Surface Inorganic Iodine Speciation in the Indian and Southern Oceans From 12°N to 70°S

Marine iodine speciation has emerged as a potential tracer of primary productivity, sedimentary inputs, and ocean oxygenation. The reaction of iodide with ozone at the sea surface has also been identified as the largest deposition sink for tropospheric ozone and the dominant source of iodine to the atmosphere. Accurate incorporation of these processes into atmospheric models requires improved understanding of iodide concentrations at the air-sea interface. Observations of sea surface iodide are relatively sparse and are particularly lacking in the Indian Ocean basin. Here we examine 127 new sea surface (≤10 m depth) iodide and iodate observations made during three cruises in the Indian Ocean and the Indian sector of the Southern Ocean. The observations span latitudes from ∼12°N to ∼70°S, and include three distinct hydrographic regimes: the South Indian subtropical gyre, the Southern Ocean and the northern Indian Ocean including the southern Bay of Bengal. Concentrations and spatial distribution of sea surface iodide follow the same general trends as in other ocean basins, with iodide concentrations tending to decrease with increasing latitude (and decreasing sea surface temperature). However, the gradient of this relationship was steeper in subtropical waters of the Indian Ocean than in the Atlantic or Pacific, suggesting that it might not be accurately represented by widely used parameterizations based on sea surface temperature. This difference in gradients between basins may arise from differences in phytoplankton community composition and/or iodide production rates. Iodide concentrations in the tropical northern Indian Ocean were higher and more variable than elsewhere. Two extremely high iodide concentrations (1241 and 949 nM) were encountered in the Bay of Bengal and are thought to be associated with sedimentary inputs under low oxygen conditions. Excluding these outliers, sea surface iodide concentrations ranged from 20 to 250 nM, with a median of 61 nM. Controls on sea surface iodide concentrations in the Indian Ocean were investigated using a state-of-the-art iodine cycling model. Multiple interacting factors were found to drive the iodide distribution. Dilution via vertical mixing and mixed layer depth shoaling are key controls, and both also modulate the impact of biogeochemical iodide formation and loss processes

Estimation of reactive inorganic iodine fluxes in the Indian and Southern Ocean marine boundary layer

Iodine chemistry has noteworthy impacts on the oxidising capacity of the marine boundary layer (MBL) through the depletion of ozone (O3) and changes to HOx (OH=HO2) and NOx (NO=NO2) ratios. Hitherto, studies have shown that the reaction of atmospheric O3 with surface seawater iodide (I-) contributes to the flux of iodine species into the MBL mainly as hypoiodous acid (HOI) and molecular iodine (I2). Here, we present the first concomitant observations of iodine oxide (IO), O3 in the gas phase, and sea surface iodide concentrations. The results from three field campaigns in the Indian Ocean and the Southern Ocean during 2015 2017 are used to compute reactive iodine fluxes in the MBL. Observations of atmospheric IO by multi-axis differential optical absorption spectroscopy (MAX-DOAS) show active iodine chemistry in this environment, with IO values up to 1 pptv (parts per trillion by volume) below latitudes of 40° S. In order to compute the sea-to-air iodine flux supporting this chemistry, we compare previously established global sea surface iodide parameterisations with new regionspecific parameterisations based on the new iodide observations. This study shows that regional changes in salinity and sea surface temperature play a role in surface seawater iodide estimation. Sea air fluxes of HOI and I2, calculated from the atmospheric ozone and seawater iodide concentrations (observed and predicted), failed to adequately explain the detected IO in this region. This discrepancy highlights the need to measure direct fluxes of inorganic and organic iodine species in the marine environment. Amongst other potential drivers of reactive iodine chemistry investigated, chlorophyll a showed a significant correlation with atmospheric IO (R D 0:7 above the 99 % significance level) to the north of the polar front. This correlation might be indicative of a biogenic control on iodine sources in this region