Kinetic model of carbonate dissolution in Martian meteorite ALH84001

The magnetites and sulfides located in the rims of carbonate globules in the Martian meteorite ALH84001 have been claimed as evidence of past life on Mars. Here, we consider the possibility that the rims were formed by dissolution and reprecipitation of the primary carbonate by the action of water. To estimate the rate of these solution-precipitation reactions, a kinetic model of magnesite-siderite carbonate dissolution was applied and used to examine the physicochemical conditions under which these rims might have formed. The results indicate that the formation of the rims could have taken place in < 50 yr of exposure to small amounts of aqueous fluids at ambient temperatures. Plausible conditions pertaining to reactions under a hypothetical ancient Martian atmosphere (1 bar CO2), the modern Martian atmosphere (8 mbar CO2), and the present terrestrial atmosphere (0.35 mbar CO2) were explored to constrain the site of the process. The results indicated that such reactions likely occurred under the latter two conditions. The possibility of Antarctic weathering must be entertained, which, if correct, would imply that the plausibly biogenic minerals (single-domain magnetite of characteristic morphology and sulfide) reported from the rims may be the products of terrestrial microbial activity. This model is discussed in terms of the available isotope data and found to be compatible with the formation of ALH84001 rims. Particularly, anticorrelated variations of radiocarbon with δ13C indicate that carbonate in ALH84001 was affected by solution-precipitation reactions immediately after its initial fall (ca. 13,000 yr ago) and then again during its recent exposure prior to collection

Investigations on vinylene carbonate, 2. Copolymerization with N-vinyl-2-pyrrolidone and ethyl vinyl ether

Functional monomers and polymers have received considerable attention in recent years, especially in the biomedical field. In this respect, poly(viny1ene carbonate) is very interesting, because the reactive carbonate groups offer the possibility of coupling with bioactive compounds containing amino groups, e. g. proteins or enzymes. Copolymerization of vinylene carbonate with other vinyl monomers will affect the amount of carbonate groups as well as other properties of the copolymers. In a previous paper we described the preparation and properties of poly(viny1ene carbonate) I), and this paper reports the copolymerization of vinylene carbonate with N-vinyl-2-pyrrolidone and with ethyl vinyl ether

CO2 perturbation experiments: similarities and differences between dissolved inorganic carbon and total alkalinity manipulations

Increasing atmospheric carbon dioxide (CO2) through human activities and invasion of anthropogenic CO2 into the surface ocean alters the seawater carbonate chemistry, increasing CO2 and bicarbonate (HCO3−) at the expense of carbonate ion (CO32−) concentrations. This redistribution in the dissolved inorganic carbon (DIC) pool decreases pH and carbonate saturation state (Ω). Several components of the carbonate system are considered potential key variables influencing for instance calcium carbonate precipitation in marine calcifiers such as coccolithophores, foraminifera, corals, mollusks and echinoderms. Unravelling the sensitivities of marine organisms and ecosystems to CO2 induced ocean acidification (OA) requires well-controlled experimental setups and accurate carbonate system manipulations. Here we describe and analyse the chemical changes involved in the two basic approaches for carbonate chemistry manipulation, i.e. changing DIC at constant total alkalinity (TA) and changing TA at constant DIC. Furthermore, we briefly introduce several methods to experimentally manipulate DIC and TA. Finally, we examine responses obtained with both approaches using published results for the coccolithophore Emiliania huxleyi. We conclude that under most experimental conditions in the context of ocean acidification DIC and TA manipulations yield similar changes in all parameters of the carbonate system, which implies direct comparability of data obtained with the two basic approaches for CO2 perturbation

Preparation, physical-chemical characterisation and cytocompatibility of calcium carbonate cements

The feasibility of calcium carbonate cements involving the recrystallisation of metastable calcium carbonate varieties has been demonstrated. Calcium carbonate cement compositions presented in this paper can be prepared straightforwardly by simply mixing water (liquid phase) with two calcium carbonate phases (solid phase) which can be easily obtained by precipitation. An original cement composition was obtained by mixing amorphous calcium carbonate and vaterite with an aqueous medium. The cement set and hardened within 2 hours at 37°C in an atmosphere saturated with water and the final composition of the cement consisted mostly of aragonite. The hardened cement was microporous and showed poor mechanical properties. Cytotoxicity tests revealed excellent cytocompatibility of calcium carbonate cement compositions. Calcium carbonates with a higher solubility than the marketed calcium phosphate cements might be of interest to increase biomedical cement resorption rates and to favour its replacement by bone tissue

1995, Spatial and temporal variability of late Neogene equatorial Pacific carbonate

High-resolution, continuous records of GRAPE wet bulk density (a carbonate proxy) from Ocean Drilling Program Leg 138 provide one the opportunity for a detailed study of eastern equatorial Pacific Ocean carbonate sedimentation during the last 6 m.y. The transect of sites drilled spans both latitude and longitude in the eastern equatorial Pacific from 90° to 110°W and from 5°S to 10°N. Two modes of variability are resolved through the use of Empirical Orthogonal Function (EOF) analysis. In the presence of large tectonic and climatic boundary condition changes over the last 6 m.y., the dominant mode of spatial variability in carbonate sedimentation is remarkably constant. The first mode accounts for over 50% of the variance in the data, and is consistent with forcing by equatorial divergence. This mode characterizes both carbonate concentration and carbonate mass accumulation rate time series. Variability in the first mode is highly coherent with insolation, indicating a strong linear relationship between equatorial Pacific car bonate sedimentation and Milankovitch variability. Frequency domain analysis indicates that the coupling to equatorial divergence in carbonate sedimentation is strongest in the precession band (19-23 k.y.) and weakest though present at lower frequencies. The second mode of variability has a consistent spatial pattern of east-west asymmetry over the past 4 m.y. only; prior to 4 Ma, a different mode of spatial variability may have been present, possibly suggesting influence by closure of the Isthmus of Panama or other tectonic changes. The second mode of variability may indicate influence by CaCO3 dissolution. The second mode of variability is not highly coherent with insolation. Comparison of the modes of carbonate variability to a 4 m.y. record of benthic δ 1 8 indicates that although overall correlation between carbonate and δ 1 8 is low, both modes of variability in carbonate sedimentation are coherent with δ 1 8 changes at some frequencies. The first mode of carbonate variability is coherent with Sites 846/849 δ 1 8 at the dominant insolation periods, and the second mode is coherent at 100 k.y. during the last 2 m.y. The coherence between carbonate sedimentation and δ 1 8 in both EOF modes suggests that multiple uncorrelated modes of variability operated within the climate system during the late Neogene

COCARDE: new view on old mounds – an international network of carbonate mound research

EGU2012-12550 Carbonate mounds are important contributors of life in different settings, from warm-water to cold-water environments, and throughout geological history. Research on modern cold-water coral carbonate mounds over the last decades made a major contribution to our overall understanding of these particular sedimentary systems. By looking to the modern carbonate mound community with cold-water corals as main framework builders, some fundamental questions could be addressed, until now not yet explored in fossil mound settings. The international network COCARDE (http://www.cocarde.eu) is a platform for exploring new insights in carbonate mound research of recent and ancient mound systems. The aim of the COCARDE network is to bring together scientific communities, studying Recent carbonate mounds in midslope environments in the present ocean and investigating fossil mounds spanning the whole Phanerozoic time, respectively. Scientific challenges in modern and ancient carbonate mound research got well defined during the ESF Magellan Workshop COCARDE in Fribourg, Switzerland (21.–24.01.2009). The Special Volume Cold-water Carbonate Reservoir systems in Deep Environments – COCARDE (Marine Geology, Vol. 282) was the major outcome of this meeting and highlights the diversity of Recent arbonate mound studies. The following first jointWorkshop and Field Seminar held in Oviedo, Spain (16.–20.09.2009) highlighted ongoing research from both Recent and fossil academic groups integrating the message from the industry. The field seminar focused on mounds from the Carboniferous platform of Asturias and Cantabria, already intensively visited by industrial and academic researchers. However, by comparing ancient, mixed carbonate-siliciclastic mound systems of Cantabria with the Recent ones in the Porcupine Seabight, striking similarities in their genesis and processes in mound development asked for an integrated drilling campaign to understand better the 3D internal mound build-up. The Oviedo Workshop and Field Seminar led to the submission of a White Paper on Carbonate Mound Drilling and the initiation of the ESF European Research Network Programme Cold-Water Carbonate Mounds in Shallow and Deep Time – The European Research Network (COCARDE-ERN) launched in June 2011. The second COCARDE Workshop and Field Seminar was held in Rabat, Morocco (24.–30.10.2011) and thematically focussed on carbonate mounds of(f) Morocco. The compact workshop invited students from Moroccan Universities to experience ongoing carbonate mound research in Recent and Ancient environments of Morocco. Two Round Tables discussed innovative approaches in carbonate mound research in Morocco (Recent vs. Ancient - offshore vs. onshore) and reviewed together with oil industry opportunities of international collaboration. The outcome of this workshop will lead into joint research projects, drilling campaigns on- and offshore, and expansion of COCARDE onto the African continent

Factors affecting metal mobilisation during oxidation of sulphidic, sandy wetland substrates

Most metals accumulate as sulphides under anoxic conditions in wetland substrates, reducing their bioavailability due to the solubility of metal sulphides. However, upon oxidation of these sulphides when the substrate is occasionally oxidised, metals can be released from the solid phase to the pore water or overlaying surface water. This release can be affected by the presence of carbonates, organic matter and clay. We compared changes of Cd, Cu and Zn mobility (CaCl2 extraction) during oxidation of a carbonate-rich and a carbonate-poor sulphidic, sandy wetland substrate. In addition, we studied how clay with low and high cation sorption capacity (bentonite and kaolinite, respectively) and organic matter (peat) can counteract Cd, Cu and Zn release during oxidation of both carbonate-rich and carbonate-poor sulphidic sediments. CaCl2-extractability of Cu, a measure for its availability, is low in both carbonate-poor and carbonate-rich substrates, whereas its variability is high. The availability of Cd and Zn is much higher and increases when peat is supplied to carbonate-poor substrates. A strong reduction of Cd and Zn extractability is observed when clay is added to carbonate-poor substrates. This reduction depends on the clay type. Most observations could be explained taking into account pH differences between treatments, with kaolinite resulting in a lower pH in comparison to bentonite. These pH differences affect the presence and characteristics of dissolved organic carbon and the metal speciation, which in turns affects the interaction of metals with the solid soil phase. In carbonate-rich substrates, Cd and Zn availability is lower and the effects of peat and clay amendment are less clear. The latter can also be attributed to the high pH and lack of pH differences between treatments

Structural Evidence for a Copper-Bound Carbonate Intermediate in the Peroxidase and Dismutase Activities of Superoxide Dismutase

Copper-zinc superoxide dismutase (SOD) is of fundamental importance to our understanding of oxidative damage. Its primary function is catalysing the dismutation of superoxide to O2 and H2O2. SOD also reacts with H2O2, leading to the formation of a strong copper-bound oxidant species that can either inactivate the enzyme or oxidise other substrates. In the presence of bicarbonate (or CO2) and H2O2, this peroxidase activity is enhanced and produces the carbonate radical. This freely diffusible reactive oxygen species is proposed as the agent for oxidation of large substrates that are too bulky to enter the active site. Here, we provide direct structural evidence, from a 2.15 Å resolution crystal structure, of (bi)carbonate captured at the active site of reduced SOD, consistent with the view that a bound carbonate intermediate could be formed, producing a diffusible carbonate radical upon reoxidation of copper. The bound carbonate blocks direct access of substrates to Cu(I), suggesting that an adjunct to the accepted mechanism of SOD catalysed dismutation of superoxide operates, with Cu(I) oxidation by superoxide being driven via a proton-coupled electron transfer mechanism involving the bound carbonate rather than the solvent. Carbonate is captured in a different site when SOD is oxidised, being located in the active site channel adjacent to the catalytically important Arg143. This is the probable route of diffusion from the active site following reoxidation of the copper. In this position, the carbonate is poised for re-entry into the active site and binding to the reduced copper. © 2012 Strange et al

Lithostratigraphy and depositional episodes of the Oligocene carbonate-rich Tikorangi Formation, Taranaki Basin, New Zealand

The subsurface Oligocene Tikorangi Formation is a unique and important oil producer in the onshore Waihapa-Ngaere Field, Taranaki Basin, being the only carbonate and fracture-producing reservoir within the basin. Core sample data from seven onshore wells (foredeep megafacies) and a single offshore well (basinal megafacies) are correlated with a suite of sonic and gamma-ray geophysical well log data to derive interpretative carbonate facies for the Tikorangi Formation. Four mixed siliciclastic-carbonate to carbonate facies have been defined: facies A-calcareous siliciclastite (75% carbonate). Single or interbedded combinations of these facies form the basis for identifying nine major lithostratigraphic units in the Tikorangi Formation that are correlatable between the eight wells in this study.The Tikorangi Formation accumulated across a shelf-slope-basin margin within a tectonically diversified basin setting, notably involving considerable off-shelf redeposition of sediment into a bounding foredeep. Analysis of gamma, sonic, and resistivity well logs identifies five major episodes of sedimentary evolution. Episode I comprises retrogradational siliciclastic-dominated redeposited units associated with foredeep subsidence. Episode II is a continuation of episode I retrogradation, but with increased mass-redeposited carbonate influx during accelerated foredeep subsidence and relative sea-level rise, the top marking the maximum flooding surface. Episode III involves a progradational sequence comprising relatively pure redeposited carbonate units associated with declining subsidence rates and minimal siliciclastic input, with movement of facies belts basinward. Episode IV consists of prograding aggradation involving essentially static facies belts dominated by often thick, periodically mass-emplaced, carbonate-rich units separated by thin background siliciclastic shale-like units. Episode V is a retrogradational sequence marking the reintroduction of siliciclastic material into the basin following uplift of Mesozoic basement associated with accelerated compressional tectonics along the Australia-Pacific plate boundary, initially diluting and ultimately extinguishing carbonate production factories and terminating deposition of the Tikorangi Formation

Lithostratigraphy and depositional episodes of the Oligocene carbonate-rich Tikorangi Formation, Taranaki Basin, New Zealand

The subsurface Oligocene Tikorangi Formation is a unique and important oil producer in the onshore Waihapa-Ngaere Field, Taranaki Basin, being the only carbonate and fracture-producing reservoir within the basin. Core sample data from seven onshore wells (foredeep megafacies) and a single offshore well (basinal megafacies) are correlated with a suite of sonic and gamma-ray geophysical well log data to derive interpretative carbonate facies for the Tikorangi Formation. Four mixed siliciclastic-carbonate to carbonate facies have been defined: facies A-calcareous siliciclastite (75% carbonate). Single or interbedded combinations of these facies form the basis for identifying nine major lithostratigraphic units in the Tikorangi Formation that are correlatable between the eight wells in this study.The Tikorangi Formation accumulated across a shelf-slope-basin margin within a tectonically diversified basin setting, notably involving considerable off-shelf redeposition of sediment into a bounding foredeep. Analysis of gamma, sonic, and resistivity well logs identifies five major episodes of sedimentary evolution. Episode I comprises retrogradational siliciclastic-dominated redeposited units associated with foredeep subsidence. Episode II is a continuation of episode I retrogradation, but with increased mass-redeposited carbonate influx during accelerated foredeep subsidence and relative sea-level rise, the top marking the maximum flooding surface. Episode III involves a progradational sequence comprising relatively pure redeposited carbonate units associated with declining subsidence rates and minimal siliciclastic input, with movement of facies belts basinward. Episode IV consists of prograding aggradation involving essentially static facies belts dominated by often thick, periodically mass-emplaced, carbonate-rich units separated by thin background siliciclastic shale-like units. Episode V is a retrogradational sequence marking the reintroduction of siliciclastic material into the basin following uplift of Mesozoic basement associated with accelerated compressional tectonics along the Australia-Pacific plate boundary, initially diluting and ultimately extinguishing carbonate production factories and terminating deposition of the Tikorangi Formation