Impacts of epigeic, anecic and endogeic earthworms on metal and metalloid mobility and availability

The introduction of earthworms into soils contaminated with metals and metalloids has been suggested to aid restoration practices. Eisenia veneta (epigeic), Lumbricus terrestris (anecic) and Allolobophora chlorotica (endogeic) earthworms were cultivated in columns containing 900 g soil with 1130, 345, 113 and 131 mg kg1 of As, Cu, Pb and Zn, respectively, for up to 112 days, in parallel with earthworm-free columns. Leachate was produced by pouring water on the soil surface to saturate the soil and generate downflow. Ryegrass was grown on the top of columns to assess metal uptake into biota. Different ecological groups affected metals in the same way by increasing concentrations and free ion activities in leachate, but anecic L. terrestris had the greatest effect by increasing leachate concentrations of As by 267%, Cu by 393%, Pb by 190%, and Zn by 429% compared to earthworm-free columns. Ryegrass grown in earthworm-bearing soil accumulated more metal and the soil microbial community exhibited greater stress. Results are consistent with earthworm enhanced degradation of organic matter leading to release of organically bound elements. The degradation of organic matter also releases organic acids which decrease the soil pH. The earthworms do not appear to carry out a unique process, but increase the rate of a process that is already occurring. The impact of earthworms on metal mobility and availability should therefore be considered when inoculating earthworms into contaminated soils as new pathways to receptors may be created or the flow of metals and metalloids to receptors may be elevated

Inverted cone convolutional neural network for deboning MRIs

Data plenitude is the power but also the bottleneck for data-driven approaches, including neural networks. In particular, Convolutional Neural Networks (CNNs) require an abundant database of training images to achieve a desired high accuracy. Current techniques employed for boosting small datasets are data augmentation and synthetic data generation, which suffer from computational complexity and imprecision compared to original datasets. In this thesis, we intercalate prior knowledge based on the temporal relation between the images in the third dimension. Specifically, we compute the gradient of subsequent images in the dataset to remove extraneous information and highlight subtle variations between the images. The approach is coined Inverted Cone because the volume of brain images below the level of the eyes is ordered to form an inverted cone geometry. The application explored in this work is deboning, or brain extraction, in brain magnetic resonance imaging (MRI) scans. We considered a limited dataset of 23 patients with and without malignant glioblastoma provided by the University of Alabama at Birmingham School of Medicine. Automatic deboning was performed by employing an optimized CNN architecture with and without the Inverted Cone processing. The classic CNN achieved a validation accuracy of 77%, while the Inverted Cone CNN model achieved a validation accuracy of 86% in a dataset of 451 brain MRI slices

Development of Management Strategies for Squash Bug (Heteroptera: Coreidae) Populations in Summer Squash

Entomolog

High-Energy Spectra of Active Galactic Nuclei. II. Absorption in Seyfert Galaxies

Absorption by cold material in a large sample of active galaxies has been analyzed in order to study statistically the behavior of absorbed sources. The analysis indicates that on the basis of the column density alone, sources can be divided into low-absorption ([NH/NHGal] ? 50) and high-absorption ([NH/NHGal] ? 50) objects. While the second group consists mostly of narrow emission line galaxies (Seyfert galaxies of type 1.9-2), the first group is less homogenous, being formed by a mixture of broad and narrow emission line objects (Seyfert 1-2 galaxies). A study of the distribution of the column density values by means of bootstrap analysis confirms the reality of this effect. One group consisting of optically selected objects is well explained within the unified theory as nuclei obscured by a molecular torus. The second group made up of X-ray- and IRAS-selected objects is more difficult to define: in these sources the absorption is underestimated owing to difficulties (1) in fitting complex absorption spectra or (2) in measuring NH values in Compton-thick sources or the absorption has a different origin than in the torus. Possible correlations of absorption with X-ray luminosity, axial ratio, and Balmer decrement have also been investigated. Previous suggestions that lower luminosity AGNs tend to be more highly absorbed than those with higher luminosity are not confirmed by the present data; neither is any evidence for a correlation of NH with axial ratio (b/a) found except for a preference of Seyfert 1-1.5 galaxies to be in face-on galaxies. While some sources (Seyfert 1-1.5 galaxies and low-absorption objects) have X-ray absorption compatible with Balmer decrement, high-absorption objects have column densities much higher than predicted from optical observations. These results are in agreement with the unified theory since the torus parameters are expected to be independent of luminosity, its orientation should be random with respect to the host galaxy, and its location should be in between the broad- and narrow-line regions. A study of the NH variability indicates that in a large fraction (70%) of the sources for which the analysis could be done, NH varies on timescales from months to years. In Seyfert 1-1.5 galaxies, the variability is associated with a region in or near the broad-line region and is explained in terms of partial covering and/or warm absorption models. In Seyfert 2 galaxies, the only variability observed is that associated with narrow emission line galaxies. The study of the column density distributions indicates that Seyfert 1-1.5 galaxies are characterized by NH = 18+9?7 ? 1021 atoms cm-2. Seyfert 1.9-2 galaxies have instead NH = 96+54?35 ? 1021 atoms cm-2 and a larger dispersion; if this group is divided into low- and high-absorption objects, NH = 14.5+7.2?5.3 ? 1021 atoms cm-2 and NH = 132.8+80.1?52.6 ? 1021 atoms cm-2, respectively, are obtained. The observed dispersion in each group is consistent with being entirely due to column density variability

Reduction of nitroarenes, azoarenes and hydrazine derivatives by an organic electron donor

Reduction of nitrobenzene by excess organic electron donor, 12, affords diphenylhydrazine in a reaction where azobenzene oxide and azobenzene are likely intermediates. No cleavage of the N-N σ-bond is seen under photoactivation conditions, whereas traces are seen under thermal activation. Hydrazone derivatives were prepared to explore the cleavage of N-N σ-bonds; the results show that a low-lying LUMO assists the transition state for accepting an electron, and the stabilisation that the potential fragments from N-N bond cleavage afford to the fragments is important in determining whether cleavage is observed

A Comparative Astrochemical Study Of The High-Mass Protostellar Objects NGC 7538 IRS 9 and IRS 1

We report the results of a spectroscopic study of the high-mass protostellar object NGC 7538 IRS 9 and compare our observations to published data on the nearby object NGC 7538 IRS 1. Both objects originated in the same molecular cloud and appear to be at different points in their evolutionary histo- ries, offering an unusual opportunity to study the temporal evolution of envelope chemistry in objects sharing a presumably identical starting composition. Observations were made with the Texas Echelon Cross Echelle Spectrograph (TEXES), a sensitive, high spectral resolution (R = {\lambda}/{\Delta}{\lambda} \simeq 100,000) mid-infrared grating spectrometer. Forty-six individual lines in vibrational modes of the molecules C2H2, CH4, HCN, NH3 and CO were detected, including two isotopologues (13CO, 12C18O) and one combination mode ({\nu}4 + {\nu}5 C2H2). Fitting synthetic spectra to the data yielded the Doppler shift, excitation temperature, Doppler b parameter, column density and covering factor for each molecule observed; we also computed column density upper limits for lines and species not detected, such as HNCO and OCS. We find differences among spectra of the two objects likely attributable to their differing radiation and thermal environments. Temperatures and column densities for the two objects are generally consistent, while the larger line widths toward IRS 9 result in less saturated lines than those toward IRS 1. Finally, we compute an upper limit on the size of the continuum-emitting region (\sim2000 AU) and use this constraint and our spectroscopy results to construct a schematic model of IRS 9.Comment: 23 pages, 15 figures, 6 tables; accepted for publication in Ap

Lermontov crater on Mercury: Geology, morphology and spectral properties of the coexisting hollows and pyroclastic deposits

Abstract We present a multidisciplinary analysis of Lermontov crater, located at 15.24°N, −48.94°E in the Kuiper quadrangle of Mercury. By means of MESSENGER multiband MDIS-WAC and monochrome MDIS-NAC images, we prepare a high-resolution geological map of the crater and its closest surroundings, highlighting the presence of coexisting hollows and pyroclastic deposits on its floor. On the photometrically corrected MDIS-WAC multiband dataset, we apply an unsupervised clustering technique that spectrally separates the different materials located both inside and outside Lermontov crater. We observe that the pyroclastic deposits located on the crater's floor have a steep, red spectral behaviour dominated by the presence of a mixture of various pyroxenes containing Ti and Ni. On the contrary, the vents' rims are characterised by several hollows whose spectral slope is bluer than that of the pyroclastic deposits. By comparing the vent hollows to the hollows located farther out on the crater floor, we observe a steeper 0.62–0.82 μm spectral trend for those within the vents. The vent hollows' spectrum is more similar to the pyroclastic one in the above mentioned wavelength range. In addition, the vent hollows 0.55 μm absorption band could be related to CaS, while the small differences in slope at 0.48 μm and 0.62 μm could be due to the presence of other volatiles compounds, such as MgS or chlorides. When compared to hollows located in other hermean geological settings, Lermontov hollows are characterised by steeper spectra. This supports the interpretation that when hollows form, their bright deposits do not completely overwrite the spectral signature of the surrounding terrain, and their spectroscopic appearance is mixed with the composition of the terrain where they form

N-Silylation of amines mediated by Et3SiH/KOtBu

Silylation of primary and secondary amines is reported, using triethylsilane as the silylating reagent in the presence of potassium tert-butoxide (KOtBu). The reaction proceeds well in the presence of 0.2 equiv of KOtBu. In competition experiments, aniline is selectively silylated over aliphatic amines. Computational studies support a catalytic mechanism which is initiated by KOtBu interacting with the silane to form KH and silylated amine. The KH then takes over the role of base in the propagation of the cyclic mechanism, and deprotonates the amine. This reacts with R3SiH to afford the product R3SiNR’R” and regenerate KH

Large scale localization of protein phosphorylation by use of electron capture dissociation mass spectrometry.

We used on-line electron capture dissociation (ECD) for the large scale identification and localization of sites of phosphorylation. Each FT-ICR ECD event was paired with a linear ion trap collision-induced dissociation (CID) event, allowing a direct comparison of the relative merits of ECD and CID for phosphopeptide identification and site localization. Linear ion trap CID was shown to be most efficient for phosphopeptide identification, whereas FT-ICR ECD was superior for localization of sites of phosphorylation. The combination of confident CID and ECD identification and confident CID and ECD localization is particularly valuable in cases where a phosphopeptide is identified just once within a phosphoproteomics experiment

Electron transfer reactions : KOtBu (but not NaOtBu) photoreduces benzophenone under activation by visible light

Long-standing controversial reports of electron transfer from KOtBu to benzophenone have been investigated and resolved. The mismatch in the oxidation potential of KOtBu (+0.10 V vs SCE in DMF) and the first reduction potential of benzophenone (of many values cited in the literature, the least negative value is −1.31 V vs SCE in DMF), preclude direct electron transfer. Experimental and computational results now establish that a complex is formed between the two reagents, with the potassium ion providing the linkage, which markedly shifts the absorption spectrum to provide a tail in the visible light region. Photoactivation at room temperature by irradiation at defined wavelength (365 or 400 nm), or even by winter daylight, leads to the development of the blue color of the potassium salt of benzophenone ketyl, whereas no reaction is observed when the reaction mixture is maintained in darkness. So, no electron transfer occurs in the ground state. However, when photoexcited, electron transfer occurs within a complex formed from benzophenone and KOtBu. TDDFT studies match experimental findings and also define the electronic transition within the complex as n → π*, originating on the butoxide oxygen. Computation and experiment also align in showing that this reaction is selective for KOtBu; no such effect occurs with NaOtBu, providing the first case where such alkali metal ion selectivity is rationalized in detail. Chemical evidence is provided for the photoactivated electron transfer from KOtBu to benzophenone: tert-butoxyl radicals are formed and undergo fragmentation to form (acetone and) methyl radicals, some of which are trapped by benzophenone. Likewise, when KOC(Et)3 is used in place of KOtBu, then ethylation of benzophenone is seen. Further evidence of electron transfer was seen when the reaction was conducted in benzene, in the presence of p-iodotoluene; this triggered BHAS coupling to form 4-methylbiphenyl in 74% yield