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Thesis for the Degree of Doctor of Philosophy - DTU Orbit

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Although <strong>the</strong> oxygen concentration decreases with increasing depth in <strong>the</strong> Baltic Sea and at some locations<br />

reaches anoxic conditions (unpublished data), an opposite trend occurs <strong>for</strong> <strong>the</strong> concentration <strong>of</strong> 129 IO3 - and<br />

127<br />

IO3 - (Figs. 9 and 10 and Paper III). A possible explanation <strong>for</strong> <strong>the</strong> high concentration <strong>of</strong> 129 IO3 - in<br />

oxygen depleted deep water <strong>of</strong> <strong>the</strong> Baltic Sea may be <strong>the</strong> transport <strong>of</strong> iodate enriched Kattegat water which<br />

flows along <strong>the</strong> bottom <strong>of</strong> <strong>the</strong> Baltic Sea and is subsequently transported to <strong>the</strong> Arkona, Bornholm and<br />

Gotland Basins. The enrichment <strong>of</strong> iodate in anoxic bottom water <strong>of</strong> <strong>the</strong> Baltic Sea may however be<br />

explained not only by <strong>the</strong> effect <strong>of</strong> saline water intrusion. Ano<strong>the</strong>r source <strong>of</strong> iodate under such anoxic<br />

conditions can be <strong>the</strong> release <strong>of</strong> iodine as iodide and iodate from sediments by digenetic processes (Yuita,<br />

1992; Muramatsu et al., 1996). Our results show that <strong>the</strong> reduction <strong>of</strong> iodate in <strong>the</strong> oxygen deficient bottom<br />

water <strong>of</strong> <strong>the</strong> Baltic proper (Figs. 9 and 10) is a slow process since higher concentrations <strong>of</strong> iodate (both<br />

isotopes) was found in bottom water when comparing with surface and intermediate waters <strong>of</strong> Baltic Sea <strong>for</strong><br />

both seasons.<br />

The results <strong>of</strong> this work shown that (i) reduction <strong>of</strong> iodate and oxidation <strong>of</strong> iodide in Skagerrak and Kattegat<br />

may be a slow process since insignificant change in 129 I and 127 I speciation was found (ii) reduction <strong>of</strong> iodate<br />

to iodide seems to be relative fast process in surface water <strong>of</strong> <strong>the</strong> sou<strong>the</strong>rn Baltic Sea; (iii) although suboxic<br />

or anoxic condition occur in some <strong>of</strong> <strong>the</strong> Baltic Sea deep waters, <strong>the</strong> concentration <strong>of</strong> 129 IO3 - increases with<br />

water depth indicating that <strong>the</strong> reduction <strong>of</strong> iodate in <strong>the</strong> anoxic bottom water <strong>of</strong> Baltic Sea seems to be a<br />

slow process. The main mechanism <strong>of</strong> iodine reduction may thus be biotically driven ra<strong>the</strong>r than abiotic.<br />

3.3.2 Spatial and temporal variation <strong>of</strong> 129 I and 127 I by analysis <strong>of</strong> archived Fucus Vesiculosus samples<br />

(in paper V). Over <strong>the</strong> past decade, liquid and gaseous release <strong>of</strong> 129 I from reprocessing facilities such as<br />

La Hague (France) and Sellafield (UK), has significantly increased <strong>the</strong> natural environmental concentrations<br />

by several orders <strong>of</strong> magnitude (Alfimov et al., 2004; Fehn et al., 2007; Aldahan et al., 2007). The relatively<br />

long half life <strong>of</strong> 129 I (15.7 myr) and <strong>the</strong> long residence time (30 kyr) <strong>of</strong> iodine in <strong>the</strong> marine environment as<br />

well as continuous releases from nuclear fuel reprocessing facilities make this isotope a suitable<br />

oceanographic tracer. Apart from marine tracer aspects we may also gain insight into <strong>the</strong> important<br />

production <strong>of</strong> volatile iodine species created by marine algae and which are released to <strong>the</strong> atmosphere.<br />

Marine algae play an important role (Leblanc et al., 2006) in <strong>the</strong> global cycle <strong>of</strong> iodine in <strong>the</strong> environment in<br />

<strong>the</strong> sense that <strong>the</strong>y accumulate seawater iodine at high concentration levels and have <strong>the</strong> ability to trans<strong>for</strong>m<br />

a part <strong>of</strong> it into volatile organic iodine (VOI), such as methyl iodide (CH3I) or diiodomethane (CH2I2;<br />

Carpenter et al. 2007) and release <strong>the</strong>m into seawater. From <strong>the</strong> seawater surface <strong>the</strong> volatile organic iodine<br />

species are released into <strong>the</strong> atmosphere and are subsequently broken down by photolysis and reactions with<br />

ozone (O3) (Jones & Carpenter, 2005; Martino et al. 2006) <strong>for</strong>ming a reactive pool <strong>of</strong> iodine species which<br />

afterwards contribute to <strong>the</strong> ozone depletion, particle <strong>for</strong>mation and cloud condensation (Küpper et al., 2008;<br />

O’Dowd et al., 2002). Despite <strong>the</strong> significant role <strong>of</strong> marine algae in <strong>the</strong> iodine cycle in <strong>the</strong> environment,<br />

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