Sensitivity analysis of radionuclide migration in compacted bentonite: a mechanistic model approach

Mechanistic model calculations for the migration of Cs, Ra, Am and Pb in compacted bentonite have been carried out to evaluate sensitivities with respect to different parameter variations. A surface chemical speciation/electric double layer model is used to calculate: (i) porewater composition and radionuclide speciation in solution and at the bentonite surface, yielding the distribution of mobile and sorbed species and (ii) interaction of diffusing species with negatively charged pore walls to obtain diffusion parameters. The basic scenario considers the interaction of compacted bentonite with a fresh-type groundwater; variations include the presence of bentonite impurities and saline groundwater. It is shown that these scenarios result in significant variations of porewater composition that affect migration via three mechanisms that can partly compensate each other: (1) effects on sorption through radionuclide complexation in solution, and competition of major cations for surface sites; (2) changes in radionuclide solution speciation leading to different diffusing species under different conditions; (3) effects on diffusion through changes in the electric double layer properties of the clay pores as a function of ionic strength.     

Removal of a cationic dye from aqueous solutions by adsorption onto bentonite clay

The ability of bentonite to remove malachite green from aqueous solutions has been studied for different adsorbate concentrations by varying the amount of adsorbent, temperature, pH and shaking time. Maximum adsorption of the dye, i.e. >90% has been achieved in aqueous solutions using 0.05 g of bentonite at a pH of 9. Thermodynamic parameters such as ΔH°, ΔS° and ΔG° were calculated from the slope and intercept of the linear plots of ln K_D against 1/T. Analysis of adsorption results obtained at 298, 308, 318 and 328 K showed that the adsorption pattern on bentonite seems to follow the Langmuir, Freundlih and D–R isotherms. The temperature increase reduces adsorption capacity by bentonite, due to the enhancement of the desorption step in the mechanism. The numerical values of sorption free energy (E_a) of 1.00–1.12 kJ mol⁻¹ indicated physical adsorption. The kinetic data indicated an intraparticle diffusion process with sorption being first order. The rate constant k was 0.526 min⁻¹. The concentration of malachite green oxalate was measured before and after adsorption by using UV–Vis spectrophotometer.     

Generation and stability of bentonite colloids at the bentonite/granite interface of a deep geological radioactive waste repository

The possible mechanisms of colloid generation at the near field/far field interface of a radioactive repository have been investigated by means of novel column experiments simulating the granite/bentonite boundary, both in dynamic and in quasi-static water flow conditions. It has been shown that solid particles and colloids can be detached from the bulk and mobilised by the water flow. The higher the flow rate, the higher the concentration of particles found in the water, according to an erosion process. However, the gel formation and the intrinsic tactoid structure of the clay play an important role in the submicron particle generation even in the compacted clay and in a confined system. In fact, once a bentonite gel is formed, in the regions where the clay is contacted with water, clay colloids can be formed even in quasi-static flow conditions. The potential relevance of these colloids in radionuclide transport has been studied by evaluating their stability in different chemical environments. The coagulation kinetics of natural bentonite colloids was experimentally studied as a function of the ionic strength and pH, by means of time-resolved light scattering techniques. It has been shown that these colloids are very stable in low saline (approximately 1 x 10(-3) M) and alkaline (pH > or = 8) waters.     

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.     

In situ anion diffusion experiments using radiotracers

Diffusion experiments in compacted bentonite have been carried out in situ using the borehole laboratory CHEMLAB. The "ordinary" anion iodide and the redox-sensitive pertechnetate ion have been investigated. In spite of strongly reducing groundwater conditions, technetium was found to diffuse mostly unreduced as TcO4-, although in some spots in the compacted clay, the activity was significantly higher, which may be explained by reduction of some TcO4- by iron-containing minerals in the bentonite. The measured concentration profiles in the clay cannot be accommodated by assuming one single diffusion process. The experimental data are modeled assuming two diffusion paths, intralamellar diffusion and diffusion in external water. The apparent diffusivity for the intralamellar diffusion was found to be 8.6 x 10(-11) m2 s(-1) for iodide with a capacity factor of 0.1, while the apparent diffusivity for the diffusion in external water was found to be 5 x 10(-14) m2 s(-1) with alpha=2.26. The corresponding values for Tc were found to be Da= 6 x 10(-11) m2 s(-1), alpha=0.1 and Da= 1 x 10(-13) m2 s(-1), alpha=0.46, respectively. The diffusion constants and capacity factors obtained in this study are in accordance with data from laboratory experiments.     

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.     

Modeling plant response to tropospheric ozone: a critical review

The advantages and disadvantages, benefits and limitations, of a number of published mathematical models representing the effects of ozone on crops and native vegetation are described. Several levels of modeling are addressed: word models, graphic models, mathematical models, and computer simulation implementation. Special attention is given to evaluating: (1) how the interaction between ozone exposure and vegetation effects is quantified, (2) the status of field testing of the model, and (3) the adequacy of information for enabling other investigators to replicate the model for further testing. Original contributions, not previously published, are made in this evaluation in the form of: (1) graphic model flow charts for published models, (2) clarification of mathematical equations for existing models, (3) graphic forms of functional relations comprising portions of models, and (4) graphic displays of model output performance versus observed data. The models that are evaluated cover acute exposure-response models, statistical and mechanistic-process models, including a partial model of ambient exposure versus ozone flux, and uptake. They also cover chronic exposure statistical approaches, including time-series modeling, mechanistic-process models, 'disintegrated' models of forest system simulations, chronic flux density-uptake-response, and models for regional effects assessment in forests and agricultural lands.     

Fractal approach in expansive clay-based materials with special focus on compacted GMZ bentonite in nuclear waste disposal: a systematic review

Environmental Science and Pollution Research - Knowledge of the behavior of highly compacted expansive clays, as an engineered barrier, in disposal of high-level nuclear waste (HLW) systems to...     

The influence of colloid formation in a granite groundwater bentonite porewater mixing zone on radionuclide speciation

In the context of deep geological storage of high level nuclear waste the repository will be designed as multiple barrier system including bentonite as buffer/backfill material and the host rock formation as geological barrier. The engineered barrier (bentonite) will be in contact with the host rock formation and consequently it can be expected that bentonite porewater will mix with formation groundwater. We simulate in this study the mixing of Grimsel groundwater (glacial melt water) with synthetic Febex porewater (assuming already saturated state) in a batch-type study and investigate the formation of colloids by laser-induced breakdown detection (LIBD) and SEM-EDX as well as the changes in radionuclide (U, Th, Eu) speciation via ultrafiltration or via time-resolved laser fluorescence spectroscopy (TRLFS) analysis in the case of Cm(III). Based on PHREEQC saturation index (SI) calculations a precipitation of calcite might be expected at low Febex porewater (FPW) content (< 20%), fluorite precipitation at FPW contents < 60% and gibbsite precipitation at FPW contents above 10%. The colloids generated in the mixing zone aggregate when the synthetic FPW content exceeds 10%. LIBD analysis of the time-dependent colloid generation/aggregation revealed a low concentration of colloids to be stable with an estimated plateau value around 100–200 ppt and an average colloid diameter around 30 nm after 140 days reaction time at FPW admixture > 10%. SEM/EDX mostly identifies Al/Si containing colloidal phases and some sulfates could be found under certain admixture ratios. TRLFS studies show that the Cm speciation is strongly influenced by colloid formation in all solutions. In the Febex pore water/GGW mixing zone with high groundwater contents (> 80%) colloids are newly formed and Cm is almost quantitatively associated with most likely polysilicilic acid colloids.     

An analytical solution to contaminant diffusion in semi-infinite clayey soils with piecewise linear adsorption

The adsorption of contaminants onto soil particles typically is nonlinear if the contaminant concentration is sufficiently high. A simplified piecewise linear adsorption isotherm consistent with experimental results is proposed as an approximation for nonlinear adsorption behavior. This approximation allows for the use of analytical solution to model solute diffusion of contaminants that exhibit nonlinear adsorption. A moving boundary is introduced to represent significant changes in the retardation factor of clay with an increase in solute concentration. The proposed analytical solutions were validated using experimental data presented in the literature. There is negligible difference between the results obtained by the proposed analytical solution and those obtained by the linear model when C_m/C₀ reached 0.5. The results also show that the model based on linear adsorption using the initial secant of the Freundlich isotherm leads to significantly lower estimated breakthrough time for the contaminant of interest than that obtained using the proposed model. The earlier breakthrough is due to an under-estimation of the amount of adsorption. The proposed method is relatively simple to apply and can be used for evaluating experimental results and verifying more complex numerical models.     

A critical review on adsorption and recovery of fluoride from wastewater by metal-based adsorbents

Environmental Science and Pollution Research - Rapid industrialization is deteriorating water quality, and fluoride pollution in water is one of the most serious environmental pollution problems....     

多孔碳材料对二噁英吸附性能的研究评述及展望

活性炭吸附已成为垃圾焚烧企业脱除烟气中二噁英类有机污染物最常用的方法。介绍了活性炭在垃圾焚烧企业的应用现状及存在的问题,系统分析了活性炭对二噁英的吸附特点,总结了烟气温度、活性炭喷入量、二噁英同系物分布、活性炭的孔结构等对二噁英脱除效率的影响。此外,概述了活性碳纤维、碳纳米管在二噁英吸附方面的研究动态。分析了碳纳米管在吸附二噁英过程中不同于活性炭的吸附机制,探讨了其未来替代活性炭作为二噁英吸附材料的可能性。     

Modeling adsorption in multicomponent systems using a Freundlich-type isotherm

The suitability of a Freundlich-type isotherm, the Sheindorf-Rebuhn-Sheintuch (SRS) equation, to represent the competitive adsorption of Sr, Cs and Co in Ca-montmorillonite suspensions was investigated. Experimental adsorption data were obtained for systems containing these cations as single-component, binary and ternary mixtures. The competition coefficient α_ij, which were obtained based on the experimental adsorption data for bicomponent systems, can be viewed as a way to quantify competitive interactions. The competition coefficients obtained for the cations under consideration indicate that their competitive interactions are of similar magnitude, with the cation least affected by competitive effects being Cs, while the adsorption of Co was more significantly affected by the presence of Cs, and Sr by the presence of Co. After α_ij-values were substituted in the SRS equation, the adsorption of systems of three or more components could be predicted. To validate the SRS equation, the adsorption values predicted by this equation for the ternary mixture Sr---Cs--- Co were compared to values determined experimentally. The SRS equation successfully modeled adsorption for the range of concentrations that followed Freundlich behavior.     

Agriculture and deforestation in the tropics: a critical theoretical and empirical review

Despite the important role that tropical forests play in human existence, their depletion, especially in the developing world, continue relentlessly. Agriculture has been cited as the major cause of this depletion. This paper discusses two main theoretical underpinnings for the role of agriculture in tropical deforestation. First, the forest biomass as input in agricultural production, and second, the competition between agriculture and forestry underlined by their relative marginal benefits. These are supported by empirical evidence from selected countries in Africa and South America. The paper suggests a need to find a win-win situation to control the spate of tropical deforestation. This may imply improved technologies in the agriculture sector in the developing world, which would lead both to increased production in the agriculture sector, and would also help control the use of tropical forest as an input in agriculture production.     

Bibliometric analysis of studies involving e-waste: a critical review

Environmental Science and Pollution Research - The correct destination of waste is an essential factor for sustainable development. Electronic waste, which is very toxic, is the type of waste with...     

Transmission of SARS-CoV-2 virus and ambient temperature: a critical review

Environmental Science and Pollution Research - The coronavirus disease 2019 (COVID-19) pandemic has brought unprecedented public health, and social and economic challenges. It remains unclear...     

Microplastics in urban waters and its effects on microbial communities: a critical review

Environmental Science and Pollution Research - Microplastic (MP) pollution is one of the emerging threats to the water and terrestrial environment, forcing a new environmental challenge due to the...     

Relationship between e-waste recycling and human health risk in India: a critical review

Informal recycling of waste (including e-waste) is an emerging source of environmental pollution in India. Polychlorinated biphenyls (PCBs), polychlorinated diphenyl ethers (PBDEs), and heavy metals, among other substances, are a major health concern for workers engaged in waste disposal and processing, and for residents living near these facilities, and are also a detriment to the natural environment. The main objective of this review article was to evaluate the status of these impacts. The review found that, huge quantity of e-waste/waste generated, only a small amount is treated formally; the remainder is processed through the informal sector. We also evaluated the exposure pathways, both direct and indirect, and the human body load markers (e.g., serum, blood, breast milk, urine, and hair), and assessed the evidence for the association between these markers and e-waste exposure. Our results indicated that the open dumping and informal e-waste recycling systems should be replaced by the best available technology and environmental practices, with proper monitoring and regular awareness programs for workers and residents. Further and more detailed investigation in this area is also recommended.