Extracting phosphorus and other elements from lake water: Chemical processes in a hypolimnetic withdrawal and treatment system.

Hypolimnetic withdrawal provides a way to remove phosphorus (P) from eutrophic lakes, but the method is still rarely combined with water treatment for capturing this P. Thus, little is known about the chemical interactions of P and other elements upon the treatment of hypolimnetic lake water. We investigated these chemical processes in a hypolimnetic withdrawal and treatment system (HWTS) in which hypolimnetic water is first led into a treatment unit for dissolved P (dP) precipitation and subsequently filtered before being circulated back into the lake. We studied three different field-scale treatment unit setups and water treatments (aeration only, aeration + calcium hydroxide (Ca(OH)2), aeration + biopolymer) to compare their effectiveness for dP removal and the geochemical properties of the resulting precipitate. In the aeration only treatment, most of the dissolved iron (dFe) (91-95%) and dP (71-91%) were removed when sand filters were used. The addition of Ca(OH)2 and biopolymer enhanced Fe flocculation, leading to more effective removal of dFe (d99-100%) and dP (88-95%) from the water. Regardless of the water treatment method, dP was always precipitated by amorphous Fe oxides formed in the hypolimnetic water upon aeration. The P content of the resulting precipitates was somewhat lower than expected (2 439-4 145 mg kg-1), which may be linked to chemical interactions between Fe and other components in the hypolimnetic water, such as organic matter. The precipitates also contained some heavy metals such as copper and zinc. We conclude that all the tested water treatments were effective in removing dP from hypolimnetic water, but the enhanced precipitation by the addition of treatment chemicals is beneficial when a mesh or other rapid filtration method is used, or when there is only negligible accumulation of dFe in the hypolimnion of the treated lake. Depending on the water treatment method and the water chemistry of the treated lake, the precipitate may have potential for nutrient recycling, although it may sometimes require preliminary processing to enhance bioavailability for plants and to reduce the concentration of heavy metals.

Ambient pressure x-ray photoelectron spectroscopy setup for synchrotron-based in situ and operando atomic layer deposition research.

An ambient pressure cell is described for conducting synchrotron-based x-ray photoelectron spectroscopy (XPS) measurements during atomic layer deposition (ALD) processes. The instrument is capable of true in situ and operando experiments in which it is possible to directly obtain elemental and chemical information from the sample surface using XPS as the deposition process is ongoing. The setup is based on the ambient pressure XPS technique, in which sample environments with high pressure (several mbar) can be created without compromising the ultrahigh vacuum requirements needed for the operation of the spectrometer and the synchrotron beamline. The setup is intended for chemical characterization of the surface intermediates during the initial stages of the deposition processes. The SPECIES beamline and the ALD cell provide a unique experimental platform for obtaining new information on the surface chemistry during ALD half-cycles at high temporal resolution. Such information is valuable for understanding the ALD reaction mechanisms and crucial in further developing and improving ALD processes. We demonstrate the capabilities of the setup by studying the deposition of TiO2 on a SiO2 surface by using titanium(IV) tetraisopropoxide and water as precursors. Multiple core levels and the valence band of the substrate surface were followed during the film deposition using ambient pressure XPS.

Li 1s core exciton in LiH studied by x-ray Raman scattering spectroscopy.

The Li 1s core excitation spectra in LiH was studied by means of x-ray Raman scattering (XRS) spectroscopy in a wide range of momentum transfers q. The analysis of the near-edge region of the measured spectra in combination with q-dependent ab initio calculations of XRS spectra based on the Bethe-Salpeter equation (BSE) reveals that the prominent peak at the excitation onset arises from two main contributions, namely a pre-edge peak associated to a p-type core exciton and strong transitions to empty states near the bottom of the conduction band, which is in contrast to previous experimental studies that attributed that feature to a single excitonic peak. The p-like angular symmetry of the core exciton is supported by BSE calculations of the relative contributions to the XRS spectra from monopole and dipole transitions and by the observed decrease of its normalised intensity for increasing momentum transfers. Higher energy spectral features in the measured XRS spectra are well reproduced by BSE, as well as by real-space multiple-scattering calculations.

A high-energy-resolution resonant inelastic X-ray scattering spectrometer at ID20 of the European Synchrotron Radiation Facility.

An end-station for resonant inelastic X-ray scattering and (resonant) X-ray emission spectroscopy at beamline ID20 of ESRF - The European Synchrotron is presented. The spectrometer hosts five crystal analysers in Rowland geometry for large solid angle collection and is mounted on a rotatable arm for scattering in both the horizontal and vertical planes. The spectrometer is optimized for high-energy-resolution applications, including partial fluorescence yield or high-energy-resolution fluorescence detected X-ray absorption spectroscopy and the study of elementary electronic excitations in solids. In addition, it can be used for non-resonant inelastic X-ray scattering measurements of valence electron excitations.

Improving the spatial and statistical accuracy in X-ray Raman scattering based direct tomography.

An algorithm to simultaneously increase the spatial and statistical accuracy of X-ray Raman scattering (XRS) based tomographic images is presented. Tomography that utilizes XRS spectroscopy signals as a contrast for the images is a new and promising tool for investigating local atomic structure and chemistry in heterogeneous samples. The algorithm enables the spatial resolution to be increased based on a deconvolution of the optical response function of the spectrometer and, most importantly, it allows for the combination of data collected from multiple analyzers and thus enhances the statistical accuracy of the measured images.

A large-solid-angle X-ray Raman scattering spectrometer at ID20 of the European Synchrotron Radiation Facility.

An end-station for X-ray Raman scattering spectroscopy at beamline ID20 of the European Synchrotron Radiation Facility is described. This end-station is dedicated to the study of shallow core electronic excitations using non-resonant inelastic X-ray scattering. The spectrometer has 72 spherically bent analyzer crystals arranged in six modular groups of 12 analyzer crystals each for a combined maximum flexibility and large solid angle of detection. Each of the six analyzer modules houses one pixelated area detector allowing for X-ray Raman scattering based imaging and efficient separation of the desired signal from the sample and spurious scattering from the often used complicated sample environments. This new end-station provides an unprecedented instrument for X-ray Raman scattering, which is a spectroscopic tool of great interest for the study of low-energy X-ray absorption spectra in materials under in situ conditions, such as in operando batteries and fuel cells, in situ catalytic reactions, and extreme pressure and temperature conditions.

Direct tomography imaging for inelastic X-ray scattering experiments at high pressure.

A method to separate the non-resonant inelastic X-ray scattering signal of a micro-metric sample contained inside a diamond anvil cell (DAC) from the signal originating from the high-pressure sample environment is described. Especially for high-pressure experiments, the parasitic signal originating from the diamond anvils, the gasket and/or the pressure medium can easily obscure the sample signal or even render the experiment impossible. Another severe complication for high-pressure non-resonant inelastic X-ray measurements, such as X-ray Raman scattering spectroscopy, can be the proximity of the desired sample edge energy to an absorption edge energy of elements constituting the DAC. It is shown that recording the scattered signal in a spatially resolved manner allows these problems to be overcome by separating the sample signal from the spurious scattering of the DAC without constraints on the solid angle of detection. Furthermore, simple machine learning algorithms facilitate finding the corresponding detector pixels that record the sample signal. The outlined experimental technique and data analysis approach are demonstrated by presenting spectra of the Si L2,3-edge and O K-edge of compressed α-quartz. The spectra are of unprecedented quality and both the O K-edge and the Si L2,3-edge clearly show the existence of a pressure-induced phase transition between 10 and 24 GPa.

Planning, performing and analyzing X-ray Raman scattering experiments.

A compilation of procedures for planning and performing X-ray Raman scattering (XRS) experiments and analyzing data obtained from them is presented. In particular, it is demonstrated how to predict the overall shape of the spectra, estimate detection limits for dilute samples, and how to normalize the recorded spectra to absolute units. In addition, methods for processing data from multiple-crystal XRS spectrometers with imaging capability are presented, including a super-resolution method that can be used for direct tomography using XRS spectra as the contrast. An open-source software package with these procedures implemented is also made available.

Temperature dependence of crystal field excitations in CuO.

We report a study on the temperature dependence of charge-neutral crystal field (dd) excitations in cupric oxide, using nonresonant inelastic x-ray scattering spectroscopy. Thanks to a very high-energy resolution (ΔE = 60 meV), we observe thermal effects on the dd excitation spectrum fine structure between temperatures of 10-320 K. The spectra broaden considerably with increasing temperature, consistently with an enhancement of the coupling between crystal field excitations and the temperature-dependent continuum of states above the band gap. We discuss this and other mechanisms that may explain this temperature dependence.

Intra- and intermolecular effects on the Compton profile of the ionic liquid 1,3-dimethylimidazolium chloride.

We present a comprehensive simulation study on the solid-liquid phase transition of the ionic liquid 1,3-dimethylimidazolium chloride in terms of the changes in the atomic structure and their effect on the Compton profile. The structures were obtained by using ab initio molecular dynamics simulations. Chosen radial distribution functions of the liquid structure are presented and found generally to be in good agreement with previous ab initio molecular dynamics and neutron scattering studies. The main contributions to the predicted difference Compton profile are found to arise from intermolecular changes in the phase transition. This prediction can be used for interpreting future experiments.

Temperature dependence of CO2 and N2 core-electron excitation spectra at high pressure.

We report a study on the temperature dependence of the core-electron excitation spectra of CO2 and N2, performed using non-resonant inelastic X-ray scattering spectroscopy. The spectra were measured at two temperatures (300 K and 850 K) and at high pressure (40 bar). For CO2 a clear temperature dependence was observed at the C and O near-edge regions. The spectra of CO2 were simulated by density functional theory calculations, and the temperature was accounted for by sampling the initial state molecular geometries using the Metropolis algorithm. This model is able to account for the experimentally observed temperature dependence of the spectrum. The experiment fortifies the status of the non-resonant inelastic X-ray scattering spectroscopy as a valuable technique for physics and chemistry for in situ studies under extreme sample conditions. Especially in the case of gas phase the sample conditions of considerably elevated temperature and pressure are unfeasible for many other spectroscopic techniques.

Iron under pressure: "Kohn tweezers" and remnant magnetism.

In this work we investigate the magnetic and structural properties of bulk Fe and Fe nanoparticles under pressure with x-ray absorption and emission spectroscopies providing answers to two fundamental questions: (a) the chicken-or-egg problem for the magnetic and structural transitions and (b) magnetism in the high pressure hcp phase. The two transitions, inextricably linked in the bulk, are clearly decoupled in the nanoparticles, with the magnetic collapse preceding the structural transition. Ultrafast x-ray emission spectroscopy detects remnant magnetism, probably antiferromagnetic fluctuations, up to pressures of about 40 GPa in the hcp phase. This could be of direct relevance to the superconductivity in ϵ-Fe [K. Shimizu et al., Nature (London) 412, 316 (2001)] through the existence of a quantum critical point and associated magnetic fluctuations.

Inelastic X-ray scattering and vibrational effects at the K-edges of gaseous N2, N2O, and CO2.

We report non-resonant inelastic X-ray scattering experiments of several gaseous samples in the inner-shell excitation energy range. The experimental near-edge spectra from all the K-edges of N(2), N(2)O, and CO(2) including the momentum transfer dependence are presented. The results are analyzed using density functional theory calculations that accurately reproduce the experimental spectral features. We observe vibrational effects in the measured spectrum and in the calculations the atomic motion is modeled using the Franck-Condon approximation and the linear coupling model. Our findings show that vibrational effects cannot be neglected in the analysis of high resolution inelastic X-ray scattering spectroscopy. The results also support the validity of the transition potential approximation for calculating core excited state potential energy surfaces.

Universal signature of hydrogen bonding in the oxygen K-edge spectrum of alcohols.

We present a study of the local electronic structure surrounding the OH group in a series of alcohols by X-ray Raman scattering at the oxygen K edge. The samples include the linear alcohols from methanol to butanol as well as the isomers isopropanol, isobutanol, and 2-butanol. For interpretation and computational benchmarks, we combine classical molecular dynamics (MD) simulations and density functional theory (DFT) spectrum calculations. The results indicate that intramolecular structure influences the spectra considerably. Nevertheless, hydrogen bonding produces a clear spectral signature that is nearly identical in all of the alcohols. The spectral calculations using MD structures closely reproduce the experimental results and support the picture provided by the MD simulations.

Intrashell electron-interaction-mediated photoformation of hollow atoms near threshold.

Double photoionization (DPI) of an atom by a single photon is a direct consequence of electron-electron interactions within the atom. We have measured the evolution of the K-shell DPI from threshold up in transition metals by high-resolution x-ray emission spectroscopy of the Kh alpha hypersatellites, photoexcited by monochromatized synchrotron radiation. The measured evolution of the single-to-double photoionization cross-section ratio with excitation energy was found to be universal. Theoretical fits suggest that near threshold DPI is predominantly a semiclassical knockout effect, rather than the purely quantum-mechanical shake-off observed at the infinite photon energy limit.

Zero sound mode in normal liquid 3He.

Inelastic x-ray scattering has been utilized to study the elementary excitations of normal liquid 3He at the temperature T=1.10+/-0.05 K and saturated vapor pressure in the wave vector range 0.15

Coherent peaks and minimal probing depth in photoemission spectroscopy of Mott-Hubbard systems.

We have measured hard x-ray photoemission spectra of pure vanadium sesquioxide (V(2)O(3)) across its metal-insulator transition. We show that, in the metallic phase, a clear correlation exists between the shakedown satellites observed in the vanadium 2p and 3p core-level spectra and the coherent peak measured at the Fermi level. Comparing experimental results and dynamical mean-field theory calculations, we estimate the Hubbard energy U in V(2)O(3) (4.20+/-0.05 eV). From our bulk-sensitive photoemission spectra we infer the existence of a critical probing depth for investigating electronic properties in strongly correlated solids.

Correlation of hydrogen bond lengths and angles in liquid water based on Compton scattering.

The temperature-dependent hydrogen-bond geometry in liquid water is studied by x-ray Compton scattering using synchrotron radiation combined with density functional theory analysis. Systematic changes, related to the weakening of hydrogen bonding, are observed in the shape of the Compton profile upon increasing the temperature. Using model calculations and published distribution functions of hydrogen-bond geometries obtained from a NMR study we find a significant correlation between the hydrogen-bond length and angle. This imposes a new constraint on the possible local structure distributions in liquid water. In particular, the angular distortions of the short hydrogen bonds are significantly restricted.

Correlation-induced double-plasmon excitation in simple metals studied by inelastic x-ray scattering.

We report a new type of peaklike structure observed in the tail of the dynamic structure factor of simple metals, measured by inelastic x-ray scattering. Based on the momentum-transfer dependence of the energy position and the intensity of this structure, it has been unambiguously attributed to intrinsic plasmon-plasmon excitations, an electronic correlation effect that was theoretically predicted by many-body perturbation theory of the homogeneous-electron-gas model beyond the random-phase approximation. This signature appears to be largely unaffected by electron-ion interaction effects. Thus a structure that is primarily caused by correlation effects in the electron gas has been found experimentally in the dynamic structure factor of simple metals.

Improving the performance of high-resolution X-ray spectrometers with position-sensitive pixel detectors.

A dispersion-compensation method to remove the cube-size effect from the resolution function of diced analyzer crystals using a position-sensitive two-dimensional pixel detector is presented. For demonstration, a resolution of 23 meV was achieved with a spectrometer based on a 1 m Rowland circle and a diced Si(555) analyzer crystal in a near-backscattering geometry, with a Bragg angle of 88.5 degrees . In this geometry the spectrometer equipped with a traditional position-insensitive detector provides a resolution of 190 meV. The dispersion-compensation method thus allows a substantial increase in the resolving power without any loss of signal intensity.