title: Enhanced Indirect Photochemical Transformation of Histidine and Histamine through Association with Chromophoric Dissolved Organic Matter.
abstract: Photochemical transformations greatly affect the stability and fate of amino acids (AAs) in sunlit aquatic ecosystems. Whereas the direct phototransformation of dissolved AAs is well investigated, their indirect photolysis in the presence of chromophoric dissolved organic matter (CDOM) is poorly understood. In aquatic systems, CDOM may act both as sorbent for AAs and as photosensitizer, creating microenvironments with high concentrations of photochemically produced reactive intermediates, such as singlet oxygen (1O2). This study provides a systematic investigation of the indirect photochemical transformation of histidine (His) and histamine by 1O2 in solutions containing CDOM as a function of solution pH. Both His and histamine showed pH-dependent enhanced phototransformation in the CDOM systems as compared to systems in which model, low-molecular-weight 1O2 sensitizers were used. Enhanced reactivity resulted from sorption of His and histamine to CDOM and thus exposure to elevated 1O2 concentrations in the CDOM microenvironment. The extent of reactivity enhancement depended on solution pH via its effects on the protonation state of His, histamine, and CDOM. Sorption-enhanced reactivity was independently supported by depressed rate enhancements in the presence of a cosorbate that competitively displaced His and histamine from CDOM. Incorporating sorption and photochemical transformation processes into a reaction rate prediction model improved the description of the abiotic photochemical transformation rates of His in the presence of CDOM.
authors.affiliation: †Institute of Biogeochemistry and Pollutant Dynamics (IBP), Department of Environmental Systems Science, ETH Zurich, 8092 Zurich, Switzerland.
authors.forename: Chiheng
authors.initials: C
authors.lastname: Chu
authors.affiliation: †Institute of Biogeochemistry and Pollutant Dynamics (IBP), Department of Environmental Systems Science, ETH Zurich, 8092 Zurich, Switzerland.
authors.forename: Rachel A
authors.initials: RA
authors.lastname: Lundeen
authors.affiliation: ‡Department of Civil and Environmental Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States.
authors.forename: Christina K
authors.initials: CK
authors.lastname: Remucal
authors.affiliation: †Institute of Biogeochemistry and Pollutant Dynamics (IBP), Department of Environmental Systems Science, ETH Zurich, 8092 Zurich, Switzerland.
authors.forename: Michael
authors.initials: M
authors.lastname: Sander
authors.affiliation: †Institute of Biogeochemistry and Pollutant Dynamics (IBP), Department of Environmental Systems Science, ETH Zurich, 8092 Zurich, Switzerland.
authors.forename: Kristopher
authors.initials: K
authors.lastname: McNeill
mesh_terms: D000327:Adsorption; D004777:Environment; D006632:Histamine / Q000528:radiation effects*; D006639:Histidine / Q000528:radiation effects*; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D008962:Models, Theoretical; D055668:Photochemical Processes; D026082:Singlet Oxygen / Q000737:chemistry; D012996:Solutions; D013696:Temperature
chemical_list: D012996:Solutions; D026082:Singlet Oxygen; D006639:Histidine; D006632:Histamine