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Photochemistry of Dissolved Organic Matter: Reactivity and application in constructed treatment wetlands

  • Author(s): Timko, Stephen Andrew
  • Advisor(s): Cooper, William J
  • et al.
Abstract

Constructed wetlands have the potential to provide low-energy treatment of pharmaceuticals and other micropollutants via photolysis. Natural dissolved organic matter (DOM) reacts with sunlight to produce reactive species such as singlet oxygen and excited triplet states of DOM that react quickly and efficiently with contaminants. To study the photo-chemistry of DOM, a unique solar-simulation system was developed, allowing for semi-continuous monitoring of absorbance and fluorescence spectra throughout the irradiation. This system was utilized to investigate the effect of solution pH on the fluorescence properties and degradation of DOM. For the first time, parallel factor (PARAFAC) analysis was utilized to deconvolute photo-labile, photo-stable, and pH- dependent fluorescent components during irradiation. Fluorescence is highly pH dependent, and as pH increases, the total amount of fluorescence loss, and the rate at which it is lost, increases significantly. This has important implications in treatment systems, as the photo-reactivity of DOM will change when pH gradients or fluctuations are observed. The photo-degradation of organic matter collected from a depth profile (0-4,500 m) the Sargasso Sea showed increased reactivity with increasing depth. Ultra-high resolution mass spectrometry (FT-MS) was used to characterize the samples, and correlation analyses between the fluorescence data and mass spectra revealed that high molecular weight, aromatic, and possibly polyphenolic compounds are contributing the most to the fluorescence properties that show the most reactivity in marine samples.

Production of singlet oxygen, hydroxyl radical, and triplet excited states of DOM along two riverine transects in the Everglades were measured. The abundance of fluorescence PARAFAC components was compared to the reactive species production, and suggested that terrestrial organic matter may be more efficient producers of reactive species than microbial- or seagrass- derived organic matter.

Finally, the relationship between optical properties of DOM samples collected around the world and their reactivity were investigated. Photo-irradiations and pH titrations were performed on all samples, and mass spectra collected via FT-MS. Humification indices, the biological index (BIX), and spectral slope from 275-295 nm were found to be most closely tied to changes in the mass spectra of the samples, and showed strong relationship to DOM source.

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