Geochemistry of Archean metasedimentary rocks from West Greenland

Archean metasedimentary rocks occur as components of the Isua supracrustals, Akilia association and Malene supracrustals of southern West Greenland. Primary structures in these rocks have been destroyed by metamorphism and deformation. Their chemistry and mineralogy is consistent with a sedimentary origin, but other possible parents (e.g. acid volcanics, altered pyroclastic rocks) cannot be excluded for some of them. There is little difference in the composition of metasedimentary rocks from the early Archean Isua supracrustals and probable correlative Akilia association. Both have a wide range in rare earth element (REE) patterns with $\text{La}{}_{\mathrm{<mtext>N</mtext>}}\text{Yb}{}_{\mathrm{<mtext>N</mtext>}}$ ranging from 0.61?5.8. The REE pattern of one Akilia sample, with low $\text{La}{}_{\mathrm{<mtext>N</mtext>}}\text{Yb}{}_{\mathrm{<mtext>N</mtext>}}$, compares favourably with that of associated tholeiites and it is likely that such samples were derived almost exclusively from basaltic sources. Other samples with very steep REE patterns are similar to felsic volcanic boulders found in a conglomeratic unit in the Isua supracrustals. Samples with intermediate REE patterns are best explained by mixing of basaltic and felsic end members. Metasedimentary rocks from the Malene supracrustals can be divided into low silica (≤55% SiO₂) and high silica (>77% SiO₂) varieties. These rocks also show much variation in $\text{La}{}_{\mathrm{<mtext>N</mtext>}}\text{Yb}{}_{\mathrm{<mtext>N</mtext>}}$ (0.46?14.0) and their origin is explained by derivation from a mixture of mafic volcanics and felsic igneous rocks. The wide range in trace element characteristics of these metasedimentary rocks argues for inefficient mixing of the various source lithologies during sedimentation. Accordingly, these data do not rigorously test models of early Archean crustal composition and evolution. The systematic variability in trace element geochemistry provides evidence for the bimodal nature of the early Archean crust.     

A 3.5 Ga record of water-limited, acidic weathering conditions on Mars

The secondary mineral budget on Earth is dominated by clay minerals, Al-hydroxides, and Fe-oxides, which are formed under the moderate pH, high water-to-rock ratio conditions typical of Earth's near-surface environment. In contrast, geochemical analyses of rocks and soils from landed missions to Mars indicate that secondary mineralogy is dominated by Mg (± Fe, Ca)-sulfates and Fe-oxides. This discrepancy can be explained as resulting from differences in the chemical weathering environment of Earth and Mars. We suggest that chemical weathering processes on Mars are dominated by: (1) a low-pH, sulfuric acid-rich environment in which the stoichiometric dissolution of labile mineral phases such as olivine and apatite (± Fe–Ti oxides) is promoted; and (2) relatively low water-to-rock ratio, such that other silicate phases with slower dissolution rates (e.g., plagioclase, pyroxene) do not contribute substantially to the secondary mineral budget at the Martian surface. Under these conditions, Al-mobilization is limited, and the formation of significant Al-bearing secondary phases (e.g., clays, Al-hydroxides, Al-sulfates) is inhibited. The antiquity of rock samples analyzed in-situ on Mars suggest that water-limited acidic weathering conditions have more than likely been the defining characteristic of the Martian aqueous environment for billions of years.     

Rare earth elements in Huronian (Lower Proterozoic) sedimentary rocks: Composition and evolution of the post-Kenoran upper crust

The Huronian sequence (Lower Proterozoicl. north of Lake Huron, contains tillites and abundant fine-grained sedimentary rocks. Analyses of rare earth elements (REE) in the matrix of tillite samples from the Gowganda Formation (~ 2.3 Gal is considered to be a reasonable estimate of upper crustal REE abundances for the region north of Lake Huron at the time of Gowganda deposition. The average is characterized by a moderately steep pattern (σLREEσHREE = 9.1) and a slight negative europium anomaly ($\text{Eu}\text{Eu1}\text{= 0.89}$). This pattern is similar to estimates of the composition of the surface of the Canadian Shield and is intermediate between estimates of typical Archean and post-Archean sedimentary rocks. REE patterns for framework granitoid clasts from the tillite suggest that K-rich granites, which were apparently unimportant in the formation of Archean sedimentary rocks, were abundant in the source regions of the Gowganda Formation. This may explain the intermediate nature of the Gowganda pattern.Comparison of the tillites and associated Gowganda mudstones suggests that previous estimates of upper crustal REE abundances, which were based on the analyses of fine-grained sedimentary rocks, may be systematically high. Relative distributions, however, are the same.Analyses of mudstones from the McKim. Pecors. Serpent Gowganda Lorrain and Gordon Lake Formations suggest rapid evolution in the composition of the exposed upper crust at the close of the Kenoran orogeny. REE patterns at the base of the Huronian are similar to typical Archean sedimentary rocks. REE characteristics change up section: patterns at the top resemble typical post-Archean sedimentary rocks.It is inferred that an essentially episodic change from an early exposed upper crust dominated by a tonalite-greenstone suite to one approximating granodioritic composition is recorded in Huronian sedimentary rocks. A deviation from the evolutionary trend of the Huronian, documented in the Gowganda Formation, may be related to the glacial origin of the Gowganda.     

Geochemical modeling of evaporation processes on Mars: Insight from the sedimentary record at Meridiani Planum

New data returned from the Mars Exploration Rover (MER) mission have revealed abundant evaporites in the sedimentary record at Meridiani Planum. A working hypothesis for Meridiani evaporite formation involves the evaporation of fluids derived from the weathering of martian basalt and subsequent diagenesis. On Earth, evaporite formation in exclusively basaltic settings is rare. However, models of the evaporation of fluids derived from experimentally weathering synthetic martian basalt provide insight into possible formation mechanisms. The thermodynamic database assembled for this investigation includes both Fe²⁺ and Fe³⁺ in Pitzer's ion interaction equations to evaluate Fe redox disequilibrium at Meridiani Planum. Modeling results suggest that evaporation of acidic fluids derived from weathering olivine-bearing basalt should produce Mg, Ca, and Fe-sulfates such as jarosite and melanterite. Calculations that model diagenesis by fluid recharge predict the eventual breakdown of jarosite to goethite as well as the preservation of much of the initial soluble evaporite component at modeled porosity values appropriate for relevant depositional environments (< 0.30). While only one of several possible formation scenarios, this simple model is consistent with much of the chemical and mineralogical data obtained on Meridiani Planum outcrop.     

Geochemistry of Archean shales from the Pilbara Supergroup,Western Australia

Archean clastic sedimentary rocks are well exposed in the Pilbara Block of Western Australia. Shales from turbidites in the Gorge Creek Group (ca. 3.4 Ae) and shales from the Whim Creek Group (ca. 2.7 Ae) have been examined. The Gorge Creek Group samples, characterized by muscovite-quartzchlorite mineralogy, are enriched in incompatible elements (K, Th, U, LREE) by factors of about two, when compared to younger Archean shales from the Yilgarn Block. Alkali and alkaline earth elements are depleted in a systematic fashion, according to size, when compared with an estimate of Archean upper crust abundances. This depletion is less notable in the Whim Creek Group. Such a pattern indicates the source of these rocks underwent a rather severe episode of weathering. The Gorge Creek Group also has fairly high B content (85 ± 29 ppm) which may indicate normal marine conditions during deposition.Rare earth element (REE) patterns for the Pilbara samples are characterized by light REE enrichment ($\text{La}{}_{\mathrm{N}}\text{Yb}{}_{\mathrm{N}}\text{≥ 7.5}$) and no or very slight Eu depletion ($\text{Eu}\text{Eu}{}^1\text{= 0.82 – 0.99}$). A source comprised of about 80% felsic igneous rocks without large negative Eu-anomalies (felsic volcanics, tonalites, trondhjemites) and 20% mafic-ultramafic volcanics is indicated by the trace element data. Very high abundances of Cr and Ni cannot be explained by any reasonable provenance model and a secondary enrichment process is called for.     

Optimization of SAGD Well Elevation

The application of steam-assisted gravity drainage (SAGD) to recover heavy oil sands is becoming increasingly important in the northern Alberta McMurray Formation because of the vast resources/reserves accessible with this mechanism. Selecting the stratigraphic elevations of SAGD well pairs is a vital decision for reservoir evaluation and planning. The inherent uncertainty in the distribution of geological variables significantly influences this decision. Geostatistical simulation is used to capture geological uncertainty, which is used can be transformed into a distribution of the best possible well pair elevations. A simple exhaustive calculation scheme is used to determine the optimum stratigraphic location of a SAGD well pair where the recovery R is maximized. There are three basic steps to the methodology: (1) model the uncertainty in the top continuous bitumen (TCB) and bottom continuous bitumen (BCB) surfaces, (2) calculate the recovery at all possible elevation increments within the TCB and BCB interval, and (3) identify the elevation that maximizes R. This is repeated for multiple TCB/BCB pairs of surfaces to assess uncertainty. The methodology is described and implemented on a subset of data from the Athabasca Oilsands in Fort McMurray, Alberta.     

Does martian soil release reactive halogens to the atmosphere?

Detailed statistical examination of Cl, Br, and S distributions, in martian soil profiles at Gusev Crater and Meridiani Planum, indicates decreasing Br abundance and weakening Br–S association towards the surface. All three elements decrease towards the surface in the order Cl < S < Br. Furthermore, Br variability decouples from potential cations such as Mg at the surface relative to the subsurface. These observations support a relative loss of surficial Br compared to S and Cl, all highly mobile elements in aqueous environments. We propose that Br may have converted preferentially to gas phases (e.g., BrO), driven either by UV photolysis or by chemical oxidants. Such volatilization pathways may in turn impart a global signature on Mars by acting as controls on oxidants such as ozone and perchlorates. S/Cl mass ratios vary with depth (∼4–5 in the subsurface; 1.8–3.6 on the surface) as well, with a strong correlation of S and Cl near the surface but more variable at depth, consistent with differential vertical mobility, but not volatilization of Cl. Elevated S/Cl in subsurface soil also suggests that the ratio may be higher in bulk soil – a key repository of martian geologic and climatic records – than previously thought.     

Experimental constraints on the evaporation of partially oxidized acid-sulfate waters at the martian surface

Isothermal evaporation experiments were carried out on an acidic (pH 2), partially oxidized (Fe²⁺/Fe_T ∼0.5) brine with a cation composition consistent with derivation from the chemical weathering of martian basalt. During evaporation, the brine composition evolved to a highly acidic (un-scaled pH −1.3) Mg-Fe-SO₄-Cl brine depleted in Ca, Al and K. Evaporite minerals identified throughout the course of the experiment include (in order of crystallization): gypsum, Mg-rich voltaite, (Mg_0.7, )SO₄·7H₂O and rhomboclase. The solid solution compositions of voltaite and (Mg_0.7, )SO₄·7H₂O, although uncommon in analogous environments on Earth, result from the distinct chemistry of evaporating martian surface fluids. Analysis of brine compositions with available thermodynamic models indicates that, although gypsum and rhomboclase precipitate at equilibrium saturation, kinetic controls on the precipitation of copiapite-group minerals affect the subsequent sulfate mineralogy and evolving chemistry of the entire system. In addition, geochemical simulations of the experimental evaporation process suggest that the appearance of voltaite and rhomboclase indicate a “metastable” evaporation pathway for martian fluids whereby bilinite and copiapite-group minerals did not form despite thermodynamic saturation. Comparison of the experimentally-produced assemblage to available observations of saline minerals at the martian surface represents a step toward systematically characterizing evaporite mineralogy as a function of Fe-oxidation in the initially dilute fluid. Deconvolving the complexity of Fe-sulfate formation in martian environments ultimately will help to exploit the sensitivity of these minerals to pH and redox conditions present at the ancient martian surface.