Rethinking heart failure: patient classification and treatment.

INTRODUCTION: Approaches to treating heart failure (HF), understanding of the most timely and effective interventions, and identification of appropriate patient subpopulations must evolve. HF has emerged as a chronic condition that needs to be managed on multiple fronts. Hospital resources are more limited than ever due to various factors that directly impact staff and hospital space available to manage and treat patients with HF. As a result, there is increasing attention to the current state of this progressive disease and ways to improve patient outcomes. PURPOSE: This paper examines HF and the current and future treatment landscape, the need to reevaluate terms and definitions, and the opportunity to treat HF with the right treatment at the right time. Treatments in development and potential new investigational therapies are also discussed. CONCLUSION: To meet the current challenge, HF treatment must adapt. For other disease states, we have more personalized, nimble, and timely treatment strategies that harness windows of opportunity to help maximize outcomes and reduce overwhelming costs to the health care system. HF treatment is evolving with new guidelines and treatments that hold the promise of greater personalization through additions to existing treatments that are directed by medical guidelines, since each patient is unique and requires more than a one-size-fits-all approach. In addition, advances in remote monitoring, in-home care, and telemedicine are creating a more individualized treatment approach. Therefore, it becomes critical for all health care decision makers to be aware of the tools and resources available in treatment guidelines, individualized treatment options, telemedicine, and other ways of expanding the existing toolbox to enhance patient centricity in HF treatment.

Trace Impurities Identified as Forensic Signatures in CMX-5 Fuel Pellets Using X-ray Spectroscopic Techniques.

Small-particle analysis is a highly promising emerging forensic tool for analysis of interdicted special nuclear materials. Integration of microstructural, morphological, compositional, and molecular impurity signatures could provide significant advancements in forensic capabilities. We have applied rapid, high-sensitivity, hard X-ray synchrotron chemical imaging to analyze impurity signatures in two differently fabricated fuel pellets from the 5th Collaborative Materials Exercise (CMX5) of the IAEA Nuclear Forensics International Working Group. The spatial distributions, chemical compositions, and morphological and molecular characteristics of impurities were evaluated using X-ray absorption near-edge structure (XANES) and X-ray fluorescence chemical imaging to discover principal impurities, their granularity, particle sizes, modes of occurrence (distinct grains vs incorporation in the UO2 lattice), and sources and mechanisms of incorporation. Differences in UO2+x stoichiometry were detected at the microscale in nominally identical UO2 ceramics (CMX5-A and CMX5-B), implying the presence of multiple UO2 host phases with characteristic microstructures and feedstock compositions. Al, Fe, Ni, W, and Zr impurities and integrated impurity signature analysis identified distinctly different pellet synthesis and processing methods. For example, two different Al, W, and Zr populations in the CMX5-B sample indicated a more complex processing history than the CMX5-A sample. K-edge XANES measurements reveal both metallic and oxide forms of Fe and Ni but with different proportions between each sample. Altogether, these observations suggest multiple sources of impurities, including fabrication (e.g., force-sieving) and feedstock (mineral oxides). This study demonstrates the potential of synchrotron techniques to integrate different signatures across length scales (angstrom to micrometer) to detect and differentiate between contrasting UO2 fuel fabrication techniques.

Diel and seasonal variations in the thermal biology of San Cristobal Lava Lizards (Microlophus bivittatus).

Thermal biology, and therefore energy acquisition and survival, of ectotherms can be affected by diel and seasonal patterns of environmental temperatures. Galápagos Lava Lizards live in seasonal environments that are characterized by a warm and wet period when reproductive activity is maximal, and cooler and drier period. With the use of radiotelemetric techniques to record lizard surface temperatures (Ts), we studied the thermal ecology of the San Cristóbal Lava Lizard (Microlophus bivittatus) during both the warm and cool seasons over two years. During the diel activity period and when operative temperatures exceeded Tset-min, at least on rock faces without canopy, 52% or less of the Ts observations fell within the laboratory-determined Tset range (36-40 °C). Therefore, lizards may have avoided very warm midday temperatures in shaded microhabitats and the lag times in changes in Ts values occurred as operative temperatures rose rapidly during late morning warming phase. Lizards effectively thermoregulated during a year with moderate warm season temperatures and during a cool season that was unseasonably warm. In contrast, lizards less effectively thermoregulated during the warmest and coolest years of the study. We did not detect intersexual differences in thermoregulation although males may thermoregulate less effectively than do females during the cool season although we were unable to detect significant differences using our nonparametric statistical techniques.

Recent biological invasion shapes species recognition and aggressive behaviour in a native species: A behavioural experiment using robots in the field.

Invasive species are a world-wide threat to biodiversity. Yet, our understanding of biological invasions remains incomplete, partly due to the difficulty of tracking and studying behavioural interactions in recently created species interactions. We tested whether the interactions between the recently introduced invasive lizard Anolis cristatellus and the native Anolis oculatus in Dominica have led to changes in species recognition and aggressive behaviour of the native species. The use of realistic robots allowed us to test the behavioural response of 131 A. oculatus males towards relevant and controlled conspecific versus heterospecific stimuli, directly in the field and in two contexts (allopatry vs. sympatry). Our results show that species recognition evolved prior to sympatry in A. oculatus. Moreover, interspecific competition resulted in an increase in the time spent displaying and a divergence in the aggressive behaviour of the native species towards conspecifics versus heterospecifics. Inherent species recognition and higher aggressive behaviour may limit species coexistence as they are expected to favour A. oculatus during territorial interactions with A. cristatellus. While more studies are needed to understand the causes of these behavioural shifts and their consequences on long-term species coexistence, the present study highlights the role of behaviour as a first response to interspecific interactions.

The duality of electron localization and covalency in lanthanide and actinide metallocenes.

Previous magnetic, spectroscopic, and theoretical studies of cerocene, Ce(C8H8)2, have provided evidence for non-negligible 4f-electron density on Ce and implied that charge transfer from the ligands occurs as a result of covalent bonding. Strong correlations of the localized 4f-electrons to the delocalized ligand π-system result in emergence of Kondo-like behavior and other quantum chemical phenomena that are rarely observed in molecular systems. In this study, Ce(C8H8)2 is analyzed experimentally using carbon K-edge and cerium M5,4-edge X-ray absorption spectroscopies (XAS), and computationally using configuration interaction (CI) calculations and density functional theory (DFT) as well as time-dependent DFT (TDDFT). Both spectroscopic approaches provide strong evidence for ligand → metal electron transfer as a result of Ce 4f and 5d mixing with the occupied C 2p orbitals of the C8H8 2- ligands. Specifically, the Ce M5,4-edge XAS and CI calculations show that the contribution of the 4f1, or Ce3+, configuration to the ground state of Ce(C8H8)2 is similar to strongly correlated materials such as CeRh3 and significantly larger than observed for other formally Ce4+ compounds including CeO2 and CeCl6 2-. Pre-edge features in the experimental and TDDFT-simulated C K-edge XAS provide unequivocal evidence for C 2p and Ce 4f covalent orbital mixing in the δ-antibonding orbitals of e2u symmetry, which are the unoccupied counterparts to the occupied, ligand-based δ-bonding e2u orbitals. The C K-edge peak intensities, which can be compared directly to the C 2p and Ce 4f orbital mixing coefficients determined by DFT, show that covalency in Ce(C8H8)2 is comparable in magnitude to values reported previously for U(C8H8)2. An intuitive model is presented to show how similar covalent contributions to the ground state can have different impacts on the overall stability of f-element metallocenes.

Courtship behavior and coloration influence conspicuousness of wolf spiders (Schizocosa ocreata (Hentz)) to avian predators.

Signalers must balance the benefits of detection by intended receivers with the costs of detection by eavesdroppers. This trade-off is exemplified by sexual signaling systems, in which signalers experience sexual selection for conspicuousness to mates as well as natural selection for crypsis to predators. In this study, we examined how courtship behavior and body coloration influenced the conspicuousness of males to avian predators in the well-studied brush-legged wolf spider system (Schizocosa ocreata (Hentz)). We focused on three behaviors (courtship, walking, and freezing) and two coloration schemes (natural coloration and idealized background-matching coloration). We presented captive blue jays (Cyanocitta cristata) with video playbacks of male spiders in a presence-absence detection task and characterized conspicuousness by measuring response latency and detectability. We found that any type of motion significantly increased detectability, and that body coloration and behavior interacted to determine detectability while the spiders were in motion. Among spiders in motion, courting spiders were detected faster than walking spiders. Stationary (frozen) spiders, in contrast, were rarely detected. These results illustrate that male S. ocreata can be both highly conspicuous and highly cryptic to avian predators. Thus, while we find that courtship is conspicuous to avian predators in this system, we suggest that behavioral plasticity may mitigate some of the predation costs of the sexual signal.

Energy-Degeneracy-Driven Covalency in Actinide Bonding.

Evaluating the nature of chemical bonding for actinide elements represents one of the most important and long-standing problems in actinide science. We directly address this challenge and contribute a Cl K-edge X-ray absorption spectroscopy and relativistic density functional theory study that quantitatively evaluates An-Cl covalency in AnCl62- (AnIV = Th, U, Np, Pu). The results showed significant mixing between Cl 3p- and AnIV 5f- and 6d-orbitals (t1u*/t2u* and t2 g*/eg *), with the 6d-orbitals showing more pronounced covalent bonding than the 5f-orbitals. Moving from Th to U, Np, and Pu markedly changed the amount of M-Cl orbital mixing, such that AnIV 6d - and Cl 3p-mixing decreased and metal 5f - and Cl 3p-orbital mixing increased across this series.

Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO2, PrO2, and TbO2.

Understanding the nature of covalent (band-like) vs ionic (atomic-like) electrons in metal oxides continues to be at the forefront of research in the physical sciences. In particular, the development of a coherent and quantitative model of bonding and electronic structure for the lanthanide dioxides, LnO2 (Ln = Ce, Pr, and Tb), has remained a considerable challenge for both experiment and theory. Herein, relative changes in mixing between the O 2p orbitals and the Ln 4f and 5d orbitals in LnO2 are evaluated quantitatively using O K-edge X-ray absorption spectroscopy (XAS) obtained with a scanning transmission X-ray microscope and density functional theory (DFT) calculations. For each LnO2, the results reveal significant amounts of Ln 5d and O 2p mixing in the orbitals of t2g (σ-bonding) and eg (π-bonding) symmetry. The remarkable agreement between experiment and theory also shows that significant mixing with the O 2p orbitals occurs in a band derived from the 4f orbitals of a2u symmetry (σ-bonding) for each compound. However, a large increase in orbital mixing is observed for PrO2 that is ascribed to a unique interaction derived from the 4f orbitals of t1u symmetry (σ- and π-bonding). O K-edge XAS and DFT results are compared with complementary L3-edge and M5,4-edge XAS measurements and configuration interaction calculations, which shows that each spectroscopic approach provides evidence for ground state O 2p and Ln 4f orbital mixing despite inducing very different core-hole potentials in the final state.

Bonding trends across the series of tricarbonato-actinyl anions [(AnO2)(CO3)3]4- (An = U-Cm): the plutonium turn.

Actinyl-tricarbonato anions [(AnO2)(CO3)3]4- (An = U-Cm) in various environments were investigated using theoretical approaches of quantum-mechanics, molecular-mechanics and cluster-models. Cations and solvent molecules in the 2nd coordination sphere affect the equatorial An←Oeq bonds more than the axial An[triple bond, length as m-dash]Oax bonds. Common actinide contraction is found for calculated and experimental axial bond lengths of 92U to 94Pu, though no longer for 94Pu to 96Cm. The tendency of U to Pu forming actinyl(vi) species dwindles away toward Cm, which already features the preferred AnIII/LnIII oxidation state of the later actinides and all lanthanides. The well known change from d-type to typical U-Pu-Cm type and then to f-type behavior is labeled as the plutonium turn, a phenomenon that is caused by f-orbital energy-decrease and f-orbital localization with increase of both nuclear charge and oxidation state, and a non-linear variation of effective f-electron population across the actinide series. Both orbital and configuration mixing and occupation of antibonding 5f type orbitals increase, weakening the AnOax bonds and reducing the highest possible oxidation states of the later actinides.

Thermal and substrate color-induced melanization in laboratory reared red-eared sliders (Trachemys scripta elegans).

Color and pigmentation patterns of the integument can facilitate crypsis, thermoregulation, and social signaling. According to the "thermal melanism hypothesis", cold environmental temperature should increase the quantity of melanin that is deposited in the integument thereby facilitating radiative warming. We studied the influences of water temperature (26°C or 31°C) and substrate color (black or white) on the degree of melanization in the red-eared slider, Trachemys scripta elegans, under laboratory conditions. Turtles reared on a black substrate, or in 26°C water, for 120 days were darker than those reared on a white substrate or in 31°C water. A potential tradeoff between the fitness benefits of crypsis and the benefits of radiative warming through melanism was detected because turtles reared in 26°C water and on a white substrate were darker than those reared on a white substrate and in 31°C water. Low temperatures limited metabolic processes because turtles reared in 26°C water grew more slowly than those reared in 31°C water. However, histological analyses revealed that melanization was a dynamic process in all treatments confirming that the degree of melanization in the cool water treatment was not influenced by the initial and relatively dark hatchling coloration in individuals that grew relatively slowly.

Nuclear Magnetic Resonance Measurements and Electronic Structure of Pu(IV) in [(Me)4N]2PuCl6.

The synthesis, electronic structure, and characterization via single-crystal X-ray diffraction, nuclear magnetic resonance (NMR) spectroscopy, and magnetic susceptibility of (Me4N)2PuCl6 are reported. NMR measurements were performed to both search for the direct (239)Pu resonance and to obtain local magnetic and electronic information at the Cl site through (35)Cl and (37)Cl spectra. No signature of (239)Pu NMR was observed. The temperature dependence of the Cl spectra was simulated by diagonalizing the Zeeman and quadrupolar Hamiltonians for (35)Cl, (37)Cl, and (14)N isotopes. Electronic structure calculations predict a magnetic Γ5 triplet ground state of Pu(IV) in the crystalline electric field of the undistorted PuCl6 octahedron. A tetragonal distortion would result in a very small splitting (∼20 cm(-1)) of the triplet ground state into a nonmagnetic singlet and a doublet state. The Cl shifts have an inflection point at T ≈ 15 K, differing from the bulk susceptibility, indicating a nonmagnetic crystal field ground state. The Cl spin-lattice relaxation time is constant to T = 15 K, below which it rapidly increases, also supporting the nonmagnetic crystal field ground state.

Malcolm†H. Chisholm (1945-2015).

Malcolm H. Chisholm, Distinguished Professor of Mathematical and Physical Sciences at The Ohio State University, passed away on November 20, 2015. He is best known for his pioneering work on the chemistry of metal-metal multiple bonds, the molecular and electronic structure and bonding of transition-metal compounds, and the exploration of excited states of complexes with metal-metal quadruple bonds.

Multiscale Speciation of U and Pu at Chernobyl, Hanford, Los Alamos, McGuire AFB, Mayak, and Rocky Flats.

The speciation of U and Pu in soil and concrete from Rocky Flats and in particles from soils from Chernobyl, Hanford, Los Alamos, and McGuire Air Force Base and bottom sediments from Mayak was determined by a combination of X-ray absorption fine structure (XAFS) spectroscopy and X-ray fluorescence (XRF) element maps. These experiments identify four types of speciation that sometimes may and other times do not exhibit an association with the source terms and histories of these samples: relatively well ordered PuO2+x and UO2+x that had equilibrated with O2 and H2O under both ambient conditions and in fires or explosions; instances of small, isolated particles of U as UO2+x, U3O8, and U(VI) species coexisting in close proximity after decades in the environment; alteration phases of uranyl with other elements including ones that would not have come from soils; and mononuclear Pu-O species and novel PuO2+x-type compounds incorporating additional elements that may have occurred because the Pu was exposed to extreme chemical conditions such as acidic solutions released directly into soil or concrete. Our results therefore directly demonstrate instances of novel complexity in the Å and µm-scale chemical speciation and reactivity of U and Pu in their initial formation and after environmental exposure as well as occasions of unexpected behavior in the reaction pathways over short geological but significant sociological times. They also show that incorporating the actual disposal and site conditions and resultant novel materials such as those reported here may be necessary to develop the most accurate predictive models for Pu and U in the environment.

Covalency in lanthanides. An X-ray absorption spectroscopy and density functional theory study of LnCl6(x-) (x = 3, 2).

Covalency in Ln-Cl bonds of Oh-LnCl6(x-) (x = 3 for Ln = Ce(III), Nd(III), Sm(III), Eu(III), Gd(III); x = 2 for Ln = Ce(IV)) anions has been investigated, primarily using Cl K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT); however, Ce L3,2-edge and M5,4-edge XAS were also used to characterize CeCl6(x-) (x = 2, 3). The M5,4-edge XAS spectra were modeled using configuration interaction calculations. The results were evaluated as a function of (1) the lanthanide (Ln) metal identity, which was varied across the series from Ce to Gd, and (2) the Ln oxidation state (when practical, i.e., formally Ce(III) and Ce(IV)). Pronounced mixing between the Cl 3p- and Ln 5d-orbitals (t2g* and eg*) was observed. Experimental results indicated that Ln 5d-orbital mixing decreased when moving across the lanthanide series. In contrast, oxidizing Ce(III) to Ce(IV) had little effect on Cl 3p and Ce 5d-orbital mixing. For LnCl6(3-) (formally Ln(III)), the 4f-orbitals participated only marginally in covalent bonding, which was consistent with historical descriptions. Surprisingly, there was a marked increase in Cl 3p- and Ce(IV) 4f-orbital mixing (t1u* + t2u*) in CeCl6(2-). This unexpected 4f- and 5d-orbital participation in covalent bonding is presented in the context of recent studies on both tetravalent transition metal and actinide hexahalides, MCl6(2-) (M = Ti, Zr, Hf, U).

Substrate color-induced melanization in eight turtle species from four chelonian groups.

Background color convergence of prey occurring through local adaptation or phenotypically plastic responses can reduce predation rates by visual predators. We assessed the capacity for substrate color-induced melanization in eight turtle species within the groups Chelydridae, Emydidae, Kinosternidae, and Trionychidae by rearing individuals on black or white substrates for 160 days. In all aquatic turtle species, integuments of the head and carapace of the individuals that were reared on a black substrate were darker than of those reared on a white substrate. In the terrestrial turtle Terrapene carolina carolina, however, no significant differences in dorsal head skin or carapace color were observed between treatments. Histological examination of tail tips in three aquatic species (Chelydra serpentina serpentina, Graptemys geographica, and Trachemys scripta elegans) indicated that substrate color-induced melanization is morphological, involving the transfer of melanosomes from basal epidermal melanocytes to adjacent keratinocytes. Interestingly, substrate color-induced melanization in a previously studied Pleurodire species apparently involves physiological color change. We could not, however, rule out physiological components to color change in the turtles of our study.

Daily and annual patterns of thermoregulation in painted turtles (Chrysemys picta marginata) living in a thermally variable marsh in Northern Michigan.

The capacity for an ectothermic reptile to thermoregulate has implications for many components of its life history. Over two years, we studied thermoregulation in a population of Midland painted turtles (Chrysemys picta marginata) in a shallow, thermally variable wetland during summer in Northern Michigan. Mean body temperature (Tb) of free-ranging turtles was greater in 2008 (25.8 °C) than in 2010 (19.7 °C). Laboratory determined thermoregulatory set point (Tset) ranged from 25 °C (Tset-min) to 31 °C (Tset-max) and was lower during the fall (17-26 °C). Deviations of Tb distributions from field measured operative temperatures (Te) and indices of thermoregulation indicated that C. picta marginata were capable of a limited degree of thermoregulation. Operative temperatures and thermal quality (de=|Tset-min-Te| and |Te-Tset-max|) cycled daily with maximal thermal quality occurring during late morning and late afternoon. The accuracy of thermoregulation (db=|Tset-min-Tb| and |Tb-Tset-max|) was maximal (db values were minimal) as Tb declined and traversed Tset during the late afternoon-early evening hours and was higher on cloudy days than on sunny days because relatively low Te values decreased the number of Tb values that were above Tset. Our index of thermal exploitation (Ex=frequency of Tb observations within Tset) was 36%, slightly lower than that reported for an Ontario population of C. picta marginata. Regression of db (thermal accuracy) on de (thermal quality) indicated that turtles invested more in thermoregulation when thermal quality was low and when water levels were high than when they were low. There were no intersexual differences in mean Tb throughout the year but females had relatively high laboratory determined Tb values in the fall, perhaps reflecting the importance of maintaining ovarian development prior to winter.

Chemical speciation of neptunium(VI) under strongly alkaline conditions. Structure, composition, and oxo ligand exchange.

Hexavalent neptunium can be solubilized in 0.5-3.5 M aqueous MOH (M = Li(+), Na(+), NMe4(+) = TMA(+)) solutions. Single crystals were obtained from cooling of a dilute solution of Co(NH3)6Cl3 and NpO2(2+) in 3.5 M [N(Me)4]OH to 5 °C. A single-crystal X-ray diffraction study revealed the molecular formula of [Co(NH3)6]2[NpO2(OH)4]3·H2O, isostructural with the uranium analogue. The asymmetric unit contains three distinct NpO2(OH)4(2-) ions, each with pseudooctahedral coordination geometry with trans-oxo ligands. The average Np═O and Np-OH distances were determined to be 1.80(1) and 2.24(1) Å, respectively. EXAFS data and fits at the Np L(III)-edge on solid [Co(NH3)6]2[NpO2(OH)4]3·H2O and aqueous solutions of NpO2(2+) in 2.5 and 3.5 M (TMA)OH revealed bond lengths nearly identical with those determined by X-ray diffraction but with an increase in the number of equatorial ligands with increasing (TMA)OH concentration. Raman spectra of single crystals of [Co(NH3)6]2[NpO2(OH)4]3·H2O reveal a ν1(O═Np═O) symmetric stretch at 741 cm(-1). Raman spectra of NpO2(2+) recorded in a 0.6-2.2 M LiOH solution reveal a single ν1 frequency of 769 cm(-1). Facile exchange of the neptunyl oxo ligands with the water solvent was also observed with Raman spectroscopy performed with (16)O- and (18)O-enriched water solvent. The combination of EXAFS and Raman data suggests that NpO2(OH)4(2-) is the dominant solution species under the conditions of study and that a small amount of a second species, NpO2(OH)5(3-), may also be present at higher alkalinity. Crystal data for [Co(NH3)6]2[NpO2(OH)4]3·H2O: monoclinic, space group C2/c, a = 17.344(4) Å, b = 12.177(3) Å, c = 15.273 Å, ß = 120.17(2)°, Z = 4, R1 = 0.0359, wR2 = 0.0729.

Tetrahalide complexes of the [U(NR)2]2+ ion: synthesis, theory, and chlorine K-edge X-ray absorption spectroscopy.

Synthetic routes to salts containing uranium bis-imido tetrahalide anions [U(NR)(2)X(4)](2-) (X = Cl(-), Br(-)) and non-coordinating NEt(4)(+) and PPh(4)(+) countercations are reported. In general, these compounds can be prepared from U(NR)(2)I(2)(THF)(x) (x = 2 and R = (t)Bu, Ph; x = 3 and R = Me) upon addition of excess halide. In addition to providing stable coordination complexes with Cl(-), the [U(NMe)(2)](2+) cation also reacts with Br(-) to form stable [NEt(4)](2)[U(NMe)(2)Br(4)] complexes. These materials were used as a platform to compare electronic structure and bonding in [U(NR)(2)](2+) with [UO(2)](2+). Specifically, Cl K-edge X-ray absorption spectroscopy (XAS) and both ground-state and time-dependent hybrid density functional theory (DFT and TDDFT) were used to probe U-Cl bonding interactions in [PPh(4)](2)[U(N(t)Bu)(2)Cl(4)] and [PPh(4)](2)[UO(2)Cl(4)]. The DFT and XAS results show the total amount of Cl 3p character mixed with the U 5f orbitals was roughly 7-10% per U-Cl bond for both compounds, which shows that moving from oxo to imido has little effect on orbital mixing between the U 5f and equatorial Cl 3p orbitals. The results are presented in the context of recent Cl K-edge XAS and DFT studies on other hexavalent uranium chloride systems with fewer oxo or imido ligands.

Striking the balance between nutrient removal, greenhouse gas emissions, receiving water quality, and costs.

This Water Environment Research Foundation study considered the relationship between varying nutrient-removal levels at wastewater treatment plants, greenhouse gas emissions, receiving water quality (measured by potential algal production), and costs. The effluent nutrient concentrations required by some U.S. permits are very low, approaching the technology-best-achievable performance. This study evaluated five different treatment levels at a nominal 40 ML/d (10 mgd) flow. Greenhouse gas emissions and costs increase gradually up to the technologies' best-achievable performance, after which they increase exponentially. The gradual increase is attributed to additional biological treatment facilities, increased energy and chemical use, and additional tertiary nitrogen and phosphorus removal processes. Within the limited focus of this study, the evaluation shows that a point of diminishing return is reached as nutrient-removal objectives approach the technology-best-achievable performance, where greenhouse gas emissions and cost of treatment increases rapidly while the potential for algal growth reduce marginally.

Rotational rehybridization and the high temperature phase of UC2.

The screened hybrid approximation (HSE) of density functional theory (DFT) is used to examine the structural, optical, and electronic properties of the high temperature phase, cubic UC(2). This phase contains C(2) units with a computed C-C distance of 1.443 Å which is in the range of a CC double bond; U is formally 4+, C(2) 4-. The closed shell paramagnetic state (NM) was found to lie lowest. Cubic UC(2) is found to be a semiconductor with a narrow gap, 0.4 eV. Interestingly, the C(2) units connecting two uranium sites can rotate freely up to an angle of 30°, indicating a hindered rotational solid. Ab-initio molecular dynamic simulations (HSE) show that the rotation of C(2) units in the low temperature phase (tetragonal UC(2)) occurs above 2000 K, in good agreement with experiment. The computed energy barrier for the phase transition from tetragonal UC(2) to cubic UC(2) is around 1.30 eV per UC(2). What is fascinating about this system is that at high temperature, the phase transformation to the cubic phase is associated with a rehybridization of the C atoms from sp to sp(3).