Apparent diffusion coefficients and chemical species of neptunium (V) in compacted Na-montmorillonite

Diffusion of neptunium (V) in compacted Na-montmorillonite was studied through the non-steady state diffusion method. In this study, two experimental attempts were carried out to understand the diffusion mechanism of neptunium. One was to establish the diffusion activation energy, which was then used to determine the diffusion process in the montmorillonite. The other was the measurement of the distribution of neptunium in the montmorillonite by a sequential batch extraction. The apparent diffusion coefficients of neptunium in the montmorillonite at a dry density of 1.0 Mg m-3 were from 3.7 x 10(-12) m2 s-1 at 288 K to 9.2 x 10(-12) m2 s-1 at 323 K. At a dry density of 1.6 Mg m-3, the apparent diffusion coefficients ranged between 1.5 x 10(-13) m2 s-1 at 288 K and 8.7 x 10(-13) m2 s-1 at 323 K. The activation energy for the diffusion of neptunium at a dry density of 1.0 Mg m-3 was 17.5 +/- 1.9 kJ mol-1. This value is similar to those reported for diffusion of other ions in free water, e.g., 18.4 and 17.4 kJ mol-1 for Na+ and Cl-, respectively. At a dry density of 1.6 Mg.m-3, the activation energy was 39.8 +/- 1.9 kJ mol-1. The change in the activation energy suggests that the diffusion process changes depending on the dry density of the compacted montmorillonite. A characteristic distribution profile was obtained by the sequential extraction procedure for neptunium diffused in compacted montmorillonite. The estimated fraction of neptunium in the pore water was between 3% and 11% at a dry density of 1.6 Mg m-3 and at a temperature of 313 K. The major fraction of the neptunium in the montmorillonite was identified as neptunyl ions sorbed on the outer surface of the montmorillonite. These findings suggested that the activation energy for diffusion and the distribution profile of the involved nuclides could become powerful parameters in understanding the diffusion mechanism.     

An integrated sorption-diffusion model for the calculation of consistent distribution and diffusion coefficients in compacted bentonite

A thermodynamic sorption model and a diffusion model based on electric double layer (EDL) theory are integrated to yield a surface chemical model that treats porewater chemistry, surface reactions, and the influence of charged pore walls on diffusing ions in a consistent fashion. The relative contribution of Stern and diffuse layer to the compensation of the permanent surface charge represents a key parameter; it is optimized for the diffusion of Cs in Kunipia-F bentonite, at a dry density of 400 kg/m3. The model is then directly used to predict apparent diffusivities (Da) of Cs, Sr, Cl-, I- and TcO4- and corresponding distribution coefficients (Kd) of Cs and Sr in different bentonites as a function of dry density, without any further adjustment of surface chemical and EDL parameters. Effective diffusivities (De) for Cs, HTO, and TcO4- are also calculated. All calculated values (Da, De, Kd) are fully consistent with each other. A comparison with published, measured data shows that the present model allows a good prediction and consistent explanation of (i) apparent and effective diffusivities for cations, anions, and neutral species in compacted bentonite, and of (ii) Kd values in batch and compacted systems.     

Study on anisotropy of effective diffusion coefficient and activation energy for deuterated water in compacted sodium bentonite

To quantify the effects of temperature on the diffusivity of deuterated water (HDO) in compacted sodium bentonite, through-diffusion experiments were conducted at elevated temperatures ranging from 298 to 333 K. Kunipia F (Na-montmorillonite content>98 wt.%; Kunimine Industries) was compacted to a dry density of 0.9 or 1.35 Mg/m(3). As montmorillonite particles were oriented perpendicular to the direction of compaction, the anisotropy of diffusivity was investigated both parallel and normal to the preferred orientation of the montmorillonite. The effective diffusion coefficient D(e) of HDO was larger when the diffusional direction was parallel as opposed to normal to the preferred orientation for both dry densities. The magnitude of D(e) and the anisotropy for HDO were in good accordance with previously reported results for tritiated water at room temperature. Activation energies of D(e) were isotropic and increased with increasing dry density over the range of 19-25 kJ/mol. This relationship was considered to be due to both pore structure development and the high activation energy of water near the montmorillonite surface.     

上海市截流外排工程污水扩散影响数值研究

城市污水截流外排工程是上海市城市水环境整治的重大战略。文章以CODCr为例,数值模拟研究了上海近岸水域东、南、西三大截流外排干线不同排污方案下污染物的输移扩散规律。结果表明,长江口的水动力条件有利于污水的稀释扩散;在现状排污条件下,无论洪枯季,引起的环境水体污染物CODCr浓度增量均不大,能够满足长江口水环境容量的要求;对于规划排放量的污水,预处理和一级处理条件下引起的环境水体污染物CODCr,浓度增量较为显著,对周围敏感目标的影响也比较大;二级处理条件下所引起的污染浓度增量比较小,对水环境的影响相对较小。因此,在规划城市污水外排工程时,建议必须近期和远期相结合,合理充分利用水体自净能力。     

成型膨润土和钛柱撑膨润土对水中Pb2+和氯乙酸吸附及再生

针对水中微量铅离子和氯乙酸的脱除,考察了成型膨润土及成型钛柱撑膨润土的吸附性能,得出对铅离子的吸附,成型膨润土、成型钛柱撑膨润土与粉末状活性炭性能相当,而对氯乙酸的吸附前两者要比粉末状活性炭低好多。确定了成型膨润土吸附氯乙酸后可用沸水煮沸30 min的方法再生,成型钛柱撑膨润土吸附氯乙酸后,可用500℃焙烧3 h的方法再生,再生的膨润土循环使用3次后性能降低明显。此外,还测得了成型的膨润土及成型的钛柱撑膨润土吸附铅离子和氯乙酸的等温线,计算出其对铅的最大吸附量分别为24.33 mg/g和15.47 mg/g。     

成型膨润土和钛柱撑膨润土对水中Pb2+和氯乙酸吸附及再生

针对水中微量铅离子和氯乙酸的脱除，考察了成型膨润土及成型钛柱撑膨润土的吸附性能，得出对铅离子的吸附，成型膨润土、成型钛柱撑膨润土与粉末状活性炭性能相当，而对氯乙酸的吸附前两者要比粉末状活性炭低好多。确定了成型膨润土吸附氯乙酸后可用沸水煮沸30 min的方法再生，成型钛柱撑膨润土吸附氯乙酸后，可用500℃焙烧3 h的方法再生，再生的膨润土循环使用3次后性能降低明显。此外，还测得了成型的膨润土及成型的钛柱撑膨润土吸附铅离子和氯乙酸的等温线，计算出其对铅的最大吸附量分别为24.33 mg/g和15.47 mg/g。     

Measurement of effective air diffusion coefficients for trichloroethene in undisturbed soil cores

In this study, we measure effective diffusion coefficients for trichloroethene in undisturbed soil samples taken from Picatinny Arsenal, New Jersey. The measured effective diffusion coefficients ranged from 0.0053 to 0.0609 cm2/s over a range of air-filled porosity of 0.23-0.49. The experimental data were compared to several previously published relations that predict diffusion coefficients as a function of air-filled porosity and porosity. A multiple linear regression analysis was developed to determine if a modification of the exponents in Millington's [Science 130 (1959) 100] relation would better fit the experimental data. The literature relations appeared to generally underpredict the effective diffusion coefficient for the soil cores studied in this work. Inclusion of a particle-size distribution parameter, d10, did not significantly improve the fit of the linear regression equation. The effective diffusion coefficient and porosity data were used to recalculate estimates of diffusive flux through the subsurface made in a previous study performed at the field site. It was determined that the method of calculation used in the previous study resulted in an underprediction of diffusive flux from the subsurface. We conclude that although Millington's [Science 130 (1959) 100] relation works well to predict effective diffusion coefficients in homogeneous soils with relatively uniform particle-size distributions, it may be inaccurate for many natural soils with heterogeneous structure and/or non-uniform particle-size distributions.     

新型高效气体扩散电极的制备与性能

评述了原位产生H₂O₂的电化学法污水处理技术中使用的主要电极,研究了用石墨制备高效气体扩散电极的方法。对石墨用HNO₃与H₃PO₄的混合液改性,石墨与聚四氟乙烯的质量比为2∶1,电极经350℃煅烧1 h,对溶解O₂还原产生H₂O₂的催化活性最高。仅在pH值很低时,电极的活性较差,在pH=3～9时,电极的活性受pH值变化影响较小。在pH=3时电解150 min,电极的电流效率始终高于72%,H₂O₂浓度达到了274.5 mg/L。     

改性膨润土颗粒对微污染水中有机物和氨氮的吸附

采用粘结剂聚乙烯醇(PVA)、造孔剂碳酸氢钠(NaHCO3)和微波强化Al改性膨润土(以下简称M-Al-Bt)制备改性膨润土颗粒(以下简称MBG),研究MBG对微污染水中有机物和氨氮(NH4-N)的吸附效果,考察了不同投加量、反应时间、pH值对腐殖酸(HA)和NH4-N的去除效果影响.结果表明,投加量3 g/L,反应时间20 min,pH=7时,MBG对微污染水中20 mg/L HA和5mg/L NH4-N的去除率分别可达98%和20%以上.HA和NH4-N共存时,存在竞争吸附,HA影响了MBG对NH4-N的去除.     

Matrix diffusion coefficients in volcanic rocks at the Nevada test site: influence of matrix porosity, matrix permeability, and fracture coating minerals

Diffusion cell experiments were conducted to measure nonsorbing solute matrix diffusion coefficients in forty-seven different volcanic rock matrix samples from eight different locations (with multiple depth intervals represented at several locations) at the Nevada Test Site. The solutes used in the experiments included bromide, iodide, pentafluorobenzoate (PFBA), and tritiated water ((3)HHO). The porosity and saturated permeability of most of the diffusion cell samples were measured to evaluate the correlation of these two variables with tracer matrix diffusion coefficients divided by the free-water diffusion coefficient (D(m)/D*). To investigate the influence of fracture coating minerals on matrix diffusion, ten of the diffusion cells represented paired samples from the same depth interval in which one sample contained a fracture surface with mineral coatings and the other sample consisted of only pure matrix. The log of (D(m)/D*) was found to be positively correlated with both the matrix porosity and the log of matrix permeability. A multiple linear regression analysis indicated that both parameters contributed significantly to the regression at the 95% confidence level. However, the log of the matrix diffusion coefficient was more highly-correlated with the log of matrix permeability than with matrix porosity, which suggests that matrix diffusion coefficients, like matrix permeabilities, have a greater dependence on the interconnectedness of matrix porosity than on the matrix porosity itself. The regression equation for the volcanic rocks was found to provide satisfactory predictions of log(D(m)/D*) for other types of rocks with similar ranges of matrix porosity and permeability as the volcanic rocks, but it did a poorer job predicting log(D(m)/D*) for rocks with lower porosities and/or permeabilities. The presence of mineral coatings on fracture walls did not appear to have a significant effect on matrix diffusion in the ten paired diffusion cell experiments.     

施工扬尘空间扩散特性的模型分析与分级管控措施

基于多个城市施工工地的扬尘监测数据,对比分析了幂函数、高斯函数和指数律模型在描述施工扬尘空间扩散特性上的适用性。以北京市某工地为例,基于CFD模拟,研究了施工扬尘的空间分布及扩散特性。通过与实测数据的对比,验证了模拟结果的准确性,分析了指数律模型在描述施工扬尘空间扩散特性上的适用性,并根据扬尘污染程度将施工区域影响范围划分为3个等级区,提出了综合评估施工扬尘污染严重程度的分级方法与管理控制措施。结果表明：指数律模型适用于描述施工扬尘空间扩散规律,幂函数模型仅适用于水平向,高斯函数模型在水平和垂直方向均不适用;围挡对施工扬尘的水平影响距离约为5倍围挡高度;工地周围可划分为重度污染区(<26 m)、中度污染区(26~42 m)和轻度污染区(42~100 m);可在各污染区布置监测点,综合评估施工扬尘污染严重程度,便于扬尘的分级管理与控制。本研究结果可为减少施工扬尘污染、提高环境空气质量提供参考。     

输煤皮带巷运煤量对扬尘运移扩散影响的数值模拟

为了掌握输煤皮带巷运煤期间的扬尘分布规律,探索更好的除尘工艺,以某大型煤矿主斜输煤皮带巷为研究背景,构建三维模型,依据气固两相流理论,运用双流体模型对不同运煤量下的粉尘浓度三维分布规律进行数值模拟。结果表明：皮带运煤量的增加,增大了煤流与风流之间的摩擦面积及巷道断面风速,提高了扬尘强度,扩大了高浓度区域范围,显著增加了巷道中下部空间的粉尘污染程度;运煤量的增加对粉尘浓度的影响程度随着距皮带距离的增加而减小;在湿式除尘设计中,可通过自动喷雾系统与煤量监测之间的联动,提高除尘效果。     

加油站油气扩散与回收效果的数值分析

加油站排放出的油气是有毒有害的气体。目前控制油品蒸发损耗的有效方法是采用油气回收系统。基于湍流模式理论,采用FLUENT软件,模拟加油站在使用油气回收系统前后空气中油气浓度分布情况及风对油气扩散的影响,得到油气浓度等值面图、直线及点上浓度变化曲线图。模拟结果表明,实施油气回收,其大气净化率可高达95％以上,因此明显减小加油站火灾隐患及环境污染,并可减少经济损失及节约加油站占地面积。另外,风对油气扩散稀释有明显的影响,如距排放口下风侧5 m处,相对于风速１ m/s,风速为5、8 m/s时的大气净化率分别为54％、71％。虽然无法降低油气排放总量,但是随着风速的增加大气净化率随之变大,可以减少油气浓度值过高造成的危害。     

Three-dimensional diffusion of non-sorbing species in porous sandstone: computer simulation based on X-ray microtomography using synchrotron radiation

The diffusion pathways of porous sandstone were examined by a three-dimensional (3-D) imaging technique based on X-ray computed tomography (CT) using the SPring-8 (Super Photon ring-8 GeV, Hyogo, Japan) synchrotron radiation facility. The analysis was undertaken to develop better understanding of the diffusion pathways in natural rock as a key factor in clarifying the detailed mechanism of the diffusion of radionuclides and water molecules through the pore spaces of natural barriers in underground nuclear waste disposal facilities. A cylindrical sample (diameter 4 mm, length 6 mm) of sandstone (porosity 0.14) was imaged to obtain a 3-D image set of 450(3) voxels=2.62(3) mm(3). Through cluster-labeling analysis of the 3-D image set, it was revealed that 89% of the pore space forms a single large pore-cluster responsible for macroscopic diffusive transport, while only 11% of the pore space is made up of isolated pores that are not involved in long-range diffusive transport. Computer simulations of the 3-D diffusion of non-sorbing random walkers in the largest pore cluster were performed to calculate the surface-to-volume ratio of the pore, tortuosity (diffusion coefficient in free space divided by that in porous rock). The results showed that (i) the simulated surface-to-volume ratio is about 60% of the results obtained by conventional pulsed-field-gradient proton nuclear magnetic resonance (NMR) laboratory experiments and (ii) the simulated tortuosity is five to seven times larger than the results of laboratory diffusion experiments using non-sorbing I(-) and Br(-). These discrepancies are probably attributed to the intrinsic sample heterogeneity and limited spatial resolution of the CT system. The permeability was also estimated based on the NMR diffusometry theory using the results of the random walk simulations via the Kozeny-Carman equation. The estimated permeability involved an error of about 20% compared with the permeability measured by the conventional method, suggesting that the diffusometry-based NMR well logging with gradient coils is applicable to the in-situ permeability measurement of strata. The present study demonstrated that X-ray CT using synchrotron radiation is a powerful tool for obtaining 3-D pore structure images without the beam-hardening artifacts inevitable in conventional CT using X-ray tubes.     

破碎站粉尘逸散规律及降尘技术的数值模拟及其应用

针对露天矿破碎站粉尘污染严重、治理技术中存在的缺陷,提出了超声波雾化喷雾降尘技术。以平朔安家岭煤矿为例,根据破碎站区域粉尘污染情况,应用数学模型对破碎站粉尘逸散规律进行解算,将模拟结果与现场实测数据对比,确定对卸载坑采用150~300μm雾滴粒径和对破碎机各产尘点采用1~10μm雾滴粒径的机体梁上外喷雾方式,通过对采取治理方案后破碎站粉尘浓度逸散的数值模拟和现场实际应用后的测试数据,显示全尘和呼吸性粉尘降尘效率分别达到94%和82%。结果表明,超声波喷雾降尘技术能有效降低破碎站粉尘浓度,保障了作业人员工作环境和安全。     

基于风洞平台实验的大型罐区溢油事故后的油气扩散模拟

通过研究江苏省境内某实体罐区发生溢油事故后油气蒸发的扩散规律,掌握罐区空气浓度的变化,以达到保障罐区环保与安全的目的.基于风洞平台实验,测定油气蒸发速率并通过实验风场数据验证数值模型的准确性,建立与实际油库1∶1的大型罐区模型,使用UDF编译环境风方程导入.通过CFD数值模拟,重点分析了罐区发生溢油事故后油气扩散规律、...     

水源水库沉积物间隙水营养盐分布特征及扩散通量

为了阐明水源水库沉积物营养盐释放对水体富营养化的贡献,以周村水库为研究对象,探讨沉积物间隙水中氮、磷营养盐的分布特征,同时采用Fick第一定律对沉积物-水界面营养盐的扩散通量进行了估算。周村水库表层沉积物间隙水中NH4+-N的浓度为6.47 to 16.82 mg·L-1,PO43--P的浓度在0.13 to 0.56 mg·L-1之间,均远高于上覆水中的营养盐浓度,表明周村水库表层沉积物具有很大的营养盐释放潜能。Fick第一定律的计算结果表明,沉积物-水界面NH4+-N与PO43--P的扩散通量分别为62.831 to 133.231和0.364 to 1.271 mg·（m2·d）-1,研究区域中间隙水中的营养盐均由沉积物向上覆水扩散,沉积物是底层水体营养盐的重要来源。     

复合纳米材料对土壤重金属离子吸持固化的模拟研究

土壤中过量重金属离子可通过食物链和地表水系统危害人群健康。通过土柱淋溶模拟实验,研究了SiO2-Al2O3-Fe2O3等复合纳米材料对土壤溶液中Cu2+、Cd2+、Pb2+、Zn2+和Ni2+的吸持与固化特征。分别向重金属含量4倍于土壤二级标准(GB15618-1995)的土壤中添加0%、4%、6%和10%的复合纳米材料,分析不同深度土壤渗滤液以及土柱上栽培植物不同部位中重金属的含量。结果表明,碱性壤质土壤中重金属向下的迁移量很少;在含4%复合纳米材料土柱中,其吸持固化土壤溶液中63%的Cu、79%的Cd、68%的Pb、89%的Zn和76%的Ni;在含6%复合纳米材料土柱中,其吸持固化土壤溶液中82%的Cu、92%的Cd、76%的Pb、91%的Zn和88%的Ni;再增加土柱中复合纳米材料的含量,其吸持固化效果并不再显著增加。     

复合改性海泡石同步处理废水中的氮磷

采用盐热和稀土掺杂制备复合改性海泡石,研究了复合改性海泡石对废水中N、P的吸附特征和去除效果。结果表明,与海泡石原矿粉比较,复合改性海泡石的脱氮除磷能力分别提高49.71%和90.14%;复合改性海泡石对N、P的吸附可以用Langmuir吸附模型描述,获得的最大吸附量分别为1.165和1.121 mg/g;修正的Elovich模型能较好地描述复合改性海泡石吸附N、P的动力学过程;用NaOH溶液可以再生吸附材料,获得较好的脱氮除磷效果,再生次数以2次为宜;用复合改性海泡石处理污水处理站的二级生化出水,最终出水的pH、N和P含量均达到《城镇污水处理厂污染物排放标准》的要求。