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

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

Influence of chemical reaction kinetics on electrokinetic remediation modelling results

A numerical model describing transport of multiple species and chemical reactions during electrokinetic treatment is presented. The transport mechanisms included in the model were electromigration and electroosmosis. The chemical reactions taken into account were water electrolysis at the electrodes, aqueous species complexation, precipitation, and dissolution. The model was applied to simulate experimental data from an acid-enhanced electrokinetic treatment of a Pb-contaminated calcareous soil. The kinetics of the main pH buffering process (i.e., calcite dissolution) was taken into account and its time-dependent behavior was described by a rate law. The influence of kinetics was evaluated by comparing the results from a set of simulations in which calcite dissolution was implemented considering thermodynamic equilibrium and another set in which the same reaction was described by the rate law. The results show that the prediction capability of the model significantly improves when the kinetic rate is taken into account.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Report of Investigations No. 131 Origin and Diagenesis of Cap Rock, Gyp Hill and Oakwood Salt Domes, Texas

UT Librarie

Catalysis and chemical mechanisms of calcite dissolution in seawater

Near-equilibrium calcite dissolution in seawater contributes significantly to the regulation of atmospheric CO_2 on 1,000-y timescales. Despite many studies on far-from-equilibrium dissolution, little is known about the detailed mechanisms responsible for calcite dissolution in seawater. In this paper, we dissolve ^(13)C-labeled calcites in natural seawater. We show that the time-evolving enrichment of δ^(13)C in solution is a direct measure of both dissolution and precipitation reactions across a large range of saturation states. Secondary Ion Mass Spectrometer profiles into the ^(13)C-labeled solids confirm the presence of precipitated material even in undersaturated conditions. The close balance of precipitation and dissolution near equilibrium can alter the chemical composition of calcite deeper than one monolayer into the crystal. This balance of dissolution–precipitation shifts significantly toward a dissolution-dominated mechanism below about Ω= 0.7. Finally, we show that the enzyme carbonic anhydrase (CA) increases the dissolution rate across all saturation states, and the effect is most pronounced close to equilibrium. This finding suggests that the rate of hydration of CO_2 is a rate-limiting step for calcite dissolution in seawater. We then interpret our dissolution data in a framework that incorporates both solution chemistry and geometric constraints on the calcite solid. Near equilibrium, this framework demonstrates a lowered free energy barrier at the solid–solution interface in the presence of CA. This framework also indicates a significant change in dissolution mechanism at Ω= 0.7, which we interpret as the onset of homogeneous etch pit nucleation

Data report: late Miocene to early Pliocene coccolithophore and foraminiferal preservation at Site U1338 from scanning electron microscopy

The late Miocene to early Pliocene carbonate-rich sediments recovered at Integrated Ocean Drilling Program (IODP) Site U1338 during the Expedition 320/321 Pacific Equatorial Age Transect (PEAT) program contain abundant calcareous nanno- and microfossils. Geochemical proxies from benthic and planktonic foraminiferal and coccolithophore calcite could be very useful at this location; however, good preservation of the calcite is crucial for the proxies to be robust. Here, we evaluate the preservation of specific benthic and planktonic foraminifer species and coccolithophores in fine fraction sediment at Site U1338 using backscattered electron (topography mode) scanning electron microscopy (BSE-TOPO SEM). Both investigated foraminiferal species, Cibicidoides mundulus and Globigerinoides sacculifer, have undergone some alteration. The C. mundulus show minor evidence for dissolution, and only some specimens show evidence of overgrowth. The Gs. sacculifer show definite signs of alteration and exhibit variable preservation, ranging from fair to poor; some specimens show minor overgrowth and internal recrystallization but retain original features such as pores, spine pits, and internal testwall growth structure, whereas in other specimens the recrystallization and overgrowth disguise many of the original features. Secondary electron and BSE-TOPO SEM images show that coccolith calcite preservation is moderate or moderate to poor. Slight to moderate etching has removed central heterococcolith features, and a small amount of secondary overgrowth is also visible. Energy dispersive spectroscopy analyses indicate that the main sedimentary components of the fine fraction sediment are biogenic CaCO3 and SiO2, with some marine barite. Based on the investigations in this data report, geochemical analyses on benthic foraminifers are unlikely to be affected by preservation, although geochemical analyses on the planktonic foraminifers should be treated cautiously because of the fair to poor and highly variable preservation

Testing the impact of diagenesis on the delta O-18 and delta C-13 of benthic foraminiferal calcite from a sediment burial depth transect in the equatorial Pacific

Stable oxygen and carbon isotope (δ18O and δ13C) values measured in foraminiferal calcite are one of the primary tools used in paleoceanography. Diagenetic recrystallisation of foraminiferal calcite can act to reset primary isotopic values but its effects are typically poorly quantified. Here we test the impact of early stage diagenesis on stable isotope records generated from a suite of drill sites in the equatorial Pacific Ocean recovered during Ocean Drilling Program (ODP) Leg 199 and Integrated Ocean Drilling Program (IODP) Expedition 320. Our selected sites form paleowater- and burial-depth transects, with excellent stratigraphic control allowing us to confidently correlate our records. We observe large inter-site differences in the preservation state of benthic foraminiferal calcite, implying very different recrystallisation histories, but negligible inter-site offsets in benthic δ18O and δ13C values. We infer that diagenetic alteration of benthic foraminiferal calcite (in sedimentary oozes) must predominantly occur at shallow burial depths (<100 m) where offsets in both the temperature and isotopic composition of waters in which the foraminifera calcified and pore-waters in which diagenesis occurs are small. Our results suggest that even extensive recrystallisation of benthic foraminiferal calcite results in minimal shifts from primary δ18O and δ13C values. This finding supports the long-held suspicion that diagenetic alteration of foraminiferal calcite is less problematic in benthic than in planktic foraminifera and that in deep–sea sediments routinely employed for palaeoceanographic studies benthic foraminifera are robust recorders of stable isotope values in the fossil record

Orbital frequencies in the carbonate sedimentary record: distorted by diagenesis?

The most important archive of Earth’s climate change through geologic history is the sedimentary rock record. Rhythmic sedimentary alternations are usually interpreted as a consequence of periodic variations in the orbital parameters of the Earth. This interpretation enables the application of cyclostratigraphy as a very precise chronometer, when based on the assumption that orbital frequencies are faithfully recorded in the sedimentary archive. However, there are numerous uncertainties with the application of this concept. Particularly in carbonates, sediment properties such as mineralogical composition and fossil associations are severely altered during post-depositional alteration (diagenesis). We here point out that the assumption of a 1:1 recording of orbital signals in many cases is questionable for carbonate rhythmites. We use computer simulations to show the effect of diagenetic overprint on records of orbital signals in the carbonate record. Such orbital signals may be distorted in terms of frequency, amplitude, and phase by diagenetic processes, and cycles not present in the insolation record may emerge. This questions the routine use of carbonate rhythmites for chronostratigraphic datin

Ongoing transients in carbonate compensation

Uptake of anthropogenic CO2 is acidifying the oceans. Over the next 2000 years, this will modify the dissolution and preservation of sedimentary carbonate. By coupling new formulas for the positions of the calcite saturation horizon, zsat, the compensation depth, zcc, and the snowline, zsnow, to a biogeochemical model of the oceanic carbonate system, we evaluate how these horizons will change with ongoing ocean acidification. Our model is an extended Havardton-Bear-type box model, which includes novel kinetic descriptions for carbonate dissolution above, between, and below these critical depths. In the preindustrial ocean, zsat and zcc are at 3939 and 4750 m, respectively. When forced with the IS92a CO2 emission scenario, the model forecasts (1) that zsat will rise rapidly (“runaway” conditions) so that all deep water becomes undersaturated, (2) that zcc will also rise and over 1000 years will pass before it will be stabilized by the dissolution of previously deposited CaCO3, and (3) that zsnow will respond slowly to acidification, rising by ∼1150 m during a 2000 year timeframe. A further simplified model that equates the compensation and saturation depths produces quantitatively different results. Finally, additional feedbacks due to acidification on calcification and increased atmospheric CO2 on organic matter productivity strongly affect the positions of the compensation horizons and their dynamics.

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

Concrete, a mixture formed by mixing cement, water, and fine and coarse mineral aggregates is used in the construction of nuclear power plants (NPPs), e.g., to construct the reactor cavity concrete that encases the reactor pressure vessel, etc. In such environments, concrete may be exposed to radiation (e.g., neutrons) emanating from the reactor core. Until recently, concrete has been assumed relatively 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. Specifically, while quartz undergoes disordering of its atomic structure resulting in a near complete lack of periodicity, i.e., similar to glassy silica, 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; i.e., an increase of around 3 orders of magnitude. Calcite however, shows little change in dissolution rates - although its density noted to reduce by around 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 (n$_c$) that are imposed on the atoms in the network. The outcomes are discussed within the context of the durability of concrete structural elements formed with calcitic/quartzitic aggregates in nuclear power plants