Phytoplankton and benthic algal response to ecosystem engineers and multiple stressors in the nearshore of Lake Huron

Resurgence of nuisance benthic algae in the Great Lakes, despite substantial efforts to reduce phosphorus loading, has stimulated renewed interest in exploring the diverse drivers of near-shore water quality. Interestingly, broad similarity in the underlying causes of shore fouling by benthic algae in Lakes Ontario, Erie, and Michigan appear to contrast with Lake Huron where system productivity and dreissenid abundance are lower. While total phosphorus was the primary predictor of chlorophyll concentrations (70–90% of variation) in the water column, we identified a series of spatial patterns that underpin this relationship (up to 28% of variation) and which integrate catchment processes, tributary influences, shoreline complexity, and distance from shore. Dreissenid mussels were the most important predictors of benthic algae cover and biomass in our models, explaining between 20 and 52% of variation. Spatial patterns explained an additional 21–48% of the variation in benthic algae cover and biomass and highlight the importance of site-specific spatial heterogeneity in benthic algae growth. Our results are consistent with the nearshore shunt hypothesis, wherein higher algal cover and biomass coincided with higher mussel density and biomass, although correlative effects with lake depth and loss of algal and mussel biomass due to physical disturbance must also be considered. These results underscore the difficulty associated with identifying the potential drivers of nearshore water quality as the diverse processes of nutrient loading, changes in catchment land use, and ecosystem change associated with invasion by dreissenids all vary in relative influence over a range of spatial scales.     

Controlling Magnetic and Optical Properties of the van der Waals Crystal CrCl3−xBrx via Mixed Halide Chemistry

Magnetic van der Waals (vdW) materials are the centerpiece of atomically thin devices with spintronic and optoelectronic functions. Exploring new chemistry paths to tune their magnetic and optical properties enables significant progress in fabricating heterostructures and ultracompact devices by mechanical exfoliation. The key parameter to sustain ferromagnetism in 2D is magnetic anisotropy—a tendency of spins to align in a certain crystallographic direction known as easy‐axis. In layered materials, two limits of easy‐axis are in‐plane (XY) and out‐of‐plane (Ising). Light polarization and the helicity of topological states can couple to magnetic anisotropy with promising photoluminescence or spin‐orbitronic functions. Here, a unique experiment is designed to control the easy‐axis, the magnetic transition temperature, and the optical gap simultaneously in a series of CrCl_3?xBr_x crystals between CrCl₃ with XY and CrBr₃ with Ising anisotropy. The easy‐axis is controlled between the two limits by varying spin–orbit coupling with the Br content in CrCl_3?x Br_x. The optical gap, magnetic transition temperature, and interlayer spacing are all tuned linearly with x. This is the first report of controlling exchange anisotropy in a layered crystal and the first unveiling of mixed halide chemistry as a powerful technique to produce functional materials for spintronic devices.     

Winds of change – Predicting water-based recreationists' support and opposition for offshore wind energy development in the Great Lakes

This study examined the factors influencing water-based recreationists' perceptions of support and opposition towards off-shore wind energy development (OWD) on Lake Erie. Much of the proposed or future Lake Erie OWD infrastructure may either be within or adjacent to public lands, waters, and protected areas, raising concerns about the potential environmental and social impacts upon recreation stakeholders. The limited body of OWD research within the United States has suggested there are numerous factors that may influence overall perceptions of support and opposition such as political orientation and beliefs in climate change. Moreover, recent research has proposed that the perceived recreation impact of OWD may be the most important predictor of support and opposition. This study confirmed this premise and found the perceived recreation impact of OWD to be the strongest predictor of support. Results of a multiple linear regression suggested that political orientation (β?=?0.135), beliefs in the anthropogenic causation of climate change (β?=?0.207), beliefs in the occurrence of climate change (β?=?0.213), and the perceived recreation impact of OWD among water-based recreationists (β?=?0.439) were significant predictors of support for OWD on Lake Erie (R²?=?0.46). Study findings corroborated previous research which suggested that regional climate change beliefs and political attitudes may influence support for OWD. From a policy and management standpoint, study results highlight the importance of assessing and communicating recreation experience and use impacts when planning, developing, and managing OWD and related decisions in the United States.     

Integrating affective learning into intelligent tutoring systems

Affectivity has influence in learning face-to-face environments and improves some aspects in students, such as motivation. For that reason, it is important to integrate affectivity elements into virtual environments. We propose a conceptual model that suggests which elements of tutor, student and dialogue should be integrated and implemented into learning systems. We design an ontology guided by methontology, and apply a mathematical evaluation (OntoQA) to determine the richness of the proposed model. The mathematical evaluation states that the proposed model has relationship richness and horizontal nature. We developed a software application implementing the conceptual model in order to prove its effectivity to generate students’ motivation. The findings suggest that the implemented affective learning ontology impacts positively the motivation in students with low academic performance, in female students and in engineering students.     

Improvement of ageing properties of rubber films prepared from radiation-vulcanized natural rubber latex

Radiation-vulcanization of natural rubber latex (NRL) with n-butyl acrylate gives a higher tensile strength for films obtained after casting. The ageing properties of radiation-vulcanized natural rubber in the presence of various antioxidants have been investigated. In order to find out suitable antioxidants for radiation-vulcanized natural rubber latex (RVNRL) films, extraction of the gel fraction was carried out in xylene with 1 wt.-% antioxidant and air bubbling. Antioxidants which give less reduction in gel fraction due to oxidative degradation during extraction are effective for ageing tests of RVNRL films. It was found that tris(nonylated phenyl) phosphite (Nonflex TNP) and 2,5-di-tert-amylhydroquinone (Antage DAH), among 12 different antioxidants tested, were the most effective antioxidants for RVNRL films.     

Photochemical Mechanism of an Atypical Algal Phytochrome

Phytochromes are bilin‐containing photoreceptors that are typically sensitive to the red/far‐red region of the visible spectrum. Recently, phytochromes from certain eukaryotic algae have become attractive targets for optogenetic applications because of their unique ability to respond to multiple wavelengths of light. Herein, a combination of time‐resolved spectroscopy and structural approaches across picosecond to second timescales have been used to map photochemical mechanisms and structural changes in this atypical group of phytochromes. The photochemistry of an orange/far‐red light‐sensitive algal phytochrome from Dolihomastix tenuilepis has been investigated by using a combination of visible, IR and X‐ray scattering probes. The entire photocycle, correlated with accompanying structural changes in the cofactor/protein, are reported. This study identifies a complex photocycle for this atypical phytochrome. It also highlights a need to combine outcomes from a range of biophysical approaches to unravel complex photochemical and macromolecular processes in multi‐domain photoreceptor proteins that are the basis of biological light‐mediated signalling.     

Citrulline malate supplementation does not improve German Volume Training performance or reduce muscle soreness in moderately trained males and females

Background

Use of supplements to aid performance is common practice amongst recreationally active individuals, including those without a sufficient evidence base. This investigation sought to assess whether acute supplementation with 8 g of citrulline malate (CM) (1.11: 1 ratio) would improve anaerobic performance.

Methods

A randomised double blind placebo control trial was employed, using a counterbalanced design. We recruited recreationally active men and women to take part in an isokinetic chair protocol, based on German Volume Training (GVT) whereby participants attempted to perform 10 sets of 10 repetitions against a force representing 70% of their peak concentric force.

Results

The number of repetitions achieved over the course of the GVT was 94.0?±?7.9 and 90.9?±?13.9 for placebo and CM respectively. There was no significant difference between the placebo and CM treatment for number of repetitions (P?=?0.33), isometric (P?=?0.60), concentric (P?=?0.38), or eccentric (P?=?0.65) peak force following the GVT. Total muscle soreness was significantly higher in the CM compared to the placebo treatment following the GVT protocol over 72 h (P?=?0.01); although this was not accompanied by a greater workload/number of repetitions in the CM group.

Conclusions

We conclude that an acute dose of CM does not significantly affect anaerobic performance using an isokinetic chair in recreational active participants. Practical implications include precaution in recommending CM supplementation. Coaches and athletes should be aware of the disparity between the chemical analyses of the products reviewed in the present investigation versus the manufacturers’ claims.

     

Mass spectrometry in the biosynthetic and structural investigation of lignins

Lignin, a resistant cell-wall constituent of all vascular plants that consists of ether and carbon-linked methoxyphenols, is still far from being structurally described in detail. The main problem in its structural elucidation is the difficulty of isolating lignin from other wood components without damaging lignin itself. Furthermore, the high number and variegated forms of linkages that occur between the monomeric units and the chemical resistance of certain ether bonds limit the extent to which analytical and degradation procedures can be used to elucidate the lignin structure. Most of our present knowledge about the molecular structure of lignin is based on the analysis of monomers, dimers or, at the most, tetramers of degraded isolated lignins. Mass spectrometry (MS), which offers advantages in terms of speed, specificity, and sensitivity, has revealed to be a very powerful technique in the structural elucidation of lignins, in combination with the great number of chemical and thermal degradation methods available in the study of lignin. Moreover, the recent development of new ionization techniques in MS-electrospray ionization (ESI)-MS and matrix-assisted laser desorption/ionization (MALDI)-MS-has provided new possibilities to also analyze the undegraded lignin macromolecule.     

Field intercomparison of the gas/particle partitioning of oxygenated organics during the Southern Oxidant and Aerosol Study (SOAS) in 2013

We present results of the first intercomparison of real-time instruments for gas/particle partitioning of organic species. Four recently-developed instruments that directly measure gas/particle partitioning in near-real time were deployed in Centreville, Alabama during the Southern Oxidant Aerosol Study (SOAS) in 2013. Two instruments were filter inlet for gases and aerosols high-resolution chemical ionization mass spectrometers (FIGAERO-HRToF-CIMS) with acetate (A-CIMS) and iodide (I-CIMS) ionization sources, respectively; the third was a semi-volatile thermal desorption aerosol GC-MS (SV-TAG); and the fourth was a high-resolution thermal desorption proton-transfer reaction mass spectrometer (HR-TD-PTRMS). Signals from these instruments corresponding to several organic acids were chosen for comparison. The campaign average partitioning fractions show good correlation. A similar level of agreement with partitioning theory is observed. Thus the intercomparison exercise shows promise for these new measurements, as well as some confidence on the measurement of low versus high particle-phase fractions. However, detailed comparison show several systematic differences that lie beyond estimated measurement errors. These differences may be due to at least eight different effects: (1) underestimation of uncertainties under low signal-to-noise; (2) inlet and/or instrument adsorption/desorption of gases; (3) differences in particle size ranges sampled; (4) differences in the methods used to quantify instrument backgrounds; (5) errors in high-resolution fitting of overlapping ion groups; (6) differences in the species included in each measurement due to different instrument sensitivities; and differences in (7) negative or (8) positive thermal decomposition (or ion fragmentation) artifacts. The available data are insufficient to conclusively identify the reasons, but evidence from these instruments and available data from an ion mobility spectrometer shows the particular importance of effects 6–8 in several cases. This comparison highlights the difficulty of this measurement and its interpretation in a complex ambient environment, and the need for further improvements in measurement methodologies, including isomer separation, and detailed study of the possible factors leading to the observed differences. Further intercomparisons under controlled laboratory and field conditions are strongly recommended.

Copyright © 2017 American Association for Aerosol Research     

Synthesis and Characterization of 5-Coordinate Tungsten Hydride Anions: [(tBu3SiNH)(tBu3SiN=)2HWR]M

Treatment of (^tBu₃SiNH)(^tBu₃SiN=)₂WH ( 1 -H) with small alkyl anions (RM) afforded tungsten alkyl hydride anions [(^tBu₃SiNH)(^tBu₃SiN=)₂HWR)]M ( 3 -(R)M: R=CH₃, M=Li; R=ⁿBu, M=Li; R=^neoPe, M=Li; R=CH₂Ph (Bn), M=K (two isomers); R=CCH, M=Na; R=CH=CH₂ (Vy), M=Li). The saturated alkyl anions 3 -(R)M ( 3 -(R)M: R=CH₃, M=Li; R=ⁿBu, M=Li; R=^neoPe, M=Li; R=CH₂Ph (Bn), M=K) degraded via apparent 1,2-RH-elimination to produce the known [(^tBu₃SiN=)₃WH]M ( 2 -HM), but the acetylide ( 3 -(C₂H)Na) and vinyl ( 3 -(Vy)Li) anions converted to their hydrogenated isomers, [(^tBu₃SiN=)₃WVy]Na ( 2 -VyNa) and [(^tBu₃SiN=)₃WEt]Li ( 2 -EtLi), respectively. The structure of 3 -(ⁿBu)Li is reported, and a discussion of tungsten-hydride coupling constants in ^tBu₃SiX-ligated (X=O, NH, N) systems is given.