Abstract Superoxide () is a reactive oxygen species (ROS) that is primarily produced by the one‐electron transfer of photooxidized chromophoric dissolved organic matter (CDOM) to O2in sunlit natural waters. Here we examine the environmental and chemical parameters (pH, ionic strength, buffer, and halides) that may influence photochemical production rates and decay pathways in natural water. Using the enzyme superoxide dismutase and H2O2measurements, we present results from an irradiated freshwater CDOM source indicating that reductive decay pathways (P/PSOD) dominate with increased pH and NaCl additions and maximal photoproduction rates () increase with carbonate compared to borate buffer. Over 2 h of irradiation, a significant decline in was seen for all samples along with a minor increase in oxidative pathways. These results imply shifts in decay pathways and production rates that seem to vary across natural waters and as a function of irradiation history.
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Controls on the photochemical production of hydrogen peroxide in Lake Erie
In Lake Erie, toxin-forming harmful algal blooms (HABs) occur following high concentrations of hydrogen peroxide (H 2 O 2 ). Correlation between H 2 O 2 concentrations and HABs revealed knowledge gaps on the controls of H 2 O 2 production in Lake Erie. One way H 2 O 2 is produced is upon absorption of sunlight by the chromophoric fraction of dissolved organic matter (CDOM). Rates of this photochemical production of H 2 O 2 may increase in proportion to the apparent quantum yield of H 2 O 2 ( Φ H 2 O 2 ,λ ) from CDOM. However, the Φ H 2 O 2 ,λ for H 2 O 2 production from CDOM remains too poorly constrained to predict the magnitude and range of photochemically produced H 2 O 2 , particularly in freshwaters like Lake Erie. To address this knowledge gap, the Φ H 2 O 2 ,λ was measured approximately biweekly from June–September 2019 in the western basin of Lake Erie along with supporting analyses ( e.g. , CDOM concentration and composition). The average Φ H 2 O 2 ,λ in Lake Erie was within previously reported ranges. However, the Φ H 2 O 2 ,λ varied 5-fold in space and time. The highest Φ H 2 O 2 ,λ was observed in the Maumee River, a tributary of Lake Erie. In nearshore waters of Lake Erie, the Φ H 2 O 2 ,λ decreased about five-fold from June through September. Integration of the controls of photochemical production of H 2 O 2 in Lake Erie show that the variability in rates of photochemical H 2 O 2 production was predominantly due to the Φ H 2 O 2 ,λ . In offshore waters, CDOM concentration also strongly influenced photochemical H 2 O 2 production. Together, the results confirm prior work suggesting that photochemical production of H 2 O 2 contributes but likely cannot account for all the H 2 O 2 associated with HABs in Lake Erie.
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- Award ID(s):
- 1736629
- PAR ID:
- 10410101
- Date Published:
- Journal Name:
- Environmental Science: Processes & Impacts
- Volume:
- 24
- Issue:
- 11
- ISSN:
- 2050-7887
- Page Range / eLocation ID:
- 2108 to 2118
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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