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At least 415 records · Page 23Linked to original sources

Investigating the complex interface where bedrock transforms to regolith

The interface where bedrock transforms to regolith is not planar but rather has a roughness that varies with the scale of observation. The complexity of this surface is manifested in both element-depth and fragment size-depth distributions and may sometimes be related to the longitudinal profiles of watershed streams. The fractal nature of the bedrock-regolith interface means that the interface has a “thickness” which is >20 m in two ridgetop examples from Pennsylvania and Puerto Rico. Such weathering thicknesses, modeled as a function of one-dimensional fluid flow, are affected by the balance between rates of weathering and erosion. One-dimensional models are consistent with weathering advance rates that vary with equilibrium solubility and porefluid velocities (and not reaction kinetics). However, fluid flow is not strictly downward and one-dimensional. Permeability of regolith changes as particle size and bulk density changes with depth. Thus, both downward and lateral flow occurs especially at reaction fronts where reactions change permeability. The rate of weathering advance is, therefore, affected by the 3-dimensional distribution of reaction zones that affect permeability across the watershed. Quantitative models of such phenomena over a range of spatial and temporal scales are needed.

Applied Geochemistry

Geolocation of man-made reservoirs across terrains of varying complexity using GIS

The Reservoir Sedimentation Survey Information System (RESIS) is one of the world's most comprehensive databases of reservoir sedimentation rates, comprising nearly 6000 surveys for 1819 reservoirs across the continental United States. Sediment surveys in the database date from 1904 to 1999, though more than 95% of surveys were entered prior to 1980, making RESIS largely a historical database. The use of this database for large-scale studies has been limited by the lack of precise coordinates for the reservoirs. Many of the reservoirs are relatively small structures and do not appear on current USGS topographic maps. Others have been renamed or have only approximate (i.e. township and range) coordinates. This paper presents a method scripted in ESRI's ARC Macro Language (AML) to locate the reservoirs on digital elevation models using information available in RESIS. The script also delineates the contributing watersheds and compiles several hydrologically important parameters for each reservoir. Evaluation of the method indicates that, for watersheds larger than 5 km2, the correct outlet is identified over 80% of the time. The importance of identifying the watershed outlet correctly depends on the application. Our intent is to collect spatial data for watersheds across the continental United States and describe the land use, soils, and topography for each reservoir's watershed. Because of local landscape similarity in these properties, we show that choosing the incorrect watershed does not necessarily mean that the watershed characteristics will be misrepresented. We present a measure termed terrain complexity and examine its relationship to geolocation success rate and its influence on the similarity of nearby watersheds. ?? 2008 Elsevier Ltd. All rights reserved.

Computers & Geosciences

Separation of copper, iron, and zinc from complex aqueous solutions for isotopic measurement

The measurement of Cu, Fe, and Zn isotopes in natural samples may provide valuable information about biogeochemical processes in the environment. However, the widespread application of stable Cu, Fe, and Zn isotope chemistry to natural water systems remains limited by our ability to efficiently separate these trace elements from the greater concentrations of matrix elements. In this study, we present a new method for the isolation of Cu, Fe, and Zn from complex aqueous solutions using a single anion-exchange column with hydrochloric acid media. Using this method we are able to quantitatively separate Cu, Fe, and Zn from each other and from matrix elements in a single column elution. Elution of the elements of interest, as well as all other elements, through the anion-exchange column is a function of the speciation of each element in the various concentrations of HCl. We highlight the column chemistry by comparing our observations with published studies that have investigated the speciation of Cu, Fe, and Zn in chloride solutions. The functionality of the column procedure was tested by measuring Cu, Fe, and Zn isotopes in a variety of stream water samples impacted by acid mine drainage. The accuracy and precision of Zn isotopic measurements was tested by doping Zn-free stream water with the Zn isotopic standard. The reproducibility of the entire column separation process and the overall precision of the isotopic measurements were also evaluated. The isotopic results demonstrate that the Cu, Fe, and Zn column separates from the tested stream waters are of sufficient purity to be analyzed directly using a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS), and that the measurements are fully-reproducible, accurate, and precise. Although limited in scope, these isotopic measurements reveal significant variations in δ 65 Cu (− 1.41 to + 0.30‰), δ 56 Fe (− 0.56 to + 0.34‰), and δ 66 Zn (0.31 to 0.49‰) among samples collected from different abandoned mines within a single watershed. Hence, Cu, Fe, and Zn isotopic measurements may be a powerful tool for fingerprinting specific metal sources and/or examining biogeochemical reactions within fresh water systems.

Chemical Geology

High-precision ID-TIMS U-Pb geochronology of perovskite (CaTiO3) from the Ice River Complex, southeastern British Columbia

Uranium‑lead perovskite in situ geochronology has become a cornerstone technique for determining the emplacement timing of alkaline, ultrapotassic, and silica-undersaturated igneous rocks, kimberlites, and carbonatites. Accurate in situ dates are dependent on the availability of matrix matched mineral reference materials which themselves are chemically well characterized and dated accurately to the highest possible precision. When dating perovskite to high precision, such as by isotope dilution thermal ionization mass spectrometry (ID-TIMS), appropriately accounting and correcting for the quantity and isotopic composition of Pb incorporated into the crystal upon crystallization (Pb i ) is a large source of uncertainty and potential inaccuracy. Unfortunately, although ultra-high precision perovskite dates are attainable with modern mass spectrometry techniques, the accuracy of applied Pb i compositions, which can be a considerable percentage of total Pb in a crystal, has not kept pace, resulting in percent level inaccuracy on precisely measured isotopic ratios. In an effort to characterize the age and initial Pb isotopic composition of a readily available, relatively pure perovskite endmember (93–98%) which will be useful as a matrix matched age reference material for in situ U-Pb geochronology, we date crystals isolated from three samples from the Ice River Complex (samples 81IR6, I90.3, and I92.30) by ID-TIMS and evaluate their suitability as known-age reference materials. We directly determine the isotopic composition of Pb i in each sample by ID-TIMS measurement of cogenetic low 238 U/ 204 Pb (μ < 500) phlogopite, apatite, and/or clinopyroxene. Using these initial common Pb isotopic compositions, which are significantly more radiogenic than those predicted by age appropriate Pb evolution models, we obtain ultra-precise weighted-mean 206 Pb/ 238 U perovskite dates of 355.83 ± 0.14, 355.04 ± 0.15, and 357.34 ± 0.12 Ma on the three Ice River samples, respectively. These dates are consistent with the relative emplacement ages previously established for units in the Ice River layered ultramafic series based on field relationships. They also demonstrate the feasibility of attaining accurate perovskite dates in instances when maximum precision is critical by utilizing ID-TIMS analysis of cogenetic low uranium phases for direct measurement of Pb i .

British Columbia

Multiresidue extraction of current-use pesticides from complex solid matrices using energized dispersive guided extraction with analysis by gas and liquid chromatography tandem mass spectroscopy

The development of sample processing techniques that recover a broad suite of pesticides from solid matrices, while mitigating coextracted matrix interferences, and reducing processing time is beneficial for high throughput analyses. The objective of this study was to evaluate the effectiveness of an automated extraction system for pesticide analyses in solid environmental samples. An Energized Dispersive Guided Extraction (EDGE) system was used to evaluate two different extraction solvents in optimizing the extraction of 210 pesticides and pesticide transformation products. A graphitized carbon cleanup step was implemented, and three elution solvents were evaluated separately for analyte recoveries. Recoveries between 70 and 130% were achieved for 167 compounds in a test soil using acetonitrile as an extraction solvent and carbon cleanup with acetonitrile and dichloromethane elutions. Nine field samples (soil, sediment, and biosolids) were extracted using the newly developed method and were compared with a previously validated pressurized liquid extraction (PLE) method using an Accelerated Solvent Extraction (ASE) system. Concentrations obtained from the two methods were comparable (linear R 2 > 0.999), suggesting similar performance between the EDGE and PLE extractions in complex matrices. The new method provided slightly better sensitivities in comparison to the PLE method, ranging from 0.09 to 2.56 ng g −1 . The method presented here significantly reduces extraction setup and runtimes while also minimizing the volume of carcinogenic solvents ( e.g. , dichloromethane) used in the laboratory and presents a sensitive multiresidue method for a wide range of pesticides in solid matrices.

Chemosphere

Long-term multidecadal data from a prairie-pothole wetland complex reveal controls on aquatic-macroinvertebrate communities

Interactions between climate and hydrogeologic settings contribute to the hydrologic and chemical variability among depressional wetlands, which influences their aquatic communities. These interactions and resulting variability have led to inconsistent results in terms of identifying reliable predictors of aquatic-macroinvertebrate community composition for depressional wetlands. This is especially true in the Prairie Pothole Region of North America where, in addition to pronounced climate variability, studies are often confounded by fish introductions. We used environmental monitoring data collected over a 24-year period from a complex of sixteen depressional wetlands and structural equation modeling techniques that incorporated theoretical and empirical relationships outlined in the Wetland Continuum to identify key environmental (climate and hydrogeologic setting) and biotic (competition and predation) drivers of aquatic-macroinvertebrate community composition for prairie-pothole wetlands. Uplands in the study area were primarily native prairie, thus, embedded wetlands were impacted minimally by agricultural influences. Additionally, study wetlands were predominately fishless. In the absence of the overwhelming influence of fishes, major drivers influencing aquatic-macroinvertebrate communities were revealed through the use of data spanning multidecadal-long climate cycles. We found variables related to the placement of wetlands along axes of the Wetland Continuum, e.g., hydrogeologic setting (relative wetland elevation) and hydroclimatic setting (proportion of wetland ponded), to be influential drivers of within-wetland habitat characteristics, such as the proportion of open-water area, which in turn was the strongest predictor of macroinvertebrate community composition. In contrast, predatory invertebrate and salamander abundance and non-predatory invertebrate biomass (i.e., predation and competition) were found to have minimal influence on community composition.

North Dakota

Complex landslide patterns explained by local intra-unit variability of stratigraphy and structure: Case study in the Tyee Formation, Oregon, USA

Lithology and geologic structure are important controls on landslide susceptibility and are incorporated into many regional landslide hazard models. Typically, metrics for mapped geologic units are used as model input variables and a single set of values for material strength are assumed, regardless of spatial heterogeneities that may exist within a map unit. Here we describe how differences in bedding thickness, grain size, inferred uniaxial compressive strength, and bedding dip control the inherent susceptibility of slopes to deep-seated failure within a single mapped geologic unit - the Tyee Formation of Oregon, USA. The Tyee, which covers over 15,000 km2 and underlies much of the Oregon Coast Range, comprises gently folded alternating beds of sandstone and siltstone deposited as turbidites, forming a 2-km thick Eocene submarine fan which has been uplifted and exhumed through the Cenozoic. Deep-seated landslides are widespread in the Tyee, but form a complex spatial pattern such that landslide density ranges from 0 to 24% of the total landscape area. These slides are often extensive and sufficiently deep to reduce local hillslope gradients, resulting in a strong negative correlation between landslide density and mean local slope. Mean annual precipitation and predicted strong ground motions from Cascadia earthquake scenarios also fail to explain the spatial distribution of deep-seated landslides. Consequently, landslide stability models, which are strongly influenced by landscape slope, pore-water pressure, and seismic acceleration, yield landslide susceptibility maps which are broadly anti-correlated with mapped deep-seated landslide density. Through a multivariable linear regression model, we show that much of the variance in deep-seated landslide density can be explained by variability of intra-unit stratigraphic and structural characteristics, which we measure at 128 sites across two study areas totaling ∼3000 km2. Our results suggest bedding dip is only weakly correlated to landslide density, but strongly influences landslide failure style. Subtle increases in bedding dip, even in the gently folded Tyee Formation, result in a substantially higher likelihood of a landslide being cataclinal, or parallel to bedding. Overall, we find a slight majority of landslides fail within these cataclinal slopes, and that these landslides tend to be larger than non-cataclinal landslides. We also show that the lithological and structural properties that influence landslide susceptibility are distinct for these two populations of landslides. Our results demonstrate how localized, intra-unit, geologic variability can exert strong control on landslide susceptibility and failure style. This suggests that in some locations, landslide hazard models could be significantly improved by incorporating detailed, spatially variable, geologic properties rather than relying solely on generalized geologic map units.

Oregon

Complexity of human and ecosystem interactions in an agricultural landscape

The complexity of human interaction in the commercial agricultural landscape and the resulting impacts on the ecosystem services of water quality and quantity is largely ignored by the current agricultural paradigm that maximizes crop production over other ecosystem services. Three examples at different spatial scales (local, regional, and global) are presented where human and ecosystem interactions in a commercial agricultural landscape adversely affect water quality and quantity in unintended ways in the Delta of northwestern Mississippi. In the first example, little to no regulation of groundwater use for irrigation has caused declines in groundwater levels resulting in loss of baseflow to streams and threatening future water supply. In the second example, federal policy which subsidizes corn for biofuel production has encouraged many producers to switch from cotton to corn, which requires more nutrients and water, counter to national efforts to reduce nutrient loads to the Gulf of Mexico and exacerbating groundwater level declines. The third example is the wholesale adoption of a system for weed control that relies on a single chemical, initially providing many benefits and ultimately leading to the widespread occurrence of glyphosate and its degradates in Delta streams and necessitating higher application rates of glyphosate as well as the use of other herbicides due to increasing weed resistance. Although these examples are specific to the Mississippi Delta, analogous situations exist throughout the world and point to the need for change in how we grow our food, fuel, and fiber, and manage our soil and water resources.

Arkansas, Louisiana, Mississippi, Missouri

Automating calibration, sensitivity and uncertainty analysis of complex models using the R package Flexible Modeling Environment (FME): SWAT as an example

Parameter optimization and uncertainty issues are a great challenge for the application of large environmental models like the Soil and Water Assessment Tool (SWAT), which is a physically-based hydrological model for simulating water and nutrient cycles at the watershed scale. In this study, we present a comprehensive modeling environment for SWAT, including automated calibration, and sensitivity and uncertainty analysis capabilities through integration with the R package Flexible Modeling Environment (FME). To address challenges (e.g., calling the model in R and transferring variables between Fortran and R) in developing such a two-language coupling framework, 1) we converted the Fortran-based SWAT model to an R function (R-SWAT) using the RFortran platform, and alternatively 2) we compiled SWAT as a Dynamic Link Library (DLL). We then wrapped SWAT (via R-SWAT) with FME to perform complex applications including parameter identifiability, inverse modeling, and sensitivity and uncertainty analysis in the R environment. The final R-SWAT-FME framework has the following key functionalities: automatic initialization of R, running Fortran-based SWAT and R commands in parallel, transferring parameters and model output between SWAT and R, and inverse modeling with visualization. To examine this framework and demonstrate how it works, a case study simulating streamflow in the Cedar River Basin in Iowa in the United Sates was used, and we compared it with the built-in auto-calibration tool of SWAT in parameter optimization. Results indicate that both methods performed well and similarly in searching a set of optimal parameters. Nonetheless, the R-SWAT-FME is more attractive due to its instant visualization, and potential to take advantage of other R packages (e.g., inverse modeling and statistical graphics). The methods presented in the paper are readily adaptable to other model applications that require capability for automated calibration, and sensitivity and uncertainty analysis.

Environmental Modelling and Software

Sulfur cycle in the Valles Caldera volcanic complex, New Mexico – Letter 1: Sulfate sources in aqueous system, and implications for S isotope record in Gale Crater on Mars

Initial in situ sulfur (S) isotope measurements of the Martian bedrock in Gale Crater have revealed an unexpectedly wide range of δ 34 S values (−47 to +28%). Generally, it is unclear what processes could have contributed to these large isotope fractionations. Therefore, we studied S sources and aqueous SO 2− 4 cycling in the Valles Caldera volcanic complex, New Mexico to better understand S isotope fractionations related to S degassing, hydrothermal activity, and low-temperature processes in aqueous environment. Overall, our study demonstrates that volcanic systems show large spatial heterogeneity in δ 34 S. Magmatic S sources are obvious in steam-dominated H 2 S degassing and precipitation of secondary minerals from hydrothermal fluids with low δ 34 S values of +0.9 ±3%. Locally, however, hydrothermal processes have resulted in more negative δ 34 S values in sulfide minerals (−18 to −4%) and more positive δ 34 S values in sulfate minerals (−1 to +3%). Major aqueous SO 2− 4 sources are oxidation of H 2 S from modern hydrothermal gas emission, and oxidation and dissolution of sulfide and sulfate minerals present in the hydrothermally altered bedrock and crater-lake sediments. The δ 34 S of aqueous SO 2− 4 in surface water and groundwater varies widely (−8 to +5%) and is similar to major S endmembers that undergo oxidation and/or dissolution by active hydrological system. Minor SO 2− 4 contributions with more positive δ 34 S values (+9 to +14%) come from deeply circulating geothermal fluids and negligible amounts from atmospheric deposition (+5 to +7% in snow). Elevated SO 2− 4 contents are mainly associated with modern and past H 2 S emissions and oxidations near the surface. On regional scale, however, most of the intracaldera bedrock is S-depleted, thus the SO 2− 4 contents are usually low in the surface aquatic system and younger sedimentary lake deposits formed at times of negligible near surface hydrothermal activity. In general, magmatic-hydrothermal processes apparently cause the largest δ 34 S variation in S-bearing minerals on volcanic terrains. Therefore, we infer that the measured wide range of δ 34 S values in the Gale sediments by the Curiosity rover on Mars can be explained by S isotope composition of magmatic-hydrothermal sulfide and sulfate minerals that were present in the initial igneous/volcanic rocks prior to crater formation. Later aqueous processes involved oxidation and dissolution of S minerals initially present in these rocks and led to subsequent formation of diagenetic fluids and alteration products enriched in SO 2− 4 with relatively large δ 34 S variation. Additionally, physical erosion, transport and deposition of detrital hydrothermal S minerals from igneous/volcanic rocks might be in part responsible for the measured wide range of δ 34 S in Gale Crater. These unique S isotope results, measured in situ on another planet for the first time, imply the importance of magmatic-hydrothermal fluids in S transport on early Mars and their subsequent alteration in low-temperature aqueous environments.

New Mexico

Tracing magmatic genesis and evolution through single zircon crystals from successive supereruptions from the Socorro Caldera Complex, USA

Large volume rhyolitic ignimbrite volcanism is a significant contributor to the evolving crust. The introduction of high-silica material into the upper crust, differentiation within the middle crust, and partial melting in the lower crust contributes to geochemical and isotopic evolution of the crust. Developing accurate models for the genetic evolution of these events is dependent upon geochronology to determine rates of magmatic processes as model constraints. We present new zircon high-precision CA-ID-TIMS U-Pb geochronology and MC-ICPMS Hf isotope geochemistry for four ignimbrites from the nested caldera complex near Socorro, New Mexico (USA), within the Mogollon-Datil volcanic field. In agreement with past 40 Ar- 39 Ar data, interpretations of new U-Pb data indicate eruptions from the Socorro caldera cluster were pulsed. These pulses were intermittently spaced, and a volcanic hiatus following the Hells Mesa Tuff at 33.442 ± 0.015 Ma was interrupted by four successive eruptions, beginning with the La Jencia Tuff at 29.158 ± 0.025 Ma and finishing with the South Canyon Tuff at 28.066 ± 0.021 Ma. Zircon age spectra became more protracted with each eruption, exhibiting age dispersions ranging from 0.347 Myr in the Hells Mesa Tuff to 4.502 Myr in the South Canyon Tuff. The increased dispersion is paralleled by an increase in the proportion of normally discordant grains, indicative of xenocryst incorporation. These protracted age spectra are not necessarily a function of thermal maturation in the middle to upper crust due to long-lived magma chambers. Rather, they are likely the result of increased melting of zircon-bearing lower crust due to deep thermal maturation from repeated juvenile magma injections based on the incorporation of zircon material at the melt source. In contrast, the Hf isotope record is volumetrically dominated by autocrystic zircon domains and becomes more radiogenic through time, recording juvenile replenishment of the lower crust during progressive melting. Together, these data record the protracted evolution of the lower crust sampled by ignimbrites, lend insight into that evolution, and emphasize the need for detailed interpretation of high-precision datasets to advance volcanic models.

Arizona, New Mexico

Angler effort and catch within a spatially complex system of small lakes.

Spatial layout of waterbodies and waterbody size can affect a creel clerk&rsquo;s ability to intercept anglers for interviews and to accurately count anglers, which will affect the accuracy and precision of estimates of effort and catch. This study aimed to quantify angling effort and catch across a spatially complex system of 19 small (<100 ha) lakes, the Fremont lakes. Total (&plusmn;SE) angling effort (hours) on individual lakes ranged from 0 (0) to 7,137 (305). Bank anglers utilized 18 of the 19 lakes, and their mean (&plusmn;SE) trip lengths (hours) ranged from 0.80 (0.31) to 7.75 (6.75), depending on the waterbody. In contrast, boat anglers utilized 14 of the 19&thinsp;lakes, and their trip lengths ranged from 1.39 (0.24) to 4.25 (0.71), depending on the waterbody. The most sought fishes, as indexed by number of lakes on which effort was exerted, were anything (17 of 19 lakes), largemouth bass Micropterus salmoides (15 of 19 lakes), and channel catfish Ictalurus punctatus (13 of 19 lakes). Bluegill Lepomis machrochirus , crappie Pomoxis spp., and largemouth bass were caught most frequently across the lakes, but catch rates varied considerably by lake. Of the 1,138 parties interviewed, most parties (93%) visited a single lake but there were 77 (7%) parties that indicated that they had visited multiple lakes during a single day. The contingent of parties that visited more than one lake a day were primarily (87%) bank anglers.. The number of lake-to-lake connections made by anglers visiting more than one waterbody during a single day was related to catch rates and total angling effort. The greater resolution that was achieved with a lake specific creel survey at Fremont lakes revealed a system of lakes with a large degree of spatial variation in angler effort and catch that would be missed by a coarser, system-wide survey that did not differentiate individual lakes.

Fisheries Research

Direct observation of heavy metal-mineral association from the Clark Fork River Superfund Complex: Implications for metal transport and bioavailability

Two sets of samples from riverbeds and adjacent floodplains, separated by 80 river kilometers, were collected from the Clark Fork River Superfund Complex, Montana, (the largest Superfund site in the United States), and studied primarily with transmission electron microscopy (TEM) with several supporting techniques to determine heavy metal-mineral association. Seven of the eight samples studied were strongly influenced by material that once resided in mining and smelting dumps and impoundments; this material was transported downstream sometime during the last century and a half from the Butte/Anaconda areas. The eighth sample was from a deeper floodplain level and dates to premining days. The TEM observations afford a direct look, down to the nanometer level, at secondary mineral formation as a result of the breakdown of sulfides and silicates in the acid environment of this massive mine-drainage system. In the shallow, oxic floodplain sediments, heavy metals of concern in this system (As, Cu, Pb, and Zn) are taken up by the formation of sulfates (particularly Pb in jarosite), as well as hydrous metal oxides (As, Cu, Pb, and Zn in and on ferrihydrite, and a possibly new vernadite-like mineral). The oxides are long-lived in these systems, as they were also found in the anoxic riverbeds. Metals are also taken up by the formation of sulfides in sulfate-reducing environments as observed in the formation of nanoclusters of chalcopyrite and sphalerite. In all samples, clays make up between 5 and 20% of the sediment and carry significant amounts of Cu and Zn. The hydrous oxides, secondary sulfides, and clays provide several routes for metal transport downstream over long distances. Besides the potential bioavailability of heavy metals exchanged on and off the hydrous metal oxides and clays, nanometer-sized sulfides may also be highly reactive in the presence of biologic systems. Copyright ?? 2005 Elsevier Ltd.

Geochimica et Cosmochimica Acta

Direct measurements of copper speciation in basaltic glasses: Understanding the relative roles of sulfur and oxygen in copper complexation in melts

Micro-analytical determination of copper (Cu) speciation in natural magmatic glasses, equilibrated below the nickel – nickel oxide (NNO) buffer, reveals that two copper species are commonly stabilized in such basaltic melts. X-ray absorption fine structure (XAFS) spectroscopic analysis of basaltic matrix glasses and melt inclusions (MI) from samples of mid-ocean ridge basalt (MORB), and from Nyamuragira, Etna and Kīlauea volcanoes show that both Cu(I)-sulfide and Cu(I)-oxide species are stabilized. The proportion of each species correlates with the measured sulfur (S) abundance of the glass. In glasses with S abundances greater than ~1000 ppm, Cu(I)-sulfide species are dominant, whereas in glasses with S abundances between 500 and 1000 ppm, both species are found to coexist. The Cu(I)-oxide species dominate at S concentrations below 500 ppm. In 1 atm S-free experimental glasses of basaltic composition that we analyzed, only Cu(I)-oxide species are detectable, regardless of the oxygen fugacity (fO2), even at relatively high fO2 values well above the NNO buffer. Our results demonstrate that XAFS techniques are highly sensitive in measuring Cu speciation in reduced (below NNO) basaltic glasses and that both oxide and sulfide complexes can be stabilized. The relative proportion of these two species is highly dependent on the concentration of S in the melt, and thus the Cu speciation in natural melts changes as S is lost from the melt by low pressure degassing.

Hawaii

Inferring presence of the western toad (Anaxyrus boreas) species complex using environmental DNA

Western toads (species complex comprised of Anaxyrus boreas , A. canorus , A. exsul , and A. nelsoni ) are widely distributed in the western United States but are declining, particularly in the southeastern extent of their range. The subspecies A. b. boreas is listed as a Species of Greatest Conservation Need in New Mexico, Colorado, Utah, and Wyoming. Reliable and sensitive methods for delineating distributions of western toads are critical for monitoring the status of the species and prioritizing conservation efforts. We developed two qPCR assays for detecting western toad DNA in environmental DNA samples. Both markers efficiently and reliably detect low concentrations of western toad DNA across their range in the conterminous U. S. without detecting non-target, sympatric species. To determine the optimal annual sampling period, we then tested these markers using repeated sampling in ponds where western toads were known to be present. Quantities of collected eDNA varied widely across samples, but sample-level detections across sites exceeded 80% for June sampling. In the later summer, detection dropped off sharply with only a single detection in the ten samples collected throughout August.

Global Ecology and Conservation

Complex demographic responses to contrasting climate drivers lead to divergent population trends across the range of a threatened alpine plant

Alpine plants are likely to be particularly vulnerable to climate change because of their restricted distributions and sensitivity to rapid environmental shifts occurring in high-elevation ecosystems. The well-studied Haleakalā silversword (‘āhinahina, Argyroxiphium sandwicense subsp. macrocephalum ) already exhibits substantial climate-associated population decline, and offers the opportunity to understand the ecological and demographic mechanisms that underlie ongoing and predicted range shifts. We use nearly four decades of demographic monitoring for this threatened Hawaiian species, in combination with other biological, ecological and climate data to explore demographic responses across its entire range. We construct and independently validate population models for two elevation zones representing the species’ lower trailing and higher stable regions. Differences in population growth rate (lambda) between trailing and stable regions were influenced most strongly by lower survival of juvenile and small adult size classes, as well as by lower recruitment and lower survival of seedlings and large adults in the trailing region. Furthermore, seed production appears to have decreased from the 1980’s to present in the trailing region, and is now significantly less than in the stable region. Lambda and several underlying vital rates were significantly associated with wetter dry season conditions in the lower trailing region, indicating water limitation. In the higher elevation stable region, in contrast, lambda and vital rates were associated with warmer air temperatures, indicating cold limitation. These contrasting demographic patterns and climate dependencies lead to a high probability of extinction over the next century in the lower region, where most plants occur, but zero probability of the same in the higher region, according to stochastic population projections. Drier future scenarios further increase the probability of extinction at low elevations. The combined results illustrate the complexity in the demographic response and future viability that can occur across the range of a single species.

Global Ecology and Conservation

Quantifying mineral abundances of complex mixtures by coupling spectral deconvolution of SWIR spectra (2.1-2.4 &mu;m) and regression tree analysis

This paper presents a methodology for assessing mineral abundances of mixtures having more than two constituents using absorption features in the 2.1-2.4 &mu;m wavelength region. In the first step, the absorption behaviour of mineral mixtures is parameterised by exponential Gaussian optimisation. Next, mineral abundances are predicted by regression tree analysis using these parameters as inputs. The approach is demonstrated on a range of prepared samples with known abundances of kaolinite, dioctahedral mica, smectite, calcite and quartz and on a set of field samples from Morocco. The latter contained varying quantities of other minerals, some of which did not have diagnostic absorption features in the 2.1-2.4 μm region. Cross validation showed that the prepared samples of kaolinite, dioctahedral mica, smectite and calcite were predicted with a root mean square error (RMSE) less than 9 wt.%. For the field samples, the RMSE was less than 8 wt.% for calcite, dioctahedral mica and kaolinite abundances. Smectite could not be well predicted, which was attributed to spectral variation of the cations within the dioctahedral layered smectites. Substitution of part of the quartz by chlorite at the prediction phase hardly affected the accuracy of the predicted mineral content; this suggests that the method is robust in handling the omission of minerals during the training phase. The degree of expression of absorption components was different between the field sample and the laboratory mixtures. This demonstrates that the method should be calibrated and trained on local samples. Our method allows the simultaneous quantification of more than two minerals within a complex mixture and thereby enhances the perspectives of spectral analysis for mineral abundances.

Geoderma

Complex channel responses to changes in stream flow and sediment supply on the lower Duchesne River, Utah

Channel responses to flow depletions in the lower Duchesne River over the past 100 years have been highly complex and variable in space and time. In general, sand-bed reaches adjusted to all perturbations with bed-level changes, whereas the gravel-bed reaches adjusted primarily through width changes. Gravel-bed reaches aggraded only when gravel was supplied to the channel through local bank erosion and degraded only during extreme flood events. A 50% reduction in stream flow and an increase in fine sediment supply to the study area occurred in the first third of the 20th century. The gravel-bed reach responded primarily with channel narrowing, whereas bed aggradation and four large-scale avulsions occurred in the sand-bed reaches. These avulsions almost completely replaced a section of sinuous channel about 14 km long with a straighter section about 7 km long. The most upstream avulsion, located near a break in valley slope and the transition from a gravel bed upstream and a sand bed downstream, transformed a sinuous sand-bed reach into a braided gravel-bed reach and eventually into a meandering gravel-bed reach over a 30-year period. Later, an increase in flood magnitudes and durations caused widening and secondary bed aggradation in the gravel-bed reaches, whereas the sand-bed reaches incised and narrowed. Water diversions since the 1950s have progressively eliminated moderate flood events, whereas larger floods have been less affected. The loss of frequent flooding has increased the duration and severity of drought periods during which riparian vegetation can establish along the channel margins. As a result, the channel has gradually narrowed throughout the study area since the late 1960s, despite the occasional occurrence of large floods. No tributaries enter the Duchesne River within the study area, so all reaches have experienced identical changes in stream flow and upstream sediment supply. ?? 2004 Elsevier B.V. All rights reserved.

Geomorphology