Swedish-German actinide migration experiment at ÄSPÖ hard rock laboratory

Within the scope of a bilateral cooperation between Svensk Kärnbränslehantering (SKB) and Forschungszentrum Karlsruhe, Institut für Nukleare Entsorgung (FZK-INE), an actinide migration experiment is currently being performed at the Äspö Hard Rock Laboratory (HRL) in Sweden. This paper covers laboratory and in situ investigations on actinide migration in single-fractured granite core samples. For the in situ experiment, the CHEMLAB 2 probe developed by SKB was used. The experimental setup as well as the breakthrough of inert tracers and of the actinides Am, Np and Pu are presented. The breakthrough curves of inert tracers were analyzed to determine hydraulic properties of the fractured samples. Postmortem analyses of the solid samples were performed to characterize the flow path and the sorbed actinides. After cutting the cores, the abraded material was analyzed with respect to sorbed actinides. The slices were scanned optically to visualize the flow path. Effective volumes and inner surface areas were measured.In the experiments, only breakthrough of Np(V) was observed. In each experiment, the recovery of Np(V) was ≤40%. Breakthrough of Am(III) and Pu(IV) as well as of Np(IV) was not observed.     

Solute transport in crystalline rocks at Äspö — I: Geological basis and model calibration

Water-conducting faults and fractures were studied in the granite-hosted Äspö Hard Rock Laboratory (SE Sweden). On a scale of decametres and larger, steeply dipping faults dominate and contain a variety of different fault rocks (mylonites, cataclasites, fault gouges). On a smaller scale, somewhat less regular fracture patterns were found. Conceptual models of the fault and fracture geometries and of the properties of rock types adjacent to fractures were derived and used as input for the modelling of in situ dipole tracer tests that were conducted in the framework of the Tracer Retention Understanding Experiment (TRUE-1) on a scale of metres. After the identification of all relevant transport and retardation processes, blind predictions of the breakthroughs of conservative to moderately sorbing tracers were calculated and then compared with the experimental data. This paper provides the geological basis and model calibration, while the predictive and inverse modelling work is the topic of the companion paper [J. Contam. Hydrol. 61 (2003) 175].The TRUE-1 experimental volume is highly fractured and contains the same types of fault rocks and alterations as on the decametric scale. The experimental flow field was modelled on the basis of a 2D-streamtube formalism with an underlying homogeneous and isotropic transmissivity field. Tracer transport was modelled using the dual porosity medium approach, which is linked to the flow model by the flow porosity. Given the substantial pumping rates in the extraction borehole, the transport domain has a maximum width of a few centimetres only. It is concluded that both the uncertainty with regard to the length of individual fractures and the detailed geometry of the network along the flowpath between injection and extraction boreholes are not critical because flow is largely one-dimensional, whether through a single fracture or a network. Process identification and model calibration were based on a single uranine breakthrough (test PDT3), which clearly showed that matrix diffusion had to be included in the model even over the short experimental time scales, evidenced by a characteristic shape of the trailing edge of the breakthrough curve. Using the geological information and therefore considering limited matrix diffusion into a thin fault gouge horizon resulted in a good fit to the experiment. On the other hand, fresh granite was found not to interact noticeably with the tracers over the time scales of the experiments.While fracture-filling gouge materials are very efficient in retarding tracers over short periods of time (hours–days), their volume is very small and, with time progressing, retardation will be dominated by altered wall rock and, finally, by fresh granite. In such rocks, both porosity (and therefore the effective diffusion coefficient) and sorption K_ds are more than one order of magnitude smaller compared to fault gouge, thus indicating that long-term retardation is expected to occur but to be less pronounced.     

Solute transport in crystalline rocks at Äspö — II: Blind predictions, inverse modelling and lessons learnt from test STT1

Based on the results from detailed structural and petrological characterisation and on up-scaled laboratory values for sorption and diffusion, blind predictions were made for the STT1 dipole tracer test performed in the Swedish Äspö Hard Rock Laboratory. The tracers used were nonsorbing, such as uranine and tritiated water, weakly sorbing ²²Na⁺, ⁸⁵Sr²⁺, ⁴⁷Ca²⁺and more strongly sorbing ⁸⁶Rb⁺, ¹³³Ba²⁺, ¹³⁷Cs⁺.Our model consists of two parts: (1) a flow part based on a 2D-streamtube formalism accounting for the natural background flow field and with an underlying homogeneous and isotropic transmissivity field and (2) a transport part in terms of the dual porosity medium approach which is linked to the flow part by the flow porosity.The calibration of the model was done using the data from one single uranine breakthrough (PDT3). The study clearly showed that matrix diffusion into a highly porous material, fault gouge, had to be included in our model evidenced by the characteristic shape of the breakthrough curve and in line with geological observations.After the disclosure of the measurements, it turned out that, in spite of the simplicity of our model, the prediction for the nonsorbing and weakly sorbing tracers was fairly good. The blind prediction for the more strongly sorbing tracers was in general less accurate. The reason for the good predictions is deemed to be the result of the choice of a model structure strongly based on geological observation. The breakthrough curves were inversely modelled to determine in situ values for the transport parameters and to draw consequences on the model structure applied. For good fits, only one additional fracture family in contact with cataclasite had to be taken into account, but no new transport mechanisms had to be invoked. The in situ values for the effective diffusion coefficient for fault gouge are a factor of 2–15 larger than the laboratory data. For cataclasite, both data sets have values comparable to laboratory data. The extracted K_d values for the weakly sorbing tracers are larger than Swedish laboratory data by a factor of 25–60, but agree within a factor of 3–5 for the more strongly sorbing nuclides. The reason for the inconsistency concerning K_ds is the use of fresh granite in the laboratory studies, whereas tracers in the field experiments interact only with fracture fault gouge and to a lesser extent with cataclasite both being mineralogically very different (e.g. clay-bearing) from the intact wall rock.     

Response of anaerobic membrane bioreactor to the presence of nano-Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript>: reactor performance,supernatant characteristics,and microbial community

Considering the increasing incorporation of manufactured nano-material into consumer products, there is a concern about its potential impacts in biological wastewater treatment. In this study, the response of anaerobic sludge to the presence of Bi₂WO₆ nano-particles (NPs) was investigated in the anaerobic membrane bioreactor (AnMBR). As the concentration of Bi₂WO₆ in the reactor was controlled around 1 mg/L, there was no significant difference in effluent water quality or bacterial activities before and after NP exposure, partially due to the microbial-induced NP aggregation and stable complex formation. However, with the increasing dosage of Bi₂WO₆ from 5 to 40 mg/L, great influences on the AnMBR performance were observed, including the reduction of COD removal efficiency, inhibition of the mechanization step, increased production of soluble microbial products, and enhanced secretion of extracellular polymer substrates. Additional investigation with high-throughput sequencing was conducted, clearly demonstrating that Bi₂WO₆ NPs induced changes in the bacterial community.     

Decomposition of SF6 in an RF Plasma Environment

Abstract

Sulfur hexafluoride (SF₆)-contained gas is a common pollutant emitted during the etching process used in the semiconductor industry. This study demonstrated the application of radio-frequency (RF) plasma in the decomposition of SF₆. The decomposition fraction of SF₆ [η_SF6 (C_in–C_out)/C_in x 100%] and the mole fraction profile of the products were investigated as functions of input power and feed O₂/SF₆ ratio in an SiO₂ reactor. The species detected in both SF₆/Ar and SF₆/O₂/Ar RF plasmas were SiF₄, SO₂, F₂, SO₂F₂, SOF₂, SOF₄, S₂F₁₀, S₂OF₁₀, S₂O₂F₁₀, and SF₄. The results revealed that at 40 W, η_SF6 exceeded 99%, and the reaction products were almost all converted into stable compounds such as SiF₄, SO₂, and F₂ with or without the addition of oxygen. Sulfur oxyfluorides such as SO₂F₂, SOF₂, SOF₄, S₂OF₁₀, and S₂O₂F₁₀ were produced only below 40 W. The results of this work can be used to design a plasma/chemical system for online use in a series of a manufacturing process to treat SF₆-containing exhaust gases.     

Decomposition of SF6 in an RF plasma environment

Sulfur hexafluoride (SFd)-contained gas is a common pollutant emitted during the etching process used in the semiconductor industry. This study demonstrated the application of radio-frequency (RF) plasma in the decomposition of SF6. The decomposition fraction of SF6 [etaSF6 (C(in)-C(out))/C(in) x 100%] and the mole fraction profile of the products were investigated as functions of input power and feed O2/SF6 ratio in an SiO2 reactor. The species detected in both SF6/Ar and SF6/O2/ Ar RF plasmas were SiF4, SO2, Fe2, SO2F2, SOF2, SOF4, S2F10, S2OF10, S2O2F10, and SF4. The results revealed that at 40 W, etaSF6 exceeded 99%, and the reaction products were almost all converted into stable compounds such as SiF4, SO2, and F2 with or without the addition of oxygen. Sulfur oxyfluorides such as SO2F2, SOF2, SOF4, S2OF10, and S2O2F10 were produced only below 40 W. The results of this work can be used to design a plasma/chemical system for online use in a series of a manufacturing process to treat SF6-containing exhaust gases.     

Transformation kinetics of 6-methoxybenzoxazolin-2-one in soil

Wheat (Triticum aestivum L.) and other cereals produce allelochemicals as natural defense compounds against weeds, fungi, insects and soil-borne diseases. The main benzoxazinoid allelochemical of wheat is 2,4-dihydroxy-7-methoxy-1,4-benzoxazin-3-one (DIMBOA), bound as beta-glucoside and released upon plant injury. When leached from wheat to soil, DIMBOA is microbially transformed to 6-methoxy-benzoxazolin-2-one (MBOA). Exploiting benzoxazinoids and their degradation products as substitutes for synthetic pesticides depends on knowledge of transformation pathways and kinetics. In an MBOA degradation experiment at a concentration of 2400 nmol g(-1) soil, the previously identified transformation products 2-amino-7-methoxy-phenoxazin-3-one (AMPO) and 2-acetylamino-7-methoxy-phenoxazin-3-one (AAMPO) were quantified. Three different kinetic models were applied to MBOA transformation kinetics; single first-order (SFO), first-order multi-compartment, and double first-order in parallel. SFO proved to be adequate and was subsequently applied to the transformations of MBOA, AMPO and AAMPO. Degradation endpoints, expressed as degradation time (DT), were calculated for MBOA, AMPO and AAMPO to test whether the maximum values for synthetic pesticides set by the European Commission and the Danish Environmental Protection Agency were exceeded. DT(50) values for MBOA and AMPO were 5.4 d and 321.5 d, respectively, and DT(90) values were 18.1 d and 1068 d, respectively. The DT(50) value for AMPO exceeded the maximum value. The persistence, concentrations and toxicity of metabolites such as AMPO should be considered when breeding cereal crops with increased levels of benzoxazinoids.     

Organic carbon oxidation induced by large-scale shallow water intrusion into a vertical fracture zone at the Äspö Hard Rock Laboratory (Sweden)

Entrance tunnel construction at the Äspö Hard Rock Laboratory opened a conductive vertical fracture zone at a depth of 70 m on March 13, 1991. Three weeks later a sharp dilution front corresponding to 80% shallow water inflow to the originally saline fracture zone arrived at the entrance tunnel depth. In spite of this large inflow of shallow water, the fracture zone has remained persistently anoxic over a subsequent period. Results from gas sampling and ¹⁴C dating of dissolved organic and inorganic carbon conclusively show that recent organic carbon is being transported into the fracture zone and oxidized to carbon dioxide. These results are important when considering possible changes of redox status in the deep groundwater environment during construction and operation of a repository for spent nuclear fuel. Opening this fracture zone to large-scale surface water inflow adds reducing capacity in the form of organic carbon. This implies that the soil cover may provide important protection against input of dissolved oxygen to fractures being drained during the open phase of the repository.