title: Triplet photochemistry of effluent and natural organic matter in whole water and isolates from effluent-receiving rivers.
abstract: Effluent organic matter (EfOM), contained in treated municipal wastewater, differs in composition from naturally occurring dissolved organic matter (DOM). The presence of EfOM may thus alter the photochemical production of reactive intermediates in rivers that receive measurable contributions of treated municipal wastewater. Quantum yield coefficients for excited triplet-state OM (3OM*) and apparent quantum yields for singlet oxygen (1O2) were measured for both whole water samples and OM isolated by solid phase extraction from whole water samples collected upstream and downstream of municipal wastewater treatment plant discharges in three rivers receiving differing effluent contributions: Hockanum R., CT (22% (v/v) effluent flow), E. Fork Little Miami R., OH (11%), and Pomperaug R., CT (6%). While only small differences in production of these reactive intermediates were observed between upstream and downstream whole water samples collected from the same river, yields of 3OM* and 1O2 varied by 30-50% between the rivers. Apparent quantum yields of 1O2 followed similar trends to those of 3OM*, consistent with 3OM* as a precursor to 1O2 formation. Higher 3OM* reactivity was observed for whole water samples than for OM isolates of the same water, suggesting differential recoveries of photoreactive moieties by solid phase extraction. 3OM* and 1O2 yields increased with increasing E2/E3 ratio (A254 nm divided by A365 nm) and decreased with increasing electron donating capacities of the samples, thus exhibiting trends also observed for reference humic and fulvic acid isolates. Mixing experiments with EfOM and DOM isolates showed evidence of quenching of triplet DOM by EfOM when measured yields were compared to theoretical yields. Together, the results suggest that effluent contributions of up to 25% (v/v) to river systems have a negligible influence on photochemical production of 3OM* and 1O2 apparently because of quenching of triplet DOM by EfOM. Furthermore, the results highlight the importance of whole water studies for quantifying in situ photoreactivity, particularly for 3OM*.
authors: †Department of Chemistry, University of Connecticut, 55 North Eagleville Road, Storrs, Connecticut 06269-3060, United States.
authors: Laleen C
authors: LC
authors: Bodhipaksha
authors: ‡Department of Chemistry, University of Mary Washington, Fredericksburg, Virginia 22401, United States.
authors: Charles M
authors: CM
authors: Sharpless
authors: §School of Earth Sciences, The Ohio State University, 125 South Oval Mall, Columbus, Ohio 43210, United States.
authors: Yu-Ping
authors: YP
authors: Chin
authors: ∥Department of Environmental Systems Science, Institute of Biogeochemistry and Pollutant Dynamics, Swiss Federal Institute of Technology (ETH) Zurich, CH-8092 Zurich, Switzerland.
authors: Michael
authors: M
authors: Sander
authors: ‡Department of Chemistry, University of Mary Washington, Fredericksburg, Virginia 22401, United States.
authors: William K
authors: WK
authors: Langston
authors: †Department of Chemistry, University of Connecticut, 55 North Eagleville Road, Storrs, Connecticut 06269-3060, United States.|⊥Environmental Engineering Program and Center for Environmental Sciences and Engineering, University of Connecticut, 261 Glenbrook Road, Storrs, Connecticut 06269-3037, United States.
authors: Allison A
authors: AA
authors: MacKay
mesh_terms: D045424:Complex Mixtures / Q000032:analysis*; D005618:Fresh Water / Q000737:chemistry*; D009930:Organic Chemicals / Q000032:analysis*; D010777:Photochemistry; D045483:Rivers / Q000737:chemistry*; D026082:Singlet Oxygen / Q000032:analysis; D062065:Wastewater / Q000737:chemistry*
chemical_list: D045424:Complex Mixtures; D009930:Organic Chemicals; D026082:Singlet Oxygen; D062065:Wastewater