A universal model to predict yields of THMs and HAAs based on UV-Visible absorption spectra.

Differential absorption spectroscopy (DAS) quantifies changes in the UV-Visible absorbance of dissolved organic matter (DOM) caused by reactions of its chromophores. As a result of its precision and sensitvity, DAS serves as a powerful tool for characterizing the formation of disinfection by-products (DBPs) in generated in DOM chlorination reactions. However, the nonlinear relationship between the intensity of DAS and DBP concentrations as well as the need to develop site-specific fitting parameters limit its practical applications. This study investigated the physico-chemical nature of DAS of chlorinated DOM through experimental measurements and theoretical calculations. Results of this study provide molecular-level evidence that electrophilic substitution reactions involving DOM reactive sites result in the emergence of DAS feaures ascribed to the "fast" chromophores. The ring opening in the cyclic enones-like structures which can be present either in the original DOM or are generated as intermediates in its chlorination, leads to the emergence of DAS features associated with the "slow" chromophores and high yields of DBPs. The kinetic study of chlorination of real waters reveals a strong linear relationship (R2 > 0.91) between ln([DBP]) and the long-wavelength (λ > 325 nm) parameter of the DAS, notably (ln(-DA350)). This relationship varies among different water sources due to the differences in the heterogeneity of Band A3 whose maximum is near 350 nm. Band A3 is one of the Gaussian bands that comprise the overall UV-Visible spectrum of DOM. A new function (f(-DA350)) is proposed in this study to quantify DBP formation. This function, which is determined by the Band A3's area, allows establishing a universal linear relationship between f(-DA350) and ln([THMs]), as well as f(-DA350) and ln([HAAs]), across various water sources. The findings of this study will stimulate further development of spectroscopy-based DBP monitoring technology for monitoring and optimization of water disinfection processes.

Characterizing photochemical production carboxyl content of dissolved organic matters using absorbance spectroscopy combined with FT-ICR MS.

Irradiation can significantly impact the structure, reactivity and environmental behavior of dissolved organic matter (DOM). The extent of these processes remains to be ascertained in more detail but the heterogeneity and site-specificity of DOM, and the lack of methods to characterize DOM at its environmentally-relevant concentrations make it a challenge. In this study, the differences of DOM response to photodegradation in four typical origins (i.e., surface water, sediment and intracellular and extracellular algal DOM) were tracked on the molecular-level using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS). Changes of the carboxyl and phenolic DOM moieties induced by irradiation were quantified by spectroscopic titrations, and the mechanism of functional groups affecting the changes of specific molecular composition was qualitatively proposed. The results demonstrated that intracellular algal organic matter (I-DOM) was most susceptible to photodegradation (ca. 63% DOM loss), then came extracellular algal organic matter (E-DOM) and surface water DOM (W-DOM) (ca. 15% DOM loss). Sediment DOM (S-DOM) was most resistant to irradiation, with a very small level of its mineralization. Lipids, lignin-like compounds and tannin-like compounds in I-DOM and E-DOM were relatively photo-labile. The photodegradation of lipids was related to the decarboxylation of carboxyl functional groups, while the photodegradation of tannin-like compounds was related to the rupture of phenolic functional groups. In comparison, the molecular composition of W-DOM and S-DOM was less affected by irradiation, which was also reflected in the fact that the carboxyl and phenolic functional groups were highly photo-resistant. This study showed that the photoactivity of DOM in surface water was closely related to the abundance of algae, so controlling the excessive reproduction of algae may have a positive effect on stability of quality and quantity of organic matter in surface water.

Interpreting pH-Dependent Differential UV/VIS Absorbance Spectra to Characterize Carboxylic and Phenolic Chromophores in Natural Organic Matter.

Natural organic matter (NOM) is critical for the biogeochemical cycles of energy and many elements in terrestrial and aquatic ecosystems, and protonation-active functional groups in NOM molecules, notably carboxylic and phenolic groups often mediate these critical environmental functions. Molecular heterogeneity, polydispersity and dynamic behavior of NOM complicate achieving an unambiguous description of its molecular properties and reactivity. This study demonstrates that differential ultraviolet-visible (UV/VIS) absorbance spectra (DAS) of NOM acquired at varying pH values exhibit several distinct features associated with the deprotonation of NOM molecules, independent of the environmental provenance of NOM (e.g., surface water, seawater, sediment, and wastewater). The protonation-active functionalities that contribute to the Gaussian distribution bands present in the DAS were identified here by comparing characteristic properties of the bands with the stoichiometries of NOM molecules ascertained by Ultrahigh-Resolution Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS). The protonation-active individual chromophores universally present in NOM molecules were identified by a genetic molecular network analysis. The observed DAS features were closely modeled via superimposing DAS spectra of 51 individual protonation-active chromophores. Molecular orbital theory was applied to further interpret the deprotonation of these chromophores, their molecular structure, electron distribution, and electron transitions measured using DAS. The high sensitivity and easy implementation of the DAS approach allows using it as a powerful tool to quantify the molecular properties and reactivity of NOM at environmental concentrations.