The period of industrialization after the second World War in Europe released SO2 and NOx by combustion of fossil fuels and contributed the formation of S and N compounds in the forest ecosystem. The Swedish forest soil systems were influenced by emissions of SO2 followed by H2SO4 deposition, consequently the pool of SO42- had increased in the forest ecosystem. This thesis studied SO42- adsorption in a podzolic Bs horizon soils taken from a Swedish forest soil system. The soil samples from five different sampling sites were collected and the results revealed different amounts of adsorbed SO42- in response to changes in equilibrium concentration and pH. This study found that the amount of adsorbed SO42- (mmol/kg) increased with an added equilibrium concentration of SO42- (mmol/l) and with a decreasing pH. This was determined by equilibration experiments. Based on the results a Freundlich-based model was developed to predict the pool of adsorbed SO42- in the soil samples. The model predicted the pool of adsorbed SO42- (mmol/kg) as a function of pH and the equilibrium concentration of SO42- (mmol/l) in the soil solution system. The extended Freundlich model was optimized in three different ways: by use of unconstrained, constrained and simplified two-point calibration. The results showed that the adsorption of sulfate in the Kloten Bs1 and Risbergshöjden B soils was higher as compared to the Tärnsjo B, Österström B, and Risfallet B soils. The coefficient of determination (R2) determined from an unconstrained fit of the extended Freundlich model (with three adjustable parameters) for Risbergshöjden B and Kloten Bs1 were R2 =0.998 and R2=0.993. Nearly as good fits were found in a constrained fit with two adjustable parameters when it was assumed that nearly 2 protons (2 H+) are co-adsorbed with one SO42- ion (Risbergshöjden B; R2=0.997 and Kloten Bs; R2=0.992). The simplified two-point calibration with two adjustable parameters showed similar parameter values for all most soils and was considered the best optimization method of extended Freundlich model, especially as it requires only limited input data.

This study investigates jarosite formation and stability patterns at the abandoned Davis Pyrite Mine in Rowe, Massachusetts. Jarosite, an iron-sulfate hydroxide, is found in acid mine drainage (AMD) environments, in acid sulfate soils, and on Mars. Jarosite and the iron oxides goethite and hematite are present at the site. Soil samples from the site were examined by XRD, SEM, and EDS. Five mineralogical areas were found, based on mineral abundance patterns. Jarosite exists in four of these areas. Two jarosite morphologies were identified. “Variable” jarosite, with partly-dissolved crystals of about 0.5 to 5 micrometers diameter, exists in spoil pile samples. “Donut” jarosite, with tightly-packed, sharp-edged crystals less than 0.5 micrometers that form a thin mantle on the surface of a second mineral, exists in native soil samples. Donut jarosite has not been previously characterized. These jarosite morphologies are controlled by the presence and relative mobility of pyrite oxidation products Fe and SO4, which in turn are controlled by water saturation levels. Three pathways are possible. On Path 1, both ions are mobile, go into solution, and variable jarosite forms at a distance from the pyrite source. On Path 2, only sulfur ions are mobile, an iron-oxide gossan develops. No jarosite forms. On Path 3, neither ion is mobile, and donut jarosite forms. On this path, Fe and SO4 ions are trapped in a thin film of stagnant water covering the pyrite. When sufficient ions are present, donut jarosite precipitates.

Acid mine drainage (AMD) is an acidic, iron-rich leachate that causes the dissolution of metals. It constitutes a worldwide problem of environmental contamination detrimental to aquatic life and water quality. AMD, however, is naturally attenuated at Davis Mine in Rowe, Massachusetts. We hypothesize that sulfate-reducing bacteria (SRB) are attenuating AMD. To elucidate the mechanisms by which SRB attenuate AMD, three research projects were conducted using a suite of molecular and geochemical techniques. First we established biological influence on the attenuation of AMD by comparing the microbial community and geochemical trends of microcosms of two contrasting areas within the site: AMD attenuating (AZ) and AMD generating (GZ) zones. The differences in geochemical trends between these zones were related to differences in microbial community membership. SRB were only detected in microcosms of the AZ, while iron oxidizers were only detected in the GZ. This study indicates that biological activity contributes to the attenuation of AMD and that SRB may have a role. To further describe the role of SRB, we determined the rates of sulfate reduction, the abundance, and membership of SRB in the second project. The sulfate reduction rate was weakly correlated with the abundance of SRB. This indicates that the SRB population may be utilizing another electron acceptor. One such electron acceptor would be iron, which was investigated in the third project. When SRB are inhibited, neither accumulation of reduced iron nor the formation of reduced iron sulfide precipitates occurred. Higher concentration of sulfide produced an increase in reduced iron and pH. Therefore, iron reduction mediated by reaction with biogenic sulfide contributes to the attenuation of AMD. This is the first report of the biological enhancement of iron reduction by acidotolerant SRB. The interdisciplinary research described in this dissertation provides evidence that SRB attenuate AMD through sulfate and iron reduction and a greater understanding of SRB in acidic environments. It also demonstrates how the biogeochemical cycling of sulfur is coupled to the iron cycle. Overall, the ubiquity and metabolic versatility of SRB offers boundless potential and exciting opportunities of study in the fields of bioremediation, geomicrobiology, and microbial ecology.

No description available.

The purpose of this thesis was to experimentally investigate the influence of increasing sulfide concentrations on the 34S isotope enrichment in sulfate during dissimilatory sulfate reduction (DSR). Two independent batch culture experiments with different maximum sulfide concentrations of up to 20 mM in the first and up to 40 mM in the second experiment were conducted using the marine sulfate reducer Desulfobacter latus. A comparison of the results from both experiments revealed a distinct offset towards more positive δ34S(SO42-) values in the 'high-sulfide' experiment, compared to the 'low-sulfide' experiment. While a Rayleigh type fractionation model was able to match the slopes - i.e., enrichment factors - of both experiments, it failed to reproduce the proper y-axis intercept in the 'high-sulfide' experiment. I therefore propose a new fractionation model that allows for a backward flow of ambient H2S into the bacterial cell and a subsequent enzymatically mediated oxidation of H2S to sulfate. The new backward flow increases with elevated H2S concentrations and is described as a first order rate constant. Unlike a Rayleigh type fractionation model, my model explains the slope and y-intercept of both experiments with a single parameter set. The new model with H2S-reflux further suggests that it can be used to determine growth kinetic parameters like the half-saturation constant through δ34S measurements. These findings support the hypothesis of microbially mediated, bi-directional S-fluxes between oxidized and reduced sulfur species. Because the S-transport during DSR appears to be bi-directional, great care must be taken when evaluating culture experiments with a Rayleigh type fractionation model, owing to the fact that an evident S-backward flow violates the prerequisites for applying the Rayleigh model. A variable S-backward flow results in variable enrichment factors which increased from -11 (no H2S) to ≈-17 ‰ (40 mM of H2S) in my experiments. I show for the first time the significance of a bi-directional H2S transport across the cell membrane during DSR and its consequences for the 34S-isotope fractionation in sulfate.

The purpose of this thesis was to experimentally investigate the influence of increasing sulfide concentrations on the 34S isotope enrichment in sulfate during dissimilatory sulfate reduction (DSR). Two independent batch culture experiments with different maximum sulfide concentrations of up to 20 mM in the first and up to 40 mM in the second experiment were conducted using the marine sulfate reducer Desulfobacter latus. A comparison of the results from both experiments revealed a distinct offset towards more positive δ34S(SO42-) values in the 'high-sulfide' experiment, compared to the 'low-sulfide' experiment. While a Rayleigh type fractionation model was able to match the slopes - i.e., enrichment factors - of both experiments, it failed to reproduce the proper y-axis intercept in the 'high-sulfide' experiment. I therefore propose a new fractionation model that allows for a backward flow of ambient H2S into the bacterial cell and a subsequent enzymatically mediated oxidation of H2S to sulfate. The new backward flow increases with elevated H2S concentrations and is described as a first order rate constant. Unlike a Rayleigh type fractionation model, my model explains the slope and y-intercept of both experiments with a single parameter set. The new model with H2S-reflux further suggests that it can be used to determine growth kinetic parameters like the half-saturation constant through δ34S measurements. These findings support the hypothesis of microbially mediated, bi-directional S-fluxes between oxidized and reduced sulfur species. Because the S-transport during DSR appears to be bi-directional, great care must be taken when evaluating culture experiments with a Rayleigh type fractionation model, owing to the fact that an evident S-backward flow violates the prerequisites for applying the Rayleigh model. A variable S-backward flow results in variable enrichment factors which increased from -11 (no H2S) to ≈-17 ‰ (40 mM of H2S) in my experiments. I show for the first time the significance of a bi-directional H2S transport across the cell membrane during DSR and its consequences for the 34S-isotope fractionation in sulfate.

Ce travail de thèse visait à développer des procédés d'élimination des sulfates permettant la réduction des teneurs en sulfates des DC et des sols gypsifères afin d'améliorer la qualité des déchets et des sols à des fins agricoles ou des applications de recyclage. Le concept de traitement des DC par lixiviation à l'eau a été étudié (colonne de lixiviation). Les sulfates contenus dans les lixiviats sont ensuite éliminés à l'aide d'un traitement chimique ou biologique. L'approche biologique mise en oeuvre dans ce travail a consisté à mettre en oeuvre la réduction biologique des sulfates au sein de bioréacteurs de conception différente (i.e. réacteur UASB, réacteur à lit fluidisé inverse (IFB) ou d'un réacteur anaérobie gas lift). L'efficacité d'élimination des sulfates la plus élevée atteinte par ces trois systèmes varie de 75 à 95%. L'eau traitée provenant du bioréacteur peut alors ensuite être réutilisé dans la colonne de lixiviation. Le traitement chimique des sulfates est une option alternative pour traiter les lixiviats. Plusieurs produits chimiques ont été testés, (chlorure de baryum, nitrate de plomb (II), le chlorure de calcium, le carbonate de calcium, l'oxyde de calcium, et du sable recouvert d'un mélange d'oxydes d'aluminium et de fer). Un rendement de 99,9% d'élimination des sulfates (par précipitation) a été atteint avec le chlorure de baryum et le nitrate de plomb (II).Pour le traitement des DMA et des sols gypseux, cinq types de substrat organique tel que les copeaux de bambou, les boues d'épuration des eaux usées municipales, de l'écorce de riz, de coques de noix de coco broyée et des boues d'épuration des eaux usées d'une ferme porcine ont été testés comme donneurs d'électrons pour la réduction biologique des sulfates. L'efficacité de la réduction des sulfates la plus élevé (84%) a été obtenue en utilisant un mélange d'écorce de riz, de coques de noix de coco broyée et des boues d'épuration des eaux usées d'une ferme porcine comme donneurs d'électrons. Ensuite, ce mélange organique a été utilisé pour le traitement des sols gypsifères. Le sol de la mine de gypse a été mélangé avec le mélange organique en différentes proportions (10, 20, 30 et 40% de sol). Le rendement le plus élevé de 59 % de réduction des sulfates a été atteint dans le mélange de sol qui contient 40 % de matière organique. L'élimination des sulfures présents dans l'effluent des procédés de réduction biologique des sulfates est nécessaire. En effet, les sulfures peuvent causer plusieurs impacts environnementaux ou être ré-oxydé en sulfate si ils sont directement rejetés dans l'environnement. Le traitement électrochimique des effluents est l'une des solutions alternatives pour la récupération du soufre élémentaire à partir des sulfures. Une électrode de graphite a été testée comme électrode permettant l'oxydation électrochimique des sulfures en soufre élémentaire. Une électrode en graphite de grande surface est nécessaire afin d'avoir une résistance électrique la plus faible possible. La vitesse d'oxydation des sulfures la plus élevée est atteinte lors de l'application d'une résistance de 30 Ω à une concentration en sulfure de 250 mg.L-1 / Solid wastes containing sulfate, such as construction and demolition debris (CDD), are an important source of pollution, which can create a lot of environmental problems. It is suggested that these wastes have to be separated from other wastes, especially organic waste, and place it in a specific area of the landfill. This results in the rapid rise of the disposal costs of these gypsum wastes. Although these wastes can be reused as soil amendment or to make building materials, a concern has been raised by regulators regarding the chemical characteristics of the material and the potential risks to human health and the environment due to CDD containing heavy metals and a high sulfate content. Soils containing gypsum, namely gypsiferous soils, also have several problems during agricultural development such as low water retention capacity, shallow depth to a hardpan and vertical crusting. In some mining areas, gypsiferous soil problems occur, coupled with acid mine drainage (AMD) problems which cause a significant environmental threat. Reduction of the sulfate content of these wastes and soils is an option to overcome the above mentioned problems. This study aimed to develop sulfate removal systems to reduce the sulfate content of CDD and gypsiferous soils in order to decrease the amount of solid wastes as well as to improve the quality of wastes and soils for recycling purposes or agricultural applications. The treatment concept leaches the gypsum contained in the CDD by water in a leaching step. The sulfate containing leachate is further treated in biotic or abiotic systems. Biological sulfate reduction systems used in this research were the Upflow Anaerobic Sludge Blanket (UASB) reactor, Inverse Fluidized Bed (IFB) Reactor and Gas Lift Anaerobic Membrane Bioreactor (GL-AnMBR). The highest sulfate removal efficiency achieved from these three systems ranges from 75 to 95%. The treated water from the bioreactor can then be reused in the leaching column. Chemical sulfate removal (abiotic system) is an alternative option to treat the CDD leachate. Several chemicals were tested including barium chloride, lead(II) nitrate, calcium chloride, calcium carbonate, calcium oxide, aluminium oxide and iron oxide coated sand. A sulfate removal efficiency of 99.9% was achieved with barium chloride and lead(II) nitrate.For AMD and gypsiferous soils treatment, five types of organic substrate including bamboo chips (BC), municipal wastewater treatment sludge (MWTS), rice husk (RH), coconut husk chip (CHC) and pig farm wastewater treatment sludge (PWTS) were tested as electron donors for biological sulfate reduction treating AMD. The highest sulfate reduction efficiency (84%) was achieved when using the combination of PWTS, RH and CHC as electron donors. Then, this organic mixture was further used for treatment of the gypsiferous soils. The gypsum mine soil (overburden) was mixed with an organic mixture in different amounts including 10, 20, 30 and 40% of soil. The highest sulfate removal efficiency of 59% was achieved in the soil mixture which contained 40% organic material.The removal of sulfide from the effluent of the biological sulfate reduction process is required as sulfide can cause several environmental impacts or be re-oxidized to sulfate if directly discharged to the environment. Electrochemical treatment is one of the alternatives for sulfur recovery from aqueous sulfide. A non-catalyzed graphite electrode was tested as electrode for the electrochemical sulfide oxidation. A high surface area of the graphite electrode is required in order to have less internal resistance as much as possible. The highest sulfide oxidation rate was achieved when using the external resistance at 30 Ω at a sulfide concentration of 250 mg L-1

This item was digitized as part of the Million Books Project led by Carnegie Mellon University and supported by grants from the National Science Foundation (NSF). Cornell University coordinated the participation of land-grant and agricultural libraries in providing historical agricultural information for the digitization project; the University of Arizona Libraries, the College of Agriculture and Life Sciences, and the Office of Arid Lands Studies collaborated in the selection and provision of material for the digitization project.

In all living organisms, biological activities such as proper functioning and co-ordination of different organs will depend on different cells and molecular interactions. In some organisms the loss of functional organs or damage of organs can be lethal, whereas in others a special process called regeneration can retrieve lost organs. The molecular details of regeneration are still not completely understood in many organisms. Echinoderms are close to vertebrates in the evolutionary tree and are well known for their amazing regeneration capacity. So we chose to investigate the molecular processes of regeneration mechanism with an interest towards our favorite groups of molecules, glycosaminoglycans (GAGs). GAGs are linear polysaccharides, expressed on all cell surfaces and extracellular space and are also known to be involved in many cellular activities. We aimed to characterize the GAGs present in Echinodermata species Amphiura filiformis and investigated their role during arm regeneration. In Paper I we characterized the structure and function of GAGs from A. filiformis and identified that A. filiformis contains CS/DS type of GAGs, but no HS. The sulfation degree of these CS/DS is close to the one of heparin, i.e. they are highly sulfated. These chains are able to bind FGF-2 growth factor and induce FGF-2 mediated cell signaling. In Paper II we further characterized these GAGs for their localization and for their role in arm regeneration in A. filiformis. Immuno- and histochemical stainings on arm sections revealed that CS/DS GAGs are localized around the podia, surrounding the water vascular system, and around the muscle tissues. Inhibition of sulfated GAG biosynthesis by chlorate treatment affected the regeneration efficiency of the arms, which may be an indication of the importance of CS/DS structures in A. filiformis arm regeneration. We also characterized some bacterial sulfatases in Paper III and a lyase in Paper IV from human and canine gut symbiotic bacteria. Here we sought to find the substrate specificity and optimal conditions for these enzymes’ activities. Our findings suggest that these polysaccharide lyase and sulfatases can be used as potential tools to characterize different GAG structures and their application could further add knowledge on diseases mechanisms related to host pathogen interactions.

La modelisation du comportement des actinides dans l'environnement necessite l'acquisition de donnees structurales et thermodynamiques sur les especes susceptibles d'etre presentes dans les milieux naturels. Le protactinium est un element possedant une tendance tres marquee vis–à–vis de l'hydrolyse, de la polymerisation et de la sorption sur tout support solide. Dans ce cas, la determination des constantes d'equilibre relatives a des especes monomeres ne peut etre effectuee qu'a l'echelle des traces (CPa < 10-10M) avec l'isotope 233Pa. Les constantes de complexation de Pa(V) avec les ions sulfate ont donc ete determinees a partir d'une etude systematique des variations du coefficient de partage de Pa(V) dans le systeme TTA/toluene/H2O/Na2SO4/HClO4/NaClO4, en fonction de differents parametres tels que les concentrations de sulfate et de protons libres, la force ionique, la temperature, et la concentration de l'extractant. Compte tenu de l'interdependance des especes en phase aqueuse, il a ete necessaire de developper un code de calcul iteratif prenant en compte les reactions de dissociation de HSO4- et de formation de NaSO4- , mais egalement l'influence de la temperature et de la force ionique. Pour chaque valeur de µ et de temperature, et pour une concentration de proton libre fixee, le programme permet de calculer l'ensemble des concentrations des especes libres en solution. Les donnees de sortie sont les volumes de solutions meres de NaClO4, HClO4 et Na2SO4 a introduire pour realiser les solutions retenues. La mesure directe de la quantite de 233Pa en phase organique et aqueuse, par spectrometrie gamma, nous a permis de calculer le coefficient de partage (D) en fonction de la concentration des ions libres SO42-. Les experiences, effectuees en changeant differents parametres, montrent une forte dependance de D avec : la temperature, la concentration de la tta, la concentration des ions libres H+ et la concentration des ions sulfate libres. Les constantes de complexation ont ete determinees à l'aide d'un traitement mathematique des donnees de partage. L'extrapolation de ces constantes à force ionique nulle a ete realisee en utilisant le modele sit pour differentes valeurs de temperature. Parallelement, une etude structurale de Pa(V) en milieu sulfurique (13 et 4 M) et en milieu fluorhydrique (HF 0, 5 et 0, 05 M) a ete realisee avec l'isotope 231Pa. Les spectres exafs et xanes ont montre l'absence de liaison Pa = O dans le cas du milieu fluorhydrique. En milieu sulfurique une seule liaison oxo a ete mise en evidence, ce qui differe des actinides V et VI qui conservent toujours leur liaison trans-dioxo.