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京都大学 / 0048 / 新制・課程博士 / 博士(地球環境学) / 甲第22815号 / 地環博第202号 / 新制||地環||39(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, 教授 木村 亮, 准教授 高井 敦史 / 学位規則第4条第1項該当 / Doctor of Global Environmental Studies / Kyoto University / DFAM

<p>Predmet izučavanja ove disertacije obuhvatio je ispitivanje uticaja starenja stabilizovanog/solidifikovanog&nbsp; (S/S)&nbsp; sedimenta&nbsp; zagađenog te&scaron;kim metalima i arsenom, i efikasnost primenjenih imobilizacionih agenasa (Portland cement, kreč, leteći pepeo, zeolit, montmorilonit i kaolinit) nakon dugogodi&scaron;njeg starenja S/S sme&scaron;a. Shodno tome ispitana je dugoročna stabilnost i postojanost dobijenih S/S sme&scaron;a sa aspekta izluživanja pomenutih metala, promene u minerolo&scaron;kim i strukturnim karakteristikama, kao i uticaj su&scaron;enja i zrenja materijala na pomenute parametre. Istraživanja u disertaciji obuhvatila su dve faze. Prva faza imala je za cilj procenu rizika i&nbsp; početnu karakterizaciju netretiranog sedimenta primenom analize pseudo-ukupnog sadržaja metala kojom je utvrđen sadržaj metala u početnom uzorku sedimenta. Druga faza uključivala je primenu tretmana stabilizacije i solidifikacije na kontaminirani sediment dodavanjem različitih imobilizacionih agenasa. Analize su se vr&scaron;ile nakon 7 i 28 dana od primenjenog S/S tretmana, kao i nakon 7 godina sa ciljem da se utvrdi uticaj vi&scaron;egodi&scaron;njeg starenja i zrenja monolitnih sme&scaron;a na mobilnost metala i strukturne karakteristike sme&scaron;a. U&nbsp; okviru&nbsp; druge faze istraživanja ispitana je toksičnost S/S sme&scaron;a primenom DIN i TCLP testova izluživanja, dok je test toksičnosti primenom bakterija Vibrio Fischeri&nbsp; doprineo u&nbsp; sagledavanju&nbsp; procene rizika S/S sme&scaron;a po organizme. Nakon 28 dana i 7 godina kori&scaron;ćena je sekvencijalna ekstrakcija za&nbsp; određivanje mobilnost i biodostupnost metala u monolitnim matriksima. U cilju&nbsp; utvrđivanja mikrostukturnih karakteristika sedimenta primenjena je rendgenska difrakciona analiza (XRD) za ispitivanje kristalnih struktura&nbsp; S/S sme&scaron;a i detekciju mineralnog sastava. Pomoću elektronskog mikroskopa i energodisperzivnog detektora&nbsp; sa X-zrakom (SEM/EDS) određena je kvalitativna i kvantitativna distribucija metala i&nbsp; drugih elemenata od interesa, dok se za identifikaciju formiranih funkcionalnih grupa u monolitnim sme&scaron;ama primenio spektrometar sa infracrvenom Furijeovom transformacijom (FTIR). Na osnovu dobijenih rezultata zaključeno je da se mobilnost te&scaron;kih metala i arsena značajno smanjila nakon 7 godina za sme&scaron;e tretirane cementom (C5), krečom (L10), letećim pepelom (F30) i kaolinitom&nbsp; (K20), a efekat stabilizacije je pokazan transformacijom metala iz direktne toksične frakcije u&nbsp; stabilnije oblike. Sme&scaron;e C5 i K20 ispoljavaju&nbsp; najmanje toksične efekate od svih sme&scaron;a, jer je procenat inhibicije&nbsp; na&nbsp; bioluminiscentnim&nbsp; bakterijama manji od 13%, dok je u pogledu izdržljivosti monolitna sme&scaron;a C5 pokazala najveću pritisnu čvrstoću od svih sme&scaron;a. Dobijeni podaci su neprocenjivi za dobijanje stvarnog uvida u dugoročnu efikasnost&nbsp; primenjenog&nbsp; tretmana i mogućnost bezbedne upotrebe ili odlaganja dobijenih S/S sme&scaron;a sa aspekta za&scaron;tite životne sredine, kao i ekonomski i ekolo&scaron;ki prihvatljivog upravljanja opasnim otpadom.</p> / <p>The subject of study in this dissertation included to investigate the&nbsp; effect&nbsp; of&nbsp; aging&nbsp; of&nbsp; stabilized/solidified&nbsp; (S/S)&nbsp; sediment&nbsp; contaminated with&nbsp; heavy&nbsp; metals&nbsp; and&nbsp; arsenic,&nbsp; and&nbsp; the&nbsp; efficacy&nbsp; of&nbsp; the&nbsp; applied immobilization&nbsp; agent&nbsp; (Portland&nbsp; cement,&nbsp; lime,&nbsp; fly&nbsp; ash,&nbsp; zeolite, montmorillonite and kaolinite) after long-term aging of S/S mixtures. The<br />long&nbsp; -&nbsp; term stability and stability of the obtained S/S mixtures from the aspect of leaching of the mentioned metals, changes in mineralogical and structural characteristics,&nbsp; as&nbsp; well&nbsp; as&nbsp; the&nbsp; influence&nbsp; of&nbsp; drying&nbsp; and maturation of the material on the mentioned parameters were examined. The&nbsp; research&nbsp; in&nbsp; the&nbsp; dissertation&nbsp; included&nbsp; two&nbsp; phases.&nbsp; The&nbsp; first&nbsp; phase aimed&nbsp; at&nbsp; risk&nbsp; assessment&nbsp; and&nbsp; initial characterization&nbsp; of&nbsp; untreated sediment using pseudo-total metal content analysis which determined the<br />metal content in the initial sediment sample.&nbsp; The second phase involved applying&nbsp; stabilization&nbsp; and&nbsp; solidification&nbsp; treatments&nbsp; to&nbsp; the&nbsp; contaminated sediment&nbsp; by&nbsp; adding&nbsp; various&nbsp; immobilizing&nbsp; agents.&nbsp; The&nbsp; analyzes&nbsp; were performed after 7 and 28&nbsp; days from the applied S/S treatment, as well as after 7 years in order to determine the influence of perennial aging and maturation&nbsp; of&nbsp; monolithic&nbsp; mixtures&nbsp; on&nbsp; metal&nbsp; mobility&nbsp; and&nbsp; structural characteristics&nbsp; of&nbsp; the&nbsp; mixtures.&nbsp; In&nbsp; the&nbsp; second&nbsp; phase&nbsp; of&nbsp; the&nbsp; study,&nbsp; the toxicity&nbsp; of&nbsp; S/S&nbsp; mixtures&nbsp; using&nbsp; DIN&nbsp; and&nbsp; TCLP&nbsp; leaching&nbsp; tests&nbsp; was examined, while&nbsp; the&nbsp; toxicity&nbsp; test&nbsp; using&nbsp; bacteria&nbsp; Vibrio&nbsp; Fischeri contributed&nbsp; to&nbsp; the assessment&nbsp; of&nbsp; the&nbsp; risk&nbsp; of&nbsp; S/S&nbsp; mixtures&nbsp; to&nbsp; organisms. After&nbsp; 28 days&nbsp; and&nbsp; 7 years,&nbsp; sequential extraction was&nbsp; used to&nbsp; determine the mobility and bioavailability of metals in monolithic matrices. In order to&nbsp; determine&nbsp; the&nbsp; microstructural&nbsp; characteristics&nbsp; of&nbsp; the&nbsp; sediment,&nbsp; x-ray diffraction analysis (XRD) was used to examine the crystal structures of&nbsp; S/S mixtures and&nbsp; to detect the mineral composition.&nbsp; The qualitative and quantitative&nbsp; distribution&nbsp; of&nbsp; metals&nbsp; and&nbsp; other&nbsp; elements&nbsp; of&nbsp; interest&nbsp; was determined using an electron microscope and an energy-dispersive X-ray detector&nbsp; (SEM&nbsp; /&nbsp; EDS),&nbsp; while&nbsp; an&nbsp; infrared&nbsp; Fourier&nbsp; transform spectrometer(FTIR) was used to identify the formed functional groups in monolithic mixtures. Based on the obtained results, it was concluded that the mobility of heavy metals and arsenic decreased significantly after 7 years&nbsp; for&nbsp; mixtures&nbsp; treated&nbsp; with&nbsp; cement&nbsp; (C5),&nbsp; lime&nbsp; (L10),&nbsp; fly ash&nbsp; (F30) and&nbsp; kaolinite&nbsp; (K20),&nbsp; and&nbsp; the&nbsp; stabilization&nbsp; effect&nbsp; was&nbsp; shown&nbsp; by transformation&nbsp; of&nbsp; metals&nbsp; from&nbsp; direct&nbsp; toxic&nbsp; fractions&nbsp; into&nbsp; more&nbsp; stable forms. Mixtures&nbsp; C5&nbsp; and&nbsp; K20&nbsp; exhibit&nbsp; the&nbsp; least&nbsp; toxic&nbsp; effects&nbsp; of&nbsp; all mixtures, because the percentage of inhibition on bioluminescent bacteria is less than 13%, while in terms of durability, the monolithic mixture C5 showed&nbsp; the&nbsp; highest&nbsp; compressive&nbsp; strength&nbsp; of&nbsp; all&nbsp; mixtures.&nbsp; The&nbsp; obtained data are invaluable for gaining real insight into the long-term efficiency of the applied treatment and the possibility of safe use&nbsp; or disposal of the obtained&nbsp; S/S&nbsp; mixtures&nbsp; from&nbsp; the&nbsp; aspect&nbsp; of&nbsp; environmental&nbsp; protection,&nbsp; as well&nbsp; as&nbsp; economically&nbsp; and&nbsp; ecologically&nbsp; acceptable&nbsp; hazardous&nbsp; waste management.</p>

Arsenik är en naturligt förekommande halvmetall som orsakar stora hälsoproblem genom exponering t.ex. via dricksvatten. På grund av arseniks negativa effekter på människors hälsa sänktes den tillåtna gränsen i dricksvatten från 50 μg/l till 10 μg/l 2003 av WHO. Arsenik förekommer i huvudsak i två oorganiska former, arsenat (AsO43-) och arsenit (AsO33-), där arsenit är en betydligt mer mobil och toxisk form. Vilken form som dominerar påverkas i första hand av redoxförhållanden men även av pH. Reduktion från arsenat till arsenit är gynnsamma vid lägre pH och vid syrefria (reducerade) förhållanden. I Sverige har tidigare användning av arsenik, t.ex. vid impregneringsanläggningar, orsakat föroreningar som än idag ligger kvar. I Hjältevad i Eksjö kommun drev Televerket under 1940- till 1980-talet en impregneringsanläggning för telefonstolpar. Impregneringsvätska, innehållande bland annat arsenik, kunde spridas inom området till största del på grund av en tank som började läcka under 1960-talet. En omfattande sanering med jordtvätt genomfördes 1997. Senare kontroller har dock påvisat stadigt ökade halter. Med anledning av de ökade halterna har ett arbete inletts för att kartlägga föroreningssituationen. Syftet med examensarbetet är att utvärdera grundvattenkemin i Hjältevad genom att visualisera föroreningsföroreningsplymen, undersöka mobiliteten genom att undersöka samband mellan halten arsenik och kemiska parametrar samt göra en fördjupad analys av spridningsrisken med hjälp av Kd-värden. Data från jord- och grundvattenprovtagningar genomförda under augusti och september 2017 bearbetades med hjälp av ArcMap och Excel. Resultatet visade att låga redoxförhållanden sannolikt har bidragit till ökad spridning av arsenik vilket till stor del förekom i den reducerade formen arsenit. De högsta halterna var koncentrerade till området kring den f.d. läckande tanken, där halter så höga som 2200 μg/l kunde uppmätas i grundvattnet. Vidare visade provtagningsresultaten att mängden förorenad jord missbedömdes vid saneringen 1997 (halter på 238 mg/kg kunde uppmätas i jorden). Slutsatsen drogs att redoxförhållanden inom området är gynnsamma för att arsenik ska förekomma i den reducerade formen arsenit, att arseniks mobilitet med stor sannolikhet är betydligt högre än vad som tidigare bedömdes samt att risker föreligger om inga åtgärder vidtas. / Arsenic is a naturally occurring metalloid that causes major health problems for people affected by exposure, e.g. through their drinking water. Due to the negative effects on human health, the permissible concentration in drinking water was lowered in 2003, from 50 μg/l to 10 μg/l. Arsenic predominantly exists in two inorganic forms, arsenate (AsO43-) and arsenite (AsO33-), where arsenite is a more mobile and toxic. Which forms that dominates is controlled by pH and redox potential. Reduction from arsenate to arsenite is favorable at lower pH and at anoxic (reduced) conditions. In Sweden previous use of arsenic, e.g. at impregnation plants, caused pollution still affecting soils and groundwater. In Hjältevad, Eksjö municipality, an impregnation plant for telephone poles was run by Televerket during the 1940s to 1980s. Impregnating fluid, including arsenic, was spread in the area, mainly due a leaky storage tank during the 1960s. The site was remediated in 1997 using soil washing. However, monitoring program demonstrated steadily increased levels in a well situated downstream the contaminated area. Due to the increased contamination levels of arsenic in the ground water, a detailed investigation was initiated to identify the pollution situation. The main objective was to investigate about the chemical and physical processes affecting the mobilization of arsenic. Groundwater and soil materials were sampled from the area and evaluated using ArcMap and Excel. In support of this evaluation, distribution coefficients (Kd) for soil materials from the aqvifer were obtained by leaching tests performed at oxidized conditions. The result showed that reducing conditions in the aquifer appeared to have caused increased mobilization of arsenic in the area and that large amounts of pollution was not removed at the remediation in 1997 (levels of 238 mg/kg arsenic could be detected in the soil). In the collected samples, arsenic mainly occurred in the reduced form arsenite. The highest levels in the groundwater were found in the area around the former leaky tank, where concentrations up to 2200 μg/l was measured. The conclusion was that large amounts of pollution was not removed at the remediation in 1997, and that arsenic mobility seems to be significantly higher than previously assessed and that action needs to be taken to stop the spread.

Vid en rent praktisk tillämpning av cirkulär ekonomi krävs det att man har kunskaper kring hur man får ett uttjänt material att bli till en ny produkt. Detta kan innefatta lagstiftning, men det finns även ett behov att se till att det inte kan orsaka negativa konsekvenser för hälsa eller miljö. Swerock önskar kunna producera ett cirkulärt ballastmaterial av överskottsmaterial från olika projekt vilket leder till frågan hur man kan miljöbedöma detta. Genom en litteraturstudie har en kunskapssammanställning genomförts för att besvara frågeställningen om vilken eller vilka testmetoder Swerock kan använda sig av för att testa material med syfte att kunna användas i vägbyggen så att materialet inte kommer att utgöra en fara för människa och miljö. Litteraturstudien i detta examensarbete behandlar bland annat lagstiftning, rapporter, studier och myndighetsdokument för att bygga en grund till förslag på miljöbedömningsförfarande som slutligen sammanställts. En jämförelse har även gjorts mellan tillhandahållna testresultat av laktestade prover från Swerock mot sammanställda haltgränser från litteraturen. Detta för att illustrera dagsläget och få en uppfattning om halter och ämnen som olika aktörer gränssatt och på vilka vis. Studien har visat att laktester är vanligt förekommande som ett sätt att bedöma miljöpåverkan hos olika typer av material och också ett tillvägagångssätt bland End of Waste-kriterier. Ekotoxikologiska test har inte befunnits vara så vanligt tillämpade men har framhållits av studier som ett lämpligt komplement till laktester. Ur litteraturstudien framkom det svenska systemet BASTA som ett sätt att farobedöma byggmaterial, där det är grundat på CLP:s faroangivelser för hälso- och miljöfarlighet. Dessa tre delar har sammanställts i det förslag på miljöbedömning som presenteras i resultatdelen. En slutsats som kan göras är att arbetet med frågeställningen om produktifiering av cirkulära material är i sin linda och att det finns möjligheter till fortsatta studier på ämnet. / In a purely practical application of circular economics it is necessary to have knowledge of how to convert a used material into a new product. This may include legislation, but there is also a need to ensure that it cannot cause negative health or environmental consequences. Swerock strives to be able to produce circular aggregate material of surplus material from various projects, which leads to the question of how this can be environmentally assessed. Through a literature study, a compilation of knowledge was made to answer the question about which test methods Swerock can use to test materials for use in road constructions to ensure that danger to humans and the environment is avoided. The literature study in this thesis covers, inter alia, legislation, reports, studies and government documents to build a basis for a proposal for an environmental assessment procedure. A comparison was also made between the provided test results of leaching test samples from Swerock and compiled content limits from the literature. This was to illustrate the current situation and get an idea of the levels and substances that different actors have set limits for and in what ways. The study has shown that leaching tests are common for assessing the environmental impact of different types of materials and also as an approach among the End of Waste criteria. Ecotoxicological tests have not been found to be as commonly applied but have been highlighted by studies as a suitable complement to leaching tests. From the literature study, the Swedish system BASTA emerged as a way of assessing hazard in building materials, where it is based on CLP's hazard statements for health and environmental hazards. These three parts have been compiled in the environmental assessment proposal presented in the results section. One conclusion that can be made is that the work on the question of the production of circular aggregate materials is in its infancy and that there are opportunities for further studies on the subject.

Löslighet och transport av sällsynta jordartsmetaller i Källfallsfältets gruvsandsmagasin Hugo de Campos Pereira Syftet med detta arbete har varit att kartlägga vilka mekanismer som styr lösligheten av sällsynta jordartsmetaller (eng. rare earth elements, REE) i sulfidhaltig anrikningssand vid den föredetta gruvan Källfallsfältet i Västmanland. För syftet har markvatten- och grundvattenprovtagning utförts, tillsammans med laktester och geokemisk modellering med Visual MINTEQ ver. 3.0. Resultaten visade att sulfidvittring är den främsta processen som styr pH i anrikningssanden, och därmed också indirekt REEs löslighet. Däremot är sulfidvittring ingen källa till REE i sig då ämnena inte föreligger sulfidbundna, något som oxiderat tillgänglighetstest NT ENVIR 006 visade. Istället går REE ut i lösning i anrikningssanden genom vittring av lättvittrade silikatmineral. Vanligtvis betraktas metall bunden i silikatform inte som geokemiskt aktiv. Jämförelser mellan laktester med olika jämviktstid visade att en kinetisk (tidsberoende) faktor föreligger, kopplad till nämnda silikatvittring, som påverkar pH och således också metallöslighet vid laktester på anrikningssanden. Vid jämförelse mellan laktester och halter i anrikningssandens mark- och grundvatten bör denna därmed vägas in. Det pH-statiska laktestet SIS-CEN/TS 14997 visade begränsad möjlighet att undersöka kinetik med anledning av att det utförs under förhållandevis kort tid, 48 timmar. REE- och Cu-halter vid syratitrering (de behandlingar med lägst syratillsatser) och enstegslakning (SIS-CEN ISO/TS 21268-2:2010) visade god, respektive förhållandevis god, överensstämmelse med uppmätta markvattenhalter. Detta visade att syratitrering och enstegslakning är laktest som är tillämpbara, respektive förhållandevis väl tillämpbara, för att uppskatta markvattenhalter i anrikningssanden. Specieringsmodellering med Visual MINTEQ ver. 3.0 visade att pH och DOC är de viktigaste parametrarna som styr REEs speciering i anrikningssandens mark-, grund och ytvatten. Samtliga REE bildar starka komplex med löst organiskt material, men koncentrationerna av DOC var generellt sett låga. I sura sulfatrika mark-, grund och ytvatten domineras specieringen av lösta sulfatkomplex, huvudsakligen (REE)SO4+, följt av fria hydratiserade joner som näst vanligaste förekomstform. Dessa resultat överensstämmer väl med tidigare modelleringsstudier av REEs speciering i sura sulfatrika vatten resulterande från gruvavfall. Med bakgrund av detta och av att REEs ekotoxicitet verkar överensstämma med den fria jon-modellen (eng. free ion model) förväntas REE uppvisa högre toxicitet vid låga pH-värden. / Solubility and transport of rare earth elements in the mine tailings of Källfallsfältet Hugo de Campos Pereira The mechanisms which govern the solubility of rare earth elements (REEs) in sulfide-containing tailings at the former mine site of Källfallsfältet (Västmanland, Sweden) were studied by the means of soil water and ground water sampling, leaching tests and geochemical modeling using Visual MINTEQ ver. 3.0. The results showed that weathering of sulfides is the primary process governing pH in the tailings, and thus also REE solubility. However, weathering of sulfides is no source for REE in itself since the elements are not bound in sulfides, which the oxidized availability test NT ENVIR 006 showed. Instead REE are released into solution by weathering of easily weathered silicates. Usually, metal bound in silicate form is not considered geochemically active. A kinetic (time dependent) factor, associated with the weathering of silicates, was found to affect pH and thus also metal solubility in leaching tests performed on the tailings. The standardized pH static leaching test (SIS-CEN/TS 14997) showed limitations in observing kinetic effects because of its relatively short equilibration time (48 h). Thus, in future studies with similar materials, leaching test kinetics should be taken into account when comparing leached concentrations with field measured concentrations. Acid titration and one step batch test (SIS-CEN ISO/TS 21268-2:2010) proved to be applicable and relatively well applicable to the tailings, respectively, in order to estimate soil solution concentrations. Speciation calculations using Visual MINTEQ ver. 3.0 showed that pH and DOC concentration are the most important factors which affect REE speciation in soil solution, ground water and surface water associated with the tailings. In acid sulfate rich solutions, low in DOC, speciation is dominated by sulfate complexes, mainly (REE)SO4+, followed by free dissolved ions as the second most common form. These results are in accordance with previous modeling studies of REE speciation in acid sulfate rich waters resulting from tailings. This, together with previous results showing that REE ecotoxicity seems to follow the free ion model, implies that the toxicity of the elements is expected to increase with decreasing pH value.

Les REFIOM (Résidus d'Epuration des Fumées d'Incinération des Ordures Ménagères) issus de l'incération des déchets ménagers contiennent des métaux lourds comme le plomb ou le cadmium et sont en France uniquement stockés en centre d'enfouissement technique de classe 1 pour dangereux, en étant stabilisés par une vitrification. Afin de trouver des solutions pour le stockage ou la valorisation à long terme des REFIOM sans danger pour l'environnement, nous avons ciblé les vitrocéramiques et les céramiques frittées à hautes températures et hautes pressions. Nous avons utilisé des méthodes de la minéralogie physique par l'intermédiaire de synthèses à hautes températures, de synthèses à hautes températures et à hautes pressions en autoclave à chauffage externe, d'observations en microscopie électronique à balayage, de microanalyses chimiques EDX (Energy Dispersive X-Ray spectrometry), d'analyses en microsondes, de caractérisation structurale par diffraction de rayons X et d'expériences de lixiviation dynamique. Nous avons mis au point des protocoles de synthèses et d'analyses. Par ce biais, nous constatons pour les vitrocéramiques que le plomb ou le cadmium sont incorporés dans des cristallites et dans des nouvelles phases cristallines, eux-mêmes englobés dans une matrice vitreuse. Cette voie dite "double barrière" (cristaux + verre) semble prometteuses pour l'immobilisation du plomb et du cadmium (au regard des analyses EDX et des expériences de lixiviation). Pour les céramiques frittées, comme pour les SYNROC (SYNthetic ROCk) synthétisées pour les déchets nucléaires, de nouvelles phases cristallines incorporant Pb et Cd sont observées et seraient a priori résistantes pour le stockage de ces éléments toxiques. Dans ces deux cas de nouveaux matériaux capables d'incorporer massivement du plomb et du cadmium ont été mis en évidence. Des tests de durabilité permettront d'envisager une valorisation éventuelle de tels matériaux / MSWI 5Municipal Solide Waste Incinerator) fly ashes from the incineration of domestic waste contain heavy metals such as lead or cadmium. In France, these fly ashes are only stored under vitrified forms in class-1 type landfills for hazardous waste. In order to find solutions for long-term storage or valorization of the MSWI fly ashes, we studied glass-ceramics and sintered ceramics at high pressures and/or hight temperature. We used methods of mineral physics to : synthetize at high temperature, synthetize at higt temperature and high pressure using autoclaves with external heating system, observe by electron microcopy, make EDX (Energy Dispersive X-Ray spectrometry) chemical microanalysis, make microprobe analysis, structurally characterize and perform leaching test. We established experimental protocols for the synthesis and analysis of produced materials. For glass-ceramics, we observe that lead and cadmium are incorporated inside expected crystallites and new crystal phases, themselves embedded by a glassy matrix. This so-called "double barrier" (crystals + glass) is a promising way towards a substainable of lead and cadmium (after EDX analysis and leaching experiements). For sintered ceramics, as for the SYNROC (SYNthetic ROCk) with nuclear waste, new crystal phases incorporating Pb and Cd are found and might display a high resistant for the storage of these toxic elements. In both cases, new materials incorporating large amounts of lead and cadmium were formed. Durability tests may give new ways for a valorization of such materials

Hydraulic fracturing operations utilized for shale gas production result in the generation of a large volume of flowback and produced water that contain suspended material, salts, hydrocarbons, metals, chemical additives, and naturally-occurring radioactive material. The water is impounded at drilling sites or treated off-site, resulting in significant generation of residual solids. These are either buried on site or are disposed in lined landfills. The objective of this study was to determine the levels of heavy metals and other elements of concern that will leach from these residual solids when placed in typical disposal environments. For this purpose, laboratory leaching experiments were employed wherein representative samples were brought into contact with a liquid to determine the constituents that would be leached by the liquid and potentially released into the environment. The samples used included sludge resulting from the physicochemical treatment of process water (TS), sludge solidified with cement kiln dust (SS), raw solids obtained by gravity separation of process water (RS), and drilling mud (DM). The samples were subjected to both single extraction (i.e. Shake Extraction Test, SET) and multiple extraction (i.e. Immersion Test, IT) leaching tests. For the shake extraction test, samples were mixed with a specific amount of leaching solution without renewal over a short time period. In the immersion test, samples were immersed in a specific amount of leaching solution that was periodically renewed over a longer period of time. For both these tests, analyses were performed on the filtered eluate. The tests were performed as per standards with modifications. Distilled de-ionized water, synthetic acid rain (pH ~ 4.2), weak acetic acid (pH ~ 2.88), and synthetic landfill leachate were used as leaching solutions to mimic specific disposal environments. Alkali metals (Li, K, Na), alkaline earth metals (Ba, Ca, Mg, Sr) and a halide (Br), which are typically associated with Marcellus shale and produced waters, leached at high concentrations from most of the residual solids sample. The SS sample, due to its stabilization with CKD, had a lower extraction efficiency as compared to the unconsolidated TS and RS samples. In EF 2.9 and EF SLL, the leaching took place under acidic conditions, while for EF DDI and EF 4.2, the leaching occurred in alkaline conditions. EF 2.9 and EF SLL were determined to be the most aggressive leaching solutions, causing the maximum solubility of most inorganic elements. Thus, high amounts of most EOCs may leach from these residual solids in MSW landfills disposed under co-disposal conditions. Agitation, pH and composition of the leaching solution were determined to be important variables in evaluating the leaching potential of a sample. The results of this study should help with the design of further research experiments being undertaken to develop environmentally responsible management/disposal strategies for these residual solids and also prove useful for regulatory authorities in their efforts to develop specific guidelines for the disposal of residuals from shale gas production operations. / Master of Science