Dissolved inorganic and particulate iodine in the oceans
Wong, George T. F.
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KeywordChemical oceanography; Iodine; Trace elements in water; Seawater composition; Atlantis II (Ship : 1963-) Cruise AII83; Atlantis II (Ship : 1963-) Cruise AII79; Atlantis II (Ship : 1963-) Cruise AII86; Chain (Ship : 1958-) Cruise CH120
Analytical methods have been developed for the determination of iodate, iodide and particulate iodine in sea water. Iodate is converted to tri-iodide and the absorbance of tri-iodide at 353 nm is measured. The precision of this method is ca. ±3%. Iodide is first separated from most other anions by an AG 1-x8 anion exchange column and then precipitated as palladous iodide with elemental palladium as the carrier. The precipitate is analyzed by neutron activation analysis. The precision of the method is ±5% and the reagent blank is 0.005 uM. Marine suspended matter is collected by passing sea water under pressure through a 0.6 u (37 mm diameter) Nuclepore filter. The iodine content of the particles is determined by neutron activation analysis. The method has excellent reproducibility and the filter blank is ca. 3 ng. Iodate is depleted in the surface waters of the Equatorial Atlantic. The depletion is more pronounced than in the Argentine Basin and possibly reflects the higher productivity in the equatorial area. Superimposed on this feature, a thin lens of water, of a few tens of meters thick and with high iodate concentrations, can be traced across the Atlantic. Along the equator, this lens occurs at 80 m at 33˚W and rises upwards to 55 m at 10˚W and it coincides with a core of highly saline water which is characteristic of the Equatorial Undercurrent. Longitudinal sections reflect the complexity of the equatorial current system. At least three cores of water with high iodate concentrations may be identified. These waters may be transported to the equatorial region from the highly productive areas along the north-western and western African coasts and the Amazon plume. In anoxic basins, the concentration of iodide increases rapidly in the mixing zone from 0.02 uM to 0.44 uM in the Cariaco Trench and from 0.01 uM to 0.23 uM in the Black Sea. The iodate concentration, meanwhile. decreases to zero. A maximum in the total iodine to salinity ratio is observed just above the oxygen-sulfide interface (15 to 17 nmoles/g); it is suggestive of particle dissolution in a strong pycnocline. Below the interface, the total iodine to salinity ratio is constant at 12.3 nmoles/g in the anoxic zone of the Cariaco Trench, whereas, in the Black Sea, it increases with depth from 10.0 to 19.4 nmoles/g and suggests a possible flux of iodide from the sediments. By considering the distribution of iodate and iodide in oxic and anoxic basins and our present analytical capability, the lower limit of the pE of the oceans is estimated to be 10.7. Thermodynamic considerations further suggest that the iodide-iodate couple is a poor indica tor for the pE of the oceans with a limited usable range of 10.0 to 10.7. In the Gulf of Maine during the winter of 1974 to 1975. the effect of winter mixing was conspicuous. Uniform concentrations of iodide and iodate were observed in the mixed layer above the sill. The absence of a depletion of iodate and the low iodide concentration (0.04 uM) in the surface waters reflect the low biological activity in this region during winters. Profiles of particulate iodine are characterized by high concentrations in the euphotic zone (>5 ng/kg), and lower concentrations (< 2 ng/kg) at greater depths. Occasionally, high concentrations have also been observed in the nepheloid layer. The iodine-containing particles are probably biogenic. A section in the Western Atlantic from 75°N to 55˚S shows evidence of the transport of particles along isopycnals and the re-suspension of surface sediments to considerable distance from the bottom. The standing crops in the top 200 m may be qualitatively correlated with the primary productivity. Thermodynamic considerations show that iodide is a metastable form at the pH of sea water. Laboratory studies fail to show the oxidation of iodide at measurable rates. Elemental iodine is unstable in sea water and undergoes hydrolysis to form hypoiodous acid in seconds. Hypoiodous acid is also unstable and has a life time of minutes to hours. It may react with organic compounds to form iodinated derivatives or it may be reduced to iodide by a reducing agent. The disproportionation of hypoiodite to form iodate seems to be a slower process. A possible chemical cycle for iodine in the marine environment is proposed.
Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts institute of Technology and the Woods Hole Oceanographic Institution February 1976
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