Rapid and nondestructive measurement of labile Mn, Cu, Zn, Pb and As in DGT by using field portable-XRF

The technique of diffusive gradients in thin films (DGT) is often employed to quantify labile metals in situ; however, it is a challenge to perform the measurements in-field. This study evaluated the capability of field-portable X-ray fluorescence (FP-XRF) to swiftly generate elemental speciation information with DGT. Biologically available metal ions in environmental samples passively preconcentrate in the thin films of DGT devices, providing an ideal and uniform matrix for XRF nondestructive detection. Strong correlation coefficients (r > 0.992 for Mn, Cu, Zn, Pb and As) were obtained for all elements during calibration. The limits of quantitation (LOQ) for the investigated elements of FP-XRF on DGT devices are 2.74 for Mn, 4.89 for Cu, 2.89 for Zn, 2.55 for Pb, and 0.48 for As (unit: µg cm(-2)). When Pb and As co-existed in the solution trials, As did not interfere with Pb detection when using Chelex-DGT. However, there was a significant enhancement of the Pb reading attributed to As when ferrihydrite binding gels were tested, consistent with Fe-oxyhydroxide surfaces absorbing large quantities of As. This study demonstrates the value of the FP-XRF technique to rapidly and nondestructively detect the metals accumulated in DGT devices, providing a new and simple diagnostic tool for on-site environmental monitoring of labile metals/metalloids

An efficient Cu(II)-bis(oxazoline)-based polymer immobilised ionic liquid phase catalyst for asymmetric carbon–carbon bond formation

The asymmetric Diels-Alder reaction between N-acryloyloxazolidinone and cyclopentadiene and the Mukaiyama-aldol reaction between methylpyruvate and 1-phenyl-1-trimethylsilyloxyethene have been catalysed by heterogeneous copper(II)-bis(oxazoline)-based polymer immobilised ionic liquid phase (PIILP) systems generated from a range of linear and cross linked ionic polymers. In both reactions selectivity and ee were strongly influenced by the choice of polymer. A comparison of the performance of a range of Cu(II)-bis(oxazoline)-PIILP catalyst systems against analogous supported ionic liquid phase (SILP) heterogeneous catalysts as well as their homogeneous counterparts has been undertaken and their relative merits evaluated.

Epitaxial ferroelectric Pb(Mg1/3Nb2/3)O3-PbTiO3 thin films on La0.7Sr0.3MnO3 bottom electrode

Epitaxial (001)-oriented 0.7Pb(Mg_0.33Nb_0.67)O₃-0.3PbTiO₃ (PMN-PT) thin films were deposited by pulsed laser deposition on vicinal SrTiO₃ (001) substrates using La_0.7Sr_0.3MnO₃ as bottom electrode. Detailed microstructural investigations of these films were carried out using X-ray diffraction (XRD), atomic force microscopy (AFM) and transmission electron microscopy (TEM). Polarization-field hysteresis curves were measured at room temperature. Spontaneous polarization P s , remnant polarization P r and coercive voltage V c were found to be 25 μC/cm², 15 μC/cm² and 0.81 V, respectively. Field dependent dielectric constant measurements exhibited butterfly shaped curves, indicating the true ferroelectric nature of these films at room temperature. The dielectric constant and the dielectric loss at 100 kHz were found to be 238 and 0.14, respectively. The local piezoelectric properties of PMN-PT films were investigated by piezoelectric force microscopy and were found to exhibit a local piezoelectric coefficient of 7.8 pm/V.

Electron impact excitation of Mg VIII: Collision strengths, transition probabilities and theoretical EUV and soft X-ray line intensities for Mg VIII

Context: Mg VIII emission lines are observed in a range of astronomical objects such as the Sun, other cool stars and in the coronal line region of Seyfert galaxies. Under coronal conditions Mg VIII emits strongly in the extreme ultraviolet (EUV) and soft X-ray spectral regions which makes it an ideal ion for plasma diagnostics.

Aims. Two theoretical atomic models, consisting of 125 fine structure levels, are developed for the Mg VIII ion. The 125 levels arise from the 2s(2)2p, 2s(2)p2, 2p(3), 2s(2)3s, 2s(2)3p, 2s(2)3d, 2s2p3s, 2s2p3p, 2s2p3d, 2p(2)3s, 2p(2)3p and 2p(2)3d configurations. Electron impact excitation collision strengths and radiative transition probabilities are calculated for both Mg VIII models, compared with existing data, and the best model selected to generate a set of theoretical emission line intensities. The EUV lines, covering 312-790 angstrom, are compared with existing solar spectra (SERTS-89 and SUMER), while the soft X-ray transitions (69-97 angstrom) are examined for potential density diagnostic line ratios and also compared with the limited available solar and stellar observational data.

Methods. The R-matrix codes Breit-Pauli RMATRXI and RMATRXII are utilised, along with the PSTGF code, to calculate the collision strengths for two Mg VIII models. Collision strengths are averaged over a Maxwellian distribution to produce the corresponding effective collision strengths for use in astrophysical applications. Transition probabilities are also calculated using the CIV3 atomic structure code. The best data are then incorporated into the modelling code CLOUDY and line intensities generated for a range of electron temperatures and densities appropriate to solar and stellar coronal plasmas.

Results. The present effective collision strengths are compared with two previous calculations. Good levels of agreement are found with the most recent, but there are large differences with the other for forbidden transitions. The resulting line intensities compare favourably with the observed values from the SERTS-89 and SUMER spectra. Theoretical soft X-ray emission lines are presented and several density diagnostic line ratios examined, which are in reasonable agreement with the limited observational data available.

AN ADSORBATE-STABILIZED VACANCY STRUCTURE FOR CU ON W(100) - A SURFACE ALLOY

Deposition of 0.5 ML of Cu on W(100) leads to the formation of a sharp c(2 x 2) structure when the surface is annealed at 800 K. A LEED intensity analysis reveals that the Cu atoms are adsorbed displacively into W sites, forming an ordered 2D surface alloy. Due to the lattice mismatch between copper and tungsten, a substantial buckling of the first layer of the alloy is also observed. The clean, bulk terminated W(100) surface is only just stable relative to the c(2 x 2) vacancy covered W(100) surface. This relative stability of the vacancy structure explains the driving force behind the formation of this alloy.

Energy levels, radiative rates and electron impact excitation rates for transitions in He-like Fe XXV, Co XXVI, Ni XXVII, Cu XXVIII and Zn XXIX

We report calculations of energy levels, radiative rates and electron impact excitation cross sections and rates for transitions in He-like Fe XXV, Co XXVI, Ni XXVII, Cu XXVIII and Zn XXIX. The grasp (general-purpose relativistic atomic structure package) is adopted for calculating energy levels and radiative rates. For determining the collision strengths and subsequently the excitation rates, the Dirac atomic R-matrix code (darc) is used. Oscillator strengths, radiative rates and line strengths are reported for all E1, E2, M1 and M2 transitions among the lowest 49 levels of each ion. Additionally, theoretical lifetimes are listed for all 49 levels of the above five ions. Collision strengths are averaged over a Maxwellian velocity distribution and the effective collision strengths obtained listed over a wide temperature range up to 10 ^7.7 K. Comparisons are made with similar data obtained using the flexible atomic code (fac) to highlight the importance of resonances, included in calculations with darc, in the determination of effective collision strengths. Discrepancies between the collision strengths from darc and fac, for some transitions, are also discussed. Finally, discrepancies between the present results of effective collision strengths with the darc code and earlier semi-relativistic R-matrix data are noted over a wide range of electron temperatures for many transitions in all ions. 

Yellow earthworms:Distinctive pigmentation associated with arsenic- and copper-tolerance in Lumbricus rubellus

Lumbricus rubellus Hoffmeister, inhabiting soil at the 19th century Devon Great Consols mine at Tavistock, Devon, UK, show high tolerance to Cu- and As-toxicity and frequently have a striking yellow coloration. Specimens from this site (mature and immature) and from an uncontaminated site on Lancaster University campus (mature) were photographed, and the slide images digitized and analyzed. All L. rubellus showed reddish-purple pigmentation of the body wall that declined in intensity posteriorly. The metal- and metalloid-resistant earthworms, whether mature or immature, showed yellowing in the posterior half of the body. The source of the coloration was intense yellow pigmentation of the chloragogenous tissue surrounding the alimentary canal. The yellow pigmentation is masked by reddish-purple body wall pigmentation anteriorly. Total As concentrations in tissues were determined for the anterior, middle and posterior sections of resistant and non-resistant L. rubellus. Highest concentrations were in the middle sections of the mature and immature resistant L. rubellus (36.17 ± 19.77 and 27.77 ± 9.02 mg As kg^-1, respectively). Resistant immature L. rubellus lost condition over 28 d in soil treated with 750 mg As kg^-1, possibly due to a higher metabolism, whilst there was no loss in condition for resistant mature L. rubellus in the treated soil. As far as the authors are aware, this is the first report of yellow pigmentation of this kind in earthworms. The pigmentation may provide a useful indicator of exposure/resistance to soil contamination. © 2002 Elsevier Science Ltd. All rights reserved.

Insight into CO Activation over Cu(100) under Electrochemical Conditions

The reduction of CO₂ on copper electrodes has attracted great attentions in the last decades, since it provides a sustainable approach for energy restore. During the CO₂ reduction process, the electron transfer to CO_ads is experimentally suggested to be the crucial step. In this work, we examine two possible pathways in CO activation, i.e. to generate COH_ads and CHO_ads, respectively, by performing the state-of-the-art constrained ab initio molecular dynamics simulations on the charged Cu(100) electrode under aqueous conditions, which is close to the realistic electrochemical condition. The free energy profile in the formation of COH_ads via the coupled proton and electron transfer is plotted. Furthermore, by Bader charge analyses, a linear relationship between C-O bond distance and the negative charge in CO fragment is unveiled. The formation of CHO_ads is identified to be a surface catalytic reaction, which requires the adsorption of H atom on the surface first. By comparing these two pathways, we demonstrate that kinetically the formation of COH_ads is more favored than that of CHO_ads, while CHO_ads is thermodynamically more stable. This work reveals that CO activation via COH_ads intermediate is an important pathway in electrocatalysis, which could provide some insights into CO₂ electroreduction over Cu electrodes.

Availability and transfer to grain of As, Cd, Cu, Ni, Pb and Zn in a barley agri-system: Impact of biochar, organic and mineral fertilizers

With biochar becoming an emerging soil amendment and a tool to mitigate climate change, there are only a few studies documenting its effects on trace element cycling in agriculture. Zn and Cu are deficient in many human diets, whilst exposures to As, Pb and Cd need to be decreased. Biochar has been shown to affect many of them mainly at a bench or greenhouse scale, but field research is not available. In our experiment we studied the impact of biochar, as well as its interactions with organic (compost and sewage sludge) and mineral fertilisers (NPK and nitrosulfate), on trace element mobility in a Mediterranean agricultural field (east of Madrid, Spain) cropped with barley. At harvesting time, we analysed the soluble fraction, the available fraction (assessed with the diffusive gradients in thin gels technique, DGT) and the concentration of trace elements in barley grain. No treatment was able to significantly increase Zn, Cu or Ni concentration in barley grain, limiting the application for cereal fortification. Biochar helped to reduce Cd and Pb in grain, whereas As concentration slightly increased. Overall biochar amendments demonstrated a potential to decrease Cd uptake in cereals, a substantial pathway of exposure in the Spanish population, whereas mineral fertilisation and sewage sludge increased grain Cd and Pb. In the soil, biochar helped to stabilise Pb and Cd, while marginally increasing As release/mobilisation. Some of the fertilisation practises or treatments increased toxic metals and As solubility in soil, but never to an extent high enough to be considered an environmental risk. Future research may try to fortify Zn, Cu and Ni using other combinations of organic amendments and different parent biomass to produce enriched biochars.

Electron-impact single ionization of Mg and Al+

Theory and experiment are compared for the electron-impact single ionization of Mg and Al+. Nonpertur- bative R matrix with pseudostates RMPS and time-dependent close-coupling TDCC calculations have been carried out that exhibit large reductions from perturbative distorted-wave results of 38% for Mg and 20% for Al+. Experimental single-ionization data available for Mg and Al+ are in reasonable accord with distorted-wave data and lie substantially above the new theoretical results. Rate coefficients, necessary for the collisional- radiative modeling of Mg and Al plasmas were generated from the RMPS ionization cross sections. In the collisional-ionization region near the ionization threshold, the resulting rates were found to be up to two times lower for Mg and three times lower for Al+ than the rates generated from experimental data.

Single and double photoionization of Be and Mg

A new version of the time-dependent close-coupling method is used to calculate the single and double photoionization of the Be and Mg atoms. Total cross sections are calculated using an implicit time propagator with a core orthogonalization method on a variable radial mesh. The double to single photoionization cross section ratios are found to be in good agreement with experiment for both Be and Mg.

A comparison of theoretical Mg VI emission line strengths with active-region observations from SERTS

R-matrix calculations of electron impact excitation rates in N-like Mg VI are used to derive theoretical electron-density-sensitive emission line ratios involving 2s²2p³ - 2s2p⁴ transitions in the 269-403 Å wavelength range. A comparison of these with observations of a solar active region, obtained during the 1989 flight of the Solar EUV Rocket Telescope and Spectrograph (SERTS), reveals good agreement between theory and observation for the 2s²2p^{3 4}S - 2s2p ^{4 4}p transitions at 399.28, 400.67, and 403.30 Å, and the 2s²2p^{3 2}p - 2s2p^{4 2}D lines at 387.77 and 387.97 Å. However, intensities for the other lines attributed to Mg VI in this spectrum by various authors do not match the present theoretical predictions. We argue that these discrepancies are not due to errors in the adopted atomic data, as previously suggested, but rather to observational uncertainties or mis-identifications. Some of the features previously identified as Mg VI lines in the SERTS spectrum, such as 291.36 and 293.15 Å, are judged to be noise, while others (including 349.16 Å) appear to be blended.