Biogeochemical transformation of Fe minerals in a petroleum-contaminated aquifer

The Bemidji aquifer in Minnesota, USA is a well-studied site of subsurface petroleum contamination. The site contains an anoxic groundwater plume where soluble petroleum constituents serve as an energy source for a region of methanogenesis near the source and bacterial Fe(III) reduction further down gradient. Methanogenesis apparently begins when bioavailable Fe(III) is exhausted within the sediment. Past studies indicate that Geobacter species and Geothrix fermentens-like organisms are the primary dissimilatory Fe-reducing bacteria at this site. The Fe mineralogy of the pristine aquifer sediments and samples from the methanogenic (source) and Fe(III) reducing zones were characterized in this study to identify microbiologic changes to Fe valence and mineral distribution, and to identify whether new biogenic mineral phases had formed. Methods applied included X-ray diffraction; X-ray fluorescence (XRF); and chemical extraction; optical, transmission, and scanning electron microscopy; and Mössbauer spectroscopy.All of the sediments were low in total Fe content (≈ 1%) and exhibited complex Fe-mineralogy. The bulk pristine sediment and its sand, silt, and clay-sized fractions were studied in detail. The pristine sediments contained Fe(II) and Fe(III) mineral phases. Ferrous iron represented approximately 50% of Fe_TOT. The relative Fe(II) concentration increased in the sand fraction, and its primary mineralogic residence was clinochlore with minor concentrations found as a ferroan calcite grain cement in carbonate lithic fragments. Fe(III) existed in silicates (epidote, clinochlore, muscovite) and Fe(III) oxides of detrital and authigenic origin. The detrital Fe(III) oxides included hematite and goethite in the form of mm-sized nodular concretions and smaller-sized dispersed crystallites, and euhedral magnetite grains. Authigenic Fe(III) oxides increased in concentration with decreasing particle size through the silt and clay fraction. Chemical extraction and Mössbauer analysis indicated that this was a ferrihydrite like-phase. Quantitative mineralogic and Fe(II/III) ratio comparisons between the pristine and contaminated sediments were not possible because of textural differences. However, comparisons between the texturally-similar source (where bioavailable Fe(III) had been exhausted) and Fe(III) reducing zone sediments (where bioavailable Fe(III) remained) indicated that dispersed detrital, crystalline Fe(III) oxides and a portion of the authigenic, poorly crystalline Fe(III) oxide fraction had been depleted from the source zone sediment by microbiologic activity. Little or no effect of microbiologic activity was observed on silicate Fe(III). The presence of residual “ferrihydrite” in the most bioreduced, anoxic plume sediment (source) implied that a portion of the authigenic Fe(III) oxides were biologically inaccessible in weathered, lithic fragment interiors. Little evidence was found for the modern biogenesis of authigenic ferrous-containing mineral phases, perhaps with the exception of thin siderite or ferroan calcite surface precipitates on carbonate lithic fragments within source zone sediments.     

The sedimentary record of drifting ice (early Wisconsin Sunnybrook deposit) in an ancestral ice-dammed Lake Ontario, Canada

Outcrops of pebbly mud (diamict) at Scarborough in Southern Ontario, Canada (the so-called Sunnybrook ‘Till’) are associated with the earliest incursion of the Laurentide Ice Sheet (LIS) into mid-continent North America some 45,000 years ago. The Sunnybrook is a blanket-like deposit containing deepwater ostracodes and occurs conformably within a thick (100 m) succession of deltaic and glaciolacustrine facies that record water depth changes in a large proglacial lake. Contextual evidence (associated facies, sedimentary structures, deposit geometry and landforms) indicates a low energy depositional setting in an ice-dammed ancestral Lake Ontario in which scouring by floating ice masses was an important process. U-shaped, iceberg-cut scours (with lateral berms) up to 7 m deep, occur on the upper surface of the Sunnybrook and are underlain by ‘sub-scour’ structures that extend several meters below the scour base. Ice-rafted concentrations of clasts (‘clast layers’), grooved surfaces formed by floating ice glissading over a muddy lake floor (‘soft sediment striations’) and melanges of sand and mud mixed by grounding ice keels (‘ice keel turbates’) are present and are all well known from modern cold environments. The wider significance of this depositional model is that the LIS margin lay east of Scarborough and did not overrun Southern Ontario. This finding is in agreement with recent data from the Erie Basin of Canada, Ohio, and Indiana where deposits formerly correlated with the Sunnybrook (and thus implying an extensive early Wisconsin ice sheet) are now regarded as Illinoian. A speculative hypothesis is proposed that relates deposition of the Sunnybrook and two younger deposits of similar sedimentology, to surge-like instabilities of the southern LIS margin.     

Process-based snowmelt modeling: does it require more input data than temperature-index modeling?

Modeling snow hydrology for cold regions remains a problematic aspect of many hydro-environmental models. Temperature-index methods are commonly used and are routinely justified under the auspices that process-based models require too many input data. To test this claim, we used a physical, process-based model to simulate snowmelt at four locations across the conterminous US using energy components estimated from measured daily maximum and minimum temperature, i.e. using only the same data required for temperature-index models. The results showed good agreement between observed and predicted snow water equivalents, average R²>0.9. We duplicated the simulations using a simple temperature-index model best fitted to the data and results were poorer, R²<0.8. At one site we applied the process-based model without substantial parameter estimation, and there were no significant (=0.05) differences between these results and those obtained using temperature-estimated parameters, despite relatively poorly predicted specific energy budget components (R²<0.8). These results encourage the use of mechanistic snowmelt modeling approaches in hydrological models, especially in distributed hydrological models for which landscape snow distribution may be controlled by spatially distributed components of the environmental energy budget.     

Observations of planview flux patterns within convective structures of the marine atmospheric surface layer

Air/sea flux variability on horizontal scales from 50 m to several km results, in part, from the presence of coherent convective structures within the atmospheric boundary layer. The horizontal distribution of fluxes within these convective updrafts and downdrafts is, therefore, central to studies of air/sea interaction and remote sensing of sea surface wind and wave fields. This study derives these flux patterns from observations of the Marine Atmospheric Surface Layer (MASL).Research aircraft flights through the MASL provide an optimal means for sampling large numbers of the above-mentioned coherent structures. The NCAR Electra flew numerous legs through the MASL at a height of 50 m during the 1987 stratocumulus phase of Project FIRE (First ISSCP (International Satellite Cloud Climatology Program) Regional Experiment).In situ measurements from these legs serve as the dataset for this paper. The data are processed in such a way as to retain only the turbulence fluctuations. Conditional sampling, based on the vertical velocity field, results in the isolation of convective updrafts and downdrafts. Compositing of the data for these two classes of convective drafts results in horizontal planviews of the vertical fluxes of buoyancy, absolute humidity, along-meanwind component of momentum, and vertical velocity. To ensure dynamical similarity, these horizontal planviews are oriented in a coordinate system aligned with the mean wind.     

The Probability Perturbation Method: A New Look at Bayesian Inverse Modeling

Building of models in the Earth Sciences often requires the solution of an inverse problem: some unknown model parameters need to be calibrated with actual measurements. In most cases, the set of measurements cannot completely and uniquely determine the model parameters; hence multiple models can describe the same data set. Bayesian inverse theory provides a framework for solving this problem. Bayesian methods rely on the fact that the conditional probability of the model parameters given the data (the posterior) is proportional to the likelihood of observing the data and a prior belief expressed as a prior distribution of the model parameters. In case the prior distribution is not Gaussian and the relation between data and parameters (forward model) is strongly non-linear, one has to resort to iterative samplers, often Markov chain Monte Carlo methods, for generating samples that fit the data likelihood and reflect the prior model statistics. While theoretically sound, such methods can be slow to converge, and are often impractical when the forward model is CPU demanding. In this paper, we propose a new sampling method that allows to sample from a variety of priors and condition model parameters to a variety of data types. The method does not rely on the traditional Bayesian decomposition of posterior into likelihood and prior, instead it uses so-called pre-posterior distributions, i.e. the probability of the model parameters given some subset of the data. The use of pre-posterior allows to decompose the data into so-called, “easy data” (or linear data) and “difficult data” (or nonlinear data). The method relies on fast non-iterative sequential simulation to generate model realizations. The difficult data is matched by perturbing an initial realization using a perturbation mechanism termed “probability perturbation.” The probability perturbation method moves the initial guess closer to matching the difficult data, while maintaining the prior model statistics and the conditioning to the linear data. Several examples are used to illustrate the properties of this method.     

Stable isotopic fingerprint of a hyporheic–hypolentic boundary in a reservoir

Stable isotopes of H₂O are used to define the hyporheic–hypolentic boundary in Ledbetter Creek as it discharges to Kentucky Lake, a constructed reservoir in western Kentucky, USA. High-resolution (centimeter-scale) sample collection and analysis were utilized to determine one-dimensional variations in δ²H and δ¹⁸O of H₂O and chloride (Cl⁻) across the boundary. During reservoir low stand in winter, the hyporheic–hypolentic zone contains water from Ledbetter Creek and groundwater separated by an interface at ~10 cm below the channel bottom. Following reservoir-stage increase in spring and summer, water from Kentucky Lake infiltrates into the hyporheic–hypolentic zone to a depth of at least 18 cm below the channel bottom. Reservoir-stage decline in autumn causes source-water mixing, largely obscuring the hyporheic–hypolentic boundary. Stable isotopes provide an effective complement to conventional tracers for delineation of water masses within the hyporheic–hypolentic zone.

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Resumen Se han utilizado isótopos estables del agua para definir el límite hiporreico-hipoléntico en Ledbetter Creek, que constituye una zona de descarga del lago Kentucky, una presa construida al Oeste de Kentucky, USA. Se ha llevado a cabo una recogida de muestras de alta resolución (a escala centimétrica) y se utilizaron los resultados para determinar las variaciones unidimensionales en δ²H y δ¹⁸O del H₂O y los cloruros (Cl⁻) alrededor del límite. Durante la época de niveles bajos en invierno, la zona hiporreica-hipolentica tiene agua procedente de Ledbetter Creek y de agua subterránea separada por una interfase de ~10 cm debajo del límite del canal. Siguiendo el incremento de los niveles en la presa en primavera y verano, el agua del Lago Kentucky se infiltra en la zona hiporreica-hipoléntica hasta una profundidad de, al menos, 18 cm bajo el límite hiporreico-hipoléntico. Los isótopos estables aportan un complemento efectivo a los trazadores convencionales para la delimitación de masas de agua dentro de la zona hiporreica-hipoléntica.

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Résumé L’utilisation des isotopes stables de la molécule d’eau a permis de définir l’interface hyporhéique-hypolentique dans la Ledbetter Creek, au point de déversement dans le réservoir artificiel que constitue le Kentucky Lake (Ouest du Kentucky, Etats-Unis). Une campagne de prélèvements à haute résolution (échelle centimétrique) a contribué à déterminer les variations unidimensionnelles des valeurs de δ2H et de δ18O de la molécule d’eau et de la concentration en chlorures (Cl⁻) de part et d’autre de l’interface. En hiver, lorsque le niveau du réservoir est minimal, la zone hyporhéique-hypolentique contient de l’eau de la Ledbetter Creek et de l’eau souterraine, séparées par un interface situé environ 10 cm sous le fond du chenal. Suite aux recharges printanières et estivales, l’eau du Kentucky Lake envahit la zone hyporhéique-hypolentique sur plus de 18 cm sous le fond du chenal. En automne, la baisse de niveau dans le réservoir occasionne un mélange des eaux, rendant diffus l’interface hyporhéique-hypolentique. Les isotopes stables constituent ainsi un complément efficace aux traceurs conventionnels pour la délimitation des masses d’eau dans la zone hyporhéique-hypolentique.

     

GPS-derived strain in northwestern California: Termination of the San Andreas fault system and convergence of the Sierra Nevada–Great Valley block contribute to southern Cascadia forearc contraction

GPS-derived velocities (1993–2002) in northwestern California show that processes other than subduction are in part accountable for observed upper-plate contraction north of the Mendocino triple junction (MTJ) region. After removing the component of elastic strain accumulation due to the Cascadia subduction zone from the station velocities, two additional processes account for accumulated strain in northern California. The first is the westward convergence of the Sierra Nevada–Great Valley (SNGV) block toward the coast and the second is the north–northwest impingement of the San Andreas fault system from the south on the northern California coastal region in the vicinity of Humboldt Bay. Sierra Nevada–Great Valley block motion is northwest toward the coast, convergent with the more northerly, north–northwest San Andreas transform fault-parallel motion. In addition to the westward-converging Sierra Nevada–Great Valley block, San Andreas transform-parallel shortening also occurs in the Humboldt Bay region. Approximately 22 mm/yr of distributed Pacific–SNGV motion is observed inland of Cape Mendocino across the northern projections of the Maacama and Bartlett Springs fault zones but station velocities decrease rapidly north of Cape Mendocino. The resultant 6–10 mm/yr of San Andreas fault-parallel shortening occurs above the southern edge of the subducted Gorda plate and at the latitude of Humboldt Bay. Part of the San Andreas fault-parallel shortening may be due to the viscous coupling of the southern edge of the Gorda plate to overlying North American plate. We conclude that significant portions of the upper-plate contraction observed north of the MTJ region are not solely a result of subduction of the Gorda plate but also a consequence of impingement of the western edge of the Sierra Nevada–Great Valley block and growth of the northernmost segments of the San Andreas fault system.     

Lessons learned in remediation and restoration in the Oklahoma prairie: A review

For almost a decade the Tallgrass Prairie Preserve in Oklahoma has been used as a field laboratory for the investigation of aspects of the remediation and restoration of oil and brine spills. Objectives of this work have included: (1) simplification of the remediation process and lowering the cost of remediation; (2) the development of methods to accelerate or jump-start the restoration process; and (3) determining appropriate metrics for assessing the status of soil ecosystem recovery. This research has resulted in a number of lessons learned that will be presented here which can be exported to other exploration and production sites, especially sites located in sensitive ecosystems. Key observations have included the role of a fertilizer amendment in linking the remediation and restoration process at an oil-impacted site, the use of nematodes as ecological indicators in the restoration of oil- and brine-impacted sites, and the development of a two-stage process for remediation of brine impacted sites that does not include significant use of gypsum.