Temperature effects on non-bridging oxygen and aluminum coordination number in calcium aluminosilicate glasses and melts

Configurational changes with temperature are important for the thermodynamic and transport properties of most aluminosilicate melts, but in general are not well understood. Here, we present high-resolution ²⁷Al and ¹⁷O NMR data on several calcium aluminosilicate glasses prepared with varying quench rates and thus with fictive temperatures that span ranges up to about 200 K. In all compositions the content of five-coordinated aluminum increases with fictive temperature, in agreement with recent high temperature NMR data on melts. In a glass of CaAl₂Si₂O₈ (“anorthite”) composition, the content of non-bridging oxygens also increases with temperature; however this effect was not observed in a sample with a much higher CaO/Al₂O₃ ratio. We present a consistent notation for reactions among structural species in these systems that clarify why in some cases, high-coordinated network cations may appear on the same side of the reaction, while in others they occur on the opposite sides: the key difference is in accounting for all coordination changes for oxygens. Mixing of non-bridging oxygens and of high-coordinated aluminum make significant contributions to the overall configurational entropy and heat capacity of the melts, as does the mixing of various bridging oxygens and of tetrahedral network cations. Other, less well known, types of increase in disorder with temperature may be important as well.     

Imaging of Buried Archaeological Materials: The Reflection Properties of Archaeological Wood

Effective marine archaeological site management demands detailed information on not only the spatial distribution of artefacts but also the degradation state of the materials present. Although sonar methods have frequently been used in an attempt to detect buried wooden shipwrecks they are currently unable to indicate their degradation state. To assess the sensitivity of acoustic measurements to changes in the degradation state of such material, and hence the potential for sonars to quantify degradation, laboratory measurements of compressional wave velocity, as well as bulk density for oak and pine samples, in varying states of decay, were undertaken. These data enabled the calculation of theoretical reflection coefficients for such materials buried in various marine sediments. As wood degrades, the reflection coefficients become more negative, resulting in the hypothesis that the more degraded wood becomes, the easier it should be to detect. Typical reflection coefficients of the order of −0.43 and −0.52 for the most degraded oak and pine samples in sand are predicted. Conversely, for wood exposed to seawater the predicted reflection coefficients are large and positive for undegraded material (0.35 for oak, 0.18 for pine) and decrease to zero or slightly below for the most degraded samples. This indicates that exposed timbers, when heavily degraded, can be acoustically transparent and so undetectable by acoustic methods. Corroboration of these experimental results was provided through comparison with high resolution seismic reflection data that has been acquired over two shipwrecks.     

Design of a 3D Chirp Sub-bottom Imaging System

Chirp sub-bottom profilers are marine acoustic devices that use a known and repeatable source signature (1–24 kHz) to produce decimetre vertical resolution cross-sections of the sub-seabed. Here the design and development of the first true 3D Chirp system is described. When developing the design, critical factors that had to be considered included spatial aliasing, and precise positioning of sources and receivers. Full 3D numerical modelling of the combined source and receiver directivity was completed to determine optimal source and receiver geometries. The design incorporates four source transducers (1.5–13 kHz) that can be arranged into different configurations, including Maltese Cross, a square and two separated pairs. The receive array comprises 240 hydrophones in 60 groups whose group-centres are separated by 25 cm in both horizontal directions, with each hydrophone group containing four individual elements and a pre-amplifier. After careful consideration, it was concluded that the only way to determine with sufficient accuracy the source–receiver geometry, was to fix the sources and receivers within a rigid array. Positional information for the array is given by a Real Time Kinematic GPS and attitude system incorporating four antennas to give position, heading, pitch and roll. It is shown that this system offers vertical positioning accuracy with a root-mean-square (rms) error less than 2.6 cm, while the horizontal positioning rms error was less than 2.0 cm. The system is configured so that the Chirp source signature can be chosen by software aboard the acquisition vessel. The complete system is described and initial navigational and seismic data results are presented. These data demonstrate that the approach of using fixed source-receiver geometry combined with RTK navigation can provide complete 3D imaging of the sub-surface.     

Characterizing and classifying urban watersheds with compositional and structural attributes

Current land-use classifications used to assess urbanization effects on stream water quality date back to the 1980s when limited information was available to characterize watershed attributes that mediate non-point source pollution. With high resolution remote sensing and widely used GIS tools, there has been a vast increase in the availability and precision of geospatial data of built environments. In this study, we leverage geospatial data to expand the characterization of developed landscapes and create a typology that allows us to better understand the impact of complex developed landscapes across the rural to urban gradient. We assess the ability of the developed landscape typology to reveal patterns in stream water chemistry previously undetected by traditional land-cover based classification. We examine the distribution of land-cover, infrastructure, topography and geology across 3876 National Hydrography Dataset Plus catchments in the Piedmont region of North Carolina, USA. From this dataset, we generate metrics to evaluate the abundance, density and position of landscape features relative to streams, catchment outlets and topographic wetness metrics. While impervious surfaces are a key distinguishing feature of the urban landscape, sanitary infrastructure, population density and geology are better predictors of baseflow stream water chemistry. Unsupervised clustering was used to generate a distinct developed landscape typology based on the expanded, high-resolution landscape feature information. Using stream chemistry data from 37 developed headwater catchments, we compared the baseflow water chemistry grouped by traditional land-cover based classes of urbanization (rural, low, medium and high density) to our composition and structure-based classification (a nine-class typology). The typology based on 22 metrics of developed landscape composition and structure explained over 50% of the variation in NO₃⁻-N, TDN, DOC, Cl⁻, and Br⁻ concentration, while the ISC-based classification only significantly explained 23% of the variation in TDN. These results demonstrate the importance of infrastructure, population and geology in defining developed landscapes and improving discrete classes for water management.     

New Modes of Environmental Governance in Greater Sage-Grouse Conservation in Oregon

Abstract

Natural resource challenges often span administrative jurisdictions and include actors and processes operating at different spatial and political scales. We applied concepts of new environmental governance to analyze Oregon’s approach to greater sage-grouse conservation. Through one in-depth case study in Lake County, we traced features of new environmental governance (cross-scale interactions, decentralization, and capacities of actors) through different governance levels. Interviews and qualitative analysis revealed that decentralization of administrative functions facilitated cross-scale interactions and relied on intermediaries, gap-filling, and perceptions of legitimacy at lower levels. State and agency guidelines steered the effort and were accompanied by financial and technical resources from multiple arenas, which increased local capacity. This study adds to the understandings of environmental governance for implementing multi-actor, multi-level conservation arrangements in resource-dependent communities. Further exploration of connections between higher levels and local contexts will reveal important, new ways to link policies with on-the-ground outcomes.     

Engagement in the Third U.S. National Climate Assessment: commitment,capacity, and communication for impact

This paper examines the dynamics of energy investments and clean energy Research and Development (R&D) using a scenario-based modeling approach. Starting from the global scenarios proposed in the RoSE model ensemble experiment, we analyze the dynamics of investments under different assumptions regarding economic and population growth as well as availability of fossil fuel resources, in the absence of a climate policy. Our analysis indicates that economic growth and the speed of income convergence across countries matters for improvements in energy efficiency, both via dedicated R&D investments but mostly through capital-energy substitution. In contrast, fossil fuel prices, by changing the relative competitiveness of energy sources, create an economic opportunity for radical innovation in the energy sector. Indeed, our results suggest that fossil fuel availability is the key driver of investments in low carbon energy innovation. However, this innovation, by itself, is not sufficient to induce emission reductions compatible with climate stabilization objectives.     

Tide-Induced Variations in the Fatty Acid Composition of Estuarine Particulate Organic Matter

The particulate organic matter (POM) in hydrodynamically variable habitats such as the lower reaches of estuaries can change in its content and quality on very short time scales (example, hourly), and these changes can potentially influence higher-level consumers in river-estuary-marine systems. Estuarine water samples were collected hourly for 12 h downstream in a small river to evaluate the fatty acid composition of POM over a tidal cycle. Fatty acid constituents of POM collected during the flood tide were dominated by the saturated, higher plant and bacterial fatty acids, whereas unsaturated, polyunsaturated, essential, and diatom-associated fatty acids dominated the POM collected during the ebb tide. Elevated algal biomass (as indicated by high chlorophyll a concentrations), diatom, and freshness indices in the POM indicated enhanced fresh autochthonous-origin materials that dominated the mixed organic pool during the ebb tide compared to more degraded detritus during the flood tide. Tidal retention of organic matter and algal primary production were the most influential factors that differentiated the fatty acid composition of estuarine POM over the short time scale. The results of this study have important implications on the quality of POM at the time of sampling, especially in estuaries where mixed organic pools have multiple inputs and are strongly influenced by tidal cycles.     

An analysis of failure mechanism constraints on pre-failure rock block deformation using TLS and roto-translation methods

Rockfall hazards increase the risk of train derailment along railway corridors in western Canada. In this study, repeated terrestrial laser scanning (TLS) datasets were collected every 2–3 months at three different sites along the Thompson and Fraser River corridors in British Columbia, referred to as the Goldpan, White Canyon, and Mile 109 sites. A total of 207 rockfall events occurring across all three sites between November 11, 2014 and October 18, 2016 were recorded in a database. For each of these rockfalls, pre-failure deformation was measured using a method of three-dimensional roto-translation block tracking. Each rockfall was classified by its deformation behaviour and further categorised based on failure mechanism, volume, lithology, and the roughness condition of the failure plane. Results reveal that detectable levels of deformation were measured in 33% of the total number of rockfall events using the present methods. Rotation deformation was most commonly observed in toppling failures with relatively steep joint orientations. Conversely, planar sliding blocks generally exhibited the least measurable deformation, with the majority not showing any precursory translation or rotation. It is postulated that overhanging rockfall configurations may suppress the expression of deformation in rockfall source blocks, though additional research is required to confirm this.