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At least 1,135 records · Page 63Linked to original sources

Testing the suitability of geologic frameworks for extrapolating hydraulic properties across regional scales

The suitability of geologic frameworks for extrapolating hydraulic conductivity ( K ) to length scales commensurate with hydraulic data is difficult to assess. A novel method is presented for evaluating assumed relations between K and geologic interpretations for regional-scale groundwater modeling. The approach relies on simultaneous interpretation of multiple aquifer tests using alternative geologic frameworks of variable complexity, where each framework is incorporated as prior information that assumes homogeneous K within each model unit. This approach is tested at Pahute Mesa within the Nevada National Security Site (USA), where observed drawdowns from eight aquifer tests in complex, highly faulted volcanic rocks provide the necessary hydraulic constraints. The investigated volume encompasses 40 mi 3 (167 km 3 ) where drawdowns traversed major fault structures and were detected more than 2 mi (3.2 km) from pumping wells. Complexity of the five frameworks assessed ranges from an undifferentiated mass of rock with a single unit to 14 distinct geologic units. Results show that only four geologic units can be justified as hydraulically unique for this location. The approach qualitatively evaluates the consistency of hydraulic property estimates within extents of investigation and effects of geologic frameworks on extrapolation. Distributions of transmissivity are similar within the investigated extents irrespective of the geologic framework. In contrast, the extrapolation of hydraulic properties beyond the volume investigated with interfering aquifer tests is strongly affected by the complexity of a given framework. Testing at Pahute Mesa illustrates how this method can be employed to determine the appropriate level of geologic complexity for large-scale groundwater modeling.

Nevada↗

Ion association in natural brines

Natural brines, both surface and subsurface, are highly associated aqueous solutions. Ion complexes in brines may be ion pairs in which the cation remains fully hydrated and the bond between the ions is essentially electrostatic, or coordination complexes in which one or more of the hydration water molecules are replaced by covalent bonds to the anion. Except for Cl − , the major simple ions in natural brines form ion pairs; trace and minor metals in brines form mainly coordination complexes. Limitations of the Debye-Hückel relations for activity coefficients and lack of data on definition and stability of all associated species in concentrated solutions tend to produce underestimates of the degree of ion association, except where the brines contain a very high proportion of Cl − . Data and calculations on closed basin brines of highly varied composition have been coupled with electrode measurements of single-ion activities in an attempt to quantify the degree of ion association. Such data emphasize the role of magnesium complexes. Trace metal contents of closed basin brines are related to complexes formed with major anions. Alkaline sulfo- or chlorocarbonate brines (western Great Basin) carry significant trace metal contents apparently as hydroxides or hydroxy polyions. Neutral high chloride brines (Bonneville Basin) are generally deficient in trace metals. With a knowledge of the thermodynamic properties of a natural water, many possible reactions with other phases (solids, gases, other liquids) may be predicted. A knowledge of these reactions is particularly important in the study of natural brines which may be saturated with many solid phases (silicates, carbonates, sulfates, etc.), which may have a high pH and bring about dissolution of other phases (silica, amphoteric hydroxides, CO 2 , etc.), and which because of their high density may form relatively stable interfaces with dilute waters.

Chemical Geology↗

The dissolution of quartz in dilute aqueous solutions of organic acids at 25°C

The dissolution of quartz in dilute aqueous solutions of organic acids at 25° and standard pressure was investigated by the batch dissolution method. The bulk dissolution rate of quartz in 20 mmole/Kg citrate solutions at pH 7 was 8 to 10 times faster than that in pure water. After 1750 hours the concentration of dissolved silica in the citrate solution was 167 μmole/Kg compared to 50 μmole/Kg in water and a 20 mmole/Kg solution of acetate at pH 7. Solutions of salicylic, oxalic, and humic acids also accelerated the dissolution of quartz in aqueous solution at pH 7. The rate of dissolution in organic acids decreased sharply with decreasing pH. The possibility of a silica-organic acid complex was investigated using UV-difference spectroscopy. Results suggest that dissolved silica is complexed by citrate, oxalate and pyruvate at pH 7 by an electron-donor acceptor complex, whereas no complexation occurs between silica and acetate, lactate, malonate, or succinate. Three models are proposed for the solution and surface complexation of silica by organic acid anions which result in the accelerated dissolution and increased solubility of quartz in organic rich water.

Geochimica et Cosmochimica Acta↗

Enrichment of trace elements in garnet amphibolites from a paleo-subduction zone: Catalina Schist, southern California

The abundance, P - T stability, solubility, and element-partitioning behavior of minerals such as rutile, garnet, sphene, apatite, zircon, zoisite, and allanite are critical variables in models for mass transfer from the slab to the mantle wedge in deep regions of subduction zones. The influence of these minerals on the composition of subduction-related magmas has been inferred (and disputed) from inverse modelling of the geochemistry of island-arc basalt, or by experiment. Although direct samples of the dehydration + partial-melting region of a mature subduction zone have not been reported from subduction complexes, garnet amphibolites from melanges of circumpacific and Caribbean blueschist terranes reflect high T (>600°C) conditions in shallower regions. Such rocks record geochemical processes that affected deep-seated, high- T portions of paleo-subduction zones. In the Catalina Schist, a subduction-zone metamorphic terrane of southern California, metasomatized and migmatitic garnet amphibolites occur as blocks in a matrix of meta-ultramafic rocks. This mafic and ultramafic complex may represent either slab-derived material accreted to the mantle wedge of a nascent subduction zone or a portion of a shear zone closely related to the slab-mantle wedge contact, or both. The trace-element geochemistry of the complex and the distribution of trace elements among the minerals of garnet amphibolites were studied by INAA, XRF, electron microprobe, and SEM. In order of increasing alteration from a probable metabasalt protolith, three common types of garnet amphibolite blocks in the Catalina Schist are: (1) non-migmatitic, clinopyroxene-bearing blocks, which are compositionally similar to MORB that has lost an albite component; (2) garnet-amphibolite blocks, which have rinds that reflect local interaction between metabasite, metaperidotite, and fluid; and (3) migmatites that are extremely enriched in Th, HFSE, LREE, and other trace elements. These trace-element enrichments are mineralogically controlled by rutile, garnet, sphene, apatite, zircon, zoisite, and allanite. Alkali and alkaline earth elements are much less enriched in the solid assemblage, and thus appear to be decoupled from the other elements in the inferred metasomatic process(es). The compositions of migmatitic garnet amphibolite blocks seem to complement that of “average” island-arc tholeiite. Trace-element metasomatism reflects fluid-solid, rather than melt-solid, interaction. The metasomatic effects indicate that H 2 O-rich fluid, perhaps with a significant component of Na-Al silicate and alkalis, carried Th, U, Sr, REE, and HFSE. Fractionations of LREE in migmatites resemble those of migmatitic metasedimentary rocks underlying the mafic and ultramafic complex. “Exotic” LREE deposited in allanite in migmatites could have been derived from fluids in equilibrium with subducted sediment. If the paleo-subduction zone represented by the mafic and ultramafic complex of the Catalina Schist had continued its thermal and fluid evolution, a selvage of similarly enriched rocks might have been generated along the slab-mantle wedge contact between ~30 and 85 km depth. Rocks affected by “subduction-zone metasomatism,” although rarely recognized at the surface, could be volumetrically significant products of the initiation of subduction and may prove to be geochemical probes of convergent margins that approach the significance of xenoliths in the study of other magmatic environments.

Geochimica et Cosmochimica Acta↗

Comparison of the partitioning behaviours of yttrium, rare earth elements, and titanium between hydrogenetic marine ferromanganese crusts and seawater

In order to evaluate details of the partitioning behaviours of Y, rare earth elements (REEs), and Ti between inorganic metal oxide surfaces and seawater, we studied the distribution of these elements in hydrogenetic marine ferromanganese (Fe-Mn) crusts from the Central Pacific Ocean. Nonphosphatized Fe-Mn crusts display shale-normalized rare earths and yttrium (REY SN ) patterns (Y inserted between Dy and Ho) that are depleted in light REEs (LREEs) and which show negative anomalies for Y sn , and positive anomalies for La SN , Eu SN , Gd SN , and in most cases, Ce sn . They show considerably smaller Y/ Ho ratios than seawater or common igneous and clastic rocks, indicating that Y and Ho are fractionated in the marine environment. Compared to P-poor crusts, REY SN patterns of phosphatized Fe-Mn crusts are similar, but yield pronounced positive Y sn anomalies, stronger positive La SN anomalies, and enrichment of the HREEs relative to the MREEs. The data suggest modification of REY during phosphatization and indicate that studies requiring primary REY distributions or isotopic ratios should be restricted to non-phosphatized (layers of) Fe-Mn crusts. Apparent bulk coefficients, K d m , describing trace metal partitioning between nonphosphatized hydrogenetic Fe-Mn crusts and seawater, are similar for Pr to Eu and decrease for Eu to Yb. Exceptionally high values of K D Ce , which are similar to those of Ti, result from oxidative scavenging of Ce and support previous suggestions that Ce (IV) is a hydroxide-dominated element in seawater. Yttrium and Gd show lower K D values than their respective neighbours in the REY series. Results of modelling the exchange equilibrium between REY dissolved in seawater and REY sorbed on hydrous Fe-Mn oxides corroborate previous studies that suggested the surface complexation of REY can be approximated by their first hydroxide binding constant. Negative “anomalies” occur for stabilities of bulk surface complexes of Gd, La, and particularly Y. The differences in inorganic surface complex stability between Y and Ho and between Gd and its REE neighbours are similar to those shown by the stabilities of complexes with aminocarboxylic acids and are significantly larger than those shown by stabilities of complexes with carboxylic acids. Hence, sorption of Y and REEs onto hydrous Fe-Mn oxides may contribute significantly to the positive Y SN and Gd SN anomalies in seawater.

Geochimica et Cosmochimica Acta↗

Application of Conjugate Gradient methods to tidal simulation

A harmonic decomposition technique is applied to the shallow water equations to yield a complex, nonsymmetric, nonlinear, Helmholtz type problem for the sea surface and an accompanying complex, nonlinear diagonal problem for the velocities. The equation for the sea surface is linearized using successive approximation and then discretized with linear, triangular finite elements. The study focuses on applying iterative methods to solve the resulting complex linear systems. The comparative evaluation includes both standard iterative methods for the real subsystems and complex versions of the well known Bi-Conjugate Gradient and Bi-Conjugate Gradient Squared methods. Several Incomplete LU type preconditioners are discussed, and the effects of node ordering, rejection strategy, domain geometry and Coriolis parameter (affecting asymmetry) are investigated. Implementation details for the complex case are discussed. Performance studies are presented and comparisons made with a frontal solver.

Advances in Water Resources↗

Machine learning for predicting soil classes in three semi-arid landscapes

Mapping the spatial distribution of soil taxonomic classes is important for informing soil use and management decisions. Digital soil mapping (DSM) can quantitatively predict the spatial distribution of soil taxonomic classes. Key components of DSM are the method and the set of environmental covariates used to predict soil classes. Machine learning is a general term for a broad set of statistical modeling techniques. Many different machine learning models have been applied in the literature and there are different approaches for selecting covariates for DSM. However, there is little guidance as to which, if any, machine learning model and covariate set might be optimal for predicting soil classes across different landscapes. Our objective was to compare multiple machine learning models and covariate sets for predicting soil taxonomic classes at three geographically distinct areas in the semi-arid western United States of America (southern New Mexico, southwestern Utah, and northeastern Wyoming). All three areas were the focus of digital soil mapping studies. Sampling sites at each study area were selected using conditioned Latin hypercube sampling (cLHS). We compared models that had been used in other DSM studies, including clustering algorithms, discriminant analysis, multinomial logistic regression, neural networks, tree based methods, and support vector machine classifiers. Tested machine learning models were divided into three groups based on model complexity: simple, moderate, and complex. We also compared environmental covariates derived from digital elevation models and Landsat imagery that were divided into three different sets: 1) covariates selected a priori by soil scientists familiar with each area and used as input into cLHS, 2) the covariates in set 1 plus 113 additional covariates, and 3) covariates selected using recursive feature elimination. Overall, complex models were consistently more accurate than simple or moderately complex models. Random forests (RF) using covariates selected via recursive feature elimination was consistently the most accurate, or was among the most accurate, classifiers between study areas and between covariate sets within each study area. We recommend that for soil taxonomic class prediction, complex models and covariates selected by recursive feature elimination be used. Overall classification accuracy in each study area was largely dependent upon the number of soil taxonomic classes and the frequency distribution of pedon observations between taxonomic classes. Individual subgroup class accuracy was generally dependent upon the number of soil pedon observations in each taxonomic class. The number of soil classes is related to the inherent variability of a given area. The imbalance of soil pedon observations between classes is likely related to cLHS. Imbalanced frequency distributions of soil pedon observations between classes must be addressed to improve model accuracy. Solutions include increasing the number of soil pedon observations in classes with few observations or decreasing the number of classes. Spatial predictions using the most accurate models generally agree with expected soil–landscape relationships. Spatial prediction uncertainty was lowest in areas of relatively low relief for each study area.

New Mexico, Utah, Wyoming↗

Coproduction and modeling spatial contact networks prevent bias about infectious hematopoietic necrosis virus transmission for Snake River Basin salmonids

Much remains unknown about variation in pathogen transmission across the geographic range of a free-ranging fish or animal species and about the influence of movement (associated with husbandry practices or animal behavior) on pathogen transmission. Salmonid hatcheries are an ideal system in which to study these processes. Salmonid hatcheries are managed for endangered species recovery, supplementation of threatened or at-risk fish stocks, support of fisheries, and ecosystem stability. Infectious hematopoietic necrosis virus (IHNV) is a rhabdovirus of significant concern to salmon aquaculture. Landscape IHNV transmission dynamics previously had been estimated only for salmonid hatcheries in the Lower Columbia River Basin (LCRB). The objectives of this study were to estimate IHNV transmission dynamics in a unique geographic region, the Snake River Basin (SRB), and to quantitatively estimate the effect of model coproduction on inference because previous assessments of coproduction have been qualitative. In contrast to the LCRB, the SRB has hatchery complexes consisting of a main hatchery and ≥1 satellite facility. Knowledge about hatchery complexes was held by a subset of project researchers but would not have been available to project modelers without coproduction. Project modelers generated and tested multiple versions of Bayesian susceptible-exposedinfected models to realistically represent the SRB and estimate the effect of coproduction. Models estimated the frequency of transmission routes, route-specific infection probabilities, and infection probabilities for combinations of salmonid hosts and IHNV lineages. Model results indicated that in the SRB, avoiding exposure to IHNV-positive adult salmonids is the most important action to prevent juvenile infections. Migrating adult salmonids exposed juvenile cohort-sites most frequently, and the infection probability was greatest following exposure to migrating adults. Without coproduction, the frequency of exposure by migrating adults would have been overestimated by 70 cohort-sites, and the infection probability following exposure to migrating adults would have been underestimated by∼0.09. The coproduced model had less uncertainty in the infection probability if no transmission route could be identified (Bayesian credible interval (BCI) width = 0.12) compared to the model without coproduction (BCI width = 0.34). Evidence for virus lineage MD specialization on steelhead and rainbow trout (both Oncorhynchus mykiss) was apparent without model coproduction. In the SRB, we found a greater probability of virus lineage UC infection in Chinook salmon (Oncorhynchus tshawytscha) compared to in O. mykiss, whereas in the LCRB, UC more clearly exhibited a generalist approach. Coproduction influenced estimates that depended on transmission routes, which operated differently at main hatcheries and satellite sites within hatchery complexes. Hatchery complexes are found outside of the SRB and are not specific to salmonid hatcheries alone. There is great potential for coproduction and modeling spatial contact networks to advance understanding about infectious disease transmission in complex production systems and surrounding free-ranging animal populations.

Idaho, Oregon, Washington↗

Mapping the 3-D extent of the Northern Lobe of the Bushveld layered mafic intrusion from geophysical data

Geophysical models image the 3D geometry of the mafic portion of the Bushveld Complex north of the Thabazimbi-Murchison Lineament (TML), critical for understanding the origin of the world's largest layered mafic intrusion and platinum group element deposits. The combination of the gravity and magnetic data with recent seismic, MT, borehole and rock property measurements powerfully constrains the models. The intrusion north of the TML is generally shallowly buried (generally <1500 m) with a modeled area of &sim;160 km &times; &sim;125 km. The modeled thicknesses are not well constrained but vary from &sim;<1000 to >12,000 m, averaging &sim;4000 m. A feeder, suggested by a large modeled thickness (>10,000 m) and funnel shape, for Lower Zone magmas could have originated near the intersection of NS and NE trending TML faults under Mokopane. The TML has been thought to be the feeder zone for the entire Bushveld Complex but the identification of local feeders and/or dikes in the TML in the models is complicated by uncertainties on the syn- and post-Bushveld deformation history. However, modeled moderately thick high density material near the intersection of faults within the central and western TML may represent feeders for parts of the Bushveld Complex if deformation was minimal. The correspondence of flat, high resistivity and density regions reflect the sill-like geometry of the Bushveld Complex without evidence for feeders north of Mokopane. Magnetotelluric models indicate that the Transvaal sedimentary basin underlies much of the Bushveld Complex north of the TML, further than previously thought and important because the degree of reaction and assimilation of the Transvaal rocks with the mafic magmas resulted in a variety of mineralization zones.

Precambrian Research↗

Towards globally customizable ecosystem service models

Scientists, stakeholders and decision makers face trade-offs between adopting simple or complex approaches when modeling ecosystem services (ES). Complex approaches may be time- and data-intensive, making them more challenging to implement and difficult to scale, but can produce more accurate and locally specific results. In contrast, simple approaches allow for faster assessments but may sacrifice accuracy and credibility. The ARtificial Intelligence for Ecosystem Services (ARIES) modeling platform has endeavored to provide a spectrum of simple to complex ES models that are readily accessible to a broad range of users. In this paper, we describe a series of five “Tier 1” ES models that users can run anywhere in the world with no user input, while offering the option to easily customize models with context-specific data and parameters. This approach enables rapid ES quantification, as models are automatically adapted to the application context. We provide examples of customized ES assessments at three locations on different continents and demonstrate the use of ARIES' spatial multi-criteria analysis module, which enables spatial prioritization of ES for different beneficiary groups. The models described here use publicly available global- and continental-scale data as defaults. Advanced users can modify data input requirements, model parameters or entire model structures to capitalize on high-resolution data and context-specific model formulations. Data and methods contributed by the research community become part of a growing knowledge base, enabling faster and better ES assessment for users worldwide. By engaging with the ES modeling community to further develop and customize these models based on user needs, spatiotemporal contexts, and scale(s) of analysis, we aim to cover the full arc from simple to complex assessments, minimizing the additional cost to the user when increased complexity and accuracy are needed.

Science of the Total Environment↗

Geologic structures related to New Madrid earthquakes near Memphis, Tennessee, based on gravity and magnetic interpretations

New inversions of gravity and magnetic data in the region north of memphis. Tennessee, and south of latitude 36?? define boundaries of regional structures and igneous complexes in the upper crust. Microseismicity patterns near interpreted boundaries suggest that igneous complexes influence the locations of microseismicity. A weak seismicity cluster occurs near one intrusion (Covington pluton), at the intersection of the southwest margin of the Missouri batholith and the southeast margin of the Reelfoot rift. A narrow seismicity trend along the Reelfoot rift axis becomes diffuse near a second intrusion (Osceola intrusive complex) and changes direction to an area along the northwest flank of the intrusion. The axial seismicity trend also contains a tight cluster of earthquakes located just outside the Osceola intrusive complex. The mechanical explanation of the two seismicity patterns is uncertain, but the first cluster may be caused by stress concentration due to the high elastic stiffness and strength of the Covington intrusion. The spatially changing seismicity pattern near the Osceola complex may be caused by the preceding factors plus interaction with faulting along the rift axis. The axial seismicity strand itself is one of several connected and interacting active strands that may produce stress concentrations at strand ends and junctions. The microseismicity clusters at the peripheries of the two intrusions lead us to conclude that these stress concentrations or stressed volumes may be locations of future moderate to large earthquakes near Memphis. Published by Elsevier Science B.V.

Engineering Geology↗

Constants for mercury binding by organic matter isolates from the Florida Everglades

Dissolved organic matter (DOM) has been implicated as an important complexing agent for Hg that can affect its mobility and bioavailability in aquatic ecosystems. However, binding constants for natural Hg-DOM complexes are not well known. We employed a competitive ligand approach to estimate conditional stability constants for Hg complexes with DOM isolates collected from Florida Everglades surface waters. The isolates examined were the hydrophobic fraction of DOM from a eutrophic, sulfidic site (F1-HPoA) and the hydrophilic fraction from an oligotrophic, low-sulfide site (2BS-HPiA). Our experimental determinations utilized overall octanol-water partitioning coefficients (D ow ) for 203 Hg at 0.01 M chloride and across pH and DOM concentration gradients. Use of this radioisotope allowed rapid determinations of Hg concentrations in both water and octanol phases without problems of matrix interference. Conditional stability constants (I = 0.06, 23°C) were log K′ = 11.8 for F1-HPoA and log K′ = 10.6 for 2BS-HPiA. These are similar to previously published stability constants for Hg binding to low-molecular-weight thiols. Further, F1-HPoA showed a pH-dependent decline in D ow that was consistent with models of Hg complexation with thiol groups as the dominant Hg binding sites in DOM. These experiments demonstrate that the DOM isolates are stronger ligands for Hg than chloride ion or ethylenediamine-tetraacetic acid. Speciation calculations indicate that at the DOM concentrations frequently measured in Everglades, 20 to 40 μM, significant complexation of Hg by DOM would be expected in aerobic (sulfide-free) surface waters.

Florida↗

Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model

Manganese oxides are important scavengers of trace metals and other contaminants in the environment. The inclusion of Mn oxides in predictive models, however, has been difficult due to the lack of a comprehensive set of sorption reactions consistent with a given surface complexation model (SCM), and the discrepancies between published sorption data and predictions using the available models. The authors have compiled a set of surface complexation reactions for synthetic hydrous Mn oxide (HMO) using a two surface site model and the diffuse double layer SCM which complements databases developed for hydrous Fe (III) oxide, goethite and crystalline Al oxide. This compilation encompasses a range of data observed in the literature for the complex HMO surface and provides an error envelope for predictions not well defined by fitting parameters for single or limited data sets. Data describing surface characteristics and cation sorption were compiled from the literature for the synthetic HMO phases birnessite, vernadite and δ-MnO 2 . A specific surface area of 746 m 2 g −1 and a surface site density of 2.1 mmol g −1 were determined from crystallographic data and considered fixed parameters in the model. Potentiometric titration data sets were adjusted to a pH IEP value of 2.2. Two site types (≡XOH and ≡YOH) were used. The fraction of total sites attributed to ≡XOH ( α ) and p K a2 were optimized for each of 7 published potentiometric titration data sets using the computer program FITEQL3.2. p K a2 values of 2.35±0.077 (≡XOH) and 6.06±0.040 (≡YOH) were determined at the 95% confidence level. The calculated average α value was 0.64, with high and low values ranging from 1.0 to 0.24, respectively. p K a2 and α values and published cation sorption data were used subsequently to determine equilibrium surface complexation constants for Ba 2+ , Ca 2+ , Cd 2+ , Co 2+ , Cu 2+ , Mg 2+ , Mn 2+ , Ni 2+ , Pb 2+ , Sr 2+ and Zn 2+ . In addition, average model parameters were used to predict additional sorption data for which complementary titration data were not available. The two-site model accounts for variability in the titration data and most metal sorption data are fit well using the p K a2 and α values reported above. A linear free energy relationship (LFER) appears to exist for some of the metals; however, redox and cation exchange reactions may limit the prediction of surface complexation constants for additional metals using the LFER.

Applied Geochemistry↗

Molecular-scale characterization of uranium sorption by bone apatite materials for a permeable reactive barrier demonstration

Uranium binding to bone charcoal and bone meal apatite materials was investigated using U L III -edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations ≤ 5500 μg U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 Å was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U−P distance at 3.5−3.6 Å was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations ≥ 5500 μg U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12 300 μg U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U-contaminated sites.

Environmental Science & Technology↗

An approach for modeling sediment budgets in supply-limited rivers

Reliable predictions of sediment transport and river morphology in response to variations in natural and human-induced drivers are necessary for river engineering and management. Because engineering and management applications may span a wide range of space and time scales, a broad spectrum of modeling approaches has been developed, ranging from suspended-sediment "rating curves" to complex three-dimensional morphodynamic models. Suspended sediment rating curves are an attractive approach for evaluating changes in multi-year sediment budgets resulting from changes in flow regimes because they are simple to implement, computationally efficient, and the empirical parameters can be estimated from quantities that are commonly measured in the field (i.e., suspended sediment concentration and water discharge). However, the standard rating curve approach assumes a unique suspended sediment concentration for a given water discharge. This assumption is not valid in rivers where sediment supply varies enough to cause changes in particle size or changes in areal coverage of sediment on the bed; both of these changes cause variations in suspended sediment concentration for a given water discharge. More complex numerical models of hydraulics and morphodynamics have been developed to address such physical changes of the bed. This additional complexity comes at a cost in terms of computations as well as the type and amount of data required for model setup, calibration, and testing. Moreover, application of the resulting sediment-transport models may require observations of bed-sediment boundary conditions that require extensive (and expensive) observations or, alternatively, require the use of an additional model (subject to its own errors) merely to predict the bed-sediment boundary conditions for use by the transport model. In this paper we present a hybrid approach that combines aspects of the rating curve method and the more complex morphodynamic models. Our primary objective was to develop an approach complex enough to capture the processes related to sediment supply limitation but simple enough to allow for rapid calculations of multi-year sediment budgets. The approach relies on empirical relations between suspended sediment concentration and discharge but on a particle size specific basis and also tracks and incorporates the particle size distribution of the bed sediment. We have applied this approach to the Colorado River below Glen Canyon Dam (GCD), a reach that is particularly suited to such an approach because it is substantially sediment supply limited such that transport rates are strongly dependent on both water discharge and sediment supply. The results confirm the ability of the approach to simulate the effects of supply limitation, including periods of accumulation and bed fining as well as erosion and bed coarsening, using a very simple formulation. Although more empirical in nature than standard one-dimensional morphodynamic models, this alternative approach is attractive because its simplicity allows for rapid evaluation of multi-year sediment budgets under a range of flow regimes and sediment supply conditions, and also because it requires substantially less data for model setup and use.

Water Resources Research↗

Salt marsh establishment controlled by sediment availability, landscape position, and anthropogenic history

Anthropogenic actions have directly and indirectly modulated salt marsh extent globally. For example, direct actions such as draining and filling of marshes for agriculture were common before the early 20th century, while development on barrier islands has indirectly reduced the capacity of back-barrier marshes to evolve in response to coastal processes. Similarly, restoration efforts span a spectrum between direct actions such as hydrologic reconnection and sediment placement to indirect actions such as shoreline protection and facilitation of upland migration. With a combination of remote sensing and synoptic in-situ observations, we demonstrate that the vegetative establishment of two disparate salt marsh complexes are strongly linked to their access to external sediment supply, position in the coastal landscape, and anthropogenic history. A marsh complex fringing Delaware Bay, in a former agricultural reclamation area, was directly modified through re-introduction of tidal forcing; vegetative establishment occurred rapidly (3% y −1 increase in vegetative cover) due to a high flood-ebb suspended sediment differential (+32 mg l −1 ), indicating sediment import. The other marsh complex, behind a sand spit fronting the Atlantic Ocean, vegetated indirectly in response to updrift beach nourishment which provided a sheltered environment for expansion. The lower suspended sediment differential (+1.3 mg l −1 ) led to a slower vegetation establishment rate (1.7% y −1 ). The directly modified and restored complex responded more rapidly than the indirectly modified and restored complex due to sediment availability. Direct restoration may be more rapid than indirect methods, and reversing anthropogenic impacts is possible on relatively short timescales, if sufficient external sediment supply exists. Siting of restoration projects can therefore leverage external forcing to accelerate recovery and enhance resilience. In light of ongoing coastal transgression, these examples also demonstrate a potential difference in return-on-restoration-investment between back-barrier marshes undergoing coastal squeeze and estuarine fringing marshes that are naturally transgressing across the coastal landscape.

New Jersey↗

Ecosystem engineering varies spatially: a test of the vegetation modification paradigm for prairie dogs

Colonial, burrowing herbivores can be engineers of grassland and shrubland ecosystems worldwide. Spatial variation in landscapes suggests caution when extrapolating single-place studies of single species, but lack of data and the need to generalize often leads to ‘model system’ thinking and application of results beyond appropriate statistical inference. Generalizations about the engineering effects of prairie dogs ( Cynomys sp.) developed largely from intensive study at a single complex of black-tailed prairie dogs C. ludovicianus in northern mixed prairie, but have been extrapolated to other ecoregions and prairie dog species in North America, and other colonial, burrowing herbivores. We tested the paradigm that prairie dogs decrease vegetation volume and the cover of grasses and tall shrubs, and increase bare ground and forb cover. We sampled vegetation on and off 279 colonies at 13 complexes of 3 prairie dog species widely distributed across 5 ecoregions in North America. The paradigm was generally supported at 7 black-tailed prairie dog complexes in northern mixed prairie, where vegetation volume, grass cover, and tall shrub cover were lower, and bare ground and forb cover were higher, on colonies than at paired off-colony sites. Outside the northern mixed prairie, all 3 prairie dog species consistently reduced vegetation volume, but their effects on cover of plant functional groups varied with prairie dog species and the grazing tolerance of dominant perennial grasses. White-tailed prairie dogs C. leucurus in sagebrush steppe did not reduce shrub cover, whereas black-tailed prairie dogs suppressed shrub cover at all complexes with tall shrubs in the surrounding habitat matrix. Black-tailed prairie dogs in shortgrass steppe and Gunnison's prairie dogs C. gunnisoni in Colorado Plateau grassland both had relatively minor effects on grass cover, which may reflect the dominance of grazing-tolerant shortgrasses at both complexes. Variation in modification of vegetation structure may be understood in terms of the responses of different dominant perennial grasses to intense defoliation and differences in foraging behavior among prairie dog species. Spatial variation in the engineering role of prairie dogs suggests spatial variation in their keystone role, and spatial variation in the roles of other ecosystem engineers. Thus, ecosystem engineering can have a spatial component not evident from single-place studies.

Ecography: Pattern and Diversity in Ecology↗

Geology of the Mayagüez area, Puerto Rico

The Mayagüez area forms the southwestern corner of Puerto Rico , west of 67° W. and south of 18° 15' N. One-third of the 640 square kms is covered by thick alluvium. Unconformities separate a basal complex, two sequences of highly folded igneous and sedimentary rocks, and a younger sequence of gently dipping sedimentary rock. The basal Bermeja complex contains serpentinite, silicified porphyritic volcanic rock with some sedimentary rock, and minor spilite, amphibolitized spilite, and amphibolite. It is exposed chiefly in some anticlinal cores in southwestern Puerto Rico . Limestone, mudstone, andesite, and basalt form the older folded sequence. The Río Loco formation, bronzite andesite porphyry in part with pillow structures, was extruded perhaps in the Cenomanian. The Mayagüez group includes most of the rocks in southwestern Puerto Rico : the Yauco mudstone, Parguera limestone, Brujo limestone, Melones limestone, Maricao basalt, Sabana Grande andesite, and El Rayo volcanic rocks. The maximum possible age range is Turonian to Maestrichtian. The group ranges in thickness from about 800 m in the south to 3800 m in the north, and it varies in lithology from limestone in the south to mudstone and volcanic rock in the north, indicating a volcanic center to the north during that time. The second folded sequence contains andesitic volcanic rock, bedded tuff, and massive limestone. The San Germán formation (Maestrichtian) includes andesite, the Cabo Rojo agglomerate member, and the Cotui limestone member. The Jicara formation, massive limestone and bedded tuff, is Paleocene; there is one exposure of an unnamed ? Eocene marl. Post-Eocene limestone and conglomerate are also exposed in the area . The structure of the basement complex is obscured by its massiveness and by the cover of younger rocks. Two major deformations have affected the rocks of southwestern Puerto Rico since Cenomanian to Santonian time. In the Maestrichtian, the first of these formed folds with a N. 60° W. trend, asymmetric or overturned to the south. Near the south coast the folding of thin Mayagüez group rocks was probably influenced by trends in the Bermeja complex which caused deviations in the regional trends and also some overturning to the north. The San Germán formation, deposited unconformably on the eroded surface of the folded Mayagüez group, contains large allochthonous blocks of older and contemporaneous rocks. These blocks, up to 2 km by 1 km in exposure, were deposited by slumping or sliding due to gravity within and at the base and top of the San Germán formation near Lajas and San Germán. Most rocks in the blocks are extremely contorted and contain deformed Foraminifera. The San Germán and Jicara formations and perhaps the ?Eocene marls were deformed into gentle open folds trending east in the area covered by this report. Oligocene, Miocene, and younger sedimentary rocks have been tilted and uplifted. Large east-west left-lateral transcurrent faults cross the area , offsetting and offset by two sets of transverse faults (N. 45° E., N. 20° W.): most faults are probably Maestrichtian to Oligocene, although minor faulting has continued to the present. Dikes and sills of quartz diorite porphyry and mica-quartz dacite porphyry intrude the ?Maestrichtian San Germán formation and older units. A diorite plug cuts the Bermeja complex, and a granodiorite plug intrudes the Mayagüez group.

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