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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.

Puerto Rico↗

The vourinos ophiolite, Greece: Cyclic units of lineated cumulates overlying harzburgite tectonite

Re-examination of the Vourinos ophiolite shows it to be composed of metamorphic tectonites, cumulates, plagiogranites, dikes, and lava. The contact between the tectonites and the cumulates is exposed and sharp. Beneath the cumulate contact, the rocks have been highly deformed and complexly folded; above that contact, they simply have been tilted vertically to expose a stratiform complex 1,500 m (4,800 ft) thick. The stratiform intrusion is characterized by cyclic units, rich in olivine at the base, and rich in feldspar at the top. Some cumulus diorites are present at the top of the section which grade into quartz diorites (plagiogranites) with hypautomorphic textures. Lineate lamination characterizes the cumulates and may indicate the direction or orientation of the Mesozoic mid-oceanic ridge crest with respect to the present position of the complex. A siliceous dike swarm cuts the upper part of the stratiform complex. The section suggests that in the case of Vourinos, a large magmatic chamber formed at a mid-oceanic ridge crest and that intrusion was a much more important process than extrusion in the formation of oceanic crust in that area. The reported presence of cumulates in many other ophiolite complexes suggests that these relations may obtain generally at most or all spreading ridges. The contact between the tectonites and the cumulates of the complex would not have corresponded with seismic M. © 1975 Geological Society of America.

Geological Society of America Bulletin↗

Significance of new potassium-argon ages from the Goldens Ranch and Moroni Formations, Sanpete-Sevier Valley area, central Utah

Exposures of volcanic-sedimentary strata are widely distributed within central Utah. We believe that these volcanic and stratified sedimentary rocks, known by different formational names in different parts of this region, are, in fact, segments of one and the same suite of rocks that formed during the early and middle Tertiary. The volcanic-sedimentary complex is exposed on both sides of a north-trending lowland formed by the collinear Juab and Sevier Valleys. West of the lowland, the complex has been named the "Goldens Ranch Formation" east of the lowland, it has been called the "Moroni Formation."; Both formations are stratigraphically alike in that each consists of a lower unit composed predominantly of water-laid, variably cemented sediments and sedimentary rocks with some tuff beds near the base, and an upper unit of intermediate-composition volcanic rocks, chiefly ash-flow tuffs, and volcanic breccias. Both formations contain abundant exotic clasts of andesite, tan and purple quartzite, and dark blue limestone and dolomite. Both formations are folded and faulted along with the underlying sedimentary units. Potassium-argon ages indicate that both the Goldens Ranch and Moroni Formations formed during the late Eocene to middle Oligocene. The geochronology and stratigraphic relations are strong evidence that the Goldens Ranch and Moroni Formations are correlative, and that they are one and the same depositional unit. During the latest Oligocene-earliest Miocene, minor monzonitic bodies intruded sedimentary units in the area. The new K-Ar data bear on the matter of the origin of the complex structural deformation in central Utah. Different workers have attributed the singular deformation either to recurrent episodes of compression stemming from the Sevier orogeny, or to repeated episodes of salt diapirism. We recognize two sequences of repeated deformation: one that occurred prior to deposition and consolidation of the Goldens Ranch and Moroni Formations, and a second that occurred after these formations were emplaced, in essence, after early Oligocene time. The Sevier orogeny ended in Paleocene time; thus, the compression and thrusting stemming from the Sevier orogeny could be responsible for the structural complexity that marks pre-Paleocene units. These same orogenic forces do not seem to be viable explanations for the broad flexures and monoclinal downwarps that mark the Goldens Ranch, Moroni, and younger formations. In our view, multiple episodes of salt diapirism more reasonably explain the structural complexity in central Utah.

Utah↗

Carbonate rocks of the Seward Peninsula, Alaska: Their correlation and paleogeographic significance

Paleozoic carbonate strata deposited in shallow platform to off-platform settings occur across the Seward Peninsula and range from unmetamorphosed Ordovician–Devonian(?) rocks of the York succession in the west to highly deformed and metamorphosed Cambrian–Devonian units of the Nome Complex in the east. Faunal and lithologic correlations indicate that early Paleozoic strata in the two areas formed as part of a single carbonate platform. The York succession makes up part of the York terrane and consists of Ordovician, lesser Silurian, and limited, possibly Devonian rocks. Shallow-water facies predominate, but subordinate graptolitic shale and calcareous turbidites accumulated in deeper water, intraplatform basin environments, chiefly during the Middle Ordovician. Lower Ordovician strata are mainly lime mudstone and peloid-intraclast grainstone deposited in a deepening upward regime; noncarbonate detritus is abundant in lower parts of the section. Upper Ordovician and Silurian rocks include carbonate mudstone, skeletal wackestone, and coral-stromatoporoid biostromes that are commonly dolomitic and accumulated in warm, shallow to very shallow settings with locally restricted circulation. The rest of the York terrane is mainly Ordovician and older, variously deformed and metamorphosed carbonate and siliciclastic rocks intruded by early Cambrian (and younger?) metagabbros. Older (Neoproterozoic–Cambrian) parts of these units are chiefly turbidites and may have been basement for the carbonate platform facies of the York succession; younger, shallow- and deep-water strata likely represent previously unrecognized parts of the York succession and its offshore equivalents. Intensely deformed and altered Mississippian carbonate strata crop out in a small area at the western edge of the terrane. Metacarbonate rocks form all or part of several units within the blueschist- and greenschist-facies Nome Complex. The Layered sequence includes mafic meta¬igneous rocks and associated calcareous metaturbidites of Ordovician age as well as shallow-water Silurian dolostones. Scattered metacarbonate rocks are chiefly Cambrian, Ordovician, Silurian, and Devonian dolostones that formed in shallow, warm-water settings with locally restricted circulation and marbles of less constrained Paleozoic age. Carbonate metaturbidites occur on the northeast and southeast coasts and yield mainly Silurian and lesser Ordovician and Devonian conodonts; the northern succession also includes debris flows with meter-scale clasts and an argillite interval with Late Ordovician graptolites and lenses of radiolarian chert. Mafic igneous rocks at least partly of Early Devonian age are common in the southern succession. Carbonate rocks on Seward Peninsula experienced a range of deformational and thermal histories equivalent to those documented in the Brooks Range. Conodont color alteration indices (CAIs) from Seward Peninsula, like those from the Brooks Range, define distinct thermal provinces that likely reflect structural burial. Penetratively deformed high-pressure metamorphic rocks of the Nome Complex (CAIs ≥5) correspond to rocks of the Schist belt in the southern Brooks Range; both record subduction during early stages of the Jurassic–Cretaceous Brooks Range orogeny. Weakly metamorphosed to unmetamorphosed strata of the York terrane (CAIs mainly 2–5), like Brooks Range rocks in the Central belt and structural allochthons to the north, experienced moderate to shallow burial during the main phase of the Brooks Range orogeny. The nature of the contact between the York terrane and the Nome Complex is uncertain; it may be a thrust fault, an extensional surface, or a thrust fault later reactivated as an extensional fault. Lithofacies and biofacies data indicate that, in spite of their divergent Mesozoic histories, rocks of the York terrane and protoliths of the Nome Complex formed as part of the same lower Paleozoic carbonate platform. Stratigraphies in both

GSA Special Papers↗

Effects of tidally varying river flow on entrainment of juvenile salmon into Sutter and Steamboat Sloughs

Survival of juvenile salmonids in the Sacramento–San Joaquin Delta (Delta) varies by migration route, and thus the proportion of fish that use each route affects overall survival through the Delta. Understanding factors that drive routing at channel junctions along the Sacramento River is therefore critical to devising management strategies that maximize survival. Here, we examine entrainment of acoustically tagged juvenile Chinook Salmon into Sutter and Steamboat sloughs from the Sacramento River. Because these sloughs divert fish away from the downstream entrances of the Delta Cross Channel and Georgiana Slough (where fish access the low-survival region of the interior Delta), management actions to increase fish entrainment into Sutter and Steamboat sloughs are being investigated to increase through-Delta survival. Previous studies suggest that fish generally “go with the flow”—as net flow into a divergence increases, the proportion of fish that enter that divergence correspondingly increases. However, complex tidal hydrodynamics at sub-daily time-scales may be decoupled from net flow. Therefore, we modeled routing of acoustic tagged juvenile salmon as a function of tidally varying hydrodynamic data, which was collected using temporary gaging stations deployed between March and May of 2014. Our results indicate that discharge, the proportion of flow that entered the slough, and the rate of change of flow were good predictors of an individual’s probability of being entrained. In addition, interactions between discharge and the proportion of flow revealed a non-linear relationship between flow and entrainment probability. We found that the highest proportions of fish are likely to be entrained into Steamboat Slough and Sutter Slough on the ascending and descending limbs of the tidal cycle, when flow changes from positive to negative. Our findings characterize how patterns of entrainment vary with tidal flow fluctuations, providing information critical for understanding the potential effect of management actions (e.g., fish guidance structures) to modify routing probabilities at this location. Main Content View Larger 1 Sponsored by the Delta Science Program and the UC Davis Muir Institute ABSTRACT Survival of juvenile salmonids in the Sacramento–San Joaquin Delta (Delta) varies by migration route, and thus the proportion of fish that use each route affects overall survival through the Delta. Understanding factors that drive routing at channel junctions along the Sacramento River is therefore critical to devising management strategies that maximize survival. Here, we examine entrainment of acoustically tagged juvenile Chinook Salmon into Sutter and Steamboat sloughs from the Sacramento River. Because these sloughs divert fish away from the downstream entrances of the Delta Cross Channel and Georgiana Slough (where fish access SFEWS Volume 19 | Issue 2 | Article 4 https://doi.org/10.15447/sfews.2021v19iss2art4 * Corresponding author: rperry@usgs.gov 1 Western Fisheries Research Center US Geological Survey Cook, WA 98605 USA 2 California Water Science Center US Geological Survey Sacramento, CA 95819 USA 3 Current address: Mid-Columbia Fish and Wildlife Conservation Office Yakima Basin Program US Fish and Wildlife Service Yakima, WA 98903 USA the low-survival region of the interior Delta), management actions to increase fish entrainment into Sutter and Steamboat sloughs are being investigated to increase through-Delta survival. Previous studies suggest that fish generally “go with the flow”—as net flow into a divergence increases, the proportion of fish that enter that divergence correspondingly increases. However, complex tidal hydrodynamics at sub-daily time-scales may be decoupled from net flow. Therefore, we modeled routing of acoustic tagged juvenile salmon as a function of tidally varying hydrodynamic data, which was collected using temporary gaging stations deployed between March and May of 2014. Our results indicate that discharge, the proportion of flow that entered the slough, and the rate of change of flow were good predictors of an individual’s probability of being entrained. In addition, interactions between discharge and the proportion of flow revealed a non-linear relationship between flow and entrainment probability. We found that the highest proportions of fish are likely to be entrained into Steamboat Slough and Sutter Slough on the ascending and descending limbs of the tidal cycle, when flow changes from positive to negative. Our findings characterize how patterns of entrainment vary with tidal flow fluctuations, providing information critical for understanding the potential effect of management RESEARCH Effects of Tidally Varying River Flow on Entrainment of Juvenile Salmon into Sutter and Steamboat Sloughs Jason G. Romine 1,3 , Russell W. Perry* 1 , Paul R. Stumpner 2 , Aaron R. Blake 2 , Jon R. Burau 2 2 VOLUME 19, ISSUE 2, ARTICLE 4 actions (e.g., fish guidance structures) to modify routing probabilities at this location. KEY WORDS Telemetry, juvenile salmon, migration routing, survival INTRODUCTION The Sacramento–San Joaquin River Delta (hereafter referred to as “the Delta”) is a complex series of channels and embayments in west central California of the United States. The Delta has undergone drastic transformation through construction of dikes, levees, reclaimed land, dredged canals and cuts, and water export projects (Nichols et al. 1986). The loss of habitat coupled with introduction of non-native piscivorous fishes has led to the decline of several salmonid stocks that utilize the Delta (Lindley 2009; National Marine Fisheries Service 2014). The physical complexity of the Delta poses significant challenges for understanding how juvenile salmon negotiate the complex channel network and survive in different migration routes. Yet such information is critical for understanding how water-management actions, such as operation of water diversions, influence survival of juvenile salmon. Through-Delta survival of juvenile Chinook Salmon that emigrate from the Sacramento River ranges from 10% to 80%, depending on river flow and migration route (Perry et al. 2018). The Delta can be broken down into four primary routes: (1) Sacramento River, (2) Steamboat and Sutter sloughs, (3) Georgiana Slough, and (4) Delta Cross Channel (DCC). Fish that remain in the Sacramento River consistently have the highest survival (Perry et al. 2010, 2013, 2018). However, fish that enter the interior Delta—the region to the south of the Sacramento River (Figure 1)—have the lowest survival among all routes and survive at less than half the rate of fish in the Sacramento River, likely as a result of longer migration times and exposure to non-native predators (Newman and Brandes 2010; Perry et al. 2018). On average, fish that migrate through Steamboat and Sutter sloughs exhibit survival similar to fish that remain in the Sacramento River at high flows but have lower survival at low flows (Perry et al. 2018). Because of differences in survival among migration routes, the proportion of fish that use each route affects the total survival of the population. Therefore, understanding the drivers behind fish routing in the Delta is imperative to inform management actions that help in the recovery of imperiled salmonid populations in the Central Valley. For example, Perry et al. (2013) found that total survival through the Delta could be increased by up to 7 percentage points by eliminating entrainment into Georgiana Slough and the DCC. These findings led to investigation of management actions to reduce entrainment into the DCC (Plumb et al. 2016) and Georgiana Slough (Perry et al. 2014). Both physical and non-physical barriers have been tested at the entrance to Georgiana Slough divergence (Perry et al. 2014; Romine et al. 2016). A non-physical barrier was able to reduce entrainment to the interior Delta through Georgiana Slough (Perry et al. 2014), but a floating fish-guidance structure reduced entrainment to a lesser extent (Romine et al. 2016). Research and engineering solutions to minimize entrainment have focused on the Georgiana Slough divergence, the DCC divergence, and the Old River divergence in the San Joaquin River (Buchanan et al. 2013; SJRG 2013). However, there has been little focus on understanding fish routing dynamics at other primary river junctions in the Delta, such as Sutter and Steamboat sloughs. Sutter and Steamboat sloughs diverge from the Sacramento about 10 km upstream from the DCC and Georgiana slough, and represent the first major junction that juvenile salmon encounter as they enter the Delta from the Sacramento River ( Figure 1 ). Because Sutter and Steamboat sloughs are upstream of the entrance to the interior Delta via the DCC and Georgiana Slough (Figure 1), juvenile salmon that enter Sutter and Steamboat sloughs avoid entrainment into the interior Delta where survival is low. Thus, management actions to increase entrainment could increase overall.

Sacramento–San Joaquin Delta↗

Sensitivity of species habitat-relationship model performance to factors of scale

Researchers have come to different conclusions about the usefulness of habitat-relationship models for predicting species presence or absence. This difference frequently stems from a failure to recognize the effects of spatial scales at which the models are applied. We examined the effects of model complexity, spatial data resolution, and scale of application on the performance of bird habitat relationship (BHR) models on the Craig Mountain Wildlife Management Area and on the Idaho portion of the U.S. Forest Service's Northern Region. We constructed and tested BHR models for 60 bird species detected on the study areas. The models varied by three levels of complexity (amount of habitat information) and three spatial data resolutions (0.09 ha, 4 ha, 10 ha). We tested these models at two levels of analysis: the site level (a homogeneous area <0.5 ha) and cover-type level (an aggregation of many similar sites of a similar land-cover type), using correspondence between model predictions and species detections to calculate kappa coefficients of agreement. Model performance initially increased as models became more complex until a point was reached where omission errors increased at a rate greater than the rate at which commission errors were decreasing. Heterogeneity of the study areas appeared to influence the effect of model complexity. Changes in model complexity resulted in a greater decrease in commission error than increase in omission error. The effect of Spatial data resolution on the performance of BHR models was influenced by the variability of the study area. BHR models performed better at cover-type levels of analysis than at the site level for both study areas. Correct-presence estimates (1 - minus percentage omission error) decreased slightly as number of species detections increased on each study area. Correct-absence estimates (1 - percentage commission error) increased as number of species detections increased on each study area. This suggests that a large number of detections may be necessary to achieve reliable estimates of model accuracy.

Idaho↗

Mineralogy, paragenesis, and mineral zoning of the Bulldog Mountain vein system, Creede District, Colorado

The Bulldog Mountain vein system, Creede district, Colorado, is one of four major epithermal vein systems from which the bulk of the district's historical Ag-Pb-Zn-Cu production has come. Ores deposited along the vein system were discovered in 1965 and were mined from 1969 to 1985.Six temporally gradational mineralization stages have been identified along the Bulldog Mountain vein system, each with a characteristic suite of minerals deposited or leached and a characteristic distribution within the vein system; some of these stages are also strongly zoned within the vein system. Stage A was dominated by deposition of rhodochrosite along the lower levels of the Bulldog Mountain ore zone. Stage B in the northern parts of the ore zone is characterized by abundant fine-grained sphalerite and galena, with lesser tetrahedrite and minor chlorite and hematite. With increasing elevation to the south, stage B ores become progressively more barite and silver rich, with alternating barite and fine-grained sphalerite + galena generations; native silver + or - acanthite assemblages are also locally abundant within southern stage B barite sulfide ores, whereas chalcopyrite and other Cu and Ag sulfides and sulfosalts are present erratically in minor amounts. Stage C in the upper and northern portions of the ore zone is characterized by abundant quartz and fluorite, minor adularia, hematite, Mn siderite, sphalerite, and galena, and major leaching of earlier barite; to the south, some barite and sulfides may have been deposited. Stage D sphalerite and galena were deposited in the upper and northern portions of the ore zone; a barite- and silver-rich facies of this stage may also be present in the southern portions of the vein system. Late in stage D, mineralogically complex assemblages containing chalcopyrite, tetrahedrite, polybasite, bornite, pyrargyrite, and a variety of other sulfides and sulfosalts were deposited in modest amounts throughout the vein system. This complex assemblage marked the transition to stage E. During stage E, the final sulfide stage, abundant botryoidal pyrite and marcasite with lesser stibnite, sphalerite, and sulfosalts were deposited primarily along the top of the Bulldog Mountain ore zone. Stage F, the final mineralization stage along the vein system, is marked by wire silver and concurrent leaching of earlier sulfides and sulfosalts; this stage may reflect the transition to a supergene environment.The sequence of mineralization stages identified in this study along the Bulldog Mountain system can be correlated with corresponding stages identified by other researchers along the OH and P veins, and the southern Amethyst vein system. Mineral zoning patterns identified along the Bulldog Mountain vein system also parallel larger scale zoning patterns across the central and southern Creede district.The complex variations in mineral assemblages documented in time and space along the Bulldog Mountain vein system were produced by the combined effects of many processes. Large-scale changes in vein mineralogy over time produced discrete mineralization stages. Short-term mineralogical fluctuations produced complex interbanding of mineralogically distinct generations. Fluid chemistry evolution within the vein system produced large-scale lateral zoning patterns within certain stages. Hypogene leaching substantially modified the distributions of some minerals. Finally, structural activity, mineral deposition, and mineral leaching modified fluid flow pathways repeatedly during mineralization, and so added to the complex mineral distribution patterns within the vein system.

Colorado↗

Wetland management reduces sediment and nutrient loading to the upper Mississippi River

Restored riparian wetlands in the Upper Mississippi River basin have potential to remove sediment and nutrients from tributaries before they flow into the Mississippi River. For 3 yr we calculated retention efficiencies of a marsh complex, which consisted of a restored marsh and an adjacent natural marsh that were connected to Halfway Creek, a small tributary of the Mississippi. We measured sediment, N, and P removal through a mass balance budget approach, N removal through denitrification, and N and P removal through mechanical soil excavation. The marsh complex had average retention rates of approximately 30 Mg sediment ha &minus;1 yr &minus;1 , 26 kg total N ha &minus;1 yr &minus;1 , and 20 kg total P ha &minus;1 yr &minus;1 . Water flowed into the restored marsh only during high-discharge events. Although the majority of retention occurred in the natural marsh, portions of the natural marsh were hydrologically disconnected at low discharge due to historical over-bank sedimentation. The natural marsh removed >60% of sediment, >10% of P, and >5% of N loads (except the first year, when it was a N source). The marsh complex was a source of NH 4 + and soluble reactive P. The average denitrification rate for the marsh complex was 2.88 mg N m &minus;2 h &minus;1 . Soil excavation removed 3600 Mg of sediment, 5.6 Mg of N, and 2.7 Mg of P from the restored marsh. The marsh complex was effective in removing sediment and nutrients from storm flows; however, retention could be increased if more water was diverted into both restored and natural marshes before entering the river.

Mississippi↗

Pb and O isotopic constraints on the source of granitic rocks from Cape Breton Island, Nova Scotia, Canada

Pb isotopic compositions of leached feldspars from twenty-three plutons in Cape Breton Island can be divided into two groups: anorthosite, syenite, and granite in the Blair River Complex, which have the least radiogenic compositions on the Island, and granitic rocks from terranes (Aspy, Bras d'Or, and Mira) to the south. Pb isotopic data for the Blair River Complex ( 206 Pb/ 204 Pb = 17.399-18.107; 207 Pb/ 204 Pb = 15.505-15.560; 208 Pb/ 204 Pb = 36.689-37.733) are consistent with an old source region ultimately derived from the mantle and contaminated by sialic crust. Oxygen isotopic compositions of syenite in the Blair River Complex ( δ 18 O = +8.0 to +8.5 permil) are slightly higher than anorthosite (+7.0 to +8.3 permil); a Silurian granite in the Blair River Complex has δ 18 O = +7.5 permil. Cambrian to Devonian plutons in the Aspy, Bras d'Or, and Mira terranes are more radiogenic ( 206 Pb/ 204 Pb = 18.192-18.981; 207 Pb/ 204 Pb = 15.574-15.712; 208 Pb/ 204 Pb =37.815-38.936) than the Blair River Complex and were generated from source regions having a predominant crustal Pb signature (high μ ). The δ 18 O values of granites and granodiorites in the Aspy terrane (+7.5 to +9.2 permil; avg = +8.6 permil) and Bras d'Or (+3.7 to +11.3 permil; avg = +9.4 permil) are also consistent with involvement of sialic crust. Many Late Proterozoic granites from the Mira terrane have anomalously low δ 18 O values (+0.2 to +5.9 permil), perhaps produced from protoliths that had undergone hydrothermal alteration prior to melting. Paleozoic granitic rocks from the Aspy, Bras d'Or, and Mira terranes cannot be uniquely distinguished on the basis of their Pb and O isotopic compositions. The granitic rocks could have been generated during terrane amalgamation from combinations of unradiogenic (Grenville-like) and more radiogenic (Avalon-like) sources.

Nova Scotia↗

Multi-stage origin of the Coast Range ophiolite, California: Implications for the life cycle of supra-subduction zone ophiolites

The Coast Range ophiolite of California is one of the most extensive ophiolite terranes in North America, extending over 700 km from the northernmost Sacramento Valley to the southern Transverse Ranges in central California. This ophiolite, and other ophiolite remnants with similar mid-Jurassic ages, represent a major but short-lived episode of oceanic crust formation that affected much of western North America. The history of this ophiolite is important for models of the tectonic evolution of western North America during the Mesozoic, and a range of conflicting interpretations have arisen. Current petrologic, geochemical, stratigraphic, and radiometric age data all favor the interpretation that the Coast Range ophiolite formed to a large extent by rapid extension in the forearc region of a nascent subduction zone. Closer inspection of these data, however, along with detailed studies of field relationships at several locales, show that formation of the ophiolite was more complex, and requires several stages of formation. Our work shows that exposures of the Coast Range ophiolite preserve evidence for four stages of magmatic development. The first three stages represent formation of the ophiolite above a nascent subduction zone. Rocks associated with the first stage include ophiolite layered gabbros, a sheeted complex, and volcanic rocks vith arc tholeiitic or (roore rarely) low-K calc-alkaline affinities. The second stage is characterized by intrusive wehrlite-clinopyroxenite complexes, intrusive gabbros, Cr-rich diorites, and volcanic rocks with high-Ca boninitic or tholeiitic ankaramite affinities. The third stage includes diorite and quartz diorite plutons, felsic dike and sill complexes, and calc-alkaline volcanic rocks. The first three stages of ophiolite formation were terminated by the intrusion of mid-ocean ridge basalt dikes, and the eruption of mid-ocean ridge basalt or ocean-island basalt volcanic suites. We interpret this final magmatic event (MORB dikes) to represent the collision of an active spreading ridge. Subsequent reorganization of relative plate motions led to sinistral transpression, along with renewed subduction and accretion of the Franciscan Complex. The latter event resulted in uplift and exhumation of the ophiolite by the process of accretionary uplift.

California↗

Reconnaissance geologic map of the Dixonville 7.5' quadrangle, Oregon

The Dixonville 7.5 minute quadrangle is situated near the edge of two major geologic and tectonic provinces the northernmost Klamath Mountains and the southeastern part of the Oregon Coast Ranges (Figure 1). Rocks of the Klamath Mountains province that lie within the study area include ultramafic, mafic, intermediate and siliceous igneous types (Diller, 1898, Ramp, 1972, Ryberg, 1984). Similar rock associations that lie to the southwest yield Late Jurassic and earliest Cretaceous radiometric ages (Dott, 1965, Saleeby, et al., 1982, Hotz, 1971, Harper and Wright, 1984). These rocks, which are part of the Western Klamath terrane (Western Jurassic belt of (Irwin, 1964), are considered to have formed within an extensive volcanic arc and rifted arc complex (Harper and Wright, 1984) that lay along western North America during the Late Jurassic (Garcia, 1979, Garcia, 1982, Saleeby, et al., 1982, Ryberg, 1984). Imbricate thrust faulting and collapse of the arc during the Nevadan orogeny, which ranged in age between about 150 to 145 Ma in the Klamath region (Coleman, 1972, Saleeby, et al., 1982, Harper and Wright, 1984) was syntectonic with, or closely followed by deposition of the volcano-lithic clastic rocks of the Myrtle Group. The Myrtle Group consists of Upper Jurassic and Lower to middle Cretaceous turbidity and mass flow deposits considered to be either arc basin and/or post-orogenic flysh basins that were syntectonic with the waning phases of arc collapse (Imlay et al., 1959, Ryberg, 1984, Garcia, 1982, Roure.and Blanchet, 1983). The intermediate and mafic igneous rocks of the Rogue arc and the pre-Nevadan sedimentary cover (the Galice Formation, (Garcia, 1979) are intruded by siliceous and intermediate plutonic rocks principally of quartz diorite and granodiorite composition (Dott, 1965, Saleeby, et al., 1982, Garcia, 1982, Harper and Wright, 1984). The plutonic rocks are locally tectonized into amphibolite, gneiss, banded gneiss and augen gneiss. Similar metamorphic rocks have yielded metamorphic ages of 165 to 150 Ma (Coleman, 1972, Hotz, 1971, Saleeby, et al., 1982, Coleman and Lanphere, 1991). The Jurassic arc rocks and sedimentary cover occur as a tectonic outlier in this region (Figure 2) as they are bound to the northwest and southeast by melange, broken formation and semi-schists of the Dothan Formation and Dothan Formation(?) that are considered part of a late Mesozoic accretion complex (Ramp, 1972, Blake, et al., 1985). The plutonism that accompanied arc formation and tectonic collapse of the arc does not intrude the structurally underlying Dothan Formation, indicating major fault displacements since the Early Cretaceous. Semischistose and schistose rocks of the accretion complex have yielded metamorphic ages of around 125-140 Ma where they have been studied to the southwest (Coleman and Lanphere, 1971, Dott, 1965, Coleman, 1972). These rocks were unroofed and unconformably overlain by marine deposits by late early Eocene time (Baldwin, 1974). The early Tertiary history of this region is controversial. The most recent interpretation is that during the Paleocene and early Eocene the convergent margin was undergoing transtension or forearc extension as suggested by the voluminous extrusion of pillow basalt and related dike complexes (Wells, et al., 1984, Snavely, 1987). This episode was followed shortly by thrust and strike-slip faulting in the late early Eocene (Ryberg, 1984). During the Eocene, the Mesozoic convergent margin association of arc, clastic basin, and accretion complex was partly unroofed and faulted against early Cenozoic rocks of the Oregon Coast Ranges (Ramp, 1972, Baldwin, 1974, Champ, 1969, Ryberg, 1984). Faults that are typical of this period of deformation include high-angle reverse faults with a very strong component of strike-slip displacement characterized by a low-angle rake of striae. Thrust and oblique-slip faults are ubiquitous in early Tertiary rocks to the northwest (Ryberg, 1984, Niem and Niem, 1990). The late Mesozoic and early Cenozoic arc and forearc rocks are unconformably overlain to the east by the late Eocene and younger, mainly continental fluvial deposits and pyroclastic flows of the Cascade arc (Peck, et al., 1964, Baldwin, 1974, Walker and MacLeod, 1991). Minor fossiliferous shallow marine sandstone is locally present. The volcanic sequence consists of a homoclinal section of about 1 to 2 kilometers of andesitic to rhyolitic flows and ash flow tuff. The section is gently east-tilted and is slightly disrupted by NE trending faults with apparent normal separation.

Oregon↗

Preliminary geologic map of the Murrieta 7.5' quadrangle, Riverside County, California

The Murrieta quadrangle is located in the northern part of the Peninsular Ranges Province and includes parts of two structural blocks, or structural subdivisions of the province. The quadrangle is diagonally crossed by the active Elsinore fault zone, a major fault zone of the San Andreas fault system, and separates the Santa Ana Mountains block to the west from the Perris block to the east. Both blocks are relatively stable internally and within the quadrangle are characterized by the presence of widespread erosional surfaces of low relief. The Santa Ana Mountains block, in the Murrieta quadrangle, is underlain by undifferentiated, thick-layered, granular, impure quartzite and well-layered, fissile, phyllitic metamorphic rock of low metamorphic grade. Both quartzite and phyllitic rocks are Mesozoic. Unconformably overlying the metamorphic rocks are remnants of basalt flows having relatively unmodified flow surfaces. The age of the basalt is about 7-8Ma. Large shallow depressions on the surface of the larger basalt remnants form vernal ponds that contain an endemic flora. Beneath the basalt the upper part of the metamorphic rocks is deeply weathered. The weathering appears to be the same as the regional Paleocene saprolitic weathering in southern California. West of the quadrangle a variable thickness sedimentary rock, physically resembling Paleogene rocks, occurs between the basalt and metamorphic rock. Where not protected by the basalt, the weathered rock has been removed by erosion. The dominant feature on the Perris block in the Murrieta quadrangle is the south half of the Paloma Valley ring complex, part of the composite Peninsular Ranges batholith. The complex is elliptical in plan view and consists of an older ring-dike with two subsidiary short-arced dikes that were emplaced into gabbro by magmatic stoping. Small to large stoped blocks of gabbro are common within the ring-dikes. A younger ring-set of hundreds of thin pegmatite dikes occur largely within the central part of the complex. These pegmatite dikes were emplaced into a domal fracture system, apparently produced by cauldron subsidence, and include in the center of the complex, a number of flat-floored granophyre bodies. The granophyre is interpreted to be the result of pressure quenching of pegmatite magma. Along the eastern edge of the quadrangle is the western part of a large septum of medium metamorphic grade Mesozoic schist. A dissected basalt flow caps the Hogbacks northeast of Temecula, and represents remnants of a channel filling flow. Beneath the basalt is a thin deposit of stream gravel. Having an age of about 10Ma, this basalt is about 2-3Ma older than the basalt flows in the Santa Ana Mountains. The Elsinore fault zone forms a complex of pull-apart basins. The west edge of the fault zone, the Willard Fault, is marked by the high, steep eastern face of the Santa Ana Mountains. The east side of the zone, the Wildomar Fault, forms a less pronounced physiographic step. In the center of the quadrangle a major splay of the fault zone, the Murrieta Hot Springs Fault, strikes east. Branching of the fault zone causes the development of a broad alluvial valley between the Willard Fault and the Murrieta Hot Springs Fault. All but the axial part of the zone between the Willard and Wildomar Faults consist of dissected Pleistocene sedimentary units. The axial part of the zone is underlain by Holocene and latest Pleistocene sedimentary units.

California↗

Mercury in Sediment, Water, and Biota of Sinclair Inlet, Puget Sound, Washington, 1989-2007

Historical records of mercury contamination in dated sediment cores from Sinclair Inlet are coincidental with activities at the U.S. Navy Puget Sound Naval Shipyard; peak total mercury concentrations occurred around World War II. After World War II, better metallurgical management practices and environmental regulations reduced mercury contamination, but total mercury concentrations in surface sediment of Sinclair Inlet have decreased slowly because of the low rate of sedimentation relative to the vertical mixing within sediment. The slopes of linear regressions between the total mercury and total organic carbon concentrations of sediment offshore of Puget Sound urban areas was the best indicator of general mercury contamination above pre-industrial levels. Prior to the 2000-01 remediation, this indicator placed Sinclair Inlet in the tier of estuaries with the highest level of mercury contamination, along with Bellingham Bay in northern Puget Sound and Elliott Bay near Seattle. This indicator also suggests that the 2000/2001 remediation dredging had significant positive effect on Sinclair Inlet as a whole. In 2007, about 80 percent of the area of the Bremerton naval complex had sediment total mercury concentrations within about 0.5 milligrams per kilogram of the Sinclair Inlet regression. Three areas adjacent to the waterfront of the Bremerton naval complex have total mercury concentrations above this range and indicate a possible terrestrial source from waterfront areas of Bremerton naval complex. Total mercury concentrations in unfiltered Sinclair Inlet marine waters are about three times higher than those of central Puget Sound, but the small numbers of samples and complex physical and geochemical processes make it difficult to interpret the geographical distribution of mercury in marine waters from Sinclair Inlet. Total mercury concentrations in various biota species were compared among geographical locations and included data of composite samples, individual specimens, and caged mussels. Total mercury concentrations in muscle and liver of English sole from Sinclair Inlet ranked in the upper quarter and third, respectively, of Puget Sound locations. For other species, concentrations from Sinclair Inlet were within the mid-range of locations (for example, Chinook salmon). Total mercury concentrations of the long-lived and higher trophic rockfish in composites and individual specimens from Sinclair Inlet tended to be the highest in Puget Sound. For a given size, sand sole, graceful crab, staghorn sculpin, surf perch, and sea cucumber individuals collected from Sinclair Inlet had higher total mercury concentrations than individuals collected from non-urban estuaries. Total mercury concentrations in individual English sole and ratfish were not significantly different than in individuals of various sizes collected from either urban or non-urban estuaries in Puget Sound. Total mercury concentrations in English sole collected from Sinclair Inlet after the 2000-2001 dredging appear to have lower total mercury concentrations than those collected before (1996) the dredging project. The highest total mercury concentrations of mussels caged in 2002 were not within the Bremerton naval complex, but within the Port Orchard Marina and inner Sinclair Inlet.

Open-File Report↗