Model of colloidal transportation of radionuclides by groundwater

The transportation of colloidal radionuclides by groundwater was subject to theoretical analysis. The far field of radioactive contamination of the underground environment (liquid waste pumping sites or storage of solidified waste) is dominated by pseudocolloids, i.e., colloidal particles of natural origin contaminated with radionuclides upon contact of groundwater with radioactive materials. Properties of real pseudocolloids were analyzed at sites of radioactive contamination of the underground environment. Based on a probabilistic approach, we developed a mathematical model of pseudocolloid transportation by groundwater, taking into account the difference in size of colloidal particles and the occurrence of nonradioactive natural particles with a similar composition in the groundwater. It is proved that nonuniform dimensions of the particles considerably affect the water transportation rate.     

地下水典型氧化还原敏感组分迁移转化的研究热点和趋势

C-N-S反应体系是地下水系统中氧化还原敏感组分循环和能量流动的关键系统,但它如何与Fe、Mn循环过程、相关功能微生物代谢路径耦合并控制氧化还原敏感组分的迁移转化却并不清楚。本文在对国内外相关文献进行归纳总结的基础上,把地下水中的氧化还原敏感组分分为氧化富集型和还原富集型,较为系统地梳理了地下水系统C、N、S循环驱动的典型氧化还原敏感组分(主要以U、Cr、Fe、As为例)迁移转化过程,指出了该领域的主要研究热点,包括C-N反应体系中典型氧化还原敏感组分的迁移转化、C-S反应体系中还原富集型组分活化和氧化富集型组分固定机理、典型氧化还原敏感组分之间的相互作用、微生物作用下典型氧化还原敏感组分的转化和富集等,并提出基于代谢路径的C-N-S反应体系及其驱动下地下水典型氧化还原敏感组分转化过程和富集机理,将成为本领域的发展趋势。     

Effect of colloids on transfer of radionuclides by subsurface water

The fluid transfer of radionuclides in the geologic medium is considered under conditions when radionuclides are contained in fluids not only as solutes but also as colloids. The effect of colloidal transport of radionuclides on the rate of spreading of radioactive contamination in an underground medium is estimated, with assessment of this effect in mathematical models describing the transport of radionuclides by subsurface water. For this purpose, the exchange of radionuclides between subsurface water, colloid, and an immobile solid phase is considered, taking into account the precipitation of colloidal particles on both the immobile solid phase and other colloidal particles and their recurrent mobilization into the liquid phase. It is noted that, in real colloidal transfer, the heterogeneity of the geologic medium and colloidal particles in subsurface water is of great importance. The known models of colloidal transfer of radionuclides are evaluated on the basis of the analysis performed.     

Solubility and sorption of redox-sensitive radionuclides (Np,Pu) in J-13 water from the Yucca Mountain site: comparison between experiment and theory

This study presents the characterization of Pu-bearing precipitates and the results from uptake studies of Np and Pu on inorganic colloidal particulates in J-13 water from the Yucca Mountain site. Plutonium solubilities determined experimentally at pH values of 6, 7, and 8.5 are about two orders of magnitude higher than those calculated using the existing thermodynamic database indicating the influence of colloidal Pu(IV) species. Solid phase characterization using X-ray diffraction revealed primarily Pu(IV) in all precipitates formed at pH 6, 7, and 8.5. The solubility controlling Pu-bearing solids precipitated at ambient temperature consisted of amorphous Pu(OH)₄(s) with several Pu–O distances between 2.3 and 2.7 Å that are characteristic for Pu(IV) colloids. High temperature (90 °C) increased solid phase crystallinity and produced Pu(IV) solids that contained Pu oxidation state impurities. X-ray absorption spectroscopic studies revealed diminished Pu–O and Pu–Pu distances that were slightly different from those in crystalline PuO₂(s). A Pu–O bond of 1.86 Å was identified that is consistent with the plutonyl(V) distance of 1.81 Å in PuO₂⁺(aq). Hematite, montmorillonite, and silica colloids were used for uptake experiments with ²³⁹Pu(V) and ²³⁷Np(V). The capacity of hematite to sorb Pu significantly exceeded that of montmorillonite and silica. A low desorption rate was indicative of highly stable Pu-hematite colloids, which may facilitate Pu transport to the accessible environment. Neptunium uptake on all mineral phases was far less than Pu(V) uptake suggesting that a potential Pu(V)–Pu(IV) reductive sorption process was involved. The temperature effect on Pu solubility and pseudocolloid formation is also discussed.     

Anomalous concentrations of radionuclides in the groundwater of Ede area,southwestern Nigeria: a direct impact of geology

An assessment of the groundwater in areas underlain by pegmatite in Ede, southwestern Nigeria was carried out to determine the concentration of Potassium-40 (⁴⁰K), Uranium-238 (²³⁸U) and Thorium-232 (²³²Th) radionuclides. In the earlier work, it was established that zircons in these pegmatites have suffered a high degree of metamictization that has enhanced continuous loss of some radionuclides since the time of emplacement of the pegmatite host rock to the present. The aim of this work is to determine whether or not there is corresponding increase in the concentration of radionuclides in groundwater in the study area. Fifteen groundwater samples were collected from both hand dug wells and boreholes in the area. Ten samples were from Ede town, two samples each from nearby communities of Iddo and Ekuro and one from Iwoye, where the bedrocks were not pegmatites. All the 15 samples were analyzed with the Sodium Iodide scintillator (NaI [Tl]) detector at the Centre for Energy Research and Development, Obafemi Awolowo University, Ile-Ife, Nigeria. The results showed varying concentrations of the radionuclides in the water samples. Activity concentrations of Potassium-40 (⁴⁰K) indicated an average value of 17.149 Bq/L for samples from Ede, 9.265 Bq/L for Iddo, 6.6 Bq/L for Ekuro, while Iwoye has a value of 21.21 Bq/L. The Uranium-238 (²³⁸U) series had an average value of 13.64 Bq/L for Ede, 13.49 Bq/L for Ekuro, 11.685 Bq/L for Iddo and 12.04 Bq/L for the lone sample from Iwoye. Thorium-232 (²³²Th) series had an average value of 11.182 Bq/L for Ede, while average values of 7.79 Bq/L and 9.025 Bq/L, respectively, were recorded for Iddo and Ekuro and 12.25 Bq/L for Iwoye. The annual effective dose level of ⁴⁰K is generally below the World Health Organization (WHO) recommended dosage of 0.1 mSv/y except for three locations, while those of ²³⁸U and ²³²Th are in excess of the standard values. The high radionuclides in the groundwater in the study area were not due to anthropogenic sources but directly due to geological processes which release the radioisotopes from rocks after weathering, continuous loss from metamict minerals and natural lateral mobility from regions of radionuclides’ release to other areas. There is thus the need to carry out systematic studies of the radionuclides concentrations on regional scale in the area which could lead to investigating on both short- and long-term health effects on organic species in these areas, and development of purification systems before utilizing water from the areas for domestic and industrial purposes.     

人工回灌对地下水年龄分布规律的影响

地下水可更新能力是评价地下水开发可持续性的关键指标,可更新能力可以用地下水年龄来定量表达。在人类活动影响下,地下水的实际更新状况已与自然条件下截然不同。基于台兰河流域地下水库建设和人工回灌工作现状,通过物理试验和数值模拟相结合的方法分别研究了入渗池位置,回灌强度和包气带厚度对地下水年龄分布规律的影响。结果表明:人工回灌使地下水年龄整体变年轻;入渗池位置和回灌强度的改变对地下水年龄分布的影响显著;包气带厚度的增大使回灌水滞留时间延长,导致地下水年龄增大,该研究可为合理评价区域地下水可更新能力提供技术指导。     

地下水溶质运移数值模拟中减少误差的新方法

地下水中污染物运移的数值模拟方法一直是学界的研究热点问题.而如何减少与消除对流-弥散方程数值解中浓度陡锋面附近的数值振荡与数值弥散,更是研究的前沿与难点.提出了一种地下水溶质运移数值模拟中减少数值弥散的新方法.该方法的核心思想是在水动力弥散系数上加上一个数值弥散估算值,得到一个修正弥散系数,用其替代方程中有明确物理意义的水动力弥散系数进行计算.并提出了一个参数——数值弥散因子(μ_NDF),可以根据研究需要进行参数分区并适当调节该因子的大小,从而达到控制数值振荡,减小数值弥散的目的.从一维到二维的多个数值算例的模拟计算结果表明,该方法能在消除数值振荡的基础上,较好地减少数值弥散,达到满意的精度.     

Considerations for conducting incubations to study the mechanisms of As release in reducing groundwater aquifers

Microbial Fe reduction is widely believed to be the primary mechanism of As release from aquifer sands in Bangladesh, but alternative explanations have been proposed. Long-term incubation studies using natural aquifer material are one way to address such divergent views. This study addresses two issues related to this approach: (1) the need for suitable abiotic controls and (2) the spatial variability of the composition of aquifer sands. Four sterilization techniques were examined using orange-colored Pleistocene sediment from Bangladesh and artificial groundwater over 8 months. Acetate (10 mM) was added to sacrificial vials before sterilization using either (1) 25 kGy of gamma irradiation, (2) three 1-h autoclave cycles, (3) a single addition of an antibiotic mixture at 1× or (4) 10× the typical dose, and (5) a 10 mM addition of azide. The effectiveness of sterilization was evaluated using two indicators of microbial Fe reduction, changes in diffuse spectral reflectance and leachable Fe(II)/Fe ratios, as well as changes in P-extractable As concentrations in the solid phase. A low dose of antibiotics was ineffective after 70 days, whereas autoclaving significantly altered groundwater composition. Gamma irradiation, a high dose of antibiotics, and azide were effective for the duration of the experiment.     

Effect of oil pollution on fresh groundwater in Kuwait

Massive oil fires in Kuwait were the aftermath of the Gulf War. This resulted in the pollution of air, water, and soil, the magnitude of which is unparalleled in the history of mankind. Oil fires damaged several oil well heads, resulting in the flow of oil, forming large oil lakes. Products of combustion from oil well fires deposited over large areas. Infiltrating rainwater, leaching out contaminants from oil lakes and products of combustion at ground surface, can reach the water table and contaminate the groundwater. Field investigations, supported by laboratory studies and mathematical models, show that infiltration of oil from oil lakes will be limited to a depth of about 2 m from ground surface. Preliminary mathematical models showed that contaminated rainwater can infiltrate and reach the water table within a period of three to four days, particularly at the Raudhatain and Umm Al-Aish regions. These are the only regions in Kuwait where fresh groundwater exists. After reaching the water table, the lateral movement of contaminants is expected to be very slow under prevailing hydraulic gradients. Groundwater monitoring at the above regions during 1992 showed minor levels of vanadium, nickel, and total hydrocarbons at certain wells. Since average annual rainfall in the region is only 120 mm/yr, groundwater contamination due to the infiltration of contaminated rainwater is expected to be a long-term one.     

Effect of Groundwater Radiolysis on the Wall—rock Alteration of Uranium Ore Deposits

Reported for the first time in this paper are the results of simulating experiments on the γ-irradiation-induced oxidation of Fe^2 under the physicochemical conditions(T=200℃，P=50MPa,Eh=-0.1V,pH=7.2)simial to those under which moderate-low temperature hydrothermal uranium deposits are formed.Evdence shows that the effect of groundwater radiolysis seems to be the major mechanism of wall-rock alteration(hematitizaton)of hydrothermal uranium deposits.Moreover,adiscussion was made of possible effects of radiolysis of the water-rock system on wall-rock alterations including argillization and decoloration of uranium ore deposits on the basis of the experimental results.     

Uranium-rich opal from the Nopal I uranium deposit, Peña Blanca, Mexico: Evidence for the uptake and retardation of radionuclides

The Nopal I uranium deposit of the Sierra Peña Blanca, Mexico, has been the focus of numerous studies because of its economic importance and its use as a natural analog for nuclear-waste disposal in volcanic tuff. Secondary uranyl minerals such as uranophane, Ca[(UO₂)(SiO₃OH)]₂(H₂O)₅, and weeksite, (K,Na)₂[(UO₂)₂(Si₅O₁₃)](H₂O)₃, occur in the vadose zone of the deposit and are overgrown by silica glaze. These glazes consist mainly of opal A, which contains small particles of uraninite, UO₂, and weeksite. Close to a fault between brecciated volcanic rocks and welded tuff, a greenish silica glaze coats the altered breccia. Yellow silica glazes from the center of the breccia pipe and from the high-grade pile coat uranyl-silicates, predominantly uranophane and weeksite. All silica glazes are strongly zoned with respect to U and Ca, and the distribution of these elements indicates curved features and spherical particles inside the coatings. The concentrations of U and Ca correlate in the different zones and both elements inversely correlate with the concentration of Si. Zones within the silica glazes contain U and Ca in a 1:1 ratio with maximum concentrations of 0.08 and 0.15 at.% for the greenish and yellow glazes, respectively, suggesting trapping of either Ca₁U₁-aqueous species or -particles in the colloidal silica. X-ray photoelectron spectroscopy (XPS), Fourier-transform infra-red spectroscopy (FTIR), and oxygen-isotope ratios measured by secondary-ion mass spectrometry (SIMS) indicate higher U⁶⁺/U⁴⁺ ratios, higher proportions of Si-OH groups and lower δ¹⁸O values for the greenish silica glaze than for the yellow silica glaze. These differences in composition reflect increasing brecciation, porosity, and permeability from the center of the breccia pipe (yellow silica glaze) toward the fault (green silica glaze), where the seepage of meteoric water and Eh are higher.     

Degradation of carbon tetrachloride in a reducing groundwater environment: implications for natural attenuation

Several laboratory experiments have demonstrated degradation of carbon tetrachloride (CT) in groundwater, but there appear to have been no corroborating long-term field studies. Investigations conducted in 1989 and 1999 at an industrial site constructed on an infilled estuarine environment in France provide data over a decade for which CT degradation could be evaluated. A Dense Non-Aqueous Phase Liquid (DNAPL) containing oil and >90% CT that was present in 1989 was absent in the extremely reducing site groundwater in both 1999 and 2000 (average Eh=−170 mV at pH 7, sulfide up to 21 mg l⁻¹, and Fe⁺² up to 3.2 mg l⁻¹). These conditions facilitated dechlorination of CT to chloroform (CF) present at up to 46 mg l⁻¹, and methylene chloride (up to 75 mg l⁻¹). Carbon disulfide (CS₂), a terminal degradation product in reducing environments in laboratory experiments, was present at a mass ratio averaging 2.4:1 CF:CS₂, indicative of abiotic degradation. The lack of detection of the separate phase CT, the ratio of CF:CS₂, the presence of low molecular weight organic acids (i.e., acetate ∼900 mg l⁻¹; citrate 360 mg l⁻¹; and propionate, up to 111 mg l⁻¹) and pyrite in conjunction with excess inorganic Cl in groundwater are all indicators of ongoing degradation of the chlorinated compounds. However, while natural attenuation of chloromethanes may be a viable adjunct to strategies designed to remediate CT in reducing groundwater, its efficacy is hard to quantify in complex field environments where upgradient sources are still present.     

乙醇对过硫酸盐氧化地下水中苯系物的影响

过硫酸盐已经被广泛用于土壤和地下水有机污染物的原位化学氧化修复。随着乙醇汽油的推广,乙醇汽油引起的地下水污染问题越来越严重,因此有必要去除该类污染物。前人研究乙醇汽油污染修复多数停留在自然修复技术,为了进一步探究去除地下水中乙醇汽油更为有效的技术手段,深入了解乙醇对降解苯系物（BTEX）存在的潜在风险,需要研究使用新的修复方法。文章通过批实验探索了过硫酸盐氧化法对乙醇汽油污染地下水的修复效果,以及Fe2+活化和过硫酸盐添加方式变化对乙醇汽油中苯系物（BTEX）和乙醇的去除影响。结果表明:活化后的过硫酸盐能够有效去除地下水中的BTEX,但会抑制BTEX的生物降解作用;当有乙醇存在时,过硫酸盐能够优先氧化BTEX,其去除速率明显高于乙醇,这与单纯生物降解作用相反。在过硫酸盐投注总量一定时,分批添加更有利于BTEX的去除,但对乙醇去除没有明显促进作用。该研究为过硫酸盐原位化学氧化技术在地下水乙醇汽油污染修复中的应用提供了重要参考。     

地下水对库岸边坡稳定性的影响

针对库岸边坡在库水位陡降时易发生失稳破坏这一特点,分析了地下水引发库岸边坡失稳的机理,指出在地下水作用下,边坡岩土物理力学性质恶化、库水浮托力以及坡体内渗透力是影响库岸边坡稳定性的重要因素,给出了考虑地下水影响的库岸边坡稳定性计算公式。对三峡库区的某边坡工程进行了分析,结果表明：边坡岩土体介质因饱水软化作用,其滑动面的力学参数值降低;库水浮托力在某种程度上有利于边坡的稳定。当库水位陡降时,坡体内产生较大的渗透力是导致边坡失稳的一个很关键的原因。同时指出,在进行库岸边坡治理设计时,采取合理的防冲刷、反滤及疏导措施,能有效地降低地下水对边坡稳定性带来的消极影响。     

Effect of sand lenses on groundwater flow and contaminant migration

The effect of homogeneous sand lenses on the groundwater flow in an otherwise homogeneous clayey deposit is examined by performing Monte Carlo simulations using a finite element flow model. In the simulations, the locations of the sand lenses are assumed to be mutually independent. The paper examines the effect on the flow field in a clayey deposit of (a) different percentages of sand lenses, (b) different hydraulic conductivities of the sand lenses, (c) different average sand lens sizes, (d) non-uniformity of the sizes of the sand lenses, and (e) localization of the sand lenses. The effect of these non-uniform flow fields on contaminant migration is then examined using a finite element contaminant transport model. For the range of cases considered it is shown that: the volume of sand lenses present has a greater influence than the shape, size, location and hydraulic conductivity of the sand lenses; simplified calculations performed using the geometric and harmonic means of hydraulic conductivity bracket the behaviour evident from more complex analyses; and the maximum impact on an aquifer separated from a waste disposal facility by a deposit containing sand lenses can be modelled to sufficient accuracy, using quite simple flow and contaminant transport models.     

浅层地下水中磺胺嘧啶与胡敏酸相互作用及相态间分布特征

研究抗生素在浅层地下水中不同相态间的分布特征,对于了解抗生素的行为特征及评估其危害具有重要的意义。本文利用三维荧光淬灭法研究了胡敏酸(humic acid, HA)对磺胺嘧啶(sulfadiazine, SD)在地下水中不同相态间分布规律的影响及相互作用,探讨了HA浓度、pH值、温度对SD在不同相态间分布的影响,对淬灭过程进行拟合并计算了分配系数、淬灭参数以及热力学参数。结果表明:地下水中SD浓度(0.5 mg/L)较低时或者HA浓度增加(0~20 mg/L)时,HA可显著促进悬浮相中SD比例的增加;SD对HA的淬灭机理为形成复合物的单一静态淬灭,结合位点数均约为1,荧光淬灭常数K_sv为5.271×10³ L/mol,淬灭速率常数K_q为5.271×10¹¹ L/(mol·s),属于自发的放热过程;体系处于低温(15 ℃)、弱碱性(8~10)pH值环境时,SD对HA的淬灭作用最强,HA对SD进入悬浮相的促进作用最明显。     

Effect of geochemical conditions on fate of organic compounds in groundwater

In situ microcosms were successfully used to study the degradation of a range of organic compounds in two pristine aquifers, one aerobic (Vejen) and one anaerobic (Villa Farm). Degradation and sorption behavior in the laboratory column microcosms packed with Villa Farm sediment was very similar to that in the in situ microcosms. However, when the columns were packed with quartz and equilibrated with aerated Villa Farm groundwater, behavior mirrored that at Vejen, indicating that oxygen rather than sediment or groundwater composition was the critical parameter. The aromatic and polyaromatic compounds (benzene, toluene,o-xylene, naphthalene) degraded under aerobic conditions only. The organochlorine compounds (trichloroethylene, tetrachloroethylene, 1,1,1-trichloroethane, 1,4-dichlorobenzene and 1,2-dichlorobenzene) showed little or no sign of degradation either aerobically or anaerobically. Interpretation of the data was complicated by strong sorption to the Villa Farm sediment but tetrachloromethane, nitrobenzene, ando-nitrophenol appeared to degrade under anaerobic conditions only. Phenol degraded rapidly under both sets of conditions.