Thesis for the Degree of Doctor of Philosophy - DTU Orbit
Thesis for the Degree of Doctor of Philosophy - DTU Orbit
Thesis for the Degree of Doctor of Philosophy - DTU Orbit
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302 V. Hansen et al. / Science <strong>of</strong> <strong>the</strong> Total Environment 412-413 (2011) 296–303<br />
August<br />
April<br />
Salinity<br />
a b<br />
c d<br />
isotopes species and oxygen is observed (Table 3). These results suggest<br />
that <strong>the</strong> oxidation conditions <strong>of</strong> surface water do not influence<br />
<strong>the</strong> iodine speciation in <strong>the</strong> studied basins. This situation is also illustrated<br />
by Figs. 4 and 5, which show that despite ra<strong>the</strong>r uni<strong>for</strong>m oxygen<br />
concentration in <strong>the</strong> surface water, <strong>the</strong>re is a large variability in<br />
<strong>the</strong> iodine isotopes distribution. The different distribution pattern <strong>of</strong><br />
iodide and iodate ( 129 I and 127 I) along <strong>the</strong> surface water <strong>of</strong> Skagerrak,<br />
Kattegat and Belt Sea (Fig. 1, station 12) is most likely due to <strong>the</strong> mixing<br />
process between saline North Sea-Atlantic and Baltic Sea fresher<br />
water (Figs. 2 and 3). North Sea surface water with high 129 I and<br />
127 I iodide concentrations and high salinity (Hou et al., 2007) enters<br />
Skagerrak and mixes with <strong>the</strong> relatively low iodide concentrations<br />
(Figs. 2 and 3) and low salinity (Fig. 5) outflow waters from <strong>the</strong> Baltic<br />
Sea in <strong>the</strong> Kattegat through <strong>the</strong> Belt Sea (station 12, Fig. 1).<br />
4.2. Iodide and iodate in surface water <strong>of</strong> Arkona Sea and Baltic Proper<br />
In <strong>the</strong> Arkona Sea, higher 129 I − / 129 IO 3 − happened in August<br />
(Fig. 3c) and could be explained as a reduction <strong>of</strong> 129 IO3 - along <strong>the</strong><br />
water pr<strong>of</strong>ile from Kattegat through <strong>the</strong> Belt Sea to 129 I - as found<br />
along <strong>the</strong> surface water <strong>of</strong> sou<strong>the</strong>rn Baltic Sea. However, ratio <strong>of</strong><br />
127 I − / 127 IO3 − , shows instead higher values in April (Fig. 2f), indicating<br />
a selective reduction <strong>of</strong> iodate that may be a significant process governing<br />
<strong>the</strong> out <strong>of</strong> equilibrium (freshly added to <strong>the</strong> environment)<br />
129 I isotope compared to <strong>the</strong> naturally equilibrated 127 I isotope. As<br />
<strong>the</strong> Arkona Basin is end-member <strong>of</strong> relatively saline water, iodide<br />
and iodate concentration are severely affected by <strong>the</strong> mixing process.<br />
Variability in <strong>the</strong> relative 129 I − / 127 I − and 129 IO 3 − / 127 IO3 − values<br />
(Fig. 4) between <strong>the</strong> sampling campaigns (August-2006 and April-<br />
2007) can reflect seasonal and input effects. Addition <strong>of</strong> huge fresh<br />
water to <strong>the</strong> system during spring snow and ice melting may preferentially<br />
alter <strong>the</strong> concentrations and iodine speciation, specifically in<br />
near coastal regions. During August, extensive algal blooming may<br />
on <strong>the</strong> o<strong>the</strong>r hand contribute to increase <strong>the</strong> iodide species, particularly<br />
near to coastal and shallow water regions. The present distribution<br />
<strong>of</strong> <strong>the</strong> studied sampling sites is ra<strong>the</strong>r limited and does not<br />
provide enough coverage to deduce specific distribution patterns <strong>of</strong><br />
<strong>the</strong> isotopes in <strong>the</strong> surface water. Fur<strong>the</strong>rmore, addition <strong>of</strong> data on iodine<br />
speciation in depth pr<strong>of</strong>iles <strong>of</strong> <strong>the</strong> sampling site will expose better<br />
<strong>the</strong> interplay between regional water transport and environmental conditions.<br />
Never<strong>the</strong>less, <strong>the</strong> data presented here has shown <strong>for</strong> <strong>the</strong> first<br />
time <strong>the</strong> extent and general distribution patterns <strong>of</strong> iodine isotopes species<br />
that add new valuable in<strong>for</strong>mation <strong>for</strong> future environmental<br />
analysis.<br />
5. Conclusions<br />
We here present data on iodine isotopes ( 129 I and 127 I) and <strong>the</strong>ir<br />
species (iodide and iodate) in surface water collected from 16 locations<br />
in August 2006 and 19 locations in April 2007 in <strong>the</strong> Baltic Proper,<br />
Kattegat and Skagerrak. From those results we draw <strong>the</strong> following<br />
conclusions: a) reduction <strong>of</strong> iodate and oxidation <strong>of</strong> iodide in Skagerrak<br />
and Kattegat may be a slow process since insignificant change in<br />
129 I and 127 I speciation was found; b) reduction <strong>of</strong> iodate to iodide<br />
seems to be a relatively fast process in surface water <strong>of</strong> <strong>the</strong> sou<strong>the</strong>rn<br />
Baltic Sea; c) oxidation conditions <strong>of</strong> <strong>the</strong> surface water are not exerting<br />
a marked effect on <strong>the</strong> iodine speciation in <strong>the</strong> studied basins; d)<br />
seasonal and input effects may alter <strong>the</strong> concentrations and speciation<br />
modes specifically in near coastal regions.<br />
Acknowledgements<br />
Oxygen (ml/L)<br />
Fig. 5. Distribution <strong>of</strong> salinity and oxygen in <strong>the</strong> surface water <strong>of</strong> Skagerrak, Kattegat and Baltic Sea, during August 2006 and April 2007.<br />
Table 3<br />
Correlation relationship (R 2 ) between iodine species and oxygen and salinity.<br />
127 I −<br />
127 IO3 −<br />
129 I −<br />
129 IO3 −<br />
127 I-<br />
127 IO3 − 129 I − 129 IO3 −<br />
Oxgyen Salinity<br />
0.14 0.44 0.52 −0.03 0.49<br />
0.37 0.36 −0.2 0.55<br />
0.79 −0.08 0.8<br />
−0.04 0.75<br />
Funding <strong>for</strong> <strong>the</strong> sampling was provided by <strong>the</strong> Swedish Meteorological<br />
and Hydrological Institute (SMHI). We thank Lars Andersson<br />
and Bodil Thorstensson and all <strong>the</strong> crew and scientific team on<br />
board <strong>of</strong> <strong>the</strong> research vessel Argos <strong>for</strong> <strong>the</strong> help during <strong>the</strong> sampling<br />
expeditions. X.L. Hou appreciates <strong>the</strong> support by “BaiRen” Project <strong>of</strong><br />
CAS (Grant No. KZCX2-YW-BR-13).