Determination of bioavailable rhenium fraction in agricultural soils

Rhenium (Re) mobility in agricultural soils was studied in order to obtain information relevant to (99)Tc mobility in soil-to-plant systems. Since water soluble Tc and Re are highly bioavailable, extraction of Re with water was carried out in addition to a total Re determination in the soils. The geometric means of total Re for paddy field, upland field and other soils were 0.34, 0.23, and 0.28 ng g(-1), respectively, while those of water soluble Re (<0.45 microm membrane filterable) were 0.053, 0.015 and 0.008 ng g(-1), respectively. There were no differences for total Re among soil uses; however, the water soluble Re/total Re ratio was significantly higher in paddy field soils (16%) than in other soil uses (6% for upland fields and 3% for other uses). Rhenium mobility and plant availability were higher in paddy fields than in other agricultural fields, and similar phenomena would be expected for (99)Tc.     

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.     

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。     

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.     

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。     

典型饮用水源地非点源污染的分布式模拟——以滁州市城西水库为例

城西水库（现改名西涧湖）是滁州市唯一地表水源,非点源污染已成为其水质污染的重要原因。基于土地覆被格局,依据非点源污染物质的产生、截留、汇流过程,构建了模拟每个栅格上污染物质向受纳水体的输出贡献量和被各种土地覆被截留量的物理过程模型。以磷素为例,对城西水库流域进行模拟。结果表明： 2000和2010年,流域向城西水库输出总磷量分别达到2 58038和2 46120 kg。库体西北部的市农科所、城郊居委会、水产研究所等地对水质危害最大。多数磷素在向库体的运移过程中被各类土地覆被有效的截留,总量在2000和2010年分别达到5 77449和5 42236 kg,占流域磷素总负荷的691%和68 8%。由于目前土地覆被布局的不尽合理,林地和草地对磷素的截留能力未能充分发挥。建议在流域水文敏感区布设林草缓冲带,将有效减少水库磷素的接纳量     

巢湖流域不同土地利用类型地表径流污染特征研究

巢湖是我国五大淡水湖之一,目前正面临着严重的环境污染与水体富营养化问题。通过对巢湖流域塘西地区大豆地,水稻田,菜地,山芋地,小麦地,集镇街道,山坡地,饲养场地,农村道路,湖滩芦苇地,荒地等１１种土地利用类型地表径流污染现状的详细调查与分析,建立了巢湖流域不同土地利用类型地表径流污染研究的一般程序与方法。     

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。     

Retention and phytoavailability of radioniobium in soils

Radioniobium is present in long-lived nuclear waste as a result of the activation of zirconium pellets associated with the nuclear fuel. The behaviour of niobium (Nb) in the environment and especially its fate in the soil-plant system has not been thoroughly investigated so far. In safety assessment of French long-lived nuclear waste disposal, data concerning the mobility and the bioavailability of Nb in soils are needed as well as general trends of its fate in the specific environment around the site of French underground research laboratory. Therefore, we investigated the mobility of 95Nb in three different soils typical of the area of north-eastern France and its uptake by two plants, rye grass (Lolium perenne L.) and winter wheat (Triticum aestivum L.). Soil:solution distribution of 95Nb was observed in 1:10 batch experiments with deionized water for a 3-day period. Results showed that K(d) values were high (in the order of 10(3) L kg(-1)) and were still significantly increasing after 3 days. A mathematical model, fitted to describe the decrease of the radioactivity after 3 days, is proposed to calculate sorption ratios--SR--(rather than K(d) values as equilibrium was not reached) over longer periods. Soil-to-plant concentration ratios (CR) were measured in shoots and roots of the two plants after cultivation on two soils spiked with (95)Nb (406kBqkg(-1)). Soil-to-root dry weight CR were high (0.30-1.52) and could probably be due to efficient uptake into the roots. However, no transfer of Nb to plant shoots was detected in any of the soils. Nb is thus a rather immobile element in soils and its transfer to plants seems limited to underground parts. It would therefore tend to accumulate in surface horizons of soils in case of long-term continuous surface release.     

The dispersion of 99Tc in the Nordic Seas and the Arctic Ocean: a comparison of model results and observations

The radionuclide (99)Tc had been discharged from the nuclear reprocessing facility in Sellafield (UK) into the Irish Sea in increased amounts in the 1990s. We compare the simulated dispersion of (99)Tc in surface water as calculated by a hydrodynamic model and an assessment box model with field-observations from 1996 to 1999 to study concentrations, pathways and travel times. The model results are consistent with the observations and show the typical pathway of dissolved radionuclides from the Irish Sea via the North Sea along the Norwegian Coast. Subsequently the contaminated water separates into three branches of which the two Arctic branches bear the potential for future monitoring of the signal in the next decades. The results of the hydrodynamic model indicate a large variability of surface concentrations in the West Spitsbergen Current which has implications for future monitoring strategies. According to the observed and simulated distributions we suggest an improved box model structure to better capture the pattern for concentrations at the surface.     

稻虾共作快速发展背景下潜江耕地时空变化特征分析

虾稻共作综合种养模式近年来在长江中下游地区快速发展,探索虾稻共作对农业土地利用的影响,对于科学调控虾稻田发展、确保粮食和生态双安全具有重要意义。该研究以虾稻共作模式发源地——湖北潜江市为研究区域,利用空间分析和破碎度指数方法,分析虾稻共作模式快速推广下潜江市农业土地利用时空格局变化。结果表明：（1）近20年来,耕地时空格局变化过程是以园林办事处（主城区）为中心的建设用地向西至广华镇、南至杨市镇不断扩张,耕地转为新增建设用地达28.64 km2,约18.59 km2耕地转换为水域;（2）耕地格局呈现破碎化,主要由城市发展过程中建设用地扩张占用耕地,以及虾稻田快速发展后造成;（3）虾稻田主要由水田转换而来,部分旱地及水域也转换为虾稻田。虾稻田的不断扩张,特别是旱地和水域转换为虾稻田,一定程度上带来耕地破碎化。因此,在我国农业劳动力不足、农民收入不高和种地积极性不强等因素下,未来虾稻田种植模式对耕地利用具有较好的潜力和空间,但也需要重点关注虾稻共作模式的可持续发展,重点基于水田发展虾稻田种养模式。     

城镇化平原河网区下垫面特征变化及洪涝影响研究

城镇化是人类改变地表最深刻、最剧烈的过程之一,针对平原区城镇化引起的洪涝加剧问题,以浙东沿海奉化江流域中下游平原为例,利用高分辨率遥感影像和地形图资料获取1990~2010年间下垫面特征信息,从土地利用类型、河网水系和地面高程3个方面,分析城镇化过程中平原河网地区下垫面特征变化及其对区域洪涝调蓄能力的影响。研究结果表明:平原区城镇化对下垫面的影响不仅表现为城镇不透水面的增加,径流系数的增大,同时城镇扩张过程中农田和水系转化为城镇用地,而后者具有相对较高的防洪标准,使得新建城区地面高程明显增大,河网调蓄能力亦呈不断减少趋势。洪涝模拟显示以上下垫面变化导致区域可调蓄洪涝的空间逐渐减少,洪涝风险程度加大,并呈现向相对低洼地带转移的趋势特征。     

Vertical distributions of (99)Tc and the (99)Tc/(137)Cs activity ratio in the coastal water off Aomori, Japan

Using a sector-field ICP-MS the vertical distributions of the ⁹⁹Tc concentration and ⁹⁹Tc/¹³⁷Cs activity ratio were measured in the coastal waters off Aomori Prefecture, Japan, where a spent-nuclear-fuel reprocessing plant has begun test operation. The ⁹⁹Tc concentrations in surface water ranged from 1.8 to 2.4 mBq/m³, no greater than the estimated background level. Relatively high ⁹⁹Tc/¹³⁷Cs activity ratios (10-12 × 10⁻⁴) would be caused by the inflow of the high-⁹⁹Tc/¹³⁷Cs water mass from the Japan Sea. There is no observable contamination from the reprocessing plant in the investigated area. The ⁹⁹Tc concentration and the ⁹⁹Tc/¹³⁷Cs activity ratio in water column showed gradual decreases with depth. Our results implied that ⁹⁹Tc behaves in a more conservative manner than ¹³⁷Cs in marine environments.     

Health risks from large-scale water pollution: trends in Central Asia

Limited data on the pollution status of spatially extensive water systems constrain health-risk assessments at basin-scales. Using a recipient measurement approach in a terminal water body, we show that agricultural and industrial pollutants in groundwater-surface water systems of the Aral Sea Drainage Basin (covering the main part of Central Asia) yield cumulative health hazards above guideline values in downstream surface waters, due to high concentrations of copper, arsenic, nitrite, and to certain extent dichlorodiphenyltrichloroethane (DDT). Considering these high-impact contaminants, we furthermore perform trend analyses of their upstream spatial-temporal distribution, investigating dominant large-scale spreading mechanisms. The ratio between parent DDT and its degradation products showed that discharges into or depositions onto surface waters are likely to be recent or ongoing. In river water, copper concentrations peak during the spring season, after thawing and snow melt. High spatial variability of arsenic concentrations in river water could reflect its local presence in the top soil of nearby agricultural fields. Overall, groundwaters were associated with much higher health risks than surface waters. Health risks can therefore increase considerably, if the downstream population must switch to groundwater-based drinking water supplies during surface water shortage. Arid regions are generally vulnerable to this problem due to ongoing irrigation expansion and climate changes.     

水稻流入施肥法及流入肥料效果研究

进行了流入施肥法可行性，流入肥肥效及替代进口肥料试验。结果表明：流入施肥法与人工撒施，均能使肥料在田间分布均匀，流入施肥法比人工撒施增产3．4％，流入施肥法是可行的，日本流入肥和国产复合肥流入施肥田间3－4d后，在田间分布都较均匀，水稻追施分蘖肥和穗肥时水的温度都在30℃左右，两种肥料的溶解度比较大，易配成溶液，适合作流以施用，日本流入肥和中国复合肥对水稻的增产效果相差不大，可用国产复合肥料替代进口肥料；吸附试验表明，施肥5d后，流入肥料和其它氮素肥料中氮素的吸附率达82．5％－89．3％，流入施肥后5d内不要排水。流入施肥法适合土地平整，田块较大，灌溉条件好，人多地少或农业人口老龄化和血吸虫疫区等平原湖区稻田。     

X-ray absorption spectroscopy studies of reactions of technetium, uranium and neptunium with mackinawite

Technetium, uranium and neptunium may all occur in the environment in more than one oxidation state (IV or VII, IV or VI and IV or V respectively). The surface of mackinawite, the first-formed iron sulfide phase in anoxic conditions, can promote redox changes so a series of laboratory experiments were carried out to explore the interactions of Tc, U and Np with this mineral. The products of reaction were characterised using X-ray absorption spectroscopy. Technetium, added as TcO4(-), is reduced to oxidation state IV and forms a TcS(2)-like species. On oxidation of the mackinawite in air to form goethite, Tc remains in oxidation state IV but in an oxide, rather than a sulfide environment. At low concentrations, uranium forms uranyl surface complexes on oxidised regions of the mackinawite surface but at higher concentrations, the uranium promotes surface oxidation and forms a mixed oxidation state oxide phase. Neptunium is reduced to oxidation IV and forms a surface complex with surface sulfide ions. The remainder of the Np coordination sphere is filled with water molecules or hydroxide ions.     

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.     

Investigating options for attenuating methane emission from Indian rice fields

The development of methods and strategies to reduce the emission of methane from paddy fields is a central component of ongoing efforts to protect the Earth's atmosphere and to avert a possible climate change. It appears from this investigation that there can be more than one strategy to contain methane emission from paddy fields, which are thought to be a major source of methane emission in tropical Asia. Promising among the mitigating options may be water management, organic amendments, fertilizer application and selection of rice cultivars. It is always better to adopt multi-pronged strategies to contain CH4 efflux from rice wetlands. Use of fermented manures with low C/N ratio, application of sulfate-containing chemical fertilizers, selection of low CH4 emitting rice cultivars, and implementation of one or two short aeration periods before the heading stage can be effective options to minimize CH4 emission from paddy fields. Among these strategies, water management, which appears to be the best cost-effective and eco-friendly way for methane mitigation, is only possible when excess water is available for reflooding after short soil drying at the right timing and stage. However, in tropical Asia, rice fields are naturally flooded during the monsoonal rainy season and fully controlled drainage is often impossible. In such situation, water deficits during the vegetative and reproductive stage may drastically affect the rice yields. Thus, care must be taken to mitigate methane emission without affecting rice yields.     

Environmental fate and distribution of technetium-99 in a deciduous forest ecosystem

The aims of the present research are to describe the uptake of ⁹⁹Tc by trees intercepting contaminated groundwater from a radioactive waste storage site, to identify the major ⁹⁹Tc pools within the woodland ecosystem and to assess the relative mobility of ⁹⁹Tc in the existing element cycle. Technetium in the groundwater freely passed through a dialysis membrane with a molecular weight exclusion limit of approximately 3500 amu and ⁹⁹Tc in the groundwater chromatographed on Biogel P-2 in a manner similar to pertechnetate anion (TcO₄⁻). Reducing conditions and organic associations at the study site were probably responsible for the relatively large amount (83–92%) of the ⁹⁹Tc that was nonextractable from soil by 0·01 m CaCl₂. More than one-third of the ⁹⁹Tc was released from the soil by oxidizing reagents, indicating the presence of chemically reduced forms. The highest average ⁹⁹Tc concentrations in vegetation were found in herbaceous plants (18 530 pCi g⁻¹ dry wt). Although ⁹⁹Tc was progressively accumulated over the growing season in tree leaves, average concentrations in tree wood and twigs were equal to or greater than concentrations in leaves. Tree wood was the major above-ground pool for ⁹⁹Tc because of the high concentrations in wood as well as the large amount of wood relative to other biomass at the site. Technetium was not easily leached from the trees by rainfall and was not readily extractable from forest floor leaf litter by water. The relative importance of return pathways for ⁹⁹Tc to the forest floor was leaf fall>stemflow >throughfall, indicating that ⁹⁹Tc was conserved by the trees. Snails and millipedes from the leaf litter layer concentrated technetium 20- and 16-fold, respectively, above levels found in the soil. Pertechnetate was rendered less bioavailable after ingestion by a leaf litter macroinvertebrate (Porcellio sp.) common to the study site.