Previous studies have shown that the photodegradation of some pollutants, induced by the excited triplet states of chromophoric dissolved organic matter (3CDOM*), can be inhibited by back-reduction processes carried out by phenolic antioxidants occurring in dissolved organic matter (DOM). Here, for the first time to our knowledge, we included such an inhibition effect into a photochemical model and applied the model predictions to sulfadiazine (SDZ), a sulfonamide antibiotic that occurs in surface waters in two forms, neutral HSDZ and anionic SDZ- (pKa = 6.5). The input parameters of the photochemical model were obtained by means of dedicated experiments, which showed that the inhibition effect was more marked for SDZ- than for HSDZ. Compared to the behavior of 2,4,6-trimethylphenol, which does not undergo antioxidant inhibition when irradiated in natural water samples, the back-reduction effect on the degradation of SDZ was proportional to the electron-donating capacity of the DOM. According to the model results, direct photolysis and ·OH reaction would account for the majority of both HSDZ and SDZ- photodegradation in waters having low dissolved organic carbon (DOC < 1 mgC L-1). With higher DOC values (> 3-4 mgC L-1) and despite the back-reduction processes, the 3CDOM* reactions are expected to account for the majority of HSDZ phototransformation. In the case of SDZ- at high DOC, most of the photodegradation would be accounted for by direct photolysis. The relative importance of the triplet-sensitized phototransformation of both SDZ- and (most importantly) HSDZ is expected to increase with increasing DOC, even in the presence of back reduction. An increase in water pH, favoring the occurrence of SDZ- with respect to HSDZ, would enhance direct photolysis at the expense of triplet sensitization. SDZ should be fairly photolabile under summertime sunlight, with predicted half-lives ranging from a few days to a couple of months depending on water conditions.

Effects of the antioxidant moieties of dissolved organic matter on triplet-sensitized phototransformation processes: Implications for the photochemical modeling of sulfadiazine

Davide Vione;Debora Fabbri;Marco Minella;
2018

Abstract

Previous studies have shown that the photodegradation of some pollutants, induced by the excited triplet states of chromophoric dissolved organic matter (3CDOM*), can be inhibited by back-reduction processes carried out by phenolic antioxidants occurring in dissolved organic matter (DOM). Here, for the first time to our knowledge, we included such an inhibition effect into a photochemical model and applied the model predictions to sulfadiazine (SDZ), a sulfonamide antibiotic that occurs in surface waters in two forms, neutral HSDZ and anionic SDZ- (pKa = 6.5). The input parameters of the photochemical model were obtained by means of dedicated experiments, which showed that the inhibition effect was more marked for SDZ- than for HSDZ. Compared to the behavior of 2,4,6-trimethylphenol, which does not undergo antioxidant inhibition when irradiated in natural water samples, the back-reduction effect on the degradation of SDZ was proportional to the electron-donating capacity of the DOM. According to the model results, direct photolysis and ·OH reaction would account for the majority of both HSDZ and SDZ- photodegradation in waters having low dissolved organic carbon (DOC < 1 mgC L-1). With higher DOC values (> 3-4 mgC L-1) and despite the back-reduction processes, the 3CDOM* reactions are expected to account for the majority of HSDZ phototransformation. In the case of SDZ- at high DOC, most of the photodegradation would be accounted for by direct photolysis. The relative importance of the triplet-sensitized phototransformation of both SDZ- and (most importantly) HSDZ is expected to increase with increasing DOC, even in the presence of back reduction. An increase in water pH, favoring the occurrence of SDZ- with respect to HSDZ, would enhance direct photolysis at the expense of triplet sensitization. SDZ should be fairly photolabile under summertime sunlight, with predicted half-lives ranging from a few days to a couple of months depending on water conditions.
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https://www.sciencedirect.com/science/article/pii/S0043135417308497?via%3Dihub
Antioxidants; Sulfadiazine; Electron Donating Capacity; Dissolved Organic Matter; Environmental Photochemistry.
Davide Vione, Debora Fabbri, Marco Minella, Silvio Canonica
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2318/1687055
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