bands (denoted as A0, A1, A2, A3, A4 and A5, respectively) have maxima located at ca. 200, 240, 276, 316, 385 and 547 nm. The bands A1-A4 were observed in the DAS of representative model chlorinated compounds. Quantum chemical (QC) calculations were carried out to examine the intrinsic nature of these bands and electronic transitions associated with them. QC data demonstrate that bands A1 and A2 are present in almost all aromatic organic species, A3 is likely to be associated with acetophenone- and/or styrene-like groups. A4 can be attributed to the engagement of m-hydroxyaromatic and flavone-type groups typical for the polyphenolic moiety in NOM and known to be the key precursors of disinfection by-product (DBP) formation. Thus, the intensity of band A4 is predicted to be an especially strong predictor of DBP formation. Graphical abstract: Image, graphical abstract