<p>Fly ash and AMD samples were characterised by standard analytical methods for selection of the test materials. Active treatment by means of mixing fly ash with AMD in beakers and a large tank at pre-determined ratios have shown that fly ash is capable of neutralising AMD and increasing the pH beyond neutral values, which optimises the removal of heavy metals and ions. The trend was: the more fly ash added the quicker was the reaction time and higher the pH values achieved. Iron was reduced by as much 99 % in beaker scale experiments via Fe(OH)3 precipitation at pH values &gt / 4.0. A 99 % decrease in aluminium concentration was observed which was attributed to the precipitation of primarily gibbsite and various other mineral phases at pH values &gt / 5.5. As the pH increases, sulphate is adsorbed via Fe(OH)3 and gypsum precipitation at elevated pH. Sulphate attenuation with fly ash was excellent, achieving 98 % attenuation with beaker scale experiments and 1:1 fly ash:AMD ratio. Sulphate attenuation with fly ash was comparable to membrane and ion exchange systems and exceeded the performance of limestone treatment. Except for the larger volumes of fly ash needed to neutralise the AMD, fly ash proved to be a feasible and cost efficient alternative to limestone treatment. Fly ash produced competing results to limestone concerning acidity removal and sulphate attenuation. The comparison highlighted the advantages of utilising fly ash in comparison to limestone and demonstrated its cost effectiveness. The results of this study have shown that fly ash could be successfully applied for the neutralisation of acid mine drainage (AMD) and effectively attenuate the sulphate load in the treated water. The critical parameters to this technology are the variations of chemical composition and mineralogy of fly ash, which could influence the pH, contact time of the neutralisation reaction, and the same is true if the AMD quality varies.</p>

Attenuation of acid mine drainage (AMD) metals originating from abandoned mines and waste rock dumps is investigated in this thesis at Slättberg in central Sweden, where acid mine leachate has been discharging for over 70 years into the receiving wetland stream and mire. Risk assessment of AMD and related polluted lands requires a holistic approach that is able to study the complexity of pollution emissions and impacted landscapes. In this thesis a link between geochemical contaminant fate modelling and landscape analysis is presented for AMD risk assessment. A simple geochemical landscape analysis tool is developed to analyse and model geochemical abundances, geochemical gradients, geochemical flow patterns and geochemical barriers in the studied stream and mire sediments. Sampling locations at geochemical barriers are identified using landscape geochemical and GIS methods. A sequential chemical extraction procedure is used to investigate fractions which are expected to act as potential sinks of the six studied metals (Cu, Fe, Mn, Ni, Pb and Zn) in the sediments. For data modelling robust statistical methods of Exploratory Data Analysis are used to treat small sample sizes with multimodal character and outlying values. The spatial variability of metal retention in the sediments is studied by multivariate data analysis methods. Results show that the developed simple geochemical landscape analysis method can be used efficiently for the risk assessment of toxic mine contaminants in the complex receiving wetland landscape. It is suggested by the analysis that the oxidising geochemical barrier in the stream sediments can be sufficiently characterised by the distribution of Fe fractions. At the AMD discharge location metal sulphide formation and organic matter adsorption control metal retention in the mire. Mires are very sensitive to changes in hydrological conditions and drying of the sediments leads to erosion and hence the release of adsorbed metals to the environment.

Many industrial activities discharge sulphate- and metal-containing wastewaters, including the manufacture of pulp and paper, mining and mineral processing, and petrochemical industries. Acid mine drainage (AMD) is an example of such sulphate- and metal-containing waste streams. Formation of AMD is generally the result of uncontrolled oxidation of the sulphide minerals present in the terrain in which the drainage flows with concomitant leaching of the metals. Acid mine drainage (AMD) and other sulphate- and metal-containing waste streams are amenable to active biological treatment. Anaerobic reduction of sulphate, reaction of produced sulphide with metal ions present in the waste stream, and biooxidation of excess sulphide are three main sub-processes involved in the active biotreatment of AMD. Anaerobic reduction of sulphate can be achieved in continuous stirred tank bioreactors with freely suspended cells or in immobilized cell bioreactors. The application of freely suspended cells in a continuous system dictates a high residence time to prevent cell wash-out, unless a biomass recycle stream is used. In an immobilized cell system biomass residence time becomes uncoupled from the hydraulic residence time, thus operation of bioreactor at shorter residence times becomes possible. In the present work, kinetics of anaerobic sulphate reduction was studied in continuous immobilized cell packed-bed bioreactors. Effects of carrier matrix, concentration of sulphate in the feed and sulphate volumetric loading rate on the performance of the bioreactor were investigated. The bioreactor performance, in terms of sulphate reduction rate, was dependent on the nature of the carrier matrix, specifically the total surface area which was provided by the matrix for the establishment of biofilm. Among the three tested carrier matrices, sand displayed the superior performance and the maximum volumetric reduction rate of 1.7 g/L-h was achieved at the shortest residence time of 0.5 h. This volumetric reduction rate was 40 and 8 folds faster than the volumetric reduction rates obtained with glass beads (0.04 g/L-h; residence time: 28.6 h) and foam BSP (0.2 g/L-h; residence time: 5.3 h), respectively. Further kinetic studies with sand as a carrier matrix indicated that the extent of volumetric reduction rate was dependent on the feed sulphate concentration and volumetric loading rate. At a constant feed sulphate concentration, increases in volumetric loading rate caused the volumetric reduction rate to pass through a maximum, while increases in feed sulphate concentrations from 1.0 g/L to 5.0 g/L led to lower volumetric reduction rates. The maximum volumetric reduction rates achieved in the bioreactors fed with initial sulphate concentration of 1.0, 2.5 and 5.0 g/L were 1.71, 0.82 and 0.68 g/L-h, respectively. The coupling of lactate utilization to sulphate reduction was observed in all experimental runs and the rates calculated based on the experimental data were in close agreement with calculated theoretical rates, using the stoichiometry of the reactions involved. The maximum volumetric reduction rates achieved in the immobilized cell bioreactors were significantly faster than those reported for freely suspended cells employed in the stirred tank bioreactors.

L’anomenat drenatge àcid de mina (AMD) ve generat per l’oxidació de sulfurs i és causa major de contaminació d’aigües a nivell mundial. L’arsènic és un del princiapls contaminants laconcentració del qual pot assolir centenars de mgL-1, és a dir, de 5 a 6 ordres de magnitud més gran que el límit de potabilitat per a l’aigua (10μg L-1) establert per la UE en 1998. En aquesta tesi, s’estudia l’impacte de la mobilització de l’arsènic al llarg de descàrregues de drenatge àcid de mina. L’oxidació de sulfurs que contenen arsènic (tal com l’arsenopirita (AsFeS), la pirita rica en arsènic (FeS2) o la marcassita (FeS2) és una de les principals fonts d’alliberament d’arsènic a l’aigua. En la primera part de la tesi, s’ha estudiat la cinètica de dissolució de l’arsenopirita i de la marcassita a pHs àcids i neutre, utilitzant reactors de flux continu, i s’han valorat els efectes del pH, de l’oxigen dissolt i de la temperatura en la dissolució d’ambdós sulfurs. A partir de les velocitats en estat estacionari establertes, es proposen les respectives lleis de dissolució que tenen en compte el lleu i el fort efecte del pH i de l’oxigen dissolt, respectivament, en llur dissolució. La incorporació d’aquestes lleis cinètiques en les bases de dades del codis geoquímics i de transport reactitu permeten fer prediccions molt més realistes. L’impacte mediambiental causat per l’arsènic alliberat a les aigües depèn de la seva atenuació natural. El principal procés que controla el destí i la mobilitat de l’arsènic aquós és l’adsorció de l’arsenat en fases de ferro precipitades. Per tant, cal tenir en compte el paper que juga l’estat d’oxidació de l’arsènic. En la segona part de la tesi, shan estudiat tant l’oxidació de l’arsènic com l’adsorció de l’arsènic. L’oxidació s’estudia en condicions abiòtiques i biòtiques a pH i composició típics d’aigües àcides de mina, fent servir experiments de tipus batch. S’hi mostra com en condicions biòtiques tenen lloc simultàniament l’oxidació de Fe(II) a Fe (III) i d’arsenit a arsenat, de manera que mentre els bacteris governen la primera, el contingut de Fe(III) domina la segona. En condicions abiòtiques, l’oxidació d’arsenit a arsenat en presència de Fe(III) és lenta, tot i que augmenta augmentant la presència de Fe(III) i de clorur amb llum de dia. L’adsorció d’arsènic en llocs d’AMD, i per tant l’atenuació d’arsènic, ocorre mitjançant l’adsorció d’arsenat en precipitats formats per oxi-hidròxids i oxi-hidròxid-sulfats de ferro (principalment schwertmannita (Fe8O8(OH)5.5(SO4)1.25), K-jarosita (KFe3(SO4)2(OH)6) i goetita (FeOOH)). S’han estudiat les capacitats d’adsorció de la jarosita i de la goetita i s’han comparat amb la de la schwertmannita. Amb aquest propòsit es van fer experiments de tipus batch a pH molt àcid i amb mostres sintetitzades de K-jarosita i de goetita. Sense la competència d’altres anions, la capacitat de la jarosita per eliminar arsenat és més alta que la de la goetita. També s’ha vist que la força iònica té un escàs efecte en l’adsorció d’ambdós minerals, però que la presència de sulfat, que és l’anió més abundant en aigües àcides de mina, minva llurs capacitas d’adsorció. Cal conèixer bé els mecanismes dominants que controlen el contingut d’arsènic en les aigües, no només en condicions de laboratori, sinó també en les condicions de camp. Per tant, en la tercera part de la tesi s’han estudiat el processos d’atenuació de l’arsènic en un sistema natural. Amb aquest objetiu s’han caracterizat exhaustivament l’aigua i els sediments del rieron provinent de la mina abandonada Tinto Santa Rosa, situada a la Faixa Pirítica Ibèrica (IPB). La característica dominant de l’aigua del rierol és un descens del pH aigües avall que va acompanyat d’un decreixement sistemàtic de les concentracions de ferro ferrós i de ferro total, d’arsenit i d’arsenat, així com d’arsènic total. A més a més, els sediments de llit mostren contiguts alts d’arsènic. Els principals mecanismes que dominen el destí i la mobilitat de l’arsènic en aquestes aigües de camp són l’oxidació del ferro i de l’arsènic i la precipitatió de compostos de Fe(III) que adsorbeixen l’arsenat. S’ha proposat un model unidimensional de trasnport reactiu, utilitzant el codi PHREEQC, per explicar i quantificar els processos mencionats que han estat estudiats en condicions de laboratori. / Acid mine drainage (AMD) generated by sulfide oxidative dissolution is a major cause of water contamination world-wide. Arsenic is one of the main AMD pollutants whose concentration can reach up to hundreds of mg L-1, i.e. 5-6 orders of magnitude higher than the limit of 10 μg L-1 for potable water established by the European Union in 1998. This thesis is concerned with the impact of arsenic mobilization along AMD discharges. Oxidation of As-bearing sulfides such as arsenopyrite (AsFeS), As-rich pyrite (FeS2) or marcasite (FeS2) is one of the main sources of arsenic release. The first part of this thesis is focused on the dissolution kinetics of arsenopyrite and marcasite at acidic to neutral pH using long term flow-through experiments. The effects of pH, dissolved oxygen and temperature on their dissolution were assessed. The respective dissolution rate laws were proposed on the basis of the steady-state rates, taking into consideration the slight pH effect and the strong dissolved oxygen effect on dissolution. The incorporation of these rate laws into the kinetic databases of geochemical and reactive transport codes allows us to obtain better realistic simulations. The environmental impact of released arsenic into waters depends on its natural attenuation. The arsenic oxidation state is considered given that the main process that controls the fate and mobility of aqueous arsenic is arsenate sorption onto precipitated Fe-phases. The second part of the thesis discusses arsenic oxidation and arsenic sorption. Oxidation was studied by means of batch experiments under abiotic and biotic conditions at typical AMD water pH and water composition. Simultaneous oxidation of Fe(II) to Fe(III) and arsenite to arsenate occurs under biotic conditions, the former mediated by bacteria, and the latter by the presence of Fe(III). Under abiotic conditions, oxidation of arsenite to arsenate in the presence of Fe(III) is slow, but is enhanced by increasing dissolved Fe(III) and chloride concentrations in the presence of light. Arsenic sorption at AMD sites, and hence arsenic attenuation, occurs via arsenate sorption on new iron-oxyhydroxide and iron-oxyhydroxide-sulphate precipitates (mainly, schwertmannite (Fe8O8(OH)5.5(SO4)1.25), jarosite (KFe3(SO4)2(OH)6) and goethite (FeOOH)). The sorption capacity of goethite and jarosite was studied and compared with the one reported for schwertmannite. To this end, batch experiments were conducted using synthetic powders of K-jarosite and goethite at highly acidic pH. In the absence of competitive effects of other anions, K-jarosite presented better removal efficiency for arsenate, and ionic strength and pH had little effect on the sorption capacity of the two minerals. In contrast, these sorption capacities diminished considerably in the presence of sulfate, which is the main anion in AMD waters. A deeper understanding of the dominant mechanisms controlling arsenic content in waters demands the study of the processes not only under laboratory but also under natural conditions. Accordingly, the third part of this thesis deals with the arsenic attenuation processes in a natural system. To this end, the acidic water and sediments of the abandoned Tinto Santa Rosa mine discharge, located in the Iberian Pyritic Belt, were studied. The most striking feature of the water was a pH decrease accompanied by a systematic decrease in ferrous iron, total iron, arsenite, arsenate and total arsenic concentration. Additionally, bed-stream sediments showed high arsenic contents. The main processes that control the fate and mobility of arsenic in waters in the field were iron and arsenic oxidation, precipitation of Fe(III)- minerals and sorption of As(V) onto them. A 1-D reactive transport model using the PHREEQC code was used to explain and quantify the aforementioned processes that had been studied previously under laboratory conditions.

Many industrial activities discharge sulphate- and metal-containing wastewaters, including the manufacture of pulp and paper, mining and mineral processing, and petrochemical industries. Acid mine drainage (AMD) is an example of such sulphate- and metal-containing waste streams. Formation of AMD is generally the result of uncontrolled oxidation of the sulphide minerals present in the terrain in which the drainage flows with concomitant leaching of the metals. Acid mine drainage (AMD) and other sulphate- and metal-containing waste streams are amenable to active biological treatment. Anaerobic reduction of sulphate, reaction of produced sulphide with metal ions present in the waste stream, and biooxidation of excess sulphide are three main sub-processes involved in the active biotreatment of AMD. Anaerobic reduction of sulphate can be achieved in continuous stirred tank bioreactors with freely suspended cells or in immobilized cell bioreactors. The application of freely suspended cells in a continuous system dictates a high residence time to prevent cell wash-out, unless a biomass recycle stream is used. In an immobilized cell system biomass residence time becomes uncoupled from the hydraulic residence time, thus operation of bioreactor at shorter residence times becomes possible. In the present work, kinetics of anaerobic sulphate reduction was studied in continuous immobilized cell packed-bed bioreactors. Effects of carrier matrix, concentration of sulphate in the feed and sulphate volumetric loading rate on the performance of the bioreactor were investigated. The bioreactor performance, in terms of sulphate reduction rate, was dependent on the nature of the carrier matrix, specifically the total surface area which was provided by the matrix for the establishment of biofilm. Among the three tested carrier matrices, sand displayed the superior performance and the maximum volumetric reduction rate of 1.7 g/L-h was achieved at the shortest residence time of 0.5 h. This volumetric reduction rate was 40 and 8 folds faster than the volumetric reduction rates obtained with glass beads (0.04 g/L-h; residence time: 28.6 h) and foam BSP (0.2 g/L-h; residence time: 5.3 h), respectively. Further kinetic studies with sand as a carrier matrix indicated that the extent of volumetric reduction rate was dependent on the feed sulphate concentration and volumetric loading rate. At a constant feed sulphate concentration, increases in volumetric loading rate caused the volumetric reduction rate to pass through a maximum, while increases in feed sulphate concentrations from 1.0 g/L to 5.0 g/L led to lower volumetric reduction rates. The maximum volumetric reduction rates achieved in the bioreactors fed with initial sulphate concentration of 1.0, 2.5 and 5.0 g/L were 1.71, 0.82 and 0.68 g/L-h, respectively. The coupling of lactate utilization to sulphate reduction was observed in all experimental runs and the rates calculated based on the experimental data were in close agreement with calculated theoretical rates, using the stoichiometry of the reactions involved. The maximum volumetric reduction rates achieved in the immobilized cell bioreactors were significantly faster than those reported for freely suspended cells employed in the stirred tank bioreactors.

La géochimie est souvent influencée par l'activité biologique. Des logiciels tels que CHESS et HYTEC modélisent la plupart des processus géochimiques et hydrodynamiques et permettent d'analyser, puis de prédire, l'évolution de systèmes complexes comme les anciens sites miniers. L'objectif est d'étendre ces outils à la prise en compte de l'activité bactérienne. Dans CHESS, la méthode de Newton-Raphson, qui calcule la spéciation géochimique à l'équilibre, a été étendue à la modélisation de systèmes réactionnels composés de cinétiques biologiques (lois de Monod, d'inhibition, thermodynamique). Les autres options de cet outil comme le couplage avec le module de transport (HYTEC) ont été maintenues. L'implémentation du code a été vérifiée par la modélisation de quelques cas tirés de la littérature. L'outil a ensuite été utilisé pour la modélisation d'expériences de dissolution réductives biologiques d'hydroxydes de fer (HFO) riches en As, réalisées au BRGM. La mobilisation non congruente de Fe et As est expliquée par la sorption sur l'HFO et par les réductions biologiques de Fe et As. L'ancien site minier de Carnoulès (Gard, France) a été étudié lors d'expériences, réalisées à l'université de Montpellier, qui retracent l'évolution géochimique de l'eau acide de drainage minier. Leur modélisation prend en compte les oxydations aérobies biologiques de Fe et As et la précipitation d'une phase amorphe de FeIII et d'AsV. Les expériences ont permis de fixer les paramètres thermodynamiques et cinétiques utilisés pour la modélisation à l'échelle du terrain. Au delà de l'étude de l'interface eau-minéral, l'extension des outils CHESS et HYTEC va permettre d'étendre considérablement le champs de leurs applications.

Thesis (M.S.)--West Virginia University, 2001. / Title from document title page. Document formatted into pages; contains viii, 109 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 51-54).

Thesis (M.S.)--West Virginia University, 2003. / Title from document title page. Document formatted into pages; contains xii, 170 p. : ill. (some col.), maps (part col.). Includes abstract. Includes bibliographical references (p. 112-116).

Thesis (M.S.)--West Virginia University, 2003. / Title from document title page. Document formatted into pages; contains vii, 69 p. : ill. (some col.), col. maps. Includes abstract. Includes bibliographical references (p. 67-69).

D. Tech. Chemical Engineering / Concerns for the limitations of conventional technology for acid mine water treatment and the potential use of waste water have led to increased interest in membrane technologies. Studying the physical properties of nanofiltration membranes is a very important development in nanofiltration separation process. For optimum separation performance, the nanofiltration membranes have to possess certain physical properties, given the appropriate interactions with solutes in the process stream. This study investigated the performance evaluation of Nano-Pro-3012 and NF90 membranes in the treatment of synthetic wastewater effluents and acid mine water and the influence of membrane characteristics on retention in nanofiltration. The research was aimed to evaluate the performance of a new acid stable nanofiltration material (Nano-Pro-3012) produced by Bio Pure Technology for the removal of heavy metals from shaft 8 at Rand Uranium wastewater treatment plant and compare with a commercially available nanofiltration membrane.