Direct conversion of calcium carbonate to C-1-C-3 hydrocarbons

With the objective of investigating the direct conversion of inorganic carbonates such as CaCO3 to hydrocarbons, assisted by transition metal ions, we have carried out studies on CaCO3 in an intimate admixture with iron oxides (FeCaCO) with a wide range of Fe/Ca mole ratios (x), prepared by co-precipitation. The hydrogen reduction of FeCaCO at 673 K gives up to 23% yield of the hydrocarbons CH4, C2H4, C2H6 and C3H8, leaving solid iron residues in the form of iron metal, oxides and carbide particles. The yield of hydrocarbons increases with x and the conversion of hydrocarbons occurs through the formation of CO. While the total yield of hydrocarbons obtained by us is comparable to that in the Fischer-Tropsch synthesis, the selectivity for C-2-C-3 hydrocarbons reported here is noteworthy.

Composite cyclodextrin-calcium carbonate porous microparticles and modified multilayer capsules: novel carriers for encapsulation of hydrophobic drugs

Novel composite cyclodextrin (CD)-CaCO3 spherical porous microparticles have been synthesized through Ca2+-CD complex formation, which influences the crystal growth of CaCO3. The CDs are entrapped and distributed uniformly in the matrix of CaCO3 microparticles during crystallization. The hydrophobic fluorescent molecules coumarin and Nile red (NR) are efficiently encapsulated into these composite CD-CaCO3 porous particles through supramolecular inclusion complexation between entrapped CDs and hydrophobic molecules. Thermogravimetric (TGA) and infrared spectroscopy (IR) analysis of composite CD-CaCO3 particles reveals the presence of large CDs and their strong interaction with calcium carbonate nanoparticles. The resulting composite CD-CaCO3 microparticles are utilized as sacrificial templates for preparation of CD-modified layer-by-layer (LbL) capsules. After dissolution of the carbonate core, CDs are retained in the interior of the capsules in a network fashion and assist in the encapsulation of hydrophobic molecules. The efficient encapsulation of the hydrophobic fluorescent dye, coumarin, was successfully demonstrated using CD-modified capsules. In vitro release of the encapsulated coumarin from the CD-CaCO3 and CD-modified capsules has been demonstrated.

Do stable isotopes in carbonate cement of Mio-Pleistocene Himalayan sediments record paleoecological and paleoclimatic changes?

Non-pedogenic carbonates, such as carbonate cement and nodules in the sandstones, are quite common in the terrestrial geological record. Unlike pedogenic carbonates, their stable isotope ratios lack investigations for paleo-climatic reconstructions. The present investigation therefore, explores the possibility of use of stable isotope studies of non-pedogenic carbonates from the Mb-Pleistocene Siwalik Group of sediments exposed in the Ramnagar sub-basin of the NW Himalaya. Petrographic studies reveal the dominance of micrite fabric in carbonate nodules both of pedogenic and non-pedogenic samples irrespective of specific stratigraphic unit However, calcite as cement in the sandstones shows the dominance of micrite fabric in the younger in age sediments. Seventy-two non-pedogenic carbonate samples from the carbonate nodules and cement in the Siwalik sandstones, ranging in age between similar to 1 Ma and 12.2 Ma, were analyzed for delta C-13 and delta O-18 values. The delta C-13 values vary from -24.77 parts per thousand to -1.1 parts per thousand and delta O-18 values vary from -15.34 parts per thousand to -7.81 parts per thousand. Pedogenic and non-pedogenic carbonates ranging in age between similar to 1 Ma and 6 Ma have largely similar delta C-13 values and the range of delta C-13 values indicate the dominance of C-4 type of vegetation. However, unlike pedogenic carbonates which showed the dominance of C-3 type of vegetation pre- 7 Ma on the basis of delta C-13 -depleted isotopic values (Singh et al., 2011), delta C-13 values are largely enriched in the corresponding aged non-pedogenic carbonates revealing no information on specific type of vegetation. Likewise, paleoprecipitational reconstructions from delta O-18 values in pedogenic carbonates showed a progressive increase in aridity from similar to 12 Ma to recent excluding short term increases in rainfall/monsoon intensity at around 10 Ma, 5 Ma, and 1.8 Ma (Singh et al., 2012). On the contrary, such reconstructions are not possible from the delta O-18 values of non-pedogenic carbonates and indeed the delta O-18 values of non-pedogenic carbonates are largely depleted to as much as 6 parts per thousand from the corresponding pedogenic carbonates. Such differences in delta C-13 and delta O-18 values of non-pedogenic carbonates from pedogenic carbonates are primarily due to the dependence of the former on groundwater conditions responsible for precipitating carbonate. Further, a comparison of isotopic values between non-pedogenic and pedogenic carbonates can be interpreted that post-6 Ma and pre-6 Ma non-pedogenic carbonates were largely formed by shallow and deep groundwater conditions respectively. The result of these investigative studies therefore, suggests that the stable delta C-13 and delta O-18 values of non-pedogenic carbonates, unlike the pedogenic carbonates and irrespective of nature of calcite fabric, showed their little importance in paleoclimatic and paleoecological reconstructions. (C) 2014 Elsevier B.V. All rights reserved.

Stable isotope evidence for ca. 2.7-Ga-old Archean cap carbonates from the Dharwar Supergroup, southern India

Carbon isotope compositions of carbonate rocks from similar to 2.7-Ga-old Neoarchean Vanivilas Formation of the Dharwar Supergroup presented earlier by us are re-evaluated in this study, besides oxygen isotope compositions of a few silica dolomite pairs. The purpose of such a revisit assumes significance in view of recent field evidences that suggest a glaciomarine origin for the matrix-supported conglomerate member, the Talya conglomerate, which underlies the carbonate rocks of the Vanivilas Formation. An in-depth analysis of carbon isotope data reveals preservation of their pristine character despite the rocks having been subjected to metamorphism to different degrees (from lower greenschist to lower amphibolite facies). The dolomitic member of Vanivilas Formation of Marikanive area is characterized by highly depleted delta C-13 value (up to -5 parts per thousand VPDB) and merits as the Indian example of ca. 2.7-Ga-old cap carbonate. This inference is further supported by estimated low temperature of equilibration documented by a few silica dolomite pairs from the Vanivilas Formation collected near Kalche area. These pairs show evidence for oxygen isotopic equilibrium at low temperatures (similar to 0-20 degrees C) with depleted water (delta O-18 = -21 parts per thousand to -15 parts per thousand VSMOW) of glacial origin. We propose that the mineral pairs were deposited during the deglaciation period when the ocean temperature was in its gradual restoration phase. The dolomite of Marikanive area is the first record of cap carbonates from the Indian subcontinent with Neoarchean antiquity.

Tracking the migration of the Indian continent using the carbonate clumped isotope technique on Phanerozoic soil carbonates

Approximately 140 million years ago, the Indian plate separated from Gondwana and migrated by almost 90 degrees latitude to its current location, forming the Himalayan-Tibetan system. Large discrepancies exist in the rate of migration of Indian plate during Phanerozoic. Here we describe a new approach to paleo-latitudinal reconstruction based on simultaneous determination of carbonate formation temperature and delta O-18 of soil carbonates, constrained by the abundances of C-13-O-18 bonds in palaeosol carbonates. Assuming that the palaeosol carbonates have a strong relationship with the composition of the meteoric water, delta O-18 carbonate of palaeosol can constrain paleo-latitudinal position. Weighted mean annual rainfall delta O-18 water values measured at several stations across the southern latitudes are used to derive a polynomial equation: delta(18)Ow = -0.006 x (LAT)(2) - 0.294 x (LAT) - 5.29 which is used for latitudinal reconstruction. We use this approach to show the northward migration of the Indian plate from 46.8 +/- 5.8 degrees S during the Permian (269 M. y.) to 30 +/- 11 degrees S during the Triassic (248 M. y.), 14.7 +/- 8.7 degrees S during the early Cretaceous (135 M. y.), and 28 +/- 8.8 degrees S during the late Cretaceous ( 68 M. y.). Soil carbonate delta O-18 provides an alternative method for tracing the latitudinal position of Indian plate in the past and the estimates are consistent with the paleo-magnetic records which document the position of Indian plate prior to 135 +/- 3 M. y.

I. Impact spallation experiments: fracture patterns and spall velocities. II. Craters in carbonate rocks: an electron paramagnetic resonance analysis of shock damage

This work is divided into two independent papers.

PAPER 1.

Spall velocities were measured for nine experimental impacts into San Marcos gabbro targets. Impact velocities ranged from 1 to 6.5 km/sec. Projectiles were iron, aluminum, lead, and basalt of varying sizes. The projectile masses ranged from a 4 g lead bullet to a 0.04 g aluminum sphere. The velocities of fragments were measured from high-speed films taken of the events. The maximum spall velocity observed was 30 m/sec, or 0.56 percent of the 5.4 km/sec impact velocity. The measured velocities were compared to the spall velocities predicted by the spallation model of Melosh (1984). The compatibility between the spallation model for large planetary impacts and the results of these small scale experiments are considered in detail.

The targets were also bisected to observe the pattern of internal fractures. A series of fractures were observed, whose location coincided with the boundary between rock subjected to the peak shock compression and a theoretical "near surface zone" predicted by the spallation model. Thus, between this boundary and the free surface, the target material should receive reduced levels of compressive stress as compared to the more highly shocked region below.

PAPER 2.

Carbonate samples from the nuclear explosion crater, OAK, and a terrestrial impact crater, Meteor Crater, were analyzed for shock damage using electron para- magnetic resonance, EPR. The first series of samples for OAK Crater were obtained from six boreholes within the crater, and the second series were ejecta samples recovered from the crater floor. The degree of shock damage in the carbonate material was assessed by comparing the sample spectra to spectra of Solenhofen limestone, which had been shocked to known pressures.

The results of the OAK borehole analysis have identified a thin zone of highly shocked carbonate material underneath the crater floor. This zone has a maximum depth of approximately 200 ft below sea floor at the ground zero borehole and decreases in depth towards the crater rim. A layer of highly shocked material is also found on the surface in the vicinity of the reference bolehole, located outside the crater. This material could represent a fallout layer. The ejecta samples have experienced a range of shock pressures.

It was also demonstrated that the EPR technique is feasible for the study of terrestrial impact craters formed in carbonate bedrock. The results for the Meteor Crater analysis suggest a slight degree of shock damage present in the β member of the Kaibab Formation exposed in the crater walls.

New insights into the formation and modification of carbonate-bearing minerals and methane gas in geological systems using multiply substituted isotopologues

This thesis describes the use of multiply-substituted stable isotopologues of carbonate minerals and methane gas to better understand how these environmentally significant minerals and gases form and are modified throughout their geological histories. Stable isotopes have a long tradition in earth science as a tool for providing quantitative constraints on how molecules, in or on the earth, formed in both the present and past. Nearly all studies, until recently, have only measured the bulk concentrations of stable isotopes in a phase or species. However, the abundance of various isotopologues within a phase, for example the concentration of isotopologues with multiple rare isotopes (multiply substituted or 'clumped' isotopologues) also carries potentially useful information. Specifically, the abundances of clumped isotopologues in an equilibrated system are a function of temperature and thus knowledge of their abundances can be used to calculate a sample’s formation temperature. In this thesis, measurements of clumped isotopologues are made on both carbonate-bearing minerals and methane gas in order to better constrain the environmental and geological histories of various samples.

Clumped-isotope-based measurements of ancient carbonate-bearing minerals, including apatites, have opened up paleotemperature reconstructions to a variety of systems and time periods. However, a critical issue when using clumped-isotope based measurements to reconstruct ancient mineral formation temperatures is whether the samples being measured have faithfully recorded their original internal isotopic distributions. These original distributions can be altered, for example, by diffusion of atoms in the mineral lattice or through diagenetic reactions. Understanding these processes quantitatively is critical for the use of clumped isotopes to reconstruct past temperatures, quantify diagenesis, and calculate time-temperature burial histories of carbonate minerals. In order to help orient this part of the thesis, Chapter 2 provides a broad overview and history of clumped-isotope based measurements in carbonate minerals.

In Chapter 3, the effects of elevated temperatures on a sample’s clumped-isotope composition are probed in both natural and experimental apatites (which contain structural carbonate groups) and calcites. A quantitative model is created that is calibrated by the experiments and consistent with the natural samples. The model allows for calculations of the change in a sample’s clumped isotope abundances as a function of any time-temperature history.

In Chapter 4, the effects of diagenesis on the stable isotopic compositions of apatites are explored on samples from a variety of sedimentary phosphorite deposits. Clumped isotope temperatures and bulk isotopic measurements from carbonate and phosphate groups are compared for all samples. These results demonstrate that samples have experienced isotopic exchange of oxygen atoms in both the carbonate and phosphate groups. A kinetic model is developed that allows for the calculation of the amount of diagenesis each sample has experienced and yields insight into the physical and chemical processes of diagenesis.

The thesis then switches gear and turns its attention to clumped isotope measurements of methane. Methane is critical greenhouse gas, energy resource, and microbial metabolic product and substrate. Despite its importance both environmentally and economically, much about methane’s formational mechanisms and the relative sources of methane to various environments remains poorly constrained. In order to add new constraints to our understanding of the formation of methane in nature, I describe the development and application of methane clumped isotope measurements to environmental deposits of methane. To help orient the reader, a brief overview of the formation of methane in both high and low temperature settings is given in Chapter 5.

In Chapter 6, a method for the measurement of methane clumped isotopologues via mass spectrometry is described. This chapter demonstrates that the measurement is precise and accurate. Additionally, the measurement is calibrated experimentally such that measurements of methane clumped isotope abundances can be converted into equivalent formational temperatures. This study represents the first time that methane clumped isotope abundances have been measured at useful precisions.

In Chapter 7, the methane clumped isotope method is applied to natural samples from a variety of settings. These settings include thermogenic gases formed and reservoired in shales, migrated thermogenic gases, biogenic gases, mixed biogenic and thermogenic gas deposits, and experimentally generated gases. In all cases, calculated clumped isotope temperatures make geological sense as formation temperatures or mixtures of high and low temperature gases. Based on these observations, we propose that the clumped isotope temperature of an unmixed gas represents its formation temperature — this was neither an obvious nor expected result and has important implications for how methane forms in nature. Additionally, these results demonstrate that methane-clumped isotope compositions provided valuable additional constraints to studying natural methane deposits.

Experiments on the production of a highly dispersible calcium carbonate. ('Experimental section' only) [Translation from: Szklo i Ceramiki 30, 133-136, 1979]

This short translation summarises experiments on the production of a highly dispersible precipitate of calcium carbonate. The translation covers the 'Experimental section' (of the original larger paper) only.

Estudo diagenético aplicado ao Membro Maruim da Formação Riachuelo , na parte terrestre da sub-bacia de Sergipe, Brasil

O Membro Maruim da Formação Riachuelo (Neoalbiano), na parte terrestre da Sub-bacia de Sergipe, contém fácies de água rasa compostas, principalmente, por rudstone/grainstone oncolítico oolítico, com baixo conteúdo e variedade de bioclastos. A correlação dos afloramentos e análise petrográfica detalhada, envolvendo catodoluminescência, microscopia eletrônica de varredura (MEV) e estudos isotópicos e análise química elementar, permitiram a reconstrução da história diagenética do intervalo estudado. As rochas carbonáticas do Membro Maruim estão completamente afetadas por processos diagenéticos associados aos estágios eogenético, mesogenético e telogenético. A dolomitização foi um dos principais produtos diagenéticos observados no estágio eogenético e encontra-se substituindo total ou parcialmente os calcários do Membro Maruim. A dolomitização concentra-se no topo dos ciclos deposicionais descritos na área de estudo e diminuem gradativamente para a base dos mesmos. As relações entre a porosidade e a dolomitização foram estudadas com base nas comparações da fábrica cristalina da dolomita preservada nos afloramentos estudados. Os resultados isotópicos das dolomitas indicam que o processo de dolomitização ocorreu a partir do refluxo de salmouras em um ambiente ligeiramente hipersalino (penesalino). As áreas mais próximas ao contato com a salmoura, fonte dos fluidos dolomitizantes, exibem menor desenvolvimento de porosidade, uma vez que nessas regiões ocorreriam processos de superdolomitização (Pedreira Carapeba). Nestas áreas a assinatura isotópica do carbono e do oxigênio é muito positiva (o valor do δ13C varia de 2.37 a 4.83 e o valor do δ18O oscila entre 0.61 e 3.92), indicando que os processos diagenéticos tardios não teriam alterado significativamente a assinatura isotópica original. As dolomitas geradas nas áreas afastadas da salmoura (pedreiras Massapé, Inorcal I, Inorcal II, Inhumas e Santo Antônio) exibem um maior desenvolvimento de porosidade e têm uma composição isotópica de carbono e oxigênio mais negativa (o valor do δ13C varia de -5.66 a 2.61 e o valor do δ18O oscila entre -4.25 e 0.38). A assinatura isotópica das dolomitas descritas nestas pedreiras também se encontra alterada por processos de dedolomitização. Os cimentos diagenéticos precipitados durante o estágio mesogenético foram os principais responsáveis pela obliteração da porosidade primária e secundária dos calcários do Membro Maruim. Adicionalmente, estes cimentos diagenéticos tardios calcitizaram as dolomitas, fechando parcialmente a porosidade secundária das mesmas. A porosidade das rochas carbonáticas também se encontra fortemente reduzida pela compactação mecânica e química. A dissolução foi o único processo que levou à geração de porosidade secundária no estágio telogenético, porém em porcentagens muito baixas. As fácies dolomíticas são as que apresentam maior desenvolvimento de porosidade secundária, como consequência dos processos de dissolução no ambiente telogenético. A dissolução compreende um dos últimos eventos diagenéticos identificados no intervalo estudado.

Microbial carbonate precipitation: Correlation of S-wave velocity with calcite precipitation

The use of microbial induced precipitation as a soil improvement technique has been growing in geotechnical domains where ureolytic bacteria that raise the pH of the system and induce calcium carbonate (CaCO3) precipitation are used. For many applications, it is useful to assess the degree of CaCO 3 precipitation by non-destructive testing. This study investigates the feasibility of S-wave velocity measurements to evaluate the amount of calcite precipitation by laboratory testing. Two sets of cemented specimen were tested. The first were samples terminated at different stages of cementation. The second were samples that went through different chemical treatments. These variations were made to find out if these factors would affect the S-wave velocity- cementation relationship. If chemical reaction efficiency was assumed to be constant throughout each test, the relationship between S-wave velocity (Vs) and the amount of CaCO3 precipitation was found to be approximately linear. This correlation between S-wave velocity and calcium carbonate precipitation validates its use as an indicator of the amount of calcite precipitation © 2011 ASCE.

Biomimetic calcium carbonate-gelatin composites as a model system for eggshell mineralization

The composite nature of mineralized natural materials is achieved through both the microstructural inclusion of an organic component and an overall microstructure that is controlled by templating onto organic macromolecules. A modification of an existing laboratory technique is developed for the codeposition of a CaCO3-gelatin composite with a controllable organic content. First, calibration curves are developed to determine the organic content of a CaCO3-gelatin composite from infrared spectra. Second, a CaCO3-gelatin composite is deposited on either glass coverslips or demineralized eggshell membranes using an automated alternating soaking process. Electron microscopy images and use of the infrared spectra calibration curves show that by altering the amount of gelatin in the ionic growth solutions, the final organic component of the mineral can be regulated over the range of 1-10%, similar to that of natural eggshell. © 2012 Materials Research Societ.

Impact of hydrated magnesium carbonate additives on the carbonation of reactive MgO cements

Reactive magnesia (MgO) cements have emerged as a potentially more sustainable and technically superior alternative to Portland cement due to their lower production temperature and ability to sequester significant quantities of CO2. Porous blocks containing MgO were found to achieve higher strength values than PC blocks. A number of variables are investigated to achieve maximum carbonation and associated high strengths. This paper focuses on the impact of four different hydrated magnesium carbonates (HMCs) as cement replacements of either 20 or 50%. Accelerated carbonation (20 C, 70-90% RH, 20% CO2) is compared with natural curing (20 C, 60-70% RH, ambient CO2). SEM, TG/DTA, XRD, and HCl acid digestion are utilized to provide a thorough understanding of the performance of MgO-cement porous blocks. The presence of HMCs resulted in the formation of larger size carbonation products with a different morphology than those in the control mix, leading to significantly enhanced carbonation and strength. © 2013 Elsevier Ltd.

Microorganisms linked to Neoproterozoic microspar carbonate sedimentation in the Jilin-Liaoning area

Molar-tooth carbonate refers to a sort of rock that has ptygmatical folded structure comparable to the ivory. This kind of carbonate exists in a special time range (from Middle to Neoproterozoic). Its origin and the possibility to use it in stratigraphic correlation of the paleocontinent is the key task of the IGCP447, a project on Proterozoic molar tooth carbonates and the evolution of the earth (2001-2005). The importance lies in that the molar-tooth structure is the key to solving problems related to Precambrian biological and global geochemical events. The molar-tooth structure is associated with microorganisms. Development and recession of such carbonates have relations with the evolution process of early lives and abrupt changes in sea carbonate geochemistry. In recent years, based on researches on petrology, geochemistry and Sr isotope of molar-tooth carbonate in the Jilin-Liaoning and Xuzhou-Huaiyang area, the authors hold that it can be used as a marker for stratigraphic sequence and sedimentary facies analyses.