title: Photochemical production of hydrogen peroxide in size-fractionated Southern California coastal waters.
abstract: Hydrogen peroxide (H(2)O(2)) photochemical production was measured in bulk and size-fractionated surf zone and source waters (Orange County, California, USA). Post-irradiation (60 min; 300 W ozone-free xenon lamp), maximum H(2)O(2) concentrations were approximately 10000 nM (source) and approximately 1500 nM (surf zone). Average initial hydrogen peroxide production rates (HPPR) were higher in bulk source waters (11+/-7.0 nM s(-1)) than the surf zone (2.5+/-1 nM s(-1)). A linear relationship was observed between non-purgeable dissolved organic carbon and absorbance coefficient (m(-1) (300 nm)). HPPR increased with increasing absorbance coefficient for bulk and size-fractionated source waters, consistent with photochemical production from CDOM. However, HPPR varied significantly (5x) for surf zone samples with the same absorbance coefficients, even though optical properties suggested CDOM from salt marsh source waters dominates the surf zone. To compare samples with varying CDOM levels, apparent quantum yields (Phi) for H(2)O(2) photochemical production were calculated. Source waters showed no significant difference in Phi between bulk, large (>1000 Da (>1 kDa)) and small (<1 kDa) size fractions, suggesting H(2)O(2) production efficiency is homogeneously distributed across CDOM size. However, surf zone waters had significantly higher Phi than source (bulk 0.086+/-0.04 vs. 0.034+/-0.013; <1 kDa 0.183+/-0.012 vs. 0.027+/-0.018; >1 kDa 0.151+/-0.090 vs. 0.016+/-0.009), suggesting additional production from non-CDOM sources. H(2)O(2) photochemical production was significant for intertidal beach sand and senescent kelp (sunlight; approximately 42 nM h(-1) vs. approximately 5 nM h(-1)), on the order of CDOM production rates previously measured in coastal and oceanic waters. This is the first study of H(2)O(2) photochemical production in size-fractionated coastal waters showing significant production from non-CDOM sources in the surf zone.
authors.affiliation: Department of Chemistry, Chapman University, Orange, CA 92866, USA. cclark@chapman.edu
authors.forename: Catherine D
authors.initials: CD
authors.lastname: Clark
authors.forename: Warren J
authors.initials: WJ
authors.lastname: De Bruyn
authors.forename: Joshua G
authors.initials: JG
authors.lastname: Jones
mesh_terms: D002140:California; D004784:Environmental Monitoring; D006861:Hydrogen Peroxide / Q000378:metabolism*; D010777:Photochemistry; D011789:Quantum Theory; D012623:Seawater / Q000032:analysis*; D014871:Water Microbiology; D014873:Water Pollutants / Q000032:analysis*
chemical_list: D014873:Water Pollutants; D006861:Hydrogen Peroxide