In the north of Sweden lots of the soil is naturally contaminated by acid sulfate. When soil gets in contact with oxygen an oxidation process begins which releases elements that may be harmful to the surroundings. When the Botniabanan was built, soil had to be transported from the railroad area to deposit sites. This study was made to investigate the suspicions a landowner had regarding if his estate had been contaminated sulphide soil soil during the building of the Botniabanan. To do that four pits were dug in the area where the soil had been deposited. Then the soil was analyzed to see the content of sulfate, iron, organic matters and water. When the results was compared to other studies it showed that the content of sulfate and organic matters was to low to classify the soil as an acid sulfate soil.

Iron oxyhrdroxide exist in a range of crystallinities and subsequent bioavailabilities with the poorly crystalline Fe oxyhrdroxide, ferrihydrite, considered the most bioavailable. Yet, as a result of the instability ferrihydrite it quickly ripens and/or transforms to more thermodynamically stable end-members bringing into question its importance in supporting long-term Fe(III)-reducing microbial communities. Furthermore, while a wide phylogenetic diversity of microorganisms capable of reducing ferrihydrite have been isolated, these organisms show diminished abilities to reduce more stable and dominant crystalline Fe phases. Therefore to address the questions of which microorganisms and what microbial processes are responsible for controlling the reduction of diverse Fe(III) minerals phases, cultivation based approaches using both batch and column-type reactors were employed. Using geochemical and phylogenetic analysis it was revealed that the Fe oxide substrate was important in dictating the mechanisms of Fe(III) reduction, and the structure of the microbial communities. While model dissimilartory Fe reducing microorganisms were capable of reducing ferrihydrite when acetate was provided as a carbon source these organisms did not enrich and were incapable of reducing crystalline Fe(III) oxides. Instead, in enrichments where crystalline Fe(III) oxides were reduced, organisms associated with fermentation and sulfate respiration dominated, this despite using freshwater media low in sulfate (less than 200 µM). In addition, these non-model Fe reducers dominated in ferrihydrite enrichments when carbon compounds other than acetate were given. Interestingly, a strong negative correlation between Fe(III) and sulfate respiration was observed with the canonical thermodynamic view that ferrihydrite should precede sulfate as a terminal electron acceptor being challenged. Further experiments with pure cultures of Desulfovibrio putealis indicated that a catalytic sulfur cycle may be responsible for greater than expected Fe(II) values under low sulfur conditions. These findings, have broad implications in predicting microbially mediated electron flow to oxidized substrates which will dictate the pathways and degree of carbon mineralization and subsequent carbon sequestration within sediments and soils. Further, given the importance of Fe(III)-reducing communities and Fe(II) in the sequestration of both inorganic and organic contaminants, these findings will have direct bearing on contaminant mitigation and remediation. / Engineering and Applied Sciences

Στην παρούσα εργασία πραγματοποιήθηκε μελέτη της κινητικής της κρυστάλλωσης του Μιραμπιλίτη (δεκαένυδρο θειικό άλας), που είναι και το θερμοδυναμικά σταθερότερο άλας του θειικού νατρίου που κρυσταλλώνεται στις συνήθεις περιβαλλοντικές συνθήκες. Η μελέτη έγινε σε ασταθή υπέρκορα διαλύματα τα οποία παρασκευάζονται με διάλυση του θειικού νατρίου. Στην συνέχεια επιλέχθηκαν τρεις οργανοφωσφορικές ενώσεις προκειμένου να διερευνηθεί η επίδρασή τους στην κινητική της κρυστάλλωσης του Μιραμπιλίτη. Το κοινό χαρακτηριστικό αυτών των οργανοφωσφορικών ενώσεων είναι ότι έχουν ιονιζόμενες ομάδες στο μόριο τους και γι’ αυτό θεωρείται ότι μπορούν να δεσμεύουν είτε μέσω προσρόφησης ή με τον σχηματισμό επιφανειακών συμπλόκων, τα ενεργά κέντρα κρυστάλλωσης. / Our work is concerned with the investigation and inhibition of crystal growth for mirabilite. Mirabilite is a hydrated sodium sulfate salt and considers extremely hazardous for building materials as marble and concrete when it crystallizes heterogeneously in pores. The compounds tested with respect to their effect on the crystal growth of mirabilite were three organophosphorus compounds: HEDP, ATMP, HMDTMPA. Those organophosphorus compounds possesses ionizable groups and therefore are consider to be able to block by absorption the active growth sites forming possibly surface complexes.

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%.

In the present study the effect of one commercially available anionic surfactant on the formation/dissociation of hydrate from a gas mixture of 90.5 % methane – 9.5% propane mixture was investigated. Surfactants are known to increase gas hydrate formation rate. Memory water was used and the experiments were carried out at three different degrees of undercooling and two different surfactant concentrations. In addition, the effect of the surfactant on storage capacity of gas into hydrate was assessed. The morphology of the growing crystals and the gas consumption were observed during the experiments. The results show that branches of porous fibre-like crystals are formed instead of dendritic crystals in the absence of any additive. Finally, the addition of 2200 ppm of SDS was found to increase the mole consumption for hydrate formation by 4.4 times.

The northern margin of South China Sea contains several favorable areas for occurrence of gas hydrate. In this study, we collected pore water samples in two piston cores (X-01 and D-01) from Xisha Trough and Dongsha area, respectively, and the concentrations of sulfate and carbon isotopic compositions of dissolved inorganic carbon (DIC) were measured. The results showed different geochemical characteristics in these two sites. The X-01 core shows relatively constant δ13C-DIC values and sulfate concentrations, which suggest that anaerobic methane oxidation (AMO) processes did not occur in this site. In contrast, very large variation in δ13C-DIC values and sulfate concentrations are revealed in D-01 core, and good linear correlations for sulfate gradients and δ13C-DIC values are observed. The calculated sulfate-methane interface (SMI) depth is 9.6 mbsf. These data indicate that an AMO process occurred in sediments with large methane flux from depth in the Dongsha area, which are comparable to other gas hydrate locations in the world oceans such as the Blake Ridge. We suggest that the Dongsha area is one of the most favorable targets for future gas hydrate exploration.

The reaction of sulfate with six podzolic horizons of the Southern Laurentians (Quebec) was investigated using batch reaction techniques. It was demonstrated that sulfate sorption increased with decreasing solution pH to a maximum sorption capacity at around pH 4.0; below this pH retention decreased. This drop in sorption capacity was related to the partial dissolution of Al surface coatings. Indeed, the amount of native sulfate and the maximum sorption during the experiment were positively correlated (R$ sp2$ = 0.982, 0.800) with the oxalate extractable Al content of these forested soils. In all six horizons, the increase in sulfate sorption as a function of equilibrium sulfate concentration was best described by the Gunary equation. Kinetic experiments showed the presence of two major stages in both sorption and desorption reactions with an initial quick change (first 6 h) in solution concentration being followed by a second step where the reactions between sulfate and the soil matrix were much slower. The time-dependence of these reactions emphasized the appropriateness of kinetic equation in describing field situations. Moreover, kinetics studies performed under highly acidic conditions demonstrated that the amount of sulfate sorbed decreased with time after an initial sorption step due to the partial dissolution of Al surface materials. Thermodynamic calculations further suggested the subsequent precipitation of jurbanite. It was then concluded that surface dissolution and mineral formation should be considered in the interpretation of results obtained from experiments aimed at determining the effect of pH on sulfate retention.

Considerable research has been done to improve hydrate formation rate. One of the ideas is to introduce mechanical mixing which later tend to complicate the design and operation of the hydrate formation processes. Another approach is to add surfactant (promoter) that will improve the hydrate formation rate and also its storage capacity to be closer to the maximum hydrate storage capacity. Surfactant is widely known as a substance that can lower the surface or interfacial tension of the water when it is dissolved in it. Surfactants are known to increase gas hydrate formation rate, increase storage capacity of hydrates and also decrease induction time. However, the role that surfactant plays in hydrate crystal formation is not well understood. Therefore, understanding of the mechanism through morphology studies is one of the important aspects to be studied so that optimal industrial processes can be designed. In the present study the effect of three commercially available anionic surfactants which differ in its alkyl chain length on the formation/dissociation of hydrate from a gas mixture of 90.5 % methane – 9.5% propane mixture was investigated. The surfactants used were sodium dodecyl sulfate (SDS), sodium tetradecyl sulfate (STS), and sodium hexadecyl sulfate (SHS). Memory water was used and the experiments for SDS were carried out at three different degrees of under-cooling and three different surfactant concentrations. In addition, the effect of the surfactant on storage capacity of gas into hydrate was assessed. The morphology of the growing crystals and the gas consumption were observed during the experiments. The results show that branches of porous fibre-like crystals are formed instead of dendritic crystals in the absence of any additive. In addition, extensive hydrate crystal growth on the crystallizer walls is observed. Also a “mushy” hydrate instead of a thin crystal film appears at the gas/water interface. Finally, the addition of SDS with concentration range between 242ppm – 2200ppm (ΔT =13.10C) was found to increase the mole consumption for hydrate formation by 14.3 – 18.7 times. This increase is related to the change in hydrate morphology whereby a more porous hydrate forms with enhanced water/gas contacts.

L'étude des systèmes polyphasés du type solide-gaz et solide-liquide occupe une place importante en cinétique hétérogène. De nombreux travaux expérimentaux et théoriques ont été entrepris pour tenter de résoudre les problèmes posés par ces systèmes. A la suite des recherches effectuées au laboratoire, consacrées à la thermodynamique des hydrates non stoechiométriques et à la cinétique de déshydratation des sels, il nous a paru intéressant de suivre les réactions d'hydratation telles que : solide 1 + eau vapeur &#8594 solide 2 et .solide 1 + eau liquide &#8594 solide 2. Pour illustrer ce travail, nous avons choisi d'examiner le comportement vis-à-vis de l'eau du sulfate de calcium hémihydraté, constituant essentiel du plâtre. En 1975, la France a produit 3,3 millions de tonnes de plâtre et s'est classée premier producteur européen et troisième producteur mondial derrière les Etats-Unis et l'U.R.S.S. Etant donné l'importance industrielle du produit, des moyens d'investigation de plus en plus perfectionnés ont été mis en oeuvre. Néanmoins, les conclusions demeurent fragmentaires et peu cohérentes. Afin de progresser dans la compréhension des mécanismes réactionnels, il est nécessaire d'entreprendre l'étude du phénomène d'hydratation selon une démarche originale: elle consiste à suivre la réaction avec l'eau vapeur. Cette méthode très intéressante sur un plan fondamental permet : D'une part, de séparer les différentes étapes et d'autre part, de stopper l'hydratation à tout moment sans séchage préalable du solide.

Il semble actuellement raisonnable de penser que la notion de réaction simple,c onduisant à un équilibre univariant du type SGn → S' + nG et mettant en jeu deux phases solides pures (SGn et S') et le gaz G. n'est qu'une approximation, justifiable dans le cas de solides qui présentent de faibles écarts à la stoechiométrie. Si l'on se réfère aux hydrates (G = H₂O), il n'est pas rare en effet que la composition chimique de la phase sous-hydratée issue d'une réaction de déshydratation s'écarte largement de la stoechiométrie et varie avec la température et la pression de vapeur d'eau. C'est ainsi, par exemple, que l'oxalate de calcium dihydraté, le sulfate de calcium (forme γ) et l'oxalate de manganèse anhydres, dissolvent des quantités d'eau non négligeables jusqu'à apparition de formes hydratées saturées. Le but de ce travail consacré pour l'essentiel à l'étude des réactions de déshydratation de sels de formules brutes apparentes SGn, est donc d'introduire la non-stoechiométrie dans le diagramme d'état puis au niveau des processus élémentaires de décomposition; par ce biais, nous proposons une interprétation possible au caractère singulier de certaines courbes, traduisant à température constante, les variations de vitesse de décomposition en fonction de la pression du gaz G. Tout écart à la stoechiométrie, en élément G provenant du gaz, d'un solide SGn, se matérialise dans le diagramme d'équilibre pression-température par l'existence d'un domaine divariant ; borner ce domaine, revient à définir la notion de courbe limite de divariance, lieu des points du plan P_G - T de précipitation commençante de nouvelles phases solides.