Adsorption of thorium and protactinium onto different particle types: experimental findings

Here we present the results of experiments investigating the adsorption of Protactinium and Thorium onto different particle types in natural seawater. Particle types studied were smectite as a representative of clay, biogenic opal from a cleaned diatom culture, manganese dioxide precipitate, and calcium carbonate. The particles were added to three different types of natural seawater (0.5 mg/L) which were first 0.2 μm-filtered, and the distribution of Pa and Th between dissolved and particulate phase (>0.2 μm) was monitored for 4 to 5 d at increasing time intervals. The tracers applied were the β-emitters ²³³Pa and ²³⁴Th. The measurement technique via β-counting for both nuclides in the same sample is reported here for the first time.The observed recoveries during the experiment range from 40 to 99 (±5) % for Th and from 51 to 105 (±6) % for Pa. The distribution coefficients (K_d) after establishment of an equilibrium cover a wide range for Th from 0.5 to 107 × 10⁶ ml/g, and from 0.03 to 166 × 10⁶ ml/g for Protactinium, depending on particle type and on the type of seawater used.Thorium revealed a specific affinity for all particle types investigated, with varying degree and adsorption kinetics. The results suggest that all particle types investigated may serve as Th carrier phases in the sediment. Pa was found to be less particle reactive than Th in most cases. Th/Pa fractionation factors (F_Th/Pa) were also obtained. Weakest fractionation was found on MnO₂ (F_Th/Pa=1), followed by the chemically cleaned biogenic opal (2.8) and smectite (5.4). The results for calcium carbonate were highly variable. Our experimental results imply that particle composition is indeed playing a role in the differing marine geochemistry of Th and Pa. We conclude that experiments with filtered natural seawater using particle concentrations on a natural level are a helpful approach when investigating the geochemical behaviour of strongly particle-reactive elements like Th and Pa in the marine environment.     

Studies of colloids and suspended particles,Cigar Lake uranium deposit,Saskatchewan, Canada

The Cigar Lake U deposit is located in northern Saskatchewan in the eastern part of the Athabasca Sandstone Basin, and consists of a high-grade ore body (up to 55% U) located at a depth of ∼430 m. As part of a study to evaluate the analog features of this deposit with respect to a disposal vault for waste nuclear fuel, colloids (1–450 nm) and suspended particles (450nm) in groundwater have been investigated to evaluate their effect on element transport through the U deposit. Tangential-flow ultrafiltration was used to concentrate particles from 501 groundwater samples in order to characterize the size distribution, concentration, composition and natural radionuclide content of particles in representative parts of the U deposit. Although Cigar Lake groundwaters contain particles in all sizes ranging from 10 nm to slightly larger than 20 μm, most samples contained a relatively high concentration of colloids in the 100–400 nm size range. Particle compositions are similar to the composition of minerals in the sandstones and ore body, suggesting that particles in groundwater are generated by the erosion of fracture-lining minerals. As a result, particle concentrations in groundwater are affected by the integrity of the host rock. In some piezometers the high initial concentrations of suspended particles, which may have been drilling artifacts, decreased during the collection of the first 350 1. Although colloid concentrations fluctuated during sampling, there are no indications that these concentrations will be permanently reduced by continued groundwater pumping. The observed colloid and suspended particle concentrations in the deep groundwaters are too low to have a significant impact on radionuclide migration, provided that radionuclide sorption is reversible. If radionuclides are irreversibly sorbed to particles they cannot sorb to the host rock and their migration can only be evaluated with an understanding of particle mobility. The data for dissolved and particulate U, Th and Ra were used to calculate field-derived distribution ratios (R_d) between particles and groundwater. The wide range of observed R_d values indicates that these radionuclides in particulate form are not in equilibrium with groundwater. U-series isotope data indicated that most of the U and Ra on particles was derived from groundwater. Some particles could have retained their U for as long as 8000 a. The U and Ra contents of particles in the ore and surrounding clay zones are significantly higher than in particles from sandstone, suggesting that the clay has been an effective barrier to particle migration.     

Particle-size effects on dissolved arsenic adsorption to an Australian laterite

In this study, arsenic adsorption to an Australian laterite has been examined for a particle-size range between 38 μm and 25 mm. The results show that particle size influences both kinetic and equilibrium characteristics of arsenic adsorption. The equilibrium adsorption capacity increases from around 100 mg kg^?1 for laterite particles coarser than 4 mm, to around 160 mg kg^?1 for laterite particles between 75 μm and 4 mm, and to over 200 mg kg^?1 for laterite particles finer than 75 μm. The kinetic adsorption data can be fitted with the pseudo-second-order reaction model, in particular for finer particles where the film diffusion and/or surface reaction are important processes. The model-fitted rate constant remains steady for laterite particles coarser than 2 mm, increases moderately with particle size in the range between 75 μm and 2 mm, and increases dramatically for laterite particles finer than 75 μm. These arsenic adsorption behaviours can be explained by the relative importance of two particle-size-dependent processes: quick external-surface adsorption (more important for fine particles) and slow intraparticle adsorption (more important for coarse particles). Most of the external-surface adsorption completes in the first hour of the experiment. To apply the studied laterite for dissolved arsenic removal, it is recommended that fine particles, in particular finer than 75 μm, should be used if the contact time is the limitation, and that coarse particles, in particular 2–4 mm, should be used if sufficient contact time is available.     

黄土高原晚上新世红粘土粒度的空间变化

对黄土高原由北到南 6个地点的晚上新世红粘土样品进行了常规粒度测量和化学提取的石英样的粒度测量。红粘土全样和石英样的平均粒径由偏北到南逐渐变细,粗颗粒含量也逐渐减少,表明红粘土可能是由偏北低空风而不是高空风搬运而来的。 3.6～ 2.6MaBP红粘土粒度与其上覆风成黄土粒度的空间变化具有可比性,但变化幅度较小.     

The mechanism of iron removal in estuaries

A survey of U.S. east coast estuaries confirms that large-scale rapid removal of iron from river water is a general phenomenon during estuarine mixing. The river-borne ‘dissolved’ iron consists almost entirely of mixed iron oxide-organic matter colloids, of diameter less than 0.45 μm, stabilized by the dissolved organic matter. Precipitation occurs on mixing because the seawater cations neutralize the negatively charged iron-bearing colloids allowing flocculation. The process has been duplicated in laboratory experiments using both natural filtered and unfiltered river water and a synthetic colloidal goethite in 0.05 μm filtered water. The colloidal nature of the iron has been further confirmed by ultracentrifugation and ultrafiltration. A major consequence of the precipitation phenomena is to reduce the effective input of ‘dissolved’ iron to the ocean by about 90% of the primary river value, equivalent to a concentration of less than 1 μmol per liter of river water.     

富钴结壳超细标准物质的加工制备

用气流磨制备了2个具有超细粒度的海山富钴结壳标准物质MCPt-1和MCPt-2。原样先经球磨成74μm(-200目),再用气流磨进行超细加工。样品粒度采用激光粒度仪检测,用粒度分布图和特征粒度来表达测量结果。两个样品的平均粒度分别为1.8μm和1.5μm(约2 000目),是目前粒度最小的标准物质。文章介绍了用于超细加工的流化床式气流磨原理与方法,展示了样品加工后的粒度分析结果,对比了国内外超细标准物质的概况。最后讨论了当前关注样品加工的重要性、超细加工的问题及超细样品分析研究的意义。     

基于分形理论研究土壤结构及其水分特征关系

为定量获得土壤结构对其水力性质的指示作用,室内实验选用华北平原子牙河流域原状土样为研究对象,用张力计法和激光粒度分析仪分别测定土壤水分特征曲线和样品粒度分布,基于分形理论计算土壤粒度分布的分形维数,采用实验测定与模型验证相结合的方法对水分特征曲线进行分析.结果表明,土壤颗粒粒度分布在[10 μm,50 μm]区间内的分段分维值是表征土壤粒度累积分布显著上升段特征的关键参数,与0~80 kPa吸力范围内的土壤水分特征曲线幂函数模型拟合参数(a、b)有极显著相关关系.研究区内土壤水分特征曲线以分形形式表达的幂函数模型为:θ=100.78×(3-D)S(D-3)/3,利用土壤结构分形特征能够有效指示其水力性质.      

Seasonal uranium distributions in the coastal waters off the Amazon and Mississippi Rivers

The chemical reactivity of uranium was investigated across estuarine gradients from two of the world’s largest river systems: the Amazon and Mississippi. Concentrations of dissolved (<0.45 μm) uranium (U) were measured in surface waters of the Amazon shelf during rising (March 1990), flood (June 1990) and low (November 1991) discharge regimes. The dissolved U content was also examined in surface waters collected across estuarine gradients of the Mississippi outflow region during April 1992, August 1993, and November (1993). All water samples were analyzed for U by isotope dilution inductively coupled plasma mass spectrometry (ICP-MS). In Amazon shelf surface waters uranium increased nonconservatively from about 0.01 μg I^?1 at the river’s mouth to over 3 μg I^?1 at the distal site, irrespective of river discharge stage. Observed large-scale U removal at salinities generally less than 15 implies a) that riverine dissolved U was extensively adsorbed by freshly-precipitated hydrous metal oxides (e.g., FeOOH, MnO₂) as a result of flocculation and aggregation, and b) that energetic resuspension and reworking of shelf sediments and fluid muds on the Amazon shelf released a chemically reactive particle/colloid to the water column which can further scavenge dissolved U across much of the estuarine gradient. In contrast, the estuarine chemistry of U is inconclusive within surface waters of the Mississippi shelf-break region. U behavior is most likely controlled less by traditional sorption and/or desorption reactions involving metal oxides or colloids than by the river’s variable discharge regime (e.g., water parcel residence time during estuarine mixing, nature of particulates, sediment storage and resuspension in, the confined lower river), and plume dispersal. Mixing of the thin freshwater lens into ambient seawater is largely defined by wind-driven rather than physical processes. As a consequence, in the Mississippi outflow region uranium predominantly displays conservative behavior; removal is evident only during anomalous river discharge regimes. ‘Products-approach’ mixing experiments conducted during the Flood of 1993 suggest the importance of small particles and/or colloids in defining a depleted U versus salinity distribution.     

Cu(Ⅱ)污染作用下膨胀土的胀缩时程效应研究

为探讨Cu(Ⅱ)对膨胀土胀缩特性的影响,针对初始状态相同的膨胀土试样,采用浓度为2.5 g·L-1、5.0 g·L-1、10.0 g·L-1的CuSO₄溶液以及去离子水进行处理,开展一系列重金属Cu(Ⅱ)污染作用下的胀缩性试验,并运用Does Response模型对胀缩时程曲线进行描述;利用马尔文激光粒度测试,分析了污染前后膨胀土的粒径分布特征。结果表明:膨胀土试样的膨胀率、收缩速率、竖向收缩率及膨胀含水率皆随Cu(Ⅱ)浓度的增大而增大,但膨胀土试样的损失含水率并不随Cu(Ⅱ)浓度的变化而变化;试样的无荷载膨胀时程曲线可分为快速增长、变减速及缓慢增长阶段;膨胀土的收缩过程可分为缓慢收缩、快速收缩与收缩稳定阶段;Does Response模型不能完全适应无荷载条件下的膨胀时程曲线,但能较好地描述收缩时程曲线;随着Cu(Ⅱ)浓度的增大,未污染膨胀土颗粒在80 μm处的粒径分布峰值消失,在47 μm处的粒径分布峰值往小粒径方向偏移,说明胶结物逐渐溶蚀,引起部分膨胀土大颗粒分解,依附在土颗粒表面的水膜面积增大,膨胀土吸水能力增强,进而导致高浓度环境中的膨胀土胀缩性较高。     

盐分对黏性土的沉积特性与表面电位影响研究

为了明晰黏土矿物和盐分浓度在沉积过程中所起的作用及物理机制,选取高岭土、膨润土及两者组成的混合土进行粒径分析试验、沉积试验和Zeta电位测试。结果显示,盐分环境下高岭土和膨润土的平均粒径增大,部分黏粒组向粉粒组转化。高岭土在蒸馏水环境下和盐水环境下,最终都形成土-水的稳定分界面,但是絮凝稳定时间在盐分环境下更短。膨润土在蒸馏水环境下处于稳定的分散体系中,在盐水环境下迅速絮凝沉积。混合土在蒸馏水环境下,上部澄清层和下部沉淀层之间存在土颗粒的悬浮层,且该层的高度最终稳定;盐水环境下,混合土则迅速的发生土水分离。随着NaCl浓度增加,膨润土和高岭土的Zeta电位绝对值降低,因此胶粒组的絮凝行为对平均粒径产生影响,进而影响其沉积特性。     

Comparison of laser grain size analysis with pipette and sieve analysis: a solution for the underestimation of the clay fraction

Classically, the grain size of soil and sediment samples is determined by the sieve method for the coarse fractions and by the pipette method, based on the ‘Stokes’ sedimentation rates, for the fine fractions. Results from the two methods are compared with results from laser diffraction size analysis, which is based on the forward scattering of monochromatic coherent light. From a point of view of laboratory efficiency, the laser sizing technique is far superior. Accuracy and reproducibility are shown by measurements on certified materials. It appears that laser grain size measurements of certified materials correspond very well with the certificated measurements. Tests were also done on a set of randomly selected sediments of fluvial, aeolian and lacustrine origin. Except for the (<2 μm) clay fraction, there is a coarsening of the mean diameter of one to two size classes (0.25 ?), caused by the non-sphericity of the particles. The platy form of the clay particles induces considerable differences (eight size classes) between pipette and laser measurements: the <2 μm grain size, defined by the pipette method corresponds with a grain size of 8 μm defined by the Laser Particle Sizer for the studied sediments. Using a higher grain size level for the clay fraction, when laser analysis is applied, enables workers in the geological and environmental field to compare classical pipette analysis with a laser sizing technique.     

奥运会及残奥会期间北京市区大气颗粒物污染特征及微观形貌类型

2008年8月和9月,北京市成功举办了第29届奥运会和第13届残奥会,对这段时间在北京市区(中国矿业大学校园综合楼五层,距奥运村3 km)采集的大气颗粒物的质量浓度和微观形貌类型进行了研究。结果表明:奥运会期间,北京市区大气PM10和PM2.5的日均质量浓度分别小于国家PM10二级标准(150μg/m3)和美国EPA的PM2.5二级标准(65μg/m3),12 h的质量浓度范围分别为7.64~81.63μg/m3和1.91~54.59μg/m3;残奥会期间,12 h的PM10质量浓度范围为33.83~106.36μg/m3,没有超标,PM2.5质量浓度变化范围为15.29~88.30μg/m3,其中出现了3 d超标天,分别为9月6日、7日和14日;从奥运期间PM2.5/PM10的比值(0.26~0.86,大部分值大于0.5)可以看出,奥运期间北京大气颗粒物以细粒子为主。与往年相比,颗粒物质量浓度出现大幅下降趋势。场发射扫描电镜观察显示,奥运会和残奥会期间样品的微观形貌类型主要有球形颗粒、烟尘集合体、不规则矿物和未知颗粒,其数量-粒径分布主要呈单峰分布,峰值均在0.1~0.2μm范围,其中球形颗粒明显占多数。各种分析数据均显示,残奥会期间样品比奥运会期间样品污染要严重。     

Fine particle deposition to initially starved,stationary, planar beds

Reported here are results from new flume experiments examining deposition and entrainment of inert, silt‐sized particles (with spherical diameters in the range from 20 to 60 μm) to and from planar, impermeable and initially starved beds underlying channel flows. Bed surfaces comprised smooth or fixed sand‐size granular roughness and provided hydraulically smooth to transitionally rough boundaries. Results of these experiments were analysed with a simple model that describes the evolution of vertically averaged concentration of suspended sediment and accommodates the simultaneous delivery to and entrainment of grains from the bed. The rate of particle arrival to a bed diminishes linearly, and the rate of particle entrainment increases by the 5/2 power, as the value of the dimensionless Saffman parameter S = u_*³/g’ν approaches a threshold value of order unity, where u is the conventional friction velocity of the turbulent channel flow, g’ is the acceleration due to gravity adjusted for the submerged buoyancy of individual particles and ν is the kinematic viscosity of the transporting fluid. This transport behaviour is consistent with the notion that non‐cohesive, silt‐sized particles can neither reach nor remain on an impermeable bed under flow conditions where mean lift imposed on stationary particles in the viscous sublayer equals or exceeds the submerged weight of individual particles. Within the size range of particles used in these experiments, particle size and the characteristic size of granular roughness, up to that of medium sand, did not affect rates of dimensionless arrival or entrainment to a significant degree. Instead, a new but consistent picture of fine‐particle transport is emerging. Silt‐sized material, at least, is subject to potentially significant interaction with the bed during intermittent suspension transport at intermediate flow speeds greater than the value required for initiation of transport (ca 20 cm sec^?1) but less than the value (ca 50 cm sec^?1) required by the Saffman criterion ensuring transport in fully passive suspension or, equivalently, ‘wash‐load’.     

黄河源区阿尼玛卿山耶和龙冰川积雪中不溶微粒组成特征及环境意义

2005年9月下旬,在黄河源区阿尼玛卿山耶和龙冰川平衡线附近挖取了6个雪坑,固定层厚采集了89个雪冰样品,分析了样品的δ¹⁸O值及不溶微粒的浓度、粒径,研究了耶和龙冰川中不溶微粒的时空分布特征及环境意义。结果表明：雪冰样品中不溶微粒浓度平均值为1.1×10⁵个·mL^-1,PM₁₀占到总粒子的99%;以微粒数浓度为权重计算的平均粒径分布在1.1~1.8 μm之间,说明耶和龙冰川积雪中不溶微粒以细粒子为主;不溶微粒的粒度谱分布不符合正态分布规律,粒子浓度的众数出现在小粒径;微粒源区输入和大气环流强度是控制积雪中不溶微粒特征的主要因素。源区输入和风场强度均较大时,积雪中不溶微粒浓度及粒径均较大;源区输入较弱而风场强度较大时,积雪中微粒浓度有所增加,粒径增加更加显著。结合HYSPLIT-4模式研究发现,在耶和龙冰川积雪中不溶微粒的浓度及粒径随雪坑深度的变化可以反映气团强度的季节变化,夏季降水增加使微粒的季节变化更加显著。西风携带的塔克拉玛干沙漠和中亚干旱区尘埃是耶和龙冰川春、秋季节积雪中不溶微粒的重要来源。     

U-238 series radioactive disequilibrium in groundwaters: implications to the origin of excess U-234 and fate of reactive pollutants

The concentrations of ²³⁸U, ²³⁴Th, ²²⁶Ra, ²²²Rn and ²¹⁰Pb and ${}^{234}\text{U}{}^{238}\text{U}$ activity ratios have been measured in several groundwater samples from Gujarat, India. In the aqueous phase the abundances of ²³⁴Th and ²¹⁰Pb are grossly deficient relative to their parents, ²³⁸U and ²²²Rn respectively. The deficiency is ascribable to the impact adsorption of ²³⁴Th and ²¹⁰Pb atoms onto particle surfaces which are very abundant in the groundwater regimes. The scavenging residence times for both these nuclides is about a day, suggesting that irreversible removal of ‘reactive’ metals and pollutants in groundwaters can occur on very short time scales. The fast removal of ²³⁴Th onto particles necessitates that in these groundwaters ²³⁴U ‘excess’ has to originate through leaching of soil grains rather than through in situ decay of dissolved ²³⁴Th in the water.     

The effect of bubble size on the rate of flotation of fine particles

Flotation experiments have been carried out in a cell in which bubbles of known size could be generated independently of the turbulence levels, which could be controlled by varying the impeller speed. The mean bubble size ranged from 75 μm to 655 μm.Results are reported for the flotation rates of fine particles, less than 50 μm diameter. The materials floated were polystyrene latex particles, quartz and zircon. These were chosen to give a wide range of specific gravity.It was found that the flotation rate was very strongly affected by the bubble size, there being an increase of up to one hundred-fold when the bubble size was reduced from 655 μm to 75 μm. Effects of particle density and impeller speed are also reported.     

Sediment particle size in the Hudson River Estuary

The particle sizes in bottom and suspended sediments from the ocean upstream for 80 km in the Hudson River Estuary were analysed. Several modes at 4, 8 and 30 μm were prevalent throughout the estuary. The average size of particles in bottom samples varied from 150 μm near the ocean to 15–20 μm in Haverstraw Bay. The bottom sediment size appears to be controlled by two components; (1) sand from the ocean and (2) the particles in the flocs.     

Vacuum dewatering and residual saturation of incompressible filter cakes

Fundamental data on the residual saturation of incompressible filter cakes which have been drained by vacuum have been measured. The effects of varying particle size, shape and distribution, type of wetting fluid and cake size have been assessed. A modified ‘threshold pressure’, below which dewatering will not occur, has been defined and an index reflecting the nature of the particles and their packing has been used to represent reduced saturation data. Irreducible saturation levels have been correlated against a capillary number, and by careful definition of the driving force term data scatter have been substantially reduced.     

Modeling study of the effects of the coagulation kernel with van der Waals forces and turbulence on the particle size distribution

In this study, variations in the size distributions due to different assumptions for the coagulation kernel are investigated. In order to evaluate how the coagulation kernel influences the form of the particle size distribution and to describe the process of the Brownian coagulation, the Brownian coagulation kernel, including the van der Waals forces, is compared with the most frequently used coagulation coefficients. Retardation should be considered for interparticle interactions for particles larger than 1μm radius. However, for particle sizes larger than 0.1 μm, the Brownian kernel is not dominant, so the retardation effect can be ignored. The inclusion of the van der Waals forces in the Brownian coagulation kernel caused a faster coagulation process in the small particle size range. Taking account of the turbulent coagulation kernel, the turbulent coagulation kernel becomes more important when the turbulent intensity is higher. The turbulent coagulation kernel affects the large particle size range and ignoring the turbulent coagulation kernel will lead to overestimation of particle number concentration in model simulation. The results of this study indicate that the inclusion of van der Waals forces or the turbulent coagulation kernel in the total coagulation kernel impacts on the modeled particle size distributions and total particle number concentration.     

Upscaling polydispersed particle transport in porous media using pore network model

Understanding particle transport in porous media is critical in the sustainability of many geotechnical and geoenvironmental infrastructure. To date, the determination of the first-order rate coefficients in the advection–dispersion equation for simulating attachment and detachment of particles in saturated porous media typically has been relied on the result of laboratory-scale experiments. However, to determine attachment and detachment coefficients under varied hydraulic and geochemical variables, this method requires a large experimental matrix because each test provides only one set of attachment and detachment coefficients. The work performed in this study developed a framework to upscale the results obtained in pore-scale modeling to the continuum scale through the use of a pore network model. The developed pore network model incorporated variables of mean particle size, the standard deviation of particle size distribution, and interparticle forces between particles and sand grains. The obtained retention profiles using the pore network model were converted into attachment coefficients in the advection–dispersion equation for long-term and large-scale simulation. Additionally, by tracking individual particles during and after the simulation, the pore network model introduced in this study can also be employed for modeling the clogging phenomenon, as well as fundamental investigation of the impact of particle size distribution on particle retention in the sand medium.