Dehalogenation of polybrominated diphenyl ethers and polychlorinated biphenyl by bimetallic, impregnated, and nanoscale zerovalent iron

Nanoscale zerovalent iron particles (nZVI), bimetallic nanoparticles (nZVI/Pd), and nZVI/Pd impregnated activated carbon (nZVI/Pd-AC) composite particles were synthesized and investigated for their effectiveness to remove polybrominated diphenyl ethers (PBDEs) and/or polychlorinated biphenyls (PCBs). Palladization of nZVI promoted the dehalogenation kinetics for mono- to tri-BDEs and 2,3,4-trichlorobiphenyl (PCB 21). Compared to nZVI, the iron-normalized rate constants for nZVI/Pd were about 2-, 3-, and 4-orders of magnitude greater for tri-, di-, and mono-BDEs, respectively, with diphenyl ether as a main reaction product. The reaction kinetics and pathways suggest an H-atom transfer mechanism. The reaction pathways with nZVI/Pd favor preferential removal of para-halogens on PBDEs and PCBs. X-ray fluorescence mapping of nZVI/Pd-AC showed that Pd mainly deposits on the outer part of particles, while Fe was present throughout the activated carbon particles. While BDE 21 was sorbed onto activated carbon composites quickly, debromination was slower compared to reaction with freely dispersed nZVI/Pd. Our XPS and chemical data suggest about 7% of the total iron within the activated carbon was zerovalent, which shows the difficulty with in-situ synthesis of a significant fraction of zerovalent iron in the microporous material. Related factors that likely hinder the reaction with nZVI/Pd-AC are the heterogeneous distribution of nZVI and Pd on activated carbon and/or immobilization of hydrophobic organic contaminants at the adsorption sites thereby inhibiting contact with nZVI.     

Arsenic localization, speciation, and co-occurrence with iron on rice (Oryza sativa L.) roots having variable Fe coatings

Arsenic contamination of rice is widespread, but the rhizosphere processes influencing arsenic attenuation remain unresolved. In particular, the formation of Fe plaque around rice roots is thought to be an important barrier to As uptake, but the relative importance of this mechanism is not well characterized. Here we elucidate the colocalization of As species and Fe on rice roots with variable Fe coatings; we used a combination of techniques--X-ray fluorescence imaging, μXANES, transmission X-ray microscopy, and tomography--for this purpose. Two dominant As species were observed in fine roots-inorganic As(V) and As(III) -with minor amounts of dimethylarsinic acid (DMA) and arsenic trisglutathione (AsGlu(3)). Our investigation shows that variable Fe plaque formation affects As entry into rice roots. In roots with Fe plaque, As and Fe were strongly colocated around the root; however, maximal As and Fe were dissociated and did not encapsulate roots that had minimal Fe plaque. Moreover, As was not exclusively associated with Fe plaque in the rice root system; Fe plaque does not coat many of the young roots or the younger portion of mature roots. Young, fine roots, important for solute uptake, have little to no iron plaque. Thus, Fe plaque does not directly intercept (and hence restrict) As supply to and uptake by rice roots but rather serves as a bulk scavenger of As predominantly near the root base.     

Effects of genotype and transpiration rate on the uptake and accumulation of perchlorate (ClO4-) in lettuce

Although evidence of perchlorate accumulation in plants exists, there is a scarcity of information concerning the key factors and mechanisms involved. To ascertain whether genotypic variation in perchlorate accumulation occurs within lettuce, hydroponic plant uptake experiments were conducted with five types of lettuce (Lactuca sativa L.), which were grown to market size atthree perchlorate (ClO4-) concentrations (1, 5, or 10 microg/L). Perchlorate accumulated in the leafy tissues to varying amounts, ranging from 4 to 192 microg/kg fresh weight (FW), and the ranking of perchlorate accumulation was crisphead > butter head > romaine > red leaf > green leaf. The effect of transpiration rate on perchlorate accumulation was further examined using crisphead, butter head, and green leaf lettuce. By growing lettuce in controlled-environment chambers with two climatic regimes, "cloudy, humid, cool" (80% RH, 18/15 degrees C, 250 micromol/m2s photosynthetic photon flux density (PPFD)) and "sunny, dry, warm" (approximately 50% RH, 28/18 degrees C, 500 micromol/m2s PPFD), up to 2.7-fold differences in transpiration rates were achieved. Across all three genotypes, the plants that transpired more water accumulated more perchlorate on a whole-head basis; however, the effect of transpiration rate on perchlorate accumulation was not as great as expected. Despite 2.0-2.7-fold differences in transpiration rate, there were only 1.2-2.0-fold differences in perchlorate accumulation. In addition to whole-head analysis, plants were sectioned into inner, middle, and outer leaves and processed separately. Overall, the ranking of perchlorate accumulation was outer leaves > middle leaves > inner leaves. Transpiration rate has a clear effect on perchlorate accumulation in lettuce, but other factors are influential and deserve exploration.     

Intramolecular Charge Transfer of 1-Aminoanthraquinone and Ultrafast Solvation Dynamics of Dimethylsulfoxide

The intramolecular charge transfer (ICT) of 1-aminoanthraquinone (AAQ) in the excited state strongly depends on its solvent properties, and the twisted geometry of its amino group has been recommended for the twisted ICT (TICT) state by recent theoretical works. We report the transient Raman spectra of AAQ in a dimethylsulfoxide (DMSO) solution by femtosecond stimulated Raman spectroscopy to provide clear experimental evidence for the TICT state of AAQ. The ultrafast (~110 fs) TICT dynamics of AAQ were observed from the major vibrational modes of AAQ including the ν_C-N + δ_CH and ν_C=O modes. The coherent oscillations in the vibrational bands of AAQ strongly coupled to the nuclear coordinate for the TICT process have been observed, which showed its anharmonic coupling to the low frequency out of the plane deformation modes. The vibrational mode of solvent DMSO, ν_S=O showed a decrease in intensity, especially in the hydrogen-bonded species of DMSO, which clearly shows that the solvation dynamics of DMSO, including hydrogen bonding, are crucial to understanding the reaction dynamics of AAQ with the ultrafast structural changes accompanying the TICT.     

The automation design advisor tool (ADAT): Development and validation of a model‐based tool to support flight deck automation design for nextgen operations

NextGen aviation will require an even greater reliance on automation than current‐day operations. Therefore, systems with problems in human–automation interaction must be identified and resolved early, well before they are introduced into operation. This paper describes a research and software development effort to build a prototype automation design advisor tool (ADAT) for flight deck automation. This tool uses models of human performance to identify perceptual, cognitive, and action‐related inefficiencies in the design of flight management systems. Aviation designers can use the tool to evaluate and compare potential flight deck automation designs and to identify potential human–automation interaction concerns. Designers can compare different flight management systems in terms of specific features and their ability to support pilot performance. ADAT provides specific, research‐based guidance for resolving problematic design issues. It was specifically designed to be flexible enough for both current‐day technologies and revolutionary NextGen designs. © 2012 Wiley Periodicals, Inc.     

Calcium and Heart Failure: How Did We Get Here and Where Are We Going?

The occurrence and prevalence of heart failure remain high in the United States as well as globally. One person dies every 30 s from heart disease. Recognizing the importance of heart failure, clinicians and scientists have sought better therapeutic strategies and even cures for end-stage heart failure. This exploration has resulted in many failed clinical trials testing novel classes of pharmaceutical drugs and even gene therapy. As a result, along the way, there have been paradigm shifts toward and away from differing therapeutic approaches. The continued prevalence of death from heart failure, however, clearly demonstrates that the heart is not simply a pump and instead forces us to consider the complexity of simplicity in the pathophysiology of heart failure and reinforces the need to discover new therapeutic approaches.     

Perchlorate in groundwater: a synoptic survey of "pristine" sites in the coterminous United States

Perchlorate is widely used as an oxidant in solid rocket propellants and energetic applications, and it has frequently been detected in groundwaters at concentrations relevant to human health. The possibility of naturally occurring perchlorate has only recently received significant attention. Relying primarily on domestic, agricultural, and recreational wells, we utilized a network of volunteers to help collect 326 groundwater samples from across the coterminous United States. Care was taken to avoid known, USEPA-documented sites of perchlorate use or release, as well as perchlorate contamination due to disinfection using hypochlorite. Using IC-ESI-MS and a Cl18O4- internal standard, we achieved a method detection limit (MDL) of 40 ng/L perchlorate and a minimum reporting level (MRL) of 120 ng/L. Of the 326 samples, 147 (45%) were below the MDL, while 42 (13%) were between the MDL and the MRL. Of the 137 samples that could be quantified, most (109) contained < 1000 ng/L perchlorate; the remaining 28 samples contained from 1000 to 10400 ng/L. Our results support the notion that perchlorate occurs naturally in many groundwaters, but the unusually high concentrations (> 10000 ng/L) previously reported for the west-central Texas area appear to be anomalous. Perchlorate concentrations were positively correlated with nitrate levels (P < 0.001) but not with chloride concentrations. Opportunities exist for follow-up studies of perchlorate's origins using isotope forensics and for further elucidation of the role of atmospheric processes in the formation or transport of perchlorate.     

On stochastic gradient and subgradient methods with adaptive steplength sequences

Traditionally, stochastic approximation (SA) schemes have been popular choices for solving stochastic optimization problems. However, the performance of standard SA implementations can vary significantly based on the choice of the steplength sequence, and in general, little guidance is provided about good choices. Motivated by this gap, we present two adaptive steplength schemes for strongly convex differentiable stochastic optimization problems, equipped with convergence theory, that aim to overcome some of the reliance on user-specific parameters. The first scheme, referred to as a recursive steplength stochastic approximation (RSA) scheme, optimizes the error bounds to derive a rule that expresses the steplength at a given iteration as a simple function of the steplength at the previous iteration and certain problem parameters. The second scheme, termed as a cascading steplength stochastic approximation (CSA) scheme, maintains the steplength sequence as a piecewise-constant decreasing function with the reduction in the steplength occurring when a suitable error threshold is met. Then, we allow for nondifferentiable objectives but with bounded subgradients over a certain domain. In such a regime, we propose a local smoothing technique, based on random local perturbations of the objective function, that leads to a differentiable approximation of the function. Assuming a uniform distribution on the local randomness, we establish a Lipschitzian property for the gradient of the approximation and prove that the obtained Lipschitz bound grows at a modest rate with problem size. This facilitates the development of an adaptive steplength stochastic approximation framework, which now requires sampling in the product space of the original measure and the artificially introduced distribution.     

Immobilization of Hg(II) in water with polysulfide-rubber (PSR) polymer-coated activated carbon

An effective mercury removal method using polymer-coated activated carbon was studied for possible use in water treatment. In order to increase the affinity of activated carbon for mercury, a sulfur-rich compound, polysulfide-rubber (PSR) polymer, was effectively coated onto the activated carbon. The polymer was synthesized by condensation polymerization between sodium tetrasulfide and 1,2-dichloroethane in water. PSR-mercury interactions and Hg-S bonding were elucidated from x-ray photoelectron spectroscopy, and Fourier transform infra-red spectroscopy analyses. The sulfur loading levels were controlled by the polymer dose during the coating process and the total surface area of the activated carbon was maintained for the sulfur loading less than 2 wt%. Sorption kinetic studies showed that PSR-coated activated carbon facilitates fast reaction by providing a greater reactive surface area than PSR alone. High sulfur loading on activated carbon enhanced mercury adsorption contributing to a three orders of magnitude reduction in mercury concentration. μ-X-ray absorption near edge spectroscopic analyses of the mercury bound to activated carbon and to PSR on activated carbon suggests the chemical bond with mercury on the surface is a combination of Hg-Cl and Hg-S interaction. The pH effect on mercury removal and adsorption isotherm results indicate competition between protons and mercury for binding to sulfur at low pH.     

Navigation in desktop virtual environments: an evaluation and recommendations for supporting usability

Virtual reality (VR) can provide useful tools for a variety of applications. However, for these tools to be effective, they must be easy to use. In virtual environments (VEs), usability is impaired by poorly designed navigation systems. Insufficient realism and missing physiological orientation and motion cues impair spatial learning in desktop VEs. Capabilities for navigation in a VE are far more varied than in reality; so much greater flexibility can be offered, but designing VEs with too many options can overwhelm users. To assist designers in building effective, usable navigation systems for VEs, navigation techniques must be evaluated to identify which features actually support users in accomplishing their tasks and which features create unnecessary problems.This study evaluates navigation in two different VEs to develop recommendations for the design of navigation systems in desktop VEs. The study consists of an objective assessment of navigation control dynamics, a guideline-based evaluation and a review of data collected during two experimental studies. The findings indicate that real-world constraints, specialised navigation techniques and feedback regarding location and direction of travel are needed to support navigation in desktop VEs.