Computational Calculation of Dissolved Organic Matter Absorption Spectra.

The absorption spectrum of dissolved organic matter (DOM) is a topic of interest to environmental scientists and engineers as it can be used to assess both the concentration and physicochemical properties of DOM. In this study, the UV-vis spectra for DOM model compounds were calculated using time-dependent density functional theory. Summing these individual spectra, it was possible to re-create the observed exponential shape of the DOM absorption spectra. Additionally, by predicting the effects of sodium borohydride reduction on the model compounds and then calculating the UV-vis absorbance spectra of the reduced compounds, it was also possible to correctly predict the effects of borohydride reduction on DOM absorbance spectra with a relatively larger decrease in absorbance at longer wavelengths. The contribution of charge-transfer (CT) interactions to DOM absorption was also evaluated, and the calculations showed that intra-molecular CT interactions could take place, while inter-molecular CT interactions were proposed to be less likely to contribute.

Computational Assessment of the Three-Dimensional Configuration of Dissolved Organic Matter Chromophores and Influence on Absorption Spectra.

The three-dimensional configuration of dissolved organic matter (DOM) is an important factor in determining the role of DOM in natural and engineered systems, yet there is still considerable uncertainty regarding the formation and potential stability of molecular aggregates within DOM. In this paper, we describe a computational assessment of the three-dimensional configuration of DOM. Specifically, we were interested in evaluating the hypothesis that DOM forms thermodynamically stable molecular aggregates that as a result were potentially shielded from water solvent molecules. Molecular dynamics simulations of DOM model compounds carefully selected based on ultrahigh-resolution mass spectrometry data revealed that, while DOM does indeed form molecular aggregates, the large majority of molecules (especially, O-atom bearing molecules) are solvent accessible. Additionally, these computations revealed that molecular aggregates are weak and dissociate when placed in organic solvents (tetrahydrofuran, methyl tert-butyl ether). Time-dependent density functional theory calculations demonstrated long-wavelength absorbance for both model DOM chromophores and their molecular aggregates. This study has important implications for determining the origin of DOM optical properties and for enhancing our collective understanding of DOM three-dimensional structures.

Fate of Zinc Oxide Nanoparticles in a Biosolid Slurry Characterized for Metal Complexation Characteristics.

Zinc oxide nanoparticles (NPs) present in domestic wastewaters may accumulate in biosolids used as fertilizer. In this paper, metal complexation by typical biosolids is explored using methods from the humics literature. Uptake of Zn from NPs in the biosolids is evaluated. Finally, the kinetics of release of Zn species are reported as a function of (i) pH and (ii) the presence of strong binding ligands (e.g., ion exchange resin promoting release). The investigation revealed that (i) metal binding sites of biosolids are analogs of humic substances, (ii) ZnO NPs do not survive in the digestion environment, and (iii) any ZnO NPs dissolve to aqueous Zn in <10 d. Kinetics of Zn in biosolids revealed that Zn release is a function of biosolid protonation. At pH 8, Zn is retained in the biosolids, whereas at pH 4.5, 10% of Zn is released from the biosolids. Adding a chelating resin to the system at pH 5.0 led to Zn release from the biosolids as per Noyes-Whitney kinetics, releasing 85% of the bound Zn in 360 h. Fifteen percent of Zn appeared to be irreversibly bound.