Partition of iodine (¹²⁹I and ¹²⁷I) isotopes in soils and marine sediments

Natural organic matter, such as humic and fulvic acids and humin, plays a key role in determining the fate and mobility of radioiodine in soil and sediments. The radioisotope ¹²⁹I is continuously produced and released from nuclear fuel reprocessing plants, and as a biophilic element, its environmental mobility is strongly linked to organic matter.Due to its long half-life (15.7 million years), ¹²⁹I builds up in the environment and can be traced since the beginning of the nuclear era in reservoirs such as soils and marine sediments. Nevertheless, partition of the isotope between the different types of organic matter in soil and sediment is rarely explored. Here we present a sequential extraction of ¹²⁹I and ¹²⁷I chemical forms encountered in a Danish soil, a soil reference material (IAEA-375), an anoxic marine sediment from Southern Norway and an oxic sediment from the Barents Sea. The different forms of iodine are related to water soluble, exchangeable, carbonates, oxides as well as iodine bound to humic acid, fulvic acid and to humin and minerals. This is the first study to identify ¹²⁹I in humic and fulvic acid and humin. The results show that 30-56% of the total ¹²⁷I and 42-60% of the total ¹²⁹I are associated with organic matter in soil and sediment samples. At a soil/sediment pH below 5.0-5.5, ¹²⁷I and ¹²⁹I in the organic fraction associate primarily with the humic acid while at soil/sediment pH > 6 ¹²⁹I was mostly found to be bound to fulvic acid. Anoxic conditions seem to increase the mobility and availability of iodine compared to oxic, while subaerial conditions (soils) reduces the availability of water soluble fraction compared to subaqueous (marine) conditions.     

Studies with natural and anthropogenic iodine isotopes: iodine distribution and cycling in the global environment

Iodine is an important trace element in geological and biological processes. We summarize here recent results and new data of experiments and observations carried out to improve the understanding of concentration levels and behavior of natural and anthropogenic iodine nuclides in the global environment. The distribution of stable iodine in the Earth's crust was estimated using concentration data in a suite of representative samples and the influence of subduction on the marine iodine cycle was investigated using (129)I systematics on iodine-rich brines from Japan. The importance of microorganisms for the natural iodine cycle is shown in recent studies of iodine sorption on soil and of iodine volatilization from terrestrial and marine environments. Levels of anthropogenic (129)I were measured in samples collected around a spent fuel reprocessing plant in Japan.     

Modelling radioiodine transport across a capillary fringe

Due to its long radioactive half-life, iodine-129 is considered to be an important radionuclide in the context of underground radioactive waste disposal safety assessment. Iodine speciates as iodide (I-) in reducing conditions and iodate (IO3-) in oxidizing conditions. As iodate is more reactive, it is much less mobile than iodide. Consequently, in considering vertically upward transport within a soil profile, iodine will tend to accumulate at the top of the capillary fringe. In this paper, a model of iodine transport across a capillary fringe is developed by coupling equations for variably saturated flow, oxygen dynamics and rate-limited sorption. Model parameters are obtained by consideration of literature values, calibration on soil column data and other supporting laboratory experiments. The results demonstrate the importance of rate kinetics on the migration and bioavailability of radioiodine in the near-surface environment.     

127I and 129I/127I isotopic ratio in marine alga Fucus virsoides from the North Adriatic Sea

The only stable iodine isotope is 127I and the natural 129I/127I ratio in the biosphere has increased from 10(-15)-10(-14) to 10(-10)-10(-9), mainly due to emissions from nuclear fuel reprocessing plants. In Europe they are located at La Hague (France) and Sellafield (England), where the ratio of 129I/127I is up to 10(-4). The marine environment, i.e. the oceans, is the major source of iodine with average concentrations of around 60 mirogL(-1) iodine in seawater. Brown algae accumulate iodine at high levels of up to 1.0% of dry weight, and therefore they are an ideal bioindicator for studying the levels of 127I and 129I in the marine environment. A radiochemical neutron activation analysis (RNAA) method, developed at our laboratory, was used for 129I determination in the brown alga Fucus virsoides (Donati) J. Agardh, and the same technique of RNAA was used for total 127I determination. The samples were collected along the coast of the Gulf of Trieste and the West coast of Istria in the North Adriatic Sea in the period from 2005 to 2006. Values of the 129I/127I ratio up to 10(-9) were found, which is in agreement with the present average global distribution of 129I. The levels of stable iodine found were in the range from 235 to 506 microg g(-1) and the levels of 129I from 1.7 to 7.3 x 10(-3)Bq kg(-1) (2.6-10.9 x 10(-7) microg g(-1)), on a dry matter basis.     

Modelling the role of humic acid in radiocaesium distribution in a British upland peat soil

The significance of exchange sites on organic matter in the retention of radiocaesium in highly organic soils remains unclear. To quantify this retention, we measured the binding of 134Cs to a humic acid isolated from a British upland peat soil, under a range of chemical conditions. We interpreted our results using Humic Ion Binding Model V, a model of humic substance chemistry which simulates ion exchange by non-specific accumulation of cations adjacent to the humic molecules. Model V could simulate the humic acid-solution partitioning of Cs under all the solution conditions used. The model was used to estimate the contribution of organic matter to Cs sorption by the whole soil composite. An estimate of Cs sorption by illite frayed edge sites was also made. These simulations show that organic matter may play only a minor role in binding Cs. even in highly organic soils.     

Use of 129I and 137Cs in soils for the estimation of 131I deposition in Belarus as a result of the Chernobyl accident

Using radioactivity measurements for 131I and 137Cs and nuclear activation analysis (NAA) or accelerator mass spectrometry (AMS) for 129I, ratios of 131I/137Cs and 129I/137Cs have been determined in soils from Belarus. We find that the pre-Chernobyl ratio of 129I/137Cs in Belarus is significantly larger than expected from nuclear weapons fallout. For the Chernobyl accident, our results support the hypothesis that there was relatively little fractionation of iodine and caesium during migration and deposition of the radioactive cloud. For sites having 137Cs > 300 Bq/kg, 129I can potentially give more reliable retroactive estimates of Chernobyl 131I deposition. However, our results suggest that 137Cs can also give reasonably good (+/-50%) estimates for 131I in Belarus.     

A dynamic model of the global iodine cycle and estimation of dose to the world population from releases of iodine-129 to the environment

A dynamic linear compartment model of the global iodine cycle has been developed for the purpose of estimating radiological impacts on the world population from releases of ¹²⁹I to the environment. The time-invariant fractional transfer rates, which describe the transport of ¹²⁹I between environmental compartments comprising the atmosphere, hydrosphere, lithosphere, and terrestrial biosphere, are estimated from an analysis of available data on concentrations for naturally occurring stable iodine and data on the global hydrologic cycle. The global radiological impacts on man from a given release of ¹²⁹I are estimated from the calculated compartment inventories as a function of time and models for the intake of iodine by a reference adult. For a constrant population of 12.2 billion, the estimated worldwide complete population dose commitment to the thyroid is 76 man-Sv/GBq (2.8 × 10⁵ man-rem/Ci) released. Estimated values of the incomplete population dose commitment at various times after a global-scale release to the atmosphere are also presented.     

A comparison of the soil migration and plant uptake of radioactive chlorine and iodine from contaminated groundwater

A 6-month soil column experiment was conducted to compare the upward migration and plant uptake of radiochlorine and radioiodine from shallow, near-surface contaminated water tables. Both fixed and fluctuating water tables were studied. After 6 months, (36)Cl activity concentrations were relatively uniform throughout the soil profile apart from an accumulation at the soil surface, which was especially marked under a fluctuating water table scenario. In contrast, (125)I (a surrogate for (129)I) tended to accumulate at the boundary between the anoxic conditions at the base of the column and the oxic conditions above, due to its redox-dependent sorption behaviour. The uptake of (36)Cl by perennial ryegrass was much greater than that of (125)I due to its greater migration into the rooting zone and its ready availability in soil solution. In the context of radioactive waste disposal, where these radionuclides may potentially be released into groundwater, (36)Cl would be expected to present a greater potential for contamination of the biosphere than (129)I.     

Redox reaction of iodine in paddy soil investigated by field observation and the I K-Edge XANES fingerprinting method

In order to elucidate the cause for the leaching of iodine in a flooded paddy field, we investigated the transformation of an iodine species affected by the water management of the paddy field. The increased concentration of iodide (I(-)) in soil solution of a flooded paddy field suggested that I(-) was leached from the soil under anaerobic conditions. The post-edge feature of X-ray absorption near-edge structure (XANES) for iodate (IO(3)(-)) spiked to soil totally disappeared after anaerobic incubation of the soils, and I(-) was dissolved in the solution. On the other hand, I(-) in contact with the soil was not likely to be oxidized to IO(3)(-) under aerobic incubation. Iodine was leached out in soil solution as I(-) under anaerobic conditions, whereas part of the iodine species was retained by soil as I(2) or organoiodine both under anaerobic and aerobic conditions.     

Assessing field-scale migration of radionuclides at the Nevada Test Site: "mobile" species

Many long-lived radionuclides are present in groundwater at the Nevada Test Site (NTS) as a result of 828 underground nuclear weapons tests conducted between 1951 and 1992. In conjunction with a comprehensive geochemical review of radionuclides ((3)H, (14)C, (36)Cl, (99)Tc and (129)I) that are presumably mobile in the subsurface, we synthesized a body of radionuclide activity data measured from groundwater samples collected at 18 monitoring wells, to qualitatively assess their migration at the NTS over distances of hundreds of meters and over timescales of decades. Tritium and (36)Cl showed little evidence of retardation, while the transport of (14)C may have been retarded by its isotopic exchange with carbonate minerals in the aquifer. Observed local reducing conditions (either natural or test-induced) will impact the mobility of certain redox-sensitive radionuclides (especially (99)Tc) that were otherwise soluble and readily transported under oxidizing conditions. Conversely, strongly oxidizing conditions may impact the mobility of (129)I which is mobile under reducing conditions. The effect of iodine speciation on its transport deserves further attention. Indication of delayed transport of some "mobile" radionuclides (especially (99)Tc) in the groundwater at the NTS suggested the importance of redox conditions of the natural system in controlling the fate and transport of radionuclides, which has implications in the enhanced performance of the potential Yucca Mountain repository, located adjacent to the NTS, to store high-level nuclear wastes as well as management of radionuclide contamination in legacy nuclear operations facilities.     

The molecular properties of humic substances isolated from a UK upland peat system: a temporal investigation.

The study concerns the possible changes in the molecular characteristics of humic materials isolated from the same source as a function of time. A great deal of data has been reported concerning the contrast in molecular characteristics of humic substances isolated from different environments. This has primarily been an attempt to identify source-specific molecular characteristics. However, data presented in this paper suggests that humic substances isolated from a single catchment have significant changes in molecular characteristics over time. Two naturally occurring peat pools (X and Y) situated upon a small organic catchment on Great Dun Fell, Cumbria, UK were sampled monthly between November 1994 and November 1996. Dissolved organic matter (DOM) from the pool water samples was fractionated using macroporous nonionic resins (XAD8 and 4), and the humic, fulvic and hydrophilic acids were collected. These fractions were analysed for elemental composition (C, H and N), weight average molecular weight, functional group content and adsorption (340 nm) of a 1 g l(-1) solution measured in a 1-cm spectrophotometer cell. The molecular characteristics were compared to those of natural DOM described by Scott et al. (1998). Scott et al. reported that drought conditions and seasonal climatic changes could have appreciable effects upon molecular characteristics of natural DOM. Results showed that the atomic H/C ratio of the humic substances increased immediately after strong drought conditions experienced in the summer of 1995. This change was temporary with atomic H/C ratio decreasing gradually over the following months. A similar decrease was observed in the carboxyl group content of the isolated compounds. The data set suggested that atomic H/C ratio in the fulvic and hydrophilic fractions exhibited seasonal characteristics of higher ratios during the late summer/early autumn months. This was not observed in the humic fraction. Humic acids exhibited a seasonal pattern of higher weight average molecular weight during the summer months. These trends were explained in terms of summer production of DOM in the catchment soils, their sequestering in the soil due to limited soil water movement during the summer months and their relative ease of dissolution when rainfall and soil water movement increased during the late summer/early autumn period. The results were found to support seasonal and long-term patterns observed in natural DOM as reported by Scott et al. (1998).     

Determination of 129I/127I in aerosol samples in Seville (Spain)

In this work we present results of the (129)I/(127)I ratio in aerosols of Seville, Southwest of Spain (37.4 degrees N,6 degrees W). A radiochemical method is applied to extract the iodine from the aerosols and prepare samples to be measured by accelerator mass spectrometry (AMS) at the ETH facility in Zürich. We have found the possibility of monitoring the (129)I/(127)I isotopic ratio on a two-days basis with sensitivities in the order of 10(4)-10(5) atoms (129)I/m(3), and values of 10(-8)-10(-9) for the isotopic ratio.     

The distribution and transformations of iodine in the environment

Iodine in the atmosphere is derived largely from seawater. It is probable that the biological production of methyl iodide is important in this transfer. Subsequent photolytic dissociation and oxidation of the methyl iodide, together with other inputs, with partial sorption of the products by aerosols, results in the atmospheric iodine being distributed between various gaseous and particulate forms. Atmospheric iodine is the major source of the iodine in soils, and the process of enrichment continues throughout soil formation and development until ultimately an equilibrium concentration is attained. The retention of iodine in soils is due mainly to the organic matter and hydrous oxides of iron and aluminum. In humid areas, only small proportions of the total soil iodine are soluble in water or available for uptake by plants. The atmosphere is also a direct source of iodine for plants, and in some situations may be more important than the soil. Iodine may be lost from soils by leaching, volatilization, and removal in crops, but the magnitude of these processes is difficult to assess. However, the amounts of iodine reported in groundwaters, and in rivers and lakes remote from human activity, suggest that some leaching of iodine is widespread. Increased amounts of iodine occur in rivers receiving effluent from sewage works. Milk and milk products are now major dietary sources of iodine because their content is often increased by concentrate feedingstuffs supplemented with iodine and/or by the use in dairies of iodophor detergents and sterilants.     

The Effect of Soil Cultivation on the Humus State of Gray Forest Soil in the Middle Urals

The results of studies on the humus state of soils in agrosystems of the Middle Urals (1984–1997) are described. It is shown that the change of agricultural technologies (crop rotation, doses of organic fertilizers, etc.) transforms environmental conditions and the direction of humus formation processes. Parameters such as the concentrations of humus and water-soluble carbon and soil potential for humus accumulation reliably characterize the humus state of arable soil and allow the mobility and migration rate of humic substances to be monitored.     

Assessing field-scale migration of radionuclides at the Nevada Test Site: “mobile” species

Many long-lived radionuclides are present in groundwater at the Nevada Test Site (NTS) as a result of 828 underground nuclear weapons tests conducted between 1951 and 1992. In conjunction with a comprehensive geochemical review of radionuclides (³H, ¹⁴C, ³⁶Cl, ⁹⁹Tc and ¹²⁹I) that are presumably mobile in the subsurface, we synthesized a body of radionuclide activity data measured from groundwater samples collected at 18 monitoring wells, to qualitatively assess their migration at the NTS over distances of hundreds of meters and over timescales of decades. Tritium and ³⁶Cl showed little evidence of retardation, while the transport of ¹⁴C may have been retarded by its isotopic exchange with carbonate minerals in the aquifer. Observed local reducing conditions (either natural or test-induced) will impact the mobility of certain redox-sensitive radionuclides (especially ⁹⁹Tc) that were otherwise soluble and readily transported under oxidizing conditions. Conversely, strongly oxidizing conditions may impact the mobility of ¹²⁹I which is mobile under reducing conditions. The effect of iodine speciation on its transport deserves further attention. Indication of delayed transport of some “mobile” radionuclides (especially ⁹⁹Tc) in the groundwater at the NTS suggested the importance of redox conditions of the natural system in controlling the fate and transport of radionuclides, which has implications in the enhanced performance of the potential Yucca Mountain repository, located adjacent to the NTS, to store high-level nuclear wastes as well as management of radionuclide contamination in legacy nuclear operations facilities.     

Detection of tritium sorption on four soil materials

In order to measure groundwater age and design nuclear waste disposal sites, it is important to understand the sorption behavior of tritium on soils. In this study, batch tests were carried out using four soils from China: silty clays from An County and Jiangyou County in Sichuan Province, both of which could be considered candidate sites for Very Low Level Waste disposal; silty sand from Beijing; and loess from Yuci County in Shanxi Province, a typical Chinese loess region. The experimental results indicated that in these soil media, the distribution coefficient of tritium is slightly influenced by adsorption time, water/solid ratio, initial tritium specific activity, pH, and the content of humic and fulvic acids. The average distribution coefficient from all of these influencing factors was about 0.1-0.2 mL/g for the four types of soil samples. This relatively modest sorption of tritium in soils needs to be considered in fate and transport studies of tritium in the environment.     

Sorption behavior of selenium on humic acid under increasing selenium concentration or increasing solid/liquid ratio

The sorption of selenium (Se) on humic acid (HA) was investigated in order to better understand the fate of stable and radioactive Se in soils and sediments. An ultrafiltration technique was used to determine size distributions of HA-sorbed-Se when increasing Se concentration and solid/liquid ratio. The results showed that the Se sorption onto HA followed the Freundlich isotherm. No solid/liquid ratio-dependence was observed especially when <3 kDa molecular size fraction was used from solid/liquid separation. The Freundlich isotherm parameters K(F) and n obtained using the <3 kDa molecular size fraction for solid/liquid separation were 3.7 x 10(2) and 0.82, respectively. In addition, since dissolved HA increased with decreased ionic strength in the HA suspension, ionic strength could promote aggregation of HA. The conformational change of HA could affect the sorption behavior of Se on HA.     

Iodine-129 in the environment of a nuclear fuel reprocessing plant: II. Iodine-129 and iodine-127 contents of soils,forage plants and deer thyroids

Concentrations of ¹²⁹I and ¹²⁷I in soils, forage plants and deer thyroids collected in the environment of the small Karlsruhe nuclear fuel reprocessing plant (WAK) were determined by neutron activation analysis. Levels of ¹²⁹I in all samples were found to be elevated by several orders of magnitude above current average biospheric background values. In particular, deer thyroids were found to have very high ¹²⁹I levels and corresponding high ¹²⁹I/¹²⁷I ratios.Using all the analytical data for ¹²⁹I and ¹²⁷I concentrations in plants it seems probable that there is a correlation between the ¹²⁹I and the natural ¹²⁷I concentrations in plants.     

129I in the environment of the La Hague nuclear fuel reprocessing plant--from sea to land

In recent years, particular attention was paid to the long-lived radionuclides discharged with authorized low-level radioactive liquid and gaseous effluents by the nuclear spent fuel reprocessing plants of La Hague and Sellafield. The knowledge of (129)I (half-life=15.7 x 10(6) a) distribution in the environment is required to assess the radiological impact to the environment and population living in the area under the direct influence of La Hague NRP discharges. Measurement difficulties of (129)I in environmental matrices, where it is usually present at trace level, limited data published on (129)I activity levels in the European and more particularly in the French territory. Studies conducted to qualify a new alternative measurement method, direct gamma-X spectrometry with experimental self-absorption correction, led to test samples collected in the La Hague marine and terrestrial environment : seaweeds, lichens, grass, bovine thyroids, etc. All these results, often already published separately for analytical purposes and treated for intercomparison exercises, are presented here together in a radioecological manner. The levels of (129)I activity and (129)I/(127)I ratios in these samples show the spatial and temporal influence of the La Hague NRP in its local near-field environment as well as at the regional scale along the French Channel coast.     

Characteristics of soil organic matter (SOM) extracted using base with subsequent pH lowering and sequential pH extraction

Humic substances from eight soils of varying properties were extracted by two different methods: (1) the traditional NaOH-extraction with subsequent acidification to different pH (approximately 1 to approximately 12) and sequential extractions using 0.01 M NaNO(3) at incremental pH (approximately 1 to approximately 11). Cumulative organic matter (OM) in the sequential extractions showed properties that were consistent with NaOH-extracted OM. The release of Al and Fe in the sequential extractions was closely related with the release of organic carbon (OC). The ratio of OC associated with humic acid (HA) and fulvic acid (FA) (the HA:FA ratio) varied widely among the soils indicating heterogeneity in their OM composition. However, a significant correlation between this HA:FA ratio and the NaOH extractable %OC content of the soils is indicative of the possible relationship between them. Between pH 5 and 7, which is a typical soil solution pH, a significant amount of HA-associated OC was soluble. In modeling metal speciation in soil solutions, it has been assumed that all dissolved organic carbon (DOC) that is active toward metal binding is associated with FA. The results of this study indicate that the validity of these assumptions based on model sensitivity alone is questionable.