The effect of CO2-fluid-rock interactions on the porosity and permeability of calcite-bearing sandstone

NASA Astrophysics Data System (ADS)

Lamy-Chappuis, B.; Yardley, B.; Grattoni, C.

2013-12-01

Brine acidification following CO2 dissolution will initiate fluid-rock interactions that could significantly modify porosity, permeability and therefore the capacity and injectivity of a reservoir. We have investigated experimentally the dissolution of calcite in sandstone cores injected with CO2-saturated brine, and the effect this has on permeability. A series of CT (Computerized Tomography) - monitored experiments were conducted on a Jurassic sandstone (porosity = 30%, permeability = 10mD, calcite content = 5% in the form of dispersed shell fragments). Brine saturated with CO2 at pressures up to 1 MPa was injected into 5cm long, 3.75cm diameter cores at a flow rate of 1 ml/min and room temperature. The data showed quasi-instantaneous dissolution of the calcite even at low CO2 concentrations (0.15 Molar) and high fluid interstitial velocities (1mm/s), with the migration of a calcite dissolution front through the core recorded by successive CT scans. The resulting permeability increase was 60 - 80% whereas the predicted permeability change for the observed increase in porosity is only 10 - 20% using the Kozeny-Carman relationship. This result is particularly significant because the effect of porosity increase on permeability is usually modelled with this relationship, irrespective of the mechanism of porosity increase. Micro-CT scans (pixel resolution: 2.5 microns) of unreacted cores were used to generate 3D porosity models with calcite either treated as solid (pre-reaction model) or converted to pores (post-reaction model). FLUENT simulations performed using these models predicted the observed large relative changes in permeability with calcite dissolution but overestimated absolute permeability by an order of magnitude. This was probably due to the scan resolution being too coarse to correctly model pore throats. The observed large change in permeability for a small change in porosity may have resulted from increase in connectivity, focused dissolution at the pore throats or reduction in tortuosity. SEM (Scanning Electron Microscope) imaging demonstrates dissolution of relatively large isolated shell fragments but this had little effect on the overall connectivity. No calcite cement was observed at the pore throats in the unreacted specimens. The micro-CT scans indicate a modest tortuosity decrease from 2.00 to 1.85 when calcite is dissolved, but this change in tortuosity results from the opening of new flow paths as the dissolution of discrete grains opened new flow paths and created shortcuts, not from changes to the sinuosity of existing pathways. We suggest that the marked discrepancy in the effect of calcite dissolution on permeability between our experimental data and standard models arises because of the very different way in which the porosity is increased (new pathways rather than inflation). While our results cast doubt on the general applicability of standard models for porosity-permeability relationships for situations in which porosity changes by grain-specific reactions, it is encouraging that pore scale modelling is able to reproduce the experimental relationships.

Impacts of seawater saturation state (ΩA = 0.4-4.6) and temperature (10, 25 °C) on the dissolution kinetics of whole-shell biogenic carbonates

NASA Astrophysics Data System (ADS)

Ries, Justin B.; Ghazaleh, Maite N.; Connolly, Brian; Westfield, Isaac; Castillo, Karl D.

2016-11-01

Anthropogenic increase of atmospheric pCO2 since the Industrial Revolution has caused seawater pH to decrease and seawater temperatures to increase-trends that are expected to continue into the foreseeable future. Myriad experimental studies have investigated the impacts of ocean acidification and warming on marine calcifiers' ability to build protective shells and skeletons. No studies, however, have investigated the combined impacts of ocean acidification and warming on the whole-shell dissolution kinetics of biogenic carbonates. Here, we present the results of experiments designed to investigate the effects of seawater saturation state (ΩA = 0.4-4.6) and temperature (10, 25 °C) on gross rates of whole-shell dissolution for ten species of benthic marine calcifiers: the oyster Crassostrea virginica, the ivory barnacle Balanus eburneus, the blue mussel Mytilus edulis, the conch Strombus alatus, the tropical coral Siderastrea siderea, the temperate coral Oculina arbuscula, the hard clam Mercenaria mercenaria, the soft clam Mya arenaria, the branching bryozoan Schizoporella errata, and the coralline red alga Neogoniolithon sp. These experiments confirm that dissolution rates of whole-shell biogenic carbonates decrease with calcium carbonate (CaCO3) saturation state, increase with temperature, and vary predictably with respect to the relative solubility of the calcifiers' polymorph mineralogy [high-Mg calcite (mol% Mg > 4) ≥ aragonite > low-Mg calcite (mol% Mg < 4)], consistent with prior studies on sedimentary and inorganic carbonates. Furthermore, the severity of the temperature effects on gross dissolution rates also varied with respect to carbonate polymorph solubility, with warming (10-25 °C) exerting the greatest effect on biogenic high-Mg calcite, an intermediate effect on biogenic aragonite, and the least effect on biogenic low-Mg calcite. These results indicate that both ocean acidification and warming will lead to increased dissolution of biogenic carbonates in future oceans, with shells/skeletons composed of the more soluble polymorphs of CaCO3 being the most vulnerable to these stressors. The effects of saturation state and temperature on gross shell dissolution rate were modeled with an exponential asymptotic function (y =B0 -B2 ·e B1 Ω) that appeals to the general Arrhenius-derived rate equation for mineral dissolution [ r = (C ·e -Ea / RT) (1 - Ω)n]. Although the dissolution curves for the investigated biogenic CaCO3 exhibited exponential asymptotic trends similar to those of inorganic CaCO3, the observation that gross dissolution of whole-shell biogenic CaCO3 occurred (albeit at lower rates) even in treatments that were oversaturated (Ω > 1) with respect to both aragonite and calcite reveals fundamental differences between the dissolution kinetics of whole-shell biogenic CaCO3 and inorganic CaCO3. Thus, applying stoichiometric solubility products derived for inorganic CaCO3 to model gross dissolution of biogenic carbonates may substantially underestimate the impacts of ocean acidification on net calcification (gross calcification minus gross dissolution) of systems ranging in scale from individual organisms to entire ecosystems (e.g., net ecosystem calcification). Finally, these experiments permit rough estimation of the impact of CO2-induced ocean acidification on the gross calcification rates of various marine calcifiers, calculated as the difference between net calcification rates derived empirically in prior studies and gross dissolution rates derived from the present study. Organisms' gross calcification responses to acidification were generally less severe than their net calcification response patterns, with aragonite mollusks (bivalves, gastropods) exhibiting the most negative gross calcification response to acidification, and photosynthesizing organisms, including corals and coralline red algae, exhibiting relative resilience.

Kinetics of carbonate mineral dissolution in CO2-acidified brines at storage reservoir conditions.

PubMed

Peng, Cheng; Anabaraonye, Benaiah U; Crawshaw, John P; Maitland, Geoffrey C; Trusler, J P Martin

2016-10-20

We report experimental measurements of the dissolution rate of several carbonate minerals in CO 2 -saturated water or brine at temperatures between 323 K and 373 K and at pressures up to 15 MPa. The dissolution kinetics of pure calcite were studied in CO 2 -saturated NaCl brines with molalities of up to 5 mol kg -1 . The results of these experiments were found to depend only weakly on the brine molality and to conform reasonably well with a kinetic model involving two parallel first-order reactions: one involving reactions with protons and the other involving reaction with carbonic acid. The dissolution rates of dolomite and magnesite were studied in both aqueous HCl solution and in CO 2 -saturated water. For these minerals, the dissolution rates could be explained by a simpler kinetic model involving only direct reaction between protons and the mineral surface. Finally, the rates of dissolution of two carbonate-reservoir analogue minerals (Ketton limestone and North-Sea chalk) in CO 2 -saturated water were found to follow the same kinetics as found for pure calcite. Vertical scanning interferometry was used to study the surface morphology of unreacted and reacted samples. The results of the present study may find application in reactive-flow simulations of CO 2 -injection into carbonate-mineral saline aquifers.

Silicate and carbonate mineral weathering in soil profiles developed on Pleistocene glacial drift (Michigan, USA): Mass balances based on soil water geochemistry

NASA Astrophysics Data System (ADS)

Jin, Lixin; Williams, Erika L.; Szramek, Kathryn J.; Walter, Lynn M.; Hamilton, Stephen K.

2008-02-01

Geochemistry of soil, soil water, and soil gas was characterized in representative soil profiles of three Michigan watersheds. Because of differences in source regions, parent materials in the Upper Peninsula of Michigan (the Tahquamenon watershed) contain only silicates, while those in the Lower Peninsula (the Cheboygan and the Huron watersheds) have significant mixtures of silicate and carbonate minerals. These differences in soil mineralogy and climate conditions permit us to examine controls on carbonate and silicate mineral weathering rates and to better define the importance of silicate versus carbonate dissolution in the early stage of soil-water cation acquisition. Soil waters of the Tahquamenon watershed are the most dilute; solutes reflect amphibole and plagioclase dissolution along with significant contributions from atmospheric precipitation sources. Soil waters in the Cheboygan and the Huron watersheds begin their evolution as relatively dilute solutions dominated by silicate weathering in shallow carbonate-free soil horizons. Here, silicate dissolution is rapid and reaction rates dominantly are controlled by mineral abundances. In the deeper soil horizons, silicate dissolution slows down and soil-water chemistry is dominated by calcite and dolomite weathering, where solutions reach equilibrium with carbonate minerals within the soil profile. Thus, carbonate weathering intensities are dominantly controlled by annual precipitation, temperature and soil pCO 2. Results of a conceptual model support these field observations, implying that dolomite and calcite are dissolving at a similar rate, and further dissolution of more soluble dolomite after calcite equilibrium produces higher dissolved inorganic carbon concentrations and a Mg 2+/Ca 2+ ratio of 0.4. Mass balance calculations show that overall, silicate minerals and atmospheric inputs generally contribute <10% of Ca 2+ and Mg 2+ in natural waters. Dolomite dissolution appears to be a major process, rivaling calcite dissolution as a control on divalent cation and inorganic carbon contents of soil waters. Furthermore, the fraction of Mg 2+ derived from silicate mineral weathering is much smaller than most of the values previously estimated from riverine chemistry.

Kinetic dissolution of carbonates and Mn oxides in acidic water: Measurement of in situ field rates and reactive transport modeling

USGS Publications Warehouse

Brown, J.G.; Glynn, P.D.

2003-01-01

The kinetics of carbonate and Mn oxide dissolution under acidic conditions were examined through the in situ exposure of pure phase samples to acidic ground water in Pinal Creek Basin, Arizona. The average long-term calculated in situ dissolution rates for calcite and dolomite were 1.65??10-7 and 3.64??10-10 mmol/(cm2 s), respectively, which were about 3 orders of magnitude slower than rates derived in laboratory experiments by other investigators. Application of both in situ and lab-derived calcite and dolomite dissolution rates to equilibrium reactive transport simulations of a column experiment did not improve the fit to measured outflow chemistry: at the spatial and temporal scales of the column experiment, the use of an equilibrium model adequately simulated carbonate dissolution in the column. Pyrolusite (MnO2) exposed to acidic ground water for 595 days increased slightly in weight despite thermodynamic conditions that favored dissolution. This result might be related to a recent finding by another investigator that the reductive dissolution of pyrolusite is accompanied by the precipitation of a mixed Mn-Fe oxide species. In PHREEQC reactive transport simulations, the incorporation of Mn kinetics improved the fit between observed and simulated behavior at the column and field scales, although the column-fitted rate for Mn-oxide dissolution was about 4 orders of magnitude greater than the field-fitted rate. Remaining differences between observed and simulated contaminant transport trends at the Pinal Creek site were likely related to factors other than the Mn oxide dissolution rate, such as the concentration of Fe oxide surface sites available for adsorption, the effects of competition among dissolved species for available surface sites, or reactions not included in the model.

Kinetics of Inorganic Calcite Dissolution in Seawater under Pressure

NASA Astrophysics Data System (ADS)

Dong, S.; Subhas, A.; Rollins, N.; Berelson, W.; Adkins, J. F.

2016-02-01

While understanding calcium carbonate dissolution is vital in constructing global carbon cycles and predicting the effect of seawater acidification as a result of increasing atmospheric CO2, there is still a major debate over the basic formulation of a dissolution rate law. The kinetics of calcium carbonate dissolution are typically described by the equation: Rate=k(1-Ω)n, while Ω=[Ca2+][CO32-]/Ksp. In this study, 13C-labeled calcite is dissolved in unlabeled seawater and the evolving d13C composition of the fluid is traced over time to establish dissolution rate. Instead of changing ion concentration to obtain varying Ω (as in our previous study; Subhas et al. 2015), we changed Ksp by conducting experiments under different pressures (described in theory as ∂lnKsp/∂P=-ΔV/RT, where ΔV is partial molal volume). This involved the construction of a pressure vessel that could hold our sample bag and provide aliquots while remaining pressurized. Pressure experiments were conducted between 0-2000PSI. Results support the conclusion in our previous study that near-equilibrium dissolution rates are highly nonlinear, but give a disparate relationship between undersaturation and dissolution rate if Ω is calculated assuming the specific ΔV embedded in CO2SYS. A revised ΔV from -37cm3 to -65cm3 would make the dissolution formulation equation agree, but clearly appears unreasonable. Our results are explained by a pressure effect on carbonate dissolution kinetics over and above the influence of pressure on Ω. If this is a phenomenon that occurs in nature, then we would predict that dissolution should be occurring shallower in the water column (as sometimes observed) than indicated by standard Ω calculations.

Ocean chemistry controls trends in foraminiferal mineralogy

NASA Astrophysics Data System (ADS)

de Nooijer, Lennart; van Dijk, Inge; Reichart, Gert-Jan

2014-05-01

Foraminifera are unicellular marine protists of which many produce a calcium carbonate shell of either aragonite or calcite. Since they are responsible for a large part of open ocean calcium carbonate precipitation, it is necessary to understand their response to changes in ocean chemistry. On geological time scales, the ratio of Mg over Ca in seawater played an important role in controlling marine aragonite versus calcite mineralogy. Here we reconstructed occurrences of aragonite and low- and high-Mg calcite producing foraminifera through the Phanerozoic. We discovered a two-step impact of seawater chemistry and mass extinction events on the evolution of foraminifera. Seawater Mg to Ca ratios favor production of either calcite, or of high magnesium carbonate and aragonite shells. However, mass extinction events controlled the timing of shifts in dominance from one mineralogy to the other. This observation suggests that ongoing ocean acidification may have important consequences for foraminiferal calcification. Although reduced carbonate saturation state increases dissolution rates of high-Mg calcite and aragonite compared to low-Mg calcite, the current high Mg/Ca of the ocean kinetically favors precipitation of high-Mg calcite and aragonite. Contrary to the differential effects of dissolution, we argue that ongoing ocean acidification is likely to particularly impact calcite producers (e.g. planktonic foraminifera, coccolithophores) compared to those precipitating high-Mg calcite and aragonite (e.g. corals).

Modeling Remineralization of Desalinated Water by Micronized Calcite Dissolution.

PubMed

Hasson, David; Fine, Larissa; Sagiv, Abraham; Semiat, Raphael; Shemer, Hilla

2017-11-07

A widely used process for remineralization of desalinated water consists of dissolution of calcite particles by flow of acidified desalinated water through a bed packed with millimeter-size calcite particles. An alternative process consists of calcite dissolution by slurry flow of micron-size calcite particles with acidified desalinated water. The objective of this investigation is to provide theoretical models enabling design of remineralization by calcite slurry dissolution with carbonic and sulfuric acids. Extensive experimental results are presented displaying the effects of acid concentration, slurry feed concentration, and dissolution contact time. The experimental data are shown to be in agreement within less than 10% with theoretical predictions based on the simplifying assumption that the slurry consists of uniform particles represented by the surface mean diameter of the powder. Agreement between theory and experiment is improved by 1-8% by taking into account the powder size distribution. Apart from the practical value of this work in providing a hitherto lacking design tool for a novel technology. The paper has the merit of being among the very few publications providing experimental confirmation to the theory describing reaction kinetics in a segregated flow system.

Calcite Dissolution Kinetics

NASA Astrophysics Data System (ADS)

Berelson, W.; Subhas, A.; Dong, S.; Naviaux, J.; Adkins, J. F.

2016-12-01

A geological buffer for high atmospheric CO2 concentrations is neutralization via reaction with CaCO3. We have been studying the dissolution kinetics of carbonate minerals using labeled 13C calcite and Picarro-based measurements of 13C enrichments in solution DIC. This methodology has greatly facilitated our investigation of dissolution kinetics as a function of water carbonate chemistry, temperature and pressure. One can adjust the saturation state Omega by changing the ion activity product (e.g. adjusting carbonate ion concentration), or by changing the solubility product (e.g. adjusting temperature or pressure). The canonical formulation of dissolution rate vs. omega has been refined (Subhas et al. 2015) and shows distinct non-linear behavior near equilibrium and rates in sea water of 1-3 e-6 g/cm2day at omega = 0.8. Carbonic anhydrase (CA), an enzyme that catalyzes the hydration of dissolved CO2 to carbonic acid, was shown (in concentrations <=0.04 g/L) to enhance the dissolution rate at low degrees of undersaturation by >500x. This result points to the importance of carbonic acid in enhancing dissolution at low degrees of undersaturation. CA activity and abundance in nature must be considered regarding the role it plays in catalyzing dissolution. We also have been investigating the role of temperature on dissolution kinetics. An increase of 16C yields an order of magnitude increase in dissolution rate. Temperature (and P) also change Omega critical, the saturation state where dissolution rates change substantially. Increasing pressure (achieved in a pressure reaction chamber we built) also shifts Omega critical closer to equilibrium and small pressure increases have large impact on dissolution kinetics. Dissolution rates are enhanced by an order of magnitude for a change in pressure of 1500 psi relative to the dissolution rate achieved by water chemistry effects alone for an omega of 0.8. We've shown that the thermodynamic determination of saturation state does not adequately describe the kinetics of dissolution. The interplay of mineral composition and surface area, solution carbonate chemistry, temperature and pressure are factors the impact carbonate dissolution rates in natural settings. We suggest that these parameters be considered in CO2 mitigation strategies.

Integrated Approach for Understanding Impurity Adsorption on Calcite: Mechanisms for Micro-scale Surface Phenomena

NASA Astrophysics Data System (ADS)

Vinson, M. D.; Arvidson, R. S.; Luttge, A.

2004-12-01

A longstanding goal within the field of environmental geochemistry has been the development of a fundamental understanding of the kinetics that governs the interactions of solution-borne impurities with the calcite mineral surface. Recent dissolution experiments using Mg2+, Mn2+, and Sr2+ have shown distinct differences in the interaction of these three impurity ions with the calcite crystal surface. Because the dissolution of carbonate minerals in soils and sediments influences the uptake and migration of groundwater contaminants, a rigorous understanding of the basic processes that occur at the mineral-fluid interface is necessary. We have used vertical scanning interferometry (VSI) coupled with scanning probe microscopy (SPM) to examine calcite crystal dissolution in the presence of Mg2+, Mn2+, and Sr2+, all known dissolution inhibitors and possible groundwater contaminants. We have studied the kinetics of impurity-crystal interactions at a pH 8.8, and in the presence or absence of dissolved inorganic carbon. Our data show that, when individually introduced into undersaturated solutions, Mg2+ and Mn2+ are shown to activate the calcite crystal surface, resulting in enhanced etch pit nucleation rates and step density. Conversely, Sr2+ is shown to cause passivation of the calcite surface. The effect is intensified when solutions are saturated with respect to atmospheric CO2. Results indicate that aqueous CO32- (or HCO3-) may influence how aqueous metal ionic complexes interact with the crystal surface. Furthermore, the influence is differently exhibited, and passivation or activation ultimately depends on the properties of the diffusing metal ion or metal-hydroxide complex. These properties include for example, differences in hydration enthalpy, the effective ionic radius, and electron shell configuration.

Hydrobiogeochemical interactions in 'anoxic' limestone drains for neutralization of acidic mine drainage

USGS Publications Warehouse

Robbins, E.I.; Cravotta, C.A.; Savela, C.E.; Nord, G.L.

1999-01-01

Processes affecting neutralization of acidic coal mine drainage were evaluated within 'anoxic' limestone drains (ALDs). Influents had pH???3.5 and dissolved oxygen <2 mg/l. Even though effluents were near neutral (pH 6 and alkalinity acidity), two of the four ALDs were failing due to clogging. Mineral-saturation indices indicated the potential for dissolution of calcite and gypsum, and precipitation of Al3+ and Fe3+ compounds. Cleavage mounts of calcite and gypsum that were suspended within the ALDs and later examined microscopically showed dissolution features despite coatings by numerous bacteria, biofilms, and Fe-Al-Si precipitates. In the drain exhibiting the greatest flow reduction, Al-hydroxysulfates had accumulated on limestone surfaces and calcite etch points, thus causing the decline in transmissivity and dissolution. Therefore, where Al loadings are high and flow rates are low, a pre-treatment step is indicated to promote Al removal before diverting acidic mine water into alkalinity-producing materials. ?? 1998 Elsevier Science Ltd.

Laboratory batch experiments and geochemical modelling of water-rock-supercritical CO2 reactions in Southern San Joaquin Valley, California oil field sediments: Implications for future carbon capture and sequestration projects.

NASA Astrophysics Data System (ADS)

Mickler, P. J.; Rivas, C.; Freeman, S.; Tan, T. W.; Baron, D.; Horton, R. A.

2015-12-01

Storage of CO2 as supercritical liquid in oil reservoirs has been proposed for enhanced oil recovery and a way to lower atmospheric CO2 levels. The fate of CO2 after injection requires an understanding of mineral dissolution/precipitation reactions occurring between the formation minerals and the existing formation brines at formation temperatures and pressures in the presence of supercritical CO2. In this study, core samples from three potential storage formations, the Vedder Fm. (Rio Bravo oil field), Stevens Fm. (Elk Hills oil field) and Temblor Fm. (McKittrick oil field) were reacted with a synthetic brine and CO2(sc) at reservoir temperature (110°C) and pressure (245-250 bar). A combination of petrographic, SEM-EDS and XRD analyses, brine chemistry, and PHREEQ-C modelling were used to identify geochemical reactions altering aquifer mineralogy. XRD and petrographic analyses identified potentially reactive minerals including calcite and dolomite (~2%), pyrite (~1%), and feldspars (~25-60%). Despite the low abundance, calcite dissolution and pyrite oxidation were dominant geochemical reactions. Feldspar weathering produced release rates ~1-2 orders of magnitude slower than calcite dissolution. Calcite dissolution increased the aqueous concentrations of Ca, HCO3, Mg, Mn and Sr. Silicate weathering increased the aqueous concentrations of Si and K. Plagioclase weathering likely increased aqueous Ca concentrations. Pyrite oxidation, despite attempts to remove O2 from the experiment, increased the aqueous concentration of Fe and SO4. SEM-EDS analysis of post-reaction samples identified mixed-layered illite-smectites associated with feldspar grains suggesting clay mineral precipitation in addition to calcite, pyrite and feldspar dissolution. The Vedder Fm. sample underwent complete disaggregation during the reaction due to cement dissolution. This may adversely affect Vedder Formation CCS projects by impacting injection well integrity.

Is the Core Top Really Modern? A Story of Chemical Erosion, Bioturbation, and Lateral Sediment Redistribution from the Eastern Equatorial Pacific

NASA Astrophysics Data System (ADS)

Mekik, F.

2016-12-01

Paleoceanographic work is based on calibrating paleo-environmental proxies using well-preserved core top sediments which represent the last one thousand years or less. However, core top sediments may be in places as old as 9000 years due to various sedimentary and diagenetic processes, such as chemical erosion, bioturbation and lateral sediment redistribution. We hypothesize that in regions with high surface ocean productivity, high organic carbon to calcite ratios reaching the seabed promote calcite dissolution in sediments, even in regions above the lysocline. This process may lead to chemical erosion of core tops which in turn may result in core top aging. The eastern equatorial Pacific (EEP), a popular site for calibration of paleoceanographic proxies, is such a place. Better understanding the relationship between core top age and dissolution will help correct biases inherent in proxy calibration because dissolution of foraminifers alters shell chemistry, and wholesale dissolution of sediments leads to core top aging and loss. We present both new and literature-based core top data of radiocarbon ages from the EEP. We created regional maps of both core top radiocarbon age and calcite preservation measured with the Globorotalia menardii Fragmentation Index (MFI; over 100 core tops). Our maps show a clear pattern of deep sea sedimentary calcite dissolution mimicking the pattern of surface ocean productivity observed from satellites and sediment traps in the EEP. Core top radiocarbon ages generally parallel the dissolution patterns observed in the region. Where this relationship does not hold true, bioturbation and/or lateral sediment redistribution may play a role. Down core radiocarbon and 230Th-normalized sediment accumulation rate data from several cores in the EEP support this hypothesis. Better understanding the role of diagenesis promotes the development of more reliable paleo-environmental proxies.

Direct Experimental Evidence for Differing Reactivity Alterations of Minerals following Irradiation: The Case of Calcite and Quartz

NASA Astrophysics Data System (ADS)

Pignatelli, Isabella; Kumar, Aditya; Field, Kevin G.; Wang, Bu; Yu, Yingtian; Le Pape, Yann; Bauchy, Mathieu; Sant, Gaurav

2016-01-01

Concrete, used in the construction of nuclear power plants (NPPs), may be exposed to radiation emanating from the reactor core. Until recently, concrete has been assumed immune to radiation exposure. Direct evidence acquired on Ar+-ion irradiated calcite and quartz indicates, on the contrary, that, such minerals, which constitute aggregates in concrete, may be significantly altered by irradiation. More specifically, while quartz undergoes disordering of its atomic structure resulting in a near complete lack of periodicity, calcite only experiences random rotations, and distortions of its carbonate groups. As a result, irradiated quartz shows a reduction in density of around 15%, and an increase in chemical reactivity, described by its dissolution rate, similar to a glassy silica. Calcite however, shows little change in dissolution rate - although its density noted to reduce by ≈9%. These differences are correlated with the nature of bonds in these minerals, i.e., being dominantly ionic or covalent, and the rigidity of the mineral’s atomic network that is characterized by the number of topological constraints (nc) that are imposed on the atoms in the network. The outcomes have major implications on the durability of concrete structural elements formed with calcite or quartz bearing aggregates in nuclear power plants.

Direct Experimental Evidence for Differing Reactivity Alterations of Minerals following Irradiation: The Case of Calcite and Quartz

PubMed Central

Pignatelli, Isabella; Kumar, Aditya; Field, Kevin G.; Wang, Bu; Yu, Yingtian; Le Pape, Yann; Bauchy, Mathieu; Sant, Gaurav

2016-01-01

Concrete, used in the construction of nuclear power plants (NPPs), may be exposed to radiation emanating from the reactor core. Until recently, concrete has been assumed immune to radiation exposure. Direct evidence acquired on Ar+-ion irradiated calcite and quartz indicates, on the contrary, that, such minerals, which constitute aggregates in concrete, may be significantly altered by irradiation. More specifically, while quartz undergoes disordering of its atomic structure resulting in a near complete lack of periodicity, calcite only experiences random rotations, and distortions of its carbonate groups. As a result, irradiated quartz shows a reduction in density of around 15%, and an increase in chemical reactivity, described by its dissolution rate, similar to a glassy silica. Calcite however, shows little change in dissolution rate - although its density noted to reduce by ≈9%. These differences are correlated with the nature of bonds in these minerals, i.e., being dominantly ionic or covalent, and the rigidity of the mineral’s atomic network that is characterized by the number of topological constraints (nc) that are imposed on the atoms in the network. The outcomes have major implications on the durability of concrete structural elements formed with calcite or quartz bearing aggregates in nuclear power plants. PMID:26822012

Direct experimental evidence for differing reactivity alterations of minerals following irradiation. The case of calcite and quartz

DOE PAGES

Pignatelli, Isabella; Kumar, Aditya; Field, Kevin G.; ...

2016-01-29

Concrete, used in the construction of nuclear power plants (NPPs), may be exposed to radiation emanating from the reactor core. Until recently, concrete has been assumed immune to radiation exposure. Direct evidence acquired on Ar+ -ion irradiated calcite and quartz indicates, on the contrary, that, such minerals, which constitute aggregates in concrete, may be significantly altered by irradiation. More specifically, while quartz undergoes disordering of its atomic structure resulting in a near complete lack of periodicity, calcite only experiences random rotations, and distortions of its carbonate groups. As a result, irradiated quartz shows a reduction in density of around 15%,more » and an increase in chemical reactivity, described by its dissolution rate, similar to a glassy silica. However, calcite shows little change in dissolution rate - although its density noted to reduce by 9%. These differences are correlated with the nature of bonds in these minerals, i.e., being dominantly ionic or covalent, and the rigidity of the mineral's atomic network that is characterized by the number of topological constraints (nc) that are imposed on the atoms in the network. Our outcomes have major implications on the durability of concrete structural elements formed with calcitic or quartzitic aggregates in nuclear power plants.« less

The Labrador Sea during the Last Glacial Maximum: Calcite dissolution or low biogenic carbonate fluxes?

NASA Astrophysics Data System (ADS)

Marshall, Nicole; de Vernal, Anne; Mucci, Alfonso; Filippova, Alexandra; Kienast, Markus

2017-04-01

Low concentrations of biogenic carbonate characterize the sediments deposited in the Labrador Sea during the last glaciation. This may reflect poor calcite preservation and/or low biogenic carbonate productivity and fluxes. Regional bottom water ventilation was reduced during the Last Glacial Maximum (LGM), so the calcite lysocline might have been shallower than at present in the deep Labrador Sea making dissolution of calcite shells in the deep Labrador Sea possible. To address the issue, a multi-proxy approach based on micropaleontological counts (coccoliths, foraminifers, palynomorphs) and biogeochemical analyses (alkenones) was applied in the investigation of core HU2008-029-004-PC recovered in the northwestern Labrador Sea. Calcite dissolution indices based on the relative abundance benthic foraminifera shells to their organic linings as well as on fragmentation of planktonic foraminifera shells were used to evaluate changes in calcite dissolution/ preservation since the LGM. In addition, the ratio of the concentrations of coccoliths, specifically of the alkenone-producer Emiliania huxleyi, and alkenones (Emiliania huxleyi: alkenones) was explored as a potential new proxy of calcite dissolution. A sharp increase in coccoliths, foraminifers and organic linings from nearly none to substantial concentrations at 12 ka, reflect a jump to significantly greater biogenic fluxes at the glacial-interglacial transition. Furthermore, conventional dissolution indices (shells/linings of benthic foraminifera and fragmentation of planktic foraminifers) reveal that dissolution is not likely responsible for the lower glacial abundances of coccoliths and foraminifers. Only the low Emiliania huxleyi: alkenones ratios in glacial sediments could be interpreted as evidence of increased dissolution during the LGM. Given the evidence of allochthonous alkenone input into the glacial Labrador Sea, the latter observations must be treated with caution. Overall, the records indicate that low biogenic fluxes during the LGM were the most likely cause of the decreased biogenic carbonate concentrations.

Common Ion Effects In Zeoponic Substrates: Dissolution And Cation Exchange Variations Due to Additions of Calcite, Dolomite and Wollastonite

NASA Technical Reports Server (NTRS)

Beiersdorfer, R. E.; Ming, D. W.; Galindo, C., Jr.

2003-01-01

c1inoptilolite-rich tuff-hydroxyapatite mixture (zeoponic substrate) has the potential to serve as a synthetic soil-additive for plant growth. Essential plant macro-nutrients such as calcium, phosphorous, magnesium, ammonium and potassium are released into solution via dissolution of the hydroxyapatite and cation exchange on zeolite charged sites. Plant growth experiments resulting in low yield for wheat have been attributed to a Ca deficiency caused by a high degree of cation exchange by the zeolite. Batch-equilibration experiments were performed in order to determine if the Ca deficiency can be remedied by the addition of a second Ca-bearing, soluble, mineral such as calcite, dolomite or wollastonite. Variations in the amount of calcite, dolomite or wollastonite resulted in systematic changes in the concentrations of Ca and P. The addition of calcite, dolomite or wollastonite to the zeoponic substrate resulted in an exponential decrease in the phosphorous concentration in solution. The exponential rate of decay was greatest for calcite (5.60 wt. % -I), intermediate for wollastonite (2.85 wt.% -I) and least for dolomite (1.58 wt.% -I). Additions of the three minerals resulted in linear increases in the calcium concentration in solution. The rate of increase was greatest for calcite (3.64), intermediate for wollastonite (2.41) and least for dolomite (0.61). The observed changes in P and Ca concentration are consistent with the solubilities of calcite, dolomite and wollastonite and with changes expected from a common ion effect with Ca. Keywords: zeolite, zeoponics, common-ion effect, clinoptilolite, hydroxyapatite

Laboratory study of fungal bioreceptivity of different fractions of composite flooring tiles showing efflorescence.

PubMed

Masaphy, Segula; Lavi, Ido; Sultz, Stephan; Zabari, Limor

2014-06-01

Fungi can grow in extreme habitats, such as natural stone and mineral building materials, sometimes causing deterioration. Efflorescence-concentrated salt deposits-results from water movement through building material; it can damage masonry materials and other bricks. Fungal isolate KUR1, capable of growth on, and dissolution of stone chips composing terrazzo-type floor tiles, was isolated from such tiles showing fiber-like crystalline efflorescence. The isolate's ribosomal DNA sequences were 100 % identical to those of Nigrospora sphaerica. The ability of KUR1 to colonize and degrade the different stone chips composing the tiles was studied in axenic culture experiments. When exposed to each of the different mineral chip types composed of dolomite, calcite, or calcite-apatite mineral in low-nutrition medium, the fungus showed selective nutrient consumption, and different growth and stone mineral dissolution rates. Micromorphological examination of the fungus-colonized chips by electron microscopy showed the production of a fungal biofilm with thin films around the hyphae on the surface of the examined chips and disintegration of the calcite-apatite fraction. More than 70 % dissolution of the introduced powdered (<1 mm particle size) mineral was obtained within 10 days of incubation for the soft calcite-apatite fraction.

Effects of selective handling of pyritic, acid-forming materials on the chemistry of pore gas and ground water at a reclaimed surface coal mine in Clarion County, PA, USA

USGS Publications Warehouse

Cravotta,, Charles A.; Dugas, Diana L.; Brady, Keith; Kovalchuck, Thomas E.

1994-01-01

A change from dragline to “selective handling” mining methods at a reclaimed surface coal mine in western Pennsylvania did not significantly affect concentrations of metals in ground water because oxidation of pyrite and dissolution of siderite were not abated. Throughout the mine, placement of pyritic material near the land surface facilitated the oxidation of pyrite, causing the consumption of oxygen (O2) and release of acid, iron, and sulfate ions. Locally in the unsaturated zone, water sampled within or near pyritic zones was acidic, with concentrations of sulfate exceeding 3,000 milligrams per liter (mg/L). However, acidic conditions generally did not persist below the water table because of neutralization by carbonate minerals. Dissolution of calcite, dolomite, and siderite in unsaturated and saturated zones produced elevated concentrations of carbon dioxide (CO2), alkalinity, calcium, magnesium, iron, and manganese. Alkalinity concentrations of 600 to 800 mg/L as CaCO3 were common in water samples from the unsaturated zone in spoil, and alkalinities of 100 to 400 mg/L as CaCO3 were common in ground-water samples from the underlying saturated zone in spoil and bedrock. Saturation indices indicated that siderite could dissolve in water throughout the spoil, but that calcite dissolution or precipitation could occur locally. Calcite dissolution could be promoted as a result of pyrite oxidation, gypsum precipitation, and calcium ion exchange for sodium. Calcite precipitation could be promoted by evapotranspiration and siderite dissolution, and corresponding increases in concentrations of alkalinity and other solutes. Partial pressures of O2 (Po2) and CO2 (Pco2) in spoil pore gas indicated that oxidation of pyrite and precipitation of ferric hydroxide, coupled with dissolution of calcite, dolomite, and siderite were the primary reactions affecting water quality. Highest vertical gradients in Po2, particularly in the near-surface zone (0-1 m), did not correlate with concentrations of total sulfur in spoil. This lack of correlation could indicate that total sulfur concentrations in spoil do not reflect the amount of reactive pyrite or that oxidation rates can be controlled more by rates of O2 diffusion than the amount of pyrite. Hence, if placed in O2-rich zones near the land surface, even small amounts of disseminated pyritic material can be relatively significant sources of acid and mineralized water.

Calcium isotope evidence for suppression of carbonate dissolution in carbonate-bearing organic-rich sediments

NASA Astrophysics Data System (ADS)

Turchyn, Alexandra V.; DePaolo, Donald J.

2011-11-01

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (δ 44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of δ 44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, δ 44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the δ 44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

Mass-balance modeling of mineral weathering rates and CO2 consumption in the forested, metabasaltic Hauver Branch watershed, Catoctin Mountain, Maryland, USA

USGS Publications Warehouse

Rice, Karen; Price, Jason R.; Szymanski, David W.

2013-01-01

Mineral weathering rates and a forest macronutrient uptake stoichiometry were determined for the forested, metabasaltic Hauver Branch watershed in north-central Maryland, USA. Previous studies of Hauver Branch have had an insufficient number of analytes to permit determination of rates of all the minerals involved in chemical weathering, including biomass. More equations in the mass-balance matrix were added using existing mineralogic information. The stoichiometry of a deciduous biomass term was determined using multi-year weekly to biweekly stream-water chemistry for a nearby watershed, which drains relatively unreactive quartzite bedrock.At Hauver Branch, calcite hosts ~38 mol% of the calcium ion (Ca2+) contained in weathering minerals, but its weathering provides ~90% of the stream water Ca2+. This occurs in a landscape with a regolith residence time of more than several Ka (kiloannum). Previous studies indicate that such old regolith does not typically contain dissolving calcite that affects stream Ca2+/Na+ ratios. The relatively high calcite dissolution rate likely reflects dissolution of calcite in fractures of the deep critical zone.Of the carbon dioxide (CO2) consumed by mineral weathering, calcite is responsible for approximately 27%, with the silicate weathering consumption rate far exceeding that of the global average. The chemical weathering of mafic terrains in decaying orogens thus may be capable of influencing global geochemical cycles, and therefore, climate, on geological timescales. Based on carbon-balance calculations, atmospheric-derived sulfuric acid is responsible for approximately 22% of the mineral weathering occurring in the watershed. Our results suggest that rising air temperatures, driven by global warming and resulting in higher precipitation, will cause the rate of chemical weathering in the Hauver Branch watershed to increase until a threshold temperature is reached. Beyond the threshold temperature, increased recharge would produce a shallower groundwater table and reduced chemical weathering rates.

The role of mineral heterogeneity on the hydrogeochemical response of two fractured reservoir rocks in contact with dissolved CO2

NASA Astrophysics Data System (ADS)

Garcia Rios, Maria; Luquot, Linda; Soler, Josep M.; Cama, Jordi

2017-04-01

In this study we compare the hydrogeochemical response of two fractured reservoir rocks (limestone composed of 100 wt.% calcite and sandstone composed of 66 wt.% calcite, 28 wt.% quartz and 6 wt.% microcline) in contact with CO2-rich sulfate solutions. Flow-through percolation experiments were performed using artificially fractured limestone and sandstone cores and injecting a CO2-rich sulfate solution under a constant volumetric flow rate (from 0.2 to 60 mL/h) at P = 150 bar and T = 60 °C. Measurements of the pressure difference between the inlet and the outlet of the samples and of the aqueous chemistry enabled the determination of fracture permeability changes and net reaction rates. Additionally, X-ray computed microtomography (XCMT) was used to characterize and localized changes in fracture volume induced by dissolution and precipitation reactions. In all reacted cores an increase in fracture permeability and in fracture volume was always produced even when gypsum precipitation happened. The presence of inert silicate grains in sandstone samples favored the occurrence of largely distributed dissolution structures in contrast to localized dissolution in limestone samples. This phenomenon promoted greater dissolution and smaller precipitation in sandstone than in limestone experiments. As a result, in sandstone reservoirs, the larger increase in fracture volume as well as the more extended distribution of the created volume would favor the CO2 storage capacity. The different distribution of created volume between limestone and sandstone experiments led to a different variation in fracture permeability. The progressive stepped permeability increase for sandstone would be preferred to the sharp permeability increase for limestone to minimize risks related to CO2 injection, favor capillary trapping and reduce energetic storage costs. 2D reactive transport simulations that reproduce the variation in aqueous chemistry and the fracture geometry (dissolution pattern) were performed using CrunchFlow. The calcite reactive surface area had to be diminished with respect to the geometric surface area in order to account for the transport control of the calcite dissolution reaction at pH < 5. The fitted reactive surface area was higher under faster flow conditions, reflecting a decrease in transport control and a more distributed reaction in sandstone compared to limestone.

A Compilation of Rate Parameters of Water-Mineral Interaction Kinetics for Application to Geochemical Modeling

DTIC Science & Technology

2004-03-01

equilibria among fluids, gases, and alteration minerals is a valid assumption in many volcanic-hosted hydrothermal systems (Arnórsson, 1983; Arnórsson et al...order n with respect to P(CO2). e. Sedimentary (disordered) dolomite. f. Hydrothermal (ordered) dolomite. 3.9 Sulfates Dissolution rate data...carbonate in sea water IV. Theory of calcite dissolution. Am. J. Sci. 274, 108-134. Bertrand C., Fritz B., and Sureau J. F. (1994) Hydrothermal

Radiocarbon dating of planktonic foraminifer shells: A cautionary tale

NASA Astrophysics Data System (ADS)

Mekik, Figen

2014-01-01

rate, bioturbation, winnowing, and calcite dissolution produce significant radiocarbon age offsets among multiple species of coexisting planktonic foraminifers and pteropod fragments. We compare the radiocarbon age of foraminifer species and pteropod fragments with estimates of percent calcite dissolved made with a sedimentary proxy (Globorotalia menardii fragmentation index—MFI) to delineate the effect of dissolution on radiocarbon age of foraminifers. Data from two core top transects on the Rio Grande Rise (RIO) and Ontong Java Plateau (OJP) and from down core sediments of varying sedimentation rates in the tropical Pacific (ME-27, MD98 2177, and MW91-9 56GGC) reveal that sediments with the greatest accumulation rates produce the least age offsets among coexisting species. Age offsets among coexisting foraminifers are about 3500 years on RIO, and 1000 years on OJP. Two core tops from RIO yield an age of the Last Glacial Maximum possibly due to mass displacement of younger sediments downslope. Foraminifer age increases with increasing dissolution and there is a consistent pattern of older foraminifer fragments coexisting with younger whole shells of the same species. The only exception is sediments which have experienced high dissolution where fragments are younger than whole shells. The age offset between fragments of G. menardii and its coexisting whole shells does not exceed the age offset among other coexisting foraminifer species in the same core tops.

Influence of CO2 on the long-term chemomechanical behavior of an oolitic limestone

NASA Astrophysics Data System (ADS)

Grgic, D.

2011-07-01

In order to study the long-term mechanical and petrographical evolutions of a carbonate rock (oolitic limestone) during storage of CO2, CO2 injection tests were performed in triaxial cells at temperature and mechanical stresses (isotropic and deviatoric) corresponding to the depth of the Dogger carbonate reservoirs of the Paris basin (˜800 m). We used a specific "flow-through" triaxial cell which allowed us to measure very low strain rates in both axial and lateral directions, while ensuring the sealing of the samples during the injection of CO2. Under isotropic loading, neither the dynamic percolation (i.e., flow-through tests) of dry supercritical/gaseous CO2, nor the diffusion of CO2, into initially saturated samples was shown to produce significant axial compaction and calcite dissolution. Indeed, even though the interstitial aqueous fluid becomes acidic, the progressive increase in dissolved species induces the H2O-CO2-calcite re-equilibrium. The dynamic injection of CO2-saturated solution induced significant axial compaction due to the dissolution of calcite at the sample/piston interface only under open flow conditions (i.e., the injected acidic solution is continuously renewed). Under closed flow conditions (i.e., acidic solution recirculation or no-flow conditions) which reproduce the physicochemical conditions of CO2 storage at the field scale better, the rapid H2O-CO2-calcite re-equilibrium inhibits calcite dissolution. Under deviatoric loading and closed conditions, the diffusion of CO2 induced a very small increase in the PSC (pressure solution creep) process which was stopped by the H2O-CO2-calcite re-equilibrium inside the sample. Therefore, a significant compaction of limestone samples was obtained only under open conditions and is mainly due to a purely chemical mechanism (calcite dissolution), while the contribution of the chemo-mechanical mechanism (PSC) was found to not be of any great importance. In the context of massive injection of CO2 at the field scale, if the reservoir can be considered as a closed system from a hydrodynamic point of view (i.e., the brine circulates in the aquifer but is not renewed by any groundwater), CO2 will not play a significant role in the chemistry of carbonate reservoirs due to the H2O-CO2-calcite re-equilibrium and will not induce reservoir compaction and affect its long-term storage capacity, whatever the stress state (isotropic or deviatoric).

Reaction processes and permeability changes during CO2-rich brine flow through fractured Portland cement

NASA Astrophysics Data System (ADS)

Abdoulghafour, H.; Luquot, L.; Gouze, P.

2012-12-01

So far, cement alteration was principally studied experimentally using batch reactor (with static or renewed fluid). All exhibit similar carbonation mechanisms. The acidic solution, formed by the dissolution of the CO2 into the pore water or directly surrounding the cement sample, diffuses into the cement and induces dissolution reactions of the cement hydrates in particular portlandite and CSH. The calcium released by the dissolution of these calcium bearing phases combining with carbonate ions of the fluid forms calcium carbonates. The cement pH, initially around 13, falls to values where carbonate ion is the most dominant element (pH ~ 9), then CaCO3 phases can precipitate. These studies mainly associate carbonation process with a reduction of porosity and permeability. Indeed an increase of volume (about 10%) is expected during the formation of calcite from portlandite (equation 2) assuming a stoichiometric reaction. Here we investigated the cement alteration mechanisms in the frame of a controlled continuous renewal of CO2-rich fluid in a fracture. This situation is that expected when seepage is activated by the mechanical failure of the cement material that initially seals two layers of distinctly different pressure: the storage reservoir and the aquifer above the caprock, for instance. We study the effect of flow rates from quasi-static flow to higher flow rates for well-connected fractures. In the quasi-static case we observed an extensive conversion of portlandite (Ca(OH)2) to calcite in the vicinity of the fracture similar to that observed in the published batch experiments. Eventually, the fracture was almost totally healed. The experiments with constant flow revealed a different behaviour triggered by the continuous renewing of the reactants and withdrawal of reaction products. We showed that calcite precipitation is more efficient for low flow rate. With intermediate flow rate, we measured that permeability increases slowly at the beginning of the experiment and then remains constant due to calcite precipitation in replacement of CSH and CH into fracture border. With higher flow rate, we measured a constant permeability which can be explained by the development of a highly hydrated Si-rich zone which maintains the initial fracture aperture during all over the experiment while noticeable mass is released from the sample. These preliminary results emphasize that more complex behaviours than that envisaged from batch experiments may take place in the vicinity of flowing fractures. We demonstrated that if only micro-cracks appear in the cement well, carbonation reaction may heal these micro-cracks and mitigate leakage whereas conductive fractures allowing high flow may represent a risk of perennial leakage because the net carbonation process, including the calcite precipitation and its subsequent re-dissolution, is sufficiently to heal the fracture. However, the precipitation of Si-rich amorphous phases may maintain the initial fracture aperture and limit the leakage rate. Keywords: leakage, cement alteration, flow rate, fracture, permeability changes, reaction processes.

Reactivity of alkaline lignite fly ashes towards CO{sub 2} in water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martin Back; Michael Kuehn; Helge Stanjek

2008-06-15

The reaction kinetics between alkaline lignite fly ashes and CO{sub 2} (pCO{sub 2} = 0.01-0.03 MPa) were studied in a laboratory CO{sub 2} flow-through reactor at 25-75{sup o}C. The reaction is characterized by three phases that can be separated according to the predominating buffering systems and the rates of CO{sub 2} uptake. Phase I (pH > 12, < 30 min) is characterized by the dissolution of lime, the onset of calcite precipitation and a maximum uptake, the rate of which seems to be limited by dissolution of CO{sub 2}. Phase II (pH < 10.5, 10-60 min) is dominated by themore » carbonation reaction. CO{sub 2} uptake in phase III (pH < 8.3) is controlled by the dissolution of periclase (MgO) leading to the formation of dissolved magnesium-bicarbonate. Phase I could be significantly extended by increasing the solid-liquid ratios and temperature, respectively. At 75{sup o}C the rate of calcite precipitation was doubled leading to the neutralization of approximately 0.23 kg CO{sub 2} per kg fly ash within 4.5 h, which corresponds to nearly 90% of the total acid neutralizing capacity. 21 refs., 5 figs., 1 tab.« less

Fractured cement reactivity during CO2-rich brine leakage: Consequences on hydrodynamic and structural properties

NASA Astrophysics Data System (ADS)

abdelghafour, H.; Luquot, L.; Gouze, P.

2013-12-01

So far, cement alteration was principally studied experimentally using batch reactor (with static or renewed fluid). All exhibit similar carbonation mechanisms. The acidic solution, formed by the dissolution of the CO2 into the pore water or directly surrounding the cement sample, diffuses into the cement and induces dissolution reactions of the cement hydrates in particular portlandite and CSH. The calcium released by the dissolution of these calcium bearing phases combining with carbonate ions of the fluid forms calcium carbonates. The cement pH, initially around 13, falls to values where carbonate ion is the most dominant element (pH ~ 9), then CaCO3 phases can precipitate. These studies mainly associate carbonation process with a reduction of porosity and permeability. Indeed an increase of volume (about 10%) is expected during the formation of calcite from portlandite assuming a stoichiometric reaction. Here we investigated the cement alteration mechanisms in the frame of a controlled continuous renewal of CO2-rich fluid in a fracture. This situation is that expected when seepage is activated by the mechanical failure of the cement material that initially seals two layers of distinctly different pressure: the storage reservoir and the aquifer above the caprock, for instance. We study the effect of flow rates from quasi-static flow to higher flow rates for well-connected fractures. In the quasi-static case we observed an extensive conversion of portlandite (Ca(OH)2) to calcite in the vicinity of the fracture similar to that observed in the published batch experiments. Eventually, the fracture was almost totally healed. The experiments with constant flow revealed a different behavior triggered by the continuous renewing of the reactants and withdrawal of the reaction products. We showed that calcite precipitation is more efficient for low flow rate. With intermediate flow rate, we measured that permeability increases slowly at the beginning of the experiment and then remains constant due to calcite precipitation in replacement of CSH and CH into fracture border. With higher flow rate, we measured a constant permeability which can be explained by the development of a highly hydrated Si-rich zone which maintains the initial fracture aperture during all over the experiment while noticeable mass is released from the sample. These results emphasize that more complex behaviors than that envisaged from batch experiments may take place in the vicinity of flowing fractures. We demonstrated that if only micro-cracks appear in the cement well, carbonation reaction may heal these micro-cracks and mitigate leakage whereas conductive fractures allowing high flow may represent a risk of perennial leakage because the net carbonation process, including the calcite precipitation and its subsequent re-dissolution, is sufficiently to heal the fracture. However, the precipitation of Si-rich amorphous phases may maintain the initial fracture aperture and limit the leakage rate.

Dissolution of cemented fractures in gas bearing shales in the context of CO2 sequestration

NASA Astrophysics Data System (ADS)

Kwiatkowski, Kamil; Szymczak, Piotr

2016-04-01

Carbon dioxide has a stronger binding than methane to the organic matter contained in the matrix of shale rocks [1]. Thus, the injection of CO2 into shale formation may enhance the production rate and total amount of produced methane, and simultaneously permanently store pumped CO2. Carbon dioxide can be injected during the initial fracking stage as CO2 based hydraulic fracturing, and/or later, as a part of enhanced gas recovery (EGR) [2]. Economic and environmental benefits makes CO2 sequestration in shales potentially very for industrial-scale operation [3]. However, the effective process requires large area of fracture-matrix interface, where CO2 and CH4 can be exchanged. Usually natural fractures, existing in shale formation, are preferentially reactivated during hydraulic fracturing, thus they considerably contribute to the flow paths in the resulting fracture system [4]. Unfortunately, very often these natural fractures are sealed by calcite [5]. Consequently the layer of calcite coating surfaces impedes exchange of gases, both CO2 and CH4, between shale matrix and fracture. In this communication we address the question whether carbonic acid, formed when CO2 is mixed with brine, is able to effectively dissolve a calcite layer present in the natural fractures. We investigate numerically fluid flow and dissolution of calcite coating in natural shale fractures, with CO2-brine mixture as a reactive fluid. Moreover, we discuss the differences between slow dissolution (driven by carbonic acid) and fast dissolution (driven by stronger hydrochloric acid) of calcite layer. We compare an impact of the flow rate and geometry of the fracture on the parameters of practical importance: available surface area, morphology of dissolution front, time scale of the dissolution, and the penetration length. We investigate whether the dissolution is sufficiently non-uniform to retain the fracture permeability, even in the absence of the proppant. The sizes of analysed fractures varying from 0.2 x 0.2 m2 up to 4 x 4 m2, together with discussion of a further upscaling, make the study relevant to the industrial applications. While the results of this study should be applicable to different shale formations throughout the world, we discuss them in the context of preparation to gas-production from Pomeranian shale basin, located in the northern Poland. [1] Mosher, K., He, J., Liu, Y., Rupp, E., & Wilcox, J. Molecular simulation of methane adsorption in micro-and mesoporous carbons with applications to coal and gas shale systems. International Journal of Coal Geology, 109, 36-44 (2013) [2] Grieser, W. V., Wheaton, W. E., Magness, W. D., Blauch, M. E., & Loghry, R, "Surface Reactive Fluid's Effect on Shale." Proceedings of the Production and Operations Symposium, 31 March-3 April 2007, Oklahoma City (SPE-106815-MS) [3] Tao, Z. and Clarens, A., Estimating the carbon sequestration capacity of shale formations using methane production rates, Environmental Science and Technology, 47, 11318-11325 (2013). [4] Zhang, X., Jeffrey, R. G., & Thiercelin, M. (2009). Mechanics of fluid-driven fracture growth in naturally fractured reservoirs with simple network geometries. Journal of Geophysical Research: Solid Earth, 114, B12406 (2009) [5] Gale, J.F., Laubach, S.E., Olson, J.E., Eichhubl, P., Fall, A. Natural fractures in shale: A review and new observations. AAPG Bulletin 98(11):2165-2216 (2014)

Porosity Development in a Coastal Setting: A Reactive Transport Model to Assess the Influence of Heterogeneity of Hydrological, Geochemical and Lithological Conditions

NASA Astrophysics Data System (ADS)

Maqueda, A.; Renard, P.; Cornaton, F. J.

2014-12-01

Coastal karst networks are formed by mineral dissolution, mainly calcite, in the freshwater-saltwater mixing zone. The problem has been approached first by studying the kinetics of calcite dissolution and then coupling ion-pairing software with flow and mass transport models. Porosity development models require high computational power. A workaround to reduce computational complexity is to assume the calcite dissolution reaction is relatively fast, thus equilibrium chemistry can be used to model it (Sanford & Konikow, 1989). Later developments allowed the full coupling of kinetics and transport in a model. However kinetics effects of calcite dissolution were found negligible under the single set of assumed hydrological and geochemical boundary conditions. A model is implemented with the coupling of FeFlow software as the flow & transport module and PHREEQC4FEFLOW (Wissmeier, 2013) ion-pairing module. The model is used to assess the influence of heterogeneities in hydrological, geochemical and lithological boundary conditions on porosity evolution. The hydrologic conditions present in the karst aquifer of Quintana Roo coast in Mexico are used as a guide for generating inputs for simulations.

TEM study of a silicate-carbonate-microbe interface prepared by focused ion beam milling

NASA Astrophysics Data System (ADS)

Benzerara, Karim; Menguy, Nicolas; Guyot, François; Vanni, Christian; Gillet, Philippe

2005-03-01

The biogeochemical alteration of an Mg-Fe orthopyroxene, reacted for 70 yr under arid conditions in a desert environment, was studied by transmission electron microscopy. For this purpose, an electron transparent cross-section of the interface between a single microorganism, an orthopyroxene and nanometer-sized calcite crystals, was prepared with a focused ion beam system. X-ray energy dispersive spectrometry and electron energy loss spectroscopy allowed one to clearly distinguish the microorganism en route to fossilization from the nanometer-sized calcite crystals, showing the usefulness of such a protocol for identifying unambiguously traces of life in rocks. A 100-nm-deep depression was observed in the orthopyroxene close to the microorganism, suggesting an enhanced dissolution mediated by the microbe. However, an Al- and Si-rich amorphous altered layer restricted to the area just below the microorganism could be associated with decreased silicate dissolution rates at this location, suggesting complex effects of the microorganism on the silicate dissolution process. The close association observed between silicate dissolution and carbonate formation at the micrometer scale suggests that Urey-type CO 2 sequestration reactions could be mediated by microorganisms under arid conditions.

Carbonate mineral dissolution kinetics in high pressure experiments

NASA Astrophysics Data System (ADS)

Dethlefsen, F.; Dörr, C.; Schäfer, D.; Ebert, M.

2012-04-01

The potential CO2 reservoirs in the North German Basin are overlain by a series of Mesozoic barrier rocks and aquifers and finally mostly by Tertiary and Quaternary close-to-surface aquifers. The unexpected rise of stored CO2 from its reservoir into close-to-surface aquifer systems, perhaps through a broken well casing, may pose a threat to groundwater quality because of the acidifying effect of CO2 dissolution in water. The consequences may be further worsening of the groundwater quality due to the mobilization of heavy metals. Buffer mechanisms counteracting the acidification are for instance the dissolution of carbonates. Carbonate dissolution kinetics is comparably fast and carbonates can be abundant in close-to-surface aquifers. The disadvantages of batch experiments compared to column experiments in order to determine rate constants are well known and have for instance been described by v. GRINSVEN and RIEMSDIJK (1992). Therefore, we have designed, developed, tested, and used a high-pressure laboratory column system to simulate aquifer conditions in a flow through setup within the CO2-MoPa project. The calcite dissolution kinetics was determined for CO2-pressures of 6, 10, and 50 bars. The results were evaluated by using the PHREEQC code with a 1-D reactive transport model, applying a LASAGA (1984) -type kinetic dissolution equation (PALANDRI and KHARAKA, 2004; eq. 7). While PALANDRI and KHARAKA (2004) gave calcite dissolution rate constants originating from batch experiments of log kacid = -0.3 and log kneutral = -5.81, the data of the column experiment were best fitted using log kacid = -2.3 and log kneutral = -7.81, so that the rate constants fitted using the lab experiment applying 50 bars pCO2 were approximately 100 times lower than according to the literature data. Rate constants of experiments performed at less CO2 pressure (pCO2 = 6 bars: log kacid = -1.78; log kneutral = -7.29) were only 30 times lower than literature data. These discrepancies in the reaction kinetics should be acknowledged when using reactive transport models, especially when modeling kinetically controlled pH-buffering processes between a CO2 leakage an a receptor like a ground water well. Currently, further experiments for the determination of the dolomite dissolution kinetics are being performed. Here, the knowledge of the dissolution rate constants can be even more important compared to the (still) fast calcite dissolution. This study is being funded by the German Federal Ministry of Education and Research (BMBF), EnBW Energie Baden-Württemberg AG, E.ON Energie AG, E.ON Gas Storage AG, RWE Dea AG, Vattenfall Europe Technology Research GmbH, Wintershall Holding AG and Stadtwerke Kiel AG as part of the CO2-MoPa joint project in the framework of the Special Program GEOTECHNOLOGIEN. Literature Lasaga, A. C., 1984. Chemical Kinetics of Water-Rock Interactions. Journal of Geophysical Research 89, 4009-4025. Palandri, J. L. and Kharaka, Y. K., 2004. A compilation of rate parameters of water-mineral interaction kinetics for application to geochemical modeling. USGS, Menlo Park, CA, USA. v. Grinsven, J. J. M. and Riemsdijk, W. H., 1992. Evaluation of batch and column techniques to measure weathering rates in soils. Geoderma 52, 41-57.

A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation

USGS Publications Warehouse

Davis, J.A.; Fuller, C.C.; Cook, A.D.

1987-01-01

The rate of Cd2+ sorption by calcite was determined as a function of pH and Mg2+ in aqueous solutions saturated with respect to calcite but undersaturated with respect to CdCO3. The sorption is characterized by two reaction steps, with the first reaching completion within 24 hours. The second step proceeded at a slow and nearly constant rate for at least 7 days. The rate of calcite recrystallization was also studied, using a Ca2+ isotopic exchange technique. Both the recrystallization rate of calcite and the rate of slow Cd2+ sorption decrease with increasing pH or with increasing Mg2+. The recrystallization rate could be predicted from the number of moles of Ca present in the hydrated surface layer. A model is presented which is consistent with the rates of Cd2+ sorption and Ca2+ isotopic exchange. In the model, the first step in Cd2+ sorption involves a fast adsorption reaction that is followed by diffusion of Cd2+ into a surface layer of hydrated CaCO3 that overlies crystalline calcite. Desorption of Cd2+ from the hydrated layer is slow. The second step is solid solution formation in new crystalline material, which grows from the disordered mixture of Cd and Ca carbonate in the hydrated surface layer. Calculated distribution coefficients for solid solutions formed at the surface are slightly greater than the ratio of equilibrium constants for dissolution of calcite and CdCO3, which is the value that would be expected for an ideal solid solution in equilibrium with the aqueous solution. ?? 1987.

Microbial control of mineral–groundwater equilibria:Macroscale to microscale

USGS Publications Warehouse

Bennett, Philip C.; Hiebert, Franz K.; Roger, Jennifer Roberts

2000-01-01

macroscaleprocesses that perturb general groundwater chemistry and therefore mineral–water equilibria; and microscale interactions, where attached organisms locally perturb mineral–water equilibria, potentially releasing limiting trace nutrients from the dissolving mineral.In the contaminated unconfined glacio-fluvial aquifer near Bemidji, Minnesota, USA, carbonate chemistry is influenced primarily at the macroscale. Under oxic conditions, respiration by native aerobic heterotrophs produces excess carbon dioxide that promotes calcite and dolomite dissolution. Aerobic microorganisms do not colonize dolomite surfaces and few occur on calcite. Within the anoxic groundwater, calcite overgrowths form on uncolonized calcite cleavage surfaces, possibly due to the consumption of acidity by dissimilatory iron-reducing bacteria. As molecular oxygen concentration increases downgradient of the oil pool, aerobes again dominate and residual hydrocarbons and ferrous iron are oxidized, resulting in macroscale carbonate-mineral dissolution and iron precipitation.

Replacement of Calcite (CaCO 3) by Cerussite (PbCO 3)

DOE PAGES

Yuan, Ke; Lee, Sang Soo; De Andrade, Vincent; ...

2016-10-21

The mobility of toxic elements, such as lead (Pb) can be attenuated by adsorption, incorporation, and precipitation on carbonate minerals in subsurface environments. Here in this paper, we report a study of the bulk transformation of single-crystal calcite (CaCO 3) into polycrystalline cerussite (PbCO 3) through reaction with acidic Pb-bearing solutions. This reaction began with the growth of a cerussite shell on top of calcite surfaces followed by the replacement of the remaining calcite core. The external shape of the original calcite was preserved by a balance between calcite dissolution and cerussite growth controlled by adjusting the Pb 2+ concentration and pH. The relation between the rounded calcite core and the surrounding lath-shaped cerussite aggregates was imaged by transmission X-ray microscopy, which revealed preferentially elongated cerussite crystals parallel to the surface and edge directions of calcite. The replacement reaction involved concurrent development ~100 nm wide pores parallel to calcite c-glide or (1more » $$\\overline{20}$$) planes, which may have provided permeability for chemical exchange during the reaction. X-ray reflectivity measurements showed no clear epitaxial relation of cerussite to the calcite (104) surface. These results demonstrate Pb sequestration through mineral replacement reactions and the critical role of nanoporosity (3% by volume) on the solid phase transformation through a dissolution-recrystallization mechanism.« less

Origin of karst conduits in calcareous sandstone and carbonate-silicate rocks: Complex role of insoluble material

NASA Astrophysics Data System (ADS)

Bruthans, Jiri; Balak, Frantisek; Schweigstillova, Jana; Vojtisek, Jan

2017-04-01

Carbonate karst is best developed in high-grade limestones and majority of the studies is focused on these rocks. Features developed by dissolution of calcite cement in quartz sandstones and dissolution of various carbonate-silicate rocks are studied far less frequently. Unlike in common karst, the insoluble residuum has to be washed out after dissolution to create high-permeability conduits in these rocks. Aquifers in a Bohemian Cretaceous Basin (BCB), the most important hydrogeological basin in the Czech Republic, consist mainly of quartz and calcareous sandstones to siltstones. These rocks are intercalated by thin layers of calcite-cemented sandstone and low-grade limestone, the latter sometimes partly impregnated by a secondary silica. Results of tracer tests show a high flow velocity in some of the aquifers. Springs with flow rate up to 500 l/s and wells with yield up to 200 l/s occur in these rocks. Dissolution features in BCB were however not yet studied in detail. For identification and characterization of rocks prone to karstification, 350 cores were sampled mostly from boreholes but also from rock outcrops in several areas of BCB. Cores were taken from intervals where: (i) high carbonate content was expected, (ii) conduits and enlarged porosity was observed in rock outcrops or wells, (iii) inflows to boreholes were determined by well logging. Calcium carbonate content was determined by calcimetry in all cores. All cores were leached in hydrochloric acid to observe the degree of disintegration after removal of calcite, which was far dominating portion of total carbonate. Polished sections were prepared from selected cores and Ca, Si, Na, K, Al content was automatically mapped by microprobe to visualize the calcium, silica, feldspar and clay mineral distribution in cores. Conduits were photo documented in the field. Two types of sediments with distinct disintegration characteristics were observed: (i) In sandstone composed of quartz grains cemented by calcite the complete disintegration occurs when calcite content exceeds 30-50%. Such calcite-rich layers are mostly few tens of cms thick and are enclosed in quartz sandstone. Groundwater flow dissolves calcite cement and turns the rock into cohesion-less sand. Sand is consequently washed out by headward erosion in drainage areas forming high capacity conduits within the sandstone. (ii) In carbonates containing secondary silica which form reinforcing structure, even 70-80% calcite content may not be sufficient for rock disintegration during leaching. Disintegration occurs only on tectonically heavily fractured zones, where secondary silica structure is fragmented. It was found that inflows into wells are often associated with zones prone to karstification. Results clearly show that form of insoluble material is critical for karstification potential. Insoluble grain size defines minimum flow velocity needed to excavate the conduits in dissolved residuum. Impregnation by secondary silica needs to be tectonically fragmented prior conduits can occur. Research was funded by the Czech Science Foundation (GA CR No. 16-19459S) and Review of groundwater resources (Ident. No. 155996).

The chemical evolution of a travertine-depositing stream: Geochemical processes and mass transfer reactions

USGS Publications Warehouse

Lorah, Michelle M.; Herman, Janet S.

1988-01-01

This field study focuses on quantitatively defining the chemical changes occurring in Falling Spring Creek, a travertine-depositing stream located in Alleghany County, Virginia. The processes of CO2outgassing and calcite precipitation or dissolution control the chemical evolution of the stream. The observed chemical composition of the water was used with the computerized geochemical model WATEQF to calculate aqueous speciation, saturation indices, and CO2 partial pressure values. Mass balance calculations were performed to obtain mass transfers of CO2 and calcite. Reaction times, estimated from stream discharge, were used with the mass transfer results to calculate rates of CO2, outgassing and calcite precipitation between consecutive sampling points. The stream, which is fed by a carbonate spring, is supersaturated with respect to CO2 along the entire 5.2-km flow path. Outgassing of CO2 drives the solution to high degrees of supersaturation with respect to calcite. Metabolic uptake of CO2 by photosynthetic plants is insignificant, because the high supply rate of dissolved carbon dioxide and the extreme agitation of the stream at waterfalls and rapids causes a much greater amount of inorganic CO2 outgassing to occur. Calcite precipitation is kinetically inhibited until near the crest of a 20-m vertical waterfall. Calcite precipitation rates then reach a maximum at the waterfall where greater water turbulence allows the most rapid escape of CO2. Physical evidence for calcite precipitation exists in the travertine deposits which are first observed immediately above the waterfall and extend for at least 1.0 km below the falls. Net calcite precipitation occurs at all times of the year but is greatest during low-flow conditions in the summer and early fall.

Skeletal aragonite dissolution from hypersaline seawater: a hypothesis

NASA Astrophysics Data System (ADS)

Qing Sun, S.

1992-05-01

Hypersaline seawater has often been invoked as a mechanism to explain the pervasive dolomitization of ancient platform carbonates, but its potential in causing skeletal aragonite dissolution of these carbonates has rarely been investigated. Previous experimental and theoretical studies have demonstrated that hypersaline seawater is undersaturated with respect to aragonite when evaporation reaches a certain degree. It is contended here that similar undersaturation could also have occurred in ancient evaporitic seas. Geological evidence from the Miocene carbonates of SE Spain, Gulf of Suez, Red Sea and Iraq suggests that this may have been the case. Despite differences in their geological settings, these carbonates have common diagenetic features including: (1) widespread dissolution of skeletal aragonite with little or no calcite cementation; and (2) pervasive dolomitization. Dolomite occurs as both a replacement of Mg calcite and mouldic pore-filling cement. The association of the dolomites with evaporites, their relatively heavy oxygen isotopic values and widespread distribution suggest a hypersaline seawater origin of these dolomites. Petrographic data indicate that skeletal aragonite was dissolved during dolomitization because the aragonite fossil moulds contain dolomite cements, but no pre-dolomitization calcite cements, implying that the dolomitizing fluids (hypersaline seawater) were probably undersaturated with respect to aragonite. The dissolved calcium may have been subsequently incorporated into the dolomite. This may help to explain the lack of calcite cementation despite the extensive skeletal aragonite dissolution.

The role of disseminated calcite in the chemical weathering of granitoid rocks

USGS Publications Warehouse

White, A.F.; Bullen, T.D.; Vivit, D.V.; Schulz, M.S.; Clow, D.W.

1999-01-01

Accessory calcite, present at concentrations between 300 and 3000 mg kg-1, occurs in fresh granitoid rocks sampled from the Merced watershed in Yosemite National Park, CA, USA; Loch Vale in Rocky Mountain National Park CO USA; the Panola watershed, GA USA; and the Rio Icacos, Puerto Rico. Calcite occurs as fillings in microfractures, as disseminated grains within the silicate matrix, and as replacement of calcic cores in plagioclase. Flow-through column experiments, using de-ionized water saturated with 0.05 atm. CO2, produced effluents from the fresh granitoid rocks that were dominated by Ca and bicarbonate and thermodynamically saturated with calcite. During reactions up to 1.7 yr, calcite dissolution progressively decreased and was superceded by steady state dissolution of silicates, principally biotite. Mass balance calculations indicate that most calcite had been removed during this time and accounted for 57-98% of the total Ca released from these rocks. Experimental effluents from surfically weathered granitoids from the same watersheds were consistently dominated by silicate dissolution. The lack of excess Ca and alkalinity indicated that calcite had been previously removed by natural weathering. The extent of Ca enrichment in watershed discharge fluxes corresponds to the amounts of calcite exposed in granitoid rocks. High Ca/Na ratios relative to plagioclase stoichiometries indicate excess Ca in the Yosemite, Loch Vale, and other alpine watersheds in the Sierra Nevada and Rocky Mountains of the western United States. This Ca enrichment correlates with strong preferential weathering of calcite relative to plagioclase in exfoliated granitoids in glaciated terrains. In contrast, Ca/Na flux ratios are comparable to or less than the Ca/Na ratios for plagioclase in the subtropical Panola and tropical Rio Icacos watersheds, in which deeply weathered regoliths exhibit concurrent losses of calcite and much larger masses of plagioclase during transport-limited weathering. These results indicate that the weathering of accessory calcite may strongly influence Ca and alkalinity fluxes from silicate rocks during and following periods of glaciation and tectonism but is much less important for older stable geomorphic surfaces.

Acidization of shales with calcite cemented fractures

NASA Astrophysics Data System (ADS)

Kwiatkowski, Kamil; Szymczak, Piotr; Jarosiński, Marek

2017-04-01

Investigation of cores drilled from shale formations reveals a relatively large number of calcite-cemented fractures. Usually such fractures are reactivated during fracking and can contribute considerably to the permeability of the resulting fracture network. However, calcite coating on their surfaces effectively excludes them from production. Dissolution of the calcite cement by acidic fluids is investigated numerically with focus on the evolution of fracture morphology. Available surface area, breakthrough time, and reactant penetration length are calculated. Natural fractures in cores from Pomeranian shale formation (northern Poland) were analyzed and classified. Representative fractures are relatively thin (0.1 mm), flat and completely sealed with calcite. Next, the morphology evolution of reactivated natural fractures treated with low-pH fluids has been simulated numerically under various operating conditions. Depth-averaged equations for fracture flow and reactant transport has been solved by finite-difference method coupled with sparse-matrix solver. Transport-limited dissolution has been considered, which corresponds to the treatment with strong acids, such as HCl. Calcite coating in reactivated natural fractures dissolves in a highly non-homogeneous manner - a positive feedback between fluid transport and calcite dissolution leads to the spontaneous formation of wormhole-like patterns, in which most of the flow is focused. The wormholes carry reactive fluids deeper inside the system, which dramatically increases the range of the treatment. Non-uniformity of the dissolution patterns provides a way of retaining the fracture permeability even in the absence of the proppant, since the less dissolved regions will act as supports to keep more dissolved regions open. Evolution of fracture morphology is shown to depend strongly on the thickness of calcite layer - the thicker the coating the more pronounced wormholes are observed. However the interaction between wormholes is the strongest when coating thickness is a few times larger than the initial aperture of the fracture. This leads to formation of favorable complex networks of wormholes which provide adequate transport of reactive fluids to fracture surfaces and - at the same time - are capable of supporting fracture surfaces. As a conclusion, acidization of the reactivated fractures with hydrochloric acid seems to be an attractive treatment to apply at fracking stage or later on as EGR. The results contribute to the discussion on the use of acidization to enhance the gas production in the shale reservoirs. This communication stresses the importance of the dissolution of calcite cement in natural fractures in shale formations, which are initially sealed and become reactivated during fracking. While this research is based on the analysis of fractures in the Pomeranian shale basin its results are general enough to be applicable to different formations worldwide.

Dissolution Rates of Biogenic Carbonate Sediments from the Bermuda Platform

NASA Astrophysics Data System (ADS)

Finlay, A. J.; Andersson, A. J.

2016-02-01

The contribution of biogenic carbonate sediment dissolution rates to overall net reef accretion/erosion (under both present and future oceanic pCO2 levels) has been strikingly neglected, despite experimental results indicating that sediment dissolution might be more sensitive to ocean acidification (OA) than calcification. Dissolution of carbonate sediments could impact net reef accretion rates as well as the formation and preservation of valuable marine and terrestrial ecosystems. Bulk sediment dissolution rates of samples from the Bermuda carbonate platform were measured in natural seawater at pCO2 values ranging from approximately 3500 μatm to 9000 μatm. This range of pCO2 levels incorporates values currently observed in porewaters on the Bermuda carbonate platform as well as a potential future increase in porewater pCO2 levels due to OA. Sediment samples from two different stations on the reef platform were analyzed for grain size and mineralogy. Dissolution rates of sediments in the dominant grain size fraction of the platform (500-1000 μm) from both stations ranged between 16.25 and 47.19 (± 0.27 to 0.79) μmoles g-1 hr-1 and are comparable to rates previously obtained from laboratory experiments on other natural carbonate sediments. At a pCO2 of 3500 μatm, rates from both samples were similar, despite their differing mineralogy. However, at pCO2 levels above 3500 μatm, the sediment sample with a greater weight percent of Mg-calcite had slightly higher dissolution rates. Despite many laboratory studies on biogenic carbonate dissolution, a significant disparity still exists between laboratory measurements and field observations. Performing additional controlled, laboratory experiments on natural sediment may help to elucidate the reasons for this disparity.

The effect of a confining unit on the geochemical evolution of ground water in the Upper Floridan aquifer system

USGS Publications Warehouse

Wicks, C.M.; Herman, J.S.

1994-01-01

In west-central Florida, sections of the Upper Floridan aquifer system range in character from confined to leaky to unconfined. The confining unit is the Hawthorn Formation, a clay-rich sequence. The presence or absence of the Hawthorn Formation affects the geochemical evolution of the ground water in the Upper Floridan aquifer system. Mass-balance and mass-transfer models suggest that, in unconfined areas, the geochemical reactions are dolomite dissolution, ion exchange (Mg for Na, K), sulfate reduction, calcite dissolution, and CO2 exchange. In the areas in which the Hawthorn Formation is leaky, the evolution of the ground water is accounted for by ion exchange, sulfate reduction, calcite dissolution, and CO2 exchange. In the confined areas, no ion exchange and only limited sulfate reduction occur, and the chemical character of the ground water is consistent with dolomite and gypsum dissolution, calcite precipitation, and CO2 ingassing. The Hawthorn Formation acts both as a physical barrier to the transport of CO2 and organic matter and as a source of ion-exchange sites, but the carbonate-mineral reactions are largely unaffected by the extent of confinement of the Upper Floridan aquifer. ?? 1994.

Quantifying Rock Weakening Due to Decreasing Calcite Mineral Content by Numerical Simulations

PubMed Central

2018-01-01

The quantification of changes in geomechanical properties due to chemical reactions is of paramount importance for geological subsurface utilisation, since mineral dissolution generally reduces rock stiffness. In the present study, the effective elastic moduli of two digital rock samples, the Fontainebleau and Bentheim sandstones, are numerically determined based on micro-CT images. Reduction in rock stiffness due to the dissolution of 10% calcite cement by volume out of the pore network is quantified for three synthetic spatial calcite distributions (coating, partial filling and random) using representative sub-cubes derived from the digital rock samples. Due to the reduced calcite content, bulk and shear moduli decrease by 34% and 38% in maximum, respectively. Total porosity is clearly the dominant parameter, while spatial calcite distribution has a minor impact, except for a randomly chosen cement distribution within the pore network. Moreover, applying an initial stiffness reduced by 47% for the calcite cement results only in a slightly weaker mechanical behaviour. Using the quantitative approach introduced here substantially improves the accuracy of predictions in elastic rock properties compared to general analytical methods, and further enables quantification of uncertainties related to spatial variations in porosity and mineral distribution. PMID:29614776

Quantifying Rock Weakening Due to Decreasing Calcite Mineral Content by Numerical Simulations.

PubMed

Wetzel, Maria; Kempka, Thomas; Kühn, Michael

2018-04-01

The quantification of changes in geomechanical properties due to chemical reactions is of paramount importance for geological subsurface utilisation, since mineral dissolution generally reduces rock stiffness. In the present study, the effective elastic moduli of two digital rock samples, the Fontainebleau and Bentheim sandstones, are numerically determined based on micro-CT images. Reduction in rock stiffness due to the dissolution of 10% calcite cement by volume out of the pore network is quantified for three synthetic spatial calcite distributions (coating, partial filling and random) using representative sub-cubes derived from the digital rock samples. Due to the reduced calcite content, bulk and shear moduli decrease by 34% and 38% in maximum, respectively. Total porosity is clearly the dominant parameter, while spatial calcite distribution has a minor impact, except for a randomly chosen cement distribution within the pore network. Moreover, applying an initial stiffness reduced by 47% for the calcite cement results only in a slightly weaker mechanical behaviour. Using the quantitative approach introduced here substantially improves the accuracy of predictions in elastic rock properties compared to general analytical methods, and further enables quantification of uncertainties related to spatial variations in porosity and mineral distribution.

Silicate versus carbonate weathering in Iceland: New insights from Ca isotopes

NASA Astrophysics Data System (ADS)

Jacobson, Andrew D.; Grace Andrews, M.; Lehn, Gregory O.; Holmden, Chris

2015-04-01

Several studies have measured riverine fluxes of Ca and carbonate alkalinity in Iceland with the aim of quantifying the role of basalt weathering in the long-term carbon cycle. A major assumption is that all of the Ca and alkalinity originates from the dissolution of Ca-bearing silicate minerals, such as plagioclase and clinopyroxene. However, hydrothermal calcite occurs throughout Iceland, and even trace levels are expected to impact river geochemistry owing to the mineral's high solubility and fast dissolution rate. To test this hypothesis, we used a new, high-precision Ca isotope MC-TIMS method (δ44/40Ca; 2σSD = ± 0.04 ‰) to trace sources of Ca in Icelandic rivers. We report elemental and Ca isotope data for rivers, high- and low-temperature groundwater, basalt, hydrothermal calcite (including Iceland Spar), and stilbite and heulandite, which are two types of zeolites commonly formed during low-grade metamorphism of basalt. In agreement with previous research, we find that rivers have higher δ44/40Ca values than basalt, with a maximum difference of ∼0.40‰. This difference may reflect isotope fractionation in the weathering zone, i.e., preferential uptake of 40Ca during clay mineral formation, adsorption, and other geochemical processes that cycle Ca. However, calcite δ44/40Ca values are also up to ∼0.40‰ higher than bedrock values, and on a diagram of δ44/40Ca versus Sr/Ca, nearly all waters plot within a plausible mixing domain bounded by the measured compositions of basalt and calcite, with glacial rivers plotting closer to calcite than non-glacial rivers. Calcite and heulandite form during hydrothermal alteration of basalt in the deep lava pile and often occur together in metabasalts now exposed at the surface. Because heulandite δ44/40Ca values are ∼1-2‰ lower than basalt, we suggest that 40Ca uptake by heudlandite explains the relatively high δ44/40Ca values of calcite and that calcite weathering in turn elevates riverine δ44/40Ca values. High mechanical erosion rates are known to facilitate the exposure and weathering of calcite, which explains the isotopic contrast between glacial and non-glacial watersheds. Using a mixing model, we find that calcite weathering provides ∼0-65% of the Ca in non-glacial rivers and ∼25-90% of the Ca in glacial rivers, with silicate weathering providing the remainder. Icelandic hydrothermal calcite contains mantle carbon. Noting that zeolite facies metamorphism and hydrothermal fluid circulation are ubiquitous characteristics of basaltic eruptions and assuming that hydrothermal calcite in other basaltic settings also contains mantle carbon, we suggest that the contribution of basalt weathering to long-term CO2 drawdown and climate regulation may be less significant than previously realized.

Arsenic mobilization in shallow aquifers due to CO 2 intrusion from storage reservoirs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiao, Ting; Dai, Zhenxue; Viswanathan, Hari S.

We developed an integrated framework of combined batch experiments and reactive transport simulations to quantify water-rock-CO 2 interactions and arsenic (As) mobilization responses to CO 2 and/or saline water leakage into USDWs. Experimental and simulation results suggest that when CO 2 is introduced, pH drops immediately that initiates release of As from clay minerals. Calcite dissolution can increase pH slightly and cause As re-adsorption. Thus, the mineralogy of the USDW is ultimately a determining factor of arsenic fate and transport. Salient results suggest that: (1) As desorption/adsorption from/onto clay minerals is the major reaction controlling its mobilization, and clay mineralsmore » could mitigate As mobilization with surface complexation reactions; (2) dissolution of available calcite plays a critical role in buffering pH; (3) high salinity in general hinders As release from minerals; and (4) the magnitude and quantitative uncertainty of As mobilization are predicated on the values of reaction rates and surface area of calcite, adsorption surface areas and equilibrium constants of clay minerals, and cation exchange capacity. Results of this study are intended to improve ability to quantify risks associated with potential leakage of reservoir fluids into shallow aquifers, in particular the possible environmental impacts of As mobilization at carbon sequestration sites.« less

Arsenic mobilization in shallow aquifers due to CO 2 intrusion from storage reservoirs

DOE PAGES

Xiao, Ting; Dai, Zhenxue; Viswanathan, Hari S.; ...

2017-06-05

We developed an integrated framework of combined batch experiments and reactive transport simulations to quantify water-rock-CO 2 interactions and arsenic (As) mobilization responses to CO 2 and/or saline water leakage into USDWs. Experimental and simulation results suggest that when CO 2 is introduced, pH drops immediately that initiates release of As from clay minerals. Calcite dissolution can increase pH slightly and cause As re-adsorption. Thus, the mineralogy of the USDW is ultimately a determining factor of arsenic fate and transport. Salient results suggest that: (1) As desorption/adsorption from/onto clay minerals is the major reaction controlling its mobilization, and clay mineralsmore » could mitigate As mobilization with surface complexation reactions; (2) dissolution of available calcite plays a critical role in buffering pH; (3) high salinity in general hinders As release from minerals; and (4) the magnitude and quantitative uncertainty of As mobilization are predicated on the values of reaction rates and surface area of calcite, adsorption surface areas and equilibrium constants of clay minerals, and cation exchange capacity. Results of this study are intended to improve ability to quantify risks associated with potential leakage of reservoir fluids into shallow aquifers, in particular the possible environmental impacts of As mobilization at carbon sequestration sites.« less

Dissolution Processes at Step Edges of Calcite in Water Investigated by High-Speed Frequency Modulation Atomic Force Microscopy and Simulation.

PubMed

Miyata, Kazuki; Tracey, John; Miyazawa, Keisuke; Haapasilta, Ville; Spijker, Peter; Kawagoe, Yuta; Foster, Adam S; Tsukamoto, Katsuo; Fukuma, Takeshi

2017-07-12

The microscopic understanding of the crystal growth and dissolution processes have been greatly advanced by the direct imaging of nanoscale step flows by atomic force microscopy (AFM), optical interferometry, and X-ray microscopy. However, one of the most fundamental events that govern their kinetics, namely, atomistic events at the step edges, have not been well understood. In this study, we have developed high-speed frequency modulation AFM (FM-AFM) and enabled true atomic-resolution imaging in liquid at ∼1 s/frame, which is ∼50 times faster than the conventional FM-AFM. With the developed AFM, we have directly imaged subnanometer-scale surface structures around the moving step edges of calcite during its dissolution in water. The obtained images reveal that the transition region with typical width of a few nanometers is formed along the step edges. Building upon insight in previous studies, our simulations suggest that the transition region is most likely to be a Ca(OH) 2 monolayer formed as an intermediate state in the dissolution process. On the basis of this finding, we improve our understanding of the atomistic dissolution model of calcite in water. These results open up a wide range of future applications of the high-speed FM-AFM to the studies on various dynamic processes at solid-liquid interfaces with true atomic resolution.

Dolomite dissolution rates and possible Holocene dedolomitization of water-bearing units in the Edwards aquifer, south-central Texas

USGS Publications Warehouse

Deike, R.G.

1990-01-01

Rates of dolomite dissolution can be used to test the concept, based on geomorphologic evidence, that a major part of the Edwards aquifer could have formed within the Holocene, a timeframe of approximately 10,000 years. During formation of the aquifer in the Edwards limestone (Cretaceous, Albian) of the Balcones fault zone, dolomite dissolution and porosity development were synchronous and the result of mixing-zone dedolomitization. Initiation of the mixing zone in the early Holocene (???11,000 years before present) is suggested by the maximum age of formation of major discharge sites that allowed the influx of meteoric water into brine-filled, dolomitic preaquifer units. Dedolomitization, the dissolution of dolomite and net precipitation of calcite, has left aquifer units that are calcitic, and 40 vol.% interconnected pore space. The mass of dolomite missing is obtained by comparison of stratigraphically equivalent altered and unaltered units. One dissolution rate (1.76 ?? 10-4 mmol dolomite kgH2O-1yr-1) is determined from this mass, 104yr reaction time, and a log-linear function describing the increase in mass discharge (three orders of magnitude) during aquifer formation. The second estimated dissolution rate is obtained from the mass transfer of dolomite to solution calculated from the increase in magnesium in pore fluids selected from the modern aquifer to represent a typical flowpath during aquifer formation. A reaction time of 104yr for this mass transfer yields a rate of 0.56 ?? 10-4 mmol dolomite kgH2O-1yr-1. Both of these rates are comparable to modern rates of dolomite dissolution (0.3 to 4.5 ?? 10-4 mmol dolomite kgH2O-1yr-1) calculated from measured reaction times in the Tertiary Floridan aquifer system in Florida and the Madison aquifer in the Mississippian Madison Limestone of the Northern Great Plains. Similarity of these rates to the estimated paleo-rates of dolomite dissolution supports a 104 yr reaction timeframe. The Holocene reaction time also can be compared to a series of reaction times calculated by assuming that the mass of dolomite missing from the Edwards was removed at rates observed in the Floridan and Madison aquifers. These reaction times (for complete removal of dolomite) range from 2700 to 58,500 yr and span the Pleistocene-Holocene boundary. Finally, an estimated dolomite reaction rate during dedolomitization of the Edwards aquifer based on surface area of exposed dolomite [mmol cm-2s-1 (millimoles per square centimeter per second)] may be approximated from reaction times. This rate is directly a function of the mass of dolomite removed and the surface area exposed per pore volume passing through the rock. The surface area is available from the observed dolomite rhomb size in unaltered rock. The rate of pore fluid movement is obtained from the averaged annual discharge. Rates during formation of the Edwards aquifer calculated from all reaction times range from 10-13 to 10-14 mmol dolomite cm-2s-1. These rates are faster than rates (10-18 mmol cm-2s-1), measured in the pure laboratory system, CaMg(CO3)2CO2H2O, but slower than rates determined in an alpine stream study (10-10 to 10-11 mmol cm-2s-1) where cold glacial melt water flows over dolostone. Dolomite dissolution rates from both the Edwards and other aquifers support the concept that a major part of the Edwards aquifer could have formed within the Holocene. ?? 1990.

X-ray driven reaction front dynamics at calcite-water interfaces

DOE PAGES

Laanait, Nouamane; Callagon, Erika Blanca R.; Zhang, Zhan; ...

2015-09-18

The interface of minerals with aqueous solutions is central to geochemical reactivity, hosting processes that span multiple spatiotemporal scales. Understanding such processes requires spatially and temporally resolved observations, and experimental controls that precisely manipulate the interfacial thermodynamic state. Using the intense radiation fields of a focused synchrotron X-ray beam, we drove dissolution at the calcite-aqueous interface and simultaneously probed the dynamics of the propagating reaction fronts using surface X-ray microscopy. Evolving surface structures are controlled by the time-dependent solution composition as characterized by a kinetic reaction model. At extreme disequilibria, the onset of reaction front instabilities was observed with velocitiesmore » of >30 nanometers per second. As a result, these instabilities are identified as a signature of transport-limited dissolution of calcite under extreme disequilibrium.« less

Castiglione (Oletta, Corsica): relationships between phenomena of calcification and tectonic fossiliferous fracture dating

NASA Astrophysics Data System (ADS)

Pereira, Elisabeth; Rouzaud, François; Salotti, Michelle; Dubois, Jean-Noël; Ferrandini, Jean; Ottaviani-Spella, Marie-Madeleine; Quinif, Yves

Six cavities have been discovered in the Oletta massif. The massif, today constitued of Schistes lustrés with several metres of calcareous layers above them, has undergone intense fracturing. The networks of cavities are organised along north-south and subequatorial directions, and form a narrow bayonnet-network. All the elements in the galleries appear to be karstic: stalagmites, stalactites and calcitic deposits along the walls; but no trace of dissolution or excavation was found. Thus, the origin of the galleries is only tectonic, while the calcitic deposits result from the dissolution of the old, thick calcareous layers above, which are no longer present. The thickness and the volume of the calcitic deposits, which is variable depending on the galleries, indicates the chronology of the different tectonic periods which have fractured the massif. Five tectonic and successsive events have been detected. Calcitic datings confirm the timing of successional fracturing, indicating also the variable age of the fossiliferous Middle Pleistocene deposits found in these cavities.

The ubiquitous nature of accessory calcite in granitoid rocks: Implications for weathering, solute evolution, and petrogenesis

USGS Publications Warehouse

White, A.F.; Schulz, M.S.; Lowenstern, J. B.; Vivit, D.V.; Bullen, T.D.

2005-01-01

Calcite is frequently cited as a source of excess Ca, Sr and alkalinity in solutes discharging from silicate terrains yet, no previous effort has been made to assess systematically the overall abundance, composition and petrogenesis of accessory calcite in granitoid rocks. This study addresses this issue by analyzing a worldwide distribution of more than 100 granitoid rocks. Calcite is found to be universally present in a concentration range between 0.028 to 18.8 g kg-1 (mean = 2.52 g kg-1). Calcite occurrences include small to large isolated anhedral grains, fracture and cavity infillings, and sericitized cores of plagioclase. No correlation exists between the amount of calcite present and major rock oxide compositions, including CaO. Ion microprobe analyses of in situ calcite grains indicate relatively low Sr (120 to 660 ppm), negligible Rb and 87Sr/86Sr ratios equal to or higher than those of coexisting plagioclase. Solutes, including Ca and alkalinity produced by batch leaching of the granitoid rocks (5% CO2 in DI water for 75 d at 25??C), are dominated by the dissolution of calcite relative to silicate minerals. The correlation of these parameters with higher calcite concentrations decreases as leachates approach thermodynamic saturation. In longer term column experiments (1.5 yr), reactive calcite becomes exhausted, solute Ca and Sr become controlled by feldspar dissolution and 87Sr/ 86Sr by biotite oxidation. Some accessory calcite in granitoid rocks is related to intrusion into carbonate wall rock or produced by later hydrothermal alteration. However, the ubiquitous occurrence of calcite also suggests formation during late stage (subsolidus) magmatic processes. This conclusion is supported by petrographic observations and 87Sr/86Sr analyses. A review of thermodynamic data indicates that at moderate pressures and reasonable CO2 fugacities, calcite is a stable phase at temperatures of 400 to 700??C. Copyright ?? 2005 Elsevier Ltd.

Interaction Between CO2-Rich Sulfate Solutions and Carbonate Reservoir Rocks from Atmospheric to Supercritical CO2 Conditions: Experiments and Modeling

NASA Astrophysics Data System (ADS)

Cama, J.; Garcia-Rios, M.; Luquot, L.; Soler Matamala, J. M.

2014-12-01

A test site for CO2 geological storage is situated in Hontomín (Spain) with a reservoir rock that is mainly composed of limestone. During and after CO2 injection, the resulting CO2-rich acid brine gives rise to the dissolution of carbonate minerals (calcite and dolomite) and gypsum (or anhydrite at depth) may precipitate since the reservoir brine contains sulfate. Experiments using columns filled with crushed limestone or dolostone were conducted under different P-pCO2 conditions (atmospheric: 1-10-3.5 bar; subcritical: 10-10 bar; and supercritical: 150-34 bar), T (25, 40 and 60 ºC) and input solution compositions (gypsum-undersaturated and gypsum-equilibrated solutions). We evaluated the effect of these parameters on the coupled reactions of calcite/dolomite dissolution and gypsum/anhydrite precipitation. The CrunchFlow and PhreeqC (v.3) numerical codes were used to perform reactive transport simulations of the experiments. Under the P-pCO2-T conditions, the volume of precipitated gypsum was smaller than the volume of dissolved carbonate minerals, yielding an increase in porosity (Δporosity up to ≈ 4%). A decrease in T favored limestone dissolution regardless of pCO2 owing to increasing undersaturation with decreasing temperature. However, gypsum precipitation was favored at high T and under atmospheric pCO2 conditions but not at high T and under 10 bar of pCO2 conditions. The increase in limestone dissolution with pCO2 was directly attributed to pH, which was more acidic at higher pCO2. Increasing pCO2, carbonate dissolution occurred along the column whereas it was localized in the very inlet under atmospheric conditions. This was due to the buffer capacity of the carbonic acid, which maintains pH at around 5 and keeps the solution undersaturated with respect to calcite and dolomite along the column. 1D reactive transport simulations reproduced the experimental data (carbonate dissolution and gypsum precipitation for different P-pCO2-T conditions). Drawing on reaction rate laws in the literature, we used the reactive surface area to fit the models to the experimental data. The values of the reactive surface area were much smaller than those calculated of the geometric areas.

A lacustrine carbonate record of Holocene seasonality and climate

USGS Publications Warehouse

Wittkop, Chad A.; Teranes, Jane L.; Dean, Walter E.; Guilderson, Thomas P.

2009-01-01

Annually laminated (varved) Holocene sediments from Derby Lake, Michigan, display variations in endogenic calcite abundance reflecting a long-(millennial-scale) decrease in burial punctuated with frequent short- (decadal-scale) oscillations due to carbonate dissolution. Since 6000 cal yr B.P., sediment carbonate abundance has followed a decreasing trend while organic-carbon abundance has increased. The correlation between organic-carbon abundance and the sum of March-April-October-November insolation has an r2 value of 0.58. We interpret these trends to represent a precession-driven lengthening of the Holocene growing season that has reduced calcite burial by enhancing net annual organic-matter production and associated calcite dissolution. Correlations with regional paleoclimate records suggest that changes in temperature and moisture balance have impacted the distribution of short- oscillations in carbonate and organic-matter abundance superimposed on the precession-driven trends.

Upper Cretaceous Shannon Sandstone Reservoirs, Powder River Basin, Wyoming: Evidence for organic acid diagenesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hansley, P.L.; Nuccio, V.F.

Comparison of the petrology of shallow and deep oil reservoirs in the Upper Cretaceous Shannon Sandstone Beds of the Steele Member of the Cody Shale strongly suggests that organic acids have had a more significant impact on the diagenetic alteration of aluminosilicate grains and carbonate cements in the deep reservoirs than in the shallow reservoirs. In shallow reservoirs, detrital grains exhibit minor dissolution, sparse and small overgrowths, and secondary porosity created by dissolution of early calcite cement. However, deeper sandstones are characterized by extensive dissolution of detrital K-feldspar and detrital glauconite grains, and precipitation of abundant, large quartz and feldsparmore » overgrowths. Throughout the Shannon and Steele, dissolution of glauconite and degradation of kerogen were probably aided by clay mineral/organic catalysis, which caused simultaneous reduction of iron and oxidation of kerogen. This process resulted in release of ferrous iron and organic acids and was promoted in the deep reservoirs by higher formation temperatures accounting for more extensive dissolution of aluminosilicate grains. Carbonic acid produced from the dissolution of early calcite cement, decarboxylation of organic matter, and influx of meteoric water after Laramide uplift produced additional dissolution of cements and grains. Dissolution by organic acids and complexing by organic acid anions, however, best explain the intensity of diagenesis and absence of dissolution products in secondary pores and on etched surfaces of framework grains in deep reservoirs.« less

Carbonate dissolution in the South Atlantic Ocean: evidence from ultrastructure breakdown in Globigerina bulloides

NASA Astrophysics Data System (ADS)

Dittert, Nicolas; Henrich, Rüdiger

2000-04-01

Ultrastructure dissolution susceptibility of the planktic foraminifer Globigerina bulloides, carbonate ion content of the water column, calcium carbonate content of the sediment surface, and carbonate/carbon weight percentage ratio derived from sediment surface samples were investigated in order to reconstruct the position of the calcite saturation horizon, the sedimentary calcite lysocline, and the calcium carbonate compensation depth (CCD) in the modern South Atlantic Ocean. Carbonate ion data from the water column refer to the GEOSECS locations 48, 103, and 109 and calcium carbonate data come from 19 GeoB sediment surface samples of 4 transects into the Brazil, the Guinea, and the Cape Basins. We present a new (paleo-) oceanographic tool, namely the Globigerina bulloides dissolution index (BDX). Further, we give evidence (a) for progressive G. bulloides ultrastructural breakdown with increasing carbonate dissolution even above the lysocline; (b) for a sharp BDX increase at the sedimentary lysocline; and (c) for the total absence of this species at the CCD. BDX puts us in the position to distinguish the upper open ocean and the upwelling influenced continental margin above from the deep ocean below the sedimentary lysocline. Carbonate ion data from water column samples, calcite weight percentage data from surface sediment samples, and carbonate/carbon weight percentage ratio appear to be good proxies to confirm BDX. As shown by BDX both the calcite saturation horizon (in the water column) and the sedimentary lysocline (at the sediment-water interface) mark the boundary between the carbonate ion undersaturated and highly corrosive Antarctic Bottom Water and the carbonate ion saturated North Atlantic Deep Water (NADW) of the modern South Atlantic.

Dissolution-Driven Permeability Reduction of a Fractured Carbonate Caprock

PubMed Central

Ellis, Brian R.; Fitts, Jeffrey P.; Bromhal, Grant S.; McIntyre, Dustin L.; Tappero, Ryan; Peters, Catherine A.

2013-01-01

Abstract Geochemical reactions may alter the permeability of leakage pathways in caprocks, which serve a critical role in confining CO2 in geologic carbon sequestration. A caprock specimen from a carbonate formation in the Michigan sedimentary Basin was fractured and studied in a high-pressure core flow experiment. Inflowing brine was saturated with CO2 at 40°C and 10 MPa, resulting in an initial pH of 4.6, and had a calcite saturation index of −0.8. Fracture permeability decreased during the experiment, but subsequent analyses did not reveal calcite precipitation. Instead, experimental observations indicate that calcite dissolution along the fracture pathway led to mobilization of less soluble mineral particles that clogged the flow path. Analyses of core sections via electron microscopy, synchrotron-based X-ray diffraction imaging, and the first application of microbeam Ca K-edge X-ray absorption near edge structure, provided evidence that these occlusions were fragments from the host rock rather than secondary precipitates. X-ray computed tomography showed a significant loss of rock mass within preferential flow paths, suggesting that dissolution also removed critical asperities and caused mechanical closure of the fracture. The decrease in fracture permeability despite a net removal of material along the fracture pathway demonstrates a nonintuitive, inverse relationship between dissolution and permeability evolution in a fractured carbonate caprock. PMID:23633894

Novel Hydroxyapatite Coatings for the Conservation of Marble and Limestone

NASA Astrophysics Data System (ADS)

Naidu, Sonia

Marble and limestone are calcite-based materials used in the construction of various structures, many of which have significant artistic and architectural value. Unfortunately, due to calcite's high dissolution rate, these stones are susceptible to chemically-induced weathering in nature. Limestone, due to its inherent porosity, also faces other environmental weathering processes that cause weakening from disintegration at grain boundaries. The treatments presently available are all deficient in one way or another. The aim of this work is to examine the feasibility of using hydroxyapatite (HAP) as a novel protective coating for marble and limestone, with two goals: i) to reduce acid corrosion of marble and ii) to consolidate physically weathered limestone. The motivation for using HAP is its low dissolution rate and structural compatibility with calcite. Mild, wet chemical synthesis routes, in which inorganic phosphate-based solutions were reacted with marble and limestone, alone and with other precursors, were used to produce HAP films. Film nucleation, growth and phase evolution were studied on marble to understand film formation and determine the optimal synthesis route. An acid resistance test was developed to investigate the attack mechanism on marble and quantify the efficacy of HAP-based coatings. Film nucleation and growth were dependent on substrate surface roughness and increased with calcium and carbonate salt additions during synthesis. Acid attack on marble occurred via simultaneous dissolution at grain boundaries, twin boundaries and grain surfaces. HAP provided intermediate protection against acid attack, when compared to two conventional treatments. Its ability to protect the stone from acid was not as significant as predicted from dissolution kinetics and this was attributed to incomplete coverage and residual porosity within the film, arising from its flake-like crystal growth habit, which enabled acid to access the underlying substrate. The effectiveness of HAP as a consolidant for weathered limestone, alone and coupled with a commercially available consolidant (ConservareRTM OH-100), was also investigated. To artificially weather limestone in the lab, a reproducible thermal degradation technique was utilised. The dynamic elastic modulus, water sorptivity and coating composition of treated stones were evaluated. HAP was found to be an effective consolidant for limestone, as it restored the elastic modulus of damaged stones to their original values and exhibited superior performance to ConservareRTM OH-100.

Planktic foraminifera form their shells by attachment of metastable carbonate particles

NASA Astrophysics Data System (ADS)

Wirth, R.; Jacob, D. E.; Eggins, S.

2016-12-01

Planktic foraminifera shells contribute up to half the inorganic carbon exported from the surface ocean to the seafloor. Their tiny calcium carbonate shells are preserved in sediments as calcite, and provide our most valuable geochemical archive of changes surface ocean conditions and climate spanning the last 100 million years. Here we show the shells of living planktic foraminifers Orbulina universa and Neogloboquadrina dutertrei consist of nano-particulate vaterite and amorphous calcium carbonate. This indicates formation via a non-classical crystallization pathway involving metastable carbonate intermediate phases before transforming to calcite, and requires a new perspective on how geochemical proxies are incorporated into planktic foraminifer shells. Our findings indicate planktic foraminifer shells could be far more susceptible to dissolution and ocean acidification than previously thought, and account for unexpected shell dissolution above the calcite saturation horizon in the ocean, which is a major uncertainty in modelling oceanic carbon fluxes.

The origin of alteration "orangettes" in Dhofar 019: Implications for the age and aqueous history of the shergottites

NASA Astrophysics Data System (ADS)

Hallis, L. J.; Kemppinen, L.; Lee, M. R.; Taylor, L. A.

2017-12-01

The shergottites are the largest group of Martian meteorites, and the only group that has not been found to contain definitive evidence of Martian aqueous alteration. Given recent reports of current liquid water at the surface of Mars, this study aimed to investigate in detail the possibility of Martian phyllosilicate within shergottite Dhofar 019. Optical and scanning electron microscopy, followed by transmission electron microscopy, confirmed the presence of alteration orangettes, with a layered structure consisting of poorly ordered Mg-phyllosilicate and calcite. These investigations identified maskelynite dissolution, followed by Mg-phyllosilicate and calcite deposition within the dissolution pits, as the method of orangette production. The presence of celestine within the orangette layers, the absence of shock dislocation features within calcite, and the Mg-rich nature of the phyllosilicate, all indicate a terrestrial origin for these features on Dhofar 019.

In-Situ Atomic Force Microscope Imaging of Calcite Etch Pit Morphology Changes in Undersaturated and 1-Hydroxyethylidene-1,1-diphosphonic Acid Poisoned Solutions

PubMed Central

Britt, David W.

2012-01-01

Morphology changes in etch pits formed on the (1014) cleavage plane of calcite were induced by varying the ratio of [Ca2+] to [CO32−] in the bulk solution as well as through the addition of the crystal poison 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP). Three distinct morphologies were noted: symmetric rhombic, asymmetric rhombic, and triangular with a rough curved hypotenuse. The latter represents a transient morphology which is only observed during the actual dissolution process, while the former morphologies persist after dissolution is halted. PMID:25125794

Ocean acidification does not affect magnesium composition or dolomite formation in living crustose coralline algae, Porolithon onkodes in an experimental system

NASA Astrophysics Data System (ADS)

Nash, M. C.; Uthicke, S.; Negri, A. P.; Cantin, N. E.

2015-09-01

There are concerns that Mg-calcite crustose coralline algae (CCA), which are key reef builders on coral reefs, will be most susceptible to increased rates of dissolution under higher pCO2 and ocean acidification. Due to the higher solubility of Mg-calcite, it has been hypothesised that magnesium concentrations in CCA Mg-calcite will decrease as the ocean acidifies, and that this decrease will make their skeletons more chemically stable. In addition to Mg-calcite, CCA Porolithon onkodes, the predominant encrusting species on tropical reefs, can have dolomite (Ca0.5Mg0.5CO3) infilling cell spaces which increases their stability. However, nothing is known about how bio-mineralised dolomite formation responds to higher pCO2. Using P. onkodes grown for 3 and 6 months in tank experiments, we aimed to determine (1) if mol % MgCO3 in new crust and new settlement was affected by increasing CO2 levels (365, 444, 676 and 904 μatm), (2) whether bio-mineralised dolomite formed within these time frames, and (3) if so, whether this was effected by CO2. Our results show that there was no significant effect of CO2 on mol % MgCO3 in any sample set, indicating an absence of a plastic response under a wide range of experimental conditions. Dolomite within the CCA cells formed within 3 months and dolomite abundance did not vary significantly with CO2 treatment. While evidence mounts that climate change will impact many sensitive coral and CCA species, the results from this study indicate that reef-building P. onkodes will continue to form stabilising dolomite infill under near-future acidification conditions, thereby retaining its higher resistance to dissolution.

Ocean acidification does not affect magnesium composition or dolomite formation in living crustose coralline algae, Porolithon onkodes in an experimental system

NASA Astrophysics Data System (ADS)

Nash, M. C.; Uthicke, S.; Negri, A. P.; Cantin, N. E.

2015-01-01

There are concerns that Mg-calcite crustose coralline algae (CCA), which are key reef builders on coral reefs, will be most susceptible to increased rates of dissolution under higher pCO2 and ocean acidification. Due to the higher solubility of Mg-calcite, it has been hypothesized that magnesium concentrations in CCA Mg-calcite will decrease as the ocean acidifies, and that this decrease will make their skeletons more chemically stable. In addition to Mg-calcite, CCA Porolithon onkodes the predominant encrusting species on tropical reefs, can have dolomite (Ca0.5Mg0.5CO3) infilling cell spaces which increases their stability. However, nothing is known about how bio-mineralised dolomite formation responds to higher pCO2. Using P. onkodes grown for 3 and 6 months in tank experiments, we aimed to determine (1) if mol % MgCO3 in new crust and new settlement affected by increasing pCO2 levels (365, 444, 676 and 904 ppm), (2) whether bio-mineralised dolomite formed within these time frames, and (3) if so, whether this was effected by pCO2. Our results show there was no significant effect of pCO2 on mol % MgCO3 in any sample set, indicating an absence of a plastic response under a wide range of experimental conditions. Dolomite within the CCA cells formed within 3 months and dolomite abundance did not vary significantly with pCO2 treatment. While evidence mounts that climate change will impact many sensitive coral and CCA species, the results from this study indicate that reef-building P. onkodes will continue to form stabilising dolomite infill under near-future acidification conditions, thereby retaining its higher resistance to dissolution.

Imminent onset and abrupt increase in duration of low aragonite and calcite saturation state events in the Southern Ocean

NASA Astrophysics Data System (ADS)

Friedrich, T.; Hauri, C.; Timmermann, A.

2015-12-01

Rapid progression of ocean acidification is a threat to key organisms of the Southern Ocean ecosystem. While the severity of ocean acidification impacts is mainly determined by the duration, intensity, and spatial extent of low aragonite or calcite saturation state events, little is known about the nature of these events, their evolving attributes, and the timing of their onset. Using output of historical and RCP 8.5 simulations from ten Earth System Models from CMIP5, we found that aragonite undersaturation, which decreases the calcification rate of pteropods and causes dissolution of their aragonitic shell, will spread rapidly after 2035, covering 70 % of the Southern Ocean surface waters by 2095. Surface aragonite undersaturation events will last for about 5 months in areas south of 60°S by 2055, and for more than 8 months by the end of the century. Overall, the duration of these events increases from 1 month to more than 6 months within fewer than 20 years in >75 % of the affected area. This abrupt change in exposure duration to unfavorable conditions may be too fast for pteropods to adapt, as these chemical changes will occur within just a few generations. As a result of two month-long calcite undersaturation events projected for the end of this century, even organisms built of the more stable calcium carbonate mineral calcite will face prolonged chemical dissolution. The threat of ocean acidification to the Southern Ocean ecosystem may be more imminent than previously thought, and may spread quickly to the southern tips of New Zealand, South America, and South Africa, with potentially far-reaching consequences to fisheries, local economies, and livelihoods.

Kinetics of carbonate dissolution in CO2-saturated aqueous system at reservoir conditions

NASA Astrophysics Data System (ADS)

Peng, Cheng; Crawshaw, John P.; Maitland, Geoffrey; Trusler, J. P. Martin

2014-05-01

In recent years, carbon capture and storage (CCS) has emerged as a key technology for limiting anthropogenic CO2 emissions while allowing the continued utilisation of fossil fuels. The most promising geological storage sites are deep saline aquifers because the capacity, integrity and injection economics are most favourable, and the environmental impact can be minimal. Many rock-fluid chemical reactions are known to occur both during and after CO2 injection in saline aquifers. The importance of rock-fluid reactions in the (CO2 + H2O) system can be understood in terms of their impact on the integrity and stability of both the formation rocks and cap rocks. The chemical interactions between CO2-acidified brines and the reservoir minerals can influence the porosity and permeability of the formations, resulting in changes in the transport processes occurring during CO2 storage. Since carbonate minerals are abundant in sedimentary rocks, one of the requirements to safely implement CO2 storage in saline aquifers is to characterise the reactivity of carbonate minerals in aqueous solutions at reservoir conditions. In this work, we reported measurements of the intrinsic rate of carbonate dissolution in CO2-saturated water under high-temperature high-pressure reservoir conditions extending up to 373 K and 14 MPa. The rate of carbonate dissolution in CO2-free HCl(aq) was also measured at ambient pressure at temperatures up to 353 K. Various pure minerals and reservoir rocks were investigated in this study, including single-crystals of calcite and magnesite, and samples of dolomite, chalks and sandstones. A specially-designed batch reactor system, implementing the rotating disc technique, was used to obtain the intrinsic reaction rate at the solid/liquid interface, free of mass transfer effects. The effective area and mineralogy of the exposed surface was determined by a combination of surface characterisation techniques including XRD, SEM, EDX and optical microscopy. The results of the study indicate that the rotating disc technique can allow accurate measurement of the carbonate dissolution rate under surface-reaction-controlled conditions, and that the carbonate dissolution rate typically increases with the increase of temperature, CO2 partial pressure and solution acidity. The study shows that the dissolution of carbonate in CO2-free acidic solutions can be described as a first order heterogeneous reaction; however, this model is not sufficient to describe the reaction kinetics of carbonate minerals in the (CO2 + H2O) system, particularly for high reactivity carbonates, such as calcite, at reservoir conditions. For these systems, both pH and the activity of CO2(aq) influence the dissolution rate. Based on the experimental results, kinetic models have been developed and parameterised to describe the dissolution of different carbonate minerals. The results of this study should facilitate more rigorous modelling of mineral dissolution in deep saline aquifers used for CO2 storage. We gratefully acknowledge the funding of QCCSRC provided jointly by Qatar Petroleum, Shell, and the Qatar Science & Technology Park. Keywords: Carbon Dioxide, Carbonate, High Pressure, High Temperature, Reaction Kinetics.

Biodegradation of Emiliania huxleyi Aggregates by natural Prokaryotic Communities under Increasing Hydrostatic Pressure.

NASA Astrophysics Data System (ADS)

Riou, V.; Para, J.; Garel, M.; Guigue, C.; Al Ali, B.; Santinelli, C.; Lefèvre, D.; Gattuso, J. P.; Goutx, M.; Panagiotopoulos, C.; Beaufort, L.; Jacquet, S.; Le Moigne, F. A. C.; Tachikawa, K.; Tamburini, C.

2016-02-01

Fluxes of particulate organic carbon (POC) and minerals are positively correlated, suggesting that minerals could enhance the flux of POC into the deep ocean. The so called "ballast effect" posits that minerals could increase sinking particle densities and/or protect the organic matter from heterotrophic degradation. Laboratory controlled experiments on coccolithophorid aggregates under atmospheric pressure show that biogenic calcite both increases particle settling velocities and preserves the organic matter. However, such experiments have yet to include genuine prokaryote rates indicators as well as the effect of increasing pressure. Here, we used the PArticle Sinking Simulator (PASS) to investigate the effect of the increasing pressure on the degradation of Emiliania huxleyi (calcifiers) aggregates. Extra care was taken to obtain culture aggregates with low prokaryotic abundance prior to exposure to natural mesopelagic prokaryotic communities. Particulate organic and inorganic carbon and dissolved organic carbon concentrations were monitored along with the lipid and carbohydrate compositions, as well as prokaryotic community abundance and specific diversity. A control experiment, without natural prokaryotic community addition, indicates that the pressure increase did not have any effect on calcite dissolution observed after ten days. In contrast, the addition of natural prokaryotic community accelerates calcite dissolution under conditions of increasing pressure. Prokaryotic community development and the lipid fraction of E. huxleyi particulate organic carbon are enhanced under increasing pressure. These results suggest that hydrostatic pressure denatures the structural integrity of the carbonate skeleton that protects the cellular organic matter.

Can we get a better knowledge on dissolution processes in chalk by using microfluidic chips?

NASA Astrophysics Data System (ADS)

Neuville, Amélie; Minde, Mona; Renaud, Louis; Vinningland, Jan Ludvig; Dysthe, Dag Kristian; Hiorth, Aksel

2017-04-01

This work has been initiated in the context of research on improving the oil recovery in chalk bedrocks. One of the methods to improve the oil recovery is to inject "smart water" (acidic water/brines). Experiments on core scale and field tests that have been carried out the last decade have clearly shown that water chemistry affects the final oil recovery. However, there is generally no consensus in the scientific community of why additional oil is released, and it is also still not understood what are the mineralogical and structural changes. Direct in situ observation of the structural changes that occur when chalk is flooded with brines could resolve many of the open questions that remain. One of the highlights of this work is thus the development of an innovative methodology where fluid/rock interactions are observed in-situ by microscopy. To do so, we create several types of custom-made microfluidic systems that embeds reactive materials like chalk and calcite. The methodology we develop can be applied to other reactive materials. We will present an experiment where a calcite window dissolves with a fluid, where we observe in-situ the topography features of the calcite window, as well as the dissolution rate [1]. The injected fluid circulates at controlled flowrates in a channel which is obtained by xurography: double sided tape is cut out with a cutter plotter and placed between the reactive window and a non-reactive support. While the calcite window reacts, its topography is measured in situ every 10 s using an interference microscope, with a pixel resolution of 4.9 μm and a vertical resolution of 50 nm. These experiments are also compared with reactive flow simulations done with Lattice Boltzmann methods. Then, we will present a dissolution experiment done with a microfluidic system that embeds chalk. In this experiment, the main flow takes place at the chalk surface, in contact with fluid flowing in a channel above the chalk sample. Thus the reaction mostly occurs at the surface of the sample. The reacting chalk surface is observed in situ by stereomicroscopy and by interferometry. The dissolution velocities are highly heterogeneous. To identify the mineral change of the surface, a posteriori measurements using field emission scanning electron microscopy (FE-SEM), and energy dispersive X-ray spectroscopy (EDS). [1] Neuville et al, 2016, Xurography for microfluidics on a reactive solid, Lab on Chip, DOI: 10.1039/c6lc01253a

A comparison of amorphous calcium carbonate crystallization in aqueous solutions of MgCl2 and MgSO4: implications for paleo-ocean chemistry

NASA Astrophysics Data System (ADS)

Han, Mei; Zhao, Yanyang; Zhao, Hui; Han, Zuozhen; Yan, Huaxiao; Sun, Bin; Meng, Ruirui; Zhuang, Dingxiang; Li, Dan; Liu, Binwei

2018-04-01

Based on the terminology of "aragonite seas" and "calcite seas", whether different Mg sources could affect the mineralogy of carbonate sediments at the same Mg/Ca ratio was explored, which was expected to provide a qualitative assessment of the chemistry of the paleo-ocean. In this work, amorphous calcium carbonate (ACC) was prepared by direct precipitation in anhydrous ethanol and used as a precursor to study crystallization processes in MgSO4 and MgCl2 solutions having different concentrations at 60 °C (reaction times 240 and 2880 min). Based on the morphology of the aragonite crystals, as well as mineral saturation indices and kinetic analysis of geochemical processes, it was found that these crystals formed with a spherulitic texture in 4 steps. First, ACC crystallized into columnar Mg calcite by nearly oriented attachment. Second, the Mg calcite changed from columnar shapes into smooth dumbbell forms. Third, the Mg calcite transformed into rough dumbbell or cauliflower-shaped aragonite forms by local dissolution and precipitation. Finally, the aragonite transformed further into spherulitic radial and irregular aggregate forms. The increase in Ca2+ in the MgSO4 solutions compared with the MgCl2 solutions indicates the fast dissolution and slow precipitation of ACC in the former solutions. The phase transition was more complete in the 0.005 M MgCl2 solution, whereas Mg calcite crystallized from the 0.005 M MgSO4 solution, indicating that Mg calcite could be formed more easily in an MgSO4 solution. Based on these findings, aragonite and Mg calcite relative to ACC could be used to provide a qualitative assessment of the chemistry of the paleo-ocean. Therefore, calcite seas relative to high-Mg calcite could reflect a low concentration MgSO4 paleo-ocean, while aragonite seas could be related to an MgCl2 or high concentration of MgSO4 paleo-ocean.

Numerical modelling of physiological and ecological impacts of ocean acidification on coccolithophores

NASA Astrophysics Data System (ADS)

Furukawa, Makoto; Sato, Toru; Suzuki, Yoshimi; Casareto, Beatriz E.; Hirabayashi, Shinichiro

2018-06-01

Ocean surface acidification due to increasing atmospheric CO2 concentration is currently attracting much attention. Coccolithophores distribute widely across the world's oceans and represent a carbon sink containing about 100 million tonnes of carbon. For this reason, there is concern about dissolution of their shells, which are made of calcium carbonate, due to decreasing pH. In this study, intracellular calcification, photosynthesis, and mass transport through biomembranes of Emiliania huxleyi were modelled numerically for understanding biological response in calcifying organisms. Unknown parameters were optimised by a generic algorithm to match existing experimental results. The model showed that the production of calcium carbonate rather than its dissolution is promoted under an acidified environment. Calcite remains at saturation levels in a coccolith even when it is below saturation levels in the external seawater. Furthermore, a coccolith can dissolve even in water where calcite saturation exceeds 1, because the saturation may be below the threshold level locally around the cell membrane. The present model also showed that the different calcification rates of E. huxleyi with respect to rising CO2 concentrations reported in the literature are due to differences in experimental conditions; in particular, how the CO2 concentration is matched. Lastly, the model was able to reproduce differences in calcification rates among coccolithophore species. The above biochemical-kinetic model was then incorporated into an ecosystem model, and the behaviour of coccolithophores in the ecosystem and the influence of increases in CO2 concentration on water quality were simulated and validated by comparison with existing experimental results. The model also suggests that increased CO2 concentration could lead to an increase in the biomass ratio of coccolithophores to diatoms at high CO2 concentrations, particularly in oligotrophic environments, and to a consequent decrease in pH due to calcium dissolution.

Reaction path modelling of in-situ mineralisation of CO2 at the CarbFix site at Hellisheidi, SW-Iceland

NASA Astrophysics Data System (ADS)

Snæbjörnsdóttir, Sandra Ó.; Gislason, Sigurdur R.; Galeczka, Iwona M.; Oelkers, Eric H.

2018-01-01

Results from injection of 175 tonnes of CO2 into the basaltic subsurface rocks at the CarbFix site in SW-Iceland in 2012 show almost complete mineralisation of the injected carbon in less than two years (Matter et al., 2016; Snæbjörnsdóttir et al., 2017). Reaction path modelling was performed to illuminate the rate and extent of CO2-water-rock reactions during and after the injection. The modelling calculations were constrained by the compositions of fluids sampled prior to, during, and after the injection, as reported by Alfredsson et al. (2013) and Snæbjörnsdóttir et al. (2017). The pH of the injected fluid, prior to CO2 dissolution was ∼9.5, whereas the pH of the background waters in the first monitoring well prior to the injections was ∼9.4. The pH of the sampled fluids used in the modelling ranged from ∼3.7 at the injection well to as high as 8.2 in the first monitoring well. Modelling results suggest that CO2-rich water-basalt interaction is dominated by crystalline basalt dissolution along a faster, high permeability flow path, but by basaltic glass dissolution along a slower, pervasive flow path through which the bulk of the injected fluid flows. Dissolution of pre-existing calcite at the onset of the injection does not have a net effect on the carbonation, but does contribute to a rapid early pH rise during the injection, and influences which carbonate minerals precipitate. At low pH, Mg, and Fe are preferentially released from crystalline basalts due to the higher dissolution rates of olivine, and to lesser extent pyroxene, compared to plagioclase and glass (Gudbrandsson et al., 2011). This favours the formation of siderite and Fe-Mg carbonates over calcite during early mineralisation. The model suggests the formation of the following carbonate mineral sequences: siderite at pH < 5, Mg-Fe-carbonates and Ca-Mg-Fe-carbonates at pH > 5, and calcite at higher pH. Other minerals forming with the carbonates are Al- and Fe-hydroxides and chalcedony, and zeolites and smectites at elevated pH. The most efficient carbonate formation is when the pH is high enough for formation of carbonates, but not so high that zeolites and smectites start to form, which compete with carbonates over both cations and pore space. The results of reaction path modelling at the CarbFix site in SW-Iceland indicate that this ;sweet spot; for mineralisation of CO2 is at pH from ∼5.2 to 6.5 in basalts at low temperature (20-50 °C).

Core-top calibration of B/Ca in Pacific Ocean Neogloboquadrina incompta and Globigerina bulloides as a surface water carbonate system proxy

NASA Astrophysics Data System (ADS)

Quintana Krupinski, Nadine B.; Russell, Ann D.; Pak, Dorothy K.; Paytan, Adina

2017-05-01

Practical methods for reconstructing past ocean carbonate chemistry are needed to study past periods of ocean acidification and improve understanding of the marine carbonate system's role in the global climate cycles. Planktic foraminiferal B/Ca may fill this role, but requires better understanding and improved proxy calibrations. We used Pacific Ocean core-top sediments to generate new calibrations of the B/Ca proxy for past carbonate system parameters in two upwelling/subpolar species of asymbiotic planktic foraminifera (Globigerina bulloides and Neogloboquadrina incompta). Both species show significant positive correlation of B/Ca with calcite saturation (Ωcalcite) and carbonate ion concentration ([3 2-CO]) across a broad range of environmental conditions. This suggests a calcification rate control on B/Ca incorporation (as Ωcalcite regulates calcification rate), in agreement with recent inorganic calcite studies. This is also consistent with a surface entrapment model of trace element incorporation into CaCO3. In neither species is B/Ca significantly correlated with pH, suggesting that pH does not directly regulate boron incorporation, and that calculation of pH directly from foraminiferal B/Ca is not suitable. Correlations between B/Ca and [B(OH)4-], [B(OH)4-/HCO3-], and [B(OH)4-]/DIC) are weaker than with Ωcalcite. Boron partition coefficients (KD =[ B / Ca ] solid /[ B4 -(OH) /HCO-3 ] seawater) show little or no correlation with [CO32-] or temperature and vary widely, providing no support for application of KD to calculate carbonate system parameters from B/Ca. We also discuss potential effects of depth-related dissolution, temperature, and salinity on B/Ca. These empirical calibrations linking foraminiferal calcite B/Ca with Ωcalcite provide a strong tool for reconstructing the past ocean carbonate system and improve our understanding of the proxy's geochemical basis.

The biokarst system and its carbon sinks in response to pH changes: A simulation experiment with microalgae

NASA Astrophysics Data System (ADS)

Xie, Tengxiang; Wu, Yanyou

2017-03-01

This study aims to explore the changes in a microalgal biokarst system as a potential carbon sink system in response to pH changes. The bidirectional isotope labeling method and mass balance calculation were adopted in a simulated biokarst environment with a series of set pH conditions and three microalgal species. Three key processes of the microalgal biokarst system, including calcite dissolution, CaCO3 reprecipitation, and inorganic carbon assimilation by microalgae, were completely quantitatively described. The combined effects of chemical dissolution and species-specific biodissolution caused a decrease in overall dissolution rate when the pH increased from 7 to 9. CaCO3 reprecipitation and the utilization of dissolved inorganic carbon originating from calcite dissolution decreased when the pH increased from 7 to 9. The three processes exhibited different effects in changing the CO2 atmosphere. The amount of photosynthetic carbon sink was larger at high pH values than at low pH values. However, the CO2 sequestration related to the biokarst process (biokarst carbon sink) increased with decreasing pH. Overall, the total amount of sequestered CO2 produced by the biokarst system (CaCO3-CO2-microalgae) shows a minimum at a specific pH then increases with decreasing pH. Therefore, various processes and carbon sinks in the biokarst system are sensitive to pH changes, and biokarst processes play an important negative feedback role in the release of CO2 by acidification. The results also suggest that the carbon sink associated with carbonate weathering cannot be neglected when considering the global carbon cycle on the scale of thousands of years (<3 ka).

Ocean acidification: Towards a better understanding of calcite dissolution

NASA Astrophysics Data System (ADS)

Wilhelmus, Monica M.; Adkins, Jess; Menemenlis, Dimitris

2016-11-01

The drastic increase of anthropogenic CO2 emissions over the past two centuries has altered the chemical structure of the ocean, acidifying upper ocean waters. The net impact of this pH decrease on marine ecosystems is still unclear, given the unprecedented rate at which CO2 is being released into the atmosphere. As part of the carbon cycle, calcium carbonate dissolution in sediments neutralizes CO2: phytoplankton at the surface produce carbonate minerals, which sink and reach the seafloor after the organisms die. On time scales of thousands of years, the calcium carbonate in these shells ultimately reacts with CO2 in seawater. Research in this field has been extensive; nevertheless, the dissolution rate law, the impact of boundary layer transport, and the feedback with the global ocean carbon cycle remain controversial. Here, we (i) develop a comprehensive numerical framework via 1D modeling of carbonate dissolution in sediments, (ii) approximate its impact on water column properties by implementing a polynomial approximation to the system's response into a global ocean biogeochemistry general circulation model (OBGCM), and (iii) examine the OBGCM sensitivity response to different formulations of sediment boundary layer properties. We find that, even though the burial equilibration time scales of calcium carbonate are in the order of thousands of years, the formulation of a bottom sediment model along with an improved description of the dissolution rate law can have consequences on multi-year to decadal time scales.

Empirical kinetics and their role in elucidating the utility of transition-state theory to mineral–water reactions. A comment upon, ''Evidence and Potential Implications of Exponential Tails to Concentration Versus Time Plots for the Batch Dissolution of Calcite'' by V. W. Truesdale

DOE PAGES

Icenhower, Jonathan P.

2015-06-23

Transition-state theory (TST) is a successful theory for understanding many different types of reactions, but its application to mineral-water systems has not been successful, especially as the system approaches saturation with respect to a rate-limiting phase. A number of investigators have proposed alternate frameworks for using the kinetic rate data to construct models of dissolution, including Truesdale (Aquat Geochem, 2015; this issue). This alternate approach has been resisted, in spite of self-evident discrepancies between TST expectations and the data. The failure of TST under certain circumstances is a result of the presence of metastable intermediaries or reaction layers that formmore » on the surface of reacting solids, and these phenomena are not anticipated by the current theory. Furthermore, alternate approaches, such as the shrinking object model advocated by Truesdale, represent a potentially important avenue for advancing the science of dissolution kinetics.« less

Experimental study of the replacement of calcite by calcium sulphates

NASA Astrophysics Data System (ADS)

Ruiz-Agudo, E.; Putnis, C. V.; Hövelmann, J.; Álvarez-Lloret, P.; Ibáñez-Velasco, A.; Putnis, A.

2015-05-01

Among the most relevant mineral replacement reactions are those involving sulphates and carbonates, which have important geological and technological implications. Here it is shown experimentally that during the interaction of calcite (CaCO3) cleavage surfaces with sulphate-bearing acidic solutions, calcite is ultimately replaced by gypsum (CaSO4 2H2O) and anhydrite (CaSO4), depending on the reaction temperature. Observations suggest that this occurs most likely via an interface-coupled dissolution-precipitation reaction, in which the substrate is replaced pseudomorphically by the product. At 120 and 200 °C gypsum and/or bassanite (CaSO4·0.5H2O) form as precursor phases for the thermodynamically stable anhydrite. Salinity promotes the formation of less hydrated precursor phases during the replacement of calcite by anhydrite. The reaction stops before equilibrium with respect to calcite is reached and during the course of the reaction most of the bulk solutions are undersaturated with respect to the precipitating phase(s). A mechanism consisting of the dissolution of small amounts of solid in a thin layer of fluid at the mineral-fluid interface and the subsequent precipitation of the product phase from this layer is in agreement with these observations. PHREEQC simulations performed in the framework of this mechanism highlight the relevance of transport and surface reaction kinetics on the volume change associated with the CaCO3-CaSO4 replacement. Under our experimental conditions, this reaction occurs with a positive volume change, which ultimately results in passivation of the unreacted substrate before calcite attains equilibrium with respect to the bulk solution.

Calcium Carbonate Dissolution Above the Lysocline: Implications of Copepod Grazing on Coccolithophores

NASA Astrophysics Data System (ADS)

White, M. M.; Waller, J. D.; Lubelczyk, L.; Drapeau, D.; Bowler, B.; Wyeth, A.; Fields, D.; Balch, W. M.

2016-02-01

Copepod-coccolithophore predator-prey interactions are of great importance because they facilitate the export of particulate inorganic and organic carbon (PIC and POC) from the surface ocean. Coccolith dissolution in acidic copepod guts has been proposed as a possible explanation for the paradox of PIC dissolution above the lysocline, but warrants further investigation. Using a new application of the 14C-microdiffusion technique, we investigated the dissolution of coccoliths in copepod guts. We considered both an estuarine predator-prey model (Acartia tonsa and Pleurochrysis carterae) and an open ocean predator-prey model (Calanus finmarchicus and Emiliania huxleyi). Additionally, we considered the impacts of pCO2 on this process to advance our understanding of the effects of ocean acidification on trophic interactions. In the estuarine predator-prey model, fecal pellets produced immediately after previously-starved copepods grazed on P. carterae had PIC/POC ratios 27-40 % lower than that of the algae, indicating PIC dissolution within the copepod gut, with no impact of pCO2 on this dissolution. Subsequent fecal pellets showed increasing PIC/POC, suggesting that calcite dissolution decreases as the gut fills. The open ocean predator-prey model showed equivocal results, indicating high variability among individual grazing behavior, and therefore no consistent impact of copepod grazing on coccolith dissolution above the lysocline in the open ocean. We will further discuss the effects of fecal pellet PIC/POC ratios on sinking rate.

Understanding the nature of atmospheric acid processing of mineral dusts in supplying bioavailable phosphorus to the oceans.

PubMed

Stockdale, Anthony; Krom, Michael D; Mortimer, Robert J G; Benning, Liane G; Carslaw, Kenneth S; Herbert, Ross J; Shi, Zongbo; Myriokefalitakis, Stelios; Kanakidou, Maria; Nenes, Athanasios

2016-12-20

Acidification of airborne dust particles can dramatically increase the amount of bioavailable phosphorus (P) deposited on the surface ocean. Experiments were conducted to simulate atmospheric processes and determine the dissolution behavior of P compounds in dust and dust precursor soils. Acid dissolution occurs rapidly (seconds to minutes) and is controlled by the amount of H + ions present. For H + < 10 -4 mol/g of dust, 1-10% of the total P is dissolved, largely as a result of dissolution of surface-bound forms. At H + > 10 -4 mol/g of dust, the amount of P (and calcium) released has a direct proportionality to the amount of H + consumed until all inorganic P minerals are exhausted and the final pH remains acidic. Once dissolved, P will stay in solution due to slow precipitation kinetics. Dissolution of apatite-P (Ap-P), the major mineral phase in dust (79-96%), occurs whether calcium carbonate (calcite) is present or not, although the increase in dissolved P is greater if calcite is absent or if the particles are externally mixed. The system was modeled adequately as a simple mixture of Ap-P and calcite. P dissolves readily by acid processes in the atmosphere in contrast to iron, which dissolves more slowly and is subject to reprecipitation at cloud water pH. We show that acidification can increase bioavailable P deposition over large areas of the globe, and may explain much of the previously observed patterns of variability in leachable P in oceanic areas where primary productivity is limited by this nutrient (e.g., Mediterranean).

Study of reverse flotation of calcite from scheelite in acidic media

NASA Astrophysics Data System (ADS)

Deng, Rongdong; Huang, Yuqing; Hu, Yuan; Ku, Jiangang; Zuo, Weiran; Yin, Wanzhong

2018-05-01

A new coated-reactive reverse flotation method based on the generation of CO2 bubbles at a calcite surface in acidic solution was used to separate calcite from scheelite. The dissolution kinetics of coated and uncoated calcite were studied in sulfuric acid. The CO2 bubbles generated on the uncoated calcite particle surface are enough to float the particle. However, most of these bubbles left the surface quickly, preventing calcite from floating. Here, a mixture of polyvinyl alcohol polymer and sodium dodecyl sulfonate was used to coat the mineral particles and form a stable membrane, resulting in the formation of a stable foam layer on the calcite surface. After the calcite is coated, the generated bubbles could be successfully captured on the calcite surface, and calcite particles could float to the air-water interface and remain there for more than one hour. Flotation tests indicated that a high-quality tungsten concentrate with a grade of more than 75% and a recovery of more than 99% could be achieved when the particle size was between 0.3 and 1.5 mm. The present results provide theoretical support for the development of a highly efficient flotation separation for carbonate minerals.

Groundwater circulation and geochemistry of a karstified bank marginal fracture system, South Andros Island, Bahamas

NASA Astrophysics Data System (ADS)

Whitaker, Fiona F.; Smart, Peter L.

1997-10-01

On the east coast of South Andros Island, Bahamas, a major bank-marginal fracture system characterised by vertically extensive cavern systems (blue holes) is developed sub-parallel to the steep-sided deep-water re-entrant of the Tongue of the Ocean. In addition to providing a discharge route for meteoric, mixed and geochemically evolved saline groundwaters, a strong local circulation occurs along the fracture system. This generates enhanced vertical mixing within voids of the fracture system, evidenced by the increasing mixing zone thickness, and the thinning and increasing salinity of brackish lens waters from north to south along the fracture system. Furthermore, tidally driven pumping of groundwaters occurs between the fracture and adjacent carbonate aquifer affecting a zone up to 200 m either side of the fracture. The resultant mixing of groundwaters of contrasting salinity and PCO 2 within and along the fracture system and with the surrounding aquifer waters, together with bacterial oxidation of organic matter, generates significant potential for locally enhanced diagenesis. Undersaturation with respect to calcite within the fresh (or brackish)-salt water mixing zone is observed in the fracture system and predicted in the adjacent aquifer, while mixing between the brackish fracture lens and surrounding high PCO 2 fresh waters causes dissolution of aragonite but not calcite. The latter gives rise to considerable secondary porosity development, because active tidal pumping ensures continued renewal of dissolutional potential. This is evidenced by calcium and strontium enrichment in the brackish lens which indicates porosity generation by aragonite dissolution at a maximum rate of 0.35% ka -1, up to twice the average estimated for the fresh water lens. In contrast saline groundwaters are depleted in calcium relative to open ocean waters suggesting the formation of calcite cements. The development of a major laterally continuous cavernous fracture zone along the margin of the carbonate platform permits enhanced groundwater flow and mixing which may result in generation of a diagenetic `halo' at a scale larger than that generally recognised around syn-sedimentary fractures in fossil carbonates. This may be characterised by increased secondary porosity where a relative fall in sea-level results in exposure and formation of a meteoric groundwater system, or cementation by `marine' calcite both below this meteoric system, and where the bank surface is flooded by seawater.

High resolution cathodoluminescence spectroscopy of carbonate cementation in Khurmala Formation (Paleocene-L. Eocene) from Iraqi Kurdistan Region, Northern Iraq

NASA Astrophysics Data System (ADS)

Omer, Muhamed F.; Omer, Dilshad; Zebari, Bahroz Gh.

2014-12-01

A combination of high resolution cathodoluminsecnce-spectroscopy (HRS-CL) with spatial electron microprobe analysis and optical microscopy is used to determine paragenesis and history of cementation in the limestones and dolostones of Khurmala Formation which is exposed in many parts of Northern Iraq. Khurmala Formation was subjected to different diagenetic processes such as micritization, compaction, dissolution, neomorphism, pyritization and cementation that occurred during marine to shallow burial stages and culminated during intermediate to deep burial later stages. Five dolomite textures are recognized and classified according to crystal size distribution and crystal-boundary shape. Dolomitization is closely associated with the development of secondary porosity that pre-and postdates dissolution and corrosion; meanwhile such porosity was not noticed in the associated limestones. Microprobe analysis revealed three types of cement, calcite, dolomite and ankerite which range in their luminescence from dull to bright. Cathodoluminescence study indicated four main texture generations. These are (1) unzoned microdolomite of planar and subhedral shape, with syntaxial rim cement of echinoderm that show dull to red luminescence, (2) equant calcite cements filling interparticle pores which shows dull luminescence and weak zonal growth, (3.1) homogenous intrinsic blue stoichiometric calcite with dull luminescence and without activators, (3.2) coarse blocky calcite cement with strong oscillatory zoning and bright orange luminescence which postdates other calcite cements, (4) ankerite cement with red to orange, non-luminescence growth zonation which is the last formed cement.

Pavement Subsidence in the Cumberland Gap Tunnel, USA: A Story of Groundwater Chemistry

NASA Astrophysics Data System (ADS)

Zhu, J.; Currens, J. C.; Webb, S. E.; Rister, B. W.

2014-12-01

Cumberland Gap Tunnel was constructed in 1996 to improve highway travel between southeastern Kentucky and northeastern Tennessee and to restore Cumberland Gap to its historical appearance. About five years after construction, the concrete pavement in the tunnel began to exhibit noticeable signs of subsidence. Ground penetrating radar surveys detected voids in many areas of the limestone roadbed aggregate beneath the pavement. Field investigations conducted by the Kentucky Geological Survey and Kentucky Transportation Center from 2006 to 2008 discovered that groundwater was flowing from the bedrock invert into the aggregate along many parts of the tunnel. Average groundwater discharge from the tunnel was measured at approximately 1700 m3/d. We analyzed 265 groundwater samples collected from aggregate in different parts of the tunnel roadbed during low and high flow conditions. Calculated calcite saturation indices indicated that the groundwater was geochemically aggressive and capable of continuously dissolving calcite in the limestone aggregate although pH values of these water samples were near neutral. We also conducted an in-situ dissolution experiment by placing eight baskets filled with limestone aggregate beneath the roadbed in different locations in the tunnel for 178 days. At the end of the experiment, the limestone aggregate in contact with groundwater exhibited visual signs of dissolution and lost mass, and the highest mass loss recorded was 3.4 percent. Mass loss calculations based on kinetic models of calcite mineral and water samples taken near the baskets matched well with the actual measured mass losses, confirming that dissolution of calcite by the groundwater was the primary cause of the roadbed subsidence problem. Based on these findings, we suggested the limestone aggregate be replaced with noncarbonate (granite) aggregate to mitigate future road subsidence. The suggestion was adopted, and the repair was completed in early 2014.

A probabilistic assessment of calcium carbonate export and dissolution in the modern ocean

NASA Astrophysics Data System (ADS)

Battaglia, Gianna; Steinacher, Marco; Joos, Fortunat

2016-05-01

The marine cycle of calcium carbonate (CaCO3) is an important element of the carbon cycle and co-governs the distribution of carbon and alkalinity within the ocean. However, CaCO3 export fluxes and mechanisms governing CaCO3 dissolution are highly uncertain. We present an observationally constrained, probabilistic assessment of the global and regional CaCO3 budgets. Parameters governing pelagic CaCO3 export fluxes and dissolution rates are sampled using a Monte Carlo scheme to construct a 1000-member ensemble with the Bern3D ocean model. Ensemble results are constrained by comparing simulated and observation-based fields of excess dissolved calcium carbonate (TA*). The minerals calcite and aragonite are modelled explicitly and ocean-sediment fluxes are considered. For local dissolution rates, either a strong or a weak dependency on CaCO3 saturation is assumed. In addition, there is the option to have saturation-independent dissolution above the saturation horizon. The median (and 68 % confidence interval) of the constrained model ensemble for global biogenic CaCO3 export is 0.90 (0.72-1.05) Gt C yr-1, that is within the lower half of previously published estimates (0.4-1.8 Gt C yr-1). The spatial pattern of CaCO3 export is broadly consistent with earlier assessments. Export is large in the Southern Ocean, the tropical Indo-Pacific, the northern Pacific and relatively small in the Atlantic. The constrained results are robust across a range of diapycnal mixing coefficients and, thus, ocean circulation strengths. Modelled ocean circulation and transport timescales for the different set-ups were further evaluated with CFC11 and radiocarbon observations. Parameters and mechanisms governing dissolution are hardly constrained by either the TA* data or the current compilation of CaCO3 flux measurements such that model realisations with and without saturation-dependent dissolution achieve skill. We suggest applying saturation-independent dissolution rates in Earth system models to minimise computational costs.

Geochemistry of spring water, southeastern Uinta Basin, Utah and Colorado

USGS Publications Warehouse

Kimball, Briant A.

1981-01-01

The chemical quality of water in the southeastern Uinta Basin, Utah and Colorado, is important to the future development of the abundant oil-shale resources of the area. This report examines the observed changes in chemistry as water circulates in both shallow and deep ground-water systems. Mass-balance and mass- transfer calculations are used to define reactions that simulate the observed water chemistry in the mixed sandstone, siltstone, and carbonate lithology of the Green River Formation of Tertiary age.The mass-transfer calculations determine a reaction path particular to this system. The early dominance of calcite dissolution produces a calcium carbonate water. After calcite saturation, deeper circulation and further rock-water interaction cause the reprecipitation of calcite, the dissolution of dolomite and plagioclase, and the oxidation of pyrite; all combining to produce a calcium magnesium sodium bicarbonate sulfate water. The calculations suggest that silica concentrations are controlled by a kaolinite-Ca-montmorillonite phase boundary. Close agreement of mineral-saturation indices calculated by both an aqueous-equilibrium model and the mass-transfer model support the selection of reactions from the mass-transfer calculations.

Conceptual model analysis of interaction at a concrete-Boom Clay interface

NASA Astrophysics Data System (ADS)

Liu, Sanheng; Jacques, Diederik; Govaerts, Joan; Wang, Lian

In many concepts for deep disposal of high-level radioactive waste, cementitious materials are used in the engineered barriers. For example, in Belgium the engineered barrier system is based on a considerable amount of cementitious materials as buffer and backfill in the so-called supercontainer embedded in the hosting geological formation. A potential hosting formation is Boom Clay. Insight in the interaction between the high-pH pore water of the cementitious materials and neutral-pH Boom Clay pore water is required. Two problems are quite common for modeling of such a system. The first one is the computational cost due to the long timescale model assessments envisaged for the deep disposal system. Also a very fine grid (in sub-millimeter), especially at interfaces has to be used in order to accurately predict the evolution of the system. The second one is whether to use equilibrium or kinetic reaction models. The objectives of this paper are twofold. First, we develop an efficient coupled reactive transport code for this diffusion-dominated system by making full use of multi-processors/cores computers. Second, we investigate how sensitive the system is to chemical reaction models especially when pore clogging due to mineral precipitation is considered within the cementitious system. To do this, we selected two portlandite dissolution models, i.e., equilibrium (fastest) and diffusion-controlled model with precipitation of a calcite layer around portlandite particles (diffusion-controlled dissolution). The results show that with shrinking core model portlandite dissolution and calcite precipitation are much slower than with the equilibrium model. Also diffusion-controlled dissolution smooths out dissolution fronts compared to the equilibrium model. However, only a slight difference with respect to the clogging time can be found even though we use a very small diffusion coefficient (10-20 m2/s) in the precipitated calcite layer.

Nonstationary porosity evolution in mixing zone in coastal carbonate aquifer using an alternative modeling approach.

PubMed

Laabidi, Ezzeddine; Bouhlila, Rachida

2015-07-01

In the last few decades, hydrogeochemical problems have benefited from the strong interest in numerical modeling. One of the most recognized hydrogeochemical problems is the dissolution of the calcite in the mixing zone below limestone coastal aquifer. In many works, this problem has been modeled using a coupling algorithm between a density-dependent flow model and a geochemical model. A related difficulty is that, because of the high nonlinearity of the coupled set of equations, high computational effort is needed. During calcite dissolution, an increase in permeability can be identified, which can induce an increase in the penetration of the seawater into the aquifer. The majority of the previous studies used a fully coupled reactive transport model in order to model such problem. Romanov and Dreybrodt (J Hydrol 329:661-673, 2006) have used an alternative approach to quantify the porosity evolution in mixing zone below coastal carbonate aquifer at steady state. This approach is based on the analytic solution presented by Phillips (1991) in his book Flow and Reactions in Permeable Rock, which shows that it is possible to decouple the complex set of equation. This equation is proportional to the square of the salinity gradient, which can be calculated using a density driven flow code and to the reaction rate that can be calculated using a geochemical code. In this work, this equation is used in nonstationary step-by-step regime. At each time step, the quantity of the dissolved calcite is quantified, the change of porosity is calculated, and the permeability is updated. The reaction rate, which is the second derivate of the calcium equilibrium concentration in the equation, is calculated using the PHREEQC code (Parkhurst and Apello 1999). This result is used in GEODENS (Bouhlila 1999; Bouhlila and Laabidi 2008) to calculate change of the porosity after calculating the salinity gradient. For the next time step, the same protocol is used but using the updated porosity and permeability distributions.

Understanding the nature of atmospheric acid processing of mineral dusts in supplying bioavailable phosphorus to the oceans

PubMed Central

Krom, Michael D.; Mortimer, Robert J. G.; Benning, Liane G.; Herbert, Ross J.; Shi, Zongbo; Kanakidou, Maria; Nenes, Athanasios

2016-01-01

Acidification of airborne dust particles can dramatically increase the amount of bioavailable phosphorus (P) deposited on the surface ocean. Experiments were conducted to simulate atmospheric processes and determine the dissolution behavior of P compounds in dust and dust precursor soils. Acid dissolution occurs rapidly (seconds to minutes) and is controlled by the amount of H+ ions present. For H+ < 10−4 mol/g of dust, 1–10% of the total P is dissolved, largely as a result of dissolution of surface-bound forms. At H+ > 10−4 mol/g of dust, the amount of P (and calcium) released has a direct proportionality to the amount of H+ consumed until all inorganic P minerals are exhausted and the final pH remains acidic. Once dissolved, P will stay in solution due to slow precipitation kinetics. Dissolution of apatite-P (Ap-P), the major mineral phase in dust (79–96%), occurs whether calcium carbonate (calcite) is present or not, although the increase in dissolved P is greater if calcite is absent or if the particles are externally mixed. The system was modeled adequately as a simple mixture of Ap-P and calcite. P dissolves readily by acid processes in the atmosphere in contrast to iron, which dissolves more slowly and is subject to reprecipitation at cloud water pH. We show that acidification can increase bioavailable P deposition over large areas of the globe, and may explain much of the previously observed patterns of variability in leachable P in oceanic areas where primary productivity is limited by this nutrient (e.g., Mediterranean). PMID:27930294

Speleothems in a wave-cut notch, Cayman Brac, British West Indies: The integrated product of subaerial precipitation, dissolution, and microbes

NASA Astrophysics Data System (ADS)

Jones, Brian

2010-12-01

A wave-cut notch that is deeply incised into the vertical cliff faces of Cayman Brac is adorned with stalactites, stalagmites, and columns. The prefix "notch" is applied to each type of speleothem in order to distinguish them from cave speleothems. These speleothemic deposits must have formed since the highstand, ~ 125,000 years ago, which was responsible for the development of the notch. The laminated notch speleothems are formed largely of aragonite (small and large crystals) and calcite (columnar, fiber, and grain-coating mats) along with minor amounts of dolomite, a Mg-Si precipitate (kerolite?), gypsum, and halite. Laminae, typically < 2 mm thick, are commonly bounded by dissolution discontinuities that truncate the older laminae and their formative aragonite and calcite crystals. The patchy tan, grey, to green surface coloration of the notch speleothems reflects the random distribution of the subaerial biofilms, which are formed of a diverse array of filamentous and non-filamentous microbes. The notch speleothems are the integrated product of precipitation and dissolution that was, in some places, microbially mediated. Interpretations based on their mineralogy and internal structures indicate that the composition of the formative waters must have temporally fluctuated with periods of precipitation being interrupted by periods of dissolution. The microbes that formed the subaerial biofilms may have influenced some of these processes. The aragonite, calcite, and kerolite (?) probably formed as evaporation and loss of Ca through precipitation progressively increased the Mg:Ca and the Si/(Ca + Mg) ratios. The dolomite, gypsum, and halite probably formed during early diagenesis during the evaporation of seawater that percolated into the interiors of the notch speleothems.

A reactive transport model for the quantification of risks induced by groundwater heat pump systems in urban aquifers

NASA Astrophysics Data System (ADS)

García-Gil, Alejandro; Epting, Jannis; Ayora, Carlos; Garrido, Eduardo; Vázquez-Suñé, Enric; Huggenberger, Peter; Gimenez, Ana Cristina

2016-11-01

Shallow geothermal resource exploitation through the use of groundwater heat pump systems not only has hydraulic and thermal effects on the environment but also induces physicochemical changes that can compromise the operability of installations. This study focuses on chemical clogging and dissolution subsidence processes observed during the geothermal re-injection of pumped groundwater into an urban aquifer. To explain these phenomena, two transient reactive transport models of a groundwater heat pump installation in an alluvial aquifer were used to reproduce groundwater-solid matrix interactions occurring in a surrounding aquifer environment during system operation. The models couple groundwater flow, heat and solute transport together with chemical reactions. In these models, the permeability distribution in space changes with precipitation-dissolution reactions over time. The simulations allowed us to estimate the calcite precipitation rates and porosity variations over space and time as a function of existent hydraulic gradients in an aquifer as well as the intensity of CO2 exchanges with the atmosphere. The results obtained from the numerical model show how CO2 exolution processes that occur during groundwater reinjection into an aquifer and calcite precipitation are related to hydraulic efficiency losses in exploitation systems. Finally, the performance of reinjection wells was evaluated over time according to different scenarios until the systems were fully obstructed. Our simulations also show a reduction in hydraulic conductivity that forces re-injected water to flow downwards, thereby enhancing the dissolution of evaporitic bedrock and producing subsidence that can ultimately result in a dramatic collapse of the injection well infrastructure.

Geochemical transformations and modeling of two deep-well injected hazardous wastes

USGS Publications Warehouse

Roy, W.R.; Seyler, B.; Steele, J.D.; Mravik, S.C.; Moore, D.M.; Krapac, I.G.; Peden, J.M.; Griffin, R.A.

1991-01-01

Two liquid hazardous wastes (an alkaline brine-like solution and a dilute acidic waste) were mixed with finely ground rock samples of three injection-related lithologies (sandstone, dolomite, and siltstone) for 155 to 230 days at 325??K-10.8 MPa. The pH and inorganic chemical composition of the alkaline waste were not significantly altered by any of the rock samples after 230 days of mixing. The acidic waste was neutralized as a consequence of carbonate dissolution, ion exchange, or clay-mineral dissolution, and hence was transformed into a nonhazardous waste. Mixing the alkaline waste with the solid phases yielded several reaction products: brucite, Mg(OH)2; calcite, CaCO3; and possibly a type of sodium metasilicate. Clay-like minerals formed in the sandstone, and hydrotalcite, Mg6Al2-CO3(OH)16??4H2O, may have formed in the siltstone at trace levels. Mixing the alkaline waste with a synthetic brine yielded brucite, calcite, and whewellite (CaC2O4??H2O). The thermodynamic model PHRQPITZ predicted that brucite and calcite would precipitate from solution in the dolomite and siltstone mixtures and in the alkaline waste-brine system. The dilute acidic waste did not significantly alter the mineralogical composition of the three rock types after 155 days of contact. The model PHREEQE indicated that the calcite was thermodynamically stable in the dolomite and siltstone mixtures.

Bony fish and their contribution to marine inorganic carbon cycling

NASA Astrophysics Data System (ADS)

Salter, Michael; Perry, Chris; Wilson, Rod; Harborne, Alistair

2016-04-01

Conventional understanding of the marine inorganic carbon cycle holds that CaCO3 (mostly as low Mg-calcite and aragonite) precipitates in the upper reaches of the ocean and sinks to a point where it either dissolves or is deposited as sediment. Thus, it plays a key role controlling the distribution of DIC in the oceans and in regulating their capacity to absorb atmospheric CO2. However, several aspects of this cycle remain poorly understood and have long perplexed oceanographers, such as the positive alkalinity anomaly observed in the upper water column of many of the world's oceans, above the aragonite and calcite saturation horizons. This anomaly would be explained by extensive dissolution of a carbonate phase more soluble than low Mg-calcite or aragonite, but major sources for such phases remain elusive. Here we highlight marine bony fish as a potentially important primary source of this 'missing' high-solubility CaCO3. Precipitation of CaCO3 takes place within the intestines of all marine bony fish as part of their normal physiological functioning, and global production models suggest it could account for up to 45 % of total new marine CaCO3 production. Moreover, high Mg-calcite containing >25 % mol% MgCO3 - a more soluble phase than aragonite - is a major component of these precipitates. Thus, fish CaCO3 may at least partially explain the alkalinity anomaly in the upper water column. However, the issue is complicated by the fact that carbonate mineralogy actually varies among fish species, with high Mg-calcite (HMC), low Mg-calcite (LMC), aragonite, and amorphous calcium carbonate (ACC) all being common products. Using data from 22 Caribbean fish species, we have generated a novel production model that resolves phase proportions. We evaluate the preservation/dissolution potential of these phases and consider potential implications for marine inorganic carbon cycling. In addition, we consider the dramatic changes in fish biomass structure that have resulted from overfishing throughout the past century, and how these changes could be affecting marine carbon cycling. Given that rising sea surface temperatures and 'ocean acidification' are both predicted to promote increased fish CaCO3 production rates, the role of fish in the marine inorganic carbon cycle could become increasingly important in the future. Consequently, it is conceivable that fish stock management could become an important carbon-regulating service employed in the face of challenges such as climate change mitigation, so it is vital that this role is properly comprehended.

Hydroxyapatite coatings for marble protection: Optimization of calcite covering and acid resistance

NASA Astrophysics Data System (ADS)

Graziani, Gabriela; Sassoni, Enrico; Franzoni, Elisa; Scherer, George W.

2016-04-01

Hydroxyapatite (HAP) has a much lower dissolution rate and solubility than calcite, especially in an acidic environment, so it has been proposed for the protection of marble against acidic rain corrosion. Promising results were obtained, but further optimization is necessary as the treated layer is often incomplete, cracked and/or porous. In this paper, several parameters were investigated to obtain a coherent, uncracked layer, and to avoid the formation of metastable, soluble phases instead of HAP: the role of the pH of the starting solution; the effect of organic and inorganic additions, and in particular that of ethanol, as it is reported to adsorb on calcite, hence possibly favoring the growth of the HAP layer. Finally, a double application of the treatment was tested. Results were compared to those obtained with ammonium oxalate treatment, widely investigated for marble protection. Results indicate that adding small amounts of ethanol to the formulation remarkably increases the acid resistance of treated samples, and yields better coverage of the surface without crack formation. The effectiveness of the treatment is further enhanced when a second treatment is applied. The efficacy of ethanol-doped DAP mixtures was found to be remarkably higher than that of ammonium oxalate based treatments.

Relation between sedimentary framework and hydrogeology in the Guarani Aquifer System in São Paulo state, Brazil

NASA Astrophysics Data System (ADS)

Hirata, Ricardo; Gesicki, Ana; Sracek, Ondra; Bertolo, Reginaldo; Giannini, Paulo César; Aravena, Ramón

2011-04-01

This paper presents the results of a new investigation of the Guarani Aquifer System (SAG) in São Paulo state. New data were acquired about sedimentary framework, flow pattern, and hydrogeochemistry. The flow direction in the north of the state is towards the southwest and not towards the west as expected previously. This is linked to the absence of SAG outcrop in the northeast of São Paulo state. Both the underlying Pirambóia Formation and the overlying Botucatu Formation possess high porosity (18.9% and 19.5%, respectively), which was not modified significantly by diagenetic changes. Investigation of sediments confirmed a zone of chalcedony cement close to the SAG outcrop and a zone of calcite cement in the deep confined zone. The main events in the SAG post-sedimentary history were: (1) adhesion of ferrugineous coatings on grains, (2) infiltration of clays in eodiagenetic stage, (3) regeneration of coatings with formation of smectites, (4) authigenic overgrowth of quartz and K-feldspar in advanced eodiagenetic stage, (5) bitumen cementation of Pirambóia Formation in mesodiagenetic stage, (6) cementation by calcite in mesodiagenetic and telodiagenetic stages in Pirambóia Formation, (7) formation of secondary porosity by dissolution of unstable minerals after appearance of hydraulic gradient and penetration of the meteoric water caused by the uplift of the Serra do Mar coastal range in the Late Cretaceous, (8) authigenesis of kaolinite and amorphous silica in unconfined zone of the SAG and cation exchange coupled with the dissolution of calcite at the transition between unconfined and confined zone, and (9) authigenesis of analcime in the confined SAG zone. The last two processes are still under operation. The deep zone of the SAG comprises an alkaline pH, Na-HCO 3 groundwater type with old water and enriched δ 13C values (<-3.9), which evolved from a neutral pH, Ca-HCO 3 groundwater type with young water and depleted δ 13C values (>-18.8) close to the SAG outcrop. This is consistent with a conceptual geochemical model of the SAG, suggesting dissolution of calcite driven by cation exchange, which occurs at a relatively narrow front recently moving downgradient at much slower rate compared to groundwater flow. More depleted values of δ 18O in the deep confined zone close to the Paraná River compared to values of relative recent recharged water indicate recharge occur during a period of cold climate. The SAG is a "storage-dominated" type of aquifer which has to be managed properly to avoid its overexploitation.

Experiments and modeling of variably permeable carbonate reservoir samples in contact with CO₂-acidified brines

DOE PAGES

Smith, Megan M.; Hao, Yue; Mason, Harris E.; ...

2014-12-31

Reactive experiments were performed to expose sample cores from the Arbuckle carbonate reservoir to CO₂-acidified brine under reservoir temperature and pressure conditions. The samples consisted of dolomite with varying quantities of calcite and silica/chert. The timescales of monitored pressure decline across each sample in response to CO₂ exposure, as well as the amount of and nature of dissolution features, varied widely among these three experiments. For all samples cores, the experimentally measured initial permeability was at least one order of magnitude or more lower than the values estimated from downhole methods. Nondestructive X-ray computed tomography (XRCT) imaging revealed dissolution featuresmore » including “wormholes,” removal of fracture-filling crystals, and widening of pre-existing pore spaces. In the injection zone sample, multiple fractures may have contributed to the high initial permeability of this core and restricted the distribution of CO₂-induced mineral dissolution. In contrast, the pre-existing porosity of the baffle zone sample was much lower and less connected, leading to a lower initial permeability and contributing to the development of a single dissolution channel. While calcite may make up only a small percentage of the overall sample composition, its location and the effects of its dissolution have an outsized effect on permeability responses to CO₂ exposure. The XRCT data presented here are informative for building the model domain for numerical simulations of these experiments but require calibration by higher resolution means to confidently evaluate different porosity-permeability relationships.« less

Fluoride enrichment in groundwater of semi-arid urban area: Khan Younis City, southern Gaza Strip (Palestine)

NASA Astrophysics Data System (ADS)

Abu Jabal, Mohamed Shaban; Abustan, Ismail; Rozaimy, Mohd Remy; Al-Najar, Hussam

2014-12-01

The aim of this study is to determine fluoride enhancement in the groundwater of semi-arid urban area of Khan Younis City, southern Gaza Strip. Physicochemical data for a total of 200 groundwater samples were analyzed. The fluoride concentrations were varied from 0.3 to 6.45 mg/L with average value of 2.87 mg/L. Correlations between fluorides with other measured ions were relatively observed, negative correlation with calcium and the positive correlation with pH, bicarbonate and sodium increase the dissolution/solubility of fluoride bearing minerals, leading to fluoride leaching into the groundwater. Fluoride enrichment in the groundwater of the area is due to water hydrochemistry, mineral-water interaction (mainly calcite and fluorite), fluorite resulted from fluorapatite dissolution. The saturation indexes evaluation indicated that 42% of the samples are over saturated with respect to calcite and 35.5% under saturated with respect to fluorite, while 40.5% approached equilibrium with respect to both calcite and fluorite. At fluoride concentrations of less than 2.2 mg/L fluorite saturation indexes show under-saturation condition for fluorite and at higher fluoride concentrations show near saturation condition.

Direct ink writing of silica-bonded calcite scaffolds from preceramic polymers and fillers.

PubMed

Fiocco, L; Elsayed, H; Badocco, D; Pastore, P; Bellucci, D; Cannillo, V; Detsch, R; Boccaccini, A R; Bernardo, E

2017-05-11

Silica-bonded calcite scaffolds have been successfully 3D-printed by direct ink writing, starting from a paste comprising a silicone polymer and calcite powders, calibrated in order to match a SiO 2 /CaCO 3 weight balance of 35/65. The scaffolds, fabricated with two slightly different geometries, were first cross-linked at 350 °C, then fired at 600 °C, in air. The low temperature adopted for the conversion of the polymer into amorphous silica, by thermo-oxidative decomposition, prevented the decomposition of calcite. The obtained silica-bonded calcite scaffolds featured open porosity of about 56%-64% and compressive strength of about 2.9-5.5 MPa, depending on the geometry. Dissolution studies in SBF and preliminary cell culture tests, with bone marrow stromal cells, confirmed the in vitro bioactivity of the scaffolds and their biocompatibility. The seeded cells were found to be alive, well anchored and spread on the samples surface. The new silica-calcite composites are expected to be suitable candidates as tissue-engineering 3D scaffolds for regeneration of cancellous bone defects.

Geochemical Interaction of Middle Bakken Reservoir Rock and CO2 during CO2-Based Fracturing

NASA Astrophysics Data System (ADS)

Nicot, J. P.; Lu, J.; Mickler, P. J.; Ribeiro, L. H.; Darvari, R.

2015-12-01

This study was conducted to investigate the effects of geochemical interactions when CO2 is used to create the fractures necessary to produce hydrocarbons from low-permeability Middle Bakken sandstone. The primary objectives are to: (1) identify and understand the geochemical reactions related to CO2-based fracturing, and (2) assess potential changes of reservoir property. Three autoclave experiments were conducted at reservoir conditions exposing middle Bakken core fragments to supercritical CO2 (sc-CO2) only and to CO2-saturated synthetic brine. Ion-milled core samples were examined before and after the reaction experiments using scanning electron microscope, which enabled us to image the reaction surface in extreme details and unambiguously identify mineral dissolution and precipitation. The most significant changes in the reacted rock samples exposed to the CO2-saturated brine is dissolution of the carbonate minerals, particularly calcite which displays severely corrosion. Dolomite grains were corroded to a lesser degree. Quartz and feldspars remained intact and some pyrite framboids underwent slight dissolution. Additionally, small amount of calcite precipitation took place as indicated by numerous small calcite crystals formed at the reaction surface and in the pores. The aqueous solution composition changes confirm these petrographic observations with increase in Ca and Mg and associated minor elements and very slight increase in Fe and sulfate. When exposed to sc-CO2 only, changes observed include etching of calcite grain surface and precipitation of salt crystals (halite and anhydrite) due to evaporation of residual pore water into the sc-CO2 phase. Dolomite and feldspars remained intact and pyrite grains were slightly altered. Mercury intrusion capillary pressure tests on reacted and unreacted samples shows an increase in porosity when an aqueous phase is present but no overall porosity change caused by sc-CO2. It also suggests an increase in permeability in the former case and possibly a minor decrease in the latter case.

Modeling low-temperature geochemical processes: Chapter 2

USGS Publications Warehouse

Nordstrom, D. Kirk; Campbell, Kate M.

2014-01-01

This chapter provides an overview of geochemical modeling that applies to water–rock interactions under ambient conditions of temperature and pressure. Topics include modeling definitions, historical background, issues of activity coefficients, popular codes and databases, examples of modeling common types of water–rock interactions, and issues of model reliability. Examples include speciation, microbial redox kinetics and ferrous iron oxidation, calcite dissolution, pyrite oxidation, combined pyrite and calcite dissolution, dedolomitization, seawater–carbonate groundwater mixing, reactive-transport modeling in streams, modeling catchments, and evaporation of seawater. The chapter emphasizes limitations to geochemical modeling: that a proper understanding and ability to communicate model results well are as important as completing a set of useful modeling computations and that greater sophistication in model and code development is not necessarily an advancement. If the goal is to understand how a particular geochemical system behaves, it is better to collect more field data than rely on computer codes.

A probabilistic assessment of calcium carbonate export and dissolution in the modern ocean

NASA Astrophysics Data System (ADS)

Battaglia, G.; Steinacher, M.; Joos, F.

2015-12-01

The marine cycle of calcium carbonate (CaCO3) is an important element of the carbon cycle and co-governs the distribution of carbon and alkalinity within the ocean. However, CaCO3 fluxes and mechanisms governing CaCO3 dissolution are highly uncertain. We present an observationally-constrained, probabilistic assessment of the global and regional CaCO3 budgets. Parameters governing pelagic CaCO3 export fluxes and dissolution rates are sampled using a Latin-Hypercube scheme to construct a 1000 member ensemble with the Bern3D ocean model. Ensemble results are constrained by comparing simulated and observation-based fields of excess dissolved calcium carbonate (TA*). The minerals calcite and aragonite are modelled explicitly and ocean-sediment fluxes are considered. For local dissolution rates either a strong, a weak or no dependency on CaCO3 saturation is assumed. Median (68 % confidence interval) global CaCO3 export is 0.82 (0.67-0.98) Gt PIC yr-1, within the lower half of previously published estimates (0.4-1.8 Gt PIC yr-1). The spatial pattern of CaCO3 export is broadly consistent with earlier assessments. Export is large in the Southern Ocean, the tropical Indo-Pacific, the northern Pacific and relatively small in the Atlantic. Dissolution within the 200 to 1500 m depth range (0.33; 0.26-0.40 Gt PIC yr-1) is substantially lower than inferred from the TA*-CFC age method (1 ± 0.5 Gt PIC yr-1). The latter estimate is likely biased high as the TA*-CFC method neglects transport. The constrained results are robust across a range of diapycnal mixing coefficients and, thus, ocean circulation strengths. Modelled ocean circulation and transport time scales for the different setups were further evaluated with CFC11 and radiocarbon observations. Parameters and mechanisms governing dissolution are hardly constrained by either the TA* data or the current compilation of CaCO3 flux measurements such that model realisations with and without saturation-dependent dissolution achieve skill. We suggest to apply saturation-independent dissolution rates in Earth System Models to minimise computational costs.

Predictive modeling of CO2 sequestration in deep saline sandstone reservoirs: Impacts of geochemical kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balashov, Victor N.; Guthrie, George D.; Hakala, J. Alexandra

2013-03-01

One idea for mitigating the increase in fossil-fuel generated CO{sub 2} in the atmosphere is to inject CO{sub 2} into subsurface saline sandstone reservoirs. To decide whether to try such sequestration at a globally significant scale will require the ability to predict the fate of injected CO{sub 2}. Thus, models are needed to predict the rates and extents of subsurface rock-water-gas interactions. Several reactive transport models for CO{sub 2} sequestration created in the last decade predicted sequestration in sandstone reservoirs of ~17 to ~90 kg CO{sub 2} m{sup -3|. To build confidence in such models, a baseline problem including rockmore » + water chemistry is proposed as the basis for future modeling so that both the models and the parameterizations can be compared systematically. In addition, a reactive diffusion model is used to investigate the fate of injected supercritical CO{sub 2} fluid in the proposed baseline reservoir + brine system. In the baseline problem, injected CO{sub 2} is redistributed from the supercritical (SC) free phase by dissolution into pore brine and by formation of carbonates in the sandstone. The numerical transport model incorporates a full kinetic description of mineral-water reactions under the assumption that transport is by diffusion only. Sensitivity tests were also run to understand which mineral kinetics reactions are important for CO{sub 2} trapping. The diffusion transport model shows that for the first ~20 years after CO{sub 2} diffusion initiates, CO{sub 2} is mostly consumed by dissolution into the brine to form CO{sub 2,aq} (solubility trapping). From 20-200 years, both solubility and mineral trapping are important as calcite precipitation is driven by dissolution of oligoclase. From 200 to 1000 years, mineral trapping is the most important sequestration mechanism, as smectite dissolves and calcite precipitates. Beyond 2000 years, most trapping is due to formation of aqueous HCO{sub 3}{sup -}. Ninety-seven percent of the maximum CO{sub 2} sequestration, 34.5 kg CO{sub 2} per m{sup 3} of sandstone, is attained by 4000 years even though the system does not achieve chemical equilibrium until ~25,000 years. This maximum represents about 20% CO{sub 2} dissolved as CO{sub 2},aq, 50% dissolved as HCO{sub 3}{sup -}{sub ,aq}, and 30% precipitated as calcite. The extent of sequestration as HCO{sub 3}{sup -} at equilibrium can be calculated from equilibrium thermodynamics and is roughly equivalent to the amount of Na+ in the initial sandstone in a soluble mineral (here, oligoclase). Similarly, the extent of trapping in calcite is determined by the amount of Ca2+ in the initial oligoclase and smectite. Sensitivity analyses show that the rate of CO{sub 2} sequestration is sensitive to the mineral-water reaction kinetic constants between approximately 10 and 4000 years. The sensitivity of CO{sub 2} sequestration to the rate constants decreases in magnitude respectively from oligoclase to albite to smectite.« less

Experimental postseismic recovery of fractured rocks assisted by calcite sealing

NASA Astrophysics Data System (ADS)

Aben, F. M.; Doan, M.-L.; Gratier, J.-P.; Renard, F.

2017-07-01

Postseismic recovery within fault damage zones involves slow healing of coseismic fractures leading to permeability reduction and strength increase with time. To better understand this process, experiments were performed by long-term fluid percolation with calcite precipitation through predamaged quartz-monzonite samples subjected to upper crustal conditions of stress and temperature. This resulted in a P wave velocity recovery of 50% of its initial drop after 64 days. In contrast, the permeability remained more or less constant for the duration of the experiment. Microstructures, fluid chemistry, and X-ray microtomography demonstrate that incipient calcite sealing and asperity dissolution are responsible for the P wave velocity recovery. The permeability is unaffected because calcite precipitates outside of the main flow channels. The highly nonparallel evolution of strength recovery and permeability suggests that fluid conduits within fault damage zones can remain open fluid conduits after an earthquake for much longer durations than suggested by the seismic monitoring of fault healing.

Fluid mediated transformation of aragonitic cuttlebone to calcite

NASA Astrophysics Data System (ADS)

Perdikouri, C.; Kasioptas, A.; Putnis, A.

2009-04-01

The aragonite to calcite transition has been studied extensively over the years because of its wide spectra of applications and of its significant geochemical interest. While studies of kinetics (e.g. Topor et al., 1981), thermodynamics (e.g. Wolf et al., 1996) and behavior of ions such as Sr and Mg (e.g. Yoshioka et al., 1986) have been made there are still unanswered questions regarding this reaction especially in the cases where the effects of fluid composition are considered. It is well known that when heated in air, aragonite transforms by a solid state reaction to calcite. The aragonite cuttlebone of the sepia officinalis that was used for our experiments undergoes a phase transition at ~370-390˚ C, measured by in situ heating experiments in a Philips X'pert X-ray powder diffractometer equipped with a HTK 1200 High temperature oven. Successive X-ray scans were taken at isothermal temperatures at 200C intervals. A similar temperature range was found by Vongsavat et al. 2006, who studied this transition in Acropora corals. It is possible however to promote this transition at considerably lower temperatures by means of a fluid mediated reaction where the replacement takes place by a dissolution-precipitation mechanism (Putnis & Putnis, 2007). We have successfully carried out hydrothermal experiments where cuttlebone has been converted to calcite at 200˚ C. Using the PhreeqC program we calculated the required composition of a solution that would be undersaturated with respect to aragonite and saturated with respect to calcite leading to dissolution of the aragonite and to a consequent precipitation of the new calcite phase, similar to the experiments described in an earlier study (Perdikouri et al, 2008). This reaction is not pseudomorphic and results in the destruction of the morphology, presumably due to the molar volume increase. A total transformation of the cuttlebone produced a fine calcite powder. The cuttlebone exhibits a unique microstructure, made up of interconnected chambers. The aragonite grown during biomineralization of the cuttlebone is interlaced with a β-chitin organic phase that provides the framework for the morphology that is observed. Experiments carried out with the same constant conditions but for different periods of time have revealed the evolution of the transformation to calcite. At shorter reaction times the product was made up of calcite powder and of well preserved aragonite septa, as was confirmed by powder X-ray diffraction. In other words, the vertical pillars appear to react at faster rates than the horizontal septa. It has been reported by Florek et al. 2008 that the septa contain higher quantities of β-chitin. The aim of this study is the investigation of these observations and the determination of the effect of the organic component on the kinetics of the aragonite to calcite transformation. Florek M., Fornal E., Gómez-Romero P., Zieba E., Paszkowicz W., Lekki J.,Nowak J., Kuczumow A. Materials Science and Engineering C, In Press (2008) Perdikouri C., Kasioptas A., Putnis C.V., Putnis A. Mineralogical Magazine 72, 111-114 (2008) Putnis A., Putnis C.V. Solid State Chemistry 180, 1783-1786 (2007) Topor N. D., Tolokonnikova L. I., Kadenatsi B. M. Journal of Thermal Analysis 20, 169-174 (1981) Vongsavat V., Winotai P., Meejoo S. Nuclear Instruments and Methods in Physics Research B 243, 167-173 (2006) Wolf G., Lerchner J., Schmidt H., Gamsjäger H., Königsberger E., Schmidt P. Journal of Thermal Analysis 46, 353-359 (1996) Yoshioka S., Ohde S., Kitano Y., Kanamori N. Marine Chemistry 18, 35-48 (1986)

Interactions between CO2, minerals, and toxic ions: Implications for CO2 leakage from deep geological storage (Invited)

NASA Astrophysics Data System (ADS)

Renard, F.; Montes-Hernandez, G.

2013-12-01

The long-term injection of carbon dioxide into geological underground reservoirs may lead to leakage events that will enhance fluid-rock interactions and question the safety of these repositories. If injection of carbon dioxide into natural reservoirs has been shown to mobilize some species into the pore fluid, including heavy metals and other toxic ions, the detailed interactions remain still debated because two main processes could interact and modify fluid composition: on the one hand dissolution/precipitation reactions may release/incorporate trace elements, and on the other hand adsorption/desorption reactions on existing mineral surfaces may also mobilize or trap these elements. We analyze here, through laboratory experiments, a scenario of a carbon dioxide reservoir that leaks into a fresh water aquifer through a localized leakage zone such as a permeable fault zone localized in the caprock and enhance toxic ions mobilization. Our main goal is to evaluate the potential risks on potable water quality. In a series of experiments, we have injected carbon dioxide into a fresh water aquifer-like medium that contained carbonate and/or iron oxide particles, pure water, and various concentrations of trace elements (copper, arsenic, cadmium, and selenium, in various states of oxidation). This analogue and simplified medium has been chosen because it contains two minerals (calcite, goethite) widespread found in freshwater aquifers. The surface charge of these minerals may vary with pH and therefore control how trace elements are adsorbed or desorbed, depending on fluid composition. Our experiments show that these minerals could successfully prevent the remobilization of adsorbed Cu(II), Cd(II), Se(IV), and As(V) if carbon dioxide is intruded into a drinking water aquifer. Furthermore, a decrease in pH resulting from carbon dioxide intrusion could reactivate the adsorption of Se(IV) and As(V) if goethite and calcite are sufficiently available in the aquifer. Our results also suggest that adsorption of cadmium and copper could be promoted by calcite dissolution. These ions adsorbed on calcite are not remobilized when carbon dioxide is intruded into the system, even if calcite dissolution is intensified. On the other hand, arsenite As(III), significantly adsorbed on goethite, is partially remobilized by carbon dioxide intrusion. These results show that carbon dioxide may, in some case remobilize some toxic ions in the pore fluid, but the pH effect may also enhance adsorption of other toxic ione on calcite and goethite particles.

Sequence-stratigraphic controls on sandstone diagenesis: An example from the Williams Fork formation, Piceance Basin, Colorado

NASA Astrophysics Data System (ADS)

Aboktef, Adel

This study documents the distribution of diagenetic alterations in Williams Fork fluvial sandstones, assess sequence stratigraphic controls on diagenetic features, and addresses diagenetic impacts on porosity. Petrographic point counts of 220 thin sections from six wells forms the database. The near absence of potassium feldspar and volcanic rock fragments in the lower Williams Fork interval and increasing plagioclase content upward represent changes in sediment provenance rather than stratigraphic variability in diagenesis. The lower Williams Fork sands are from sedimentary sources whereas middle and upper Williams Fork sands include input from magmatic arcs and basement uplifts. Compaction, early and late cementation, dissolution, and replacement by calcite or clay minerals combined to alter Williams Fork sandstones. Infiltration of clays occurred prior to any burial. Chlorite, quartz, non-ferroan calcite, compaction and dissolution features, and kaolinite formed during eo-diagenesis at <70°C. More quartz, compaction and dissolution features, plus albite, illite, mixed-layer illite/smectite, ferroan calcite, and dolomite formed in the meso-diagenetic realm (>70°C). Four of these features show spatial variability with respect to systems tracts. Infiltrated clays are concentrated in lowstand systems tracts (LST) and highstand systems tracts (HST) because accommodation space rose slow or fell during deposition of those sands, which led to prolonged sand body exposure on floodplain and ample opportunities for downward percolation of mud during flood events. Concentration of pseudomatrix (mud intraclasts) in HST and LST deposits resulted from floodplain erosion when base-level fell with decreasing accommodation space. Authigenic chlorite formed in the HST and transgressive systems tracts (TST) of the upper half of the Williams Fork Formation because volcanic clasts are abundant in that interval. Quartz overgrowths are more likely to exceed 7% in TST deposits for reasons that are unknown. High total clay content (infiltrated, grain coatings, pseudomatrix) does inhibit quartz overgrowths in all systems tracts. Williams Fork sandstones form low-permeability tight-gas reservoirs. Primary porosity was almost entirely destroyed by compaction and cementation. Reservoir rock resulted from one of two pathways. Eogenetic authigenic chlorite and/or calcite inhibited quartz cementation, minimized compaction and protected some primary porosity. Alternately, dissolution of framework grains or cements created secondary porosity. The later pathway tends to be the more dominant.

Magnesium-isotope fractionation during low-Mg calcite precipitation in a limestone cave - Field study and experiments

NASA Astrophysics Data System (ADS)

Immenhauser, A.; Buhl, D.; Richter, D.; Niedermayr, A.; Riechelmann, D.; Dietzel, M.; Schulte, U.

2010-08-01

The chemical and isotopic composition of speleothem calcite and particularly that of stalagmites and flowstones is increasingly exploited as an archive of past environmental change in continental settings. Despite intensive research, including modelling and novel approaches, speleothem data remain difficult to interpret. A possible way foreword is to apply a multi-proxy approach including non-conventional isotope systems. For the first time, we here present a complete analytical dataset of magnesium isotopes (δ 26Mg) from a monitored cave in NW Germany (Bunker Cave). The data set includes δ 26Mg values of loess-derived soil above the cave (-1.0 ± 0.5‰), soil water (-1.2 ± 0.5‰), the carbonate hostrock (-3.8 ± 0.5‰), dripwater in the cave (-1.8 ± 0.2‰), speleothem low-Mg calcite (stalactites, stalagmites; -4.3 ± 0.6‰), cave loam (-0.6 ± 0.1‰) and runoff water (-1.8 ± 0.1‰) in the cave, respectively. Magnesium-isotope fractionation processes during weathering and interaction between soil cover, hostrock and solute-bearing soil water are non-trivial and depend on a number of variables including solution residence times, dissolution rates, adsorption effects and potential neo-formation of solids in the regolith and the carbonate aquifer. Apparent Mg-isotope fractionation between dripwater and speleothem low-Mg calcite is about 1000ln αMg-cc-Mg(aq) = -2.4‰. A similar Mg-isotope fractionation (1000ln αMg-cc-Mg(aq) ≈ -2.1‰) is obtained by abiogenic precipitation experiments carried out at aqueous Mg/Ca ratios and temperatures close to cave conditions. Accordingly, 26Mg discrimination during low-Mg calcite formation in caves is highly related to inorganic fractionation effects, which may comprise dehydration of Mg 2+ prior to incorporation into calcite, surface entrapment of light isotopes and reaction kinetics. Relevance of kinetics is supported by a significant negative correlation of Mg-isotope fractionation with the precipitation rate for inorganic precipitation experiments.

Experimental study of terrestrial plant litter interaction with aqueous solutions

NASA Astrophysics Data System (ADS)

Fraysse, F.; Pokrovsky, O. S.; Meunier, J.-D.

2010-01-01

Quantification of silicon and calcium recycling by plants is hampered by the lack of physico-chemical data on reactivity of plant litter in soil environments. We applied a laboratory experimental approach for determining the silica and calcium release rates from litter of typical temperate and boreal plants: pine ( Pinus laricio), birch ( Betula pubescens), larch ( Larix gmelinii), elm ( Ulmus laevis Pall.), tree fern ( Dicksonia squarrosa), and horsetail (Equisetum arvense) in 0.01 M NaCl solutions, pH of 2-10 and temperature equals to 5, 25 and 40 °C. Open system, mixed-flow reactors equipped with dialysis compartment and batch reactors were used. Comparative measurements were performed on intact larch needles and samples grounded during different time, sterilized or not and with addition or not of sodium azide in order to account for the effect of surface to mass ratio and possible microbiological activity on the litter dissolution rates. Litter degradation results suggest that the silica release rate is independent on dissolved organic carbon release (cell breakdown) which implies the presence of phytoliths in a pure "inorganic" pool not complexed with organic matter. Calcium and DOC are released at the very first stage of litter dissolution while Si concentration increases gradually suggesting the presence of Ca and Si in two different pools. The dry-weight normalized dissolution rate at circum-neutral pH range (approx. 1-10 μmol/g DW/day) is 2 orders of magnitude higher than the rates of Si release from common soil minerals (kaolinite, smectite, illite). Minimal Ca release rates evaluated from batch and mixed-flow reactors are comparable with those of most reactive soil minerals such as calcite and apatite, and several orders of magnitude higher than the dissolution rates of major rock-forming silicates (feldspars, pyroxenes). The activation energy for Si liberation from plant litter is approx. 50 kJ/mol which is comparable with that of surface-controlled mineral dissolutions. It is shown that the Si release rate from the above-ground forest biomass is capable of producing the Si concentrations observed in soil solutions of surficial horizons and contribute significantly to the Si flux from the soil to the river.

Reactive transport modelling of groundwater chemistry in a chalk aquifer at the watershed scale

NASA Astrophysics Data System (ADS)

Mangeret, A.; De Windt, L.; Crançon, P.

2012-09-01

This study investigates thermodynamics and kinetics of water-rock interactions in a carbonate aquifer at the watershed scale. A reactive transport model is applied to the unconfined chalk aquifer of the Champagne Mounts (France), by considering both the chalk matrix and the interconnected fracture network. Major element concentrations and main chemical parameters calculated in groundwater and their evolution along flow lines are in fair agreement with field data. A relative homogeneity of the aquifer baseline chemistry is rapidly reached in terms of pH, alkalinity and Ca concentration since calcite equilibrium is achieved over the first metres of the vadose zone. However, incongruent chalk dissolution slowly releases Ba, Mg and Sr in groundwater. Introducing dilution effect by rainwater infiltration and a local occurrence of dolomite improves the agreement between modelling and field data. The dissolution of illite and opal-CT, controlling K and SiO2 concentrations in the model, can be approximately tackled by classical kinetic rate laws, but not the incongruent chalk dissolution. An apparent kinetic rate has therefore been fitted on field data by inverse modelling: 1.5 × 10- 5 molchalk L - 1water year - 1. Sensitivity analysis indicates that the CO2 partial pressure of the unsaturated zone is a critical parameter for modelling the baseline chemistry over the whole chalk aquifer.

Phase-dependent phytoavailability of thallium--a synthetic soil experiment.

PubMed

Vaněk, Aleš; Mihaljevič, Martin; Galušková, Ivana; Chrastný, Vladislav; Komárek, Michael; Penížek, Vít; Zádorová, Tereza; Drábek, Ondřej

2013-04-15

The study deals with the environmental stability of Tl-modified phases (ferrihydrite, goethite, birnessite, calcite and illite) and phytoavailability of Tl in synthetically prepared soils used in a model vegetation experiment. The data presented here clearly demonstrate a strong relationship between the mineralogical position of Tl in the model soil and its uptake by the plant (Sinapis alba L.). The maximum rate of Tl uptake was observed for plants grown on soil containing Tl-modified illite. In contrast, soil enriched in Ksat-birnessite had the lowest potential for Tl release and phytoaccumulation. Root-induced dissolution of synthetic calcite and ferrihydrite in the rhizosphere followed by Tl mobilization was detected. Highly crystalline goethite was more stable in the rhizosphere, compared to ferrihydrite, leading to reduced biological uptake of Tl. Based on the results obtained, the mineralogical aspect must be taken into account prior to general environmental recommendations in areas affected by Tl. Copyright © 2013 Elsevier B.V. All rights reserved.

Calcite growth-rate inhibition by fulvic acid and magnesium ion—Possible influence on biogenic calcite formation

NASA Astrophysics Data System (ADS)

Reddy, Michael M.

2012-08-01

Increases in ocean surface water dissolved carbon dioxide (CO2) concentrations retard biocalcification by reducing calcite supersaturation (Ωc). Reduced calcification rates may influence growth-rate dependent magnesium ion (Mg) incorporation into biogenic calcite modifying the use of calcifying organisms as paleoclimate proxies. Fulvic acid (FA) at biocalcification sites may further reduce calcification rates. Calcite growth-rate inhibition by FA and Mg, two common constituents of seawater and soil water involved in the formation of biogenic calcite, was measured separately and in combination under identical, highly reproducible experimental conditions. Calcite growth rates (pH=8.5 and Ωc=4.5) are reduced by FA (0.5 mg/L) to 47% and by Mg (10-4 M) to 38%, compared to control experiments containing no added growth-rate inhibitor. Humic acid (HA) is twice as effective a calcite growth-rate inhibitor as FA. Calcite growth rate in the presence of both FA (0.5 mg/L) and Mg (10-4 M) is reduced to 5% of the control rate. Mg inhibits calcite growth rates by substitution for calcium ion at the growth site. In contrast, FA inhibits calcite growth rates by binding multiple carboxylate groups on the calcite surface. FA and Mg together have an increased affinity for the calcite growth sites reducing calcite growth rates.

Calcite growth-rate inhibition by fulvic acid and magnesium ion—Possible influence on biogenic calcite formation

USGS Publications Warehouse

Reddy, Michael M.

2012-01-01

Increases in ocean surface water dissolved carbon dioxide (CO2) concentrations retard biocalcification by reducing calcite supersaturation (Ωc). Reduced calcification rates may influence growth-rate dependent magnesium ion (Mg) incorporation into biogenic calcite modifying the use of calcifying organisms as paleoclimate proxies. Fulvic acid (FA) at biocalcification sites may further reduce calcification rates. Calcite growth-rate inhibition by FA and Mg, two common constituents of seawater and soil water involved in the formation of biogenic calcite, was measured separately and in combination under identical, highly reproducible experimental conditions. Calcite growth rates (pH=8.5 and Ωc=4.5) are reduced by FA (0.5 mg/L) to 47% and by Mg (10−4 M) to 38%, compared to control experiments containing no added growth-rate inhibitor. Humic acid (HA) is twice as effective a calcite growth-rate inhibitor as FA. Calcite growth rate in the presence of both FA (0.5 mg/L) and Mg (10−4 M) is reduced to 5% of the control rate. Mg inhibits calcite growth rates by substitution for calcium ion at the growth site. In contrast, FA inhibits calcite growth rates by binding multiple carboxylate groups on the calcite surface. FA and Mg together have an increased affinity for the calcite growth sites reducing calcite growth rates.

Templating Growth of a Pseudomorphic Lepidocrocite Microshell at the Calcite–Water Interface

DOE PAGES

Yuan, Ke; Lee, Sang Soo; Wang, Jun; ...

2018-01-05

The growth of lepidocrocite (gamma-FeOOH) has been observed through oxidation of Fe(II) on calcite (CaCO 3). Here, we seek to understand the structural relation between lepidocrocite and the calcite substrate and its growth mechanism. The formation of iron oxyhydroxide layers having distinct morphologies was observed during the dissolution of calcite in acidic Fe(II)-rich solutions. A pseudomorphic lepidocrocite shell together with multiple iron oxyhydroxide layers encapsulated within the shell was imaged by optical and transmission X-ray microscopies. The presence of a several-nanometer-thick ordered lepidocrocite film was observed by X-ray reflectivity, with the lepidocrocite (100) plane oriented parallel to the calcite (104)more » surface. Lath-shaped lepidocrocite aggregates formed during the initial precipitation, which eventually grew into clusters of parallel platy crystals. The formation of a nanometer-thick well-ordered lepidocrocite film on a pristine calcite surface appears critical for the subsequent pseudomorphic overgrowth. Detachment of the lepidocrocite film from the dissolving calcite surface yielded a free-standing pseudomorphic iron oxyhydroxide shell, suggesting weak interactions between the shell and the calcite substrate. This growth mechanism yields the potential of using carbonate minerals as templates for pseudomorphic synthesis of iron oxyhydroxides having well-defined size and morphology.« less

Carbon dioxide generation and drawdown during active orogenesis of siliciclastic rocks in the Southern Alps, New Zealand

NASA Astrophysics Data System (ADS)

Menzies, Catriona D.; Wright, Sarah L.; Craw, Dave; James, Rachael H.; Alt, Jeffrey C.; Cox, Simon C.; Pitcairn, Iain K.; Teagle, Damon A. H.

2018-01-01

Collisional mountain building influences the global carbon cycle through release of CO2 liberated by metamorphic reactions and promoting mechanical erosion that in turn increases chemical weathering and drawdown of atmospheric CO2. The Southern Alps is a carbonate-poor, siliciclastic mountain belt associated with the active Australian Pacific plate boundary. On-going, rapid tectonic uplift, metamorphism and hydrothermal activity are mobilising carbon. Here we use carbon isotope measurements of hot spring fluids and gases, metamorphic host rocks, and carbonate veins to establish a metamorphic carbon budget. We identify three major sources for CO2 within the Southern Alps: (1) the oxidation of graphite; (2) consumption of calcite by metamorphic reactions at the greenschist-amphibolite facies boundary, and (3) the dissolution of groundmass and vein-hosted calcite. There is only a minor component of mantle CO2 arising on the Alpine Fault. Hot springs have molar HCO3-/Ca2+ ∼9, which is substantially higher than produced by the dissolution of calcite indicating that deeper metamorphic processes must dominate. The total CO2 flux to the near surface environment in the high uplift region of the Southern Alps is estimated to be ∼6.4 × 108 mol/yr. Approximately 87% of this CO2 is sourced from coupled graphite oxidation (25%) and disseminated calcite decarbonation (62%) reactions during prograde metamorphism. Dissolution of calcite and mantle-derived CO2 contribute ∼10% and ∼3% respectively. In carbonate-rich orogens CO2 production is dominated by metamorphic decarbonation of limestones. The CO2 flux to the atmosphere from degassing of hot springs in the Southern Alps is 1.9 to 3.2 × 108 mol/yr, which is 30-50% of the flux to the near surface environment. By contrast, the drawdown of CO2 through surficial chemical weathering ranges between 2.7 and 20 × 109 mol/yr, at least an order of magnitude greater than the CO2 flux to the atmosphere from this orogenic belt. Thus, siliciclastic mountain belts like the Southern Alps are net sinks for atmospheric CO2, in contrast to orogens involving abundant carbonate rocks, such as the Himalaya, that are net CO2 sources.

Fabrication of low-crystalline carbonate apatite foam bone replacement based on phase transformation of calcite foam.

PubMed

Maruta, Michito; Matsuya, Shigeki; Nakamura, Seiji; Ishikawa, Kunio

2011-01-01

Carbonate apatite (CO(3)Ap) foam may be an ideal bone substitute as it is sidelined to cancellous bone with respect to its chemical composition and structure. However, CO(3)Ap foam fabricated using α-tricalcium phosphate foam showed limited mechanical strength. In the present study, feasibility of the fabrication of calcite which could be a precursor of CO(3)Ap was studied. Calcite foam was successfully fabricated by the so-called "ceramic foam" method using calcium hydroxide coated polyurethane foam under CO(2)+O(2) atmosphere. Then the calcite foam was immersed in Na(2)HPO(4) aqueous solution for phase transformation based on dissolution-precipitation reaction. When CaO-free calcite foam was immersed in Na(2)HPO(4) solution, low-crystalline CO(3)Ap foam with 93-96% porosity and fully interconnected porous structure was fabricated. The compressive strength of the foam was 25.6 ± 6 kPa. In light of these results, we concluded that the properties of the precursor foam were key factors for the fabrication of CO(3)Ap foams.

Investigating the hydrological significance of stalagmite geochemistry (Mg, Sr) using Sr isotope and particulate element records across the Late Glacial-to-Holocene transition

NASA Astrophysics Data System (ADS)

Belli, R.; Borsato, A.; Frisia, S.; Drysdale, R.; Maas, R.; Greig, A.

2017-02-01

The trace element and Sr isotope records in two coeval stalagmites characterized by different growth rates and flow regimes at Savi cave (Grotta Savi, NE Italy) reveal different sources and incorporation mechanisms for Mg and Sr. Mg is sourced primarily from dissolved cave host rock while particulate Mg derived from soil plays a subordinate role. The presence of particulate-borne Mg is inferred from the co-variation of Mg and particle-associated elements (Th, Al and Mn) which are preferentially concentrated in open columnar calcite layers. Variation in Mg concentrations corrected for particle-influenced components, the Mgc parameter, is controlled by water-rock interaction, with higher and lower Mgc during dry and wet phases, respectively. This is thought to reflect incongruent dissolution of Mg-rich phases. Correction of Sr concentrations for contributions from airborne exogenic Sr, based on 87Sr/86Sr ratios, yields the bedrock-only contribution (Src). Src variation in stalagmite calcite is influenced by speleothem growth rate and by variation of the calcite-water Sr partitioning in wet and dry phases, and only to a minor extent by incongruent dissolution of Mg-rich phases. Concentration profiles for Mgc and Srcg (corrected for growth rate effects) show inverse correlations and are inferred to show hydrological significance which is captured in a hydrological index, HI. We suggest HI provides robust information on water-rock interaction related to hydrological changes and can be utilized in both wet and semi-arid environments, provided the corrections for soil Mg and exogenic Sr can be applied with confidence. Application of the HI index allows correction of Grotta Savi oxygen isotope data, to yield a δ18Oc time series that shows when changes in moisture sources and atmospheric reorganization, or changes in moisture amount, were significant. This is especially evident during the Younger Dryas (YD). The Savi record supports the concept of a two-phase YD, marked by an increase of moisture and stronger impact of Adriatic and Mediterranean Sea influences over the northern Adriatic region from 12.3 ka onwards. Then, a large-scale atmospheric reorganization and gradual northward shift of the Polar Front caused a progressive reduction of sea influence over the region from 12.1 ka, supporting the concept of a hemispheric change.

Simulation of permeability evolution of leakage pathway in carbonate-rich caprocks in carbon sequestration

NASA Astrophysics Data System (ADS)

Guo, B.; Fitts, J. P.; Dobossy, M. E.; Peters, C. A.

2013-12-01

Geologic carbon sequestration in deep saline aquifers is a promising strategy for mitigating climate change. A major concern is the possibility of brine and CO2 migration through the caprock such as through fractures and faults. In this work, we examine the extent to which mineral dissolution will substantially alter the porosity and permeability of caprock leakage pathways as CO2-acidified brine flows through them. Three models were developed. Firstly, a reactive transport model, Permeability Evolution of Leakage pathway (PEL), was developed to simulate permeability evolution of a leakage pathway during the injection period, and assumes calcite is the only reactive mineral. The system domain is a 100 m long by 0.2 m diameter cylindrical flow path with fixed boundaries containing a rock matrix with an initial porosity of 30% and initial permeability of 1×10-13 m2. One example result is for an initial calcite volume fraction (CVF) of 0.20, in which all the calcite is dissolved after 50 years and the permeability reaches 3.2×10-13 m2. For smaller values of CVF, the permeability reaches its final value earlier but the increase in permeability is minimal. For a large value of CVF such as 0.50, the permeability could eventually reach 1×10-12 m2, but the large amount of dissolved calcium buffers the solution and slows the reaction. After 50 years the permeability change is negligible. Thus, there is a non-monotonic relationship between the amount of calcite in the rock and the resulting permeability change because of the competing dynamics of calcite dissolution and alkalinity build-up. In the second model, PEL was coupled to an existing basin-scale multiphase flow model, Princeton's Estimating Leakage Semi-Analytical (ELSA) model. The new model, ELSA-PEL, estimates the brine and CO2 leakage rates during the injection period under conditions of permeability evolution. The scenario considered in this work is for 50 years of CO2 injection into the Mt. Simon formation in the Michigan basin at an injection rate of 1 Mt/y. As an example, for a CVF value of 5%, the brine leakage rate after fifty years for a leakage pathway 1,000 m distance from the injection well is 0.88 kg/s, which is 2.4% larger than if there were no geochemical evolution of the permeability. In a sensitivity analysis with regard to the distance between the leakage pathway and the injection well, it was found that the cumulative leakage first increases with the distance and the relationship reverses after a certain distance. When the leakage pathway is farther away, the pressure increment drops leading to less acid brine flow; meanwhile, the time before the CO2 plume reaches the pathway is longer and this lengthens the reaction time with brine. Thirdly, we explored the role that SO2 would play if it were present as a co-injectant in carbon sequestration. The reaction considered is SO2 hydrolysis to form sulfurous acid. We expect the sulfurous acid will erode the calcite faster than carbonic acid because it is a stronger acid. Contrary to intuition, the simulation results showed a decrease in permeability due to CaSO3 precipitation in replacement of CaCO3, as CaSO3 has a larger molar volume.

Long-term flow-through column experiments and their relevance to natural granitoid weathering rates

USGS Publications Warehouse

White, Arthur F.; Schulz, Marjorie S.; Lawrence, Corey R.; Vivit, Davison V.; Stonestrom, David A.

2017-01-01

Four pairs of fresh and partly-weathered granitoids, obtained from well-characterized watersheds—Merced River, CA, USA; Panola, GA, USA; Loch Vale, CO, USA, and Rio Icacos, Puerto Rico—were reacted in columns under ambient laboratory conditions for 13.8 yrs, the longest running experimental weathering study to date. Low total column mass losses (<1 wt. %), correlated with the absence of pitting or surface roughening of primary silicate grains. BET surface area (SBET) increased, primarily due to Fe-oxyhydroxide precipitation. Surface areas returned to within factors of 2 to 3 of their original values after dithionite extraction. Miscible displacement experiments indicated homogeneous plug flow with negligible immobile water, commonly cited for column experiments. Fresh granitoid effluent solute concentrations initially declined rapidly, followed by much slower decreases over the next decade. Weathered granitoid effluent concentrations increased modestly over the same time period, indicating losses of natural Fe-oxide and/or clay coatings and the increased exposure of primary mineral surfaces. Corresponding (fresh and weathered) elemental effluent concentrations trended toward convergence during the last decade of reaction. NETPATH/PHREEQC code simulations indicated non-stoichiometric dissolution involving Ca release from disseminated calcite and excess K release from interlayer biotite. Effluent 87Sr/85Sr ratios reflected a progressive weathering sequence beginning and ending with 87Sr/85Sr values of plagioclase with an additional calcite input and a radiogenic biotite excursion proportional to the granitoid ages.Effluents became thermodynamically saturated with goethite and gibbsite, slightly under-saturated with kaolinite and strongly under-saturated with plagioclase, consistent with kinetically-limited weathering in which solutes such as Na varied with column flow rates. Effluent Na concentrations showed no clear trend with time during the last decade of reaction (fresh granitoids) or increased slowly with time (weathered granitoids). Analysis of cumulative Na release indicated that plagioclase dissolution achieved steady state in 3 of the 4 fresh granitoids during the last decade of reaction. Surface-area normalized plagioclase dissolution rates exhibited a narrow range (0.95 to 1.26 10-13 moles m-2 s-1), in spite of significant stoichiometric differences (An0.21 to An0.50). Rates were an order of magnitude slower than previously reported in shorter duration experiments but generally 2 to 3 orders of magnitude faster than corresponding natural analogs. CrunchFlow simulations indicated that more than a hundredfold decrease in column flow rates would be required to produce near-saturation reaction affinities that would start to slow plagioclase weathering to real-world levels. Extending simulations to approximate long term weathering in naturally weathered profiles required additional decreases in the intrinsic plagioclase dissolution and kaolinite precipitation rates and relatively large decreases in the fluid flow rate, implying that exposure to reactive mineral surfaces is significantly limited in the natural environment compared to column experiments.

Long-term flow-through column experiments and their relevance to natural granitoid weathering rates

NASA Astrophysics Data System (ADS)

White, Art F.; Schulz, Marjorie S.; Lawrence, Corey R.; Vivit, Davison V.; Stonestrom, David A.

2017-04-01

Four pairs of fresh and partly-weathered granitoids, obtained from well-characterized watersheds-Merced River, CA, USA; Panola, GA, USA; Loch Vale, CO, USA, and Rio Icacos, Puerto Rico-were reacted in columns under ambient laboratory conditions for 13.8 yrs, the longest running experimental weathering study to date. Low total column mass losses (<1 wt.%), correlated with the absence of pitting or surface roughening of primary silicate grains. BET surface area (SBET) increased, primarily due to Fe-oxyhydroxide precipitation. Surface areas returned to within factors of 2-3 of their original values after dithionite extraction. Miscible displacement experiments indicated homogeneous plug flow with negligible immobile water, commonly cited for column experiments. Fresh granitoid effluent solute concentrations initially declined rapidly, followed by much slower decreases over the next decade. Weathered granitoid effluent concentrations increased modestly over the same time period, indicating losses of natural Fe-oxide and/or clay coatings and the increased exposure of primary mineral surfaces. Corresponding (fresh and weathered) elemental effluent concentrations trended toward convergence during the last decade of reaction. NETPATH/PHREEQC code simulations indicated non-stoichiometric dissolution involving Ca release from disseminated calcite and excess K release from interlayer biotite. Effluent 87Sr/85Sr ratios reflected a progressive weathering sequence beginning and ending with 87Sr/85Sr values of plagioclase with an additional calcite input and a radiogenic biotite excursion proportional to the granitoid ages. Effluents became thermodynamically saturated with goethite and gibbsite, slightly under-saturated with kaolinite and strongly under-saturated with plagioclase, consistent with kinetically-limited weathering in which solutes such as Na varied with column flow rates. Effluent Na concentrations showed no clear trend with time during the last decade of reaction (fresh granitoids) or increased slowly with time (weathered granitoids). Analysis of cumulative Na release indicated that plagioclase dissolution achieved steady state in 3 of the 4 fresh granitoids during the last decade of reaction. Surface-area normalized plagioclase dissolution rates exhibited a narrow range (0.95-1.26 10-13 moles m-2 s-1), in spite of significant stoichiometric differences (An0.21 to An0.50). Rates were an order of magnitude slower than previously reported in shorter duration experiments but generally 2-3 orders of magnitude faster than corresponding natural analogs. CrunchFlow simulations indicated that more than a hundredfold decrease in column flow rates would be required to produce near-saturation reaction affinities that would start to slow plagioclase weathering to real-world levels. Extending simulations to approximate long term weathering in naturally weathered profiles required additional decreases in the intrinsic plagioclase dissolution and kaolinite precipitation rates and relatively large decreases in the fluid flow rate, implying that exposure to reactive mineral surfaces is significantly limited in the natural environment compared to column experiments.

Chemical and isotopic evidence for hydrogeochemical processes occurring in the Lincolnshire Limestone

NASA Astrophysics Data System (ADS)

Bishop, Philip K.; Lloyd, John W.

1990-12-01

Over 150 groundwater samples from the Lincolnshire Limestone have been analysed for pH, major ions and δ 13C ratios. Where possible, field E h and iodide concentrations were measured and methane concentrations were determined for 12 samples. Stable isotope ratios were determined for soil and rock carbonate samples. A system of zonation allows the division of hydrogeochemical processes occurring in the aquifer. The use of hydrochemical and isotope data in modelling exercises enables the re-evaluation and possible enhancement of the understanding of hydrogeochemical processes. The carbonate chemistry of outcrop groundwaters is explained by calcite saturation being achieved under open-system conditions in the soil zone. δ 13C ratios in the range - 15.99 to - 10.57‰ may be generated from a stoichiometric reaction with possible additional partial and/or simultaneous exchange with soil CO 2 or carbonate. The isotopic composition of soil carbonate shows the effects of precipitation from soil waters. The incongruent dissolution of primary depositional limestone carbonate results in increasing magnesium and strontium concentrations and increasing δ 13C ratios for the groundwaters with flow down the hydraulic gradient. As a result of incongruent dissolution, secondary calcite may be precipitated onto fissure surfaces. Significant nitrate and sulphate reduction in non-saline groundwaters is not supported by the results of hydrochemical and isotope modelling exercises. However, sulphate reduction and methane fermentation may be affecting the isotopic and chemical compositions of saline groundwaters. Sodium-calcium ion exchange leads to limited calcite dissolution deep in the aquifer, but the evolution of these groundwaters is confused by the uncertain effects of oxidation of organic carbon and mixing with a saline end-member solution.

Mechanical changes caused by CO2-driven cement dissolution in the Morrow B Sandstone at reservoir conditions: Experimental observations

NASA Astrophysics Data System (ADS)

Wu, Z.; Luhmann, A. J.; Rinehart, A. J.; Mozley, P.; Dewers, T. A.

2017-12-01

Carbon Capture, Utilization and Storage (CCUS) in transmissive reservoirs is a proposed mechanism in reducing CO2 emissions. Injection of CO2 perturbs reservoir chemistry, and can modify porosity and permeability and alter mineralogy. However, little work has been done on the coupling of rock alteration by CO2 injection and the mechanical integrity of the reservoir. In this study, we perform flow-through experiments on calcite- and dolomite-cemented Pennsylvanian Morrow B Sandstone (West Texas, USA) cores. We hypothesize that poikilotopic calcite cement has a larger impact on chemo-mechanical alteration than disseminated dolomite cement given similar CO2 exposure. With one control brine flow-through experiment and two CO2-plus-brine flow-through experiments for each cement composition, flow rates of 0.1 and 0.01 ml/min were applied under 4200 psi pore fluid pressure and 5000 psi confining pressure at 71 °C. Fluid chemistry and permeability data enable monitoring of mineral dissolution. Ultrasonic velocities were measured pre-test using 1.2 MHz source-receiver pairs at 0.5 MPa axial load and show calcite-cemented samples with higher dynamic elastic moduli than dolomite-cemented samples. Velocities measured post-experiment will identify changes from fluid-rock interaction. We plan to conduct cylinder-splitting destructive mechanical test (Brazil test) to measure the pristine and altered tensile strength of different cemented sandstones. The experiments will identify extents to which cement composition and texture control chemo-mechanical degradation of CCUS reservoirs. Funding for this project is provided by the U.S. Department of Energy's (DOE) National Energy Technology Laboratory (NETL) through the Southwest Regional Partnership on Carbon Sequestration (SWP) under Award No. DE-FC26-05NT42591. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525.

Questa baseline and pre-mining ground-water quality investigation. 3. Historical ground-water quality for the Red River Valley, New Mexico

USGS Publications Warehouse

LoVetere, Sara H.; Nordstrom, D. Kirk; Maest, Ann S.; Naus, Cheryl A.

2003-01-01

Historical ground-water quality data for 100 wells in the Red River Valley between the U.S. Geological Survey streamflow-gaging station (08265000), near Questa, and Placer Creek east of the town of Red River, New Mexico, were compiled and reviewed. The tabulation included 608 water-quality records from 23 sources entered into an electronic database. Groundwater quality data were first collected at the Red River wastewater-treatment facility in 1982. Most analyses, however, were obtained between 1994 and 2002, even though the first wells were developed in 1962. The data were evaluated by considering (a) temporal consistency, (b) quality of sampling methods, (c) charge imbalance, and (d) replicate analyses. Analyses that qualified on the basis of these criteria were modeled to obtain saturation indices for gypsum, calcite, fluorite, gibbsite, manganite, and rhodocrosite. Plots created from the data illustrate that water chemistry in the Red River Valley is predominantly controlled by calcite dissolution, congruent gypsum dissolution, and pyrite oxidation.

What was the groundwater quality before mining in a mineralized region? Lessons from the Questa Project

USGS Publications Warehouse

Nordstrom, D. Kirk

2008-01-01

The U.S. Geological Survey, in cooperation with the New Mexico Environment Department and supported by Molycorp, Inc (currently Chevron Minerals), has completed a 5-year investigation (2001-2006) to determine the pre-mining ground-water quality at Molycorp's Questa molybdenum mine in northern New Mexico. Current mine-site ground waters are often contaminated with mine-waste leachates and no data exists on premining ground-water quality so that pre-mining conditions must be inferred. Ground-water quality undisturbed by mining is often worse than New Mexico standards and data are needed to help establish closure requirements. The key to determining pre-mining conditions was to study the hydrogeochemistry of a proximal natural analog site, the Straight Creek catchment. Main rock types exposed to weathering include a Tertiary andesite and the Tertiary Amalia tuff (rhyolitic composition), both hydrothermally altered to various degrees. Two types of ground water are common in mineralized areas, acidic ground waters in alluvial debris fans with pH 3-4 and bedrock ground waters with pH 6-8. Siderite, ferrihydrite, rhodochrosite, amorphous to microcrystalline Al(OH)3, calcite, gypsum, barite, and amorphous silica mineral solubilities control concentrations of Fe(II), Fe(III), Mn(II), Al, Ca, Ba, and SiO2, depending on pH and solution composition. Concentrations at low pH are governed by element abundance and mineral weathering rates. Concentrations of Zn and Cd range from detection up to about 10 and 0.05 mg/L, respectively, and are derived primarily from sphalerite dissolution. Concentrations of Ni and Co range from detection up to 1 and 0.4 mg/L, respectively, and are derived primarily from pyrite dissolution. Concentrations of Ca and SO4 are derived from secondary gypsum dissolution and weathering of calcite and pyrite. Metal:sulfate concentration ratios are relatively constant for acidic waters, suggesting consistent weathering rates, independent of catchment. These trends, combined with lithology, mineralogy, and mineral solubility controls, provide useful constraints on pre-mining ground-water quality for the mine site where the lithology is known.

Viruses Occur Incorporated in Biogenic High-Mg Calcite from Hypersaline Microbial Mats

PubMed Central

De Wit, Rutger; Gautret, Pascale; Bettarel, Yvan; Roques, Cécile; Marlière, Christian; Ramonda, Michel; Nguyen Thanh, Thuy; Tran Quang, Huy; Bouvier, Thierry

2015-01-01

Using three different microscopy techniques (epifluorescence, electronic and atomic force microscopy), we showed that high-Mg calcite grains in calcifying microbial mats from the hypersaline lake “La Salada de Chiprana”, Spain, contain viruses with a diameter of 50–80 nm. Energy-dispersive X-ray spectrometer analysis revealed that they contain nitrogen and phosphorus in a molar ratio of ~9, which is typical for viruses. Nucleic acid staining revealed that they contain DNA or RNA. As characteristic for hypersaline environments, the concentrations of free and attached viruses were high (>1010 viruses per g of mat). In addition, we showed that acid treatment (dissolution of calcite) resulted in release of viruses into suspension and estimated that there were ~15 × 109 viruses per g of calcite. We suggest that virus-mineral interactions are one of the possible ways for the formation of nano-sized structures often described as “nanobacteria” and that viruses may play a role in initiating calcification. PMID:26115121

Thermodynamic Simulation of Carbonate Cements-Water-Carbon Dioxide Equilibrium in Sandstone for Prediction of Precipitation/Dissolution of Carbonate Cements

PubMed Central

Zhong, Xinyan; Shang, Ruishu; Huang, Lihong

2016-01-01

Carbonate cements, such as calcite, dolomite, ferrocalcite and ankerite, play important roles in the formation of pores in sandstones: precipitation of carbonate cements modifies pores and inhibits compaction, while dissolution creates secondary pores. This work proposed a precipitation-dissolution model for carbonate cements-CO2-H2O system by means of ion equilibrium concentration ([M2+], M = Ca, Mg, Fe or Mn) with different factors, such as temperature, depth, pH, PCO2, variable rock composition and overpressure. Precipitation-dissolution reaction routes were also analyzed by minimization of the total Gibbs free energy (ΔG). Δ[M2+], the variation of [Ca2+], [Fe2+], [Mg2+] or [Mn2+] for every 100 m of burial depths, is used to predict precipitation or dissolution. The calculation results indicate that the increasing temperature results in decrease of equilibrium constant of reactions, while the increasing pressure results in a relatively smaller increase of equilibrium constant; As a result, with increasing burial depth, which brings about increase of both temperature and pressure, carbonate cements dissolve firstly and produces the maximal dissolved amounts, and then precipitation happens with further increasing depth; For example, calcite is dissolving from 0.0 km to 3.0 km with a maximal value of [Ca2+] at depth of 0.8 km, and then precipitates with depth deeper than 3.0 km. Meanwhile, with an increasing CO2 mole fraction in the gaseous phase from 0.1% to 10.0% in carbonate systems, the aqueous concentration of metal ions increases, e.g., dissolved amount of CaFe0.7Mg0.3(CO3)2 increases and reaches maximum of 1.78 mmol·L-1 and 8.26 mmol·L-1 at burial depth of 0.7 km with CO2 mole fraction of 0.1% and 10.0%, respectively. For the influence of overpressure in the calcite system, with overpressure ranging from 36 MPa to 83 MPa, pH reaches a minimum of 6.8 at overpressure of 51 MPa; meanwhile, Δ[Ca2+] increases slightly from -2.24 mmol·L-1 to -2.17 mmol·L-1 and remains negative, indicating it is also a precipitation process at burial depth of 3.9 km where overpressure generated. The method used in this study can be applied in assessing burial precipitation-dissolution processes and predicting possible pores in reservoirs with carbonate cement-water-carbon dioxide. PMID:27907043

Thermodynamic Simulation of Carbonate Cements-Water-Carbon Dioxide Equilibrium in Sandstone for Prediction of Precipitation/Dissolution of Carbonate Cements.

PubMed

Duan, Yiping; Feng, Mingshi; Zhong, Xinyan; Shang, Ruishu; Huang, Lihong

2016-01-01

Carbonate cements, such as calcite, dolomite, ferrocalcite and ankerite, play important roles in the formation of pores in sandstones: precipitation of carbonate cements modifies pores and inhibits compaction, while dissolution creates secondary pores. This work proposed a precipitation-dissolution model for carbonate cements-CO2-H2O system by means of ion equilibrium concentration ([M2+], M = Ca, Mg, Fe or Mn) with different factors, such as temperature, depth, pH, [Formula: see text], variable rock composition and overpressure. Precipitation-dissolution reaction routes were also analyzed by minimization of the total Gibbs free energy (ΔG). Δ[M2+], the variation of [Ca2+], [Fe2+], [Mg2+] or [Mn2+] for every 100 m of burial depths, is used to predict precipitation or dissolution. The calculation results indicate that the increasing temperature results in decrease of equilibrium constant of reactions, while the increasing pressure results in a relatively smaller increase of equilibrium constant; As a result, with increasing burial depth, which brings about increase of both temperature and pressure, carbonate cements dissolve firstly and produces the maximal dissolved amounts, and then precipitation happens with further increasing depth; For example, calcite is dissolving from 0.0 km to 3.0 km with a maximal value of [Ca2+] at depth of 0.8 km, and then precipitates with depth deeper than 3.0 km. Meanwhile, with an increasing CO2 mole fraction in the gaseous phase from 0.1% to 10.0% in carbonate systems, the aqueous concentration of metal ions increases, e.g., dissolved amount of CaFe0.7Mg0.3(CO3)2 increases and reaches maximum of 1.78 mmol·L-1 and 8.26 mmol·L-1 at burial depth of 0.7 km with CO2 mole fraction of 0.1% and 10.0%, respectively. For the influence of overpressure in the calcite system, with overpressure ranging from 36 MPa to 83 MPa, pH reaches a minimum of 6.8 at overpressure of 51 MPa; meanwhile, Δ[Ca2+] increases slightly from -2.24 mmol·L-1 to -2.17 mmol·L-1 and remains negative, indicating it is also a precipitation process at burial depth of 3.9 km where overpressure generated. The method used in this study can be applied in assessing burial precipitation-dissolution processes and predicting possible pores in reservoirs with carbonate cement-water-carbon dioxide.

Geochemical evolution of groundwater in the Culebra dolomite near the Waste Isolation Pilot Plant, southeastern New Mexico, USA

USGS Publications Warehouse

Siegel, M.D.; Anderholm, S.

1994-01-01

The Culebra Dolomite Member of the Rustler Formation, a thin (10 m) fractured dolomite aquifer, lies approximately 450 m above the repository horizon of the Waste Isolation Pilot Plant (WIPP) in southeastern New Mexico, USA. Salinities of water in the Culebra range roughly from 10,000 to 200,000 mg/L within the WIPP site. A proposed model for the post-Pleistocene hydrochemical evolution of the Culebra tentatively identifies the major sources and sinks for many of the groundwater solutes. Reaction-path simulations with the PHRQPITZ code suggest that the Culebra dolomite is a partial chemical equilibrium system whose composition is controlled by an irreversible process (dissolution of evaporites) and equilibrium with gypsum and calcite. Net geochemical reactions along postulated modern flow paths, calculated with the NETPATH code, include dissolution of halite, carbonate and evaporite salts, and ion exchange. R-mode principal component analysis revealed correlations among the concentrations of Si, Mg, pH, Li, and B that are consistent with several clay-water reactions. The results of the geochemical calculations and mineralogical data are consistent with the following hydrochemical model: 1. (1) solutes are added to the Culebra by dissolution of evaporite minerals 2. (2) the solubilities of gypsum and calcite increase as the salinity increases; these minerals dissolve as chemical equilibrium is maintained between them and the groundwater 3. (3) equilibrium is not maintained between the waters and dolomite; sufficient Mg is added to the waters by dissolution of accessory carnallite or polyhalite such that the degree of dolomite supersaturation increases with ionic strength 4. (4) clays within the fractures and rock matrix exert some control on the distribution of Li, B, Mg, and Si via sorption, ion exchange, and dissolution. ?? 1994.

Chromatographic-ICPMS methods for trace element and isotope analysis of water and biogenic calcite

NASA Astrophysics Data System (ADS)

Klinkhammer, G. P.; Haley, B. A.; McManus, J.; Palmer, M. R.

2003-04-01

ICP-MS is a powerful technique because of its sensitivity and speed of analysis. This is especially true for refractory elements that are notoriously difficult using TIMS and less energetic techniques. However, as ICP-MS instruments become more sensitive to elements of interest they also become more sensitive to interference. This becomes a pressing issue when analyzing samples with high total dissolved solids. This paper describes two trace element methods that overcome these problems by using chromatographic techniques to precondition samples prior to analysis by ICP-MS: separation of rare earth elements (REEs) from seawater using HPLC-ICPMS, and flow-through dissolution of foraminiferal calcite. Using HPLC in combination with ICP-MS it is possible to isolate the REEs from matrix, other transition elements, and each other. This method has been developed for small volume samples (5ml) making it possible to analyze sediment pore waters. As another example, subjecting foram shells to flow-through reagent addition followed by time-resolved analysis in the ICP-MS allows for systematic cleaning and dissolution of foram shells. This method provides information about the relationship between dissolution tendency and elemental composition. Flow-through is also amenable to automation thus yielding the high sample throughput required for paleoceanography, and produces a highly resolved elemental matrix that can be statistically analyzed.

Hydrogeochemical processes in the Plio-Quaternary Remila aquifer (Khenchela, Algeria)

NASA Astrophysics Data System (ADS)

Aouidane, Laiche; Belhamra, Mohamed

2017-06-01

The Remila Plain is a synclinal structure in northeast Algeria, situated within a semi-arid climate zone and composed of Mio-Pliocene-Quaternary deposits. Within the syncline, the Plio-Quaternary aquifer is the main source of drinking water for cattle and for agricultural irrigation water. This work aims to investigate the origin of groundwater mineralization and to identify the primary hydrogeochemical processes controlling groundwater evolution in the Remila aquifer. A total of 86 water samples from boreholes were analyzed for major, minor and stable isotopes (18O, 2H) over three seasons: first during low water levels in 2013, second during high water levels in 2014 and third for stable isotopes during low water levels in 2015. The analysis showed that the aquifer is controlled by five principal geochemical processes: (I) the dissolution of evaporite rocks, (II) cation exchange and reverse exchange reactions, (III) congruent dissolution of carbonates (calcite, dolomite) coupled with the dissolution of gypsum and calcite precipitation, (IV) sulfate reduction under anaerobic conditions, and (V) saltwater intrusion in the northeastern Sabkha plains. The 18O and deuterium concentrations in groundwater are very low, indicating that the aquifer is recharged by evaporated rainfall originating from the north slope of the Aurès Mountains which confirms that the aquifer is recharged in the southern part of the plain.

Groundwater hydrochemistry in the active layer of the proglacial zone, Finsterwalderbreen, Svalbard

USGS Publications Warehouse

Cooper, R.J.; Wadham, J.L.; Tranter, M.; Hodgkins, R.; Peters, N.E.

2002-01-01

Glacial bulk meltwaters and active-layer groundwaters were sampled from the proglacial zone of Finsterwalderbreen during a single melt season in 1999, in order to determine the geochemical processes that maintain high chemical weathering rates in the proglacial zone of this glacier. Results demonstrate that the principle means of solute acquisition is the weathering of highly reactive moraine and fluvial active-layer sediments by supra-permafrost groundwaters. Active-layer groundwater derives from the thaw of the proglacial snowpack, buried ice and glacial bulk meltwaters. Groundwater evolves by sulphide oxidation and carbonate dissolution. Evaporation- and freeze-concentration of groundwater in summer and winter, respectively produce Mg-Ca-sulphate salts on the proglacial surface. Re-dissolution of these salts in early summer produces groundwaters that are supersaturated with respect to calcite. There is a pronounced spatial pattern to the geochemical evolution of groundwater. Close to the main proglacial channel, active layer sediments are flushed diurnally by bulk meltwaters. Here, Mg-Ca-sulphate deposits become exhausted in the early season and geochemical evolution proceeds by a combination of sulphide oxidation and carbonate dissolution. At greater distances from the channel, the dissolution of Mg-Ca-sulphate salts is a major influence and dilution by the bulk meltwaters is relatively minor. The influence of sulphate salt dissolution decreases during the sampling season, as these salts are exhausted and waters become increasingly routed by subsurface flowpaths. ?? 2002 Elsevier Science B.V. All rights reserved.

Hot spring deposits on a cliff face: A case study from Jifei, Yunnan Province, China

NASA Astrophysics Data System (ADS)

Jones, Brian; Peng, Xiaotong

2014-04-01

A cliff face in the Jifei karst area, southwest China, is covered by a spectacular succession of precipitates that formed from the hot spring water that once flowed down its surface. This layered succession is formed of aragonite layers that are formed largely of “fountain dendrites”, calcite layers that are formed mostly of “cone dendrites”, and microlaminated layers that contain numerous microbes and extracellular polymeric substances (EPS). Many of the aragonite crystals are hollow due to preferential dissolution of their cores. The calcite cone dendrites are commonly covered with biofilms, reticulate Si-Mg coatings, and other precipitates. The microbial layers include dodecahedral calcite crystals and accessory minerals that include opal-A, amorphous Si-Mg coatings, trona, barite, potassium sulfate crystals, mirabillite, and gaylussite. Interpretation of the δ18O(calcite) and δ18O(aragonite) indicates precipitation from water with a temperature of 54 to 66 °C. The active hot spring at the top of the cliff presently ejects water at a temperature of 65 °C. Layers, 1 mm to 6 cm thick, record temporal changes in the fluids from which the precipitates formed. This succession is not, however, formed of recurring cycles that can be linked to diurnal or seasonal changes in the local climate. Indeed, it appears that the climatic contrast between the wet season and the dry season had little impact on precipitation from the spring waters that flowed down the cliff face. Integration of currently available evidence suggests that the primary driving force was aperiodic changes in the CO2 content of the spring waters because that seems to be the prime control on the saturation levels that underpinned precipitation of the calcite and aragonite as well as the dissolution of the aragonite. Such variations in the CO2 content of the spring water were probably due to changes that took place in the subterranean plumbing system of the spring.

Reactive transport modelling of groundwater chemistry in a chalk aquifer at the watershed scale.

PubMed

Mangeret, A; De Windt, L; Crançon, P

2012-09-01

This study investigates thermodynamics and kinetics of water-rock interactions in a carbonate aquifer at the watershed scale. A reactive transport model is applied to the unconfined chalk aquifer of the Champagne Mounts (France), by considering both the chalk matrix and the interconnected fracture network. Major element concentrations and main chemical parameters calculated in groundwater and their evolution along flow lines are in fair agreement with field data. A relative homogeneity of the aquifer baseline chemistry is rapidly reached in terms of pH, alkalinity and Ca concentration since calcite equilibrium is achieved over the first metres of the vadose zone. However, incongruent chalk dissolution slowly releases Ba, Mg and Sr in groundwater. Introducing dilution effect by rainwater infiltration and a local occurrence of dolomite improves the agreement between modelling and field data. The dissolution of illite and opal-CT, controlling K and SiO(2) concentrations in the model, can be approximately tackled by classical kinetic rate laws, but not the incongruent chalk dissolution. An apparent kinetic rate has therefore been fitted on field data by inverse modelling: 1.5×10(-5) mol(chalk)L (-1) water year (-1). Sensitivity analysis indicates that the CO(2) partial pressure of the unsaturated zone is a critical parameter for modelling the baseline chemistry over the whole chalk aquifer. Copyright © 2012 Elsevier B.V. All rights reserved.

A dissolution model that accounts for coverage of mineral surfaces by precipitation in core floods

NASA Astrophysics Data System (ADS)

Pedersen, Janne; Jettestuen, Espen; Madland, Merete V.; Hildebrand-Habel, Tania; Korsnes, Reidar I.; Vinningland, Jan Ludvig; Hiorth, Aksel

2016-01-01

In this paper, we propose a model for evolution of reactive surface area of minerals due to surface coverage by precipitating minerals. The model is used to interpret results from an experiment where a chalk core was flooded with MgCl2 for 1072 days, giving rise to calcite dissolution and magnesite precipitation. The model successfully describes both the long-term behavior of the measured effluent concentrations and the more or less homogeneous distribution of magnesite found in the core after 1072 days. The model also predicts that precipitating magnesite minerals form as larger crystals or aggregates of smaller size crystals, and not as thin flakes or as a monomolecular layer. Using rate constants obtained from literature gave numerical effluent concentrations that diverged from observed values only after a few days of flooding. To match the simulations to the experimental data after approximately 1 year of flooding, a rate constant that is four orders of magnitude lower than reported by powder experiments had to be used. We argue that a static rate constant is not sufficient to describe a chalk core flooding experiment lasting for nearly 3 years. The model is a necessary extension of standard rate equations in order to describe long term core flooding experiments where there is a large degree of textural alteration.

Amplitude of late Miocene sea-level fluctuations from karst development in reef-slope deposits (SE Spain)

NASA Astrophysics Data System (ADS)

Reolid, Jesús; Betzler, Christian; Braga, Juan Carlos

2016-11-01

A prograding late Miocene carbonate platform in southern Spain revealing different sea-level pinning points was analysed with the aim to increase the accuracy of reconstruction of past sea-level changes. These pinning points are distinct diagenetic zones (DZ) and the position of reef-framework deposits. DZ1 is defined by the dissolution of bioclastic components and DZ2 by calcitic cement precipitation in dissolution pores. Calcite cements are granular and radiaxial fibrous, and are of meteoric origin as deduced from cathodoluminescence, EDX spectroscopy, as well as from δ13C and δ18O isotope analyses. DZ3 has moldic porosity after aragonitic bioclasts with minor granular calcitic cements. DZ1 and DZ2 indicate karstification and the development of a coastal palaeoaquifer during a sea-level lowstand. DZ3 diagenetic features are related to the final subaerial exposure of the section during the Messinian Salinity Crisis. Facies and diagenetic data reveal a complete cycle of sea-level fall (23 ± 1 m) and rise (31 ± 1 m). A robust age model based on magneto- and cyclostratigraphy for these deposits places this cycle between 5.89 and 5.87 Ma. Therefore, for the first time, this work allows a direct comparison of an outcrop with a pelagic marine proxy record of a specific Neogene sea-level fluctuation.

Inverse geochemical modeling of groundwater evolution with emphasis on arsenic in the Mississippi River Valley alluvial aquifer, Arkansas (USA)

USGS Publications Warehouse

Sharif, M.U.; Davis, R.K.; Steele, K.F.; Kim, B.; Kresse, T.M.; Fazio, J.A.

2008-01-01

Inverse geochemical modeling (PHREEQC) was used to identify the evolution of groundwater with emphasis on arsenic (As) release under reducing conditions in the shallow (25-30 m) Mississippi River Valley Alluvial aquifer, Arkansas, USA. The modeling was based on flow paths defined by high-precision (??2 cm) water level contour map; X-ray diffraction (XRD), scanning electron microscopic (SEM), and chemical analysis of boring-sediments for minerals; and detailed chemical analysis of groundwater along the flow paths. Potential phases were constrained using general trends in chemical analyses data of groundwater and sediments, and saturation indices data (MINTEQA2) of minerals in groundwater. Modeling results show that calcite, halite, fluorite, Fe oxyhydroxide, organic matter, H2S (gas) were dissolving with mole transfers of 1.40E - 03, 2.13E - 04, 4.15E - 06, 1.25E + 01, 3.11, and 9.34, respectively along the dominant flow line. Along the same flow line, FeS, siderite, and vivianite were precipitating with mole transfers of 9.34, 3.11, and 2.64E - 07, respectively. Cation exchange reactions of Ca2+ (4.93E - 04 mol) for Na+ (2.51E - 04 mol) on exchange sites occurred along the dominant flow line. Gypsum dissolution reactions were dominant over calcite dissolution in some of the flow lines due to the common ion effect. The concentration of As in groundwater ranged from <0.5 to 77 ??g/L. Twenty percent total As was complexed with Fe and Mn oxyhydroxides. The redox environment, chemical data of sediments and groundwater, and the results of inverse geochemical modeling indicate that reductive dissolution of Fe oxyhydroxide is the dominant process of As release in the groundwater. The relative rate of reduction of Fe oxyhydroxide over SO42 - with co-precipitation of As into sulfide is the limiting factor controlling dissolved As in groundwater. ?? 2007 Elsevier B.V. All rights reserved.

Post-deformational relocation of mica grains in calcite-dolomite marbles identified by cathodoluminescence microscopy

NASA Astrophysics Data System (ADS)

Kuehn, Rebecca; Duschl, Florian; Leiss, Bernd

2017-04-01

Hot-cathodoluminescence-microscopy (CL) reveals micas which are rotated or shifted within a calcite fabric from a foliation parallel to a random orientation. This feature has been recognized in calcite-dolomite marble samples from the locations Hammerunterwiesenthal, Erzgebirge, Germany and the Alpi Apuane, Italy. As obtained from petrographic thin section analysis, the micas either moved totally within a single calcite grain or from a grain boundary position, and then the calcite grain growth was dragged with the movement of the mica grain. In the moved-through grain, features like fluid-inclusions, twins or cleavage faces are erased and a new, clear calcite phase developed. This indicates dissolution-precipitation as process which led to the new calcite phase. As former deformation features are erased it can be assumed that the mica relocation is a fluid-driven, post-deformational equilibration process. In CL the new calcite mineral phase shows a zonation indicating a polycyclic process. Calcite CL gradually changes from a very dark purple, exactly as the surrounding grains, to a bright orange CL and supports the idea of fluid-induced deformation relocation. We suppose a specific lattice relationship between mica and calcite as initial driving factor for mica relocation. This recrystallization mechanism is probably supported by fluids - either from an external source or developed during retrograde metamorphosis fluid inclusion studies shall identify formation temperatures and origin of involved fluids and thereby clarify the timing of the post-deformational mica rotation. EBSD analysis of involved calcite and mica grains shall reveal a possible systematic relationship between the orientation of the hosting grains, the orientation of the mica and the final position of the mica. It will be interesting to learn in the future, if this kind of calcite-mica microstructure is a general phenomenon and how it can contribute to the understanding of fabric development.

Calcite growth-rate inhibition by fulvic acids isolated from Big Soda Lake, Nevada, USA, The Suwannee River, Georgia, USA and by polycarboxylic acids

USGS Publications Warehouse

Reddy, Michael M.; Leenheer, Jerry

2011-01-01

Calcite crystallization rates are characterized using a constant solution composition at 25°C, pH=8.5, and calcite supersaturation (Ω) of 4.5 in the absence and presence of fulvic acids isolated from Big Soda Lake, Nevada (BSLFA), and a fulvic acid from the Suwannee River, Georgia (SRFA). Rates are also measured in the presence and absence of low-molar mass, aliphatic-alicyclic polycarboxylic acids (PCA). BSLFA inhibits calcite crystal-growth rates with increasing BSLFA concentration, suggesting that BSLFA adsorbs at growth sites on the calcite crystal surface. Calcite growth morphology in the presence of BSLFA differed from growth in its absence, supporting an adsorption mechanism of calcite-growth inhibition by BSLFA. Calcite growth-rate inhibition by BSLFA is consistent with a model indicating that polycarboxylic acid molecules present in BSLFA adsorb at growth sites on the calcite crystal surface. In contrast to published results for an unfractionated SRFA, there is dramatic calcite growth inhibition (at a concentration of 1 mg/L) by a SRFA fraction eluted by pH 5 solution from XAD-8 resin, indicating that calcite growth-rate inhibition is related to specific SRFA component fractions. A cyclic PCA, 1, 2, 3, 4, 5, 6-cyclohexane hexacarboxylic acid (CHXHCA) is a strong calcite growth-rate inhibitor at concentrations less than 0.1 mg/L. Two other cyclic PCAs, 1, 1 cyclopentanedicarboxylic acid (CPDCA) and 1, 1 cyclobutanedicarboxylic acid (CBDCA) with the carboxylic acid groups attached to the same ring carbon atom, have no effect on calcite growth rates up to concentrations of 10 mg/L. Organic matter ad-sorbed from the air onto the seed crystals has no effect on the measured calcite crystal-growth rates.

Biological reduction of chlorinated solvents: Batch-scale geochemical modeling

NASA Astrophysics Data System (ADS)

Kouznetsova, Irina; Mao, Xiaomin; Robinson, Clare; Barry, D. A.; Gerhard, Jason I.; McCarty, Perry L.

2010-09-01

Simulation of biodegradation of chlorinated solvents in dense non-aqueous phase liquid (DNAPL) source zones requires a model that accounts for the complexity of processes involved and that is consistent with available laboratory studies. This paper describes such a comprehensive modeling framework that includes microbially mediated degradation processes, microbial population growth and decay, geochemical reactions, as well as interphase mass transfer processes such as DNAPL dissolution, gas formation and mineral precipitation/dissolution. All these processes can be in equilibrium or kinetically controlled. A batch modeling example was presented where the degradation of trichloroethene (TCE) and its byproducts and concomitant reactions (e.g., electron donor fermentation, sulfate reduction, pH buffering by calcite dissolution) were simulated. Local and global sensitivity analysis techniques were applied to delineate the dominant model parameters and processes. Sensitivity analysis indicated that accurate values for parameters related to dichloroethene (DCE) and vinyl chloride (VC) degradation (i.e., DCE and VC maximum utilization rates, yield due to DCE utilization, decay rate for DCE/VC dechlorinators) are important for prediction of the overall dechlorination time. These parameters influence the maximum growth rate of the DCE and VC dechlorinating microorganisms and, thus, the time required for a small initial population to reach a sufficient concentration to significantly affect the overall rate of dechlorination. Self-inhibition of chlorinated ethenes at high concentrations and natural buffering provided by the sediment were also shown to significantly influence the dechlorination time. Furthermore, the analysis indicated that the rates of the competing, nonchlorinated electron-accepting processes relative to the dechlorination kinetics also affect the overall dechlorination time. Results demonstrated that the model developed is a flexible research tool that is able to provide valuable insight into the fundamental processes and their complex interactions during bioremediation of chlorinated ethenes in DNAPL source zones.

Geochemistry of speleothems affected by aragonite to calcite recrystallization - Potential inheritance from the precursor mineral

NASA Astrophysics Data System (ADS)

Domínguez-Villar, David; Krklec, Kristina; Pelicon, Primož; Fairchild, Ian J.; Cheng, Hai; Edwards, Lawrence R.

2017-03-01

Formerly aragonite speleothems recrystallized to calcite result from solutions subsaturated in aragonite and supersaturated in calcite that infiltrate into the speleothem through the interconnected porosity. In most cases, the crystal replacement takes place through a thin solution film. This diagenetic process can occur under open or semi-closed geochemical conditions. Thus, secondary calcite crystals record the composition of the fluid at the time of diagenesis affected by calcite partition coefficients and fractionation factors (open system) or partly inherit the composition of the primary aragonite (semi-closed system). So, whether or not recrystallized aragonite speleothems can record reliable geochemical signals from the time of speleothem primary deposition still is an open debate. We studied a stalagmite from Eagle Cave (Spain) predominantly composed of secondary calcite that replaced aragonite, although a core of primary aragonite extending 45 mm along the growth direction was preserved at the base of the sample. We obtained Mg and Sr compositional maps, paired U-Th dating and δ18O and δ13C profiles across the diagenetic front. Additionally, two parallel isotope records were obtained along the speleothem growth direction in the aragonite and calcite sectors. Our results support that recrystallization of this speleothem took place in open system conditions for δ18O, δ13C, Mg and Sr, but in semi-closed system conditions for U and Th. The recrystallization of this sample took place during one or several events, likely after the Younger Dryas as a result of climate change influencing drip water composition. Based on compositional zoned patterns, we suggest that the advance of diagenetic fronts in this speleothem had an average rate of 50 ± 45 μm/yr. Such recrystallization rate can transform any aragonite speleothem into calcite within a few centuries. We suggest that the volume of water interacting with the speleothem at the time of recrystallization is of critical importance for inheritance of different elements. The volume of solution is controlled by (1) the discharge of water passing through the sample and (2) the lapse time between aragonite dissolution and calcite precipitation. Hydrology and hydrochemistry of the interacting solution, together with the mineralogy and texture of the speleothem are the essential controls for the diagenesis of the speleothem. Recrystallization of aragonite speleothems does not follow stratigraphical levels of the sample but occurs along sites with preferential flow paths in any sector of the speleothem. In these cases the relationship between age and distance from base is not preserved. However, alternation of periods of recrystallization with periods of aragonite precipitation causing speleothem accretion can result in recrystallized speleothems with coherent distance from the base-age relationship. Thus, early diagenesis of speleothems affected by seasonal or inter-annual oscillation of drip waters supersaturated and subsaturated in aragonite may provide best-scenario conditions for dating and preservation of paleoenvironmental records along recrystallized speleothems. However, even in this scenario, the variable discharge and the diagenetic rate control the geochemical inheritance from the primary aragonite crystals.

Origin and significance of postore dissolution collapse breccias cemented with calcite and barite at the Meikle gold deposit, Northern Carlin trend, Nevada

USGS Publications Warehouse

Emsbo, P.; Hofstra, A.H.

2003-01-01

The final event in a complicated hydrothermal history at the Meikle gold deposit was gold deficient but caused extensive postore dissolution of carbonate, collapse brecciation, and precipitation of calcite and barite crystals in the resulting cavities. Although previously interpreted to be part of the Carlin-type hydrothermal system, crosscutting relationships and U-Th-Pb geochronology constrain this hydrothermal event to late Pliocene time (ca. 2 Ma), nearly 36 Ma after ore formation. Mineralogic, fluid inclusion, and stable isotope data indicate that postore hydrothermal fluids were reduced, H2S-rich, unevolved meteoric waters ((??18O = -17???) of low temperature (ca. 65??C). The ??18O values of barite and calcite indicate that these minerals were in isotopic equilibrium, requiring that barite SO4 was derived from the oxidation of reduced sulfur; however, preexisting sulfides in breccia cavities were not oxidized. The ??34S (15???) values of barite are higher than those of local bulk sulfide and supergene alunite indicating that SO4 was not derived from supergene oxidation of local sulfide minerals. The 15 per mil ??34S value suggests that the H2S in the fluids may have been leached from sulfur-rich organic matter in the local carbonaceous sedimentary rocks. A reduced H2S-rich fluid is also supported by the bright cathodoluminescence of calcite which indicates that it is Mn rich and Fe poor. Calcite has a narrow range of ??13C values (0.3-1.8???) that are indistinguishable from those of the host Bootstrap limestone, indicating that CO2 in the fluid was from dissolution of the local limestone. These data suggest that dissolution and brecciation of the Bootstrap limestone occurred where H2S-rich fluids encountered more oxidizing fluids and formed sulfuric acid (H2SO4). Intense fracturing in the mine area by previous structural and hydrothermal events probably provided conduits for the descent of oxidized surface water which mixed with the underlying H2S-rich waters to form the dissolving acid. The surface-derived fluid apparently contained sufficient oxygen to produce H2SO4 from H2S but not enough to alter pyrite to Fe oxide. Although H2S is an important gold-transporting ligand, the temperature was too low to transport a significant amount of gold. The presence of analogous calcite- and barite-lined cavities in other Carlin-type deposits suggests that the generation (and oxidation) of H2S-rich meteoric waters was a common phenomenon in north-central Nevada. Previous sulfur isotope studies have also shown that the Paleozoic sedimentary rocks were the principal source of H2S in Devonian sedimentary exhalative-type, Jurassic intrusion-related, Eocene Carlin-type, and Miocene low-sulfidation gold deposits in the region. The similar sulfur source in all of these systems suggests that basin brines, magmatic fluids, and meteoric waters all evolved to be H2S-rich ore fluids by circulation through Paleozoic sedimentary rocks. Thus, although not directly related to gold mineralization, the recent hydrologic history of the deposit provides important clues to earlier ore-forming processes that were responsible for gold mineralization.

Aragonite preservation in late Quaternary sediment cores on the Brazilian Continental Slope: implications for intermediate water circulation

NASA Astrophysics Data System (ADS)

Gerhardt, S.; Groth, H.; Rühlemann, C.; Henrich, R.

We present late Quaternary records of aragonite preservation determined for sediment cores recovered on the Brazilian Continental Slope (1790-2585m water depth) where North Atlantic Deep Water (NADW) dominates at present. We have used various indirect dissolution proxies (carbonate content, aragonite/calcite contents, and sand percentages) as well as gastropodal abundances and fragmentation of Limacina inflata to determine the state of aragonite preservation. In addition, microscopic investigations of the dissolution susceptibility of three Limacina species yielded the Limacina Dissolution Index which correlates well with most of the other proxies. Excellent preservation of aragonite was found in the Holocene section, whereas aragonite dissolution gradually increases downcore. This general pattern is attributed to an overall increase in aragonite corrosiveness of pore waters. Overprinted on this early diagenetic trend are high-frequency fluctuations of aragonite preservation, which may be related to climatically induced variations of intermediate water masses.

On the existence of stationary reaction fronts in precipitation-dissolution systems

NASA Astrophysics Data System (ADS)

Kondratiuk, Paweł; Nizinkiewicz, Hanna; Ladd, Anthony JC; Szymczak, Piotr

2014-05-01

Coupled precipitation-dissolution processes are ubiquitous in hydrogeochemical systems which are out of chemical equilibrium. However, as already remarked by Ortoleva et al. [1], the precipitation front will in general move with a velocity different form that of a dissolution front; thus the distance between them will increase in time. However, there are a number of systems where the both fronts appear to move with the same velocity. One example is the terra rossa formation process [2], in which kaolinite precipitation produces hydrogen ions that dissolve the underlying calcite. In this case the velocities of the dissolution and precipitation front agree to within 1%, which does not seem accidental. In this communication, we propose a possible mechanism of such a front synchronization, and study its further implications for the dynamics of the system. [1] P. Ortoleva et al., Physica D: 19, 334 (1986) [2] E. Merino and A. Banjerjee, J. Geol., 116, 62 (2008)

Stable carbon isotopes and lipid biomarkers provide new insight into the formation of calcite and siderite concretions in organic-matter rich deposits

NASA Astrophysics Data System (ADS)

Baumann, Lydia; Birgel, Daniel; Wagreich, Michael; Peckmann, Jörn

2015-04-01

Carbonate concretions from two distinct settings have been studied for their petrography, stable carbon and oxygen isotopes, and lipid biomarker content. Carbonate concretions are in large part products of microbial degradation of organic matter, as for example by sulfate-reducing bacteria, iron-reducing bacteria, and methanogenic archaea. For these prokaryotes certain lipid biomarkers such as hopanoids, terminally-branched fatty acids (bacteria) and isoprenoids (archaea) are characteristic. Two different types of concretions were studied: a) Upper Miocene septarian calcite concretions of the southern Vienna Basin embedded in brackish sediments represented by partly bituminous calcareous sands, silts and clays; b) Paleocene-Eocene siderite concretions enclosed in marine, sandy to silty turbidites with varying carbonate contents and marl layers from the Upper Gosau Subgroup in northern Styria. Calcite concretions consist of abundant calcite microspar (80-90 vol.%), as well as detrital minerals and iron oxyhydroxides. The septarian cracks show beginning cementation with dog-tooth calcite to varying degrees. Framboidal pyrite occurs in some of the calcite concretions, pointing to bacterial sulfate reduction. Siderite concretions consist of even finer carbonate crystals, mainly siderite (40-70 vol.%) but also abundant ferroan calcite, accompanied by iron oxyhydroxides and detrital minerals. The δ13C values of the calcite concretions (-6.8 to -4.1o ) most likely reflect a combination of bacterial organic matter oxidation and input of marine biodetrital carbonate. The δ18O values range from -8.9 to -7.8o agreeing with a formation within a meteoric environment. The surrounding host sediment shows about 1-2o higher δ13C and δ18O values. The siderite δ13C values (-11.1 to -7.5o ) point to microbial respiration of organic carbon and the δ18O values (-3.5 to +2.2o ) agree with a marine depositional environment. In contrast to the calcite concretions, the stable isotope composition of the host sediment differs significantly from the siderite concretions. The δ13C values of the Gosau host sediment reflect marine conditions, whereas the oxygen isotope values are best explained by meteoric overprint. Lipid biomarkers have been extracted before and after dissolution of the concretions in order to assess their authenticity and to exclude recent surface contamination. In the following, only the biomarkers extracted after dissolution are discussed, since they are thought to be related to concretion formation. The calcite concretions comprise abundant plant wax derived long-chain n-alkanes, reflecting high terrestrial input. Bacterial, terminally-branched fatty acids were found, but in overall low abundance. The siderite concretions did not yield biomarkers due to their high maturity. No archaeal biomarkers were found in any of the concretions. Considering the presence of framboidal pyrite, the moderately low δ13C values, and the biomarker inventory, bacterial sulfate reduction apparently contributed to the formation of the calcite concretions in a brackish environment. In contrast, ongoing sulfate reduction and resultant hydrogen sulfide production inhibit siderite precipitation. Therefore, the low δ13C values of the siderite concretions are best explained by bacterial iron reduction.

Microfacies and diagenesis of the Middle Jurassic Dhruma carbonates, southwest Riyadh, Saudi Arabia

NASA Astrophysics Data System (ADS)

El-Sorogy, Abdelbaset S.; Galmed, Mahmoud A.; Al-Kahtany, Khaled; Al-Zahrani, Ali

2017-06-01

In order to document the microfacies analysis and diagenetic alterations of the Middle Jurassic Dhruma Formation at southwest Riyadh City of central Saudi Arabia, a stratigraphic section was studied in detail at Khashm adh Dhi'bi area. Mudstones, wackstones, packstones, grainstones and boundstones are the main microfacies types in the studied area. These microfacies types with field investigations and fossil content indicated an environment ranging from deep shelf to organic buildup on platform margins for the studied carbonates. Cementation and recrystallization, dissolution, fragmentation and compaction, silicification, dolomitization, and bioerosion were the main diagenetic alterations affected the carbonate rocks of the Dhruma Formation. Cementation and recrystallization are represented by equant calcite crystals, Dog-tooth fringes of thin isopachous calcites and blocky low Mg-calcites. Gastrochaenolites, Trypanites and Meandropolydora spp. were the most bioeroders in coral heads and large bivalves and hardgrounds. These bioeroders indicated a long post-mortem period during the early diagenetic stage.

Modelling karst aquifer evolution in fractured, porous rocks

NASA Astrophysics Data System (ADS)

Kaufmann, Georg

2016-12-01

The removal of material in soluble rocks by physical and chemical dissolution is an important process enhancing the secondary porosity of soluble rocks. Depending on the history of the soluble rock, dissolution can occur either along fractures and bedding partings of the rock in the case of a telogenetic origin, or within the interconnected pore space in the case of eogenetic origin. In soluble rocks characterised by both fractures and pore space, dissolution in both flow compartments is possible. We investigate the dissolution of calcite both along fractures and within the pore space of a limestone rock by numerical modelling. The limestone rock is treated as fractured, porous aquifer, in which the hydraulic conductivity increases with time both for the fractures and the pore spaces. We show that enlargement of pore space by dissolution will accelerate the development of a classical fracture-dominated telogenetic karst aquifer, breakthrough occurs faster. In the case of a pore-controlled aquifer as in eogenetic rocks, enlargement of pores results in a front of enlarged pore spaces migrating into the karst aquifer, with more homogeneous enlargement around this dissolution front, and later breakthrough.

Nanobacteria-like calcite single crystals at the surface of the Tataouine meteorite

PubMed Central

Benzerara, Karim; Menguy, Nicolas; Guyot, François; Dominici, Christian; Gillet, Philippe

2003-01-01

Nanobacteria-like objects evidenced at the surface of the orthopyroxenes of the Tataouine meteorite in South Tunisia have been studied by scanning and transmission electron microscopies. A method of micromanipulation has been developed to ensure that exactly the same objects were studied by both methods. We have shown that the nanobacteria-like objects are spatially correlated with filaments of microorganisms that colonized the surface of the meteoritic pyroxene during its 70 years of residence in the aridic Tataouine soil. Depressions of a few micrometers in depth are observed in the pyroxene below the carbonates, indicating preferential dissolution of the pyroxene and calcite precipitation at these locations. The nanobacteria-like small rods that constitute calcium carbonate rosettes are well crystallized calcite single crystals surrounded by a thin amorphous layer of carbonate composition that smoothes the crystal edges and induces rounded shapes. Those morphologies are unusual for calcite single crystals observed in natural samples. A survey of recent literature suggests that the intervention of organic compounds derived from biological activity is likely in their formation. PMID:12792020

Nanobacteria-like calcite single crystals at the surface of the Tataouine meteorite.

PubMed

Benzerara, Karim; Menguy, Nicolas; Guyot, Francois; Dominici, Christian; Gillet, Philippe

2003-06-24

Nanobacteria-like objects evidenced at the surface of the orthopyroxenes of the Tataouine meteorite in South Tunisia have been studied by scanning and transmission electron microscopies. A method of micromanipulation has been developed to ensure that exactly the same objects were studied by both methods. We have shown that the nanobacteria-like objects are spatially correlated with filaments of microorganisms that colonized the surface of the meteoritic pyroxene during its 70 years of residence in the aridic Tataouine soil. Depressions of a few micrometers in depth are observed in the pyroxene below the carbonates, indicating preferential dissolution of the pyroxene and calcite precipitation at these locations. The nanobacteria-like small rods that constitute calcium carbonate rosettes are well crystallized calcite single crystals surrounded by a thin amorphous layer of carbonate composition that smoothes the crystal edges and induces rounded shapes. Those morphologies are unusual for calcite single crystals observed in natural samples. A survey of recent literature suggests that the intervention of organic compounds derived from biological activity is likely in their formation.

Hydrodynamic-Driven Stability Analysis of Morphological Patterns on Stalactites and Implications for Cave Paleoflow Reconstructions

NASA Astrophysics Data System (ADS)

Camporeale, Carlo; Ridolfi, Luca

2012-06-01

A novel hydrodynamic-driven stability analysis is presented for surface patterns on speleothems, i.e., secondary sedimentary cave deposits, by coupling fluid dynamics to the geochemistry of calcite precipitation or dissolution. Falling film theory provides the solution for the flow-field and depth perturbations, the latter being crucial to triggering patterns known as crenulations. In a wide range of Reynolds numbers, the model provides the dominant wavelengths and pattern celerities, in fair agreement with field data. The analysis of the phase velocity of ridges on speleothems has a potential as a proxy of past film flow rates, thus suggesting a new support for paleoclimate analyses.

Monohydrocalcite: a promising remediation material for hazardous anions

PubMed Central

Fukushi, Keisuke; Munemoto, Takashi; Sakai, Minoru; Yagi, Shintaro

2011-01-01

The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO3·H2O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO4 in solution (>30 μM) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO4 than calcite and aragonite. The modes of PO4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly higher than simple adsorption on calcite. PMID:27877452

Monohydrocalcite: a promising remediation material for hazardous anions.

PubMed

Fukushi, Keisuke; Munemoto, Takashi; Sakai, Minoru; Yagi, Shintaro

2011-12-01

The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO 3 ·H 2 O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO 4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO 4 in solution (>30 μM) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO 4 than calcite and aragonite. The modes of PO 4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly higher than simple adsorption on calcite.

Monohydrocalcite: a promising remediation material for hazardous anions

NASA Astrophysics Data System (ADS)

Fukushi, Keisuke; Munemoto, Takashi; Sakai, Minoru; Yagi, Shintaro

2011-12-01

The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO3·H2O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO4 in solution (>30 μM) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO4 than calcite and aragonite. The modes of PO4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly higher than simple adsorption on calcite.

Uptake of CO2, SO2, HNO3 and HCl on calcite (CaCO3) at 300 K: mechanism and the role of adsorbed water.

PubMed

Santschi, Ch; Rossi, M J

2006-06-01

All experimental observations of the uptake of the four title compounds on calcite are consistent with the presence of a reactive bifunctional surface intermediate Ca(OH)(HCO3) that has been proposed in the literature. The uptake of CO2 and SO2 occurs on specific adsorption sites of crystalline CaCO3(s) rather than by dissolution in adsorbed water, H2O(ads). SO2 primarily interacts with the bicarbonate moiety whereas CO2, HNO3 and HCl all react first with the hydroxyl group of the surface intermediate. Subsequently, the latter two react with the bicarbonate group to presumably form Ca(NO3)2 and CaCl2.2H2O. The effective equilibrium constant of the interaction of CO2 with calcite in the presence of H2O(ads) is kappa = deltaCO2/(H2O(ads)[CO2]) = 1.62 x 10(3) bar(-1), where CO2 is the quantity of CO2 adsorbed on CaCO3. The reaction mechanism involves a weakly bound precursor species that is reversibly adsorbed and undergoes rate-controlling concurrent reactions with both functionalities of the surface intermediate. The initial uptake coefficients gamma0 on calcite powder depend on the abundance of H2O(ads) under the present experimental conditions and are on the order of 10(-4) for CO2 and 0.1 for SO2, HNO3 and HCl, with gamma(ss) being significantly smaller than gamma0 for HNO3 and HCl, thus indicating partial saturation of the uptake. At 33% relative humidity and 300 K there are 3.5 layers of H2O adsorbed on calcite that reduce to a fraction of a monolayer of weakly and strongly bound water upon pumping and/or heating.

Investigating calcite growth rates using a quartz crystal microbalance with dissipation (QCM-D)

NASA Astrophysics Data System (ADS)

Cao, Bo; Stack, Andrew G.; Steefel, Carl I.; DePaolo, Donald J.; Lammers, Laura N.; Hu, Yandi

2018-02-01

Calcite precipitation plays a significant role in processes such as geological carbon sequestration and toxic metal sequestration and, yet, the rates and mechanisms of calcite growth under close to equilibrium conditions are far from well understood. In this study, a quartz crystal microbalance with dissipation (QCM-D) was used for the first time to measure macroscopic calcite growth rates. Calcite seed crystals were first nucleated and grown on sensors, then growth rates of calcite seed crystals were measured in real-time under close to equilibrium conditions (saturation index, SI = log ({Ca2+}/{CO32-}/Ksp) = 0.01-0.7, where {i} represent ion activities and Ksp = 10-8.48 is the calcite thermodynamic solubility constant). At the end of the experiments, total masses of calcite crystals on sensors measured by QCM-D and inductively coupled plasma mass spectrometry (ICP-MS) were consistent, validating the QCM-D measurements. Calcite growth rates measured by QCM-D were compared with reported macroscopic growth rates measured with auto-titration, ICP-MS, and microbalance. Calcite growth rates measured by QCM-D were also compared with microscopic growth rates measured by atomic force microscopy (AFM) and with rates predicted by two process-based crystal growth models. The discrepancies in growth rates among AFM measurements and model predictions appear to mainly arise from differences in step densities, and the step velocities were consistent among the AFM measurements as well as with both model predictions. Using the predicted steady-state step velocity and the measured step densities, both models predict well the growth rates measured using QCM-D and AFM. This study provides valuable insights into the effects of reactive site densities on calcite growth rate, which may help design future growth models to predict transient-state step densities.

Numerical Modelling of Speleothem and Dripwater Chemistry: Interpreting Coupled Trace Element and Isotope Proxies for Climate Reconstructions

NASA Astrophysics Data System (ADS)

Owen, R.; Day, C. C.; Henderson, G. M.

2016-12-01

Speleothem palaeoclimate records are widely used but are often difficult to interpret due to the geochemical complexity of the soil-karst-cave system. Commonly analysed proxies (e.g. δ18O, δ13C and Mg/Ca) may be affected by multiple processes along the water flow path from atmospheric moisture source through to the cave drip site. Controls on speleothem chemistry include rainfall and aerosol chemistry, bedrock chemistry, temperature, soil pCO2, the degree of open-system dissolution and prior calcite precipitation. Disentangling the effects of these controls is necessary to fully interpret speleothem palaeoclimate records. To quantify the effects of these processes, we have developed an isotope-enabled numerical model based on the geochemical modelling software PHREEQC. The model calculates dripwater chemistry and isotopes through equilibrium bedrock dissolution and subsequent iterative CO2 degassing and calcite precipitation. This approach allows forward modelling of dripwater and speleothem proxies, both chemical (e.g. Ca concentration, pH, Mg/Ca and Sr/Ca ratios) and isotopic (e.g. δ18O, δ13C, δ44Ca and radiocarbon content), in a unified framework. Potential applications of this model are varied and the model may be readily expanded to include new isotope systems or processes. Here we focus on calculated proxy co-variation due to changes in model parameters. Examples include: - The increase in Ca concentration, decrease in δ13C and increase in radiocarbon content as bedrock dissolution becomes more open-system. - Covariation between δ13C, δ44Ca and trace metal proxies (e.g. Mg/Ca) predicted by changing prior calcite precipitation. - The effect of temperature change on all proxies through the soil-karst-cave system. Separating the impact of soil and karst processes on geochemical proxies allows more quantitative reconstruction of the past environment, and greater understanding in modern cave monitoring studies.

Microbial diversity and impact on carbonate geochemistry across a changing geochemical gradient in a karst aquifer

PubMed Central

Gray, Cassie J; Engel, Annette S

2013-01-01

Although microbes are known to influence karst (carbonate) aquifer ecosystem-level processes, comparatively little information is available regarding the diversity of microbial activities that could influence water quality and geological modification. To assess microbial diversity in the context of aquifer geochemistry, we coupled 16S rRNA Sanger sequencing and 454 tag pyrosequencing to in situ microcosm experiments from wells that cross the transition from fresh to saline and sulfidic water in the Edwards Aquifer of central Texas, one of the largest karst aquifers in the United States. The distribution of microbial groups across the transition zone correlated with dissolved oxygen and sulfide concentration, and significant variations in community composition were explained by local carbonate geochemistry, specifically calcium concentration and alkalinity. The waters were supersaturated with respect to prevalent aquifer minerals, calcite and dolomite, but in situ microcosm experiments containing these minerals revealed significant mass loss from dissolution when colonized by microbes. Despite differences in cell density on the experimental surfaces, carbonate loss was greater from freshwater wells than saline, sulfidic wells. However, as cell density increased, which was correlated to and controlled by local geochemistry, dissolution rates decreased. Surface colonization by metabolically active cells promotes dissolution by creating local disequilibria between bulk aquifer fluids and mineral surfaces, but this also controls rates of karst aquifer modification. These results expand our understanding of microbial diversity in karst aquifers and emphasize the importance of evaluating active microbial processes that could affect carbonate weathering in the subsurface. PMID:23151637

Microbial diversity and impact on carbonate geochemistry across a changing geochemical gradient in a karst aquifer.

PubMed

Gray, Cassie J; Engel, Annette S

2013-02-01

Although microbes are known to influence karst (carbonate) aquifer ecosystem-level processes, comparatively little information is available regarding the diversity of microbial activities that could influence water quality and geological modification. To assess microbial diversity in the context of aquifer geochemistry, we coupled 16S rRNA Sanger sequencing and 454 tag pyrosequencing to in situ microcosm experiments from wells that cross the transition from fresh to saline and sulfidic water in the Edwards Aquifer of central Texas, one of the largest karst aquifers in the United States. The distribution of microbial groups across the transition zone correlated with dissolved oxygen and sulfide concentration, and significant variations in community composition were explained by local carbonate geochemistry, specifically calcium concentration and alkalinity. The waters were supersaturated with respect to prevalent aquifer minerals, calcite and dolomite, but in situ microcosm experiments containing these minerals revealed significant mass loss from dissolution when colonized by microbes. Despite differences in cell density on the experimental surfaces, carbonate loss was greater from freshwater wells than saline, sulfidic wells. However, as cell density increased, which was correlated to and controlled by local geochemistry, dissolution rates decreased. Surface colonization by metabolically active cells promotes dissolution by creating local disequilibria between bulk aquifer fluids and mineral surfaces, but this also controls rates of karst aquifer modification. These results expand our understanding of microbial diversity in karst aquifers and emphasize the importance of evaluating active microbial processes that could affect carbonate weathering in the subsurface.

Contrasting diagenetic histories of concretions vs. host rocks, Lion Mountain Member, Riley formation (upper Cambrian), Texas

DOE Office of Scientific and Technical Information (OSTI.GOV)

McBride, E.F.

1988-02-01

White, elliptical, calcite-cemented concretion nuclei up to 1 m long contrast markedly in color, composition, and diagenetic history from more glauconite-rich concretion rinds and from dark-green glaucarenite host rocks. Concretion nuclei are loosely packed deposits of trilobite carapaces and minor quartz and glauconite that have intergranular volumes of 58%. The nuclei are shell-lag deposits that were cemented by calcite at the sea floor or after burial of a few meters. Concretion rinds, composed of subequal amounts of quartz and compactionally deformed glauconite, have an intergranular volume of only 32% and minor quartz overgrowths that preceded pore-occluding calcite cement. The rindsmore » underwent burial for several million years to tens of millions of years to depths of several hundred meters before they were cemented. The host rock is predominately glauconite with very minor quartz and calcite cement. Strontium isotopic ratios of host-rock calcite cement are variable (0.7084 to 0.7093), but the lowest value suggests precipitation during the Middle Ordovician. In the absence of significant amounts of carbonate cement, the host rock underwent complete dissolution of trilobite carapaces and maximum compaction with total loss of porosity through squashing of glauconite grains. Maximum burial during this stage was completed by the end of Ordovician time.« less

Kinetics of ikaite precipitation and dissolution in seawater-derived brines at sub-zero temperatures to 265 K

NASA Astrophysics Data System (ADS)

Papadimitriou, Stathys; Kennedy, Hilary; Kennedy, Paul; Thomas, David N.

2014-09-01

The kinetics of calcium carbonate hexahydrate (ikaite) precipitation and dissolution were investigated in seawater and seawater-derived brines at sub-zero temperatures using the constant addition experimental technique. The steady state rate of these two processes was found to be a function of the deviation of the solution from equilibrium with respect to ikaite and conformed to the same empirical rate law as the anhydrous CaCO3 polymorphs, calcite and aragonite. In addition to the saturation state of the brine with respect to ikaite, the salinity of the brine and the temperature of the reaction evidently exerted some control on the ikaite precipitation kinetics, while the dissolution kinetics of the polymorph were not noticeably influenced by these two parameters. The experimental salinity and temperature conditions were equivalent to those at thermal equilibrium between brine and ice in the sea ice cover of polar seas. Simple modelling of the CO2 system by extrapolation of the oceanic equivalent to sea ice brines showed that the physical concentration of seawater ions and the changes in ikaite solubility as a function of salinity and temperature, both inherent in the sea ice system, would be insufficient to drive the emergent brines to ikaite supersaturation and precipitation in sea ice down to -8 °C. The loss of dissolved inorganic carbon to the gas phase of sea ice and to sympagic autotrophs are two independent mechanisms which, in nature, could prompt the brine CO2 system towards ikaite supersaturation and precipitation. Under these conditions, the steady state precipitation rate of ikaite was found to be fast enough for rapid formation within short time scales (days to weeks) in sea ice. The observed ikaite dissolution kinetics were also found conducive to short turn-over time scales of a few hours to a few days in corrosive solutions, such as surface seawater.

An assessment of calcite crystal growth mechanisms based on crystal size distributions

USGS Publications Warehouse

Kile, D.E.; Eberl, D.D.; Hoch, A.R.; Reddy, M.M.

2000-01-01

Calcite crystal growth experiments were undertaken to test a recently proposed model that relates crystal growth mechanisms to the shapes of crystal size distributions (CSDs). According to this approach, CSDs for minerals have three basic shapes: (1) asymptotic, which is related to a crystal growth mechanism having constant-rate nucleation accompanied by surface-controlled growth; (2) lognormal, which results from decaying-rate nucleation accompanied by surface-controlled growth; and (3) a theoretical, universal, steady-state curve attributed to Ostwald ripening. In addition, there is a fourth crystal growth mechanism that does not have a specific CSD shape, but which preserves the relative shapes of previously formed CSDs. This mechanism is attributed to supply-controlled growth. All three shapes were produced experimentally in the calcite growth experiments by modifying nucleation conditions and solution concentrations. The asymptotic CSD formed when additional reactants were added stepwise to the surface of solutions that were supersaturated with respect to calcite (initial Ω = 20, where Ω = 1 represents saturation), thereby leading to the continuous nucleation and growth of calcite crystals. Lognormal CSDs resulted when reactants were added continuously below the solution surface, via a submerged tube, to similarly supersaturated solutions (initial Ω = 22 to 41), thereby leading to a single nucleation event followed by surface-controlled growth. The Ostwald CSD resulted when concentrated reactants were rapidly mixed, leading initially to high levels of supersaturation (Ω >100), and to the formation and subsequent dissolution of very small nuclei, thereby yielding CSDs having small crystal size variances. The three CSD shapes likely were produced early in the crystallization process, in the nanometer crystal size range, and preserved during subsequent growth. Preservation of the relative shapes of the CSDs indicates that a supply-controlled growth mechanism was established and maintained during the constant-composition experiments. CSDs having shapes intermediate between lognormal and Ostwald also were generated by varying the initial levels of supersaturation (initial Ω = 28.2 to 69.2) in rapidly mixed solutions. Lognormal CSDs were observed for natural calcite crystals that are found in septarian concretions occurring in southeastern Colorado. Based on the model described above, these CSDs indicate initial growth by surface control, followed by supply-controlled growth. Thus, CSDs may be used to deduce crystal growth mechanisms from which geologic conditions early in the growth history of a mineral can be inferred. Conversely, CSD shape can be predicted during industrial crystallization by applying the appropriate conditions for a particular growth mechanism.

Geochemistry of and radioactivity in ground water of the Highland Rim and Central Basin aquifer systems, Hickman and Maury counties, Tennessee

USGS Publications Warehouse

Hileman, G.E.; Lee, R.W.

1993-01-01

A reconnaissance of the geochemistry of and radioactivity in ground water from the Highland Rim and Central Basin aquifer systems in Hickman and Maury Counties, Tennessee, was conducted in 1989. Water in both aquifer systems typically is of the calcium or calcium magnesium bicarbonate type, but concentrations of calcium, magnesium, sodium, potassium, chloride, and sulfate are greater in water of the Central Basin system; differences in the concentrations are statistically significant. Dissolution of calcite, magnesium-calcite, dolomite, and gypsum are the primary geochemical processes controlling ground-water chemistry in both aquifer systems. Saturation-state calculations using the computer code WATEQF indicated that ground water from the Central Basin system is more saturated with respect to calcite, dolomite, and gypsum than water from the Highland Rim system. Geochemical environments within each aquifer system are somewhat different with respect to dissolution of magnesium-bearing minerals. Water samples from the Highland Rim system had a fairly constant calcium to magnesium molar ratio, implying congruent dissolution of magnesium-bearing minerals, whereas water samples from the Central Basin system had highly variable ratios, implying either incongruent dissolution or heterogeneity in soluble constituents of the aquifer matrix. Concentrations of radionuclides in water were low and not greatly different between aquifer systems. Median gross alpha activities were 0.54 picocuries per liter in water from each system; median gross beta activities were 1.1 and 2.3 picocuries per liter in water from the Highland Rim and Central Basin systems, respectively. Radon-222 concentrations were 559 and 422 picocuries per liter, respectively. Concentrations of gross alpha and radium in all samples were substantially less than Tennessee?s maximum permissible levels for community water-supply systems. The data indicated no relations between concentrations of dissolved radionuclides (uranium, radium-226, radium-228, radon-222, gross alpha, and gross beta) and any key indicators of water chemistry, except in water from the Highland Rim system, in which radon-222 was moderately related to pH and weakly related to dissolved magnesium. The only relation among radiochemical constituents indicated by the data was between radium-226 and gross alpha activity; this relation was indicated for water from both aquifer systems.

Hydrothermal karst and associated breccias in Neoproterozoic limestone from the Barker-Villa Cacique area (Tandilia belt), Argentina

NASA Astrophysics Data System (ADS)

Dristas, Jorge A.; Martínez, Juan C.; van den Kerkhof, Alfons M.; Massonne, Hans-Joachim; Theye, Thomas; Frisicale, María C.; Gregori, Daniel A.

2017-07-01

In the Barker-Villa Cacique area (Tandilia belt), remarkable megabreccias, limestone breccias and phosphate-bearing breccias hosted in black limestone and along the contact with the upper section of the sedimentary succession are exposed. These rocks are the result of extensive hydrothermal alteration of the original micritic limestone and other fine-grained clastic sediments. Typical alteration minerals are sericite, chlorite, interstratified chlorite/K-white mica, kaolinite, dickite, pyrite, chalcopyrite, goethite, quartz, calcite, Fe-calcite, dolomite, ankerite, fluor-apatite, barite and aluminium-phosphate-sulfate (APS) minerals. Quartz and calcite cements from hydraulic breccias in the limestone contain low-salinity aqueous fluid inclusions. Corresponding homogenization temperatures display 200-220 °C and 110-140 °C in hydrothermal quartz, and 130-150 °C in late calcite cement. Carbon and oxygen stable isotope analyses of carbonates from the Loma Negra quarry (LNQ) support the major role of hydrothermal activity. A significant difference was found between δ18Ocar values from unaltered micritic limestone (ca. 23.8‰ SMOW) and secondary calcite (ca. 18.5‰ SMOW). The lower δ18Ocar values are interpreted as a result of calcite precipitation from hot hydrothermal fluids. At a late stage, the hydrothermal fluid containing H2S mixed with descending and oxidizing meteoric waters. Circulation of the ensuing acid fluids resulted in the partly dissolution and collapse brecciation of the Loma Negra Formation. The hydrothermal stage can be tentatively dated ca. 590-620 Ma corresponding to the Brasiliano orogeny.

Estimation of the reactive mineral surface area during CO2-rich fluid-rock interaction: the influence of neogenic phases

NASA Astrophysics Data System (ADS)

Scislewski, A.; Zuddas, P.

2010-12-01

Mineral dissolution and precipitation reactions actively participate to control fluid chemistry during water-rock interaction. It is however, difficult to estimate and well normalize bulk reaction rates if the mineral surface area exposed to the aqueous solution and effectively participating on the reactions is unknown. We evaluated the changing of the reactive mineral surface area during the interaction between CO2-rich fluids and Albitite/Granitoid rocks (similar mineralogy but different abundances), reacting under flow-through conditions. Our methodology, adopting an inverse modeling approach, is based on the estimation of dissolution rate and reactive surface area of the different minerals participating in the reactions by the reconstruction the chemical evolution of the interacting fluids. The irreversible mass-transfer processes is defined by a fractional degree of advancement, while calculations were carried out for Albite, Microcline, Biotite and Calcite assuming that the ion activity of dissolved silica and aluminium ions was limited by the equilibrium with quartz and kaolinite. Irrespective of the mineral abundance in granite and albitite, we found that mineral dissolution rates did not change significantly in the investigated range of time where output solution’s pH remained in the range between 6 and 8, indicating that the observed variation in fluid composition depends not on pH but rather on the variation of the parent mineral’s reactive surface area. We found that the reactive surface area of Albite varied by more than 2 orders of magnitude, while Microcline, Calcite and Biotite surface areas changed by 1-2 orders of magnitude. We propose that parent mineral chemical heterogeneity and, particularly, the stability of secondary mineral phases may explain the observed variation of the reactive surface area of the minerals. Formation of coatings at the dissolving parent mineral surfaces significantly reduced the amount of surface available to react with CO2-rich fluids, decreasing the effective reactive surface area. Predictive models of CO2 sequestration under geological conditions should take into account the inhibiting role of surface coating formation. The CO2 rich fluid-rock interactions may also have significant consequences on metal mobilization. Our results indicated that the formation of stable carbonate complexes enhances the solubility of uranium minerals of both albitite and granite, facilitating the U(IV) oxidation, and limiting the extent of uranium adsorption onto particles in oxidized waters. This clearly produces an increase of the uranium mobility with significant consequences for the environment.

Dissolution of Calcite in the Twilight Zone: Bacterial Control of Dissolution of Sinking Planktonic Carbonates Is Unlikely

PubMed Central

Bissett, Andrew; Neu, Thomas R.; de Beer, Dirk

2011-01-01

We investigated the ability of bacterial communities to colonize and dissolve two biogenic carbonates (Foraminifera and oyster shells). Bacterial carbonate dissolution in the upper water column is postulated to be driven by metabolic activity of bacteria directly colonising carbonate surfaces and the subsequent development of acidic microenvironments. We employed a combination of microsensor measurements, scanning electron microscopy (SEM), confocal laser scanning microscopy (CLSM) and image analysis and molecular documentation of colonising bacteria to monitor microbial processes and document changes in shell surface topography. Bacterial communities rapidly colonised shell surfaces, forming dense biofilms with extracellular polymeric substance (EPS) deposits. Despite this, we found no evidence of bacterially mediated carbonate dissolution. Dissolution was not indicated by Ca2+ microprofiles, nor was changes in shell surface structure related to the presence of colonizing bacteria. Given the short time (days) settling carbonate material is actually in the twilight zone (500–1000 m), it is highly unlikely that microbial metabolic activity on directly colonised shells plays a significant role in dissolving settling carbonates in the shallow ocean. PMID:22102861

Dissolution of calcite in the twilight zone: bacterial control of dissolution of sinking planktonic carbonates is unlikely.

PubMed

Bissett, Andrew; Neu, Thomas R; Beer, Dirk de

2011-01-01

We investigated the ability of bacterial communities to colonize and dissolve two biogenic carbonates (Foraminifera and oyster shells). Bacterial carbonate dissolution in the upper water column is postulated to be driven by metabolic activity of bacteria directly colonising carbonate surfaces and the subsequent development of acidic microenvironments. We employed a combination of microsensor measurements, scanning electron microscopy (SEM), confocal laser scanning microscopy (CLSM) and image analysis and molecular documentation of colonising bacteria to monitor microbial processes and document changes in shell surface topography. Bacterial communities rapidly colonised shell surfaces, forming dense biofilms with extracellular polymeric substance (EPS) deposits. Despite this, we found no evidence of bacterially mediated carbonate dissolution. Dissolution was not indicated by Ca²⁺ microprofiles, nor was changes in shell surface structure related to the presence of colonizing bacteria. Given the short time (days) settling carbonate material is actually in the twilight zone (500-1000 m), it is highly unlikely that microbial metabolic activity on directly colonised shells plays a significant role in dissolving settling carbonates in the shallow ocean.

Biogenic Calcium Carbonate with Hierarchical Organic-Inorganic Composite Structure Enhancing the Removal of Pb(II) from Wastewater.

PubMed

Zhou, Xueli; Liu, Weizhen; Zhang, Jian; Wu, Can; Ou, Xinwen; Tian, Chen; Lin, Zhang; Dang, Zhi

2017-10-18

Calcium carbonate from geological sources (geo-CaCO 3 , e.g., calcite, aragonite) is used extensively in removing heavy metals from wastewater through replacement reaction. However, geo-CaCO 3 has an intrinsically compact crystalline structure that results in low efficiency in pollutant removal and thus its use may produce enormous sludge. In this work, biogenic calcium carbonate (bio-CaCO 3 ) derived from oyster shells was used to remove Pb(II) from wastewater and found to significantly outperform geo-CaCO 3 (calcite). The thermodynamics study revealed that the maximum adsorption capacity of bio-CaCO 3 for Pb(II) was three times that of geo-CaCO 3 , reaching up to 1667 mg/g. The kinetics study disclosed that the dissolution kinetics and the rate of intraparticle diffusion of bio-CaCO 3 were faster than those of geo-CaCO 3 . Extensive mechanism research through X-ray powder diffraction (XRD), scanning electron microscopy (SEM), N 2 adsorption/desorption test and mercury intrusion porosimetry showed that the hierarchical porous organic-inorganic hybrid structure of bio-CaCO 3 expedited the dissolution of CaCO 3 to provide abundant CO 3 2- active sites and facilitated the permeation and diffusion of Pb(II) into the bulk solid phases. In addition, Fourier transform infrared spectroscopy (FTIR) study, X-ray photoelectron spectroscopy (XPS) analysis, and the examination of Pb(II) removal ability of bio-CaCO 3 after calcination indicated that the organic functional groups of bio-CaCO 3 also facilitated the immobilization of Pb(II) into CaCO 3 particles, although the major contribution was from the hierarchical porous structure of bio-CaCO 3 .

Origin of increased sulfate in groundwater at the ETF disposal site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thornton, E.C.

1997-09-01

Treated effluent being discharged to the vadose zone from the C-018H Effluent Treatment Facility (ETF) at the Hanford Site has infiltrated vertically to the unconfined aquifer, as indicated by increasing tritium activity levels in the groundwater. Well 699-48-77A, in particular, exhibits increased levels of tritium and also sulfate in the groundwater. The origin of increased sulfate levels in the groundwater is attributed to the dissolution of gypsum as the effluent flows through the vadose zone. This is supported by the observation that sulfate was found to be present in soils collected from the vadose zone at an average value ofmore » about 10.6 ppm. The maximum observed sulfate concentration of 190 mg/L from well 699-48-77A was observed on August 6, 1996, and is less than the maximum value of 879 mg/L that potentially could be achieved if water in the vadose zone was to attain saturation with respect to gypsum and calcite. It is suggested that infiltration rates were high enough that the effluent did not completely equilibrate with gypsum in the vadose zone, and thus, sulfate levels remained below gypsum saturation levels. Sulfate levels appear to be dropping, which may be attributed to the completion of the dissolution of the bulk of gypsum present along the vadose zone flow path traversed by the effluent. Geochemical modeling was undertaken to evaluate the influence of effluent chemistry on sulfate concentration levels in the presence of excess calcite and gypsum. In general, the effect is fairly minor for dilute solutions, but becomes more significant for concentrated solutions.« less

The geochemical evolution of aqueous sodium in the Black Creek Aquifer, Horry and Georgetown counties, South Carolina

USGS Publications Warehouse

Zack, Allen L.; Roberts, Ivan

1988-01-01

The Black Creek aquifer contains dilute seawater near the North Carolina State line, probably the result of incomplete flushing of ancient seawater. Data do not indicate that the dilute seawater has migrated toward areas of fresh ground-water withdrawals. The concentration of chloride in ground-water samples ranges from 5 to 720 milligrams per liter and that of sodium from 160 to 690 milligrams per liter. Ion-exchange reactions (sodium for calcium and fluoride for hydroxyl) occur with the calcium carbonate dissolution reaction which produces calcium, bicarbonate, and hydroxyl ions. The reaction sequence and stoichiometry result in an aqueous solution in which the sum of bicarbonate and chloride equivalents per liter is equal to the equivalents per liter of sodium. Calcium ions are exchanged for sodium ions derived from sodium-rich clays upgradient of the dilute seawater. The cation-exchange reaction equilibrates at a sodium concentration of 280 milligrams per liter. Amounts of sodium greater than 280 milligrams per liter are contributed from dilute seawater. The cation-exchange reaction approaches an equilibrium which represents a mass-action limit in terms of the ratio of sodium to calcium in solution versus the ratio of exchangeable sodium to calcium on clay surfaces. Where the limit of calcium carbonate solubility is approached and dissolution ceases, some precipitation of calcite probably takes place. The dissolution of calcite exposes fossil shark teeth which release fluoride ions to the ground water through anion exchange with aqueous hydroxyl ions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szcześ, Aleksandra, E-mail: aszczes@poczta.umcs.lublin.pl; Czemierska, Magdalena; Jarosz-Wilkołazka, Anna

Extracellular polymeric substance (EPS) extracted from Rhodococcus opacus bacterial strain was used as a matrix for calcium carbonate precipitation using the vapour diffusion method. The total exopolymer and water-soluble exopolymer fraction of different concentrations were spread on the mica surface by the spin-coating method. The obtained layers were characterized using the atomic force microscopy measurement and XPS analysis. The effects of polymer concentration, initial pH of calcium chloride solution and precipitation time on the obtained crystals properties were investigated. Raman spectroscopy and scanning electron microscopy were used to characterize the precipitated minerals. It was found that the type of precipitatedmore » CaCO{sub 3} polymorph and the crystal size depend on the kind of EPS fraction. The obtained results indicates that the water soluble fraction favours vaterite dissolution and calcite growth, whereas the total EPS stabilizes vaterite and this effect is stronger at basic pH. It seems to be due to different contents of the functional group of EPS fractions. - Highlights: • CaCO{sub 3} crystal size and polymorph can be controlled by EPS substance obtained from R. opacus. • The water soluble fraction favours vaterite dissolution and calcite growth. • The total EPS stabilizes vaterite. • This effect is stronger at basic pH.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saller, A.H.; Schlanger, S.O.

Two wells drilled along the margin of Enewetak Atoll penetrated approximately 1000 m of upper Eocene, Oligocene, and lower Miocene carbonates. Strontium isotope stratigraphy indicates relatively continuous deposition of carbonate from 40 Ma to 20 Ma. Depositional environments show a gradual basinward progradation of facies with slope carbonates passing upward into fore-reef, reef, back-reef, and lagoonal carbonates. Slope strata contain wackestones and packstones with submarine-cemented lithoclasts, coral, coralline algae fragments, benthic rotaline forams, planktonic forams, and echinoderm fragments. Fore-reef strata are dominantly packstones and boundstones containing large pieces of coral, abundant benthic forams, coralline algae fragments, stromatoporoids( ), and minormore » planktonic forams. Reef and near-reef sediments include coralgal boundstones and grainstones with abundant benthic forams. Halimeda and miliolid forams are common in lagoonward parts of the back reef. Sponge borings, geopetal structures, and fractures are common in reef and fore-reef strata. Lagoonal strata are wackestones and packstones with common mollusks, coral, coralline algae, and benthic forams (rotaline and miliolid). Diagenesis has extensively altered strata near the atoll margin. Aragonite dissolution and calcite cements (radiaxial and cloudy prismatic) are abundant in fore-reef, reef, and some back-reef strata. Petrographic and geochemical data indicate aragonite dissolution and calcite cementation in seawater at burial depths of 100 to 300 m. Dolomite occurs in slope and deeply buried reefal carbonates. Most dolomitization occurred at burial depths of more than 1000 m in cool marine waters circulating through the atoll. lagoonal strata are not significantly altered by marine diagenesis and still contain abundant primary aragonite and magnesium calcite.« less

Geochemical Processes During Managed Aquifer Recharge With Desalinated Seawater

NASA Astrophysics Data System (ADS)

Ganot, Y.; Holtzman, R.; Weisbrod, N.; Russak, A.; Katz, Y.; Kurtzman, D.

2018-02-01

We study geochemical processes along the variably-saturated zone during managed aquifer recharge (MAR) with reverse-osmosis desalinated seawater (DSW). The DSW, post-treated at the desalination plant by calcite dissolution (remineralization) to meet the Israeli water quality standards, is recharged into the Israeli Coastal Aquifer through an infiltration pond. Water quality monitoring during two MAR events using suction cups and wells inside the pond indicates that cation exchange is the dominant subsurface reaction, driven by the high Ca2+ concentration in the post-treated DSW. Stable isotope analysis shows that the shallow groundwater composition is similar to the recharged DSW, except for enrichment of Mg2+, Na+, Ca2+, and HCO3-. A calibrated variably-saturated reactive transport model is used to predict the geochemical evolution during 50 years of MAR for two water quality scenarios: (i) post-treated DSW (current practice) and (ii) soft DSW (lacking the remineralization post-treatment process). The latter scenario was aimed to test soil-aquifer-treatment (SAT) as an alternative post-treatment technique. Both scenarios provide an enrichment of ˜2.5 mg L-1 in Mg2+ due to cation exchange, compared to practically zero Mg2+ currently found in the Israeli DSW. Simulations of the alternative SAT scenario provide Ca2+ and HCO3- remineralization due to calcite dissolution at levels that meet the Israeli standard for DSW. The simulated calcite content reduction in the sediments below the infiltration pond after 50 years of MAR was low (<1%). Our findings suggest that remineralization using SAT for DSW is a potentially sustainable practice at MAR sites overlying calcareous sandy aquifers.

Concomitant Zn-Cd and Pb retention in a carbonated fluvio-glacial deposit under both static and dynamic conditions.

PubMed

Lassabatere, Laurent; Spadini, Lorenzo; Delolme, Cécile; Février, Laureline; Galvez Cloutier, Rosa; Winiarski, Thierry

2007-11-01

The chemical and physical processes involved in the retention of 10(-2)M Zn, Pb and Cd in a calcareous medium were studied under saturated dynamic (column) and static (batch) conditions. Retention in columns decreased in order: Pb>Cd approximately Zn. In the batch experiments, the same order was observed for a contact time of less than 40h and over, Pb>Cd>Zn. Stronger Pb retention is in accordance with the lower solubility of Pb carbonates. However, the equality of retained Zn and Cd does not fit the solubility constants of carbonated solids. SEM analysis revealed that heavy metals and calcareous particles are associated. Pb precipitated as individualized Zn-Cd-Ca- free carbonated crystallites. All the heavy metals were also found to be associated with calcareous particles, without any change in their porosity, pointing to a surface/lattice diffusion-controlled substitution process. Zn and Cd were always found in concomitancy, though Pb fixed separately at the particle circumferences. The Phreeqc 2.12 interactive code was used to model experimental data on the following basis: flow fractionation in the columns, precipitation of Pb as cerrusite linked to kinetically controlled calcite dissolution, and heavy metal sorption onto proton exchanging sites (presumably surface complexation onto a calcite surface). This model simulates exchanges of metals with surface protons, pH buffering and the prevention of early Zn and Cd precipitation. Both modeling and SEM analysis show a probable significant decrease of calcite dissolution along with its contamination with metals.

A 2.5D Reactive Transport Model for Fracture Alteration Simulation

DOE PAGES

Deng, Hang; Molins, Sergi; Steefel, Carl; ...

2016-06-30

Understanding fracture alteration resulting from geochemical reactions is critical in predicting fluid migration in the subsurface and is relevant to multiple environmental challenges. Here in this paper, we present a novel 2.5D continuum reactive transport model that captures and predicts the spatial pattern of fracture aperture change and the development of an altered layer in the near-fracture region. The model considers permeability heterogeneity in the fracture plane and updates fracture apertures and flow fields based on local reactions. It tracks the reaction front of each mineral phase and calculates the thickness of the altered layer. Given this treatment, the modelmore » is able to account for the diffusion limitation on reaction rates associated with the altered layer. The model results are in good agreement with an experimental study in which a CO 2-acidified brine was injected into a fracture in the Duperow Dolomite, causing dissolution of calcite and dolomite that result in the formation of a preferential flow channel and an altered layer. Finally, with an effective diffusion coefficient consistent with the experimentally observed porosity of the altered layer, the model captures the progressive decrease in the dissolution rate of the fast-reacting mineral in the altered layer.« less

Uranium in foraminiferal calcite as a recorder of seawater uranium concentrations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Russell, A.D.; Emerson, S.; Nelson, B.K.

The authors present results of an investigation of uranium/calcium ratios in cleaned foraminiferal calcite as a recorder of seawater uranium concentrations. For accurate reconstruction of past seawater uranium content, shell calcite must incorporate uranium in proportion to seawater concentration and must preserve its original uranium composition over time. Laboratory culture experiments with live benthic (Amphistegina lobifera) and live planktonic (Globigerinell calida) foraminifera show that the U/Ca ratio of cleaned calcite tests is proportional to the concentration of uranium in solution. After correcting results for the presence of initial calcite, the apparent distribution coefficient D = (U/Ca[sub calcite])/(U/Ca)[sub solution] = 10.6more » [+-] 0.3 (x10[sup [minus]3]) for A. lobifera and D = 7.9 [+-] 0.1 (x10[sup [minus]3]) for G. calida. U/Ca ratios in planktonic foraminifera from core tops collected above 3900 m in the equatorial Atlantic and above 2100 m in the Pacific Ocean show no significant difference among the species analyzed. D estimated form core top samples ranges from 7.6 [+-] 0.4 (x10[sup [minus]3]) for O. universa to 8.4 [+-] 0.5 (x10[sup [minus]3]) for G. ruber. In benthic species C. wuellerstorfi, D = 7.0 [+-] 0.8 (x10[sup [minus]3]). U/Ca and Mg/Ca in G. tumida and G. sacculifer from core tops taken near and below the regional lysocline decrease with water depth. Smaller decreases in U/Ca and Mg/Ca with depth were observed in C. wuellerstorfi. In the planktonic species, the authors believe that U/CA and Mg/Ca are lower in the more dissolution-resistant fraction of calcite, leading to lower U/Ca in more highly dissolved samples.« less

Significance of a Shelf-wide Dissolution Event during the Paleocene-Eocene Thermal Maximum, Maryland and New Jersey, USA

NASA Astrophysics Data System (ADS)

Bralower, T. J.; Kump, L. R.; Robinson, M. M.; Self-Trail, J. M.; Zachos, J. C.

2016-12-01

Continental-shelf sediments of the US Atlantic margin experienced a brief episode of carbonate dissolution during the onset of the Paleocene-Eocene Thermal Maximum (PETM). Dissolution is represented by reduced percentages of carbonate, and calcareous microfossil distribution and preservation trends, in cores from Maryland and New Jersey. The base and the top of the dissolution zone are abrupt compared to the gradual nature of the onset of the carbon isotope excursion (CIE). The thickness of the dissolution zone varies from 9 cm in the Bass River core (outer paleoshelf) to 1.6 m in the CamDor core (middle paleoshelf). The decrease in %CaCO3 suggests dissolution locally removed 83 to 100% of the initial biogenic carbonate. Shelf-wide dissolution during the onset of the PETM may be a regional event, associated, for example, with eutrophication. Samples from across the paleoshelf contain abundant fine-grained framboidal pyrite, which suggests photic-zone euxinia occurred before, during, and after the dissolution event. Dissolution may also be associated with oxidation of this pyrite during later exposure to oxidizing groundwaters, although the restricted duration of the dissolution interval argues against this. Alternatively, the dissolution event may have global significance related to surface ocean-water acidification or shoaling of the calcite compensation depth (CCD) to shelf depths. The event began near the onset of the CIE on the shelf, whereas dissolution in deep-sea sections began later. Earlier shelf dissolution is consistent with surface ocean acidification while later deep-sea dissolution is thought to be associated with shoaling of the CCD. In our presentation, we weigh evidence for each of these possibilities and test them using the global dataset.

Hydrothermal replacement of calcite by Mg-carbonates

NASA Astrophysics Data System (ADS)

Jonas, Laura; Mueller, Thomas; Dohmen, Ralf

2014-05-01

The transport of heat and mass through the Earth's crust is coupled to mineral reactions and the exchange of isotopes and elements between different phases. Carbonate minerals are a major constituent of the Earth's crust and play an important role in different physical, chemical and even biological processes. In this experimental study, the element exchange reaction between calcite (CaCO3) and a Mg-rich fluid phase is investigated under hydrothermal conditions. Single crystals of calcite (2x2x2 mm) react with 1 ml of a 1 M MgCl2 solution at 200° C in a Teflon-lined steel autoclave for different times between one day and four weeks. The reaction leads to the formation of a porous reaction front and the pseudomorphic replacement of calcite by dolomite [CaMg(CO3)2] and magnesite (MgCO3). Scanning electron microscopy revealed that the reaction rim consists of small Mg-carbonate rhombs closely attached to each other, suggesting that the replacement reaction takes place by a dissolution-precipitation mechanism. Typically, the observed reaction front can be divided into two different domains. The outer part of the reaction rim, i.e. from the mineral surface in contact to the fluid inwards, consists of magnesite, whereas the inner part of the rim surrounding the unreacted calcite core consists of Ca-rich dolomite. The formation of a porous microstructure that varies in different parts of the reaction rim is a direct result of the large molar volume change induced by the replacement of calcite by magnesite and dolomite. The developing porosity therefore creates fluid pathways that promote the progress of the reaction front towards the unreacted core of the single crystal. Compositional profiles measured perpendicular to the mineral surface across the reactions rims using electron microprobe (EMPA) further revealed a compositional gradient within the reaction rim with regard to the structure-forming elements Mg and Ca. Here, the amount of Mg incorporated in both product phases increases with increasing distance from the unreacted calcite core, countered by a decrease of Ca incorporated. Both the coexistence of two different product phases and the distinct compositional gradient within the forming reaction rim are unequivocal signs of a chemical zonation of Ca and Mg in the fluid phase which mediates the element exchange between the reaction interface and the bulk solution. Atomic adsorption spectroscopy revealed that the Ca/Mg ratio in the reacted fluid increases as a function of time, reflecting the progressive exchange of Mg and Ca between the fluid and the solid phase. The time-dependence of the evolving Ca/Mg ratio can be fitted with a square root of time relation that indicates a transport controlled reaction. We interpret the hydrothermal replacement of calcite to operate via a dissolution/re-precipitation mechanism, whereas the reaction progress is controlled by the transport of the structure forming elements through the developing reaction rim.

Diagenetic evolution and stable isotopes of Lower Permian platform marginal carbonates (Trogkofel Limestone, Carnic Alps, Austria)

NASA Astrophysics Data System (ADS)

Schaffhauser, Maria; Krainer, Karl; Sanders, Diethard Gerald; Spötl, Christoph

2010-05-01

The Trogkofel massif in the Carnic Alps, Austria/Italy, consists of a succession up to 400 m thick of limestones deposited along a platform margin (Trogkofel Limestone; Artinskian). The top of the Trogkofel Limestone is erosively overlain by the Tarvis Breccia. Up-section, the Trogkofel Limestone consists of well-bedded shallow-water bioclastic limestones with intercalated mud mounds, overlain by thick-bedded to unbedded limestones (bioclastic grainstones, packstones, rudstones) and cementstone mounds rich in phylloid algae, Tubiphytes, bryozoans and Archaeolithoporella. In the cementstone mounds, bioclasts are coated by thick fringes and botryoids of fibrous calcite, and of calcite spar that probably represents calcitized aragonite. Primary and intrinsic pores are filled by microbialite, and/or by mudstone to bioclastic wackestone. Shallow-water bioclastic grainstones are cemented by isopachous fringes of fibrous calcite, or by sparry calcite. Throughout the succession, evidence for meteoric-vadose dissolution is present. The Trogkofel Limestone is riddled by palaeokarstic dykes and caverns filled by (a) isopachous cement fringes up to a few decimetres thick, and/or (b) by red, geopetally-laminated lime mudstone to bio-lithoclastic wackestone; geopetal laminasets locally display convolute bedding. Small dissolution cavities are filled by grey internal sediment, or by crystal silt. Brecciated internal sediments overlain by unbrecciated, geopetally-laminated infillings record deformation during or after deposition of the Trogkofel Limestone. Polyphase fractures cemented by calcite may cross-cut both internal sediments and host rock. In the Trogkofel Limestone, local dolomitization is common. Replacement dolomites show a wide range of shapes and fabrics, including: (a) fine-crystalline anhedral xenotopic fabric, (b) coarse-crystalline subhedral to euhedral, hypidiotopic to idiotopic fabric of turbid or optically zoned crystals, and (c) saddle dolomite as replacement and filling of fractures. Closely below the erosional surface at the top of the Trogkofel Limestone, the dolomite is characterized by vuggy porosity. The Tarvis Breccia, which represents coarse alluvial fan deposits, in turn, is thick-bedded, poorly sorted, typically clast-supported, and consists of angular lithoclasts embedded in a matrix of former lime mudstone. Both, matrix as well as lithoclasts, are dolomitized. Various types of cement (isopachous, botryoidal, microbialite, calcite spar), karstic cavity fills (isopachous cements, internal sediments), and replacement dolomites of the Trogkofel section, as well as of the Tarvis Breccia were analysed for their stable isotopic composition. δ18O and δ13C data produced so far allow to differentiate between replacement dolomites and saddle dolomite of the Trogkofel Limestone and the Tarvis Breccia. Saddle dolomite shows the most depleted oxygen isotope values, suggesting formation during relatively high temperatures. Carbon isotope values are invariably positive in all dolomite types indicating lacking influence of organic diagenesis on the alkalinity of the deep-burial pore water. Matrix dolomite from the Tarvis Breccia shows slightly positive δ18O values. Calcite cements show a wide range in δ18O values (ca. -1 to -7 permil VPDB), which overlaps the composition of unaltered brachiopod shells (ca. -3 permil VPDB). Oxygen isotope values of calcite cements reveal a trend towards depleted δ18O values. This trend is reflecting most likely increasing temperature.

Carbonate dissolution in mixed waters due to ocean acidification

NASA Astrophysics Data System (ADS)

Koski, K.; Wilson, J. L.

2009-12-01

Much of the anthropogenically released carbon dioxide has been stored as a dissolved gas in the ocean, causing a 0.1 decrease in ocean surface pH, with models predicting that by 2100 the surface ocean pH will be 0.5 below pre-industrial levels. In mixed ocean water - fresh water environments (e.g. estuaries, coastal aquifers, and edges of ice sheets), the decreased ocean pH couples with the mixed water geochemistry to make water more undersaturated with respect to calcium carbonate than ocean acidification alone. Mixed-water calcite dissolution may be one of the first directly observable effects of ocean acidification, as the ocean water and the fresh water can both be saturated with respect to calcium carbonate while their mixture will be undersaturated. We present a basic quantitative model describing mixed water dissolution in coastal or island freshwater aquifers, using temporally changing ocean pH, sea level, precipitation, and groundwater pumping. The model describes the potential for an increased rate of speleogenesis and porosity/permeability development along the lower edge of a fresh water lens aquifer. The model accounts the indirect effects of rising sea level and a growing coastal population on these processes. Applications are to freshwater carbonate aquifers on islands (e.g. the Bahamas) and in coastal areas (e.g. the unconfined Floridan aquifer of the United States, the Yucatan Peninsula of Mexico).

Impact of trace metals on the water structure at the calcite surface

NASA Astrophysics Data System (ADS)

Wolthers, Mariette; Di Tommaso, Devis; De Leeuw, Nora

2014-05-01

Carbonate minerals play an important role in regulating the chemistry of aquatic environments, including the oceans, aquifers, hydrothermal systems, soils and sediments. Through mineral surface processes such as dissolution, precipitation and sorption, carbonate minerals affect the biogeochemical cycles of not only the constituent elements of carbonates, such as Ca, Mg, Fe and C, but also H, P and trace elements. Surface charging of the calcite mineral-water interface, and its reactivity towards foreign ions can be quantified using a surface structural model that includes, among others, the water structure at the interface (i.e. hydrogen bridging) [1,2] in accordance with the CD-MUSIC formalism [3]. Here we will show the impact of foreign metals such as Mg and Sr on the water structure around different surface sites present in etch pits and on growth terraces at the calcite (10-14) surface. We have performed Molecular Dynamics simulations of metal-doped calcite surfaces, using different interatomic water potentials. Results show that the local environment around the structurally distinct sites differs depending on metal presence, suggesting that metal substitutions in calcite affect its reactivity. The information obtained in this study will help in improving existing macroscopic surface model for the reactivity of calcite [2] and give more general insight in mineral surface reactivity in relation to crystal composition. [1] Wolthers, Charlet, & Van Cappellen (2008). Am. J. Sci., 308, 905-941. [2] Wolthers, Di Tommaso, Du, & de Leeuw (2012). Phys. Chem. Chem. Phys. 14, 15145-15157. [3] Hiemstra and Van Riemsdijk (1996) J. Colloid Interf. Sci. 179, 488-508.

Calcite crystal growth rate inhibition by polycarboxylic acids

USGS Publications Warehouse

Reddy, M.M.; Hoch, A.R.

2001-01-01

Calcite crystal growth rates measured in the presence of several polycarboxyclic acids show that tetrahydrofurantetracarboxylic acid (THFTCA) and cyclopentanetetracarboxylic acid (CPTCA) are effective growth rate inhibitors at low solution concentrations (0.01 to 1 mg/L). In contrast, linear polycarbocylic acids (citric acid and tricarballylic acid) had no inhibiting effect on calcite growth rates at concentrations up to 10 mg/L. Calcite crystal growth rate inhibition by cyclic polycarboxyclic acids appears to involve blockage of crystal growth sites on the mineral surface by several carboxylate groups. Growth morphology varied for growth in the absence and in the presence of both THFTCA and CPTCA. More effective growth rate reduction by CPTCA relative to THFTCA suggests that inhibitor carboxylate stereochemical orientation controls calcite surface interaction with carboxylate inhibitors. ?? 20O1 Academic Press.

Spontaneous transition of replacive to displacive growth of dolomite in burial dolomitization, and of serpentine in serpentinization

NASA Astrophysics Data System (ADS)

Merino, E.; Canals, A.

2011-12-01

Burial dolostones consist of huge volumes of dolomite that has replaced limestone volume for volume, with patches < 10 meters across of thin, equidistant "zebra" veins that are displacive. Characteristically, the contact between the two dolomite types is, under the microscope, seamless. This has long puzzled carbonate petrologists, who have mistaken the displacive dolomite veins for "void-filling cements" and therefore expect a sharp contact between the two dolomite types. The replacive dolomite forms not by dissolution-precipitation as usually assumed, but by dolomite-growth-driven pressure solution of the host calcite -- if the host is sufficiently viscous, or rigid. The local stress induced by the dolomite growth self-adjusts automatically so as to force the rates of dolomite growth and calcite pressure-solution to be mutually equal at each moment of the replacement. That is why replacement is always isovolumetric. But the dolomite-for-calcite replacement is self-accelerating via Ca2+ (each replacement increment releases Ca2+, which increases the activity product for dolomite and thus the rate of the next replacement increment, and so on), and crystalline carbonates are non-newtonian solids of the softening kind (as shown experimentally, Heard & Raleigh 1972). Thus, when the dolomite-for-calcite replacement becomes fast enough to reduce the local rock viscosity sufficiently, and if aqueous Mg2+ has not run out by then, the replacive growth will inevitably, and seamlessly, transition to displacive growth. This is when incipient zebra veins start to form. Each vein interacts with its neighbors via the induced stress they exert on each other, which leads to a "weeding" feedback that pressure dissolves some veins (the ones that find themselves too close to their neighbors), leaving the surviving ones more equidistant than before. Dolomitic zebra veins, or "rhythmites", are a good example of syntaxial veins. The same process and feedbacks, via Mg2+ instead of via Ca2+, take place in the serpentinization of ultrabasic rocks, leading also to displacive zebra veins of serpentine in seamless contact with the host, replacive serpentine. The origin of the dolomite zebra veins above turns out to have a serendipitous proof. The same feedback that causes the dolomite-for-calcite replacement to self-accelerate exponentially, raises the pore-fluid Ca2+ concentration also exponentially. Consequently, when the rheological replacement-to-displacement transition takes place, the displacive dolomite is growing under such a huge Ca2+ concentration that some Ca2+, even as submicroscopic calcitic slivers, is forced to substitute for Mg2+ in the structure of the growing dolomite, deforming and curving it. This is why the displacive zebra veins always consist of dolomite crystals that are curved, called saddle dolomite. It also explains why some calcite forms right after the dolomite veins stop growing, as a cement and/or back-replacing dolomite.

Modeling the growth and interaction of stylolite networks, using the discrete element method for pressure solution

NASA Astrophysics Data System (ADS)

Makedonska, N.; Sparks, D. W.; Aharonov, E.

2012-12-01

Pressure solution (also termed chemical compaction) is considered the most important ductile deformation mechanism operating in the Earth's upper crust. This mechanism is a major player in a variety of geological processes, including evolution of sedimentary basins, hydrocarbon reservoirs, aquifers, earthquake recurrence cycles, and fault healing. Pressure solution in massive rocks often localizes into solution seams or stylolites. Field observations of stylolites often show elastic/brittle interactions in regions between pressure solution features, including and shear fractures, veins and pull-apart features. To understand these interactions, we use a grain-scale model based on the Discrete Element Method that allows granular dissolution at stressed contacts between grains. The new model captures both the slow chemical compaction process and the more abrupt brittle fracturing and sliding between grains. We simulate a sample of rock as a collection of particles, each representing either a grain or a unit of rock, bonded to each other with breakable cement. We apply external stresses to this sample, and calculate elastic and frictional interactions between the grains. Dissolution is modeled by an irreversible penetration of contacting grains into each other at a rate that depends on the contact stress and an adjustable rate constant. Experiments have shown that dissolution rates at grain contacts are greatly enhanced when there is a mineralogical contrast. Therefore, we dissolution rate constant can be increased to account for an amount of impurities (e.g. clay in a quartz or calcite sandstone) that can accumulate on dissolving contacts. This approach allows large compaction and shear strains within the rock, while allowing examination of local grain-scale heterogeneity. For example, we will describe the effect of pressure solution on the distribution of contact forces magnitudes and orientations. Contact forces in elastic granular packings are inherently heteregeneous, but stress-dependent dissolution tends to equalize them. We apply our model to the simulation of stylolite networks, particularly the interaction of stylolite tips. The stress concentrations from these tips are transmitted through the intervening rock, which can cause elastic strain, brittle damage and frictional sliding. Our model shows that grain rearrangement and compaction rate depend on the surface friction coefficient of grains. Simulation results show the development of shear zones between stylolites, and a high porosity process zone at the tips of stylolites. These features, which have been observed in field studies, are modeled and predicted for the first time. This modeling tool holds a promise to provide many new insights regarding the coupling between pressure solution and brittle deformation, i.e. between mechanical and chemical compaction.

Fabrication of B-type carbonate apatite blocks by the phosphorization of free-molding gypsum-calcite composite.

PubMed

Zaman, Chowdury Tanira; Takeuchi, Akari; Matsuya, Shigeki; Zaman, Q H M Shawket; Ishikawa, Kunio

2008-09-01

B-type carbonate apatite (CO3Ap) block may be an ideal artificial bone substitute because it is closer in chemical composition to bone mineral. In the present study, the feasibility to fabricate CO3Ap blocks was investigated using compositional transformation, which was based on the dissolution-precipitation reaction of a gypsum-calcite composite with free-molding behavior. For the compositional change, or phosphorization, gypsum-calcite composites of varying CaCO3 contents were immersed in 1 mol/L (NH4)3PO4 aqueous solution at 100 degrees C for 24 hours. No macroscopic changes were found after the treatment, whereas microscopic change was observed at SEM level. X-ray diffraction, Fourier transform infrared spectroscopy and CHN analysis indicated that the composites were B-type CO3Ap containing approximately 6-7 wt% of CO3, a value similar to that of biological bone apatite. Diametral tensile strength of the CO3Ap block was approximately 1-3 MPa. Based on the results obtained, it was therefore concluded that gypsum-calcite was a good candidate for the fabrication of CO3Ap blocks, coupled with the advantage that the composite can be molded to any shape by virtue of the setting property of gypsum.

Crystalline order of a water/glycine film coadsorbed on the (104) calcite surface.

PubMed

Magdans, Uta; Torrelles, Xavier; Angermund, Klaus; Gies, Hermann; Rius, Jordi

2007-04-24

For biomineralization processes, the interaction of the surface of calcite crystals with organic molecules is of particular importance. Especially, biologically controlled biomineralization as in exoskeletons of mollusks and echinoderms, e.g., sea urchin with single-crystal-like spines and shells,1-3 requires molecular control of seed formation and growth process. So far, experiments showing the obvious influence of organic molecules on the morphology and habit of calcite crystals have demonstrated the molecular dimension of the interaction.4-7 Details of the kinetics of growth and dissolution of mineral surfaces influenced by additives are available,8,9 but other experimental data about the structure of the organic/inorganic interface on the atomic scale are rare. On the other hand, complicated organic macromolecules which are involved in biomineralization are numerous, with only a small fraction solved in structure and function so far.10-13 Therefore, model systems have to be designed to provide a basic understanding for the interaction process.14 Using grazing incidence X-ray diffraction combined with molecular modeling techniques, we show that glycine molecules order periodically on the calcite (104) face in competition with the solvent water when exposed to an aqueous solution of the most simple amino acid. In contrast to the general concept of the charge-matching fit of organic molecules on mineral surfaces,4,14 glycine is not attached to the calcite surface directly but substitutes for water molecules in the second hydration layer.

Seasonal variations in modern speleothem calcite growth in Central Texas, U.S.A

USGS Publications Warehouse

Banner, J.L.; Guilfoyle, A.; James, E.W.; Stern, L.A.; Musgrove, M.

2007-01-01

Variations in growth rates of speleothem calcite have been hypothesized to reflect changes in a range of paleoenvironmental variables, including atmospheric temperature and precipitation, drip-water composition, and the rate of soil CO2 delivery to the subsurface. To test these hypotheses, we quantified growth rates of modern speleothem calcite on artificial substrates and monitored concurrent environmental conditions in three caves across the Edwards Plateau in central Texas. Within each of two caves, different drip sites exhibit similar annual cycles in calcite growth rates, even though there are large differences between the mean growth rates at the sites. The growth-rate cycles inversely correlate to seasonal changes in regional air temperature outside the caves, with near-zero growth rates during the warmest summer months, and peak growth rates in fall through spring. Drip sites from caves 130 km apart exhibit similar temporal patterns in calcite growth rate, indicating a controlling mechanism on at least this distance. The seasonal variations in calcite growth rate can be accounted for by a primary control by regional temperature effects on ventilation of cave-air CO2 concentrations and/or drip-water CO2 contents. In contrast, site-to-site differences in the magnitude of calcite growth rates within an individual cave appear to be controlled principally by differences in drip rate. A secondary control by drip rate on the growth rate temporal variations is suggested by interannual variations. No calcite growth was observed in the third cave, which has relatively high values of and small seasonal changes in cave-air CO2. These results indicate that growth-rate variations in ancient speleothems may serve as a paleoenvironmental proxy with seasonal resolution. By applying this approach of monitoring the modern system, speleothem growth rate and geochemical proxies for paleoenviromnental change may be evaluated and calibrated. Copyright ?? 2007, SEPM (Society for Sedimentary Geology).

The Impact of the Flow Field Heterogeneity and of the Injection Rate on the Effective Reaction Rates in Carbonates: a Study at the Pore Scale

NASA Astrophysics Data System (ADS)

Nunes, J. P. P.; Bijeljic, B.; Blunt, M. J.

2015-12-01

Carbonate rocks are notoriously difficult to characterize. Their abrupt facies variations give rise to drastic changes in the petrophysical properties of the reservoir. Such heterogeneity, when further associated with variations in rock mineralogy due to diagenetic processes, result in a challenging scenario to model from the pore to the field scale. Micro-CT imaging is one of the most promising technologies to characterize porous rocks. The understanding at the pore scale of reactive and non-reactive transport is being pushed forward by recent developments in both imaging capability - 3D images with resolution of a few microns - and in modeling techniques - flow simulations in giga-cell models. We will present a particle-based method capable of predicting the evolution of petrophysical properties of carbonate cores subjected to CO2 injection at reservoir conditions (i.e. high pressures and temperatures). Reactive flow is simulated directly on the voxels of high resolution micro-CT images of rocks. Reactants are tracked using a semi-analytical streamline tracing algorithm and rock-fluid interaction is controlled by the diffusive flux of particles from the pores to the grains. We study the impact of the flow field heterogeneity and of the injection rate on the sample-averaged (i.e. effective) reaction rate of calcite dissolution in three rocks of increasing complexity: a beadpack, an oolitic limestone and a bioclastic limestone. We show how decreases in the overall dissolution rate depend on both the complexity of the pore space and also on the flow rate. This occurs even in chemically homogenous rocks. Our results suggest that the large differences observed between laboratory and field scale rates could, in part, be explained by the inhomogeneity in the flow field at the pore scale and the consequent transport-limited flux of reactants at the solid surface. Our results give valuable insight into the processes governing carbonate dissolution and provide a starting point to the refinement of upscaling techniques for reactive flows. Potential impacts for reservoir development and monitoring will also be discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saller, A.H.; Schlanger, S.O.

Two wells drilled along the margin of Enewetak Atoll penetrated approximately 1,000 m of upper eocene, Oligocene, and lower Miocene carbonates. STrontium isotope stratigraphy indicates relatively continuous deposition of carbonate from 40 Ma to 20 Ma. Depositional environments show a gradual basinward progradation of facies with slope carbonates passing upward into fore-reef, reef, back-reef, and lagoonal carbonates. Slope strata contain wackestones and packstones with submarine-cemented lithoclasts, coral, coralline algae fragments, benthic rotaline forams, planktonic forams, and echinoderm fragments. Fore-reef strata are dominantly packstones and boundstones containing large pieces of coral, abundant benthic forams, coralline algae fragments, stromatoporoids(.), and minor planktonicmore » forams. Reef and near-reef sediments include coralgal boundstones and grainstones with abundant benthic forams. Halimeda and miliolid forams are common in lagoonward parts of the back reef. Sponge borings, geopetal structures, and fractures are common in reef and fore-reef strata. Lagoonal strata are wackestones and packstones with common mollusks, coral, coralline algae, and benthic forams (rotaline and miliolid). Diagenesis has extensively altered strata near the atoll margin. Aragonite dissolution and calcite cements (radiaxial and cloudy prismatic are abundant in fore-reef, reef, and some back-reef strata). Petrographic and geochemical data indicate arogonite dissolution and calcite cementation in seawater at burial depths of 100 to 300 m. Dolomite occurs in slope and deeply buried reefal carbonates.« less

Controls on dripwater chemistry of Oregon Caves National Monument, northwestern United States

NASA Astrophysics Data System (ADS)

Rushdi, Ahmed I.; Ersek, Vasile; Mix, Alan C.; Clark, Peter U.

2018-02-01

Cave dripwater chemistry of Oregon Caves National Monument (OCNM) was studied, where the parameters pH, total alkalinity, calcium, magnesium, strontium, sodium and barium were analyzed at quasi-monthly intervals from 2005 to 2007. Different statistical analyses have been used to investigate the variability of the chemical parameters in the different sites in the OCNM cave system. The dripwater varies in response to seasonal changes in rainfall. The drip rates range from zero in summer to continuous flow in winter, closely following the rainfall intensity. Spatial variations of dripwater chemistry, which is nonlinearly related to dripwater discharge likely, reflect the chemical composition of bedrock and overlying soil, and the residence time of the ground water within the aquifer. The residence time of infiltrated water in bedrock cracks control the dissolution carbonate bedrock, reprecipitation of calcium carbonate and the degree of saturation of dripwater with respect to calcium carbonate minerals. Spatiotemporal fluctuations of dripwater Mg/Ca and Sr/Ca ratios are controlled by dissolution of carbonate bedrock and the degree of calcite reprecipitation in bedrock cracks. This suggests that trace elements in speleothem deposits at the OCNM may serve as paleoclimatological proxies for precipitation, if interpreted within the context of understanding local bedrock chemistry.

Diagenesis of the Machar Field (British North Sea) chalk: Evidence for decoupling of diagenesis in fractures and the host rock

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maliva, R.G.; Dickson, J.A.D.; Smalley, P.C.

1995-01-02

The Chalk Group (Cretaceous/Tertiary) in the Machar Field (British North Sea) contains both fracture-filling and microcrystalline calcite cements. Modeling of fluid-rock interaction using data on light stable isotopes obtained by whole rock analyses and laser ablation analyses of calcite cements reveal that the fracture and matrix diagenetic systems were largely decoupled. The calcium and carbonate of the fracture-filling calcite cements were derived largely from the adjacent chalk matrix. The fracture diagenetic system had a high water-rock ratio, which maintained a relatively stable water {delta}{sup 18}O ratio during calcite dissolution and precipitation. The chalk matrix, on the contrary, had a lowmore » molar water-rock ratio during recrystallization, which resulted in increases in the pore-water {delta}{sup 18}O value during recrystallization at elevated temperatures. This evolution of the pore-water {delta}{sup 18}O value is manifested by highly variable cement {delta}{sup 18}O values. The present-day formation waters of the Machar Field have {sup 87}Sr/{sup 86}Sr ratios significantly higher than the whole rock and fracture-filling cement calcite values, evidence that the chemical composition of the formation waters is not representative of that of the pore waters during chalk recrystallization. Little diagenesis is therefore now occurring in the Machar Field. The diagenetic systems of the chalk matrix and fractures both had a high degree of openness with respect to carbon, because of the introduction of organically derived bicarbonate rather than advection of water through the chalk. The bulk of calcite cementation in fractures and the recrystallization and cementation of the chalk matrix occurred at temperatures in the 80--100 C range, at or just below the present-day reservoir temperature of 97 C.« less

Sulfur, carbon, and oxygen isotope variations in submarine hydrothermal deposits of Guaymas Basin, Gulf of California, USA

USGS Publications Warehouse

Peter, J.M.; Shanks, Wayne C.

1992-01-01

Sulfur, carbon, and oxygen isotope values were measured in sulfide, sulfate, and carbonate from hydrothermal chimney, spire, and mound samples in the southern trough of Guaymas Basin, Gulf of California, USA. ??34S values of sulfides range from -3.7 to 4.5%. and indicate that sulfur originated from several sources: 1. (1) dissolution of 0??? sulfide contained within basaltic rocks, 2. (2) thermal reduction of seawater sulfate during sediment alteration reactions in feeder zones to give sulfide with positive ??34S, and 3. (3) entrainment or leaching of isotopically light (negative-??34S) bacteriogenic sulfide from sediments underlying the deposits. ??34S of barite and anhydrite indicate sulfur derivation mainly from unfractionated seawater sulfate, although some samples show evidence of sulfate reduction and sulfide oxidation reactions during mixing within chimneys. Oxygen isotope temperatures calculated for chimney calcites are in reasonable agreement with measured vent fluid temperatures and fluid inclusion trapping temperatures. Hydrothermal fluids that formed calcite-rich chimneys in the southern trough of Guaymas Basin were enriched in 18O with respect to seawater by about 2.4??? due to isotopic exchange with sedimentary and/or basaltic rocks. Carbon isotope values of calcite range from -9.6 to -14.0??? ??34CpDB, indicating that carbon was derived in approximately equal quantities from the dissolution of marine carbonate minerals and the oxidation of organic matter during migration of hydrothermal fluid through the underlying sediment column. Statistically significant positive, linear correlations of ??34S, ??34C, and ??18O of sulfides and calcites with geographic location within the southern trough of Guaymas Basin are best explained by variations in water/rock ( w r) ratios or sediment reactivity within subsurface alteration zones. Low w r ratios and the leaching of detrital carbonates and bacteriogenic sulfides at the southern vent sites result in relatively high ??13C and low ??34S in chimney carbonates and sulfides, respectively. In the north, where the depletion of alkalis in vent fluids indicates higher w r ratios, positive ??34S and more negative ??13c are due to increased contributions from organic matter oxidation and sulfate reduction reactions. ?? 1992.

Major geochemical processes in the evolution of carbonate-Aquifer systems

USGS Publications Warehouse

Hanshaw, B.B.; Back, W.

1979-01-01

As a result of recent advances by carbonate petrologists and geochemists, hydrologists are provided with new insights into the origin and explanation of many aquifer characteristics and hydrologic phenomena. Some major advances include the recognition that: (1) most carbonate sediments are of biological origin; (2) they have a strong bimodal size-distribution; and (3) they originate in warm shallow seas. Although near-surface ocean water is oversaturated with respect to calcite, aragonite, dolomite and magnesite, the magnesium-hydration barrier effectively prevents either the organic or inorganic formation of dolomite and magnesite. Therefore, calcareous plants and animals produce only calcite and aragonite in hard parts of their bodies. Most carbonate aquifers that are composed of sand-size material have a high initial porosity; the sand grains that formed these aquifers originated primarily as small shells, broken shell fragments of larger invertebrates, or as chemically precipitated oolites. Carbonate rocks that originated as fine-grained muds were initially composed primarily of aragonite needles precipitated by algae and have extremely low permeability that requires fracturing and dissolution to develop into aquifers. Upon first emergence, most sand beds and reefs are good aquifers; on the other hand, the clay-sized carbonate material initially has high porosity but low permeability, a poor aquifer property. Without early fracture development in response to influences of tectonic activity these calcilutites would not begin to develop into aquifers. As a result of selective dissolution, inversion of the metastable aragonite to calcite, and recrystallization, the porosity is collected into larger void spaces, which may not change the overall porosity, but greatly increases permeability. Another major process which redistributes porosity and permeability in carbonates is dolomitization, which occurs in a variety of environments. These environments include back-reefs, where reflux dolomites may form, highly alkaline, on-shore and continental lakes, and sabkha flats; these dolomites are typically associated with evaporite minerals. However, these processes cannot account for most of the regionally extensive dolomites in the geologic record. A major environment of regional dolomitization is in the mixing zone (zone of dispersion) where profound changes in mineralogy and redistribution of porosity and permeability occur from the time of early emergence and continuing through the time when the rocks are well-developed aquifers. The reactions and processes, in response to mixing waters of differing chemical composition, include dissolution and precipitation of carbonate minerals in addition to dolomitization. An important control on permeability distribution in a mature aquifer system is the solution of dolomite with concomitant precipitation of calcite in response to gypsum dissolution (dedolomitization). Predictive models developed by mass-transfer calculations demonstrate the controlling reactions in aquifer systems through the constraints of mass balance and chemical equilibrium. An understanding of the origin, chemistry, mineralogy and environments of deposition and accumulation of carbonate minerals together with a comprehension of diagenetic processes that convert the sediments to rocks and geochemical, tectonic and hydrologic phenomena that create voids are important to hydrologists. With this knowledge, hydrologists are better able to predict porosity and permeability distribution in order to manage efficiently a carbonate-aquifer system. ?? 1979.

Effects and limitations of elemental sulphur applications for enhanced phytoextraction.

PubMed

Fässler, Erika; Stauffer, Werner; Gupta, Satish K; Schulin, Rainer

2012-08-01

The application of elemental sulphur (S) to heavy metal contaminated soils is a strategy to increase metal extraction by plants. Here, we examined to which degree the efficiency of phytoextraction could be enhanced by increasing the S application rate on afield where S had already been applied for 6 years. For this purpose, the field experiment was continued for another two years doubling the S application rate on half of the S treatment plots, while continuing application at the previous rate on the other half. Doubling the application rate significantly accelerated the dissolution of calcite and the decrease in soil pH and also increased cadmium (Cd) and zinc (Zn) uptake by sunflower and tobacco. But even in a best-case-scenario remediation of the site would still take more than a century. The results indicate that we reached the maximum potential of S application to enhance metal phytoextraction on the study site. Further decrease in pH by additional S applications would bear an excessive risk of decreasing yields and increasing metal leaching out of the root zone.

In-situ growth of calcite at Devils Hole, Nevada: Comparison of field and laboratory rates to a 500,000 year record of near-equilibrium calcite growth

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.; Riggs, A.C.

2000-01-01

Calcite grew continuously for 500,000 years on the submerged walls of an open fault plane (Devils Hole) in southern Nevada, U.S.A. at rates of 0.3 to 1.3 mm/ka, but ceased growing approximately 60,000 years ago, even though the fault plane remained open and was continuously submerged. The maximum initial in-situ growth rate on pre-weighed crystals of Iceland spar placed in Devils Hole (calcite saturation index, SI, is 0.16 to 0.21 at 33.7??C) for growth periods of 0.75 to 4.5 years was 0.22 mm/ka. Calcite growth on seed crystals slowed or ceased following initial contact with Devils Hole groundwater. Growth rates measured in synthetic Ca-HCO3 solutions at 34??C, CO2 partial pressures of 0.101, 0.0156 (similar to Devils Hole groundwater) and 0.00102 atm, and SI values of 0.2 to 1.9 were nearly independent of P(CO)(2), decreased with decreasing saturation state, and extrapolated through the historical Devils Hole rate. The results show that calcite growth rate is highly sensitive to saturation state near equilibrium. A calcite crystal retrieved from Devils Hole, and used without further treatment of its surface, grew in synthetic Devils Hole groundwater when the saturation index was raised nearly 10-fold that of Devils Hole water, but the rate was only 1/4 that of fresh laboratory crystals that had not contacted Devils Hole water. Apparently, inhibiting processes that halted calcite growth in Devils Hole 60,000 years ago continue today.

In-situ growth of calcite at Devils Hole, Nevada--Comparison of field and laboratory rates to a 500,000 year record of near-equilibrium calcite growth

USGS Publications Warehouse

Plummer, Niel; Busenberg, Eurybiades; Riggs, Alan C.

2000-01-01

Calcite grew continuously for 500,000 years on the submerged walls of an open fault plane (Devils Hole) in southern Nevada, U.S.A. at rates of 0.3 to 1.3 mm/ka, but ceased growing approximately 60,000 years ago, even though the fault plane remained open and was continuously submerged. The maximum initial in-situ growth rate on pre-weighed crystals of Iceland spar placed in Devils Hole (calcite saturation index, SI, is 0.16 to 0.21 at 33.7 °C) for growth periods of 0.75 to 4.5 years was 0.22 mm/ka. Calcite growth on seed crystals slowed or ceased following initial contact with Devils Hole groundwater. Growth rates measured in synthetic Ca-HCO3 solutions at 34 °C, CO2 partial pressures of 0.101, 0.0156 (similar to Devils Hole groundwater) and 0.00102 atm, and SI values of 0.2 to 1.9 were nearly independent of PCO2, decreased with decreasing saturation state, and extrapolated through the historical Devils Hole rate. The results show that calcite growth rate is highly sensitive to saturation state near equilibrium. A calcite crystal retrieved from Devils Hole, and used without further treatment of its surface, grew in synthetic Devils Hole groundwater when the saturation index was raised nearly 10-fold that of Devils Hole water, but the rate was only 1/4 that of fresh laboratory crystals that had not contacted Devils Hole water. Apparently, inhibiting processes that halted calcite growth in Devils Hole 60,000 years ago continue today.

Flow Through Cement Fracture Under Geological Carbon Sequestration Conditions: Critical Residence Time as a Unifying Parameter for Fracture Opening or Self-Sealing Behavior

NASA Astrophysics Data System (ADS)

Li, L.; Brunet, J. P. L.; Karpyn, Z.; Huerta, N. J.

2016-12-01

During geological carbon sequestration (GCS) large quantities of CO2 are injected in underground formations. Cement fractures represent preferential leakage pathways in abandoned wells upon exposure to CO2-rich fluid. Contrasting self- healing and fracture opening behavior have been observed while a unifying framework is still missing. The modelling of this process is challenging as it involves complex chemical, mechanical and transport interactions. We developed a process-based reactive transport model that explicitly simulates flow and multi-component reactive transport in fractured cement by reproducing experimental observations of sharp flow rate reduction during exposure to carbonated water. Mechanical interactions have not been included. The simulation shows a similar reaction network as in diffusion-controlled systems without flow. That is, CO2-rich water induced portlandite dissolution, releasing calcium that further reacted with carbonate to form calcite. This created localized changes in porosity and permeability inducing large differences in the long term response of the system through a complex positive feedback loop (e.g., a decrease in local permeability induces a decrease in flow that in turn amplifies the precipitation of calcite through a reduced acidic brine flow). The calibrated model was used to generate 250 numerical experiments of CO2-flooding in cement fractures with varying initial hydraulic apertures (b) and residence times (τ) defined as the ratio of fracture volume over flow rate. A long τ leads to slow replenishment of carbonated water, calcite precipitation, and self-sealing. The opposite occurs when τ is small with short fractures and fast flow rates. Simulation results indicate that a critical residence time τc - the minimum τ required for self-sealing -divides the conditions that trigger the diverging opening and self-sealing behavior. The τc value depends on the initial aperture size (see figure). Among the 250 simulated fracture cases, significant changes in effective permeability - self-healing or opening - typically occurs within hours to a day, thus providing a supporting argument for the extrapolation of short-term laboratory observations (hours to months) to long-term predictions at relevant GCS time scales (years to hundreds of years).

Textural and isotopic evidence for Ca-Mg carbonate pedogenesis

NASA Astrophysics Data System (ADS)

Diaz-Hernandez, J. L.; Sánchez-Navas, A.; Delgado, A.; Yepes, J.; Garcia-Casco, A.

2018-02-01

Models for evaluating the terrestrial carbon cycle must take into account not only soil organic carbon, represented by a mixture of plant and animal remains, but also soil inorganic carbon, contained in minerals, mainly in calcite and dolomite. Thick soil caliches derived from weathering of mafic and ultramafic rocks must be considered as sinks for carbon storage in soils. The formation of calcite and dolomite from pedogenic alteration of volcanic tephras under an aridic moisture regime is studied in an unusually thick 3-m soil profile on Gran Canaria island (Canary Islands, Spain). The biological activity of the pedogenic environment (soil respiration) releases CO2 incorporated as dissolved inorganic carbon (DIC) in waters. It drives the formation of low-magnesian calcite and calcian dolomite over basaltic substrates, with a δ13C negative signature (-8 to -6‰ vs. V-PDB). Precipitation of authigenic carbonates in the soil is accompanied by the formation of Mg-rich clay minerals and quartz after the weathering of basalts. Mineralogical, textural, compositional, and isotopic variations throughout the soil profile studied indicate that dolomite formed at greater depths and earlier than the calcite. The isotopic signatures of the surficial calcite and deeper dolomite crusts are primary and resulted from the dissolution-precipitation cycles that led to the formation of both types of caliches under different physicochemical conditions. Dolomite formed within a clay-rich matrix through diffusive transport of reactants. It is precipitated from water with more negative δ18O values (-1.5 to -3.5‰ vs. V-SMOW) in the subsoil compared to those of water in equilibrium with surficial calcite. Thus, calcite precipitated after dolomite, and directly from percolating solutions in equilibrium with vadose water enriched in δ18O (-0.5 to +1.5‰) due to the evaporation processes. The accumulation of inorganic carbon reaches 586.1 kg m-2 in the soil studied, which means that the carbon sequestration capacity of mafic rocks must be taken into account for certain terrestrial settings. Dolomite together with calcite should be assessed when quantifying carbon stored in arid-semiarid soils as a result of the natural weathering processes.

Development and calibration of a reactive transport model for carbonate reservoir porosity and permeability changes based on CO 2 core-flood experiments

DOE PAGES

Smith, Megan M.; Hao, Y.; Carroll, S. A.

2017-01-02

Here, beneficial pore space and permeability enhancements are likely to occur as CO 2-charged fluids partially dissolve carbonate minerals in carbonate reservoir formations used for geologic CO 2 storage. The ability to forecast the extent and impact of changes in porosity and permeability will aid geologic CO 2 storage operations and lower uncertainty in estimates of long-term storage capacity. Our work is directed toward developing calibrated reactive transport models that more accurately capture the chemical impacts of CO 2-fluid-rock interactions and their effects on porosity and permeability by matching pressure, fluid chemistry, and dissolution features that developed as a resultmore » of reaction with CO 2-acidified brines at representative reservoir conditions. We present new results from experiments conducted on seven core samples from the Arbuckle Dolostone (near Wellington, Kansas, USA, recovered as part of the South-Central Kansas CO 2 Demonstration). Cores were obtained from both target reservoir and lower-permeability baffle zones, and together these samples span over 3–4 orders of magnitude of permeability according to downhole measurements. Core samples were nondestructively imaged by X-ray computed tomography and the resulting characterization data were mapped onto a continuum domain to further develop a reactive transport model for a range of mineral and physical heterogeneity. We combine these new results with those from previous experimental studies to more fully constrain the governing equations used in reactive transport models to better estimate the transition of enhanced oil recovery operations to long-term geology CO 2 storage. Calcite and dolomite kinetic rate constants (mol m –2 s –1) derived by fitting the results from core-flood experiments range from k calcite,25C = 10 –6.8 to 10 –4.6, and k dolomite,25C = 10 –7.5 to 10 –5.3. The power law-based porosity-permeability relationship is sensitive to the overall pore space heterogeneity of each core. Stable dissolution fronts observed in the more homogeneous dolostones could be accurately simulated using an exponential value of n = 3. Furthermore, unstable dissolution fronts consisting of preferential flowpaths could be simulated using an exponential value of n = 3 for heterogeneous dolostones, and larger values ( n = 6–8) for heterogeneous limestones.« less

Development and calibration of a reactive transport model for carbonate reservoir porosity and permeability changes based on CO 2 core-flood experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Megan M.; Hao, Y.; Carroll, S. A.

Here, beneficial pore space and permeability enhancements are likely to occur as CO 2-charged fluids partially dissolve carbonate minerals in carbonate reservoir formations used for geologic CO 2 storage. The ability to forecast the extent and impact of changes in porosity and permeability will aid geologic CO 2 storage operations and lower uncertainty in estimates of long-term storage capacity. Our work is directed toward developing calibrated reactive transport models that more accurately capture the chemical impacts of CO 2-fluid-rock interactions and their effects on porosity and permeability by matching pressure, fluid chemistry, and dissolution features that developed as a resultmore » of reaction with CO 2-acidified brines at representative reservoir conditions. We present new results from experiments conducted on seven core samples from the Arbuckle Dolostone (near Wellington, Kansas, USA, recovered as part of the South-Central Kansas CO 2 Demonstration). Cores were obtained from both target reservoir and lower-permeability baffle zones, and together these samples span over 3–4 orders of magnitude of permeability according to downhole measurements. Core samples were nondestructively imaged by X-ray computed tomography and the resulting characterization data were mapped onto a continuum domain to further develop a reactive transport model for a range of mineral and physical heterogeneity. We combine these new results with those from previous experimental studies to more fully constrain the governing equations used in reactive transport models to better estimate the transition of enhanced oil recovery operations to long-term geology CO 2 storage. Calcite and dolomite kinetic rate constants (mol m –2 s –1) derived by fitting the results from core-flood experiments range from k calcite,25C = 10 –6.8 to 10 –4.6, and k dolomite,25C = 10 –7.5 to 10 –5.3. The power law-based porosity-permeability relationship is sensitive to the overall pore space heterogeneity of each core. Stable dissolution fronts observed in the more homogeneous dolostones could be accurately simulated using an exponential value of n = 3. Furthermore, unstable dissolution fronts consisting of preferential flowpaths could be simulated using an exponential value of n = 3 for heterogeneous dolostones, and larger values ( n = 6–8) for heterogeneous limestones.« less

Dissolution-precipitation reactions and permeability evolution from reactions of CO2-rich aqueous solutions with fractured basalt

NASA Astrophysics Data System (ADS)

Wells, R. K.; Xiong, W.; Bae, Y.; Sesti, E.; Skemer, P. A.; Giammar, D.; Conradi, M.; Ellis, B. R.; Hayes, S. E.

2015-12-01

The injection of CO2 into fractured basalts is one of several possible solutions to mitigate global climate change; however, research on carbonation in natural basalts in relation to carbon sequestration is limited, which impedes our understanding of the processes that may influence the viability of this strategy. We are conducting bench-scale experiments to characterize the mineral dissolution and precipitation and the evolution of permeability in synthetic and natural basalts exposed to CO2-rich fluids. Analytical methods include optical and electron microscopy, electron microprobe, Raman spectroscopy, nuclear magnetic resonance (NMR), and micro X-ray computed tomography (μCT) with variable flow rates. Reactive rock and mineral samples consist of 1) packed powders of olivine or natural basalt, and 2) sintered cores of olivine or a synthetic basalt mixture. Each sample was reacted in a batch reactor at 100 °C, and 100 bars CO2. Magnesite is detected within one day in olivine packed beds, and within 15 days in olivine sintered cores. Forsterite and synthetic basalt sinters were also reacted in an NMR apparatus at 102 °C and 65 bars CO2. Carbonate signatures are observed within 72 days of reaction. Longer reaction times are needed for carbonate precipitation in natural basalt samples. Cores from the Columbia River flood basalt flows that contain Mg-rich olivine and a serpentinized basalt from Colorado were cut lengthwise, the interface mechanically roughened or milled, and edges sealed with epoxy to simulate a fractured interface. The cores were reacted in a batch reactor at 50-150 °C and 100 bars CO2. At lower temperatures, calcite precipitation is rare within the fracture after 4 weeks. At higher temperatures, numerous calcite and aragonite crystals are observed within 1 mm of the fracture entrance along the roughened fracture surface. In flow-through experiments, permeability decreased along the fracture paths within a few hours to several days of flow.

Estimation of past seepage volumes from calcite distribution in the Topopah Spring Tuff, Yucca Mountain, Nevada

USGS Publications Warehouse

Marshall, B.D.; Neymark, L.A.; Peterman, Z.E.

2003-01-01

Low-temperature calcite and opal record the past seepage of water into open fractures and lithophysal cavities in the unsaturated zone at Yucca Mountain, Nevada, site of a proposed high-level radioactive waste repository. Systematic measurements of calcite and opal coatings in the Exploratory Studies Facility (ESF) tunnel at the proposed repository horizon are used to estimate the volume of calcite at each site of calcite and/or opal deposition. By estimating the volume of water required to precipitate the measured volumes of calcite in the unsaturated zone, seepage rates of 0.005 to 5 liters/year (l/year) are calculated at the median and 95th percentile of the measured volumes, respectively. These seepage rates are at the low end of the range of seepage rates from recent performance assessment (PA) calculations, confirming the conservative nature of the performance assessment. However, the distribution of the calcite and opal coatings indicate that a much larger fraction of the potential waste packages would be contacted by this seepage than is calculated in the performance assessment.

The hydrogeochemical evolution of a barrier island freshwater reservoir: Conceptual understanding and identification of key processes

NASA Astrophysics Data System (ADS)

Seibert, Stephan; Holt, Tobias; Greskowiak, Janek; Freund, Holger; Böttcher, Michael E.; Massmann, Gudrun

2017-04-01

Coastal aquifers play an important role in satisfying the water demands for many people in the world. However, exposition to storm surges, climate change and extensive abstraction pose a threat to current and future use of these valuable water resources in many cases. To mitigate water quality constraints and ensure safe water supply applications, an in-depth understanding of relevant process that determine the water quality is required. We investigated two freshwater reservoirs below the barrier island Spiekeroog, Germany. The main freshwater reservoir is located at the western part of the island, ˜350 years old and has a vertical extension of ˜45m. The other investigated freshwater reservoir is located at the east of Spiekeroog, only a few decades old and has a vertical extension <7m. The ultimate goal of our work is to identify, quantify and model the processes governing the water quality evolution of freshwater reservoirs below barrier islands. During sampling campaigns in 2011, 2014 and 2016, field parameters were measured and samples for major cation and anion analysis were taken from 16 freshwater wells. Additional samples were taken in 2011 (3H-3He, δ18O, δD), 2014 (DOC, HS-, NH4+, phosphate) and 2016 (DOC, HS-, NH4+, phosphate, 3H-3He, δ18O, δD, δ13C-DIC). Based on the collected data, we conceptualized some important hydrogeochemical processes that are potentially relevant at Spiekeroog. This includes cation exchange, calcite dissolution and redox reactions. The expected freshening time of the main aquifer was estimated by means of the retardation formula for sharp fronts and corresponds to ˜880 years. A 1D PHREEQC simulation showed, however, that the effects of ongoing freshening on the present water quality (after ˜350 years) are negligible. Calculated decalcification rates amount to ˜4.4 mm/year which corresponds to ˜1.5 m downward movement of the decalcification front within the last 350 years. pH values ranging between 7.5-8.5 confirm that groundwater at Spiekeroog is in equilibrium with calcite and underline that calcite dissolution is an important process. With respect to the redox system, the data indicates oxygen and nitrate reduction within the first meters of the saturated zone but Mn-Oxide and Fe-Oxide reduction rates seem to be low in the aquifer based on measured dissolved Mn(2+) and Fe(2+) concentrations. The absence of dissolved Fe(2+) could be explained by the formation of iron sulfide minerals which is in agreement with observed sulfate reduction at greater depth indicated by elevated H2S concentrations and PHREEQC speciation calculations.

Effect of temperature on the reaction pathway of calcium carbonate formation via precursor phases

NASA Astrophysics Data System (ADS)

Purgstaller, Bettina; Mavromatis, Vasileios; Konrad, Florian; Dietzel, Martin

2016-04-01

It has been earlier postulated that some biogenic and sedimentary calcium carbonate (CaCO3) minerals (e.g. calcite and aragonite) are secondary in origin and have originally formed via a metastable calcium carbonate precursor phase (e.g. amorphous CaCO3, [1-2]). Such formation pathways are likely affected by various physicochemical parameters including aqueous Mg and temperature. In an effort to improve our understanding on the formation mechanism of CaCO3 minerals, precipitation experiments were carried out by the addition of a 0.6 M (Ca,Mg)Cl2 solution at distinct Mg/Ca ratios (1/4 and 1/8) into a 1 M NaHCO3 solution under constant pH conditions(8.3 ±0.1). The formation of CaCO3 was systematically examined as a function of temperature (6, 12, 18 and 25 ±0.3° C). During the experimental runs mineral precipitation was monitored by in situ Raman spectroscopy as well as by continuous sampling and analyzing of precipitates and reactive solutions. The results revealed two pathways of CaCO3 formation depending on the initial Mg/Ca ratio and temperature: (i) In experiments with a Mg/Ca ratio of 1/4 at ≤ 12° C as well as in experiments with a Mg/Ca ratio of 1/8 at ≤ 18° C, ikaite (CaCO3 6H2O) acts as a precursor phase for aragonite formation. (ii) In contrast higher temperatures induced the formation of Mg-rich amorphous CaCO3 (Mg-ACC) which was subsequently transformed to Mg-rich calcite. In situ Raman spectra showed that the transformation of Mg-ACC to Mg-calcite occurs at a higher rate (˜ 8 min) compared to that of ikaite to aragonite (> 2 h). Thus, the formation of aragonite rather than of Mg-calcite occurs due to the slower release of Ca2+and CO32- ions into the Mg-rich reactive solution during retarded ikaite dissolution. This behavior is generally consistent with the observation that calcite precipitation is inhibited at elevated aqueous Mg/Ca ratios. [1] Addadi L., Raz S. and Weiner S. (2003) Advanced Materials 15, 959-970. [2] Rodriguez-Blanco J. D., Shaw S., Bots P., Roncal-Herrero T. and Benning L. G (2014) Geochimica et Cosmochimica Acta 127, 204-220

Reacidification modeling and dose calculation procedures for calcium-carbonate-treated lakes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scheffe, R.D.

1987-01-01

Two dose calculation models and a reacidification model were developed and applied to two Adirondack acid lakes (Woods Lake and Cranberry Pond) that were treated with calcite during May 30-31, 1985 as part of the EPRI-funded Lake Acidification Mitigation Project. The first dose model extended Sverdrup's (1983) Lake Liming model by incorporating chemical equilibrium routines to eliminate empirical components. The model simulates laboratory column water chemistry profiles (spatially and temporally) and dissolution efficiencies fairly well; however, the model predicted conservative dissolution efficiencies for the study lakes. Time-series water chemistry profiles of the lakes suggest that atmospheric carbon dioxide intrusion ratemore » was far greater than expected and enhanced dissolution efficiency. Accordingly, a second dose model was developed that incorporated ongoing CO/sub 2/ intrusion and added flexibility in the handling of solid and dissolved species transport. This revised model simulated whole-lake water chemistry throughout the three week dissolution period. The Acid Lake Reacidification Model (ALaRM) is a general mass-balance model developed for the temporal prediction of the principal chemical species in both the water column and sediment pore water of small lakes and ponds.« less

Water chemistry at Snowshoe Mountain, Colorado: mixed processes in a common bedrock

USGS Publications Warehouse

Hoch, A.R.; Reddy, M.M.

2001-01-01

At Snowshoe Mountain the primary bedrock is quite homogeneous, but weathering processes vary as waters moves through the soils, vadose zone and phreatic zone of the subsurface. In the thin soil, physical degradation of tuff facilitates preferential dissolution of potassium ion from glass within the rock matrix, while other silicate minerals remain unaltered. In the vadose zone, in the upper few meters of fractured bedrock, dilute water infiltrates during spring snowmelt and summer storms, leading to preferential dissolution of augite exposed on fracture surfaces. Deeper yet, in the phreatic zone of the fractured bedrock, Pleistocene calcite fracture fillings dissolve, and dioctahedral and trioctahedral clays form as penetrative weathering alters feldspar and pyroxene. Alkalinity is generated and silica concentrations are buffered by mineral alteration reactions.

Impacts of Near-Future Ocean Acidification and Warming on the Shell Mechanical and Geochemical Properties of Gastropods from Intertidal to Subtidal Zones.

PubMed

Leung, Jonathan Y S; Connell, Sean D; Nagelkerken, Ivan; Russell, Bayden D

2017-11-07

Many marine organisms produce calcareous shells as the key structure for defense, but the functionality of shells may be compromised by ocean acidification and warming. Nevertheless, calcifying organisms may adaptively modify their shell properties in response to these impacts. Here, we examined how reduced pH and elevated temperature affect shell mechanical and geochemical properties of common grazing gastropods from intertidal to subtidal zones. Given the greater environmental fluctuations in the intertidal zone, we hypothesized that intertidal gastropods would exhibit more plastic responses in shell properties than subtidal gastropods. Overall, three out of five subtidal gastropods produced softer shells at elevated temperature, while intertidal gastropods maintained their shell hardness at both elevated pCO 2 (i.e., reduced pH) and temperature. Regardless of pH and temperature, degree of crystallization was maintained (except one subtidal gastropod) and carbonate polymorph remained unchanged in all tested species. One intertidal gastropod produced less soluble shells (e.g., higher calcite/aragonite) in response to reduced pH. In contrast, subtidal gastropods produced only aragonite which has higher solubility than calcite. Overall, subtidal gastropods are expected to be more susceptible than intertidal gastropods to shell dissolution and physical damage under future seawater conditions. The increased vulnerability to shell dissolution and predation could have serious repercussions for their survival and ecological contributions in the future subtidal environment.

Ecological and taphonomical influences on coccoliths in surface sediments in the shelf of the Yellow and East China Seas

NASA Astrophysics Data System (ADS)

Jin, Xiaobo; Liu, Chuanlian

2017-05-01

Coccoliths, combined with sediment grain size, carbonate calcium and organic matters content, were analyzed to assess the ecological and taphonomical influences on coccolith distribution patterns in surface sediments in the continental shelf of the Yellow and East China Seas. Coccolith abundances ranged from 0 to 2.08×109 coccoliths g-1 sediment. The increasing abundance from the coastal inner shelf to the seaward middle shelf generally reflects the ecological fact that living coccolithophores are more abundant in the mesotrophic shelf waters than in the eutrophic coastal waters, although their deposits are still controlled by taphonomical effects, such as bottom (tidal) currents and calcite preservation conditions. Most abundant coccoliths are found in the fine-grained sediments of southwestern Cheju Island, where both ecology and taphonomy favor coccolith preservation. Still, large densities of coccoliths (>108 coccoliths g-1 sediment) are also found in coarse-grained relict sediments in the middle shelf. Coccolith assemblages were predominated by Gephyrocapsa oceanica and Emiliania huxleyi. The relative abundance of E. huxleyi, in addition to ecological reasons, may relate to selective post-mortem dissolution, since small E. huxleyi coccoliths are more susceptible to dissolution. Coccolith calcite has minor contributions (<1% to 12%) to total sediment CaCO3, and the main parts are attributed to terrigenous CaCO3 debris and relict shell fragments.

Isotopic exchange in mineral-fluid systems. IV. The crystal chemical controls on oxygen isotope exchange rates in carbonate-H 2O and layer silicate-H 2O systems

NASA Astrophysics Data System (ADS)

Cole, David R.

2000-03-01

Oxygen isotope exchange between minerals and water in systems far from chemical equilibrium is controlled largely by surface reactions such as dissolution-precipitation. In many cases, this behavior can be modeled adequately by a simple pseudo-first order rate model that accounts for changes in surface area of the solid. Previous modeling of high temperature isotope exchange data for carbonates, sulfates, and silicates indicated that within a given mineral group there appears to be a systematic relationship between rate and mineral chemistry. We tested this idea by conducting oxygen isotope exchange experiments in the systems, carbonate-H 2O and layer silicate-H 2O at 300 and 350°C, respectively. Witherite (BaCO 3), strontianite (SrCO 3) and calcite (CaCO 3) were reacted with pure H 2O for different lengths of time (271-1390 h) at 300°C and 100 bars. The layer silicates, chlorite, biotite and muscovite were reacted with H 2O for durations ranging from 132 to 3282 h at 350°C and 250 bars. A detailed survey of grain sizes and grain habits using scanning electron microscopy (SEM) indicated that grain regrowth occurred in all experiments to varying extents. Changes in the mean grain diameters were particularly significant in experiments involving withertite, strontianite and biotite. The variations in the extent of oxygen isotope exchange were measured as a function of time, and fit to a pseudo-first order rate model that accounted for the change in surface area of the solid during reaction. The isotopic rates (ln r) for the carbonate-H 2O system are -20.75 ± 0.44, -18.95 ± 0.62 and -18.51 ± 0.48 mol O m -2 s -1 for calcite, strontianite and witherite, respectively. The oxygen isotope exchange rates for layer silicate-H 2O systems are -23.99 ± 0.89, -23.14 ± 0.74 and -22.40 ± 0.66 mol O m -2 s -1 for muscovite, biotite and chlorite, respectively. The rates for the carbonate-H 2O systems increase in order from calcite to strontianite to witherite. This order clearly reflects the influence of the change in cation chemistry, i.e., Ba > Sr > Ca. A similar pattern is observed for the layer silicate-H 2O systems, where chlorite>biotite>muscovite. The link between cation chemistry and rate is more complicated in this case, but in general, the order follows a trend where Mg-Fe > K-Mg > K, with an associated increase in Si and Al, and decrease in hydroxyl. The isotopic-chemical relations suggest that oxygen isotope exchange behavior monitored experimentally in this study is the net result of bond-breaking and dissolution of the mineral, complex ion formation in solution and growth of the mineral, whose structure is controlled, in large part, by the lattice energy. We compared the rates against the electrostatic attractive lattice energies (neglecting the repulsive forces), normalized per number of cations. The correlations between rates and lattice energies are quite good for both mineral-H 2O systems. The increase in rates correlated with a decrease in the electrostatic attractive lattice energies, i.e., the greater the lattice energy required to break up the crystal, the more sluggish the rates for both chemical and isotopic exchange. By establishing an unambiguous relationship between rate, lattice energy, and ultimately temperature, we can begin to develop empirical equations useful in predicting rates of isotopic exchange for minerals for which experimental data are lacking.

Kinetic and thermodynamic factors controlling the distribution of SO32- and Na+ in calcites and selected aragonites

USGS Publications Warehouse

Busenberg, E.; Plummer, Niel

1985-01-01

Significant amounts of SO42-, Na+, and OH- are incorporated in marine biogenic calcites. Biogenic high Mg-calcites average about 1 mole percent SO42-. Aragonites and most biogenic low Mg-calcites contain significant amounts of Na+, but very low concentrations of SO42-. The SO42- content of non-biogenic calcites and aragonites investigated was below 100 ppm. The presence of Na+ and SO42- increases the unit cell size of calcites. The solid-solutions show a solubility minimum at about 0.5 mole percent SO42- beyond which the solubility rapidly increases. The solubility product of calcites containing 3 mole percent SO42- is the same as that of aragonite. Na+ appears to have very little effect on the solubility product of calcites. The amounts of Na+ and SO42- incorporated in calcites vary as a function of the rate of crystal growth. The variation of the distribution coefficient (D) of SO42- in calcite at 25.0??C and 0.50 molal NaCl is described by the equation D = k0 + k1R where k0 and k1 are constants equal to 6.16 ?? 10-6 and 3.941 ?? 10-6, respectively, and R is the rate of crystal growth of calcite in mg??min-1??g-1 of seed. The data on Na+ are consistent with the hypothesis that a significant amount of Na+ occupies interstitial positions in the calcite structure. The distribution of Na+ follows a Freundlich isotherm and not the Berthelot-Nernst distribution law. The numerical value of the Na+ distribution coefficient in calcite is probably dependent on the number of defects in the calcite structure. The Na+ contents of calcites are not very accurate indicators of environmental salinities. ?? 1985.

A kinetics database and scripts for PHREEQC

NASA Astrophysics Data System (ADS)

Hu, B.; Zhang, Y.; Teng, Y.; Zhu, C.

2017-12-01

Kinetics of geochemical reactions has been increasingly used in numerical models to simulate coupled flow, mass transport, and chemical reactions. However, the kinetic data are scattered in the literature. To assemble a kinetic dataset for a modeling project is an intimidating task for most. In order to facilitate the application of kinetics in geochemical modeling, we assembled kinetics parameters into a database for the geochemical simulation program, PHREEQC (version 3.0). Kinetics data were collected from the literature. Our database includes kinetic data for over 70 minerals. The rate equations are also programmed into scripts with the Basic language. Using the new kinetic database, we simulated reaction path during the albite dissolution process using various rate equations in the literature. The simulation results with three different rate equations gave difference reaction paths at different time scale. Another application involves a coupled reactive transport model simulating the advancement of an acid plume in an acid mine drainage site associated with Bear Creek Uranium tailings pond. Geochemical reactions including calcite, gypsum, and illite were simulated with PHREEQC using the new kinetic database. The simulation results successfully demonstrated the utility of new kinetic database.

Bacterial bio-mediated calcite precipitation for monumental stones conservation: methods of evaluation.

PubMed

Tiano, P; Biagiotti, L; Mastromei, G

1999-05-01

The weathering of monumental stones is a complex process inserted in the more general 'matter transformation cycle' operated by physical, chemical and biological factors. The consequence of these combined actions is a loss of cohesion with dwindling and scaling of stone material and the induction of a progressive mineral matrix dissolution. In the case of calcareous stones, calcite leaching increases the material porosity and decreases its mechanical features with a general weakening of the superficial structural strength. Attempts to stop, or at least to slow down, deterioration of monumental stones has been made by conservative treatments with both inorganic or organic products. More recent studies show a new approach to hinder these phenomena by inducing a bio-mediated precipitation of calcite directly inside the stone porosity. This can be achieved either through the application of organic matrix macromolecules extracted from sea shells or of living bacteria. The effectiveness of the treatment using calcinogenic bacteria has been evaluated with laboratory tests specifically developed to evaluate the parameters such as : porosity, superficial strength and chromatic changes, influenced by the treatment itself. The results obtained seem to indicate that this type of treatment might not be suitable for monumental stone conservation.

Phosphatic precipitates associated with actinomycetes in speleothems from Grand Cayman, British West Indies

NASA Astrophysics Data System (ADS)

Jones, Brian

2009-07-01

Calcitic speleothems from a cave located on the north central coast of Grand Cayman commonly include corrosion surfaces that developed when calcite precipitation ceased and corrosion mediated by condensates became the operative process. Dissolution features associated with these surfaces, including etched crystal surfaces, microcavities, and solution-widened boundaries between crystals, are commonly occupied by microbes and microbial mats that have been replaced by calcium phosphate and/or coated with calcium phosphate. No mineralized microbes were found in the calcite crystals that form the speleothems. The morphology of the mineralized hyphae (eight morphotypes) and spores (nine morphotypes) are indicative of actinomycetes, a group of microbes that are ideally adapted to life in oligotrophic cave environs. Superb preservation of the delicate hyphae, aerial hyphae, and delicate ornamentation on the hyphae and spores indicate that the microbes underwent rapid mineralized while close to their original life positions. Although these actinomycetes were extremely susceptible to replacement by calcium phosphate, there is no evidence that they directly or indirectly controlled precipitation. Nevertheless, the association between the P-rich precipitates and microbes shows that the use of phosphorus as a proxy for seasonal climate changes in paleoclimate analyses must be treated with caution.

Isotopic analysis for degradation diagnosis of calcite matrix in mortar.

PubMed

Dotsika, E; Psomiadis, D; Poutoukis, D; Raco, B; Gamaletsos, P

2009-12-01

Mortar that was used in building as well as in conservation and restoration works of wall paintings have been analysed isotopically (delta(13)C and delta(18)O) in order to evaluate the setting environments and secondary processes, to distinguish the structural components used and to determine the exact causes that incurred the degradation phenomena. The material undergoes weathering and decay on a large proportion of its surface and in depth, due to the infiltration of water through the structural blocks. Mineralogical analysis indicated signs of sulphation and dissolution/recrystallisation processes taking place on the material, whereas stable isotopes provided information relative to the origin of the CO(2) and water during calcite formation and degradation processes. Isotopic change of the initial delta(13)C and delta(18)O in carbonate matrix was caused by alteration of the primary source of CO(2) and H(2)O in mortar over time, particularly by recrystallisation of calcite with porewater, evaporated or re-condensed water, and CO(2) from various sources of atmospheric and biogenic origin. Human influence (surface treatment) and biological growth (e.g. fungus) are major exogenic processes which may alter delta(18)O and delta(13)C in lime mortar.

Growth and development of spring towers at Shiqiang, Yunnan Province, China

NASA Astrophysics Data System (ADS)

Jones, Brian; Peng, Xiaotong

2017-01-01

Throughout the world, high artesian pressures in hydrothermal areas have led to the growth of tall spring towers that have their vents at their summits. The factors that control their development and formative precipitates are poorly understood because these springs, irrespective of location, are mostly inactive. Spring towers found at Shiqiang (Yunnan Province, China), which are up to 4 m high and 3 m in diameter, are formed largely of calcite and aragonite crystal bushes, euhedral calcite crystals and coated grains with alternating Fe-poor and Fe-rich zones, calcite rafts, and cements formed of various combinations of calcite, aragonite, strontianite, Mg-Si reticulate, needle fiber calcite, calcified and non-calcified microbes, diatoms, and insects. Collectively, the limestones that form the towers can be divided into (1) Group A that are friable, porous and form the cores of the towers and have δ18OSMOW values of + 15.7 to + 19.7‰ (average 17.8‰) and δ13CPDB values of + 5.1 to + 6.9‰ (average 5.9‰), and (2) Group B that are hard and well lithified and found largely around the vents and the tower sides, and have δ18OSMOW values of + 13.0 to + 22.0‰ (average 17.6‰) and δ13CPDB values of + 1.4 to + 3.6‰ (average 2.6‰). The precipitates and the isotopic values indicate that these were thermogene springs. Growth of the Shiqiang spring towers involved (1) Phase IA when precipitation of calcite and aragonite bushes formed the core of the tower and Phase IB when calcite, commonly Fe-rich, was precipitated locally, (2) Phase II that involved the precipitation of white cements, formed of calcite, aragonite, strontianite, and Mg-Si reticulate coatings in cavities amid the Phase I precipitates, and (3) Phase III, which formed probably after spring activity ceased, when needle-fiber calcite was precipitated and the mounds were invaded by microbes (some now calcified), diatoms, and insects. At various times during this complex history, pore waters mediated dissolution of the calcite and aragonite and sometimes partial alteration of the aragonite. The diverse array of precipitates, depositional fabrics and diagenetic changes clearly indicate that the composition of the spring water changed frequently. Growth of the spring towers at Shiqiang continued until there was insufficient artesian pressure to lift the water above the top of the tower vent.

Coupled Thermo-Hydro-Chemical (THC) Modeling of Hypogene Karst Evolution in a Prototype Mountain Hydrologic System

NASA Astrophysics Data System (ADS)

Chaudhuri, A.; Rajaram, H.; Viswanathan, H. S.; Zyvoloski, G.

2011-12-01

Hypogene karst systems are believed to develop when water flowing upward against the geothermal gradient dissolves limestone as it cools. We present a comprehensive THC model incorporating time-evolving fluid flow, heat transfer, buoyancy effects, multi-component reactive transport and aperture/permeability change to investigate the origin of hypogene karst systems. Our model incorporates the temperature and pressure dependence of the solubility and dissolution kinetics of calcite. It also allows for rigorous representation of temperature-dependent fluid density and its influence on buoyancy forces at various stages of karstification. The model is applied to investigate karstification over geological time scales in a prototype mountain hydrologic system. In this system, a high water table maintained by mountain recharge, drives flow downward through the country rock and upward via a high-permeability fault/fracture. The pressure boundary conditions are maintained constant in time. The fluid flux through the fracture remains nearly constant even though the fracture aperture and permeability increase by dissolution, largely because the permeability of the country rock is not altered significantly due to slower dissolution rates. However, karstification by fracture dissolution is not impeded even though the fluid flux stays nearly constant. Forced and buoyant convection effects arise due to the increased permeability of the evolving fracture system. Since in reality the aperture varies significantly within the fracture plane, the initial fracture aperture is modeled as a heterogeneous random field. In such a heterogeneous aperture field, the water initially flows at a significant rate mainly through preferential flow paths connecting the relatively large aperture zones. Dissolution is more prominent at early time along these flow paths, and the aperture grows faster within these paths. With time, the aperture within small sub-regions of these preferential flow paths grows to a point where the permeability is large enough for the onset of buoyant convection. As a result, a multitude of buoyant convection cells form that take on a two-dimensional (2D) maze-like appearance, which could represent a 2D analog of the three-dimensional (3D) mazework pattern widely thought to be characteristic of hypogene cave systems. Although computational limitations limited us to 2D, we suggest that similar process interactions in a 3D network of fractures and faults could produce a 3D mazework.

Diagenesis and late-stage porosity development in the pennsylvanian strawn formation, val verde basin, Texas, U.S.A

USGS Publications Warehouse

Newell, K. David; Goldstein, R.H.; Burdick, C.J.

2005-01-01

The Middle Pennsylvanian (Desmoinesian) Strawn Formation in the Trans-Pecos area of Texas was deposited during relative tectonic quiescence that prevailed before rapid infilling of the Val Verde Basin. It represents one of a series of backstepping carbonate ramps formed on the craton side of this foreland basin. Strawn Formation carbonate rocks in three cores - Conoco Anna McClung #3-1, Alex Mitchell S2-1R, and Creek Ranch #10-1 - show several shallowing-up ward sequences, each a few meters thick. The Creek Ranch core displays the deepest-water characteristics of the three cores; the lower part of this core is dominated by graded bedding. The Mitchell and McClung cores contain skeletal-rich carbonates. Both of these cores display characteristics of shallow-water bank or lagoonal environments. All three cores have approximately the same diagenetic history. Primary fluid inclusions indicate early porosity-occluding interparticle and mold-filling calcite precipitated from water with a narrow range of salinities. Modal salinities are that of seawater, but slightly lesser salinities (indicating mixing of seawater and meteoric water) and slightly greater salinities (indicating evaporative concentration of seawater) are also indicated. The influence of meteoric groundwater can be detected by stable-isotope analyses of the early cements at stratigraphic levels that correlate to the tops of the major shallowing-upward depositional sequences. However, subaerial exposure surfaces are not demonstrated in these cores but were likely to be present updip. Most porosity is cement-reduced vugs, dissolution-enlarged (and cement-reduced) molds (> 1/16 mm, < 4 mm), and fractures. Minor intraparticle, intercrystalline, and shelter porosity is also present. Reservoir porosity is caused by fracturing and a late-stage dissolution event. Dissolution in the Creek Ranch core is not as pronounced as in the other cores because of a dearth of skeletal material. Porous zones in the McClung and Mitchell cores are associated with open fractures spatially, which commonly interconnect with nearby molds and vugs. This complex porosity system occurred after stylolitization, as evidenced by "cuticles" of insoluble styloliticresidue thatbridge across small dissolution-enlarged fractures. Porosity detected by wireline logs therefore is mostly effective porosity. The open-fracture network may have been caused by thrusting of the Strawn Formation, most likely in Permian time. Late-stage cement reduction of porosity occurs in two stages-first by calcite spar, then saddle dolomite. These cements are unevenly distributed. Both of these cements contain primary oil-filled fluid inclusions. Homogenization temperatures of primary aqueous fluid inclusions in saddle dolomites indicate that the Strawn Formation has been subjected to a temperature of at least 136??C (roughly 45??C over present formation temperature), which correlates to a vitrinite reflectance equivalent of 1.22%. Homogenization temperatures, in conjunction with oxygen isotope compositions, indicate that fracture-filling calcite spars and the later saddle dolomites precipitated from isotopically positive fluids, which were probably connate waters that had undergone extensive rock-water interaction. These observations suggest that thrusting of carbonate shelf strata, in a proximal foreland setting, was responsible for creation of latestage fracture porosity. In turn, tectonic expulsion of undersaturated, heated, connate water into the Strawn Formation enhanced the porosity. As this expulsed water cooled, it reached saturation with respect to calcite and dolomite, and these cements partly filled the available porosity. These processes of reservoir creation might be expected in other proximal foreland settings.

Organic-inorganic interactions at oil-water contacts: quantitative retracing of processes controlling the CO2 occurrence in Norwegian oil reservoirs

NASA Astrophysics Data System (ADS)

van Berk, Wolfgang; Schulz, Hans-Martin

2010-05-01

Crude oil quality in reservoirs can be modified by degradation processes at oil-water contacts (OWC). Mineral phase assemblages, composition of coexisting pore water, and type and amount of hydrocarbon degradation products (HDP) are controlling factors in complex hydrogeochemical processes in hydrocarbon-bearing siliciclastic reservoirs, which have undergone different degrees of biodegradation. Moreover, the composition of coexisting gas (particularly CO2 partial pressure) results from different pathways of hydrogeochemical equilibration. In a first step we analysed recent and palaeo-OWCs in the Heidrun field. Anaerobic decomposition of oil components at the OWC resulted in the release of methane and carbon dioxide and subsequent dissolution of feldspars (anorthite and adularia) leading to the formation of secondary kaolinite and carbonate phases. Less intensively degraded hydrocarbons co-occur with calcite, whereas strongly degraded hydrocarbons co-occur with solid solution carbonate phase (siderite, magnesite, calcite) enriched in δ13C. To test such processes quantitatively in a second step, CO2 equilibria and mass transfers induced by organic-inorganic interactions have been hydrogeochemically modelled in different semi-generic scenarios with data from the Norwegian continental shelf (acc. Smith & Ehrenberg 1989). The model is based on chemical thermodynamics and includes irreversible reactions representing hydrolytic disproportionation of hydrocarbons according to Seewald's (2006) overall reaction (1a) which is additionally applied in our modelling work in an extended form including acetic acid (1b): (1) R-CH2-CH2-CH3 + 4H2O -> R + 2CO2 + CH4 + 5H2, (2) R-CH2-CH2-CH3 + 4H2O -> R + 1.9CO2 + 0.1CH3COOH + 0.9CH4 + 5H2. Equilibrating mineral assemblages (different feldspar types, quartz, kaolinite, calcite) are based on the observed primary reservoir composition at 72 °C. Modelled equilibration and coupled mass transfer were triggered by the addition and reaction of different amounts of HDP. Modelled CO2 partial pressure values in a multicomponent gas phase equilibrated with K-feldspar, quartz, kaolinite, and calcite resemble measured data. Similar CO2 contents result from acetic acid addition (eq. 1b). Equilibration with albite or anorthite reduces the release of CO2 into the multicomponent gas phase dramatically, by 1 or 4 orders of magnitude compared with the equilibration with K-feldspar (van Berk et al., 2009). Third and based on data by Ehrenberg & Jakobsen (2001), the effects of organic-inorganic interactions at OWCs in Brent Group reservoir sandstones from the Gullfaks Oilfield (offshore Norway) have been hydrogeochemically modelled. Observed local changes in mineral phase assemblage compositions (content of different feldspar types, kaolinite, carbonate) and CO2 partial pressures are attributed to varying degrees of oil-biodegradation (up to more than 10 %; Horstadt et al. 1992). Modelling results are congruent with observations and indicate that (i) intense dissolution of anorthite, (ii) less intense dissolution of albite, (iii) minor dissolution of K-feldspar, (iv) intense precipitation of kaolinite and quartz, (v) less intense precipitation of carbonate, and (vi) formation of CO2 partial pressures are driven by the release of HDP. References Ehrenberg SN & Jakobsen KG (2001) Plagioclase dissolution related to biodegradation of oil in Brent Group sandstones (Middle Jurassic) of Gullfaks Field, northern North Sea. Sedimentology, 48, 703-721. Smith JT & Ehrenberg SN (1989) Correlation of carbon dioxide abundance with temperature in clastic hydrocarbon reservoirs: relationship to inorganic chemical equilibrium. Marine and Petroleum Geology, 6, 129-135. Seewald JS (2003) Organic-inorganic interactions in petroleum-producing sedimentary basins. Nature, 426, 327-333. van Berk, W, Schulz, H-M & Fu, Y (2009) Hydrogeochemical modelling of CO2 equilibria and mass transfer induced by organic-inorganic interactions in siliciclastic petroleum reservoirs. Geofluids, 9, 253-262.

Geochemistry of fluoride in the Black Creek aquifer system of Horry and Georgetown Counties, South Carolina--and its physiological implications

USGS Publications Warehouse

Zack, Allen L.

1980-01-01

High concentrations of fluoride in ground-water supplies in certain areas of Horry and Georgetown Counties, S.C., have been the cause of dental fluorosis (tooth mottling) among persons who have lived in these areas and have ingested the water as children. Geochemical evidence and laboratory experiments demonstrate that fluorapatite in the form of fossil shark teeth is the source of fluoride, and that the fluoride ions are liberated to the ground-water system through anion exchange, rather than by dissolution. Calcite-cemented quartz sand in the upper third of the Black Creek Formation of Late Cretaceous age contains the fossil shark teeth. As ground water progresses downdip, the calcite matrix dissolves and hydrolyzes, releasing bicarbonate, hydroxyl, and calcium ions. The calcium ions are immediately exchanged for sodium ions adsorbed on sodium-rich clays, and the bicarbonate ions accumulate. As the shark teeth are exposed, the hydroxyl ions in solution exchange with fluoride ions on fluorapatite surfaces. Experiments using fossil shark teeth show that sodium chloride in solution inhibits the rate of exchange of fluoride ions from tooth surfaces for hydroxyl ions in solution. The amount of fluoride removed from water and exchanged for hydroxyl ions in the presence of pure hydroxylapatite (hog teeth) was greater in saline water than in freshwater.

Diagenetic evaluation of Pannonian lacustrine deposits in the Makó Trough, southeastern Hungary

NASA Astrophysics Data System (ADS)

Szőcs, Emese; Milovský, Rastislav; Gier, Susanne; Hips, Kinga; Sztanó, Orsolya

2017-04-01

The Makó Trough is the deepest sub-basin of the Pannonian Basin. As a possible shale gas and tight gas accumulation the area was explored by several hydrocarbon companies. In this study, we present the preliminary results on the diagenetic history and the porosity evolution of sandstones and shales. Petrographic (optical microscopy, CL, blue light microscopy) and geochemical methods (SEM-EDX, WDX, O and C stable isotopes) were applied on core samples of Makó-7 well (3408- 5479 m). Processes which influenced the porosity evolution of the sandstones were compaction, cementation, mineral replacement and dissolution. The most common diagenetic minerals are carbonates (non-ferroan and Fe-bearing calcite, dolomite and ankerite), clay minerals (kaolinite, mixed layer illite-smectite and chlorite) and other silicates (quartz and feldspar). Initial clay mineral and ductile grain content also influences reservoir quality. The volumetrically most significant diagenetic minerals are calcite and clay minerals. The petrography of calcite is variable (bright orange to dull red luminescence color, pore-filling cement, replacive phases which are occasionally scattered in the matrix). The δ13 C-PDB values of calcite range from 1.7 ‰ to -5.5 ‰, while δ18 O-PDB values range from 0.5 ‰ to -9.1 ‰, no depth related trend was observed. These data suggest that calcite occurs in more generations, i.e. eogenetic pre-compactional and mesogenetic post-compactional. Kaolinite is present in mottles in size similar to detrital grains, where remnants of feldspars can be seen. This indicates feldspar alteration via influx of water rich in organic derived carbon dioxide. Secondary porosity can be observed in carbonates and feldspars at some levels, causing the improvement of the reservoir quality.

Diagenetic evidence for an epigenetic origin of the Courtbrown Zn-Pb deposit, Ireland

NASA Astrophysics Data System (ADS)

Reed, Christopher P.; Wallace, Malcolm W.

2001-08-01

Mineralisation at the Courtbrown deposit in south-western Ireland is concentrated in the basal section of the Chadian Waulsortian Limestone, immediately above the Courceyan Ballysteen Limestone. Two episodes of sulphide deposition have been identified: an early stage of minor pyrite precipitation, and a later base-metal-rich mineralisation event. Sphalerite, galena and pyrite of the later mineralisation event occur predominantly as replacement phases along stylolites, dissolution seams, and within the micritic matrix of the host limestone. These sulphide minerals also occur as cements within late stage fractures. The following diagenetic phases are present in the Waulsortian and Ballysteen Limestones in the Courtbrown area (from oldest to youngest): non-luminescent synsedimentary calcite cements, non-luminescent equant calcite cements, bright luminescent calcite cement, dull luminescent calcite cement, planar dolomite cement and replacement dolomite (regional dolomite), saddle dolomite cement, and fibrous dull luminescent calcite cement filling pressure-shadows around the sulphide minerals. Homogenisation temperatures for primary fluid inclusions within dull luminescent calcite cements (precipitated penecontemporaneously with base-metal mineralisation) range from 160 to 200 °C, with a mode at 170-180 °C. These values are unlikely to be representative of mineralisation temperatures as the fluid inclusions may have been significantly affected by heating and/or deformation during late burial (maximum paleotemperatures from Ro and CAI data around 310 °C). The observed paragenetic sequence indicates that mineralisation is completely epigenetic. As the earliest mineralisation is hosted by macro-stylolites, the sequence must have obtained a minimum burial depth of around 800 m prior to the onset of mineralisation. A burial depth of 800 m would correspond to an approximate early Chadian age for the Courtbrown area. Pressure-shadows around sphalerite further indicate that mineralisation preceded the major phase of Variscan deformation. Therefore, the base-metal mineralisation at Courtbrown is epigenetic, and the age of mineralisation is in the range of 350 to 307 Ma.

Crystallization of ikaite and its pseudomorphic transformation into calcite: Raman spectroscopy evidence

NASA Astrophysics Data System (ADS)

Sánchez-Pastor, N.; Oehlerich, Markus; Astilleros, José Manuel; Kaliwoda, Melanie; Mayr, Christoph C.; Fernández-Díaz, Lurdes; Schmahl, Wolfgang W.

2016-02-01

Ikaite (CaCO3·6H2O) is a metastable phase that crystallizes in nature from alkaline waters with high phosphate concentrations at temperatures close to 0 °C. This mineral transforms into anhydrous calcium carbonate polymorphs when temperatures rise or when exposed to atmospheric conditions. During the transformation in some cases the shape of the original ikaite crystal is preserved as a pseudomorph. Pseudomorphs after ikaite are considered as a valuable paleoclimatic indicator. In this work we conducted ikaite crystal growth experiments at near-freezing temperatures using the single diffusion silica gel technique, prepared with a natural aqueous solution from the polymictic lake Laguna Potrok Aike (51°57‧S, 70°23‧W) in Patagonia, Argentina. The ikaite crystals were recovered from the gels and the transformation reactions were monitored by in situ Raman spectroscopy at two different temperatures. The first spectra collected showed the characteristic features of ikaite. In successive spectra new bands at 1072, 1081 and 1086 cm-1 and changes in the intensity of bands corresponding to the OH modes were observed. These changes in the Raman spectra were interpreted as corresponding to intermediate stages of the transformation of ikaite into calcite and/or vaterite. After a few hours, the characteristics of the Raman spectrum were consistent with those of calcite. While ikaite directly transforms into calcite at 10 °C in contact with air, at 20 °C this transformation involves the formation of intermediate, metastable vaterite. During the whole process the external shape of ikaite crystals was preserved. Therefore, this transformation showed the typical characteristics of a pseudomorphic mineral replacement, involving the generation of a large amount of porosity to account for the large difference in molar volumes between ikaite and calcite. A mechanism involving the coupled dissolution of ikaite and crystallization of calcite/vaterite is proposed for this replacement.

Experimental study of carbonate formation in oceanic peridotite

NASA Astrophysics Data System (ADS)

Grozeva, Niya G.; Klein, Frieder; Seewald, Jeffrey S.; Sylva, Sean P.

2017-02-01

Interactions of CO2-rich aqueous fluids with mantle peridotite have major implications for geochemical budgets and microbial life in the shallow oceanic lithosphere through the formation of carbonate minerals and reduced carbon species. However, the underlying mechanisms controlling the transformation of CO2 to carbonates in ultramafic-hosted hydrothermal systems remain incompletely understood. A long-term laboratory experiment was conducted at 300 °C and 35 MPa to investigate serpentinization and carbonate formation pathways during hydrothermal alteration of peridotite. Powdered harzburgite was initially reacted with a Ca-rich aqueous fluid for 14,592 h (608 days) and changes in fluid composition were monitored with time. Once the system reached a steady state, a CO2(aq)-rich fluid was injected and allowed to react with the system for 5907 h (246 days). Fluid speciation and mineral analyses suggest that serpentinization of harzburgite in the CO2-poor system led to the precipitation of serpentine, brucite, magnetite, and minor calcite, in addition to other minor phases including chlorite and sulfur-poor Ni sulfides. The addition of the CO2(aq)-rich fluid caused dolomite, Ca-rich dolomite, and high-Mg calcite to form at the expense of olivine, calcite, and brucite, while serpentine remained unreactive. Replacement textures and mineral assemblages mimic those documented in carbonate-altered seafloor serpentinites, particularly those from the Mid-Atlantic Ridge and the Iberia Margin. In contrast to thermodynamic predictions, magnesite did not form in the experiment because the dissolution of clinopyroxene, in combination with the lack of serpentine reactivity, maintained low Mg/Ca ratios in solution. Clinopyroxene dissolution and unreactive serpentine may similarly maintain low Mg/Ca ratios in submarine serpentinization systems and limit magnesite formation in subseafloor environments. Results of this study suggest that the formation of Ca-Mg carbonates by mineral carbonation is favorable in subseafloor serpentinization systems and likely represents a significant, but poorly quantified, carbon sink in hydrothermally altered oceanic lithosphere at slow-spreading mid-ocean ridges.

Face-specific Replacement of Calcite by Amorphous Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Liesegang, M.; Milke, R.; Neusser, G.; Mizaikoff, B.

2016-12-01

Amorphous silica, composed of nanoscale spheres, is an important biomineral, alteration product of silicate rocks on the Earth's surface, and precursor material for stable silicate minerals. Despite constant progress in silica sphere synthesis, fundamental knowledge of natural silica particle interaction and ordering processes leading to colloidal crystals is absent so far. To understand the formation pathways of silica spheres in a geologic environment, we investigated silicified Cretaceous mollusk shell pseudomorphs from Coober Pedy (South Australia) using focused ion beam (FIB)-SEM tomography, petrographic microscopy, µ-XRD, and EMPA. The shells consist of replaced calcite crystals (<2 mm) composed of ordered arrays of uniform, close-packed silica spheres 300 ± 10 nm in size. Concentric layered spheres composed of 40 nm-sized subparticles provide evidence that, at least in the final stage, particle aggregation was the major sphere growth mechanism. Silica sphere arrays in periodically changing orientations perfectly replicate polysynthetic twinning planes of calcite. FIB-SEM tomography shows that cubic closed-packed sphere arrangements preserve the twin lamellae, while the twin plane consists of a submicrometer layer of randomly ordered spheres and vacancies. To transfer crystallographic information from parent to product, the advancement of synchronized dissolution and precipitation fronts along lattice planes is essential. We assume that the volume-preserving replacement process proceeds via a face-specific dissolution-precipitation mechanism with intermediate subparticle aggregation and subsequent layer-by-layer deposition of spheres along a planar surface. Porosity created during the replacement reaction allows permanent fluid access to the propagating reaction interface. Fluid pH and ionic strength remain constant throughout the replacement process, permitting continuous silica nanoparticle formation and diffusion-limited colloid aggregation. Our study provides a natural example of the transformation of an atomic crystal to an amorphous, mesoscale ordered material; thus, links the research fields of natural colloidal crystal formation, carbonate-silica replacement, and crystallization by oriented particle aggregation (CPA).

A reaction-transport model for calcite precipitation and evaluation of infiltration fluxes in unsaturated fractured rock.

PubMed

Xu, Tianfu; Sonnenthal, Eric; Bodvarsson, Gudmundur

2003-06-01

The percolation flux in the unsaturated zone (UZ) is an important parameter addressed in site characterization and flow and transport modeling of the potential nuclear-waste repository at Yucca Mountain, NV, USA. The US Geological Survey (USGS) has documented hydrogenic calcite abundances in fractures and lithophysal cavities at Yucca Mountain to provide constraints on percolation fluxes in the UZ. The purpose of this study was to investigate the relationship between percolation flux and measured calcite abundances using reactive transport modeling. Our model considers the following essential factors affecting calcite precipitation: (1) infiltration, (2) the ambient geothermal gradient, (3) gaseous CO(2) diffusive transport and partitioning in liquid and gas phases, (4) fracture-matrix interaction for water flow and chemical constituents, and (5) water-rock interaction. Over a bounding range of 2-20 mm/year infiltration rate, the simulated calcite distributions capture the trend in calcite abundances measured in a deep borehole (WT-24) by the USGS. The calcite is found predominantly in fractures in the welded tuffs, which is also captured by the model simulations. Simulations showed that from about 2 to 6 mm/year, the amount of calcite precipitated in the welded Topopah Spring tuff is sensitive to the infiltration rate. This dependence decreases at higher infiltration rates owing to a modification of the geothermal gradient from the increased percolation flux. The model also confirms the conceptual model for higher percolation fluxes in the fractures compared to the matrix in the welded units, and the significant contribution of Ca from water-rock interaction. This study indicates that reactive transport modeling of calcite deposition can yield important constraints on the unsaturated zone infiltration-percolation flux and provide useful insight into processes such as fracture-matrix interaction as well as conditions and parameters controlling calcite deposition.

Fulvic acid like organic compounds control nucleation of marine calcite under suboxic conditions

NASA Astrophysics Data System (ADS)

Neuweiler, Fritz; D'Orazio, Valeria; Immenhauser, Adrian; Geipel, Gerhard; Heise, Karl-Heinz; Cocozza, Claudio; Miano, Teodoro M.

2003-08-01

Intracrystalline organic compounds, enclosed within in situ precipitated marine microcrystalline calcite (automicrite), might represent either an inclusion or the catalyst of such precipitation. We use evidence from a Lower Cretaceous deep-water carbonate mound to show (1) the original source, (2) the degree of condensation, (3) the redox conditions involved, and (4) the catalytic role of natural organic matter for the precipitation of automicrite. Fluorescence spectrometry of the intracrystalline organic fraction extracted from these carbonates identifies a marine fulvic acid like organic compound with a low degree of polycondensation. This finding points to a temporal correlation of the initial stage of geopolymer formation with the precipitation of automicrite. Furthermore, the rare earth element (REE) distribution patterns in the mineral show a consistent positive Ce anomaly, suggesting an episode of reductive dissolution of iron-manganese oxyhydroxides during automicrite formation. In general, a relative enrichment of middle-weight REEs is observed, resulting in a convex distribution pattern typical for, e.g., phosphate concretions or humic acid material. By merging the results of spectrometry and REE geochemistry we thus conclude that the marine calcite precipitation was catalyzed by marine fulvic acid like compounds during the early stages of humification under suboxic conditions. This indicates that humification, driven by the presence of a benthic biomass, is more important for calcite authigenesis than any site-specific microbial metabolism. The Neoproterozoic rise of carbonate mounds supports this hypothesis; there is molecular evidence for early metazoan divergence then, but not for a major evolutionary episode of microorganisms.

Morphology Controls on Calcite Recrystallization.

PubMed

Heberling, Frank; Paulig, Leonie; Nie, Zhe; Schild, Dieter; Finck, Nicolas

2016-11-01

Environmental scientists and geoscientists working in different fields regard the reactivity of calcite and corresponding changes in its trace elemental- or isotopic composition from diametrically opposed points of view. As one extreme, calcite based environmental remediation strategies rely on the fast recrystallization of calcite and the concurrent uptake and immobilization of pollutants. Paleo-ecological investigations denote the other extreme, and rely on the invariability of calcite composition over geological periods of time. We use long-term radiotracer experiments to quantify recrystallization rates of seven types of calcite powder with diverse morphology and particle size distribution. On the one hand our results demonstrate the long-term metastability of calcite with equilibrated crystal surfaces even at isotopic dis-equilibrium. On the other hand, we document the extremely high reactivity and interfacial free energy of freshly ground, rough calcite. Our results indicate that bulk calcite recrystallization is an interfacial free energy driven Ostwald-ripening process, in which particle roughness effects dominate over the effect of crystal habitus and particle size. We confirm that the dynamic equilibrium exchange of crystal constituents between kink sites involves an activation barrier of about 25 kJ/mol. At room temperature the equilibrium exchange is limited to a near surface region and proceeds at a rate of (3.6 ± 1.4)·10 -13 mol/(m 2 ·s).

Effect of organic ligands on Mg partitioning and Mg isotope fractionation during low-temperature precipitation of calcite in the absence of growth rate effects

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Immenhauser, Adrian; Buhl, Dieter; Purgstaller, Bettina; Baldermann, Andre; Dietzel, Martin

2017-06-01

Calcite growth rate has been previously shown to be the dominating parameter controlling both Mg partitioning and Mg isotope fractionation during calcite growth. In natural calcite precipitation environments - characterized by abundant organic material - the presence of dissolved organic molecules may affect these two parameters. In order to assess the role of organic molecules, steady state calcite growth experiments have been performed at 25 °C, 1 bar pCO2 and constant, within analytical uncertainty growth rate (rp = 10-7.4 mol m-2 s-1) in the presence of aqueous Mg and six organic ligands in the concentration range from 0.01 to 10 mM. The organic ligands used in this study are: (i) acetic acid, (ii) citric acid, (iii) glutamic acid, (iv) salycilic acid, (v) glycine, and (vi) ethylenediaminetetraacetic acid (EDTA). These contain one or more carboxyl- and amino-groups that are commonly present in natural organic substances found in lacustrine, fluvial, soil, cave, as well as in marine and earliest diagenetic porewater environments. Results shown here indicate that the presence of these carboxyl- and amino-groups promotes an increase in the partition coefficient of Mg in calcite (DMg = (Mg/Ca)calcite/(Mg/Ca)fluid) that can be attributed to their adsorption onto the calcite surfaces and the subsequent reduction of the active sites of growth. This increase of DMg values as a function of the supersaturation degree of calcite in the fluid phase can be described by the linear equation:

Decoupling the Impacts of Heterotrophy and Autotrophy on Sulfuric Acid Speleogenesis

NASA Astrophysics Data System (ADS)

Jones, A. A.; Bennett, P.

2013-12-01

Within caves such as Movile Caves (Romania), the Frasassi Caves (Italy), and Lower Kane Cave (LKC, Wyoming, USA) the combination of abiotic autoxidation and microbiological oxidation of H2S produces SO42- and H+ that promotes limestone dissolution through sulfuric-acid speleogenesis (SAS). Microbial sulfide oxidation by sulfur-oxidizing bacteria (SOB) has been shown recently to be the dominant process leading to speleogenesis in these caves. However, due to the inherently large diversity of microbial communities within these environments, there are a variety of metabolic pathways that can impact limestone dissolution and carbon cycling to varying degrees. In order to investigate these variations we outfitted a continuous flow bioreactor with a Picarro Wavelength-Scanned Cavity Ring Down Spectrometer (WS-CRDS) that continuously monitored and logged 12CO2 and 13CO2 at ppmv sensitivity and isotope ratios at <0.3‰ precision in simulated cave atmospheres. Bioreactors containing Madison Limestone were inoculated with either a monoculture of the mixotrophic sulfur-oxidizing Thiothrix unzii or a mixed environmental (LKC) sulfur-metabolizing community. Ca2+ and pH were also continuously logged in order to quantify the impact of microbial metabolism on limestone dissolution rate. We found an order of magnitude of variability in limestone dissolution rates that were closely tied to microbial metabolism. In monocultures, limestone dissolution was inhibited by excessive reduced sulfur as T. unzii prefers to store sulfur internally as So under these conditions, generating no acidity. The headspace was depleted in 13C when sulfur was being stored as So and enriched in 13C when sulfur was being converted to SO42-. This suggests a preference for a heterotrophy during periods of high sulfur input and autotrophy when sulfur input is low. This was corroborated by an increase in SO42- during low sulfide input and microscope images showed loss of internal sulfur within the filaments during these periods. In both monoculture and LKC environmental cultures, dissolution rates were highest when sulfur-substrate was limited and CO2 was supplied with no organic carbon. Under these conditions δ13C values were as much as 20‰ higher than abiotic conditions and signifies autotrophic carbon fixation which discriminates against 13C. 16S rRNA sequences confirm that autotrophic SOB dominate within this reactor. In contrast, when acetate was supplied with no supplied CO2, δ13C was relatively constant, maintaining values between -31‰ and as low as -37‰. This signifies heterotrophic metabolism where lighter 12C is preferentially consumed resulting in lighter CO2 in the headspace. 16S rRNA sequences confirm that heterotrophic sulfur-reducing bacteria dominate the community within this reactor. When both acetate and CO2 were supplied the heterotrophic behavior appeared to dominate the system which resulted in a significant drop (15‰) in δ13C and a correlative drop in limestone dissolution rate. These results suggest that chemoautotrophy increases the rate of SAS and CO2 flux within the cave environment while heterotrophy leads to slower SAS or even calcite precipitation. Furthermore, changes in carbon substrate (CO2 vs. Acetate) or sulfur substrate concentrations caused an immediate microbial response that could be observed in all measured chemical variables.

Effect of whole catchment liming on the episodic acidification of two adirondack streams

USGS Publications Warehouse

Newton, R.M.; Burns, Douglas A.; Blette, V.L.; Driscoll, C.T.

1996-01-01

During the fall of 1989 7.7Mg/ha of calcium carbonate was applied on two tributary catchments (40 ha and 60 ha) to Woods Lake, a small (25 ha) acidic headwater lake in the western Adirondack region of New York. Stream-water chemistry in both catchment tributaries responded immediately. Acid-neutralizing capacity (ANC) increased by more than 200 ??eq/L in one of the streams and more than 1000 ??eq/L in the other, from pre-liming values which ranged from -25 to +40 ??eq/L. The increase in ANC was primarily due to increases in dissolved Ca2+ concentrations. Most of the initial response of the streams was due to the dissolution of calcite that fell directly into the stream channels and adjacent wetlands. A small beaver impoundment and associated wetlands were probably responsible for the greater response observed in one of the streams. After the liming of subcatchmentIV (60 ha), Ca2+ concentrations increased with increasing stream discharge in the stream during fall rain events, suggesting a contribution from calcite dissolved within the soil and transported to the stream by surface runoff or shallow interflow. Concentrations of other ions not associated with the calcite (e.g. Na+) decreased during fall rain events, presumably due to mixing of solute-rich base flow with more dilute shallow interflow. The strong relation between changes in Ca2+ and changes in NO3- concentrations during spring snowmelt, (r2 = 0.93, slope = 0.96, on an equivalent basis) suggests that both solutes had a common source in the organic horizon of the soil. Increases in NO3- concentrations during snowmelt were balanced by increases in Ca2+ that was released either directly from the calcite or from exchange sites, mitigating episodic acidification of the stream. However, high ambient NO3- concentrations and relatively low ambient Ca2+ concentrations in the stream during the spring caused the stream to become acidic despite the CaCO3 treatment. In stream WO2 (40ha), Ca2+ concentrations were much higher than in stream WO4 because of the dissolution of calcite which fell directly into the upstream beaver pond and its associated wetlands. Calcium concentrations decreased as both NO3- concentrations and stream discharge increased, due to the dilution of Ca-enriched beaver pond water by shallow interflow. Despite this dilution, Ca2+ concentrations were high enough to more than balance strong acid anion (SO42-, NO3-, Cl-) concentrations, resulting in a positive ANC in this stream throughout the year. These data indicate that liming of wetlands and beaver ponds is more effective than whole catchment liming in neutralizing acidic surface waters. ?? 1996 Kluwer Academic Publishers.

Aragonite-calcite precipitation in vertical fractures of the "Erzberg" siderite deposit (Austria): Hydrogeochemical and neotectonic implications

NASA Astrophysics Data System (ADS)

Boch, Ronny; Wang, Xianfeng; Kluge, Tobias; Kurz, Walter; Leis, Albrecht; Lin, Ke; Pluch, Hannes; Mittermayr, Florian; Dietzel, Martin

2017-04-01

The ore deposit "Erzberg" represents the worldwide largest FeCO3 occurrence and is amongst Austria's most prominent geological places due to its historic, economic and scientific value. The iron-ore (siderite/ankerite) bearing Devonian carbonates of the open pit mine locally host sequential aragonite-calcite precipitates infilling vertical fractures. These typically laminated carbonates are referred to as erzbergite in mineral collections. To study their formation conditions we recovered samples on-site, i.e. from the rare veins being cm to dm in horizontal and tenths of meters in vertical extension. Additionally, samples from our university collection and private collectors were investigated. Some of the fractures filled with aragonite/calcite further exhibit cataclastic sediments, damage zones and slickenside striations. Modern water samples were collected from fractures currently accessible to conduct hydrochemical analyses and modeling. Selected precipitates were analyzed applying microscopic techniques, XRD, electron microprobe elemental mapping, stable and clumped isotopes, and 238U-234U-230Th radiometric dating. Erzbergite veins show either uni- or bidirectional growth, i.e. on one or both fracture/fault planes toward complete infilling depending on vadose water flow. The laminated precipitates are dominated by aragonite relative to pristine as well as partially diagenetic (Mg)-calcite. Intercalated and recurrent brownish Fe-rich layers consisting of goethite, quartz, muscovite are probably of detrital origin. Stable C and O isotopes of the precipitates reveal pronounced spatiotemporal variations in which low δ18O values (-10.4 to -5.1 ‰ VPDB) reflect a meteoric origin and low temperatures of the erzbergite depositing solutions. Carbonate clumped isotope measurements verify formation temperatures ≤25 °C. High δ13C values (-0.7 to +6.8 ‰ VPDB) of the precipitates indicate an origin from dissolution of local ankerite and limestone, without a significant proportion from soil CO2. Prominently high δ13C in DIC (≤+3.8 ‰) were also measured in modern fracture waters next to elevated sulfate (up to 226 mg/l) and high total dissolved solid contents (up to 1273 mg/l). These results suggest intense water-rock interaction based on sulfide oxidation and sulfuric acid evolution providing an efficient mechanism for host rock dissolution, mobilization and typically rapid aragonite-calcite mineralization. Sulfide accessories are widespread at Erzberg and the brownish Fe-rich layers within erzbergite could be explained by corrosion of Fe-sulfides and/or Fe-carbonates. The aragonite-calcite lamination is interpreted as an event lamination (not annual), i.e. variable aqueous Mg2+/Ca2+ ratios and CaCO3 supersaturation states triggering the polymorphism. U-Th analyses yielded surprisingly young ages for erzbergite dated so far, i.e. late Pleistocene and mostly younger than the last glacial maximum. A 4 cm thick sample composed of aragonite exclusively and filling a tenths of meters extending fracture formed 10.4 ±0.2 (sample base, initiation) to 1.03 ±0.04 kyr BP (top, fracture filled). Another 25 cm laminated aragonite-calcite precipitate covers 14.2 ±0.2 to 5.0 ±0.2 kyr. Thus, the precipitates support geologically young and rather short time intervals of infilling and we consider it unlikely that the fractures are much older. An intimate connection with neotectonic activity entailing new vadose water flow routes and fresh reaction surfaces in fractures would be in accordance with our hydrogeochemical and field observations.

Rethinking CCD's Significance in Estimating Late Neogene Whole Ocean Carbonate Budget

NASA Astrophysics Data System (ADS)

Si, W.; Rosenthal, Y.

2017-12-01

The global averaged calcite compensation depth (CCD) record is conventionally used to reconstruct two correlatable parameters of the carbonate system - the alkalinity budget of the ocean and/or the saturation state of the ocean. Accordingly, the available CCD reconstructions have been interpreted to suggest either relative stable (Pearson and Palmer, 2000) or increased alkalinity of the ocean over the past 15 Ma (Tyrrell and Zeebe, 2004; Pälike et al., 2012). However, CCD alone is insufficient to constrain the carbonate system because the weathering flux of alkalinity into the ocean is not only balanced by CaCO3 dissolution on the seafloor but also by the biologic production in the euphotic zone and, the CCD records cannot be readily interpreted as changes in either process. Here, we present evidence of the co-evolution of surface CaCO3 production and deepsea dissolution through the late Neogene. By examining separately the mass accumulation rates (MAR) of coccoliths, planktonic foraminifera, and quantifying dissolution (using a proxy revised from Broecker et al., 1999) in seventeen deepsea cores from multiple depth-transects, we find that 1) MAR of dissolution-resistant coccoliths was substantially higher in the mid Miocene and declining on a global scale towards the present; 2) unlike coccoliths, MAR of planktonic foraminifera, shows no apparent secular trend through that time; 3) the revised dissolution index, shows significantly improved preservation of planktonic foraminiferal shells over that time, particularly at intermediate water depth and exhibits close association between changes in preservation with key climatic events. Our new records have two immediate implications. First, the substantially weakened pelagic biogenic carbonate production from mid Miocene to present alone could account for the improved preservation of deepsea carbonates without calling for a scenario of increased weathering input. Second, with the constrain of global averaged CCD records, the net accumulation of pelagic carbonate has declined over the course of late Neogene. Hence, the weathering alkalinity input should have decreased since 15 Ma, as oppose to the weathering hypothesis (Raymo et al., 1988).

Experimental diagenesis: insights into aragonite to calcite transformation of Arctica islandica shells by hydrothermal treatment

NASA Astrophysics Data System (ADS)

Casella, Laura A.; Griesshaber, Erika; Yin, Xiaofei; Ziegler, Andreas; Mavromatis, Vasileios; Müller, Dirk; Ritter, Ann-Christine; Hippler, Dorothee; Harper, Elizabeth M.; Dietzel, Martin; Immenhauser, Adrian; Schöne, Bernd R.; Angiolini, Lucia; Schmahl, Wolfgang W.

2017-03-01

Biomineralised hard parts form the most important physical fossil record of past environmental conditions. However, living organisms are not in thermodynamic equilibrium with their environment and create local chemical compartments within their bodies where physiologic processes such as biomineralisation take place. In generating their mineralised hard parts, most marine invertebrates produce metastable aragonite rather than the stable polymorph of CaCO3, calcite. After death of the organism the physiological conditions, which were present during biomineralisation, are not sustained any further and the system moves toward inorganic equilibrium with the surrounding inorganic geological system. Thus, during diagenesis the original biogenic structure of aragonitic tissue disappears and is replaced by inorganic structural features. In order to understand the diagenetic replacement of biogenic aragonite to non-biogenic calcite, we subjected Arctica islandica mollusc shells to hydrothermal alteration experiments. Experimental conditions were between 100 and 175 °C, with the main focus on 100 and 175 °C, reaction durations between 1 and 84 days, and alteration fluids simulating meteoric and burial waters, respectively. Detailed microstructural and geochemical data were collected for samples altered at 100 °C (and at 0.1 MPa pressure) for 28 days and for samples altered at 175 °C (and at 0.9 MPa pressure) for 7 and 84 days. During hydrothermal alteration at 100 °C for 28 days most but not the entire biopolymer matrix was destroyed, while shell aragonite and its characteristic microstructure was largely preserved. In all experiments up to 174 °C, there are no signs of a replacement reaction of shell aragonite to calcite in X-ray diffraction bulk analysis. At 175 °C the replacement reaction started after a dormant time of 4 days, and the original shell microstructure was almost completely overprinted by the aragonite to calcite replacement reaction after 10 days. Newly formed calcite nucleated at locations which were in contact with the fluid, at the shell surface, in the open pore system, and along growth lines. In the experiments with fluids simulating meteoric water, calcite crystals reached sizes up to 200 µm, while in the experiments with Mg-containing fluids the calcite crystals reached sizes up to 1 mm after 7 days of alteration. Aragonite is metastable at all applied conditions. Only a small bulk thermodynamic driving force exists for the transition to calcite. We attribute the sluggish replacement reaction to the inhibition of calcite nucleation in the temperature window from ca. 50 to ca. 170 °C or, additionally, to the presence of magnesium. Correspondingly, in Mg2+-bearing solutions the newly formed calcite crystals are larger than in Mg2+-free solutions. Overall, the aragonite-calcite transition occurs via an interface-coupled dissolution-reprecipitation mechanism, which preserves morphologies down to the sub-micrometre scale and induces porosity in the newly formed phase. The absence of aragonite replacement by calcite at temperatures lower than 175 °C contributes to explaining why aragonitic or bimineralic shells and skeletons have a good potential of preservation and a complete fossil record.

Leaching of boron, arsenic and selenium from sedimentary rocks: II. pH dependence, speciation and mechanisms of release.

PubMed

Tabelin, Carlito Baltazar; Hashimoto, Ayaka; Igarashi, Toshifumi; Yoneda, Tetsuro

2014-03-01

Sedimentary rocks excavated in Japan from road- and railway-tunnel projects contain relatively low concentrations of hazardous trace elements like boron (B), arsenic (As) and selenium (Se). However, these seemingly harmless waste rocks often produced leachates with concentrations of hazardous trace elements that exceeded the environmental standards. In this study, the leaching behaviors and release mechanisms of B, As and Se were evaluated using batch leaching experiments, sequential extraction and geochemical modeling calculations. The results showed that B was mostly partitioned with the residual/crystalline phase that is relatively stable under normal environmental conditions. In contrast, the majority of As and Se were associated with the exchangeable and organics/sulfides phases that are unstable under oxidizing conditions. Dissolution of water-soluble phases controlled the leaching of B, As and Se from these rocks in the short term, but pyrite oxidation, calcite dissolution and adsorption/desorption reactions became more important in the long term. The mobilities of these trace elements were also strongly influenced by the pH of the rock-water system. Although the leaching of Se only increased in the acidic region, those of B and As were enhanced under both acidic and alkaline conditions. Under strongly acidic conditions, the primarily release mechanism of B, As and Se was the dissolution of mineral phases that incorporated and/or adsorbed these elements. Lower concentrations of these trace elements in the circumneutral pH range could be attributed to their strong adsorption onto minerals like Al-/Fe-oxyhydroxides and clays, which are inherently present and/or precipitated in the rock-water system. The leaching of As and B increased under strongly alkaline conditions because of enhanced desorption and pyrite oxidation while that of Se remained minimal due to its adsorption onto Fe-oxyhydroxides and co-precipitation with calcite. Copyright © 2013 Elsevier B.V. All rights reserved.

Microstructural record of cataclastic and dissolution-precipitation processes from shallow crustal carbonate strike-slip faults, Northern Calcareous Alps (Austria)

NASA Astrophysics Data System (ADS)

Bauer, Helene; Grasemann, Bernhard; Decker, Kurt

2015-04-01

The concept of coseismic slip and aseismic creep deformation along faults is supported by the variability of natural fault rocks and their microstructures. Faults in carbonate rocks are characterized by very narrow principal slip zones (cm to mm wide) containing (ultra)cataclastic fault rocks that accommodate most of the fault displacement. Fluidization of ultracataclastic sub layers and thermal decomposition of calcite due to frictional heating have been proposed as possible indicators for seismic slip. Dissolution-precipitation (DP) processes are possible mechanism of aseismic sliding, resulting in spaced cleavage solution planes and associated veins, indicating diffusive mass transfer and precipitation in pervasive vein networks. We investigated exhumed, sinistral strike-slip faults in carbonates of the Northern Calcareous Alps. The study presents microstructural investigations of natural carbonate fault rocks that formed by cataclastic and dissolution-precipitation related deformation processes. Faults belong to the eastern segment of the Salzachtal-Ennstal-Mariazell-Puchberg (SEMP) fault system that was formed during eastward lateral extrusion of the Eastern Alps in Oligocene to Lower Miocene. The investigated faults accommodated sinistral slip between several tens and few hundreds of meters. Microstructural analysis of fault rocks was done with scanning electron microscopy and optical microscopy. Deformation experiments of natural fault rocks are planned to be conducted at the Sapienza University of Roma and should be available at the meeting. The investigated fault rocks give record of alternating cataclastic deformation and DP creep. DP fault rocks reveal various stages of evolution including early stylolites, pervasive pressure solution seams and cleavage, localized shear zones with syn-kinematic calcite fibre growth and mixed DP/cataclastic microstructures, involving pseudo sc- and scc'-fabrics. Pressure solution seams host fine grained kaolinit, chlorite and illite while the protolith shows only weak evidence of detrital clay content. Our studies suggest that velocity weakening and strengthening mechanisms alternated during the accumulation of displacement along the SEMP fault zone.

Diagenesis of the Oligocene-Miocene rocks of the Upper Floridan and Intermediate aquifer systems by meteoric and mixing-zone waters in southwest Florida

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weedman, S.D.; McCartan, L.

1993-03-01

Optical and SEM of samples from 6 cores of Oligocene and Miocene rocks that compose portions of the Florida and Intermediate aquifers and the intervening semiconfining unit documents meteoric and mixing-zone (seawater and fresh carbonate ground water) diagenesis inferred to have occurred over several cycles of sea level change. Dolomite, limestone, sandstone, and claystone of the Suwannee Formation and the Arcadia Formation (Hawthorn Group) were examined. Core samples from time-equivalent strata in two E--W transects in Manatee, Hardee, Highlands, Sarasota, and DeSoto Counties are estimated to be 16--33 Ma on the basis of [sup 87]Sr/[sup 86]Sr ratios from unaltered molluskmore » shells and by molluscan biostratigraphy. Lithostratigraphic correlations are based on examination of 19 cores, 62 thin sections, 60 geophysical logs, and mineralogy determined by X-ray diffraction. Diagenetic indicators that the authors tracked petrographically include shell micritization, shell dissolution, equant and (or) fibrous CaCO[sub 3] cement, neomorphism, dolomite, etched phosphate grains, echinoderm fragment syntaxial overgrowths, and amorphous silica pore lining. Infiltration of meteoric water caused dissolution of carbonate minerals, especially aragonite, and precipitation of equant calcite crystals in voids of dissolved fossils and in pore spaces between grains. The silica was precipitated as pore linings in zones having soil textures. Observed replacement of calcite by limpid dolomite is consistent with modeling predictions of mixing-zone diagenesis. Etched crystals of limpid dolomite may indicate freshwater dissolution of a mixing-zone precipitate. Mapping of regional unconformities revealed pronounced thickening and thinning of some units. Evidence of meteoric water diagenesis is observed in the upper 600 ft of the transects examined. Evidence of mixing-zone diagenesis is observed at varying depths, but appears to increase in abundance and thickness toward the west.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gorman, Brian P

Project Description: The general objective of the proposed research is to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, pCO 2, and modest ranges in T and P. This will be accomplished by studying both reaction rates and solubility from changes in solution chemistry, and making nanoscale observations of calcite precipitate surface morphology and composition at the micro-to-nano-scale to provide an understanding of controlling reaction mechanisms and pathways. The specific objectives necessary to reach the general objective are: a) determination of how pCO 2, Ca 2+, ionic strength andmore » “foreign” ions influence reaction rates; and b) investigate the influence of these parameters on apparent kinetic solubility from dissolution and precipitation reactions. This information will clearly be central to the construction of reliable reaction-transport models to predict reservoir and formation response to increased CO 2 in saline waters. This program was initially collaborative with John Morse at Texas A&M, however his passing shortly after the beginning of this program resulted in abbreviated research time and effort. Summary of Results: Early studies using electron microscopy and spectroscopy indicated that carbonate precipitation from natural seawater (NSW) conditions onto aragonite substrates was mediated by a surface amorphous calcium carbonate layer. It was hypothesized that this ACC layer (observed after < 5days reaction time) was responsible for the abnormal reaction kinetics and also served as a metastable seed layer for growth of epitaxial aragonite. Further studies of the ACC formation mechanism indicated a strong dependence on the Mg concentration in solution. Subsequent studies at shorter times (10 hrs) on calcite substrates and in a wide range of supersaturation conditions did not indicate any ACC layer. Instead, an epitaxial layer by layer growth mechanism was confirmed by grazing incidence X-ray diffraction, µ-Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, and electron diffraction. Extended time studies out to 45 days confirmed the epitaxial relationship of the overgrowth layer with the substrate. Under NSW conditions, overgrowths were found to have ~0.4 to 0.8 nm / hr growth rates and accommodating 4 at% Mg, resulting in a highly strained overgrowth layer. Following the initial layer by layer growth mechanism, the growth changes to Stranski-Krastanov type after a critical thickness of approximately 100 nm.« less

Characterizing particle-scale equilibrium adsorption and kinetics of uranium(VI) desorption from U-contaminated sediments

USGS Publications Warehouse

Stoliker, Deborah L.; Liu, Chongxuan; Kent, Douglas B.; Zachara, John M.

2013-01-01

Rates of U(VI) release from individual dry-sieved size fractions of a field-aggregated, field-contaminated composite sediment from the seasonally saturated lower vadose zone of the Hanford 300-Area were examined in flow-through reactors to maintain quasi-constant chemical conditions. The principal source of variability in equilibrium U(VI) adsorption properties of the various size fractions was the impact of variable chemistry on adsorption. This source of variability was represented using surface complexation models (SCMs) with different stoichiometric coefficients with respect to hydrogen ion and carbonate concentrations for the different size fractions. A reactive transport model incorporating equilibrium expressions for cation exchange and calcite dissolution, along with rate expressions for aerobic respiration and silica dissolution, described the temporal evolution of solute concentrations observed during the flow-through reactor experiments. Kinetic U(VI) desorption was well described using a multirate SCM with an assumed lognormal distribution for the mass-transfer rate coefficients. The estimated mean and standard deviation of the rate coefficients were the same for all <2 mm size fractions but differed for the 2–8 mm size fraction. Micropore volumes, assessed using t-plots to analyze N2 desorption data, were also the same for all dry-sieved <2 mm size fractions, indicating a link between micropore volumes and mass-transfer rate properties. Pore volumes for dry-sieved size fractions exceeded values for the corresponding wet-sieved fractions. We hypothesize that repeated field wetting and drying cycles lead to the formation of aggregates and/or coatings containing (micro)pore networks which provided an additional mass-transfer resistance over that associated with individual particles. The 2–8 mm fraction exhibited a larger average and standard deviation in the distribution of mass-transfer rate coefficients, possibly caused by the abundance of microporous basaltic rock fragments.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pham Minh, Doan, E-mail: doan.phamminh@mines-albi.fr; Nzihou, Ange; Sharrock, Patrick

Highlights: • Carbonated apatite (CAP) could be easily obtained from CaCO{sub 3} and orthophosphates. • Highest CaCO{sub 3} dissolution and apatitic carbonate content were obtained with H{sub 3}PO{sub 4}. • A-B-type CAP was formed. • The synthesized CAP was thermally stable up to 1000 °C. • This CAP showed high biomineralization activity before and after thermal treatment. - Abstract: The one-step synthesis of carbonated hydroxyapatite (CAP) using calcite and different orthophosphates was investigated in a closed batch reactor. Only orthophosphoric acid could lead to the complete decomposition of calcite particles, when the reaction temperature was set at 80 °C. Onmore » the other hand, the reaction time and the dilution of the initial calcite suspension had no significant influence on the formation of the solid products. CAP was formed as the main crystalline calcium phosphate with the carbonate content in the range of 4.2–4.6 wt.%. The thermal decarbonation of the synthesized CAP started at 750 °C but it was only significant at 1000 °C under air atmosphere. This thermal decarbonation was total at 1200 °C or above. All CAP samples and products following thermal treatments were found bioactive in the test using simulated body fluid (SBF) solution.« less

Effects of Bacillus subtilis endospore surface reactivity on the rate of forsterite dissolution

NASA Astrophysics Data System (ADS)

Harrold, Z.; Gorman-Lewis, D.

2013-12-01

Primary mineral dissolution products, such as silica (Si), calcium (Ca) and magnesium (Mg), play an important role in numerous biologic and geochemical cycles including microbial metabolism, plant growth and secondary mineral precipitation. The flux of these and other dissolution products into the environment is largely controlled by the rate of primary silicate mineral dissolution. Bacteria, a ubiquitous component in water-rock systems, are known to facilitate mineral dissolution and may play a substantial role in determining the overall flux of dissolution products into the environment. Bacterial cell walls are complex and highly reactive organic surfaces that can affect mineral dissolution rates directly through microbe-mineral adsorption or indirectly by complexing dissolution products. The effect of bacterial surface adsorption on chemical weathering rates may even outweigh the influence of active processes in environments where a high proportion of cells are metabolically dormant or cell metabolism is slow. Complications associated with eliminating or accounting for ongoing metabolic processes in long-term dissolution studies have made it challenging to isolate the influence of cell wall interactions on mineral dissolution rates. We utilized Bacillus subtilis endospores, a robust and metabolically dormant cell type, to isolate and quantify the effects of bacterial surface reactivity on forsterite (Mg2SiO4) dissolution rates. We measured the influence of both direct and indirect microbe-mineral interactions on forsterite dissolution. Indirect pathways were isolated using dialysis tubing to prevent mineral-microbe contact while allowing free exchange of dissolved mineral products and endospore-ion adsorption. Homogenous experimental assays allowed both direct microbe-mineral and indirect microbe-ion interactions to affect forsterite dissolution rates. Dissolution rates were calculated based on silica concentrations and zero-order dissolution kinetics. Additional analyses including Mg concentrations, microprobe and BET analyses support mineral dissolution rate calculations and stoichiometry considerations. All experimental assays containing endospores show increased forsterite dissolution rates relative to abiotic controls. Forsterite dissolution rates increased by approximately one order of magnitude in dialysis bound, biotic experiments relative to abiotic assays. Homogenous biotic assays exhibited a more complex dissolution rate profile that changes over time. All microbially mediated forsterite dissolution rates returned to abiotic control rates after 10 to 15 days of incubation. This shift in dissolution rate likely corresponds to maximum endospore surface adsorption capacity. The Bacillus subtilis endospore surface serves as a first-order proxy for studying the effect of metabolizing microbe surfaces on silicate dissolution rates. Comparisons with published abiotic, microbial, and organic acid mediated forsterite dissolution rates will provide insight on the importance of bacterial surfaces in primary mineral dissolution processes.

Early Silurian (Llandoverian) Leask Point and Charlton Bay bioherms, Manitoulin Island, Ontario, Canada

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mielczarek, W.; Copper, P.

1986-08-01

About 300 bioherms are known in the Llandoverian Manitoulin Formation of eastern Manitoulin Island. In the South Bay area, the large Leask Piont bioherm and Charlton Bay patch-reef complex lack a distinct skeletal growth framework. Bioherms consist of mudstone and wackestone, with isolated lenses of bafflestone, boundstone, floatstone. Fossils are scarce, but crinozoans and bryozoans comprise about 90% of the bioclasts. Other fauna include stromatoporoids, corals, brachiopods, gastropods, trilobites, and probable algae (algae are difficult to identify and may have played a significant role). Faunal ratios remained relatively constant during mound growth. Soft substrates with sedimentation rates of a fewmore » millimeters per year are suggested by bedding type and morphologic dominance of lamellar and tabular corals and stromatoporoids. An increased sedimentation rate, resulting from shoaling, is indicated by more overturned, broadly conical corals in the upper parts of the mounds. Shoaling may be responsible for cessation of mound growth. Lithoclasts are more common in the upper parts of the mounds. They formed when semiconsolidated muds were disturbed and redeposited during storms. Megarippled interreef surface areas, largely devoid of coral growth, indicate mud instability at Charlton Bay. Lack of suitable stable substrates may have hampered coral development. Dolomitization was postdepositional. The diagenetic sequence occurred in three stages: 1)selective pyritization and silicification, formation of an early muddy dolomite replacing the mud fraction of the dolostone, lithification and formation of rare calcite cement and neomorphic syntaxial rims; 2)clear, coarse dolomite replacing pore-filling calcite cement, syntaxial rims, and unaltered macrofossils, stylolitization, grain-to-grain dissolution; and 3)a late dolomite found mainly as fine rhombs in stylolites, solution seams, and intraskeletal pore space.« less

Experimental Constraints on Fluid-Rock Reactions during Incipient Serpentinization of Harzburgite

NASA Astrophysics Data System (ADS)

Klein, F.; Grozeva, N. G.; Seewald, J.; McCollom, T. M.; Humphris, S. E.; Moskowitz, B. M.; Berquo, T. S.; Kahl, W. A.

2014-12-01

The exposure of mantle peridotite to water at crustal levels leads to a cascade of interconnected dissolution-precipitation and reduction-oxidation reactions - a process referred to as serpentinization. These reactions have major implications for microbial life through the provision of hydrogen (H2). To simulate incipient serpentinization and the release of H2 under well-constrained conditions, we reacted uncrushed harzburgite with chemically modified seawater at 300°C and 35 MPa for ca. 1.5 years (13441 hours), monitored changes in fluid chemistry over time, and examined the secondary mineralogy at the termination of the experiment. Approximately 4 mol % of the protolith underwent alteration forming serpentine, accessory magnetite, chlorite, and traces of calcite and heazlewoodite. Alteration textures bear remarkable similarities to those found in partially serpentinized abyssal peridotites. Neither brucite nor talc precipitated during the experiment. Given that the starting material contained ~3.8 times more olivine than orthopyroxene on a molar basis, mass balance requires that dissolution of orthopyroxene was significantly faster than dissolution of olivine. However, the H2 release rate was not uniform, slowing from ~2 nmol H2(aq) gperidotite-1 s-1 at the beginning of the experiment to ~0.2 nmol H2(aq) gperidotite-1 s-1 at its termination. Serpentinization consumed water but did not release significant amounts of dissolved species (other than H2) suggesting that incipient hydration reactions involved a volume increase of ~40%. The reduced access of water to olivine surfaces due to filling of fractures and coating of primary minerals with alteration products led to decreased rates of serpentinization and H2 release. While this concept might seem at odds with completely serpentinized seafloor peridotites, reaction-driven fracturing offers an intriguing solution to the seemingly self-limiting nature of serpentinization. Indeed, the reacted sample revealed a number of textural features diagnostic of incipient reaction-driven fracturing. Reaction-driven and tectonic fracturing must have far reaching impacts on the release rate of H2 in peridotite-hosted hydrothermal systems and therefore represent key mechanisms in regulating the supply of reduced gases to microbial ecosystems.

Isotopic analysis of groundwater and carbonate system in the Surdulica geothermal aquifer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hadzisehovic, M; Miljevic, N.; Sipka, V.

1993-01-01

The authors present here results of their investigation of the isotopic chemical composition of groundwater and carbonates in the Surdulica geothermal aquifer, Serbia. They considered the effects of carbonate dissolution and measured [sup 13]C, [sup 14]C, D, [sup 18]O, [sup 3]H, field pH, temperature, Na[sup +], CA [sup 2+], Mg[sup 2+], HCO[sub 3] and other aqueous species from 30 springs and boreholes. Geothermal waters are supersaturated with calcite. Carbon isotope compositions vary with carbonate mineral dissolution. The [delta]D and [delta][sup 18]O of groundwater samples fit the meteoric water line, and indicate that groundwater is recharged mainly from higher altitudes andmore » the cold season. Different groundwater residence times point out two mechanisms for their formation: fissure flow for young waters and standard diffusion processes for old ones.« less

A Comparison of Analytical and Numerical Methods for Modeling Dissolution and Other Reactions in Transport Limited Systems

NASA Astrophysics Data System (ADS)

Hochstetler, D. L.; Kitanidis, P. K.

2009-12-01

Modeling the transport of reactive species is a computationally demanding problem, especially in complex subsurface media, where it is crucial to improve understanding of geochemical processes and the fate of groundwater contaminants. In most of these systems, reactions are inherently fast and actual rates of transformations are limited by the slower physical transport mechanisms. There have been efforts to reformulate multi-component reactive transport problems into systems that are simpler and less demanding to solve. These reformulations include defining conservative species and decoupling of reactive transport equations so that fewer of them must be solved, leaving mostly conservative equations for transport [e.g., De Simoni et al., 2005; De Simoni et al., 2007; Kräutle and Knabner, 2007; Molins et al., 2004]. Complex and computationally cumbersome numerical codes used to solve such problems have also caused De Simoni et al. [2005] to develop more manageable analytical solutions. Furthermore, this work evaluates reaction rates and has reaffirmed that the mixing rate,▽TuD▽u, where u is a solute concentration and D is the dispersion tensor, as defined by Kitanidis [1994], is an important and sometimes dominant factor in determining reaction rates. Thus, mixing of solutions is often reaction-limiting. We will present results from analytical and computational modeling of multi-component reactive-transport problems. The results have applications to dissolution of solid boundaries (e.g., calcite), dissolution of non-aqueous phase liquids (NAPLs) in separate phases, and mixing of saltwater and freshwater (e.g. saltwater intrusion in coastal carbonate aquifers). We quantify reaction rates, compare numerical and analytical results, and analyze under what circumstances which approach is most effective for a given problem. References: DeSimoni, M., et al. (2005), A procedure for the solution of multicomponent reactive transport problems, Water Resources Research, 41(W11410). DeSimoni, M., et al. (2007), A mixing ratios-based formulation for multicomponent reactive transport, Water Resources Research, 43(W07419). Kitanidis, P. (1994), The Concept of the Dilution Index, Water Resources Research, 30(7), 2011-2026. Kräutle, S., and P. Knabner (2007), A reduction scheme for coupled multicomponent transport-reaction problems in porous media: Generalization to problems with heterogeneous equilibrium reactions Water Resources Research, 43. Molins, S., et al. (2004), A formulation for decoupling components in reactive transport porblems, Water Resources Research, 40, 13.

Differential rates of feldspar weathering in granitic regoliths

USGS Publications Warehouse

White, A.F.; Bullen, T.D.; Schulz, M.S.; Blum, A.E.; Huntington, T.G.; Peters, N.E.

2001-01-01

Differential rates of plagioclase and K-feldspar weathering commonly observed in bedrock and soil environments are examined in terms of chemical kinetic and solubility controls and hydrologic permeability. For the Panola regolith, in the Georgia Piedmont Province of southeastern United States, petrographic observations, coupled with elemental balances and 87Sr/86Sr ratios, indicate that plagioclase is being converted to kaolinite at depths > 6 m in the granitic bedrock. K-feldspar remains pristine in the bedrock but subsequently weathers to kaolinite at the overlying saprolite. In contrast, both plagioclase and K-feldspar remain stable in granitic bedrocks elsewhere in Piedmont Province, such as Davis Run, Virginia, where feldspars weather concurrently in an overlying thick saprolite sequence. Kinetic rate constants, mineral surface areas, and secondary hydraulic conductivities are fitted to feldspar losses with depth in the Panola and Davis Run regoliths using a time-depth computer spreadsheet model. The primary hydraulic conductivities, describing the rates of meteoric water penetration into the pristine granites, are assumed to be equal to the propagation rates of weathering fronts, which, based on cosmogenic isotope dating, are 7 m/106 yr for the Panola regolith and 4 m/106 yr for the Davis Run regolith. Best fits in the calculations indicate that the kinetic rate constants for plagioclase in both regoliths are factors of two to three times faster than K-feldspar, which is in agreement with experimental findings. However, the range for plagioclase and K-feldspar rates (kr = 1.5 x 10-17 to 2.8 x 10-16 mol m-2 s-1) is three to four orders of magnitude lower than for that for experimental feldspar dissolution rates and are among the slowest yet recorded for natural feldspar weathering. Such slow rates are attributed to the relatively old geomorphic ages of the Panola and Davis Run regoliths, implying that mineral surface reactivity decreases significantly with time. Differential feldspar weathering in the low-permeability Panola bedrock environment is more dependent on relative feldspar solubilities than on differences in kinetic reaction rates. Such weathering is very sensitive to primary and secondary hydraulic conductivities (qp and qs), which control both the fluid volumes passing through the regolith and the thermodynamic saturation of the feldspars. Bedrock permeability is primarily intragranular and is created by internal weathering of networks of interconnected plagioclase phenocrysts. Saprolite permeability is principally intergranular and is the result of dissolution of silicate phases during isovolumetric weathering. A secondary to primary hydraulic conductivity ratio of qs/qp = 150 in the Panola bedrock results in kinetically controlled plagioclase dissolution but thermodynamically inhibited K-feldspar reaction. This result is in accord with calculated chemical saturation states for groundwater sampled in the Panola Granite. In contrast, greater secondary conductivities in the Davis Run saprolite, qs/qp = 800, produces both kinetically controlled plagioclase and K-feldspar dissolution. Faster plagioclase reaction, leading to bedrock weathering in the Panola Granite but not at Davis Run, is attributed to a higher anorthite component of the plagioclase and a wetter and warmer climate. In addition, the Panola Granite has an abnormally high content of disseminated calcite, the dissolution of which precedes the plagioclase weathering front, thus creating additional secondary permeability. Copyright ?? 2001 Elsevier Science Ltd.

Elevated Colonization of Microborers at a Volcanically Acidified Coral Reef

PubMed Central

Enochs, Ian C.; Manzello, Derek P.; Tribollet, Aline; Valentino, Lauren; Kolodziej, Graham; Donham, Emily M.; Fitchett, Mark D.; Carlton, Renee; Price, Nichole N.

2016-01-01

Experiments have demonstrated that ocean acidification (OA) conditions projected to occur by the end of the century will slow the calcification of numerous coral species and accelerate the biological erosion of reef habitats (bioerosion). Microborers, which bore holes less than 100 μm diameter, are one of the most pervasive agents of bioerosion and are present throughout all calcium carbonate substrates within the reef environment. The response of diverse reef functional groups to OA is known from real-world ecosystems, but to date our understanding of the relationship between ocean pH and carbonate dissolution by microborers is limited to controlled laboratory experiments. Here we examine the settlement of microborers to pure mineral calcium carbonate substrates (calcite) along a natural pH gradient at a volcanically acidified reef at Maug, Commonwealth of the Northern Mariana Islands (CNMI). Colonization of pioneer microborers was higher in the lower pH waters near the vent field. Depth of microborer penetration was highly variable both among and within sites (4.2–195.5 μm) over the short duration of the study (3 mo.) and no clear relationship to increasing CO2 was observed. Calculated rates of biogenic dissolution, however, were highest at the two sites closer to the vent and were not significantly different from each other. These data represent the first evidence of OA-enhancement of microboring flora colonization in newly available substrates and provide further evidence that microborers, especially bioeroding chlorophytes, respond positively to low pH. The accelerated breakdown and dissolution of reef framework structures with OA will likely lead to declines in structural complexity and integrity, as well as possible loss of essential habitat. PMID:27467570

Elevated Colonization of Microborers at a Volcanically Acidified Coral Reef.

PubMed

Enochs, Ian C; Manzello, Derek P; Tribollet, Aline; Valentino, Lauren; Kolodziej, Graham; Donham, Emily M; Fitchett, Mark D; Carlton, Renee; Price, Nichole N

2016-01-01

Experiments have demonstrated that ocean acidification (OA) conditions projected to occur by the end of the century will slow the calcification of numerous coral species and accelerate the biological erosion of reef habitats (bioerosion). Microborers, which bore holes less than 100 μm diameter, are one of the most pervasive agents of bioerosion and are present throughout all calcium carbonate substrates within the reef environment. The response of diverse reef functional groups to OA is known from real-world ecosystems, but to date our understanding of the relationship between ocean pH and carbonate dissolution by microborers is limited to controlled laboratory experiments. Here we examine the settlement of microborers to pure mineral calcium carbonate substrates (calcite) along a natural pH gradient at a volcanically acidified reef at Maug, Commonwealth of the Northern Mariana Islands (CNMI). Colonization of pioneer microborers was higher in the lower pH waters near the vent field. Depth of microborer penetration was highly variable both among and within sites (4.2-195.5 μm) over the short duration of the study (3 mo.) and no clear relationship to increasing CO2 was observed. Calculated rates of biogenic dissolution, however, were highest at the two sites closer to the vent and were not significantly different from each other. These data represent the first evidence of OA-enhancement of microboring flora colonization in newly available substrates and provide further evidence that microborers, especially bioeroding chlorophytes, respond positively to low pH. The accelerated breakdown and dissolution of reef framework structures with OA will likely lead to declines in structural complexity and integrity, as well as possible loss of essential habitat.

Weathering and weathering rates of natural stone

NASA Astrophysics Data System (ADS)

Winkler, Erhard M.

1987-06-01

Physical and chemical weathering were studied as separate processes in the past. Recent research, however, shows that most processes are physicochemical in nature. The rates at which calcite and silica weather by dissolution are dependent on the regional and local climatic environment. The weathering of silicate rocks leaves discolored margins and rinds, a function of the rocks' permeability and of the climatic parameters. Salt action, the greatest disruptive factor, is complex and not yet fully understood in all its phases, but some of the causes of disruption are crystallization pressure, hydration pressure, and hygroscopic attraction of excess moisture. The decay of marble is complex, an interaction between disolution, crack-corrosion, and expansion-contraction cycies triggered by the release of residual stresses. Thin spalls of granites commonly found near the street level of buildings are generally caused by a combination of stress relief and salt action. To study and determine weathering rates of a variety of commercial stones, the National Bureau of Standards erected a Stone Exposure Test Wall in 1948. Of the many types of stone represented, only a few fossiliferous limestones permit a valid measurement of surface reduction in a polluted urban environment.

Distinction between epigenic and hypogenic maze caves

NASA Astrophysics Data System (ADS)

Palmer, Arthur N.

2011-11-01

Certain caves formed by dissolution of bedrock have maze patterns composed of closed loops in which many intersecting fractures or pores have enlarged simultaneously. Their origin can be epigenic (by shallow circulation of meteoric groundwater) or hypogenic (by rising groundwater or production of deep-seated solutional aggressiveness). Epigenic mazes form by diffuse infiltration through a permeable insoluble caprock or by floodwater supplied by sinking streams. Most hypogenic caves involve deep sources of aggressiveness. Transverse hypogenic cave origin is a recently proposed concept in which groundwater of mainly meteoric origin rises across strata in the distal portions of large flow systems, to form mazes in soluble rock sandwiched between permeable but insoluble strata. The distinction between maze types is debated and is usually based on examination of diagnostic cave features and relation of caves to their regional setting. In this paper, the principles of mass transfer are applied to clarify the limits of each model, to show how cave origin is related to groundwater discharge, dissolution rate, and time. The results show that diffuse infiltration and floodwater can each form maze caves at geologically feasible rates (typically within 500 ka). Transverse hypogenic mazes in limestone, to enlarge significantly within 1 Ma, require an unusually high permeability of the non-carbonate beds (generally ≥ 10-4 cm/s), large discharge, and calcite saturation no greater than 90%, which is rare in deep diffuse flow in sedimentary rocks. Deep sources of aggressiveness are usually required. The origin of caves by transverse hypogenic flow is much more favorable in evaporite rocks than in carbonate rocks.

Results of a hydrogeological and hydrogeochemical study of a semi-arid karst aquifer in Tezbent plateau, Tebessa region, northeast of Algeria

NASA Astrophysics Data System (ADS)

Belfar, Dalila; Fehdi, Chemseddine; Baali, Fethi; Salameh, Elias

2017-06-01

The Hammamet Plain, situated in the northwest of the Tezbent mountain range, northeast of Algeria, drains carbonate aquifers through some important karst springs. The physical and chemical characteristics of spring and well water samples were studied for 2 years to assess the origin of groundwater and determine the factors driving the geochemical composition. The ionic speciation and mineral dissolution/precipitation was calculated. Water wells, characterizing groundwater circulation at shallow depths, are moderate to high mineralized waters of Na-HCO3 type. In contrast to the shallow environment, the CO2-rich, deeper waters are of the Ca-HCO3-SO4 type and undergo significant changes in the baseline chemistry along flow lines with increasing residence time. The main factors controlling the groundwater composition and its seasonal variations are the geology, because of the presence of carbonate formations, the elevation and the rate of karst development. In both groups, the carbonate chemistry is diagnostic of the effect of karst development. The supersaturation with respect to calcite indicates CO2 degassing, occurring either inside the aquifer in open conduits, or at the outlet in reservoirs. The undersaturation with respect to calcite shows the existence of fast flow and short residence time conditions inside the aquifer. Interaction between groundwater and surrounding host rocks is believed to be the main process responsible for the observed chemical characteristics of groundwater in the study area.

Limpets counteract ocean acidification induced shell corrosion by thickening of aragonitic shell layers

NASA Astrophysics Data System (ADS)

Langer, G.; Nehrke, G.; Baggini, C.; Rodolfo-Metalpa, R.; Hall-Spencer, J.; Bijma, J.

2014-08-01

Specimens of the patellogastropod limpet Patella caerulea were collected within (pHlow-shells) and outside (pHn-shells) a CO2 vent site at Ischia, Italy. Four pHlow-shells and four pHn-shells were sectioned transversally and scanned for polymorph distribution by means of confocal Raman microscopy. The pHlow-shells displayed a twofold increase in aragonite area fraction and size normalised aragonite area. Size normalised calcite area was halved in pHlow-shells. Taken together with the increased apical and the decreased flank size normalised thickness of the pHlow-shells, these data led us to conclude that low pH exposed P. caerulea specimens counteract shell dissolution by enhanced shell production. The latter is different from normal elongation growth and proceeds through addition of aragonitic layers only, while the production of calcitic layers is confined to elongation growth. Therefore aragonite cannot be regarded as a per se disadvantageous polymorph under ocean acidification conditions.

A facile magnesium-containing calcium carbonate biomaterial as potential bone graft.

PubMed

He, Fupo; Zhang, Jing; Tian, Xiumei; Wu, Shanghua; Chen, Xiaoming

2015-12-01

The calcium carbonate is the main composition of coral which has been widely used as bone graft in clinic. Herein, we readily prepared novel magnesium-containing calcium carbonate biomaterials (MCCs) under the low-temperature conditions based on the dissolution-recrystallization reaction between unstable amorphous calcium carbonate (ACC) and metastable vaterite-type calcium carbonate with water involved. The content of magnesium in MCCs was tailored by adjusting the proportion of ACC starting material that was prepared using magnesium as stabilizer. The phase composition of MCCs with various amounts of magnesium was composed of one, two or three kinds of calcium carbonates (calcite, aragonite, and/or magnesian calcite). The different MCCs differed in topography. The in vitro degradation of MCCs accelerated with increasing amount of introduced magnesium. The MCCs with a certain amount of magnesium not only acquired higher compressive strength, but also promoted in vitro cell proliferation and osteogenic differentiation. Taken together, the facile MCCs shed light on their potential as bone graft. Copyright © 2015 Elsevier B.V. All rights reserved.

Limpets counteract ocean acidification induced shell corrosion by thickening of aragonitic shell layers

NASA Astrophysics Data System (ADS)

Langer, G.; Nehrke, G.; Baggini, C.; Rodolfo-Metalpa, R.; Hall-Spencer, J. M.; Bijma, J.

2014-12-01

Specimens of the patellogastropod limpet Patella caerulea were collected within (pHlow-shells) and outside (pHn-shells) a CO2 vent site at Ischia, Italy. Four pHlow-shells and four pHn-shells were sectioned transversally and scanned for polymorph distribution by means of confocal Raman microscopy. The pHlow-shells displayed a twofold increase in aragonite area fraction and size-normalised aragonite area. Size-normalised calcite area was halved in pHlow-shells. Taken together with the increased apical and the decreased flank size-normalised thickness of the pHlow-shells, these data led us to conclude that low-pH-exposed P. caerulea specimens counteract shell dissolution by enhanced shell production. This is different from normal elongation growth and proceeds through addition of aragonitic parts only, while the production of calcitic parts is confined to elongation growth. Therefore, aragonite cannot be regarded as a disadvantageous polymorph per se under ocean acidification conditions.

The calcite → aragonite transformation in low-Mg marble: Equilibrium relations, transformations mechanisms, and rates

USGS Publications Warehouse

Hacker, Bradley R.; Rubie, David C.; Kirby, Stephen H.; Bohlen, Steven R.

2005-01-01

Experimental transformation of a rather pure natural calcite marble to aragonite marble did not proceed via the expected straightforward polymorphic replacement. Instead, the small amount of Mg in the starting material (0.36 wt %) was excluded from the growing aragonite and diffused preferentially into the remaining calcite grains, producing Mg-rich calcite rods that persisted as relicts. Nucleation of aragonite occurred exclusively on grain boundaries, with aragonite [001] oriented subparallel to calcite [0001]. The aragonite crystals preferentially consumed the calcite crystal on which they nucleated, and the reaction fronts developed preferentially along the {010} and {110} planes of aragonite. Each aragonite neoblast that grew was nearly free of Mg (typically <0.1 wt %). The excess Mg was taken up by the calcite grains in between, stabilizing them and causing a few volume percent rodlike relicts of Mg-enriched calcite (up to 10 wt % MgO) to be left behind by the advancing reaction front. The aragonite growth rates are approximately linear and range from ∼3 × 10−11 m s−1 at 600°C to ∼9 × 10−9 m s−1 at 850°C, with an apparent activation enthalpy of 166 ± 91 kJ mol−1. This reaction mechanism and the resultant texture are akin to cellular precipitation reactions in metals. Similar transformation textures have been reported from high-Mg marbles in Japan and China that disproportionated to low-Mg calcite and dolomite.

Feedbacks stablizing wetland geometry on a pattened landscape

NASA Astrophysics Data System (ADS)

Dong, X.; Heffernan, J. B.; Murray, A. B.

2017-12-01

Karst morphology is highly varied across different climatic and geologic regions of the world. Big Cypress National Preserve in SW Florida, features regularly distributed wetland depressions, located on exposed limestone bedrock. In this study, we explored the development of wetland depressions over the past 10kyrs of landscape formation. Specifically, we are interested in (1) whether the wetland depressions on the landscape have reached equilibrium size, and (2) if so, what are feedback mechanisms that contributed to stabilizing these depressions. We hypothesized three stabilizing feedback mechanisms. HYP1: increased size of depressions reduces landscape hydrological connectivity, which resulted in reduced landscape capacity to export dissolution products, hence lower weathering rate. HYP2: expansion of depression area increases tree biomass within the depression, which increased average evapotranspiration (ET) within the dome. The greater difference of ET rate between depression and upland leads to a lower water table in the depression. As a result, more subsurface water, carrying dissolved calcium, flows from catchment to depression. With lower export capacity and more calcium moving into the depression zones, rate of calcite precipitation increases, which lowers net weathering rate. HYP3: increasingly thicker sediment cover in the wetland depression over time decreases chemical transport capacity. This lowers both transport of CO2 from shallower soil to bedrock and transport of dissolution products from bedrock to surface. Both of these processes reduce bedrock-weathering rate. We built a 3-D numerical simulation model that partitioned the relative importance of different mechanisms. Preliminary results show that (1) there is an equilibrium size for wetland depressions for both radius and depth dimension; (2) current depressions are formed by coalescence of several nearby small depressions during development; (3) the soil cover feedback (HYP3) is the major feedback stabilizing depth of depressions, while reduced landscape connectivity (HYP1) and increased local exchange of dissolved calcium caused by differential ET between catchment and depression (HYP2) is the major radius stabilizing feedback.

Effect of bacteria and dissolved organics on mineral dissolution kinetics:

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg; Shirokova, Liudmila; Benezeth, Pascale; Zabelina, Svetlana

2010-05-01

Quantification of the effect of microorganisms and associated organic ligands on mineral dissolution rate is one among the last remaining challenges in modeling of water-rock interactions under earth surface and subsurface environments. This is especially true for deep underground settings within the context of CO2 capture, sequestration and storage. First, elevated CO2 pressures create numerous experimental difficulties for performing robust flow-through experiments at a given saturation state. Second, reactivity of main rock-forming minerals in abiotic systems at pCO2 >> 1 atm and circumneutral pH is still poorly constrained. And third, most of microbial habitats of the subsurface biosphere are not suitable for routine culturing in the laboratory, many of them are anaerobic and even strictly anaerobic, and many bacteria and archae cultures can live only in the consortium of microorganisms which is very hard to maintain at a controlled and stable biomass concentration. For experimental modeling of bio-mineral interactions in the laboratory, two other main conceptual challenges exist. Typical concentration of dissolved organic carbon that serves as a main nutrient for heterotrophic bacteria in underground waters rarely exceeds 3-5 mg/L. Typical concentration of DOC in nutrient media used for bacteria culturing is between 100 and 10,000 mg/L. Therefore, performing mineral-bacteria interactions in the laboratory under environmentally-sound conditions requires significant dilution of the nutrient media or the use of flow-through reactors. Concerning the effect of organic ligands and bacterial excudates on rock-forming mineral dissolution, at the present time, mostly empirical (phenomenological) approach can be used. Indeed, the pioneering studies of Stumm and co-workers have established a firm basis for modeling the catalyzing and inhibiting effects of ligands on metal oxide dissolution rate. This approach, very efficient for studying the interaction of organic and inorganic ligands with trivalent metal oxides, is based on applying multiple spectroscopic techniques allowing to reveal the chemical structure of adsorbed complexes. However, due to i) low surface area of most rock-forming minerals (carbonates, non-clay silicates), ii) difficulties of applying surface spectroscopic techniques at elevated pressures, and iii) very complex nature of bacterial exometabolites, it is not possible at the present time, to use rigorous surface complexation approach for rationalizing ligand- and bacteria-affected mineral dissolution under sub-surface CO2 storage environment. In this work, we present examples of overcoming these difficulties via concerted study of olivine, wollastonite and calcite interaction with heterotrophic bacteria and methanogenic archaes.

Temperature reconstruction from dripwater hydrochemistry, speleothem fabric and speleothem δ13C: towards an integrated approach in temperate climate caves

NASA Astrophysics Data System (ADS)

Borsato, Andrea; Frisia, Silvia; Johnston, Vanessa; Spötl, Christoph

2017-04-01

Accurate reconstruction of past climate records from speleothem minerals requires a thorough understanding of both environmental and hydrologic conditions underpinning their formation. These conditions likely influenced how speleothems incorporate chemical signals that are used as climate proxies. Thus, a thorough investigation of environmental and hydrologic parameters is a pre-requisite to gain robust palaeoclimate reconstructions from stalagmites. Here, we present a systematic study of soil, dripwater and speleothems in temperate climate caves at different altitudes, which allowed the assessment of how mean annual air temperature in the infiltration area (MATinf) influences vegetation cover, soil pCO2 and, eventually, pCO2 of karst water and cave air. Our study demonstrates that for caves developed in pure carbonate rocks, the soil and aquifer pCO2 are directly related to the MATinf (Borsato et al., 2015). It is well known that soil and aquifer pCO2 control carbonate dissolution and the carbonate-carbonic acid system. By establishing a relationship between dripwater pCO2 and MATinf, we show that dripwater Ca content and calcite saturation state SIcc) are correlated with MATinf when unaffected by Prior Calcite Precipitation. In particular, dripwater saturation (SIcc = 0) is reached at a MATinf of 4.4°C in our study area. This MATinf delineates a ''speleothem limit", above which speleothems composed of sparitic calcite should not form (Borsato et al., 2016). In fact, sparitic calcite speleothems do not form, today, in caves with a MATinf < 4.4°C. This relationship offers the opportunity to estimate past MATinf from fossil sparitic calcite speleothems found in high-altitude caves by comparing the required SIcc for their formation to the present-day dripwater SIcc. Furthermore, soil and aquifer pCO2 control dripwater DIC δ13C as well as calcite δ13C in speleothems that were not significantly influenced by kinetic fractionation. A linear correlation between calcite δ13C and MATinf was obtained for modern sparitic speleothems that formed at isotopic equilibrium (Johnston et al., 2013). The combination of these two approaches (present-day dripwater SIcc and calcite δ13C in sparitic speleothems) can be used to reconstruct the past MATinf for high-altitude caves. References: Borsato et al., (2015). Earth Surf. Proc. Land. 40, 1158-1170. Borsato et al., (2016). Geochim. Cosmochim. Ac. 177, 275-297. Johnston et al., (2013). Clim. Past 9, 99-118.

Experimental Study of Sr Partitioning into Calcite at Various Linear Growth Rates and Temperatures: Preliminary Results.

NASA Astrophysics Data System (ADS)

Gabitov, R. I.; Watson, B. E.

2004-05-01

The surface of a crystal in equilibrium with surrounding fluid can have a composition that differs from the bulk crystal. If growth rate of the crystal exceeds a minimum value at which partitioning-equilibrium can be maintained, then the crystal surface composition may be "captured" by the newly-formed lattice. The degree of this entrapment increases with increasing crystal growth rate. Non-equlibrium partitioning of Sr into calcite probably occurs by this entrapment mechanism. Sr and calcite are geochemically significant in understanding the thermal history of the ocean because the substitution of Sr for Ca in calcite is temperature dependent. To improve our understanding of the partitioning of Sr into calcite, we conducted two different types of experiment: 1) calcite growth from Sr-bearing solution with analysis of the crystal cross-section by electron microprobe (bulk crystal-liquid runs); and 2) treatment of calcite cleavage surfaces with Sr-bearing solutions and examination of the top few nm surface layer by X-ray photoelectron spectroscopy (surface-liquid runs). In the series of bulk-liquid experiments crystals were grown by three different procedures: 1) precipitation on glass slide (pre-coated with calcite), where a steady flow of CaCl2 - SrCl2 and Na2CO3 solutions were mixed just before passage through a tube and allowed to drip onto a slide ("cave"-type experiments, ionic strength I=0.01); 2) growth from a CaCl2 - NH4Cl - SrCl2 solution by diffusion of CO2 from an ammonium carbonate source ("drift" experiments, I=0.52); 3) coarsening of small calcite crystals in the CaCO3-SrCO3-NaCl-H2O system at 800-950° C and 0.5-1 kb in a cold seal apparatus. The growth rate of individual crystals was determined by periodic monitoring of crystal size with time or roughly by comparison of final size with duration of the experiment. Surface-liquid experiments were performed by treatment of cleavage surfaces of natural calcite fragments in a Sr(ClO4)2 solution for 1 minute. After treatment the remaining solution was blown out by a stream of nitrogen to preclude the precipitation of Sr phase. We observed that the precipitated calcite crystals can be very different in size even if the runs have the same input rate of calcite components. The cave-type and cold-seal runs yielded 15-40 μ m calcites, but in the drift experiments crystal size varied between 60 μ m and 1 mm. Electron microprobe analysis across the large crystals show that the concentration of Sr is higher in the center and decreases toward the edge. This is probably due to the cube-root dependence of radial growth on the volume change of the growing crystals. Like previous workers who measured bulk uptake of Sr as a function of precipitation rate, we observed that increased growth rate (V, nm/s) enhances Sr uptake into the crystal, raising Kdbulk/liquid=(Sr/Ca)bulk/(Sr/Ca)liquid. Kdbulk/liquid = 0.03 to 0.06 when log(V)=-1.1 to -0.6 at 25° C in the cave-type runs (I=0.01). At higher ionic strength (I=0.52) and T=55° C, Kdbulk/liquid=0.11 to 0.15 when log(V)=-0.6 to 0.4 in the drift experiments. XPS analysis of surface-liquid experiments yielded higher Kdsurface/liquid=(Sr/Ca)surface/(Sr/Ca)liquid values compared with Kdbulk/liquid. This combined evidence supports the idea that Sr is enriched at the calcite surface relative to the bulk crystal during crystal growth.

Testing CO2 Sequestration in an Alkaline Soil Treated with Flue Gas Desulfurization Gypsum (FGDG)

NASA Astrophysics Data System (ADS)

Han, Y.; Tokunaga, T. K.

2012-12-01

Identifying effective and economical methods for increasing carbon storage in soils is of interest for reducing soil CO2 fluxes to the atmosphere in order to partially offset anthropogenic CO2 contributions to climate change This study investigates an alternative strategy for increasing carbon retention in soils by accelerating calcite (CaCO3) precipitation and promoting soil organic carbon (SOC) complexation on mineral surfaces. The addition of calcium ion to soils with pH > 8, often found in arid and semi-arid regions, may accelerate the slow process of calcite precipitation. Increased ionic strength from addition of a soluble Ca source also suppresses microbial activity which oxidizes SOC to gaseous CO2. Through obtaining C mass balances in soil profiles, this study is quantifying the efficiency of gypsum amendments for mitigating C losses to the atmosphere. The objective of this study is to identify conditions in which inorganic and organic C sequestration is practical in semi-arid and arid soils by gypsum treatment. As an inexpensive calcium source, we proposed to use flue gas desulfurization gypsum (FGDG), a byproduct of fossil fuel burning electric power plants. To test the hypothesis, laboratory column experiments have been conducted in calcite-buffered soil with addition of gypsum and FGDG. The results of several months of column monitoring are demonstrating that gypsum-treated soil have lowered amounts of soil organic carbon loss and increased inorganic carbon (calcite) production. The excess generation of FGDG relative to industrial and agricultural needs, FGDG, is currently regarded as waste. Thus application of FGDG application in some soils may be an effective and economical means for fixing CO2 in soil organic and inorganic carbon forms.Soil carbon cycle, with proposed increased C retention by calcite precipitation and by SOC binding onto soil mineral surfaces, with both processes driven by calcium released from gypsum dissolution.

The Effect of Micrite on Velocity, Its Sensitivity to Pressure, and Dissolution of Carbonates

NASA Astrophysics Data System (ADS)

El Husseiny, A.; Vanorio, T.

2014-12-01

This study investigates the effect of micrite on the acoustic properties of well-controlled microstructures created in the laboratory to closely mimic carbonate rocks. In particular, we examine the effect of micrite content on the elastic stiffness rock, its sensitivity to pressure, and induced dissolution upon saturation with a reactive fluid. We followed Dunham's classification and fabricated the samples by mixing coarse (sand size) and very fine (micrite size) calcite grains in different ratios, with the addition of cement and then cold-compressing the mixture. The acoustic velocities were measured under bench-top conditions and as functions of confining pressure before and after the injection of a CO2aqueous solution. Our bench-top measurements indicated that micrite makes the frame of the carbonate samples stiffer. Since the sensitivity of the elastic stiffness to pressure decreases as the content of micrite increases (see figure 1), we hypothesize a stiffer pore structure (i.e., rounder pores) in micrite-richer fabrics. Furthermore, the presence of micrite makes the carbonate sample more reactive upon dissolution. The concentration of Ca+2 cations in the fluid measured at the outlet after the injection of the CO2 aqueous solution shows larger dissolution in the micrite-rich samples likely due to the higher surface area of the micrite aggregates. The content of micrite also seems to affect the evolution of stiffness as dissolution proceeds. As the content of micrite increases, the enhanced dissolution translates into a marked softening of the rock frame. We conclude that the content of micrite can play an important role in the complex rock-fluid interaction of carbonates as well as when comparing Gassmann's predictions to velocity measurements of saturated carbonates.

Ultrasonic Monitoring of CO2 Uptake and Release from Sand Packs*

NASA Astrophysics Data System (ADS)

Toffelmier, D. A.; Dufrane, W. L.; Bonner, B. P.; Viani, B. E.; Berge, P. A.

2002-12-01

Sequestration of atmospheric CO2 occurs naturally during the formation of calcite cement in sedimentary rock. Acceleration of this process has been proposed as a means of reducing the atmospheric concentration of CO2, which is a major cause of global warming. Calcite may also be precipitated when highly alkaline waste fluid is introduced into the vadose zone from leaking storage tanks. Seismic methods have potential for monitoring these processes. We devised an experiment, guided by geochemical modeling, to determine how the formation of calcite cement in unsaturated sand affects wave propagation. We used the ultrasonic pulse transmission method to measure compressional (P) and shear (S) wave velocities at ultrasonic frequencies (100-500 kHz) through packs of Ottawa sand containing chemically active pore fluids. The samples were saturated with water containing 0.1mol/L of Ca(OH)2 and 0.1mol/L of NaCl and then drained by flowing water saturated, CO2 free N2 gas, to a residual saturation of ~5%, so that the remaining pore fluid resides mainly in pendular spaces between the sand grains. Ambient air saturated with water and containing atmospheric concentration of CO2 was then passed through the sample to effect the precipitation of calcite. Finally, pure water saturated CO2, was flushed through the sample to dissolve most of the precipitated calcite. Over a three day period, measurable changes in Vp and Vs were observed following water saturation, desaturation, calcite precipitation, and calcite dissolution treatments. Changes in the contents of the pore space require waveforms to be recorded before and after each stage of the experiment so both the short and long range effects can be seen. Wave velocities were slow, as is typical for unconsolidated materials, for the dry sand, with values of 365m/s for Vp and 163m/s for Vs. Compressional velocities increased upon desaturation (443m/s), and again following calcite precipitation (460m/s). The compressional velocity measured following the CO2 flush to dissolve the calcite decreased (451m/s). The shear velocities varied similarly to the compressional velocities except that the dry sand shear velocity was faster than the other shear velocities. These preliminary results suggest that ultrasonics could provide a tool to locate the path of certain types of waste fluid in the vadose zone. *This work was performed under the auspices of the U.S. Department of Energy by the University of California, Lawrence Livermore National Laboratory under contract number W-7405-ENG-48 and was supported specifically by the Environmental Management Science Program of the Office of Environmental Management and the Office of Energy Research.

Influence of cell culture medium composition on in vitro dissolution behavior of a fluoride-containing bioactive glass.

PubMed

Shah, Furqan A; Brauer, Delia S; Wilson, Rory M; Hill, Robert G; Hing, Karin A

2014-03-01

Bioactive glasses are used clinically for bone regeneration, and their bioactivity and cell compatibility are often characterized in vitro, using physiologically relevant test solutions. The aim of this study was to show the influence of varying medium characteristics (pH, composition, presence of proteins) on glass dissolution and apatite formation. The dissolution behavior of a fluoride-containing bioactive glass (BG) was investigated over a period of one week in Eagle's Minimal Essential Medium with Earle's Salts (MEM), supplemented with either, (a) acetate buffer, (b) 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) buffer, (c) HEPES + carbonate, or (d) HEPES + carbonate + fetal bovine serum. Results show pronounced differences in pH, ion release, and apatite formation over 1 week: Despite its acidic pH (pH 5.8 after BG immersion, as compared to pH 7.4-8.3 for HEPES-containing media), apatite formation was fastest in acetate buffered (HEPES-free) MEM. Presence of carbonate resulted in formation of calcite (calcium carbonate). Presence of serum proteins, on the other hand, delayed apatite formation significantly. These results confirm that the composition and properties of a tissue culture medium are important factors during in vitro experiments and need to be taken into consideration when interpreting results from dissolution or cell culture studies. Copyright © 2013 Wiley Periodicals, Inc.

Stalagmite carbon isotopes and dead carbon proportion (DCP) in a near-closed-system situation: An interplay between sulphuric and carbonic acid dissolution

NASA Astrophysics Data System (ADS)

Bajo, Petra; Borsato, Andrea; Drysdale, Russell; Hua, Quan; Frisia, Silvia; Zanchetta, Giovanni; Hellstrom, John; Woodhead, Jon

2017-08-01

In this study, the 'dead carbon proportion' (DCP) calculated from combined U-Th and radiocarbon analyses was used to explore the carbon isotope systematics in Corchia Cave (Italy) speleothems, using the example of stalagmite CC26 which grew during the last ∼12 ka. The DCP values in CC26 are among the highest ever recorded in a stalagmite, spanning the range 44.8-68.8%. A combination of almost closed-system conditions and sulphuric acid dissolution (SAD) are proposed as major drivers in producing such a high DCP with minor contribution from old organic matter from the deep vadose zone. The long-term decrease in both DCP and δ13C most likely reflects post-glacial soil recovery above the cave, with a progressive increase of soil CO2 contribution to the total dissolved inorganic carbon (DIC). Pronounced millennial-scale shifts in DCP and relatively small coeval but antipathetic changes in δ13C are modulated by the effects of hydrological variability on open and closed-system dissolution, SAD and prior calcite precipitation. Hence, the DCP in Corchia Cave speleothems represents an additional proxy for rainfall amount.

Variability in magnesium, carbon and oxygen isotope compositions, and trace element contents of brachiopod shells: implications for paleoceanographic studies

NASA Astrophysics Data System (ADS)

Rollion-Bard, Claire; Saulnier, Ségolène; Vigier, Nathalie; Schumacher, Aimryc; Chaussidon, Marc; Lécuyer, Christophe

2016-04-01

Magnesium content in the ocean is ≈ 1290 ppm and is one of the most abundant elements. It is involved in the carbon cycle via the dissolution and precipitation of carbonates, especially Mg-rich carbonates as dolomites. The Mg/Ca ratio of the ocean is believed to have changed through time. The causes of these variations, i.e. hydrothermal activity change or enhanced precipitation of dolomite, could be constrained using the magnesium isotope composition (δ26Mg) of carbonates. Brachiopods, as marine environmental proxies, have the advantage to occur worldwide in a depth range from intertidal to abyssal, and have been found in the geological record since the Cambrian. Moreover, as their shell is in low-Mg calcite, they are quite resistant to diagenetic processes. Here we report δ26Mg, δ18O, δ13C values along with trace element contents of one modern brachiopod specimen (Terebratalia transversa) and one fossil specimen (Terebratula scillae, 2.3 Ma). We combined δ26Mg values with oxygen and carbon isotope compositions and trace element contents to look for possible shell geochemical heterogeneities in order to investigate the processes that control the Mg isotope composition of brachiopod shells. We also evaluate the potential of brachiopods as a proxy of past seawater δ26Mg values. The two investigated brachiopod shells present the same range of δ26Mg variation (up to 2 ‰)). This variation cannot be ascribed to changes in environmental parameters, i.e. temperature or pH. As previously observed, the primary layer of calcite shows the largest degree of oxygen and carbon isotope disequilibrium relative to seawater. In contrast, the δ26Mg value of this layer is comparable to that of the secondary calcite layer value. In both T. scillae and T. transversa, negative trends are observable between magnesium isotopic compositions and oxygen and carbon isotopic compositions. These trends, combined to linear relationships between δ26Mg values and REE contents, are best explained by kinetic effects linked to changes in growth rate during the brachiopod life. The innermost calcite layer of T. transversa is in isotopic equilibrium for both oxygen and magnesium and could therefore be the best target for reconstructing past δ26Mg values of seawater.

Evaluating the Mn/Ca Ratio of Foraminiferal Calcite Determined by Flow-Through ICP-MS as a Proxy for Terrigenous Input, Upwelling, and Carbon Rain Rate

NASA Astrophysics Data System (ADS)

Klinkhammer, G. P.; Mix, A. C.; Benway, H. M.; Haley, B. A.

2004-12-01

The Mn/Ca ratio of the biogenic calcite preserved in deep-sea sediments has potential as a tracer of terrestrial input, upwelling, and carbon rain rate over geologic time scales. The basis for this potential lies in features of the Mn cycle in the oceans, which are well known. Manganese is a biogeochemically reactive element, but has a lower affinity for dissolved oxygen and organic matter than iron, making it more stable over short time scales, and less affected by speciation. Depth profiles of Mn in oligotrophic ocean waters show a sharp contrast between low concentrations in deep water (0.20 nM) and relatively high concentrations in the mixed layer (2-5 nM). Mn oxides are stable in high oxygen environments but reduced in the suboxic conditions found in the oxygen minimum zone (OMZ). This behavior makes the intermediate water to surface water concentration ratio of Mn sensitive to the intensity of the OMZ, an artifact of the carbon rain rate, and dust/river input. In sediments, suboxic dissolution is balanced by the formation of carbonate making Mn highly reactive during early diagenesis. These features of the Mn cycle in seawater make the Mn/Ca ratio of foraminifera an attractive paleoproxy, but only if the primary signature can be recovered after diagenetic alteration. Recently our laboratory developed a flow-through extraction system that gives us fresh insight into this problem by making it possible to separate mineral phases associated with the foraminiferal fraction by differences in their solubilities. This paper examines foraminiferal Mn/Ca ratios in core tops and down core records from the eastern equatorial Pacific determined with this new technique. We access the potential of flow-through Mn/Ca by comparing its record to those of Mg/Ca and stable isotopes.

Deep-water facies and petrography of the Galoc clastic unit, offshore Palawan, Philippines (south China Sea)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Link, M.H.; Helmold, K.P.

1988-02-01

The lower Miocene Galoc clastic unit, offshore Palawan, Philippines, is about 500-600 ft thick. The unit overlies the Galoc Limestone and is overlain by the Pelitic Pagasa Formation. The Galoc clastic unit consists of alternating quartzose sandstone, mudstone, and resedimented carbonate deposited at bathyal depths, mainly as turbidites. The deep-water deposits are confined to the axis of a northeast-trending trough in which slope, submarine channel, interchannel, depositional lobe, slump, and basinal facies are recognized. Eroded shallow-marine carbonate lithoclasts are commonly incorporated within the siliciclastic turbidites. The main reservoir sandstones occur in submarine channels and depositional lobes. The sandstones are texturallymore » submature, very fine to medium-grained feldspathic litharenites and subarkoses. The sandstones have detrital modes of Q78:F11:L11 and Qm51:F11:Lt38, with partial modes of the monocrystalline components of Qm82:P13:K5. Lithic fragments include chert, shale, schist, volcanic rock fragments, and minor plutonic rock fragments. Porosity in the better reservoir sandstones ranges from 11 to 25%, and calcite is the dominant cement. Dissolution textures and inhomogeneity of calcite distribution suggest that at least half of the porosity in the sandstones has formed through the leaching of calcite cement and labile framework grains. A source terrain of quartzo-feldspathic sediments and metasediments, chert, volcanics, and acid-intermediate plutonic rocks is visualized.« less

Mineral dissolution and precipitation during CO 2 injection at the Frio-I Brine Pilot: Geochemical modeling and uncertainty analysis

DOE PAGES

Ilgen, A. G.; Cygan, R. T.

2015-12-07

During the Frio-I Brine Pilot CO 2 injection experiment in 2004, distinct geochemical changes in response to the injection of 1600 tons of CO 2 were recorded in samples collected from the monitoring well. Previous geochemical modeling studies have considered dissolution of calcite and iron oxyhydroxides, or release of adsorbed iron, as the most likely sources of the increased ion concentrations. We explore in this modeling study possible alternative sources of the increasing calcium and iron, based on the data from the detailed petrographic characterization of the Upper Frio Formation “C”. Particularly, we evaluate whether dissolution of pyrite andmore » oligoclase (anorthite component) can account for the observed geochemical changes. Due to kinetic limitations, dissolution of pyrite and anorthite cannot account for the increased iron and calcium concentrations on the time scale of the field test (10 days). However, dissolution of these minerals is contributing to carbonate and clay mineral precipitation on the longer time scales (1000 years). The one-dimensional reactive transport model predicts carbonate minerals, dolomite and ankerite, as well as clay minerals kaolinite, nontronite and montmorillonite, will precipitate in the Frio Formation “C” sandstone as the system progresses towards chemical equilibrium during a 1000-year period. Cumulative uncertainties associated with using different thermodynamic databases, activity correction models (Pitzer vs. B-dot), and extrapolating to reservoir temperature, are manifested in the difference in the predicted mineral phases. Furthermore, these models are consistent with regards to the total volume of mineral precipitation and porosity values which are predicted to within 0.002%.« less

Hydrodynamic control of inorganic calcite precipitation in Huanglong Ravine, China: Field measurements and theoretical prediction of deposition rates

NASA Astrophysics Data System (ADS)

Zaihua, Liu; Svensson, U.; Dreybrodt, W.; Daoxian, Yuan; Buhmann, D.

1995-08-01

Hydrochemical and hydrodynamical investigations are presented to explain tufa deposition rates along the flow path of the Huanglong Ravine, located in northwestern Sichuan province, China, on an altitude of about 3400 m asl. Due to outgassing of CO 2 the mainly spring-fed stream exhibits, along a valley of 3.5 km, calcite precipitation rates up to a few mm/year. We have carried out in situ experiments to measure calcite deposition rates at rimstone dams, inside of pools and in the stream-bed. Simultaneously, the downstream evolution of water chemistry was investigated at nine locations with respect to Ca 2+, Mg 2+, Na +, Cl -, SO 42-, and alkalinity. Temperature, pH, and conductivity were measured in situ, while total hardness, Ca T, and alkalinity have been determined immediately after sampling, performing standard titration methods. The water turned out to be of an almost pure CaMgHCO 3 type. The degassing of CO 2 causes high supersaturation with respect to calcite and due to calcite precipitation the Ca 2+ concentration decreases from 6·10 -3 mole/1 upstream down to 2.5·10 -3 mole/1 at the lower course. Small rectangular shaped tablets of pure marble were mounted under different flow regimes, i.e., at the dam sites with fast water flow as well as inside pools with still water. After the substrate samples had stayed in the water for a period of a few days, the deposition rates were measured by weight increase, up to several tens of milligrams. Although there were no differences in hydrochemistry, deposition rates in fast flowing water were higher by as much as a factor of four compared to still water, indicating a strong influence of hydrodynamics. While upstream rates amounted up to 5 mm/year, lower rates of about 1 mm/year were observed downstream. Inspection of the marble substrate surfaces by EDAX and SEM (scanning electron microscope) revealed authigeneously grown calcite crystals of about 10 μm. Their shape and habit are indicative of a chemically controlled inorganic origin. By applying a mass transfer model for calcite precipitation taking into account the reaction rates at the surface given by Plummer et al. (1978), slow conversion of CO 2 into H + and HCO 3- , and diffusional mass transport across a diffusion boundary layer, we have calculated the deposition rates from the hydrochemistry of the corresponding locations. The calculated rates agree within a factor of two with the experimental results. Our findings confirm former conclusions with respect to fast flow conditions: reasonable rates of calcite precipitation can be estimated in reducing the PWP-rate calculated from the chemical composition of the water by a factor of about ten, thus correcting for the influence of the diffusion boundary layer.

Strain rate dependent calcite microfabric evolution - An experiment carried out by nature

NASA Astrophysics Data System (ADS)

Rogowitz, Anna; Grasemann, Bernhard; Huet, Benjamin; Habler, Gerlinde

2014-12-01

A flanking structure developed along a secondary shear zone in calcite marbles, on Syros (Cyclades, Greece), provides a natural laboratory for directly studying the effects of strain rate variations on calcite deformation at identical pressure and temperature conditions. The presence and rotation of a fracture during progressive deformation caused extreme variations in finite strain and strain rate, forming a localized ductile shear zone that shows different microstructures and textures. Textures and the degree of intracrystalline deformation were measured by electron backscattered diffraction. Marbles from the host rocks and the shear zone, which deformed at various strain rates, display crystal-preferred orientation, suggesting that the calcite preferentially deformed by intracrystalline-plastic deformation. Increasing strain rate results in a switch from subgrain rotation to bulging recrystallization in the dislocation-creep regime. With increasing strain rate, we observe in fine-grained (3 μm) ultramylonitic zones a change in deformation regime from grain-size insensitive to grain-size sensitive. Paleowattmeter and the paleopiezometer suggest strain rates for the localized shear zone around 10-10 s-1 and for the marble host rock around 10-12 s-1. We conclude that varying natural strain rates can have a first-order effect on the microstructures and textures that developed under the same metamorphic conditions.

Influence of water on clumped-isotope bond reordering kinetics in calcite

NASA Astrophysics Data System (ADS)

Brenner, Dana C.; Passey, Benjamin H.; Stolper, Daniel A.

2018-03-01

Oxygen self-diffusion in calcite and many other minerals is considerably faster under wet conditions relative to dry conditions. Here we investigate whether this "water effect" also holds true for solid-state isotope exchange reactions that alter the abundance of carbonate groups with multiple rare isotopes ('clumped' isotope groups) via the process of solid-state bond reordering. We present clumped-isotope reordering rates for optical calcite heated under wet, high-pressure (100 MPa) conditions. We observe only modest increases in reordering rates under such conditions compared with rates for the same material reacted in dry CO2 under low-pressure conditions. Activation energies under wet, high-pressure conditions are indistinguishable from those for dry, low-pressure conditions, while rate constants are resolvably higher (up to ∼3 times) for wet, high-pressure relative to dry, low-pressure conditions in most of our interpretations of experimental results. This contrasts with the water effect for oxygen self-diffusion in calcite, which is associated with lower activation energies, and diffusion coefficients that are ≥103 times higher compared with dry (pure CO2) conditions in the temperature range of this study (385-450 °C). The water effect for clumped-isotopes leads to calculated apparent equilibrium temperatures ("blocking temperatures") for typical geological cooling rates that are only a few degrees higher than those for dry conditions, while O self-diffusion blocking temperatures in calcite grains are ∼150-200 °C lower in wet conditions compared with dry conditions. Since clumped-isotope reordering is a distributed process that occurs throughout the mineral volume, our clumped-isotope results support the suggestion of Labotka et al. (2011) that the water effect in calcite does not involve major changes in bulk (volume) diffusivity, but rather is primarily a surface phenomenon that facilitates oxygen exchange between the calcite surface and external fluids. We explore the mechanism(s) by which clumped isotope reordering rates may be modestly increased under wet, high-pressure conditions, including changes in defect concentrations in the near surface environment due to reactions at the water-mineral interface, and lattice deformation resulting from pressurization of samples.

Comparison of rates of ureolysis between Sporosarcina pasteurii and an indigenous groundwater community under conditions required to precipitate large volumes of calcite

NASA Astrophysics Data System (ADS)

Tobler, Dominique J.; Cuthbert, Mark O.; Greswell, Richard B.; Riley, Michael S.; Renshaw, Joanna C.; Handley-Sidhu, Stephanie; Phoenix, Vernon R.

2011-06-01

Ureolysis-driven calcite precipitation has potential to seal porosity and fracture networks in rocks thus preventing groundwater flow and contaminant transport. In this study urea hydrolysis and calcite precipitation rates for the model bacterium Sporosarcina pasteurii were compared with those of indigenous groundwater communities under conditions required to precipitate large volumes of calcite (up to 50 g L -1). We conducted microcosm experiments in oxic artificial and anoxic natural groundwaters (collected from the Permo-Triassic sandstone aquifer at Birmingham, UK) that were inoculated with aerobically grown S. pasteurii. The rate constants for urea hydrolysis, kurea, ranged between 0.06 and 3.29 d -1 and were only affected by inoculum density. Higher Ca 2+ concentration (50-500 mM Ca 2+) as well as differences in fO 2 did not inhibit the ureolytic activity of S. pasteurii and did not significantly impact kurea. These results demonstrate that S. pasteurii has potential to improve calcite precipitation in both oxic and anoxic groundwaters, especially if indigenous communities lack ureolytic activity. Urea hydrolysis by indigenous groundwater communities was investigated in anoxic, natural groundwaters amended with urea and CaCl 2. A notable increase in ureolysis rates was measured only when these communities were stimulated with dilute nutrients (with best results from blackstrap molasses). Furthermore, there was a considerable lag time (12-20 days) before ureolysis and calcite precipitation began. Calculated ureolysis rate constants, kurea, ranged between 0.03 and 0.05 d -1 and were similar to kurea values produced by S. pasteurii at low inoculum densities. Overall, this comparative study revealed that the growth of ureolytic microorganisms present within groundwaters can easily be stimulated to enhance rates of urea hydrolysis in the subsurface, and thus can be used to induce calcite precipitation in these environments. The time required for urea hydrolysis to begin is almost instantaneous if an inoculum of S. pasteurii is included, while it may take several weeks for ureolytic groundwater communities to grow and become ureolytically active.

Incorporation of Eu(III) into Calcite under Recrystallization conditions.

PubMed

Hellebrandt, S E; Hofmann, S; Jordan, N; Barkleit, A; Schmidt, M

2016-09-13

The interaction of calcite with trivalent europium under recrystallization conditions was studied on the molecular level using site-selective time-resolved laser fluorescence spectroscopy (TRLFS). We conducted batch studies with a reaction time from seven days up to three years with three calcite powders, which differed in their specific surface area, recrystallization rates and impurities content. With increase of the recrystallization rate incorporation of Eu(3+) occurs faster and its speciation comes to be dominated by one species with its excitation maximum at 578.8 nm, so far not identified during previous investigations of this process under growth and phase transformation conditions. A long lifetime of 3750 μs demonstrates complete loss of hydration, consequently Eu must have been incorporated into the bulk crystal. The results show a strong dependence of the incorporation kinetics on the recrystallization rate of the different calcites. Furthermore the investigation of the effect of different background electrolytes (NaCl and KCl) demonstrate that the incorporation process under recrystallization conditions strongly depends on the availability of Na(+). These findings emphasize the different retention potential of calcite as a primary and secondary mineral e.g. in a nuclear waste disposal site.

Incorporation of Eu(III) into Calcite under Recrystallization conditions

PubMed Central

Hellebrandt, S. E.; Hofmann, S.; Jordan, N.; Barkleit, A.; Schmidt, M.

2016-01-01

The interaction of calcite with trivalent europium under recrystallization conditions was studied on the molecular level using site-selective time-resolved laser fluorescence spectroscopy (TRLFS). We conducted batch studies with a reaction time from seven days up to three years with three calcite powders, which differed in their specific surface area, recrystallization rates and impurities content. With increase of the recrystallization rate incorporation of Eu3+ occurs faster and its speciation comes to be dominated by one species with its excitation maximum at 578.8 nm, so far not identified during previous investigations of this process under growth and phase transformation conditions. A long lifetime of 3750 μs demonstrates complete loss of hydration, consequently Eu must have been incorporated into the bulk crystal. The results show a strong dependence of the incorporation kinetics on the recrystallization rate of the different calcites. Furthermore the investigation of the effect of different background electrolytes (NaCl and KCl) demonstrate that the incorporation process under recrystallization conditions strongly depends on the availability of Na+. These findings emphasize the different retention potential of calcite as a primary and secondary mineral e.g. in a nuclear waste disposal site. PMID:27618958

Time and metamorphic petrology: Calcite to aragonite experiments

USGS Publications Warehouse

Hacker, B.R.; Kirby, S.H.; Bohlen, S.R.

1992-01-01

Although the equilibrium phase relations of many mineral systems are generally well established, the rates of transformations, particularly in polycrystalline rocks, are not. The results of experiments on the calcite to aragonite transformation in polycrystalline marble are different from those for earlier experiments on powdered and single-crystal calcite. The transformation in the polycrystalline samples occurs by different mechanisms, with a different temperature dependence, and at a markedly slower rate. This work demonstrates the importance of kinetic studies on fully dense polycrystalline aggregates for understanding mineralogic phase changes in nature. Extrapolation of these results to geological time scales suggests that transformation of calcite to aragonite does not occur in the absence of volatiles at temperatures below 200??C. Kinetic hindrance is likely to extend to higher temperatures in more complex transformations.

Estimation of dissolution rate from in vivo studies of synthetic vitreous fibers.

PubMed

Eastes, W; Potter, R M; Hadley, J G

2000-11-01

Although the dissolution rate of a fiber was originally defined by a measurement of dissolution in simulated lung fluid in vitro, it is feasible to determine it from animal studies as well. The dissolution rate constant for a fiber may be extracted from the decrease in long fiber diameter observed in certain intratracheal instillation experiments or from the observed long fiber retention in short-term biopersistence studies. These in vivo dissolution rates agree well with those measured in vitro for the same fibers. For those special types of fibers, the high-alumina rock wool fibers that could not be measured in vitro, the method provides a way of obtaining a chemical dissolution rate constant from an animal study. The inverse of the in vivo dissolution rate, the fiber dissolution time, correlates well with the weighted half life of long fibers in a biopersistence study, and the in vivo dissolution rate may be estimated accurately from this weighted half-life.

Lab-Scale Study of the Calcium Carbonate Dissolution and Deposition by Marine Cyanobacterium Phormidium subcapitatum

NASA Technical Reports Server (NTRS)

Karakis, S. G.; Dragoeva, E. G.; Lavrenyuk, T. I.; Rogochiy, A.; Gerasimenko, L. M.; McKay, D. S.; Brown, I. I.

2006-01-01

Suggestions that calcification in marine organisms changes in response to global variations in seawater chemistry continue to be advanced (Wilkinson, 1979; Degens et al. 1985; Kazmierczak et al. 1986; R. Riding 1992). However, the effect of [Na+] on calcification in marine cyanobacteria has not been discussed in detail although [Na+] fluctuations reflect both temperature and sea-level fluctuations. The goal of these lab-scale studies therefore was to study the effect of environmental pH and [Na+] on CaCO3 deposition and dissolution by marine cyanobacterium Phormidium subcapitatum. Marine cyanobacterium P. subcapitatum has been cultivated in ASN-III medium. [Ca2+] fluctuations were monitored with Ca(2+) probe. Na(+) concentrations were determined by the initial solution chemistry. It was found that the balance between CaCO3 dissolution and precipitation induced by P. subcapitatum grown in neutral ASN III medium is very close to zero. No CaCO3 precipitation induced by cyanobacterial growth occurred. Growth of P. subcapitatum in alkaline ASN III medium, however, was accompanied by significant oscillations in free Ca(2+) concentration within a Na(+) concentration range of 50-400 mM. Calcium carbonate precipitation occurred during the log phase of P. subcapitatum growth while carbonate dissolution was typical for the stationary phase of P. subcapitatum growth. The highest CaCO3 deposition was observed in the range of Na(+) concentrations between 200-400 mM. Alkaline pH also induced the clamping of P. subcapitatum filaments, which appeared to have a strong affinity to envelop particles of chemically deposited CaCO3 followed by enlargement of those particles size. EDS analysis revealed the presence of Mg-rich carbonate (or magnesium calcite) in the solution containing 10-100 mM Na(+); calcite in the solution containing 200 mM Na(+); and aragonite in the solution containing with 400 mM Na(+). Typical present-day seawater contains xxmM Na(+). Early (Archean) seawater was likely less saline. The division of marine cyanobacterium P. subcapitatum is associated with periodic deposition and dissolution of CaCO3, the rhythms and intensity of which are dependent on concentrations of both OH(-) and Na(+). Thus, the role of present-day marine cyanobacteria in the global carbonate cycle might be reduced to aggregation and recrystallization of available CaCO3 particles in marine water rather than long-term precipitation and accumulation of CaCO3 deposits. For lower Na(+) concentrations, precipitation of carbonates by cyanobacteria would be even less significant. These results suggest that the lack of calcified cyanobacteria in stromatalite-bearing Precambrian sequences can be explained not only by high dissolved inorganic carbon concentrations but also by lower salinity, as well as possible lower pH compared to present-day oceans.

Distribution of Minor Elements in Calcite From the Unsaturated Zone at Yucca Mountain, Nevada

NASA Astrophysics Data System (ADS)

Marshall, B. D.; Whelan, J. F.

2001-12-01

Calcite is sporadically distributed in fractures and cavities in the volcanic rocks that form the 500- to 700-m-thick unsaturated zone at Yucca Mountain. Previous work has shown that the calcite precipitated from water moving downward through the unsaturated zone since the volcanic rocks were emplaced approximately 13 Ma. Calcite thus serves as a proxy for the chemistry and amounts of past percolation, two parameters that are important in predictions of the future behavior of the potential radioactive waste repository at Yucca Mountain. Latest calcite, which began forming between approximately 5 and 2 Ma, typically displays fine-scale growth zoning defined by distributions of Mn (inferred from cathodoluminescence), Mg, and Sr. Electron microprobe (EPMA) mapping of outermost calcite reveals Mg growth zoning1 and higher overall concentrations of Mg in late calcite than in older calcite. Micro X-ray fluorescence (micro-XRF) maps were obtained by slow rastering of the samples over a 100-watt X-ray source collimated through a final aperture of 100 μ m. Although the spatial resolution of the micro-XRF mapping is much less than that of EPMA, this technique reveals distributions of some elements to which EPMA is less sensitive. Micro-XRF maps show that Sr is spatially correlated with Mg; Sr concentrations range to 500 μ g/g at the resolution of the 100-μ m collimator. Because both Mg and Sr have similar calcite-water distribution coefficients much less than one, the Mg/Sr in calcite reflects the Mg/Sr of the water that precipitated the calcite. The distribution coefficient for Mn is greater than one and variations in Mn are not correlated with Mg and Sr. Covariation of Mg and Sr in the percolating water may be explained by reactions that affect the rate of uptake of chemical constituents from the overlying rock and soil, and/or evaporation. Late calcite has lower δ 13C values, probably due to a regional change from wetter to drier climate conditions. The higher Mg and Sr concentrations in the late calcite may record lower deposition rates and decreased percolation fluxes due to the drier climate. 1 Wilson, N.S.F., Cline, J.S., and Lundberg, S.A.W., 2000, Paragenesis and chemical composition of secondary mineralization at Yucca Mountain, Nevada, Geol. Soc. Am. Abs. Prog., v. 32, p. A260.

Copper-nickel-rich, amalgamated ferromanganese crust-nodule deposits from Shatsky Rise, NW Pacific

USGS Publications Warehouse

Hein, J.R.; Conrad, T.A.; Frank, M.; Christl, M.; Sager, W.W.

2012-01-01

A unique set of ferromanganese crusts and nodules collected from Shatsky Rise (SR), NW Pacific, were analyzed for mineralogical and chemical compositions, and dated using Be isotopes and cobalt chronometry. The composition of these midlatitude, deep-water deposits is markedly different from northwest-equatorial Pacific (PCZ) crusts, where most studies have been conducted. Crusts and nodules on SR formed in close proximity and some nodule deposits were cemented and overgrown by crusts, forming amalgamated deposits. The deep-water SR crusts are high in Cu, Li, and Th and low in Co, Te, and Tl concentrations compared to PCZ crusts. Thorium concentrations (ppm) are especially striking with a high of 152 (mean 56), compared to PCZ crusts (mean 11). The deep-water SR crusts show a diagenetic chemical signal, but not a diagenetic mineralogy, which together constrain the redox conditions to early oxic diagenesis. Diagenetic input to crusts is rare, but unequivocal in these deep-water crusts. Copper, Ni, and Li are strongly enriched in SR deep-water deposits, but only in layers older than about 3.4 Ma. Diagenetic reactions in the sediment and dissolution of biogenic calcite in the water column are the likely sources of these metals. The highest concentrations of Li are in crust layers that formed near the calcite compensation depth. The onset of Ni, Cu, and Li enrichment in the middle Miocene and cessation at about 3.4 Ma were accompanied by changes in the deep-water environment, especially composition and flow rates of water masses, and location of the carbonate compensation depth.

Major hydrogeochemical processes in an acid mine drainage affected estuary.

PubMed

Asta, Maria P; Calleja, Maria Ll; Pérez-López, Rafael; Auqué, Luis F

2015-02-15

This study provides geochemical data with the aim of identifying and quantifying the main processes occurring in an Acid Mine Drainage (AMD) affected estuary. With that purpose, water samples of the Huelva estuary were collected during a tidal half-cycle and ion-ion plots and geochemical modeling were performed to obtain a general conceptual model. Modeling results indicated that the main processes responsible for the hydrochemical evolution of the waters are: (i) the mixing of acid fluvial water with alkaline ocean water; (ii) precipitation of Fe oxyhydroxysulfates (schwertmannite) and hydroxides (ferrihydrite); (iii) precipitation of Al hydroxysulfates (jurbanite) and hydroxides (amorphous Al(OH)3); (iv) dissolution of calcite; and (v) dissolution of gypsum. All these processes, thermodynamically feasible in the light of their calculated saturation states, were quantified by mass-balance calculations and validated by reaction-path calculations. In addition, sorption processes were deduced by the non-conservative behavior of some elements (e.g., Cu and Zn). Copyright © 2014 Elsevier Ltd. All rights reserved.

Three-dimensional imaging of dislocation propagation during crystal growth and dissolution

PubMed Central

Schenk, Anna S.; Kim, Yi-Yeoun; Kulak, Alexander N.; Campbell, James M.; Nisbet, Gareth; Meldrum, Fiona C.; Robinson, Ian K.

2015-01-01

Atomic level defects such as dislocations play key roles in determining the macroscopic properties of crystalline materials 1,2. Their effects range from increased chemical reactivity 3,4 to enhanced mechanical properties 5,6. Dislocations have been widely studied using traditional techniques such as X-ray diffraction and optical imaging. Recent advances have enabled atomic force microscopy to study single dislocations 7 in two-dimensions (2D), while transmission electron microscopy (TEM) can now visualise strain fields in three-dimensions (3D) with near atomic resolution 8–10. However, these techniques cannot offer 3D imaging of the formation or movement of dislocations during dynamic processes. Here, we describe how Bragg Coherent Diffraction Imaging (BCDI) 11,12 can be used to visualize in 3D, the entire network of dislocations present within an individual calcite crystal during repeated growth and dissolution cycles. These investigations demonstrate the potential of BCDI for studying the mechanisms underlying the response of crystalline materials to external stimuli. PMID:26030304

High-pressure deformation of calcite marble and its transformation to aragonite under non-hydrostatic conditions

USGS Publications Warehouse

Hacker, B.R.; Kirby, S.H.

1993-01-01

We conducted deformation experiments on Carrara marble in the aragonite and calcite stability fields to observe the synkinematic transformation of calcite to aragonite, and to identify any relationships between transformation and deformation or sample strength. Deformation-induced microstructures in calcite crystals varied most significantly with temperature, ranging from limited slip and twinning at 400??C, limited recrystallization at 500??C, widespread recrystallization at 600 and 700??C, to grain growth at 800-900??C. Variations in confining pressure from 0.3 to 2.0 GPa have no apparent effect on calcite deformation microstructures. Aragonite grew in 10-6-10-7 s-1strain rate tests conducted for 18-524 h at confining pressures of 1.7-2.0 GPa and temperatures of 500-600??C. As in our previously reported hydrostatic experiments on this same transformation, the aragonite nucleated on calcite grain boundaries. The extent of transformation varied from a few percent conversion near pistons at 400??C, 2.0 GPa and 10-4 s-1 strain rate in a 0.8 h long experiment, to 98% transformation in a 21-day test at a strain rate of 10-7 s-7, a temperature of 600??C and a pressure of 2.0 GPa. At 500??C, porphyroblastic 100-200 ??m aragonite crystals grew at a rate faster than 8 ?? 10-1m s-1. At 600??C, the growth of aragonite neoblasts was slower, ???6 ?? 10-1 m s -1, and formed 'glove-and-finger' cellularprecipitation-like textures identical to those observed in hydrostatic experiments. The transformation to aragonite is not accompanied by a shear instability or anisotropic aragonite growth, consistent with its relatively small volume change and latent heat in comparison with compounds that do display those features. ?? 1993.

Greenschist-Facies Pseudotachylytes and Gouge: a Microstructural Study of the Deformation Propagation at the Boundary Between Hp-Metabasite and Calcite Bearing Metasediments

NASA Astrophysics Data System (ADS)

Crispini, L.; Scambelluri, M.; Capponi, G.

2013-12-01

Recent friction experiments on calcite-bearing systems reproduce pseudotachylyte structures, that are diagnostic of dinamic calcite recrystallization related to seismic slip in the shallow crust. Here we provide the study of a pseudotachylyte (PT) bearing low angle oblique-slip fault. The fault is linked to the exhumation of Alpine HP-ophiolites and it is syn- to post-metamorphic with respect to retrograde greenschist facies metamorphism. The observed microstructures developed at the brittle-ductile transition and suggest that seismic and interseismic slip was enhanced by interaction with fluids. The fault zone is in-between high-pressure eclogite-facies metabasites (hangingwall) and calcite bearing metasediments (footwall). The mafic rocks largely consist of upper greenschist facies hornblende, albite, chlorite, epidote with relict eclogitic garnet, Na-pyroxene and rutile; metasediments correspond to calcschist and micaschist with quartz, phengite, zoisite, chlorite, calcite and relics of garnet. Key features of the oucrop are: the thickness and geometry of the PT and gouge; the multiple production of PT characterized by overprinting plastic and brittle deformation; the occurrence in footwall metasediments of mm-thick bands of finely recrystallized calcite coeval with PT development in the hangingwall. The damage zone is ca. 2 m-thick and is characterized by two black, ultra-finegrained straight and sharp Principal Slip Zones (PSZ) marked by PT. The damage zone shows a variety of fault rocks (cataclasite and ultracataclasite, gouge and PT) with multiple crosscutting relationships. Within the two main PSZ, PT occurs in 10-20 cm thick layer, in small scale injection veins and in microfractures. In the mafic hanging wall, the PT is recrystallized and does not preserve glass: it shows flow structures with subrounded, embayed and rebsorbed quartz in a fine grained matrix composed of isotropic albite + chlorite + quartz + epidote + titanite, suggesting recrystallization at ca. 270-300°C, 8-10 km of the original glass. PT show plastic deformations overprinted by shear bands and fracturing. The matrix of cataclastic layers has the same mineral assemblage as PT and clasts of recrystallised PT, to indicate polyphase PSZ formation. In the metasedimentary footwall, the original foliation is deflected parallel to the PSZ and is cut by cm-spaced shear bands parallel to PSZ. Deformation propagates in the footwall through mm-thick injections veins, shear bans, P-shears and veins. Pockets of recrystallized PT occur along the pre-existing mylonitic foliation of metasediments. Worthnote is the presence of mm-thick deformation bands (CDB) that are post-mylonitic foliation and mainly composed of fine grained calcite bounded by dissolution seams or ribbon grains of deformed calcite. CDB are characterised by subrounded embayed and rebsorbed quartz grains rimmed by new Ca-Mg amphibole, K-feldspar (90-93%K), in a dinamic recrystallized calcite 2-10 micron in size and slightly elongated. The features of the CDB suggest that these structures can be considered as diagnostic of localised deformation during coesismic slip in metasedimentary rocks.

Application of the flow-through time-resolved analysis technique to trace element determination in ostracod shells

NASA Astrophysics Data System (ADS)

Börner, Nicole; De Baere, Bart; Francois, Roger; Frenzel, Peter; Schwalb, Antje

2014-05-01

Trace element analyses of ostracod shells are a vital tool for paleoenvironmental reconstructions from lake sediments (Börner et al., 2013). Conventional batch dissolution ICP-MS is the most common way for analyzing trace elements in ostracod shells. However, due to dissolution or secondary overgrowth the primary signal may be masked. Resulting variations in trace element composition have been identified to be in the order of a magnitude range. Therefore, the application of the newly developed flow-through technique will be assessed. The flow-through time-resolved analysis technique allows to chemically separate mineral phases of different solubility such as, in particular, original shell calcite from overgrowth calcite, and thus to correct the measurements for the biogenic signal. During a flow-through experiment, eluent is continuously pumped through a sample column, typically a filter in which the ostracod valves are loaded. The gradual dissolution of the substrate is controlled by a combination of eluent type, eluent temperature and eluent flow rate. The dissolved sample then flows directly to a mass spectrometer. The resulting data is a chromatogram, featuring different mineral phases dissolving as time progresses. Hence, the flow-through technique provides a detailed geochemical fingerprint of the substrate and therefore additional data relative to conventional methods. To calibrate this technique for the application to ostracods we use ostracod shells from Southern Tibetan Plateau lakes, which feature an alkaline environment but show highly diverse hydrochemistry. Cleaned as well as uncleaned ostracod shells show similarity in their trace element signals, allowing measurements without prior cleaning of the shells, and thus more time-efficient sample throughput. Measurements of unclean shells are corrected for the biogenic signal using an equation from Klinkhammer et al. (2004). Another advantage is that the measurements can be carried out on single ostracod shells, as not every single sediment sample contains enough adult intact specimens of all required genera, making batch cleaning dissolution impossible. The flow-through time-resolved analysis technique gives an accurate and high-resolution dataset. The trace elemental data for living ostracods compared to the hydrological data from each sampling site provides a calibration dataset for further hydrological and thus climatological reconstruction of a sediment core from Nam Co. Mg/Ca and Sr/Ca ratios in ostracod shells will provide information about past water temperature and salinity resulting from changes in precipitation vs. evaporation ratios and monsoon activity. Further, we will exploit Mn/Ca, Fe/Ca and U/Ca ratios as redox indicators to reconstruct oxygenation cycles and Ba/Ca ratios to detect changes in productivity and/or salinity. This reconstruction should provide a more extensive insight in past climatic change, e.g. precipitation - evaporation balance, lake level and circulation changes, and the recording of environmental signatures by ostracod shells. Börner, N., De Baere, B., Yang, Q., Jochum, K.P., Frenzel, P., Andreae, M.O., Schwalb, A., 2013. Ostracod shell chemistry as proxy for paleoenvironmental change. Quaternary International 313-314, 17-37. Klinkhammer, G.P., Haley, B.A., Mix, A.C., Benway, H., Cheseby, M., 2004. Evaluation of automated flow-through time-resolved analysis of foraminifera for Mg/Ca paleothermometry. Paleoceanography 19, PA4030.

Comparison on Response and Dissolution Rates Between Ursodeoxycholic Acid Alone or in Combination With Chenodeoxycholic Acid for Gallstone Dissolution According to Stone Density on CT Scan: Strobe Compliant Observation Study.

PubMed

Lee, Jae Min; Hyun, Jong Jin; Choi, In Young; Yeom, Suk Keu; Kim, Seung Young; Jung, Sung Woo; Jung, Young Kul; Koo, Ja Seol; Yim, Hyung Joon; Lee, Hong Sik; Lee, Sang Woo; Kim, Chang Duck

2015-12-01

Medical dissolution of gallstone is usually performed on radiolucent gallstones in a functioning gallbladder. However, absence of visible gallstone on plain abdominal x-ray does not always preclude calcification. This study aims to compare the response and dissolution rates between ursodeoxycholic acid (UDCA) alone or in combination with chenodeoxycholic acid (CDCA) according to stone density on computed tomography (CT) scan. A total of 126 patients underwent dissolution therapy with either UDCA alone or combination of CDCA and UDCA (CNU) from December 2010 to March 2014 at Korea University Ansan Hospital. In the end, 81 patients (CNU group = 44, UDCA group = 37) completed dissolution therapy for 6 months. Dissolution rate (percentage reduction in the gallstone volume) and response to therapy (complete dissolution or partial dissolution defined as reduction in stone volume of >50%) were compared between the 2 groups. Dissolution and response rates of sludge was also compared between the 2 groups. The overall response rate was 50.6% (CNU group 43.2% vs UDCA group 59.5%, P = 0.14), and the overall dissolution rate was 48.34% (CNU group 41.5% vs UDCA group 56.5%, P = 0.13). When analyzed according to stone density, response rate was 33.3%, 87.1%, 30.0%, and 6.2% for hypodense, isodense, hyperdense, and calcified stones, respectively. Response rate (85.7% vs 88.2%, P = 0.83) and dissolution rate (81.01% vs 85.38%, P = 0.17) of isodense stones were similar between CNU and UDCA group. When only sludge was considered, the overall response rate was 87.5% (CNU group 71.4% vs UDCA group 94.1%, P = 0.19), and the overall dissolution rate was 85.42% (CNU group 67.9% vs UDCA group 92.7%, P = 0.23). Patients with isodense gallstones and sludge showed much better response to dissolution therapy with CNU and UDCA showing comparable efficacy. Therefore, CT scan should be performed before medication therapy if stone dissolution is intended.

A Bayesian, multivariate calibration for Globigerinoides ruberMg/Ca

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khider, D.; Huerta, G.; Jackson, C.

The use of Mg/Ca in marine carbonates as a paleothermometer has been challenged by observations that implicate salinity as a contributing influence on Mg incorporation into biotic calcite and that dissolution at the sea-floor alters the original Mg/Ca. Yet, these factors have not yet been incorporated into a single calibration model. In this paper, we introduce a new Bayesian calibration for Globigerinoides ruber Mg/Ca based on 186 globally distributed core top samples, which explicitly takes into account the effect of temperature, salinity, and dissolution on this proxy. Our reported temperature, salinity, and dissolution (here expressed as deep-water ΔCO 2- 3)more » sensitivities are (±2σ) 8.7±0.9%/°C, 3.9±1.2%/psu, and 3.3±1.3%/μmol.kg -1 below a critical threshold of 21 μmol/kg in good agreement with previous culturing and core-top studies. We then perform a sensitivity experiment on a published record from the western tropical Pacific to investigate the bias introduced by these secondary influences on the interpretation of past temperature variability. This experiment highlights the potential for misinterpretations of past oceanographic changes when the secondary influences of salinity and dissolution are not accounted for. Finally, multiproxy approaches could potentially help deconvolve the contributing influences but this awaits better characterization of the spatio-temporal relationship between salinity and δ 18O sw over millennial and orbital timescales.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wronkiewicz, David; Paul, Varum; Abousif, Alsedik

The most effective mechanism to limit CO 2 release from underground Geologic Carbon Sequestration (GCS) sites over multi-century time scales will be to convert the CO 2 into solid carbonate minerals. This report describes the results from four independent research investigations on carbonate mineralization: 1) Colloidal calcite particles forming in Maramec Spring, Missouri, provide a natural analog to evaluate reactions that may occur in a leaking GCS site. The calcite crystals form as a result of physiochemical changes that occur as the spring water rises from a depth of more than 190'. The resultant pressure decrease induces a loss ofmore » CO 2 from the water, rise in pH, lowering of the solubility of Ca 2+ and CO 3 2-, and calcite precipitation. Equilibrium modelling of the spring water resulted in a calculated undersaturated state with respect to calcite. The discontinuity between the observed occurrence of calcite and the model result predicting undersaturated conditions can be explained if bicarbonate ions (HCO 3 -) are directly involved in precipitation process rather than just carbonate ions (CO 3 2-). 2) Sedimentary rocks in the Oronto Group of the Midcontinent Rift (MCR) system contain an abundance of labile Ca-, Mg-, and Fe-silicate minerals that will neutralize carbonic acid and provide alkaline earth ions for carbonate mineralization. One of the challenges in using MCR rocks for GCS results from their low porosity and permeability. Oronto Group samples were reacted with both CO 2-saturated deionized water at 90°C, and a mildly acidic leachant solution in flow-through core-flooding reactor vessels at room temperature. Resulting leachate solutions often exceeded the saturation limit for calcite. Carbonate crystals were also detected in as little as six days of reaction with Oronto Group rocks at 90oC, as well as experiments with forsterite-olivine and augite, both being common minerals this sequence. The Oronto Group samples have poor reservoir rock characteristics, none ever exceeded a permeability value of 2.0 mD even after extensive dissolution of calcite cement during the experiments. The overlying Bayfield Group – Jacobsville Formation sandstones averaged 13.4 ± 4.3% porosity and a single sample tested by core-flooding revealed a permeability of ~340 mD. The high porosity-permeability characteristics of these sandstones will allow them to be used for GCS as a continuous aquifer unit with the overlying Mt. Simon Formation. 3) Anaerobic sulfate reducing bacteria (SRB) can enhance the conversion rate of CO 2 into solid minerals and thereby improve long-term storage. SRB accelerated carbonate mineralization reactions between pCO 2 values of 0.0059 and 14.7 psi. Hydrogen, lactate and formate served as suitable electron donors for SRB metabolism. The use of a 13CO 2 spiked gas source also produced carbonate minerals with ~53% of the carbon being derived from the gas phase. The sulfate reducing activity of the microbial community was limited, however, at 20 psi pCO 2 and carbonate mineralization did not occur. Inhibition of bacterial metabolism may have resulted from the acidic conditions or CO 2 toxicity. 4) Microbialite communities forming in the high turbidity and hypersaline water of Storrs’ Lake, San Salvador Island, The Bahamas, were investigated for their distribution, mineralogy and microbial diversity. Molecular analysis of the organic mats on the microbialites indicate only a trace amount of cyanobacteria, while anaerobic and photosynthetic non-sulfur bacteria of the phyla Chloroflexi and purple sulfur bacteria of class Gammaproteobacteria were abundant.« less

Dissolution rate enhancement of gliclazide by ordered mixing.

PubMed

Saharan, Vikas A; Choudhury, Pratim K

2011-09-01

The poorly water soluble antidiabetic drug gliclazide was selected to study the effect of excipients on dissolution rate enhancement. Ordered mixtures of micronized gliclazide with lactose, mannitol, sorbitol, maltitol and sodium chloride were prepared by manual shaking of glass vials containing the drug and excipient(s). Different water soluble excipients, addition of surfactant and superdisintegrant, drug concentration and carrier particle size influenced the dissolution rate of the drug. Dissolution rate studies of the prepared ordered mixtures revealed an increase in drug dissolution with all water soluble excipients. The order of dissolution rate improvement for gliclazide was mannitol > lactose > maltitol > sorbitol > sodium chloride. Composite granules of the particle size range 355-710 μm were superior in increasing the drug dissolution rate from ordered mixtures. Reducing the carrier particle size decreased the dissolution rate of the drug as well as the increase in drug concentration. Kinetic modeling of drug release data fitted best the Hixson-Crowell model, which indicates that all the ordered mixture formulations followed the cube root law fairly well.

Chemical evolution of groundwater in the Wilcox aquifer of the northern Gulf Coastal Plain, USA

NASA Astrophysics Data System (ADS)

Haile, Estifanos; Fryar, Alan E.

2017-12-01

The Wilcox aquifer is a major groundwater resource in the northern Gulf Coastal Plain (lower Mississippi Valley) of the USA, yet the processes controlling water chemistry in this clastic aquifer have received relatively little attention. The current study combines analyses of solutes and stable isotopes in groundwater, petrography of core samples, and geochemical modeling to identify plausible reactions along a regional flow path ˜300 km long. The hydrochemical facies evolves from Ca-HCO3 upgradient to Na-HCO3 downgradient, with a sequential zonation of terminal electron-accepting processes from Fe(III) reduction through SO4 2- reduction to methanogenesis. In particular, decreasing SO4 2- and increasing δ34S of SO4 2- along the flow path, as well as observations of authigenic pyrite in core samples, provide evidence of SO4 2- reduction. Values of δ13C in groundwater suggest that dissolved inorganic carbon is contributed both by oxidation of sedimentary organic matter and calcite dissolution. Inverse modeling identified multiple plausible sets of reactions between sampled wells, which typically involved cation exchange, pyrite precipitation, CH2O oxidation, and dissolution of amorphous Fe(OH)3, calcite, or siderite. These reactions are consistent with processes identified in previous studies of Atlantic Coastal Plain aquifers. Contrasts in groundwater chemistry between the Wilcox and the underlying McNairy and overlying Claiborne aquifers indicate that confining units are relatively effective in limiting cross-formational flow, but localized cross-formational mixing could occur via fault zones. Consequently, increased pumping in the vicinity of fault zones could facilitate upward movement of saline water into the Wilcox.

Influence of a major exposure surface on the development of microporous micritic limestones - Example of the Upper Mishrif Formation (Cenomanian) of the Middle East

NASA Astrophysics Data System (ADS)

Deville de Periere, M.; Durlet, C.; Vennin, E.; Caline, B.; Boichard, R.; Meyer, A.

2017-05-01

Microporous platform top limestones of the Cenomanian Mishrif Formation (offshore Qatar) were studied in order to investigate the diagenetic processes associated with the top-Mishrif subaerial unconformity and its influence on the development of microporosity in underlying carbonates. Petrographical and stable isotope results indicate that complex diagenetic changes occurred during subaerial exposure of the Mishrif Formation, including pervasive dissolution and meteoric cementation, as well as neomorphism of the micritic matrix. Micrites at the top of the Mishrif Formation are coarse (i.e. > 2 μm), sub-rounded and very dull luminescent under cathodoluminescence. In this uppermost part of the studied interval, the limestone matrix first underwent dissolution of unstable grains in the vadose zone, with subsequent precipitation of low-magnesium calcite (LMC) overgrowths within an oxidising phreatic setting. This process explains the poor luminescence of the micrite crystals and their relatively coarse crystallometry which results in the present day in relatively good reservoir properties. δ13C ratios within the microporous limestones are negative (up to - 4‰ V-PDB) due to the incorporation of isotopically light carbon derived from palaeosols which developed during exposure. By contrast, fine (i.e. < 2 μm), polyhedral and bright luminescent micritic matrix with higher δ13C values (up to + 4‰ V-PDB) and lower permeability are dominant within the underlying carbonate interval. These fine micrites are likely to be the product of early neomorphic recrystallisation in the lowermost part of the palaeo-aquifer associated with the Top-Mishrif Unconformity, and were precipitated from meteoric or mixed dysoxic waters which were slightly supersaturated with respect to calcite.

Environmental characterisation of coal mine waste rock in the field: an example from New Zealand

NASA Astrophysics Data System (ADS)

Hughes, J.; Craw, D.; Peake, B.; Lindsay, P.; Weber, P.

2007-08-01

Characterisation of mine waste rock with respect to acid generation potential is a necessary part of routine mine operations, so that environmentally benign waste rock stacks can be constructed for permanent storage. Standard static characterisation techniques, such as acid neutralisation capacity (ANC), maximum potential acidity, and associated acid-base accounting, require laboratory tests that can be difficult to obtain rapidly at remote mine sites. We show that a combination of paste pH and a simple portable carbonate dissolution test, both techniques that can be done in the field in a 15 min time-frame, is useful for distinguishing rocks that are potentially acid-forming from those that are acid-neutralising. Use of these techniques could allow characterisation of mine wastes at the metre scale during mine excavation operations. Our application of these techniques to pyrite-bearing (total S = 1-4 wt%) but variably calcareous coal mine overburden shows that there is a strong correlation between the portable carbonate dissolution technique and laboratory-determined ANC measurements (range of 0-10 wt% calcite equivalent). Paste pH measurements on the same rocks are bimodal, with high-sulphur, low-calcite rocks yielding pH near 3 after 10 min, whereas high-ANC rocks yield paste pH of 7-8. In our coal mine example, the field tests were most effective when used in conjunction with stratigraphy. However, the same field tests have potential for routine use in any mine in which distinction of acid-generating rocks from acid-neutralising rocks is required. Calibration of field-based acid-base accounting characteristics of the rocks with laboratory-based static and/or kinetic tests is still necessary.

Does the dose-solubility ratio affect the mean dissolution time of drugs?

PubMed

Lánský, P; Weiss, M

1999-09-01

To present a new model for describing drug dissolution. On the basis of the new model to characterize the dissolution profile by the distribution function of the random dissolution time of a drug molecule, which generalizes the classical first order model. Instead of assuming a constant fractional dissolution rate, as in the classical model, it is considered that the fractional dissolution rate is a decreasing function of the dissolved amount controlled by the dose-solubility ratio. The differential equation derived from this assumption is solved and the distribution measures (half-dissolution time, mean dissolution time, relative dispersion of the dissolution time, dissolution time density, and fractional dissolution rate) are calculated. Finally, instead of monotonically decreasing the fractional dissolution rate, a generalization resulting in zero dissolution rate at time origin is introduced. The behavior of the model is divided into two regions defined by q, the ratio of the dose to the solubility level: q < 1 (complete dissolution of the dose, dissolution time) and q > 1 (saturation of the solution, saturation time). The singular case q = 1 is also treated and in this situation the mean as well as the relative dispersion of the dissolution time increase to infinity. The model was successfully fitted to data (1). This empirical model is descriptive without detailed physical reasoning behind its derivation. According to the model, the mean dissolution time is affected by the dose-solubility ratio. Although this prediction appears to be in accordance with preliminary application, further validation based on more suitable experimental data is required.

Dissolved CO2 Increases Breakthrough Porosity in Natural Porous Materials.

PubMed

Yang, Y; Bruns, S; Stipp, S L S; Sørensen, H O

2017-07-18

When reactive fluids flow through a dissolving porous medium, conductive channels form, leading to fluid breakthrough. This phenomenon is caused by the reactive infiltration instability and is important in geologic carbon storage where the dissolution of CO 2 in flowing water increases fluid acidity. Using numerical simulations with high resolution digital models of North Sea chalk, we show that the breakthrough porosity is an important indicator of dissolution pattern. Dissolution patterns reflect the balance between the demand and supply of cumulative surface. The demand is determined by the reactive fluid composition while the supply relies on the flow field and the rock's microstructure. We tested three model scenarios and found that aqueous CO 2 dissolves porous media homogeneously, leading to large breakthrough porosity. In contrast, solutions without CO 2 develop elongated convective channels known as wormholes, with low breakthrough porosity. These different patterns are explained by the different apparent solubility of calcite in free drift systems. Our results indicate that CO 2 increases the reactive subvolume of porous media and reduces the amount of solid residual before reactive fluid can be fully channelized. Consequently, dissolved CO 2 may enhance contaminant mobilization near injection wellbores, undermine the mechanical sustainability of formation rocks and increase the likelihood of buoyance driven leakage through carbonate rich caprocks.

Co-Precipitation of Trace Metals in Groundwater & Vadose Zone Calcite: In Situ Containment & Stabilization of Strontium-90 & Other Divalent Metals & Radionuclid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferris, F. Grant

2003-06-01

A suite of experiments were performed to investigate the partitioning of Sr2+ (to mimic the radionuclide 90Sr) between calcite and artificial groundwater in response to the hydrolysis of urea by Bacillus pasteurii under conditions that simulate in-situ aquifer conditions. Experiments were performed at 10, 15 and 20 C over 7 days in microcosms inoculated with B. pasteurii ATCC 11859 and containing an artificial groundwater and urea (AGW), and an AGW including a Sr contaminant treatment. During the experiments ammonium concentration from bacterial urea hydrolysis increased asymptotically, and derived rate constants (kurea) that were between 13 and 10 times greater atmore » 20 C, than at 15 and 10 C. Calcite precipitation was initiated after similar amounts of urea had been hydrolysed ({approx} 4.0 mmoles L-1) and a similar critical saturation state (mean Scritical = 53, variation = 20%) had been reached, independent of temperature and Sr treatment. Because of the positive relationship between urea hydrolysis rate and temperature, precipitation began by the end of day 1 at 20 C, and between days 1 and 2 at 15 and 10 C. The rate of calcite precipitation increased with, and was fundamentally controlled by S, irrespective of temperature, which connects the dissimilar patterns of urea hydrolysis and dissolved concentrations which are exhibited at the different experiments. The presence of Sr slightly slowed calcite precipitation rates at equivalent values of S, which may reflect the screening of active nucleation and crystal growth sites by Sr. Instantaneous heterogeneous partitioning coefficients (DSr) exhibited a positive association with calcite precipitation rates, but were greater at higher experimental temperatures at equivalent precipitation rates (20 C mean = 0.46; 15 C mean = 0.24; 10 C mean = 0.29). This is likely to reflect the large ionic radius of the Sr ion, which cannot fully co-ordinate relative to ions smaller than Ca at equilibrium conditions, but i s increasingly co-precipitated as all ions are indiscriminately incorporated at higher precipitation rates. The temperature dependence is likely to reflect the higher miscibility of ions in minerals, commonly observed in geochemical systems at higher temperatures.« less

Effect of oxalate on the dissolution rates of oligoclase and tremolite (journal version)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mast, M.A.; Drever, J.I.

1987-01-01

The effect of oxalate, a strong chelator for Al and other cations, on the dissolution rates of oligoclase feldspar and tremolite amphibole was investigated in a flow-through reactor at 22 deg C. Oxalate at concentrations of 0.5 and 1 mM has essentially no effect on the dissolution rate of tremolite, nor on the steady-state rate of release of Si from oligoclase. The fact that oxalate has no effect on dissolution rate suggests that detachment of Si rather than Al or Mg is the rate-limiting step. At pH 4 and 9, oxalate has no effect on the steady-state rate of releasemore » of Al, and dissolution is congruent. At pH 5 and 7, oligoclase dissolution is congruent in the presence of oxalate, but in the absence of oxalate Al is preferentially retained in the solid relative to Si. The rate of dissolution of tremolite is independent of pH over the pH range 2-5, and decreases at higher pH. The rate of dissolution of oligoclase was independent of pH over the pH range 4-9. Since the dissolution rate of these minerals is independent of pH and organic ligand concentration, the effect of acid deposition from the atmosphere on the rate of supply of cations from weathering of granitic rocks should be minor.« less

Cyanobacterial diversity and related sedimentary facies as a function of water flow conditions: Example from the Monasterio de Piedra Natural Park (Spain)

NASA Astrophysics Data System (ADS)

Berrendero, Esther; Arenas, Concha; Mateo, Pilar; Jones, Brian

2016-05-01

The River Piedra in the Monasterio de Piedra Natural Park (NE Spain) is a modern tufa-depositing river that encompasses various depositional environments that are inhabited by different cyanobacterial populations. Molecular (16S rDNA) and morphological analyses of the cyanobacteria from different facies showed that Phormidium incrustatum dominates in the fast-flowing water areas where the mean depositional rate is 1.6 cm/year. Stromatolites in these areas are formed of palisades of hollow calcite tubes (inner diameter of 6.0-7.5 μm, walls 2-12 μm thick) that formed through calcite encrustation around the filaments followed by decay of the trichomes. In contrast, in slow-flowing water areas with lower depositional rates (mean depositional rate of 0.3 cm/year), Phormidium aerugineo-caeruleum is the dominant species. In these areas, randomly oriented calcite tubes (inner diameter of 5-6 μm, walls 3-8 μm thick) formed by calcite encrustation, are found in thin and uneven laminae and as scattered tubes in the loose lime mud and sand-sized carbonate sediment. Although this species did not build laminated deposits, it gave cohesiveness to the loose sediment. In the stepped and low waterfalls, with intermediate deposition rates (mean depositional rate of 0.9 cm/year), both species of Phormidium are found in association with spongy moss and algal boundstones, which is consistent with the variable flow conditions in this setting. The calcite encrustations on the cyanobacteria from different environments exhibit irregular patterns that may be linked to changes in the calcite saturation index. The physicochemical conditions associated with extracellular polymeric substances may be more significant to CaCO3 precipitation in microbial mats in slow-flowing water conditions than in fast-flowing water conditions. These results show that flow conditions may influence the distribution of different cyanobacteria that, in turn, leads to the development of different sedimentary facies and structures in fluvial carbonate systems.

Growth and Mortality of Coccolithophores during spring in the Celtic Sea

NASA Astrophysics Data System (ADS)

Mayers, K.; Poulton, A. J.; Giering, S. L. C.; Daniels, C. J.; Wells, S. R.; Tarran, G.

2016-02-01

Coccolithophores are an important group of single celled protists which dominate pelagic calcite production, however little is currently known about the mortality rates within this group, or their importance in shelf seas regarding productivity and nutrient recycling. Measurements of coccolithophore calcification and cellular calcite quotas, as well as dilution experiments for microzooplankton grazing rates, were made during a spring cruise (April, 2015) in the Celtic Sea (NW European Shelf) and within an April bloom of Emiliania huxleyi. Calcite production and coccolithophore cell numbers showed a general positive trend throughout the progression of the spring bloom, ranging from 15 - 34µmol C m-3d-1 and 6 - 94 cells ml-1. Cell normalised calcification rates declined from 3 - 0.6 pmol C cell-1d-1 due to a shift from a mixed community to an E. huxleyi dominated one. Within the E. huxleyi bloom we recorded high daily calcite production (6049 µmol C m-3d-1) and cell normalised calcification of 3 pmol C cell-1d-1. This is significantly higher than E. huxleyi dominated sites in the Iceland Basin and more similar to a bloom on the Patagonian Shelf. Within the E. huxleyi bloom, mortality rates were 0.23 d-1 compared with growth rates of 0.29 d-1, meaning 80% of daily calcification was removed by grazers. In this study, coccolithophore mortality rates are presented from the central Celtic Sea throughout spring, and compared with an April E. huxleyi bloom in terms of species composition, trends in calcite production and composition of the phytoplankton community. These observations will potentially elucidate the role grazing plays in the fate of calcium carbonate, bloom formation and community composition.

Manganese-calcium intermixing facilitates heteroepitaxial growth at the (1014) calcite-water interface

DOE PAGES

Xu, Man; Riechers, Shawn L.; Ilton, Eugene S.; ...

2017-09-05

For this research, in situ atomic force microscopy (AFM) measurements were performed to probe surface precipitates that formed on the (10more » $$\\bar{1}$$4) surface of calcite (CaCO 3) single crystals following reaction with Mn2 +-bearing aqueous solutions. Three-dimensional epitaxial islands were observed to precipitate and grow on the surfaces. In situ time-sequenced measurements demonstrated that the growth rates were commensurate with those obtained for epitaxial islands formed on calcite crystals reacted with Cd2 +-bearing aqueous solutions of the same range in supersaturation with respect to the pure metal carbonate phase. This finding was unexpected as rhodochrosite (MnCO 3) and calcite display a 10% lattice mismatch, based on the area of their (10$$\\bar{1}$$4) surface unit cells, whereas the lattice mismatch is only 4% for otavite (CdCO 3) and calcite. Coatings of varying thicknesses were therefore synthesized by reacting calcite single crystals in calcite-equilibrated aqueous solutions with up to 250 μM MnCl 2. Ex situ X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray reflectivity (XRR), and AFM measurements of the reacted crystals demonstrated the formation of an epitaxial (Mn,Ca)CO 3 solid solution. The epitaxial solid solution had a spatially complex composition, whereby the first few nanometers were rich in Ca and the Mn content increased with distance from the original calcite surface, culminating in a topmost region of almost pure MnCO 3 for the thickest coatings. The effective lattice mismatch was therefore much smaller than the nominal mismatch thus explaining the measured growth rates. Lastly, these findings highlight the strong influence played by the substrate on the composition of surface precipitates in aqueous conditions.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lighty, R.G.; Russell, K.L.

Transect mapping and petrologic studies reveal a new depositional model and limited diagenesis of a well-exposed Pleistocene reef outcrop at Ambergris Cay, northern Belize. This emergent shelf-edge reef forms a rocky wave-washed headland at the northern terminus of the present-day 250 km long flourishing Belize Barrier Reef. Previously, the Belize reef outcrop was thought to extend southward in the subsurface beneath the modern barrier reef as a Pleistocene equivalent. The authors study indicate that this outcrop is a large, coral patch reef and not part of a barrier reef trend. Sixteen transects 12.5 m apart described in continuous cm incrementsmore » from fore reef to back reef identified: extensive deposits of broken Acropora cervicornis; small thickets of A. palmata with small, oriented branches; and muddy skeletal sediments with few corals or reef rubble. Thin section and SEM studies show three phases of early submarine cementation: syntaxial and rosette aragonite; Mg-calcite rim cement and peloids; and colloidal Mg-calcite geopetal fill. Subaerial exposure in semi-arid northern Belize caused only minor skeletal dissolution, some precipitation of vadose whisker calcite, and no meteoric phreatic diagenesis. Facies geometry, coral assemblages, lack of rubble deposits, coralline algal encrustations and Millepora framework, and recognition of common but discrete submarine cements, all indicate that this Pleistocene reef was an isolated, coral-fringed sediment buildup similar to may large patch reefs existing today in moderate-energy shelf environments behind the modern barrier reef in central and southern Belize.« less

Perlinhibin, a Cysteine-, Histidine-, and Arginine-Rich Miniprotein from Abalone (Haliotis laevigata) Nacre, Inhibits In Vitro Calcium Carbonate Crystallization

PubMed Central

Mann, Karlheinz; Siedler, Frank; Treccani, Laura; Heinemann, Fabian; Fritz, Monika

2007-01-01

We have isolated a 4.785 Da protein from the nacreous layer of the sea snail Haliotis laevigata (greenlip abalone) shell after demineralization with acetic acid. The sequence of 41 amino acids was determined by Edman degradation supported by mass spectrometry. The most abundant amino acids were cysteine (19.5%), histidine (17%), and arginine (14.6%). The positively charged amino acids were almost counterbalanced by negatively charged ones resulting in a calculated isoelectric point of 7.86. Atomic-force microscopy studies of the interaction of the protein with calcite surfaces in supersaturated calcium carbonate solution or calcium chloride solution showed that the protein bound specifically to calcite steps, inhibiting further crystal growth at these sites in carbonate solution and preventing crystal dissolution when carbonate was substituted with chloride. Therefore this protein was named perlinhibin. X-ray diffraction investigation of the crystal after atomic-force microscopy growth experiments showed that the formation of aragonite was induced on the calcite substrate around holes caused by perlinhibin crystal-growth inhibition. The strong interaction of the protein with calcium carbonate was also shown by vapor diffusion crystallization. In the presence of the protein, the crystal surfaces were covered with holes due to protein binding and local inhibition of crystal growth. In addition to perlinhibin, we isolated and sequenced a perlinhibin-related protein, indicating that perlinhibin may be a member of a family of closely related proteins. PMID:17496038

The effect of a new formaldehyde-free binder on the dissolution rate of glass wool fibre in physiological saline solution.

PubMed

Potter, Russell M; Olang, Nassreen

2013-04-12

The in-vitro dissolution rate of fibres is a good predictor of the in-vivo behavior and potential health effects of inhaled fibres. This study examines the effect of a new formaldehyde-free carbohydrate-polycarboxylic acid binder on the in-vitro dissolution rate of biosoluble glass fibres. Dissolution rate measurements in pH 7.4 physiological saline solution show that the presence of the binder on wool insulation glass fibres has no effect on their dissolution. There is no measurable difference between the dissolution rates of continuous draw fibres before and after binder was applied by dipping. Nor is there a measurable difference between the dissolution rates of a production glass wool sample with binder and that same sample after removal of the binder by low-temperature ashing. Morphological examination shows that swelling of the binder in the solution is at least partially responsible for the development of open channels around the glass-binder interface early in the dissolution. These channels allow fluid to reach the entire glass surface under the binder coating. There is no evidence of any delay in the dissolution rate as a result of the binder coating.

The effect of a new formaldehyde-free binder on the dissolution rate of glass wool fibre in physiological saline solution

PubMed Central

2013-01-01

The in-vitro dissolution rate of fibres is a good predictor of the in-vivo behavior and potential health effects of inhaled fibres. This study examines the effect of a new formaldehyde-free carbohydrate-polycarboxylic acid binder on the in-vitro dissolution rate of biosoluble glass fibres. Dissolution rate measurements in pH 7.4 physiological saline solution show that the presence of the binder on wool insulation glass fibres has no effect on their dissolution. There is no measurable difference between the dissolution rates of continuous draw fibres before and after binder was applied by dipping. Nor is there a measurable difference between the dissolution rates of a production glass wool sample with binder and that same sample after removal of the binder by low-temperature ashing. Morphological examination shows that swelling of the binder in the solution is at least partially responsible for the development of open channels around the glass-binder interface early in the dissolution. These channels allow fluid to reach the entire glass surface under the binder coating. There is no evidence of any delay in the dissolution rate as a result of the binder coating. PMID:23587247

CO2 outburst events in relation to seismicity: Constraints from microscale geochronology, geochemistry of late Quaternary vein carbonates, SW Turkey

NASA Astrophysics Data System (ADS)

Ünal-İmer, Ezgi; Uysal, I. Tonguç; Zhao, Jian-Xin; Işık, Veysel; Shulmeister, James; İmer, Ali; Feng, Yue-Xing

2016-08-01

Vein and breccia carbonates precipitated in a highly fractured/faulted carbonate bedrock in SW Turkey were investigated through high-resolution U-series geochronology, microstructural and geochemical studies including C-O-Sr isotope and rare-earth element and yttrium (REY) analyses. Petrographical observations and geochronological data are interpreted as evidence that the calcite veins formed through a crack-seal mechanism, mostly accompanied/initiated by intensive hydraulic fracturing of the host limestone in response to high-pressure fluids, which is manifested by multi-stage breccia deposits. Microscale U-series dates (272.6-20.5 kyr) and geochemical compositions of the vein/breccia samples provide information on the timing and mechanism of the vein formation and identify the source of CO2-bearing fluids responsible for the carbonate precipitation. δ18OVPDB and δ13CVPDB values of the calcite veins range between -5.9 and -1.7‰, and -10.6 and -4.6‰, respectively. The isotopic compositions of the veins show highly fluctuating values as calcite grew successively perpendicular to vein walls, which, in combination with microstructural and geochronological constraints, are interpreted to reflect episodic CO2 degassing events associated with seismic and aseismic deformation. Oxygen and Sr isotope compositions (δ18OVPDB: -5.9 to -1.7‰; 87Sr/86Sr: 0.7082 to 0.7085) together with REY concentrations indicate deep infiltration of meteoric waters with various degrees of interactions mostly with the host limestone and siliciclastic parts of the basement rocks. Oxygen and carbon isotope compositions suggest CO2 degassing through intensive limestone dissolution. While majority of the veins display similar Post-Archaean Australian Shale (PAAS)-normalised REY variations, some of the veins show positive EuPAAS anomalies, which could be indicative of contributions from a deeply derived, heated, and reduced fluid component, giving rise to multiple fluid sources for the calcite veins. Vein calcite formed in fault-induced fractures offers insights into structural features, genetic characterisation of the parental fluids, and late Quaternary degassing of subsurface CO2 accumulations.

Micro- and Nanostructures of SAFOD Core Samples - First Results

NASA Astrophysics Data System (ADS)

Janssen, C.; Wirth, R.; Rybacki, E.; Naumann, R.; Kemnitz, H.; Wenk, H.; Dresen, G. H.

2009-12-01

Microstructures and chemical composition of ultra-cataclastic rocks from the San Andreas Fault drill hole (SAFOD) were examined using TEM, SEM and XRD analyses. The ultra-cataclasites are mainly composed of quartz, clay minerals (illite/smectite, chlorite), feldspar (plagioclase) and calcite with grain sizes between 200 nm and 500 μm. In particular we found: (1) amorphous materials, identified by transmission electron microscopy. Chemical analyses suggest that all amorphous material was formed by comminution (crush-origin) of fragments rather than by melting (melt-origin) and that the observed amorphous phases may act as hydrodynamic lubricating layers that reduce friction in the San Andreas Fault. (2) Pressure solution seams and localized precipitation of hydrous mixed-layered clay minerals suggest intensive dissolution-precipitation processes. These may lead to a thin film covering slip surfaces. (3) Authigenic clay minerals forming a flocculated fabric. (4) The fine-grained (< 1μm) gouge matrix contains clasts (feldspar, quartz) and is frequently cut by fault-related veins. The veins are filled with calcite or quartz. Observed micorstructures in the fine-grained matrix suggest comminution and sliding of the nanoscale grains. Open pore spaces up to 2.25 μm3 have been formed during and after deformation within the gouge matrix. These were possibly filled with hydrothermal fluids at elevated pore fluid pressure preventing closure. (5) Detrital quartz and feldspar grains are partly dissolved and replaced by authigenic illite-smectite (I-S) mixed-layer clay minerals. TEM imaging of these grains reveal that initial alteration processes started within pores and small fissures of grains. The crystallographic-preferred orientation of illite and I/S grains is rather weak with a maximum m.r.d. (multiples of random orientation) of 2.3. (6) Some older fault-related vein-calcites show evidence for intense intracrystalline plasticity (deformation twins and dislocation creep). Dislocation densities in calcite grains indicate a local maximum stress of about 40 MPa. The younger fault-related vein-calcite generation with elongated to fibrous habit suggests slow opening by aseismic slip. These crystals are not fractured or twinned (or only less); indicating that healing processes (cementation) outlasted deformation.

Magnesite Step Growth Rates as a Function of the Aqueous Magnesium:Carbonate Ratio

DOE PAGES

Bracco, Jacquelyn N.; Stack, Andrew G.; Higgins, Steven R.

2014-10-01

Step velocities of monolayer-height steps on the (101 ⁻4) magnesite surface have been measured as functions of the aqueous magnesium-to-carbonate ratio and saturation index (SI) using a hydrothermal atomic force microscope (HAFM). At SI ≤ 1.9 and 80-90 °C, step velocities were found to be invariant with changes in the magnesium-to-carbonate ratio, an observation in contrast with standard models for growth and dissolution of ionically-bonded, multi-component crystals. However, at high saturation indices (SI = 2.15), step velocities displayed a ratio dependence, maximized at magnesium-to-carbonate ratios slightly greater than 1:1. Traditional affinity-based models were unable to describe growth rates at themore » higher saturation index. Step velocities also could not be modeled solely through nucleation of kink sites, in contrast to other minerals whose bonding between constituent ions is also dominantly ionic in nature, such as calcite and barite. Instead, they could be described only by a model that incorporates both kink nucleation and propagation. Based on observed step morphological changes at these higher saturation indices, the step velocity maximum at SI = 2.15 is likely due to the rate of attachment to propagating kink sites overcoming the rate of detachment from kink sites as the latter becomes less significant under far from equilibrium conditions.« less

Dissolution of cinnabar (HgS) in the presence of natural organic matter

USGS Publications Warehouse

Waples, J.S.; Nagy, K.L.; Aiken, G.R.; Ryan, J.N.

2005-01-01

Cinnabar (HgS) dissolution rates were measured in the presence of 12 different natural dissolved organic matter (DOM) isolates including humic, fulvic, and hydrophobic acid fractions. Initial dissolution rates varied by 1.3 orders of magnitude, from 2.31 ?? 10-13 to 7.16 ?? 10-12 mol Hg (mg C)-1 m-2 s-1. Rates correlate positively with three DOM characteristics: specific ultraviolet absorbance (R2 = 0.88), aromaticity (R2 = 0.80), and molecular weight (R2 = 0.76). Three experimental observations demonstrate that dissolution was controlled by the interaction of DOM with the cinnabar surface: (1) linear rates of Hg release with time, (2) significantly reduced rates when DOM was physically separated from the surface by dialysis membranes, and (3) rates that approached constant values at a specific ratio of DOM concentration to cinnabar surface area, suggesting a maximum surface coverage by dissolution-reactive DOM. Dissolution rates for the hydrophobic acid fractions correlate negatively with sorbed DOM concentrations, indicating the presence of a DOM component that reduced the surface area of cinnabar that can be dissolved. When two hydrophobic acid isolates that enhanced dissolution to different extents were mixed equally, a 20% reduction in rate occurred compared to the rate with the more dissolution-enhancing isolate alone. Rates in the presence of the more dissolution-enhancing isolate were reduced by as much as 60% when cinnabar was prereacted with the isolate that enhanced dissolution to a lesser extent. The data, taken together, imply that the property of DOM that enhances cinnabar dissolution is distinct from the property that causes it to sorb irreversibly to the cinnabar surface. Copyright ?? 2005 Elsevier Ltd.

Manganese-calcium intermixing facilitates heteroepitaxial growth at the 10 1 ¯ 4 calcite-water interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Man; Riechers, Shawn L.; Ilton, Eugene S.

2017-10-01

In situ atomic force microscopy (AFM) measurements were performed to probe surface precipitates that formed on the (10-14) surface of calcite (CaCO3) single crystals following reaction with Mn2+-bearing aqueous solutions with a range of initial concentrations. Three-dimensional epitaxial islands were observed to precipitate and grow on the surfaces and in situ time-sequenced measurements demonstrated that their growth rates were commensurate with those obtained for epitaxial islands formed on calcite crystals reacted with Cd2+-bearing aqueous solutions of the same range in supersaturation with respect to the pure metal carbonate phase. This finding was unexpected as rhodochrosite (MnCO3) and calcite display amore » 10% lattice mismatch, based on the area of their (10-14) surface unit cells, whereas the lattice mismatch is only 4% for otavite (CdCO3) and calcite. Coatings of varying thicknesses were therefore synthesized by reacting calcite single crystals with calcite-equilibrated aqueous solutions with concentrations of up to 250 µM MnCl2 and analyzed to determine the composition of the surface precipitates. Ex situ X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray reflectivity (XRR), and AFM measurements of the reacted crystals demonstrated the formation of an epitaxial (Mn,Ca)CO3 solid solution with a spatially complex composition atop the calcite surface, whereby the first few nanometers were rich in Ca and the Mn content increased with distance from the original calcite surface, culminating in a topmost region of almost pure MnCO3 for the thickest coatings. These findings explain the measured growth rates (the effective lattice mismatch was much smaller than nominal mismatch) and highlight the strong influence played by the substrate on the composition of surface precipitates in aqueous conditions.« less

Subduction Metamorphism of Ophicarbonates beyond the Stability of Antigorite: insights into Carbonate Dissolution vs. Decarbonation from the Almirez ultramafic massif (S. Spain)

NASA Astrophysics Data System (ADS)

Menzel, Manuel; Garrido, Carlos J.; López Sánchez Vizcaíno, Vicente; Marchesi, Claudio; Hidas, Károly

2017-04-01

Subduction zone processes play a key role in determining the time and length-scales of long-term element cycles like the deep carbon cycle. Recent improvements in thermodynamic modelling of fluid properties at high pressure and new experiments have underlined the importance of carbonate dissolution by subduction fluids from dehydration reactions for the transfer of carbon out of the subducting slab. However, natural case studies are scarce, in particular regarding the impact of fluids generated by serpentinite dehydration, which are considered as a major dissolution agent for carbon due to the high temperature of antigorite breakdown (about 650°C) and the potentially large volumes of hydrated peridotites occurring in the upper part of the subducting oceanic mantle lithosphere. Here we report the occurrence of meta-ophicarbonate lenses within prograde Chl-harzburgites in the Almirez ultramafic massif (Betic Cordillera, S. Spain). The presence of these lenses indicates that carbonate minerals were preserved beyond the stability conditions of antigorite and were not dissolved by deserpentinization fluids. The largest meta-ophicarbonate lens in the Almirez Chl-harzburgites measures 8 x 160 m and is composed of a high-grade assemblage of olivine, Ti-clinohumite, diopside, chlorite, dolomite, calcite and Cr-bearing magnetite with a granofelsic to banded appearance. In this assemblage we identified, for the first time in the Betic Cordillera, aragonite inclusions in olivine and diopside using coupled EBSD and chemical mapping. Calcite-dolomite thermometry and thermodynamic equilibrium modelling constrain the peak metamorphic conditions to 1.7 - 1.9 GPa and 680 °C at very low XCO2. These conditions compare well with P-T-estimates for the surrounding Chl-harzburgites. There is strong evidence that the protolith of the carbonate rocks within Chl-harzburgites was an ophicarbonate zone: bulk rock contents of Ni and Cr are similarly high in the carbonate rocks as in Atg-serpentinites and Chl-harzburgites of the Almirez massif, and their major element compositions plot on the CaCO3-antigorite mixing line. As the meta-ophicarbonates are enclosed within prograde Chl-harzburgites, they have experienced a high fluid flux triggered by the antigorite breakdown in surrounding serpentinites at about 660 °C, with a high potential to dissolve carbonates. However, these carbonate lenses retain high amounts of dolomite and calcite (40 - 45 vol%), and their phase assemblages and stable isotope compositions of carbonate (δ18O = 13-17 ‰ V-SMOW and δ13C = -0.5-1 ‰ V-PDB) do not indicate a major fluid-induced decarbonation. The survival of carbonate may be due to the fact that antigorite dehydration occurred at up to 50 - 70 °C lower temperatures in the presence of CaCO3 than in pure serpentinites. This could lead to the formation of a relatively impermeable shell of carbonate-bearing olivine-diopside fels around the meta-ophicarbonates prior to the main serpentinite dehydration, thus protecting the carbonate-richer assemblages from dissolution. The example of the meta-ophicarbonates at Almirez suggests that this mechanism may lead to recycling of substantial amounts of carbon into the deep mantle via subduction of carbonate-bearing serpentinites. Funding: We acknowledge funding from the People programme (Marie Curie Actions - ITN) of the European Union FP7 under REA Grant Agreement n°608001.

Low temperature dissolution flowsheet for Pu metal

DOE PAGES

Daniel, Jr., William E.; Almond, Philip M.; Rudisill, Tracy S.

2017-06-30

The Savannah River National Laboratory was requested to develop a Pu metal dissolution flowsheet at two reduced temperature ranges for implementation in the Savannah River Site H-Canyon facility. The dissolution and H 2 generation rates during Pu metal dissolution were investigated using a dissolving solution at ambient temperature (20–30°C) and for an intermediate temperature of 50–60°C. The Pu metal dissolution rate measured at 57°C was approximately 20 times slower than at boiling (112–116°C). As a result, the dissolution rate at ambient temperature (24°C) was approximately 80 times slower than the dissolution rate at boiling. Hydrogen concentrations were less than detectablemore » (<0.1 vol%).« less

Physical heterogeneity control on effective mineral dissolution rates

NASA Astrophysics Data System (ADS)

Jung, Heewon; Navarre-Sitchler, Alexis

2018-04-01

Hydrologic heterogeneity may be an important factor contributing to the discrepancy in laboratory and field measured dissolution rates, but the governing factors influencing mineral dissolution rates among various representations of physical heterogeneity remain poorly understood. Here, we present multiple reactive transport simulations of anorthite dissolution in 2D latticed random permeability fields and link the information from local grid scale (1 cm or 4 m) dissolution rates to domain-scale (1m or 400 m) effective dissolution rates measured by the flux-weighted average of an ensemble of flow paths. We compare results of homogeneous models to heterogeneous models with different structure and layered permeability distributions within the model domain. Chemistry is simplified to a single dissolving primary mineral (anorthite) distributed homogeneously throughout the domain and a single secondary mineral (kaolinite) that is allowed to dissolve or precipitate. Results show that increasing size in correlation structure (i.e. long integral scales) and high variance in permeability distribution are two important factors inducing a reduction in effective mineral dissolution rates compared to homogeneous permeability domains. Larger correlation structures produce larger zones of low permeability where diffusion is an important transport mechanism. Due to the increased residence time under slow diffusive transport, the saturation state of a solute with respect to a reacting mineral approaches equilibrium and reduces the reaction rate. High variance in permeability distribution favorably develops large low permeability zones that intensifies the reduction in mixing and effective dissolution rate. However, the degree of reduction in effective dissolution rate observed in 1 m × 1 m domains is too small (<1% reduction from the corresponding homogeneous case) to explain several orders of magnitude reduction observed in many field studies. When multimodality in permeability distribution is approximated by high permeability variance in 400 m × 400 m domains, the reduction in effective dissolution rate increases due to the effect of long diffusion length scales through zones with very slow reaction rates. The observed scale dependence becomes complicated when pH dependent kinetics are compared to the results from pH independent rate constants. In small domains where the entire domain is reactive, faster anorthite dissolution rates and slower kaolinite precipitation rates relative to pH independent rates at far-from-equilibrium conditions reduce the effective dissolution rate by increasing the saturation state. However, in large domains where less- or non-reactive zones develop, higher kaolinite precipitation rates in less reactive zones increase the effective anorthite dissolution rates relative to the rates observed in pH independent cases.

Characterization of elemental release during microbe granite interactions at T = 28 °C

NASA Astrophysics Data System (ADS)

Wu, Lingling; Jacobson, Andrew D.; Hausner, Martina

2008-02-01

This study used batch reactors to characterize the mechanisms and rates of elemental release (Al, Ca, K, Mg, Na, F, Fe, P, Sr, and Si) during interaction of a single bacterial species ( Burkholderia fungorum) with granite at T = 28 °C for 35 days. The objective was to evaluate how actively metabolizing heterotrophic bacteria might influence granite weathering on the continents. We supplied glucose as a C source, either NH 4 or NO 3 as N sources, and either dissolved PO 4 or trace apatite in granite as P sources. Cell growth occurred under all experimental conditions. However, solution pH decreased from ˜7 to 4 in NH 4-bearing reactors, whereas pH remained near-neutral in NO 3-bearing reactors. Measurements of dissolved CO 2 and gluconate together with mass-balances for cell growth suggest that pH lowering in NH 4-bearing reactors resulted from gluconic acid release and H + extrusion during NH 4 uptake. In NO 3-bearing reactors, B. fungormum likely produced gluconic acid and consumed H + simultaneously during NO 3 utilization. Over the entire 35-day period, NH 4-bearing biotic reactors yielded the highest release rates for all elements considered. However, chemical analyses of biomass show that bacteria scavenged Na, P, and Sr during growth. Abiotic control reactors followed different reaction paths and experienced much lower elemental release rates compared to biotic reactors. Because release rates inversely correlate with pH, we conclude that proton-promoted dissolution was the dominant reaction mechanism. Solute speciation modeling indicates that formation of Al-F and Fe-F complexes in biotic reactors may have enhanced mineral solubilities and release rates by lowering Al and Fe activities. Mass-balances further reveal that Ca-bearing trace phases (calcite, fluorite, and fluorapatite) provided most of the dissolved Ca, whereas more abundant phases (plagioclase) contributed negligible amounts. Our findings imply that during the incipient stages of granite weathering, heterotrophic bacteria utilizing glucose and NH 4 only moderately elevate silicate weathering reactions that consume atmospheric CO 2. However, by enhancing the dissolution of non-silicate, Ca-bearing trace minerals, they could contribute to high Ca/Na ratios commonly observed in granitic watersheds.

Do biofilms and clays alter the chemistry and fabric of a hyper-alklaine, saline, non-marine carbonate precipitate?

NASA Astrophysics Data System (ADS)

Rogerson, Michael; Saunders, Paul; Mercedes-Martin, Ramon; Brasier, Alex; Pedley, Martyn

2015-04-01

Non-marine carbonates comprise a hugely diverse family of deposits, which reflect a constellation of forcing factors from local hydraulics to regional climatology. However, the two dominant controls on precipitation are solution chemistry and benthic microbial biogeochemistry. Here, we present a unifying concept for understanding how these controls influence deposit characteristics, and re-emphasise the importance of biofilms. It is generally accepted that biofilms play an important part in the precipitation of authigenic minerals in a wide variety of settings. In carbonate settings, biofilms are recognised to increase the amount of calcite precipitation and alter the geometry and coarse scale petrography of the precipitate. They determine at what water marginal water chemistries calcite starts to precipitate and microbialites give way to chemical limestones. Biofilms also interact with ambient water, controlling chemical accumulation transport. New evidence, drawn from unique experimental approaches, is demonstrating that biofilm influence extends to control of calcite trace element composition, and crystal scale fabric. Under tightly controlled temperature and chemical conditions, fully replicated experiments show that Mg incorporation into tufa carbonate defies the expected thermodynamic control. However, there is a pronounced influence on (Mg/Ca)calcite from precipitation rate, so that rapidly forming precipitates develop with very low magnesium content indicating kinetic control on fractionation. Calcite precipitation rate in these experiments is controlled by biofilm growth rate and reflects kinetic fractionation arises from the electrochemical activity of extracellular organic acids. These effects are therefore likely to occur wherever these molecules occur, including stromatolites, soil and lake carbonates and (via colloidal organic acids) speleothems. The presence of Extracellular polymeric substances (EPS), even without the presence of cells, also alters precipitation style. Spherular and shrubby calcite growths are well known from the geological record, but their environmental significance is not clear. Sterile, microcosm experiments have shown that these forms occur in saline, hyperalkaline settings ' but only in the presence of organic acid molecules in solution. The presence of inorganic materials (hydrated magnesium clays) does not impact on precipitate morphology, and reduces the precipitation rate of calcite.

Mechanism of Urea Crystal Dissolution in Water from Molecular Dynamics Simulation.

PubMed

Anand, Abhinav; Patey, G N

2018-01-25

Molecular dynamics simulations are used to determine the mechanism of urea crystal dissolution in water under sink conditions. Crystals of cubic and tablet shapes are considered, and results are reported for four commonly used water models. The dissolution rates for different water models can differ considerably, but the overall dissolution mechanism remains the same. Urea dissolution occurs in three stages: a relatively fast initial stage, a slower intermediate stage, and a final stage. We show that the long intermediate stage is well described by classical rate laws, which assume that the dissolution rate is proportional to the active surface area. By carrying out simulations at different temperatures, we show that urea dissolution is an activated process, with an activation energy of ∼32 kJ mol -1 . Our simulations give no indication of a significant diffusion layer, and we conclude that the detachment of molecules from the crystal is the rate-determining step for dissolution. The results we report for urea are consistent with earlier observations for the dissolution of NaCl crystals. This suggests that the three-stage mechanism and classical rate laws might apply to the dissolution of other ionic and molecular crystals.

Diagenesis of Upper Carboniferous rocks in the Ouachita foreland shelf in mid-continent USA: an overview of widespread effects of a Variscan-equivalent orogeny

USGS Publications Warehouse

Walton, A.W.; Wojcik, K.M.; Goldstein, R.H.; Barker, C.E.

1995-01-01

Diagenesis of Upper Carboniferous foreland shelf rocks in southeastern Kansas took place at temperatures as high as 100-150?? C at a depth of less than 2 km. High temperatures are the result of the long distance (hundreds of kilometers) advection of groundwater related to collisional orogeny in the Ouachita tectonic belt to the south. Orogenic activity in the Ouachita area was broadly Late Carboniferous, equivalent to the Variscan activity of Europe. Mississippi Valley-type Pb-Zn deposits and oil and gas fields in the US midcontinent and elsewhere are commonly attributed to regional groundwater flow resulting from such collisional events. This paper describes the diagenesis and thermal effects in sandstone and limestone of Upper Carboniferous siliciclastic and limestone-shale cyclothems, the purported confining layer of a supposed regional aquifer. Diagenesis took place in early, intermediate, and late stages. Many intermediate and late stage events in the sandstones have equivalents in the limestones, suggesting that the causes were regional. The sandstone paragenesis includes siderite cement (early stage), quartz overgrowths (intermediate stage), dissolution of feldspar and carbonates, followed by minor Fe calcite, pore-filling kaolinite and sub-poikilotopic Ca ankerite (late stage). The limestone paragenesis includes calcite cement (early stage); megaquartz, chalcedony, and Fe calcite spar (intermediate stage); and dissolution, Ca-Fe dolomite and kaolinite (late stage). The Rm value of vitrinite shows a regional average of 0.6-0.7%; Rock-Eval TmaX suggests a comparable degree of organic maturity. The Th of aqueous fluid inclusions in late stage Ca-Fe-Mg carbonates ranges from 90 to 160?? and Tmice indicates very saline water (>200000 ppm NaCl equivalent); ??18O suggests that the water is of basinal origin. Local warm spots have higher Rm, Tmax, and Th. The results constrain numerical models of regional fluid migration, which is widely viewed as an artesian flow from recharge areas in the Ouachita belt across the foreland basin onto the foreland shelf area. Such models must account for heating effects that extend at least 500 km from the orogenic front and affect both supposed aquifer beds and the overlying supposed confining layer. Warm spots indicate either more rapid or more prolonged flow locally. Th and Tmice data show the highest temperatures coincided with high salinity fluids. ?? 1995 Springer-Verlag.

Experimental investigation of the Heletz shale caprocks sealing capacity: implication for CO2 geological storage integrity

NASA Astrophysics Data System (ADS)

Abdoulghafour, Halidi; Gouze, Philippe; Luquot, Linda; Arif, Mohamed; Iglauer, Stefan

2017-04-01

Using a combination of core flooding experiments and wettability measurements, we evaluate the sealing efficiency of Heletz caprock under CO2 sequestration conditions. The flow through experiments consisted of flowing CO2 enriched fluid into two micro-fractured cylindrical cores (15 mm length - 9 mm diameter, with hydraulic aperture: 2.7 µm for the sample named H18A and 13 µm for sample named H18B) and monitoring the permeability changes, the evolution of the chemistry from the inlet and outlet fluid. The changes in microstructures and mineralogy were also studied using an environmental scanning electrons microscope (ESEM) and X-ray micro-tomography (XRMT) images. The fracture permeability was found to decrease significantly in the two experiments from 14.1×10-12 m2 to 5.0×10-12 m2 for experiment H18B and from 6.5×10-13 m2 to 2.8×10-13 m2 for experiment H18A. Calcite dissolution and reconversion of k-feldspar to illite and kaolinite were the main reaction on sample H18B while "calcite precipitation" in batch condition was the dominant reaction on sample H18A. Accordingly, the decrease in permeability was induced by the dispersion of dissolution products and the re-organization of clay particles within the fracture for sample H18B as shown by micro-tomography and ESEM images. The fracture healing due to the calcite and clay mineral precipitation along the fracture was attested by ESEM image for sample H18A. The results of capillary pressure breakthrough calculated by applying the Washburn equation and the reservoir scaling method from intrusion of mercury are approximately 380 kPa and 310 kPa for H18B and H18A respectively. Although, these values are sensibly different but close to each other and in good agreement to indicate the weak storage capacity of the heletz caprock. Subsequently less than 90 m of CO2 column height can be efficiently stored in the Heletz reservoir. Thus the self-mitigation of the CO2 leakage is expected only when few quantity of CO2 will be injected.

Effect of oxalate on the dissolution rates of oligoclase and tremolite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mast, M.A.; Drever, J.I.

1987-09-01

The effect of oxalate, a strong chelator for Al and other cations, on the dissolution rates of oligoclase feldspar and tremolite amphibole was investigated in a flow-through reactor at 22/sup 0/C. Oxalate at concentrations of 0.5 and 1 mM has essentially no effect on the dissolution rate of tremolite, nor on the steady-state rate of release of Si from oligoclase. The fact that oxalate has no effect on dissolution rate suggests that detachment of Si rather than Al or Mg is the rate-limiting step. At pH 4 and 9, oxalate has no effect on the steady-state rate of release ofmore » Al, and dissolution is congruent. At pH 5 and 7, oligoclase dissolution is congruent in the presence of oxalate, but in the absence of oxalate Al is preferentially retained in the solid relative to Si. Large transient spikes of Al or Si are observed when oxalate is added to or removed from the system. The cause of the spikes is unknown; the authors suggest adsorption feldspar surfaces away from sites of active dissolution as a possibility. The rate of dissolution of tremolite is independent of pH over the pH range 2-5, and decreases at higher pH. The rate of dissolution of oligoclase in these experiments was independent of pH over the pH range 4-9. Since the dissolution rate of these minerals is independent of pH and organic ligand concentration, the effect of acid deposition from the atmosphere on the rate of supply of cations from weathering of granitic rocks should be minor.« less

Stirring effect on kaolinite dissolution rate

NASA Astrophysics Data System (ADS)

Metz, Volker; Ganor, Jiwchar

2001-10-01

Experiments were carried out measuring kaolinite dissolution rates using stirred and nonstirred flow-through reactors at pHs 2 to 4 and temperatures of 25°C, 50°C, and 70°C. The results show an increase of kaolinite dissolution rate with increasing stirring speed. The stirring effect is reversible, i.e., as the stirring slows down the dissolution rate decreases. The effect of stirring speed on kaolinite dissolution rate is higher at 25°C than at 50°C and 70°C and at pH 4 than at pHs 2 and 3. It is suggested that fine kaolinite particles are formed as a result of stirring-induced spalling or abrasion of kaolinite. These very fine particles have an increased ratio of reactive surface area to specific surface area, which results in enhancement of kaolinite dissolution rate. A balance between production and dissolution of the fine particles explains both the reversibility and the temperature and pH dependence of the stirring effect. Since the stirring effect on kaolinite dissolution rate varies with temperature and pH, measurement of kinetic parameters such as activation energy may be influenced by stirring. Therefore, standard use of nonagitated reaction vessels for kinetic experiments of mineral dissolution and precipitation is recommended, at least for slow reactions that are surface controlled.

Universal Linear Scaling of Permeability and Time for Heterogeneous Fracture Dissolution

NASA Astrophysics Data System (ADS)

Wang, L.; Cardenas, M. B.

2017-12-01

Fractures are dynamically changing over geological time scale due to mechanical deformation and chemical reactions. However, the latter mechanism remains poorly understood with respect to the expanding fracture, which leads to a positively coupled flow and reactive transport processes, i.e., as a fracture expands, so does its permeability (k) and thus flow and reactive transport processes. To unravel this coupling, we consider a self-enhancing process that leads to fracture expansion caused by acidic fluid, i.e., CO2-saturated brine dissolving calcite fracture. We rigorously derive a theory, for the first time, showing that fracture permeability increases linearly with time [Wang and Cardenas, 2017]. To validate this theory, we resort to the direct simulation that solves the Navier-Stokes and Advection-Diffusion equations with a moving mesh according to the dynamic dissolution process in two-dimensional (2D) fractures. We find that k slowly increases first until the dissolution front breakthrough the outbound when we observe a rapid k increase, i.e., the linear time-dependence of k occurs. The theory agrees well with numerical observations across a broad range of Peclet and Damkohler numbers through homogeneous and heterogeneous 2D fractures. Moreover, the theory of linear scaling relationship between k and time matches well with experimental observations of three-dimensional (3D) fractures' dissolution. To further attest to our theory's universality for 3D heterogeneous fractures across a broad range of roughness and correlation length of aperture field, we develop a depth-averaged model that simulates the process-based reactive transport. The simulation results show that, regardless of a wide variety of dissolution patterns such as the presence of dissolution fingers and preferential dissolution paths, the linear scaling relationship between k and time holds. Our theory sheds light on predicting permeability evolution in many geological settings when the self-enhancing process is relevant. References: Wang, L., and M. B. Cardenas (2017), Linear permeability evolution of expanding conduits due to feedback between flow and fast phase change, Geophys. Res. Lett., 44(9), 4116-4123, doi: 10.1002/2017gl073161.

Warm Tropical Sea Surface Temperatures During the Pliocene: a New Record from Mg/Ca and δ18O In Situ Techniques

NASA Astrophysics Data System (ADS)

Wycech, J.; Kelly, D.; Kozdon, R.; Fournelle, J.; Valley, J. W.

2013-12-01

The Pliocene Warm Period (PWP) was a global warming event that punctuated Earth's climate history ~3 Ma, and study of its geologic record is providing important constraints for models predicting future climate change. Many sea surface temperature (SST) reconstructions for the PWP indicate amplified polar warmth with minimal or absent warming in the tropics - a phenomenon termed the cool tropics paradox. Key pieces of evidence for the lack of tropical warmth are oxygen isotope (δ18O) and Mg/Ca ratios in planktic foraminiferal shells. However, the δ18O data used to reconstruct surface-ocean conditions are derived from whole foraminiferal shells with the assumption that their geochemical compositions are well preserved and homogeneous. To the contrary, most planktic foraminiferal shells found in deep-sea sediments are an aggregate mixture of three carbonate phases (18O-depleted pre-gametogenic calcite, 18O-rich gametogenic calcite added during reproduction, and very 18O-rich diagenetic calcite) that formed under different physiological and/or environmental conditions. Here we report preliminary results of an ongoing study that uses secondary ion mass spectrometry (SIMS) and electron probe microanalysis (EPMA) to acquire in situ δ18O and Mg/Ca data, respectively, from 3-10 μm domains within individual planktic foraminiferal shells (Globigerinoides sacculifer) preserved in a PWP record recovered at ODP Site 806 in the West Pacific Warm Pool. SIMS analyses show that the δ18O of gametogenic calcite is 1-2‰ higher than in the pre-gametogenic calcite of Gs. sacculifer. Mass-balance calculations using the mean δ18O of gametogenic and pre-gametogenic calcites predict a whole-shell δ18O that is ~1.9‰ lower than the published whole-shell δ18O for Gs. sacculifer in this same deep-sea section. Removal of 18O-depleted, pre-gametogenic calcite via dissolution cannot fully account for this isotopic offset since the mean δ18O of whole shells (-1.3‰) is higher than that of gametogenic calcite (-2.1‰); hence, we attribute the elevated whole-shell values to the addition of 18O-rich carbonate by post-depositional diagenesis. By contrast, in situ measurements indicate that the Mg/Ca ratios in the pre-gametogenic and gametogenic calcites are indistinguishable, and in situ Mg/Ca ratios are comparable to those of whole shells. Use of Mg/Ca calculated SSTs (~30°C) and published whole-shell δ18O to determine the δ18O of seawater (δ18Osw) yields unrealistically high values (2.1‰), while a similar computation using pre-gametogenic δ18O yields a more acceptable δ18Osw (-0.2‰) for this region during the PWP. This latter finding corroborates the view that the published whole-shell δ18O record has been compromised by diagenesis and demonstrates the potential of SIMS δ18O analysis to enhance our ability to reconstruct hydrographic conditions under differing climatic regimes.

A simple reactive-transport model of calcite precipitation in soils and other porous media

NASA Astrophysics Data System (ADS)

Kirk, G. J. D.; Versteegen, A.; Ritz, K.; Milodowski, A. E.

2015-09-01

Calcite formation in soils and other porous media generally occurs around a localised source of reactants, such as a plant root or soil macro-pore, and the rate depends on the transport of reactants to and from the precipitation zone as well as the kinetics of the precipitation reaction itself. However most studies are made in well mixed systems, in which such transport limitations are largely removed. We developed a mathematical model of calcite precipitation near a source of base in soil, allowing for transport limitations and precipitation kinetics. We tested the model against experimentally-determined rates of calcite precipitation and reactant concentration-distance profiles in columns of soil in contact with a layer of HCO3--saturated exchange resin. The model parameter values were determined independently. The agreement between observed and predicted results was satisfactory given experimental limitations, indicating that the model correctly describes the important processes. A sensitivity analysis showed that all model parameters are important, indicating a simpler treatment would be inadequate. The sensitivity analysis showed that the amount of calcite precipitated and the spread of the precipitation zone were sensitive to parameters controlling rates of reactant transport (soil moisture content, salt content, pH, pH buffer power and CO2 pressure), as well as to the precipitation rate constant. We illustrate practical applications of the model with two examples: pH changes and CaCO3 precipitation in the soil around a plant root, and around a soil macro-pore containing a source of base such as urea.

Reactive transport modelling to infer changes in soil hydraulic properties induced by non-conventional water irrigation

NASA Astrophysics Data System (ADS)

Valdes-Abellan, Javier; Jiménez-Martínez, Joaquín; Candela, Lucila; Jacques, Diederik; Kohfahl, Claus; Tamoh, Karim

2017-06-01

The use of non-conventional water (e.g., treated wastewater, desalinated water) for different purposes is increasing in many water scarce regions of the world. Its use for irrigation may have potential drawbacks, because of mineral dissolution/precipitation processes, such as changes in soil physical and hydraulic properties (e.g., porosity, permeability), modifying infiltration and aquifer recharge processes or blocking root growth. Prediction of soil and groundwater impacts is essential for achieving sustainable agricultural practices. A numerical model to solve unsaturated water flow and non-isothermal multicomponent reactive transport has been modified implementing the spatio-temporal evolution of soil physical and hydraulic properties. A long-term process simulation (30 years) of agricultural irrigation with desalinated water, based on a calibrated/validated 1D numerical model in a semi-arid region, is presented. Different scenarios conditioning reactive transport (i.e., rainwater irrigation, lack of gypsum in the soil profile, and lower partial pressure of CO2 (pCO2)) have also been considered. Results show that although boundary conditions and mineral soil composition highly influence the reactive processes, dissolution/precipitation of carbonate species is triggered mainly by pCO2, closely related to plant roots. Calcite dissolution occurs in the root zone, precipitation takes place under it and at the soil surface, which will lead a root growth blockage and a direct soil evaporation decrease, respectively. For the studied soil, a gypsum dissolution up to 40 cm depth is expected at long-term, with a general increase of porosity and hydraulic conductivity.

Aragonite→calcite transformation studied by EPR of Mn 2+ ions

NASA Astrophysics Data System (ADS)

Lech, J.; Śl|zak, A.

1989-05-01

The irreversible transformation aragonite→calcite has been studied both at different fixed heating rates (5, 10, 15 and 20 K/min) and at different fixed temperatures. Apparent progression rates of the transformation were observed above 685 K. At 730 K the transformation became sudden and violent. Time developments of the transformation at fixed temperatures have been discussed in terms of Avrami-Lichti's approach to transitions involving nucleation processes.

Responses of the tropical gorgonian coral Eunicea fusca to ocean acidification conditions

NASA Astrophysics Data System (ADS)

Gómez, C. E.; Paul, V. J.; Ritson-Williams, R.; Muehllehner, N.; Langdon, C.; Sánchez, J. A.

2015-06-01

Ocean acidification can have negative repercussions from the organism to ecosystem levels. Octocorals deposit high-magnesium calcite in their skeletons, and according to different models, they could be more susceptible to the depletion of carbonate ions than either calcite or aragonite-depositing organisms. This study investigated the response of the gorgonian coral Eunicea fusca to a range of CO2 concentrations from 285 to 4,568 ppm (pH range 8.1-7.1) over a 4-week period. Gorgonian growth and calcification were measured at each level of CO2 as linear extension rate and percent change in buoyant weight and calcein incorporation in individual sclerites, respectively. There was a significant negative relationship for calcification and CO2 concentration that was well explained by a linear model regression analysis for both buoyant weight and calcein staining. In general, growth and calcification did not stop in any of the concentrations of pCO2; however, some of the octocoral fragments experienced negative calcification at undersaturated levels of calcium carbonate (>4,500 ppm) suggesting possible dissolution effects. These results highlight the susceptibility of the gorgonian coral E. fusca to elevated levels of carbon dioxide but suggest that E. fusca could still survive well in mid-term ocean acidification conditions expected by the end of this century, which provides important information on the effects of ocean acidification on the dynamics of coral reef communities. Gorgonian corals can be expected to diversify and thrive in the Atlantic-Eastern Pacific; as scleractinian corals decline, it is likely to expect a shift in these reef communities from scleractinian coral dominated to octocoral/soft coral dominated under a "business as usual" scenario of CO2 emissions.

Carbonate chemistry of surface waters in a temperate karst region: the southern Yorkshire Dales, UK

NASA Astrophysics Data System (ADS)

Pentecost, Allan

1992-11-01

A detailed study of surface water chemistry is described from an important limestone region in northern England. Major ions and pH were determined for 485 sites (springs, seeps, streams, rivers and lakes) during summertime. The saturation state of the waters with respect to calcite was determined as the calcite saturation ratio (Ω). An unexpectedly large number of samples were found to be supersaturated (65.5% of the 268 km of watercourses surveyed). As a consequence, several streams entering major cave systems were incapable of further limestone solution, at least during periods of low flow. Many waters were supersaturated from their source and some deposited travertine. A significant negative correlation was found between spring discharge and both (Ω) and pH. Supersaturation was caused primarily by atmospheric degassing, with some contribution from aquatic plant photosynthesis. The median total dissolved inorganic carbon and Ca concentrations were 2.49 and 1.35 millimoles 1 -1 respectively. Calcium originated exclusively from limestone, and carbon dioxide mainly from the soil and dissolved limestone. South facing catchments provided springwaters with significantly higher levels of TDIC and Ca when compared with north facing catchments. The study suggests that acid rain made a measurable contribution to limestone dissolution. Carboniferous limestone denudation rates were estimated as 54 to 63 m 3 km -2 a -1 (54 to 63 mm 1000 years -1). About 50% of the Mg came from limestone and the remainder, together with most K, Na, SO 4 and Cl from precipitation. Concentrations of dissolved nutrients were low, medians for NO 3, NH 4, total PO 4 and SiO 3 were 24 μmol, 1.4 μmol, 0.64 μmol and 15.5 μmol 1 -1 respectively. The concentration of a further 23 trace elements was determined.

Interannual sedimentary effluxes of alkalinity in the southern North Sea: model results compared with summer observations

NASA Astrophysics Data System (ADS)

Pätsch, Johannes; Kühn, Wilfried; Dorothea Six, Katharina

2018-06-01

For the sediments of the central and southern North Sea different sources of alkalinity generation are quantified by a regional modelling system for the period 2000-2014. For this purpose a formerly global ocean sediment model coupled with a pelagic ecosystem model is adapted to shelf sea dynamics, where much larger turnover rates than in the open and deep ocean occur. To track alkalinity changes due to different nitrogen-related processes, the open ocean sediment model was extended by the state variables particulate organic nitrogen (PON) and ammonium. Directly measured alkalinity fluxes and those derived from Ra isotope flux observation from the sediment into the pelagic are reproduced by the model system, but calcite building and calcite dissolution are underestimated. Both fluxes cancel out in terms of alkalinity generation and consumption. Other simulated processes altering alkalinity in the sediment, like net sulfate reduction, denitrification, nitrification, and aerobic degradation, are quantified and compare well with corresponding fluxes derived from observations. Most of these fluxes exhibit a strong positive gradient from the open North Sea to the coast, where large rivers drain nutrients and organic matter. Atmospheric nitrogen deposition also shows a positive gradient from the open sea towards land and supports alkalinity generation in the sediments. An additional source of spatial variability is introduced by the use of a 3-D heterogenous porosity field. Due to realistic porosity variations (0.3-0.5) the alkalinity fluxes vary by about 4 %. The strongest impact on interannual variations of alkalinity fluxes is exhibited by the temporal varying nitrogen inputs from large rivers directly governing the nitrate concentrations in the coastal bottom water, thus providing nitrate necessary for benthic denitrification. Over the time investigated the alkalinity effluxes decrease due to the decrease in the nitrogen supply by the rivers.

Comparison of the diagenetic and reservoir quality evolution between the anticline crest and flank of an Upper Jurassic carbonate gas reservoir, Abu Dhabi, United Arab Emirates

NASA Astrophysics Data System (ADS)

Morad, Daniel; Nader, Fadi H.; Gasparrini, Marta; Morad, Sadoon; Rossi, Carlos; Marchionda, Elisabetta; Al Darmaki, Fatima; Martines, Marco; Hellevang, Helge

2018-05-01

This petrographic, stable isotopic and fluid inclusion microthermometric study of the Upper Jurassic limestones of an onshore field, Abu Dhabi, United Arab Emirates (UAE) compares diagenesis in flanks and crest of the anticline. The results revealed that the diagenetic and related reservoir quality evolution occurred during three phases, including: (i) eogenesis to mesogenesis 1, during which reservoir quality across the field was either deteriorated or preserved by calcite cementation presumably derived from marine or evolved marine pore waters. Improvement of reservoir quality was due to the formation of micropores by micritization of allochems and creation of moldic/intragranular pores by dissolution of peloids and skeletal fragments. (ii) Obduction of Oman ophiolites and formation of the anticline of the studied field was accompanied by cementation by saddle dolomite and blocky calcite. High homogenization temperatures (125-175 °C) and high salinity (19-26 wt% NaCl eq) of the fluid inclusions, negative δ18OVPDB values (-7.7 to -2.9‰), saddle shape of dolomite, and the presence of exotic cements (i.e. fluorite and sphalerite) suggest that these carbonates were formed by flux of hot basinal brines, probably related to this tectonic compression event. (iii) Mesogenesis 2 during subsidence subsequent to the obduction event, which resulted in extensive stylolitization and cementation by calcite. This calcite cement occluded most of the remaining moldic and inter-/intragranular pores of the flank limestones (water zone) whereas porosity was preserved in the crest. This study contributes to: (1) our understanding of differences in the impact of diagenesis on reservoir quality evolution in flanks and crests of anticlines, i.e. impact of hydrocarbon emplacement on diagenesis, and (2) relating various diagenetic processes to burial history and tectonic events of foreland basins in the Arabian Gulf area and elsewhere.

Strain rate dependent calcite microfabric evolution at natural conditions

NASA Astrophysics Data System (ADS)

Rogowitz, Anna; Grasemann, Bernhard; Huet, Benjamin; Habler, Gerlinde

2014-05-01

Crystal plastic deformational behaviour of calcite has been the focus of many experimental studies. Different strain rates, pressure and temperature conditions have been addressed to investigate a wide range of deformation regimes. However, a direct comparison with natural fault rocks remains difficult because of extreme differences between experimental and natural strain rates. A flanking structure developed in almost pure calcite marble on Syros (Cyclades, Greece). Due to rotation of a planar feature (crack) a heterogeneous strain field in the surrounding area occurred resulting in different strain domains and the formation of the flanking structure. Assuming that deformation was active continuously during the development of the flanking structure, the different strain domains correspond to different strain-rate domains. The outcrop thus represents the final state of a natural experiment and gives us a great opportunity to get natural constraints on strain rate dependent deformation behaviour of calcite. Comparing the microfabrics in the 1 to 2.5 cm thick shear zone and the surrounding host rocks, which formed under the same metamorphic conditions but with different strain rates, is the central focus of this study. Due to the extreme variation in strain and strain rate, different microstructures and textures can be observed corresponding to different deformation mechanisms. With increasing strain rate we observe a change in dominant deformation mechanism from dislocation glide to dislocation creep and finally diffusion creep. Additionally, a change from subgrain rotation to bulging recrystallization can be observed in the dislocation creep regime. Crystallographic preferred orientations (CPO) and the grade of intracrystalline deformation were measured on a FEI Quanta 3D FEG instrument equipped with an EDAX Digiview IV EBSD camera. At all strain rates clear CPOs developed leading to the assumption that calcite preferentially deforms within the dislocation creep field. However, we can also find clear evidence for grain size sensitive deformation mechanisms at smaller grain sizes (3.6 μm) consistent with experimental observations and determined flaw laws. The results of this study are compared with experimental data, closing the gap between experimental and natural geological strain rates.

Acoustic activation of water-in-oil microemulsions for controlled salt dissolution.

PubMed

Baxamusa, Salmaan; Ehrmann, Paul; Ong, Jemi

2018-06-18

The dynamic nature of the oil-water interface allows for sequestration of material within the dispersed domains of a microemulsion. Microstructural changes should therefore change the dissolution rate of a solid surface in a microemulsion. We hypothesize that microstructural changes due to formulation and cavitation in an acoustic field will enable control over solid dissolution rates. Water-in-oil microemulsions were formulated using cyclohexane, water, Triton X-100, and hexanol. The microstructure and solvation properties of Winsor Type IV formulations were characterized. Dissolution rates of KH 2 PO 4 (KDP), were measured. A kinetic analysis isolated the effect of the microstructure, and rate enhancements due to cavitation effects on the microstructure were characterized by measuring dissolution rates in an ultrasonic field. Dispersed aqueous domains of 2-6 nm radius dissolve a solid block of KDP at 0-10 nm/min. Dissolution rate is governed not by the domain-surface collision frequency but rather by a dissolution probability per domain-surface encounter. Higher probabilities are correlated with larger domains. Rapid and reversible dissolution rate increases of up to 270× were observed under ultrasonic conditions, with <20% of the increase due to bulk heating effects. The rest is attributed to cavitation-induced changes to the domain microstructure, providing a simple method for remotely activating and de-activating dissolution. Copyright © 2018 Elsevier Inc. All rights reserved.

Nanosizing of drugs: Effect on dissolution rate

PubMed Central

Dizaj, S. Maleki; Vazifehasl, Zh.; Salatin, S.; Adibkia, Kh.; Javadzadeh, Y.

2015-01-01

The solubility, bioavailability and dissolution rate of drugs are important parameters for achieving in vivo efficiency. The bioavailability of orally administered drugs depends on their ability to be absorbed via gastrointestinal tract. For drugs belonging to Class II of pharmaceutical classification, the absorption process is limited by drug dissolution rate in gastrointestinal media. Therefore, enhancement of the dissolution rate of these drugs will present improved bioavailability. So far several techniques such as physical and chemical modifications, changing in crystal habits, solid dispersion, complexation, solubilization and liquisolid method have been used to enhance the dissolution rate of poorly water soluble drugs. It seems that improvement of the solubility properties ofpoorly water soluble drugscan translate to an increase in their bioavailability. Nowadays nanotechnology offers various approaches in the area of dissolution enhancement of low aqueous soluble drugs. Nanosizing of drugs in the form of nanoparticles, nanocrystals or nanosuspensions not requiring expensive facilities and equipment or complicated processes may be applied as simple methods to increase the dissolution rate of poorly water soluble drugs. In this article, we attempted to review the effects of nanosizing on improving the dissolution rate of poorly aqueous soluble drugs. According to the reviewed literature, by reduction of drug particle size into nanometer size the total effective surface area is increased and thereby dissolution rate would be enhanced. Additionally, reduction of particle size leads to reduction of the diffusion layer thickness surrounding the drug particles resulting in the increment of the concentration gradient. Each of these process leads to improved bioavailability. PMID:26487886

Simultaneous in vitro and in vivo evaluation of both trimethoprim and sulfamethoxazole from certain dosage forms.

PubMed

Meshali, M; El-Sabbagh, H; Ghanem, A; Foda, A

1983-06-01

The dissolution rates of trimethoprim (T), and sulphamethoxazole (S), from different brands of tablets and suspensions were studied at pH = 1.1 and 7.2. The bioavailabilities of both drugs in humans were studied by the urine excretion method. The dissolution rates were dependent on the pH of the dissolution medium, the solubilities of the drugs at the pH involved, the dosage form and the brand studied. While the dissolution rates of T from all brands studied were consistent with their pH-dependent solubility, those of S were not. The dissolution rates of S from suspensions were found to be equal at pH = 7.2, but different at pH = 1.1. A correlation existed between the dissolution rate of T at pH = 1.1 from tablets and the excretion rate in humans. With S, however, no such correlation was observed at either pH.

How does natural groundwater flow affect CO2 dissolution in saline aquifers?

NASA Astrophysics Data System (ADS)

Rosenzweig, R.; Michel-Meyer, I.; Tsinober, A.; Shavit, U.

2017-12-01

The dissolution of supercritical CO2 in aquifer brine is one of the most important trapping mechanisms in CO2 geological storage. Diffusion-limited dissolution is a very slow process. However, since the CO2-rich water is slightly denser than the CO2-free water, when CO2-free water is overlaid by heavier CO2-rich water, convective instability results in fingers of dense CO2-rich water that propagate downwards, causing CO2-unsaturated water to move upwards. This convection process significantly accelerates the dissolution rate of CO2 into the aquifer water.Most previous works have neglected the effect of natural groundwater flow and assumed it has no effect on the dissolution dynamics. However, it was found that in some of the saline aquifers groundwater flow rate, although small, is not zero. In this research, we study the effect of groundwater flow on dissolution by performing laboratory experiments in a bead pack cell using a mixture of methanol and ethylene-glycol as a CO2 analog while varying the water horizontal flow rate. We find that water horizontal flow decreases the number of fingers, their wavelength and their propagation velocity. When testing high water flow rates, no fingers were developed and the dissolution process was entirely diffusive. The effect of water flow on the dissolution rate did not show a clear picture. When increasing the horizontal flow rate the convective dissolution flux slightly decreased and then increased again. It seems that the combination of density-driven flow, water horizontal flow, mechanical dispersion and molecular diffusion affect the dissolution rate in a complex and non-monotonic manner. These intriguing dynamics should be further studied to understand their effect on dissolution trapping.

High temperature dissolution of chromium substituted nickel ferrite in nitrilotriacetic acid medium

NASA Astrophysics Data System (ADS)

Sathyaseelan, V. S.; Chandramohan, P.; Velmurugan, S.

2016-12-01

High temperature (HT) dissolution of chromium substituted nickel ferrite was carried out with relevance to the decontamination of nuclear reactors by way of chemical dissolution of contaminated corrosion product oxides present on stainless steel coolant circuit surfaces. Chromium substituted nickel ferrites of composition, NiFe(2-x)CrxO4 (x ≤ 1), was synthetically prepared and characterized. HT dissolution of these oxides was carried out in nitrilotriacetic acid medium at 160 °C. Dissolution was remarkably increased at 160 °C when compared to at 85 °C in a reducing decontamination formulation. Complete dissolution could be achieved for the oxides with chromium content 0 and 0.2. Increasing the chromium content brought about a marked reduction in the dissolution rate. About 40 fold decrease in rate of dissolution was observed when chromium was increased from 0 to 1. The rate of dissolution was not very significantly reduced in the presence of N2H4. Dissolution of oxide was found to be stoichiometric.

Coccolithophore responses to environmental variability in the South China Sea: species composition and calcite content

NASA Astrophysics Data System (ADS)

Jin, Xiaobo; Liu, Chuanlian; Poulton, Alex J.; Dai, Minhan; Guo, Xianghui

2016-08-01

Coccolithophore contributions to the global marine carbon cycle are regulated by the calcite content of their scales (coccoliths) and the relative cellular levels of photosynthesis and calcification rates. All three of these factors vary between coccolithophore species and with response to the growth environment. Here, water samples were collected in the northern basin of the South China Sea (SCS) during summer 2014 in order to examine how environmental variability influenced species composition and cellular levels of calcite content. Average coccolithophore abundance and their calcite concentration in the water column were 11.82 cells mL-1 and 1508.3 pg C mL-1, respectively, during the cruise. Water samples can be divided into three floral groups according to their distinct coccolithophore communities. The vertical structure of the coccolithophore community in the water column was controlled by the trophic conditions, which were regulated by mesoscale eddies across the SCS basin. The evaluation of coccolithophore-based calcite in the surface ocean also showed that three key species in the SCS (Emiliania huxleyi, Gephyrocapsa oceanica, Florisphaera profunda) and other larger, numerically rare species made almost equal contributions to total coccolith-based calcite in the water column. For Emiliania huxleyi biometry measurements, coccolith size positively correlated with nutrients (nitrate, phosphate), and it is suggested that coccolith length is influenced by light and nutrients through the regulation of growth rates. Larger-sized coccoliths were also linked statistically to low pH and calcite saturation states; however, it is not a simple cause and effect relationship, as carbonate chemistry was strongly co-correlated with the other key environmental factors (nutrients, light).

Feldspar dissolution rates in the Topopah Spring Tuff, Yucca Mountain, Nevada

USGS Publications Warehouse

Bryan, C.R.; Helean, K.B.; Marshall, B.D.; Brady, P.V.

2009-01-01

Two different field-based methods are used here to calculate feldspar dissolution rates in the Topopah Spring Tuff, the host rock for the proposed nuclear waste repository at Yucca Mountain, Nevada. The center of the tuff is a high silica rhyolite, consisting largely of alkali feldspar (???60 wt%) and quartz polymorphs (???35 wt%) that formed by devitrification of rhyolitic glass as the tuff cooled. First, the abundance of secondary aluminosilicates is used to estimate the cumulative amount of feldspar dissolution over the history of the tuff, and an ambient dissolution rate is calculated by using the estimated thermal history. Second, the feldspar dissolution rate is calculated by using measured Sr isotope compositions for the pore water and rock. Pore waters display systematic changes in Sr isotopic composition with depth that are caused by feldspar dissolution. The range in dissolution rates determined from secondary mineral abundances varies from 10-16 to 10-17 mol s-1 kg tuff-1 with the largest uncertainty being the effect of the early thermal history of the tuff. Dissolution rates based on pore water Sr isotopic data were calculated by treating percolation flux parametrically, and vary from 10-15 to 10-16 mol s-1 kg tuff-1 for percolation fluxes of 15 mm a-1 and 1 mm a-1, respectively. Reconciling the rates from the two methods requires that percolation fluxes at the sampled locations be a few mm a-1 or less. The calculated feldspar dissolution rates are low relative to other measured field-based feldspar dissolution rates, possibly due to the age (12.8 Ma) of the unsaturated system at Yucca Mountain; because oxidizing and organic-poor conditions limit biological activity; and/or because elevated silica concentrations in the pore waters (???50 mg L-1) may inhibit feldspar dissolution. ?? 2009 Elsevier Ltd. All rights reserved.

Rheology and microstructure of synthetic halite/calcite porphyritic aggregates in torsion

NASA Astrophysics Data System (ADS)

Marques, F. O.; Burlini, L.; Burg, J.-P.

2010-03-01

Polymer jacketed porphyritic samples of 70% halite + 30% coarse calcite were subjected to torsion deformation to investigate the effects of a mixture of coarse calcite on the microstructure and mechanical properties of a two-phase aggregate. The experiments were run at 100 and 200 °C, a confining pressure of 250 MPa, and a constant shear strain rate of 3E-4 s -1. Ultimate strengths of single-phase halite synthetic aggregates at 100 and 200 °C were ca. 32 and 8 Nm, respectively, and of the two-phase aggregate 39 and 18 Nm, respectively; this shows that the two-phase aggregate was much stronger, especially at 200 °C. Stepping strain rate tests show that the two-phase aggregate behaved as power-law viscous, with stress exponents of ca. 19 and 13 at 100 °C at 200 °C, respectively. From these high exponents, we infer that the active deformation mechanisms were not efficient enough to rapidly relax the applied stress. Halite stress exponents at 100 and 200 °C are typically much lower, in the order of 4-6, which means that the calcite porphyroclasts were obstacles to halite plastic flow and hampered stress relaxation. The drop of the stress exponent with temperature indicates that the main deformation mechanism(s) was temperature sensitive. Matrix halite deformed plastically, while calcite rotated rigidly or deformed in a brittle fashion, with grain size reduction by fracturing (e.g. bookshelf and boudinage). We conclude that halite was softer than calcite in the investigated temperature range. Strain was homogeneous at the sample scale but not at the grain scale where the foliation delineated by plastically flattened halite contoured the rigid calcite clasts. The microstructures experimentally produced at 100 and 200 °C are very similar and find their counterparts in natural mylonites: rolling structures, σ and δ porphyroclast systems, bookshelf and boudinage in brittle calcite porphyroclasts, and ductile y and c' micro shear bands in the halite matrix.

Deep-biosphere consortium of fungi and prokaryotes in Eocene subseafloor basalts.

PubMed

Bengtson, S; Ivarsson, M; Astolfo, A; Belivanova, V; Broman, C; Marone, F; Stampanoni, M

2014-11-01

The deep biosphere of the subseafloor crust is believed to contain a significant part of Earth's biomass, but because of the difficulties of directly observing the living organisms, its composition and ecology are poorly known. We report here a consortium of fossilized prokaryotic and eukaryotic micro-organisms, occupying cavities in deep-drilled vesicular basalt from the Emperor Seamounts, Pacific Ocean, 67.5 m below seafloor (mbsf). Fungal hyphae provide the framework on which prokaryote-like organisms are suspended like cobwebs and iron-oxidizing bacteria form microstromatolites (Frutexites). The spatial inter-relationships show that the organisms were living at the same time in an integrated fashion, suggesting symbiotic interdependence. The community is contemporaneous with secondary mineralizations of calcite partly filling the cavities. The fungal hyphae frequently extend into the calcite, indicating that they were able to bore into the substrate through mineral dissolution. A symbiotic relationship with chemoautotrophs, as inferred for the observed consortium, may be a pre-requisite for the eukaryotic colonization of crustal rocks. Fossils thus open a window to the extant as well as the ancient deep biosphere. © 2014 The Authors. Geobiology Published by John Wiley & Sons Ltd.

Water-rock interaction and geochemistry of groundwater from the Ain Azel aquifer, Algeria.

PubMed

Belkhiri, Lazhar; Mouni, Lotfi; Tiri, Ammar

2012-02-01

Hydrochemical, multivariate statistical, and inverse geochemical modeling techniques were used to investigate the hydrochemical evolution within the Ain Azel aquifer, Algeria. Cluster analysis based on major ion contents defined 3 main chemical water types, reflecting different hydrochemical processes. The first group water, group 1, has low salinity (mean EC = 735 μS/cm). The second group waters are classified as Cl-HCO(3)-alkaline earth type. The third group is made up of water samples, the cation composition of which is dominated by Ca and Mg with anion composition varying from dominantly Cl to dominantly HCO(3) plus SO(4). The varifactors obtained from R-mode FA indicate that the parameters responsible for groundwater quality variations are mainly related to the presence and dissolution of some carbonate, silicate, and evaporite minerals in the aquifer. Inverse geochemical modeling along groundwater flow paths indicates the dominant processes are the consumption of CO(2), the dissolution of dolomite, gypsum, and halite, along with the precipitation of calcite, Ca-montmorillonite, illite, kaolinite, and quartz. © Springer Science+Business Media B.V. 2011

Diagenetic comparisons between non-tropical Cenozoic limestones of New Zealand and tropical Mississippian limestones from Indiana, USA: Is the non-tropical model better than the tropical model?

NASA Astrophysics Data System (ADS)

Dodd, J. Robert; Nelson, Campbell S.

1998-10-01

Mississippian limestones exposed in Indiana, U.S.A., were deposited in a shallow tropical ocean. However, many properties of these limestones are more like those of modern and Cenozoic non-tropical limestones such as those found in New Zealand. The dominant skeletal grains in the Indiana limestones are calcitic echinoderms, bryozoans, and brachiopods. The dominant skeletal grains in most Cenozoic limestones of New Zealand are calcitic bryozoans, echinoderms, bivalve molluscs, and foraminifera. In contrast, modern and Cenozoic tropical limestones contain an abundance of aragonitic green algae, corals, and molluscs. Early in diagenesis the metastable aragonite dissolves and reprecipitates as calcite, causing early cementation of the sediments. Originally aragonitic fossils that have dissolved can be identified as molds that are commonly filled with secondary calcite. Because they contained little aragonite, most of the Indiana and New Zealand limestones did not have an abundant source of early cement. Except for local cases in which grains were cemented in contact with carbonate supersaturated seawater, grainstones were relatively deeply buried with little cement between the grains. This resulted in mechanical and chemical compaction of skeletal grains, producing a `fitted fabric' with greatly reduced pore space, either open or filled with cement between the grains. Cement in these aragonite-poor grainstones comes largely from pressure dissolution between grains and along stylolitic seams in the rock, features that are common only after burial beyond a few hundred meters. The final product of deeply buried (up to 2000 m) Cenozoic New Zealand grainstones is similar to the Mississippian grainstones of Indiana. In the Indiana limestones we have only the final product of this extensive burial diagenesis. However, the New Zealand sediments and rocks reveal all steps of formation of the final deeply buried limestone. The reason for the scarcity of originally aragonitic fossil grains in Paleozoic rocks worldwide is unknown. Organisms with aragonitic skeletons such as some molluscan groups and calcareous green algae were present, but seldom in much abundance. The aragonitic scleractinian corals had not yet evolved. Previous researchers have noted that non-skeletal precipitates such as ooids and cements have at times during the Paleozoic been predominantly aragonite and at other times calcite. They have attributed this difference to secular variation in seawater chemistry (icehouse vs. greenhouse seas). Abundance of aragonitic and calcitic skeletal grains does not follow this pattern.

Fluvial/lacustrine diagenesis: Significance for hydrocarbon production and entrapment in the carboniferous Albert Fm, Moncton basin, NB

DOE Office of Scientific and Technical Information (OSTI.GOV)

Noble, J.P.A.; Chowdhury, A.H.; Yu, H.

1996-12-31

The Carboniferous Horton Group Albert Formation sediments include lacustrine source-rock oil shales and fluvial porous reservoir sandstones. The petrography, stable isotopes, fluid inclusions, cathodoluminescence and mirror/trace element chemistry of these sandstones are used to establish the diagenetic history and controlling factors. Early diagenetic calcite, quartz and albite cements with minor chlorite and kaolinite are variably present and related to depositional mineralogy and lake levels winch controlled the porewater chemistry. Antitaxial veins occurring preferentially in shales are shown, from heavy {delta}C{sup 13} values and fluid inclusions, to be related to methanogenesis in overpressured zones at shallow depths. Later burial calcite andmore » extensive albitisation are related to mineral reactions during the phase of rapid subsidence at temperatures of 80{degrees} to 150{degrees} in the deepest segment of the basin, together with significant dissolution of carbonates and feldspars related mainly to organic acids generated by organic maturation processes. Mass balance calculations indicate that not enough organic matter was present to account for all the estimated secondary porosity and some evidence suggests that reactions between kaolinite and calcite/ankerite to produce chlorite, and mixed layer illite-smectite ordering reactions, produced significant secondary porosity. Burial history reconstructions and thermal modelling of the Albert Fm. sediments using Arrhenius type maturity models and reflectance and rock-eval data suggest locally variable maturation and reservoir production related to the locally different fault tectonic histories characteristic of strike-slip lacustrine segmented basins. The Horton depositional cycle was followed by major dextral transpression with local faulting and inversion and vein cementation.« less

Fluvial/lacustrine diagenesis: Significance for hydrocarbon production and entrapment in the carboniferous Albert Fm, Moncton basin, NB

DOE Office of Scientific and Technical Information (OSTI.GOV)

Noble, J.P.A.; Chowdhury, A.H.; Yu, H.

1996-01-01

The Carboniferous Horton Group Albert Formation sediments include lacustrine source-rock oil shales and fluvial porous reservoir sandstones. The petrography, stable isotopes, fluid inclusions, cathodoluminescence and mirror/trace element chemistry of these sandstones are used to establish the diagenetic history and controlling factors. Early diagenetic calcite, quartz and albite cements with minor chlorite and kaolinite are variably present and related to depositional mineralogy and lake levels winch controlled the porewater chemistry. Antitaxial veins occurring preferentially in shales are shown, from heavy [delta]C[sup 13] values and fluid inclusions, to be related to methanogenesis in overpressured zones at shallow depths. Later burial calcite andmore » extensive albitisation are related to mineral reactions during the phase of rapid subsidence at temperatures of 80[degrees] to 150[degrees] in the deepest segment of the basin, together with significant dissolution of carbonates and feldspars related mainly to organic acids generated by organic maturation processes. Mass balance calculations indicate that not enough organic matter was present to account for all the estimated secondary porosity and some evidence suggests that reactions between kaolinite and calcite/ankerite to produce chlorite, and mixed layer illite-smectite ordering reactions, produced significant secondary porosity. Burial history reconstructions and thermal modelling of the Albert Fm. sediments using Arrhenius type maturity models and reflectance and rock-eval data suggest locally variable maturation and reservoir production related to the locally different fault tectonic histories characteristic of strike-slip lacustrine segmented basins. The Horton depositional cycle was followed by major dextral transpression with local faulting and inversion and vein cementation.« less

Injection of CO2-saturated water through a siliceous sandstone plug from the Hontomin test site (Spain): experiment and modeling.

PubMed

Canal, J; Delgado, J; Falcón, I; Yang, Q; Juncosa, R; Barrientos, V

2013-01-02

Massive chemical reactions are not expected when injecting CO(2) in siliceous sandstone reservoirs, but their performance can be challenged by small-scale reactions and other processes affecting their transport properties. We have conducted a core flooding test with a quartzarenite plug of Lower Cretaceous age representative of the secondary reservoir of the Hontomín test site. The sample, confined at high pressure, was successively injected with DIW and CO(2)-saturated DIW for 49 days while monitoring geophysical, chemical, and hydrodynamic parameters. The plug experienced little change, without evidence of secondary carbonation. However, permeability increased by a factor of 4 (0.022-0.085 mD), and the V(P)/V(S) ratio, whose change is related with microcracking, rose from ~1.68 to ~1.8. Porosity also increased (7.33-8.1%) from the beginning to the end of the experiment. Fluid/rock reactions were modeled with PHREEQC-2, and they are dominated by the dissolution of Mg-calcite. Mass balances show that ~4% of the initial carbonate was consumed. The results suggest that mineral dissolution and microcracking may have acted in a synergistic way at the beginning of the acidic flooding. However, dissolution processes concentrated in pore throats can better explain the permeability enhancement observed over longer periods of time.

Freshwater biodissolution rates of limestone in the temperate climate of the Dinaric karst in Slovenia

NASA Astrophysics Data System (ADS)

Mulec, J.; Prelovšek, M.

2015-01-01

Dissolution rates in two freshwater karst systems were determined by using tablets of dense micrite-biopelmicrite Cretaceous limestone. Submerged limestone tablets in riverbeds were subjected to a natural gradient from complete darkness to direct sunlight. Higher light rates significantly (p < 0.05) increased the epilithic biomass of phototrophs and the overall dissolution rates, which were highest at the Unica spring (- 49.2 μm a- 1), but the exact portion of light-dependent dissolution remains elusive. In the karst river Unica, with its big fluctuations in environmental parameters (e.g., discharge), light rates can be used in estimating the dissolution rates enhanced by phototrophs. Natural biofilms in aquatic systems have important implications for landform evolution, and the impact on limestone dissolution rates is comparable with rates of debris falling from steep slopes.

Difference in the Dissolution Behaviors of Tablets Containing Polyvinylpolypyrrolidone (PVPP) Depending on Pharmaceutical Formulation After Storage Under High Temperature and Humid Conditions.

PubMed

Takekuma, Yoh; Ishizaka, Haruka; Sumi, Masato; Sato, Yuki; Sugawara, Mitsuru

Storage under high temperature and humid conditions has been reported to decrease the dissolution rate for some kinds of tablets containing polyvinylpolypyrrolidone (PVPP) as a disintegrant. The aim of this study was to elucidate the properties of pharmaceutical formulations with PVPP that cause a decrease in the dissolution rate after storage under high temperature and humid conditions by using model tablets with a simple composition. Model tablets, which consisted of rosuvastatin calcium or 5 simple structure compounds, salicylic acid, 2-aminodiphenylmethane, 2-aminobiphenyl, 2-(p-tolyl)benzoic acid or 4.4'-biphenol as principal agents, cellulose, lactose hydrate, PVPP and magnesium stearate as additives, were made by direct compression. The model tables were wrapped in paraffin papers and stored for 2 weeks at 40°C/75% relative humidity (RH). Dissolution tests were carried out by the paddle method in the Japanese Pharmacopoeia 16th edition. Model tablets with a simple composition were able to reproduce a decreased dissolution rate after storage at 40°C/75% RH. These tablets showed significantly decreased water absorption activities after storage. In the case of tablets without lactose hydrate by replacing with cellulose, a decreased dissolution rate was not observed. Carboxyl and amino groups in the structure of the principal agent were not directly involved in the decreased dissolution. 2-Benzylaniline tablets showed a remarkably decreased dissolution rate and 2-aminobiphenyl and 2-(p-tolyl)benzoic acid tablets showed slightly decreased dissolution rates, though 4,4'-biphenol tablets did not show a decrease dissolution rate. We demonstrated that additives and structure of the principal agent were involved in the decreased in dissolution rate for tablets with PVPP. The results suggested that one of the reasons for a decreased dissolution rate was the inclusion of lactose hydrate in tablets. The results also indicated that compounds as principal agents with low affinity for PVPP may be easily affected by airborne water under high temperature and humid conditions. This article is open to POST-PUBLICATION REVIEW. Registered readers (see "For Readers") may comment by clicking on ABSTRACT on the issue's contents page.

Ages and Origins of Calcite and Opal in the Exploratory Studies Facility Tunnel, Yucca Mountain, Nevada

USGS Publications Warehouse

Paces, James B.; Neymark, Leonid A.; Marshall, Brian D.; Whelan, Joseph F.; Peterman, Zell E.

2001-01-01

Deposits of calcite and opal are present as coatings on open fractures and lithophysal cavities in unsaturated-zone tuffs at Yucca Mountain, Nevada, site of a potential high-level radioactive waste repository. Outermost layers of calcite and opal have radiocarbon ages of 16,000 to 44,000 years before present and thorium-230/uranium ages of 28,000 to more than 500,000 years before present. These ages are young relative to the 13-million-year age of the host rocks. Multiple subsamples from the same outer layer typically show a range of ages with youngest ages from the thinnest subsamples. Initial uranium-234/uranium-238 activity ratios between 1 and 9.5 show a distinct negative correlation with thorium-230/uranium age and are greater than 4 for all but one sample younger than 100,000 years before present. These data, along with micrometer-scale layering and distinctive crystal morphologies, are interpreted to indicate that deposits formed very slowly from water films migrating through open cavities. Exchanges of carbon dioxide and water vapor probably took place between downward-migrating liquids and upward-migrating gases at low rates, resulting in oversaturation of mineral constituents at crystal extremities and more or less continuous deposition of very thin layers. Therefore, subsamples represent mixtures of older and younger layers on a scale finer than sampling techniques can resolve. Slow, long-term rates of deposition (less than about 5 millimeters of mineral per million years) are inferred from subsamples of outermost calcite and opal. These growth rates are similar to those calculated assuming that total coating thicknesses of 10 to 40 millimeters accumulated over 12 million years. Calcite has a wide range of delta carbon-13 values from about -8.2 to 8.5 per mil and delta oxygen-18 values from about 10 to 21 per mil. Systematic microsampling across individual mineral coatings indicates basal (older) calcite tends to have the largest delta carbon-13 values and smallest delta oxygen-18 values compared to calcite from intermediate and outer positions. Basal calcite has relatively small strontium-87/strontium-86 ratios, between 0.7105 and 0.7120, that are similar to the initial isotopic compositions of the strontium-rich tuff units, whereas outer calcite has more radiogenic strontium-87/strontium-86 ratios between 0.7115 and 0.7127. Isotopic compositions of strontium, oxygen, and carbon in the outer (youngest) unsaturated-zone calcite are coincident with those measured in Yucca Mountain calcrete, which formed by pedogenic processes. The physical and isotopic data from calcite and opal indicate that they formed from solutions of meteoric origin percolating through a limited network of connected fracture pathways in the unsaturated zone rather than by inundation from ascending ground water originating in the saturated zone. Mineral assemblages, textures, and distributions within the unsaturated zone are distinctly different from those deposited below the water table at Yucca Mountain. The calcite and opal typically are present only on footwall surfaces of a small fraction of fractures and only on floors of a small fraction of lithophysal cavities. The similarities in the carbon, oxygen, and strontium isotopic compositions between fracture calcite and soil-zone calcite, as well as the gradation of textures from detritus-rich micrite in the soil to detritus-free spar 10 to 30 meters below the surface, also support a genetic link between the two depositional environments. Older deposits contain oxygen isotope compositions that indicate elevated temperatures of mineral formation during the early stages of deposition; however, in the youngest deposits these values are consistent with deposition under geothermal gradients similar to modern conditions. Correlations between mineral ages and varying Pleistocene climate conditions are not apparent from the current data. Cumulative evidence from calcite and opal deposits indicate

Quartz dissolution. I - Negative crystal experiments and a rate law. II - Theory of rough and smooth surfaces

NASA Technical Reports Server (NTRS)

Gratz, Andrew J.; Bird, Peter

1993-01-01

The range of the measured quartz dissolution rates, as a function of temperature and pOH, extent of saturation, and ionic strength, is extended to cover a wider range of solution chemistries, using the negative crystal methodology of Gratz et al. (1990) to measure the dissolution rate. A simple rate law describing the quartz dissolution kinetics above the point of zero charge of quartz is derived for ionic strengths above 0.003 m. Measurements were performed on some defective crystals, and the mathematics of step motion was developed for quartz dissolution and was compared with rough-face behavior using two different models.

The use of ordered mixtures for improving the dissolution rate of low solubility compounds.

PubMed

Nyström, C; Westerberg, M

1986-03-01

The dissolution rate of micronized griseofulvin has been investigated, both for the agglomerated raw material and the material formulated as an ordered mixture, by means of the USP XX paddle method. During the experiments, which were performed at sink condition and constant temperature, the effects of adding a surfactant and of agitation were tested. The ordered mixture with sodium chloride gave a fast dissolution rate, practically independent of the test parameters. Micronized griseofulvin alone gave dissolution profiles that were improved by adding polysorbate 80 and by increased agitation, but the dissolution rates obtained were much lower than those for the ordered mixture. It was concluded that the rate limiting step in the dissolution of griseofulvin as the raw material is the penetration of the dissolution medium into the agglomerates. With an ordered mixture, these agglomerates were deaggregated during the mixing process, producing a system in which the entire external surface area of the primary particles was exposed to the dissolution medium. This conclusion was supported by calculation of the contact surface areas taking part in the dissolution process for the systems tested. The procedure developed in this study could be applied to preformulation work where a cohesive, low solubility drug of hydrophobic nature is to be formulated.

Calcite Precipitation and Trace Metal Partitioning in Groundwater and the Vadose Zone: Remediation of Strontium-90 and Other Divalent Metals and Radionuclides in Arid Western Environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

F. Grant Ferris

2003-04-12

In situ remediation is an emerging technology that will play an important role in DOE's environmental restoration program, and is an area where enhancement in fundamental understanding will lead to significantly improved cleanup tools. In situ remediation technologies have inherent advantages because they do not require the costly removal, transport, and disposal of contamination. In addition, these technologies minimize worker exposure because contaminated materials are not brought to the surface. Finally, these technologies will minimize the generation of secondary waste streams with their associated treatment and disposal. A particularly promising in situ remediation technology is bioremediation. For inorganic contaminants suchmore » as radionuclides and metals, in situ bioremediation can be used to alter the mobility or reduce the toxicity of radionuclides and metals by changing the valence state of the radionuclides and metals, degrading or producing complexing ligands, or facilitating partitioning on to or off of solid phases. The purpose of the research presented here was to explore microbially facilitated partitioning of metal and radionuclides by their co-precipitation with calcium carbonate. Although this approach is a very attractive cleanup alternative, its practical implementation requires improved scientific understanding of the geochemical and biological mechanisms involved, particularly with respect to rates and mechanisms of microbially facilitated calcite precipitation. Of interest for this investigation is the in situ manipulation of calcite precipitation by the microbially catalyzed hydrolysis of urea. The production of ammonia during microbial decomposition of urea tends to drive pH upwards, and results in formation of alkaline conditions. When solution concentrations of Ca2+ and HCO3- are high enough, calcium carbonate precipitation may occur. A series of water samples collected from four wells tapping the aquifer underlying Eastern Snake River Plain (ESRP) in the vicinity of the Idaho National Engineering and Environmental Laboratory (INEEL) all tested positively for the presence of urea degrading bacteria. Calcite precipitation experiments were conducted with isolated ESRP urea degrading bacteria and B. pasteurii (ATCC 11859), a known urea hydrolyzer. In all of the experiments, visible white precipitates developed within the first thirty minutes after inoculation. The identity of the precipitates as calcite was confirmed by X-ray diffraction. Scanning electron micrographs of the solids revealed both spherical and amorphous precipitates, with microbes in close association with the minerals. The kinetics of calcite precipitation at 10 to 20 C was subsequently investigated using an artificial groundwater (AGW) medium based on the aqueous chemistry of the ESRP aquifer. Experimental data was fit using unconstrained nonlinear regression and optimization to determine rate constants and points of critical supersaturation (Scritical i.e., calcite nucleation). The highest rates of calcite precipitation (ca. 0.8 mmole L-1 day-1) occurred near Scritical. While unique time course trajectories of dissolved Ca2+ concentrations were observed at the different experimental temperatures, the calcite precipitation rates all followed the same asymptotic profile decreasing progressively with saturation state regardless of temperature. This emphasizes the fundamental kinetic dependence of calcite precipitation on saturation state, which connects the otherwise dissimilar temporal patterns of calcite precipitation that evolved under the different temperature and biogeochemical regimes of the experiments.« less

The effect of fuel chemistry on UO2 dissolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Casella, Amanda; Hanson, Brady; Miller, William

2016-08-01

The dissolution rate of both unirradiated UO2 and used nuclear fuel has been studied by numerous countries as part of the performance assessment of proposed geologic repositories. In the scenario of waste package failure and groundwater infiltration into the fuel, the effects of variables such as temperature, dissolved oxygen, and water and fuel chemistry on the dissolution rates of the fuel are necessary to provide a quantitative estimate of the potential release over geologic time frames. The primary objective of this research was to determine the influence these parameters have on the dissolution rate of unirradiated UO2 under repository conditionsmore » and compare them to the rates predicted by current dissolution models. Both unirradiated UO2 and UO2 doped with varying concentrations of Gd2O3, to simulate used fuel composition after long time periods where radiolysis has minor contributions to dissolution, were examined. In general, a rise in temperature increased the dissolution rate of UO2 and had a larger effect on pure UO2 than on those doped with Gd2O3. Oxygen dependence was observed in the UO2 samples with no dopant and increased as the temperature rose; in the doped fuels less dependence was observed. The addition of gadolinia into the UO2 matrix showed a significant decrease in the dissolution rate. The matrix stabilization effect resulting from the dopant proved even more beneficial in lowering the dissolution rate at higher temperatures and dissolved O2 concentrations in the leachate where the rates would typically be elevated.« less

Strain rate dependent calcite microfabric evolution - an experiment carried out by nature

NASA Astrophysics Data System (ADS)

Rogowitz, A.; Huet, B.; Grasemann, B.; Habler, G.

2013-12-01

The deformation behaviour of calcite has been studied extensively in a number of experiments. Different strain rates and pressure and temperature conditions have been used to investigate a wide range of deformation regimes. However, a direct comparison with natural fault rocks remains difficult because of extreme differences between experimental and natural strain rates. A secondary shear zone (flanking structure) developed in almost pure calcite marble on Syros (Greece). Due to rotation of an elliptical inclusion (crack) a heterogeneous strain field in the surrounding area occurred resulting in different strain domains and the formation of the flanking structure. Assuming that deformation was active continuously during the development of the flanking structure, the different strain domains correspond to different strain-rate domains. The outcrop thus represents the final state of a natural experiment and gives us a great opportunity to get natural constraints on strain rate dependent deformation behaviour of calcite. Comparing the microfabrics in the 1 to 2.5 cm thick shear zone and the surrounding host rocks, which formed under the same metamorphic conditions but with different strain rates, is the central focus of this study. Due to the extreme variation in strain and strain rate, different microstructures and textures can be observed corresponding to different deformation mechanisms. With increasing strain rate we observe a change in dominant deformation mechanism from dislocation glide to dislocation creep and finally diffusion creep. Additionally, a change from subgrain rotation (SGR) to bulging (BLG) recrystallization can be observed in the dislocation creep regime. Textures and the degree of intracrystalline deformation have been measured by electron back scatter diffraction (EBSD). At all strain rates clear CPOs developed leading to the assumption that calcite preferentially deforms within the dislocation creep field. However, we can also find clear evidence for grain size sensitive deformation mechanisms at smaller grain sizes (3.6 μm) consistent with experimental observations and determined flaw laws. Although mylonitic layers evolve at high (10^-10 s^-1) and intermediate strain rates (10^-11 s^-1) by SGR recrystallization we observe variations in texture leading to the assumption that at varying strain rates different gliding systems were active. The results of this study are compared with experimental data, closing the gap between experimental and natural geological strain rates.

Dissolution patterns of biocompatible glasses in 2-amino-2-hydroxymethyl-propane-1,3-diol (Tris) buffer.

PubMed

Fagerlund, S; Hupa, L; Hupa, M

2013-02-01

A continuous flow measurement system with sensitive on-line ion analysis has been applied to study the initial dissolution behaviour of biocompatible glasses in Tris. Altogether 16 glasses with widely varying compositions were studied. The measurement system allowed for quantitative determination of the time-dependent rates of dissolution of sodium, potassium, calcium, magnesium, silicon and phosphorus during the first 10-15 min in contact with Tris solution. The dissolution rates of the different ions showed significant glass to glass variations, but all glasses studied showed one of four distinct dissolution patterns. The ion dissolution rates after an exposure of 1000 s, expressed as the normalized surface-specific mass loss rates, were compared with the in vitro and in vivo reactivity of the glasses as predicted by models in the literature. The results showed a clear correlation between the dissolution rates of the glasses in Tris and their reactivity as measured by other different methods. Consequently, the measured short-term dissolution patterns could be used to determine which glasses are suitable as bioactive, biodegradable, or inert biomaterials for medical devices. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Linking varve-formation processes to climate and lake conditions at Tiefer See (NE Germany)

NASA Astrophysics Data System (ADS)

Dräger, Nadine; Kienel, Ulrike; Plessen, Birgit; Ott, Florian; Brademann, Brian; Pinkerneil, Sylvia; Brauer, Achim

2017-04-01

Annually laminated (varved) lake sediments represent unique archives in continental areas providing both, precise chronologies and seasonally resolving proxy data. Monitoring of physical, chemical and biological processes influencing lake sediment formation are a suitable approach for detailed proxy understanding of varved sediment records. Lake Tiefer See (NE Germany) indicates deposition of varved sediments today as well as millennia ago (Dräger et al., 2016; Kienel et al., 2013). Therefore, the lake provides the possibility to trace current seasonal layer formation in the lake and to pair these data to climate and lake conditions (Kienel et al., 2016). Lake Tiefer See was formed during the last glaciation and is part of the Klocksin Lake Chain, a subglacial channel system that crosses the Pomeranian terminal moraine. The lake is a mesotrophic hard water lake with a maximum depth of 63 m and a surface area of 0.75 km2. During four consecutive years (2012-2015) the particulate matter deposition was trapped at bi-weekly to monthly resolution at three different water depths (5, 12 and 50 m). The sediment trap material was analysed for sediment flux and organic matter and calcite content. In addition, we monitored limnological parameters (e.g. temperature, pH, conductivity, oxygen content) as well as the meteorological conditions (e.g. temperature, wind speed and direction, precipitation) with a monitoring and climate station installed on the lake. These data describe strength and duration of lake mixing and lake stagnation phases. Our results show distinct seasonal peaks in sediment formation, which correspond to the spring and summer productivity phases comprising of diatom blooms and calcite precipitation. This observation is in line with microfacies results from surface sediment cores. The content of biogenic calcite content decreases in the trapped material with increasing water depth indicating dissolution processes. However, the strength of calcite dissolution varies between seasons and years. We will discuss the depositional processes in relation to conditions in the water column and to meteorological data. This study is a contribution to the Virtual Institute of Integrated Climate and Landscape Evolution Analysis -ICLEA- of the Helmholtz Association; grant number VH-VI-415. Dräger N, Brauer A, Theuerkauf M, Szeroczyńska K, Tjallingii R, Plessen B, Kienel U and Brauer A (2016) A varve micro-facies and varve preservation record of climate change and human impact for the last 6000 years at Lake Tiefer See (NE Germany). The Holocene online first. Kienel U, Dulski P, Ott F, Lorenz S and Brauer A (2013) Recently induced anoxia leading to the preservation of seasonal laminae in two NE-German lakes. Journal of paleolimnology 50 (4): 535-544. Kienel U, Kirillin G, Brademann B, Plessen B, Lampe R and Brauer A (2016) Effects of spring warming and mixing duration on diatom deposition in deep Tiefer See, NE Germany. Journal of paleolimnology 57 (1): 37-49.

Dissolution of quartz in aqueous basic solution, 106-236 C - Surface kinetics of 'perfect' crystallographic faces

NASA Technical Reports Server (NTRS)

Gratz, Andrew J.; Bird, Peter; Quiro, Glenn B.

1990-01-01

A highly accurate method, called the negative crystal method, for determining the rate of dissolution on specific crystallographic faces of crystals was developed, in which the dissolution rates of nominally perfect crystal faces are obtained by measuring the size of individual negative crystals during a sequence of dissolution steps. The method was applied to determine the apparent activation energy and rate constants for the dissolution of quartz in 0.01 M KOH solutions at temperatures from 106 to 236 C. Also investigated were the effects of hydroxyl activity and ionic strength. The apparent activation energies for the dissolution of the prism and of the rhomb were determined.

Influence of lysozyme on the precipitation of calcium carbonate: a kinetic and morphologic study

NASA Astrophysics Data System (ADS)

Jimenez-Lopez, Concepcion; Rodriguez-Navarro, Alejandro; Dominguez-Vera, Jose M.; Garcia-Ruiz, Juan M.

2003-05-01

Several mechanisms have been proposed to explain the interactions between proteins and mineral surfaces, among them a combination of electrostatic, stereochemical interactions and molecular recognition between the protein and the crystal surface. To identify the mechanisms of interaction in the lysozyme-calcium carbonate model system, the effect of this protein on the precipitation kinetics and morphology of calcite crystals was examined. The solution chemistry and morphology of the solid were monitored over time in a set of time-series free-drift experiments in which CaCO 3 was precipitated from solution in a closed system at 25°C and 1 atm total pressure, in the presence and absence of lysozyme. The precipitation of calcite was preceded by the precipitation of a metastable phase that later dissolved and gave rise to calcite as the sole phase. With increasing lysozyme concentration, the nucleation of both the metastable phase and calcite occurred at lower Ω calcite, indicating that lysozyme favored the nucleation of both phases. Calcite growth rate was not affected by the presence of lysozyme, at least at protein concentrations ranging from 0 mg/mL to 10 mg/mL. Lysozyme modified the habit of calcite crystals. The degree of habit modification changed with protein concentration. At lower concentrations of lysozyme, the typical rhombohedral habit of calcite crystals was modified by the expression of {110} faces, which resulted from the preferential adsorption of protein on these faces. With increasing lysozyme concentration, the growth of {110}, {100}, and finally {001} faces was sequentially inhibited. This adsorption sequence may be explained by an electrostatic interaction between lysozyme and calcite, in which the inhibition of the growth of {110}, {100}, and {001} faces could be explained by a combined effect of the density of carbonate groups in the calcite face and the specific orientation (perpendicular) of these carbonate groups with respect to the calcite surface. Overgrowth of calcite in the presence of lysozyme demonstrated that the protein favored and controlled the nucleation on the calcite substrate. Overgrowth crystals nucleated epitaxially in lines which run diagonal to rhombohedral {104} faces.

A reaction limited in vivo dissolution model for the study of drug absorption: Towards a new paradigm for the biopharmaceutic classification of drugs.

PubMed

Macheras, Panos; Iliadis, Athanassios; Melagraki, Georgia

2018-05-30

The aim of this work is to develop a gastrointestinal (GI) drug absorption model based on a reaction limited model of dissolution and consider its impact on the biopharmaceutic classification of drugs. Estimates for the fraction of dose absorbed as a function of dose, solubility, reaction/dissolution rate constant and the stoichiometry of drug-GI fluids reaction/dissolution were derived by numerical solution of the model equations. The undissolved drug dose and the reaction/dissolution rate constant drive the dissolution rate and determine the extent of absorption when high-constant drug permeability throughout the gastrointestinal tract is assumed. Dose is an important element of drug-GI fluids reaction/dissolution while solubility exclusively acts as an upper limit for drug concentrations in the lumen. The 3D plots of fraction of dose absorbed as a function of dose and reaction/dissolution rate constant for highly soluble and low soluble drugs for different "stoichiometries" (0.7, 1.0, 2.0) of the drug-reaction/dissolution with the GI fluids revealed that high extent of absorption was found assuming high drug- reaction/dissolution rate constant and high drug solubility. The model equations were used to simulate in vivo supersaturation and precipitation phenomena. The model developed provides the theoretical basis for the interpretation of the extent of drug's absorption on the basis of the parameters associated with the drug-GI fluids reaction/dissolution. A new paradigm emerges for the biopharmaceutic classification of drugs, namely, a model independent biopharmaceutic classification scheme of four drug categories based on either the fulfillment or not of the current dissolution criteria and the high or low % drug metabolism. Copyright © 2018. Published by Elsevier B.V.

Montmorillonite dissolution kinetics: Experimental and reactive transport modeling interpretation

NASA Astrophysics Data System (ADS)

Cappelli, Chiara; Yokoyama, Shingo; Cama, Jordi; Huertas, F. Javier

2018-04-01

The dissolution kinetics of K-montmorillonite was studied at 25 °C, acidic pH (2-4) and 0.01 M ionic strength by means of well-mixed flow-through experiments. The variations of Si, Al and Mg over time resulted in high releases of Si and Mg and Al deficit, which yielded long periods of incongruent dissolution before reaching stoichiometric steady state. This behavior was caused by simultaneous dissolution of nanoparticles and cation exchange between the interlayer K and released Ca, Mg and Al and H. Since Si was only involved in the dissolution reaction, it was used to calculate steady-state dissolution rates, RSi, over a wide solution saturation state (ΔGr ranged from -5 to -40 kcal mol-1). The effects of pH and the degree of undersaturation (ΔGr) on the K-montmorillonite dissolution rate were determined using RSi. Employing dissolution rates farthest from equilibrium, the catalytic pH effect on the K-montmorillonite dissolution rate was expressed as Rdiss = k·aH0.56±0.05 whereas using all dissolution rates, the ΔGr effect was expressed as a non-linear f(ΔGr) function Rdiss = k · [1 - exp(-3.8 × 10-4 · (|ΔGr|/RT)2.13)] The functionality of this expression is similar to the equations reported for dissolution of Na-montmorillonite at pH 3 and 50 °C (Metz, 2001) and Na-K-Ca-montmorillonite at pH 9 and 80 °C (Cama et al., 2000; Marty et al., 2011), which lends support to the use of a single f(ΔGr) term to calculate the rate over the pH range 0-14. Thus, we propose a rate law that also accounts for the effect of pOH and temperature by using the pOH-rate dependence and the apparent activation energy proposed by Rozalén et al. (2008) and Amram and Ganor (2005), respectively, and normalizing the dissolution rate constant with the edge surface area of the K-montmorillonite. 1D reactive transport simulations of the experimental data were performed using the Crunchflow code (Steefel et al., 2015) to quantitatively interpret the evolution of the released cations and to elucidate the stoichiometry of the reaction. After the implementation of (i) the obtained f(ΔGr) term in the K-montmorillonte dissolution rate law, (ii) a fraction of highly reactive particles and surfaces and (iii) the cation exchange reactions between the interlayer K+ and the released Al3+, Mg2+, Ca2+ and H+, the simulations agreed with the experimental concentrations at the outlet. This match indicates that fast dissolution of fine particles and highly reactive sites and exchange between the interlayer K and dissolved structural cations (Al and Mg) and protons are responsible for the temporary incongruency of the K-montmorillonite dissolution reaction. As long as dissolution of the bulk sample predominates, the reaction is stoichiometric.

The effect of temperature on experimental and natural chemical weathering rates of granitoid rocks

USGS Publications Warehouse

White, A.F.; Blum, A.E.; Bullen, T.D.; Vivit, D.V.; Schulz, M.; Fitzpatrick, J.

1999-01-01

The effects of climatic temperature variations (5-35??C) on chemical weathering are investigated both experimentally using flow-through columns containing fresh and weathered granitoid rocks and for natural granitoid weathering in watersheds based on annual solute discharge. Although experimental Na and Si effluent concentrations are significantly higher in the fresh relative to the weathered granitoids, the proportional increases in concentration with increasing temperature are similar. Si and Na exhibit comparable average apparent activation energies (E(a)) of 56 and 61 kJ/mol, respectively, which are similar to those reported for experimental feldspar dissolution measured over larger temperature ranges. A coupled temperature-precipitation model, using an expanded database for solute discharge fluxes from a global distribution of 86 granitoid watersheds, produces an apparent activation energy for Si (51 kJ/mol), which is also comparable to those derived from the experimental study. This correlation reinforces evidence that temperature does significantly impact natural silicate weathering rates. Effluent K concentrations in the column study are elevated with respect to other cations compared to watershed discharge due to the rapid oxidation/dissolution of biotite. K concentrations are less sensitive to temperature, resulting in a lower average E(a) value (27 kJ/mol) indicative of K loss from lower energy interlayer sites in biotite. At lower temperatures, initial cation release from biotite is significantly faster than cation release from plagioclase. This agrees with reported higher K/Na ratios in cold glacial watersheds relative to warmer temperate environments. Increased release of less radiogenic Sr from plagioclase relative to biotite at increasing temperature produces corresponding decreases in 87Sr/86Sr ratios in the column effluents. A simple mixing calculation using effluent K/Na ratios, Sr concentrations and 87Sr/86Sr ratios for biotite and plagioclase approximates stoichiometric cation ratios from biotite/plagioclase dissolution at warmer temperatures (35??C), but progressively overestimates the relative proportion of biotite with decreasing temperature. Ca, Mg, and Sr concentrations closely correlate, exhibit no consistent trends with temperature, and are controlled by trace amounts of calcite or exchange within weathered biotite. The inability of the watershed model to differentiate a climate signal for such species correlates with the lower temperature dependence observed in the experimental studies.

Strain rate dependent activation of slip systems in calcite marbles from Syros (Cyclades, Greece)

NASA Astrophysics Data System (ADS)

Rogowitz, Anna; Grasemann, Bernhard; Morales, Luiz F. G.; Huet, Benjamin; White, Joseph C.

2017-04-01

The activation of certain slip systems in calcite has been experimentally proven to be highly temperature dependent, but also the strain rate plays an important role on the activation of the dominant slip system. In this study, observations from a flanking structure (i.e. shear zone) that developed under lower greenschist-facies conditions, in an almost pure calcite marble (Syros Island, Greece) are presented. The shear zone is characterized by a strain gradient from the slightly deformed tips (γ ˜ 50) to the highly strained centre (γ up to 1000) while the host rock is moderately deformed (γ ˜ 3). During the shear zone development, the strain gradient coincided with a strain rate gradient with strain rate varying from 10-13 to 10-9 s-1. The studied outcrop thus represents the final state of a natural experiment and gives us a great opportunity to get natural constraints on strain rate dependent mechanical behaviour in a calcite marble. Detailed microstructural analyses have been performed via optical microscopy, electron microscopy, electron backscatter diffraction mapping and transmission electron microscopy, on samples from the highly strained shear zone and the host rock. The analyses show that the calcite microfabric varies depending on position within the shear zone, indicating activation of different deformation, recrystallization mechanisms and slip systems at different strain rates. Up to strain rates of ˜10-10 s-1 the marble deformed exclusively within the dislocation creep field, showing a change in recrystallization mechanism and dominant active slip system. While the marble preferentially recrystallized by grain boundary migration at relatively low strain rates (˜10-13 s-1), subgrain rotation recrystallization seems to be the dominant mechanism at higher strain rates (˜10-12 to 10-10 s-1). At higher strain rates (˜10-9 s-1), the recrystallization mechanism is bulging, resulting in the development of an extremely fine grained ultramylonite (average grain size ˜3 μm) accompanied by a switch in deformation mechanism from dislocation creep to a combined deformation by grain boundary sliding and dislocation activity. Constraints on dominant active slip system depending on deformation strain rate have been made by a combination of misorientation analyses and viscoplastic self-consistent modelling.

Thermodynamics of magnesian calcite solid-solutions at 25°C and 1 atm total pressure

USGS Publications Warehouse

Busenberg, Eurybiades; Plummer, Niel

1989-01-01

The stability of magnesian calcites was reexamined, and new results are presented for 28 natural inorganic, 12 biogenic, and 32 synthetic magnesian calcites. The magnesian calcite solid-solutions were separated into two groups on the basis of differences in stoichiometric solubility and other physical and chemical properties. Group I consists of solids of mainly metamorphic and hydrothermal origin, synthetic calcites prepared at high temperatures and pressures, and synthetic solids prepared at low temperature and very low calcite supersaturations () from artificial sea water or NaClMgCl2CaCl2solutions. Group I solids are essentially binary s of CaCO2 and MgCO2, and are thought to be relatively free of structural defects. Group II solid-solutions are of either biogenic origin or are synthetic magnesian calcites and protodolomites (0–20 and ∼ 45 mole percent MgCO3) prepared at high calcite supersaturations () from NaClNa2SO4MgCl2CaCl2 or NaClMgCl2CaCl2 solutions. Group II solid-solutions are treated as massively defective solids. The defects include substitution foreign ions (Na+ and SO42−) in the magnesian calcite lattice (point defects) and dislocations (~2 · 109 cm−2). Within each group, the excess free energy of mixing, GE, is described by the mixing model , where x is the mole fraction of the end-member Ca0.5Mg0.5CO3 in the solid-solution. The values of A0and A1 for Group I and II solids were evaluated at 25°C. The equilibrium constants of all the solids are closely described by the equation ln , where KC and KD are the equilibrium constants of calcite and Ca0.5Mg0.5CO3. Group I magnesian calcites were modeled as sub-regular solid-solutions between calcite and dolomite, and between calcite and “disordered dolomite”. Both models yield almost identical equilibrium constants for these magnesian calcites. The Group II magnesian calcites were modeled as sub-regular solid-solutions between defective calcite and protodolomite. Group I and II solid-solutions differ significantly in stability. The rate of crystal growth and the chemical composition of the aqueous solutions from which the solids were formed are the main factors controlling stoichiometric solubility of the magnesian calcites and the density of crystal defects. The literature on the occurrence and behavior of magnesian calcites in sea water and other aqueous solutions is also examined.

Origin and diagenetic evolution of gypsum and microbialitic carbonates in the Late Sag of the Namibe Basin (SW Angola)

NASA Astrophysics Data System (ADS)

Laurent, Gindre-Chanu; Edoardo, Perri; Ian, Sharp R.; Peacock, D. C. P.; Roger, Swart; Ragnar, Poulsen; Hercinda, Ferreira; Vladimir, Machado

2016-08-01

Ephemeral evaporitic conditions developed within the uppermost part of the transgressive Late Sag sequence in the Namibe Basin (SW Angola), leading to the formation of extensive centimetre- to metre-thick sulphate-bearing deposits and correlative microbialitic carbonates rich in pseudomorphs after evaporite crystals. The onshore pre-salt beds examined in this study are located up to 25 m underneath the major mid-Aptian evaporitic succession, which is typified at the outcrop by gypsiferous Bambata Formation and in the subsurface by the halite-dominated Loeme Formation. Carbonate-evaporite cycles mostly occur at the top of metre-thick regressive parasequences, which progressively onlap and overstep landward the former faulted (rift) topography, or fill major pre-salt palaeo-valleys. The sulphate beds are made up of alabastrine gypsum associated with embedded botryoidal nodules, dissolution-related gypsum breccia, and are cross-cut by thin satin-spar gypsum veins. Nodular and fine-grained fabrics are interpreted as being diagenetic gypsum deposits resulting from the dissolution and recrystallisation of former depositional subaqueous sulphates, whereas gypsum veins and breccia result from telogenetic processes. The carbonates display a broader diversity of facies, characterised by rapid lateral variations along strike. Thin dolomitic and calcitic bacterial-mediated filamentous microbialitic boundstones enclose a broad variety of evaporite pseudomorphs and can pass laterally over a few metres into sulphate beds. Dissolution-related depositional breccias are also common and indicate early dissolution of former evaporite layers embedded within the microbialites. Sulphate and carbonate units are interpreted as being concomitantly deposited along a tide-dominated coastal supra- to intertidal- sabkha and constitute high-frequency hypersaline precursor events, prior to the accumulation of the giant saline mid-Aptian Bambata and Loeme Formations. Petrographic and geochemical analyses reveal successive dissolution, recrystallisation and cementation phases that occurred during burial, uplift and exhumation, implying a complex diagenetic evolution of both gypsum and carbonates, influenced by pore fluids of diverse composition which distinctly varied from meso- to telogenetic domains.

In situ nanoscale observations of gypsum dissolution by digital holographic microscopy.

PubMed

Feng, Pan; Brand, Alexander S; Chen, Lei; Bullard, Jeffrey W

2017-06-01

Recent topography measurements of gypsum dissolution have not reported the absolute dissolution rates, but instead focus on the rates of formation and growth of etch pits. In this study, the in situ absolute retreat rates of gypsum (010) cleavage surfaces at etch pits, at cleavage steps, and at apparently defect-free portions of the surface are measured in flowing water by reflection digital holographic microscopy. Observations made on randomly sampled fields of view on seven different cleavage surfaces reveal a range of local dissolution rates, the local rate being determined by the topographical features at which material is removed. Four characteristic types of topographical activity are observed: 1) smooth regions, free of etch pits or other noticeable defects, where dissolution rates are relatively low; 2) shallow, wide etch pits bounded by faceted walls which grow gradually at rates somewhat greater than in smooth regions; 3) narrow, deep etch pits which form and grow throughout the observation period at rates that exceed those at the shallow etch pits; and 4) relatively few, submicrometer cleavage steps which move in a wave-like manner and yield local dissolution fluxes that are about five times greater than at etch pits. Molar dissolution rates at all topographical features except submicrometer steps can be aggregated into a continuous, mildly bimodal distribution with a mean of 3.0 µmolm -2 s -1 and a standard deviation of 0.7 µmolm -2 s -1 .

Automated potentiometric procedure for studying dissolution kinetics acidic drugs under sink conditions.

PubMed

Underwood, F L; Cadwallader, D E

1978-08-01

An automated potentiometric procedure was used for studying in vitro dissolution kinetics of acidic drugs. Theoretical considerations indicated that the pH-stat method could be used to establish approximate sink conditions or, possibly, a perfect sink. Data obtained from dissolution studies using the pH-stat method were compared with data obtained from known sink and nonsink conditions. These comparisons indicated that the pH-stat method can be used to establish a sink condition for dissolution studies. The effective diffusion layer thicknesses for benzoic and salicylic acids dissolving in water were determined, and a theoretical dissolution rate was calculated utilizing these values. The close agreement between the experimental dissolution rates obtained under pH-stat conditions and theoretical dissolution rates indicated that perfect sink conditions were established under the experimental conditions used.

Statistical compilation of NAPAP chemical erosion observations

USGS Publications Warehouse

Mossotti, Victor G.; Eldeeb, A. Raouf; Reddy, Michael M.; Fries, Terry L.; Coombs, Mary Jane; Schmiermund, Ron L.; Sherwood, Susan I.

2001-01-01

In the mid 1980s, the National Acid Precipitation Assessment Program (NAPAP), in cooperation with the National Park Service (NPS) and the U.S. Geological Survey (USGS), initiated a Materials Research Program (MRP) that included a series of field and laboratory studies with the broad objective of providing scientific information on acid rain effects on calcareous building stone. Among the several effects investigated, the chemical dissolution of limestone and marble by rainfall was given particular attention because of the pervasive appearance of erosion effects on cultural materials situated outdoors. In order to track the chemical erosion of stone objects in the field and in the laboratory, the Ca 2+ ion concentration was monitored in the runoff solution from a variety of test objects located both outdoors and under more controlled conditions in the laboratory. This report provides a graphical and statistical overview of the Ca 2+ chemistry in the runoff solutions from (1) five urban and rural sites (DC, NY, NJ, NC, and OH) established by the MRP for materials studies over the period 1984 to 1989, (2) subevent study at the New York MRP site, (3) in situ study of limestone and marble monuments at Gettysburg, (4) laboratory experiments on calcite dissolution conducted by Baedecker, (5) laboratory simulations by Schmiermund, and (6) laboratory investigation of the surface reactivity of calcareous stone conducted by Fries and Mossotti. The graphical representations provided a means for identifying erroneous data that can randomly appear in a database when field operations are semi-automated; a purged database suitable for the evaluation of quantitative models of stone erosion is appended to this report. An analysis of the sources of statistical variability in the data revealed that the rate of stone erosion is weakly dependent on the type of calcareous stone, the ambient temperature, and the H + concentration delivered in the incident rain. The analysis also showed that the rate of stone erosion is strongly dependent on the rain-delivery conditions and on the surface morphology and orientation.

Effect of carbonate content on the mechanical behaviour of clay fault-gouges

NASA Astrophysics Data System (ADS)

Bakker, Elisenda; Niemeijer, André; Hangx, Suzanne; Spiers, Chris

2015-04-01

Carbon dioxide capture and storage (CCS) in depleted oil and gas reservoirs is considered to be the most promising technology to achieve large-scale reduction in anthropogenic emissions. In order to retain the stored CO2 from the atmosphere for the very long-term, i.e. on timescales of the order of 103-104 years, it is essential to maintain the integrity of the caprock, and more specifically of any faults penetrating the seal. When selecting suitable CO2-storage reservoirs, pre-exisiting faults within the caprock require close attention, as changes in the stress state resulting from CO2-injection may induce fault slip motion which might cause leakage. Little is known about the effect of fluid-rock interactions on the mineral composition, mechanical properties and the integrity and sealing capacity of the caprock. Previous studies on the effect of mineral composition on the frictional properties of fault gouges have shown that friction is controlled by the dominant phase unless there is a frictionally weak, through-going fabric. However, the effect on stability is less clear. Since long-term CO2-exposure might cause chemical reactions, potentially resulting in the dissolution or precipitation of carbonate minerals, a change in mineralogy could affect the mechanical stability of a caprock significantly. Calcite, for example, is known to be prone to micro-seismicity and shows a transition from velocity-strengthening to velocity-weakening behaviour around 100-150°C. Therefore, we investigated the effect of varying clay:carbonate ratios on fault friction behaviour, fault reactivation potential and slip stability, i.e. seismic vs. aseismic behaviour. Three types of simulated fault gouges were used: i) carbonate-free, natural clay-rich caprock samples, consisting of predominantly phyllosilicates (~80%) and quartz ~20%), ii) pure calcite, and iii) mixtures of carbonate-free clay-rich caprock and pure calcite, with predetermined clay:carbonate ratios. For the natural clay-rich caprock material we used Opalinus Claystone (Mont Terri, Switserland), which is considered to be an analogue for many shaly caprocks in Europe. We performed rotary shear experiments at in-situ reservoir conditions (T = 20-150˚C, σneff = 50 MPa, Pp = 25 MPa) at shear velocities of 0.22 -100 μm/s. Preliminary results show that the frictional strength of the carbonate-free, natural clay-rich caprock samples is 40-50% lower than for the pure calcite samples. Typical steady-state friction coefficient values obtained for the carbonate-free clay samples are ~0.3-0.4. These values are significantly smaller than the values of ~0.6-0.7 obtained for pure calcite. The friction coefficient values obtained for the mixture plot between the carbonate-free and pure calcite values. The samples show predominantly velocity-strengthening behaviour. However, the 90% pure calcite (and 10% clay-rich caprock) and 100% pure calcite samples show velocity-weakening behaviour at 100-150°C. This suggests that large amounts of carbonates, and thus significant carbonate precipitation as a result of CO2-exposure, are required to cause a transition from aseismic to seismic behaviour, at least under the experimental conditions investigated here.

ENVIRONMENTALMANAGEMENT SCIENCE PROGRAM PROJECT NUMBER 87016 CO-PRECIPITATION OF TRACEMETALS INGROUNDWATER AND VADOSE ZONE CALCITE: IN SITU CONTAINMENT AND STABILIZATION OF STRONTIUM-90 ANDOTHER DIVALENT METALS AND RADIONUCLIDES AT ARIDWESTERN DOE SITES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferris, F. Grant; Fujita, Yoshiko; Smith, Robert W.

2004-06-15

Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) weapons complex. In situ containment and stabilization of these contaminants in vadose zones or groundwater is a cost-effective treatment strategy. Our facilitated approach relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal coprecipitation) by increasing groundwater pH and alkalinity (Fujita et al., 2000; Warren et al., 2001). Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface ureamore » hydrolyzing microorganisms. Because the precipitation processes are irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from groundwater. The rate at which trace metals are incorporated into calcite is a function of calcite precipitation kinetics, adsorption interactions between the calcite surface and the trace metal in solution (Zachara et al., 1991), solid solution properties of the trace metal in calcite (Tesoriero and Pankow, 1996), and also the surfaces upon which the calcite is precipitating. A fundamental understanding of the coupling of calcite precipitation and trace metal partitioning, and how this occurs in aquifers and vadose environments is lacking. This report summarizes work undertaken during the second year of this project.« less

Dissolution Rates and Mineral Lifetimes of Phosphate Containing Minerals and Implications for Mars

NASA Astrophysics Data System (ADS)

Adcock, C. T.; Hausrath, E.

2011-12-01

The objectives of NASA's Mars Exploration Program include exploring the planet's habitability and the possibility of past, present, or future life. This includes investigating "possible supplies of bioessential elements" [1]. Phosphate is one such bioessential element for life as we understand it. Phosphate is also abundant on Mars [2], and the phosphate rich minerals chlorapatite, fluorapatite, and merrillite have been observed in Martian meteorites [3]. Surface rock analyses from the MER Spirit also show the loss of a phosphate rich mineral from the rocks Wishstone and Watchtower at Gusev Crater [4,5], implying mineral dissolution. Dissolution rates of phosphate containing minerals are therefore important for characterizing phosphate mobility and bioavailability on Mars. Previous studies have measured dissolution rates of fluorapatite [6-8]. However, chlorapatite and merrillite (a non-terrestrial mineral similar to whitlockite) are more common phosphate minerals found in Martian meteorites [3], and few dissolution data exist for these minerals. We have begun batch dissolution experiments on chlorapatite, synthesized using methods of [9], and whitlockite, synthesized using a method modified from [10]. Additionally, we are dissolving Durango fluorapatite to compare to dissolution rates in literature, and natural Palermo whitlockite to compare to dissolution rates of our synthesized whitlockite. Batch dissolution experiments were performed after [8], using a 0.01 molar KNO3 solution with 0.1500g-0.3000g mineral powders and starting solution volumes of 180ml in LDPE reaction vessels. HNO3 or KOH were used to adjust initial pH as required. Dissolution rates are calculated from the rate of change of elemental concentration in solution as a function of time, and normalized to the mineral surface area as measured by BET. Resulting rates will be used to calculate mineral lifetimes for the different phosphate minerals under potential Mars-like aqueous conditions, and in future reactive transport modeling.

Influence of deformation on dolomite rim growth kinetics

NASA Astrophysics Data System (ADS)

Helpa, Vanessa; Rybacki, Erik; Grafulha Morales, Luiz Fernando; Dresen, Georg

2015-04-01

Using a gas-deformation apparatus stacks of oriented calcite (CaCO3) and magnesite (MgCO3) single crystals were deformed at T = 750° C and P = 400 MPa to examine the influence of stress and strain on magnesio-calcite and dolomite (CaMg[CO3]2) growth kinetics. Triaxial compression and torsion tests performed at constant stresses between 7 and 38 MPa and test durations between 4 and 171 hours resulted in bulk strains of 0.03-0.2 and maximum shear strains of 0.8-5.6, respectively. The reaction rims consist of fine-grained (2-7 μm) dolomite with palisade-shaped grains growing into magnesite reactants and equiaxed granular dolomite grains next to calcite. In between dolomite and pure calcite, magnesio-calcite grains evolved with an average grain size of 20-40 μm. Grain boundaries tend to be straighter at high bulk strains and equilibrium angles at grain triple junctions are common within the magnesio-calcite layer. Transmission electron microscopy shows almost dislocation free palisades and increasing dislocation density within granular dolomite towards the magnesio-calcite boundary. Within magnesio-calcite grains, dislocations are concentrated at grain boundaries. Variation of time at fixed stress (˜17 MPa) yields a parabolic time dependence of dolomite rim width, indicating diffusion-controlled growth, similar to isostatic rim growth behavior. In contrast, the magnesio-calcite layer growth is enhanced compared to isostatic conditions. Triaxial compression at given time shows no significant change of dolomite rim thickness (11±2 μm) and width of magnesio-calcite layers (33±5 μm) with increasing stress. In torsion experiments, reaction layer thickness and grain size decrease from the center (low stress/strain) to the edge (high strain/stress) of samples. Chemical analysis shows nearly stoichiometric composition of dolomite palisades, but enhanced Ca content within granular grains, indicating local disequilibrium with magnesio-calcite, in particular for twisted samples. The shift from local equilibrium is ˜3 mol% in triaxial compression and ˜7 mol% in torsion. Electron backscatter diffraction analysis reveals a crystallographic preferred orientation (CPO) within the reaction layers with [0001] axes parallel to the compression/rotation axis and poles of {2-1-10} and {10-10} prismatic planes parallel to the reaction interface. Compared to isostatic annealing, the CPO is more pronounced and the amount of low-angle grain boundaries is increased. At the imposed experimental conditions, most of the bulk deformation is accommodated by calcite single, which is stronger than magnesite. Application of flow laws for magnesio-calcite and dolomite suggest that the fine-grained reaction products should deform by grain boundary diffusion creep, resulting in lower flow strength than the single crystal reactants. However, microstructural observations indicate that deformation of granular dolomite and magnesio-calcite is at least partially assisted by dislocation creep, which would result in an almost similar strength to calcite. Therefore, flattening of the reaction layers during triaxial compression may be counterbalanced by enhanced reaction rates, resulting in almost constant layer thickness, independent of the applied stress. For simple shear, the reduced reaction kinetics in the high stress/strain region of twisted samples may be related to increased nucleation rates, resulting in a lower grain size and rim thickness.

How does the composition affect the mechanical behaviour of simulated clay-rich fault gouges?

NASA Astrophysics Data System (ADS)

Bakker, Elisenda; Spiers, Christopher J.; Hangx, Suzanne J. T.

2014-05-01

CO2 capture and storage (CCS) in depleted oil and gas reservoirs is seen as one of the most promising large-scale CO2-mitigation strategies. Prediction of the effect of fluid-rock interaction on the mechanical integrity and sealing capacity of a reservoir-seal system, on timescales of the order of 1,000 or 10,000 years, is important to ensure the safety and containment of a reservoir in relation to long-term CO2 storage. However, most chemical reactions in rock/CO2/brine systems are slow, which means that long-term effects of fluids on rock composition, microstructure, mechanical properties and transport properties cannot be easily reproduced under laboratory conditions. One way to overcome this problem is to use simulated fault gouges in experiments, investigating a range of possible mineralogical compositions resulting from CO2-exposure. Previous studies have shown that the mechanical and transport properties of clay-rich fault gouges are significantly influenced by the mineralogy, particularly by the presence and relative amount of secondary phases, such as quartz and/or carbonate. In CCS settings, where dissolution and/or precipitation of carbonates may play an important role, the carbonate:clay ratio is expected to influence fault frictional behaviour. This is supported by the different behaviour of phyllosilicates, which generally show stable slip behaviour (aseismic), compared to carbonates, which have shown to become prone to unstable slip (potentially seismic) with increasing temperature. However, little is known about the mechanical and transport properties of carbonate/clay mixtures. We investigated the effect of the carbonate:clay ratio on fault friction, fault reactivation potential and slip stability, i.e. seismic vs. aseismic behaviour, as well as transmissivity evolution during and after fault reactivation. We used two types of starting material, derived from crushed Opalinus Claystone (Mont Terri, Switzerland): i) untreated samples consisting mainly of phyllosilicates (60%), quartz (~20%) and calcite (~15-25%) and ii) "leached" samples consisting of phyllosilicate (65%) and quartz (35%), where the removal of the calcite represents a worst-case scenario for rock/CO2/brine (dissolution) reactions. We performed triaxial direct shear experiments at relevant in-situ temperatures (60-120°C) under saturated conditions (Pp = 25 MPa), using demineralized water as pore fluid, at an effective normal stress (σn) of 50 MPa and shear velocities of 0.22 to 10.9 μm/s. Preliminary results show that the shear strength of the leached samples decreases by ~10-15% with respect to the natural, untreated clay samples. Typical steady-state friction coefficient values obtained for the natural samples are in the range 0.27-0.33, whereas for the leached samples they vary between 0.24 and 0.27. These values are significantly lower than typical friction coefficient values obtained for pure calcite (i.e. 0.62 to 0.71). Both natural and leached samples show velocity strengthening behaviour. The slip stability of the natural gouge appears to be slightly more temperature dependent, showing somewhat higher values of the stability (rate and state friction) parameter (a-b) for lower temperatures.

Contact Angle Measurements: an Alternative Approach Towards Understanding the Mechanism of Increased Drug Dissolution from Ethylcellulose Tablets Containing Surfactant and Exploring the Relationship Between Their Contact Angles and Dissolution Behaviors.

PubMed

Liu, Tiaotiao; Hao, Jingqiang; Yang, Baixue; Hu, Beibei; Cui, Zhixiang; Li, Sanming

2018-05-01

The addition of surfactant in tablet was a well-defined approach to improve drug dissolution rate. While the selected surfactant played a vital role in improving the wettability of tablet by medium, it was equally important to improve the dissolution rate by permeation effect due to production of pores or the reduced inter-particle adhesion. Furthermore, understanding the mechanism of dissolution rate increased was significant. In this work, contact angle measurement was taken up as an alternative approach for understanding the dissolution rate enhancement for tablet containing surfactant. Ethylcellulose, as a substrate, was used to prepare tablet. Four surfactants, sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), dodecyltrimethylammonium bromide (DTAB), and sodium lauryl sulfonate (SLS), were used. Berberine hydrochloride, metformin hydrochloride, and rutin were selected as model drugs. The contact angle of tablet in the absence and presence of surfactant was measured to explore the mechanism. The dissolution test was investigated to verify the mechanism and to establish a correlation with the contact angle. The result showed that the mechanism was the penetration effect rather than the wetting effect. The dissolution increased with a reduction in the contact angle. DTAB was found to obtain the highest level of dissolution enhancement and the lowest contact angle, while SDS, SDBS, and SLS were found to be the less effective in both dissolution enhancement and contact angle decrease. Therefore, contact angle was a good indicator for dissolution behavior besides exploring the mechanism of increased dissolution, which shows great potential in formula screening.

Effects of natural organic matter properties on the dissolution kinetics of zinc oxide nanoparticles

USGS Publications Warehouse

Jiang, Chuanjia; Aiken, George R.; Hsu-Kim, Heileen

2015-01-01

The dissolution of zinc oxide (ZnO) nanoparticles (NPs) is a key step of controlling their environmental fate, bioavailability, and toxicity. Rates of dissolution often depend upon factors such as interactions of NPs with natural organic matter (NOM). We examined the effects of 16 different NOM isolates on the dissolution kinetics of ZnO NPs in buffered potassium chloride solution using anodic stripping voltammetry to directly measure dissolved zinc concentrations. The observed dissolution rate constants (kobs) and dissolved zinc concentrations at equilibrium increased linearly with NOM concentration (from 0 to 40 mg C L–1) for Suwannee River humic and fulvic acids and Pony Lake fulvic acid. When dissolution rates were compared for the 16 NOM isolates, kobs was positively correlated with certain properties of NOM, including specific ultraviolet absorbance (SUVA), aromatic and carbonyl carbon contents, and molecular weight. Dissolution rate constants were negatively correlated to hydrogen/carbon ratio and aliphatic carbon content. The observed correlations indicate that aromatic carbon content is a key factor in determining the rate of NOM-promoted dissolution of ZnO NPs. The findings of this study facilitate a better understanding of the fate of ZnO NPs in organic-rich aquatic environments and highlight SUVA as a facile and useful indicator of NOM interactions with metal-based nanoparticles.

[Key physical parameters of hawthorn leaf granules by stepwise regression analysis method].

PubMed

Jiang, Qie-Ying; Zeng, Rong-Gui; Li, Zhe; Luo, Juan; Zhao, Guo-Wei; Lv, Dan; Liao, Zheng-Gen

2017-05-01

The purpose of this study was to investigate the effect of key physical properties of hawthorn leaf granule on its dissolution behavior. Hawthorn leaves extract was utilized as a model drug. The extract was mixed with microcrystalline cellulose or starch with the same ratio by using different methods. Appropriate amount of lubricant and disintegrating agent was added into part of the mixed powder, and then the granules were prepared by using extrusion granulation and high shear granulation. The granules dissolution behavior was evaluated by using equilibrium dissolution quantity and dissolution rate constant of the hypericin as the indicators. Then the effect of physical properties on dissolution behavior was analyzed through the stepwise regression analysis method. The equilibrium dissolution quantity of hypericin and adsorption heat constant in hawthorn leaves were positively correlated with the monolayer adsorption capacity and negatively correlated with the moisture absorption rate constant. The dissolution rate constants were decreased with the increase of Hausner rate, monolayer adsorption capacity and adsorption heat constant, and were increased with the increase of Carr index and specific surface area. Adsorption heat constant, monolayer adsorption capacity, moisture absorption rate constant, Carr index and specific surface area were the key physical properties of hawthorn leaf granule to affect its dissolution behavior. Copyright© by the Chinese Pharmaceutical Association.

Template-assisted mineral formation via an amorphous liquid phase precursor route

NASA Astrophysics Data System (ADS)

Amos, Fairland F.

The search for alternative routes to synthesize inorganic materials has led to the biomimetic route of producing ceramics. In this method, materials are manufactured at ambient temperatures and in aqueous solutions with soluble additives and insoluble matrix, similar to the biological strategy for the formation of minerals by living organisms. Using this approach, an anionic polypeptide additive was used to induce an amorphous liquid-phase precursor to either calcium carbonate or calcium phosphate. This precursor was then templated on either organic or inorganic substrates. Non-equilibrium morphologies, such as two-dimensional calcium carbonate films, one-dimensional calcium carbonate mesostructures and "molten" calcium phosphate spherulites were produced, which are not typical of the traditional (additive-free) solution grown crystals in the laboratory. In the study of calcium carbonate, the amorphous calcium carbonate mineral formed via the liquid-phase precursor, either underwent a dissolution-recrystallization event or a pseudo-solid-state transformation to produce different morphologies and polymorphs of the mineral. Discrete or aggregate calcite crystals were formed via the dissolution of the amorphous phase to allow the reprecipitation of the stable crystal. Non-equilibrium morphologies, e.g., films, mesotubules and mesowires were templated using organic and inorganic substrates and compartments. These structures were generated via an amorphous solid to crystalline solid transformation. Single crystalline tablets and mesowires of aragonite, which are reported to be found only in nature as skeletal structures of marine organisms, such as mollusk nacre and echinoderm teeth, were successfully synthesized. These biomimetic structures were grown via the polymer-induced liquid-phase precursor route in the presence of magnesium. Only low magnesium-bearing calcite was formed in the absence of the polymer. A similar approach of using a polymeric additive was implemented in calcium phosphate. Spherulitic crystals and films, seemingly formed from a molten state, were produced. These structures served as nucleating surfaces for the radial formation of calcium oxalate minerals. The composite calcium phosphate-calcium oxalate assemblies are similar to the core-shell structures found in certain kidney stones.

A model for interpretation of brine-dependent spontaneous imbibition experiments

NASA Astrophysics Data System (ADS)

Evje, S.; Hiorth, A.

2011-12-01

Previous experimental results for spontaneous imbibition experiments in the context of chalk cores have revealed a rather puzzling behavior: the oil recovery curves, both the shape as well as the steady state level which is reached, depend strongly on the brine composition. In particular, it has been demonstrated that Mg,SO42-, and Ca 2+ play a central role in this physico-chemical system. A good theoretical understanding of these experimental results, in terms of mathematical models that can suggest possible explanations of the lab experiments as well as predict behavior not yet tested in the lab, seems to still be lacking. The purpose of this paper is to try to shed light on some important modeling aspects. The model we propose is an extended version of the classical Buckley-Leverett (BL) equation for two-phase spontaneous imbibition where the water saturation equation has been coupled to a system of reaction-diffusion (RD) equations describing water-rock chemistry relevant for chalk core plugs. As far as water-rock chemistry is concerned we focus in this work on the combined effect of transport and dissolution/precipitation of calcite, magnesite, and anhydrite. The line we pursue is to couple changes of the wetting state, expressed in terms of the relative permeability and capillary pressure functions, to the water-rock chemistry behavior. More precisely, we build into the model the mechanism that the rock surface will become more water-wet at the places where dissolution of calcite takes place. In particular, we illustrate and analyze how different compositions of the imbibing brine then lead to different water-rock interaction scenarios which in turn gives qualitative and quantitative differences in the solution of the saturation equation describing spontaneous imbibition. Comparison with relevant experimental behavior is included as well as illustration of some possible interesting and non-trivial characteristic features of the model reflecting the nonlinear coupling mechanisms between the RD model for the water-rock chemistry and the BL equation for the water-oil transport.

Synergistic effect of reductive and ligand-promoted dissolution of goethite.

PubMed

Wang, Zimeng; Schenkeveld, Walter D C; Kraemer, Stephan M; Giammar, Daniel E

2015-06-16

Ligand-promoted dissolution and reductive dissolution of iron (hydr)oxide minerals control the bioavailability of iron in many environmental systems and have been recognized as biological iron acquisition strategies. This study investigated the potential synergism between ligands (desferrioxamine B (DFOB) or N,N'-Di(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED)) and a reductant (ascorbate) in goethite dissolution. Batch experiments were performed at pH 6 with ligand or reductant alone and in combination, and under both oxic and anoxic conditions. Goethite dissolution in the presence of reductant or ligand alone followed classic surface-controlled dissolution kinetics. Ascorbate alone does not promote goethite dissolution under oxic conditions due to rapid reoxidation of Fe(II). The rate coefficients for goethite dissolution by ligands are closely correlated with the stability constants of the aqueous Fe(III)-ligand complexes. A synergistic effect of DFOB and ascorbate on the rate of goethite dissolution was observed (total rates greater than the sum of the individual rates), and this effect was most pronounced under oxic conditions. For HBED, macroscopically the synergistic effect was hidden due to the inhibitory effect of ascorbate on HBED adsorption. After accounting for the concentrations of adsorbed ascorbate and HBED, a synergistic effect could still be identified. The potential synergism between ligand and reductant for iron (hydr)oxide dissolution may have important implications for iron bioavailability in soil environments.

Final report for DOE Grant No. DE-FG02-07ER64404 - Field Investigations of Microbially Facilitated Calcite Precipitation for Immobilization of Strontium-90 and Other Trace Metals in the Subsurface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Robert W; Fujita, Yoshiko; Ginn, Timothy R

2012-10-12

Subsurface radionuclide and metal contaminants throughout the U.S. Department of Energy (DOE) complex pose one of DOE's greatest challenges for long-term stewardship. One promising stabilization mechanism for divalent ions, such as the short-lived radionuclide 90Sr, is co-precipitation in calcite. We have previously found that that nutrient addition can stimulate microbial ureolytic activity that this activity accelerates calcite precipitation and co-precipitation of Sr, and that higher calcite precipitation rates can result in increased Sr partitioning. We have conducted integrated field, laboratory, and computational research to evaluate the relationships between ureolysis and calcite precipitation rates and trace metal partitioning under environmentally relevantmore » conditions, and investigated the coupling between flow/flux manipulations and precipitate distribution. A field experimental campaign conducted at the Integrated Field Research Challenge (IFRC) site located at Rifle, CO was based on a continuous recirculation design; water extracted from a down-gradient well was amended with urea and molasses (a carbon and electron donor) and re-injected into an up-gradient well. The goal of the recirculation design and simultaneous injection of urea and molasses was to uniformly accelerate the hydrolysis of urea and calcite precipitation over the entire inter-wellbore zone. The urea-molasses recirculation phase lasted, with brief interruptions for geophysical surveys, for 12 days followed by long-term monitoring which continued for 13 months. Following the recirculation phase we found persistent increases in urease activity (as determined from 14C labeled laboratory urea hydrolysis rates) in the upper portion of the inter-wellbore zone. We also observed an initial increase (approximately 2 weeks) in urea concentration associated with injection activities followed by decreasing urea concentration and associated increases in ammonium and dissolved inorganic carbon (DIC) following the termination of injection. Based on the loss of urea and the appearance of ammonium, a first order rate constant for urea hydrolysis of 0.18 day-1 rate with an associate Rf for ammonium of 11 were estimated. This rate constant is approximately 6 times higher than estimated for previous field experiments conducted in eastern Idaho. Additionally, DIC carbon isotope ratios were measured for the groundwater. Injected urea had a ´13C of 40.7±0.4 ° compared to background groundwater DIC of ´13C of -16.0±0.2°. Observed decreases in groundwater DIC ´13C of up to -19.8° followed temporal trends similar to those observed for ammonium and suggest that both the increase in ammonium and the sift in ´13C are the result of urea hydrolysis. Although direct observation of calcite precipitation was not possible because of the high pre-existing calcite content in the site sediments, an observed ´13C decrease for solid carbonates from sediment samples collect following urea injection (compared to pre-injection values) is likely the result of the incorporation of inorganic carbon derived from urea hydrolysis into newly formed solid carbonates.« less

Dissolution of Fe(III) (hydr) oxides by metal-EDTA complexes

NASA Astrophysics Data System (ADS)

Ngwack, Bernd; Sigg, Laura

1997-03-01

The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA CaEDTA ≫ PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced.

Solid solution partitioning of Sr2+, Ba2+, and Cd2+ to calcite

USGS Publications Warehouse

Tesoriero, A.J.; Pankow, J.F.

1996-01-01

Although solid solutions play important roles in controlling the concentrations of minor metal ions in natural waters, uncertainties regarding their compositions, thermodynamics, and kinetics usually prevent them from being considered. A range of precipitation rates was used here to study the nonequilibrium and equilibrium partitioning behaviors of Sr2+, Ba2+, and Cd2+ to calcite (CaCO3(s)). The distribution coefficient of a divalent metal ion Me2+ for partitioning from an aqueous solution into calcite is given by DMe = (XMeCO3(s)/[Me2+])/(XCaCO3(s)/[Ca 2+]). The X values are solid-phase mole fractions; the bracketed values are the aqueous molal concentrations. In agreement with prior work, at intermediate to high precipitation rates R (nmol/mg-min), DSr, DBa, and DCd were found to depend strongly on R. At low R, the values of DSr, DBa, and DCd became constant with R. At 25??C, the equilibrium values for DSr, DBa, and DCd for dilute solid solutions were estimated to be 0.021 ?? 0.003, 0.012 ?? 0.005, and 1240 ?? 300, respectively. Calculations using these values were made to illustrate the likely importance of partitioning of these ions to calcite in groundwater systems. Due to its large equilibrium DMe value, movement of Cd2+ will be strongly retarded in aquifers containing calcite; Sr2+ and Ba2+ will not be retarded nearly as much.

An upscaled rate law for magnesite dissolution in heterogeneous porous media

NASA Astrophysics Data System (ADS)

Wen, Hang; Li, Li

2017-08-01

Spatial heterogeneity in natural subsurface systems governs water fluxes and residence time in reactive zones and therefore determines effective rates of mineral dissolution. Extensive studies have documented mineral dissolution rates in natural systems, although a general rate law has remain elusive. Here we fill this gap by answering two questions: (1) how and to what extent does spatial heterogeneity affect water residence time and effectively-dissolving surface area? (2) what is the upscaled rate law that quantifies effective dissolution rates in natural, heterogeneous media? With data constraints from experimental work, 240 Monte-Carlo numerical experiments of magnesite dissolution within quartz matrix were run with spatial distributions characterized by a range of permeability variance σ2lnκ (0.5-6.0) and correlation length (2-50 cm). Although the total surface area and global residence time (τa) are the same in all experiments, the water fluxes through reactive magnesite zones varies between 0.7 and 72.8% of the total water fluxes. Highly heterogeneous media with large σ2lnκ and long λ divert water mostly into non-reactive preferential flow paths, therefore bypassing and minimizing flow in low permeability magnesite zones. As a result, the water residence time in magnesite zones (i.e., reactive residence time τa,r) is long and magnesite dissolution quickly reaches local equilibrium, which leads to small effective surface area and low dissolution rates. Magnesite dissolution rates in heterogeneous media vary from 2.7 to 100% of the rates in the equivalent homogeneous media, with effectively-dissolving surface area varying from 0.18 to 6.83 m2 (out of 51.71 m2 total magnesite surface area). Based on 240 numerical experiments and 45 column experiments, a general upscaled rate law in heterogeneous media, RMgCO3,ht =kAe,hm(1 - exp(-τa/τa,r))α, was derived to quantify effective dissolution rates. The dissolution rates in heterogeneous media are a function of the rate constants k being those measured under well-mixed conditions, effective surface area in equivalent homogeneous media Ae,hm, and the heterogeneity factor (1 - exp(-τa/τa,r))α. The heterogeneity factor quantify heterogeneity effects and depends on the relative magnitude of global residence time (τa) and reactive residence time (τa,r), as well as the shape factor α(= 5 σlnκ2) of the gamma distribution for reactive residence times. Exponential forms of rate laws have been used at the micro-scale describing direct interactions among water and mineral surface, and at the catchment scale describing weathering rates and concentration-discharge relationships. These observations highlight the key role of mineral-water contact time in determining dissolution rates at different scales. This work also emphasizes the importance of critical interfaces between reactive and non-reactive zones as determined by the details of spatial patterns and effective surface area as a scaling factor that quantifies dissolution rates in heterogeneous media across scales.

Estimating the time for dissolution of spent fuel exposed to unlimited water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leider, H.R.; Nguyen, S.N.; Stout, R.B.

1991-12-01

The release of radionuclides from spent fuel cannot be precisely predicted at this point because a satisfactory dissolution model based on specific chemical processes is not yet available. However, preliminary results on the dissolution rate of UO{sub 2} and spent fuel as a function of temperature and water composition have recently been reported. This information, together with data on fragment size distribution of spent fuel, are used to estimate the dissolution response of spent fuel in excess flowing water within the framework of a simple model. In this model, the reaction/dissolution front advances linearly with time and geometry is preserved.more » This also estimates the dissolution rate of the bulk of the fission products and higher actinides, which are uniformly distributed in the UO{sub 2} matrix and are presumed to dissolve congruently. We have used a fuel fragment distribution actually observed to calculate the time for total dissolution of spent fuel. A worst-case estimate was also made using the initial (maximum) rate of dissolution to predict the total dissolution time. The time for total dissolution of centimeter size particles is estimated to be 5.5 {times} 10{sup 4} years at 25{degrees}C.« less

Role of fluids in experimental calcite-bearing faults at seismic deformation conditions.

NASA Astrophysics Data System (ADS)

Violay, M.; Nielsen, S.; Cinti, D.; Spagnuolo, E.; Di Toro, G.; Smith, S.

2012-04-01

Fluids play a fundamental physical (fluid pressure, temperature buffering, etc.) and chemical (dissolution, hydrolytic weakening, etc.) role in controlling fault strength and earthquake nucleation, propagation and arrest. However, due to technical challenges, the influence of water at deformation conditions typical of earthquakes (i.e., slip rates of 1 m/s, displacements of 0.1-5 m, normal stress of tens of MPa) remains poorly constrained experimentally. Here we present results from high velocity friction experiments performed with a rotary shear apparatus (SHIVA: Slow to HIgh Velocity (friction) Apparatus) on Carrara marble. SHIVA is equipped with (1) an environmental/vacuum chamber to perform experiments in the absence of room-humidity, (2) a pressure vessel to perform experiments with fluids (up to 15 MPa confining pressure), including devices to determine fluid composition (Ca2+, Mg2+, HCO3-, etc). Experiments were conducted on hollow cylinders (50/30 mm ext/int diameter) of Carrara (98% calcite) marble at velocities of 1-6.5 m/s, displacements up to a few meters, normal stresses up to 40 MPa and fluid pressures between 0 (under vacuum) and 15 MPa (fluid-saturated conditions, with H2O in chemical equilibrium with the marble). Rock and fluid samples were recovered for post-run analysis to determine deformation mechanisms and changes in fluid composition. Under these deformation conditions: 1) the friction coefficient decays rapidly from a peak (= static) μp ~ 0.8 at the initiation of sliding towards a steady-state μss ~ 0.1. The absolute values of both peak and steady-state friction are not significantly influenced by the presence of fluids; 2) the decay from peak to steady-state friction is more abrupt in presence of fluids; 3) during deceleration of the friction apparatus, the friction coefficient recovers almost instantaneously to a value, μr, of 0.2-0.6 ( strength recovery) resulting in a small static stress drop. Strength recovery is smaller in the presence of fluids. 4) the fluid (H2O) after the experiment is enriched in Ca2+, Mg2+ and HCO3-. This chemical evolution suggests breakdown reactions (decarbonation of calcite) promoted by frictional heating and controlled by the presence of H2O. We conclude that the large decrease in friction and abrupt weakening, especially in the presence of fluids, indicates that calcite-bearing rocks are prone to earthquake nucleation and seismic rupture propagation (see the L'Aquila 2009 earthquake sequence). The chemical changes observed in water springs after large earthquakes in carbonatic rocks is similar to those found in these experiments, suggesting that the weakening mechanisms triggered in the experiments might occur in nature.

In Situ Observation of Dissolution of Oxide Inclusions in Steelmaking Slags

NASA Astrophysics Data System (ADS)

Sharma, Mukesh; Mu, Wangzhong; Dogan, Neslihan

2018-05-01

Better understanding of removal of non-metallic inclusions is of importance in the steelmaking process to control the cleanliness of steel. In this study, the dissolution rate of Al2O3 and Al2TiO5 inclusions in a liquid CaO-SiO2-Al2O3 slag was measured using high-temperature confocal scanning laser microscopy (HT-CSLM) at 1550°C. The dissolution rate of inclusions is expressed as a function of the rate of decrease of the radius of solid particles with time. It is found that Al2O3 inclusions have a slower dissolution rate than that of Al2TiO5 inclusions at 1550°C. The rate-limiting steps are investigated in terms of a shrinking core model. It is shown that the rate-limiting step for dissolution of both inclusion types is mass transfer in the slag at 1550°C.

Dissolution enhancement of gliclazide using pH change approach in presence of twelve stabilizers with various physico-chemical properties.

PubMed

Talari, Roya; Varshosaz, Jaleh; Mostafavi, Seyed Abolfazl; Nokhodchi, Ali

2009-01-01

The micronization using milling process to enhance dissolution rate is extremely inefficient due to a high energy input, and disruptions in the crystal lattice which can cause physical or chemical instability. Therefore, the aim of the present study is to use in situ micronization process through pH change method to produce micron-size gliclazide particles for fast dissolution hence better bioavailability. Gliclazide was recrystallized in presence of 12 different stabilizers and the effects of each stabilizer on micromeritic behaviors, morphology of microcrystals, dissolution rate and solid state of recrystallized drug particles were investigated. The results showed that recrystallized samples showed faster dissolution rate than untreated gliclazide particles and the fastest dissolution rate was observed for the samples recrystallized in presence of PEG 1500. Some of the recrystallized drug samples in presence of stabilizers dissolved 100% within the first 5 min showing at least 10 times greater dissolution rate than the dissolution rate of untreated gliclazide powders. Micromeritic studies showed that in situ micronization technique via pH change method is able to produce smaller particle size with a high surface area. The results also showed that the type of stabilizer had significant impact on morphology of recrystallized drug particles. The untreated gliclazide is rod or rectangular shape, whereas the crystals produced in presence of stabilizers, depending on the type of stabilizer, were very fine particles with irregular, cubic, rectangular, granular and spherical/modular shape. The results showed that crystallization of gliclazide in presence of stabilizers reduced the crystallinity of the samples as confirmed by XRPD and DSC results. In situ micronization of gliclazide through pH change method can successfully be used to produce micron-sized drug particles to enhance dissolution rate.

General solution for diffusion-controlled dissolution of spherical particles. 1. Theory.

PubMed

Wang, J; Flanagan, D R

1999-07-01

Three classical particle dissolution rate expressions are commonly used to interpret particle dissolution rate phenomena. Our analysis shows that an assumption used in the derivation of the traditional cube-root law may not be accurate under all conditions for diffusion-controlled particle dissolution. Mathematical analysis shows that the three classical particle dissolution rate expressions are approximate solutions to a general diffusion layer model. The cube-root law is most appropriate when particle size is much larger than the diffusion layer thickness, the two-thirds-root expression applies when the particle size is much smaller than the diffusion layer thickness. The square-root expression is intermediate between these two models. A general solution to the diffusion layer model for monodispersed spherical particles dissolution was derived for sink and nonsink conditions. Constant diffusion layer thickness was assumed in the derivation. Simulated dissolution data showed that the ratio between particle size and diffusion layer thickness (a0/h) is an important factor in controlling the shape of particle dissolution profiles. A new semiempirical general particle dissolution equation is also discussed which encompasses the three classical particle dissolution expressions. The success of the general equation in explaining limitations of traditional particle dissolution expressions demonstrates the usefulness of the general diffusion layer model.

Morphological evolution of dissolving feldspar particles with anisotropic surface kinetics and implications for dissolution rate normalization and grain size dependence: A kinetic modeling study

NASA Astrophysics Data System (ADS)

Zhang, Li; Lüttge, Andreas

2009-11-01

With previous two-dimensional (2D) simulations based on surface-specific feldspar dissolution succeeding in relating the macroscopic feldspar kinetics to the molecular-scale surface reactions of Si and Al atoms ( Zhang and Lüttge, 2008, 2009), we extended our modeling effort to three-dimensional (3D) feldspar particle dissolution simulations. Bearing on the same theoretical basis, the 3D feldspar particle dissolution simulations have verified the anisotropic surface kinetics observed in the 2D surface-specific simulations. The combined effect of saturation state, pH, and temperature on the surface kinetics anisotropy has been subsequently evaluated, found offering diverse options for morphological evolution of dissolving feldspar nanoparticles with varying grain sizes and starting shapes. Among the three primary faces on the simulated feldspar surface, the (1 0 0) face has the biggest dissolution rate across an extensively wide saturation state range and thus acquires a higher percentage of the surface area upon dissolution. The slowest dissolution occurs to either (0 0 1) or (0 1 0) faces depending on the bond energies of Si-(O)-Si ( ΦSi-O-Si/ kT) and Al-(O)-Si ( ΦAl-O-Si/ kT). When the ratio of ΦSi-O-Si/ kT to ΦAl-O-Si/ kT changes from 6:3 to 7:5, the dissolution rates of three primary faces change from the trend of (1 0 0) > (0 1 0) > (0 0 1) to the trend of (1 0 0) > (0 0 1) > (0 1 0). The rate difference between faces becomes more distinct and accordingly edge rounding becomes more significant. Feldspar nanoparticles also experience an increasing degree of edge rounding from far-from-equilibrium to close-to-equilibrium. Furthermore, we assessed the connection between the continuous morphological modification and the variation in the bulk dissolution rate during the dissolution of a single feldspar particle. Different normalization treatments equivalent to the commonly used mass, cube assumption, sphere assumption, geometric surface area, and reactive surface area normalizations have been used to normalize the bulk dissolution rate. For each of the treatments, time consistence and grain size dependence of the normalized dissolution rate have been evaluated and the results revealed significant dependences on the magnitude of surface kinetic anisotropy under differing environmental conditions. In general, the normalized dissolution rates are strongly dependent on grain size. Time-consistent normalization treatment varies with the investigated condition. The modeling results suggest that the sphere-, cube-, and BET-normalized dissolution rates are appropriate under the far-from-equilibrium conditions at low pH where these normalizations are time-consistent and are slightly dependent on grain size.

Olivine dissolution from Indian dunite in saline water.

PubMed

Agrawal, Amit Kumar; Mehra, Anurag

2016-11-01

The rate and mechanism of olivine dissolution was studied using naturally weathered dunite FO 98.21 (Mg 1.884 Fe 0.391 SiO 4 ) from an Indian source, that also contains serpentine mineral lizardite. A series of batch dissolution experiments were carried out to check the influence of temperature (30-75 ∘ C), initial dunite concentration (0.5 and 20 g/L), and salinity (0-35 g/L NaCl) under fixed head space CO 2 pressure (P[Formula: see text] = 1 barg) on dunite dissolution. Dissolved Mg, Si, and Fe concentrations were determined by inductive coupled plasma atomic emission spectroscopy. End-product solids were characterized by scanning electron microscopy and X-ray diffraction. Initially, rates of dissolution of Si and Mg were observed to be in stoichiometric proportion. After 8 h, the dissolution rate was observed to decline. At the end of the experiment (504 h), an amorphous silica-rich layer was observed over the dunite surface. This results in decay of the dissolution rate. The operating conditions (i.e., salinity, temperature, and mineral loading) affect the dissolution kinetics in a very complex manner because of which the observed experimental trends do not exhibit a direct trend.

Mass transfer constraints on the chemical evolution of an active hydrothermal system, Valles caldera, New Mexico

USGS Publications Warehouse

White, A.F.; Chuma, N.J.; Goff, F.

1992-01-01

Partial equilibrium conditions occur between fluids and secondary minerals in the Valles hydrothermal system, contained principally in the Tertiary rhyolitic Bandelier Tuff. The mass transfer processes are governed by reactive phase compositions, surface areas, water-rock ratios, reaction rates, and fluid residence times. Experimental dissolution of the vitric phase of the tuff was congruent with respect to Cl in the solid and produced reaction rates which obeyed a general Arrhenius release rate between 250 and 300??C. The 18O differences between reacted and unreacted rock and fluids, and mass balances calculations involving Cl in the glass phase, produced comparable water-rock ratios of unity, confirming the importance of irreversible reaction of the vitric tuff. A fluid residence time of approximately 2 ?? 103 years, determined from fluid reservoir volume and discharge rates, is less than 0.2% of the total age of the hydrothermal system and denotes a geochemically and isotopically open system. Mass transfer calculations generally replicated observed reservoir pH, Pco2, and PO2 conditions, cation concentrations, and the secondary mineral assemblage between 250 and 300??C. The only extraneous component required to maintain observed calcite saturation and high Pco2 pressures was carbon presumably derived from underlying Paleozoic limestones. Phase rule constraints indicate that Cl was the only incompatible aqueous component not controlled by mineral equilibrium. Concentrations of Cl in the reservoir directly reflect mass transport rates as evidenced by correlations between anomalously high Cl concentrations in the fluids and tuff in the Valles caldera relative to other hydrothermal systems in rhyolitic rocks. ?? 1992.

Dissolution of Uranium Oxides Under Alkaline Oxidizing Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Steven C.; Peper, Shane M.; Douglas, Matthew

2009-11-01

Bench scale experiments were conducted to determine the dissolution characteristics of uranium oxide powders (UO2, U3O8, and UO3) in aqueous peroxide-carbonate solutions. Experimental parameters included H2O2 concentration, carbonate counter cation (NH4+, Na+, K+, and Rb+), and pH. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M. The three uranium oxide powders exhibited different dissolution patterns however, UO3 exhibited prompt complete dissolution. Carbonate counter cation affected the dissolution kinetics. There is minimal impact of solution pH, over the range 8.8 to 10.6, on initial dissolution rate.

Effect of chemical composition of man-made vitreous fibers on the rate of dissolution in vitro at different pHs.

PubMed

Christensen, V R; Jensen, S L; Guldberg, M; Kamstrup, O

1994-10-01

Measurements of rates of dissolution of typical insulation wool fibers (glasswool and basalt based stonewool) and an experimental fiber were made using a flow-through equipment. The liquids used were a modified Gamble's solution, adjusted to pH 4.8 and 7.7 +/- 0.2, respectively. The dissolution of SiO2 and CaO was determined over periods of up to three months. The rate of dissolution of stonewool fibers was lower than that of glasswool fibers at pH 7.7, whereas the opposite was true at pH 4.8. The stonewool fibers dissolve congruently, but glasswool fibers tend to dissolve with leaching. The rates of dissolution of fibers of different compositions, including insulation wool (glasswool, basalt-based stonewool, slagwool) and experimental fibers were screened using a stationary set-up. Both the chemical composition and pH influenced the rates of dissolution. At pH 7.7 alumina was a determining component and at pH 4.8 the content of SiO2 and CaO was determinant. One experimental fiber with a high content of alumina was an exception having a fairly high rate of dissolution both at pH 4.8 and 7.7.

Effect of chemical composition of man-made vitreous fibers on the rate of dissolution in vitro at different pHs.

PubMed Central

Christensen, V R; Jensen, S L; Guldberg, M; Kamstrup, O

1994-01-01

Measurements of rates of dissolution of typical insulation wool fibers (glasswool and basalt based stonewool) and an experimental fiber were made using a flow-through equipment. The liquids used were a modified Gamble's solution, adjusted to pH 4.8 and 7.7 +/- 0.2, respectively. The dissolution of SiO2 and CaO was determined over periods of up to three months. The rate of dissolution of stonewool fibers was lower than that of glasswool fibers at pH 7.7, whereas the opposite was true at pH 4.8. The stonewool fibers dissolve congruently, but glasswool fibers tend to dissolve with leaching. The rates of dissolution of fibers of different compositions, including insulation wool (glasswool, basalt-based stonewool, slagwool) and experimental fibers were screened using a stationary set-up. Both the chemical composition and pH influenced the rates of dissolution. At pH 7.7 alumina was a determining component and at pH 4.8 the content of SiO2 and CaO was determinant. One experimental fiber with a high content of alumina was an exception having a fairly high rate of dissolution both at pH 4.8 and 7.7. PMID:7882962

Preparation, characterization and in vivo evaluation of amorphous atorvastatin calcium nanoparticles using supercritical antisolvent (SAS) process.

PubMed

Kim, Min-Soo; Jin, Shun-Ji; Kim, Jeong-Soo; Park, Hee Jun; Song, Ha-Seung; Neubert, Reinhard H H; Hwang, Sung-Joo

2008-06-01

In this work, amorphous atorvastatin calcium nanoparticles were successfully prepared using the supercritical antisolvent (SAS) process. The effect of process variables on particle size and distribution of atorvastatin calcium during particle formation was investigated. Solid state characterization, solubility, intrinsic dissolution, powder dissolution studies and pharmacokinetic study in rats were performed. Spherical particles with mean particle size ranging between 152 and 863 nm were obtained by varying process parameters such as precipitation vessel pressure and temperature, drug solution concentration and feed rate ratio of CO2/drug solution. XRD, TGA, FT-IR, FT-Raman, NMR and HPLC analysis indicated that atorvastatin calcium existed as anhydrous amorphous form and no degradation occurred after SAS process. When compared with crystalline form (unprocessed drug), amorphous atorvastatin calcium nanoparticles were of better performance in solubility and intrinsic dissolution rate, resulting in higher solubility and faster dissolution rate. In addition, intrinsic dissolution rate showed a good correlation with the solubility. The dissolution rates of amorphous atorvastatin calcium nanoparticles were highly increased in comparison with unprocessed drug by the enhancement of intrinsic dissolution rate and the reduction of particle size resulting in an increased specific surface area. The absorption of atorvastatin calcium after oral administration of amorphous atorvastatin calcium nanoparticles to rats was markedly increased.

The differences between the branded and generic medicines using solid dosage forms: In-vitro dissolution testing

PubMed Central

Al Ameri, Mubarak Nasser; Nayuni, Nanda; Anil Kumar, K.G.; Perrett, David; Tucker, Arthur; Johnston, Atholl

2011-01-01

Introduction Dissolution is the amount of substance that goes into solution per unit time under standardised conditions of liquid/solid interface, solvent composition and temperature. Dissolution is one of the most important tools to predict the in-vivo bioavailability and in some cases to determine bioequivalence and assure interchangeability. Aim To compare the differences in dissolution behaviour of solid dosage forms between innovators (reference products) and their generic counterparts (tested products). Methods Four replicates for each batch of 37 tested medicines was carried out using A PT-DT70 dissolution tester from Pharma Test. A total of 13 branded medicines and 24 generic counterparts were obtained locally and internationally to detect any differences in their dissolution behaviour. They were tested according to the British Pharmacopeia, European Pharmacopeia and the US Pharmacopeia with the rate of dissolution determined by ultra-violet Spectrophotometery. Results Most tested medicines complied with the pharmacopoeial specifications and achieved 85% dissolution in 60 min. However, some generic medicines showed significant differences in dissolution rate at 60 and 120 min. Many generic medicines showed a slower dissolution rate than their branded counterparts such as the generic forms of omeprazole 20 mg. Some showed an incomplete dissolution such as the generic form of nifedipine 10 mg. Other generics showed faster dissolution rate than their branded counterpart such as the generic forms of meloxicam 15 mg. Moreover, some generics from different batches of the same manufacturer showed significant differences in their dissolution rate such as the generic forms of meloxicam 7.5 mg. Nevertheless, some generic medicines violated the EMA and the FDA guidelines for industry when they failed to achieve 85% dissolution at 60 min, such as the generic form of diclofenac sodium 50 mg. Conclusion Most medicines in this study complied with the pharmacopeial limits. However, some generics dissolved differently than their branded counterparts. This can clearly question the interchangeability between the branded and its generic counterpart or even among generics. PMID:25755988

The Northwest Africa (NWA) 5790 meteorite: A mesostasis-rich nakhlite with little or no Martian aqueous alteration

NASA Astrophysics Data System (ADS)

Tomkinson, Tim; Lee, Martin R.; Mark, Darren F.; Dobson, Katherine J.; Franchi, Ian A.

2015-02-01

Northwest Africa (NWA) 5790 is the most recently discovered member of the nakhlite group. Its mineralogy differs from the other nakhlites with a high abundance mesostasis (38.1 ± 3.6 vol%) and scarcity of olivine (4.0 ± 2.2 vol%). Furthermore, zoning of augite phenocrysts, and other petrographic and chemical characteristics suggest that NWA 5790 samples the chilled margin of its parent lava flow/sill. NWA 5790 contains calcite and rare clay minerals that are evidence for its exposure to liquid water. The calcite forms a cement to coatings of dust on the outer surface of the find and extends into the interior of the meteorite within veins. The presence of microbial remains within the coating confirms that the dust and its carbonate cement are terrestrial in origin, consistent with the carbon and oxygen isotope composition of the calcite. The clay minerals are finely crystalline and comprise ~0.003 vol% of the meteorite. δD values of the clay minerals range from -212 ± 109‰ to -96 ± 132‰, and cannot be used to distinguish between a terrestrial or Martian origin. As petrographic results are also not definitive, we conclude that secondary minerals produced by Martian groundwaters are at best very rare within NWA 5790. The meteorite has therefore sampled a region of the lava flow/sill with little or no exposure to the aqueous solutions that altered other nakhlites. This isolation could relate to the scarcity of olivine in NWA 5790 because dissolution of olivine in other nakhlites by Martian groundwaters enhanced their porosity and permeability, and provided solutes for secondary minerals.

Thermochemical sulphate reduction can improve carbonate petroleum reservoir quality

NASA Astrophysics Data System (ADS)

Jiang, Lei; Worden, Richard H.; Yang, Changbing

2018-02-01

Interest in the creation of secondary pore spaces in petroleum reservoirs has increased because of a need to understand deeper and more complex reservoirs. The creation of new secondary porosity that enhances overall reservoir quality in deeply buried carbonate reservoirs is controversial and some recent studies have concluded it is not an important phenomenon. Here we present petrography, geochemistry, fluid inclusion data, and fluid-rock interaction reaction modeling results from Triassic Feixianguan Formation, Sichuan Basin, China, core samples and explore the relative importance of secondary porosity due to thermochemical sulphate reduction (TSR) during deep burial diagenesis. We find that new secondary pores result from the dissolution of anhydrite and possibly from dissolution of the matrix dolomite. Assuming porosity before TSR was 16% and the percentage of anhydrite was 6%, modelling shows that, due to TSR, 1.6% additional porosity was created that led to permeability increasing from 110 mD (range 72-168 mD within a 95% confidence interval) to 264 mD (range 162-432 mD within a 95% confidence interval). Secondary porosity results from the density differences between reactant anhydrite and product calcite, the addition of new water during TSR, and the generation of acidity during the reaction of new H2S with the siderite component in pre-existing dolomite in the reservoir. Fluid pressure was high during TSR, and approached lithostatic pressure in some samples; this transient overpressure may have led to the maintenance of porosity due to the inhibition of compactional processes. An additional 1.6% porosity is significant for reserve calculations, especially considering that it occurs in conjunction with elevated permeability that results in faster flow rates to the production wells.

Bryozoans as indicators of global change: predictable shifts in morphology and carbonate mineralogy in response to warming and ocean acidification

NASA Astrophysics Data System (ADS)

Swezey, D. S.; Bean, J. R.; Ninokawa, A. T.; Sanford, E.

2014-12-01

Recent studies have documented variation in skeletal structure and carbonate mineralogy across a broad range of marine invertebrate taxa. Intraspecific changes in growth, morphology, and carbonate composition may occur in response to local and global changes in temperature, carbonate saturation state, and nutrient availability. Recurring upwelling along the west coast of the United States creates an alongshore mosaic of Ocean Acidification (OA), which may induce plastic responses and/or select for adaptive skeletal construction that can withstand pCO2 and temperature changes. Calcifying bryozoans provide a unique study system for investigating carbonate precipitation under variable conditions. Using a newly constructed flow-through CO2 control apparatus, we tested whether three laboratory-reared populations of the bryozoans Membranipora serrilamella, M. tuberculata and Celleporella cornuta showed differences in growth, calcification, and skeletal composition in response to simulated future OA conditions. Under elevated pCO2 (1200 μatm), bryozoans showed no significant differences in growth rate (new zooids added) compared to clones reared under current atmospheric values. However, C. cornuta colonies raised under high CO2 were significantly lighter, with less carbonate per zooid compared to colonies grown in present-day conditions (400 μatm). Scanning electron microscopy revealed that elevated pCO2 led to dissolution of bryozoan skeletons, which did not occur at 400 μatm. Structural changes in M. tuberculata and C. cornuta colonies may be related to the dissolution of high magnesium calcite skeletal components. Analyses of bryozoan morphological responses along with environmental proxies (δ13C, δ18O, and Mg/Ca ratios) could yield high resolution records of temperature and pH, which could be used to help reconstruct environmental variation along the California coast.

Impact of CO2 injection protocol on fluid-solid reactivity: high-pressure and temperature microfluidic experiments in limestone

NASA Astrophysics Data System (ADS)

Jimenez-Martinez, Joaquin; Porter, Mark; Carey, James; Guthrie, George; Viswanathan, Hari

2017-04-01

Geological sequestration of CO2 has been proposed in the last decades as a technology to reduce greenhouse gas emissions to the atmosphere and mitigate the global climate change. However, some questions such as the impact of the protocol of CO2 injection on the fluid-solid reactivity remain open. In our experiments, two different protocols of injection are compared at the same conditions (8.4 MPa and 45 C, and constant flow rate 0.06 ml/min): i) single phase injection, i.e., CO2-saturated brine; and ii) simultaneous injection of CO2-saturated brine and scCO2. For that purpose, we combine a unique high-pressure/temperature microfluidics experimental system, which allows reproducing geological reservoir conditions in geo-material substrates (i.e., limestone, Cisco Formation, Texas, US) and high resolution optical profilometry. Single and multiphase flow through etched fracture networks were optically recorded with a microscope, while processes of dissolution-precipitation in the etched channels were quantified by comparison of the initial and final topology of the limestone micromodels. Changes in hydraulic conductivity were quantified from pressure difference along the micromodel. The simultaneous injection of CO2-saturated brine and scCO2, reduced the brine-limestone contact area and also created a highly heterogeneous velocity field (i.e., low velocities regions or stagnation zones, and high velocity regions or preferential paths), reducing rock dissolution and enhancing calcite precipitation. The results illustrate the contrasting effects of single and multiphase flow on chemical reactivity and suggest that multiphase flow by isolating parts of the flow system can enhance CO2 mineralization.

The effect of iron content and dissolved O2 on dissolution rates of clinopyroxene at pH 5.8 and 25°C: Preliminary results

USGS Publications Warehouse

Hoch, A.R.; Reddy, M.M.; Drever, J.I.

1996-01-01

Dissolution experiments using augite (Mg0.87Ca0.85Fe0.19Na0.09Al0.03Si2O6) and diopside (Mg0.91Ca0.93Fe0.07Na0.03Al0.03Si2O6) were conducted in flow-through reactors (5-ml/h flow rate). A pH of 5.8 was maintained by bubbling pure CO2 through a solution of 0.01 M KHCO3 at 25°C. Two experiments were run for each pyroxene type. In one experiment dissolved O2 concentration in reactors was 0.6 (±0.1) ppm and in the second dissolved O2 was 1.5 (±0.1) ppm. After 60 days, augite dissolution rates (based on Si release) were approximately three times greater in the 1.5 ppm. dissolved O2 experiments than in the sealed experiments. In contrast, diopside dissolution rates were independent of dissolved O2 concentrations. Preliminary results from the augite experiments suggest that dissolution rate is directly related to oxidation of iron. This effect was not observed in experiments performed on iron-poor diopside. Additionally, dissolution rates of diopside were much slower than those of augite, again suggesting a relationship between Fe content, Fe oxidation and dissolution rates.

Does the stepwave model predict mica dissolution kinetics?

NASA Astrophysics Data System (ADS)

Kurganskaya, Inna; Arvidson, Rolf S.; Fischer, Cornelius; Luttge, Andreas

2012-11-01

The micas are a unique class of minerals because of their layered structure. A frequent question arising in mica dissolution studies is whether this layered structure radically changes the dissolution mechanism. We address this question here, using data from VSI and AFM experiments involving muscovite to evaluate crystallographic controls on mica dissolution. These data provide insight into the dissolution process, and reveal important links to patterns of dissolution observed in framework minerals. Under our experimental conditions (pH 9.4, 155 °C), the minimal global rate of normal surface retreat observed in VSI data was 1.42 × 10-10 mol/m2/s (σ = 27%) while the local rate observed at deep etch pits reached 416 × 10-10 mol/m2/s (σ = 49%). Complementary AFM data clearly show crystallographic control of mica dissolution, both in terms of step advance and the geometric influence of interlayer rotation (stacking periodicity). These observations indicate that basal/edge surface area ratios are highly variable and change continuously over the course of reaction, thus obviating their utility as characteristic parameters defining mica reactivity. Instead, these observations of overall dissolution rate and the influence of screw dislocations illustrate the link between atomic step movement and overall dissolution rate defined by surface retreat normal to the mica surface. Considered in light of similar observations available elsewhere in the literature, these relationships provide support for application of the stepwave model to mica dissolution kinetics. This approach provides a basic mechanistic link between the dissolution kinetics of phyllosilicates, framework silicates, and related minerals, and suggests a resolution to the general problem of mica reactivity.

Comparison of Dissolution Similarity Assessment Methods for Products with Large Variations: f2 Statistics and Model-Independent Multivariate Confidence Region Procedure for Dissolution Profiles of Multiple Oral Products.

PubMed

Yoshida, Hiroyuki; Shibata, Hiroko; Izutsu, Ken-Ichi; Goda, Yukihiro

2017-01-01

The current Japanese Ministry of Health Labour and Welfare (MHLW)'s Guideline for Bioequivalence Studies of Generic Products uses averaged dissolution rates for the assessment of dissolution similarity between test and reference formulations. This study clarifies how the application of model-independent multivariate confidence region procedure (Method B), described in the European Medical Agency and U.S. Food and Drug Administration guidelines, affects similarity outcomes obtained empirically from dissolution profiles with large variations in individual dissolution rates. Sixty-one datasets of dissolution profiles for immediate release, oral generic, and corresponding innovator products that showed large variation in individual dissolution rates in generic products were assessed on their similarity by using the f 2 statistics defined in the MHLW guidelines (MHLW f 2 method) and two different Method B procedures, including a bootstrap method applied with f 2 statistics (BS method) and a multivariate analysis method using the Mahalanobis distance (MV method). The MHLW f 2 and BS methods provided similar dissolution similarities between reference and generic products. Although a small difference in the similarity assessment may be due to the decrease in the lower confidence interval for expected f 2 values derived from the large variation in individual dissolution rates, the MV method provided results different from those obtained through MHLW f 2 and BS methods. Analysis of actual dissolution data for products with large individual variations would provide valuable information towards an enhanced understanding of these methods and their possible incorporation in the MHLW guidelines.

Improving the API dissolution rate during pharmaceutical hot-melt extrusion I: Effect of the API particle size, and the co-rotating, twin-screw extruder screw configuration on the API dissolution rate.

PubMed

Li, Meng; Gogos, Costas G; Ioannidis, Nicolas

2015-01-15

The dissolution rate of the active pharmaceutical ingredients in pharmaceutical hot-melt extrusion is the most critical elementary step during the extrusion of amorphous solid solutions - total dissolution has to be achieved within the short residence time in the extruder. Dissolution and dissolution rates are affected by process, material and equipment variables. In this work, we examine the effect of one of the material variables and one of the equipment variables, namely, the API particle size and extruder screw configuration on the API dissolution rate, in a co-rotating, twin-screw extruder. By rapidly removing the extruder screws from the barrel after achieving a steady state, we collected samples along the length of the extruder screws that were characterized by polarized optical microscopy (POM) and differential scanning calorimetry (DSC) to determine the amount of undissolved API. Analyses of samples indicate that reduction of particle size of the API and appropriate selection of screw design can markedly improve the dissolution rate of the API during extrusion. In addition, angle of repose measurements and light microscopy images show that the reduction of particle size of the API can improve the flowability of the physical mixture feed and the adhesiveness between its components, respectively, through dry coating of the polymer particles by the API particles. Copyright © 2014. Published by Elsevier B.V.

Transient changes in shallow groundwater chemistry during the MSU ZERT CO2 injection experiment

USGS Publications Warehouse

Apps, J.A.; Zheng, Lingyun; Spycher, N.; Birkholzer, J.T.; Kharaka, Y.; Thordsen, J.; Kakouros, E.; Trautz, R.

2011-01-01

Food-grade CO2 was injected into a shallow aquifer through a perforated pipe placed horizontally 1-2 m below the water table at the Montana State University Zero Emission Research and Technology (MSU-ZERT) field site at Bozeman, Montana. The possible impact of elevated CO2 levels on groundwater quality was investigated by analyzing 80 water samples taken before, during, and following CO2 injection. Field determinations and laboratory analyses showed rapid and systematic changes in pH, alkalinity, and conductance, as well as increases in the aqueous concentrations of trace element species. The geochemical data were first evaluated using principal component analysis (PCA) in order to identify correlations between aqueous species. The PCA findings were then used in formulating a geochemical model to simulate the processes likely to be responsible for the observed increases in the concentrations of dissolved constituents. Modeling was conducted taking into account aqueous and surface complexation, cation exchange, and mineral precipitation and dissolution. Reasonable matches between measured data and model results suggest that: (1) CO2 dissolution in the groundwater causes calcite to dissolve. (2) Observed increases in the concentration of dissolved trace metals result likely from Ca+2-driven ion exchange with clays (smectites) and sorption/desorption reactions likely involving Fe (hydr)oxides. (3) Bicarbonate from CO2 dissolution appears to compete for sorption with anionic species such as HAsO4-2, potentially increasing dissolved As levels in groundwater. ?? 2011 Published by Elsevier Ltd.

ENVIRONMENTAL MANAGEMENT SCIENCE PROGRAM PROJECT NUMBER 87016 CO-PRECIPITATION OF TRACE METALS IN GROUNDWATER AND VADOSE ZONE CALCITE: IN SITU CONTAINMENT AND STABILIZATION OF STRONTIUM-90 AND OTHER DIVALENT METALS AND RADIONUCLIDES AT ARID WESTERN DOE SITES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferris, F. Grant; Fujita, Yoshiko; Smith, Robert W.

2004-06-15

Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) weapons complex. In situ containment and stabilization of these contaminants in vadose zones or groundwater is a cost-effective treatment strategy. Our facilitated approach relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal coprecipitation) by increasing groundwater pH and alkalinity (Fujita et al., 2000; Warren et al., 2001). Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface ureamore » hydrolyzing microorganisms. Because the precipitation processes are irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from groundwater. The rate at which trace metals are incorporated into calcite is a function of calcite precipitation kinetics, adsorption interactions between the calcite surface and the trace metal in solution (Zachara et al., 1991), solid solution properties of the trace metal in calcite (Tesoriero and Pankow, 1996), and also the surfaces upon which the calcite is precipitating. A fundamental understanding of the coupling of calcite precipitation and trace metal partitioning, and how this occurs in aquifers and vadose environments is lacking. This report summarizes work undertaken during the second year of this project.« less

In vitro dynamic solubility test: influence of various parameters.

PubMed Central

Thélohan, S; de Meringo, A

1994-01-01

This article discusses the dissolution of mineral fibers in simulated physiological fluids (SPF), and the parameters that affect the solubility measurement in a dynamic test where an SPF runs through a cell containing fibers (Scholze and Conradt test). Solutions simulate either the extracellular fluid (pH 7.6) or the intracellular fluid (pH 4.5). The fibers have various chemical compositions and are either continuously drawn or processed as wool. The fiber solubility is determined by the amount of SiO2 (and occasionally other ions) released in the solution. Results are stated as percentage of the initial silica content released or as dissolution rate v in nm/day. The reproducibility of the test is higher with the less soluble fibers (10% solubility), than with highly soluble fibers (20% solubility). The influence of test parameters, including SPF, test duration, and surface area/volume (SA/V), has been studied. The pH and the inorganic buffer salts have a major influence: industrial glasswool composition is soluble at pH 7.6 but not at pH 4.5. The opposite is true for rock- (basalt) wool composition. For slightly soluble fibers, the dissolution rate v remains constant with time, whereas for highly soluble fibers, the dissolution rate decreases rapidly. The dissolution rates believed to occur are v1, initial dissolution rate, and v2, dissolution rate of the residual fibers. The SA of fibers varies with the mass of the fibers tested, or with the fiber diameter at equal mass. Volume, V, is the chosen flow rate. An increase in the SA/V ratio leads to a decrease in the dissolution rate.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7882964

In vitro dynamic solubility test: influence of various parameters.

PubMed

Thélohan, S; de Meringo, A

1994-10-01

This article discusses the dissolution of mineral fibers in simulated physiological fluids (SPF), and the parameters that affect the solubility measurement in a dynamic test where an SPF runs through a cell containing fibers (Scholze and Conradt test). Solutions simulate either the extracellular fluid (pH 7.6) or the intracellular fluid (pH 4.5). The fibers have various chemical compositions and are either continuously drawn or processed as wool. The fiber solubility is determined by the amount of SiO2 (and occasionally other ions) released in the solution. Results are stated as percentage of the initial silica content released or as dissolution rate v in nm/day. The reproducibility of the test is higher with the less soluble fibers (10% solubility), than with highly soluble fibers (20% solubility). The influence of test parameters, including SPF, test duration, and surface area/volume (SA/V), has been studied. The pH and the inorganic buffer salts have a major influence: industrial glasswool composition is soluble at pH 7.6 but not at pH 4.5. The opposite is true for rock- (basalt) wool composition. For slightly soluble fibers, the dissolution rate v remains constant with time, whereas for highly soluble fibers, the dissolution rate decreases rapidly. The dissolution rates believed to occur are v1, initial dissolution rate, and v2, dissolution rate of the residual fibers. The SA of fibers varies with the mass of the fibers tested, or with the fiber diameter at equal mass. Volume, V, is the chosen flow rate. An increase in the SA/V ratio leads to a decrease in the dissolution rate.(ABSTRACT TRUNCATED AT 250 WORDS)

CALCIUM CARBONATE DISSOLUTION RATE IN LIMESTONE CONTACTORS

EPA Science Inventory

The rate of carbonate mineral dissolution from limestone was studied using a rotating disk apparatus and samples of limestone of varied composition. The purpose of this study was to determine the effect of limestone composition on the kinetics of carbonate mineral dissolution. Th...

Calcium Solubility In Zeolite Synthetic-Apatite Mixtures

NASA Technical Reports Server (NTRS)

Beiersdorfer, R.; Ming, D. W.

1999-01-01

Life support systems at a lunar or martian outpost will require the ability to produce food growing in 1) treated lunar or martian regolith; 2) a synthetic soil, or 3) some combination of both. Zeoponic soil, composed of NH4 (-) and K-exchanged clinoptilolite (Cp) and synthetic apatite (Ap), can provide slow-release fertilization via dissolution and ion-exchange. Equilibrium studies indicate that KNH4, P, and Mg are available to plants at sufficient levels, however, Ca is deficient. Ca availability can be increased by adding a second Ca-bearing mineral: calcite (Cal); dolomite (Dol); or wollastonite (Wol). Additions of Cal, Dol, and Wol systematically change the concentrations of Ca and P in solution. Cal has the greatest effect, Dol the least, and Wol is intermediate.

Modelling and shadowgraph imaging of cocrystal dissolution and assessment of in vitro antimicrobial activity for sulfadimidine/4-aminosalicylic acid cocrystals.

PubMed

Serrano, Dolores R; Persoons, Tim; D'Arcy, Deirdre M; Galiana, Carolina; Dea-Ayuela, Maria Auxiliadora; Healy, Anne Marie

2016-06-30

The aim of this work was to evaluate the influence of crystal habit on the dissolution and in vitro antibacterial and anitiprotozoal activity of sulfadimidine:4-aminosalicylic acid cocrystals. Cocrystals were produced via milling or solvent mediated processes. In vitro dissolution was carried out in the flow-through apparatus, with shadowgraph imaging and mechanistic mathematical models used to observe and simulate particle dissolution. In vitro activity was tested using agar diffusion assays. Cocrystallisation via milling produced small polyhedral crystals with antimicrobial activity significantly higher than sulfadimidine alone, consistent with a fast dissolution rate which was matched only by cocrystals which were milled following solvent evaporation. Cocrystallisation by solvent evaporation (ethanol, acetone) or spray drying produced flattened, plate-like or quasi-spherical cocrystals, respectively, with more hydrophobic surfaces and greater tendency to form aggregates in aqueous media, limiting both the dissolution rate and in vitro activity. Deviation from predicted dissolution profiles was attributable to aggregation behaviour, supported by observations from shadowgraph imaging. Aggregation behaviour during dissolution of cocrystals with different habits affected the dissolution rate, consistent with in vitro activity. Combining mechanistic models with shadowgraph imaging is a valuable approach for dissolution process analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

Dissolution enhancement of tadalafil by liquisolid technique.

PubMed

Lu, Mei; Xing, Haonan; Yang, Tianzhi; Yu, Jiankun; Yang, Zhen; Sun, Yanping; Ding, Pingtian

2017-02-01

This study aimed to enhance the dissolution of tadalafil, a poorly water-soluble drug by applying liquisolid technique. The effects of two critical formulation variables, namely drug concentration (17.5% and 35%, w/w) and excipients ratio (10, 15 and 20) on dissolution rates were investigated. Pre-compression tests, including particle size distribution, flowability determination, Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC), X-ray diffractometry (XRD) and scanning electron microscopy (SEM), were carried out to investigate the mechanism of dissolution enhancement. Tadalafil liquisolid tablets were prepared and their quality control tests, dissolution study, contact angle measurement, Raman mapping, and storage stability test were performed. The results suggested that all the liquisolid tablets exhibited significantly higher dissolution rates than the conventional tablets and pure tadalafil. FT-IR spectrum reflected no drug-excipient interactions. DSC and XRD studies indicated reduction in crystallinity of tadalafil, which was further confirmed by SEM and Raman mapping outcomes. The contact angle measurement demonstrated obvious increase in wetting property. Taken together, the reduction of particle size and crystallinity, and the improvement of wettability were the main mechanisms for the enhanced dissolution rate. No significant changes were observed in drug crystallinity and dissolution behavior after storage based on XRD, SEM and dissolution results.

Interactive effects of temperature, food and skeletal mineralogy mediate biological responses to ocean acidification in a widely distributed bryozoan.

PubMed

Swezey, Daniel S; Bean, Jessica R; Ninokawa, Aaron T; Hill, Tessa M; Gaylord, Brian; Sanford, Eric

2017-04-26

Marine invertebrates with skeletons made of high-magnesium calcite may be especially susceptible to ocean acidification (OA) due to the elevated solubility of this form of calcium carbonate. However, skeletal composition can vary plastically within some species, and it is largely unknown how concurrent changes in multiple oceanographic parameters will interact to affect skeletal mineralogy, growth and vulnerability to future OA. We explored these interactive effects by culturing genetic clones of the bryozoan Jellyella tuberculata (formerly Membranipora tuberculata ) under factorial combinations of dissolved carbon dioxide (CO 2 ), temperature and food concentrations. High CO 2 and cold temperature induced degeneration of zooids in colonies. However, colonies still maintained high growth efficiencies under these adverse conditions, indicating a compensatory trade-off whereby colonies degenerate more zooids under stress, redirecting energy to the growth and maintenance of new zooids. Low-food concentration and elevated temperatures also had interactive effects on skeletal mineralogy, resulting in skeletal calcite with higher concentrations of magnesium, which readily dissolved under high CO 2 For taxa that weakly regulate skeletal magnesium concentration, skeletal dissolution may be a more widespread phenomenon than is currently documented and is a growing concern as oceans continue to warm and acidify. © 2017 The Author(s).

Interactive effects of temperature, food and skeletal mineralogy mediate biological responses to ocean acidification in a widely distributed bryozoan

PubMed Central

Bean, Jessica R.; Ninokawa, Aaron T.; Hill, Tessa M.; Gaylord, Brian; Sanford, Eric

2017-01-01

Marine invertebrates with skeletons made of high-magnesium calcite may be especially susceptible to ocean acidification (OA) due to the elevated solubility of this form of calcium carbonate. However, skeletal composition can vary plastically within some species, and it is largely unknown how concurrent changes in multiple oceanographic parameters will interact to affect skeletal mineralogy, growth and vulnerability to future OA. We explored these interactive effects by culturing genetic clones of the bryozoan Jellyella tuberculata (formerly Membranipora tuberculata) under factorial combinations of dissolved carbon dioxide (CO2), temperature and food concentrations. High CO2 and cold temperature induced degeneration of zooids in colonies. However, colonies still maintained high growth efficiencies under these adverse conditions, indicating a compensatory trade-off whereby colonies degenerate more zooids under stress, redirecting energy to the growth and maintenance of new zooids. Low-food concentration and elevated temperatures also had interactive effects on skeletal mineralogy, resulting in skeletal calcite with higher concentrations of magnesium, which readily dissolved under high CO2. For taxa that weakly regulate skeletal magnesium concentration, skeletal dissolution may be a more widespread phenomenon than is currently documented and is a growing concern as oceans continue to warm and acidify. PMID:28424343

Reactive transport modelling of a high-pH infiltration test in concrete

NASA Astrophysics Data System (ADS)

Chaparro, M. Carme; Soler, Josep M.; Saaltink, Maarten W.; Mäder, Urs K.

2017-06-01

A laboratory-scale tracer test was carried out to characterize the transport properties of concrete from the Radioactive Waste Disposal Facility at El Cabril (Spain). A hyperalkaline solution (K-Ca-OH, pH = 13.2) was injected into a concrete sample under a high entry pressure in order to perform the experiment within a reasonable time span, obtaining a decrease of permeability by a factor of 1000. The concentrations of the tracers, major elements (Ca2+, SO4 2 - , K+ and Na+) and pH were measured at the outlet of the concrete sample. A reactive transport model was built based on a double porosity conceptual model, which considers diffusion between a mobile zone, where water can flow, and an immobile zone without any advective transport. The numerical model assumed that all reactions took place in the immobile zone. The cement paste consists of C-S-H gel, portlandite, ettringite, calcite and gypsum, together with residual alite and belite. Two different models were compared, one with portlandite in equilibrium (high initial surface area) and another one with portlandite reaction controlled by kinetics (low initial surface area). Overall the results show dissolution of alite, belite, gypsum, quartz, C-S-H gel and ettringite and precipitation of portlandite and calcite. Permeability could have decreased due to mineral precipitation.

Mesozoic (Lower Jurassic) red stromatactis limestones from the Southern Alps (Arzo, Switzerland): calcite mineral authigenesis and syneresis-type deformation

NASA Astrophysics Data System (ADS)

Neuweiler, Fritz; Bernoulli, Daniel

2005-02-01

The Broccatello lithological unit (Lower Jurassic, Hettangian to lower parts of Upper Sinemurian) near the village of Arzo (southern Alps, southern Switzerland) is a mound-shaped carbonate deposit that contains patches of red stromatactis limestone. Within the largely bioclastic Broccatello unit, the stromatactis limestone is distinguished by its early-diagenetic cavity system, a relatively fine-grained texture, and an in-situ assemblage of calcified siliceous sponges (various demosponges and hexactinellids). A complex shallow subsurface diagenetic pathway can be reconstructed from sediment petrography in combination with comparative geochemical analysis (carbon and oxygen isotopes; trace and rare earth elements, REE + Y). This pathway includes organic matter transformation, aragonite and skeletal opal dissolution, patchy calcification and lithification, sediment shrinkage, sagging and collapse, partial REE remobilization, and multiple sediment infiltration. These processes occurred under normal-marine, essentially oxic conditions and were independent from local, recurring syn-sedimentary faulting. It is concluded that the stromatactis results from a combination of calcite mineral authigenesis and syneresis-type deformation. The natural stromatactis phenomenon may thus be best explained by maturation processes of particulate polymer gels expected to form in fine-grained carbonate sediments in the shallow subsurface. Conditions favorable for the evolution of stromatactis appear to be particularly frequent during drowning of tropical or subtropical carbonate platforms.

Obtaining the porewater composition of a clay rock by modeling the in- and out-diffusion of anions and cations from an in-situ experiment.

PubMed

Appelo, C A J; Vinsot, A; Mettler, S; Wechner, S

2008-10-23

A borehole in the Callovo-Oxfordian clay rock in ANDRA's underground research facility was sampled during 1 year and chemically analyzed. Diffusion between porewater and the borehole solution resulted in concentration changes which were modeled with PHREEQC's multicomponent diffusion module. In the model, the clay rock's pore space is divided in free porewater (electrically neutral) and diffuse double layer water (devoid of anions). Diffusion is calculated separately for the two domains, and individually for all the solute species while a zero-charge flux is maintained. We explain how the finite difference formulas for radial diffusion can be translated into mixing factors for solutions. Operator splitting is used to calculate advective flow and chemical reactions such as ion exchange and calcite dissolution and precipitation. The ion exchange reaction is formulated in the form of surface complexation, which allows distributing charge over the fixed sites and the diffuse double layer. The charge distribution affects pH when calcite dissolves, and modeling of the experimental data shows that about 7% of the cation exchange capacity resides in the diffuse double layer. The model calculates the observed concentration changes very well and provides an estimate of the pristine porewater composition in the clay rock.

Stabilized phosphogypsum: class C fly ash: Portland type II cement composites for potential marine application.

PubMed

Guo, T; Malone, R F; Rusch, K A

2001-10-01

Phosphogypsum (PG, CaSO4 x H20), a byproduct of phosphoric acid manufacturing, contains low levels of Ra226. PG can be stabilized with portland type II cement and class C fly ash for use in marine environments, thus eliminating the airborne vector of transmission for radon gas. An augmented simplex centroid design with pseudocomponents was used to select 10 PG:class C fly ash:portland type II cement compositions. The 43 cm3 blocks were fabricated and subjected to a 1.5-yr field submergence test and a 28-d saltwater dynamic leaching study. All field composites survived with no signs of degradation. Dynamic leaching resulted in effective calcium diffusion coefficients ranging from 0.21 to 7.5 x 10(-14)m2 s(-1). Effective diffusion depths, calculated for t=1 and 30 yr, ranged from 0.4 to 2.2 mm and from 2.0 to 11.9 mm, respectively. Scanning electron microscopy and wavelength dispersive microprobe and X-ray diffraction analyses of the leached composites identified a 40-60-microm calcite layer that was absent in the control composites. This suggests that a reaction between the composites and the saltwater results in the precipitation of calcite onto the block surface, encapsulating the composites and protecting them from saltwater attack and dissolution.

Relating Mechanical Behavior and Microstructural Observations in Calcite Fault Gouge

NASA Astrophysics Data System (ADS)

Carpenter, B. M.; Di Stefano, G.; Viti, C.; Collettini, C.

2013-12-01

Many important earthquakes, magnitude 5-7, nucleate and/or propagate through carbonate-dominated lithologies. Additionally, the presence of precipitated calcite in (cement) and near (vein fill) faults indicates that the mechanical behavior of carbonate-dominated material likely plays an important role in shallow- and mid-crustal faulting. We report on laboratory experiments designed to explore the mechanical behavior of calcite and relate that behavior to post experiment microstructural observations. We sheared powdered gouge of Carrara Marble, >98% CaCO3, at constant normal stresses between 1 and 50 MPa under saturated conditions at room temperature. We performed velocity-stepping tests, 0.1-1000 μm/s, to evaluate frictional stability, and slide-hold-slide tests, 1-10,000 seconds, to measure the amount of frictional healing. Small subsets of experiments were performed under different environmental conditions and shearing velocities to better elucidate physicochemical processes and their role in the mechanical behavior of calcite fault gouge. All experimental samples were collected for SEM analysis. We find that the frictional healing rate is 7X higher under saturated conditions than under nominally dry conditions. We also observe a divergence between the rates of creep relaxation (increasing) and frictional healing (decreasing) as shear velocity is increased from 1 to 3000 μm/s. Our highest healing rates are observed at our lowest normal stresses. We observe a frictional strength of μ = 0.64, consistent with previous data under similar conditions. Furthermore, although we observe velocity-weakening frictional behavior in both the saturated and dry cases, rate- and-state friction parameters are distinctly different for each case. Our combined observations of rapid healing and of velocity-weakening frictional behavior indicate that faults where calcite-dominated gouge is present are likely to be seismic and have the ability to regain their strength quickly. Furthermore, our mechanical results highlight the important role of fluids in the evolution of frictional strength and thus fault behavior.

(W7860)Monte Carlo Simulations of the Dissolution of Borosilicate and Aluminoborosilicate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kerisit, Sebastien; Pierce, Eric M

2011-01-01

The aim of this study was to provide atomic-level insights into the dissolution behavior of borosilicate and aluminoborosilicate glasses in dilute aqueous solutions. In the first part of this work, the effects of different structural features, such as the presence of non-bridging oxygens (NBO) or the formation of boroxol rings, on glass dissolution were evaluated separately and led to the following conclusions. (1) The dependence of the dissolution rate on the amount of NBO was found to be linear at all Si/B ratios and the accelerating effect of NBO was shown to increase with increasing Si/B ratio. (2) The formationmore » of boroxol rings and of clusters of boroxol rings resulted in an increase of the dissolution rate at all Si/B ratios and, again, the extent of the rate increase was strongly dependent on the Si/B ratio. (3) For aluminosilicate glasses, the implementation of the aluminum avoidance rule was found to increase the rate of dissolution relative to that obtained for a random distribution. In the second part of this work, the dissolution of the NeB glasses studied by Pierce et al. [Pierce E. M., Reed L. R., Shaw W. J., McGrail B. P., Icenhower J. P., Windisch C. F., Cordova E. A. and Broady J. (2010) Experimental determination of the effect of the ratio of B/Al on glass dissolution along the nepheline (NaAlSiO4) - Malinkoite (NaBSiO4) join. Geochim. Cosmochim. Acta 74, 2634-2654] was modeled in dilute aqueous solutions. Pierce et al. concluded from their study that either the rupture of the Al-O bonds or that of the Si O bonds was the rate-limiting step controlling the dissolution of the NeB glasses. The simulations refined this conclusion and showed that, at low B/Al ratios, the rupture of both Al O Si and Si O Si linkages contributed to the dissolution rate whereas, at high B/Al ratios, the dissolution rate was independent of the rupture of Al-O-Si linkages and was controlled by S1 sites (silicon sites at the glass-water interface with one connection to nearest-neighbor sites) and dissolution via detachment of clusters.« less

Ultra-thin clay layers facilitate seismic slip in carbonate faults.

PubMed

Smeraglia, Luca; Billi, Andrea; Carminati, Eugenio; Cavallo, Andrea; Di Toro, Giulio; Spagnuolo, Elena; Zorzi, Federico

2017-04-06

Many earthquakes propagate up to the Earth's surface producing surface ruptures. Seismic slip propagation is facilitated by along-fault low dynamic frictional resistance, which is controlled by a number of physico-chemical lubrication mechanisms. In particular, rotary shear experiments conducted at seismic slip rates (1 ms -1 ) show that phyllosilicates can facilitate co-seismic slip along faults during earthquakes. This evidence is crucial for hazard assessment along oceanic subduction zones, where pelagic clays participate in seismic slip propagation. Conversely, the reason why, in continental domains, co-seismic slip along faults can propagate up to the Earth's surface is still poorly understood. We document the occurrence of micrometer-thick phyllosilicate-bearing layers along a carbonate-hosted seismogenic extensional fault in the central Apennines, Italy. Using friction experiments, we demonstrate that, at seismic slip rates (1 ms -1 ), similar calcite gouges with pre-existing phyllosilicate-bearing (clay content ≤3 wt.%) micro-layers weaken faster than calcite gouges or mixed calcite-phyllosilicate gouges. We thus propose that, within calcite gouge, ultra-low clay content (≤3 wt.%) localized along micrometer-thick layers can facilitate seismic slip propagation during earthquakes in continental domains, possibly enhancing surface displacement.

Effect of organic ligands on Mg partitioning and Mg isotope fractionation during low-temperature precipitation of calcite

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Immenhauser, Adrian; Buhl, Dieter; Purgstaller, Bettina; Baldermann, Andre; Dietzel, Martin

2016-04-01

Calcite growth experiments have been performed at 25 oC and 1 bar pCO2 in the presence of aqueous Mg and six organic ligands in the concentration range from 10-5 to 10-3 M. These experiments were performed in order to quantify the effect of distinct organic ligands on the Mg partitioning and Mg stable isotope fractionation during its incorporation in calcite at similar growth rates normalized to total surface area. The organic ligands used in this study comprise of (i) acetate acid, (ii) citrate, (iii) glutamate, (iv) salicylate, (v) glycine and (vi) ethylenediaminetetraacetic acid (EDTA), containing carboxyl- and amino-groups. These fuctional groups are required for bacterial activity and growth as well as related to biotic and abiotic mineralization processes occurring in sedimentary and earliest diagenetic aquatic environments (e.g. soil, cave, lacustrine, marine). The results obtained in this study indicate that the presence of organic ligands promotes an increase in the partition coefficient of Mg in calcite (DMg = (Mg/Ca)calcite (Mg/Ca)fluid). This behaviour can be explained by the temporal formation of aqueous Mg-ligand complexes that are subsequently adsorbed on the calcite surfaces and thereby reducing the active growth sites of calcite. The increase of DMg values as a function of the supersaturation degree of calcite in the fluid phase can be described by the linear equation LogDMg =0.3694 (±0.0329)×SIcalcite - 1.9066 (±0.0147); R2=0.92 In contrast, the presence of organic ligands, with exception of citrate, does not significantly affect the Mg isotope fractionation factor between calcite and reactive fluid (Δ26Mgcalcite-fluid = -2.5 ±0.1). Citrate likely exhibits larger fractionation between the Mg-ligand complexes and free aqueous Mg2+, compared to the other organic ligands studied in this work, as evidenced by the smaller Δ26Mgcalcite-fluid values. These results indicate that in Earth's surface calcite precipitating environments that are characterized by low dissolved organic carbon levels, the presence of organic ligands is rather unlikely to significantly affect the Mg isotope composition of precipitated calcite.

Integrating In Vitro, Modeling, and In Vivo Approaches to Investigate Warfarin Bioequivalence

PubMed Central

Wen, H; Fan, J; Vince, B; Li, T; Gao, W; Kinjo, M; Brown, J; Sun, W; Jiang, W; Lionberger, R

2017-01-01

We demonstrate the use of modeling and simulation to investigate bioequivalence (BE) concerns raised about generic warfarin products. To test the hypothesis that the loss of isopropyl alcohol and slow dissolution in acidic pH has significant impact on the pharmacokinetics of warfarin sodium tablets, we conducted physiologically based pharmacokinetic absorption modeling and simulation using formulation factors or in vitro dissolution profiles as input parameters. Sensitivity analyses indicated that warfarin pharmacokinetics was not sensitive to solubility, particle size, density, or dissolution rate in pH 4.5, but was affected by dissolution rate in pH 6.8 and potency. Virtual BE studies suggested that stressed warfarin sodium tablets with slow dissolution rate in pH 4.5 but having similar dissolution rate in pH 6.8 would be bioequivalent to the unstressed warfarin sodium tablets. A four‐way, crossover, single‐dose BE study in healthy subjects was conducted to test the same hypothesis and confirmed the simulation conclusion. PMID:28379643

Dynamic leaching studies of 48 MWd/kgU UO2 commercial spent nuclear fuel under oxic conditions

NASA Astrophysics Data System (ADS)

Serrano-Purroy, D.; Casas, I.; González-Robles, E.; Glatz, J. P.; Wegen, D. H.; Clarens, F.; Giménez, J.; de Pablo, J.; Martínez-Esparza, A.

2013-03-01

The leaching of a high-burn-up spent nuclear fuel (48 MWd/KgU) has been studied in a carbonate-containing solution and under oxic conditions using a Continuously Stirred Tank Flow-Through Reactor (CSTR). Two samples of the fuel, one prepared from the centre of the pellet (labelled CORE) and another one from the fuel pellet periphery, enriched with the so-called High Burn-Up Structure (HBS, labelled OUT) have been used.For uranium and actinides, the results showed that U, Np, Am and Cm gave very similar normalized dissolution rates, while Pu showed slower dissolution rates for both samples. In addition, dissolution rates were consistently two to four times lower for OUT sample compared to CORE sample.Considering the fission products release the main results are that Y, Tc, La and Nd dissolved very similar to uranium; while Cs, Sr, Mo and Rb have up to 10 times higher dissolution rates. Rh, Ru and Zr seemed to have lower dissolution rates than uranium. The lowest dissolution rates were found for OUT sample.Three different contributions were detected on uranium release, modelled and attributed to oxidation layer, fines and matrix release.

Evaluation of correlation between dissolution rates of loxoprofen tablets and their surface morphology observed by scanning electron microscope and atomic force microscope.

PubMed

Yoshikawa, Shinichi; Murata, Ryo; Shida, Shigenari; Uwai, Koji; Suzuki, Tsuneyoshi; Katsumata, Shunji; Takeshita, Mitsuhiro

2010-01-01

We observed the surface morphological structures of 60 mg tablets of Loxonin, Loxot, and Lobu using scanning electron microscope (SEM) and atomic force microscope (AFM) to evaluate the dissolution rates. We found a significant difference among the initial dissolution rates of the three kinds of loxoprofen sodium tablets. Petal forms of different sizes were commonly observed on the surface of the Loxonin and Loxot tablets in which loxoprofen sodium was confirmed by measuring the energy-dispersible X-ray (EDX) spectrum of NaKalpha using SEM. However, a petal form was not observed on the surface of the Lobu tablet, indicating differences among the drug production processes. Surface area and particle size of the principal ingredient in tablets are important factors for dissolution rate. The mean size of the smallest fine particles constituting each tablet was also determined with AFM. There was a correlation between the initial dissolution rate and the mean size of the smallest particles in each tablet. Visualizing tablet surface morphology using SEM and AFM provides information on the drug production processes and initial dissolution rate, and is associated with the time course of pharmacological activities after tablet administration.

Estimating rock and slag wool fiber dissolution rate from composition.

PubMed

Eastes, W; Potter, R M; Hadley, J G

2000-12-01

A method was tested for calculating the dissolution rate constant in the lung for a wide variety of synthetic vitreous silicate fibers from the oxide composition in weight percent. It is based upon expressing the logarithm of the dissolution rate as a linear function of the composition and using a different set of coefficients for different types of fibers. The method was applied to 29 fiber compositions including rock and slag fibers as well as refractory ceramic and special-purpose, thin E-glass fibers and borosilicate glass fibers for which in vivo measurements have been carried out. These fibers had dissolution rates that ranged over a factor of about 400, and the calculated dissolution rates agreed with the in vivo values typically within a factor of 4. The method presented here is similar to one developed previously for borosilicate glass fibers that was accurate to a factor of 1.25. The present coefficients work over a much broader range of composition than the borosilicate ones but with less accuracy. The dissolution rate constant of a fiber may be used to estimate whether disease would occur in animal inhalation or intraperitoneal injection studies of that fiber.

Elevated CO2 affects shell dissolution rate but not calcification rate in a marine snail.

PubMed

Nienhuis, Sarah; Palmer, A Richard; Harley, Christopher D G

2010-08-22

As CO(2) levels increase in the atmosphere, so too do they in the sea. Although direct effects of moderately elevated CO(2) in sea water may be of little consequence, indirect effects may be profound. For example, lowered pH and calcium carbonate saturation states may influence both deposition and dissolution rates of mineralized skeletons in many marine organisms. The relative impact of elevated CO(2) on deposition and dissolution rates are not known for many large-bodied organisms. We therefore tested the effects of increased CO(2) levels--those forecast to occur in roughly 100 and 200 years--on both shell deposition rate and shell dissolution rate in a rocky intertidal snail, Nucella lamellosa. Shell weight gain per day in live snails decreased linearly with increasing CO(2) levels. However, this trend was paralleled by shell weight loss per day in empty shells, suggesting that these declines in shell weight gain observed in live snails were due to increased dissolution of existing shell material, rather than reduced production of new shell material. Ocean acidification may therefore have a greater effect on shell dissolution than on shell deposition, at least in temperate marine molluscs.

The analysis of thermoluminescent glow peaks of natural calcite after beta irradiation.

PubMed

Yildirim, R Güler; Kafadar, V Emir; Yazici, A Necmeddin; Gün, Esen

2012-09-01

In this study, the thermoluminescence properties of natural calcite samples were examined in detail. The glow curve of the sample irradiated with beta radiation shows two main peaks, P1 (at 115 °C) and P4 (at 254 °C). The additive dose, variable heating rate, computer glow curve deconvolution, peak shape and three point methods have been used to evaluate the trapping parameters, namely the order of kinetics (b), activation energy (E) and the frequency factor (s) associated with the dosimetric thermoluminescent glow peaks (P1 and P4) of natural calcite after different dose levels with beta irradiation.

Temperature Dependence of the Structural Parameters in the Transformation of Aragonite to Calcite, as Determined from In Situ Synchrotron Powder X-ray-Diffratction Data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Antao, Sytle M.; Hassan, Ishmael; West Indies)

The temperature dependency of the crystal structure and the polymorphic transition of CaCO{sub 3} from aragonite to calcite were studied using Rietveld structure refinement and high-temperature in situ synchrotron powder X-ray-diffraction data at ambient pressure, P. The orthorhombic metastable aragonite at room P, space group Pmcn, transforms to trigonal calcite, space group R{bar 3}c, at about T{sub c} = 468 C. This transformation occurs rapidly; it starts at about 420 C and is completed by 500 C, an 80 C interval that took about 10 minutes using a heating rate of 8 C/min. Structurally, from aragonite to calcite, the distributionmore » of the Ca atom changes from approximately hexagonal to cubic close-packing. A 5.76% discontinuous increase in volume accompanies the reconstructive first-order transition. Besides the change in coordination of the Ca atom from nine to six from aragonite to calcite, the CO{sub 3} groups change by a 30{sup o} rotation across the transition.« less

CO2-brine-mineral Reactions in Geological Carbon Storage: Results from an EOR Experiment

NASA Astrophysics Data System (ADS)

Chapman, H.; Wigley, M.; Bickle, M.; Kampman, N.; Dubacq, B.; Galy, A.; Ballentine, C.; Zhou, Z.

2012-04-01

Dissolution of CO2 in brines and reactions of the acid brines ultimately dissolving silicate minerals and precipitating carbonate minerals are the prime long-term mechanisms for stabilising the light supercritical CO2 in geological carbon storage. However the rates of dissolution are very uncertain as they are likely to depend on the heterogeneity of the flow of CO2, the possibility of convective instability of the denser CO2-saturated brines and on fluid-mineral reactions which buffer brine acidity. We report the results of sampling brines and gases during a phase of CO2 injection for enhanced oil recovery in a small oil field. Brines and gases were sampled at production wells daily for 3 months after initiation of CO2 injection and again for two weeks after 5 months. Noble gas isotopic spikes were detected at producing wells within days of initial CO2 injection but signals continued for weeks, and at some producers for the duration of the sampling period, attesting to the complexity of gas-species pathways. Interpretations are complicated by the previous history of the oil field and re-injection of produced water prior to injection of CO2. However water sampled from some producing wells during the phase of CO2 injection showed monotonic increases in alkalinity and in concentrations of major cations to levels in excess of those in the injected water. The marked increase in Na, and smaller increases in Ca, Mg, Si, K and Sr are interpreted primarily to result from silicate dissolution as the lack of increase in S and Cl concentrations preclude additions of more saline waters. Early calcite dissolution was followed by re-precipitation. 87Sr/86Sr ratios in the waters apparently exceed the 87Sr/86Sr ratios of acetic and hydrochloric acid leaches of carbonate fractions of the reservoir rocks and the silicate residues from the leaching. This may indicate incongruent dissolution of Sr or larger scale isotopic heterogeneity of the reservoir. This is being investigated further by analyses of rock and mineral clasts from core. A surprising result of this study is the extent to which CO2 has dissolved in brines to drive fluid-rock reactions during the short duration of this experiment. However, simple one-dimensional flow modelling with lateral diffusion of CO2 into brines demonstrates that the natural heterogeneities in permeability in the reservoir on the scale of ~ 1 m are sufficient to cause extensive fingering of the CO2 along the highest permeability horizons. Because flow of brines is fastest in the relatively high permeability layers adjacent to the CO2-bearing layers, production of this more CO2-rich water dominates the output from production wells.

The long-term impact of magnesium in seawater on foraminiferal mineralogy: Mechanism and consequences

NASA Astrophysics Data System (ADS)

Dijk, I.; Nooijer, L. J.; Hart, M. B.; Reichart, G.-J.

2016-03-01

Foraminifera are unicellular protists, primarily known for their calcium carbonate shells that provide an extensive fossil record. This record, ranging from Cambrian to present shows both major shifts and gradual changes in the relative occurrence of taxa producing different polymorphs of carbonate. Here we present evidence for coupling between shifts in calcite- versus aragonite-producing species and periods with, respectively, low and high seawater Mg/Ca throughout the Phanerozoic. During periods when seawater Mg/Ca is <2 mol/mol, low-Mg calcite-producing species dominate the foraminiferal community. Vice versa, high-Mg calcite- and aragonite-producing species are more abundant during periods with relatively high seawater Mg/Ca. This alteration in dominance of the phase precipitated is due to selective recovery of groups producing the favorable polymorph after shifts from calcite to aragonite seas. In addition, relatively high extinction rates of species producing the mineral phase not favored by the seawater Mg/Ca of that time may be responsible for this alteration. These results imply that the current high seawater Mg/Ca will, in the long term, favor prevalence of high-Mg and aragonite-producing foraminifera over calcite-producing taxa, possibly shifting the balance toward a community in which calcite production is less dominant.

Dissolution behavior of MgO based inert matrix fuel for the transmutation of minor actinides

NASA Astrophysics Data System (ADS)

Mühr-Ebert, E. L.; Lichte, E.; Bukaemskiy, A.; Finkeldei, S.; Klinkenberg, M.; Brandt, F.; Bosbach, D.; Modolo, G.

2018-07-01

This study explores the dissolution properties of magnesia-based inert matrix nuclear fuel (IMF) containing transuranium elements (TRU). Pure MgO pellets as well as MgO pellets containing CeO2, as surrogate for TRU oxides, and are considered as model systems for genuine magnesia based inert matrix fuel were fabricated. The aim of this study is to identify conditions at which the matrix material can be selectively dissolved during the head-end reprocessing step, allowing a separation of MgO from the actinides, whereas the actinides remain undissolved. The dissolution behavior was studied in macroscopic batch experiments as a function of nitric acid concentration, dissolution medium volume, temperature, stirring velocity, and pellet density (85, 90, 96, and 99%TD). To mimic pellets with various burn-ups the density of the here fabricated pellets was varied. MgO is soluble even under mild conditions (RT, 2.5 mol/L HNO3). The dissolution rates of MgO at different acid concentrations are rather similar, whereas the dissolution rate is strongly dependent on the temperature. Via a microscopic approach, a model was developed to describe the evolution of the pellet surface area during dissolution and determine a surface normalized dissolution rate. Moreover, dissolution rates of the inert matrix fuel containing CeO2 were determined as a function of the acid concentration and temperature. During the dissolution of MgO/CeO2 pellets the MgO dissolves completely, while CeO2 (>99%) remains undissolved. This study intends to provide a profound understanding of the chemical performance of magnesia based IMF containing fissile material. The feasibility of the dissolution of magnesia based IMF with nitric acid is discussed.

Effects of alteration product precipitation on glass dissolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strachan, Denis M.; Neeway, James J.

2014-06-01

Understanding the mechanisms that control the durability of nuclear waste glass is paramount if reliable models are to be constructed so that the glass dissolution rate in a given geological repository can be calculated. Presently, it is agreed that (boro)silicate glasses dissolve in water at a rate dependent on the solution concentration of orthosilicic acid (H 4SiO 4) with higher [H 4SiO 4] leading to lower dissolution rates. Once the reaction has slowed as a result of the buildup of H 4SiO 4, another increase in the rate has been observed that corresponds to the precipitation of certain silica-bearing alterationmore » products. However, it has also been observed that the concentration of silica-bearing solution species does not significantly decrease, indicating saturation, while other glass tracer elements concentrations continue to increase, indicating that the glass is still dissolving. In this study, we have used the Geochemist’s Workbench code to investigate the relationship between glass dissolution rates and the precipitation rate of a representative zeolitic silica-bearing alteration product, analcime [Na(AlSi 2O 6)∙H 2O]. To simplify the calculations, we suppressed all alteration products except analcime, gibbsite (Al(OH) 3), and amorphous silica. The pseudo-equilibrium-constant matrix for amorphous silica was substituted for the glass pseudo-equilibrium-constant matrix because it has been shown that silicate glasses act as a silica-only solid with respect to kinetic considerations. In this article, we present the results of our calculations of the glass dissolution rate at different values for the analcime precipitation rate constant and the effects of varying the glass dissolution rate constant at a constant analcime precipitation rate constant. From the simulations we conclude, firstly, that the rate of glass dissolution is dependent on the kinetics of formation of the zeolitic phase. Therefore, the kinetics of secondary phase formation is an important parameter that should be taken into account in future glass dissolution modeling efforts. Secondly, the results indicate that, in the absence of a gel layer, the glass dissolution rate controls the rate of analcime precipitation in the long term. Finally, the meaning of these results pertinent to long-term glass durability is discussed.« less

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

NASA Astrophysics Data System (ADS)

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong; Chorover, Jon; O'Day, Peggy A.

2017-06-01

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium (U) concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this work, the dissolution rates of K- and Na-compreignacite (K2(UO2)6O4(OH)6·8H2O and Na2(UO2)6O4(OH)6·8H2O, respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved carbonate concentration (ca. 0.2 and 2.8 mmol L-1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area, and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total U mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved U was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57 · 10-10 vs. 1.28 · 10-13 mol m-2 s-1 [log R = -9.81 and -12.89] and 5.79 · 10-10 vs. 3.71 · 10-13 mol m-2 s-1 [log R = -9.24 and -12.43] for K- and Na-compreignacite, respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for U mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. This study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as U in porous geomedia.

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2(UO 2) 6O 4(OH) 6·8H 2O and Na 2(UO 2) 6O 4(OH) 6·8H 2O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmolmore » L -1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were about 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57·10 -10 vs. 1.28·10 -13 mol m -2 s -1 [log R = -9.81 and -12.89] and 5.79·10 -10 vs. 3.71·10 -13 mol m -2 s -1 [log R = -9.24 and -12.43] for K- and Na-compreignacite respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for uranium mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. Finally, this study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as uranium in porous geomedia.« less

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

DOE PAGES

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong; ...

2017-06-01

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2(UO 2) 6O 4(OH) 6·8H 2O and Na 2(UO 2) 6O 4(OH) 6·8H 2O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmolmore » L -1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were about 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57·10 -10 vs. 1.28·10 -13 mol m -2 s -1 [log R = -9.81 and -12.89] and 5.79·10 -10 vs. 3.71·10 -13 mol m -2 s -1 [log R = -9.24 and -12.43] for K- and Na-compreignacite respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for uranium mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. Finally, this study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as uranium in porous geomedia.« less

The influence of kinetics on the oxygen isotope composition of calcium carbonate

NASA Astrophysics Data System (ADS)

Watkins, James M.; Nielsen, Laura C.; Ryerson, Frederick J.; DePaolo, Donald J.

2013-08-01

Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25 μM dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3-, CO32- and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite-water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

Addition of Sodium Bicarbonate to Irrigation Solution May Assist in Dissolution of Uric Acid Fragments During Ureteroscopy.

PubMed

Paonessa, Jessica E; Williams, James C; Lingeman, James E

2018-04-01

We hypothesized that adding sodium bicarbonate (bicarb) to normal saline (NS) irrigation during ureteroscopy in patients with uric acid (UA) nephrolithiasis may assist in dissolving small stone fragments produced during laser lithotripsy. In vitro testing was performed to determine whether dissolution of UA fragments could be accomplished within 1 hour. In total 100% UA renal calculi were fragmented, filtered, and separated by size. Fragment sizes were <0.5 mm and 0.5 to 1 mm. Similar amounts of stone material were agitated in solution at room temperature. Four solutions were tested (NS, NS +1 ampule bicarb/L, NS +2, NS +3). Both groups were filtered to remove solutions after fixed periods. Filtered specimens were dried and weighed. Fragment dissolution rates were calculated as percent removed per hour. Additional testing was performed to determine whether increasing the temperature of solution affected dissolution rates. For fragments <0.5 mm, adding 2 or 3 bicarb ampules/L NS produced a dissolution rate averaging 91% ± 29% per hour. This rate averaged 226% faster than NS alone. With fragments 0.5 to 1 mm, addition of 2 or 3 bicarb ampules/L NS yielded a dissolution rate averaging 22% ± 7% per hour, which was nearly five times higher than NS alone. There was a trend for an increase in mean dissolution rate with higher temperature but this increase was not significant (p = 0.30). The addition of bicarbonate to NS more than doubles the dissolution rate of UA stone fragments and fragments less than 0.5 mm can be completely dissolved within 1 hour. Addition of bicarb to NS irrigation is a simple and inexpensive approach that may assist in the dissolution of UA fragments produced during ureteroscopic laser lithotripsy. Further studies are needed to determine whether a clinical benefit exists.

Kinetics and mechanism of natural fluorapatite dissolution at 25 °C and pH from 3 to 12

NASA Astrophysics Data System (ADS)

Chaïrat, Claire; Schott, Jacques; Oelkers, Eric H.; Lartigue, Jean-Eric; Harouiya, Najatte

2007-12-01

The dissolution rates of natural fluorapatite (FAP), Ca 10(PO 4) 6F 2, were measured at 25 °C in mixed-flow reactors as a function of pH from 3.0 to 11.7, and aqueous calcium, phosphorus, and fluoride concentration. After an initial preferential Ca and/or F release, stoichiometric Ca, P, and F release was observed. Measured FAP dissolution rates decrease with increasing pH at 3 ⩽ pH ⩽ 7, FAP dissolution rates are pH independent at 7 ⩽ pH ⩽ 10, and FAP dissolution rates again decrease with increasing pH at pH ⩾ 10. Measured FAP dissolution rates are independent of aqueous Ca, P, and F concentration at pH ≈ 3 and pH ≈ 10. Apatite dissolution appears to be initiated by the relatively rapid removal from the near surface of F and the Ca located in the M1 sites, via proton for Ca exchange reactions. Dissolution rates are controlled by the destruction of this F and Ca depleted surface layer. The destruction of this layer is facilitated by the adsorption/penetration of protons into the surface at acidic conditions, and by surface hydration at neutral and basic conditions. Taking into account these two parallel mechanisms, measured fluorapatite forward dissolution rates can be accurately described using r+(molms)=6.61×10-6{aK}/{1+aK+aCa4aF1.4aOH0.6aH6K}+3.69×10-8[tbnd CaOH2+] where ai refers to the activity of the ith aqueous species, [tbnd CaOH2+] denotes the concentration of hydrated calcium sites at the surface of the leached layer (mol m -2), and Kex and Kads stand for the apparent stability constants of the Ca 2+/H + exchange and adsorption/penetration reactions, respectively.

Coherent anti-Stokes Raman Scattering (CARS) Microscopy Visualizes Pharmaceutical Tablets During Dissolution

PubMed Central

Fussell, Andrew L.; Kleinebudde, Peter; Herek, Jennifer; Strachan, Clare J.; Offerhaus, Herman L.

2014-01-01

Traditional pharmaceutical dissolution tests determine the amount of drug dissolved over time by measuring drug content in the dissolution medium. This method provides little direct information about what is happening on the surface of the dissolving tablet. As the tablet surface composition and structure can change during dissolution, it is essential to monitor it during dissolution testing. In this work coherent anti-Stokes Raman scattering microscopy is used to image the surface of tablets during dissolution while UV absorption spectroscopy is simultaneously providing inline analysis of dissolved drug concentration for tablets containing a 50% mixture of theophylline anhydrate and ethyl cellulose. The measurements showed that in situ CARS microscopy is capable of imaging selectively theophylline in the presence of ethyl cellulose. Additionally, the theophylline anhydrate converted to theophylline monohydrate during dissolution, with needle-shaped crystals growing on the tablet surface during dissolution. The conversion of theophylline anhydrate to monohydrate, combined with reduced exposure of the drug to the flowing dissolution medium resulted in decreased dissolution rates. Our results show that in situ CARS microscopy combined with inline UV absorption spectroscopy is capable of monitoring pharmaceutical tablet dissolution and correlating surface changes with changes in dissolution rate. PMID:25045833

Convective dissolution of carbon dioxide in saline aquifers

NASA Astrophysics Data System (ADS)

Neufeld, Jerome A.; Hesse, Marc A.; Riaz, Amir; Hallworth, Mark A.; Tchelepi, Hamdi A.; Huppert, Herbert E.

2010-11-01

Geological carbon dioxide (CO2) storage is a means of reducing anthropogenic emissions. Dissolution of CO2 into the brine, resulting in stable stratification, increases storage security. The dissolution rate is determined by convection in the brine driven by the increase of brine density with CO2 saturation. We present a new analogue fluid system that reproduces the convective behaviour of CO2-enriched brine. Laboratory experiments and high-resolution numerical simulations show that the convective flux scales with the Rayleigh number to the 4/5 power, in contrast with a classical linear relationship. A scaling argument for the convective flux incorporating lateral diffusion from downwelling plumes explains this nonlinear relationship for the convective flux, provides a physical picture of high Rayleigh number convection in a porous medium, and predicts the CO2 dissolution rates in CO2 accumulations. These estimates of the dissolution rate show that convective dissolution can play an important role in enhancing storage security.

Specific effects of background electrolytes on the kinetics of step propagation during calcite growth

NASA Astrophysics Data System (ADS)

Ruiz-Agudo, Encarnación; Putnis, Christine V.; Wang, Lijun; Putnis, Andrew

2011-07-01

The mechanisms by which background electrolytes modify the kinetics of non-equivalent step propagation during calcite growth were investigated using Atomic Force Microscopy (AFM), at constant driving force and solution stoichiometry. Our results suggest that the acute step spreading rate is controlled by kink-site nucleation and, ultimately, by the dehydration of surface sites, while the velocity of obtuse step advancement is mainly determined by hydration of calcium ions in solution. According to our results, kink nucleation at acute steps could be promoted by carbonate-assisted calcium attachment. The different sensitivity of obtuse and acute step propagation kinetics to cation and surface hydration could be the origin of the reversed geometries of calcite growth hillocks (i.e., rate of obtuse step spreading < rate of acute step spreading) observed in concentrated (ionic strength, IS = 0.1) KCl and CsCl solutions. At low IS (0.02), ion-specific effects seem to be mainly associated with changes in the solvation environment of calcium ions in solution. With increasing electrolyte concentration, the stabilization of surface water by weakly paired salts appears to become increasingly important in determining step spreading rate. At high ionic strength (IS = 0.1), overall calcite growth rates increased with increasing hydration of calcium in solution (i.e., decreasing ion pairing of background electrolytes for sodium-bearing salts) and with decreasing hydration of the carbonate surface site (i.e., increasing ion pairing for chloride-bearing salts). Changes in growth hillock morphology were observed in the presence of Li +, F - and SO42-, and can be interpreted as the result of the stabilization of polar surfaces due to increased ion hydration. These results increase our ability to predict crystal reactivity in natural fluids which contain significant amounts of solutes.

The Dissolution Behavior of Borosilicate Glasses in Far-From Equilibrium Conditions

DOE PAGES

Neeway, James J.; Rieke, Peter C.; Parruzot, Benjamin P.; ...

2018-02-10

An area of agreement in the waste glass corrosion community is that, at far-from-equilibrium conditions, the dissolution of borosilicate glasses used to immobilize nuclear waste is known to be a function of both temperature and pH. The aim of this work is to study the effects of temperature and pH on the dissolution rate of three model nuclear waste glasses (SON68, ISG, AFCI). The dissolution rate data are then used to parameterize a kinetic rate model based on Transition State Theory that has been developed to model glass corrosion behavior in dilute conditions. To do this, experiments were conducted atmore » temperatures of 23, 40, 70, and 90 °C and pH(22 °C) values of 9, 10, 11, and 12 with the single-pass flow-through (SPFT) test method. Both the absolute dissolution rates and the rate model parameters are compared with previous results. Rate model parameters for the three glasses studied here are nearly equivalent within error and in relative agreement with previous studies though quantifiable differences exist. The glass dissolution rates were analyzed with a linear multivariate regression (LMR) and a nonlinear multivariate regression performed with the use of the Glass Corrosion Modeling Tool (GCMT), with which a robust uncertainty analysis is performed. This robust analysis highlights the high degree of correlation of various parameters in the kinetic rate model. As more data are obtained on borosilicate glasses with varying compositions, a mathematical description of the effect of glass composition on the rate parameter values should be possible. This would allow for the possibility of calculating the forward dissolution rate of glass based solely on composition. In addition, the method of determination of parameter uncertainty and correlation provides a framework for other rate models that describe the dissolution rates of other amorphous and crystalline materials in a wide range of chemical conditions. As a result, the higher level of uncertainty analysis would provide a basis for comparison of different rate models and allow for a better means of quantifiably comparing the various models.« less

The dissolution behavior of borosilicate glasses in far-from equilibrium conditions

NASA Astrophysics Data System (ADS)

Neeway, James J.; Rieke, Peter C.; Parruzot, Benjamin P.; Ryan, Joseph V.; Asmussen, R. Matthew

2018-04-01

An area of agreement in the waste glass corrosion community is that, at far-from-equilibrium conditions, the dissolution of borosilicate glasses used to immobilize nuclear waste is known to be a function of both temperature and pH. The aim of this work is to study the effects of temperature and pH on the dissolution rate of three model nuclear waste glasses (SON68, ISG, AFCI). The dissolution rate data are then used to parameterize a kinetic rate model based on Transition State Theory that has been developed to model glass corrosion behavior in dilute conditions. To do this, experiments were conducted at temperatures of 23, 40, 70, and 90 °C and pH (22 °C) values of 9, 10, 11, and 12 with the single-pass flow-through (SPFT) test method. Both the absolute dissolution rates and the rate model parameters are compared with previous results. Rate model parameters for the three glasses studied here are nearly equivalent within error and in relative agreement with previous studies though quantifiable differences exist. The glass dissolution rates were analyzed with a linear multivariate regression (LMR) and a nonlinear multivariate regression performed with the use of the Glass Corrosion Modeling Tool (GCMT), with which a robust uncertainty analysis is performed. This robust analysis highlights the high degree of correlation of various parameters in the kinetic rate model. As more data are obtained on borosilicate glasses with varying compositions, a mathematical description of the effect of glass composition on the rate parameter values should be possible. This would allow for the possibility of calculating the forward dissolution rate of glass based solely on composition. In addition, the method of determination of parameter uncertainty and correlation provides a framework for other rate models that describe the dissolution rates of other amorphous and crystalline materials in a wide range of chemical conditions. The higher level of uncertainty analysis would provide a basis for comparison of different rate models and allow for a better means of quantifiably comparing the various models.

The Dissolution Behavior of Borosilicate Glasses in Far-From Equilibrium Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neeway, James J.; Rieke, Peter C.; Parruzot, Benjamin P.

An area of agreement in the waste glass corrosion community is that, at far-from-equilibrium conditions, the dissolution of borosilicate glasses used to immobilize nuclear waste is known to be a function of both temperature and pH. The aim of this work is to study the effects of temperature and pH on the dissolution rate of three model nuclear waste glasses (SON68, ISG, AFCI). The dissolution rate data are then used to parameterize a kinetic rate model based on Transition State Theory that has been developed to model glass corrosion behavior in dilute conditions. To do this, experiments were conducted atmore » temperatures of 23, 40, 70, and 90 °C and pH(22 °C) values of 9, 10, 11, and 12 with the single-pass flow-through (SPFT) test method. Both the absolute dissolution rates and the rate model parameters are compared with previous results. Rate model parameters for the three glasses studied here are nearly equivalent within error and in relative agreement with previous studies though quantifiable differences exist. The glass dissolution rates were analyzed with a linear multivariate regression (LMR) and a nonlinear multivariate regression performed with the use of the Glass Corrosion Modeling Tool (GCMT), with which a robust uncertainty analysis is performed. This robust analysis highlights the high degree of correlation of various parameters in the kinetic rate model. As more data are obtained on borosilicate glasses with varying compositions, a mathematical description of the effect of glass composition on the rate parameter values should be possible. This would allow for the possibility of calculating the forward dissolution rate of glass based solely on composition. In addition, the method of determination of parameter uncertainty and correlation provides a framework for other rate models that describe the dissolution rates of other amorphous and crystalline materials in a wide range of chemical conditions. As a result, the higher level of uncertainty analysis would provide a basis for comparison of different rate models and allow for a better means of quantifiably comparing the various models.« less

Effects of acid deposition on dissolution of carbonate stone during summer storms in the Adirondack Mountains, New York, 1987-89

USGS Publications Warehouse

Schuster, Paul F.; Reddy, Michael M.; Sherwood, S.I.

1994-01-01

This study is part of a long-term research program designed to identify and quantify acid rain damage to carbonate stone. Acidic deposition accelerates the dissolution of carbonate-stone monuments and building materials. Sequential sampling of runoff from carbonate-stone (marble) and glass (reference) microcatchments in the Adirondack Mountains in New York State provided a detailed record of the episodic fluctuations in rain rate and runoff chemistry during individual summer storms. Rain rate and chemical concentrations from carbonate-stone and glass runoff fluctuated three to tenfold during storms. Net calcium-ion concentrations from the carbonatestone runoff, a measure of stone dissolution, typically fluctuated twofold during these storms. High net sulfate and net calcium concentrations in the first effective runoff at the start of a storm indicated that atmospheric pollutants deposited on the stone surface during dry periods formed calcium sulfate minerals, an important process in carbonate stone dissolution. Dissolution of the carbonate stone generally increased up to twofold during coincident episodes of low rain rate (less than 5 millimeters per hour) and decreased rainfall (glass runoff) pH (less than 4.0); episodes of high rain rate (cloudbursts) were coincident with a rapid increase in rainfall pH and also a rapid decrease in the dissolution of carbonate-stone. During a storm, it seems the most important factors causing increased dissolution of carbonate stone are coincident periods of low rain rate and decreased rainfall pH. Dissolution of the carbonate stone decreased slightly as the rain rate exceeded about 5 millimeters per hour, probably in response to rapidly increasing rainfall pH during episodes of high rain rate and shorter contact time between the runoff and the stone surface. High runoff rates resulting from cloudbursts remove calcium sulfate minerals formed during dry periods prior to storms and also remove dissolution products formed in large measure by chemical weathering as a result of episodes of low rain rate and decreased rainfall pH during a storm.

Diurnal variation in rates of calcification and carbonate sediment dissolution in Florida Bay

USGS Publications Warehouse

Yates, K.K.; Halley, R.B.

2006-01-01

Water quality and circulation in Florida Bay (a shallow, subtropical estuary in south Florida) are highly dependent upon the development and evolution of carbonate mud banks distributed throughout the Bay. Predicting the effect of natural and anthropogenic perturbations on carbonate sedimentation requires an understanding of annual, seasonal, and daily variations in the biogenic and inorganic processes affecting carbonate sediment precipitation and dissolution. In this study, net calcification rates were measured over diurnal cycles on 27 d during summer and winter from 1999 to 2003 on mud banks and four representative substrate types located within basins between mud banks. Substrate types that were measured in basins include seagrass beds of sparse and intermediate density Thalassia sp., mud bottom, and hard bottom communities. Changes in total alkalinity were used as a proxy for calcification and dissolution. On 22 d (81%), diurnal variation in rates of net calcification was observed. The highest rates of net carbonate sediment production (or lowest rates of net dissolution) generally occurred during daylight hours and ranged from 2.900 to -0.410 g CaCO3 m-2 d-1. The lowest rates of carbonate sediment production (or net sediment dissolution) occurred at night and ranged from 0.210 to -1.900 g CaCO3 m -2 night-1. During typical diurnal cycles, dissolution during the night consumed an average of 29% of sediment produced during the day on banks and 68% of sediment produced during the day in basins. Net sediment dissolution also occurred during daylight, but only when there was total cloud cover, high turbidity, or hypersalinity. Diurnal variation in calcification and dissolution in surface waters and surface sediments of Florida Bay is linked to cycling of carbon dioxide through photosynthesis and respiration. Estimation of long-term sediment accumulation rates from diurnal rates of carbonate sediment production measured in this study indicates an overall average accumulation rate for Florida Bay of 8.7 cm 1000 yr-1 and suggests that sediment dissolution plays a more important role than sediment transport in loss of sediment from Florida Bay. ?? 2006 Estuarine Research Federation.

Feasibility of Using Gluconolactone, Trehalose and Hydroxy-Propyl Gamma Cyclodextrin to Enhance Bendroflumethiazide Dissolution Using Lyophilisation and Physical Mixing Techniques.

PubMed

Saleh, Ashraf; McGarry, Kenneth; Chaw, Cheng Shu; Elkordy, Amal Ali

2018-02-01

Hydrophobic drugs are facing a major challenge in dissolution rate enhancement and solubility in aqueous solutions; therefore, a variety of methods have been used to improve dissolution rate and/or solubility of bendroflumethiazide as a model hydrophobic drug. In this study, two main methods (physical mixing and lyophilisation) were used with gluconolactone, hydroxyl propyl γ-ccyclodextrin, and trehalose to explore this challenge. Bendroflumethiazide, practically insoluble in water, was mixed with one of the three excipients gluconolactone, hydroxyl propyl γ-cyclodextrin, and trehalose in three different ratios 1:1, 1:2, 1:5. To the best of our knowledge, the dissolution of the drug has not been previously enhanced by using either these methods or any of the used excipients. Samples containing drug and each of the excipients were characterized via dissolution testing, Fourier Transform infra-red spectroscopy, differential scanning calorimetry, and scanning electron microscopy. The used methods showed a significant enhancement in dug dissolution rate; physical mixing significantly, p < 0.05, increased the percentage of the drug released with time; for example, bendroflumethiazide dissolution in distilled water was improved from less than 20% to 99.79% within 90 min for physically mixed drug-cyclodextrin 1:5. The lyophilisation process was enhanced and the drug dissolution rate and the highest drug dissolution was achieved for (drug-gluconolactone 1:1) with 98.98% drug release within 90 min. the physical mixing and freeze drying processes significantly increased the percentage of drug release with time.

Jarosite dissolution rates in perchlorate brine

NASA Astrophysics Data System (ADS)

Legett, Carey; Pritchett, Brittany N.; Elwood Madden, Andrew S.; Phillips-Lander, Charity M.; Elwood Madden, Megan E.

2018-02-01

Perchlorate salts and the ferric sulfate mineral jarosite have been detected at multiple locations on Mars by both landed instruments and orbiting spectrometers. Many perchlorate brines have eutectic temperatures <250 K, and may exist as metastable or stable liquids for extended time periods, even under current Mars surface conditions. Therefore, jarosite-bearing rocks and sediments may have been altered by perchlorate brines. Here we measured jarosite dissolution rates in 2 M sodium perchlorate brine as well as dilute water at 298 K to determine the effects of perchlorate anions on jarosite dissolution rates and potential reaction products. We developed a simple method for determining aqueous iron concentrations in high salinity perchlorate solutions using ultraviolet-visible spectrophotometry that eliminates the risk of rapid oxidation reactions during analyses. Jarosite dissolution rates in 2 M perchlorate brine determined by iron release rate (2.87 × 10-12 ±0.85 × 10-12 mol m-2 s-1) were slightly slower than the jarosite dissolution rate measured in ultrapure (18.2 MΩ cm-1) water (5.06 × 10-12 mol m-2 s-1) using identical methods. No additional secondary phases were observed in XRD analyses of the reaction products. The observed decrease in dissolution rate may be due to lower activity of water (ɑH2O = 0.9) in the 2 M NaClO4 brine compared with ultrapure water (ɑH2O = 1). This suggests that the perchlorate anion does not facilitate iron release, unlike chloride anions which accelerated Fe release rates in previously reported jarosite and hematite dissolution experiments. Since dissolution rates are slower in perchlorate-rich solutions, jarosite is expected to persist longer in perchlorate brines than in dilute waters or chloride-rich brines. Therefore, if perchlorate brines dominate aqueous fluids on the surface of Mars, jarosite may remain preserved over extended periods of time, despite active aqueous processes.

The influence of co-formers on the dissolution rates of co-amorphous sulfamerazine/excipient systems.

PubMed

Gniado, Katarzyna; Löbmann, Korbinian; Rades, Thomas; Erxleben, Andrea

2016-05-17

A comprehensive study on the dissolution properties of three co-amorphous sulfamerazine/excipient systems, namely sulfamerazine/deoxycholic acid, sulfamerazine/citric acid and sulfamerazine/sodium taurocholate (SMZ/DA, SMZ/CA and SMZ/NaTC; 1:1 molar ratio), is reported. While all three co-formers stabilize the amorphous state during storage, only co-amorphization with NaTC provides a dissolution advantage over crystalline SMZ and the reasons for this were analyzed. In the case of SMZ/DA extensive gelation of DA protects the amorphous phase from crystallization upon contact with buffer, but at the same time prevents the release of SMZ into solution. Disk dissolution studies showed an improved dissolution behavior of SMZ/CA compared to crystalline SMZ. However, enhanced dissolution properties were not seen in powder dissolution testing due to poor dispersibility. Co-amorphization of SMZ and NaTC resulted in a significant increase in dissolution rate, both in powder and disk dissolution studies. Copyright © 2016. Published by Elsevier B.V.

Mg/Ca, Sr/Ca and Ca isotope ratios in benthonic foraminifers related to test structure, mineralogy and environmental controls

NASA Astrophysics Data System (ADS)

Gussone, Nikolaus; Filipsson, Helena L.; Kuhnert, Henning

2016-01-01

We analysed Mg/Ca, Sr/Ca and Ca isotope ratios of benthonic foraminifers from sediment core tops retrieved during several research cruises in the Atlantic Ocean, in order to improve the understanding of isotope fractionation and element partitioning resulting from biomineralisation processes and changes in ambient conditions. Species include foraminifers secreting tests composed of hyaline low magnesium calcite, porcelaneous high magnesium calcite as well as aragonite. Our results demonstrate systematic isotope fractionation and element partitioning patterns specific for these foraminiferal groups. Calcium isotope fractionation is similar in porcelaneous and hyaline calcite tests and both groups demonstrate the previously described anomaly with enrichment of heavy isotopes around 3-4 °C (Gussone and Filipsson, 2010). Calcium isotope ratios of the aragonitic species Hoeglundina elegans, on the other hand, are about 0.4‰ lighter compared to the calcitic species, which is in general agreement with stronger fractionation in inorganic aragonite compared to calcite. However, the low and strongly variable Sr content suggests additional processes during test formation, and we propose that transmembrane ion transport or a precursor phase to aragonite may be involved. Porcelaneous tests, composed of high Mg calcite, incorporate higher amounts of Sr compared to hyaline low Mg calcite, in agreement with inorganic calcite systematics, but also porcelaneous tests with reduced Mg/Ca show high Sr/Ca. While calcium isotopes, Sr/Ca and Mg/Ca in benthonic foraminifers primarily appear to fractionate and partition with a dominant inorganic control, δ44/40Ca temperature and growth rate dependencies of benthonic foraminifer tests favour a dominant contribution of light Ca by transmembrane transport relative to unfractionated seawater Ca to the calcifying fluid, thus controlling the formation of foraminiferal δ44/40Ca and Sr/Ca proxy signals.

CO2-rich geothermal areas in Iceland as natural analogues for geologic carbon sequestration

NASA Astrophysics Data System (ADS)

Thomas, D.; Maher, K.; Bird, D. K.; Brown, G. E.; Arnorsson, S.

2013-12-01

Geologic CO2 sequestration into mafic rocks via silicate mineral dissolution and carbonate precipitation has been suggested as a way to mitigate industrial CO2 emissions by storing CO2 in a stable form. Experimental observations of irreversible reaction of basalt with supercritical or gaseous and aqueous CO2 have resulted in carbonate precipitation, but there are no universal trends linking the extent of mineralization and type of reaction products to the bulk rock composition, glass percentage or mineralogy of the starting material. Additionally, concern exists that CO2 leakage from injection sites and migration through the subsurface may induce mineral dissolution and desorption of trace elements, potentially contaminating groundwater. This study investigates low-temperature (≤180°C) basaltic geothermal areas in Iceland with an anomalously high input of magmatic CO2 as natural analogues of the geochemical processes associated with the injection of CO2 into mafic rocks and possible leakage. Fluids that contain >4 mmol/kg total CO2 are common along the divergent Snæfellsnes Volcanic Zone in western Iceland and within the South Iceland Seismic Zone in southwest Iceland. The meteorically derived waters contain up to 80 mmol/kg dissolved inorganic carbonate (DIC). The aqueous concentration of major cations and trace elements is greater than that in Icelandic surface and groundwater and increases with DIC and decreasing pH. Concentrations of As and Ni in some samples are several times the World Health Organization (WHO) guidelines for safe drinking water. Thermodynamic modeling indicates that waters approach saturation with respect to calcite and/or aragonite, kaolinite and amorphous silica, and are undersaturated with respect to plagioclase feldspar, clinozoisite and Ca-zeolites. Petrographic study of drill cuttings from wells that intersect the CO2-rich areas indicates that the sites have undergone at least two stages of hydrothermal alteration: initial high-temperature and late stage low-temperature alteration. Imaging results from scanning electron microscopy show that calcite has replaced hydrothermally altered silicate minerals, such as albitic plagioclase. CO2-rich low-temperature fluids are not in equilibrium with correlative high-temperature hydrothermal mineral assemblages, indicating that the kinetics of mineral dissolution and secondary mineral precipitation, along with fluid residence times, are important controls on CO2 alteration and mineral formation at low temperatures. Our results have implications for predicting mineral product formation and trace element release during geologic carbon sequestration into hydrothermally altered basalts.

Unravelling the depositional origins and diagenetic alteration of carbonate breccias

NASA Astrophysics Data System (ADS)

Madden, Robert H. C.; Wilson, Moyra E. J.; Mihaljević, Morana; Pandolfi, John M.; Welsh, Kevin

2017-07-01

Carbonate breccias dissociated from their platform top counterparts are little studied despite their potential to reveal the nature of past shallow-water carbonate systems and the sequential alteration of such systems. A petrographic and stable isotopic study allowed evaluation of the sedimentological and diagenetic variability of the Cenozoic Batu Gading Limestone breccia of Borneo. Sixteen lithofacies representing six facies groups have been identified mainly from the breccia clasts on the basis of shared textural and compositional features. Clasts of the breccia are representative of shallow carbonate platform top and associated flank to basinal deposits. Dominant inputs are from rocky (karstic) shorelines or localised seagrass environments, coral patch reef and larger foraminiferal-rich deposits. Early, pre-brecciation alteration (including micritisation, rare dissolution of bioclasts, minor syntaxial overgrowth cementation, pervasive neomorphism and calcitisation of bioclasts and matrix) was mainly associated with marine fluids in a near surface to shallow burial environment. The final stages of pre-brecciation diagenesis include mechanical compaction and cementation of open porosity in a shallow to moderate depth burial environment. Post-brecciation diagenesis took place at increasingly moderate to deep burial depths under the influence of dominantly marine burial fluids. Extensive compaction, circum-clast dissolution seams and stylolites have resulted in a tightly fitted breccia fabric, with some development of fractures and calcite cements. A degree of facies-specific controls are evident for the pre-brecciation diagenesis. Pervasive mineralogical stabilisation and cementation have, however, led to a broad similarity of diagenetic features in the breccia clasts thereby effectively preserving depositional features of near-original platform top and margin environments. There is little intra-clast alteration overprint associated with subsequent clast reworking and post-brecciation diagenesis. The diagenetic-, and to an extent depositional- and clast-characteristics of the Batu Gading deposits are diagnostic of breccia origins. The predominance of: early and pervasive stabilisation of calcitic components, pervasive compaction resulting in a fitted texture, and paucity of meteoric dissolution or cementation effects are collectively all indicators of slope deposition and lithification. These features are comparable with other regional and global examples of submarine slope breccias, and in particular those also from syntectonic settings (Wannier, 2009). The results of this study, along with regional analogues, suggest the potential for reworked carbonate debris in slope settings to be a viable way of investigating carbonate platform variability and their subsequent alteration in the absence of preserved platform top or margin deposits.

Rate of production, dissolution and accumulation of biogenic solids in the ocean

NASA Technical Reports Server (NTRS)

Arrhenius, G.

1988-01-01

The equatorial current system, by its response to global circulation changes, provides a unique recording mechanism for long range climatic oscillations. A permanent record of the changes in rate of upwelling and organic production is generated in the equatorial deep sea sediments, particularly by such biogenic components which are unaffected by secondary dissolution. In order to determine the rates of accumulation of various sedimentary components, a reliable differential measurement of age of the strata must be obtained. Various approaches to this problem are reviewed, and sources of error discussed. Secondary dissolution of calcium carbonate introduces a substantial and variable difference between the dissolution-modified, and hence a priori unknown, rate of deposition on one hand and the rate of accumulation, derivable from the observed concentration, on the other. The cause and magnitude of these variations are of importance, particularly since some current dating schemes are based on assumed constancy in the rate of accumulation of this and, in some cases, also all other sedimentary components. The concepts used in rate evaluation are discussed with emphasis on the difference between the state of dissolution, an observable property of the sediment, and the rate of dissolution, a parameter that requires deduction of the carbonate fraction dissolved, and of the time differential. As a most likely cause of the enhanced state of dissolution of the interglacial carbonate sediments is proposed the lowered rates of biogenic production and deposition, which cause longer exposure of the carbonate microfossils to corrosion in the bioturbated surface layer of the sediment. Historical perspective is included in the discussion in view of the dedication of the Symposium to Hans Pettersson, the leader of the Swedish Deep Sea Expedition 1947-1948, an undertaking that opened a new era in deep sea research and planetary dynamics.

Evaluation and selection of bio-relevant dissolution media for a poorly water-soluble new chemical entity.

PubMed

Tang, L; Khan, S U; Muhammad, N A

2001-11-01

The purpose of this work is to develop a bio-relevant dissolution method for formulation screening in order to select an enhanced bioavailable formulation for a poorly water-soluble drug. The methods used included a modified rotating disk apparatus for measuring intrinsic dissolution rate of the new chemical entity (NCE) and the USP dissolution method II for evaluating dissolution profiles of the drug in three different dosage forms. The in vitro dissolution results were compared with the in vivo bioavailability for selecting a bio-relevant medium. The results showed that the solubility of the NCE was proportional to the concentration of sodium lauryl sulfate (SLS) in the media. The apparent intrinsic dissolution rate of the NCE was linear to the rotational speed of the disk, which indicated that the dissolution of the drug is a diffusion-controlled mechanism. The apparent intrinsic dissolution rate was also linear to the surfactant concentration in the media, which was interpreted using the Noyes and Whitney Empirical Theory. Three formulations were studied in three different SLS media using the bulk drug as a reference. The dissolution results were compared with the corresponding bioavailability results in dogs. In the 1% SLS--sink conditions--the drug release from all the formulations was complete and the dissolution results were discriminative for the difference in particle size of the drug in the formulations. However, the data showed poor IVIV correlation. In the 0.5% SLS medium--non-sink conditions--the dissolution results showed the same rank order among the tested formulations as the bioavailability. The best IVIV correlation was obtained from the dissolution in 0.25% SLS medium, an over-saturated condition. The conclusions are: a surfactant medium increases the apparent intrinsic dissolution rate of the NCE linearly due to an increase in solubility. A low concentration of surfactant in the medium (0.25%) is more bio-relevant than higher concentrations of surfactant in the media for the poorly water-soluble drug. Creating sink conditions (based on bulk drug solubilities) by using a high concentration of a surfactant in the dissolution medium may not be a proper approach in developing a bio-relevant dissolution method for a poorly water-soluble drug.

Kinetics and mechanism of hydroxyapatite crystal dissolution in weak acid buffers using the rotating disk method.

PubMed

Wu, M S; Higuchi, W I; Fox, J L; Friedman, M

1976-01-01

The model given in this report and the rotating disk method provide a useful combination in the study of dental enamel and hydroxyapatite dissolution kinetics. The present approach is a significant improvement over earlier studies, and both the ionic activity product that governs the dissolution reaction and the apparent surface dissolution reaction rate constant may be simultaneously obtained. Thus, these investigations have established the baseline for the dissolution rate studies under sink conditions. Concurrent studies, under conditions where the acidic buffer mediums are partially saturated with respect to hydroxyapatite have shown another dissolution site for hydroxyapatite that operates at a higher ionic activity product but has a much smaller apparent surface reaction rate constant. This has raised the question of whether the presence of this second site may interfere with the proper theoretical analysis of the experimental results obtained under sink conditions. A preliminary analysis of the two-site model has shown that the dissolution kinetics of hydroxyapatite under sink conditions is almost completely governed by the sink condition site (KHAP = 10(-124.5), k' = 174) established in this report. The difference between the predicted dissolution rate for the one-site model and the two-site model are generally of the order of 4 to 5% where the experiments are conducted under sink conditions and over the range of variables covered in the present study.

Mineralogical, crystallographic, and isotopic constraints on the precipitation of aragonite and calcite at Shiqiang and other hot springs in Yunnan Province, China

NASA Astrophysics Data System (ADS)

Jones, Brian; Peng, Xiaotong

2016-11-01

Two active spring vent pools at Shiqiang (Yunnan Province, China) are characterized by a complex array of precipitates that coat the wall around the pool and the narrow ledges that surround the vent pool. These precipitates include arrays of aragonite crystals, calcite cone-dendrites, red spar calcite, unattached dodecahedral and rhombohedral calcite crystals, and late stage calcite that commonly coats and disguises the earlier formed precipitates. Some of the microbial mats that grow on the ledges around the pools have been partly mineralized by microspheres that are formed of Si and minor amounts of Fe. The calcite and aragonite that are interspersed with each other at all scales are both primary precipitates. Some laminae, for example, change laterally from aragonite to calcite over distances of only a few millimetres. The precipitates at Shiqiang are similar to precipitates found in and around the vent pools of other springs found in Yunnan Province, including those at Gongxiaoshe, Zhuyuan, Eryuan, and Jifei. In all cases, the δDwater and δ18Owater indicate that the spring water is of meteoric origin. These are thermogene springs with the carrier CO2 being derived largely from the mantle and reaction of the waters with bedrock. Variations in the δ13Ctravertine values indicate that the waters in these springs were mixed, to varying degrees, with cold groundwater and its soil-derived CO2. Calcite and aragonite precipitation took place once the spring waters had become supersaturated with respect to CaCO3, probably as a result of rapid CO2 degassing. These precipitates, which were not in isotopic equilibrium with the spring water, are characterized by their unusual crystal morphologies. The precipitation of calcite and aragonite, seemingly together, can probably be attributed to microscale variations in the saturation levels that are, in turn, attributable to microscale variations in the rate of CO2 degassing.

A Review: Pharmaceutical and Pharmacokinetic Aspect of Nanocrystalline Suspensions.

PubMed

Shah, Dhaval A; Murdande, Sharad B; Dave, Rutesh H

2016-01-01

Nanocrystals have emerged as a potential formulation strategy to eliminate the bioavailability-related problems by enhancing the initial dissolution rate and moderately super-saturating the thermodynamic solubility. This review contains an in-depth knowledge of, the processing method for formulation, an accurate quantitative assessment of the solubility and dissolution rates and their correlation to observe pharmacokinetic data. Poor aqueous solubility is considered the major hurdle in the development of pharmaceutical compounds. Because of a lack of understanding with regard to the change in the thermodynamic and kinetic properties (i.e., solubility and dissolution rate) upon nanosizing, we critically reviewed the literatures for solubility determination to understand the significance and accuracy of the implemented analytical method. In the latter part, we reviewed reports that have quantitatively studied the effect of the particle size and the surface area change on the initial dissolution rate enhancement using alternative approaches besides the sink condition dissolution. The lack of an apparent relationship between the dissolution rate enhancement and the observed bioavailability are discussed by reviewing the reported in vivo data on animal models along with the particle size and food effect. The review will provide comprehensive information to the pharmaceutical scientist in the area of nanoparticulate drug delivery.

Mineralogical and isotopic record of biotic and abiotic diagenesis of the Callovian-Oxfordian clayey formation of Bure (France)

NASA Astrophysics Data System (ADS)

Lerouge, C.; Grangeon, S.; Gaucher, E. C.; Tournassat, C.; Agrinier, P.; Guerrot, C.; Widory, D.; Fléhoc, C.; Wille, G.; Ramboz, C.; Vinsot, A.; Buschaert, S.

2011-05-01

The Callovian-Oxfordian (COx) clayey unit is being studied in the Eastern part of the Paris Basin at depths between 400 and 500 m depth to assess of its suitability for nuclear waste disposal. The present study combines new mineralogical and isotopic data to describe the sedimentary history of the COx unit. Petrologic study provided evidence of the following diagenetic mineral sequence: (1) framboidal pyrite and micritic calcite, (2) iron-rich euhedral carbonates (ankerite, sideroplesite) and glauconite (3) limpid calcite and dolomite and celestite infilling residual porosity in bioclasts and cracks, (4) chalcedony, (5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ 34S (-38‰ to +34.5‰), providing evidence of bacterial sulphate reduction processes in changing sedimentation conditions. The most negative values (-38‰ to -22‰), measured in the lower part of the COx unit indicate precipitation of pyrite in a marine environment with a continuous sulphate supply. The most positive pyrite δ 34S values (-14‰ up to +34.5‰) in the upper part of the COx unit indicate pyrite precipitation in a closed system. Celestite δ 34S values reflect the last evolutionary stage of the system when bacterial activity ended; however its deposition cannot be possible without sulphate supply due to carbonate bioclast dissolution. The 87Sr/ 86Sr ratio of celestite (0.706872-0.707040) is consistent with deposition from Jurassic marine-derived waters. Carbon and oxygen isotopic compositions of bulk calcite and dolomite are consistent with marine carbonates. Siderite, only present in the maximum clay zone, has chemical composition and δ 18O consistent with a marine environment. Its δ 13C is however lower than those of marine carbonates, suggesting a contribution of 13C-depleted carbon from degradation of organic matter. δ 18O values of diagenetic chalcedony range between +27‰ and +31‰, suggesting precipitation from marine-derived pore waters. Late calcite crosscutting a vein filled with chalcedony and celestite, and late euhedral quartz in a limestone from the top of the formation have lower δ 18O values (˜+19‰), suggesting that they precipitated from meteoric fluids, isotopically close to present-day pore waters of the formation. Finally, the study illustrates the transition from very active, biotic diagenesis to abiotic diagenesis. This transition appears to be driven by compaction of the sediment, which inhibited movement of bacterial cells by reduction of porosity and pore sizes, rather than a lack of inorganic carbon or sulphates.

Regional hardening of Upper Cretaceous Chalk in eastern England, UK: trace element and stable isotope patterns in the Upper Cenomanian and Turonian Chalk and their significance

NASA Astrophysics Data System (ADS)

Jeans, Christopher V.; Long, Dee; Hu, Xiu-Fang; Mortimore, Rory N.

2014-12-01

The regional hardening of the Late Cenomanian to Early Turonian Chalk of the Northern Province of eastern England has been investigated by examining the pattern of trace elements and stable carbon and oxygen isotopes in the bulk calcite of two extensive and stratigraphically adjacent units each 4 to 5 m thick of hard chalk in Lincolnshire and Yorkshire. These units are separated by a sequence, 0.3-1.3 m thick, of variegated marls and clayey marls. Modelling of the geochemistry of the hard chalk by comparison with the Standard Louth Chalk, combined with associated petrographic and geological evidence, indicates that (1) the hardening is due to the precipitation of a calcite cement, and (2) the regional and stratigraphical patterns of geochemical variation in the cement are largely independent of each other and have been maintained by the impermeable nature of the thin sequence of the clay-rich marls that separate them. Two phases of calcite cementation are recognised. The first phase was microbially influenced and did not lithify the chalk. It took place predominantly in oxic and suboxic conditions under considerable overpressure in which the Chalk pore fluids circulated within the units, driven by variations in compaction, temperature, pore fluid pressure and local tectonics. There is evidence in central and southern Lincolnshire of the loss of Sr and Mgenriched pore fluids to the south during an early part of this phase. The second phase of calcite precipitation was associated with the loss of overpressure in probably Late Cretaceous and in Cenozoic times as the result of fault movement in the basement penetrating the overlying Chalk and damaging the seal between the two chalk units. This greatly enhanced grain pressures, resulting in grain welding and pressure dissolution, causing lithification with the development of stylolites, marl seams, and brittle fractures. Associated with this loss of overpressure was the penetration of the chalk units by allochthonous fluids, rich in sulphate and hydrocarbons, derived probably from the North Sea Basin. Microbial sulphate-reduction under anoxic conditions within these allochthonous fluids has been responsible for dissolving the fine-grained iron and manganese oxides within the chalk, locally enriching the Fe and Mn content of the calcite cement. The possibility is discussed that the pattern of cementation preserved in these regionally hard chalks of Late Cenomanian and Early Turonian age may be different from that preserved in the younger (late Turonian to Campanian) more basinal chalks of eastern England.

Interface dissolution control of the 14C profile in marine sediment

USGS Publications Warehouse

Keir, R.S.; Michel, R.L.

1993-01-01

The process of carbonate dissolution at the sediment-water interface has two possible endmember boundary conditions. Either the carbonate particles dissolve mostly before they are incorporated into the sediment by bioturbation (interface dissolution), or the vertical mixing is rapid relative to their extermination rate (homogeneous dissolution). In this study, a detailed radiocarbon profile was determined in deep equatorial Pacific sediment that receives a high rate of carbonate supply. In addition, a box model of sediment mixing was used to simulate radiocarbon, carbonate content and excess thorium profiles that result from either boundary process following a dissolution increase. Results from homogeneous dissolution imply a strong, very recent erosional event, while interface dissolution suggests that moderately increased dissolution began about 10,000 years ago. In order to achieve the observed mixed layer radiocarbon age, increased homogeneous dissolution would concentrate a greater amount of clay and 230Th than is observed, while for interface dissolution the predicted concentrations are too small. These results together with small discontinuities beneath the mixed layer in 230Th profiles suggest a two-stage increase in interface dissolution in the deep Pacific, the first occurring near the beginning of the Holocene and the second more recently, roughly 5000 years ago. ?? 1993.

Evaluation of melt granulation and ultrasonic spray congealing as techniques to enhance the dissolution of praziquantel.

PubMed

Passerini, Nadia; Albertini, Beatrice; Perissutti, Beatrice; Rodriguez, Lorenzo

2006-08-02

Praziquantel (PZQ), an anthelminthic drug widely used in developing countries, is classified in Class II in the Biopharmaceutics Classification Systems; this means that PZQ has very low water solubility and high permeability, thus the dissolution is the absorption rate-limiting factor. The aim of this work was to evaluate the suitability of melt granulation and ultrasonic spray congealing as techniques for enhancing the dissolution rate of PZQ. Granules in high shear mixer were prepared by melt granulation, using polyethylene glycol 4000 or poloxamer 188 as meltable binders and alpha-lactose monohydrate as a filler. Quite regularly shaped granules having main size fraction in the range 200-500 microm were obtained using both formulations; however, only poloxamer 188 granules demonstrated a significant (P=0.05) increase of the PZQ dissolution rate compared to pure drug. To evaluate the potential of ultrasonic spray congealing, Gelucire 50/13 microparticles having different drug to carrier ratios (5, 10, 20 and 30%, w/w) were then prepared. The results showed that all the microparticles had a significant higher dissolution rate (P=0.05) respect to pure PZQ. The increase of the PZQ content considerably decreased the dissolution rate of the drug: 5 and 10% PZQ loaded systems evidenced dissolution significantly enhanced compared to 20 and 30% PZQ microparticles. The microparticle's characterisation, performed by Differential Scanning Calorimetry, Hot Stage Microscopy, X-ray powder diffraction and FT-Infrared analysis, evidenced the absence of both modifications of the solid state of PZQ and of significant interactions between the drug and the carrier. In conclusion, melt granulation and ultrasonic spray congealing could be proposed as solvent free, rapid and low expensive manufacturing methods to increase the in vitro dissolution rate of PZQ.

Improvement of the dissolution rate of artemisinin by means of supercritical fluid technology and solid dispersions.

PubMed

Van Nijlen, T; Brennan, K; Van den Mooter, G; Blaton, N; Kinget, R; Augustijns, P

2003-03-26

The purpose of this study was to enhance the dissolution rate of artemisinin in order to improve the intestinal absorption characteristics. The effect of: (1) micronisation and (2) formation of solid dispersions with PVPK25 was assessed in an in vitro dissolution system [dissolution medium: water (90%), ethanol (10%) and sodium lauryl sulphate (0.1%)]. Coulter counter analysis was used to measure particle size. X-ray diffraction and DSC were used to analyse the physical state of the powders. Micronisation by means of a jet mill and supercritical fluid technology resulted in a significant decrease in particle size as compared to untreated artemisinin. All powders appeared to be crystalline. The dissolution rate of the micronised forms improved in comparison to the untreated form, but showed no difference in comparison to mechanically ground artemisinin. Solid dispersions of artemisinin with PVPK25 as a carrier were prepared by the solvent method. Both X-ray diffraction and DSC showed that the amorphous state was reached when the amount of PVPK25 was increased to 67%. The dissolution rate of solid dispersions with at least 67% of PVPK25 was significantly improved in comparison to untreated and mechanically ground artemisinin. Modulation of the dissolution rate of artemisinin was obtained by both particle size reduction and formation of solid dispersions. The effect of particle size reduction on the dissolution rate was limited. Solid dispersions could be prepared by using a relatively small amount of PVPK25. The formation of solid dispersions with PVPK25 as a carrier appears to be a promising method to improve the intestinal absorption characteristics of artemisinin. Copyright 2003 Elsevier Science B.V.

Calcium and Oxygen Isotopic Composition of Calcium Carbonates

NASA Astrophysics Data System (ADS)

Niedermayr, Andrea; Eisenhauer, Anton; Böhm, Florian; Kisakürek, Basak; Balzer, Isabelle; Immenhauser, Adrian; Jürgen Köhler, Stephan; Dietzel, Martin

2016-04-01

Different isotopic systems are influenced in multiple ways corresponding to the crystal structure, dehydration, deprotonation, adsorption, desorption, isotope exchange and diffusion processes. In this study we investigated the structural and kinetic effects on fractionation of stable Ca- and O-isotopes during CaCO3 precipitation. Calcite, aragonite and vaterite were precipitated using the CO2 diffusion technique[1]at a constant pH of 8.3, but various temperatures (6, 10, 25 and 40° C) and precipitation rates R (101.5 to 105 μmol h-1 m-2). The calcium isotopic fractionation between solution and vaterite is lower (Δ44/40Ca= -0.10 to -0.55 ‰) compared to calcite (-0.69 to -2.04 ‰) and aragonite (-0.91 to -1.55 ‰). In contrast the fractionation of oxygen isotopes is highest for vaterite (32.1 ‰), followed by aragonite (29.2 ‰) and calcite (27.6 ‰) at 25° C and equilibrium. The enrichment of 18O vs. 16O in all polymorphs decreases with increasing precipitation rate by around -0.7 ‰ per log(R). The calcium isotopic fractionation between calcite/ vaterite and aqueous Ca2+ increases with increasing precipitation rate by ˜0.45 ‰ per log(R) and ˜0.1 ‰ per log(R) at 25° C and 40° C, respectively. In contrast the fractionation of Ca-isotopes between aragonite and aqueous Ca2+ decreases with increasing precipitation rates. The large enrichment of 18O vs. 16O isotopes in carbonates is related to the strong bond of oxygen to the small and highly charged C4+-ion. In contrast equilibrium isotopic fractionation between solution and calcite or vaterite is nearly zero as the Ca-O bond length is similar for calcite, vaterite and the hydrated Ca. Aragonite incorporates preferentially the lighter 40Ca isotope as it has very large Ca-O bonds in comparison to the hydrated Ca. At the crystal surface the lighter 40Ca isotopes are preferentially incorporated as dehydration and diffusion of lighter isotopes are faster. Consequently, the surface becomes enriched in 40Ca. On the other hand, 40Ca may desorb more easily, especially if the bond strength is lower as in the case of aragonite. For kinetic oxygen isotopic fractionation, the faster deprotonation of HC16O3- and the faster incorporation of C16O32- at the surfaces causes a smaller enrichment of 18O in all three polymorphs, which will be preserved at higher precipitation rates. In consequence to the different behavior of calcium and oxygen isotopes, they can be useful for multiproxy applications. Thereby calcium isotopes can be used to identify kinetic effects, especially if both aragonite and calcite, can be analyzed in one sample. Oxygen isotopes are more strongly related to temperature. [1]A. Niedermayr, S.J. Köhler and M. Dietzel (2013), Chemical Geology, 340, 105-120.

Effect of the size of nanoparticles on their dissolution within metal-glass nanocomposites under sustained irradiation

NASA Astrophysics Data System (ADS)

Vu, T. H. Y.; Ramjauny, Y.; Rizza, G.; Hayoun, M.

2016-01-01

We investigate the dissolution law of metallic nanoparticles (NPs) under sustained irradiation. The system is composed of isolated spherical gold NPs (4-100 nm) embedded in an amorphous silica host matrix. Samples are irradiated at room temperature in the nuclear stopping power regime with 4 MeV Au ions for fluences up to 8 × 1016 cm-2. Experimentally, the dependence of the dissolution kinetics on the irradiation fluence is linear for large NPs (45-100 nm) and exponential for small NPs (4-25 nm). A lattice-based kinetic Monte Carlo (KMC) code, which includes atomic diffusion and ballistic displacement events, is used to simulate the dynamical competition between irradiation effects and thermal healing. The KMC simulations allow for a qualitative description of the NP dissolution in two main stages, in good agreement with the experiment. Moreover, the perfect correlation obtained between the evolution of the simulated flux of ejected atoms and the dissolution rate in two stages implies that there exists an effect of the size of NPs on their dissolution and a critical size for the transition between the two stages. The Frost-Russell model providing an analytical solution for the dissolution rate, accounts well for the first dissolution stage but fails in reproducing the data for the second stage. An improved model obtained by including a size-dependent recoil generation rate permits fully describing the dissolution for any NP size. This proves, in particular, that the size effect on the generation rate is the principal reason for the existence of two regimes. Finally, our results also demonstrate that it is justified to use a unidirectional approximation to describe the dissolution of the NP under irradiation, because the solute concentration is particularly low in metal-glass nanocomposites.

Kinetics of dissolution of UO2 in nitric acid solutions: A multiparametric study of the non-catalysed reaction

NASA Astrophysics Data System (ADS)

Cordara, T.; Szenknect, S.; Claparede, L.; Podor, R.; Mesbah, A.; Lavalette, C.; Dacheux, N.

2017-12-01

UO2 pellets were prepared by densification of oxides obtained from the conversion of the oxalate precursor. Then characterized in order to perform a multiparametric study of the dissolution in nitric acid medium. In this frame, for each sample, the densification rate, the grain size and the specific surface area of the prepared pellets were determined prior to the final dissolution experiments. By varying the concentration of the nitric acid solution and temperature, three different and successive steps were identified during the dissolution. Under the less aggressive conditions considered, a first transient step corresponding to the dissolution of the most reactive phases was observed at the solid/solution interface. Then, for all the tested conditions, a steady state step was established during which the normalised dissolution rate was found to be constant. It was followed by a third step characterized by a strong and continuous increase of the normalised dissolution rate. The duration of the steady state, also called "induction period", was found to vary drastically as a function of the HNO3 concentration and temperature. However, independently of the conditions, this steady state step stopped at almost similar dissolved material weight loss and dissolved uranium concentration. During the induction period, no important evolution of the topology of the solid/liquid interface was evidenced authorizing the use of the starting reactive specific surface area to evaluate the normalised dissolution rates thus the chemical durability of the sintered pellets. From the multiparametric study of UO2 dissolution proposed, oxidation of U(IV) to U(VI) by nitrate ions at the solid/liquid interface constitutes the limiting step in the overall dissolution mechanism associated to this induction period.

Investigations of subsurface flow constructed wetlands and associated geomaterial resources in the Akumal and Reforma regions, Quintana Roo, Mexico

NASA Astrophysics Data System (ADS)

Krekeler, Mark P. S.; Probst, Pete; Samsonov, Misha; Tselepis, Cynthia M.; Bates, William; Kearns, Lance E.; Maynard, J. Barry

2007-12-01

Subsurface flow constructed wetlands in the village of Akumal, Quintana Roo, Mexico were surveyed to determine the general status of the wetland systems and provide baseline information for long term monitoring and further study. Twenty subsurface flow wetlands were surveyed and common problems observed in the systems were overloading, poor plant cover, odor, and no secondary containment. Bulk mineral composition of aggregate from two subsurface flow constructed wetlands was determined to consist solely of calcite using bulk powder X-ray diffraction. Some soil structure is developed in the aggregate and aggregate levels in wetlands drop at an estimated rate between 3 and 10 cm/year for overloaded wetlands owing to dissolution. Mineral composition from fresh aggregate samples commonly is a mixture of calcite and aragonite. Trace amounts of Pb, Zn, Co, and Cr were observed in fresh aggregate. Coefficients of permeability ( k) varied from 0.006 to 0.027 cm/s with an average values being 0.016 cm/s. Grain size analysis of fresh aggregate samples indicates there are unimodal and multimodal size distributions in the samples with modes in the coarse and fine sand being common. Investigations of other geologic media from the Reforma region indicate that a dolomite with minor amounts of Fe-oxide and palygorskite is abundant and may be a better aggregate source that the current materials used. A Ca-montmorillonite bed was identified in the Reforma region as well and this unit is suitable to serve as a clay liner to prevent leaks for new and existing wetland systems. These newly discovered geologic resources should aid in the improvement of subsurface flow constructed wetlands in the region. Although problems do exist in these wetlands with respect to design, these systems represent a successful implementation of constructed wetlands at a community level in developing regions.

Prolonged carbonate diagenesis under an evolving late cenozoic climate; Nullarbor Plain, southern Australia

NASA Astrophysics Data System (ADS)

Miller, Cody R.; James, Noel P.; Bone, Yvonne

2012-06-01

The Nullarbor Plain in southern Australia, the largest areal karst on the globe, is a ~ 240,000 km2 uplifted succession of Cenozoic marine carbonates whose surface has been exposed for 14 to 15 m.y. The middle Miocene Nullarbor Limestone forms the upper surface of the plain and hosts a complex and prolonged record of meteoric diagenesis. Such a complete record offers unique insights into the effects of climate, tectonics, sea level, topography, and hydrology on the style and placement of numerous diagenetic events in flat low lying carbonate plains. Alteration took place during three broad phases comprising eight stages that are interpreted to have formed against a background of dramatic climate change. Middle Miocene phase one diagenesis took place under a humid climate and resulted in rapid mineral equilibration, calcite cementation, extensive karst development, and finally widespread lacustrine and palustrine sedimentation. Resultant palustrine sediments, especially terrestrial ooids, are now preserved at the surface and in underlying karst cavities. Latest middle Miocene to middle Pliocene phase two diagenesis occurred during a prolonged period (~ 8 m.y.) of temperate climate and resulted in initial deep cave dissolution during low sea levels and later shallow cave development in the course of a high sea level. Onset of a somewhat more arid climate in the latest Pliocene led to the development of the modern desolate landscape of the Plain. This final phase of diagenesis involved creation of solution pits filled with black limestone pebbles, open and closed dolines with associated colluvium fill, and pervasive pedogenic calcrete. The Nullarbor Plain demonstrates that low lying carbonate plains can have low surficial erosion rates, precisely record relative sea level positions, be able to have extensive caves with extended periods of arrested calcite precipitation, and finally host extensive terrestrial ooid deposits. The importance of this comprehensive paragenetic record is its applicability to not only recognize unconformities in the rock record but to better appreciate the climate in which they formed.

Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

USGS Publications Warehouse

Tuttle, M.L.W.; Breit, G.N.

2009-01-01

Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop-Zones A-C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite-smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C were acquired over 1 Ma. Compositional differences between soil and Zone C are largely attributed to illuvial processes, formation of additional Fe(III) oxides and incorporation of modern organic matter.

Coupled alkali feldspar dissolution and secondary mineral precipitation in batch systems: 4. Numerical modeling of kinetic reaction paths

NASA Astrophysics Data System (ADS)

Zhu, Chen; Lu, Peng; Zheng, Zuoping; Ganor, Jiwchar

2010-07-01

This paper explores how dissolution and precipitation reactions are coupled in batch reactor experimental systems at elevated temperatures. This is the fourth paper in our series of "Coupled Alkali Feldspar Dissolution and Secondary Mineral Precipitation in Batch Systems". In our third paper, we demonstrated via speciation-solubility modeling that partial equilibrium between secondary minerals and aqueous solutions was not attained in feldspar hydrolysis batch reactors at 90-300 °C and that a strong coupling between dissolution and precipitation reactions follows as a consequence of the slower precipitation of secondary minerals ( Zhu and Lu, 2009). Here, we develop this concept further by using numerical reaction path models to elucidate how the dissolution and precipitation reactions are coupled. Modeling results show that a quasi-steady state was reached. At the quasi-steady state, dissolution reactions proceeded at rates that are orders of magnitude slower than the rates measured at far from equilibrium. The quasi-steady state is determined by the relative rate constants, and strongly influenced by the function of Gibbs free energy of reaction ( ΔG) in the rate laws. To explore the potential effects of fluid flow rates on the coupling of reactions, we extrapolate a batch system ( Ganor et al., 2007) to open systems and simulated one-dimensional reactive mass transport for oligoclase dissolution and kaolinite precipitation in homogeneous porous media. Different steady states were achieved at different locations along the one-dimensional domain. The time-space distribution and saturation indices (SI) at the steady states were a function of flow rates for a given kinetic model. Regardless of the differences in SI, the ratio between oligoclase dissolution rates and kaolinite precipitation rates remained 1.626, as in the batch system case ( Ganor et al., 2007). Therefore, our simulation results demonstrated coupling among dissolution, precipitation, and flow rates. Results reported in this communication lend support to our hypothesis that slow secondary mineral precipitation explains part of the well-known apparent discrepancy between lab measured and field estimated feldspar dissolution rates ( Zhu et al., 2004). Here we show how the slow secondary mineral precipitation provides a regulator to explain why the systems are held close to equilibrium and show how the most often-quoted "near equilibrium" explanation for an apparent field-lab discrepancy can work quantitatively. The substantiated hypothesis now offers the promise of reconciling part of the apparent field-lab discrepancy.

From Peptides to Proteins: Systematic Control of Net Molecular Charge and Hydrophilicity on the Kinetics of Calcite Growth

NASA Astrophysics Data System (ADS)

Elhadj, S.; de Yoreo, J. J.; Hoyer, J. J.; Dove, P. M.

2006-12-01

The compartment-specific compositions of biologic molecules isolated from biominerals suggest that control of mineral growth may be linked to biochemical features. Here we define a systematic relationship between the ability of biomolecules in solution to promote the growth of calcite (CaCO3) and their net negative molecular charge and hydrophilicity. The degree of enhancement is dependent on peptide composition, but not on peptide sequence. Data analysis shows that this rate enhancement arises from an increase in the kinetic coefficient. We interpret the mechanism of growth enhancement to be a catalytic process whereby biomolecules reduce the magnitude of the diffusive barrier, Ek, by perturbations that displace water molecules- a water shell destruction mechanism. The result is a decrease in the repulsive barrier for attachment of solutes to the solid phase. This previously unrecognized relationship also rationalizes recently reported data showing acceleration of calcite growth rates over rates measured in the pure system by nanomolar levels of abalone nacre proteins. These findings show that the growth-modifying properties of small model peptides may be scaled up to analyze mineralization processes that are mediated by more complex proteins. We suggest that enhancement of calcite growth may now be estimated a priori from the composition of peptide sequences and the calculated values of hydrophilicity and net molecular charge without need for detailed tests for each biomolecule. This insight may contribute to an improved understanding of mineralization in diverse systems of biomineralization.

Dissolution of Uranium(IV) Oxide in Solutions of Ammonium Carbonate and Hydrogen Peroxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Steven C.; Peper, Shane M.; Douglas, Matthew

2009-09-12

Understanding the dissolution characteristics of uranium oxides is of fundamental scientific interest. Bench scale experiments were conducted to determine the optimal dissolution parameters of uranium(IV) oxide (UO2) powder in solutions of ammonium carbonate [(NH4)2CO3] and hydrogen peroxide (H2O2). Experimental parameters included variable peroxide and carbonate concentrations, and temperature. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M (1:1 to 40:1 mol ratio H2O2:U), with no apparent maximum rate reached under the limited conditions used in our study. Temperature ranging studies show the dissolution rate of UO2 inmore » 1 M (NH4)2CO3 and 0.1 M H2O2 (2:1 mol ratio H2O2:U) increases linearly from 15 °C to 60 °C, again with no apparent maximum rate reached. Dissolution of UO2 in solutions with constant [H2O2] and [(NH4)2CO3] ranging from 0.5 to 2 M showed no difference in rate; however dissolution was significantly reduced in 0.05 M (NH4)2CO3 solution. The results of this study demonstrate the influence of [H2O2], [(NH4)2CO3], and temperature on the dissolution of UO2 in peroxide-containing (NH4)2CO3 solutions. Future studies are planned to elucidate the solution and solid state complexes in these systems.« less

Disintegration rate and properties of active pharmaceutical ingredient particles as determined from the dissolution time profile of a pharmaceutical formulation: an inverse problem.

PubMed

Horkovics-Kovats, Stefan

2014-02-01

Dissolution profile of a finished dosage form (FDF) contains hidden information regarding the disintegration of the form and the particle properties of the active pharmaceutical ingredient. Here, an extraction of this information from the dissolution profile without limitation to sink conditions is provided. In the article, mathematical relationships between the continuously measured dissolution profile of an FDF containing uniform or heterogeneous particles and its disintegration rate are developed. Further, the determinability of the disintegration kinetics and particle properties released from an FDF using the derived recurrent procedure was analyzed. On the basis of the theoretical data sets, it was demonstrated that the introduced analysis of dissolution profiles correctly identifies the disintegration rate of FDF containing multiple particle types. Furthermore, for known disintegration rates, the intrinsic lifetime of particles (time needed for total particle dissolution in infinite volume) released from the FDF and their relative amount can be determined. The extractable information from FDF dissolution time profiles can be utilized in designing of the formulation process, resulting in improved understanding of FDF properties, contributing thus to the implementation of quality by design in the FDF development. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.

An efficient phosphorus scavenging from aqueous solution using magnesiothermally modified bio-calcite.

PubMed

Ahmad, Munir; Ahmad, Mahtab; Usman, Adel R A; Al-Faraj, Abdullah S; Ok, Yong Sik; Hussain, Qaiser; Abduljabbar, Adel S; Al-Wabel, Mohammad I

2018-07-01

Bio-calcite (BC) derived from waste hen eggshell was subjected to thermal treatments (calcined bio-calcite (CBC)). The BC and CBC were further modified via magnesiothermal treatments to produce modified bio-calcite (MBC) and modified calcined bio-calcite (MCBC), respectively, and evaluated as a novel green sorbent for P removal from aqueous solutions in the batch experiments. Modified BC exhibited improved structural and chemical properties, such as porosity, surface area, thermal stability, mineralogy and functional groups, than pristine material. Langmuir and Freundlich models well described the P sorption onto both thermally and magnesiothermally sorbents, respectively, suggesting mono- and multi-layer sorption. Langmuir predicted highest P sorption capacities were in the order of: MCBC (43.33 mg g -1 ) > MBC (35.63 mg g- 1 ) > CBC (34.38 mg g -1 ) > BC (30.68 mg g -1 ). The MBC and MCBC removed 100% P up to 50 mg P L -1 , which reduced to 35.43 and 39.96%, respectively, when P concentration was increased up to 1000 mg L -1 . Dynamics of P sorption was well explained by the pseudo-second-order rate equation, with the highest sorption rate of 4.32 mg g -1  min -1 for the MCBC. Hydroxylapatite [Ca 10 (PO 4 ) 6 (OH) 2 ] and brushite [CaH(PO 4 )·2H 2 O] were detected after P sorption onto the modified sorbents by X-ray diffraction analysis, suggesting chemisorption as the operating sorption mechanism.

Low-magnesium calcite produced by coralline algae in seawater of Late Cretaceous composition

PubMed Central

Stanley, Steven M.; Ries, Justin B.; Hardie, Lawrence A.

2002-01-01

Shifts in the Mg/Ca ratio of seawater driven by changes in midocean ridge spreading rates have produced oscillations in the mineralogy of nonskeletal carbonate precipitates from seawater on time scales of 108 years. Since Cambrian time, skeletal mineralogies of anatomically simple organisms functioning as major reef builders or producers of shallow marine limestones have generally corresponded in mineral composition to nonskeletal precipitates. Here we report on experiments showing that the ambient Mg/Ca ratio actually governs the skeletal mineralogy of some simple organisms. In modern seas, coralline algae produce skeletons of high-Mg calcite (>4 mol % MgCO3). We grew three species of these algae in artificial seawaters having three different Mg/Ca ratios. All of the species incorporated amounts of Mg into their skeletons in proportion to the ambient Mg/Ca ratio, mimicking the pattern for nonskeletal precipitation. Thus, the algae calcified as if they were simply inducing precipitation from seawater through their consumption of CO2 for photosynthesis; presumably organic templates specify the calcite crystal structure of their skeletons. In artificial seawater with the low Mg/Ca ratio of Late Cretaceous seas, the algae in our experiments produced low-Mg calcite (<4 mol % MgCO3), the carbonate mineral formed by nonskeletal precipitation in those ancient seas. Our results suggest that many taxa that produce high-Mg calcite today produced low-Mg calcite in Late Cretaceous seas. PMID:12399549

21 CFR 320.1 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-04-01

..., where applicable, content uniformity, disintegration times, and/or dissolution rates. (d) Pharmaceutical..., disintegration times and/or dissolution rates. (e) Bioequivalence means the absence of a significant difference...

Secondary calcification and dissolution respond differently to future ocean conditions

NASA Astrophysics Data System (ADS)

Silbiger, N. J.; Donahue, M. J.

2015-01-01

Climate change threatens both the accretion and erosion processes that sustain coral reefs. Secondary calcification, bioerosion, and reef dissolution are integral to the structural complexity and long-term persistence of coral reefs, yet these processes have received less research attention than reef accretion by corals. In this study, we use climate scenarios from RCP 8.5 to examine the combined effects of rising ocean acidity and sea surface temperature (SST) on both secondary calcification and dissolution rates of a natural coral rubble community using a flow-through aquarium system. We found that secondary reef calcification and dissolution responded differently to the combined effect of pCO2 and temperature. Calcification had a non-linear response to the combined effect of pCO2 and temperature: the highest calcification rate occurred slightly above ambient conditions and the lowest calcification rate was in the highest temperature-pCO2 condition. In contrast, dissolution increased linearly with temperature-pCO2 . The rubble community switched from net calcification to net dissolution at +271 μatm pCO2 and 0.75 °C above ambient conditions, suggesting that rubble reefs may shift from net calcification to net dissolution before the end of the century. Our results indicate that (i) dissolution may be more sensitive to climate change than calcification and (ii) that calcification and dissolution have different functional responses to climate stressors; this highlights the need to study the effects of climate stressors on both calcification and dissolution to predict future changes in coral reefs.

Secondary calcification and dissolution respond differently to future ocean conditions

NASA Astrophysics Data System (ADS)

Silbiger, N. J.; Donahue, M. J.

2014-09-01

Climate change threatens both the accretion and erosion processes that sustain coral reefs. Secondary calcification, bioerosion, and reef dissolution are integral to the structural complexity and long-term persistence of coral reefs, yet these processes have received less research attention than reef accretion by corals. In this study, we use climate scenarios from RCP8.5 to examine the combined effects of rising ocean acidity and SST on both secondary calcification and dissolution rates of a natural coral rubble community using a flow-through aquarium system. We found that secondary reef calcification and dissolution responded differently to the combined effect of pCO2 and temperature. Calcification had a non-linear response to the combined effect of pCO2-temperature: the highest calcification rate occurred slightly above ambient conditions and the lowest calcification rate was in the highest pCO2-temperature condition. In contrast, dissolution increased linearly with pCO2-temperature. The rubble community switched from net calcification to net dissolution at +272 μatm pCO2 and 0.84 °C above ambient conditions, suggesting that rubble reefs may shift from net calcification to net dissolution before the end of the century. Our results indicate that dissolution may be more sensitive to climate change than calcification, and that calcification and dissolution have different functional responses to climate stressors, highlighting the need to study the effects of climate stressors on both calcification and dissolution to predict future changes in coral reefs.

Low temperature dissolution flowsheet for plutonium metal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daniel, W. E.; Almond, P. M.; Rudisill, T. S.

2016-05-01

The H-Canyon flowsheet used to dissolve Pu metal for PuO 2 production utilizes boiling HNO 3. SRNL was requested to develop a complementary dissolution flowsheet at two reduced temperature ranges. The dissolution and H 2 generation rates of Pu metal were investigated using a dissolving solution at ambient temperature (20-30 °C) and for an intermediate temperature of 50-60 °C. Additionally, the testing included an investigation of the dissolution rates and characterization of the off-gas generated from the ambient temperature dissolution of carbon steel cans and the nylon bags that contain the Pu metal when charged to the dissolver.

Effective Permeability Change in Wellbore Cement with Carbon Dioxide Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Um, Wooyong; Jung, Hun Bok; Martin, Paul F.

2011-11-01

Portland cement, a common sealing material for wellbores for geological carbon sequestration was reacted with CO{sub 2} in supercritical, gaseous, and aqueous phases at various pressure and temperature conditions to simulate cement-CO{sub 2} reaction along the wellbore from carbon injection depth to the near-surface. Hydrated Portland cement columns (14 mm diameter x 90 mm length; water-to-cement ratio = 0.33) including additives such as steel coupons and Wallula basalt fragments were reacted with CO{sub 2} in the wet supercritical (the top half) and dissolved (the bottom half) phases under carbon sequestration condition with high pressure (10 MPa) and temperature (50 C)more » for 5 months, while small-sized hydrated Portland cement columns (7 mm diameter x 20 mm length; water-to-cement ratio = 0.38) were reacted with CO{sub 2} in dissolved phase at high pressure (10 MPa) and temperature (50 C) for 1 month or with wet CO{sub 2} in gaseous phase at low pressure (0.2 MPa) and temperature (20 C) for 3 months. XMT images reveal that the cement reacted with CO{sub 2} saturated groundwater had degradation depth of {approx}1 mm for 1 month and {approx}3.5 mm for 5 month, whereas the degradation was minor with cement exposure to supercritical CO{sub 2}. SEM-EDS analysis showed that the carbonated cement was comprised of three distinct zones; the innermost less degraded zone with Ca atom % > C atom %, the inner degraded zone with Ca atom % {approx} C atom % due to precipitation of calcite, the outer degraded zone with C atom % > Ca atom % due to dissolution of calcite and C-S-H, as well as adsorption of carbon to cement matrix. The outer degraded zone of carbonated cement was porous and fractured because of dissolution-dominated reaction by carbonic acid exposure, which resulted in the increase in BJH pore volume and BET surface area. In contrast, cement-wet CO{sub 2}(g) reaction at low P (0.2 MPa)-T (20 C) conditions for 1 to 3 months was dominated by precipitation of micron-sized calcite on the outside surface of cement, which resulted in the decrease in BJH pore volume and BET surface area. Cement carbonation and pore structure change are significantly dependent on pressure and temperature conditions as well as the phase of CO{sub 2}, which controls the balance between precipitation and dissolution in cement matrix. Geochemical modeling result suggests that ratio of solid (cement)-to-solution (carbonated water) has a significant effect on cement carbonation, thus the cement-CO{sub 2} reaction experiment needs to be conducted under realistic conditions representing the in-situ wellbore environment of carbon sequestration field site. Total porosity and air permeability for a duplicate cement column with water-to-cement ratio of 0.38 measured after oven-drying by Core Laboratories using Boyle's Law technique and steady-state method were 31% and 0.576 mD. A novel method to measure the effective liquid permeability of a cement column using X-ray micro-tomography images after injection of pressurized KI (potassium iodide) is under development by PNNL. Preliminary results indicate the permeability of a cement column with water-to-cement ratio of 0.38 is 4-8 mD. PNNL will apply the method to understand the effective permeability change of Portland cement by CO{sub 2}(g) reaction under a variety of pressure and temperature conditions to develop a more reliable well-bore leakage risk model.« less

Inhibition of calcite precipitation by natural organic material: Kinetics, mechanism, and thermodynamics

USGS Publications Warehouse

Lin, Y.-P.; Singer, P.C.; Aiken, G.R.

2005-01-01

The inhibition of calcite precipitation by natural organic material (NOM) in solutions seeded with calcite was investigated using a pH-stat system. Experiments were carried out using three NOMs with different physical/chemical properties. For each of the materials, inhibition was found to be more effective at lower carbonate/calcium ratios and lower pH values. The reduction in the precipitation rate could be explained by a Langmuir adsorption model using a conditional equilibrium constant. By identification of the type of site on the NOM molecules that is involved in the adsorption reaction, the "conditional" equilibrium constants obtained at different solution compositions converged to a single "nonconditional" value. The thermodynamic data determined at 25??C and 1 atm suggest that the interaction between NOM molecules and the calcite surface is chemisorptive in nature and that adsorption is an endothermic reaction driven by the entropy change. The greatest degree of inhibition was observed for the NOM with the highest molecular weight and aromatic carbon content. For a given type of NOM, the degree of inhibition of calcite precipitation was dictated by the balance between the enthalpy change and the entropy change of the adsorption reaction. ?? 2005 American Chemical Society.

A New Multi-Basin Calibration for Estimating Paleo-Temperature Using Mg/Ca from Tests of Neogloboquadrina dutertrei

NASA Astrophysics Data System (ADS)

Collins, M. S.; Hertzberg, J. E.; Mekik, F.; Schmidt, M. W.

2017-12-01

Based on the thermodynamics of solid-solution substitution of Mg for Ca in biogenic calcite, magnesium to calcium ratios in planktonic foraminifera have been proposed as a means by which variations in habitat water temperatures can be reconstructed. Doing this accurately has been a problem, however, as we demonstrate that various calibration equations provide disparate temperature estimates from the same Mg/Ca dataset. We examined both new and published data to derive a globally applicable temperature-Mg/Ca relationship and from this relationship to accurately predict habitat depth for Neogloboquadrina dutertrei - a deep chlorophyll maximum dweller. N. dutertrei samples collected from Atlantic core tops were analyzed for trace element compositions at Texas A&M University, and the measured Mg/Ca ratios were used to predict habitat temperatures using multiple pre-existing calibration equations. When combining Atlantic and previously published Pacific Mg/Ca datasets for N. dutertrei, a notable dissolution effect was evident. To overcome this issue, we used the G. menardii Fragmentation Index (MFI) to account for dissolution and generated a multi-basin temperature equation using multiple linear regression to predict habitat temperature. However, the correlations between Mg/Ca and temperature, as well as the calculated MFI percent dissolved, suggest that N. dutertrei Mg/Ca ratios are affected equally by both variables. While correcting for dissolution makes habitat depth estimation more accurate, the lack of a definitively strong correlation between Mg/Ca and temperature is likely an effect of variable habitat depth for this species because most calibration equations have assumed a uniform habitat depth for this taxon.

Dissolution and sorption of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT) residues from detonated mineral surfaces.

PubMed

Jaramillo, Ashley M; Douglas, Thomas A; Walsh, Marianne E; Trainor, Thomas P

2011-08-01

Composition B (Comp B) is a commonly used military formulation composed of the toxic explosive compounds 2,4,6-trinitrotoluene (TNT), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Numerous studies of the temporal fate of explosive compounds in soils, surface water and laboratory batch reactors have been conducted. However, most of these investigations relied on the application of explosive compounds to the media via aqueous addition and thus these studies do not provide information on the real world loading of explosive residues during detonation events. To address this we investigated the dissolution and sorption of TNT and RDX from Comp B residues loaded to pure mineral phases through controlled detonation. Mineral phases included nontronite, vermiculite, biotite and Ottawa sand (quartz with minor calcite). High Performance Liquid Chromatography and Attenuated Total Reflectance Fourier Transform Infrared spectroscopy were used to investigate the dissolution and sorption of TNT and RDX residues loaded onto the mineral surfaces. Detonation resulted in heterogeneous loading of TNT and RDX onto the mineral surfaces. Explosive compound residues dissolved rapidly (within 9 h) in all samples but maximum concentrations for TNT and RDX were not consistent over time due to precipitation from solution, sorption onto mineral surfaces, and/or chemical reactions between explosive compounds and mineral surfaces. We provide a conceptual model of the physical and chemical processes governing the fate of explosive compound residues in soil minerals controlled by sorption-desorption processes. Published by Elsevier Ltd.

EFFECTS OF PORE STRUCTURE CHANGE AND MULTI-SCALE HETEROGENEITY ON CONTAMINANT TRANSPORT AND REACTION RATE UPSCALING

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lindquist, W. Brent; Jones, Keith W.; Um, Wooyong

2013-02-15

This project addressed the scaling of geochemical reactions to core and field scales, and the interrelationship between reaction rates and flow in porous media. We targeted reactive transport problems relevant to the Hanford site - specifically the reaction of highly caustic, radioactive waste solutions with subsurface sediments, and the immobilization of 90Sr and 129I through mineral incorporation and passive flow blockage, respectively. We addressed the correlation of results for pore-scale fluid-soil interaction with field-scale fluid flow, with the specific goals of (i) predicting attenuation of radionuclide concentration; (ii) estimating changes in flow rates through changes of soil permeabilities; and (iii)more » estimating effective reaction rates. In supplemental work, we also simulated reactive transport systems relevant to geologic carbon sequestration. As a whole, this research generated a better understanding of reactive transport in porous media, and resulted in more accurate methods for reaction rate upscaling and improved prediction of permeability evolution. These scientific advancements will ultimately lead to better tools for management and remediation of DOE’s legacy waste problems. We established three key issues of reactive flow upscaling, and organized this project in three corresponding thrust areas. 1) Reactive flow experiments. The combination of mineral dissolution and precipitation alters pore network structure and the subsequent flow velocities, thereby creating a complex interaction between reaction and transport. To examine this phenomenon, we conducted controlled laboratory experimentation using reactive flow-through columns. Results and Key Findings: Four reactive column experiments (S1, S3, S4, S5) have been completed in which simulated tank waste leachage (STWL) was reacted with pure quartz sand, with and without Aluminum. The STWL is a caustic solution that dissolves quartz. Because Al is a necessary element in the formation of secondary mineral precipitates (cancrinite), conducting experiments under conditions with and without Al allowed us to experimentally separate the conditions that lead to quartz dissolution from the conditions that lead to quartz dissolution plus cancrinite precipitation. Consistent with our expectations, in the experiments without Al, there was a substantial reduction in volume of the solid matrix. With Al there was a net increase in the volume of the solid matrix. The rate and extent of reaction was found to increase with temperature. These results demonstrate a successful effort to identify conditions that lead to increases and conditions that lead to decreases in solid matrix volume due to reactions of caustic tank wastes with quartz sands. In addition, we have begun to work with slightly larger, intermediate-scale columns packed with Hanford natural sediments and quartz. Similar dissolution and precipitation were observed in these colums. The measurements are being interpreted with reactive transport modeling using STOMP; preliminary observations are reported here. 2) Multi-Scale Imaging and Analysis. Mineral dissolution and precipitation rates within a porous medium will be different in different pores due to natural heterogeneity and the heterogeneity that is created from the reactions themselves. We used a combination of X-ray computed microtomography, backscattered electron and energy dispersive X-ray spectroscopy combined with computational image analysis to quantify pore structure, mineral distribution, structure changes and fluid-air and fluid-grain interfaces. Results and Key Findings: Three of the columns from the reactive flow experiments at PNNL (S1, S3, S4) were imaged using 3D X-ray computed microtomography (XCMT) at BNL and analyzed using 3DMA-rock at SUNY Stony Brook. The imaging results support the mass balance findings reported by Dr. Um’s group, regarding the substantial dissolution of quartz in column S1. An important observation is that of grain movement accompanying dissolution in the unconsolidated media. The resultant movement changes the anticipated findings for pore and throat size distributions. For column S3, with cancrinite precipitation accompanying quartz dissolution, the precitiation halts much of the grain movement and more systematic distributions are obtained. Column S4, which was sealed with caustic solution acted as a control sample to study reactive effects during periods when columns S1 and S3 were sealed between flow experiments. No significant changes are observed in S4 with time. At Princeton, the imaging and analysis work focused on the effects of mineral precipitation and advancing our understanding of the impacts of these reactions on reactive transport in subsurface sediments. These findings are described in detail below, and have been published in L.E. Crandell, C.A. Peters, W. Um, K.W. Jones, W.B. Lindquist, 2012. “Changes in the pore network structure of Hanford sediment after reaction with caustic tank wastes.” Journal of Contaminant Hydrology 131 (2012) 89–99. 3) Multi-Scale Modeling and Up-Scaling. Using an array of modeling approaches, we examined pore-scale variations in physical and mineralogical properties, flow velocities, and (for unsaturated conditions) wetting fluid/grain surface areas, and permeability evolution. Results and Key Findings: To predict the column permeability and estimate the impact of mineral precipitation, pore network models were informed using the pore and throat-size distributions from the imaging analyses. As a comparison, supplemental analyses were performed on Viking sandstone specimens from the Alberta sedimentary basin. In another part of this study we sought to understand how carbonate rocks in contact with CO2-rich brines change due to the precipitation or dissolution of fast-reacting minerals such as calcite and dolomite. Using a newly developed reactive-transport pore-network model we were able to identify the conditions that lead to significant permeability changes. These findings are presented below and are compiled in a publication that is under review: J.P. Nogues, J.P. Fitts, M.A. Celia, C.A. Peters. “Permeability evolution due to dissolution and precipitation of carbonates using reactive transport modeling in pore networks”, Submitted: Water Resources Research, 2013.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jones, B.; Renault, R.W.

Platy calcite crystals, which have their c axis parallel to their shortest length axis, are common components of travertine deposits found around some hot springs in the Kenya Rift Valley. They are composite crystals formed of numerous paper-thin subcrystals. Individual plates allowed to grow without obstruction develop a hexagonal motif. The Kenyan crystals typically form in hot (>75 C) waters that have a low Ca content (<10 mg/l), a high CO{sub 2} content, and a high rate of CO{sub 2} degassing. At Chemurkeu, aggregates of numerous small platy crystals collectively form lattice crystals that superficially resemble ray crystals. The wallsmore » of the lattice crystals are formed of large platy crystals that have their long and intermediate length axes aligned parallel to the plane of the long axis of the lattice crystal. Internally, the lattice crystals are formed of small platy calcite crystals arranged in a boxlike pattern that creates the appearance of a lattice when viewed in thin section. Lattice crystals are highly porous, with each pore being enclosed by platy crystals. At Lorusio, travertines are mainly formed of pseudodentrites that are constructed by numerous small platy crystals attached to a main stem which is a large platy crystal that commonly curves along its long axis. The pseudodentrites are the main construction blocks in ledges and lilypads that form in the vent pool and spring outflow channels, where the water is too hot for microbes other than hyperthermophiles. The platy calcite crystals in the Kenyan travertines are morphologically similar to platy calcite crystals that form as scale in pipes in the geothermal fields of New Zealand and hydrothermal angel wing calcite from the La Fe mine in Mexico. Comparison of the Kenyan and New Zealand crystals indicates that platy calcite crystals form from waters with a low Ca{sup 2+} content and a high CO{sub 3}/Ca ratio due to rapid rates of CO{sub 2} degassing.« less

Effect of basin physical characteristics on solute fluxes in nine alpine/subalpine basins, Colorado, USA

USGS Publications Warehouse

Sueker, J.K.; Clow, D.W.; Ryan, J.N.; Jarrett, R.D.

2001-01-01

Alpine/subalpine basins may exhibit substantial variability in solute fluxes despite many apparent similarities in basin characteristics. An evaluation of controls on spatial patterns in solute fluxes may allow development of predictive tools for assessing basin sensitivity to outside perturbations such as climate change or deposition of atmospheric pollutants. Relationships between basin physical characteristics, determined from geographical information system (GIS) tools, and solute fluxes and mineral weathering rates were explored for nine alpine/subalpine basins in Rocky Mountain National Park, Colorado, using correlation analyses for 1993 and 1994 data. Stream-water nitrate fluxes were correlated positively with basin characteristics associated with the talus environment; i.e., the fractional amounts of steep slopes (??? 30??), unvegetated terrain and young debris (primarily Holocene till) in the basins, and were correlated negatively with fractional amounts of subalpine meadow terrain. Correlations with nitrate indicate the importance of the talus environment in promoting nitrate flux and the mitigating effect of areas with established vegetation, such as subalpine meadows. Total mineral weathering rates for the basins ranged from about 300 to 600 mol ha-1 year -1. Oligoclase weathering accounted for 30 to 73% of the total mineral weathering flux, and was positively correlated with the amount of old debris (primarily Pleistocene glacial till) in the basins. Although calcite is found in trace amounts in bedrock, calcite weathering accounted for up to 44% of the total mineral weathering flux. Calcite was strongly correlated with steep slope, unvegetated terrain, and young debris-probably because physical weathering in steep-gradient areas exposes fresh mineral surfaces that contain calcite for chemical weathering. Oligoclase and calcite weathering are the dominant sources of alkalinity in the basins. However, atmospherically deposited acids consume much of the alkalinity generated by weathering of calcite and other minerals in the talus environment. Published in 2001 by John Wiley and Sons, Ltd.

Effect of basin physical characteristics on solute fluxes in nine alpine/subalpine basins, Colorado, USA

NASA Astrophysics Data System (ADS)

Sueker, Julie K.; Clow, David W.; Ryan, Joseph N.; Jarrett, Robert D.

2001-10-01

Alpine/subalpine basins may exhibit substantial variability in solute fluxes despite many apparent similarities in basin characteristics. An evaluation of controls on spatial patterns in solute fluxes may allow development of predictive tools for assessing basin sensitivity to outside perturbations such as climate change or deposition of atmospheric pollutants. Relationships between basin physical characteristics, determined from geographical information system (GIS) tools, and solute fluxes and mineral weathering rates were explored for nine alpine/subalpine basins in Rocky Mountain National Park, Colorado, using correlation analyses for 1993 and 1994 data. Stream-water nitrate fluxes were correlated positively with basin characteristics associated with the talus environment; i.e., the fractional amounts of steep slopes ( 30°), unvegetated terrain and young debris (primarily Holocene till) in the basins, and were correlated negatively with fractional amounts of subalpine meadow terrain. Correlations with nitrate indicate the importance of the talus environment in promoting nitrate flux and the mitigating effect of areas with established vegetation, such as subalpine meadows. Total mineral weathering rates for the basins ranged from about 300 to 600 mol ha-1 year-1. Oligoclase weathering accounted for 30 to 73% of the total mineral weathering flux, and was positively correlated with the amount of old debris (primarily Pleistocene glacial till) in the basins. Although calcite is found in trace amounts in bedrock, calcite weathering accounted for up to 44% of the total mineral weathering flux. Calcite was strongly correlated with steep slope, unvegetated terrain, and young debris - probably because physical weathering in steep-gradient areas exposes fresh mineral surfaces that contain calcite for chemical weathering. Oligoclase and calcite weathering are the dominant sources of alkalinity in the basins. However, atmospherically deposited acids consume much of the alkalinity generated by weathering of calcite and other minerals in the talus environment. Published in 2001 by John Wiley & Sons, Ltd.

Evidence for Seismic and Aseismic Slip along a Foreland Thrust Fault, Southern Appalachians

NASA Astrophysics Data System (ADS)

Newman, J.; Wells, R. K.; Holyoke, C. W.; Wojtal, S. F.

2013-12-01

Studies of deformation along ancient thrust faults form the basis for much of our fundamental understanding of fault and shear zone processes. These classic studies interpreted meso- and microstructures as formed during aseismic creep. Recent experimental studies, and studies of naturally deformed rocks in seismically active regions, reveal similar microstructures to those observed locally in a carbonate foreland thrust from the southern Appalachians, suggesting that this thrust fault preserves evidence of both seismic and aseismic deformation. The Copper Creek thrust, TN, accommodated 15-20 km displacement, at depths of 4-6 km, as estimated from balanced cross-sections. At the Diggs Gap exposure of the Copper Creek thrust, an approximately 2 cm thick, vein-like shear zone separates shale layers in the hanging wall and footwall. The shear zone is composed of anastomosing layers of ultrafine-grained calcite and/or shale as well as aggregate clasts of ultrafine-grained calcite or shale. The boundary between the shear zone and the hanging wall is sharp, with slickensides along the boundary, parallel to the shear zone movement direction. A 350 μm-thick layer of ultrafine-grained calcite separates the shear zone and the footwall. Fault parallel and perpendicular calcite veins are common in the footwall and increase in density towards the shear zone. Microstructures within the vein-like shear zone that are similar to those observed in experimental studies of unstable slip include: ultrafine-grained calcite (~0.34 μm), nano-aggregate clasts (100-300 nm), injection structures, and vein-wrapped and matrix-wrapped clasts. Not all structures within the shear zone and ultrafine-grained calcite layer suggest seismic slip. Within the footwall veins and calcite aggregate clasts within the shear zone, pores at twin-twin intersections suggest plasticity-induced fracturing as the main mechanism for grain size reduction. Interpenetrating grain boundaries in ultrafine-grained calcite and a lack of a lattice preferred orientation suggest ultrafine-grained calcite deformed by diffusion creep accommodated grain boundary sliding. These structures suggest a strain-rate between 10-15 - 10-11 s-1, using calcite flow laws at temperatures 150-250 °C. Microstructures suggest both seismic and aseismic slip along this ancient fault zone. During periods of aseismic slip, deformation is accommodated by plasticity-induced fracturing and diffusion creep. Calcite veins suggest an increase in pore-fluid pressure, contributing to fluidized and unstable flow, but also providing the calcite that deformed by diffusion creep during aseismic creep.

DISSOLUTION OF PLUTONIUM METAL IN 8-10 M NITRIC ACID

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudisill, T. S.; Pierce, R. A.

2012-07-02

The H-Canyon facility will be used to dissolve Pu metal for subsequent purification and conversion to plutonium dioxide (PuO{sub 2}) using Phase II of HB-Line. To support the new mission, the development of a Pu metal dissolution flowsheet which utilizes concentrated (8-10 M) nitric acid (HNO{sub 3}) solutions containing potassium fluoride (KF) is required. Dissolution of Pu metal in concentrated HNO{sub 3} is desired to eliminate the need to adjust the solution acidity prior to purification by anion exchange. The preferred flowsheet would use 8-10 M HNO{sub 3}, 0.015-0.07 M KF, and 0.5-1.0 g/L Gd to dissolve the Pu upmore » to 6.75 g/L. An alternate flowsheet would use 8-10 M HNO{sub 3}, 0.05-0.2 M KF, and 1-2 g/L B to dissolve the Pu. The targeted average Pu metal dissolution rate is 20 mg/min-cm{sup 2}, which is sufficient to dissolve a “standard” 2250-g Pu metal button in 24 h. Plutonium metal dissolution rate measurements showed that if Gd is used as the nuclear poison, the optimum dissolution conditions occur in 10 M HNO{sub 3}, 0.04-0.05 M KF, and 0.5-1.0 g/L Gd at 112 to 116 °C (boiling). These conditions will result in an estimated Pu metal dissolution rate of ~11-15 mg/min-cm{sup 2} and will result in dissolution times of 36-48 h for standard buttons. The recommended minimum and maximum KF concentrations are 0.03 M and 0.07 M, respectively. The data also indicate that lower KF concentrations would yield dissolution rates for B comparable to those observed with Gd at the same HNO{sub 3} concentration and dissolution temperature. To confirm that the optimal conditions identified by the dissolution rate measurements can be used to dissolve Pu metal up to 6.75 g/L in the presence of representative concentrations of Fe and Gd or B, a series of experiments was performed to demonstrate the flowsheets. In three of the five experiments, the offgas generation rate during the dissolution was measured and samples were analyzed for hydrogen gas (H{sub 2}). The use of 10 M HNO{sub 3} containing 0.03-0.05 M KF, 0.5-1.0 g/L Gd, and 1.9 g/L Fe resulted in complete dissolution of the metal in 2.0-3.5 h. When B was used as the neutron poison, 10 M HNO{sub 3} solutions containing 0.05-0.1 M KF, 1.9 g/L Fe, and 1 g/L B resulted in complete dissolution of the metal in 0.75-2.0 h. Dissolution rates estimated using data from the flowsheet demonstrations agreed reasonably well with the measured rates; although, a discrepancy was observed in the Gd system. The presence of 1 g/L Gd or B in the dissolving solution had about the same effect on the dissolution rate. The predominant Pu valence in the dissolving solution was Pu(IV). The concentration of Pu(VI) was evaluated by UV-visible spectroscopy and was estimated to be significantly less than 1 wt %. The offgas generation rates and H{sub 2} concentrations measured in the offgas from experiments performed using 10 M HNO{sub 3} containing 0.05 M KF, 1.9 g/L Fe and either 1 g/L Gd or B were approximately the same. These data support the conclusion that the presence of either 1 g/L Gd or B had the same general effect on the dissolution rate. The calculated offgas generation during the dissolutions was 0.6 mol offgas/mol of Pu. The H{sub 2} concentration measured in the offgas from the dissolution using Gd as the neutron poison was approximately 0.5 vol %. In the B system, the H{sub 2} ranged from nominally 0.8 to 1 vol % which is about the same as measured in the Gd system within the uncertainty of the analysis. The offgas generation rate for the dissolution performed using 10 M HNO{sub 3} containing 0.03 M KF, 0.5 g/L Gd, and 1.9 g/L Fe was approximately a factor of two less than produced in the other dissolutions; however, the concentration of H{sub 2} measured in the offgas was higher. The adjusted concentration ranged from 2.7 to 8.8 vol % as the dissolution proceeded. Higher concentrations of H{sub 2} occur when the Pu dissolution proceeds by a metal/acid reaction rather than nitrate oxidation. The higher H{sub 2} concentration could be attributed to the reduced activity of the fluoride due to complexation with Pu as the dissolution progressed. Dissolution of Pu metal at 20 °C in 10 M HNO{sub 3} containing 0.05 M KF showed that the Pu metal dissolves slowly without any visible gas generation. As the Pu metal dissolves, it forms a more-dense Pu-bearing solution which sank to the bottom of the dissolution vessel. The dissolved Pu did not form a boundary layer around the sample and failed to distribute homogeneously due to minimal (thermally-induced) mixing. This indicates that in the H-Canyon dissolver insert, the Pu will diffuse out of the insert into the bulk dissolver solution where it will disperse. At 35 °C, the Pu metal dissolved without visible gas generation. However, due to thermal currents caused by maintaining the solution at 35 °C, the dissolved Pu distributed evenly throughout the dissolver solution. It did not form a boundary layer around the sample.« less

Tissue dissolution by a novel multisonic ultracleaning system and sodium hypochlorite.

PubMed

Haapasalo, Markus; Wang, Zhejun; Shen, Ya; Curtis, Allison; Patel, Payal; Khakpour, Mehrzad

2014-08-01

This study aimed to evaluate the effectiveness of a novel Multisonic Ultracleaning System (Sonendo Inc, Laguna Hills, CA) in tissue dissolution in comparison with conventional irrigation devices. Pieces of bovine muscle tissue (68 ± 2 mg) were placed in 0.7-mL test tubes (height: 23.60 mm, inner diameter: 6.00 mm, outer diameter: 7.75 mm) and exposed to 5 minutes of irrigation by different devices. Endodontic devices included the Multisonic Ultracleaning System, the Piezon Master 700 (EMS, Dallas, TX) ultrasonic system with agitation, the EndoVac negative-pressure irrigation system (SybronEndo, Orange, CA), and a conventional positive-pressure 27-G irrigation needle at a flow rate of 10 mL/min. The systems were tested with 0.5%, 3%, and 6% sodium hypochlorite (NaOCl) at room temperature (21°C) as well as 40°C. Irrigation with sterile water was used as a control. The mass of tissue specimens was measured and recorded before and after the use of each device, and if the specimen was completely dissolved visually within 5 minutes, the dissolution time was recorded. The rate of tissue dissolution (%/s) was then calculated. The Multisonic Ultracleaning System had the fastest rate of tissue dissolution (P < .05), at 1.0% ± 0.1% per second using 0.5% NaOCl, 2.3% ± 0.9% per second using 3% NaOCl, and 2.9% ± 0.7% per second using 6% NaOCl. This tissue dissolution rate was more than 8 times greater than the second fastest device tested (P < .01), the Piezon Master 700 ultrasonic system, which resulted in a tissue dissolution rate of 0.328% ± 0.002% per second using 6% NaOCl at 40°C. For all irrigation devices tested, the rate of tissue dissolution increased with a higher concentration and temperature of the NaOCl solution. The novel Multisonic Ultracleaning System achieved a significantly faster tissue dissolution rate when compared with the other systems examined in vitro. Copyright © 2014 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Dissolution of covalent adaptable network polymers in organic solvent

NASA Astrophysics Data System (ADS)

Yu, Kai; Yang, Hua; Dao, Binh H.; Shi, Qian; Yakacki, Christopher M.

2017-12-01

It was recently reported that thermosetting polymers can be fully dissolved in a proper organic solvent utilizing a bond-exchange reaction (BER), where small molecules diffuse into the polymer, break the long polymer chains into short segments, and eventually dissolve the network when sufficient solvent is provided. The solvent-assisted dissolution approach was applied to fully recycle thermosets and their fiber composites. This paper presents the first multi-scale modeling framework to predict the dissolution kinetics and mechanics of thermosets in organic solvent. The model connects the micro-scale network dynamics with macro-scale material properties: in the micro-scale, a model is developed based on the kinetics of BERs to describe the cleavage rate of polymer chains and evolution of chain segment length during the dissolution. The micro-scale model is then fed into a continuum-level model with considerations of the transportation of solvent molecules and chain segments in the system. The model shows good prediction on conversion rate of functional groups, degradation of network mechanical properties, and dissolution rate of thermosets during the dissolution. It identifies the underlying kinetic factors governing the dissolution process, and reveals the influence of different material and processing variables on the dissolution process, such as time, temperature, catalyst concentration, and chain length between cross-links.

High temperature dissolution of oxides in complexing media

NASA Astrophysics Data System (ADS)

Sathyaseelan, Valil S.; Rufus, Appadurai L.; Subramanian, Hariharan; Bhaskarapillai, Anupkumar; Wilson, Shiny; Narasimhan, Sevilimedu V.; Velmurugan, Sankaralingam

2011-12-01

Dissolution of transition metal oxides such as magnetite (Fe 3O 4), mixed ferrites (NiFe 2O 4, ZnFe 2O 4, MgFe 2O 4), bonaccordite (Ni 2FeBO 5) and chromium oxide (Cr 2O 3) in organic complexing media was attempted at higher temperatures (80-180 °C). On increasing the temperature from 80 to 180 °C, the dissolution rate of magnetite in nitrilo triacetic acid (NTA) medium increased six folds. The trend obtained for the dissolution of other oxides was ZnFe 2O 4 > NiFe 2O 4 > MgFe 2O 4 > Cr 2O 3, which followed the same trend as the lability of their metal-oxo bonds. Other complexing agents such as ethylene diamine tetra acetic acid (EDTA), pyridine dicarboxylic acid (PDCA), citric acid and reducing agents viz., oxalic acid and ascorbic acid were also evaluated for their oxide dissolution efficiency at 160 °C. EDTA showed maximum dissolution rate of 21.4 μm/h for magnetite. Addition of oxalic acid/ascorbic acid to complexing media (NTA/EDTA) showed identical effect on the dissolution of magnetite. Addition of hydrazine, another reducing agent, to NTA decreased the rate of dissolution of magnetite by 50%.