Chlorofluorocarbons and noble gas measured on water bottle samples during three POLARSTERN cruises

We use a 27 year long time series of repeated transient tracer observations to investigate the evolution of the ventilation time scales and the related content of anthropogenic carbon (Cant) in deep and bottom water in the Weddell Sea. This time series consists of chlorofluorocarbon (CFC) observations from 1984 to 2008 together with first combined CFC and sulphur hexafluoride (SF6) measurements from 2010/2011 along the Prime Meridian in the Antarctic Ocean and across the Weddell Sea. Applying the Transit Time Distribution (TTD) method we find that all deep water masses in the Weddell Sea have been continually growing older and getting less ventilated during the last 27 years. The decline of the ventilation rate of Weddell Sea Bottom Water (WSBW) and Weddell Sea Deep Water (WSDW) along the Prime Meridian is in the order of 15-21%; the Warm Deep Water (WDW) ventilation rate declined much faster by 33%. About 88-94% of the age increase in WSBW near its source regions (1.8-2.4 years per year) is explained by the age increase of WDW (4.5 years per year). As a consequence of the aging, the Cant increase in the deep and bottom water formed in the Weddell Sea slowed down by 14-21% over the period of observations.

A study of the properties and applications of electrostatic charged particle oscillators

This investigation originated from work by Dr. A.H. McIlraith of the National Physical Laboratory who, in 1966, described a new type of charged particle oscillator. This makes use of two equal cylindrical electrodes to constrain the particles in such a way that they follow extremely long oscillatory paths between the electrodes under the influence of an electrostatic field alone. The object of this work has been to study the principle of the oscillator in detail and to investigate its properties and applications. Any device which is capable of creating long electron trajectories has potential application in the field of ultra high vacuum technology. It was therefore considered that a critical review of the problems associated with the production and measurement of ultra high vacuum was relevant in the initial stages of the work. The oscillator has been applied with a considerable degree of success as a high energy electrostatic ion source. This offers several advantages over existing ion sources. It can be operated at much lower pressures without the need of a magnetic field. The oscillator principle has also been applied as a thermionic ionization gauge and has been compared with other ionization gauges to pressures as low as 5 x 10- 11 torr.. This new gauge exhibited a number of advantages over most of the existing gauges. Finally the oscillator has been used in an evaporation ion pump and has exhibited fairly high pumping speeds for argon gas relative to those for nitrogen. This investigation supports the original work of Dr. A.H. McIlraith and shows that his proposed oscillator has considerable potential in the fields of vacuum technology and electron physics.

Design and Implementation of Tools for STM Studies in UHV and at the Solid-Liquid Interface

This thesis presents details of the design and development of novel tools and instruments for scanning tunneling microscopy (STM), and may be considered as a repository for several years' worth of development work. The author presents design goals and implementations for two microscopes. First, a novel Pan-type STM was built that could be operated in an ambient environment as a liquid-phase STM. Unique features of this microscope include a unibody frame, for increased microscope rigidity, a novel slider component with large Z-range, a unique wiring scheme and damping mechanism, and a removable liquid cell. The microscope exhibits a high level of mechanical isolation at the tunnel junction, and operates excellently as an ambient tool. Experiments in liquid are on-going. Simultaneously, the author worked on designs for a novel low temperature, ultra-high vacuum (LT-UHV) instrument, and these are presented as well. A novel stick-slip vertical coarse approach motor was designed and built. To gauge the performance of the motor, an in situ motion sensing apparatus was implemented, which could measure the step size of the motor to high precision. A new driving circuit for stick-slip inertial motors is also presented, that o ffers improved performance over our previous driving circuit, at a fraction of the cost. The circuit was shown to increase step size performance by 25%. Finally, a horizontal sample stage was implemented in this microscope. The build of this UHV instrument is currently being fi nalized. In conjunction with the above design projects, the author was involved in a collaborative project characterizing N-heterocyclic carbene (NHC) self-assembled monolayers (SAMs) on Au(111) films. STM was used to characterize Au substrate quality, for both commercial substrates and those manufactured via a unique atomic layer deposition (ALD) process by collaborators. Ambient and UHV STM was then also used to characterize the NHC/Au(111) films themselves, and several key properties of these films are discussed. During this study, the author discovered an unexpected surface contaminant, and details of this are also presented. Finally, two models are presented for the nature of the NHC-Au(111) surface interaction based on the observed film properties, and some preliminary theoretical work by collaborators is presented.

Degenerate Gases of Strontium for Studies of Quantum Magnetism

We describe the construction and characterization of a new apparatus that can produce degenerate quantum gases of strontium. The realization of degenerate gases is an important first step toward future studies of quantum magnetism. Three of the four stable isotopes of strontium have been cooled into the degenerate regime. The experiment can make nearly pure Bose-Einstein condensates containing approximately 1x10^4 atoms, for strontium-86, and approximately 4x10^5 atoms, for strontium-84. We have also created degenerate Fermi gases of strontium-87 with a reduced temperature, T/T_F of approximately 0.2. The apparatus will be able to produce Bose-Einstein condensates of strontium-88 with straightforward modifications. We also report the first experimental and theoretical results from the strontium project. We have developed a technique to accelerate the continuous loading of strontium atoms into a magnetic trap. By applying a laser addressing the 3P1 to 3S1 transition in our magneto-optical trap, the rate at which atoms populate the magnetically-trapped 3P2 state can be increased by up to 65%. Quantum degenerate gases of atoms in the metastable 3P0 and 3P2 states are a promising platform for quantum simulation of systems with long-range interactions. We have performed an initial numerical study of a method to transfer the ground state degenerate gases that we can currently produce into one of the metastable states via a three-photon transition. Numerical simulations of the Optical Bloch equations governing the three-photon transition indicate that >90% of a ground state degenerate gas can be transferred into a metastable state.

SOVLENT REACTIVITY AND INTERFACE EVOLUTION AT MODEL ELECTRODES FOR ENERGY APPLICATIONS

The Li-ion rechargeable battery (LIB) is widely used as an energy storage device, but has significant limitations in battery cycle life and safety. During initial charging, decomposition of the ethylene carbonate (EC)-based electrolytes of the LIB leads to the formation of a passivating layer on the anode known as the solid electrolyte interphase (SEI). The formation of an SEI has great impact on the cycle life and safety of LIB, yet mechanistic aspects of SEI formation are not fully understood. In this dissertation, two surface science model systems have been created under ultra-high vacuum (UHV) to probe the very initial stage of SEI formation at the model carbon anode surfaces of LIB. The first model system, Model System I, is an lithium-carbonate electrolyte/graphite C(0001) system. I have developed a temperature programmed desorption/temperature programmed reaction spectroscopy (TPD/TPRS) instrument as part of my dissertation to study Model System I in quantitative detail. The binding strengths and film growth mechanisms of key electrolyte molecules on model carbon anode surfaces with varying extents of lithiation were measured by TPD. TPRS was further used to track the gases evolved from different reduction products in the early-stage SEI formation. The branching ratio of multiple reaction pathways was quantified for the first time and determined to be 70.% organolithium products vs. 30% inorganic lithium product. The obtained branching ratio provides important information on the distribution of lithium salts that form at the very onset of SEI formation. One of the key reduction products formed from EC in early-stage SEI formation is lithium ethylene dicarbonate (LEDC). Despite intensive studies, the LEDC structure in either the bulk or thin-film (SEI) form is unknown. To enable structural study, pure LEDC was synthesized and subject to synchrotron X-ray diffraction measurements (bulk material) and STM measurements (deposited films). To enable studies of LEDC thin films, Model System II, a lithium ethylene dicarbonate (LEDC)-dimethylformamide (DMF)/Ag(111) system was created by a solution microaerosol deposition technique. Produced films were then imaged by ultra-high vacuum scanning tunneling microscopy (UHV-STM). As a control, the dimethylformamide (DMF)-Ag(111) system was first prepared and its complex 2D phase behavior was mapped out as a function of coverage. The evolution of three distinct monolayer phases of DMF was observed with increasing surface pressure — a 2D gas phase, an ordered DMF phase, and an ordered Ag(DMF)2 complex phase. The addition of LEDC to this mixture, seeded the nucleation of the ordered DMF islands at lower surface pressures (DMF coverages), and was interpreted through nucleation theory. A structural model of the nucleation seed was proposed, and the implication of ionic SEI products, such as LEDC, in early-stage SEI formation was discussed.

Development of gripping devices based on electroadhesive forces

In a context of technological innovation, the aim of this thesis is to develop a technology that has gained interest in both scientific and industrial realms. This technology serves as a viable alternative to outdated and energy-consuming industrial systems. Electro-adhesive devices (EADs) leverage electrostatic forces for grasping objects or adhering to surfaces. The advantage of employing electrostatics lies in its adaptability to various materials without compromising the structure or chemistry of the object or surface. These benefits have led the industry to explore this technology as a replacement for costly vacuum systems and suction cups currently used for handling most products. Furthermore, the broad applicability of this technology extends to extreme environments, such as space with ultra-high vacuum conditions. Unfortunately, research in this area has yet to yield practical results for industrially effective gripper prototyping. This is primarily due to the inherent complexity of electro-adhesive technology, which operates on basic capacitive principles that does not find satisfying physical descriptions. This thesis aims to address these challenges through a series of studies, starting with the manufacturing process and testing of an EAD that has become the standard in our laboratory. It then delves into material and electrode geometry studies to enhance system performance, ultimately presenting potential industrial applications of the technology. All the presented results are encouraging, as they have yielded shear force values three times higher than those previously reported in the literature. The various applications have demonstrated the significant effectiveness of EADs as brakes or, more broadly, in exerting shear forces. This opens up the possibility of utilizing cutting-edge technologies to push the boundaries of technology to the fullest.

Nonlinear optical effects manifested by electromagnetic induced transparency in cold atoms

This dissertation reports experimental studies of nonlinear optical effects manifested by electromagnetically induced transparency (EIT) in cold Rb atoms. The cold Rb atoms are confined in a magneto-optic trap (MOT) obtained with the standard laser cooling and trapping technique. Because of the near zero Doppler shift and a high phase density, the cold Rb sample is well suited for studies of atomic coherence and interference and related applications, and the experiments can be compared quantitatively with theoretical calculations. It is shown that with EIT induced in the multi-level Rb system by laser fields, the linear absorption is suppressed and the nonlinear susceptibility is enhanced, which enables studies of nonlinear optics in the cold atoms with slow photons and at low light intensities. Three independent experiments are described and the experimental results are presented. First, an experimental method that can produce simultaneously co-propagating slow and fast light pulses is discussed and the experimental demonstration is reported. Second, it is shown that in a three-level Rb system coupled by multi-color laser fields, the multi-channel two-photon Raman transitions can be manipulated by the relative phase and frequency of a control laser field. Third, a scheme for all-optical switching near single photon levels is developed. The scheme is based on the phase-dependent multi-photon interference in a coherently coupled four-level system. The phase dependent multi-photon interference is observed and switching of a single light pulse by a control pulse containing ∼20 photons is demonstrated. These experimental studies reveal new phenomena manifested by quantum coherence and interference in cold atoms, contribute to the advancement of fundamental quantum optics and nonlinear optics at ultra-low light intensities, and may lead to the development of new techniques to control quantum states of atoms and photons, which will be useful for applications in quantum measurements and quantum photonic devices.

Rapid analysis of multiclass antibiotic residues and some of their metabolites in hospital, urban wastewater and river water by ultra-highperformance liquid chromatography coupled to quadrupole-linear ion trap tandem mass spectrometry

The present work describes the development of a fast and robust analytical method for the determination of 53 antibiotic residues, covering various chemical groups and some of their metabolites, in environmental matrices that are considered important sources of antibiotic pollution, namely hospital and urban wastewaters, as well as in river waters. The method is based on automated off-line solid phase extraction (SPE) followed by ultra-high-performance liquid chromatography coupled to quadrupole linear ion trap tandem mass spectrometry (UHPLC–QqLIT). For unequivocal identification and confirmation, and in order to fulfill EU guidelines, two selected reaction monitoring (SRM) transitions per compound are monitored (the most intense one is used for quantification and the second one for confirmation). Quantification of target antibiotics is performed by the internal standard approach, using one isotopically labeled compound for each chemical group, in order to correct matrix effects. The main advantages of the method are automation and speed-up of sample preparation, by the reduction of extraction volumes for all matrices, the fast separation of a wide spectrum of antibiotics by using ultra-high-performance liquid chromatography, its sensitivity (limits of detection in the low ng/L range) and selectivity (due to the use of tandem mass spectrometry) The inclusion of β-lactam antibiotics (penicillins and cephalosporins), which are compounds difficult to analyze in multi-residue methods due to their instability in water matrices, and some antibiotics metabolites are other important benefits of the method developed. As part of the validation procedure, the method developed was applied to the analysis of antibiotics residues in hospital, urban influent and effluent wastewaters as well as in river water samples

Sensorless synchronization method for thin-film direct optical broadband monitoring system

Optical monitoring systems are necessary to manufacture multilayer thin-film optical filters with low tolerance on spectrum specification. Furthermore, to have better accuracy on the measurement of film thickness, direct monitoring is a must. Direct monitoring implies acquiring spectrum data from the optical component undergoing the film deposition itself, in real time. In making film depositions on surfaces of optical components, the high vacuum evaporator chamber is the most popular equipment. Inside the evaporator, at the top of the chamber, there is a metallic support with several holes where the optical components are assembled. This metallic support has rotary motion to promote film homogenization. To acquire a measurement of the spectrum of the film in deposition, it is necessary to pass a light beam through a glass witness undergoing the film deposition process, and collect a sample of the light beam using a spectrometer. As both the light beam and the light collector are stationary, a synchronization system is required to identify the moment at which the optical component passes through the light beam.

Analysis and quantification of vitamin D metabolites in serum by ultra-performance liquid chromatography coupled to tandem mass spectrometry and high-resolution mass spectrometry: a method comparison and validation.

RATIONALE: The aim of the work was to develop and validate a method for the quantification of vitamin D metabolites in serum using ultra-high-pressure liquid chromatography coupled to mass spectrometry (LC/MS), and to validate a high-resolution mass spectrometry (LC/HRMS) approach against a tandem mass spectrometry (LC/MS/MS) approach using a large clinical sample set. METHODS: A fast, accurate and reliable method for the quantification of the vitamin D metabolites, 25-hydroxyvitamin D2 (25OH-D2) and 25-hydroxyvitamin D3 (25OH-D3), in human serum was developed and validated. The C3 epimer of 25OH-D3 (3-epi-25OH-D3) was also separated from 25OH-D3. The samples were rapidly prepared via a protein precipitation step followed by solid-phase extraction (SPE) using an HLB μelution plate. Quantification was performed using both LC/MS/MS and LC/HRMS systems. RESULTS: Recovery, matrix effect, inter- and intra-day reproducibility were assessed. Lower limits of quantification (LLOQs) were determined for both 25OH-D2 and 25OH-D3 for the LC/MS/MS approach (6.2 and 3.4 µg/L, respectively) and the LC/HRMS approach (2.1 and 1.7 µg/L, respectively). A Passing & Bablok fit was determined between both approaches for 25OH-D3 on 662 clinical samples (1.11 + 1.06x). It was also shown that results can be affected by the inclusion of the isomer 3-epi-25OH-D3. CONCLUSIONS: Quantification of the relevant vitamin D metabolites was successfully developed and validated here. It was shown that LC/HRMS is an accurate, powerful and easy to use approach for quantification within clinical laboratories. Finally, the results here suggest that it is important to separate 3-epi-25OH-D3 from 25OH-D3. Copyright © 2012 John Wiley & Sons, Ltd.

Comparison between a linear ion trap and a triple quadruple MS in the sensitive detection of large peptides at femtomole amounts on column.

In addition to the importance of sample preparation and extract separation, MS detection is a key factor in the sensitive quantification of large undigested peptides. In this article, a linear ion trap MS (LIT-MS) and a triple quadrupole MS (TQ-MS) have been compared in the detection of large peptides at subnanomolar concentrations. Natural brain natriuretic peptide, C-peptide, substance P and D-Junk-inhibitor peptide, a full D-amino acid therapeutic peptide, were chosen. They were detected by ESI and simultaneous MS(1) and MS(2) acquisitions. With direct peptide infusion, MS(2) spectra revealed that fragmentation was peptide dependent, milder on the LIT-MS and required high collision energies on the TQ-MS to obtain high-intensity product ions. Peptide adsorption on surfaces was overcome and peptide dilutions ranging from 0.1 to 25 nM were injected onto an ultra high-pressure LC system with a 1 mm id analytical column and coupled with the MS instruments. No difference was observed between the two instruments when recording in LC-MS(1) acquisitions. However, in LC-MS(2) acquisitions, a better sensitivity in the detection of large peptides was observed with the LIT-MS. Indeed, with the three longer peptides, the typical fragmentation in the TQ-MS resulted in a dramatic loss of sensitivity (> or = 10x).