This study utilizes new geochemical analyses of fluids (formation water and gas) collected predominately from Devonian organic-rich shales and reservoir sandstones from the northern Appalachian Basin margin to investigate basin scale hydrologic processes, water-rock reactions, microbial activity, and natural gas generation. Elemental and isotopic composition of co-produced formation waters and natural gas show that the majority of methane in Devonian organic-rich shales and reservoir sandstones is thermogenic in origin with localized accumulations of microbial gas. Microbial methanogenesis appears to be primarily limited by redox buffered conditions favoring microbial sulfate reduction. Thermal maturity (bioavailability) of shale organic matter and the paucity of formation waters may also explain the lack of extensive microbial methane accumulations. Iodine and strontium isotopes, coupled to elemental chemistry demonstrate basin scale fluid flow and clay mineral diagenesis. Evidence for this is based on anomalously high ¹²⁹I/I values sourced from uranium deposits (fissiogenic production of ¹²⁹I) at the structural front of the Appalachian Basin. Radiogenic ⁸⁷Sr/⁸⁶Sr (up to 0.7220), and depleted boron and potassium concentrations support smectite clay diagenesis at temperatures greater than 120 °C. The development of fissiogenic ¹²⁹I as a tracer of basin scale fluid flow is a novel application of iodine isotopes provided that the sources of cosmogenic and anthropogenic ¹²⁹I are reasonably well constrained. The anomalously high ¹²⁹I/I in Appalachian Basin brines may be alternatively explained by microbial fractionation based on a correlation with decreasing δ¹³C-DIC values and decreasing sulfate concentrations in the range of sulfate reduction. These results demonstrate that the microbial fractionation of iodine isotopes may be possible and an important consideration when interpreting ¹²⁹I/I, regardless of the source of ¹²⁹I. Results from this study have important implications for understanding the controls on and origins of natural gas production in sedimentary basins; tectonically and topographically driven basin scale fluid flow, including diagenetically induced waterrock reactions and mineral ore deposition related to orogenesis; and an improvement of the use of iodine isotopes for understanding large scale fluid flow, and possibly its use as a tracer of organic matter diagenesis and the distribution of radionuclides in the environment.

The geology, hydrogeology, and groundwater geochemistry are described for an interface aquifer in Eastern Ontario exhibiting anomalously high proportions of iodine (I) as iodide (I-) and dissolved methane (CH4). The studied area is unique in that it shows a significant marine influence, attributed to the most recent Champlain Sea incursion 10 – 12 ka BP, which has implications for I and CH4 enrichment. I and CH4 in groundwater are found in high proportions in reducing fossil seawaters, which are typically observed in depressions in the bedrock surface that are overlain by thick layers of glaciomarine muds. I is released via microbial decomposition of marine phytoplankton into mud porewaters, where it is then leached to underlying groundwaters. 129I and 14C isotopic signatures of I and C compounds highlight the importance of allochthonous I and C sources in the Champlain Sea basin derived from glacial abrasion of the surrounding terrain and imported via glacial meltwater. CH4 is microbial in origin, with marine phytoplankton from the Champlain Sea incursion and ancient terrestrial organic matter from an Early Wisconsinian interstadial period (60 – 75 ka BP) as the dominant substrates. A thermogenic CH4 component was observed for areas underlain by the Billings shale unit. Both I and CH4 originate at least partially from the same marine phytoplankton source within the muds, demonstrate similar controls on enrichment, and have a Spearman’s rank coefficient of 0.62, indicating that the correlation between I and CH4 in groundwater in the studied area is significant.

This thesis concerned with iodine status, sources in human body, and measurements especially here in Canada, where iodine status for the Canadian population is not well known. With the recent re-emergence of iodine deficiency among individuals in other industrial countries, understanding the main sources of iodine to the Canadian population is necessary to ensure fortification strategies are justified and effective. Uncertinaty has arisen to the importance of iodized salt recently, along with medical warnings to reduce salt consumbtion. This conflicts give rise to improve scientific research and hone thier methods with new applications. The research question here is that: Can we benefit from the existence of long-lived radioiodine-129 in the environment and explore its potential as a tracer? To answer this question, the study was divided into an introductory chapter contains a review about the topic, then three research chapters. The second chapter was devoted to study the possibility of extracting 129I from human urine. As for third chapter of the thesis, it was about refining a method that already established, and use it to extract 129I from breastmilk using combustion, then determine the radiological dose of 129I in infants’ thyroid. While the fourth chapter was devoted to investigate the main sources of 127I and 129I in the Canadian diet based on daily food consumption and modelling the urinary iodine concentration for adults and infants through the novel application of a well-established compartment model implemented in AMBER. The path of this thesis was crowned with a set of results, which are detailed in the end of each chapter as follow: 1- The advantage of accelerator mass spectrometry (AMS) helps to measure 129I in human urine for the first time. The result for 25 participants from Ottawa ranged from 3.3 x 106 atoms/L to 884 x 106 atoms/L with a median of 108.7 x 106 atoms/L, and the 129I/127I ratio ranged from 7.38 x 10-12 to 3.97 x 10-10 with a mean of 1.3 x 10-10. 2- The concentration of 127I and 129I in Ottawa urine samples were significantly correlated and generally similar to the 129I concentrations and 129I/127I ratios from environmental samples collected around Ottawa. 3- This correlation suggests that 129I could be a potential nutritional tracer of dietary iodine. 4- In chapter 3, the 129I in breastmilk ranged from 1.26x108 atoms/L to 6.64x108 atoms/L with a median of 2.10 x108 atoms/L, and the 129I/127I ratio ranged from 1.27x10-10 to 9.9x10-10 with a median of 2.13x10-10. 5- A correlation was also observed between 127I and 129I concentrations in breastmilk. 6- The isotopic ratios in breastmilk were similar to Canadian cow’s’ milk, indicating that the milk of both cows and humans is a reflection of the 129I concentration of their local environment and the food ingested. 7- Result from chapter 3 confirms that humans are exposed to the 129I from birth through their mother breastmilk, giving them an average dose of 1.10 x10-4 Bq/year and thyroid dose rate equal to 5.92 x10-10 Sv/year. 8- In fourth chapter, the daily milk consumption was measured for 78 mother-infants’ pairs, and ranged from 275 -1202 g/day, with a mean of 731 g/day. This value agrees well with global infant milk intake which estimated at 730g/day. 9- The daily iodine intake from breastmilk ranged from 11.2 µg/day to 476.2 µg/day with a median of 127.9 µg/day. 10- The urinary iodine concentrations were estimated without urine collection using iodine biokinetic model, giving a median urinary iodine concentration (n=78) at 304.7 µg/L. The result was compared to those measured by Health Canada (median= 398.7 µg/L), showing a moderate correlation (r= 0.496). 11- A further comparison of the results was made based on gender shows that the difference between UIC in male and female infants measured by Health Canada and those estimated by AMBER is non-significant. 12- Through AMBER software, the influence of seven common diets on UICs was assessed to determine which foods play an important role in ensuring iodine adequacy. We observed that the main source of iodine in a vegan diet is grain products providing up to 70%, while in remaining diets the main source of iodine was dairy products (50-69%) when they are consumed. 13- The contribution of iodized salt to all Canadian diets was ranked second, after dairy, unless the diet is vegan or ovo-vegetarian, where dairy is not consumed, iodized salt was ranked first. 14- Among 23 scenarios for seven different diets, the urinary iodine-129 concentrations ranged from 1.4 x10-7 to 3.3 x10-7 µg/L with a median of 3.1 x10-7 µg/L, and the isotopic 129I/127I ratio ranged from 1.1 x10-9 to 1.2 x10-8 with a median of 2.8 x10-9. 15- In contrast to stable iodine, the highest isotopic ratio was observed in vegan diet, while the lowest was observed in ketogenic diet. This suggests that grain products are the main contributor of 129I to humans. 16- Despite being the primary contributors of stable iodine (127I), salt and dairy show a lower contribution of 129I. Based on this we can qualitatively predict the source of iodine 127 using isotopic ratio 129I/127I. For example, in cases where the isotopic ratio was between 10-8 and 10-9, therefore, the main sources of iodine in this person may be from grains products, vegetables, and fruits; and in cases where the isotopic ratio was between 10-10 and 10-11, therefore, the main sources of iodine in this person may be from dairy products and some contribution from salt. This study has shown the capability of 129I to be used in biomedical fields. In this thesis 129I used as a nutritional tracer where it helps to detect the sources of stable iodine in human body based on isotopic ratio. The extraction method invented in Chapter 2 can be used to evaluate 129I exposure directly in the human body for those who live nearby nuclear fuel reprocessing plants. An additional application for this method can be in assessing 129I in human to investigate 131I uptake in the event of a nuclear emergency using 129I in urine as a proxy. Moreover, the extraction technique used Chapter 3, can be extended to other biological samples such as thyroid or brain. Furthermore, Chapter 4 shows that with the right estimation of daily iodine intake and urine volume, a biokinetic model of iodine, built in the AMBER software, can predict urinary iodine concentration with a high degree of accuracy without collecting urine samples.

129I is of major concern because of its biophilic nature, excessive inventory, long half-life (~16 million yrs), and high mobility in the natural environment that depends on its chemical speciation. Iodide (I-) has the highest mobility than iodate (IO3-) and is the predominant species in the terrestrial environment due to prevailing pH and Eh conditions. In order to transform I- to less mobile organo-iodine (OI), strong oxidants are necessary to activate the first electron transfer step from I- to reactive intermediates. The aim of this study was to determine the influence of naturally occurring aerobic bacteria isolated from an 129I contaminated aquifer (F-area of the Savannah River Site, SC) on I- oxidation and OI formation. It was demonstrated that 3 of 136 strains accumulated I- (0.2~2%) in the presence of H2O2, when incubated in the presence of an environmentally relevant concentration of I- (0.1 microM). The accumulation was likely through electrophilic substitution resulting in the iodination of cellular constituents. The results indicated that culturable I--accumulating bacteria are not directly responsible for the high fraction of oxidized iodine species (IO3- and OI, >50% of total I) present in the SRS F-area. Several bacterial strains were found to be capable of stimulating I- oxidation through excretion of oxidants and enzymes. Organic acids in spent liquid medium from 27 of 84 aerobic bacterial cultures enhanced H2O2-dependent I- oxidation 2-10 fold. Organic acids enhanced I- oxidation by (1) lowering the pH of the spent medium and (2) reacting with H2O2 to form peroxy carboxylic acids, which are strong oxidizing agents. In the absence of H2O2, spent medium from 44 of 84 bacteria cultures showed I- oxidizing capacities. One I- oxidizing bacterium was studied to characterize its extracellular I- oxidizing component(s). The I- oxidizing capability from the spent medium was inactive by treatments with heat and H2O2 and absent under anaerobic conditions. Conversely, NADH, NADPH and FMN additions stimulated I- oxidation in the spend medium. These results indicate an oxidase(s) catalyzed I- oxidation. Understanding the bacterial activities involved with I- oxidation and OI formation is expected to help reduce 129I mobility in water-soil systems.

Iodine-129 is a naturally and anthropogenically produced radioisotope (half-life: 15.7 million years) the majority of which is produced by nuclear fuel reprocessing. These releases have dispersed 129I throughout the environment making it possible to use 129I as a tracer. It is also of concern for the disposal of radioactive waste. This research develops a new laboratory method for 129I extraction and analysis, and explores the geochemical cycling and environmental fate of 129I in remote catchments following the Fukushima-Daiichi Nuclear Accident (FDNA). A new technique was developed to investigate 129I partitioning and quantitatively extract it from solid samples. Samples are combusted and volatilized iodine is trapped in solution. The efficiency is traced using the iodine isotope, 125I. This technique was proven using standard reference materials and is used in other chapters of this thesis. A baseline study of 129I in Yukon watersheds was undertaken to determine the impact of anthropogenic 129I emissions and identify possible sources. Using atmospheric back-trajectory modeling, sources of 129I from Fukushima, nuclear fuel reprocessing and marine volatilization were identified in remote watersheds. Peat moss samples showed significant retention of 129I in modern samples. Following the reconnaissance study, a catchment scale investigation of anthropogenic 129I cycling was undertaken through precipitation and runoff monitoring. 129I was found to be an excellent indicator of initial snowmelt contributions to discharge due to enrichment by dry deposition. Furthermore, water source transitions in discharge were recorded by 129I, 127I and the 129I/127I ratio showing iodine can be used as a tracer of hydrologic processes. A mass balance found that 77% of the 129I mass input accumulates annually, primarily in organic soils. Sampling of Vancouver, B.C. precipitation and groundwater was done following the FDNA to determine the fate of 129I and evaluate it as a tracer of groundwater recharge. Immediately following the FDNA the 129I concentration in precipitation increased 6 times above background. Groundwater samples also showed 129I increases consistent with expected recharge times indicating FDNA derived 129I was transported into groundwater with minimal retardation, likely via preferential flowpaths.

Since the beginning of the nuclear era, starting during the 1940s, large amount of radioactivity has been released into the environment. This thesis deals with the temporal and spatial distribution of the anthropogenic radioisotope 129I (T1/2= 15.7 Myr) in northern Europe. A routine sample preparation procedure for extraction of iodine from milligram amounts of solid materials has been developed and aimed for measuring the 129I concentration by the ultra-sensitive accelerator mass spectrometry method. The technique was further used for the analysis of 129I in sediments collected from two lakes in Sweden and one lake in Finland as well as sediments from two sites in the Baltic Sea. In addition, 129I concentrations in aerosol samples from northern and southern Sweden covering the period 1983 to 2000 have been measured. The results reveal a gradual increase in the anthropogenic 129I fluxes since the 1950s that are linked to emissions from the nuclear fuel reprocessing facilities in Sellafield (UK) and La Hague (France). A sharp increase coinciding with the Chernobyl accident is identified from the Swedish lakes located in areas characterised by relatively high Chernobyl fallout. Numerical modeling of the 129I deposition predicts that >50% of the flux to the lake sediments is related to the liquid emissions from the reprocessing facilities. The modeling also reasonably simulates the contribution of the Chernobyl event to the total 129I flux. The novel time series from northern Europe on 129I in aerosols show about one order of magnitude higher concentration in northern compared to southern Sweden. Estimate of 129I dry fallout based on the aerosol data suggests <25% contribution to the total fallout. The distribution of 129I in the sediment archives demonstrates the potential of the isotope as a new time marker for chronological and environmental investigations.

Two long-lived halogen radionuclides (36Cl, T1/2 = 301 kyr, and 129I, T1/2 = 15.7 Myr) have been studied by means of Accelerator Mass Spectrometry (AMS) at the Uppsala Tandem Laboratory. The 36Cl measurements in natural samples using a medium-sized tandem accelerator (~1 MeV/amu) have been considered. A gas-filled magnetic spectrometer (GFM) was proposed for the separation of 36Cl from its isobar, 36S. Semi-empirical Monte-Carlo ion optical calculations were conducted to define optimal conditions for separating 36Cl and 36S. A 180° GFM was constructed and installed at the dedicated AMS beam line. 129I has been measured in waters from the Arctic and North Atlantic Oceans. Most of the 129I currently present in the Earth's surface environment can be traced back to liquid and gaseous releases from the nuclear reprocessing facilities at Sellafield (UK) and La Hague (France). The anthropogenic 129I inventory in the central Arctic Ocean was found to increase proportionally to the integrated 129I releases from these reprocessing facilities. The interaction and origin of water masses in the region have been clearly distinguished with the help of 129I labeling. Predictions based on a compartment model calculation showed that the Atlantic Ocean and deep Arctic Ocean are the major sinks for the reprocessed 129I. The variability in 129I concentration measured in seawater along a transect from the Baltic Sea to the North Atlantic suggests strong enrichment in the Skagerrak–Kattegat basin. The 129I inventory in the Baltic and Bothnian Seas is equal to ~0.3% of the total liquid releases from the reprocessing facilities. A lake sediment core sampled in northeastern Ireland was analyzed for 129I to study the history of the Sellafield releases, in particular the nuclear accident of 1957. High 129I concentration was observed corresponding to 1990 and later, while no indication of the accident was found. The results of this thesis research clearly demonstrate the uniqueness and future potential of 129I as a tracer of processes in both marine and continental archives.

Radionuclides, 129I and 239,240Pu, are major products or by-products of nuclear fission and among the top risk drivers for waste disposal at the Savannah River Sites (SRS) and Rocky Flats Environmental Technology Sites (RFETS), respectively, due to their perceived mobility in the environment, excessive inventory, toxicity, and long half-life. The objective of this study is to investigate the role of natural organic matter in retarding or facilitating the migration of 129I and 239,240Pu in the Department of Energy (DOE) sites. Measurements of 127I and 129I in humic acids (HAs) and fulvic acids (FAs) obtained by five successive alkaline, two glycerol and one citric acid-alkaline extractions, demonstrated that these extractable humic substances (HS) together account for 54-56 percent and 46 percent of the total 127I and 129I in the soil, respectively. The variations among 127I and 129I concentrations, isotopic ratios (129I/127I), chemical properties of all these humic substances indicated iodine was bound to a small-size aromatic subunit (~10 kDa), while the large-size subunit (~90 kDa), which likely linked the small-size unit through some weak chemical forces, determined the relative mobility of iodine bound to organic matter. Soil resuspension experiments simulating surface runoff or stormflow and erosion events were conducted with soils collected from SRS. Results showed that 72-77 percent of the newly-introduced I- or IO3- were irreversibly sequestered into the organic-rich soil, while the rest was transformed into colloidal and dissolved organo-iodine by the soil. The resulting iodine remobilization contradicts the conventional view that considers only I- or IO3- as the mobile forms. Quantitative structure analysis by 13C DPMAS NMR and solution state 1H NMR on these humic substances indicate that iodine is closely related to the aromatic regions containing esterified products of phenolic and fomic acid or other aliphatic carboxylic acids, amide functionalities, quinone-like structure activated by electron-donating groups (e.g., NH2) or hemicelluloses-lignin-like complex with phenyl-glycosidic linkage. The micro-molecular environment, such as the hydrophobic aliphatic periphery hindering the active aromatic cores and the hydrophilic polysaccharides favoring its accessibility towards hydrophilic iodine species, play another key role in the interactions between iodine and SOM. NMR spectra of the colloidal organic Pu carrier which can potentially be released from the soil during the surface runoff or stormflow showed Pu was transported, at sub-pM concentrations, by a cutin-derived soil degradation products containing siderophore-like moieties and virtually all mobile Pu.