Despite recent interest in understanding long-term trends in ocean acidity, natural variations of carbon chemistry on short timescales are still poorly understood. Unfortunately, historical observations of the oceanic CO2 system are relatively few in number. Such data are particularly scarce along the highly productive Canadian Pacific coast. However, hydrographic data such as temperature, salinity, oxygen and nutrients have been collected regularly in this region. I developed a fully cross-validated statistical model to predict the aragonite saturation state (Ωarag), a biologically relevant measure of the carbonate system. Different sensitivity tests were performed to assess the robustness of the statistical modelling skill to different model structures. In particular, this study found that in situ temperature and O2 used together were strong predictors of Ωarag. The carbon data used to build this statistical model came from five hydrographic surveys along the Pacific coast of Canada (in July 1998, August 2004, late May 2007, February 2010 and early August 2010) that contain direct measurements of CO2 system parameters. Only data from a depth range of 0-750 m were used, as data from below 750 m showed biases due to calcium carbonate dissolution. Although processes such as solar warming and gas exchange occur in the surface and could possibly introduce biases in the model, I show that these surface data can be included. The ability of the statistical models to compute robust estimates of Ωarag was assessed by exploring the generalizability of the model through cross-validation procedures using different partitions of the data. By predicting lnΩarag rather than Ωarag directly, I obtained a strong and robust predictive relationship. This MLR model form yielded a high value in the squared correlation coefficient between predicted and observed values (0.96) and a low percentage in erroneous prediction of undersaturated conditions (3.1%). This relationship was found to be insensitive to changes in spatial domain or interannual variability in the data. These results suggest that the model can be used to estimate the distribution of Ωarag along the outer west coast of Canada when basic hydrographic data on temperature and O2 are available. Predictions of Ωarag from historical observations (1980-2009) in this region reveal that the saturation horizon (Ωarag=1) tended to be more stable in winter and spring and highly variable and occasionally shallow in summer and fall during and following the upwelling season. Undersaturation with respect to aragonite was more likely to occur at shallower depths over the shelf relative to adjacent offshore waters likely as a result of upwelling. The Ωarag saturation horizon tended to be more variable in depth on the shelf compared to offshore waters. The saturation horizon tended to occur at deeper depths over the Queen Charlotte Sound (QCS) shelf and be more stable with respect to the west coast of Vancouver island (WCVI). Thus, the WCVI may experience adverse effects of ocean acidification more acutely than QCS. The use of this approach may provide insight into natural variability and the key controls of Ωarag in future studies at a low cost. However, this predictive model cannot hind-cast data to evaluate the presence of the anthropogenic signal. / Graduate

No description available.

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).

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.

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).

Thesis (M.S.)--University of North Carolina Wilmington, 2008. / Title from PDF title page (viewed May 26, 2009) Includes bibliographical references (p. 49-56)

The subsumed work of this dissertation is comprised of three independent but interrelated studies which seek to further the understanding of processes which govern the coprecipitation of trace elements with calcite and aragonite minerals. These studies investigate the effects of: 1) pressure on crystal morphology and trace element incorporation to aragonite; 2) growth rate on uranium partitioning between calcite and fluid; 3) aqueous Mg/Ca on the magnesium partitioning to low-magnesium calcite. The importance of this work is to determine how the environment of formation and growth rate influences the geochemistry of CaCO3 in order to improve existing paleoproxies and develop new ones. In the first study a series of experiments were conducted at 1, 25, 75, 100, and 345 bars of nitrogen – this range covers pressures at the oceanic floor. Aragonite precipitation was induced by the one-time addition of a Na2CO3 solution to an artificial seawater. Results suggest that oceanic floor pressures could affect the crystallization of CaCO3 by altering mineralogical composition and aragonite crystal size. In the second study calcite crystallized from NH4Cl-CaCl2-U solution by diffusion of CO2. The calcite growth rate was monitored by sequential spiking of the calcite-precipitating fluids with REE dopants. The resulting crystals were analyzed using Secondary Ion Mass Spectrometry (SIMS). Results showed that the partitioning of uranium increases with increasing growth rate. Growth entrapment model (GEM) and unified uptake kinetics model (UUKM) explain the obtained data.In the third study CaCO3 precipitated in NaCl solution by continuous addition of CaCl2, MgCl2, and either Na2CO3 or NaHCO3. The Mg/Ca of the fluid was adjusted in an attempt to produce calcite where Mg/Ca would match Mg/Ca in foraminifera shells. It was observed that multiple CaCO3 polymorphs precipitated from fluids at high pH (Na2CO3 doping experiments). This result underscores the potential control of pH and/or supersaturation state on CaCO3 polymorph precipitated from low Mg/Ca solutions. Calcite was the only mineral crystallized at low pH (NaHCO3 doping experiments). It was determined that Mg partition coefficient between calcite and fluid (KMg) negatively correlates with Mg/Ca(Fluid) when it exceeds 0.5 mol/mol; no systematic correlation was observed when 0.05< Mg/Ca(Fluid)<0.5 mol/mol.

This study considers the chemical alteration of archaeological freshwater shell above the water table at Lyon's Bluff, located in east-central Mississippi, changes in trace element concentrations between unfired and fired shell, and the effect bacteria have on archaeological freshwater shell. Thin-section petrography, X-ray diffraction, cathodoluminescence, and scanning electron microscopy were conducted on archaeological shell from four layers from Unit 20N20W, with a depth of 80 cm spanning 450 years. ICP-MS analysis was also conducted on a modern freshwater shell. Results of the microscopy indicate pristine crystal structure. ICP-MS data show that certain trace elements within the shell maintain their concentration after firing at 500°C. The broader implications are: 1) that diagenetic alteration does not hinder chemical sourcing of shell at Lyon’s Bluff, and 2) that certain trace elements are more reliable than others, namely Sr2+, Al2+, Ba2+, and Mn2+, when conducting provenance studies on shell temper.

Fluid-rock interaction causes an exchange of isotopes or elements through various reactions. The rate of these reactions strongly depends on temperature. The interaction involves dissolution precipitation, chemical exchange reactions, redox reactions, diffusion, and their combinations. The goal of studying fluid-rock interaction is to understand the change in mineral chemistry of the rock materials when in contact with an aqueous solution. These processes occur in all regions of the Earth where aqueous solutions are found. This work is comprised of three independent studies which provide an understanding about crystallization processes under multiple hydrothermal conditions with geological and environmental applications. In the chapter 1, subsurface rock and CO2-saturated brine reactions were evaluated under laboratory hydrothermal conditions when injected carbon dioxide is in contact with sedimentary strata at a planned sequestration sites at Kemper County Mississippi. Five rock samples were taken from different depths using core cuttings for experimentation. The results reveal no reaction of clay particles and CO2-rich fluid; in contrast, in samples from the depth of the unconformity, significant formation of secondary minerals occurred by reaction with the rock sample at the unconformity. The second study focuses on the incorporation of uranium (VI) into the crystal lattice of calcite at hydrothermal conditions. This study was designed to understand uranium (VI) behaviors in a calcite-fluid system at elevated temperatures due to decay of radioactive waste from nuclear power plants. The results showed uranyl hydroxide formation was preferred at hydrothermal conditions, 120 – 350 oC. The incorporation of U6+ in calcite lattices was evaluated, though the data showed a limited amount of U6+ entrapment. The third study focuses on quantification of the retention of Mg/Ca, Sr/Ca, and d18O during the aragonite-calcite transformation process as well as evaluation of the transformation rate. The results show partial retention of Mg and Sr during aragonite transformation to calcite in Mg-, Sr-free solutions, but no retention of d18O. Aragonite oxygen isotope composition was erased during mineral transformation because fractionation was controlled by temperature and the d18O of the bulk solution.

This thesis describes a sequence of experiments which have been performed with the intention to produce synthetic nacre. Synthetic nacre is a biomimetic material based on nacre, a material which can be found in mollusc shells. Nacre is a nanocomposite which has improved mechanical properties compared to the principal component aragonite (95% wt%). The improved properties of nacre are derived from the polymeric components in the composite which allows from redistribution of forces under load. Carbonates sequester CO2 in the geological CO2-cycle. If precursor are sourced correctly, the CaCO3 in synthetic nacre can temporarily sequester CO2. Crystals with the intended pseudohexagonal morphology have been synthesised. However, subsequent quantitative analysis could not support these findings in a follow-up experiment. This discrepancy might have been caused by differences in the method. Moist nanopaper was found to be mineralisable while maintaining a layered structure.