Characteristics of intracellular algogenic organic matter and its reactivity with hydroxyl radicals.

The aim of this study was to investigate the reactivity of intracellular algogenic organic matter (IOM) with hydroxyl radicals (·OH), a key reaction species in advanced oxidation processes. IOM was extracted from two green algae, Chlamydomonas reinhardtii and Scenedesmus sp., and two blue-green algae, Anabaena sp. and Microcystis aeruginosa using a freeze-thaw method. The second-order rate constants of the extracted IOM with ·OH were determined as 7.95 × 108 MC-1 s-1 (Chlamydomonas reinhardtii), 6.71 × 108 MC-1 s-1 (Scenedesmus sp.), 4.02 × 108 MC-1 s-1 (Anabaena sp.), and 4.45 × 108 MC-1 s-1 (Microcystis aeruginosa). These rate constants were significantly higher than values reported for dissolved organic matter in various water sources. This implies that IOM formation during algal bloom season could change the ·OH water matrix demand and adversely affect the performance of advanced oxidation processes. To investigate the physical and chemical composition characteristics of IOM and their relationship to the rate constants determined for the reaction between IOM and ·OH, liquid chromatography-organic carbon detection (LC-OCD) and fluorescence excitation-emission matrix & parallel factor analysis (FEEM-PARAFAC) were used. The IOM mainly consisted of low molecular weight (LMW) matter and protein-related compounds, as evidenced LMW neutrals (38-65%), biopolymers (7-19%), and tryptophan-like compounds (74-94%). Based on the composition characteristics of IOM, it was concluded that the molecular weight and the presence of nitrogen-containing compounds are influential parameters for determining the reactivity of IOM with ·OH.

Characteristics and fate of natural organic matter during UV oxidation processes.

Advanced oxidation processes (AOPs) are widely used in water treatments. During oxidation processes, natural organic matter (NOM) is modified and broken down into smaller compounds that affect the characteristics of the oxidized NOM by AOPs. In this study, NOM was characterized and monitored in the UV/hydrogen peroxide (H2O2) and UV/persulfate (PS) processes using a liquid chromatography-organic carbon detector (LC-OCD) technique, and a combination of excitation-emission matrices (EEM) and parallel factor analysis (PARAFAC). The percentages of mineralization of NOM in the UV/H2O2 and UV/PS processes were 20.5 and 83.3%, respectively, with a 10 mM oxidant dose and a contact time of 174 s (UV dose: approximately 30,000 mJ). Low-pressure, Hg UV lamp (254 nm) was applied in this experiment. The steady-state concentration of SO4- was 38-fold higher than that of OH at an oxidant dose of 10 mM. With para-chlorobenzoic acid (pCBA) as a radical probe compound, we experimentally determined the rate constants of Suwannee River NOM (SRNOM) with OH (kOH/NOM = 3.3 × 108 M-1s-1) and SO4- (kSO4-/NOM = 4.55 × 106 M-1s-1). The hydroxyl radical and sulfate radical showed different mineralization pathways of NOM, which have been verified by the use of LC-OCD and EEM/PARAFAC. Consequently, higher steady-state concentrations of SO4-, and different reaction preferences of OH and SO4- with the NOM constituent had an effect on the mineralization efficiency.