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Modelling long-term redox processes and oxygen scavenging in fractured crystalline rocks
KTH, School of Chemical Science and Engineering (CHE), Chemical Engineering and Technology.
2007 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [sv]

Under de senaste decennierna har i många länder, inkluderat Sverige, långt gångna planer utvecklats för ett djupförvar av högaktivt kärnavfall. Som en del i det svenska förvarskonceptet skall avfallet inneslutas i kopparkapslar som omslutes av återfyllnadsmaterial med mycket låg genomsläpplighet av vatten. Dessutom skall kapslarna förläggas på ca 500 meters djup i granitberggrunden, vilken fungerar som en naturlig barriär för transport av radionuklider till markytan. Dessa naturliga och konstruerade barriärer väljs och utformas så att förvarets funktion kan säkras under hundra tusentals år. En viktig fråga för säkerhetsanalysen för ett sådant förvar är utvecklingen av redoxförhållandena över långa tider. Korrosionen av kopparkapslarna går fortare under oxiderande förhållanden och rörligheten hos frisläppta radionuklider ökar.

I den första delen av avhandlingen studerades förmågan hos berget att upprätthålla reducerande förhållanden på förvarsdjupet över långa tider. En modellstruktur har utvecklats med målet att ta hänsyn till alla processer som bedömts viktiga för utarmning av inträngande syre från markytan över långa tider. Förenklingar introducerades så att transparenta analytiska lösningar kunde erhållas som förenklar utvärdering av resultat och tillåter identifiering av osäkra parametrar. Komplexa system löstes numeriskt för fall då analytiska lösningar ej kunde erhållas, samt för att validera förenklingar som ligger till grund för de analytiska lösningarna. Resultat redovisades för rådande förhållanden samt för förhållanden som bedömdes rimliga under smältfasen av en glaciationsperiod. Det visade sig att de hydrauliska egenskaperna har stor påverkan på inträngningsdjupet av syre längs flödesvägar i berget. Kvoten mellan den flödesvätta ytan och flödet visade sig vara en viktig parameter som bestämmer omfattningen av interaktionen mellan löst syre i grundvattnet och reducerande mineral i berget.

Resultaten visar att för korta tider, beroende på mängd reducerande mineral och reaktionshastighet, kan kemisk reaktionskinetik bestämma förbrukningshastigheten av syre. För längre tider begränsas förbrukningen av intern diffusion i stora partiklar och bergmatrisen. Det visade sig att hänsyn måste tas till många osäkerheter för att kunna göra tillförlitliga kvantitativa uppskattningar av omfattningen av syreinträngningen.

I den andra delen av avhandlingen undersöktes konsekvenserna av inträngande syre på korrosion av kopparkapslarna. En mekanism föreslogs också för bildande av sulfid nära kapseln. Sulfid är en annan korrodent som kan bildas mikrobiellt i reducerande miljöer från sulfat och en organisk reduktant såsom metan. Beräkningarna visar att mer än 50 kg av koppar inte är sannolikt att korrodera över en miljon år.

Abstract [en]

Advanced plans for the construction of a deep geological repository for highly radioactive wastes from nuclear power plants have evolved during the past decades in many countries including Sweden. As part of the Swedish concept, the waste is to be encapsulated in canisters surrounded by low permeability backfill material. The copper canisters will be deposited at around 500 metres depth in granitic rock, which acts as a natural barrier for the transport of radionuclides to the ground surface. These natural and engineered barriers are chosen and designed to ensure the safety of the repository over hundred of thousands of years. One issue of interest for the safety assessment of such a repository is the redox evolution over long times. An oxidising environment would enhance the corrosion of the copper canisters, and increases the mobility of any released radionuclides.

In the first part of the present thesis, the ability of the host rock to ensure a reducing environment at repository depth over long times was studied. A model framework was developed with the aim to capture all processes that are deemed to be important for the scavenging of intruding oxygen from the ground surface over long times. Simplifications allowing for analytical solutions were introduced for transparency reasons so that evaluation of results is straight-forward, and so that uncertain parameter values easily can be adjusted. More complex systems were solved numerically for cases when the analytical simplifications are not applicable, and to validate the simplifications underlying the analytical solutions. Results were presented for prevailing present day conditions as well as for conditions deemed to be likely during the melting phase of a period of glaciation. It was shown that the hydraulic properties have a great influence on the oxygen intrusion length downstream along flow-paths in the rock. An important parameter that determines the extent of interaction between the dissolved oxygen and the reducing minerals in the rock was shown to be the flow-wetted surface to flow-rate ratio.

The results show that for an initial period of time, depending on the amount of reducing minerals and reaction rates, chemical reaction kinetics may control the rate of the overall depletion of oxygen. For longer times, internal diffusion resistance in large particles or in the rock matrix become rate limiting for the overall process. It was found that there are many uncertainties that have to be considered in order to make reliable quantitative predictions on the extent of oxygen intrusion.

In the second part of the thesis, the impact of intruding oxygen on the corrosion of the copper canisters was explored. Also, a mechanism for the production of sulphide close to the deposition holes was studied. Sulphide is another corroding agent that may be produced microbially in a reducing environment from sulphate in the presence of organic reductants such as methane. From calculation results it was found that corrosion of more than 50 kg of copper is not likely over a period of one million years

Place, publisher, year, edition, pages
Stockholm: KTH , 2007. , viii, 81 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2007:60
Keyword [en]
Redox chemistry, hydrogeological model, groundwater chemistry, mineral interaction
National Category
Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-4491ISBN: 978-91-7178-756-9 (print)OAI: oai:DiVA.org:kth-4491DiVA: diva2:12531
Public defence
2007-10-15, F3, Lindstedtsvägen 26, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20100818Available from: 2007-09-19 Created: 2007-09-19 Last updated: 2010-08-18Bibliographically approved
List of papers
1. Long term redox evolution in granitic rocks: modelling the redox front propagation in the rock matrix
Open this publication in new window or tab >>Long term redox evolution in granitic rocks: modelling the redox front propagation in the rock matrix
2007 (English)In: Applied Geochemistry, ISSN 0883-2927, E-ISSN 1872-9134, Vol. 22, no 11, 2381-2396 p.Article in journal (Refereed) Published
Abstract [en]

Redox evolution in groundwaters in granitic rocks is considered to be largely due to reactions between dissolved species in the groundwater and minerals that line the walls of fractures in the bedrock. In a long term perspective, however, the reducing fracture minerals eventually become depleted. In this situation, O-2 diffuses out from the fractures and reacts with reducing species present in the porous rock matrix. The rock matrix contains the main reservoir of reducing capacity in the form of reducing minerals such as biotite. The aim of this work is to emphasize the coupled transport and reaction processes deemed important for the redox evolution in recharge groundwaters over long times, i.e. thousands of years. Results indicate that matrix diffusion of O-2 becomes limiting for the redox reactions rapidly after the reducing capacity of the fractures is depleted. The numerical model results are verified by simplified cases solved analytically. From the analytical solutions insights also are gained into when different mechanisms dominate the overall reaction, which is more difficult if only numerical results are available.

Keyword
Groundwater; Minerals; Numerical methods; Redox reactions; Granitic rocks; Redox evolution; Redox front propagation; Rock matrix; Rocks; biotite; granite; groundwater; numerical model; oxygen; recharge; redox conditions; transport process
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-7488 (URN)10.1016/j.apgeochem.2007.05.007 (DOI)000251201900009 ()2-s2.0-35348958339 (Scopus ID)
Note
QC 20100818. Uppdaterad från In press till Published 20100818.Available from: 2007-09-19 Created: 2007-09-19 Last updated: 2017-12-14Bibliographically approved
2. Long-term oxygen depletion from infiltrating groundwaters: model development and application to intra-glaciation and glaciation conditions
Open this publication in new window or tab >>Long-term oxygen depletion from infiltrating groundwaters: model development and application to intra-glaciation and glaciation conditions
2008 (English)In: Journal of Contaminant Hydrology, ISSN 0169-7722, E-ISSN 1873-6009, Vol. 100, no 1-2, 72-89 p.Article in journal (Refereed) Published
Abstract [en]

Processes that control the redox conditions in deep groundwaters have been studied. The understanding of such processes in a long-term perspective is important for the safety assessment of a deep geological repository for high-level nuclear waste. An oxidising environment at the depth of the repository would increase the solubility and mobility of many radionuclides, and increase the potential risk for radioactive contamination at the ground surface. Proposed repository concepts also include engineered barriers such as copper canisters, the corrosion of which increases considerably in an oxidising environment compared to prevailing reducing conditions. Swedish granitic rocks are typically relatively sparsely fractured and are best treated as a dual-porosity medium with fast flowing channels through fractures in the rock with a surrounding porous matrix, the pores of which are accessible from the fracture by diffusive transport. Highly simplified problems have been explored with the aim to gain understanding of the underlying transport processes, thermodynamics and chemical reaction kinetics. The degree of complexity is increased successively, and mechanisms and processes identified as of key importance are included in a model framework. For highly complex models, analytical expressions are riot fully capable of describing the processes involved, and in such cases the solutions are obtained by numerical calculations. Deep in the rock the main source for reducing capacity is identified as reducing minerals. Such minerals are found inside the porous rock matrix and as infill particles or coatings in fractures in the rock. The model formulation also allows for different flow modes such as flow along discrete fractures in sparsely fractured rocks and along flowpaths in a fracture network. The scavenging of oxygen is exemplified for these cases as well as for more comprehensive applications, including glaciation considerations. Results show that chemical reaction kinetics control the scavenging of oxygen during a relatively short time with respect to the lifetime of the repository. For longer times the scavenging of oxygen is controlled by transport processes in the porous rock matrix. The penetration depth of oxygen along the flowpath depends largely on the hydraulic properties, which may vary significantly between different locations and situations. The results indicate that oxygen, in the absence of easily degradable organic matter, may reach long distances along a flow path during the life-time of the repository (hundreds to thousands of metres in a million years depending on e.g. hydraulic properties of the flow path and the availability of reducing capacity). However, large uncertainties regarding key input parameters exist leading to the conclusion that the results from the model must be treated with caution pending more accurate and validated data. Ongoing and planned experiments are expected to reduce these uncertainties, which are required in order to make more reliable predictions for a safety assessment of a nuclear waste repository.

Keyword
Groundwater chemistry; Mineral interaction; Model; Redox front propagation; Association reactions; Chemical reactions; Copper; Elastic moduli; Fluid mechanics; Fracture; Fracture fixation; Free radical polymerization; Garnets; Geological repositories; Glacial geology; Groundwater; Hydraulics; Hydrogeology; Intersections; Matrix algebra; Mineralogy; Minerals; Newtonian flow; Nonmetals; Nuclear physics; Numerical analysis; Organic compounds; Oxygen; Petroleum deposits; Petroleum reservoirs; Radioactive wastes; Radioactivity; Radioisotopes; Reaction kinetics; Risk assessment; Rocks; Silicate minerals; Sulfate minerals; Underground reservoirs; Analytical expressions; Chemical reaction kinetics; Complex modeling; Copper canisters; Deep geological repository; Deep groundwaters; Degree of complexity; Diffusive transport; Discrete fractures; Dual-porosity; Engineered barriers; Flow modes; Flow paths; Flow-paths; Fracture networks; Fractured rocks; Granitic rocks; Ground surfaces; Hydraulic properties; Key input; Life-time; Long distances; Long term perspective; Model development; Model formulation; Model framework; Nuclear waste; Nuclear waste repositories; Numerical calculations; Organic matter (OM); Oxygen depletion; Penetration depths; Porous matrixes; Porous rocks; Potential risks; Radioactive contamination; Redox conditions; Reducing capacity; Reducing conditions; Safety assessments; Short time; Transport processes; Process control; copper; ground water; mineral; organic matter; oxygen; radioisotope; sodium chlorite; chemical reaction; corrosion; glaciation; groundwater; infill; infiltration; kinetics; modeling; numerical method; oxygen; porous medium; radioactive waste; radionuclide; redox conditions; risk assessment; safety; thermodynamics; water chemistry; article; calculation; chemical reaction; conceptual framework; corrosion; depletion; diffusion; dissolution; glaciation; granite; kinetics; mathematical model; oxidation reduction reaction; priority journal; radioactive contamination; rock; thermodynamics; validation process; water contamination; water flow; water supply; Fresh Water; Geologic Sediments; Ice Cover; Models, Theoretical; Oxidation-Reduction; Oxygen; Porosity; Radioactive Waste; Refuse Disposal; Solubility; Sweden; Water Movements
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-7489 (URN)10.1016/j.jconhyd.2008.05.010 (DOI)000259387600007 ()18644316 (PubMedID)2-s2.0-48349117845 (Scopus ID)
Note
QC 20100818. Uppdaterad från Submitted till Published 20100818.Available from: 2007-09-19 Created: 2007-09-19 Last updated: 2017-12-14Bibliographically approved
3. Corrosion of copper canisters through microbially mediated sulphate reduction
Open this publication in new window or tab >>Corrosion of copper canisters through microbially mediated sulphate reduction
2006 (English)In: Scientific Basis for Nuclear Waste Management XXIX / [ed] VanIseghem P., 2006, Vol. 932, 861-868 p.Conference paper, Published paper (Refereed)
Abstract [en]

A biogeochemical model was developed with an aim to illustrate the transport and reaction processes that may be involved in copper canister corrosion by sulphide in a deep repository for nuclear waste. Sulphide concentrations in the groundwaters in Sweden are relatively low and are generally considered to be of little importance for corrosion of the copper canisters. Sulphate, however, is present in relatively large amounts (50-700 mg/L) and may be reduced to sulphide by reaction with organic matter. Mediated by microbes, the reduction rate may be increased considerably compared to abiotic reduction. Microbially mediated sulphate reduction occurs in many natural environments, provided that reactive organic matter is available. Groundwater analyses indicate relatively high concentrations of dissolved methane (up to 16 mg/L) which thermodynamically is a suitable reducing agent. This processes could occur in fractures in the bedrock provided that substrates are continuously supplied and that there is a sink for the reaction products. In the repository, the copper canisters may provide a sink for sulphide that yields a favourable environment for the microbe population. The model domain includes a canister with surrounding backfill material intersected by a hydraulically conductive fracture. Transport of substrates and reaction products in the fracture and backfill as well as microbially mediated reaction at the fracture opening is included in the model. Results indicate that microbially produced sulphide could potentially contribute to canister corrosion.

Series
Materials Research Society Symposium Proceedings, ISSN 0272-9172 ; 932
Keyword
Groundwater; Microorganisms; Reaction kinetics; Reduction; Sulfur compounds; Transport properties; Copper canisters; Microbially mediated sulphate reduction; Reaction products; Reducing agent; Copper corrosion
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-7490 (URN)000239003700102 ()2-s2.0-33746101447 (Scopus ID)1-55899-889-6 (ISBN)
Conference
29th International Symposium on the Scientific Basis for Nuclear Waste Management, Ghent, Belgium, Sep. 12-16, 2005, Mat Res Soc
Note
QC 20100818Available from: 2007-09-19 Created: 2007-09-19 Last updated: 2011-10-05Bibliographically approved
4. Two-dimensional Dynamic Model of a Copper Sulphide Ore Bed
Open this publication in new window or tab >>Two-dimensional Dynamic Model of a Copper Sulphide Ore Bed
2003 (English)In: Hydrometallurgy, ISSN 0304-386X, E-ISSN 1879-1158, Vol. 71, 67-74 p.Article in journal (Refereed) Published
Abstract [en]

A two-dimensional dynamic model for bioleaching of secondary copper minerals from a pile has been developed. In the model. aeration of the pile is considered to be due to natural convection caused by the density gradient in the air within the bed. The rate of sulphide mineral dissolution is modelled according to the unreacted core model. The transport of ferric ions from the particle surface to the reaction zone is calculated considering film diffusion, diffusion within the particle and reaction kinetics. The rate of oxidation of the ferrous ion by bacteria attached to the ore surface is modelled using the Michaelis-Menten relationship. The influences of temperature, dissolved ferric iron and dissolved oxygen in the leaching solution are considered in the kinetic formulation. The set of partial differential equations is solved using the FEMLAB(R) software. The model was used to study the influence of process variables on copper recovery in the bed with time. This model is a useful tool to aid the design and optimisation of industrial operations.

Keyword
copper leaching, modelling, dynamic model, bacterial leaching
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-7491 (URN)000186357900009 ()
Note
QC 20110204 Konferensbidrag till: International Biohydeometallurgy Symposium OURO PRETO, BRAZIL, SEP 16-19, 2001 Available from: 2007-09-19 Created: 2007-09-19 Last updated: 2017-12-14Bibliographically approved

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