Improving the representation of stream water sources in surrogate nutrient models with water isotope data.

An important part of meeting nutrient reduction goals in the lower Great Lakes basin and assessing the success of different land management strategies is modeling nutrient losses from agricultural land. This study aimed to improve the representation of water source contributions to streamflow in generalized additive models for predicting nutrient fluxes from three headwater agricultural streams in southern Ontario monitored during the Multi-Watershed Nutrient Study (MWNS). The previous development of these models represented baseflow contributions to streamflow using the baseflow proportion derived using an uncalibrated recursive digital filter. Recursive digital filters are commonly used to partition stream discharge into separate components from slower and faster pathways. In this study, we calibrated the recursive digital filter using stream water source information from stable isotopes of oxygen in water. Across sites, optimization of the filter parameters reduced bias in baseflow estimates by as much as 68 %. In most cases, calibrating the filter also improved agreement between filter-derived baseflow and baseflow calculated from isotope and streamflow data: the average Kling-Gupta Efficiencies using default and calibrated parameters were 0.44 and 0.82, respectively. When incorporated into the generalized additive models, the revised baseflow proportion predictor was more often statistically significant, improved model parsimony, and reduced prediction uncertainty. Moreover, this information allowed for a more rigorous interpretation of how different stream water sources influence nutrient losses from the agricultural MWNS watersheds.

Total and dissolved phosphorus losses from agricultural headwater streams during extreme runoff events.

Eutrophication continues to be a concerning global water quality issue. Managing and mitigating harmful algal blooms demands clear information on the conditions promoting large phosphorus losses from contributing watersheds. Of particular concern is the amount and form of phosphorus loading to receiving water bodies during extreme runoff events, which are expected to increase in frequency due to climate change. Five years (2015 to 2020) of water quantity and quality data from 11 agricultural watersheds in the lower Great Lakes basin were analyzed and used to model total and dissolved phosphorus losses. This study aimed to assess temporal dynamics in phosphorus concentrations and losses over runoff events covering a wide range of hydrologic conditions and to quantify their relative importance on annual phosphorus losses. Event concentration-discharge relationships for total and dissolved phosphorus were hysteretic and had contrasting dominant patterns across watersheds. The proportion of annual phosphorus losses during events was highly variable between watersheds, accounting for 47-94 %. Extreme events were particularly impactful: as few as three events per year were found to be responsible for nearly half of total phosphorus (20-50 %) and total dissolved phosphorus (14-44 %) losses. Variability in total and dissolved phosphorus losses and concentrations over a wide range of flow conditions suggests that event magnitude is an important control on the relative mobility of particulate and dissolved phosphorus fractions. This study showed that insights into nutrient dynamics and phosphorus budgets in the lower Great Lakes basin and agriculture dominated environments more broadly can be gained by assessing event nutrient losses with respect to flow conditions and patterns in concentration-discharge relationships.

Novel predictors related to hysteresis and baseflow improve predictions of watershed nutrient loads: An example from Ontario's lower Great Lakes basin.

Eutrophication has re-emerged in the lower Great Lakes basin resulting in critical water quality issues. Models that accurately predict nutrient loading from streams are needed to inform appropriate nutrient management decisions. Generalized additive models (GAMs) that use surrogate data from sensors to predict nutrient loads offer an alternative to commonly applied linear regression and may better handle relationship non-linearities and skewed water quality data. Five years (2015-2020) of water quantity and quality data from 11 agricultural watersheds in southern Ontario were used to develop GAMs to predict total phosphorus (TP) and nitrate (NO3-) loads. This study aimed to 1) use GAMs to predict nutrient loads using both common and novel predictors and 2) quantify and examine the variability in seasonal and annual nutrient loads. Along with routine surrogate model predictors (i.e., flow, turbidity, and seasonality), the addition of the baseflow proportion and the hydrograph position of flow observations improved model performance. Conversely, including the antecedent precipitation index minimally affected model performance, regardless of constituent. Seasonal and annual patterns in TP and NO3- load predictions mirrored that of the hydrologic regime. This study showed that parsimonious GAMs featuring novel model predictors can be used to predict nutrient loads while accounting for the partitioning of surface and subsurface flow paths and hysteresis between streamflow and water quality parameters that are frequently observed in a wide range of environments.

Morphology, directed self-assembly and pattern transfer from a high molecular weight polystyrene-block-poly(dimethylsiloxane) block copolymer film.

The self-assembly of block copolymers with large feature sizes is inherently challenging as the large kinetic barrier arising from chain entanglement of high molecular weight (MW) polymers limits the extent over which long-range ordered microdomains can be achieved. Here, we illustrate the evolution of thin film morphology from a diblock copolymer of polystyrene-block-poly(dimethylsiloxane) exhibiting total number average MW of 123 kg mol-1, and demonstrate the formation of layers of well-ordered cylindrical microdomains under appropriate conditions of binary solvent mix ratio, commensurate film thickness, and solvent vapor annealing time. Directed self-assembly of the block copolymer within lithographically patterned trenches occurs with alignment of cylinders parallel to the sidewalls. Fabrication of ordered cobalt nanowire arrays by pattern transfer was also implemented, and their magnetic properties and domain wall behavior were characterized.

Interface electronic structure at the topological insulator-ferrimagnetic insulator junction.

An interface electron state at the junction between a three-dimensional topological insulator film, Bi2Se3, and a ferrimagnetic insulator film, Y3Fe5O12 (YIG), was investigated by measurements of angle-resolved photoelectron spectroscopy and x-ray absorption magnetic circular dichroism. The surface state of the Bi2Se3 film was directly observed and localized 3d spin states of the Fe3+ in the YIG film were confirmed. The proximity effect is likely described in terms of the exchange interaction between the localized Fe 3d electrons in the YIG film and delocalized electrons of the surface and bulk states in the Bi2Se3 film.

UV-solvent annealing of PDMS-majority and PS-majority PS-b-PDMS block copolymer films.

The response of polystyrene-block-poly(dimethylsiloxane) (PS-b-PDMS) thin films to UV exposure during solvent vapor annealing is described, in order to improve their applicability in nanolithography and nanofabrication. Two BCPs were examined, one with the PS block as majority (f PS = 68%, M n = 53 kg mol-1), the other with PDMS block as majority (f PDMS = 67%, M n = 44 kg mol-1). A 5 min UV irradiation was applied during solvent vapor annealing which led to both partial crosslinking of the polymer and a small increase in the temperature of the annealing chamber. This approach was effective for improving the correlation length of the self-assembled microdomain arrays and in limiting subsequent flow of the PDMS in the PDMS-majority BCP to preserve the post-anneal morphology. Ordering and orientation of microdomains were controlled by directed self-assembly of the BCPs in trench substrates. Highly-ordered perpendicular nanochannel arrays were obtained in the PDMS-majority BCP.

HDQLIFE: development and assessment of health-related quality of life in Huntington disease (HD).

PURPOSE: Huntington disease (HD) is a chronic, debilitating genetic disease that affects physical, emotional, cognitive, and social health. Existing patient-reported outcomes (PROs) of health-related quality of life (HRQOL) used in HD are neither comprehensive, nor do they adequately account for clinically meaningful changes in function. While new PROs examining HRQOL (i.e., Neuro-QoL-Quality of Life in Neurological Disorders and PROMIS-Patient-Reported Outcomes Measurement Information System) offer solutions to many of these shortcomings, they do not include HD-specific content, nor have they been validated in HD. HDQLIFE addresses this by validating 12 PROMIS/Neuro-QoL domains in individuals with HD and by using established PROMIS methodology to develop new, HD-specific content. METHODS: New item pools were developed using cognitive debriefing with individuals with HD, and expert, literacy, and translatability reviews. Existing item banks and new item pools were field tested in 536 individuals with prodromal, early-, or late-stage HD. RESULTS: Moderate to strong relationships between Neuro-QoL/PROMIS measures and generic self-report measures of HRQOL, and moderate relationships between Neuro-QoL/PROMIS and clinician-rated measures of similar constructs supported the validity of Neuro-QoL/PROMIS in individuals with HD. Exploratory and confirmatory factor analysis, item response theory, and differential item functioning analyses were utilized to develop new item banks for Chorea, Speech Difficulties, Swallowing Difficulties, and Concern with Death and Dying, with corresponding six-item short forms. A four-item short form was developed for Meaning and Purpose. CONCLUSIONS: HDQLIFE encompasses both validated Neuro-QoL/PROMIS measures, as well as five new scales in order to provide a comprehensive assessment of HRQOL in HD.

Magnetophotonic crystal with cerium substituted yttrium iron garnet and enhanced Faraday rotation angle.

Magnetophotonic crystals (MPCs) comprising cerium-substituted yttrium iron garnet (CeYIG) sandwiched by two Bragg mirrors were fabricated by vacuum annealing. CeYIG was deposited on Bragg mirrors at room temperature and annealed in 5 Pa of residual air. No ceria or other non-garnet phases were detected. Cerium 3 + ions substituted on the yttrium sites and no cerium 4 + ions were found. The Faraday rotation angle of the MPC was -2.92° at a wavelength of λ = 1570 nm was 30 times larger than that of the CeYIG film. These results showed good agreement with calculated values derived using a matrix approach.

Logic circuit prototypes for three-terminal magnetic tunnel junctions with mobile domain walls.

Spintronic computing promises superior energy efficiency and nonvolatility compared to conventional field-effect transistor logic. But, it has proven difficult to realize spintronic circuits with a versatile, scalable device design that is adaptable to emerging material physics. Here we present prototypes of a logic device that encode information in the position of a magnetic domain wall in a ferromagnetic wire. We show that a single three-terminal device can perform inverter and buffer operations. We demonstrate one device can drive two subsequent gates and logic propagation in a circuit of three inverters. This prototype demonstration shows that magnetic domain wall logic devices have the necessary characteristics for future computing, including nonlinearity, gain, cascadability, and room temperature operation.

Quantitative Susceptibility Mapping Suggests Altered Brain Iron in Premanifest Huntington Disease.

BACKGROUND AND PURPOSE: In patients with premanifest (nonsymptomatic) and advanced Huntington disease, changes in brain iron levels in the basal ganglia have been previously reported, especially in the striatum. Quantitative susceptibility mapping by using MR phase imaging allows in vivo measurements of tissue magnetic susceptibility, which has been shown to correlate well with iron levels in brain gray matter and is believed to be more specific than other imaging-based iron measures. The purpose of this study was to investigate the use of magnetic susceptibility as a biomarker of disease progression. MATERIALS AND METHODS: Fifteen subjects with premanifest Huntington disease and 16 age-matched healthy controls were scanned at 7T. Magnetic susceptibility, effective relaxation, and tissue volume in deep gray matter structures were quantified and compared with genetic and clinical measures. RESULTS: Subjects with premanifest Huntington disease showed significantly higher susceptibility values in the caudate nucleus, putamen, and globus pallidus, indicating increased iron levels in these structures. Significant decreases in magnetic susceptibility were found in the substantia nigra and hippocampus. In addition, significant volume loss (atrophy) and an increase effective relaxation were observed in the caudate nucleus and putamen. Susceptibility values in the caudate nucleus and putamen were found to be inversely correlated with structure volumes and directly correlated with the genetic burdens, represented by cytosine-adenine-guanine repeat age-product-scaled scores. CONCLUSIONS: The significant magnetic susceptibility differences between subjects with premanifest Huntington disease and controls and their correlation with genetic burden scores indicate the potential use of magnetic susceptibility as a biomarker of disease progression in premanifest Huntington disease.

Geometrically frustrated Fe2P-like systems: beyond the Fe-trimer approximation.

Fe(2)P-like structures can be strongly frustrated magnets due to their Kagome/triangular intercalated-layer structure. A complete magnetic solution of the complex spin architecture, and hence the full potential of the magnetic phenomena in Fe(2)P-like material prototypes, is yet to be found. A previous magnetic model for a representative FeCrAs-like system used a mean-field effective-spin to describe the 3g-Wyckoff located Fe-triangles. Such an approach demonstrated the outstanding magnetocaloric properties of the material but left the question of whether the intra-trimer interaction could lead to new physical phenomena and therefore more potentially useful properties. In this work Monte Carlo simulations are employed in order to understand both the influence of the additional degrees of freedom introduced by the Fe-trimers and the changes caused by all the possible exchange couplings between them. Complex scenarios arise, in which FM coupling in the trimers gives rise to both in-plane and out-of-plane inter-layer AFM states; whereas AFM exchange in the trimers gives rise to three distinct states, i.e. AFM-canted layers, a non-collinear superposition of ferromagnetic Kagome/triangular orderings, and tilted inter-planar AFM order. These last three configurations generate a double bifurcated magnetic phase diagram while the first one mimics the behavior seen in a model that treats the trimer as an effective-spin under an applied magnetic field.

Oxygen partial pressure dependence of magnetic, optical and magneto-optical properties of epitaxial cobalt-substituted SrTiO3 films.

Cobalt-substituted SrTiO3 films (SrTi0.70Co0.30O(3-δ)) were grown on SrTiO3 substrates using pulsed laser deposition under oxygen pressures ranging from 1 µTorr to 20 mTorr. The effect of oxygen pressure on structural, magnetic, optical, and magneto-optical properties of the films was investigated. The film grown at 3 µTorr has the highest Faraday rotation (FR) and magnetic saturation moment (M(s)). Increasing oxygen pressure during growth reduced M(s), FR and optical absorption in the near-infrared. This trend is attributed to decreasing Co2+ ion concentration and oxygen vacancy concentration with higher oxygen partial pressure during growth.

Simulation methods for solvent vapor annealing of block copolymer thin films.

Recent progress in modelling the solvent vapor annealing of thin film block copolymers is examined in the context of a self-consistent field theory framework. Key control variables in determining the final microdomain morphologies include swelling ratio or swollen film solvent volume fraction, swollen film thickness, substrate and vapor atmosphere surface energies, effective volume fraction, and effective Flory-Huggins interaction parameter. The regime of solvent vapor annealing studied is where the block copolymer has a high enough Flory-Huggins parameter that ordered structures form during swelling and are then trapped in the system through quenching. Both implicit and explicit consideration of the solvent vapor is considered to distinguish the cases in which solvent vapor leads to a non-bulk morphology. Block-selective solvents are considered based on the experimental systems of polystyrene-b-polydimethylsiloxane annealed with toluene and heptane. The results of these simulations are compared with these experiments.

SrGa(0.7)Co(0.3)O(3-δ) perovskite-cobalt oxide-metal nanocomposite films: magnetic and optical properties.

Two-phase nanocomposite films consisting of metallic Co nanoparticles below 50 nm diameter in a perovskite matrix were grown by pulsed laser deposition onto (LaAlO3)0.3(Sr2AlTaO6)0.7 (LSAT) and silicon substrates from a target of SrGa0.73Co0.27O3. The particles made up about 6% by volume of the film and were present within the film and at the substrate interface. The saturation magnetization of the film was up to 85 emu cm(-3) at 80 nm thickness and the Faraday rotation (FR) tracked the out-of-plane hysteresis loop, reaching 3000 deg cm(-1) at 10 kOe for 1550 nm wavelength. The magneto-optical figure of merit defined as FR divided by optical absorption was 0.04-0.06 deg dB(-1) due to the high optical absorption of the Co particles.

Multiferroic behavior of templated BiFeO3-CoFe2O4 self-assembled nanocomposites.

Self-assembled BiFeO3-CoFe2O4 nanocomposites were templated into ordered structures in which the ferrimagnetic CoFe2O4 pillars form square arrays of periods 60-100 nm in a ferroelectric BiFeO3 matrix. The ferroelectricity, magnetism, conductivity, and magnetoelectric coupling of the ordered nanocomposites were characterized by scanning probe microscopy. The insulating BiFeO3 matrix exhibited ferroelectric domains, whereas the resistive CoFe2O4 pillars exhibited single-domain magnetic contrast with high anisotropy due to the magnetoelasticity of the spinel phase. Magnetoelectric coupling was observed in which an applied voltage led to reversal of the magnetic pillars.

Integration of bulk-quality thin film magneto-optical cerium-doped yttrium iron garnet on silicon nitride photonic substrates.

Cerium substituted yttrium iron garnet (Ce:YIG) films were grown on yttrium iron garnet (YIG) seed layers on silicon nitride films using pulsed laser deposition. Optimal process conditions for forming garnet films on silicon nitride are presented. Bulk or near-bulk magnetic and magneto-optical properties were observed for 160 nm thick Ce:YIG films grown at 640 °C on rapid thermal annealed 40 nm thick YIG grown at 640 °C and 2 Hz pulse rate. The effect of growth temperature and deposition rate on structural, magnetic and magneto-optical properties has been investigated.

Combinatorial pulsed laser deposition of magnetic and magneto-optical Sr(GaxTiyFe0.34-0.40)O3-δ perovskite films.

Ferromagnetic Sr(GaxTiyFe0.34-0.40)O3-δ (0.1 ≤ x, y ≤ 0.5) films with single-crystal perovskite structure were epitaxially grown on (001) (LaAlO3)0.3(Sr2AlTaO6)0.7 substrates by combinatorial pulsed laser deposition (CPLD) and compared with previous results from films grown from single targets. In CPLD films the Fe was present as both Fe(2+) and Fe(3+). The distribution of Sr, Ga, Ti, and O was homogeneous, but Fe-rich nanowires with diameter of 3 nm were present perpendicular to the film plane. The unit cell was tetragonally distorted with the ratio of out-of-plane to in-plane lattice parameter decreasing from 1.06 to 1.02 as the Ga content increased. The magnetic easy axis of the films changed from out-of-plane when Ti content y > 0.3 to isotropic as the Ga content increased, consistent with a reduction in magnetoelastic anisotropy. The Ga lowered the Faraday rotation and the magnetization but increased the optical transmittance.

A nonreciprocal racetrack resonator based on vacuum-annealed magnetooptical cerium-substituted yttrium iron garnet.

Vacuum annealed polycrystalline cerium substituted yttrium iron garnet (CeYIG) films deposited by radio frequency magnetron sputtering on non-garnet substrates were used in nonreciprocal racetrack resonators. CeYIG annealed at 800°C for 30 min provided a large Faraday rotation angle, close to the single crystal value. Crystallinity, magnetic properties, refractive indices and absorption coefficients were measured. The resonant transmission peak of the racetrack resonator covered with CeYIG was non-reciprocally shifted by applying an in-plane magnetic field.

Protocol for an HTA report: Does therapeutic writing help people with long-term conditions? Systematic review, realist synthesis and economic modelling.

INTRODUCTION: Long-term medical conditions (LTCs) cause reduced health-related quality of life and considerable health service expenditure. Writing therapy has potential to improve physical and mental health in people with LTCs, but its effectiveness is not established. This project aims to establish the clinical and cost-effectiveness of therapeutic writing in LTCs by systematic review and economic evaluation, and to evaluate context and mechanisms by which it might work, through realist synthesis. METHODS: Included are any comparative study of therapeutic writing compared with no writing, waiting list, attention control or placebo writing in patients with any diagnosed LTCs that report at least one of the following: relevant clinical outcomes; quality of life; health service use; psychological, behavioural or social functioning; adherence or adverse events. Searches will be conducted in the main medical databases including MEDLINE, EMBASE, PsycINFO, The Cochrane Library and Science Citation Index. For the realist review, further purposive and iterative searches through snowballing techniques will be undertaken. Inclusions, data extraction and quality assessment will be in duplicate with disagreements resolved through discussion. Quality assessment will include using Grading of Recommendations Assessment, Development and Evaluation (GRADE) criteria. Data synthesis will be narrative and tabular with meta-analysis where appropriate. De novo economic modelling will be attempted in one clinical area if sufficient evidence is available and performed according to the National Institute for Health and Care Excellence (NICE) reference case.