Modeling aluminum-silicon chemistries and application to Australian acidic playa lakes as analogues for Mars

Recent Mars missions have stimulated considerable thinking about the surficial geochemical evolution of Mars. Among the major relevant findings are the presence in Meridiani Planum sediments of the mineral jarosite (a ferric sulfate salt) and related minerals that require formation from an acid-salt brine and oxidizing environment. Similar mineralogies have been observed in acidic saline lake sediments in Western Australia (WA), and these lakes have been proposed as analogues for acidic sedimentary environments on Mars. The prior version of the equilibrium chemical thermodynamic FREZCHEM model lacked Al and Si chemistries that are needed to appropriately model acidic aqueous geochemistries on Earth and Mars. The objectives of this work were to (1) add Al and Si chemistries to the FREZCHEM model, (2) extend these chemistries to low temperatures (<0 °C), if possible, and (3) use the reformulated model to investigate parallels in the mineral precipitation behavior of acidic Australian lakes and hypothetical Martian brines.FREZCHEM is an equilibrium chemical thermodynamic model parameterized for concentrated electrolyte solutions using the Pitzer approach for the temperature range from <−70 to 25 °C and the pressure range from 1 to 1000 bars. Aluminum chloride and sulfate mineral parameterizations were based on experimental data. Aluminum hydroxide and silicon mineral parameterizations were based on Gibbs free energy and enthalpy data. New aluminum and silicon parameterizations added 12 new aluminum/silicon minerals to this Na-K-Mg-Ca-Fe(II)-Fe(III)-Al-H-Cl-Br-SO₄-NO₃-OH-HCO₃-CO₃-CO₂-O₂-CH₄-Si-H₂O system that now contain 95 solid phases.There were similarities, differences, and uncertainties between Australian acidic, saline playa lakes and waters that likely led to the Burns formation salt accumulations on Mars. Both systems are similar in that they are dominated by (1) acidic, saline ground waters and sediments, (2) Ca and/or Mg sulfates, and (3) iron precipitates such as jarosite and hematite. Differences include: (1) the dominance of NaCl in many WA lakes, versus the dominance of Fe-Mg-Ca-SO₄ in Meridiani Planum, (2) excessively low K⁺ concentrations in Meridiani Planum due to jarosite precipitation, (3) higher acid production in the presence of high iron concentrations in Meridiani Planum, and probably lower rates of acid neutralization and hence, higher acidities on Mars owing to colder temperatures, and (4) lateral salt patterns in WA lakes. The WA playa lakes display significant lateral variations in mineralogy and water chemistry over short distances, reflecting the interaction of acid ground waters with neutral to alkaline lake waters derived from ponded surface runoff. Meridiani Planum observations indicate that such lateral variations are much less pronounced, pointing to the dominant influence of ground water chemistry, vertical ground water movements, and aeolian processes on the Martian surface mineralogy.     

Hydrogeochemical and Flow Modeling of Aquitard Percolation in the Cariri Valley-Northeast Brazil

Flow modeling and hydrogeochemical inversion calculations were performed on the aquifer systems of the Crato-Juazeiro Graben in the Araripe Sedimentary Basin of the Cariri Valley, Northeast Brazil, in order to assess aquifer interconnections through an aquitard of the Araripe Plateau. Steady state hydraulic head numeric calculations with the finite difference method used Modflow software with hydrologically based boundary conditions and a piezometric surface as initial condition. Hydrogeochemical inversion with PHREEQC was performed for two water samples representing typical initial and final waters along the flow path. Flow simulation shows that approximately 20% of all recharge water from the superior aquifer system passes through the Santana aquitard reaching the middle aquifer system. Quantification of mineral dissolution/precipitation processes, ion exchange and microbiological redox reactions taking place in the aquifer systems also indicates hydraulic interconnection of the superior and middle aquifer systems through the Santana aquitard.     

Characteristics of Valadares Island aquifer,Paranaguá coastal plain,Brazil

. Aquifer characterization in terms of geologic–geomorphological considerations, pumping test and hydrochemistry has been carried out to evaluate the groundwater potential of one of the delicate coastal island systems in Parana State, Brazil. The Valadares Island, lying in the Atlantic coastal zone, represents a stabilized beach ridge having a thickness of more than 20 m unconsolidated quartz-rich sand. Field and laboratory investigations suggest that this homogeneous coastal aquifer can partially meet the local domestic demand of fresh water even though it is in hydraulic continuity with the estuarine and tidal systems of Paranaguá bay. Efficiency of the aquifer to hold and release water was determined by conducting a pumping test in one of the partially penetrating wells in the island for 24 h. The physical, chemical and biological analyses of samples from 12 5-cm diameter wells of the area have indicated that groundwater needs purification for drinking purpose. It is advocated that the groundwater potential of the island aquifer is worth considering for sustained but controlled exploitation.     

Aspects of the geology, petrology and chemistry of some Angolan carbonatites

Using published data and the results of a new study, the main characteristics of seven Angolan carbonatite complexes are here presented. With the exception of the Lupongola complex which intrudes anorthosites, the remaining complexes are hosted by Precambrian silicic rocks. The complexes are of central or dike type and are well exposed. They represent some of the seven morpholithological types present in the province and have some intermediate lithochemical features between those of Brazilian and East African examples.Sovites at Lupongola are the richest in Sr and F, and also have the highest CaO/MgO and La/Y ratios of all sovites studied. Carbonatites from Bonga and Bailundo are the richest in P₂O₅, while those from Coola and Longonjo are the richest in BaO. Ferrocarbonatites from Bailundo and Virulundo have the highest REE contents. TiO₂ contents are usually low. Only Bonga carbonatites show well-defined variation between Ba and Mn contents and the index CaO/(CaO+Fe₂O₃+FeO+MnO+MgO).The CO₂-SiO₂-(Al₂O₃+Na₂O+K₂O) diagram distinguishes silicified carbonatites, feldspar-bearing carbonatites in which the main silicate mineral is K-feldspar, carbonatites and fenites. Potassic fenitization of country rocks is well developed at Bailundo, Bonga and Virulundo, and probably it also affected cogenetic nepheline syenites at Tchivira and Monte Verde.Fluorcarbonates of Ca and REE are encountered in all chemical varieties of carbonatites, and crystallized during late stages of rock formation. They have a strong influence both on total REE contents and on the slopes of chondrite-normalized patterns. Fluorapatite and pyrochlore are other important potential REE host minerals in the rocks studied. The REE patterns usually have discrete negative Ce anomalies, and sometimes show very discrete negative Eu anomalies. Apart from these anomalies, some rocks have very near-linear patterns, but most show inflections, which may occur between light and middle, and between middle and heavy REE. The origins of these variations are still uncertain.Other aspects of rock geochemistry show that, while some features could be explained by crystal fractionation differentiation processes, late-stage or secondary chemical modifications were widespread.     

Satellite observation of Brazil Current inshore thermal front in the SW South Atlantic: Space/time variability and sea surface temperatures

A data set of 199 sea surface temperature maps derived from the Advanced Very High Resolution Radiometer for the period 2000–2002 was processed to derive the position of the surface inshore thermal front of the Brazil Current (BCIF) in the SE Brazilian coastal and oceanic area. After the derivation of the position of the BC front for each image, the ensemble of digital frontal vectors was processed using the algorithm of frontal density (FD). For each 5′×5′ cell in the domain the calculated FD provided an index expressing the presence and persistence of the front in the area or the probability of finding the front in the region. In the paper we present the results of the FD analysis to get a better view of the space and time variability of the BC front in the region. The highest values of FD were in general observed close to or at the shelf break zone (between 200 and 1000 m isobaths). From 20°S to 23°S there is a tendency of BCIF to be positioned over the outer shelf, inshore of the 200 m isobaths. SE of Cape Sao Tome and S of Cape Frio it was observed a bimodal spatial distribution of highest FD caused by the presence of two semi-permanent frontal eddies. After moving offshore near Cape Frio, the BCIF tends to return to the shelf break zone south of 24°S probably due to a potential vorticity conservation mechanism. The position of the highest FD values calculated for different seasons confirms previous studies in that BCIF is closer to the coast during the summer and furthest offshore in the winter. Statistical analysis of the SST data gave for the BCIF an average SST gradient of 0.31°C km⁻¹ with a standard deviation of 0.15°C km⁻¹. A mean frontal width of 6 km was inferred from the average SST gradient and typical temperatures near the front at both sides, at outer shelf and in the BC itself. A Weibull probability density function can be fitted to describe the BCIF SST gradients with scale factor c=0.3460°C km⁻¹ and shape factor k=2.1737. The BCIF SST gradient showed a seasonal variability with the smallest gradients in summer (~0.24 °C km⁻¹) and the highest in autumn (~0.33 °C km⁻¹). Using a three harmonic Fourier fit for the SST field near the BCIF, at the outer shelf and at interior of BC, it was possible to derive an analytical model for the time variability of the SST gradient of BCIF.     

Richardson's Law in Large-Eddy Simulations of Boundary-Layer Flows

Relative dispersion in a neutrally stratified planetary boundary layer (PBL) is investigated by means of large-eddy simulations (LES). Despite the small extension of the inertial range of scales in the simulated PBL, our Lagrangian statistics turn out to be compatible with the Richardson t³ law for the average of square particle separation, where t is time. This emerges from the application of non-standard methods of analysis through which a precise measure of the Richardson constant was also possible. Its value is estimated as C₂ 0.5, in close agreement with recent experiments and three-dimensional direct numerical simulations.     

Influence of particle and surface quality on the vitrinite reflectance of dispersed organic matter: Comparative exercise using data from the qualifying system for reflectance analysis working group of ICCP

The development of a qualifying system for reflectance analysis has been the scope of a working group within the International Committee for Coal and Organic Petrology (ICCP) since 1999, when J. Koch presented a system to qualify vitrinite particles according to their size, proximity to bright components and homogeneity of the surface. After some years of work aimed at improving the classification system using photomicrographs, it was decided to run a round robin exercise on microscopy samples. The classification system tested consists of three qualifiers ranging from excellent to low quality vitrinites with an additional option for unsuitable vitrinites. This paper reports on the results obtained by 22 analysts who were asked to measure random reflectance readings on vitrinite particles assigning to each reading a qualifier. Four samples containing different organic matter types and a variety of vitrinite occurrences have been analysed. Results indicated that the reflectance of particles classified as excellent, good or poor compared to the total average reflectance did not show trends to be systematically lower or higher for the four samples analysed. The differences in reflectance between the qualifiers for any given sample were lower than the scatter of vitrinite reflectance among participants. Overall, satisfactory results were obtained in determining the reflectance of vitrinite in the four samples analysed. This was so for samples having abundant and easy to identify vitrinites (higher plant-derived organic matter) as well as for samples with scarce and difficult to identify particles (samples with dominant marine-derived organic matter). The highest discrepancies were found for the organic-rich oil shales where the selection of the vitrinite population to measure proved to be particularly difficult. Special instructions should be provided for the analysis of this sort of samples. The certainty of identification of the vitrinite associated with the vitrinite reflectance values reported has been assessed through a reliability index which takes into account the number of readings and the coefficient of variation. The same statistical approach as that followed in the ICCP vitrinite reflectance accreditation program for single seam coals has been used for data evaluation. The results indicated low to medium dispersion for 17 out of 22 participants. This, combined with data from other sets of comparative analyses over a long period, is considered an encouraging result for the establishment of an accreditation program on vitrinite reflectance measurements in dispersed organic matter.     

Application of Laser‐Induced Breakdown Spectroscopy and Hyperspectral Images for Direct Evaluation of Chemical Elemental Profiles of Coprolites

This study demonstrates the application of laser‐induced breakdown spectroscopy (LIBS) and hyperspectral imaging to the investigation of coprolite and fossil samples. Solid samples from the Permian (seven coprolites and one fossil), Cretaceous (one coprolite) and Oligo‐Miocene (two coprolites) periods were directly analysed, and emission spectra from 186 to 1042 nm were obtained in several areas covering coprolite/fossil and rock material. Initial exploratory analyses were performed using principal component analysis with the data set normalised by the norm (Euclidean norm = 1). After identification and selection of emission lines of eleven elements (Al, Ca, Cr, Fe, K, Mg, Mn, Na, Ni, P and Si), the signals were normalised again by the relative intensity of the selected element. Phosphorus was identified mainly in the coprolites, while K and Na were primarily found in the rock material. In several cases, there was a positive correlation between Ca and P. A sample from the Oligo‐Miocene series was also analysed using inductively coupled plasma‐optical emission spectrometry (ICP‐OES) (rock and coprolites were analysed separately). Based on the quantitative results from ICP‐OES, it was confirmed that the tendency was the same as that observed with the results obtained from LIBS directly in the solid sample.