Recent Developments in Advanced Oxidation Processes for Organics-Polluted Soil Reclamation

Soil pollution has become a substantial environmental problem which is amplified by overpopulation in different regions. In this review, the state of the art regarding the use of Advanced Oxidation Processes (AOPs) for soil remediation is presented. This review aims to provide an outline of recent technologies developed for the decontamination of polluted soils by using AOPs. Depending on the decontamination process, these techniques have been presented in three categories: the Fenton process, sulfate radicals process, and coupled processes. The review presents the achievements of, and includes some reflections on, the status of these emerging technologies, the mechanisms, and influential factors. At the present, more investigation and development actions are still desirable to bring them to real full-scale implementation.

Phenomenological Model of Nonlinear Dynamics and Deterministic Chaotic Gas Migration in Bentonite: Experimental Evidence and Diagnostic Parameters

Understanding gas migration in compacted clay materials, e.g., bentonite and claystone, is important for the design and performance assessment of an engineered barrier system of a radioactive waste repository system, as well as many practical applications. Existing field and laboratory data on gas migration processes in low-permeability clay materials demonstrate the complexity of flow and transport processes, including various types of instabilities, caused by nonlinear dynamics of coupled processes of liquid–gas exchange, dilation, fracturing, fracture healing, etc., which cannot be described by classical models of fluid dynamics in porous media. We here show that the complexity of gas migration processes can be explained using a phenomenological concept of nonlinear dynamics and deterministic chaos theory. To do so, we analyzed gas pressure and gas influx (i.e., input) and outflux (i.e., output), recorded during the gas injection experiment in the compact Mx80-D bentonite sample, and calculated a set of the diagnostic parameters of nonlinear dynamics and chaos, such a global embedding dimension, a correlation dimension, an information dimension, and a spectrum of Lyapunov exponents, as well as plotted 2D and 3D pseudo-phase-space strange attractors, based on the univariate influx and outflux time series data. These results indicate the presence of phenomena of low-dimensional deterministic chaotic behavior of gas migration in bentonite. In particular, during the onset of gas influx in the bentonite core, before the breakthrough, the development of gas flow pathways is characterized by the process of chaotic gas diffusion. After the breakthrough, with inlet-to-outlet movement of gas, the prevailing process is chaotic advection. During the final phase of the experiment, with no influx to the sample, the relaxation pattern of gas outflux is resumed back to a process of chaotic diffusion. The types of data analysis and a proposed phenomenological model can be used to establish the basic principles of experimental data-gathering, modeling predictions, and a research design.

Multifunctional Membranes—A Versatile Approach for Emerging Pollutants Removal

This paper presents a comprehensive literature review surveying the most important polymer materials used for electrospinning processes and applied as membranes for the removal of emerging pollutants. Two types of processes integrate these membrane types: separation processes, where electrospun polymers act as a support for thin film composites (TFC), and adsorption as single or coupled processes (photo-catalysis, advanced oxidation, electrochemical), where a functionalization step is essential for the electrospun polymer to improve its properties. Emerging pollutants (EPs) released in the environment can be efficiently removed from water systems using electrospun membranes. The relevant results regarding removal efficiency, adsorption capacity, and the size and porosity of the membranes and fibers used for different EPs are described in detail.

Predicting Corrosion Delamination Failure in Active Implantable Medical Devices: Analytical Model and Validation Strategy

The ingress of body fluids or their constituents is one of the main causes of failure of active implantable medical devices (AIMDs). Progressive delamination takes its origin at the junctions where exposed electrodes and conductive pathways enter the implant interior. The description of this interface is considered challenging because electrochemically-diffusively coupled processes are involved. Furthermore, standard tests and specimens, with clearly defined 3-phase boundaries (body fluid-metal-polymer), are lacking. We focus on polymers as substrate and encapsulation and present a simple method to fabricate reliable test specimens with defined boundaries. By using silicone rubber as standard material in active implant encapsulation in combination with a metal surface, a corrosion-triggered delamination process was observed that can be universalised towards typical AIMD electrode materials. Copper was used instead of medical grade platinum since surface energies are comparable but corrosion occurs faster. The finding is that two processes are superimposed there: First, diffusion-limited chemical reactions at interfaces that undermine the layer adhesion. The second process is the influx of ions and body fluid components that leave the aqueous phase and migrate through the rubber to internal interfaces. The latter observation is new for active implants. Our mathematical description with a Stefan-model coupled to volume diffusion reproduces the experimental data in good agreement and lends itself to further generalisation.

Slope stability analysis of a landfill subjected to leachate recirculation and aeration considering bio-hydro coupled processes

During the operation of landfills, leachate recirculation and aeration are widely applied to accelerate the waste stabilization process. However, these strategies may induce high pore pressures in waste, thereby affecting the stability of the landfill slope. Therefore, a three-dimensional numerical analysis for landfill slope stability during leachate recirculation and aeration is performed in this study using strength reduction method. The bio-hydro coupled processes of waste are simulated by a previously reported landfill coupled model programmed on the open-source platform OpenFOAM and then incorporated into the slope stability analysis. The results show that both increasing the injection pressure for leachate recirculation and maximum anaerobic biodegradation rate will reduce the factor of safety (FS) of the landfill slope maximally by 0.32 and 0.62, respectively, due to increased pore pressures. The ignorance of both waste biodegradation and gas flow will overestimate the slope stability of an anaerobic bioreactor landfill by about 20–50%, especially when the landfilled waste is easily degradable. The FS value of an aerobic bioreactor landfill slope will show a significant reduction (maximally by 53% in this study) when the aeration pressure exceeds a critical value and this value is termed as the safe aeration pressure. This study then proposes a relationship between the safe aeration pressure and the location of the air injection screen (i.e., the horizontal distance between the top of the injection screen and the slope surface) to avoid landfill slope failure during aeration. The findings of this study can provide insights for engineers to have a better understanding of the slope stability of a bioreactor landfill and to design and control the leachate recirculation and aeration systems in landfills.

Impact of the heterogeneity of the sandy Opalinus clay facies at the Mont Terri underground research laboratory on radionuclide migration

The assessment of the safety of a deep geological repository (DGR) for high-level radioactive wastes over assessment time scales of up to 1 million years requires an in-depth understanding of the multi-scale coupled processes that affect the repository system evolution over time, to reduce uncertainties and conservatism in safety analyses. This is in particular required with respect to the challenges of a comparative assessment of different repository concepts in different host rocks within the process of a site selection for a DGR for heat-generating radioactive wastes in Germany. The collaborative project “Integrity of nuclear waste repository systems – Cross-scale system understanding and analysis (iCross)” conducted jointly by five research centres of the Helmholtz Association and co-funded by the Initiative and Networking Fund of the Helmholtz Association and the Federal Ministry of Education and Research (BMBF) has been initiated with the overall objective to improve the understanding of coupled thermal-hydraulic-mechanical-chemical-(micro)biological (THMCB) processes and to develop simulation tools that enable a holistic close to reality description of the long-term evolution of the repository system. Geological formations, such as those foreseen as potential host rocks for DGRs, and their surroundings are heterogeneous on various length scales ranging from nanometers to kilometers. Therefore, the aim of this work in the context of iCross is to evaluate the effects of mineralogical, geochemical and microstructural heterogeneities of repository host rocks on radionuclide transport in the repository far field, using the sandy facies of the Opalinus clay (SF-OPA) from the Mont Terri underground research laboratory (St. Ursanne, Switzerland) as an example. Here, we address in particular the migration behaviour of Ra-226 as an important radionuclide to be considered in safety cases for deep geological disposal of spent nuclear fuel. To assess the impact of the heterogeneities in SF-OPA on radionuclide transport, a complementary approach combining microstructural characterisation methods, experimental techniques for the determination of transport parameters of the rock matrix and the mobility of Ra-226 with innovative developments in reactive transport modelling on the pore and continuum scales was pursued. One of the results was that although the limited clay content in SF-OPA decreases the total amount of Ra bound to the illite phase, the solid solutions of sulphate and carbonate compensate for this and provide a major fixation mechanism.

An interdisciplinary view of the long-term evolution of repository systems across scales: the iCROSS project

The interdisciplinary project “Integrity of nuclear waste repository systems – Cross-scale system understanding and analysis (iCROSS)” combines research competencies of Helmholtz scientists related to the topics of nuclear, geosciences, biosciences and environmental simulations in collaborations overarching the research fields energy and earth and environment. The focus is to understand and analyze close-to-real long-term evolutionary pathways of radioactive waste repositories across nanoscales to repository scales. The project is subdivided into work packages dealing with laboratory studies, field experiments in underground research laboratories (URLs), advanced modelling studies and the integration and alignment of data and information using virtual reality methods. In this sense, the project structure aims at a holistic view on relevant processes across scales in order to comprehensively simulate potential repository evolutions. Within the multi-barrier system of a repository for heat-generating radioactive waste, a number of complex reactions proceed, including dissolution, redox processes, biochemical reactions, gas evolution and solid/liquid interface and (co)precipitation reactions. At the same time, thermal and external mechanical stress has an impact on the conditions in a deep geological repository. All those processes are highly coupled, with multiple interdependencies on various scales and have a strong impact on radionuclide mobility and retention. In recent years, substantial progress was achieved in describing coupled thermal-hydro-mechanical-chemical-biological (THM/CB) processes in numerical simulations. A realistic and concise description of these coupled processes on different time and spatial scales is, at present, a largely unresolved scientific and computational challenge. The close interaction of experimental and simulation teams aims at a more accurate quantification and assessment of processes and thus, the reduction of uncertainties and of conservative assumptions and eventually to a close-to-real perception of the repository evolution. One focus of iCROSS is directed to relevant processes in a clay rock repository. In this context, the iCROSS team became a full member of the international Mont Terri consortium and worked in close collaboration with international and German institutions in URL projects. Respective experiments specifically deal with coupled processes at the reactive interfaces in a repository near field (e.g. the steel/bentonite and bentonite/concrete interfaces). Within iCROSS, the impact of secondary phase formation on radionuclide transport is investigated. At Mont Terri, experiments are in preparation to study radionuclide transport phenomena in clay rock formations within temperature gradients and in facies exhibiting significant heterogeneities on different scales (nm to cm). Beside those studies, high resolution exploration methods for rock characterization are developed and tested and the effect of temperature and other boundary conditions on the strength, creep properties and healing of faults within Opalinus clay are quantified. Multiphysics models coupled to reactive transport simulation have been further developed and applied to laboratory and field experiments. Results are digitally analyzed and illustrated in a visualization center, in order to enhance the comprehension of coupled processes in repository systems across scales. The present contribution provides an overview on the project and reports selected results. The impact of considering complex coupled processes in repository subsystems for the assessment of the integrity of a given (generic) repository arrangement is discussed.

International collaboration in disposal research: comparative modeling of coupled processes in the DECOVALEX project

This presentation gives an overview of an international research collaboration for advancing the understanding and modeling of coupled thermo-hydro-mechanical-chemical (THMC) processes in geological systems. The creation of the international DECOVALEX project, now running for more than 25 years, was motivated by the recognition that prediction of these coupled effects is an essential part of the performance and safety assessment of geologic disposal systems for radioactive waste and spent nuclear fuel. DECOVALEX emphasizes joint analysis and comparative modeling of state-of-the-art field and laboratory experiments, across a range of host rock options and repository designs. Participating research teams are from radioactive waste management organizations, national research institutes, regulatory agencies, universities, and consulting groups, providing a wide range of perspectives and solutions to these complex problems. The presentation provides examples of the research contributions made collectively in past DECOVALEX tasks and also touches on the unique modeling challenges tackled in the ongoing project phase, referred to as DECOVALEX-2023. The current phase comprises 17 partner organizations, about 50 modeling teams, and 7 modeling tasks, which cover a broad portfolio from fundamental studies on gas migration to full-scale in situ heater experiments in different host rocks to performance assessment studies. Together, these examples illustrate that the insight and scientific knowledge gained within the DECOVALEX project would not have been possible if one group had studied these complex THMC modeling challenges alone rather than within a truly collaborative setting.

Open Source Software Library for Thermo-Hydro-Mechanical Coupled Processes in Python

This contributed poster shows the current state of development of a finite element implementation as part of an open source software library (OSSL) for the simulation of thermo-hydro-mechanical (THM) coupled processes. The reliable handling of numerical methods is fundamental for the understanding of scientific interrelationships and thus, a crucial prerequisite for modeling THM scenarios, as well as for the understanding and evaluation of preliminary safety investigations during the site selection process for the storage of high-level radioactive waste. There are several motivations for developing an in-house OSSL, which will allow us to: Build capacity and maintenance within BASE (Federal Office for the Safety of Nuclear Waste Management) regarding issues of the numerical modeling of safety-relevant aspects on the long-term safety analyses specified by the German legislator in the site selection process. Develop a collection of known benchmarks and evaluation examples for the comparison of different software tools, applying a uniform interface to simplify the use of the available highly specialized open source codes. Diversify the testing possibilities regarding the preliminary safety investigations by means of our own, independent modeling software. Document basic THM scenarios for internal or, if necessary, public technical training, e.g., density-driven fluid flow (Fig. 1), convergence in salt, temperature propagation in the repository area, crack development, diffusive or advective mass transport. Ensure transparency and, in principle, might allow for appropriately proven-quality (validated) and documented simulation tools for the public regarding questions about the preliminary safety investigations during the site selection process. The development of the OSSL is mainly based on the scripting language Python, which allows the necessary flexibility for the diverse fields of application and at the same time enables maximum transparency for all aspects of the source code. To ensure the high quality of the software, state of the art development tools are used (e.g., version control, automated tests, and documentation generation). Figure 1 shows our preliminary simulation results of the so-called Elder problem (Elder, 1967), a popular standard benchmark for thermo-hydrogeological coupling in which fluid motion in a porous medium is driven by buoyancy forces.