Application of space-charge electrostatic precipitator for collection of oil mist from pyrolysis gases

A novel electrostatic precipitator CAROLA® is developed for collection of fine oil mists. It operates on the principle of unipolar particle charging in the corona discharge and particle precipitation under the field of space charge. The pilot precipitator was tested at different gas temperatures. It is shown that the increase of gas temperature changes the characteristics of the corona discharge and particle size distribution, especially for droplets sub-micron droplets. The CAROLA® precipitator was used for collection of oil mist from pyrolysis gases at the HALOCLEAN® plant. The flow rate of biomass in the HALOCLEAN® plant was 15-30 kg/h. The particle mass concentration in the raw gas was over 100 g/Nm. The operation voltage of the precipitator was 10-12 kV and corona current up to 0,1 mA. Single stage electrostatic precipitator ensured mass collection efficiency 97-99,5% for pyrolysis oil mist.

Passive scene imaging of absorbing gases by narrowband dielectric filter modulation

This paper examines a method for locating within a scene a distribution of an absorbing gas using a passive imaging technique. An oscillatory modulation of the angle of a narrowband dielectric filter located in front of a camera imaging a scene, gives rise to an intensity modulation that differs in regions occupied by the absorbing gas. A preliminary low cost system has been constructed from readily available components which demonstrates how the location of gas within a scene can be implemented. Modelling of the system has been carried out, especially highlighting the transmission effects of the dielectric filter upon different regions of the image.

Detection of phospholipid oxidation in oxidatively stressed cells by reversed-phase HPLC coupled with positive-ionization electrospray MS

Measurement of lipid peroxidation is a commonly used method of detecting oxidative damage to biological tissues, but the most frequently used methods, including MS, measure breakdown products and are therefore indirect. We have coupled reversed-phase HPLC with positive-ionization electrospray MS (LC-MS) to provide a method for separating and detecting intact oxidized phospholipids in oxidatively stressed mammalian cells without extensive sample preparation. The elution profile of phospholipid hydroperoxides and chlorohydrins was first characterized using individual phospholipids or a defined phospholipid mixture as a model system. The facility of detection of the oxidized species in complex mixtures was greatly improved compared with direct-injection MS analysis, as they eluted earlier than the native lipids, owing to the decrease in hydrophobicity. In U937 and HL60 cells treated in vitro with t-butylhydroperoxide plus Fe2+, lipid oxidation could not be observed by direct injection, but LC-MS allowed the detection of monohydroperoxides of palmitoyl-linoleoyl and stearoyl-linoleoyl phosphatidylcholines. The levels of hydroperoxides observed in U937 cells were found to depend on the duration and severity of the oxidative stress. In cells treated with HOCl, chlorohydrins of palmitoyloleoyl phosphatidylcholine were observed by LC-MS. The method was able to detect very small amounts of oxidized lipids compared with the levels of native lipids present. The membrane-lipid profiles of these cells were found to be quite resistant to damage until high concentrations of oxidants were used. This is the first report of direct detection by LC-MS of intact oxidized phospholipids induced in cultured cells subjected to oxidative stress.

Design of a low power - high temperature heated ceramic sensor to detect halogen gases

The design, construction and optimization of a low power-high temperature heated ceramic sensor to detect leaking of halogen gases in refrigeration systems are presented. The manufacturing process was done with microelectronic assembly and the Low Temperature Cofire Ceramic (LTCC) technique. Four basic sensor materials were fabricated and tested: Li2SiO3, Na2SiO3, K2SiO3, and CaSiO 3. The evaluation of the sensor material, sensor size, operating temperature, bias voltage, electrodes size, firing temperature, gas flow, and sensor life was done. All sensors responded to the gas showing stability and reproducibility. Before exposing the sensor to the gas, the sensor was modeled like a resistor in series and the calculations obtained were in agreement with the experimental values. The sensor response to the gas was divided in surface diffusion and bulk diffusion; both were analyzed showing agreement between the calculations and the experimental values. The sensor with 51.5%CaSiO3 + 48.5%Li 2SiO3 shows the best results, including a stable current and response to the gas. ^

Design of a Low Power – High Temperature Heated Ceramic Sensor to Detect Halogen Gases

The design, construction and optimization of a low power-high temperature heated ceramic sensor to detect leaking of halogen gases in refrigeration systems are presented. The manufacturing process was done with microelectronic assembly and the Low Temperature Cofire Ceramic (LTCC) technique. Four basic sensor materials were fabricated and tested: Li2SiO3, Na2SiO3, K2SiO3, and CaSiO3. The evaluation of the sensor material, sensor size, operating temperature, bias voltage, electrodes size, firing temperature, gas flow, and sensor life was done. All sensors responded to the gas showing stability and reproducibility. Before exposing the sensor to the gas, the sensor was modeled like a resistor in series and the calculations obtained were in agreement with the experimental values. The sensor response to the gas was divided in surface diffusion and bulk diffusion; both were analyzed showing agreement between the calculations and the experimental values. The sensor with 51.5%CaSiO3 + 48.5%Li2SiO3 shows the best results, including a stable current and response to the gas.

Environmental analysis of polar herbicides in complex organic-rich matrices by high performance liquid chromatography atmospheric pressure ionization mass spectrometry (HPLC-API-MS)

A comprehensive forensic investigation of sensitive ecosystems in the Everglades Area is presented. Assessing the background levels of contamination in these ecosystems represents a vital resource to build up forensic evidence required to enforce future environmental crimes within the studied areas. This investigation presents the development and validation of a fractionation and isolation method for two families of herbicides commonly applied in the vicinity of the study area, including phenoxy acids like 2,4-D, MCPA, and silvex; as well as the most common triazine-based herbicides like atrazine, prometyne, simazine and related metabolites like DIA and DEA. Accelerated solvent extraction (ASE) and solid phase extraction (SPE) were used to isolate the analytes from abiotic matrices containing large amounts of organic material. Atmospheric-pressure ionization (API) with electrospray ionization in negative mode (ESP-), and Chemical Ionization in the positive mode (APCI+) were used to perform the characterization of the herbicides of interest.

Analysis of bio-derived platform chemicals in ionic liquid media by desorption/ionization mass spectrometry

In this work, desorption/ionization mass spectrometry was employed for the analysis of sugars and small platform chemicals that are common intermediates in biomass transformation reactions. Specifically, matrix-assisted laser desorption/ionization (MALDI) and desorption electrospray ionization (DESI) mass spectrometric techniques were employed as alternatives to traditional chromatographic methods. Ionic liquid matrices (ILMs) were designed based on traditional solid MALDI matrices (2,5-dihydroxybenzoic acid (DHB) and α-cyano-4-hydroxycinnamic acid (CHCA)) and 1,3-dialkylimidazolium ionic liquids ([BMIM]Cl, [EMIM]Cl, and [EMIM]OAc) that have been employed as reaction media for biomass transformation reactions such as the conversion of carbohydrates to valuable platform chemicals. Although two new ILMs were synthesized ([EMIM][DHB] and [EMIM][CHCA] from [EMIM]OAc), chloride-containing ILs did not react with matrices and resulted in mixtures of IL and matrix in solution. Compared to the parent solid matrices, much less matrix interference was observed in the low mass region of the mass spectrum (< 500 Da) using each of the IL-matrices. Furthermore, the formation of a true ILM (i.e. a new ion pair) does not appear to be necessary for analyte ionization. MALDI sample preparation techniques were optimized based on the compatibility with analyte, IL and matrix. ILMs and IL-matrix mixtures of DHB allowed for qualitative analysis of glucose, fructose, sucrose and N-acetyl-D-glucosamine. Analogous CHCA-containing ILMs did not result in appreciable analyte signals under similar conditions. Small platform compounds such as 5-hydroxymethylfurfural (HMF) and levulinic acid were not detected by direct analysis using MALDI-MS. Furthermore, sugar analyte signals were only detected at relatively high matrix:IL:analyte ratios (1:1:1) due to significant matrix and analyte suppression by the IL ions. Therefore, chemical modification of analytes with glycidyltrimethylammonium chloride (GTMA) was employed to extend this method to quantitative applications. Derivatization was accomplished in aqueous IL solutions with fair reaction efficiencies (36.9 – 48.4 % glucose conversion). Calibration curves of derivatized glucose-GTMA yielded good linearity in all solvent systems tested, with decreased % RSDs of analyte ion signals in IL solutions as compared to purely aqueous systems (1.2 – 7.2 % and 4.2 – 8.7 %, respectively). Derivatization resulted in a substantial increase in sensitivity for MALDI-MS analyses: glucose was reliably detected at IL:analyte ratios of 100:1 (as compared to 1:1 prior to derivatization). Screening of all test analytes resulted in appreciable analyte signals in MALDI-MS spectra, including both HMF and levulinic acid. Using appropriate internal standards, calibration curves were constructed and this method was employed for monitoring a model dehydration reaction of fructose to HMF in [BMIM]Cl. Calibration curves showed wide dynamic ranges (LOD – 100 ng fructose/μg [BMIM]Cl, LOD – 75 ng HMF/μg [BMIM]Cl) with correlation coefficients of 0.9973 (fructose) and 0.9931 (HMF). LODs were estimated from the calibration data to be 7.2 ng fructose/μg [BMIM]Cl and 7.5 ng HMF/μg [BMIM]Cl, however relatively high S/N ratios at these concentrations indicate that these values are likely overestimated. Application of this method allowed for the rapid acquisition of quantitative data without the need for prior separation of analyte and IL. Finally, small molecule platform chemicals HMF and levulinic acid were qualitatively analyzed by DESI-MS. Both HMF and levulinic acid were easily ionized and the corresponding molecular ions were easily detected in the presence of 10 – 100 times IL, without the need for chemical modification prior to analysis. DESI-MS analysis of ILs in positive and negative ion modes resulted in few ions in the low mass region, showing great potential for the analysis of small molecules in IL media.

Chemical and isotopic compositions of water, particulates, plankton, gases, sediments, and minerals from the Kara Sea and lower Ob and Yenisei Rivers

The Kara Sea is an area uniquely suitable for studying processes in the river-sea system. This is a shallow sea, into which two great Siberian rivers, Yenisei and Ob, flow. From 1995 to 2003, the sea was studied by six international expeditions onboard the R/V Akademik Boris Petrov. This publication summarizes the results obtained, within the framework of this project, at the Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences. Various hydrogeochemical parameters, concentrations and isotopic composition of organic and carbonate carbon of the sediments, plankton, particulate organic matter, hydrocarbons, and dissolved CO2 were examined throughout the whole sea area at more than 200 sites. The d13C varies from -22 and -24 per mil where Atlantic waters enter the Kara Sea and in the north-eastern part of the water area to -27 per mil in the Yenisei and Ob estuaries. The value of d13C of the plankton is only weakly correlated with the d13C of the organic matter from the sediments and is lower by as much as 3-4 per mil. The paper presents the results obtained from a number of meridional river-sea profiles. It was determined from the relations between the isotopic compositions of plankton and particulate matter that the river waters carry material consisting of 70% detrital-humus matter and 30% planktonogenic material in the river part, and the material contained in the offshore waters consists of 30% terrigenous components, with the contribution of bioproducers amounting to 70%. The carbon isotopic composition of the plankton ranges from -29 to -35 per mil in the riverine part, from -28 to -27 per mil in the estuaries, and from -27.0 to -25 per mil in the marine part. The relative lightness of the carbon isotopic composition of plankton in Arctic waters is explained by the temperature effect, elevated CO2 concentrations, and long-distance CO2 supply to the sea with river waters. The data obtained on the isotopic composition of CO2 in the surface waters of the Kara Sea were used to map the distribution of d13C. The complex of hydrocarbon gases extracted from the waters included methane, C2-C5, and unsaturated C2=-C4= hydrocarbons, for which variations in the concentrations in the waters were studied along river-estuary-sea profiles. The geochemistry of hydrocarbon gases in surface fresh waters is characterized by comparable concentrations of methane (0.3-5 µl/l) and heavier hydrocarbons, including unsaturated ones. Microbiological methane with d13C from -105 to -90 per mil first occurs in the sediments at depths of 40-200 cm. The sediments practically everywhere display traces of methane oxidation in the form of a shift of the d13C of methane toward higher values and the occurrence of autogenic carbonate material, including ikaite, enriched in the light isotope. Ikaite (d13C from -25 to -60 per mil) was found and examined in several profiles. The redox conditions in the sediments varied from normal in the southern part of the sea to highly oxidized along the Novaya Zemlya Trough. Vertical sections through the sediments of the latter exemplify the complete suppression of the biochemical activity of microorganisms. Our data provide insight into the biogeochemistry of the Kara Sea and make it possible to specify the background values needed for ecological control during the future exploration operations and extraction of hydrocarbons in the Kara Sea.

Simulation of greenhouse gases following land-use change to bioenergy crops using the ECOSSE model : a comparison between site measurements and model predictions

This work contributes to the ELUM (Ecosystem Land Use Modelling & Soil Carbon GHG Flux Trial) project, which was commissioned and funded by the Energy Technologies Institute (ETI). We acknowledge the E-OBS data set from the EU-FP6 project ENSEMBLES (http://ensembles-eu.metoffice.com) and the data providers in the ECA&D project (http://www.ecad.eu).

Nanofiber control of ultracold quantum gases

While a great amount of attention is being given to the development of nanodevices, both through academic research and private industry, the field is still on the verge. Progress hinges upon the development of tools and components that can precisely control the interaction between light and matter, and that can be efficiently integrated into nano-devices. Nanofibers are one of the most promising candidates for such purposes. However, in order to fully exploit their potential, a more intimate knowledge of how nanofibers interact with single neutral atoms must be gained. As we learn more about the properties of nanofiber modes, and the way they interface with atoms, and as the technology develops that allows them to be prepared with more precisely known properties, they become more and more adaptable and effective. The work presented in this thesis touches on many topics, which is testament to the broad range of applications and high degree of promise that nanofibers hold. For immediate use, we need to fully grasp how they can be best implemented as sensors, filters, detectors, and switches in existing nano-technologies. Areas of interest also include how they might be best exploited for probing atom-surface interactions, single-atom detection and single photon generation. Nanofiber research is also motivated by their potential integration into fundamental cold atom quantum experiments, and the role they can play there. Combining nanofibers with existing optical and quantum technologies is a powerful strategy for advancing areas like quantum computation, quantum information processing, and quantum communication. In this thesis I present a variety of theoretical work, which explores a range of the applications listed above. The first work presented concerns the use of the evanescent fields around a nanofiber to manipulate an existing trapping geometry and therefore influence the centre-of-mass dynamics of the atom. The second work presented explores interesting trapping geometries that can be achieved in the vicinity of a fiber in which just four modes are allowed to propagate. In a third study I explore the use of a nanofiber as a detector of small numbers of photons by calculating the rate of emission into the fiber modes when the fiber is moved along next to a regularly separated array of atoms. Also included are some results from a work in progress, where I consider the scattered field that appears along the nanofiber axis when a small number of atoms trapped along that axis are illuminated orthogonally; some interesting preliminary results are outlined. Finally, in contrast with the rest of the thesis, I consider some interesting physics that can be done in one of the trapping geometries that can be created around the fiber, here I explore the ground states of a phase separated two-component superfluid Bose-Einstein condensate trapped in a toroidal potential.

Analyses of hydrocarbon gases and sulphate in sediments from the King George Basin, Antarctica

Thermogenic hydrocarbons, formed by the thermal alteration of organic matter, are encountered in several piston core stations in the King George Basin, Anatarctica. These hemipelagic sediments are being deposited in an area of active hydrothermalism, associated with the back-arc spreading in the Bransfield Strait. The lateral extent of sediments infiltrated by the hydrothermally influenced interstitial fluids is characterized by basalt diapiric intrusions and is delineated by an acoustically turbid zone in the sediments of the eastern part of the basin. Iron-sulphide-bearing veins and fractures cut across the sediment in several cores; they appear to be conduits for flow of hydrothermally altered fluids. These zones have the highest C2+ and ethene contents. The thermogenic hydrocarbons have molecular C1/(C2 + C3) ratios typically < 50 and delta13CH4 values between -38? and -48?, indicating an organic source which has undergone strong thermal stress. Several sediment cores also have mixed gas signatures, which indicate the presence of substantial amounts of bacterial gas, predominantly methane. Hydrocarbon generation in the King George Basin is thought to be a local phenomenon, resulting from submarine volcanism with temperatures in the range 70-150°C. There are no apparent seepages of hydrocarbons into the water column, and it is not believed that significant accumulation of thermogenic hydrocarbons reside in the basin.

Composition of noble gases in sediments and metasediments

Solar-type helium (He) and neon (Ne) in the Earth's mantle were suggested to be the result of solarwind loaded extraterrestrial dust that accumulated in deep-sea sediments and was subducted into the Earth's mantle. To obtain additional constraints on this hypothesis, we analysed He, Ne and argon (Ar) in high pressure-low temperature metamorphic rocks representing equivalents of former pelagic clays and cherts from Andros (Cyclades, Greece) and Laytonville (California, USA). While the metasediments contain significant amounts of 4He, 21Ne and 40Ar due to U, Th and K decay, no solar-type primordial noble gases were observed. Most of these were obviously lost during metamorphism preceding 30 km subduction depth. We also analysed magnetic fines from two Pacific ODP drillcore samples, which contain solar-type He and Ne dominated by solar energetic particles (SEP). The existing noble gas isotope data of deep-sea floor magnetic fines and interplanetary dust particles demonstrate that a considerable fraction of the extraterrestrial dust reaching the Earth has lost solar wind (SW) ions implanted at low energies, leading to a preferential occurrence of deeply implanted SEP He and Ne, fractionated He/Ne ratios and measurable traces of spallogenic isotopes. This effect is most probably caused by larger particles, as these suffer more severe atmospheric entry heating and surface ablation. Only sufficiently fine-grained dust may retain the original unfractionated solar composition that is characteristic for the Earth's mantle He and Ne. Hence, in addition to the problem of metamorphic loss of solar noble gases during subduction, the isotopic and elemental fractionation during atmospheric entry heating is a further restriction for possible subduction hypotheses.