Changes in the hydro-climatic regime of the Hunza Basin in the Upper Indus under CMIP6 climate change projections.

The Upper Indus Basin (UIB) heavily depends on its frozen water resources, and an accelerated melt due to the projected climate change may significantly alter future water availability. The future hydro-climatic regime and water availability of the Hunza basin (a sub-basin of UIB) were analysed using the newly released Coupled Model Intercomparison Project Phase 6 (CMIP6) climate projections. A data and parameter parsimonious precipitation-runoff model, the Distance Distribution Dynamics (DDD) model, was used with energy balance-based subroutines for snowmelt, glacier melt and evapotranspiration. The DDD model was set up for baseline (1991-2010), mid-century (2041-2060) and end-century (2081-2100) climates projections from two global circulation models (GCM), namely EC-Earth3 and MPI-ESM. The projections indicate a substantial increase in temperature (1.1-8.6 °C) and precipitation (12-32%) throughout the twenty-first century. The simulations show the future flow increase between 23-126% and the future glacier melt increase between 30-265%, depending on the scenarios and GCMs used. Moreover, the simulations suggest an increasing glacier melt contribution from all elevations with a significant increase from the higher elevations. The findings provide a basis for planning and modifying reservoir operation strategies with respect to hydropower generation, irrigation withdrawals, flood control, and drought management.

Simulating the hydrological regime of the snow fed and glaciarised Gilgit Basin in the Upper Indus using global precipitation products and a data parsimonious precipitation-runoff model.

In many high altitude river basins, the hydro-climatic regimes and the spatial and temporal distribution of precipitation are little known, complicating efforts to quantify current and future water availability. Scarce, or non-existent, gauged observations at high altitudes coupled with complex weather systems and orographic effects further prevent a realistic and comprehensive assessment of precipitation. Quantifying the contribution from seasonal snow and glacier melt to the river runoff for a high altitude, melt dependent region is especially difficult. Global scale precipitation products, in combination with precipitation-runoff modelling may provide insights to the hydro-climatic regimes for such data scarce regions. In this study two global precipitation products; the high resolution (0.1°â€¯× 0.1°), newly developed ERA5-Land, and a coarser resolution (0.55°â€¯× 0.55°) JRA-55, are used to simulate snow/glacier melts and runoff for the Gilgit Basin, a sub-basin of the Indus. A hydrological precipitation-runoff model, the Distance Distribution Dynamics (DDD), requires minimum input data and was developed for snow dominated catchments. The mean of total annual precipitation from 1995 to 2010 data was estimated at 888 mm and 951 mm by ERA5-Land and JRA-55, respectively. The daily runoff simulation obtained a Kling Gupta efficiency (KGE) of 0.78 and 0.72 with ERA5-Land and JRA-55 based simulations, respectively. The simulated snow cover area (SCA) was validated using MODIS SCA and the results are quite promising on daily, monthly and annual scales. Our result showed an overall contribution to the river flow as about 26% from rainfall, 37-38% from snow melt, 31% from glacier melt and 5% from soil moisture. These melt simulations are in good agreement with the overall hydro-climatic regimes and seasonality of the area. The proxy energy balance approach in the DDD model, used to estimate snow melt and evapotranspiration, showed robust behaviour and potential for being employed in data poor basins.

Bending the Curve of Global Freshwater Biodiversity Loss: An Emergency Recovery Plan.

Despite their limited spatial extent, freshwater ecosystems host remarkable biodiversity, including one-third of all vertebrate species. This biodiversity is declining dramatically: Globally, wetlands are vanishing three times faster than forests, and freshwater vertebrate populations have fallen more than twice as steeply as terrestrial or marine populations. Threats to freshwater biodiversity are well documented but coordinated action to reverse the decline is lacking. We present an Emergency Recovery Plan to bend the curve of freshwater biodiversity loss. Priority actions include accelerating implementation of environmental flows; improving water quality; protecting and restoring critical habitats; managing the exploitation of freshwater ecosystem resources, especially species and riverine aggregates; preventing and controlling nonnative species invasions; and safeguarding and restoring river connectivity. We recommend adjustments to targets and indicators for the Convention on Biological Diversity and the Sustainable Development Goals and roles for national and international state and nonstate actors.

Scapular Osteochondroma in a Skeletally Mature Man.

A 27-year-old man was referred to physical therapy by his primary care physician for chronic, intermittent right shoulder girdle pain. Radiographs of the shoulder were noncontributory. Examination revealed a nontender, firm mass, due to which the patient was referred back to his physician for further diagnostic testing, including scapular radiographs. Radiographs of the scapula demonstrated an osseous lesion projecting from the ventral inferior scapula. J Orthop Sports Phys Ther 2020;50(3):168. doi:10.2519/jospt.2020.9325.

Ligand-Dependent Colloidal Stability Controls the Growth of Aluminum Nanocrystals.

The precise size- and shape-controlled synthesis of monodisperse Al nanocrystals remains an open challenge, limiting their utility for numerous applications that would take advantage of their size and shape-dependent optical properties. Here we pursue a molecular-level understanding of the formation of Al nanocrystals by titanium(IV) isopropoxide-catalyzed decomposition of AlH3 in Lewis base solvents. As determined by electron paramagnetic resonance spectroscopy of intermediates, the reaction begins with the formation of Ti3+-AlH3 complexes. Proton nuclear magnetic resonance spectroscopy indicates isopropoxy ligands are removed from Ti by Al, producing aluminum(III) isopropoxide and low-valent Ti3+ catalysts. These Ti3+ species catalyze elimination of H2 from AlH3 inducing the polymerization of AlH3 into colloidally unstable low-valent aluminum hydride clusters. These clusters coalesce and grow while expelling H2 to form colloidally stable Al nanocrystals. The colloidal stability of the Al nanocrystals and their size is determined by the molecular structure and density of coordinating atoms in the reaction, which is controlled by choice of solvent composition.

Aluminum Nanocrystals: A Sustainable Substrate for Quantitative SERS-Based DNA Detection.

Since its discovery in the 1970s, surface-enhanced Raman scattering (SERS) has been primarily associated with substrates composed of nanostructured noble metals. Here we investigate chemically synthesized nanocrystal aggregates of aluminum, an inexpensive, highly abundant, and sustainable metal, as SERS substrates. Al nanocrystal aggregates are capable of substantial near-infrared SERS enhancements, similar to Au nanoparticles. The intrinsic nanoscale surface oxide of Al nanocrystals supports molecule-substrate interactions that differ dramatically from noble metal substrates. The preferential affinity of the single-stranded DNA (ssDNA) phosphate backbone for the Al oxide surface preserves both the spectral features and nucleic acid cross sections relative to conventional Raman spectroscopy, enabling quantitative ssDNA detection and analysis.

Plasmon-induced selective carbon dioxide conversion on earth-abundant aluminum-cuprous oxide antenna-reactor nanoparticles.

The rational combination of plasmonic nanoantennas with active transition metal-based catalysts, known as 'antenna-reactor' nanostructures, holds promise to expand the scope of chemical reactions possible with plasmonic photocatalysis. Here, we report earth-abundant embedded aluminum in cuprous oxide antenna-reactor heterostructures that operate more effectively and selectively for the reverse water-gas shift reaction under milder illumination than in conventional thermal conditions. Through rigorous comparison of the spatial temperature profile, optical absorption, and integrated electric field enhancement of the catalyst, we have been able to distinguish between competing photothermal and hot-carrier driven mechanistic pathways. The antenna-reactor geometry efficiently harnesses the plasmon resonance of aluminum to supply energetic hot-carriers and increases optical absorption in cuprous oxide for selective carbon dioxide conversion to carbon monoxide with visible light. The transition from noble metals to aluminum based antenna-reactor heterostructures in plasmonic photocatalysis provides a sustainable route to high-value chemicals and reaffirms the practical potential of plasmon-mediated chemical transformations.Plasmon-enhanced photocatalysis holds promise for the control of chemical reactions. Here the authors report an Al@Cu2O heterostructure based on earth abundant materials to transform CO2 into CO at significantly milder conditions.

Walking the Walk: A Giant Step toward Sustainable Plasmonics.

The use of earth-abundant materials is at the frontier of nanoplasmonics research, where their availability and low cost can enable practical mainstream applications and commercial viability. Aluminum is of specific interest in this regard, due to its ability to support plasmon resonances throughout the ultraviolet (UV), visible, and infrared regions of the spectrum. However, the lack of accurate dielectric data has critically limited the agreement between theoretical predictions and experimental measurements of the optical properties of Al nanostructures compared, for example, to the agreement enjoyed by the noble/coinage metals. As reported in this issue of ACS Nano, efforts by Cheng et al. to determine the dielectric function of pristine Al show that Al has substantially lower loss than was indicated by previously reported dielectric data for Al, including a 2-fold lower loss for the UV region compared to that in previous studies. These results provide data that are essential for accurate agreement between theory and experiment for Al plasmonic nanostructures, placing this earth-abundant metal on sound footing as a new and highly promising material for sustainable plasmonics by design.

Al-Pd Nanodisk Heterodimers as Antenna-Reactor Photocatalysts.

Photocatalysis uses light energy to drive chemical reactions. Conventional industrial catalysts are made of transition metal nanoparticles that interact only weakly with light, while metals such as Au, Ag, and Al that support surface plasmons interact strongly with light but are poor catalysts. By combining plasmonic and catalytic metal nanoparticles, the plasmonic "antenna" can couple light into the catalytic "reactor". This interaction induces an optical polarization in the reactor nanoparticle, forcing a plasmonic response. When this "forced plasmon" decays it can generate hot carriers, converting the catalyst into a photocatalyst. Here we show that precisely oriented, strongly coupled Al-Pd nanodisk heterodimers fabricated using nanoscale lithography can function as directional antenna-reactor photocatalyst complexes. The light-induced hydrogen dissociation rate on these structures is strongly dependent upon the polarization angle of the incident light with respect to the orientation of the antenna-reactor pair. Their high degree of structural precision allows us to microscopically quantify the photocatalytic activity per heterostructure, providing precise photocatalytic quantum efficiencies. This is the first example of precisely designed heterometallic nanostructure complexes for plasmon-enabled photocatalysis and paves the way for high-efficiency plasmonic photocatalysts by modular design.

Heterometallic antenna-reactor complexes for photocatalysis.

Metallic nanoparticles with strong optically resonant properties behave as nanoscale optical antennas, and have recently shown extraordinary promise as light-driven catalysts. Traditionally, however, heterogeneous catalysis has relied upon weakly light-absorbing metals such as Pd, Pt, Ru, or Rh to lower the activation energy for chemical reactions. Here we show that coupling a plasmonic nanoantenna directly to catalytic nanoparticles enables the light-induced generation of hot carriers within the catalyst nanoparticles, transforming the entire complex into an efficient light-controlled reactive catalyst. In Pd-decorated Al nanocrystals, photocatalytic hydrogen desorption closely follows the antenna-induced local absorption cross-section of the Pd islands, and a supralinear power dependence strongly suggests that hot-carrier-induced desorption occurs at the Pd island surface. When acetylene is present along with hydrogen, the selectivity for photocatalytic ethylene production relative to ethane is strongly enhanced, approaching 40:1. These observations indicate that antenna-reactor complexes may greatly expand possibilities for developing designer photocatalytic substrates.

Aluminum Nanocrystals as a Plasmonic Photocatalyst for Hydrogen Dissociation.

Hydrogen dissociation is a critical step in many hydrogenation reactions central to industrial chemical production and pollutant removal. This step typically utilizes the favorable band structure of precious metal catalysts like platinum and palladium to achieve high efficiency under mild conditions. Here we demonstrate that aluminum nanocrystals (Al NCs), when illuminated, can be used as a photocatalyst for hydrogen dissociation at room temperature and atmospheric pressure, despite the high activation barrier toward hydrogen adsorption and dissociation. We show that hot electron transfer from Al NCs to the antibonding orbitals of hydrogen molecules facilitates their dissociation. Hot electrons generated from surface plasmon decay and from direct photoexcitation of the interband transitions of Al both contribute to this process. Our results pave the way for the use of aluminum, an earth-abundant, nonprecious metal, for photocatalysis.

Pronounced Linewidth Narrowing of an Aluminum Nanoparticle Plasmon Resonance by Interaction with an Aluminum Metallic Film.

Aluminum nanocrystals and fabricated nanostructures are emerging as highly promising building blocks for plasmonics in the visible region of the spectrum. Even at the individual nanocrystal level, however, the localized plasmons supported by Al nanostructures possess a surprisingly broad spectral response. We have observed that when an Al nanocrystal is coupled to an underlying Al film, its dipolar plasmon resonance linewidth narrows remarkably and shows an enhanced scattering efficiency. This behavior is observable in other plasmonic metals, such as gold; however, it is far more dramatic in the aluminum nanoparticle-film system, reducing the dipolar plasmon linewidth by more than half. A substrate-mediated hybridization of the dipolar and quadrupolar plasmons of the nanoparticle reduces the radiative losses of the dipolar plasmon. While this is a general effect that applies to all metallic nanoparticle-film systems, this finding specifically provides a new mechanism for narrowing plasmon resonances in aluminum-based systems, quite possibly expanding the potential of Al-based plasmonics in real-world applications.

Molecular Plasmonics.

Graphene supports surface plasmons that have been observed to be both electrically and geometrically tunable in the mid- to far-infrared spectral regions. In particular, it has been demonstrated that graphene plasmons can be tuned across a wide spectral range spanning from the mid-infrared to the terahertz. The identification of a general class of plasmonic excitations in systems containing only a few dozen atoms permits us to extend this versatility into the visible and ultraviolet. As appealing as this extension might be for active nanoscale manipulation of visible light, its realization constitutes a formidable technical challenge. We experimentally demonstrate the existence of molecular plasmon resonances in the visible for ionized polycyclic aromatic hydrocarbons (PAHs), which we reversibly switch by adding, then removing, a single electron from the molecule. The charged PAHs display intense absorption in the visible regime with electrical and geometrical tunability analogous to the plasmonic resonances of much larger nanographene systems. Finally, we also use the switchable molecular plasmon in anthracene to demonstrate a proof-of-concept low-voltage electrochromic device.

Distinguishing between plasmon-induced and photoexcited carriers in a device geometry.

The use of surface plasmons, charge density oscillations of conduction electrons of metallic nanostructures, to boost the efficiency of light-harvesting devices through increased light-matter interactions could drastically alter how sunlight is converted into electricity or fuels. These excitations can decay directly into energetic electron-hole pairs, useful for photocurrent generation or photocatalysis. However, the mechanisms behind plasmonic carrier generation remain poorly understood. Here we use nanowire-based hot-carrier devices on a wide-bandgap semiconductor to show that plasmonic carrier generation is proportional to internal field-intensity enhancement and occurs independently of bulk absorption. We also show that plasmon-induced hot electrons have higher energies than carriers generated by direct excitation and that reducing the barrier height allows for the collection of carriers from plasmons and direct photoexcitation. Our results provide a route to increasing the efficiency of plasmonic hot-carrier devices, which could lead to more efficient devices for converting sunlight into usable energy.

Aluminum nanocrystals.

We demonstrate the facile synthesis of high purity aluminum nanocrystals over a range of controlled sizes from 70 to 220 nm diameter with size control achieved through a simple modification of solvent ratios in the reaction solution. The monodisperse, icosahedral, and trigonal bipyramidal nanocrystals are air-stable for weeks, due to the formation of a 2-4 nm thick passivating oxide layer on their surfaces. We show that the nanocrystals support size-dependent ultraviolet and visible plasmon modes, providing a far more sustainable alternative to gold and silver nanoparticles currently in widespread use.

Temperature-controlled optical stimulation of the rat prostate cavernous nerves.

Optical nerve stimulation (ONS) may be useful as a diagnostic tool for intraoperative identification and preservation of the prostate cavernous nerves (CN), responsible for erectile function, during prostate cancer surgery. Successful ONS requires elevating the nerve temperature to within a narrow range (~42 to 47°C) for nerve activation without thermal damage to the nerve. This preliminary study explores a prototype temperature-controlled optical nerve stimulation (TC-ONS) system for maintaining a constant (±1°C) nerve temperature during short-term ONS of the rat prostate CNs. A 150-mW, 1455-nm diode laser was operated in continuous-wave mode, with and without temperature control, during stimulation of the rat CNs for 15 to 30 s through a fiber optic probe with a 1-mm-diameter spot. A microcontroller opened and closed an in-line mechanical shutter in response to an infrared sensor, with a predetermined temperature set point. With TC-ONS, higher laser power settings were used to rapidly and safely elevate the CNs to a temperature necessary for a fast intracavernous pressure response, while also preventing excessive temperatures that would otherwise cause thermal damage to the nerve. With further development, TC-ONS may provide a rapid, stable, and safe method for intraoperative identification and preservation of the prostate CNs.

Balancing water resources development and environmental sustainability in Africa: a review of recent research findings and applications.

Sustainable development in Africa is dependent on increasing use of the continent's water resources without significantly degrading ecosystem services that are also fundamental to human wellbeing. This is particularly challenging in Africa because of high spatial and temporal variability in the availability of water resources and limited amounts of total water availability across expansive semi-arid portions of the continent. The challenge is compounded by ambitious targets for increased water use and a rush of international funding to finance development activities. Balancing development with environmental sustainability requires (i) understanding the boundary conditions imposed by the continent's climate and hydrology today and into the future, (ii) estimating the magnitude and spatial distribution of water use needed to meet development goals, and (iii) understanding the environmental water requirements of affected ecosystems, their current status and potential consequences of increased water use. This article reviews recent advancements in each of these topics and highlights innovative approaches and tools available to support sustainable development. While much remains to be learned, scientific understanding and technology should not be viewed as impediments to sustainable development on the continent.

Methyl tertiary-butyl ether mode of action for cancer endpoints in rodents.

There are no reports of studies that evaluate if methyl tertiary-butyl ether (MTBE) exposure causes cancer in humans. This evaluation of MTBE carcinogenicity is based on the results of animal studies. A weak tumorigenic response was reported for both MTBE and TBA in one tumor type (kidney) in male rats, for MTBE in one other tumor type (testicular) in male rats, for MTBE in one tumor type (liver) in female mice, and for TBA in one tumor type (thyroid) in female mice. The weight of the evidence does not support a genotoxic mode of action (MOA). Non-genotoxic MOAs have been demonstrated or suggested that correspond to the weak tumorigenic responses. These MOAs either do not occur in humans or humans are much less susceptible to these effects. It is, therefore, unlikely that humans would be exposed to sufficient levels of MTBE to cause these tumorigenic responses.

Wetland Restoration Response Analysis using MODIS and Groundwater Data.

Vegetation cover and groundwater level changes over the period of restorationare the two most important indicators of the level of success in wetland ecohydrologicalrestoration. As a result of the regular presence of water and dense vegetation, the highestevapotranspiration (latent heat) rates usually occur within wetlands. Vegetation cover andevapotranspiration of large areas of restoration like that of Kissimmee River basin, SouthFlorida will be best estimated using remote sensing technique than point measurements.Kissimmee River basin has been the area of ecological restoration for some years. Thecurrent ecohydrological restoration activities were evaluated through fractional vegetationcover (FVC) changes and latent heat flux using Moderate Resolution ImagingSpectroradiometer (MODIS) data. Groundwater level data were also analyzed for selectedeight groundwater monitoring wells in the basin. Results have shown that the averagefractional vegetation cover and latent heat along 10 km buffer of Kissimmee River betweenLake Kissimmee and Lake Okeechobee was higher in 2004 than in 2000. It is evident thatover the 5-year period of time, vegetated and areas covered with wetlands have increasedsignificantly especially along the restoration corridor. Analysis of groundwater level data(2000-2004) from eight monitoring wells showed that, the average monthly level ofgroundwater was increased by 20 cm and 34 cm between 2000 and 2004, and 2000 and2003, respectively. This change was more evident for wells along the river.

Socioeconomic drivers of deforestation in the Northern Ecuadorian Amazon.

Investigations of land use/land cover (LULC) change and forest management are limited by a lack of understanding of how socioeconomic factors affect land use. This lack also constrains the predictions of future deforestation, which is especially important in the Amazon basin, where large tracts of natural forest are being converted to managed uses. Research presented in this article was conducted to address this lack of understanding. Its objectives are (a) to quantify deforestation in the Northern Ecuadorian Amazon (NEA) during the periods 1986-1996 and 1996-2002; and (b) to determine the significance and magnitude of the effects of socioeconomic factors on deforestation rates at both the parroquia (parish) and finca (farm) levels. Annual deforestation rates were quantified via satellite image processing and geographic information systems. Linear spatial lag regression analyses were then used to explore relationships between socioeconomic factors and deforestation. Socioeconomic factors were obtained, at the finca level, from a detailed household survey carried out in 1990 and 1999, and at the parroquia level from data in the 1990 and 2001 Ecuadorian censuses of population. We found that the average annual deforestation rate was 2.5% and 1.8%/year for 1986-1996 and 1996-2002, respectively. At the parroquia level, variables representing demographic factors (i.e., population density) and accessibility factors (i.e., road density), among others, were found to be significantly related to deforestation. At the farm level, the factors related to deforestation were household size, distance by road to main cities, education, and hired labor. The findings of this research demonstrate both the severity of deforestation in the Northern Ecuadorian Amazon and the array of factors affecting deforestation in the tropics.