Thesis for the Degree of Doctor of Philosophy - DTU Orbit

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1.5 Scope of the study The overall aim with this study was to improve and develop techniques for speciation analysis of iodine, especially I-129, and to apply these techniques on environmental samples. • Develop a rapid on-line HPLC-ICP-MS method for the direct speciation analysis of 127 I in water samples. • Develop a method for the quantification of organic iodine species in fresh water and seawater samples. • Improvement of the method for 129 I and 127 I speciation analysis in soil and sediments samples: Extraction and fractionation of iodine organic matter in soil and sediment samples. • Speciation analysis of iodine as iodide, iodate and total iodine in seawater samples collected from the Baltic Proper, Skagerrak and Kattegat. • Speciation analysis of iodine ( 129 I and 127 I) as iodide, iodate and total iodine in fresh water samples from Denmark and Sweden by alkaline oxidation (NaOH – NaClO) of iodine organic species and anion exchange chromatography for separation of iodide and iodate. • To investigate the spatial and temporal variation of 129 I and 127 I by analysis of archived Fucus Vesiculosus samples from Denmark 26
2. Analytical procedures used in this work 2.1 Experimental materials. Analytical standards were produced from solution of 129 I (NIST-SRM-4949c) purchased from National Institute of Standard and Technology (NIST) (Gaithersburg, MD, USA). The standard was diluted with iodine carrier and used for calibration during AMS analysis. Carrier free 125 I (NaI form) was purchased from Amersham Biotech (UK). Carrier iodine-127 (Woodward iodine with low iodine- 129 content) purchased from MICAL Specialty Chemicals, New Jersey. All reagents including tetramethylammonium hydroxide (TMAH) solution (25%), nitric acid (HNO3), ammonium acetate – acetic acid (NH4Ac-HAc), hydroxylammonium chloride (NH2OH HCl), potassium nitrate (KNO3), trichloromethane (CHCl3), sodium nitrite (NaNO2), silver nitrate (AgNO3), potassium disulfite (K2S2O5), sodium hypochloride (NaClO), used in the experiment were of analytical reagent grade. Bio-Rad AG1- × 4 anion exchange resin 50–100 mesh was purchased from Bio-Rad laboratories, Richmond, CA and converted to NO3 - form. The anion exchange resin was swelled in water and transferred to a column of ø 1.0 × 20 cm. Table 3 Summary of sample analyzed in this study Sample Sample Sampling area/ Relevant paper amount location IAEA-375 soil 10g From Novozybkov, Bryansk, Russia collected in July 1990 Paper IV, Danish soil 10g Top 10 cm of 2mm sieved soil collected from 12 different locations in Denmark in 2003 Paper IV Oxic marine 10g The upper 2-3 cm layer from Barents Sea, August Paper IV sediment 1994 Anoxic marine 10g The upper 40 cm layer from South Norway, August Paper IV sediment 1994 Seawater 400mL Collected from 19 locations in the Baltic Sea, Kattegat and Skagerrak Basin in August 2006 and Paper II, III, April 2007 Unpublished results Rain and lake 400mL Collected from different locations in Denmark and Paper VI water Sweden in 2007 Fresh and 3-10 mL Collected from different locations in Denmark in Unpublished seawater 2008- 2009 results Seaweed 0.1g From Rømø, Klint and Bornholm from 1999-2010 Paper V Table 3 List detailed information concerning samples used in this study. 2.2 On-line HPLC-ICP-MS method for the direct speciation analysis of 127 I in water samples (unpublished results). In this study all critical steps of HPLC-ICP-MS method development for analysis of iodine as iodide and iodate are summarized. Parameters such as selection of chromatographic column, mobile phase, flow rate, volume of sample injected, standard and sample preparation, stability of prepared 27
Page 1 and 2: Chemical Speciation Analysis and En
Page 3 and 4: Thesis for the Degree of Doctor of
Page 5 and 6: Abstract This thesis deals with che
Page 7 and 8: environment since they reflect the
Page 9 and 10: organiske jodformer. Adsorption af
Page 11 and 12: None of this would have been possib
Page 13 and 14: Abbreviations and acronyms b+ - pos
Page 15 and 16: 3.1 Analytical Development………
Page 17 and 18: Table 1 Some properties of iodine P
Page 19 and 20: In soils/sediments iodine occurs as
Page 21 and 22: Table 2 Nuclear properties of iodin
Page 23 and 24: Liquid scintillation counting (LSC)
Page 25 and 26: The bioavailability of radioactive
Page 27: data (Englund et al., 2010; Hou et
Page 31 and 32: 2.3 Quantification of total iodine
Page 33 and 34: Fig. 5 Quantification of total iodi
Page 35 and 36: iodate were measured by counting 12
Page 37 and 38: Fig. 6 Sequential extraction proced
Page 39 and 40: a Fig. 8 Calibration curve for (a)
Page 41 and 42: experiment was subjected to combust
Page 43 and 44: Table 7 Adsorption of iodine specie
Page 45 and 46: numbers 11-14), which is about the
Page 47 and 48: marine environment from nuclear fue
Page 49 and 50: 127 I - (ppb) 127 IO3 - (ppb) a b 1
Page 51 and 52: Although the oxygen concentration d
Page 53 and 54: 129 I TBq 2,00E+00 1,80E+00 1,60E+0
Page 55 and 56: • Adsorption of iodine species on
Page 57 and 58: Reference Aldahan A, Kekli A, Possn
Page 59 and 60: Fuge R& Johnson C. 1986. The geoche
Page 61 and 62: Lo´pez-Gutie´rrez JM, Garcı ´a-
Page 63 and 64: Shinohara K. 2004. Measurement and
Page 65 and 66: http://www.irsn.fr/EN/news/Document
Page 67 and 68: Review Analytica Chimica Acta 632 (
Page 69 and 70: Table 1 Nuclear properties and prod
Page 71 and 72: Fig. 2. Liquid discharges of 129 I
Page 73 and 74: Fig. 5. Schematic diagram and pictu
Page 75 and 76: 129 I in iodide and iodate is then
Page 77 and 78: Fig. 8. Diagram of air sampler for
Page 79 and 80:
Fig. 10. Iodine L3-edge (a) and K-e
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analysis of 129 I in water sample a
Page 83 and 84:
Yi P, Aldahan A, Hansen V, Possnert
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FIGURE 1. Sampling sites (the red s
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FIGURE 3. Horizontal distribution o
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FIGURE 5. Time series data of 129 I
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Environmental Science & Technology
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prepared using KI and KIO3. No diff
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of their contribution to the Baltic
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Fig. S-1 Sampling sites (the red so
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Fig. S-3 Vertical distribution of I
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Fig. S-5 Marine discharges function
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Fig.S-7 Relationship between I-129
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Table S-1 Results of I-129 and I-12
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S17
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Paper III Hansen,V., Yi, P., Hou, X
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conversion process between iodide a
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Table 1 Analytical results of 129 I
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August April I-129 iodide ( 10 8 at
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References Aldahan A, Kekli A, Poss
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Partition of iodine ( 129 I and 127
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Norway (Table 1). CTD-casts with ox
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5. Discussion 5.1. Separation of hu
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In the present study 40e60% of 129
Page 127 and 128:
Hutta, M., Gora, R., 2003. Novel st
Page 129 and 130:
Analysis of 129 I and 127 I in arch
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et al., 2002). Due to the fact that
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espectively. The iodine was leached
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salinities in the same area. Apart
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North Sea. 129 I/ 127 I ratios in w
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Table 2 Analytical results of 129-I
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129 I/ 127 I 1,40E-07 1,20E-07 1,00
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References Aldahan A, Englund E, Po
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O’Dowd, C.; Jimenez, J. L.; Bahre
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Iodine ( 129 I and 127 I) speciatio
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water in winter by molecular oxygen
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0.2 M KNO3. The effluent and the wa
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maximum values is at 0.03-0.06×10
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into the English Channel from the L
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References Aldahan A, Kekli A, Poss
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Risø-PhD-81(EN)
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Thesis for the Degree of Doctor of Philosophy - DTU Orbit

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