O processo de adsorção vem sendo utilizado como uma técnica eficaz para a remoção de íons metálicos em efluentes. Neste trabalho são apresentados os estudos para avaliar da capacidade de adsorção de cobalto em caulinita, um adsorvente de baixo custo, visando à remoção deste íon de soluções aquosas. Foi analisada a área superficial específica (S) em 25 amostras de materiais preparadas de diferentes modos: caulinita, bentonita e carvão ativado e, misturas de caulinita-bentonita e caulinita-carvão ativado. Estas misturas foram preparadas pela adição de 10, 20, 30, 40 e 50% de carvão ativado ou bentonita à caulinita. As amostras de caulinita-carvão ativado e caulinita in natura foram calcinadas a 600 e 1000 °C por 4 horas. Foi escolhida para os testes de adsorção a mistura de caulinita com 10% de carvão ativado por apresentar a melhor relação custo benefício em relação à S. Os parâmetros de adsorção investigados nesta mistura foram: tempo de contato, pH, concentração inicial de soluto, competição iônica e força iônica. Verificou-se que o tempo de contato e o pH otimizados para o propósito do trabalho foram 30 min e pH 6. Nestas condições a eficiência de remoção do íon cobalto da solução foi superior a 80%. Verificou-se que a presença de íons Cr e Zn, bem como o aumento da força iônica diminuem a capacidade de adsorção do Co na mistura adsorvente. As isotermas de Langmuir e Freundlich apresentaram R2 iguais a 0,906 e 0,597, respectivamente. Os parâmetros determinados nestas isotermas indicaram um processo espontâneo, ou seja, energeticamente favorável, para a adsorção do Co nas condições e que foram realizadas este trabalho. / The adsorption process has been used as an efficient technique for the removal of metallic ions in industrial effluent. In this work, it is presented the studies to evaluate the adsorption capacity of cobalt in kaolinite, a low cost adsorbent, aiming at the removal of this ion from aqueous solutions. The specific surface area (S) was analyzed in 25 samples prepared in different ways: kaolinite, bentonite and activated carbon and, mixtures of kaolinite-bentonite and kaolinite-activated carbon. These mixtures were prepared by adding to kaolinite 10, 20, 30, 40 or 50% of activated charcoal or bentonite. Samples of kaolinite-activated charcoal mixture and raw kaolinite were also calcined at 600 and 1000 °C for 4 hours. The adsorption parameters investigated for these adsorbents were: contact time, pH, solute initial concentration, ionic competition and ionic strength. It was found that the optimized contact time and pH, for the purpose of this work, were 30 min and pH 6. Under these conditions the cobalt ion removal efficiency was greater than 80%. It was verified that the presence of Cr and Zn ions, as well as the increase in ionic strength caused a decrease in the adsorption capacity of Co in the adsorbent mixture. The Langmuir and Freundlich isotherms presented R2 equal to 0.906 and 0.597, respectively. The parameters determined by these isotherms indicated a spontaneous process, i.e., energetically favorable, for the adsorption of Co under the conditions that this work was carried out.

京都大学 / 新制・課程博士 / 博士(地球環境学) / 甲第23557号 / 地環博第214号 / 新制||地環||41(附属図書館) / 京都大学大学院地球環境学舎地球環境学専攻 / (主査)教授 勝見 武, 准教授 高井 敦史, 教授 木村 亮 / 学位規則第4条第1項該当 / Doctor of Global Environmental Studies / Kyoto University / DFAM

The compacted bentonites are used as buffer and backfill materials for engineering barriers for high-level nuclear waste repositories located underground. For this purpose, it is very important to evaluate the swelling characteristics of this clay. The swelling capacity is one of the most important properties of the bentonite clay. The swelling behaviour is due two mechanisms, the crystalline swelling and the osmotic swelling. These mechanisms produce an increase in the distance between the layers of montmorillonite which is one component of bentonite. The result of the swelling capacity is the swelling pressure. It has been studied in several investigations. The results of experimental tests have been collected and compared in this thesis, considering only the Na-dominant bentonite and sand and distilled water as test solution. The experimental tests show that there is only an unique relation between different bentonites in the Na-dominant bentonite and sand mixture swollen depending on its final dry density. Also, the relation between the swelling pressure and the clay void ratio shows the mechanism of the swelling pressure. On the other hand, a mechanistic model is used to predict the swelling pressure of fully saturated bentonite and sand mixture in distilled water. Firstly, it has been compared with the results of experimental tests and it should be pointed out that the model gives good predictions. In addition, the model has been used to make sensitivity analysis with different parameters of bentonite. The most important conclusions in this section show that the swelling pressure mainly depends on the distance among particles. Also, the sensitivity analyses indicate which parameters should be fitted more carefully for future studies to validate this model with different bentonites.

Majoriteten av de svenska betongdammarna uppfördes under 1900-talet och börjar därför närma sig sin uppskattade livslängd; 50-160 år. Några av dessa betongdammar används för att utvinna vattenkraft. Vattenkraft är Sveriges största energikälla och utgör ca 45% av vår totala elproduktion. Det ställs därför krav på att reparera samtliga betongdammar inför fortsatt förvaltning och för att bibehålla vår elproduktion. Betongdammar sammanlänkas med hjälp av dilatationsfogar. Dilatationsfogar hjälper betongkonstruktionen att stå emot de rörelser som sker under temperaturvariationer. På grund av dilatationsfogens placering i konstruktionen så är det väldigt svårt att genomföra och säkerställa en reparation. Inuti dilatationsfogens plåtfogbandskanal, i fallen där dilatationsfogen besitter två fogband, används bitumen som ett vattenstopp. Varje dilatationsfog som tätas med bitumen genererar en klimatpåverkan om ca 0,5 till 1,5 kg CO2-e per fog. Om fogbanden, inom dilatationsfogen, eller betongen i närheten av dessa skadas så kan därav bitumen lackas ut och följa med vattnet nedströms. Om detta sker så genereras en ökad miljö- och klimatpåverkan. Då nytt material måste produceras för att avlasta bitumenförlusten, fogbanden måste reparareras och bituminet släpps ut i naturen. Därför är det även av intresse att minimera eller helt ta bort det nuvarande vattenstoppet av bitumen.   I ett försök att minimera komplexiteten och trappa ned på bitumenanvändningen undersöks i detta examensarbete en reparation med hjälp av bentonitpellets. Reparationen sker via ett borrhål som sedan återfylls med bentonitpellets. Det finns två betongdammar i Sverige som använt sig utav denna metodik. Examensarbetet syftar således till att utvärdera hur denna reparationsmetodik står sig, dels längre fram i tiden, mot andra alternativ och framtida förväntningar om att eventuellt kunna ersätta bituminet mot andra material. Inledningsvis undersöktes bentonitpelletsens svällförmåga samt hur materialet ansamlar sig fukt. Detta genom nya framtagna metoder, som delvis, är baserade på tidigare standarder. Med hjälp utav dessa nya metoder kunde materialegenskaper också utvärderas mer långsiktigt. För att utvärdera långtidsperspektiv tilläts bentonitpelletsen att genomgå frostcykler i ett temperaturväxlingsskåp. Där fem dygn i temperaturväxlingsskåpet, uppskattningsvis, motsvarar de svenska klimatförhållanden i norra Sverige som förväntas inträffa under ett år. Bentonitpelletsen utvärderades sedan via samma testmetodik efter 1,5 och 3 år. Resultatet från bentonitpelletsens fuktupptagningsförmåga visade på en skillnad mellan de olika sorterna. Den rena Na-bentonitens fuktupptagningsförmåga står sig bättre med tiden, jämfört mot de kemiskt framställda Na-bentonitpelletserna. Resultaten från svällförmågan tyder dock på att samtliga bentonitpellets upplever en försämring allt eftersom. Om vattenkvoten är låg innan frostcykler så ökar bentonitpelletsens svällförmåga, på grund av att den uttorkas. Efter den första experimentella delen, och insamlade materialkunskaper från denna, uppfördes en miniatyrversion av en verklig dilatationsfog. Bakgrunden till detta genomförande var att man ville undersöka hur stort tryck som bentonitpelletsen klarar av att hålla tillbaka innan materialet går till brott. Vattenfalls konstruktörer uppförde testriggen och denna bestod främst utav plåt. En delad betongkub, med ett hål i mitten, placerades i konstruktionen. Hålet fylldes därefter upp av bentonitpellets. För att kunna åskåda hur materialet betedde sig under tryckförsök bekläddes konstruktionens ovandel med plexiglas. På denna plexiglasskiva installerades en manometer. Med hjälp av manometern, och ett konstant inflöde av vatten, kunde trycket i testriggen uppmätas och regleras. När den sedimenterade bentonitpelletsen går till brott så sjunker trycket på manometern. Resultatet från tryckförsöken visar på ett samband mellan bentonitpelletsens deklarerade svälltryck och det tillförda vattentrycket. Beroende på inflödet kan en reparation med bentonitpellets maximalt klara av att hålla tillbaka ett tryck motsvarande 5 till 12 höjdmeter av vatten – där det exakta värdet baseras på tiden den tillåtits att sedimentera. Dessa värden gäller för dess initiala förmåga. Hur materialet står emot vattentryck längre fram i tiden behöver fortsatt utvärdering. Baserat på studiens resultat så kommer inte den tidigare genomförda reparationen, i en av betongdammarna, att hålla – eftersom denna reparation överstiger 12 höjdmeter. Baserat på informationen som presenterats i denna rapport råder det en fortsatt osäkerhet om bentonit kan användas i betongkonstruktioner. Området kräver således fortsatt forskning för att säkerställa dess långsiktiga hållbarhet inom betongkonstruktionen. / Most of Sweden’s concrete dams were built during the 1900’s. Therefore, they are starting to reach the estimated end of their life-cycle; 50-160 years. Some of these concrete dams are used for hydroelectric purposes. Hydroelectric power is one of Sweden’s primary source for electricity, which approximately makes for 45% of our total electric production. Hence, the need for reparation is increasing for further management and maintaining our electricity production in these concrete dams. Concrete dams are linked by expansion joints. These expansion joints help to reduce the stress, during swelling and shrinking, in the concrete caused by temperature variation. Due to the placement of these expansions joint, they become difficult to repair as well as ensuring the success of a reparation. Inside the expansion joint there are dimbands. The dimbands can be sealed with bitumen to help their water stopping abilities. For every expansion joint that is sealed with bitumen the estimated climate impact is 0,5 to 1,5 kg CO2-e per joint. If the dimbands, inside the expansion joint, or the surrounding concrete gets damaged or breaks the bitumen varnishes downstream. This generates for an increased environmental and climate impact, due to the need for new bitumen and steel to fill and seal the leak and oils being released into the surroundings. Therefore, it is also of interest to reduce the usage of bitumen or remove it completely from these dimbands. To minimize the complexity and reduce the usage of bitumen this thesis will evaluate a reparation method with bentonite pellets. The reparation method consists of a borehole, which is then backfilled, with bentonite pellets. There are two concrete dams in Sweden which have used this method. Therefore, this thesis work also aims to evaluate how this reparation will last, regarding time, against other options and future expectations regarding the replacement of bitumen. To begin, the bentonite pellets where first evaluated based on their swelling capabilities and moisture absorption. These attributes were tested by new methods, which are partly based on previous standards. These new methods for the material properties also allowed for long-term evaluation. To evaluate how the bentonite pellets would react over time they were placed in a temperature change cabinet. Five days in these cabinets, were assumed to, correspond to the Northern Swedish climate changes that takes place over a year.  The bentonite pellets were then evaluated by the new methods after 1,5 and 3 years. The results, for both swelling and moisture absorption, showed a difference depending on the bentonite type. The pure Na-bentonite moisture absorption has better absorption capabilities over time, compared to chemically produced Na-bentonite. The results from swelling shows that, regardless of bentonite type, they all induce worse swelling capabilities over time. Although, if they begin thawing cycles at a lower water content their swelling capabilities increases due to the bentonite experiencing exsiccation.  After the first experimental part, and this newly gathered material knowledge, a miniature version of a concrete dams’ expansion joint were built. The background to this was to research how many altitude meters (mVp) the bentonite pellets could withstand before collapse. Vattenfalls engineers built the testrigg, expansion joint, which primarily consisted of steel. A splintered concrete cube, with a predrilled hole in the middle, was then placed in this steel cartridge. The hole was then filled with bentonite pellets. To see the sequence of the material reaction during pressure tests the testrigg had a top of plexiglass. A manometer was then attached to the plexiglass. The manometer, and a consistent flow of water, allowed for the pressure to be monitored and regulated. When the sedimented bentonite pellets collapses the pressure drops.  Results from the pressure tests show a correlation between the bentonite pellets declared swelling pressure and the externally supplied water pressure. Depending on the inflow the bentonite pellets can withstand a pressure between 5 to 12 meters of water height – where the exact value is given by the time it is allowed to sediment. These values only consider the initial expansion of the material. Further research is required to evaluate how much water pressure the material can withstand over time. Based on the findings of this study one of the previously repaired concrete dams’ bentonite seal will collapse in due time, since the reparation exceeds 12 meters in height. Based on the information provided in this thesis it is difficult to decide whether a bentonite seal will be beneficial for the concrete structure. Further research is required to ensure the sustainability of using bentonite inside concrete structures.

>Magister Scientiae - MSc / Studies involving the use of natural clays such as bentonite, montmorillonite and natural zeolite clinoptilolite in water treatment have been reported. Researchers suggested cost effective processes, such as ion-exchange and adsorption for the removal of heavy metals from waste waters by using naturally occurring and synthetic materials. The current study investigated application of natural adsorbents in brine treatment. Brines are hypersaline waters generated in power stations and mining industries rich in Mg2+, K+, Ca2+,Na+, so,': cr and traces of heavy metals, thus there is a need for these brines to be treated to recover potable water and remove problematic elements. Natural adsorbents have been successfully used in waste water treatment because of their high surface area and high adsorptive properties when they are conditioned with acid or base. The natural adsorbents used in this study were obtained from Ecca Holdings company (Cape bentonite mine) Western Cape in South Africa, comprising bentonite clay and natural zeolite (clinoptilolite) and another clinoptilolite sample was obtained from Turkey. These adsorbents were investigated in their natural and pretreated form for removal of toxic elements in brine water. The pretreatment was aimed at removing Na+, K+, Ca2+, Mg2+ from the clinoptilolite as well as the bentonite and replacing these cations with the H+ cation to activate the materials. The cation exchange capacity (CEC) of natural zeolite from South Africa was found to be 2.14 meq/ g, Turkish Clinoptilolite was 2.98 meq/ g while South African bentonite was 1.73 meq/g. at 25°C using ammonium acetate (pH 8.2) method. Characterization of these natural adsorbents was done prior to pretreatment and after the treatment. ICP-AES analysis was used for determination of toxic elements in brines before and after sorption. The morphology of clays was characterized by X-ray diffraction (XRD), Brunauer Emmett Teller (N2-BET) and Scanning electron microscopy (SEM) for confirmatory purposes and X-ray Fluorescent spectroscopy (XRF) was used for the composition analysis of the natural adsorbent. The results from batch experiments prior to pretreatment of the natural adsorbents showed that these natural adsorbents contained Mg2+, K+, Ca2+, Na+ in their structures as charge balancing cations, thus needed pretreatment to remove the cations. The natural adsorbents were pre-treated with 0.02M HCI. After the pretreatment of natural adsorbents it was possible to enhance the percentage removal of the major cations from brine, and the Na+ and Mg2+ removal achieved (86 % and 85% respectively) from brine was more than C02+ (70% ) the SC was the adsorbent one that gave highest removal of cations in the brines. Trace elements removal was high with Cu2+and Zn2+ being the highest of toxic elements in brine. The optimum contact for the toxic element removal was found to be 30 min for the Turkish clinoptilolite and 1 hr for the South African clinoptilolite and South African bentonite clay. Leaching of Ae+ and Si4+ during adsorption was also investigated and it was found that less than 1 ppm of A13+ and Si4+ were leached into the solution during adsorption experiments indicating that these materials were stable. The investigation of pH showed that natural adsorbents did not perform well at low pH of 4 and 6. The adsorbents were able to work efficiently at the natural pH of 8.52 of the brine solution. These results show that natural adsorbents hold great potential to remove cationic major components and selected heavy metal species from industrial brine wastewater. Heterogeneity of natural adsorbents samples, even when they have the same origin, could be a problem when wastewater treatment systems utilizing natural clinoptilolite and bentonite are planned to be developed. Therefore, it is very important to characterize the reserves fully in order to make them attractive in developing treatment technologies.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第17868号 / 工博第3777号 / 新制||工||1577(附属図書館) / 30688 / 京都大学大学院工学研究科社会基盤工学専攻 / (主査)教授 寶 馨, 教授 木村 亮, 准教授 立川 康人 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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In the Swedish concept for final disposal of spent nuclear fuel, referred to as KBS-3, a three-layered protection system is used. The system consists of a copper canister holding the spent nuclear fuel deposited 500 meters in a repository built in groundwater saturated granitic rock. The copper canisters are placed in deposition holes, buffered and backfilled by bentonite clay. One of the challenges associated with this system is the long-term exposure of the engineered barriers i.e. the canister including the spent fuel and the cast iron insert as well as the bentonite buffer to ionizing radiation. The possible effects of radiation on the materials in the engineered barriers have been studied not only by the Swedish Nuclear Fuel and Waste Co (SKB), but also by academia nationally and internationally. In this work, literature studies have been carried out to investigate whether all possible/potential effects of ionizing radiation from the spent nuclear fuel on the engineered barriers have been considered by SKB. Apart from a general summary of the relevant issues in chapter one, regions within the KBS-3 design where enhanced radiation may occur have been identified and the related radiation induced processes have been summarized in chapter two. These issues include effects of water-radiolysis on the spent fuel, the cast-iron insert and other ferrous materials, the copper shell and the bentonite buffer. Three types of possible damages have been identified: the microstructural defects in the ferrous materials by direct radiation, the radiation-induced microstructural alterations of the spent fuel and the bentonite and radiation-induced oxidation i.e. dissolution of the fuel and corrosion of the ferrous metals and the copper. The relevant SKB documents have been identified (in chapter 3) to be the SR-Site main report, the underlying Process reports and reports of FUD-programs. Apart from these documents, other SKB technical reports and open literature are used as basis for assessing whether all the issues mentioned in chapter two of this study have been considered by SKB.  According to the assessment, most of the significant issues mentioned in chapter two have been mentioned and discussed in the identified SKB documents. In the main safety assessment, i.e. the SR-Site project, the significance of most of the radiation processes has been based on dose levels expected at the different regions within the KBS-3 design. Irrespective of the assessments in SR-Site though, the current understanding of the relevant issues and plans for future research efforts summarized in FUD-programs reflect the research developments. However, the recent developments in understanding of radiation-induced effects on montmorillonite and the corrosion of copper in argon atmosphere need to be given due importance in coming FUD-programs. A separate investigation of radiation effects on FSW-joints may contribute to removal of the remaining uncertainties. In addition, mechanism involved in radiation-induced fuel dissolution and copper corrosion may require more research efforts than those planned. / Det svenska konceptet för slutförvar av använt kärnbränsle, KBS-3, består av tre barriärer som är tänkt att skydda omgivningen mot joniserande strålning från använt kärnbränsle. Systemet består av specialtillverkade kopparkapslar som innehåller det använda kärnbränslet. Kapslarna förvaras i deponeringshål 500 meter ner i berggrunden och är inneslutna i bentonitlera. En av frågeställningarna associerade med djupt geologiskt förvar av kärnbränsle är hur de konstruerade barriärna, alltså kopparhöljen som omsluter gjutjärninsatsen och det använda kärnbränslet samt bentonitleran, kan påverkas av joniserande strålning från det använda kärnbränslet. Möjliga strålningseffekter på de skyddande barriärna har studerats nationellt och internationellt. Syftet med denna studie var att utvärdera huruvida SKB har i sina säkerhetsanalyser av slutförvaret tagit tillräcklig hänsyn till effekter av joniserande strålning på de konstruerade barriärna. Studien består av tre kapitel där kapitel 1 utgör en generell sammanfattning av frågeställningar kopplade till KBS-3 barriärer. I kapitel 2 har områden i och omkring de konstruerade barriärna där joniserande strålning från använt kärnbränsle kan förekomma identifierats och möjliga strålningsinducerade processer i dessa områden sammanfattats. Tre typer av möjliga strålningsinducerade skador har identifierats: 1) strålningsinducerade mikrostrukturella defekter i metaller som förekommer i systemet, 2) strålningsinducerade mikrostrukturella förändringar i använt kärnbränsle och i bentonitleran samt 3) strålningsinducerad oxidation, dvs. upplösning av det använda kärnbränslet och korrosion av metaller som förekommer i systemet. SKB-dokumenten som identifierats (i kapital 3) som relevanta för utvärderingen i denna studie är följande: Säkerhetsanalysen (SR-Site), tekniska rapporter som ligger till grund för SR-Site och FUD-programmen. Enligt bedömningen i denna studie har SKB tagit hänsyn till de flesta relevanta frågeställningarna kopplade till strålningsinducerade effekterna på de konstruerade barriärna. I SR-Site har de flesta bedömningar relaterade till och om signifikansen hos de strålningsinducerade processerna baserats på doser och dosrater som förväntas förekomma i och omkring de konstruerade barriärna. Oavsett bedömningarna i SR-Site har dock de mest relevanta frågeställningarna tagits upp i FUD-programmen och framtida forskningsinsatser i enlighet med det som av SKB har uttryckts som behov av en utökad processförståelse. Dessa frågeställningar reflekterar väl de mest signifikanta utvecklingarna som rapporterats i öppna vetenskapliga studier om strålningsinducerade processer som kan förekomma i ett djupt geologiskt förvar för använt kärnbränsle. De senaste rapporterade observationerna om strålningseffekter på montmorillonit och kopperkorrosion i argonatmosfär måste dock tas upp och diskuteras i de kommande FUD-programmen. Separata studier av strålningseffekter på koppardelar som har behandlats med FSW-teknik rekommenderas. För att uppnå en bättre och djupare förståelse för de förekommande mekanismerna i strålningsinducerad upplösning av använt kärnbränsle krävs sannolikt mera forskningsinsatser än de planerade.

Svensk Kärnbränslehantering AB beslutade 2009 att bygga ett slutförvar av använt kärnbränsle i anslutning till kärnkraftverket i Forsmark. Tekniken för slutförvaret går ut på att omge kapslarna med bentonitlera som skydd mot vatten och bergsrörelser. Studier har dock påpekat att bentonitleran riskerar att kemiskt erodera om jonstyrkan (baskatjonerna) i grundvattnet som omsluter förvaringen blir för låg. Baskatjoner består av natrium, kalium, kalcium och magnesium. Dessa joner är viktiga för bland annat att neutralisera syror i mark och vatten. Förekomsten av dessa har sedan 90-talet minskat men kan påverkas av både ökad nederbördsmängd och ökad temperatur i vissa regioner. Baskatjoner kan lakas ur marken när pH minskar eller komma via deposition från nederbörden. Studien syftar till att utreda vilka faktorer som påverkar dels förekomsten av baskatjoner, dels dess trender i tre olika vattentyper i Forsmark: grunt grundvatten, sjövatten och vattendrag. Dataunderlaget för baskatjonerna kom från Svensk Kärnbränslehantering AB och nederbördsmängd och temperatur från Sveriges Meteorologiska och Hydrologiska Institut. De statistiska testerna som utfördes var främst Wilcoxon rank-sum test, Spearmans rangkorrelation, Mann-Kendalls trend- test och Sen’s slope-metoden. Analyserna har utförts med statistikprogramvaran R och de geografiska med QGIS. Resultatet visade att flera provtagningspunkter låg på en låg altitud och inom samma delavrinningsområde. Det fanns små skillnader i baskatjonskoncentrationen i de tre vattentyperna oberoende av berggrund, jordart eller terräng. Dock återfanns högst koncentration i de flesta fall i grunt grundvatten vilket kunde bero på höga halter natrium från havsvattnet samt kalksten i jordlagren. Korrelationerna var få varav sulfat var den som tydligast visade på ett förhållande med baskatjonerna i alla tre vattentyperna. Inte heller kunde en samvariation med temperatur och nederbörd statistiskt säkerställas. Trenderna visade på minskande koncentration av baskatjoner i grunt grundvatten och i sjövatten. Om dessa trender fortsätter utifrån studiens resultat kan det på sikt finnas en risk för erodering av bentonitleran runt kapslarna till följd av landhöjning och utbyte av det nuvarande bräckta grundvattnet. / The Swedish Nuclear Fuel and Waste Management Company decided in 2009 to build a final repository for spent nuclear fuel in connection with the nuclear power plant in Forsmark. The technology for the final repository involves surrounding the capsules with bentonite clay as protection against water and rock movements. However, studies have pointed out that the bentonite clay is at risk of chemically eroding if the ionic strength of the groundwater surrounding the repository becomes too low. Base cations consist of sodium, potassium, calcium, and magnesium. These ions are important for neutralizing acids in soil and water. The occurrence of these has decreased since the 90s but can be affected by both increased rainfall and increased temperature in certain regions. Base cations can further be leached from the soil when the pH decreases or come via deposition from precipitation. This study aims to investigate which factors affect the presence of base cations and their trends in three different types of water in Forsmark: shallow groundwater, lake water and stream water. The data set for the base cations came from the Swedish Nuclear Fuel and Waste Management Company and rainfall and temperature from the Swedish Meteorological and Hydrological Institute. The statistical tests performed were mainly the Wilcoxon rank-sum test, Spearman's rank correlation, Mann-Kendall's trend test and Sen's slope method. The analyzes have been performed with the statistical software R and the geographic ones with QGIS. The result showed that several sampling points were at a low altitude and within the same sub-catchment. There were small differences in base cation concentration in the three water types regardless of bedrock, soil type or terrain. However, the highest concentration was found in most cases in shallow groundwater, which could be due to high levels of sodium from seawater and limestone in the soil layers. The correlations were few, of which sulfate was the one that most clearly showed a relationship with the base cations in all three water types. Nor could a co-variation with temperature and precipitation be statistically ensured. The trends showed a decreasing concentration of base cations in shallow groundwater and in lake water. If the trends continue based on the results, in the long term there may be a risk of erosion of the bentonite clay that surrounds the capsules because of land uplift and replacement of the current brackish ground water.

Canada is in the process of implementing a Deep Geologic Repository (DGR) to dispose of used nuclear waste. Adsorption behaviour of both Se(-II) and Tc(IV) onto granite, shale, limestone, illite, and MX-80 bentonite has been elucidated. Se(-II) adsorption onto granite and MX-80 bentonite displays a decrease in Rd with an increase in solution pH. Se(-II) adsorption onto granite decreases with an increase in solution ionic strength. Se(-II) adsorption onto MX-80 bentonite does not return evidence which supports an apparent effect due to the ionic strength. Tc(IV) adsorption onto shale, limestone, illite, and MX-80 bentonite remains constant as the solution pH increases. Ionic strength does not affect the magnitude of Tc(IV) adsorption across the adsorbents, however an increase in ionic strength accelerates Tc(IV) adsorption. Se(-II) surface complexation models are best simulated with the following surface complexes: ≡Feldspar_sSe-, ≡Biotite_sOH2HSe, ≡Albite_sSe-, ≡Montmorillonite_sSe-, and ≡Montmorillonite_sOH2HSe. Tc(IV) adsorption is best simulated with: ≡Biotite_sOTcO(OH), ≡Quartz_sOTcO(OH), (≡Feldspar_sOH)2TcO(OH)-, ≡Montmorillonite_sOTcO(OH), (≡Albite_sOH)2TcO(OH)-, ≡Illite_sOTcO(OH), and ≡Chlorite_sOTcO(OH). Se(-II) adsorption onto granite and MX-80 bentonite in CR-10 solution returns Rd values of (1.80 ± 0.10) m3∙kg-1 and (0.47 ± 0.38) m3∙kg-1, respectively. Tc(IV) adsorption onto granite and MX-80 bentonite in CR-10 solution returned Rd values of (1.47 ± 0.25) m3∙kg-1 and (2.19 ± 0.33) m3∙kg-1, respectively. Tc(IV) adsorption onto shale, limestone, illite, and MX-80 bentonite in SR-270-PW solution returned Rd values of (0.16 ± 0.10) m3∙kg-1, (0.44 ± 0.21) m3∙kg-1, (1.86 ± 0.44) m3∙kg-1, and (0.23 ± 0.10) m3∙kg-1, respectively. This thesis will further deepen the understanding of Se(-II) and Tc(IV) adsorption. / Thesis / Doctor of Philosophy (PhD) / Determining the adsorption of Se(-II) and Tc(IV) onto granite, shale, limestone, illite, and MX-80 bentonite is beneficial to choosing a location within Canada to locate a used nuclear fuel repository. This thesis aims to quantify the adsorption behaviour of Se(-II) and Tc(IV) in Ca-Na-Cl and Na-Ca-Cl solutions with respect to a varying solution ionic strength and pH. Quantification of the adsorption was accomplished with adsorption experiments used in conjunction with geochemical simulations. New simulated surfaces specific to granite, shale, and MX-80 bentonite have been developed to complete these simulations. A final achievement was quantifying the adsorption of Se(-II) and Tc(IV) in groundwater representative solutions specific to locations considered for the used nuclear fuel repository.