Influence of microorganisms on the behavior of technetium and other elements in paddy soil surface water

Insolubilization patterns of technetium (Tc) and other trace elements (Sc, Co, Zn, Se, Rb, Sr, Y, Nb, Ce, Pm, Gd, Lu, Hf, and Re) in surface water covering paddy fields were compared to gain insight into the behavior of Tc in an agricultural environment. The insolubilization of Tc, which did not pass through a 0.2-microm-pore-size filter, was mainly caused by bacteria. Among the 14 other elements investigated, Nb was insolubilized by bacteria and the amounts of insoluble Nb were positively correlated with those of Tc. Although Re is a chemical analog of Tc, no similarity was observed. These results suggest that Tc behaves similarly to Nb in the insolubilization in surface water covering paddy fields.     

Environmental conditions for the formation of insoluble Tc in water ponds located above paddy fields

Optimum conditions for the formation of insoluble Tc (Tc in >0.2 microm size fraction) were studied using a microcosm including water ponds above a paddy field to understand Tc behavior in such fields. In the microcosm, soluble TcO(4)(-) was converted to insoluble forms, but no changes in the form of Tc were observed in filtered microcosm samples which were microorganisms-free. The formation of insoluble Tc was inhibited by the addition of the antibiotic chloramphenicol. In addition, the reduction of soluble Tc(VII)O(4)(-) to low-valence oxide was not observed in the filtered microcosm samples, although reducing conditions were present. These results indicated that bacteria were involved in the formation of insoluble Tc. Since oxidizing conditions influence bacterial metabolism, the formation of insoluble Tc by bacteria was studied under aerobic and anaerobic conditions. The results showed that anaerobic conditions were favorable for the formation of insoluble Tc. In addition, the addition of formate as an electron donor to a microcosm sample facilitated the formation of insoluble Tc. The results suggested that insoluble Tc in the water ponds above paddy fields was caused by bacteria, which were shown to couple the oxidation of formate to the reduction of Tc(VII) during anaerobic respiration.     

Influence of climatic conditions and soil type on 99TcO4- uptake by rye grass

Climatic changes over the long term will modify significantly the biosphere, with glaciation events probably taking place in the next 100 000 years. This is important to safety assessments of nuclear waste disposal facilities that contain high-level and long-lived waste.The soils will evolve toward new situations, and their properties will be consequently modified (e.g. an increase of soil organic matter may be expected in a cooler climate). These changes in soil properties would affect the mobility and the soil-to-plant transfer of radionuclides such as (99)Tc. This study aimed at simulating the cooling of climatic conditions for soils representative of a Jurassic limestone plateau, and the effect on transfer parameters of (99)TcO(4)(-) in the soil-plant systems was investigated. The cooler conditions were simulated by increasing elevation, a surrogate for climate change. Soils were sampled in similar geological background and topography at different elevations in the north east of France (Lorraine and Jura). Soil/solution distribution coefficients (K(d)) of (99)TcO(4)(-) were measured on soil samples in short-term batch experiments with 1:10 soil:solution ratio. Rye grass was grown on the soils spiked with (99)TcO(4)(-) at temperature regimes adapted to each soil. Also, two different temperature regimes (cold and temperate) were applied to one soil to test the effect of plant physiology and evapotranspiration on (99)TcO(4)(-) uptake. K(d) values did not show significant differences among soils in aerobic conditions, and were not significantly different from 0. During plant culture, reduction of (99)Tc was never totally achieved in soils, including in a peaty OM soil. Concentration ratios (CR) were calculated on a dry weight basis and ranged from 20 to 370. CR were always higher in high temperature regimes than in cold temperatures. They were also inversely correlated with soil organic matter (OM) content. A decrease of CR values from 5 to 10-fold was observed with increasing soil OM. Results suggested that the water holding capacity, in which (99)Tc is diluted, the nitrification potential of the soils and the evapotranspiration of plants (efficiency of uptake of soluble (99)TcO(4)(-)) were strongly involved in these differences.     

论水稻土肥力进化与土壤质量——以太湖地区为例

太湖地区是我国古老农业区之一。在六七千年之前先民已开始种植水稻 ,随着耕作培肥措施不断加强 ,与土壤肥力进化同步伴随着耕作轮作制的不断演进 ,由轮荒———沤田———水旱轮作———三熟制的变化 ,土壤基础肥力稳步提高 ,稻麦单位面积产量逐年上升。该区水稻土历经数千年的耕肥与平田整地等人为活动 ,在起源土壤背景上发育成五类水稻土 ,这五类水稻土经过培肥改良均达到水旱轮作高产稳产阶段 ,尽管地力上还存在不同程度的差异 ,这不能不说是人为定向培育的成果。在一般情况下 ,土壤质量是由土壤肥力决定的 ,基础肥力高低是农业生产优质高产低耗的关键 ,在评价土壤质量时必需首先予以关注。当然 ,随着工业的发展 ,土壤污染所波及的农产品超标问题 ,也应在评价土壤质量时予以关注 ,并作为评价因素在综合评价体系中占有应有的份量     

Availability of 99Tc in undisturbed soil cores

Models for safety assessment of radioactive waste repositories need accurate values of the soil-to-plant transfer of radionuclides. In oxidizing environments, (99)Tc is expected to occur as pertechnetate ((99)TcO(4)(-)). Due to its high mobility, leaching of this element in the field might be important, potentially affecting the reliability of estimated transfer parameters of (99)Tc as measured in closed experimental systems such as hydroponics or pot experiments. The aim of this experiment was to measure the leaching of (99)Tc in undisturbed irrigated soil cores under cultivation as well as plant uptake and to study the possible competition between the two transfer pathways. Undisturbed soil cores (50 x 50 cm) were sampled from a Rendzic Leptosol (R), a colluvial Fluvic Cambisol (F) and a Dystric Cambisol (D) using PVC tubes (three cores sampled per soil type). Each core was equipped with a leachate collector at the bottom, allowing the monitoring of (99)Tc leaching through the cores. Cores were placed in a greenhouse and maize (Zea mays L., cv. DEA, Pioneer) was sown. After 135 d, maize was harvested and radioactivity determined in both plant and water samples. Results showed that during the growing period, leaching of (99)Tc was limited, due to the high evapotranspiration rate of maize. After harvest, leaching of (99)Tc went on because of the absence of evapotranspiration. Effective uptake (EU) of (99)Tc in leaves and grains was calculated. EU reached 70% of the input in the leaves and was not significantly different among soils. These results confirmed those obtained from pot experiments, even though leaching was allowed to occur in close-to-reality hydraulical conditions. As a consequence, it was concluded that pot experiments are an adequate surrogate for more complex "close-to-reality" experimental systems for measuring transfer factors.     

中亚热带红壤区不同土地利用土壤田间持水量估测

田间持水量是衡量土壤保水性的重要指标,也是进行农田灌溉、作物水管理和水文模型的重要参数,但其测定繁琐而耗时,迫切需要一种简捷精确的估测方法。采集了50个来自稻田和旱地的1 m深原状土壤剖面样,然后基于土壤基本理化性质,利用多元逐步回归方法对土壤田间持水量进行模型预测。结果显示:(1)对于稻田土壤,田间持水量主要受容重和有机碳影响,而对于旱地则主要受土壤质地影响;(2)构建的田间持水量传递函数,对于稻田土壤预测精确度较高,调整的确定系数达到0.79,对于旱地则相对较弱。研究表明土地利用方式对田间持水量精确估测影响较大,利用土壤传递函数法对田间持水量的快速获取有一定参考价值。     

Soil availability,plant uptake and soil to plant transfer of 99Tc--a review

The fission yield of 99Tc from 239Pu and 235U is similar to that of 137Cs or 90Sr and it is therefore an important component of nuclear weapons fall-out, nuclear waste and releases from nuclear facilities. There is particular current interest in 99Tc transfer from soil to plants for: (a) environmental impact assessments for terrestrial nuclear waste repositories, and (b) assessments of the potential for phytoextraction of radionuclides from contaminated effluent and soil. Vascular plants have a high 99Tc uptake capacity, a strong tendency to transport it to shoot material and accumulate it in vegetative rather than reproductive structures. The mechanisms that control 99Tc entry to plants have not been identified and there has been little discussion of the potential for phytoextraction of 99Tc contaminated effluents or soil. Here we review soil availability, plant uptake mechanisms and soil to plant transfer of 99Tc in the light of recent advances in soil science, plant molecular biology and phytoextraction technologies. We conclude that 99Tc might not be highly available in the long term from up to 50% of soils worldwide, and that no single mechanism that might be easily targeted by recombinant DNA technologies controls 99Tc uptake by plants. Overall, we suggest that Tc might be less available in terrestrial ecosystems than is often assumed but that nevertheless the potential of phytoextraction as a decontamination strategy is probably greater for 99Tc than for any other nuclide of radioecological interest.     

Soil migration and plant uptake of technetium from a fluctuating water table

Soil columns (50x15 cm) were used to determine the potential for 95mTc (as a surrogate for 99Tc which is an important component of some radioactive waste) to migrate from a contaminated, fluctuating water table, through sandy loam soil and into perennial ryegrass. Upward migration was significantly retarded with, generally, only the bottom few centimetres of soil becoming contaminated over the 6 months of the experiment. This is thought to have been due to the presence of anoxic conditions within the water table leading to the reduction of pertechnetate to Tc(IV) species which are relatively insoluble. However, some evidence of very slow upward migration over time was found. Only a small and inconsistent transfer of activity into the perennial ryegrass was observed. Whilst these observations would suggest that 99Tc is less important than radionuclides such as 129I and 36Cl in terms of the risk associated with radioactive waste disposal, the potential for a slow upward migration, and/or a pulse-release following the re-oxidation of reduced soil in which 99Tc has accumulated should not be overlooked.     

Sea-to-land transfer of technetium-99 through the use of contaminated seaweed as an agricultural soil conditioner

The use of seaweed as an agricultural soil conditioner gives rise to a potential pathway for the transfer of Technetium-99 ((99)Tc) from marine to terrestrial ecosystems and thence to man. However, to date there is little information on the extent of the release of (99)Tc from seaweed into soil and the mechanisms involved. This pot experiment has shown that (99)Tc is released fairly rapidly from Fucus vesiculosus into a sandy coastal soil. Despite low temperature conditions, 60% of the (99)Tc added with the seaweed had accumulated in the soil 15 weeks after addition. Concurrent CO(2) monitoring (used as a measure of microbial decomposition or catabolism) suggested that the initial (99)Tc release (up to 40% in the first 8 weeks) was due to leaching from the seaweed and that microbial decomposition was responsible for the release of the remaining (99)Tc in the latter phase (12-15 weeks).     

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.     

稻鸭、稻鱼共作对稻田P素动态变化的影响

以稻鸭和稻鱼生态系统为研究对象，通过大田试验研究了稻田P的动态变化及转化规律，及其对环境的影响。结果表明，施P后土壤和田面水P含量立即达到最大值，一周后迅速降低。相对于空白（CK），养鸭处理（RD）和养鱼处理（RF）田面水总P浓度、溶解P浓度、土壤速效P含量和水稻吸P量显著增加，而土壤全P含量有所增加。研究还表明，水稻吸P量与田面水溶解P、土壤速效P显著相关。对田面水P素径流流失的潜在环境效应分析表明，施P后的一周左右是控制P素流失的关键时期；由于养鸭养鱼能提高稻田P含量，在稻鸭、稻鱼共作期间，要注意避免农田排水和防止因降雨引起的田面水外溢。同时，由于鸭子和鱼能提高土壤有效养分含量，降低化肥的施用量，进而降低了化肥损失所造成的环境危害。     

长江三角洲水田保护性耕作制度的碳收集效应估算

耕作制度对农田土壤有机碳的稳定和积累作用显著，探讨耕作制度演变下农田土壤碳库动态，将有助于农田土壤碳收集的技术选择及政策制定。利用已发表的田间定位试验数据，构建不同耕作制度下长江三角洲水田耕层土壤有机碳密度的估算模型。依据该区近20多年来耕作制度演变动态，对保护性耕作制度的土壤碳收集效应进行了初步估算。结果表明，油菜面积的扩大、小麦的少免耕和作物秸秆的还田分别约增加土壤耕层有机碳0.94 Tg、2.76 Tg和3.95 Tg，其中以麦稻复种转向油稻复种的单位面积碳收集效应为最高。最后，就碳收集效应估算的方法进行了相关讨论，并就土壤碳收集研究和如何提高土壤碳收集潜力提出了一些建议。     

安徽省土壤氟含量及其赋存特征

氟是生态系统中一种重要微量元素,过量和不足都会影响人和动物健康,人体氟主要来自饮水和食物,土壤氟含量、形态以及土壤理化性质等影响着水和食物氟含量。以安徽省主要类型土壤为材料,采用连续化学提取的方法,测定了安徽省主要类型土壤全氟、水溶氟以及不同形态氟含量,分析了土壤氟形态与土壤理化性质的关系。结果表明：安徽土壤全氟含量1066～1 2367 mg/kg,平均为4852 mg/kg,全氟含量高低排序为菜地土＞潮土＞石灰土＞黄棕壤＞黄褐土＞水稻土＞砂姜黑土＞黄红壤,成土母质是影响土壤全氟含量的主要因素。土壤水溶氟含量042～2248 mg/kg,平均为338 mg/kg,水溶氟含量高低排序为菜地土＞砂姜黑土＞潮土＞黄棕壤＞黄褐土＞水稻土＞石灰土＞黄红壤,北高南低。土壤氟主要赋存形态是矿物态氟,占土壤全氟95%以上,水溶氟、交换态氟、铁锰氧化物结合态氟和有机结合态氟占土壤全氟5%左右。土壤水溶性氟含量与土壤pH呈极显著正相关,与土壤全磷含量呈显著正相关,相关系数分别为0660 2和0353 9,土壤交换态氟与土壤小于0001 mm土粒含量和土壤阳离子交换量呈显著正相关,相关系数分别为0338 4和0345 8,有机结合态氟与土壤有机含量呈极显著正相关,相关系数为0526 8     

Determination of technetium-99 using electrothermal vaporization inductively coupled plasma-mass spectrometry (ETV-ICP-MS) and NH4OH as chemical modifier

In recent years, developments in ICP-MS have led to improved methods for determination of long-lived radionuclides. This paper reports the use of NH(4)OH as a matrix modifier and ETV sample introduction for the determination of technetium-99 ((99)Tc) in a variety of environmental and biological samples, using Re as carrier and (99m)Tc as yield monitor in the chemical separation method. Addition of an excess of NH(4)OH led to a stable (99)Tc signal, reduced memory effect, better reproducibility and reduced detection limits. Following radiochemical separation of (99)Tc from the sample matrix, detection limits in the order of a few microBq have been achieved. ETV has also proved applicable for rapid, direct analysis of a number of environmental samples having relatively high concentrations of (99)Tc (sediment extracts and river water close to nuclear installations). However, in this case, control of matrix effects (signal reduction and enhancement) using standard additions is necessary.     

不同水耕年限稻田土壤水分运动特征研究

利用田间染色示踪和室内样品分析相结合的方法,研究了江汉平原不同水耕年限稻田土壤水分运动特征及其影响因素,期望为制定合理的稻田水分管理措施提供科学依据。结果表明:新稻田(水耕17a)与老稻田(水耕大于100a)土壤理化性质差异显著,引发土壤剖面内不同水分运动特征。新稻田垂直渗漏较老稻田明显,表现为新稻田有更大的染色深度。老稻田染色区域主要集中在耕作层,染色面积为48.52%;犁底层和底土层染色面积较小,仅为3.17%和0.2%。除耕作层外,新稻田其他土层染色面积均大于老稻田,且优先流特征较老稻田明显。老稻田侧向水分运动较新稻田强烈,其侧流剖面的染色面积(15.35%)显著高于新稻田(8.45%),老稻田侧向水流主要发生在犁底层以上。为减少稻田水分渗漏损失,老稻田可以通过减少农田-田埂-沟渠过渡区侧渗实现,而新稻田可采取少量多次的灌溉原则。     

Ecological lessons from the Chernobyl accident

The Chernobyl nuclear accident in 1986 not only caused serious ecological problems in both the Ukraine and Belarus, which continue to the present day, but also contaminated a large part of the higher latitudes of the northern hemisphere. In this paper an overview is given of the latter problems in upland UK, where ecological problems still remain some 17 years after initial contamination. Following deposition of radiocaesium and radioiodine in May 1986, measurements of radioactivity in grass and soil indicated a rapidly declining problem as the radioiodine decayed and the radiocaesium became immobilised by attachment to clay particles. However, these studies, as well as the advice received by the Ministry of Agriculture, Fisheries and Food, were based on lowland agricultural soils, with high clay and low organic matter contents. The behaviour of radiocaesium in upland UK turned out to be dominated by high and persistent levels of mobility and bioavailability. This resulted in the free passage of radiocaesium through the food chain and into sheep. Consequently the Ministry banned the sale and movement of sheep over large areas of upland Britain, with bans remaining on some farms to the present day. Present day predictions suggest that these bans will continue in some cases for some years to come. The causes of radiocaesium mobility in upland areas have subsequently been the subject of intense investigation centred around vegetation and, in particular, soil characteristics. Soil types were identified which were particularly vulnerable in this respect and, where these coincided with high levels of deposition, sheep bans tended to be imposed. While much of the earlier work suggested that a low clay content was the main reason for continuing mobility, a very high organic matter content is now also believed to play a major role, this being a characteristic of wet and acidic upland UK soils. The overall message from this affair is the importance of a fundamental understanding of biogeochemical pathways in different ecosystems when attempting to predict the impacts of large-scale contamination.     

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.     

Accumulation of 99Tc in duckweed Lemna minor L. as a function of growth rate and 99Tc concentration.

This study focuses on the question of whether short-term studies can be used to forecast the accumulation of the long-lived fission product 99Tc in duckweed, Lemna minor L., grown in the field; in other words, are the accumulation parameters independent of changing growth rates typical of natural populations of duckweed. Two processes determine the 99Tc accumulation: (i) uptake and release of 99TcO4-, characterised by a concentration factor, Kd, and (ii) first-order reduction and complexation of TcVII, characterised by kred. At various 99Tc concentrations, the growth, total Tc and TcO4- accumulation were monitored over 10 days; parameters were fitted and compared with earlier results. Both Kd and kred turn out to be independent of time, concentration and growth rate up to a concentration of 10(-6)mol l(-1) 99TcO4-. Concentrations above this level result in toxic effects. The Tc accumulation in field populations of duckweed at Tc concentrations which generally occur in the environment can be forecasted by using the results from short-term experiments.     

99Tc in seawater in the West Spitsbergen Current and adjacent areas

99Tc levels were measured in seawater samples collected between 2000 and 2002 in the West Spitsbergen Current (WSC) and along the western coast of Svalbard or Spitzbergen and compared with available oceanographic 3-D modelling results for the late 1990s. Additional data from related regions are also presented in order to support the data interpretation. The seawater in the Arctic fjord Kongsfjorden on the western coast of Svalbard is influenced by the WSC, as shown by the 99Tc levels in surface water. By means of the WSC, 99Tc reaches the Eastern Fram Strait, where one branch of the WSC turns west into the East Greenland Current (EGC), and another branch continues northwards into the Arctic Ocean. Surface seawater collected in the central part of the WSC during a cruise on board the R/V "Polarstern" in the summer of 2000, showed higher levels of (99)Tc than samples measured in Kongsfjorden in the spring of 2000. However, all levels measured in surface water are of the same order of magnitude. Data from sampling of deeper water in the WSC and EGC provide information pertaining to the lateral distribution of 99Tc. In all vertical profiling surveys (conducted in spring and summer), the highest levels of 99Tc were found in surface water. Comparison with oceanographic 3-D modelling indicates both significant seasonal variations in the lateral stratification of the WSC and variations with depth over shorter vertical distances. This information can be applied in sampling strategies, environmental monitoring, long-range transport of pollutants and physical oceanography.     

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.