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Abstract: Changes in the characteristics of a leaf litter-derived humic substance (LLHS) that resulted from its adsorption onto kaolinite or exposure to simulated solar irradiation were tracked using selected spectroscopic descriptors, apparent weight-average molecular weight (MWw) and pyrene binding. Heterogeneity within the original bulk LLHS was confirmed by a range of different characteristics obtained from ultrafiltration-based size fractions. In general, trends of some changing LLHS characteristics were similar for the adsorption and irradiation processes when tracked against percent carbon removal. For example, the overall values of specific ultraviolet absorbance (SUVA), MWw, and humification index (HIX) all decreased with increasing irradiation time and with increasing concentration of mineral adsorbent in the respective experiments, indicating that both processes resulted in less aromatic and smaller-sized LLHS components remaining in solution. In addition, both the adsorption and irradiation experiments resulted in enrichment of the relative distribution of protein-like fluorescence (PLF), implying the PLF-related components had low affinities for phototransformation and mineral surface adsorption. Despite these apparently similar overall trends in LLHS characteristics caused by the adsorption and irradiation processes, closer examination revealed considerable differences in how the two processes altered the original material. Net production of intermediate-sized constituents was observed only with the irradiation experiments. In addition, residual LLHS resulting from the adsorptive fractionation experiments exhibited consistently higher pyrene binding versus the irradiated LLHS despite having comparable MWw values. Changes in LLHS characteristics due to adsorption by kaolinite were likely caused by physical mechanisms (primarily hydrophobic interactions between LLHS components and the kaolinite surface) whereas the irradiation-induced changes appear to have been governed by the combined effects of several alteration mechanisms, including the transformation of more condensed aromatic structures to less aromatic constituents, conformational changes resulting from selective photooxidation, and the photochemical disruption of intramolecular charge-transfer interactions. [Copyright &y& Elsevier]

Changes in selected spectroscopic and chromatographic characteristics of water-soluble organic matter (WSOM) extracted from leaf litter and its ability to bind pyrene were monitored throughout 14 day microbial incubation experiments. To provide additional insight into the microbial transformation of the WSOM, incubation experiments were similarly conducted with controlled-composition mixtures of glucose and dissolved humic substances (HS) that were base extracted from the same leaf litter source. Microbial transformation increased the specific ultraviolet absorbance and number-average molecular weight of residual WSOM while polydispersity values decreased. Fluorescence measurements revealed loss of protein- like fluorescence and enhancement of fulvic- and humic-like fluorescence in residual WSOM. Overall, the incubation results suggest that nonaromatic and smaller sized carbon structures were being degraded while the microbial activity produced humic-like aromatic components in solution. Together, these changes resulted in enhanced pyrene binding by the altered WSOM. Consistent findings resulted from mixtures of glucose and the leaf litter HS. Changes in measured operational descriptors were more pronounced for mixtures containing a higher percentage of glucose, suggesting that utilization of labile constituents may be necessary for formation of unknown structures associated with high pyrene binding capabilities. Simple mass balance, end member mixing models often failed to predict changes in pyrene binding brought about by microbial transformation, suggesting that microbial utilization of labile constituents is not the predominant process governing the enhanced pyrene binding. [ABSTRACT FROM AUTHOR]

The primary mechanism responsible for the dynamic fluorescence quenching of polycyclic aromatic compounds (PACs) by Ag+ ions is enhanced intersystem crossing from the lowest singlet excited state to the lowest triplet excited state. For some PACs, however, exciplex formation with Ag+ in polar organic solvents has also been reported. Quenching of pyrene fluorescence by Ag+ in two polar solvent systems (aqueous and ethanolic solutions) was examined here using steady-state and time-resolved fluorescence techniques. In both solvents, quenching led to the formation of a pyrene–Ag+ exciplex, (1Py⋯Ag+)*, which rapidly equilibrated with excited singlet pyrene molecules (1Py*) and Ag+ ions. The exciplex and pyrene monomer emission spectra strongly overlapped, with the dominant exciplex peaks in water and ethanol red shifted from the 0–0 transition of pyrene by 5.08 and 2.56 kJ/mol, respectively. Rate constants for the formation and dissociation of the exciplex were much larger than the radiative and nonradiative decay rate constants for both the excited state monomer and exciplex. The short exciplex fluorescence lifetimes and very low quantum yields observed in the two solvents can be attributed to enhanced nonradiative decay processes for the exciplex. The emission quantum yield of the exciplex formed in aqueous solution was approximately an order of magnitude larger than that in ethanolic solution, which is likely to be attributable to the higher polarity of water versus ethanol. [Copyright &y& Elsevier]

Summary: Changes in disinfection byproduct (DBP) precursors during storm events have not been intensively studied to date despite their dramatic impact on downstream drinking water supplies. For this study, variations in dissolved organic matter (DOM) spectroscopic properties and DBP formation potentials (DBPFPs), and the correlations among these various parameters, were investigated in river water samples collected under two contrasting storm event conditions (a strong summer storm versus a weak fall event). Fluorescence excitation–emission matrices (EEMs) combined with parallel factor analysis revealed that a combination of two humic-like components (C1 and C2) dominated the EEM data of the storm samples. Measured DOM characteristics and DBPFPs varied over a wider range during the more intense summer storm, exhibiting higher values of specific ultraviolet absorbance and C1/C2 ratio at high flow conditions. Variations in the fluorescence index were less pronounced during the two storm events. The spectroscopic changes were well explained by the input of terrestrial DOM sources from the surrounding catchments during the storms. Different trends of the formation potentials for trihalomethanes and haloacetic acids on the recession limb of the hydrographs suggest that the structures responsible for DBP precursors during storm events may not be the same for the two classes of DBPs. The ultraviolet light-absorbing moieties in DOM appear to play major roles in generating DBPs, as evidenced by their strong positive correlations with DBPFPs. Higher correlations with DBPFP for C1 versus C2 suggest that humic-like substances associated with more aromatic and condensed structures have a greater proclivity to generate DBP upon chlorination. [Copyright &y& Elsevier]

Abstract: A new, simple, and rapid method to determine Setschenow (i.e., salting-out) constants for luminescent organic compounds in aqueous solutions has been developed using steady-state and time-resolved fluorescence measurements. Application of the new method was demonstrated using pyrene in the presence of nonquenching (K+) and dynamically quenching (Cs+) akali metal chloride salt solutions at room temperature. For these two model systems, Setschenow constants for pyrene salting-out by KCl and CsCl were determined to be 0.211 and 0.355M−1, respectively. We expect that the methodology reported in this paper can be applied equally well to interactions between a variety of salting-out agents and fluorescent biological and/or environmental molecules in aqueous solutions. [Copyright &y& Elsevier]