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1. Speciation and cycling of iodine in the subtropical North Pacific Ocean

   https://doi.org/10.3389/fmars.2023.1272968  

   Ştreangă, Iulia-Mădălina; Repeta, Daniel J.; Blusztajn, Jerzy S.; Horner, Tristan J. (January 2024, Frontiers in Marine Science)

   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. 

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2. The Distribution and Redox Speciation of Iodine in the Eastern Tropical North Pacific Ocean

   https://doi.org/10.1029/2019GB006302  

   Moriyasu, Rintaro; Evans, Natalya; Bolster, Kenneth M.; Hardisty, Dalton S.; Moffett, James W. (February 2020, Global Biogeochemical Cycles)

   Abstract The distributions of iodate (IO₃⁻), iodide (I⁻), nitrite (NO₂⁻), and oxygen (O₂) were determined on two zonal transects and one meridional transect in the Eastern Tropical North Pacific (ETNP) in 2018. Iodine is a useful tracer of in situ redox transformations and inputs within the water column from continental margins. In oxygenated waters, iodine is predominantly present as oxidized iodate. In the oxygen deficient zone (ODZ) in the ETNP, a substantial fraction is reduced to iodide, with the highest iodide concentrations coincident with the secondary nitrite maxima. These features resemble ODZs in the Arabian Sea and Eastern Tropical South Pacific (ETSP). Maxima in iodide and nitrite were associated with a specific water mass, referred to as the 13 °C Water, the same water mass that contains the highest concentrations of iodide within the ETSP. Physical processes leading to patchiness in the 13 °C Water relative to other water masses could account for the patchiness frequently observed in iodide and nitrite, probably reflecting subsurface mesoscale features such as eddies. Throughout much of the ETNP ODZ, iodine concentrations were higher than the mean oceanic value. This “excess iodine” is attributed to lateral inputs from sedimentary margins. Excess iodine maxima are centered within a potential density of 26.2–26.6 kg/m³, a density range that intersects with reducing shelf sediments and is almost identical to the ETSP. Evidently, margin input processes are significant throughout the basin and can influence the nitrogen and iron cycles as well, as in the ETSP. 

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3. Nitrification in a Subterranean Estuary: An Ex Situ and In Situ Method Comparison Determines Nitrate Is Available for Discharge

   https://doi.org/10.1029/2023JG007876  

   Wilson, Stephanie_J; Song, Bongkeun; Anderson, Iris_C; Tobias, Craig_R (June 2024, Journal of Geophysical Research: Biogeosciences)

   Abstract Subterranean estuaries (STEs) form in the subsurface where fresh groundwater and seawater meet and mix. Subterranean estuaries support a variety of biogeochemical processes including those transforming nitrogen (N). Groundwater is often enriched with dissolved inorganic nitrogen (DIN), and transformations in the STE determine the fate of that DIN, which may be discharged to coastal waters. Nitrification oxidizes ammonium (NH₄⁺) to nitrate, making DIN available for N removal via denitrification. We measured nitrification at an STE, in Virginia, USA using in situ and ex situ methods including conservative mixing models informed by in situ geochemical profiles, an in situ experiment with¹⁵NH₄⁺tracer injection, and ex situ sediment slurry incubations with¹⁵NH₄⁺tracer addition. All methods indicated nitrification in the STE, but the ex situ sediment slurries revealed higher rates than both the in situ tracr experiment and mixing model estimations. Nitrification rates ranged 55.0–183.16 μmol N m⁻² d⁻¹based on mixing models, 94.2–225 μmol N m⁻² d⁻¹in the in situ tracer experiment, and 36.6–109 μmol N m⁻² d⁻¹slurry incubations. The in situ tracer experiment revealed higher rates and spatial variation not captured by the other methods. The geochemical complexity of the STE makes it difficult to replicate in situ conditions with incubations and calculations based on chemical profiles integrate over longer timescales, therefore, in situ approaches may best quantify transformation rates. Our data suggest that STE nitrification produces NO₃⁻, altering the DIN pool discharged to overlying water via submarine groundwater discharge. 

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4. Elevated Tropospheric Iodine Over the Central Continental United States: Is Iodine a Major Oxidant of Atmospheric Mercury?

   https://doi.org/10.1029/2024GL109247  

   Lee, C F; Elgiar, T; David, L M; Wilmot, T Y; Reza, M; Hirshorn, N; McCubbin, I B; Shah, V; Lin, J C; Lyman, S N; et al (September 2024, Geophysical Research Letters)

   Abstract Previous efforts to measure atmospheric iodine have focused on marine and coastal regions. We report the first ground‐based tropospheric iodine monoxide (IO) radical observations over the central continental United States. Throughout April 2022, IO columns above Storm Peak Laboratory, Colorado (3,220 m.a.s.l.) ranged from 0.7 ± 0.5 to 3.6 ± 0.5 × 10¹²(average: 1.9 × 10¹² molec cm⁻²). IO was consistently elevated in air masses transported from over the Pacific Ocean. The observed IO columns were up to three times higher and the range was larger than predicted by a global model, which warrants further investigation into iodine sources, sinks, ozone loss, and particle formation. IO mixing ratios increased with altitude. At the observed levels, iodine may be competitive with bromine as an oxidant of elemental mercury at cold temperatures typical of the free troposphere. Iodine‐induced mercury oxidation is missing in atmospheric models, understudied, and helps explain model underestimation of oxidized mercury measurements. 

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5. Global impacts of tropospheric halogens (Cl, Br, I) on oxidants and composition in GEOS-Chem

   https://doi.org/10.5194/acp-16-12239-2016  

   Sherwen, Tomás; Schmidt, Johan A.; Evans, Mat J.; Carpenter, Lucy J.; Großmann, Katja; Eastham, Sebastian D.; Jacob, Daniel J.; Dix, Barbara; Koenig, Theodore K.; Sinreich, Roman; et al (January 2016, Atmospheric Chemistry and Physics)

   We present a simulation of the global present-day composition of the troposphere which includes the chemistry of halogens (Cl, Br, I). Building on previous work within the GEOS-Chem model we include emissions of inorganic iodine from the oceans, anthropogenic and biogenic sources of halogenated gases, gas phase chemistry, and a parameterised approach to heterogeneous halogen chemistry. Consistent with Schmidt et al. (2016) we do not include sea-salt debromination. Observations of halogen radicals (BrO, IO) are sparse but the model has some skill in reproducing these. Modelled IO shows both high and low biases when compared to different datasets, but BrO concentrations appear to be modelled low. Comparisons to the very sparse observations dataset of reactive Cl species suggest the model represents a lower limit of the impacts of these species, likely due to underestimates in emissions and therefore burdens. Inclusion of Cl, Br, and I results in a general improvement in simulation of ozone (O₃) concentrations, except in polar regions where the model now underestimates O₃ concentrations. Halogen chemistry reduces the global tropospheric O₃ burden by 18.6 %, with the O₃ lifetime reducing from 26 to 22 days. Global mean OH concentrations of 1.28  ×  10⁶ molecules cm⁻³ are 8.2 % lower than in a simulation without halogens, leading to an increase in the CH₄ lifetime (10.8 %) due to OH oxidation from 7.47 to 8.28 years. Oxidation of CH₄ by Cl is small (∼  2 %) but Cl oxidation of other VOCs (ethane, acetone, and propane) can be significant (∼  15–27 %). Oxidation of VOCs by Br is smaller, representing 3.9 % of the loss of acetaldehyde and 0.9 % of the loss of formaldehyde. 

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