Abstract Marine microbes produce extracellular reactive oxygen species (ROS) such as superoxide and hydrogen peroxide (H2O2) as a result of regulated and nonregulated physiological and metabolic reactions. ROS production can be a sink and cryptic recycling flux of dissolved oxygen that may rival other key fluxes in the global oxygen cycle; however, the low abundance and high turnover rate of ROS makes this figure difficult to constrain. One key step in determining the disparity between the gross production of ROS and the net sink of dissolved oxygen lies in understanding the degradation pathways of H2O2in the marine water column. In this study, we use isotope‐labeling techniques to determine the redox fate of H2O2in a range of marine environments off the West Coast of California. We find that H2O2reduction is greater than or equal to H2O2oxidation at most sampled depths, with notable exceptions in some surface and intermediate water depths. The observation that H2O2oxidation can exceed reduction in the dark ocean indicates the presence of an oxidizing decay pathway that is not among the known suite of microbially mediated enzymatic pathways (i.e., catalase and peroxidase), pointing to an abiotic and/or a nonenzymatic decay pathway at intermediate water depths. These results highlight the complexity and heterogeneity of ROS decay pathways in natural waters and their unconstrained regulation of oxygen levels within the ocean.
more »
« less
Depth-resolved photochemical production of hydrogen peroxide in the global ocean using remotely sensed ocean color
Hydrogen peroxide (H 2 O 2 ) is an important reactive oxygen species (ROS) in natural waters, affecting water quality via participation in metal redox reactions and causing oxidative stress for marine ecosystems. While attempts have been made to better understand H 2 O 2 dynamics in the global ocean, the relative importance of various H 2 O 2 sources and losses remains uncertain. Our model improves previous estimates of photochemical H 2 O 2 production rates by using remotely sensed ocean color to characterize the ultraviolet (UV) radiation field in surface water along with quantitative chemical data for the photochemical efficiency of H 2 O 2 formation. Wavelength- and temperature-dependent efficiency (i.e., apparent quantum yield, AQY) spectra previously reported for a variety of seawater sources, including coastal and oligotrophic stations in Antarctica, the Pacific Ocean at Station ALOHA, the Gulf of Mexico, and several sites along the eastern coast of the United States were compiled to obtain a “marine-average” AQY spectrum. To evaluate our predictions of H 2 O 2 photoproduction in surface waters using this single AQY spectrum, we compared modeled rates to new measured rates from Gulf Stream, coastal, and nearshore river-outflow stations in the South Atlantic Bight, GA, United States; obtaining comparative differences of 33% or less. In our global model, the “marine-average” AQY spectrum was used with modeled solar irradiance, together with satellite-derived surface seawater temperature and UV optical properties, including diffuse attenuation coefficients and dissolved organic matter absorption coefficients estimated with remote sensing-based algorithms. The final product of the model, a monthly climatology of depth-resolved H 2 O 2 photoproduction rates in the surface mixed layer, is reported for the first time and provides an integrated global estimate of ∼21.1 Tmol yr −1 for photochemical H 2 O 2 production. This work has important implications for photo-redox reactions in seawater and improves our understanding of the role of solar irradiation on ROS cycling and the overall oxidation state in the oceans.
more »
« less
- Award ID(s):
- 1924763
- PAR ID:
- 10457355
- Date Published:
- Journal Name:
- Frontiers in Remote Sensing
- Volume:
- 3
- ISSN:
- 2673-6187
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
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.more » « less
-
The distribution of iodine in the surface ocean – of which iodide-iodine is a large destructor of tropospheric ozone (O3) – can be attributed to bothin situ(i.e., biological) andex situ(i.e., mixing) drivers. Currently, uncertainty regarding the rates and mechanisms of iodide (I-) oxidation render it difficult to distinguish the importance ofin situreactions vsex situmixing in driving iodine’s distribution, thus leading to uncertainty in climatological ozone atmospheric models. It has been hypothesized that reactive oxygen species (ROS), such as superoxide (O2•−) or hydrogen peroxide (H2O2), may be needed for I-oxidation to occur at the sea surface, but this has yet to be demonstrated in natural marine waters. To test the role of ROS in iodine redox transformations, shipboard isotope tracer incubations were conducted as part of the Bermuda Atlantic Time Series (BATS) in the Sargasso Sea in September of 2018. Incubation trials evaluated the effects of ROS (O2•−, H2O2) on iodine redox transformations over time and at euphotic and sub-photic depths. Rates of I-oxidation were assessed using a129I-tracer (t1/2~15.7 Myr) added to all incubations, and129I/127I ratios of individual iodine species (I-, IO3-). Our results show a lack of I-oxidation to IO3-within the resolution of our tracer approach – i.e., <2.99 nM/day, or <1091.4 nM/yr. In addition, we present new ROS data from BATS and compare our iodine speciation profiles to that from two previous studies conducted at BATS, which demonstrate long-term iodine stability. These results indicate thatex situprocesses, such as vertical mixing, may play an important role in broader iodine species’ distribution in this and similar regions.more » « less
-
Abstract The Gulf of Maine holds significant ecological and economic value for fisheries and communities in north-eastern North America. However, there is apprehension regarding its vulnerability to the effects of increasing atmospheric CO2. Substantial recent warming and the inflow of low alkalinity waters into the Gulf of Maine have raised concerns about the impact of ocean acidification on resident marine calcifiers (e.g. oysters, clams, mussels). With limited seawater pH records, the natural variability and drivers of pH in this region remain unclear. To address this, we present coastal water pH proxy records using boron isotope (δ11B) measurements in long-lived, annually banded, crustose coralline algae (1920–2018 CE). These records indicate seawater pH was low (~ 7.9) for much of the last century. Contrary to expectation, we also find that pH has increased (+ 0.2 pH units) over the past 40 years, despite concurrent rising atmospheric CO2. This increase is attributed to an increased input of high alkalinity waters derived from the Gulf Stream. This delayed onset of ocean acidification is cause for concern. Once ocean circulation-driven buffering effects reach their limit, seawater pH decline may occur swiftly. This would profoundly harm shellfisheries and the broader Gulf of Maine ecosystem.more » « less
-
Iodine intersects with the marine biogeochemical cycles of several major elements and can influence air quality through reactions with tropospheric ozone. Iodine is also an element of interest in paleoclimatology, whereby iodine-to-calcium ratios in marine carbonates are widely used as a proxy for past ocean redox state. While inorganic iodine in seawater is found predominantly in its reduced and oxidized anionic forms, iodide (I−) and iodate (IO3−), the rates, mechanisms and intermediate species by which iodine cycles between these inorganic pools are poorly understood. Here, we address these issues by characterizing the speciation, composition and cycling of iodine in the upper 1,000 m of the water column at Station ALOHA in the subtropical North Pacific Ocean. We first obtained high-precision profiles of iodine speciation using isotope dilution and anion exchange chromatography, with measurements performed using inductively coupled plasma mass spectrometry (ICP-MS). These profiles indicate an apparent iodine deficit in surface waters approaching 8% of the predicted total, which we ascribe partly to the existence of dissolved organic iodine that is not resolved during chromatography. To test this, we passed large volumes of seawater through solid phase extraction columns and analyzed the eluent using high-performance liquid chromatography ICP-MS. These analyses reveal a significant pool of dissolved organic iodine in open ocean seawater, the concentration and complexity of which diminish with increasing water depth. Finally, we analyzed the rates of IO3−formation using shipboard incubations of surface seawater amended with129I−. These experiments suggest that intermediate iodine species oxidize to IO3−much faster than I−does, and that rates of IO3−formation are dependent on the presence of particles, but not light levels. Our study documents the dynamics of iodine cycling in the subtropical ocean, highlighting the critical role of intermediates in mediating redox transformations between the major inorganic iodine species.more » « less
An official website of the United States government

