Encounters with an unearthly mudstone: Understanding the first mudstone found on Mars

The Sheepbed mudstone forms the base of the strata examined by the Curiosity rover in Gale Crater on Mars, and is the first bona fide mudstone known on another planet. From images and associated data, this contribution proposes a holistic interpretation of depositional regime, diagenesis and burial history. A lake basin probably received sediment pulses from alluvial fans. Bed cross‐sections show millimetre to centimetre‐scale layering due to distal pulses of fluvial sediment injections (fine‐grained hyperpycnites), fall‐out from river plumes, and some aeolian supply. Diagenetic features include mineralized synaeresis cracks and millimetre‐scale nodules, as well as stratiform cementation. Clay minerals were initially considered due to in situ alteration, but bulk rock chemistry and mineralogy suggests that sediments were derived from variably weathered source rocks that probably contained pre‐existing clay minerals. X‐ray diffraction analyses show contrasting clay mineralogy in closely spaced samples, consistent with at least partial detrital supply of clay minerals. A significant (ca 30 wt%) amorphous component is consistent with little post‐depositional alteration. Theoretical modelling of diagenetic reactions, as well as kinetic considerations, suggest that the bulk of diagenetic clay mineral formation occurred comparatively late in diagenesis. Diagenetic features (synaeresis cracks and nodules) were previously thought to reflect early diagenetic gas formation, but an alternative scenario of synaeresis crack formation via fabric collapse of flocculated clays appears more likely. The observed diagenetic features, such as solid nodules, hollow nodules, matrix cement and ‘raised ridges’ (synaeresis cracks) can be explained with progressive alteration of olivine/glass in conjunction with centrifugal and counter diffusion of reactive species. Anhydrite‐filled fractures in the Sheepbed mudstone occurred late in diagenesis when fluid pressures built up to exceed lithostatic pressure. Generating fluid overpressure by burial to facilitate hydraulic fracturing suggests a burial depth of at least 1000 m for the underlying strata that supplied these fluids.     

Pressure dependence of melt viscosities on the join diopside-albite

The pressure dependence of melt viscosities on the join diopside-albite has been studied using falling-sphere viscometry. The five melt compositions investigated are: diopside, Ab₂₅Di₇₅, Ab₅₀Di₅₀, Ab₇₅Di₂₅ and albite. Experiments were performed at 1500° and 1600°C and at pressures of 5, 10, 15, 20 and 25 kbar. The positive and negative pressure dependence of the viscosity of diopside and albite, respectively, were confirmed. All intermediate compositions show an initial decrease in viscosity with increasing pressure; however, melt of Ab₂₅Di₇₅ composition passes through a minimum viscosity at approximately 12 kbar and 1600°C. This behavior is analogous to the variation in the viscosity of water with pressure at low temperature.

It is suggested that the three-dimensional, fully polymerized, albite structure dominates flow at low pressures. With increasing pressure, disruption of this structure and decrease in the average size of the flow units leads to domination by the diopside structure. The variation in viscosity with composition along the join at one atmosphere can be adequately modelled using the and (1965) configurational entropy model with an additional two-lattice configurational entropy of mixing term. The pressure dependence of viscosity in the diopside-albite system, however, cannot be predicted by the model, because there is an absence of information on the pressure dependence of the model parameters.

It is probable that relatively polymerized magmas (e.g. rhyolites to SiO₂-saturated basalts) show a negative pressure dependence of viscosity to depths where they originate in the lower crust or upper mantle. In contrast, the most depolymerized, naturally-occurring melts, such as strongly SiO₂-undersaturated basalts and picrites, may exhibit a viscosity minimum. The viscosity of these melts may be sufficiently high at depths within the upper mantle to inhibit their segregation, rise and eventual eruption at the surface.     

Analytical model for screening potential CO<Subscript>2</Subscript> repositories

Assessing potential repositories for geologic sequestration of carbon dioxide using numerical models can be complicated, costly, and time-consuming, especially when faced with the challenge of selecting a repository from a multitude of potential repositories. This paper presents a set of simple analytical equations (model), based on the work of previous researchers, that could be used to evaluate the suitability of candidate repositories for subsurface sequestration of carbon dioxide. We considered the injection of carbon dioxide at a constant rate into a confined saline aquifer via a fully perforated vertical injection well. The validity of the analytical model was assessed via comparison with the TOUGH2 numerical model. The metrics used in comparing the two models include (1) spatial variations in formation pressure and (2) vertically integrated brine saturation profile. The analytical model and TOUGH2 show excellent agreement in their results when similar input conditions and assumptions are applied in both. The analytical model neglects capillary pressure and the pressure dependence of fluid properties. However, simulations in TOUGH2 indicate that little error is introduced by these simplifications. Sensitivity studies indicate that the agreement between the analytical model and TOUGH2 depends strongly on (1) the residual brine saturation, (2) the difference in density between carbon dioxide and resident brine (buoyancy), and (3) the relationship between relative permeability and brine saturation. The results achieved suggest that the analytical model is valid when the relationship between relative permeability and brine saturation is linear or quasi-linear and when the irreducible saturation of brine is zero or very small.     

<Emphasis Type="Italic">Spartina alterniflora</Emphasis> Biomass Allocation and Temperature: Implications for Salt Marsh Persistence with Sea-Level Rise

To predict the impacts of climate change, a better understanding is needed of the foundation species that build and maintain biogenic ecosystems. Spartina alterniflora Loisel (smooth cordgrass) is the dominant salt marsh-building plant along the US Atlantic coast. It maintains salt marsh elevation relative to sea level by the accumulation of aboveground biomass, which promotes sediment deposition and belowground biomass, which accretes as peat. Peat accumulation is particularly important in elevation maintenance at high latitudes where sediment supply tends to be limited. Latitudinal variation in S. alterniflora growth was quantified in eight salt marshes from Massachusetts to South Carolina. The hypothesis that allocation to aboveground and belowground biomass is phenotypically plastic was tested with transplant experiments among a subset of salt marshes along this gradient. Reciprocal transplants revealed that northern S. alterniflora decreased allocation to belowground biomass when grown in the south. Some northern plants also died when moved south, suggesting that northern S. alterniflora may be stressed by future warming. Southern plants that were moved north showed phenotypic plasticity in biomass allocation, but no mortality. Belowground biomass also decomposed more quickly in southern marshes. Our results suggest that warming will lead northern S. alterniflora to decrease belowground allocation and that belowground biomass will decompose more quickly, thus decreasing peat accumulation. Gradual temperature increases may allow for adaptation and acclimation, but our results suggest that warming will lower the ability of salt marshes to withstand sea-level rise.     

Formation, reactivity, and aging of ferric oxide particles formed from Fe(II) and Fe(III) sources: Implications for iron bioavailability in the marine environment

Freshly formed amorphous ferric oxides (AFO) in the water column are potentially highly reactive, but with reactivity declining rapidly with age, and have the capacity to partake in reactions with dissolved species and to be a significant source of bioavailable iron. However, the controls on reactivity in aggregated oxides are not well understood. Additionally, the mechanism by which early rapid aging occurs is not clear. Aging is typically considered in terms of changes in crystallinity as the structure of an iron oxide becomes more stable and ordered with time thus leading to declining reactivity. However, there has been recognition of the role that aggregation can play in determining reactivity, although it has received limited attention. Here, we have formed AFO in seawater in the laboratory from either an Fe(II) or Fe(III) source to produce either AFO(II) or AFO(III). The changes in reactivity of these two oxides following formation was measured using both ligand-promoted dissolution (LPD) and reductive dissolution (RD). The structure of the two oxides was examined using light scattering and X-ray adsorption techniques. The dissolution rate of AFO(III) was greater than that of AFO(II), as measured by both dissolution techniques, and could be attributed to both the less ordered molecular structure and smaller primary particle size of AFO(III). From EXAFS analysis shortly (90 min) following formation, AFO(II) and AFO(III) were shown to have the same structure as aged lepidocrocite and ferrihydrite respectively. Both oxides displayed a rapid decrease in dissolution rate over the first hours following formation in a pattern that was very similar when normalised. The early establishment and little subsequent change of crystal structure for both oxides undermined the hypothesis that increasing crystallinity was responsible for early rapid aging. Also, an aging model describing this proposed process could only be fitted to the data with kinetic parameters that were inconsistent with such a mechanism. The similar aging patterns and existence of diffusion limited cluster aggregation (DLCA) suggested that loss of Fe centre accessibility due to aggregation is the likely cause of early rapid aging of AFO. A simple model describing the loss of surface area during the aggregate growth, measured using dynamic light scattering (DLS), produced aging patterns that matched the reactivity loss of AFO(III) measured using RD but not LPD. The difference between the two measures of dissolution rate could not be explained, but indicated that different measures of reactivity respond differentially to various parameters controlling reactivity. Analysis of aggregate structure using aggregation kinetics and static light scattering (SLS) suggested that restructuring during aggregation was occurring at an aggregate level for AFO(III), but only minimally so for AFO(II). While our investigations support the contention that aggregation is responsible for early rapid aging, the role of aggregate structure is remains unclear.     

Characterization and cycling of atmospheric mercury along the central US Gulf Coast

Concentrations of atmospheric Hg species, elemental Hg (Hg^°), reactive gaseous Hg (RGM), and fine particulate Hg (Hg-PM_2.5) were measured at a coastal site near Weeks Bay, Alabama from April to August, 2005 and January to May, 2006. Mean concentrations of the species were 1.6 ± 0.3 ng m⁻³, 4.0 ± 7.5 pg m⁻³ and 2.7 ± 3.4 pg m⁻³, respectively. A strong diel pattern was observed for RGM (midday maximum concentrations were up to 92.7 pg m⁻³), but not for Hg^° or Hg-PM_2.5. Elevated RGM concentrations (>25 pg m⁻³) in April and May of 2005 correlated with elevated average daytime O₃ concentrations (>55 ppbv) and high light intensity (>500 W m⁻²). These conditions generally corresponded with mixed continental-Gulf and exclusively continental air mass trajectories. Generally lower, but still elevated, RGM peaks observed in August, 2005 and January–March, 2006 correlated significantly (p < 0.05) with peaks in SO₂ concentration and corresponded to periods of high light intensity and lower average daytime O₃ concentrations. During these times air masses were dominated by trajectories that originated over the continent. Elevated RGM concentrations likely resulted from photochemical oxidation of Hg^° by atmospheric oxidants. This process may have been enhanced in and by the near-shore environment relative to inland sites. The marine boundary layer itself was not found to be a significant source of RGM.     

Submarine Groundwater Discharge-Derived Nutrient Loads to San Francisco Bay: Implications to Future Ecosystem Changes

Submarine groundwater discharge (SGD) was quantified at select sites in San Francisco Bay (SFB) from radium (²²³Ra and ²²⁴Ra) and radon (²²²Rn) activities measured in groundwater and surface water using simple mass balance box models. Based on these models, discharge rates in South and Central Bays were 0.3?C7.4?m³?day^?1?m^?1. Although SGD fluxes at the two regions (Central and South Bays) of SFB were of the same order of magnitude, the dissolved inorganic nitrogen (DIN) species associated with SGD were different. In the South Bay, ammonium (NH ₄ ⁺ ) concentrations in groundwater were three-fold higher than in open bay waters, and NH ₄ ⁺ was the primary DIN form discharged by SGD. At the Central Bay site, the primary DIN form in groundwater and associated discharge was nitrate (NO ₃ ^? ). The stable isotope signatures (??¹⁵N_NO3 and ??¹⁸O_NO3) of NO ₃ ^? in the South Bay groundwater and surface waters were both consistent with NO ₃ ^? derived from NH ₄ ⁺ that was isotopically enriched in ¹⁵N by NH ₄ ⁺ volatilization. Based on the calculated SGD fluxes and groundwater nutrient concentrations, nutrient fluxes associated with SGD can account for up to 16?% of DIN and 22?% of DIP in South and Central Bays. The form of DIN contributed to surface waters from SGD may impact the ratio of NO ₃ ^? to NH ₄ ⁺ available to phytoplankton with implications to bay productivity, phytoplankton species distribution, and nutrient uptake rates. This assessment of nutrient delivery via groundwater discharge in SFB may provide vital information for future bay ecological wellbeing and sensitivity to future environmental stressors.     

Dynamic propagation criteria for catastrophic failure in planar landslides

Quantitative assessment of the risk of submarine landslides is an essential part of the design process for offshore oil and gas developments in deep water, beyond the continental shelf. Landslides may be triggered by a reduction in shear strength of subsea sediments over a given zone, caused for example by seismic activity. Simple criteria are then needed to identify critical conditions whereby the zone of weakness could grow catastrophically to cause a landslide. A number of such criteria have been developed over the last decade, based either on ideas drawn from fracture mechanics, or considering the equilibrium of the initial weakened zone and adjacent process zones of gradually softening material. Accounting for the history of the weak zone initiation is critical for derivation of reliable propagation criteria, in particular considering dynamic effects arising from accumulating kinetic energy of the failing material, which will allow the failure to propagate from a smaller initial zone of weakened sediments. Criteria are developed here for planar conditions, taking full account of such dynamic effects, which are shown to be capable of reducing the critical length of the softened zone by 20% or more compared with criteria based on static conditions. A numerical approach is used to solve the governing dynamic equations for the sliding material, the results from which justify assumptions that allow analytical criteria to be developed for the case where the initial softening occurs instantaneously. The effect of more gradual softening is also explored. Copyright © 2016 John Wiley & Sons, Ltd.     

Application of environmental groundwater tracers at the Sulphur Bank Mercury Mine, California, USA

Boron, chloride, sulfate, δD, δ¹⁸O, and ³H concentrations in surface water and groundwater samples from the Sulphur Bank Mercury Mine (SBMM), California, USA were used to examine geochemical processes and provide constraints on evaporation and groundwater flow. SBMM is an abandoned sulfur and mercury mine with an underlying hydrothermal system, adjacent to Clear Lake, California. Results for non-³H tracers (i.e., boron, chloride, sulfate, δD, and δ¹⁸O) identify contributions from six water types at SBMM. Processes including evaporation, mixing, hydrothermal water input and possible isotopic exchange with hydrothermal gases are also discerned. Tritium data indicate that hydrothermal waters and other deep groundwaters are likely pre-bomb (before ~1952) in age while most other waters were recharged after ~1990. A boron-based steady-state reservoir model of the Herman Impoundment pit lake indicates that 71–79% of its input is from meteoric water with the remainder from hydrothermal contributions. Results for groundwater samples from six shallow wells over a 6–month period for δD and δ¹⁸O suggests that water from Herman Impoundment is diluted another 3% to more than 40% by infiltrating meteoric water, as it leaves the site. Results for this investigation show that environmental tracers are an effective tool to understand the SBMM hydrogeologic regime.

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Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.

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Résumé Les concentrations en bore, chlorure, sulfate, δD, δ¹⁸O, et ³H d’échantillons d’eaux de surface et souterraine prélevés dans le banc de soufre de la mine de mercure (SBMM en anglais) en Californie, USA, ont été utilisées pour étudier les processus géochimiques et pour fournir des contraintes à l’évaporation et à l’écoulement des eaux souterraines. La SBMM est une mine de soufre et de mercure abandonnée, adjacente au lac Clear en Californie et sous laquelle se trouve un système hydrothermal.Les résultats des traceurs autres que le tritium (bore, chlorure, sulfate, δD, et δ¹⁸O) ont permis d’identifier des contributions de six types d’eaux à SBMM. Des processus tels que l’évaporation, le mélange, l’entrée d’eau hydrothermale et de possibles échanges isotopiques avec des gaz hydrothermaux ont également été identifiés. Les données de tritium montrent que les eaux hydrothermales et d’autres eaux profondes sont probablement d’age antérieure à la bombe (avant ~1952), alors que la plupart des autres eaux sont issues de la recharge après ~1990. Un modèle de réservoir représentant le lac situé dans la partie Herman Impoundment de l’ancienne mine, en régime permanent et basé sur le bore, montre que 71–79% de l’eau provient des précipitations, le reste provenant de contributions hydrothermales. Les résultats de δD et δ¹⁸O pour des échantillons d’eau souterraine de six puits peu profonds sur une période de 6 mois suggèrent que l’eau de Hermann Impoundment est encore diluée entre 3% jusqu’à plus de 40% lorsqu’elle quitte le site du fait de l’infiltration d’eau météorique. Les résultats de cette étude montrent que les traceurs environnementaux constituent un outil efficace pour comprendre le régime hydrogéologique de la SBMM.

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Resumen Se han utilizado datos de concentraciones de boro, cloruros, sulfatos, δD, δ¹⁸O, y ³H en muestras de aguas superficiales y subterráneas procedentes de la Mina de Mercurio Sulphur Bank (SBMM), California, USA, para estudiar los procesos geoquímicos y caracterizar la evaporación y el flujo del agua subterránea. SBMM es una mina abandonada de azufre y mercurio con un sistema hidrotermal subyacente, cercano al Lago Clear, California.Los resultados de los trazadores que no son ³H (por ejemplo, boro, cloruros, sulfatos δD, y δ¹⁸O) identifican las contribuciones de seis tipos de agua en la SBMM. Se han identificado diversos procesos, como evaporación, mezcla, entrada de agua hidrotermal y la posibilidad de intercambios isotópicos con gases hidrotermales. Los datos de tritio indican que las aguas hidrotermales y otras aguas subterráneas profundas son probablemente pre-bombas (previas a ~1952) en edad mientras que la mayoría de las otras aguas se han recargado después de ~1990. Un modelo estacionario basado en el boro de la fosa del lago Herman Impoundment indica que el 71–79% de su entrada procede de agua meteórica con restos de contribución hidrotermal. Los resultados para las muestras de aguas subterráneas procedentes de seis pozos superficiales en un periodo de 6 meses para δD y δ¹⁸O sugieren que el agua procedente de Herman Impoundment se diluye en otro 3% hasta más del 40% debido a la infiltración de agua meteórica., que sale del sitio. Los resultados de esta investigación muestran que los trazadores ambientales son una herramienta efectiva para entender el régimen hidrogeológico de la SBMM.