The new Maximum Contaminant Level (MCL) of arsenic in drinking water has caused a significant increase in the volume of arsenic-bearing solid residuals (ABSR) generated by drinking water utilities. Iron sorbents are being widely utilized for water treatment and comprise the bulk of the waste generated. Based on Toxicity Characteristic Leaching Procedure (TCLP) results, these ABSR may be disposed in municipal solid waste (MSW) landfills. However unlike the conditions in the TCLP, a mature landfill is a biotic, reducing environment where iron and arsenic may be reduced and, as a consequence, arsenic may be released to the leachate. The primary route of iron reduction in landfills is microbially mediated and biomineralization is a common by-product. In this case, biomineralization is the transformation of ferric (hydr)oxides into ferrous iron crystalline forms, such as siderite, vivianite and iron sulfide, and into mixed valent mineral forms, such as magnetite and green rust. In this work, biomineralization is evaluated as a possible process to control arsenic leaching from ABSR in landfills. Understanding biomineralization impacts, however, requires a precise knowledge of the various mechanisms of arsenic release under landfill conditions. To this end, we describe flow-through laboratory column experiments in which controlled conditions similar to those found in a mature landfill prevail. In these simulated landfill column experiments, the results show that biomineralization would naturally occur in typical non-hazardous MSW landfills. Without any intervention, As leaching was higher than 80% of the initial quantity loaded, in contrast to Fe leaching values, which were less than 10% of the initial quantity loaded. Phosphate and bicarbonate played an important role in the experiments, as probably arsenic competitors for sorption sites and as components of the secondary iron mineral phases, vivianite and siderite respectively. Although these minerals have less surface area and adsorption capacity than AFH, they were a key constituent on the retention of the As that was left in the columns by re-adsorbing As species, and more important by coating the AFH with some of the initially loaded As.

The maximum contaminant level (MCL) for arsenic in drinking water was reduced to 10 parts per billion in 2006 by the USEPA. As a result, approximately 10,000 tons of arsenic-bearing residuals (ABSRs) are estimated to be generated every year from water treatment processes. It has also been established that the standard Toxicity Characteristic Leaching Procedure (TCLP), underestimates arsenic leaching from ABSRs, particularly under mature, mixed solid waste landfill conditions. This makes it critical to investigate stabilization technologies that would ensure long-term stability of arsenic residuals after disposal. Arsenic is ubiquitously associated with iron oxides in natural environments as well as water treatment residuals. Hence, knowledge of iron oxide transformations under landfill conditions is critical to understanding the fate and mobility of the associated arsenic. In this work, the effect of high local Fe(II) concentrations on ferrihydrite transformation pathways was studied. Magnetite was the sole transformation product in the presence of high local Fe(II) concentrations. In the absence of high Fe(II) concentrations, goethite was the major transformation product along with minor quantities of magnetite. These results have implications for arsenic mobility from ABSRs since goethite and magnetite have different arsenic sorption capacities and mechanisms. Two technologies were investigated for the stabilization of ABSRs - Arsenic Crystallization Technology (ACT) and Microencapsulation. The strategy for ACT was to convert ABSRs into minerals with a high arsenic capacity and long-term stability under landfill conditions. Scorodite, arsenate hydroxyapatites, ferrous arsenate, arsenated schwertmannite, tooeleite and silica-amended tooeleite, were synthesized and evaluated for their potential to serve as arsenic sinks using TCLP and a simulated landfill leachate test. Ferrous arsenate type solids and arsenated schwertmannite showed most promise in terms of low arsenic leachability and favorable synthesis conditions. Microencapsulation involved coating arsenic-loaded ferrihydrite with a mineral having high stability under landfill conditions. Based on results from a previous study, vivianite was investigated as a potential encapsulant for ABSRs. A modified version of the TCLP was used to evaluate the effectiveness of microencapsulation. Although vivianite did not prove to be a promising encapsulant, our efforts offer useful insights for the development of a successful microencapsulation technology for arsenic stabilization.

L'azote et le phosphore sont à l'origine de problèmes environnementaux entraînant un stress environnemental sur les écosystèmes aquatiques, comme l'eutrophisation et la toxicité. Pour contrer ces impacts, l'utilisation de procédés de traitement avancés est nécessaire pour respecter les réglementations strictes en matière de rejet. Une augmentation annuelle de l'utilisation des nutriments par la société est observée alors que les réserves mondiales de phosphore (P) et potassium (K) sont limitées. Compte tenu de leur importance dans toute vie, la récupération de ces nutriments à partir des eaux usées a retenu l'attention des chercheurs et est devenue un domaine de recherche très important. Les stations de traitement des eaux usées (STEP) sont considérées comme l'un des points d'accumulation importants de phosphore avec environ 1,3 million de tonnes d'élimination de P par an via le traitement des eaux usées dans le monde (Li et Li 2017). La valorisation du P des eaux usées pourrait ainsi couvrir environ 15 à 20% de la demande mondiale de phosphore (Yuan et al. 2012). Par conséquent, les stations d'épuration sont désormais considérées comme des installations de récupération des ressources de l'eau (StaRRE), un lieu où la valorisation et la gestion des biodéchets sont poursuivies. Les procédés électrochimiques peuvent être utilisés comme traitement tertiaire pour l'élimination du P (Tran et al. 2012). De nos jours, il suscite également l'intérêt des chercheurs en tant que nouvel outil pour les processus de récupération des nutriments tels que l'électrodialyse, l'électrocoagulation, le dosage électrochimique de magnésium, etc. Par contre, des applications à l'échelle pilote et à grande échelle nécessitent encore davantage d'investigations et de recherches. Dans ce projet de recherche, une technique d'électrocoagulation est appliquée pour la première fois pour récupérer le phosphore sous forme de vivianite à partir des eaux usées. En fait, la récupération du phosphore sous forme de vivianite, une pratique innovante, a attiré une attention considérable en raison de son omniprésence naturelle, de sa facilité d'accès et de sa valeur économique prévisible (Wu et al. 2019). Le processus d'électrocoagulation proposé utilise une anode de fer sacrificielle pour produire des ions ferreux formés lors de la dissolution de l'anode. Ces ions réagiront avec les ions du phosphore dans les eaux usées, en particulier PO₄³⁻ , HPO₄²⁻ et H₂PO₄⁻, entraînant la formation de vivianite, Fe₃(PO₄)₂,8H₂O, utilisable dans différents types d'application : engrais à libération lente, batterie Li-ion, peinture. . .Dans le cadre de ce projet, la modélisation électrochimique avec PHREEQC est utilisée afin d'étudier la dissolution de l'anode de fer, les conditions optimales de la précipitation de vivianite, les facteurs limitant cette formation et le suivi du processus de la précipitation dans une matrice d'eau usées complexe. PHREEQC a été démontré d'être un outil puissant pour effectuer des calculs de spéciation et l'évaluation de l'indice de saturation qui détermine le taux de précipitation. La partie expérimentale du travail couvre la récupération de vivianite en utilisant la méthode d'électrocoagulation. Cette récupération est évaluée dans des réacteurs de laboratoire opérés en mode batch et en mode continu afin d'évaluer respectivement, la récupération de vivianite comme une nouvelle route de récupération de P et la cinétique de sa précipitation a différentes valeurs de pH. / Nitrogen and phosphorus are causing environmental problems leading to environmental stress on aquatic ecosystems such as eutrophication and toxicity. To counteract these impacts, the use of advanced treatment processes is required to meet the strict discharge regulations. An annual increase in nutrient use by society is observed while global phosphorus (P) and potassium (K) reserves are becoming limited. Given their importance in all life, the recoveryof these nutrients from waste water has gained the attention of researchers and has become a highly important research field. Waste water treatment plants (WWTPs) are considered one of the important accumulation points of phosphorus with around 1.3 million tons of P-removed globally per year via sewage treatment (Li et Li 2017). P-recovery from wastewater could thus cover around 15-20% of the global phosphorus demand (Yuan et al. 2012). Therefore, WWTPs are now considered as Water Resource Recovery Facilities (WRRFs), a place where biowaste valorization and management are pursued. Electrochemical processes can be used as tertiary treatment for P-removal (Tran et al. 2012). Nowadays, it is also gaining the interest of researchers as a new tool for nutrient recovery processes such as electrodialysis, electrocoagulation, electrochemical magnesium dosage, etc.Based on a literature review, it could be concluded that all these processes have currently only been studied at pilot-scale, and full-scale application still needs more investigation and research. In this research project, an electrocoagulation technique was applied for the first time to recover phosphorus from wastewater as vivianite. In fact, vivianite phosphorus recovery, an innovative practice, has attracted considerable attention for its natural ubiquity, easy accessibility and foreseeable economic value (Wu et al. 2019). The proposed electrocoagulation process uses a sacrificial iron anode to produce ferrous ions formed during anode dissolution,reacting with ions in wastewater, in particular PO₄³⁻ , HPO₄²⁻ et H₂PO₄ , resulting in the formation of vivianite, Fe₃(PO₄)₂,8H₂O, that can be used in different types of application : slow release fertilizer, Li-ion battery, paint . . . As part of this project, electrochemical modelling with PHREEQC was used to study the dissolution of the iron anode, the optimal conditions for vivianite precipitation, the factors limiting its formation and the monitoring of the precipitation process in a complex wastewater matrix. PHREEQC was found to be a powerful tool to perform speciation calculations and the evaluation of the saturation index which determines the rate of precipitation. The experimental part of the work studied the recovery of vivianite using electrocoagulation. This recovery was evaluated in lab-scale reactors operating in batch mode and in continuous mode in order to evaluate respectively, the recovery of vivianite as a new route of recovery of P and the kinetics of its precipitation at different pH values.

Lowering the Maximum Contaminant Level (MCL) for arsenic in drinking water in the U.S., has caused a significant increase in the volume of Arsenic Bearing Solid Residuals (ABSRs) generated by drinking water utilities. Most of the affected utilities are smaller water treatment facilities, especially in the arid Southwest, and are expected to use adsorption onto solid sorbents for arsenic removal. Because of their high adsorption capacity and low cost, iron sorbents are used treatment technology and, when the sorbent's capacity is spent, these ABSRs are disposed in municipal solid waste (MSW) landfills and as a consequence arsenic is likely being released into leachate. However, a mature landfill is a biotic, reducing environment, which causes arsenic reduction and mobilization from the ABSRs. It is well documented that iron and sulfur redox cycles largely control arsenic cycling and, because iron and sulfur are ubiquitous in MSW, it is suspected that they play key roles in arsenic disposition in the landfill microcosm. The purpose of this study is to investigate the degree to which sulfate can prevent arsenic from leaching into landfill through biomineralization and to study ABSRs biogeochemical weathering effect on arsenic sequestration. The primary routes of iron and sulfate reduction in landfills are microbially mediated and biomineralization is a common by-product. In this case, biomineralization is the transformation of ferric (hydr) oxides into ferrous iron phase and sulfate into sulfide minerals such as: siderite (FeCO₃), vivianite (Fe₃(PO₄)₂), iron sulfide (FeS), goethite (α-FeOOH), and realgar (AsS). In this work, long-term microbial reduction and biomineralization of iron, sulfur, and arsenic species are evaluated as processes that both cause arsenic release from landfilled ABSRs and may possibly provide a means to re-sequester As in a recalcitrant solid state. The work uses long-term, continuous flow-through laboratory-scale columns in which controlled conditions similar to those found in a mature landfill prevail. In these simulated landfill column experiments, formation of biominerals, same as those that would naturally occur in typical non-hazardous MSW landfills, will be investigated. The feed contains lactate as the carbon source and primary electron donor, and ferric iron, arsenate, and a range of sulfate concentrations as primary electron acceptors. Our results suggest that biomineralization changes the stability of arsenic through a number of different processes including (i) release of arsenic through reductive dissolution of iron-based ABSRs; and (ii) readsorption/incorporation of released arsenic to secondary biominerals. The influence of biominerals, which have less surface area and adsorption capacity than original AFH, on the retention of arsenic is also investigated in this study. Our results show that the concentration of sulfate fed to the system affects the biomineral formation, and that the relative amounts and sequence of precipitation of biominerals affect the free arsenic concentration that can seemingly be engineered by the concentration of sulfate fed to the system. Comparison between the columns with different sulfate concentrations indicate that inflow sulfate concentration higher than 2.08 mM decreases As mobilization to <50%.

This thesis focuses on the vibrational spectroscopy of the aragonite and vivianite arsenate minerals (erythrite, annabergite and hörnesite), specifically the assignment of the spectra. The infrared and Raman spectra of cerussite have been assigned according to the vibrational symmetry species. The assignment of satellite bands to 18O isotopes has been discussed with respect to the use of these bands to the quantification of the isotopes. Overtone and combination bands have been assigned according to symmetry species and their corresponding fundamental vibrations. The vibrational spectra of cerussite have been compared with other aragonite group minerals and the differences explained on the basis of differing chemistry and crystal structures of these minerals. The single crystal spectra of natural erythrite has been reported and compared with the synthetic equivalent. The symmetry species of the vibrations have been assigned according to single crystal and factor group considerations. Deuteration experiments have allowed the assignment of water vibrational freque ncies to discrete water molecules in the crystal structure. Differences in the spectra of other vivianite arsenates, namely annabergite and hörnesite, have been explained by consideration of their differing chemistry and crystal structures. A novel approach to the assignment of site occupancy of ions in the erythrite - annabergite solid solution has been reported. This approach has utilised vibrational spectroscopy, in conjunction with careful consideration of the crystal structures of the minerals. It has been shown that in the erythrite - annabergite solid solution Coprefers metal site 2 contrasting nickel which prefers site 1. This study in conjunction with other studies has yielded the trend that the more electronegative metal prefers to occupy site 1, with the least electronegative metal preferring to occupy site 2. Fundamentally this thesis has increased the knowledge base of the spectroscopic properties of the aragonite and the vivianite minerals. The site occupancy of metal ion substitutions in solid solution series of the vivianite group of minerals has been further enhanced, with novel method of studying the site occupancy of ions in solid solutions has been developed. A detailed knowledge and understanding of factor group analysis applied to the study of minerals has been achieved.

In dieser Dissertation wurden das Auftreten und die ökologische Bedeutung Vivianits in Süßwassersedimenten erforscht. Vivianit ist das am weitensten verbreitete reduzierte Eisenphosphatmineral, das sich in Gewässersedimenten bildet. Über die Mechanismen der Vivianitbildung in Sedimenten und die quantitative Rolle des Minerals für die Speicherung von Phosphor ist bisher wenig bekannt. Die neuen Erkenntnisse dieser Arbeit basieren auf der Entwicklung einer neuartigen Methode, die eine direkte Identifikation Vivianits mittels Röntgendiffraktometrie in Sedimenten erlaubte. Es gelang erstmalig, Vivianit in Oberflächensedimenten zu quantifizieren. Die vorliegende Arbeit zeigt, dass Vivianit signifikant, mit 10-40 %, zur Phosphorretention in Süßwassersedimenten beitragen kann. Die Untersuchung der Bildungsbedingungen Vivianits in unterschiedlichen Gewässersedimenten Norddeutschlands zeigte, dass das molare Schwefel zu Eisen Verhältnis des Sediments als ein wichtiger Indikator für die Bedingungen identifiziert, welche die Triebkräfte für die An- und Abwesenheit Vivianits darstellen. Eine Eutrophierung von Gewässern und der damit verbundene Anstieg der Sulfidproduktion kann dabei die Bildung Vivianits beeinträchtigen, und eine Abnahme des Phosphorbindungsvermögens des Sediments zur Folge haben. Die vorliegende Arbeit macht deutlich, dass eine artifizielle Erhöhung des Eisengehaltes des Sediments im Rahmen einer Seenrestaurierung eine Vivianitbildung induzieren kann und so langfristig zu einem erhöhten Phosphorrückhalt führt. Sättigungsberechnungen ergaben, dass ein hinsichtlich Vivianits übersättigtes Porenwasser kein sicheres Indiz für die Anwesenheit des Minerals ist. Die Berechnungen sind nicht in der Lage die kleinskaligen chemischen Bedingungen im Porenraum des Sediments abzubilden. Die Untersuchungen zeigen, dass die Bildung von Vivianit einen wichtigen Prozess der Phosphorbindung in Gewässersedimenten darstellt, der bislang jedoch weitestgehend vernachlässigt wurde. / In this thesis, the occurrence and environmental relevance of vivianite in freshwater sediments were explored. Vivianite is the most common reduced iron phosphate mineral which forms in sedimentary environments. Not much is known about the mechanisms which lead to vivianite formation in surface sediments, and about the quantitative role of vivianite in phosphorus sequestration. The development of a novel sediment preparation technique allowed the direct identification of vivianite by powder X-ray diffraction. Notably, for the first time, vivianite was quantified in surface freshwater sediments. The study examplifies that vivianite can significantly contribute to the phosphorus retention in surface freshwater sediments, accounting for 10-40 % of total sedimentary phosphorus. The exploration of vivianite in different surface freshwater sediments located in northern Germany revealed that the sedimentary sulphur to iron ratio is a valuable indicator for the conditions that are important drivers behind the formation or absence of vivianite. It has been demonstrated that eutrophication and the accompanied increase in sulphide production hampers vivianite formation, leading to a decreased phosphorus binding capacity of sediments through increased sediment sulphidization. The present study also revealed, that an iron addition as a measure of lake restoration can trigger vivianite formation, and significantly increases the long-term phosphorus retention of sediments. Pore water equilibrium calculations demonstrated that supersaturated pore water is not sufficient to predict the occurrence of the mineral in situ. Those calculations often fail to predict the occurrence of vivianite because they do not adequately represent chemical conditions within sediment microenvironments. In summary, the formation of vivianite in aquatic sediments constitutes an important process in phosphorus sequestration which has so far largely been ignored.