Using Two-Dimensional Correlation Size Exclusion Chromatography (2D-CoSEC) and EEM-PARAFAC to Explore the Heterogeneous Adsorption Behavior of Humic Substances on Nanoparticles with Respect to Molecular Sizes.

The adsorption behaviors of different constituents within bulk humic substances (HS) on two nanoparticles, TiO2 and ZnO, were examined by using two-dimensional correlation size exclusion chromatography (2D-CoSEC) and excitation emission matrix-parallel factor analysis (EEM-PARAFAC), which separated bulk HS into different size fractions and fluorescent components, respectively. Subtle changes in the size distributions of HS with increasing adsorbents were successfully identified and tracked via the 2D-CoSEC. From adsorption isotherm experiments, three different HS constituent groups with respect to sizes and fluorescence features were identified by the 2D-CoSEC and EEM-PARAFAC, respectively. The chromatographically separated HS size groups presented dissimilar adsorption behaviors in terms of adsorption affinity and isotherm nonlinearity. The sequence orders of adsorption, interpreted from the 2D-CoSEC, was consistent with those of the isotherm model parameters individually calculated for different HS size subfractions, signifying the promising application of 2D-CoSEC in obtaining an insight into the heterogeneous adsorption of HS in terms of molecular sizes. EEM-PARAFAC results also supported the major finding of the 2D-CoSEC as shown by the preferential adsorption of the fluorescent components associated with large molecular sizes.

Non-catalytic and catalytic degradation of effluent dissolved organic matter under UVA-and UVC-irradiation tracked by advanced spectroscopic tools.

Non-catalytic and catalytic photodegradation of effluent dissolved organic matter (EfDOM) was examined under two different light sources (UVA and UVC). The degradation behavior was tracked by dissolved organic carbon (DOC), UV absorbance, and different fluorescent components. Catalytic UV irradiation resulted in much higher degradation rates than those without photocatalysts (TiO2 and ZnO) regardless of the tracking variables. For non-catalytic degradation, the highest removal rates of UV absorbance were found at wavelengths close to the irradiation of either UVC or UVA, while the photocatalytic degradation rates were consistently higher at longer wavelengths. The pseudo first-order rates of UV absorbance individually calculated at several representative wavelengths were very consistent with the sequential orders interpreted from two-dimensional correlation spectroscopy (2D-COS). Excitation emission matrix - parallel factor analysis (EEM-PARAFAC) identified one tryptophan-like (C1) and two humic-like (C2 and C3) components from EfDOM samples. Among those, C1 exhibited the lowest adsorption extent and the highest degradation rates for both photocatalysts, suggesting that the photocatalysis is mainly governed by hydroxyl radicals in aqueous solution. All observed degradation behaviors were well explained by the irradiation wavelengths, the extent of adsorption onto catalysts, and the presumed structure of the tracked component. Our study demonstrated that EEM-PARAFAC and 2D-COS could provide further insights into both non-catalytic and catalytic degradation of EfDOM upon UV-irradiation.

Insight into photocatalytic degradation of dissolved organic matter in UVA/TiO2 systems revealed by fluorescence EEM-PARAFAC.

Photocatalytic degradation of dissolved organic matter (DOM) using TiO2 as a catalyst and UVA as a light source was examined under various experimental settings with different TiO2 doses, solution pH, and the light intensities. The changes in UV absorbance and fluorescence with the irradiation time followed a pseudo-first order model much better than those of dissolved organic carbon. In general, the degradation rates were increased by higher TiO2 doses and light intensities. However, the exact photocatalytic responses of DOM to the irradiation were affected by many other factors such as aggregation of TiO2, light scattering, hydroxyl radicals produced, and DOM sorption on TiO2. Fluorescence excitation-emission matrix (EEM) coupled with parallel factor analysis (PARAFAC) revealed that the DOM changes in fluorescence could be described by the combinations of four dissimilar components including one protein-like, two humic-like, and one terrestrial humic-like components, each of which followed well the pseudo-first order model. The photocatalytic degradation rates were higher for protein-like versus humic-like component, whereas the opposite order was displayed for the degradation rates in the absence of TiO2, suggesting different dominant mechanisms operating between the systems with and without TiO2. Our results based on EEM-PARAFAC provided new insights into the underlying mechanisms associated with the photocatalytic degradation of DOM as well as the potential environmental impact of the treated water. This study demonstrated a successful application of EEM-PARAFAC for photocatalytic systems via directly comparing the kinetic rates of the individual DOM components with different compositions.

Spatial variability in chromophoric dissolved organic matter for an artificial coastal lake (Shiwha) and the upstream catchments at two different seasons.

Selected water quality parameters and spectroscopic characteristics of dissolved organic matter (DOM) were examined during two different seasons for an artificial coastal lake (Shiwha Lake in South Korea), which are affected by seawater exchange due to the operation of a tidal power plant and external organic loadings from the upstream catchments. The coastal lake exhibited much lower concentrations of organic matter and nutrients than the upstream sources. The spectroscopic properties of the lake DOM were easily distinguished from those of the catchment sources as revealed by a lower absorption coefficient, lower degree of humification, and higher spectral slopes. The observed DOM properties suggest that the lake DOM may be dominated by smaller molecular size and less condensed structures. For the lake and the upper streams, higher absorption coefficients and fluorescence peak intensities but lower spectral slopes and humification index were found for the premonsoon versus the monsoon season. However, such seasonal differences were less pronounced for the industrial channels in the upper catchments. Three distinctive fluorophore groups including microbial humic-like, tryptophan-like, and terrestrial humic-like fluorescence were decomposed from the fluorescence excitation-emission matrix (EEM) of the DOM samples by parallel factor analysis (PARAFAC) modeling. The microbial humic-like component was the most abundant for the industrial channels, suggesting that the component may be associated with anthropogenic organic pollution. The terrestrial humic-like component was predominant for the upper streams, and its relative abundance was higher for the rainy season. Our principal component analysis (PCA) results demonstrated that exchange of seawater and seasonally variable input of allochthonous DOM plays important roles in determining the characteristics of DOM in the lake.