Sorption characteristics of a nonionic surfactant during remediation of contaminated soil with different organic content

Surfactant enhanced subsurface remediation has gained importance in soil remediation. Since surfactants can be sorbed on soils, the concentration of free surfactant could drop below the critical micelle concentration, CMC, which may reduce the ability of the surfactant to solubilize the contaminants in soils. ^ The main goal of this research was to study the factors affecting the surfactant sorption on soil such as surfactant concentration, soil organic content, and organic contaminants in soil and to determine the organic contaminants removed from soils by surfactant. The results would be served as the basis for the implementation of a future study in the pilot scale and field scale for surfactant enhanced subsurface remediation. ^ This research study investigated the relationship between the organic content of soils and the sorption characteristics of a nonionic surfactant, Triton X-100. The experiments were performed using uncontaminated soils and soil contaminated with naphthalene and decane. The first part of the experiments were conducted in batch mode utilizing surface tension technique to determine the CMC of surfactant Triton X-100 and the effective CMC in the soil/aqueous system. The sorption of Triton X-100 was calculated from the surface tension measurements. The second part of the experiments utilized the SPME/GC/FID technique to determine the concentration of the contaminants solubilized from the soils by the surfactant Triton X-100 at different concentrations. ^ The results indicated that when the concentration of surfactant was lower than the CMC, the amount of surfactant sorbed on soil increased with the increasing surfactant concentration and the surfactant sorption characteristics of the uncontaminated soils could be modeled by the Freundlich isotherm. For the contaminated soils, the amount of surfactant sorbed was higher than those for the uncontaminated soils. The amount of surfactant sorbed on soils also depends on the organic content in the soils. The higher the organic content in the soil, higher is the amount of surfactant sorbed onto the soil. When the concentration of surfactant was higher than the CMC, the amount of surfactant added into the soil/aqueous system will increase the number of micelle and it increase the solubilization of organic contaminant from the soils. The ratio of the moles of organic contaminant solubilized to the moles of surfactant present as micelles is called the molar solubilization ratio (MSR). MSR value for naphthalene was about 0.16 for the soil-water systems. The organic content of soil did not appear to affect MSR for naphthalene. On the other hand, the MSR values for decane were 0.52, 0.39 and 0.38 for soils with 25%, 50% and 75% organic content, respectively. ^

Ab initio quantum chemical studies on neutral-radical reactions of ethynyl (C2H) and cyano (CN) with unsaturated hydrocarbons

An Ab Initio/RRKM study of the reaction mechanism and product branching ratios of neutral-radical ethynyl (C2H) and cyano (CN) radical species with unsaturated hydrocarbons is performed. The reactions studied apply to cold conditions such as planetary atmospheres including Titan, the Interstellar Medium (ISM), icy bodies and molecular clouds. The reactions of C2H and CN additions to gaseous unsaturated hydrocarbons are an active area of study. NASA's Cassini/Huygens mission found a high concentration of C2H and CN from photolysis of ethyne (C2H2) and hydrogen cyanide (HCN), respectively, in the organic haze layers of the atmosphere of Titan. The reactions involved in the atmospheric chemistry of Titan lead to a vast array of larger, more complex intermediates and products and may also serve as a chemical model of Earth's primordial atmospheric conditions. The C2H and CN additions are rapid and exothermic, and often occur barrierlessly to various carbon sites of unsaturated hydrocarbons. The reaction mechanism is proposed on the basis of the resulting potential energy surface (PES) that includes all the possible intermediates and transition states that can occur, and all the products that lie on the surface. The B3LYP/6-311g(d,p) level of theory is employed to determine optimized electronic structures, moments of inertia, vibrational frequencies, and zero-point energy. They are followed by single point higher-level CCSD(T)/cc-vtz calculations, including extrapolations to complete basis sets (CBS) of the reactants and products. A microcanonical RRKM study predicts single-collision (zero-pressure limit) rate constants of all reaction paths on the potential energy surface, which is then used to compute the branching ratios of the products that result. These theoretical calculations are conducted either jointly or in parallel to experimental work to elucidate the chemical composition of Titan's atmosphere, the ISM, and cold celestial bodies.<.

Investigation of particle identification methods for the analysis of the photoproduction of neutral kaons on a liquid deuterium target

The Photoproduction of neutral kaons off a deuteron target has been investigated at the Tohoku University Laboratory of Nuclear Science. The PID methods investigated incorporated a combination of momentum, velocity (β=v/c), and energy deposition per unit length (dE/dx) measurements. The analysis demonstrates that energy deposition and time of flight are exceedingly useful. A higher signal to background ratio was achieved for hard cuts in combination. A probabilistic likelihood estimation approach (LE) as a method for PID was also explored. The probability of a particle being correctly identified by this LE method and the preliminary results denote the need for highly precise limitations on the distributions from which the parameters would be extracted. It was confirmed that these PID are applicable approaches to properly identify pions for the analysis of this experiment. However, the background evident in the mass spectra points to the need for a higher level of proton identification.

Surfactant solubilization and subsequent bioavailability of phenanthrene

Contamination of soil, sediment and groundwater by hydrophobic organic compounds (HOCs) is a matter of growing concern because groundwater is a valuable and limited resource, and because such contamination is difficult to address. This investigation involved an experimental evaluation of the addition of several surfactant solutions to aqueous and soil-water systems contaminated with phenanthrene, a selected HOC. The results are presented in terms of: * phenanthrene solubilization achieved through surfactant addition * observed effects of surfactant addition on the mineralization of phenanthrene * estimation of relative toxicities of various surfactants using toxicity assays * literature-reported biodegradability/persistence of selected surfactants * surfactant sorption/precipitation onto soil and its impacts on proposed use of surfactant-amended remediation Surfactants were observed to facilitate the transfer of phenanthrene from the soil-sorbed phase to the aqueous pseudophase, however, surfactant solubilization did not translate into enhanced phenanthrene biodegradation.

The effect of ultrasonic waves on the phase behavior of a surfactant-brine-oil system

Acknowledgements The authors would like to gratefully acknowledge and appreciate the School of Engineering, University of Aberdeen, Aberdeen, Scotland, UK, for the provision of the laboratory facilities necessary for completing this work.

The effect of ultrasonic waves on the phase behavior of a surfactant-brine-oil system

Acknowledgements The authors would like to gratefully acknowledge and appreciate the School of Engineering, University of Aberdeen, Aberdeen, Scotland, UK, for the provision of the laboratory facilities necessary for completing this work.

Emergence of additional visible range photoluminescence due to aggregation of cyanine dye:astraphloxin on carbon nanotubes dispersed with anionic surfactant

Self-organization of organic molecules with carbon nanomaterials leads to formation of functionalized molecular nano-complexes with advanced features. We present a study of physical and chemical properties of carbon nanotube-surfactant-indocarbocyanine dye (astraphloxin) in water focusing on aggregation of the dye and resonant energy transfer from the dye to the nanotubes. Self-assembly of astraphloxin is evidenced in absorbance and photoluminescence depending dramatically on the concentrations of both the dye and surfactant in the mixtures. We observed an appearance of new photoluminescence peaks in visible range from the dye aggregates. The aggregates characterized with red shifted photoluminescence peaks at 595, 635 and 675 nm are formed mainly due to the presence of surfactant at the premicellar concentration. The energy transfer from the dye to the nanotubes amplifying near-infrared photoluminescence from the nanotubes is not affected by the aggregation of astraphloxin molecules providing important knowledge for further development of advanced molecular nano-complexes. The aggregation with the turned-on peaks and the energy transfer with amplified photoluminescence create powerful tools of visualization and/or detection of the nanotubes in visible and near-infrared spectral range, respectively, boosting its possible applications in sensors, energy generation/storage, and healthcare.

Surfactant-mediated variation of band-edge emission in CdS nanocomposites

The optical-structural characteristics of the direct optical band-gap semiconducting series of surfactant template-mediated laminar (CdS)x(CdCl2)y(CnH2n+4N)z nanocomposites are reported. X-ray diffraction measurements of the nanocomposites exhibited interlaminar distances in the range 2.9-3.6 nm with observations of eighth order {0 0 l} diffraction planes indicative of a high degree of laminarity and crystallographic order. Diffuse reflectance measurements have determined that the profile of their emission spectrum is that of a direct band-gap with absorption edges in the range 2.11-2.40 eV, depending on the CdS mole fraction in the nanocomposite. Photoluminescence (PL) excitation and time-resolved PL spectroscopies give an estimate of the maximum relative absorbance of the nanocomposites at ∼420 nm while the minimum was observed at ∼560 nm. The main emission was observed at ∼700 nm with emission from doubly ionized sulphur vacancies observed at ∼615 nm at room temperature. The CdS-containing nanocomposite is thus a surfactant-mediated modular system with variable band-gap energy emission.

Formation of positron-atom bound states in collisions between Rydberg Ps and neutral atoms

Predicted 20 years ago, positron binding to neutral atoms has not yet been observed experimentally. A scheme is proposed to detect positron-atom bound states by colliding Rydberg positronium (Ps) with neutral atoms. Estimates of the charge-transfer reaction cross section are obtained using the first Born approximation for a selection of neutral atom targets and a wide range of incident Ps energies and principal quantum numbers. We also estimate the corresponding Ps ionization cross section. The accuracy of the calculations is tested by comparison with earlier predictions for charge transfer in Ps collisions with hydrogen and antihydrogen. We describe an existing Rydberg Ps beam suitable for producing positron-atom bound states and estimate signal rates based on the calculated cross sections and realistic experimental parameters. We conclude that the proposed methodology is capable of producing such states and of testing theoretical predictions of their binding energies.

Towards NIR emission: 2-(1H-tetrazol-1-yl)pyridine as versatile ligand for the synthesis of two new families of cationic and neutral Ir(III) complexes.

In the last decades, cyclometalated Ir(III) complexes have drawn a large interest for their unique properties: they are excellent triplet state emitters, thus the emission is phosphorescent in nature; typically high quantum yields and good stability make them good candidates for luminescent materials. Moreover, through an opportune choice of the ligands, it is possible to tune the emission along the whole visible spectra. Thanks to these interesting features, Ir(III) complexes have found different applications in several areas of applied science, from OLEDs to bioimaging. In particular, regarding the second application, a remarkable red-shift in the emission is required, in order to minimize the problem of the tissue penetration and the possible damages for the organisms. With the aim of synthesizing a new family of NIR emitting Ir(III) complexes, we envisaged the possibility to use for the first time 2-(1H-tetrazol-1-yl)pyridine as bidentate ligand able to provide the required red-shift of the emission of the final complexes. Exploiting the versatility of the ligand, I prepared two different families of heteroleptic Ir(III) complexes. In detail, in the first case the 2-(1H-tetrazol-1-yl)pyridine was used as bis-chelating N^N ligand, leading to cationic complexes, while in the second case it was used as cyclometalating C^N ligand, giving neutral complexes. The structures of the prepared molecules have been characterised by NMR spectroscopy and mass spectrometry. Moreover, the neutral complexes’ emissive properties have been measured: emission spectra have been recorded in solution at both room temperature and 77K, as well as in PMMA matrix. DFT calculation has then been performed and the obtained results have been compared to experimental ones.

Rheology and Microfluidic flows of a cationic surfactant and hydrotropic salt mixture

Thesis (Ph.D.)--University of Washington, 2016-08

Efficacité comparée du lavage pulmonaire thérapeutique par ventilation liquidienne totale et par solution diluée de surfactant exogène dans un modèle ovin de syndrome d’inhalation méconiale

Introduction : Le syndrome d’aspiration méconiale (SAM) est une pathologie respiratoire du nouveau-né qui, dans les cas les plus sévères, peut rester réfractaire aux traitements couramment utilisés et nécessiter in fine le recours à une oxygénation membranaire extracorporelle. Le développement d’un ventilateur liquidien par l’équipe Inolivent a ouvert une nouvelle voie thérapeutique en rendant possible l’utilisation de la ventilation liquidienne totale (VLT) qui utilise un perfluorocarbone liquide afin d’assurer les échanges gazeux tout en effectuant un lavage pulmonaire thérapeutique. En 2011, l’équipe Inolivent a montré la supériorité de la VLT pour retirer le méconium et assurer les échanges gazeux de façon plus efficace que le traitement contrôle, le lavage thérapeutique avec une solution diluée de surfactant exogène (S-LBA). À ce jour, il n’a jamais été montré la possibilité de ramener des agneaux en respiration spontanée au décours d’une VLT pour le traitement d’un SAM sévère. Les objectifs de cette étude sont i) montrer la possibilité de ramener des agneaux nouveau-nés en respiration spontanée sans aide respiratoire après le traitement d’un SAM sévère par VLT, ii) comparer l’efficacité avec le lavage par S-LBA. Méthodes : 12 agneaux nouveau-nés anesthésiés et curarisés ont été instrumentés chirurgicalement. Après l’induction d’un SAM sévère, les agneaux ont subi un lavage pulmonaire thérapeutique soit par VLT (n = 6) ou par S-LBA (n = 6). Les agneaux ont été sevrés de toute ventilation mécanique et suivit en respiration spontanée durant 36 h. Résultats : Il est possible de ramener en respiration spontanée des agneaux nouveau-nés traités par VLT pour le traitement d’un SAM sévère. Le temps nécessaire au sevrage de la ventilation mécanique conventionelle a été plus court chez le groupe S-LBA. Conclusion : Notre étude met en lumière pour la première fois connue à ce jour, la possibilité de ramener en respiration spontanée des agneaux nouveau-nés suivant une VLT dans le traitement d’un SAM sévère. Ces résultats très importants ouvrent la voie à des études sur l’utilisation de la VLT dans le traitement de détresses respiratoires aigües.

Decoherence models for discrete-time quantum walks and their application to neutral atom experiments

We discuss decoherence in discrete-time quantum walks in terms of a phenomenological model that distinguishes spin and spatial decoherence. We identify the dominating mechanisms that affect quantum-walk experiments realized with neutral atoms walking in an optical lattice. From the measured spatial distributions, we determine with good precision the amount of decoherence per step, which provides a quantitative indication of the quality of our quantum walks. In particular, we find that spin decoherence is the main mechanism responsible for the loss of coherence in our experiment. We also find that the sole observation of ballistic-instead of diffusive-expansion in position space is not a good indicator of the range of coherent delocalization. We provide further physical insight by distinguishing the effects of short- and long-time spin dephasing mechanisms. We introduce the concept of coherence length in the discrete-time quantum walk, which quantifies the range of spatial coherences. Unexpectedly, we find that quasi-stationary dephasing does not modify the local properties of the quantum walk, but instead affects spatial coherences. For a visual representation of decoherence phenomena in phase space, we have developed a formalism based on a discrete analogue of the Wigner function. We show that the effects of spin and spatial decoherence differ dramatically in momentum space.

Time-Dependent Effects of Acute Exercise-Induced Arousal on Long-Term Memory for Emotional and Neutral Stimuli

Psychological research has strongly documented the memory-enhancing effects of emotional arousal, while the effects of acute aerobic exercise on memory are not well understood. Manipulation of arousal has been shown to enhance long-term memory for emotional stimuli in a time-dependent fashion. This presents an opportunity to investigate the role of acute exercise in memory modulation. The purpose of this study was to determine the time-dependent relationship between acute exercise-induced arousal and long-term emotional memory. Participants viewed pleasant, neutral, and unpleasant images before or after completing a high-intensity session of cycling exercise. Salivary alpha-amylase, a biomarker of central norepinephrine, was measured as an indicator of arousal. No effects of exercise on recognition memory were revealed, however; a single session of high-intensity cycling increased salivary alpha-amylase. Our results also indicate that the influence of exercise on emotional responsiveness should be considered in further exploration of the memory-enhancing potential of acute exercise.

Multiscale Schemes for the BGK--Vlasov--Poisson System in the Quasi-Neutral and Fluid Limits. Stability Analysis and First Order Schemes

This paper deals with the development and the analysis of asymptotically stable and consistent schemes in the joint quasi-neutral and fluid limits for the collisional Vlasov-Poisson system. In these limits, the classical explicit schemes suffer from time step restrictions due to the small plasma period and Knudsen number. To solve this problem, we propose a new scheme stable for choices of time steps independent from the small scales dynamics and with comparable computational cost with respect to standard explicit schemes. In addition, this scheme reduces automatically to consistent discretizations of the underlying asymptotic systems. In this first work on this subject, we propose a first order in time scheme and we perform a relative linear stability analysis to deal with such problems. The framework we propose permits to extend this approach to high order schemes in the next future. We finally show the capability of the method in dealing with small scales through numerical experiments.