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11 recordsLinked to original sources

Chemical and structural degradation of CH3NH3PbI3 propagate from PEDOT:PSS interface in the presence of humidity

Understanding interfacial reactions that occur between the active layer and charge-transport layers can extend the stability of perovskite solar cells. In this study, the exposure of methylammonium lead iodide (CH 3 NH 3 PbI 3 ) thin films prepared on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)-coated glass to 70% relative humidity (R.H.) leads to a perovskite crystal structure change from tetragonal to cubic within 2 days. Interface-sensitive photoluminescence measurements indicate that the structural change originates at the PEDOT:PSS/perovskite interface. During exposure to 30% R.H., the same structural change occurs over a much longer time scale (>200 days), and a reflection consistent with the presence of (CH 3 ) 2 NH 2 PbI 3 is detected to coexist with the cubic phase by X-ray diffraction pattern. The authors propose that chemical interactions at the PEDOT:PSS/perovskite interface, facilitated by humidity, promote the formation of dimethylammonium, (CH 3 ) 2 NH 2 + . The partial A-site substitution of CH 3 NH 3 + for (CH 3 ) 2 NH 2 + to produce a cubic (CH 3 NH 3 ) 1− x [(CH 3 ) 2 NH 2 ] x PbI 3 phase explains the structural change from tetragonal to cubic during short-term humidity exposure. When (CH 3 ) 2 NH 2 + content exceeds its solubility limit in the perovskite during longer humidity exposures, a (CH 3 ) 2 NH 2 + -rich, hexagonal phase of (CH 3 NH 3 ) 1− x [(CH 3 ) 2 NH 2 ] x PbI 3 emerges. These interfacial interactions may have consequences for device stability and performance beyond CH 3 NH 3 PbI 3 model systems and merit close attention from the perovskite research community.

Advanced Materials Interfaces

A new groundwater energy transport model for the MODFLOW hydrologic simulator

Heat transport in the subsurface is an important aspect of research related to the effects of a warming climate on ecological services (i.e., cold-water refugia); the development of geothermal resources for energy banking schemes (i.e., aquifer thermal energy storage [ATES]); and the effects of temperature on other aspects of groundwater quality, such as nutrient cycling. Historically, simulation of heat transport using the MODFLOW groundwater simulator and related codes was performed by scaling the input parameters of a solute-transport model to emulate heat transport. However, that approach required additional pre- and post-processing of input and output and could not account for the variation in effective thermal storage and transport properties during transient, unsaturated flow, for example. True heat-transport capabilities in the context of MODFLOW were first introduced in a variant called USG-Transport. More recently, a new groundwater energy-transport (GWE) model type has been added to MODFLOW 6, the core version of the MODFLOW hydrologic simulator. GWE supports the simulation of heat transport on structured or unstructured grids as well as within and between features of advanced packages that represent streams, lakes, multi-aquifer wells, and the unsaturated zone. GWE is integrated within MODFLOW 6 and is accessible through the FloPy Python package and the MODFLOW 6 application programming interface (API). An example simulation demonstrates conduction between grid cells through both the water and the solid aquifer material, including thermal bleeding from saturated overburden cells into a groundwater flow field.

Groundwater

Alternative waste residue materials for passive in situ prevention of sulfide-mine tailings oxidation: A field evaluation

Novel solutions for sulfide-mine tailings remediation were evaluated in field-scale experiments on a former tailings repository in northern Sweden. Uncovered sulfide-tailings were compared to sewage-sludge biosolid amended tailings over 2 years. An application of a 0.2 m single-layer sewage-sludge amendment was unsuccessful at preventing oxygen ingress to underlying tailings. It merely slowed the sulfide-oxidation rate by 20%. In addition, sludge-derived metals (Cu, Ni, Fe, and Zn) migrated and precipitated at the tailings-to-sludge interface. By using an additional 0.6 m thick fly-ash sealing layer underlying the sewage sludge layer, a solution to mitigate oxygen transport to the underlying tailings and minimize sulfide-oxidation was found. The fly-ash acted as a hardened physical barrier that prevented oxygen diffusion and provided a trap for sludge-borne metals. Nevertheless, the biosolid application hampered the application, despite the advances in the effectiveness of the fly-ash layer, as sludge-borne nitrate leached through the cover system into the underlying tailings, oxidizing pyrite. This created a 0.3 m deep oxidized zone in 6-years. This study highlights that using sewage sludge in unconventional cover systems is not always a practical solution for the remediation of sulfide-bearing mine tailings to mitigate against sulfide weathering and acid rock drainage formation.

Skellefte�;Stockholm

Framework for implementing damping scaling factors in U.S. Geological Survey National Seismic Hazard Models

Traditionally, probabilistic seismic hazard analysis (PSHA) has focused on calculating ground motion hazard curves for elastic, 5%-damped pseudo spectral accelerations, Sa(T,5%), which are used as the basis for engineering design parameters and targets for ground motion selection and modification. However, structures and geotechnical systems can exhibit a wide range of damping ratios both above and below the 5% level, depending on the construction material, structural system, nonstructural elements, or subsurface soil properties. When spectral parameters at such damping levels are required for certain applications, 5%-damped accelerations have traditionally been extracted from PSHA-based hazard curves and adjusted outside of the hazard integral using damping scaling factors (DSF) such as those from Newmark & Hall (1982). Recent advances in the development of more rigorous and comprehensive damping scaling models (e.g., Rezaeian et al., 2014; Rezaeian et al., 2021) have allowed for the modeling of means and standard deviations of DSFs as functions of earthquake source and path properties for crustal, intraslab, and subduction interface tectonic environments. These DSF models can be applied to ground motion model (GMM) estimates of Sa(T,5%) for a given earthquake rupture scenario to produce a corresponding mean and standard deviation Sa at a specified damping ratio β, Sa(T,β). In this study, the DSF models of Rezaeian et al. (2014) and Rezaeian et al. (2021) are implemented within the U.S. Geological Survey National Seismic Hazard Model (NSHM) PSHA framework to calculate probabilistic hazard curves for spectral accelerations at damping ratios from 0.5% to 30%. The DSF models are applied directly to the mean and standard deviation of Sa(T,5%) predictions from each GMM in the NSHM logic tree. Resulting hazard curves and uniform hazard and risk spectra for Sa(T,β) are presented for several geographic locations and compared with corresponding spectra estimated using current design practices by applying the same DSFs outside of the PSHA calculation. Key differences between the two methods for estimating Sa(T,β) are discussed, and potential strategies are presented for the implementation and usage of the hazard-consistent Sa(T,β) in building codes. Comparing the results to those from DSFs used in current design practices that are mainly based on Newmark & Hall (1982) is not explored in this study.

Conference Paper

Controls on rind thickness on basaltic andesite clasts weathering in Guadeloupe

A clast of low porosity basaltic andesite collected from the B horizon of a soil developed on a late Quaternary volcaniclastic debris flow in the Bras David watershed on Basse-Terre Island, Guadeloupe, exhibits weathering like that observed in many weathered clasts of similar composition in other tropical locations. Specifically, elemental profiles measured across the core-rind interface document that primary minerals and glass weather to Fe oxyhydroxides, gibbsite and minor kaolinite in the rind. The earliest reaction identified in the core is oxidation of Fe in pyroxene but the earliest reaction that creates significant porosity is plagioclase dissolution. Elemental loss varies in the order Ca???Na>K???Mg>Si>Al>Fe???P??Ti, consistent with the relative reactivity of phases in the clast from plagioclase???pyroxene???glass>apatite>ilmenite. The rind surrounds a core of unaltered material that is more spherical than the original clast. The distance from the core-rind boundary to a visually prominent rind layer, L, was measured as a proxy for the rind thickness at 36 locations on a slab cut vertically through the nominal center of the clast. This distance averaged 24.4??3.1mm. Maximum and minimum values for L, 35.8 and 20.6mm, were observed where curvature of the core-rind boundary is greatest (0.12mm-1) and smallest (0.018mm-1) respectively. Extrapolating from other rinds in other locations, the rate of rind formation is estimated to vary by a factor of about 2 (from ~4 to 7??10-14ms-1) from low to high curvature. The observation of a higher rate of rind formation for a higher curvature interface is consistent with a diffusion-limited model for weathering rind formation. The diffusion-limited model predicts that, like rind thickness, values of the thickness of the reaction front (h) for a given reaction, defined as the zone over which a parent mineral such as plagioclase completely weathers to rind material, should also increase with curvature. Values of h were quantified as a function of interface curvature using bulk chemical analysis (500<h<2000??m). Values of h were also quantified by measuring loss of matrix glass and increase in porosity as a function of curvature. In contrast to rind thickness, h shows no consistent increase with curvature. This contradiction is attributed to the mm-scale roughness of the interface which is related to phenocryst grain size. Therefore, the overall rind formation rate is strongly affected by curvature measured at the scale of the clast, while mineral reaction rates documented by reaction front thickness are strongly affected by curvature at the scale of phenocrysts. Similarly, the weathering advance rate (ms-1) for the entire Bras David watershed can be extrapolated from the clast weathering rate if roughness at the watershed scale equals values of approximately 400-800. ?? 2010 Elsevier B.V.

Chemical Geology

Unifying research on the fragmentation of terrestrial and aquatic habitats: patches, connectivity and the matrix in riverscapes

While there is an increasing emphasis in terrestrial ecology on determining the influence of the area that surrounds habitat patches (the landscape &lsquo;matrix&rsquo;) relative to the characteristics of the patches themselves, research on these aspects in running waters is still rather underrepresented. Here we outline conceptual foundations of matrix ecology for stream and river ecosystems (&lsquo;riverscapes&rsquo;). We discuss how a hierarchical, patch-based perspective is necessary for the delineation of habitat patches and the surrounding matrix, through which we may identify two classes of habitat edges in riverscapes (i.e. edges between the terrestrial&ndash;aquatic interface and edges within streams). Under this conceptual framework, we discuss the role of the matrix in influencing between-patch movement, and resource quality and quantity within and among habitat patches in riverscapes. We also review types of empirical and modelling approaches which may advance our understanding of fragmentation effects in these systems. We identify five key challenges for understanding fragmentation and matrix effects more completely: (i) defining populations and their status (i.e. quantifying the demographic contribution of habitat patches to metapopulation dynamics), (ii) scaling from metapopulations to metacommunities (particularly searching for generalities in species responses to landscape heterogeneity), (iii) scaling from metacommunities to metaecosystems (i.e. exploring the interactive role of the terrestrial&ndash;aquatic and within-stream matrix effects on the flow of material and energy at the network scale), (iv) understanding temporal dynamics in matrix permeability and (v) revealing the utility of different patch and matrix representations for modelling connectivity relationships. Fragmentation of habitats is a critical issue in the conservation and management of stream networks across spatial scales. Although the effects of individual barriers (e.g. dams) are well documented, we argue that a more comprehensive patch&ndash;matrix landscape model will improve our understanding of fragmentation effects and improve management in riverscapes.

Freshwater Biology

The roles of organic matter in the formation of uranium deposits in sedimentary rocks

Because reduced uranium species have a much smaller solubility than oxidized uranium species and because of the strong association of organic matter (a powerful reductant) with many uranium ores, reduction has long been considered to be the precipitation mechanism for many types of uranium deposits. Organic matter may also be involved in the alterations in and around tabular uranium deposits, including dolomite precipitation, formation of silicified layers, iron-titanium oxide destruction, dissolution of quartz grains, and precipitation of clay minerals. The diagenetic processes that produced these alterations also consumed organic matter. Consequently, those tabular deposits that underwent the more advanced stages of diagenesis, including methanogenesis and organic acid generation, display the greatest range of alterations and contain the smallest amount of organic matter. Because of certain similarities between tabular uranium deposits and Precambrian unconformity-related deposits, some of the same processes might have been involved in the genesis of Precambrian unconformity-related deposits. Hydrologic studies place important constraints on genetic models of various types of uranium deposits. In roll-front deposits, oxidized waters carried uranium to reductants (organic matter and pyrite derived from sulfate reduction by organic matter). After these reductants were oxidized at any point in the host sandstone, uranium minerals were reoxidized and transported further down the flow path to react with additional reductants. In this manner, the uranium ore migrated through the sandstone at a rate slower than the mineralizing ground water. In the case of tabular uranium deposits, the recharge of surface water into the ground water during flooding of lakes carried soluble humic material to the water table or to an interface where humate precipitated in tabular layers. These humate layers then established the chemical conditions for mineralization and related alterations. In the case of Precambrian unconformity-related deposits, free thermal convection in the thick sandstones overlying the basement rocks carried uranium to concentrations of organic matter in the basement rocks.

Ore Geology Reviews

The international river interface cooperative: Public domain flow and morphodynamics software for education and applications

This paper describes a new, public-domain interface for modeling flow, sediment transport and morphodynamics in rivers and other geophysical flows. The interface is named after the International River Interface Cooperative (iRIC), the group that constructed the interface and many of the current solvers included in iRIC. The interface is entirely free to any user and currently houses thirteen models ranging from simple one-dimensional models through three-dimensional large-eddy simulation models. Solvers are only loosely coupled to the interface so it is straightforward to modify existing solvers or to introduce other solvers into the system. Six of the most widely-used solvers are described in detail including example calculations to serve as an aid for users choosing what approach might be most appropriate for their own applications. The example calculations range from practical computations of bed evolution in natural rivers to highly detailed predictions of the development of small-scale bedforms on an initially flat bed. The remaining solvers are also briefly described. Although the focus of most solvers is coupled flow and morphodynamics, several of the solvers are also specifically aimed at providing flood inundation predictions over large spatial domains. Potential users can download the application, solvers, manuals, and educational materials including detailed tutorials at www.-i-ric.org . The iRIC development group encourages scientists and engineers to use the tool and to consider adding their own methods to the iRIC suite of tools.

Advances in Water Resources

Spatial decision‐support tools to guide restoration and seed‐sourcing in the Desert Southwest

Altered disturbance regimes and shifting climates have increased the need for large‐scale restoration treatments across the western United States. Seed‐sourcing remains a considerable challenge for revegetation efforts, particularly on public lands where policy favors the use of native, locally sourced plant material to avoid maladaptation. An important area of emphasis for public agencies has been the development of spatial tools to guide selection of genetically appropriate seed. When genetic information is not available, current seed transfer guidelines stipulate use of climate‐based or provisional seed transfer zones, which serve as a proxy for local adaptation by representing climate gradients to which plants are commonly adapted. Despite this guidance, little emphasis has been placed on identifying best practices for deriving provisional seed zones or on incorporating predictions from future climate. We describe a flexible, multivariate procedure for deriving such zones that incorporates a broad range of climatic characteristics while accounting for covariation among climate variables. With this approach, we derive provisional seed zones for four regions in the Desert Southwest (the Mojave Desert, Sonoran Desert, Colorado Plateau, and Southern Great Basin). To facilitate future‐resilient restoration designs, we project each zone into its relative position in the future climate based on near‐term, RCP4.5 and RCP8.5 emissions scenarios. Although provisional seed zones are useful in a variety of contexts, there are also situations in which site‐specific guidance is preferable. To meet this need, we implement Climate Distance Mapper, an interactive decision‐support tool designed to help practitioners match seed sources with restoration sites through an accessible online interface. The application allows users to rank the suitability of seed sources anywhere on the landscape based on multivariate climate distances. Users can perform calculations for either the current or future climates. Additionally, tools are available to guide sample effort in regional‐scale seed collections or to partition the landscape into climate clusters representing suitable planting sites for different seed sources. Our tools and analytic procedures represent a flexible and reproducible framework for advancing native plant development programs in the Desert Southwest and beyond.

Ecosphere

A working environment for digital planetary data processing and mapping using ISIS and GRASS GIS

Since the beginning of planetary exploration, mapping has been fundamental to summarize observations returned by scientific missions. Sensor-based mapping has been used to highlight specific features from the planetary surfaces by means of processing. Interpretative mapping makes use of instrumental observations to produce thematic maps that summarize observations of actual data into a specific theme. Geologic maps, for example, are thematic interpretative maps that focus on the representation of materials and processes and their relative timing. The advancements in technology of the last 30 years have allowed us to develop specialized systems where the mapping process can be made entirely in the digital domain. The spread of networked computers on a global scale allowed the rapid propagation of software and digital data such that every researcher can now access digital mapping facilities on his desktop. The efforts to maintain planetary missions data accessible to the scientific community have led to the creation of standardized digital archives that facilitate the access to different datasets by software capable of processing these data from the raw level to the map projected one. Geographic Information Systems (GIS) have been developed to optimize the storage, the analysis, and the retrieval of spatially referenced Earth based environmental geodata; since the last decade these computer programs have become popular among the planetary science community, and recent mission data start to be distributed in formats compatible with these systems. Among all the systems developed for the analysis of planetary and spatially referenced data, we have created a working environment combining two software suites that have similar characteristics in their modular design, their development history, their policy of distribution and their support system. The first, the Integrated Software for Imagers and Spectrometers (ISIS) developed by the United States Geological Survey, represents the state of the art for processing planetary remote sensing data, from the raw unprocessed state to the map projected product. The second, the Geographic Resources Analysis Support System (GRASS) is a Geographic Information System developed by an international team of developers, and one of the core projects promoted by the Open Source Geospatial Foundation (OSGeo). We have worked on enabling the combined use of these software systems throughout the set-up of a common user interface, the unification of the cartographic reference system nomenclature and the minimization of data conversion. Both software packages are distributed with free open source licenses, as well as the source code, scripts and configuration files hereafter presented. In this paper we describe our work done to merge these working environments into a common one, where the user benefits from functionalities of both systems without the need to switch or transfer data from one software suite to the other one. Thereafter we provide an example of its usage in the handling of planetary data and the crafting of a digital geologic map. ?? 2010 Elsevier Ltd. All rights reserved.

Conference Paper

Topography of closed depressions, scarps, and grabens in the North Tharsis region of Mars: implications for shallow crustal discontinuities and graben formation

Using Viking Orbiter images, detailed photoclinometric profiles were obtained across 10 irregular depressions, 32 fretted fractures, 49 troughs and pits, 124 solitary scarps, and 370 simple grabens in the north Tharsis region of Mars. These data allow inferences to be made on the shallow crustal structure of this region. The frequency modes of measured scarp heights correspond with previous general thickness estimates of the heavily cratered and ridged plains units. The depths of the flat-floored irregular depressions (55-175 m), fretted fractures (85-890 m), and troughs and pits (60-1620 m) are also similar to scarp heights (thicknesses) of the geologic units in which these depressions occur, which suggests that the depths of these flat-floored features were controlled by erosional base levels created by lithologic contacts. Although the features have a similar age, both their depths and their observed local structural control increase in the order listed above, which suggests that the more advanced stages of associated fracturing facilitated the development of these depressions by increasing permeability. If a ground-ice zone is a factor in development of these features, as has been suggested, our observation that the depths of these features decrease with increasing latitude suggests that either the thickness of the ground-ice zone does not increase poleward or the depths of the depressions were controlled by the top of the ground-ice zone whose depth may decrease with latitude. Deeper discontinuities are inferred from fault-intersection depths of 370 simple grabens (assuming 60° dipping faults that initiate at a mechanical discontinuity) in Tempe Terra and Alba Patera and from the depths of the large, flat-floored troughs in Tempe Terra. The frequency distributions of these fault-intersection and large trough depths show a concentration at 1.0-1.6 km depth, similar to data obtained for Syria, Sinai, and Lunae Plana. The consistency of these depth data over such a large region of western Mars suggests that a discontinuity or a process that transcends local and regional geology is responsible for the formation of these features. If this discontinuity is represented by the base of the cryosphere, its uniform depth over 55° of latitude suggests that the cryosphere did not thicken poleward. Alternatively, the concentration of depths at 1.0-1.6 km may represent the upper level of noneruptive dike ascent (lateral dike propagation) of Mars, which is controlled by gravity and atmospheric pressure and magma and country-rock characteristics, and was probably controlled, in part, by ground ice. Fault-intersection depths in the north Tharsis region locally extend down to a depth of 5-7 km. The depth data between 2 and 3 km are attributed to the discontinuity at the interface of megaregolith and basement or to the upper limit of noneruptive dike ascent of magma with a high volatile content. Intersection depths greater than 3 km, which were found at Alba Patera, may be due to the megaregolith-basement discontinuity, which was buried and depressed by volcanic loading, or to the upper level of noneruptive dike ascent of magma with a low volatile content. The near absence of narrow simple grabens with fault-initiation depths less than 0.6-1.0 km in this study area, as well as in most of western Mars, suggests that this depth represents the minimum depth that normal faults can initiate; at shallower depths tension cracks or joints would form instead. This hypothesis is supported by the application of the Griffith failure criterion to this minimum depth of normal fault initiation, which suggests that shallow crustal materials have a tensile strength of 2-4 MPa throughout most of western Mars, in close agreement with previous estimates of tensile strength of martian basaltic rock.

Icarus