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.     

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.     

Iodine uptake by spinach (Spinacia oleracea L.) plants grown in solution culture: effects of iodine species and solution concentrations

A hydroponic experiment was carried out to investigate the effects of iodine species and solution concentrations on iodine uptake by spinach (Spinacia oleracea L.). Five iodine concentrations (0, 1, 10, 50 and 100 microM) for iodate (IO(3)(-)) and iodide (I(-)) were used. Results show that higher concentrations of I(-) (> or =10 microM) had some detrimental effect on plant growth, while IO(3)(-) had little effect on the biomass production of spinach plants. Increases in iodine concentration in the growth solution significantly enhanced I concentrations in plant tissues. The detrimental effect of I(-) on plant growth was probably due to the excessively high accumulation of I in plant tissues. The solution-to-spinach leaf transfer factors (TF(leaf), fresh weight basis) for plants treated with iodide were between 14.2 and 20.7 at different solution concentrations of iodide; TF(leaf) for plants treated with iodate decreased gradually from 23.7 to 2.2 with increasing solution concentrations of iodate. The distribution coefficients (DCs) of I between leaves and roots were constantly higher for plants treated with iodate than those treated with iodide. DCs for plants treated with iodide increased with increasing solution concentrations of iodide, while DCs for plants treated with iodate (around 5.5) were similar across the range of solution concentrations of iodate used in this experiment. The implications of iodine accumulation in leafy vegetables in human iodine nutrition are also discussed.     

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.     

The volatilisation and sorption of (129)I in coniferous forest,grassland and frozen soils

129I is a potentially important radionuclide in safety assessments of proposed deep geological radioactive waste repositories due to its radiotoxicity, high mobility and long physical half-life (15.7 million years). In soils, iodine is present both in an inorganic form and in organohalide complexes, some of which are volatile under natural environmental conditions.This study has examined volatilisation, sorption and the effect of freezing on sorption and loss of (125)I (physical half-life 60.2 days), as a surrogate for (129)I, within coniferous forest and grassland soils. The results do not suggest that volatilisation from these soils is a significant pathway for the transport of (129)I. Strong and specific sorption of iodine to humic substances has been demonstrated, which is reduced at freezing temperatures. It is hypothesised that rapid sorption to soil humic substances can significantly reduce volatilisation rates. The effect of freezing conditions on iodine extractability from soils suggests a microbially mediated sorption process.     

Inorganic iodine incorporation into soil organic matter: evidence from iodine K-edge X-ray absorption near-edge structure

The transformation of inorganic iodine (I⁻ and IO₃⁻) incubated in soils with varying amounts of organic matter (Andosols from the surface layer of an upland field and forest, as well as Acrisols from surface and subsurface layers of an upland field) was investigated by using the iodine K-edge X-ray absorption near-edge structure (XANES). After 60 d of reaction, both I⁻ and IO₃⁻ were transformed into organoiodine in surface soils containing sufficient amounts of organic matter, whereas IO₃⁻ remained unchanged in the subsurface soil of Acrisols with low organic matter contents. Transformation of IO₃⁻ into organoiodine was not retarded when the microbial activity in soil was reduced by γ-ray irradiation, suggesting that microbial activity was not essential for the transformation of inorganic iodine into organoiodine. Soil organic matter has the ability to transform inorganic iodine into organoiodine.     

Analysis of soil characteristics of different land uses and metal bioaccumulation in wheat grown around rivers: possible human health risk assessment

The present study was conducted to determine the physico-chemical properties and heavy metal contents in soils under three land uses (agricultural, riverbank and roadside) from areas situated around rivers (Beas and Sutlej) in Punjab, India. Heavy metal contents in wheat samples (grain and fodder) growing in the area were also analyzed in order to find out potential human health risk through wheat consumption. The studied soils under the three land uses were found to be basic in nature with sandy texture, low soil organic matter and other soil nutrients. Comparatively higher amounts of soil nutrients were observed in soils under agricultural land use as compared to riverbank and roadside land uses. The amounts of heavy metals (Cr, Cu, Co and Pb) analyzed in soils were lower than the various national and international maximum permissible limits, but heavy metal contents observed in wheat fodder samples exceeded the maximum permissible limits for fodder. The soil-to-plant metal bioaccumulation factor was found to be highest for Cu (3.812 for soil–wheat grain and 1.874 for soil–wheat fodder), which showed the bioaccumulation of heavy metals from soils to crops, and the wheat straw-to-grain translocation factor was found to be highest for Co (4.375). The hazard index calculated to assess non-carcinogenic health risks was found above 1 for children, meaning that the wheat grains can pose health risks to children.     

Chemical associations of artificial radionuclides in Cumbrian soils

The distributions of radionuclides in the surface layer of four soils of contrasting types from west Cumbria, UK, have been studied in detail. All the soils contain enhanced levels of artificial radionuclides derived from low-level discharges both to sea and to atmosphere from the British Nuclear Fuels reprocessing plant at Sellafield. The bulk of the activity is held in the top 15 cm of soil profiles, suggesting that radionuclide mobility is limited. Sequential extraction experiments have identified major associations of plutonium with organic matter and of caesium with silicates but there is no preferential association of ruthenium with any single soil component.     

鄱阳湖水土环境及其水生维管束植物重金属污染

位于鄱阳湖流域乐安河中下游的德兴铜矿,是我国著名的大型铜业基地,是鄱阳湖流域重金属污染的主要来源之一。2003年7月至8月对鄱阳湖部分流域的水质、沉积物、底泥及水生维管束植物等样品的重金属污染进行了研究调查,采用原子吸收分光光度法分别对样品中的Cu、Zn、Pb、Cd等重金属含量进行了测定,并对测定结果进行了评价。研究结果表明,鄱阳湖流域水体中的重金属含量均达到地表水评价标准中的Ⅰ类标准,底泥、土壤等已受到了一定程度的重金属污染。而水生植物对重金属元素都具有不同程度的富集能力,植物对重金属的富集作用与土壤背景值有一定的相关性,土壤中重金属的背景值越高,植物对重金属的富集量也相应增加。     

Mercury pollution in Wuchuan mercury mining area,Guizhou, Southwestern China: The impacts from large scale and artisanal mercury mining

To evaluate the environmental impacts from large scale mercury mining (LSMM) and artisanal mercury mining (AMM), total mercury (THg) and methyl mercury (MeHg) were determined in mine waste, ambient air, stream water and soil samples collected from Wuchuan mercury (Hg) mining area, Guizhou, Southwestern China. Mine wastes from both LSMM and AMM contained high THg concentrations, which are important Hg contamination sources to the local environment. Total gaseous mercury (TGM) concentrations in the ambient air near AMM furnaces were highly elevated, which indicated that AMM retorting is a major source of Hg emission. THg concentrations in the stream water varied from 43 to 2100 ng/L, where the elevated values were mainly found in the vicinity of AMM and mine waste heaps of LSMM. Surface soils were seriously contaminated with Hg, and land using types and organic matter played an important role in accumulation and transportation of Hg in soil. The results indicated heavy Hg contaminations in the study area, which were resulted from both LSMM and AMM. The areas impacted by LSMM were concentrated in the historical mining and smelting facilities, while Hg pollution resulted from AMM can be distributed anywhere in the Hg mining area.     

Geochemical speciation of heavy metals in semiarid soils of the central Ebro Valley (Spain)

This study describes the chemical speciation of Fe, Mn, Zn and Cr in four selected soil types representative of the more abundant agricultural soils in the central Ebro river valley in Aragón. Gypsisols, Calcisols, Solonchaks and Solonetzs represent around 20% of the total soil surface in the region. A total of 12 selected sites have been sampled and five subsamples were taken in each site to create a composite sample. The four elements have been analysed by the sequential extraction procedure of Tessier et al. [Anal. Chem. 51 (1979) 844.] by emission atomic spectrometry of solid state (ICP OES). Very little amounts of Fe and Mn were retrieved from the exchangeable phase, the ready available for biogeochemistry cycles in the ecosystems. Therefore, low quantities of Fe and Mn can be taken up by plants in these alkaline soils. Cr was not detected in the bioavailable forms as well as Zn that was only present in negligible amounts in very few samples. The absence of mobile forms of Cr in all soils eliminates the toxic risk both in the trophic chain and from its migration downwards the soil profile. The largest contents of Fe, Zn and Cr were retrieved from the residual phase where metals are strongly bound to minerals, whereas Mn from the carbonate and oxide phases amounts 80% of its total content. Gypsisols and Calcisols have the lowest metal contents while the highest are found in Solonetzs and Solonchaks.     

Does soil adhesion matter when predicting radiocaesium transfer to animals?

A sward will often have significant amounts of soil adhered to the vegetation surfaces which will be ingested by grazing animals. If the soil is contaminated by radioactive fallout then it can serve as a dietary source of radionuclides, in addition to any root uptake by the plants. This study is an attempt to quantitatively assess the importance of soil adhesion as a source of radiocaesium to sheep using the RUINS model which simulates radiocaesium transfer in grazing systems.The method of simulating the contamination of vegetation surfaces used by the RUINS model is described, and the importance of the availability of radiocaesium associated with adhered soil relative to plant incorporated radiocaesium discussed. Two sets of simulations are presented: one in which the soil is treated as a medium providing a uniform availability of radiocaesium, and the second in which account is taken of the partitioning of radiocaesium in the soil between ‘fixed’ and ‘labile’ phases.The results demonstrate that, because of the reduced absorption in the gut of radiocaesium associated with soil, animals grazing pastures with significant amounts of radiocaesium associated with adhered soil will not be as contaminated as radiocaesium activity concentrations measured in bulk vegetation samples would suggest. Therefore, the extent of soil adhesion needs to be considered if predictions of radiocaesium contamination of animal products are to be made on the basis of measured activities of sampled vegetation. However, soil adhesion is unlikely to be a significant dietary source of available radiocaesium, unless the soil concerned exhibits an unusually high bioavailability of radiocaesium. Moreover the simulation results indicate that differences in availability between soil types observed experimentally are consistent with the partitioning between fixed and labile soil compartments made by the RUINS model.     

Soil As contamination and its risk assessment in areas near the industrial districts of Chenzhou City, Southern China

In order to assess soil As contamination and potential risk for human, soil, paddy rice, vegetable and human hair samples from the areas near the industrial districts in Chenzhou, southern China were sampled and analyzed. The results showed that the anthropogenic industrial activities have caused in local agricultural soils to be contaminated with As in a range of 11.0-1217 mg/kg. The GIS-based map shows that soil contamination with As occurred on a large scale, which probably accounted for up to 30% of the total area investigated. Soil As concentration abruptly decreased with an increase in the distance from the polluting source. High As concentrations were found in the rice grain that ranged from 0.5 to 7.5 mg/kg, most of which exceed the maximal permissible limit of 1.0 mg/kg dry matter. Arsenic accumulated in significantly different levels between leafy vegetables and non-leafy vegetables. Non-leafy vegetables should be recommended in As-contaminated soils, as their edible parts were found in relatively low As level. Arsenic concentrations in 95% of the total human hair samples in the contaminated districts were above the critical value, 1.0 mg/kg, set by the World Health Organization. Arsenic could be enriched in human hair to very high levels without being affected by As containing water. The results revealed that the soils and plants grown on them are major contributors to elevate hair As in the industrial population. Therefore, the potential impact on human health of ingestion/inhalation of soil As around the industrial districts seems to be rather serious. Hence proper treatments for As contaminated soils are urgently needed to reduce the contamination.     

The ecological effects of trichloroacetic acid in the environment

Trichloroacetic acid (TCAA) is a member of the family of compounds known as chloroacetic acids, which includes mono-, di- and trichloroacetic acid. The significant property these compounds share is that they are all phytotoxic. TCAA once was widely used as a potent herbicide. However, long after TCAA's use as a herbicide was discontinued, its presence is still detected in the environment in various compartments. Methods for quantifying TCAA in aqueous and solid samples are summarized. Concentrations in various environmental compartments are presented, with a discussion of the possible formation of TCAA through natural processes. Concentrations of TCAA found to be toxic to aquatic and terrestrial organisms in laboratory and field studies were compiled and used to estimate risk quotients for soil and surface waters. TCAA levels in most water bodies not directly affected by point sources appear to be well below toxicity levels for the most sensitive aquatic organisms. Given the phytotoxicity of TCAA, aquatic plants and phytoplankton would be the aquatic species to monitor for potential effects. Given the concentrations of TCAA measured in various soils, there appears to be a risk to terrestrial organisms. Soil uptake of TCAA by plants has been shown to be rapid. Also, combined uptake of TCAA from soil and directly from the atmosphere has been shown. Therefore, risk quotients derived from soil exposure may underestimate the risk TCAA poses to plants. Moreover, TCE and TCA have been shown to be taken up by plants and converted to TCAA, thus leading to an additional exposure route. Mono- and di-chloroacetic acids can co-occur with TCAA in the atmosphere and soil and are more phytotoxic than TCAA. The cumulative effects of TCAA and compounds with similar toxic effects found in air and soil must be considered in subsequent terrestrial ecosystem risk assessments.     

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.     

Effects of readily dispersible colloid on adsorption and transport of Zn, Cu, and Pb in soils

Soil colloids (<0.002 mm) were extracted from three types of soils to make the colloid-bound forms of Zn, Cu, and Pb solution. The clay mineral types and composition of the colloids, the adsorption characteristics of the colloids, and the effect of readily dispersible colloid on the transport of metals and the quality of the soils and groundwater were studied. The results showed that the adsorption capacity of Cu, Zn, and Pb was greater for the Aquic Vertisols (Shajiang Black soil) as compared to the Udic Luvisols (Brown soil) and Usdic Luvisols (Cinnamon soil), due to the difference of clay content and clay mineral composition in the different soils. The adsorption capacity of Pb was much higher than that of Zn and Cu for the same soils, which would contribute to the chemical properties of metals and specific adsorption characters of the colloids. The mobility of Zn in soils was greater than that of Cu and Pb, while similar trend was found in the transportation processes for Zn and Cu. The concentration of Zn and Cu in leachates increased as the leaching solution volume increased, but the migration of Pb was negligible, and the concentration of Pb could not been detected in leachates even after 7.5 pore volume leaching solution. The influence of mobility on Zn and Cu transport was different for different type of colloids. The mobility caused by readily dispersible colloids from Aquic Vertisols was greater as compared to that of Udic Luvisols and Usdic Luvisols. Analysis of soils after column leaching indicated that Zn was distributed much deeper than Cu, but Pb was almost not migrated, and mainly accumulated in the soil surface. Therefore, Zn had greater tendency for the groundwater pollution than Cu and Pb, and Pb tends to contaminate the surface soils.     

An overview of BORIS: Bioavailability of Radionuclides in Soils

The ability to predict the consequences of an accidental release of radionuclides relies mainly on the level of understanding of the mechanisms involved in radionuclide interactions with different components of agricultural and natural ecosystems and their formalisation into predictive models. Numerous studies and databases on contaminated agricultural and natural areas have been obtained, but their use to enhance our prediction ability has been largely limited by their unresolved variability. Such variability seems to stem from incomplete knowledge about radionuclide interactions with the soil matrix, soil moisture, and biological elements in the soil and additional pollutants, which may be found in such soils. In the 5th European Framework Programme entitled Bioavailability of Radionuclides in Soils (BORIS), we investigated the role of the abiotic (soil components and soil structure) and biological elements (organic compounds, plants, mycorrhiza, and microbes) in radionuclide sorption/desorption in soils and radionuclide uptake/release by plants. Because of the importance of their radioisotopes, the bioavailability of three elements, caesium, strontium, and technetium has been followed. The role of one additional non-radioactive pollutant (copper) has been scrutinised in some cases. Role of microorganisms (e.g., K(d) for caesium and strontium in organic soils is much greater in the presence of microorganisms than in their absence), plant physiology (e.g., changes in plant physiology affect radionuclide uptake by plants), and the presence of mycorrhizal fungi (e.g., interferes with the uptake of radionuclides by plants) have been demonstrated. Knowledge acquired from these experiments has been incorporated into two mechanistic models CHEMFAST and BIORUR, specifically modelling radionuclide sorption/desorption from soil matrices and radionuclide uptake by/release from plants. These mechanistic models have been incorporated into an assessment model to enhance its prediction ability by introducing the concept of bioavailability factor for radionuclides.     

基于Hydrus-1D模型的太湖流域农田系统水分渗漏和氮磷淋失特征分析

在土壤水分长期定位观测基础上,应用Hydrus-1D模型对太湖流域典型稻麦轮作农田土壤水分渗漏进行动态模拟,并结合深层土壤溶液取样及氮磷浓度测定,分析了当前耕作方式下农田水分渗漏和氮磷淋失特征。结果表明,土壤水渗漏与降雨、灌溉及前期土壤含水率有关;麦季深层渗漏量小但持续时间长,而稻季单次渗漏量大却持续时间短。模拟时段内铵态氮和可溶解性总磷的淋失主要发生在稻季,淋失量分别为2.62、0.49 kg/hm²,分别占稻麦轮作期总淋失量的96.0%、96.0%,而硝态氮淋失主要发生在麦季,淋失量为57.97 kg/hm²,占总淋失量的80.2%;无机氮淋失的主要形态为硝态氮,其淋失量占总淋失量的96.4%。综合看来,硝态氮应作为主要阻控对象,以减少农田面源污染对地下水及太湖水体的污染风险。此外,氮磷淋失在6、7月份即休耕期和水稻生长早期容易达到峰值,应得到重视。     

Plant uptake of radiocaesium from artificially contaminated soil monoliths covering major European soil types

Uptake of ¹³⁷Cs was measured in different agricultural plant species (beans, lettuce, barley and ryegrass) grown in 5 undisturbed soil monoliths covering major European soil types. The first cultivation was made three years after soil contamination and plants were grown during 3 successive years. The plant–soil ¹³⁷Cs transfer factors varied maximally 12-fold among soils and 35-fold among species when grown on the same soil. Single correlations between transfer factors and soil properties were found, but they varied widely with plant type and can hardly be used as a predictive tool because of the few soils used. The variation of ¹³⁷Cs concentrations in plants among soils was related to differences in soil solution ¹³⁷Cs and K concentrations, consistent with previous observations in hydroponics and pot trials. Absolute values of transfer factors could not be predicted based on a model validated for pot trials. The ¹³⁷Cs activity concentration in soil solution decreased significantly (11- to 250-fold) for most soils in the 1997–1999 period and is partly explained by decreasing K in soil solution. Transfer factors of lettuce showed both increasing and decreasing trends between 2 consecutive years depending on soil type. The trends could be explained by the variation in ¹³⁷Cs and K concentrations in soil solution. It is concluded that differences in ¹³⁷Cs transfer factors among soils and trends in transfer factors as a function of time can be explained from soil solution composition, as shown previously for pot trials, although absolute values of transfer factors could not be predicted.     

重庆市汞污染的观测研究

为研究重庆市区汞污染状况,2004年9~11月,同步观测了重庆市近郊铁山坪小流域（TSP）和观音桥(GYQ)两个区域的全沉降、穿透水、地表径流和土壤中的总汞含量,估算了小流域中汞的输入输出通量,分析了城区和郊区的大气汞沉降和分布特征。结果表明,重庆已在一定程度上受到汞污染。在TSP,湿沉降是汞输入的主要方式,也就是说,在TSP,细颗粒是大气汞的主要来源,表层土则是大气汞的一个主要的汇。GYQ区域的汞污染比TSP相对严重。在GYQ,除了湿沉降以外,干沉降是汞来源的重要形式,表明在GYQ,粗颗粒可能对大气汞有很大的贡献。因此,本地源的排放对城区的影响比对郊区的影响大,尤其是城区火电站附近的土壤样品比郊区土壤的汞含量高很多,说明火电站是大气汞的重要来源之一。