Dissertations / Theses on the topic 'Aragonite'

Thesis (M.S.)--Miami University, Dept. of Geology, 2002.
Title from first page of PDF document. Document formatted into pages; contains vi, 78 p. : ill. Includes bibliographical references (p. 37-40).

Ce travail de thèse porte sur un matériau (le Geocorail) formé par polarisation cathodique d’un treillis en acier disposé au sein d’un milieu sédimentaire marin. L’application de ce procédé est dédiée au renforcement des ouvrages côtiers dans la lutte contre le recul du trait de côte. L’objectif de cette étude est d’apporter des réponses relatives à l’influence des paramètres du procédé sur les propriétés physico-chimiques de ce matériau ainsi que l’évolution de celui-ci en condition d’abandon, c’est-à-dire lorsque la polarisation est arrêtée. Cette étude a été réalisée à travers une démarche expérimentale couplée avec des modèles numériques. Ces travaux ont été réalisés sur un matériau modèle formé en laboratoire et ont permis de mettre en évidence l’anisotropie de diffusion au sein de ce matériau dont l’épaisseur, la porosité et la masse volumique sont essentiellement contrôlées par la densité de courant et la durée de la polarisation. Ces deux derniers paramètres favorisent la formation de liant, constitué de brucite (Mg(OH)2) et d’aragonite (CaCO3), servant à l’agglomération du sédiment en place. La géométrie de ce sédiment est en outre un facteur primordial pour l’optimisation des propriétés du matériau. En ce qui concerne sa stabilité chimique en l’absence de polarisation, les analyses expérimentales et les modèles numériques ont révélé que l’aragonite se substitue à la brucite avec un rendement massique relativement faible, probablement lié à la forte diffusivité des matériaux analysés. La faible variation de la porosité et de la masse volumique (inférieur à 5% en 18 mois) rassure cependant de la stabilité du Geocorail dont les propriétés pourraient même s’améliorer avec le temps. Enfin, des modèles numériques de croissance et d’évolution de ce matériau à l’abandon ont été élaborés. Des voies d’amélioration ont également été proposées pour une meilleure prédiction de ces propriétés, voire la prédiction des propriétés mécaniques
This PhD work focused on the study of a material (Geocorail) formed by cathodic polarization applied in a marine sedimentary environment and used for the reinforcement of coastal structures in the fight against coastline recession. The objective of this study is to provide answers relative to the influence of the process parameters on the physico-chemical properties of this material as well as the evolution of the material under abandonment conditions, i.e. when the polarization is stopped. This was achieved through an experimental approach coupled with numerical models. This work was carried out on a laboratory material and its diffusion anisotropy within this material, the thickness, porosity and density of which are essentially controlled by the applied current density and the polarization time. These two parameters promote the formation of a binder, consisting of brucite (Mg(OH)2) and aragonite (CaCO3), which serves to agglomerate the sediments in place. The geometry of this sediment is also a key factor in optimizing the properties of this material. With regard to its chemical stability in the absence of polarization, experimental analyses and numerical models revealed that brucite substitutes for aragonite with a relatively low mass yield, probably linked to the high diffusivity of the studied materials. The small variation in porosity and density (less than 5% in 18 months) however ensures the stability of the Geocorail, whose properties could even improve with time. Finally, numerical models of the growth and evolution in abandon condition were developed. Some ways of improvement were also proposed for a better prediction of these properties, and even for the mechanical characterization using numerical methods

Abstract Aragonite is a minor secondary mineral in many limestone caves throughout the world. It has been claimed that it is the second-most common cave mineral after calcite (Hill & Forti 1997). Aragonite occurs as a secondary mineral in the vadose zone of some caves in New South Wales. Aragonite is unstable in fresh water and usually reverts to calcite, but it is actively depositing in some NSW caves. A review of current literature on the cave aragonite problem showed that chemical inhibitors to calcite deposition assist in the precipitation of calcium carbonate as aragonite instead of calcite. Chemical inhibitors work by physically blocking the positions on the calcite crystal lattice which would have otherwise allowed calcite to develop into a larger crystal. Often an inhibitor for calcite has no effect on the aragonite crystal lattice, thus aragonite may deposit where calcite deposition is inhibited. Another association with aragonite in some NSW caves appears to be high evaporation rates allowing calcite, aragonite and vaterite to deposit. Vaterite is another unstable polymorph of calcium carbonate, which reverts to aragonite and calcite over time. Vaterite, aragonite and calcite were found together in cave sediments in areas with low humidity in Wollondilly Cave, Wombeyan. Several factors were found to be associated with the deposition of aragonite instead of calcite speleothems in NSW caves. They included the presence of ferroan dolomite, calcite-inhibitors (in particular ions of magnesium, manganese, phosphate, sulfate and heavy metals), and both air movement and humidity. Aragonite deposits in several NSW caves were examined to determine whether the material is or is not aragonite. Substrates to the aragonite were examined, as was the nature of the bedrock. The work concentrated on Contact Cave and Wiburds Lake Cave at Jenolan, Sigma Cave, Wollondilly Cave and Cow Pit at Wombeyan and Piano Cave and Deep Hole (Cave) at Walli. Comparisons are made with other caves. The study sites are all located in Palaeozoic rocks within the Lachlan Fold Belt tectonic region. Two of the sites, Jenolan and Wombeyan, are close to the western edge of the Sydney Basin. The third site, Walli, is close to a warm spring. The physical, climatic, chemical and mineralogical influences on calcium carbonate deposition in the caves were investigated. Where cave maps were unavailable, they were prepared on site as part of the study. %At Jenolan Caves, Contact Cave and Wiburds Lake Cave were examined in detail, %and other sites were compared with these. Contact Cave is located near the eastern boundary of the Late Silurian Jenolan Caves Limestone, in an area of steeply bedded and partially dolomitised limestone very close to its eastern boundary with the Jenolan volcanics. Aragonite in Contact Cave is precipitated on the ceiling as anthodites, helictites and coatings. The substrate for the aragonite is porous, altered, dolomitised limestone which is wedged apart by aragonite crystals. Aragonite deposition in Contact Cave is associated with a concentration of calcite-inhibiting ions, mainly minerals containing ions of magnesium, manganese and to a lesser extent, phosphates. Aragonite, dolomite and rhodochrosite are being actively deposited where these minerals are present. Calcite is being deposited where minerals containing magnesium ions are not present. The inhibitors appear to be mobilised by fresh water entering the cave as seepage along the steep bedding and jointing. During winter, cold dry air pooling in the lower part of the cave may concentrate minerals by evaporation and is most likely associated with the ``popcorn line'' seen in the cave. Wiburds Lake Cave is located near the western boundary of the Jenolan Caves Limestone, very close to its faulted western boundary with Ordovician cherts. Aragonite at Wiburds Lake Cave is associated with weathered pyritic dolomitised limestone, an altered, dolomitised mafic dyke in a fault shear zone, and also with bat guano minerals. Aragonite speleothems include a spathite, cavity fills, vughs, surface coatings and anthodites. Calcite occurs in small quantities at the aragonite sites. Calcite-inhibitors associated with aragonite include ions of magnesium, manganese and sulfate. Phosphate is significant in some areas. Low humidity is significant in two areas. Other sites briefly examined at Jenolan include Glass Cave, Mammoth Cave, Spider Cave and the show caves. Aragonite in Glass Cave may be associated with both weathering of dolomitised limestone (resulting in anthodites) and with bat guano (resulting in small cryptic forms). Aragonite in the show caves, and possibly in Mammoth and Spider Cave is associated with weathering of pyritic dolomitised limestone. Wombeyan Caves are developed in saccharoidal marble, metamorphosed Silurian Wombeyan Caves Limestone. Three sites were examined in detail at Wombeyan Caves: Sigma Cave, Wollondilly Cave and Cow Pit (a steep sided doline with a dark zone). Sigma Cave is close to the south east boundary of the Wombeyan marble, close to its unconformable boundary with effusive hypersthene porphyry and intrusive gabbro, and contains some unmarmorised limestone. Aragonite occurs mainly in a canyon at the southern extremity of the cave and in some other sites. In Sigma Cave, aragonite deposition is mainly associated with minerals containing calcite-inhibitors, as well as some air movement in the cave. Calcite-inhibitors at Sigma Cave include ions of magnesium, manganese, sulfate and phosphate (possibly bat origin), partly from bedrock veins and partly from breakdown of minerals in sediments sourced from mafic igneous rocks. Substrates to aragonite speleothems include corroded speleothem, bedrock, ochres, mud and clastics. There is air movement at times in the canyon, it has higher levels of CO2 than other parts of the cave and humidity is high. Air movement may assist in the rapid exchange of CO2 at speleothem surfaces. Wollondilly Cave is located in the eastern part of the Wombeyan marble. At Wollondilly Cave, anthodites and helictites were seen in an inaccessible area of the cave. Paramorphs of calcite after aragonite were found at Jacobs Ladder and the Pantheon. Aragonite at Star Chamber is associated with huntite and hydromagnesite. In The Loft, speleothem corrosion is characteristic of bat guano deposits. Aragonite, vaterite and calcite were detected in surface coatings in this area. Air movement between the two entrances of this cave has a drying effect which may serve to concentrate minerals by evaporation in some parts of the cave. The presence of vaterite and aragonite in fluffy coatings infers that vaterite may be inverting to aragonite. Calcite-inhibitors in the sediments include ions of phosphate, sulphate, magnesium and manganese. Cave sediment includes material sourced from detrital mafic rocks. Cow Pit is located near Wollondilly Cave, and cave W43 is located near the northern boundary of the Wombeyan marble. At Cow Pit, paramorphs of calcite after aragonite occur in the walls as spheroids with minor huntite. Aragonite is a minor mineral in white wall coatings and red phosphatic sediments with minor hydromagnesite and huntite. At cave W43, aragonite was detected in the base of a coralloid speleothem. Paramorphs of calcite after aragonite were observed in the same speleothem. Dolomite in the bedrock may be a source of magnesium-rich minerals at cave W43. Walli Caves are developed in the massive Belubula Limestone of the Ordovician Cliefden Caves Limestone Subgroup (Barrajin Group). At the caves, the limestone is steeply bedded and contains chert nodules with dolomite inclusions. Gypsum and barite occur in veins in the limestone. At Walli Caves, Piano Cave and Deep Hole (Deep Cave) were examined for aragonite. Gypsum occurs both as a surface coating and as fine selenite needles on chert nodules in areas with low humidity in the caves. Aragonite at Walli caves was associated with vein minerals and coatings containing calcite-inhibitors and, in some areas, low humidity. Calcite-inhibitors include sulfate (mostly as gypsum), magnesium, manganese and barium. Other caves which contain aragonite are mentioned. Although these were not major study sites, sufficient information is available on them to make a preliminary assessment as to why they may contain aragonite. These other caves include Flying Fortress Cave and the B4-5 Extension at Bungonia near Goulburn, and Wyanbene Cave south of Braidwood. Aragonite deposition at Bungonia has some similarities with that at Jenolan in that dolomitisation of the bedrock has occurred, and the bedding or jointing is steep allowing seepage of water into the cave, with possible oxidation of pyrite. Aragonite is also associated with a mafic dyke. Wyanbene cave features some bedrock dolomitisation, and also features low grade ore bodies which include several known calcite-inhibitors. Aragonite appears to be associated with both features. Finally, brief notes are made of aragonite-like speleothems at Colong Caves (between Jenolan and Wombeyan), a cave at Jaunter (west of Jenolan) and Wellington (240\,km NW of Sydney).

Abstract Aragonite is a minor secondary mineral in many limestone caves throughout the world. It has been claimed that it is the second-most common cave mineral after calcite (Hill & Forti 1997). Aragonite occurs as a secondary mineral in the vadose zone of some caves in New South Wales. Aragonite is unstable in fresh water and usually reverts to calcite, but it is actively depositing in some NSW caves. A review of current literature on the cave aragonite problem showed that chemical inhibitors to calcite deposition assist in the precipitation of calcium carbonate as aragonite instead of calcite. Chemical inhibitors work by physically blocking the positions on the calcite crystal lattice which would have otherwise allowed calcite to develop into a larger crystal. Often an inhibitor for calcite has no effect on the aragonite crystal lattice, thus aragonite may deposit where calcite deposition is inhibited. Another association with aragonite in some NSW caves appears to be high evaporation rates allowing calcite, aragonite and vaterite to deposit. Vaterite is another unstable polymorph of calcium carbonate, which reverts to aragonite and calcite over time. Vaterite, aragonite and calcite were found together in cave sediments in areas with low humidity in Wollondilly Cave, Wombeyan. Several factors were found to be associated with the deposition of aragonite instead of calcite speleothems in NSW caves. They included the presence of ferroan dolomite, calcite-inhibitors (in particular ions of magnesium, manganese, phosphate, sulfate and heavy metals), and both air movement and humidity. Aragonite deposits in several NSW caves were examined to determine whether the material is or is not aragonite. Substrates to the aragonite were examined, as was the nature of the bedrock. The work concentrated on Contact Cave and Wiburds Lake Cave at Jenolan, Sigma Cave, Wollondilly Cave and Cow Pit at Wombeyan and Piano Cave and Deep Hole (Cave) at Walli. Comparisons are made with other caves. The study sites are all located in Palaeozoic rocks within the Lachlan Fold Belt tectonic region. Two of the sites, Jenolan and Wombeyan, are close to the western edge of the Sydney Basin. The third site, Walli, is close to a warm spring. The physical, climatic, chemical and mineralogical influences on calcium carbonate deposition in the caves were investigated. Where cave maps were unavailable, they were prepared on site as part of the study. %At Jenolan Caves, Contact Cave and Wiburds Lake Cave were examined in detail, %and other sites were compared with these. Contact Cave is located near the eastern boundary of the Late Silurian Jenolan Caves Limestone, in an area of steeply bedded and partially dolomitised limestone very close to its eastern boundary with the Jenolan volcanics. Aragonite in Contact Cave is precipitated on the ceiling as anthodites, helictites and coatings. The substrate for the aragonite is porous, altered, dolomitised limestone which is wedged apart by aragonite crystals. Aragonite deposition in Contact Cave is associated with a concentration of calcite-inhibiting ions, mainly minerals containing ions of magnesium, manganese and to a lesser extent, phosphates. Aragonite, dolomite and rhodochrosite are being actively deposited where these minerals are present. Calcite is being deposited where minerals containing magnesium ions are not present. The inhibitors appear to be mobilised by fresh water entering the cave as seepage along the steep bedding and jointing. During winter, cold dry air pooling in the lower part of the cave may concentrate minerals by evaporation and is most likely associated with the ``popcorn line'' seen in the cave. Wiburds Lake Cave is located near the western boundary of the Jenolan Caves Limestone, very close to its faulted western boundary with Ordovician cherts. Aragonite at Wiburds Lake Cave is associated with weathered pyritic dolomitised limestone, an altered, dolomitised mafic dyke in a fault shear zone, and also with bat guano minerals. Aragonite speleothems include a spathite, cavity fills, vughs, surface coatings and anthodites. Calcite occurs in small quantities at the aragonite sites. Calcite-inhibitors associated with aragonite include ions of magnesium, manganese and sulfate. Phosphate is significant in some areas. Low humidity is significant in two areas. Other sites briefly examined at Jenolan include Glass Cave, Mammoth Cave, Spider Cave and the show caves. Aragonite in Glass Cave may be associated with both weathering of dolomitised limestone (resulting in anthodites) and with bat guano (resulting in small cryptic forms). Aragonite in the show caves, and possibly in Mammoth and Spider Cave is associated with weathering of pyritic dolomitised limestone. Wombeyan Caves are developed in saccharoidal marble, metamorphosed Silurian Wombeyan Caves Limestone. Three sites were examined in detail at Wombeyan Caves: Sigma Cave, Wollondilly Cave and Cow Pit (a steep sided doline with a dark zone). Sigma Cave is close to the south east boundary of the Wombeyan marble, close to its unconformable boundary with effusive hypersthene porphyry and intrusive gabbro, and contains some unmarmorised limestone. Aragonite occurs mainly in a canyon at the southern extremity of the cave and in some other sites. In Sigma Cave, aragonite deposition is mainly associated with minerals containing calcite-inhibitors, as well as some air movement in the cave. Calcite-inhibitors at Sigma Cave include ions of magnesium, manganese, sulfate and phosphate (possibly bat origin), partly from bedrock veins and partly from breakdown of minerals in sediments sourced from mafic igneous rocks. Substrates to aragonite speleothems include corroded speleothem, bedrock, ochres, mud and clastics. There is air movement at times in the canyon, it has higher levels of CO2 than other parts of the cave and humidity is high. Air movement may assist in the rapid exchange of CO2 at speleothem surfaces. Wollondilly Cave is located in the eastern part of the Wombeyan marble. At Wollondilly Cave, anthodites and helictites were seen in an inaccessible area of the cave. Paramorphs of calcite after aragonite were found at Jacobs Ladder and the Pantheon. Aragonite at Star Chamber is associated with huntite and hydromagnesite. In The Loft, speleothem corrosion is characteristic of bat guano deposits. Aragonite, vaterite and calcite were detected in surface coatings in this area. Air movement between the two entrances of this cave has a drying effect which may serve to concentrate minerals by evaporation in some parts of the cave. The presence of vaterite and aragonite in fluffy coatings infers that vaterite may be inverting to aragonite. Calcite-inhibitors in the sediments include ions of phosphate, sulphate, magnesium and manganese. Cave sediment includes material sourced from detrital mafic rocks. Cow Pit is located near Wollondilly Cave, and cave W43 is located near the northern boundary of the Wombeyan marble. At Cow Pit, paramorphs of calcite after aragonite occur in the walls as spheroids with minor huntite. Aragonite is a minor mineral in white wall coatings and red phosphatic sediments with minor hydromagnesite and huntite. At cave W43, aragonite was detected in the base of a coralloid speleothem. Paramorphs of calcite after aragonite were observed in the same speleothem. Dolomite in the bedrock may be a source of magnesium-rich minerals at cave W43. Walli Caves are developed in the massive Belubula Limestone of the Ordovician Cliefden Caves Limestone Subgroup (Barrajin Group). At the caves, the limestone is steeply bedded and contains chert nodules with dolomite inclusions. Gypsum and barite occur in veins in the limestone. At Walli Caves, Piano Cave and Deep Hole (Deep Cave) were examined for aragonite. Gypsum occurs both as a surface coating and as fine selenite needles on chert nodules in areas with low humidity in the caves. Aragonite at Walli caves was associated with vein minerals and coatings containing calcite-inhibitors and, in some areas, low humidity. Calcite-inhibitors include sulfate (mostly as gypsum), magnesium, manganese and barium. Other caves which contain aragonite are mentioned. Although these were not major study sites, sufficient information is available on them to make a preliminary assessment as to why they may contain aragonite. These other caves include Flying Fortress Cave and the B4-5 Extension at Bungonia near Goulburn, and Wyanbene Cave south of Braidwood. Aragonite deposition at Bungonia has some similarities with that at Jenolan in that dolomitisation of the bedrock has occurred, and the bedding or jointing is steep allowing seepage of water into the cave, with possible oxidation of pyrite. Aragonite is also associated with a mafic dyke. Wyanbene cave features some bedrock dolomitisation, and also features low grade ore bodies which include several known calcite-inhibitors. Aragonite appears to be associated with both features. Finally, brief notes are made of aragonite-like speleothems at Colong Caves (between Jenolan and Wombeyan), a cave at Jaunter (west of Jenolan) and Wellington (240\,km NW of Sydney).

Ocean chemistry has oscillated throughout Earth history to favour the dominant non-biogenic polymorph of calcium carbonate (CaCO3) to be either calcite or aragonite (Sandberg, 1983). Throughout the Phanerozoic these oscillations have occurred to facilitate aragonite-dominant conditions three times and calcite-dominant conditions twice. These aragonite-calcite seas conditions have previously been viewed as a global phenomenon where conditions fluctuate over time, but not in space, and represent the main environmental context in which the evolution of CaCO3 biomineralisation has occurred (Stanley and Hardie, 1998). CaCO3 is one of the most widely distributed minerals in the marine environment, occurring throughout geological history, both biogenically and non-biogenically (Lowenstam and Weiner, 1989). Marine non-biogenic precipitates are commonly found as carbonate ooids, sedimentary cements and muds (Nichols, 2009). Biogenic CaCO3 is formed via biomineralisation in calcifying organisms (Lowenstam and Weiner, 1989; Allemand et al., 2004), and is much more abundant than the non-biogenic forms. Although CaCO3 is abundant, it only accounts for a small proportion of the global carbon budget. Biogenic CaCO3 is representative of a larger proportion of the global carbon budget than non-biogenically formed CaCO3 (Berelson et al., 2007). The main driving force controlling the precipitation of CaCO3 polymorphs is the Mg:Ca molar ratio of seawater (Morse et al., 2007). However, other parameters such as temperature (Burton and Walter, 1984; Morse et al, 1997; Balthasar and Cusack, 2015), pCO2 (Lee and Morse, 2010), and SO4 (Morse et al., 2007) are also known to influence CaCO3 polymorph formation but are often overlooked in the context of aragonite-calcite seas. Fluctuations in these parameters of Mg:Ca ratio, SO42+ and pCO2 of seawater have been suggested to cause shifts in original composition of non-biogenic marine carbonates, and in turn viewed as the main driving mechanisms facilitating the switch between aragonite and calcite dominance (Morse et al., 1997; Lee and Morse, 2010; Bots et al., 2011). Specifically the influence of temperature is important because it is likely to result in aragonite-calcite sea conditions to vary spatially (Balthasar and Cusack, 2015). Today marine temperatures are changing across the latitudes due to environmental factors. Global CO2 levels have increased significantly since industrialisation (Doney et al., 2009), with 33% entering the oceans and reducing pH (Raven et al., 2005) accelerating climate change (IPCC, 2013) and influencing marine calcification (Fitzer et al., 2014a; 2015b; Bach, 2015; Zhao et al., 2017). Strong links between the carbon cycle and climate change observed in the rock record give evidence that environmental changes such as pCO2 and global warming have impacts on calcification and marine biota (Hönish et al., 2012). The first objective was to determine the influence of Mg:Ca ratio, temperature and water movement on the first-formed precipitates of non-biogenic CaCO3 precipitation yielded via a continuous addition technique experiments (Chapter 3). CaCO3 precipitation was induced by continuously adding bicarbonate to a bulk solution of known Mg:Ca ratio (1,2 or 3), and fixed salinity of 35 (practical salinity scale), at 20°C and 30ºC in still conditions, and then repeated with the solution being shaken at 80rpm mimicking more natural marine conditions. The mineralogy and crystal morphology of precipitates was determined using Raman Spectroscopy and Scanning Electron Microscopy. Results in Chapter 3 indicated that polymorphs co-precipitate, with the ratio of aragonite to calcite increasing with increased Mg:Ca ratio and elevated temperature. The main difference between still and shaken conditions was that overall, more crystals of aragonite compared to calcite precipitate in shaking conditions. The crystal size is less influenced in aragonite, but calcite crystals were smaller. These results contradict current views on aragonite-calcite seas as spatially homogenous ocean states need to be re-examined to include the effect of temperature on the spatial distribution of CaCO3 polymorphs. Examining polymorph growth under these experimental constraints allows us to gain a better understanding of how temperature and Mg:Ca together control non-biogenic aragonite and calcite precipitation providing a more realistic environmental framework in which to evaluate the evolution of biomineralisation. To further this work, the same continuous addition technique was used with the presence of sulphate in the mother solution (Chapter 4). Sulphate being the 4th most common marine ion (Halvey et al., 2012) and known to have an influence on mineralogy (Kontrec et al., 2004). The presence of sulphate increase the aragonite to calcite proportion formed compared to sulphate-free conditions (Chapter 4). Elevated temperature with sulphate further increased the proportion of aragonite to calcite facilitated (Chapter 4). In the presence of sulphate the main difference between sulphate-free environments and those with sulphate environments was: in still conditions the presence of sulphate increased the crystal number more than the crystal size at 20°C; at 30°C or in shaken conditions the presence of sulphate increased the crystal size of aragonite to calcite much more than it had influence on the crystal number. Non-biogenically the influence of sulphate lowered the threshold of Mg:Ca ratio that the switch between calcite and aragonite would be facilitated at (Bots et al., 2011). This would have implications for marine calcification as pure calcite seas would become very rare and imply that organisms would be forming calcified hard parts out with the supported mineralogies. Biogenic application of these results is complex however as organisms often have the ability to select aragonite as their main polymorph for their own functional requirements (Weiner and Dove, 2003). The growth parameters of non-biogenic polymorph formations grown from artificial seawater can be used to understand how organism control can influence the polymorph formation under similar conditions (Kawano et al., 2009). Assessing the elemental composition of mussel shells grown under know conditions of temperature and pCO2 allowed the environmental influences on mineralogy be assessed under possible the projected changes in climate forecast to occur by 2100 by IPCC (2013). Prior to this research, no study had used Mytilus edulis shell elemental composition to test the influence of aragonite-calcite sea conditions on mineralogy. This research compiles a detailed source of information on the constraints from environmental sources such as temperature and pCO2, on the elemental concentrations within shell formation and what potential changes could occur in response to a changing marine environment (Chapter 5). Here elevated temperature significantly increased the concentration of magnesium in calcite, but did not influence the magnesium concentration of aragonite unless combined with elevated pCO2. The concentrations of sulphur in calcite were significantly decreased at elevated pCO2 or combined increased temperature and pCO2 as concentrations of sodium were found to be increased under these conditions. In aragonite the concentrations of both sulphur and sodium were significantly different under all scenarios. Strontium did not yield any significant results in this research in either calcite or aragonite. Results observed indicate that the shell elemental concentrations are influenced differently in aragonite or calcite, and further influenced by environmental conditions based on the original mineralogy. This suggests that physiological mechanisms under the constraints of increased temperature and pCO2 can override the seawater chemistry influences of aragonite-calcite seas impacting on mineralogy.
This research allows comparison of how non-biogenic and biogenic CaCO3 formation is influenced by seawater chemistry and environmental parameters to determine the dominant mineralogy. Increased temperature in both formations has shown to increase the impact of magnesium on calcite enabling the facilitation of aragonite. However, magnesium has influence on biogenic aragonite in extreme combined conditions of elevated temperature and pCO2. This work indicates that CaCO3 formation is complex and requires a multi-variable approach to understanding the mechanisms that facilitate the dominant mineralogy. By including variables such as temperature, this research suggests that aragonite-calcite seas conditions do not facilitate globally homogeneous switches in mineralogy, but the mineralogy is indeed influenced on latitudinal scales by other factors that influence the mechanisms involved.

Waters from mines (acid mine drainage-AMD), contain elevated concentrations of SO-24, Fe and other contaminant metals, which can persist in the environment during centuries. The purpose of AMD treatments is to retain metals and to neutralize the acidity. One of the employed treatment systems is the anoxic limestone drainage (ALD), characterized by low maintenance and cost. The efficiency of the ALD is however limited by secondary mineral precipitation (ppt) causing the passivation (pass) of the limestone grains and the pores clogging. The presence of aqueous sulfate leads to gypsum (gyp) ppt, which contributes to pass and affects the ALD¿s efficiency. This PhD study is focused on the loss of reactivity of calcite (cal), aragonite (ar) and dolomite (dol) due to grain coating or clogging of porosity. To this end, three types of experiments were conducted: column, batch and in-situ AFM experiments. Columns experiments were carried out injecting synthetic acidic solutions (sulfate with Fe(III) or Al pH 2-3, H2SO4) at constant flow (6x10-4 and 1x10-3 L m-2 s-1) in the columns packed with cal, ar or dol grains. The columns worked efficiently removing aqueous metals as long as cal dissolved and buffered the solution pH. However, Ca released from dissolving cal and the sulfate in solution, promoted gyp ppt on the cal surfaces preventing his dissolution (diss). This pass process limited the efficiency of the columns. Larger input sulfate concentrations or higher pH led to shorter pass times. Observations with X-ray microtomography and X-ray microdiffraction showed the coating of gyp on the cal and secondary oxyhydroxides between the grains. This favored the formation of preferential flow paths, isolating regions of non-reacted grains. An improved experimental design (mixing limestone grains and glass beads) minimized the formation of these preferential flow paths. Experimental results have been modeled with the CrunchFlow reactive transport code. Fitting of the results required a decrease in the reactive surface area of cal, which is consistent with the pass process. Batch experiments (pH 2 H2SO4 solution equilibrated with respect to CaSO4¿2H2O) were performed to study the coupled reactions of diss of cal, ar and dol and ppt of gyp. The three carbonate minerals acted as carbonate substrates on which gyp grew. Along the experiments three stages were distinguished: gyp ppt induction time, diss of the carbonate substrate coupled with gyp ppt, and achievement of equilibrium with respect to the carbonate mineral. The induction time was similar during diss of cal and ar (same diss rate). During diss of the carbonate minerals the pH raised from 2 to ~7, decreasing the carbonate mineral diss rate and stopping the gyp ppt as equilibrium with respect to CaCO3 was approached. The gyp ppt rates were similar when cal and ar dissolved, regardless the morphology of substrate. In-situ atomic force microscopy (AFM) experiments were performed to study the cal and dol diss and gyp ppt in Na2SO4 and CaSO4 solutions (pH 2-6). The carbonate diss took place at the (104) cleavage surfaces in sulfate-rich solutions undersaturated with respect to gyp, by the formation of characteristic rhombohedral-shaped etch pits. Rounding of the etch pit corners was observed as solutions approached close-to-equilibrium conditions with respect to cal. The calculated diss rates of cal at pH 4.8 and 5.6 agreed with the values reported in the literature. When using solutions previously equilibrated with respect to gyp, gyp ppt coupled with cal diss showed short gyp nucleation induction times. The gyp precipitate quickly coated the cal surface, forming arrow-like forms parallel to the crystallographic orientations of the cal etch pits. Gyp ppt coupled with dol diss was slower than that of cal, indicating the diss rate to be the rate-controlling step. The resulting gyp coating partially covered the surface during the experimental duration of a few hours.
Las aguas que proceden de minas (en ingles acid mine drainage-AMD) contienen altas concentraciones de SO4 y metales contaminantes que pueden perdurar siglos en el medio ambiente. El objetivo de los tratamientos de AMD es retener los metales y neutralizar la acidez de las AMD. Uno de los sistemas de tratamiento usado, es el drenaje anóxico a través de caliza (clz) (en inglés anoxic limestone drainage, ALD) que necesita escaso mantenimiento y bajo presupuesto. La eficiencia de los ALD está limitada por la precipitación (ppt) de minerales secundarios (yeso e Me-hydroxidos) que causa el recubrimiento de los granos de clz (pasivación, pass) y la colmatación de los poros reduciendo la reactividad de la clz y su poder tampón. Esta tesis esta enfocada en los procesos que afectan a los minerales carbonatos usados en el ALD y en la pérdida de reactividad de la calcita (cal), aragonita (arag) y dolomita (dol) debido a la pass. Con este fin se llevaron a cabo tres tipos de experimentos (25 °C, 1 atm): de columna, batch e in situ con microscopio de fuerza atómica (AFM). Experimentos de columnas: Se inyectaron soluciones ácidas sintéticas (pH2) ricas en Fe (III) o Al con flujo constante de 6x10-4 o 1x10-3 L m-2 s-1 en columnas rellenadas con granos de cal, arag o dol. Las columnas han retenido los metales durante la disolución (diss) de los carbonatos, aumentado el pH e promoviendo la ppt (ppt) de oxihidróxidos de los metales. El Ca liberado durante la diss, junto con el sulfato, ha precipitado como yeso causando el recubrimiento de la superficie de los granos. El recubrimiento impide la diss de los carbonatos y limita la eficiencia de las columnas. Altas concentraciones de sulfato y pH más ácidos produjeron tiempos de pass más rápidos. Mediante micro-tomografía de rayos X (mCT) y micro-difracción de rayos X (mXRD), se mostró que el recubrimiento de los granos de carbonatos se debe a la ppt de yeso y que los oxihidróxidos precipitan entre los granos, la cual cosa favoreció la formación de flujos preferenciales, aislando regiones donde no se producen reacciones entre solución circulante y granos. El flujo preferencial se ha visto reducido cuando se han mezclado los carbonatos con esferas de vidrio. Los resultados experimentales se han modelado con el código CrunchFlow ajustando el valor de del área reactiva de la cal en el modelo con los datos experimentales, corroborando el proceso de pass en los experimentos. Se realizaron experimentos de tipo batch para estudiar la diss de cal, dol y arag (granulometria: 100-300 mm;1-2 mm, y 1.5 x 1.2 x 0.5 cm) y la ppt de yeso sobre la superficie de los carbonatos y a pH 2 (solución de H2SO4 equilibrada respecto al CaSO4¿2H2O). A lo largo de los experimentos se han distinguido tres fases: tiempo de inducción para la nucleación del yeso; fase de diss de los carbonatos con la simultánea ppt de yeso; equilibrio alcanzado entre la solución y el mineral carbonatado. Durante la diss de carbonatos, el pH subió de 2 a ~7, ralentizando la cinética de diss y la velocidad de ppt de yeso hasta llegar a cero una vez alcanzado el equilibrio con CaCO3. Además resultó que independientemente del sustrato la velocidad de ppt del yeso fue similar. Los experimentos in situ AFM se realizaron con soluciones de Na2SO4 y CaSO4 y pH entre 2-6 para estudiar el proceso acoplado de la diss de cal o dol con la ppt de yeso. La diss de los carbonatos tuvo lugar en las superficies de exfoliación (104). Se han observado distintas formas de diss (etch pits), con estructura típica romboédrica y el redondeo de los bordes de los etch pits conforme se aproximaban a condiciones de equilibrio con respecto a la cal. El yeso precipitado recubrió rápidamente la superficie de la cal, con morfología de flecha y ejes paralelos a las orientaciones cristalográficas de los etch pits de la cal. La ppt del yeso en el caso de la diss de dol fue más lento y parcial, lo que indica que la velocidad de diss controla la velocidad de las reacciones.
Les aigües que procedeixen de l'activitat minera, conegudes com aigües àcides de mina (en anglès acid mine drainage, AMD) contenen normalment altes concentracions de sulfat, ferro i altres metalls contaminants associats. Aquests contaminants poden perdurar en el medi ambient fins a segles després del cessament de l'activitat minera. Els principals objectius dels tractaments AMD són la retenció de metalls (precipitació dels metalls contaminants) i la neutralització de l'acidesa de les aigües. Un dels possibles sistemes de tractament passiu, i dels més utilitzats, és el drenatge anòxic amb calcària (en anglès, anoxic limestone drainage, ALD), o sistemes derivats (per exemple, la reducció i els sistemes de producció d'alcalinitat), que es caracteritzen pel poc manteniment requerit i el baix cost. No obstant, l'eficiència dels sistemes d'ALD està limitada per la precipitació de minerals secundaris que causa la passivació (recobriment) dels grans de calcària i l'obstrucció dels porus entre ells, reduint així la reactivitat de la calcària i, per tant, el poder tampó. La presència de sulfat aquós indueix la precipitació de guix, que contribueix en gran mesura a la passivació de la calcària i afecta l'eficiència dels sistemes de tractament. Aquesta Tesi té com a objectiu principal millorar els nostres coneixements sobre el funcionament de minerals carbonats utilitzats en ALD i la pèrdua de la reactivitat de la calcita, aragonita i dolomita a causa del recobriment dels grans o l'obstrucció dels porus entre grans. Amb aquesta finalitat, es s’han dut a terme tres tipus d'experiments: (1) experiments de columna, (2) de tipus batch i (3) experiments in situ amb AFM. (1) Els experiments de columnes emplenades amb grans de calcita, aragonita o dolomita (de diàmetre 1-2 mm) es van realitzar per estudiar el comportament dels sistemes de tractament passiu emprats en el drenatge àcid de mines (AMD). Es van injectar solucions àcides sintètiques (principalment a pH2, H2SO4) rica en ferro (Fe (III)) o alumini. Durant els experiments, el flux de la solució d'entrada es va mantenir constant a la velocitat de Darcy de 6x10-4 a 1x10-3 L m-2 s-1. Les columnes han eliminat eficientment el ferro i l’alumini aquosos mentre que la dissolució dels carbonats ha tamponat el pH de la solució (augment del pH i inducció de la precipitació d’oxihidróxids de Fe (III) - o d'Al). No obstant, el Ca alliberat en solució pels minerals carbonats, juntament amb el sulfat aquós, va induir la precipitació de guix, que és la principal causa de recobriment (passivació) a les superfícies dels grans. Aquest recobriment ha impedit conseqüentment la dissolució de calcita limitant l'eficiència de les columnes. Concentracions més altes del sulfat d'entrada i pH més àcids van originar temps de passivació més ràpids. La caracterització de l'estructura dels porus i de la composició química dels sòlids mitjanament la per micro-tomografia de raigs X (MCT) i micro-difracció de raigs X (mXRD), va mostrar que el recobriment dels grans de carbonats és degut a la precipitació de guix i que els oxihidróxids secundaris tendeixen a precipitar entre els grans. La precipitació de minerals secundaris va afavorir la formació de fluxos preferents, aïllant regions on no es produeixen reaccions entre la solució circulant i els grans. L'efecte de la formació del flux preferent s'ha reduït utilitzant un disseny diferent a les columnes (barrejant els grans de carbonats amb esferes de vidre inerts). Els resultats experimentals s'han modelitzat amb el codi de transport reactiu CrunchFlow. Per tal que les dades experimentals i les del model coincidissin s'ha ajustat al valor de l'àrea reactiva de la calcita en el model, consistentment amb el procés de passivació en els experiments. (2) Es van dur a terme experiments de tipus batch a 25 ° C, pressió atmosfèrica i pH 2 (solució de H2SO4 equilibrada respecte al CaSO4 • 2H2O) per estudiar les reaccions de dissolució de la calcita i aragonita acoblades a la precipitació de guix. Es van utilitzar tres tipus de mostra sòlida (pols (100-300 μm), grans (1-2 mm) i fragments (1.5 x 1.2 x 0.5 cm)) que van actuar com a substrats de mineral carbonat en què va créixer el guix. Al llarg dels experiments s'han distingit tres fases: temps d'inducció de la precipitació del guix, dissolució del substrat de mineral carbonat, juntament amb la precipitació de guix, i l'assoliment de l'equilibri de la solució respecte el mineral carbonat. El temps d'inducció va ser similar durant la dissolució de calcita i aragonita, ja que tots dos minerals dissolen amb la mateixa velocitat de dissolució. Durant la dissolució de minerals carbonats, el pH va pujar de 2 a aproximadament 7, alentint tant la velocitat de dissolució dels carbonats com la taxa de precipitació de guix per arribar a zero un cop assolit l'equilibri amb CaCO3 (calcita o aragonita) va ser aconseguit. La velocitat de precipitació del guix va ser similar independentment del substrat (calcita o aragonita), tot i la morfologia del mateix substrat. 3) Es van realitzar experiments in-situ amb el microscopi de força atòmica (AFM) per estudiar el procés global de la dissolució de calcita i dolomita i la precipitació de guix en solucions Na2SO4 i CaSO4 amb valors de pH entre 2 i 6 i temperatura ambient (23 ± 1 ° C). La dissolució dels minerals carbonats va tenir lloc a les superfícies de clivatge (104) usant solucions riques en sulfat i subsaturades respecte al guix. Es va observar la formació de forats de dissolució (etch pits) amb les típiques formes romboèdriques. També s’observa l'arrodoniment de les vores dels etch pits quan les solucions s’acostaven a a les vores l'equilibri respecte de la calcita. Les velocitats de dissolució de la calcita calculades a pH 4.8 i 5.6 va coincidir amb els valors de la literatura. En solucions prèviament equilibrades amb el guix, la precipitació de guix acoblada a la dissolució de calcita s’aconseguí amb temps d'inducció més curts. El guix precipitat va recobrir ràpidament la superfície de la calcita, amb morfologia de fletxa i eixos paral·lels a les orientacions cristal·logràfiques dels etch pits de la calcita. La precipitació de guix, juntament amb la dissolució de dolomita, va ser més lenta que la de calcita, la qual cosa indica que la velocitat de dissolució va ser el procés que controla la velocitat. El revestiment de guix ha cobert parcialment la superfície de la calcita durant l’experiment.

Thesis: S.B., Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences, 2017.
Cataloged from PDF version of thesis.
Includes bibliographical references (pages 21-23).
Calcite and aragonite speleothems have been used for the past few decades to provide paleoclimate information, but in speleothems of mixed mineralogy the signal of mineral changes can complicate understanding of climate signals also present. This mineral signal must therefore be examined and controlled for. In this work, ICP-MS (inductively-coupled plasma mass spectrometry) analysis of trace element (strontium and magnesium) incorporation into calcium carbonate provides additional evidence for a shift in CaCO3 polymorphs identified via XRD (xray diffraction) analysis of speleothem AB-2 from Anjohibe Cave, Madgascar. The ICP-MS Sr/Ca data qualitatively supports the Sr/Ca data collected by the XRF core scanner, exhibiting a sharp decrease in value across the identified mineral transition. A corresponding increase in Mg/Ca revealed by the ICP-MS provides further evidence for a change from aragonite to calcite at this location. This mineralogical change occurred between 870-880 CE (+/- 13 years) is nearly concurrent with a shift in [delta]13C isotopes that was identified in previous work on this speleothem and attributed to an ecological shift in dominant photosynthetic pathways (Bums et al 2016). A second, control section was identified as pure calcite by XRD analysis, but revealed Mg/Ca and Sr/Ca ratios characteristic of mineralogical transitions, suggesting that there may have been layers of aragonite that have recrystallized to calcite since deposition.
by Kaylee Brent.
S.B.

A new paradigm for the formation of calcified skeletons suggests mineralization proceeds through amorphous calcium carbonate (ACC) precursors. The implications of this strategy in carbonate crystallization are widespread, particularly for understanding factors controlling impurity and isotopic signatures in calcium carbonates. The first chapter is a literature review of the biomineralization processes used by two important model organisms: the sea urchin larva and the foraminifera. Sea urchin larvae provide a thoroughly studied example of mineralization by an ACC pathway that is under biological control through regulation of protein chemistry and the local mineralization environment. A review of how foraminifera produce their test structures is also examined to explore the question of how organisms regulate the Mg content in proportion to the temperature their environments of formation. The second chapter demonstrates that acidic biomolecules regulate the composition of ACC for a suite of model carboxylated molecules. The physical basis for the systematic trend in Mg content is related to the ability of the affinity of the biomolecule for binding Ca versus Mg. The third chapter builds on these findings to explore the transformation of Mg-rich ACC precursors to calcites of exceptionally high Mg-contents that could not be produced by classical step-dominated growth processes. The data indicate that these materials are likely a result of a nucleation-dominated pathway. The final, fourth chapter develops Raman spectroscopy-based calibrations for determining Mg contents in ACC. The calibrations are based upon peak position or peak width of the carbonate υ₁ stretch.
Ph. D.

Biosignatures have been extensively studied at hot springs sites, such as Yellowstone, because liquid water is fundamental to the existence of life but also owing to the influx of mineral nutrients in these environments. However, some hot springs have upper temperatures exceeding the boundaries capable of sustaining life in all the spring facies, particularly those nearest the vent. Cold springs provide the same nutrient-rich environment with more ambient temperatures potentially capable of sustaining a diverse consortium of microorganisms across the entirety of the system. Ten Mile Graben Cold Springs, located in Southern Utah, is one such site known for its biota and preservation potential. This study aimed to observe the possible effects of the microorganisms on aragonite and calcite precipitation. Scanning electron microscope imagery observed biogenic fabric such as botryoidal aragonite and aragonite microspheres; however, the δ13C enrichment values of +2.80‰ to +7.30‰ imply the springs were dominantly precipitated through CO2 degassing. This discrepancy in the chemical and morphological data has been observed at other astrobiology analog sites such as Yellowstone; therefore, travertine and tufa seemingly do not preserve isotopic chemical biosignatures.

L'étude des interactions entre la déformation et les transformations de phase a été entreprise en prenant comme exemple la transition polymorphique calcite-aragonite. Celle-ci a été obtenue expérimentalement dans les deux sens grâce aux presses triaxiales à milieu de confinement solide ou gazeux, pour une pression comprise entre 0,6 GPa et 1,3 GPa et une température d'environ 400°C. L'observation par . microscopie électronique en transmission des microstructures de déformation de chacune des phases et de la morphologie des interfaces montre que la transition procède par un mécanisme de nuc1éation et croissance. L'existence de relations épi tactiques entre les deux phases suggère 9ue la croissance s'effectue par migration d'interface cohérente et non par diffusion sur de grandes distances. " Dans le système calcite-aragonite, la phase de haute " pression (Ar) est plastiquement moins déformable que la phase de basse pression (Ca). Ceci est montré par les plus fortes densités de défauts présents dans la calcite lorsque les deux phases sont déformées simultanément. La forte densité de dislocations produites dans la calcite pourrait conduire à la plasticité de tr"ansformation au cours de la transition aragonite calcite. Une étude préliminaire des microstructures de déformation plastique de l'aragonite Il)ontre que ce minéral se déforme principalement par glissement "de dislocations hoo } dans le plan (010) et par mac1age mécanique { 1 JO } * L'analyse de l'énergie élastique liée aux défauts introduits au cours de la déformation plastique, a été entreprise pour les deux phases. Les calculs montrent que l'effet de cette énergie sur la transformation de phase ne serait significatif que pour les densités de dislocations de l'ordre de IOII cm-2, densités rarement observées dans les conditions naturelles de déformation. Cependant, les sous-joints constituent des sites de haute énergie favorisant la nuc1éation d'une nouvelle phase. Les résultats expérimentaux montrent en effet une accélération de la cinétique de la transition aragonite calcite lorsque les échantillons sont préalablement déformés.

Thesis (Ph. D.)--Joint Program in Oceanography/Applied Ocean Science and Engineering (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2013.
Cataloged from PDF version of thesis.
Includes bibliographical references.
Predicting the response of net community calcification (NCC) to ocean acidification OA and declining aragonite saturation state [Omega]a requires a thorough understanding of controls on NCC. The diurnal control of light and net community production (NCP) on NCC confounds the underlying control of [Omega]a on NCC and must be averaged out in order to predict the general response of NCC to OA. I did this by generating a general NCC-[Omega]a correlation based on data from 15 field and mesocosm studies around the globe. The general relationship agrees well with results from mesocosm experiments. This general relationship implies that NCC will transition from net calcification to net dissolution at a [Omega]a of 1.0 ± 0.6 and predicts that NCC will decline by 50% from 1880 to 2100, for a reef of any percent calcifier cover and short reef water residence time. NCC will also decline if percent calcifier cover declines, as evidenced by estimates of NCC in two Caribbean reefs having declined by an estimated 50-90% since 1880. The general NCC-([Omega]a relationship determined here, along with changes in percent calcifier cover, will be useful in predicting changes in NCC in response to OA and for refining models of reef water [Omega]a.
by Whitney Nicole Bernstein.
Ph.D.

Whitings on both the Great Bahama Bank (GBB) and Little Bahama Bank (LBB) were evaluated using data collected from 2000-2010 by the Moderate Resolution Imaging Spectroradiometer (MODIS) instruments onboard the Terra and Aqua satellites. A semi-objective method was developed to classify whiting patches from other look-alike features using the recently developed Floating Algae Index (FAI) algorithm, an empirical cloud masking algorithm, and a gradient analysis from the 250-m resolution MODIS data. A total of 1,500 images with minimal cloud cover was used to calculate long-term and seasonal trends as well as an average daily coverage for both banks. Annual and monthly frequency of occurrences for whitings at every location was also calculated. Based on the results, the distribution of whitings over the GBB was restricted between 25–30'N and 23–45'N and occurred most frequently on the edge of the bank. Whitings were observed throughout the LBB and at much higher frequencies than in the GBB, especially on the east side from November to February. Results from daily whiting coverage indicate whitings cover nearly twice as much area over the LBB compared to the GBB. Whitings show a clear seasonal variation with respect to coverage on both banks. Whiting coverage over the LBB has a clear seasonal variation with peak coverage in spring (April) and fall (November) and minimum coverage during summer. Whiting coverage over the GBB peaks in spring (April), but no second peak or seasonal minimum was observed. Sea surface temperature (SST), photosynthetically available radiation (PAR) and wind were compared to the observed long-term and seasonal trends of whiting coverage. Using multi-variable analyses, the influence of SST and PAR on monthly whiting coverage over the GBB from 2000-2010 was found to be statistically significant, though the correlation between the three values was low. The results indicate that these parameters may not directly influence whiting origin and coverage but rather have an effect through influence mechanism, for example through phytoplankton blooms. It is hypothesized that whitings are directly influenced by cyanobacterial phytoplankton, which are dependent on SST and PAR. Long-term trends in whiting coverage differ between the two banks. In general, whiting coverage appeared to be decreasing from 2000-2010 over the LBB, while the opposite trend was observed over the GBB during the same time period. It is currently unclear what led to these opposite trends due to lack of long-term, in-situ measurements of the water environments in the two banks. However, this is the first study that documents the long-term trends for both banks, from which one may infer that the processes affecting whiting occurrence in the two banks vary greatly and future research is needed to understand the driving forces of whitings in order to improve the current understanding of their contributions in the global carbon cycle.

Un nouveau procédé, basé sur une adaptation innovante du principe de protection cathodique des ouvrages métalliques en milieu marin, consiste à favoriser la précipitation d’un agglomérat calcomagnésien sur plusieurs centimètres d’épaisseur. En présence de sable et de coquillages, cet agglomérat pourrait permettre de stabiliser des zones littorales en cours d’érosion ou d’améliorer l’ancrage d’enrochements brise-lames. L’objectif de ce travail est d’étudier et de comprendre les mécanismes réactionnels de formation de cet agglomérat permettant une précipitation en volume loin de la cathode afin d’en optimiser la vitesse de formation ainsi que ses propriétés mécaniques. Premièrement, il a été montré dans ces travaux que le milieu électrolytique pouvait influer sur la croissance du dépôt, avec une possible inhibition de formation de carbonate de calcium pour les faibles potentiels. L’influence des produits de corrosion dans le mécanisme de protection cathodique a également été mise en évidence grâce à des polarisations effectuées dans NaCl, eau de mer artificielle et naturelle. Deuxièmement, des essais d’un mois en courant imposé ont été menés du laboratoire jusqu’au site naturel, afin de se rapprocher des conditions réelles. La densité de courant appliquée ainsi que les conditions hydrodynamiques sont des facteurs clefs étroitement liés l’un à l’autre, influant sur la masse et le rapport Ca/Mg. Ces travaux ont aussi permis de mettre en avant l’influence du temps de polarisation sur la composition du dépôt calcomagnésien, présentant une cinétique de croissance stable mais une fluctuation de composition après 15, 30 et 60 jours. Cette variation interne du rapport Ca/Mg, attribuée à un processus de « dissolution/précipitation » dépendant du gradient de pH, ainsi que la répartition de ces éléments au sein du dépôt pourraient jouer un rôle majeur dans l’évolution de la tenue mécanique du dépôt au cours du temps
A new method, based on an innovative adaptation of cathodic protection principle of metal structures in marine environment, is to promote the precipitation of a calcareous agglomerate several centimeters thick. In the presence of sand and shells, this cluster could stabilize coastal areas being eroded or improve anchorage of breakwater riprap. The objective of this work is to study and understand the reaction mechanisms allowing to create a voluminous calcareous deposit away from the cathode and to optimize deposition time as well as its mechanical properties. First, it was shown in this work that the electrolytic medium could affect the growth of the deposit, with a possible inhibition of formation of calcium carbonate fot the low potential. The influence of corrosion products in the cathodic protection mechanism was also highlighted through polarizations performed in NaCl, artificial and natural sea water. Second, one month test with impressed current were conducted from laboratory to natural site, in order to get closer of real conditions. Current density and hydrodynamic conditions are key factors closely bonded to each other, affecting the mass and composition of the Ca/Mg ratio. This work has also helped to highlight the influence of the polarization time on the composition, with stable growth kinetics but a composition’s evolution after 15, 30 and 60 days. This internal variation of the Ca/Mg ratio attributed to a process of « dissolution/precipitation » is pH dependent and the distribution of these elements within the deposit could play a major role in the evolution of the mechanical strength of deposit over time

Erosion corrosion of plumbing materials in domestic water systems is a complex phenomenon driven by water quality, hydrodynamic and electrochemical factors. Erosion corrosion accounts for over a third of copper hot water system failures in the U.S., hundreds of millions in damage, and may be expected to increase with newer Legionella control strategies including increased use of water recirculation and high temperatures. Additionally, some nonleaded alloys introduced after the passage of a new federal law restricting lead content in plumbing, have been anecdotally implicated as failing prematurely from erosion corrosion compared to traditional alloys. This dissertation includes 1) a critical review of the literature, 2) investigation of a recent rapid erosion corrosion failure in a large building plumbing system, 3) replication of this phenomena in copper and nonleaded brass in laboratory studies, and 4) evaluation of 12 nonleaded alloys against conventional leaded brass. Current plumbing codes and guidelines to prevent erosion corrosion were found to be widely inconsistent and lacking scientific evidence. Large-scale recirculating hot water pipe-loop experiments demonstrated that an aggressive hard water with entrained aragonite (CaCO3) particles could cause fully penetrative failures (i.e., leaks) in brand new copper pipe and nonleaded brass fittings in just 3-49 days. This represents the first time rapid erosion corrosion failures have ever been replicated in the laboratory under conditions similar to those encountered in practice. The entrained particulates dramatically accelerated attack on metals, especially at pipe bends. In general, lowering pH, increasing flow velocity, increasing temperatures, entrainment of particles (of bigger sizes), and addition of chlorine disinfectant increased erosion corrosion rates. These results scientifically proved that hard waters are not inherently less aggressive than soft water, and in fact if CaCO3 solids form they can be much more aggressive. Finally, cavitation and erosion corrosion resistance of 12 nonleaded alloys was evaluated against leaded brass; stainless steels demonstrated superior performance, silicon brass had the greatest susceptibility and remaining alloys were in the middle. This performance data can aid decision making regarding choice of alloys for various water applications. Our work over the years, including involvement in the Flint Water Crisis, demonstrated that practicing trustworthy science as a public good requires commitment to scientific rigor, truth-seeking, managing conflicts of interest, and comprehensible evidence-based science communication. Critical problems in 21st century public science were highlighted including perverse incentives, misconduct, postmodernist "science anarchist" thought, and ineffectiveness of U.S. water utilities in communicating tap water safety to the American public.
Ph. D.

Les mécanismes sous-jacents à la formation des coquilles chez les mollusques, et particulièrement chez les bivalves et les gastéropodes, font l'objet d'un nombre croissant d'études ces dernières années. Ces travaux ont notamment permis de mettre en évidence l'existence d'une plasticité morphologique intra-spécifique de la calcification chez plusieurs espèces de mollusques. Au cours de cette thèse, nous avons choisi d'aborder cette notion de plasticité du processus de biominéralisation à travers 3 cas particuliers : la réparation coquillière chez le gastéropode marin Haliotis tuberculata, la greffe d'un tissu minéralisant chez l'huître perlière Pinctada margaritifera, et la composition de la coquille d'un gastéropode terrestre (Helix aspersa maxima). Chez H. Tuberculata et P. Margaritifera, les résultats obtenus soulignent l'existence d'un réagencement, plus ou moins important, des tissus minéralisants suite au stress (lésion de la coquille/greffe), allant d'une simple variation de la vitesse de minéralisation (réparation), à une modification structurelle importante du tissu minéralisant (greffe). Concernant Helix aspersa maxima, les composantes matricielles de la coquille chez cette espèce présentent des caractéristiques "atypiques" : interaction très faible (voir inexistante) avec le CaCO3 in vitro. Par ailleurs, les séquences partielles des protéines matricielles obtenues au cours de ce travail ne présentent pas d'homologies avec les séquences présentes dans les bases de données actuelles. Le changement drastique d'environnement pourrait être à l'origine de cette disparité entre les matrices d'organismes marins et celle de notre modèle (Helix aspersa maxima)
The mechanisms underlying the formation of shells in molluscs, especially bivalves and gastropods, are the subject of a growing number of studies in recent years. These works had enabled to highlight the existence of an intra-specific morphological plasticity of calcification in several species of molluscs. In this thesis, we chose to approach this concept of plasticity of the biomineralization process through three specific cases: the shell repair in the marine gastropod Haliotis tuberculata, transplantation of a mineralizing tissue in the pearl oyster Pinctada margaritifera, and the composition of the shell of a land snail (Helix aspersa maxima). In H. Tuberculata and P. Margaritifera, the results emphasized the existence of a rearrangement, more or less important of mineralizing tissues following stress (shell lesion / transplant), ranging from a simple change in the rate of mineralization (repair), to an important structural change of the mineralizing tissue (transplant). On Helix aspersa maxima, the matrix components of the shell in this species have "atypical" characteristics: very weak interaction (or not) with CaCO3 in vitro. In addition, partial sequences of matrix proteins obtained in this work showed no homology with sequences in current databases. The drastic change of environment could be the cause of this disparity between the matrices of marine organisms and that of our model (Helix aspersa maxima)

An evaluation of the relative rates of sediment transport of an oolitic aragonite sand and a quartz quarry sand as possible beach renourishment materials has been conducted. When comparing equal volumes, the aragonite experienced less transport than the quartz in both the longshore and in the onshore-offshore directions. When comparing equal size fractions, in sizes 0.35mm and smaller, aragonite was less transportable. The quartz was less transportable in the sizes greater than 0.35mm. This trend was observed in two separate experiments and is attributed to the effective density ratio of aragonite to quartz, dissimilarities in roundness and sphericity, and to differential entrainment and transport of these materials in suspension and bed load within the confines of the inherent bed roughness. The effective density ratio of aragonite to quartz is highest in the smaller grain sizes and decreases with increasing grain size because the larger aragonitic grains possess fewer oolitic lamellae per grain and resemble their initial biogenic nucleus. In the smaller size fractions where suspension transport is thought to predominate, a larger quartz grain is hydraulically equivalent to a smaller aragonite grain due to the greater density of the aragonite. The aragonite has a higher settling velocity out of suspension and it is less entrainable, due to sheltering effects in the bed matrix allowing a lower position in the velocity profile and a larger reactive angle to the flow. As grain size increases above 0.35mm, the density of the aragonite approaches that of the quartz. The principle of hydraulic equivalence suggests that for two materials of similar density, there should be no difference in the entrainment and transportability between equal size fractions. The preferential transport of the aragonite relative to the quartz in the size fractions greater than 0.35mm is attributed to the difference in their shape, where the rounder aragonite is more easily rolled in traction as the size of both the aragonite and quartz exceed the background bed roughness. The physical characteristics of aragonite indicate that it has a hydraulic behavior similar to a quartz sand of a slightly larger size. If renourishment is undertaken on John U. Lloyd Beach with aragonite, the most probable source material would be a mining stockpile (mean size 0.52mm) from Ocean Cay in the Bahamas. Based on a theoretical (mean size only) method of the U.S. Army Corps of Engineers, utilization of this stockpile material would reduce the erosion rate on Lloyd Beach by 10%. The results of my study indicate that beach losses could be further reduced by using this aragonite due its higher density. Secondary characteristics such as density and shape of the renourishment material manifest themselves differently in the suspension and bed load modes of transport and should be considered when choosing a borrow source. Additional transport studies need to be done utilizing larger volumes of material and monitored over a longer time interval.

On retrouve CaCO3 dans de nombreux matériaux du Vivant, comme par exemple le corail, les carapaces et les coquilles de différents crustacés et mollusques. La croissance des différentes formes allotropiques de CaCO3, aragonite, calcite et vatérite, en présence de molécules biologiques, est influencée en terme d'organisation cristalline, de microstructure et d'ordre a grande échelle (texture et ultrastructure). La voie électrochimique a été choisie dans ce travail pour sa vitesse de formation de dépôt ainsi qu'un bon contrôle des paramètres instrumentaux. Nous avons sélectionné l'aragonite dans le dépôt ainsi que sa croissance texturée rappelant celle de la nacre de Haliotis tuberculata tuberculata avec toutefois une orientation cristalline moins prononcée. Une croissance en plaquettes pseudo-hexagonales orientées, présentant un double-maclage et une orientation d'environ 60° les unes par rapport aux autres, rappelle les observations faites sur les nacres de différents mollusques. Une étude par diffraction des rayons X sur des dépôts obtenus en présence de chitosan et de molécules organiques extraites de nacres naturelles montre leur influence sur la texture cristalline, les mailles de l'aragonite et les groupements carbonate. Le décalage de l'atome de carbone par rapport au plan des oxygènes de ce groupement révèle la déformation induite par les molécules durant la croissance cristalline. Cette étude montre que par une approche minérale-organique synthétique, on peut se rapprocher des processus conduisant a la croissance de cristaux biogéniques naturels, pour la texture, la distorsion de mailles, la structure et le facies cristallin
Calcium carbonate can be found in many natural materials, such as coral and shells of various crustaceans and mollusks. The growth of its various polymorphs, aragonite, calcite and vaterite, in the presence of biological molecules, affect their organization in terms of crystalline microstructure and long range order (texture and ultrastructure). Electrodeposition was chosen in this work for its growth speed and a good control of instrumental parameters. We have selected the growth of aragonite, mimicking the texture of the nacre of Haliotis tuberculata tuberculata but with a less pronounced crystal orientation. A growth of oriented pseudo-hexagonal platelets, with a double-twinning and a relative orientation of approximately 60° to each other, seems to be close to the observations on natural nacres of different molluscs. A X-ray diffraction study of the deposits obtained in the presence of chitosan and organic molecules extracted from natural nacres shows their influence on the crystalline texture but also on the lattice of aragonite and on the carbonate groups. The aplanarity of carbonate groups shows the deformation induced by the molecules during the crystal growth. This study shows that a mineral-organic synthetic approach can give new insights on the process leading to the growth of natural biogenic crystals in terms of crystalline orientation, lattice distortion, structure and crystalline microstructure

PURPOSE: To evaluate the clinical and MRI outcomes after the implantation of a nanostructured cell free aragonite-based scaffold in patients affected by knee chondral and osteochondral lesions. METHODS: 126 patients (94 men, 32 women; age 32.7±8.8 years) were included according to the following criteria: grade III or IV chondra/osteochondral lesions in the femoral condyles or throclea; 2) no limb axial deviation (i.e. varus or valgus knee > 5°); 3) no signs of knee instability; 4) no concurrent tibial or patellar chondral/osteochondral defects. All patients were treated by arthrotomic implantation of an aragonite based-scaffold by a press-fit technique. Patients were prospectively evaluated by IKDC, Tegner, Lysholm and KOOS scores preoperatively and then at 6, 12, 18 and 24-months follow-up. MRI was also performed to evaluate the amount of defect filling by regenerated cartilage. Failures were defined as the need for re-intervention in the index knee within the follow-up period. RESULTS: Average defect size was 2±1.3 cm2 and in most cases a single scaffold was used. A significant improvement in each clinical score was recorded from basal level to 24 months’ follow-up. In particular, the IKDC subjective score increased from 42.14±16 to 70.94±24.69 and the Tegner score improved from 2.95±1.90 to 4.82±1.85 (p<0.0005). Lysholm score and all the subscales of KOOS showed a similar trend over time. Age of the patient at implantation, size of the defect and BMI were correlated with lower clinical outcome. The presence of OA didn’t influence the clinical results. MRI evaluation showed a significant increase in defect filling over time, with the highest value reached at 24 months. Failures occurred in eleven patients (8.7%). CONCLUSION: The aragonite-based biomimetic osteochondral scaffold proved to be safe, and encouraging clinical and radiographic outcomes were documented up to 2 years’ follow-up.

Les microbialites sont des roches organo-sédimentaires dont les processus de formation restent mal compris. L'objectif central de cette thèse est de mieux comprendre les conditions environnementales permettant le développement de microbialites actuels provenant de 10 lacs volcaniques mexicains. Une grande diversité de compositions minéralogiques des microbialites a été observée, comprenant divers carbonates et la quasi omniprésence de silicates de magnésium authigènes. A partir de cette étude nous proposons une valeur minimale d'alcalinité permettant le développement des microbialites. De plus, une corrélation positive entre l'alcalinité et la teneur en sodium des lacs est apparue. Cette corrélation pourrait s'expliquer par des niveaux différents d'évaporation des lacs et/ou des degrés différents d'altération des silicates alentours. L'étude plus particulière des silicates de magnésium a révélé que ces phases sont faiblement cristallisées, semblables à la kérolite et ont un fort potentiel de fossilisation des microorganismes et de la matière organique. Ces silicates de magnésium sont parfois associés à du fer dont l'origine pose question dans ces environnements alcalins et oxygénés. Nous avons mis en évidence la présence de différents types de phases porteuses du fer : des hydroxydes doubles lamellaires (hydrotalcites), des oxy(hydroxy)des, des silicates de magnésium et des sulfures. Nous proposons plus spécifiquement que l'hydrotalcite pourrait être issue de l'altération des basaltes par la circulation de fluides souterrains et plus généralement que cette phase pourrait être un précurseur des silicates de magnésium abondamment observés dans les microbialites actuels
The processes leading to the formation of microbialites, which are organo-sedimentary rocks, are not well understood. The main goal of this thesis is to better understand the environmental conditions allowing the development of modern microbialites. Here we performed geochemical analyses of water solutions and mineralogical analyses of microbialites in 10 Mexican volcanic lakes. We found a large diversity of microbialites in terms of mineralogical composition, with occurrence of diverse carbonate phases as well as the frequent presence of authigenic magnesium silicate phases. From this study, we infer a minimum alkalinity value for the formation of lacustrine microbialites. Moreover, we observe a positive correlation between the alkalinity and the sodium content of the lakes. This may relate to variations in evaporation intensity and/or various degrees of weathering of the surrounding silicates. The study of Mg-silicates revealed that this phase is similar to kerolite, a poorly crystalline hydrated talc phase, and has a strong potential for the fossilization of microorganisms and organic matter. These silicates are sometimes associated with iron, the origin of which remains uncertain in these alkaline and oxidized environments. By the mineralogical study of several microbialites, we found several phases bearing iron: layered double hydroxides (hydrotalcites), Mg-silicates, oxy(hydroxi)des and sulfides. We propose more specifically that hydrotalcite could be the by-product of basalts weathering by groundwater. We propose more generally that hydrotalcite could be a precursor phase of Mg-silicates abundantly observed in modern microbialites

Ce travail concerne l'étude de l'oreille interne chez l'Amphibien Urodèle Pleurodeles waltl, à partir de deux approches, l'une morphologique et cellulaire, l'autre cristallographique et chimique. Une étude anatomique de l'oreille interne chez l'adulte, et une description de l'ontogenèse de cet organe durant les périodes embryonnaires et larvaires ont été réalisées pour la première fois chez cet Amphibien. Cette étude a permis de réaliser une description des cellules sensorielles et des otoconies. Chez l'adulte, en MEB, 6 catégories de cellules sensorielles ont été décrites dans les macules du saccule, de l'utricule, de la lagéna, dans la papille amphibienne et les crêtes des canaux semi-circulaires. Plus particulièrement dans les crêtes de ces canaux, la présence de cellules, pourvues d'un long kinétocil terminé par un bulbe et de nombreux stéréocils, est signalée pour la première fois chez les Amphibiens, et probablement chez les Vertébrés. Le but principal de ce travail est l'étude morphologique, cristallographique et chimique des otoconies de l'oreille interne du Pleurodèle. Au cours du développement, les premières otoconies sont détectées dans l'otocyste. L'un des aspects les plus importants de ces résultats concerne les otoconies du saccule dont les structures morphologiques et cristallographiques changent au cours du développement. A l'éclosion, les otoconies sont polyédriques et calcitiques dans le saccule, cylindriques dans l'utricule. Durant les stades ultérieurs, dans le saccule, les otoconies s'agglomèrent et constituent un otolithe polyédrique et calcitique. Au stade larvaire 44, des otoconies fusiformes et aragonitiques apparaissent à la surface de l'otolithe. Au stade 52, les analyses de diffraction des rayons X indiquent une structure cristallographique à la fois calcitique et aragonitique. Chez l'adulte, toutes les otoconies sacculaires sont alors aragonitiques. Dans l'utricule, les otoconies restent calcitiques jusque chez l'adulte. Dans le sac endolymphatique, elles apparaissent au stade 45, et dans la lagéna au stade 49 ; elles restent aragonitiques y compris chez l'adulte. Les analyses par EDXS indiquent que les otoconies contiennent une grande quantité de calcium, avec des traces de sodium, magnésium, phosphore, soufre, chlore et potassium. Mais seules les otoconies aragonitiques contiennent des traces de strontium. C'est la première fois que la présence de strontium est démontrée dans les otoconies d'une espèce animale non marine. Sur le plan de l'évolution, le Pleurodèle constitue bien une espèce intermédiaire entre les animaux aquatiques et les animaux terrestres. Dans l'arbre phylogénétique, le Pleurodèle est probablement à la tête d'une lignée évolutive isolée.

Biology
Ph.D.
Deep-water or cold-water corals are abundant and highly diverse, greatly increase habitat heterogeneity and species richness, thereby forming one of the most significant ecosystems in the deep sea. Despite this remote location, they are not removed from the different anthropogenic disturbances that commonly impact their shallow-water counterparts. The global decrease in seawater pH due to increases in atmospheric CO2 are changing the chemical properties of the seawater, decreasing the concentration of carbonate ions that are important elements for different physiological and ecological processes. Predictive models forecast a shoaling of the carbonate saturation in the water column due to OA, and suggest that cold-water corals are at high risk, since large areas of suitable habitat will experience suboptimal conditions by the end of the century. The main objective of this study was to explore the fate of the deep-water coral community in time of environmental change. To better understand the impact of climate change this study focused in two of the most important elements of deep-sea coral habitat, the reef forming coral Lophelia pertusa and the octocoral community, particularly the gorgonian Callogorgia delta. By means of controlled experiments, I examined the effects of long- and short-term exposures to seawater simulating future scenarios of ocean acidification on calcification and feeding efficiency. Finally In order to understand how the environment influences the community assembly, and ultimately how species cope with particular ecological filters, I integrated different aspects of biology such functional diversity and ecology into a more evolutionary context in the face of changing environment. My results suggest that I) deep-water corals responds negatively to future OA by lowering the calcification rates, II) not all individuals respond in the same way to OA with high intra-specific variability providing a potential for adaptation in the long-term III) there is a disruption in the balance between accretion and dissolution that in the long term can shift from net accretion to net dissolution, and IV) there is an evolutionary implication for certain morphological features in the coral community that can give an advantage under stresfull conditions. Nevertheless, the suboptimal conditions that deep-water corals will experience by the end of the century could potentially threaten their persistence, with potentially negative consequences for the future stability of this already fragile ecosystem.
Temple University--Theses

Introduzione La cartilagine articolare è un tessuto altamente specializzato che non rigenera spontaneamente in seguito a lesioni. Negli ultimi anni, diversi compositi bioingegnerizzati sono stati sviluppati per la riparazione dell’intera unità osteocondrale. Scopo di questo studio è valutare i risultati clinici e strumentali a breve termine di un innovativo scaffold acellulare bifasico di aragonite, nel trattamento di lesioni osteocondrali del ginocchio. Materiali e metodi Dodici pazienti sono stati valutati prospetticamente, dopo approvazione del comitato etico dell’Università di Anversa. I pazienti sono stati rivalutati clinicamente, attraverso la somministrazione di score clinici KOOS, Lysholm, IKDC e Tegner e con risonanza magnetica a 6, 12, 18 e 24 mesi dall’intervento chirurgico. Il test non parametrico dei ranghi di Wilcoxon per campioni non indipendenti è stato condotto per l'analisi dei risultati. Risultati Le lesioni erano situate sul CFM in 3 pazienti, sul CFL in 4 e sulla troclea femorale in 5 pazienti. 9 pazienti erano uomini e 3 donne, età media di 31.4±8.0 anni. I pazienti hanno riportato un aumento statisticamente significativo di tutti gli score clinici, con un aumento dello score KOOS da 47.3±13.6 pre-operatorio a 85.6±11.7 ad ultimo follow-up (p=0.005). Un trend simile si è avuto per gli altri score. I pazienti hanno riportato anche un aumento del tegner score, da un basale di 2.75±1.6 ad un valore di 4.8±1.2 a due anni dall’intervento chirurgico. La risonanza magnetica ha dimostrato un riempimento della lesione del 96.4%±5.7 a due anni di follow-up. Conclusioni I risultati a breve termine di questo innovativo scaffold di aragonite dimostrano che la tecnica è sicura, riproducibile. I risultati sono promettenti con un aumento di tutti gli score clinici ed anche dell’attività sportiva. I risultati della risonanza magnetica sono davvero singolari. Uno studio randomizzato, multicentrico è tuttora in corso in Europa, Stati Uniti e Israele.
Introduction The articular cartilage is a very complex tissue that does not repair on it's own. In these last years, different bioengineered scaffolds have been developed to repair the entire osteochondral lesion. The aim of this study is to evaluate the clinical and MRI results at short term follow-up of this innovative, aragonite based, acellular scaffold. Materials and methods Twelve patients have been prospectively enrolled after approval of the University of Antwerp ethical commitee. Patients were evaluated clinically and by MRI at 6-12-18 and 24 months. The non parametric test of Wilcoxon has been conducted for the analysis of clinical results. Results In 3 patients the lesion was located on the MFC, in 4 patients on the LFC and in 5 on the throclea. 9 patients were man, 3 females. Mean age was 31.4±8.0 years. All patients reported a significant increase of all clinical scores. KOOS went from 47.3±13.6 at baseline to 85.6±11.7 at last follow-up (p=0.005). An increase of the tegner score was also reported by all patients, from a basal score of 2.75±1.6 to 4.8±1.2 at last follow-up. The MRI showed a 96.4 % filling of the lesion at two years control. Conclusions The results at short term follow-up demonstrate that this technique is safe and reproducible. Results are promising with an increase of all clinical scores. Also MRI results are unique. A randomized controlled trial is now ongoing in USA, Europe and Italy.

Biology
Ph.D.
Ocean acidification is the reduction in seawater pH due to the absorption of anthropogenic carbon dioxide by the oceans. Reductions in seawater pH can inhibit the precipitation of aragonite, a calcium carbonate mineral used by marine calcifiers such as corals. Lophelia pertusa is a cold-water coral that forms large reef structures which enhance local biodiversity on the seafloor, and is found commonly from 300-600 meters on hard substrata in the Gulf of Mexico. The present study sought to investigate the potential impacts of ocean acidification on L. pertusa in the Gulf of Mexico through combined field and laboratory analyses. A field component characterized the carbonate chemistry of L. pertusa habitats in the Gulf of Mexico, an important step in establishing a baseline from which future changes in seawater pH can be measured, in addition to collecting in situ data for the design and execution of perturbation experiments in the laboratory. A series of recirculating aquaria were designed and constructed for the present study, and support the maintenance and experimentation of live L. pertusa in the laboratory. Finally, experiments testing L. pertusa's mortality and growth responses to ocean acidification were conducted in the laboratory, which identified thresholds for calcification and a range of sensitivities to ocean acidification by individual genotype. The results of this study permit the monitoring of ongoing ocean acidification in the deep Gulf of Mexico, and show that ocean acidfication's impacts may not be consistent across individuals within populations of L. pertusa.
Temple University--Theses

Dans le travail de cette these, nous nous sommes interesses a l'analyse par radioactivation neutronique des elements-traces dans un corail (materiau utilise dans la chirurgie de l'os) et a l'etude de l'effet de la temperature sur la structure cristalline du corail. Nous avons etabli la cinetique de diffusion d'elements-traces dans un corail implante in vivo dans le but de fournir de nouvelles donnees relatives a la resorption du biomateriau: du corail naturel avait ete implante dans les machoires d'ovins et, pendant neuf mois, toutes les quatre semaines environ, des biopsies ont ete prelevees et analysees. Ainsi, le suivi des teneurs des elements as, au, br, cd, k, mn, mo, rb, sb, se, u, w, zn et na a pu etre realise au cours du temps. Un essai de calcul de coefficient de diffusion a ete fait en se basant sur un modele mathematique reduit. La nature de la structure cristalline du corail est un element determinant dans la resorption ou le rejet du corail. C'est la raison pour laquelle nous avons etudie l'effet de la temperature sur les parametres cristallins du biomateriau. Dans ce but, nous avons utilise l'analyse thermique differentielle et la diffraction-x a haute temperature pour analyser la temperature de transition de phase aragonite-calcite

Les reliefs longeant la côté du SAHEL Tunisien sont constitués, essentiellement, par des dépôts tyrrhéniens. Ces derniers se présentent sous forme de cordons littoraux parallèles à la côté, derrière lesquels se sont déposés des marnes et sables très fins lagunaires. À l’Est de ces cordons se sont développés des sables bioclastiques à Strombes, correspondant à la fin du Tyrrhénien. En plus de leur richesse en structures sédimentaires (terriers, traces de racines, stratifications obliques, structures bulleuses, etc…), les dépôts tyrrhéniens étaient affectés par une diagénèse précoce considérable à savoir : cimentation, dissolution, néomorphisme, pédogénèse. Ce dernier processus diagénétique est suivi, localement (région d’EL ALIA - LA CHEBBA) par une dolomitisation sommitale.

Le développement considérable réalisé ces dix dernières années dans les techniques de diffraction sur des échantillons sous forme de poudre même très texturés (temps d’enregistrement raisonnable et très bonne résolution) et les progrès fascinants des moyens de calcul sur des machines individuelles rendent possible l’accès à des informations précises et avec des temps de calcul raisonnablement courts. Dans ce travail, nous avons appliqué l’analyse combinée basée sur la méthode de Rietveld pour étudier des échantillons de carbonates de calcium naturels de coquilles de certaines espèces de mollusques (structure, texture, tailles anisotropes…etc. ) et synthétiques par biomimétisme dans le but de comprendre l’influence des différents facteurs intervenants dans la croissance et la forme des grains des différents polymorphes de CaCO3. Dans les échantillons naturels, nous avons clairement mis en évidence l’existence de déformations de mailles cristallines dues à la présence des macromolécules intra-cristallines et extra-cristallines, en complément d’études du même genre réalisées sur des échantillons broyés. Dans les échantillons synthétiques obtenus par une méthode de synthèse simple, nous avons analysé l’effet de l’ajout d’acide polyacrylique, en termes de modulateur de croissance des polymorphes de CaCO3. La simulation des digrammes de diffraction anisotropes réalisée sur ces deux types d’échantillons nous a permis d’accéder aux informations pertinentes de façon précise (tailles anisotropes des cristallites, structure, texture, proportion volumique des polymorphes)
The tremendous development of powder diffraction techniques achieved over the last ten years even operational on strongly textured samples within good resolutions, together with the fascinating development of individual calculating capabilities, make it possible to access precise information in reasonably short times. In this work, we apply the combined analysis based on the Rietveld method to study samples of natural calcium carbonates from two living species of molluscan shells and of synthetic CaCO3 in order to understand the influence of the different parameters in the growth and shape of the crystallites of the different polymorphs of CaCO3. In natural species we clearly put into evidence the existence of distortions of crystalline cells due to the presence of the intra- and extra-crystalline macromolecules, in opposition with similar studies operated on powderised samples. In synthetic samples we studied, using a simple synthesis method and taking as a model the polyacrylic acid, the role of the soluble macromolecules in the growth of the CaCO3 polymorphs. The simulation of the anisotropic diffraction diagrams on both sample types allowed us to reach pertaining information within good precision (anisotropic sizes of the crystallites, structure, texture, volume fraction of the polymorphs

Les microbialites sont des roches organo-sédimentaires dont les processus de formation restent mal compris. L'objectif central de cette thèse est de mieux comprendre les conditions environnementales permettant le développement de microbialites actuels provenant de 10 lacs volcaniques mexicains. Une grande diversité de compositions minéralogiques des microbialites a été observée, comprenant divers carbonates et la quasi omniprésence de silicates de magnésium authigènes. A partir de cette étude nous proposons une valeur minimale d'alcalinité permettant le développement des microbialites. De plus, une corrélation positive entre l'alcalinité et la teneur en sodium des lacs est apparue. Cette corrélation pourrait s'expliquer par des niveaux différents d'évaporation des lacs et/ou des degrés différents d'altération des silicates alentours. L'étude plus particulière des silicates de magnésium a révélé que ces phases sont faiblement cristallisées, semblables à la kérolite et ont un fort potentiel de fossilisation des microorganismes et de la matière organique. Ces silicates de magnésium sont parfois associés à du fer dont l'origine pose question dans ces environnements alcalins et oxygénés. Nous avons mis en évidence la présence de différents types de phases porteuses du fer : des hydroxydes doubles lamellaires (hydrotalcites), des oxy(hydroxy)des, des silicates de magnésium et des sulfures. Nous proposons plus spécifiquement que l'hydrotalcite pourrait être issue de l'altération des basaltes par la circulation de fluides souterrains et plus généralement que cette phase pourrait être un précurseur des silicates de magnésium abondamment observés dans les microbialites actuels
The processes leading to the formation of microbialites, which are organo-sedimentary rocks, are not well understood. The main goal of this thesis is to better understand the environmental conditions allowing the development of modern microbialites. Here we performed geochemical analyses of water solutions and mineralogical analyses of microbialites in 10 Mexican volcanic lakes. We found a large diversity of microbialites in terms of mineralogical composition, with occurrence of diverse carbonate phases as well as the frequent presence of authigenic magnesium silicate phases. From this study, we infer a minimum alkalinity value for the formation of lacustrine microbialites. Moreover, we observe a positive correlation between the alkalinity and the sodium content of the lakes. This may relate to variations in evaporation intensity and/or various degrees of weathering of the surrounding silicates. The study of Mg-silicates revealed that this phase is similar to kerolite, a poorly crystalline hydrated talc phase, and has a strong potential for the fossilization of microorganisms and organic matter. These silicates are sometimes associated with iron, the origin of which remains uncertain in these alkaline and oxidized environments. By the mineralogical study of several microbialites, we found several phases bearing iron: layered double hydroxides (hydrotalcites), Mg-silicates, oxy(hydroxi)des and sulfides. We propose more specifically that hydrotalcite could be the by-product of basalts weathering by groundwater. We propose more generally that hydrotalcite could be a precursor phase of Mg-silicates abundantly observed in modern microbialites

On retrouve CaCO3 dans de nombreux matériaux du Vivant, comme par exemple le corail, les carapaces et les coquilles de différents crustacés et mollusques. La croissance des différentes formes allotropiques de CaCO3 , aragonite, calcite et vatérite, en présence de molécules biologiques, est influencée en terme d'organisation cristalline, de microstructure et d'ordre à grande échelle (texture et ultrastructure). La voie électrochimique a été choisie dans ce travail pour sa vitesse de formation de dépôt ainsi qu'un bon contrôle des paramètres instrumentaux. Nous avons sélectionné l'aragonite dans le dépôt ainsi que sa croissance texturée rappelant celle de la nacre de Haliotis tuberculata tuberculata avec toutefois une orientation cristalline moins prononcée. Une croissance en plaquettes pseudo-hexagonales orientées, présentant un double-maclage et une orientation d'environ 60° les unes par rapport aux autres, rappelle les observations faites sur les nacres de différents mollusques. Une étude par diffraction des rayons X sur des dépôts obtenus en présence de chitosan et de molécules organiques extraites de nacres naturelles montre leur influence sur la texture cristalline, les mailles de l'aragonite et les groupements carbonate. Le décalage de l'atome de carbone par rapport au plan des oxygènes de ce groupement révèle la déformation induite par les molécules durant la croissance cristalline. Cette étude montre que par une approche minérale-organique synthétique, on peut se rapprocher des processus conduisant à la croissance d'organo-cristaux naturels, pour la texture, la distortion de mailles, la structure et le faciès cristallin.

Les controles globaux de la diagenese des carbonates de plates-formes, recifs et mangroves en atlantique et pacifique, allant de l'holocene a 23 ma, sont au nombre de 6: 1. La sedimentation de haute energie, 2. Les paleotemperatures oceaniques, 3. Les variations du niveau des oceans, 4. Les phases d'emersion-submersion, 5. Les sols phosphato-bauxitiques, 6. Les relations avec l'expansion oceanique. En consequence, les variations thermo-glacio-eustatiques controlent les variations de la nappe phreatique ou lentille de ghyben-herzberg des plates-formes, iles et atolls, et donc la diagenese. La diagenese aragonitique comporte lithification et dissolution. La diagenese calcitique augmente avec le temps, l'ion sr#+#+ en etant le marqueur. La diagenese bauxitique et surtout phosphatee nait par evolution pedogenetique de produits volcano-sedimentaires pieges dans les karsts. Elle contribue a la diagenese dolomitique (li, mn, mg. . . ). La diagenese dolomite dans 2 exemples: mangrove d'andros, bahama, et facies corallien a rhodolithes du pacifique, montre le role d'ions tels que li, na, k, mn, et le transport de l'ion mg#+# par les molecules d'eau. La dolomitisation est une suite de relais ioniques ou n'interviennent que les equilibres d'hydratation et de deshydratation de l'ion mg#+#+. Li, mn, na, k, sont des catalyseurs et les mineraux pre- ou paradolomitiques pourraient se former. Ces differentes diageneses sont contemporaines et concurrentes, pour donner un etat de carbonate plus stable: calcite, puis dolomite

Phreatic overgrowths on speleothems (POS) are one of many sea-level proxies available to Quaternary geologists in Mallorca; these carbonate encrustations form at the air-water interface in cave passages flooded with brackish water. POS are ideal for reconstruction of western Mediterranean sea level because they are widespread in Mallorca's caves, can be precisely dated by U-series methods, constrain sea-level stands to sub-meter elevation, and are well preserved and accessible in the subterranean environment. This research investigates the POS depositional environment, which is relatively understudied compared to the other proxies used for sea-level reconstructions. This disparity has led to assumptions on many aspects of the POS precipitation. Further, POS are typically composed of calcite, but sometimes the metastable polymorph aragonite is present instead. Two caves were studied because of the presence of a modern POS horizon of aragonite and calcite: Cova des Pas de Vallgornera (Vallgornera) and Coves del Drac (Drac), respectively. High-resolution air and water physical parameters were collected for the first time, along with monthly water samples for stable isotope and elemental analysis. This 16-month record was supplemented with detailed geochemical studies throughout the project, including water-column profiles and CO2 sampling campaigns. The water level in both caves preserves the semi-diurnal Mediterranean Sea tide signal, with a lag of approximately four hours. The fluctuation in both caves is slightly attenuated, and the direct effects of barometric pressure and precipitation could not be discerned from the primary control of tidal pumping. Calculations based on salinity and isotope analysis show that less than 20% of the solution in each cave is seawater. Degassing of CO2 from the cave water to air was documented at both locations, with sporadic calcium carbonate supersaturation. These conditions are strongly dependent on annual cave ventilation, which becomes active during winter when cold, dense tropospheric air sinks into the subsurface. In addition to seasonal thermo-circulation, fluctuating water level displaces cave air and likely initiates tropospheric exchange throughout the year. This process primarily occurs through fissures in thin overlying bedrock at Vallgornera and through the large entrance in Drac. Higher elemental ratios (Mg:Ca, Sr:Ca, Mg:Sr) known to enhance aragonite precipitation or inhibit calcite precipitation were recorded in Vallgornera's water. A linear correlation with salinity was not observed, so higher ratios in Vallgornera must be contributed from differences in lithology, bedrock weathering intensity, or nearby rising thermal waters. In summary, this research confirms POS strengths as sea-level proxies from geochemical and hydrological perspectives. These carbonate encrustations are precipitated at the air-water interface, which fluctuates as an attenuated expression of Mediterranean Sea tide. Degassing of CO2 from the cave water to air, which promotes calcium carbonate supersaturation, is the major control on POS deposition, and is facilitated by winter ventilation and likely water-level fluctuations. CO2 degassing (and theoretically precipitation of POS) in isotopic equilibrium is possible in caves with restricted ventilation (small/sealed entrances, small passages). Aragonite may be precipitated instead of calcite because of local modifications to the geochemical system from bedrock weathering or contributions from deep groundwater.

Cette recherche vise à synthétiser différents types et formes de particules de carbonate de calcium (CaCO3) à l'échelle submicrométrique et nanométrique, et à étudier leurs applications en tant que charges renforçantes pour les composites de caoutchouc naturel (NR). L'étude a donc été divisée en deux parties. Premièrement, la procédure de préparation des particules de CaCO3 était basée sur la méthode de précipitation en solution entre les ions carbonate (CO32-) et les ions calcium (Ca2+). La deuxième partie concerne l'étude des propriétés mécaniques des composites NR/CaCO3. La première partie a commencé par la précipitation de (NH4)2CO3 et de CaCl2 dissous dans 50 % en poids de saccharose comme milieu aqueux. Cette condition a entraîné la formation de CaCO3 sphérique, ce qui a été mis en évidence au microscope électronique à balayage (MEB). L'analyse au microscope électronique à transmission (TEM) a révélé une taille de particule de 0,42 ± 0,14 µm avec un rapport d'aspect d'environ un. Lorsque la réaction de précipitation s'est produite en présence d’huile d'olive saponifiée, la propriété de surface du CaCO3 est passée d'hydrophile (angle de contact avec l'eau de 28 ± 2°) à superhydrophobe (angle de contact avec l'eau de 163 ± 2°). Les phases polymorphes typiques de CaCO3 ont été caractérisées par diffraction des rayons X (DRX), infrarouge à transformée de Fourier par réflexion totale atténuée (ATR-FTIR) et spectroscopie Raman. Ces techniques ont révélé que le CaCO3 sphérique non traité et traité représentait environ 99 % du polymorphe de la vatérite. Dans le processus de précipitation utilisant des solutions aqueuses 1 M de Na2CO3 et 1 M de CaCl2 réalisé à 80 ± 1 °C, du CaCO3 sous forme de fibres agglomérées a été obtenu avec un rapport d'aspect compris entre 8 et 9. Le CaCO3 superhydrophobe sous cette forme a également été synthétisé avec succès. L'angle de contact avec l'eau des fibres traitées et non traitées est respectivement de 29 ± 2° et 167 ± 2°. De plus, le CaCO3 sphérique dispersé dans l'eau à 80°C a donné naissance à des nanoparticules de CaCO3 en forme de fibre qui ont été obtenues via la transformation de la vatérite sphérique en aragonite nanofilaire longue avec le rapport d'aspect le plus élevé de 156,9 par rapport aux autres formes de CaCO3. La fibre CaCO3 non traitée était hydrophile avec un angle de contact avec l'eau de 31 ± 1°, tandis que la fibre CaCO3 traitée avec du savon donnait un angle de contact avec l'eau de 165 ± 5° ; elle était donc superhydrophobe similaire aux autres polymorphes de CaCO3 synthétisés. La DRX a révélé que le CaCO3 en forme de fibres, non traitées et traitées, contenait en majorité de l'aragonite et en moindre mesure de la vatérite et de la calcite. La stabilité thermique de différents types de CaCO3 a également été évaluée par analyse thermogravimétrique (TGA). Les résultats ont montré la calcination des cristaux de CaCO3, du saccharose et du savon. La deuxième partie a consisté à incorporer le CaCO3 préparé (0, 5, 10, 20, 40, à 60 pce) dans du latex naturel (NR). Il a été constaté que la vatérite CaCO3 non traitée et traitée était stable dans le milieu latex NR. De plus, les polymorphes du CaCO3 non traité et traité en forme de fibres étaient également stables dans leurs formes lorsqu'ils étaient ajoutés au latex NR. Les propriétés mécaniques du NR/CaCO3 comprenaient la résistance à la traction, l'allongement à la rupture, la résistance à la déchirure et la dureté Shore A. Il a été constaté que la résistance à la traction des composites NR/CaCO3 augmentait lorsque la charge de CaCO3 augmentait. La résistance à la traction du NR s'est améliorée de 22,68 ± 2,22 MPa de NR pur jusqu'à 23,94 ± 0,97 MPa lorsque des poudres de CaCO3 sphériques non traitées (20 phr) ont été ajoutées, et à 25,28 ± 0,80 MPa de CaCO3 sphérique traité (20 phr) de NR rempli. (...)
This research aims to synthesize different types and shapes of calcium carbonate (CaCO3) particles at a submicrometric and nanoscale, and investigate their applications as reinforcing fillers for natural rubber (NR) composites. The study was therefore divided into two parts. Firstly, the preparation procedure of CaCO3 particles was based on the solution precipitation method between carbonate ions and calcium ions. The second part focused on investigating the mechanical properties of NR/CaCO3 composites. The first part started with the precipitation of (NH4)2CO3 and CaCl2 dissolved in 50% by weight of sucrose as the aqueous medium. This condition resulted in spherical CaCO3 with particle size of 0.42±0.14 µm with an aspect ratio of about one. When the precipitation reaction occurred in the presence of olive soap, the surface property of the CaCO3 was changed from hydrophilic (water contact angle of 28±2o) to superhydrophobic powders (water contact angle of 163±2o). The typical polymorphic phases of CaCO3 were characterized. The results revealed that both untreated and treated spherical CaCO3 were about 99% of the vaterite polymorph. In the precipitation process using Na2CO3 and CaCl2 aqueous solutions performed at 80±1C, bundle-liked CaCO3 was obtained with an aspect ratio in the range of 8–9. The superhydrophobic bundle-liked CaCO3 was also successfully synthesized by soap treatment. The water contact angle of untreated and treated bundle-liked are 29±2o, and 167±2o, respectively. Furthermore, the spherical CaCO3 dispersed in water at 80C resulted in the fiber-shaped CaCO3 nanoparticles which were achieved via the polymorph transformation from spherical vaterite to long nano-wired aragonite with the highest aspect ratio of 156.9. The untreated fiber CaCO3 was hydrophilic with a water contact angle of 31±1o, while the treated fiber CaCO3 with soap resulted in 165±5o of water contact angle, hence it was superhydrophobic similar to other synthesized CaCO3 polymorphs. The XRD revealed that the untreated and treated bundle-liked and fiber-shaped CaCO3 contained the majority of aragonite followed by vaterite and calcite polymorphs. The second part was carried out to incorporate the prepared CaCO3 (0,5,10,20,40,60 phr) in NR latex. It was found that the CaCO3 polymorphs were stable in the NR latex medium. The mechanical properties of NR/CaCO3 included tensile strength, elongation at break, tear strength, and hardness Shore A. It was found that the tensile strength of NR/CaCO3 composites increased when CaCO3 loading was increased. The tensile strength of NR improved from 22.68±2.22 MPa of neat NR up to 23.94±0.97 MPa when untreated spherical CaCO3 powders (20 phr) were added, and to 25.28±0.80 MPa of treated spherical CaCO3 (20 phr) filled NR. The maximum tensile strength of NR/untreated bundle-liked CaCO3 was 30.59±3.50 MPa at 40 phr of loading while 31.51±1.02 MPa of NR/treated bundle-liked CaCO3 at filler loading 20 phr was obtained. The treated CaCO3-filled NR vulcanizates gave higher tensile strength than the untreated ones. This was caused by better compatibility of filler dispersion between the hydrophobicity of treated CaCO3 and hydrophobic property of NR. As a result, it was found that the NR filled with untreated fiber CaCO3 particle provided the highest tensile strength of 31.66±1.80 MPa at 10 phr of filler loading, over other types of CaCO3. The nanoparticle, large surface area, and high aspect ratio of fiber/ long nano wired of CaCO3 enhanced the interfacial adhesion between CaCO3 and NR matrix which could transfer stress from rubber to filler effectively during stretching. This resulted in the reinforcing efficacy of the fiber CaCO3. In summaroze, the prepared CaCO3 powders have the potential to broaden their application not only as diluents or additives but also as reinforcing agents

La caracterisation des proprietes vibrationnelles des sulfates mso#4 et des carbonates mco#3, (m=sr,ba,pb) orthorhombiques (d#2h#1#6), est realisee par la spectroscopie raman. La plupart des bandes prevue par la symetrie sont observees, et l'influence du cation est mise en evidence sur la base des frequences et des intensites des raies. L'ensemble des resultats sur monocristaux montre un comportement particulier des composes du plomb, par les frequences, intensite et largeur des bandes. La largeur des bandes traduit des desordres importants dans la structure. Ces particularites sont attribuees a la presence du doublet d'electrons non lies 6s#2 du plomb. Deux modeles sont utilises pour interpreter les intensites relatives des bandes, ceux-ci rendent correctement compte des resultats obtenus pour les sulfates. L'etude spectroscopique des solutions solides en fonction de la composition montre un comportement a un mode, pour les solutions solides uniquement d'alcalino-terreux (ba-sr), et un comportement mixte a un et au moins a deux modes pour les systemes contenant le plomb. L'eu#3#+ est utilise comme sonde ponctuelle structurale. Les excitations selectives ou non indiquent des sites bien definis pour (ba,sr)so#4, alors que pour sbso#4 on obtient par excitation non selective des spectres comparables a ceux des verres, et par excitation selective on identifie des sites bien definis. Ceci traduit un desordre statique dans pbso#4. Le champ cristallin est plus faible dans pbso#4 que dans (ba,sr)so#4, du a des liaisons metal-oxygene a caractere plus covalent. L'imprecision des donnees cristallographiques ne met pas en evidence l'effet sterique du doublet d'electrons non lie du plomb, cependant il apparait nettement dans les proprietes vibrationnelles

Changements de phase associés aux discontinuités sismiques de 400 et 700km et conséquences sur la rhéologie du manteau. Etude des transitions polymorphiques entre les trois structures alpha , beta et gamma que peut prendre l'olivine et la décomposition de spinelle en pérovskite et magnésiowüstite. Etude réalisée en microscopie électronique en transmission sur des échantillons provenant de météorites choquées ou synthétisées à très haute pression et température dans une cellule à enclume de diamant.

Cold seep-carbonates are the microbially mediated by-products of the anaerobic oxidation of methane (AOM) at seafloor cold seeps, and are widespread about modern continental margins and in the geologic record. Some modern and Miocene examples of cold seep-carbonates from the East Coast Basin, North Island, New Zealand have been analysed in this study, to characterise and determine their carbonate fabrics, elemental and mineralogical composition, and stable δ18O and δ13C isotope signatures, so as to provide insights into the diagenetic changes associated with the lithification and burial of seep-carbonates. The ancient samples were collected from the onshore middle Miocene Tauwhareparae (TWP) seep deposit, while the modern samples were obtained from the National Institute of Water and Atmosphere (NIWA) Cruise TAN0616 (November 2006) from Ritchie Ridge, offshore Hikurangi Margin. A paragenetic sequence of diagenetic events involving early aragonitic phases, followed by late calcitic phases is defined for the seep-carbonates. This sequence likely has relevance for understanding the fluid-cement histories of seep-carbonates more widely. Two main carbonate mineralogies occur in each of the sample groups - modern samples are aragonitic or dolomitic, while the ancient ones consist dominantly of either aragonite or calcite. Thus, aragonite common to both sample groups, and is interpreted to represent the initial primary carbonate precipitate in hydrocarbon seep provinces under specific fluid flux and local pore-water chemistry conditions. Aragonite morphologies range from microcrystalline carbonate ('micarb'), to acicular aragonites that may form botryoids or spherulites. Dolomite occurs in those modern samples which appear to constitute exhumed remnants of a former subsurface 'seep plumbing system', and so are strictly not true seabed 'seep-carbonates', but instead are part of the larger hydrocarbon seep province. Calcite in the ancient samples is either a product of alteration and neomorphic transformation of aragonite, or derives from late stage cementation from burial fluids. As a result of their formation processes, the calcites are generally recrystallised and have equant or 'cellular' textures. Stable δ13C and δ18O isotope cross-plots reveal a large spread of values for the sample groups. Ancient samples range from δ13C -8 to -50 PDB and δ18O -5.5 to +2 PDB. Modern samples have δ13C values from -6 to -41 PDB and δ18O values ranging from +2.6 to +6.7 PDB. The δ13C values suggest the majority of the methane that formed these seep-carbonates is of thermogenic origin, although some mixing from other carbon sources may have occurred. The positive δ18O signatures are suggestive of carbonate formation during dissociation of gas hydrates, while the negative values possibly indicate that some of the formation fluids were warmer than normal in the 17 - 30 C range.

The purpose of this thesis is to analyse the spatial and temporal variability of the aragonite saturation state (ΩAR), commonly used as an indicator of ocean acidification, in the North-East Atlantic. When the aragonite saturation state decreases below a certain threshold, ΩAR <1, calcifying organisms (i.e. molluscs, pteropods, foraminifera, crabs, etc.) are subject to dissolution of shells and aragonite structures. This objective agrees with the challenge 'Ocean, climate change and acidification' of the EU COST Ocean Governance for Sustainability project, which aims to combine the information collected on the state of health of the oceans. Two open-sources data products, EMODnet and GLODAPv2, have been integrated and analysed for the first time in the North-East Atlantic region. The integrated dataset contains 1038 ΩAR vertical profiles whose time distribution spans from 1970 to 2014. The ΩAR has been computed from CO2SYS software considering different combinations of input parameters, pH, Total Alkalinity (TAlk) and Dissolved Inorganic Carbon (DIC), associated with Temperature, Salinity and Pressure at in situ conditions. A sensitivity analysis has been performed to better understand the data consistency of ΩAR computed from the different combinations of pH, Talk and DIC and to verify the difference among observed TAlk and DIC parameters and their output values from the CO2SYS tool. Maps of ΩAR have been computed with the best data coverage obtained from the two datasets, at different levels of depth in the area of investigation and they have been compared to the work of Jiang et al. (2015). The results are consistent and show similar horizontal and vertical patterns. The study highlights some aragonite undersaturated values (ΩAR <1) below 500 meters depth, suggesting a potential effect of acidification in the considered time period. This thesis aims to be a preliminary work for future studies that will be able to design the ΩAR variability on a decadal distribution based on the extended time-series acquired in this work.

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.

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.

Masters of Science
This study was conducted to investigate hydrogeochemical processes controlling the evolution of groundwater chemistry and their influence on water quality in the Heuningnes Catchment. The role or influence of hydrogeochemical processes in groundwater quality in aquifer systems remains poorly understood. One of the ways of improving such understanding is to employ different techniques to explore key processes that govern groundwater quality in aquifer systems. Therefore, the present study investigated hydrogeochemical processes of groundwater resources and identified key processes that explained its quality from a spatiotemporal perspective. The quantitative approach that provides the ability to assess relationships between variables both spatially and temporally was applied. Groundwater sampling was done on four occasions during July 2017, October 2017, March 2018, and July 2018. Identification of hydrogeochemical processes controlling the evolution of groundwater chemistry and quality was done using various complementary tools. These tools included classification of the main water types, evaluation of water-rock interaction by means of stoichiometry analysis and bivariate correlation plots, inverse geochemical modelling, and statistical analysis (hierarchical cluster analysis and factor analysis). Physical parameters were measured in situ, while water samples were collected from boreholes, piezometers, springs, and artesian boreholes for laboratory analysis for major ions analysis. Descriptive and bivariate statistical methods were used to summarise and evaluate the strength of the relationship between variables, while multivariate statistical methods were applied to group similar samples based on their chemical compositions. Tri linear Piper diagrams were generated to characterize water type based on double normalizing the proportions of cations and anions, while correlation and stoichiometric analysis were applied to identify hydrogeochemical processes influencing groundwater chemistry. The results generated from the trilinear Piper diagrams confirmed the dominance of sodium and chloride ions in waters of the Heuningnes Catchment. Groundwater of a Na/Cl type is typical for a coastal aquifer characterised by saline, deep ancient groundwater. The lower parts of the Catchment were characterised by saline groundwater. The results indicated that shallow groundwater samples within the study area were more mineralised as compared to deep groundwater with EC values ranging between 20.8 and 2990 mS/m, with waters within the Table Mountain Group region (TMG), recording the lowest values. Deep groundwater for boreholes and artesian boreholes located upstream in the Catchment was fresh and yielded some of the lowest EC values recorded with an EC value below 50 mS/m. Generally, EC values increased from the upper TMG region of the Catchment towards the Bokkeveld shale region downstream and were highest during the dry season of 2018. The results indicated strong geological influences on water chemistry. Bivariate correlation and stoichiometric analysis identified cation exchange, adsorption, evaporation, weathering of carbonates, sulphates and silicate minerals as processes influencing the chemistry of groundwater in the Heuningnes Catchment. The Saturation Index (SI) results showed a change of calcite, dolomite, aragonite, gypsum, anhydrite, halite, melantinterite, siderite and sylvite from being undersaturated to oversaturated at some areas for the different seasons along the flow path. The mass-balance modelling results indicated that ion exchange and reverse ion exchange processes were more dominant at low elevations along the same flow path during the dry periods. However, at high elevations along the flow path, silicate weathering was the dominant process taking place. The findings of this study demonstrated the influence of hydrogeochemical processes in changing the water chemistry along the flow paths. In conclusion, the study showed the value of utilising various assessment tools as complementary techniques to improve the understanding about hydrogeochemical processes, and its influence on evolution of groundwater chemistry and quality. Based on the findings of the study the following recommendations were made for future studies; the sample points or sample boreholes in the study Catchment should be increased; and to have more sampling trips to enable better comparison between the possible processes