Comprehensive Two-Dimensional Gas Chromatography: Instrumental and Methodological Development

Comprehensive two-dimensional gas chromatography (GC×GC) offers enhanced separation efficiency, reliability in qualitative and quantitative analysis, capability to detect low quantities, and information on the whole sample and its components. These features are essential in the analysis of complex samples, in which the number of compounds may be large or the analytes of interest are present at trace level. This study involved the development of instrumentation, data analysis programs and methodologies for GC×GC and their application in studies on qualitative and quantitative aspects of GC×GC analysis. Environmental samples were used as model samples. Instrumental development comprised the construction of three versions of a semi-rotating cryogenic modulator in which modulation was based on two-step cryogenic trapping with continuously flowing carbon dioxide as coolant. Two-step trapping was achieved by rotating the nozzle spraying the carbon dioxide with a motor. The fastest rotation and highest modulation frequency were achieved with a permanent magnetic motor, and modulation was most accurate when the motor was controlled with a microcontroller containing a quartz crystal. Heated wire resistors were unnecessary for the desorption step when liquid carbon dioxide was used as coolant. With use of the modulators developed in this study, the narrowest peaks were 75 ms at base. Three data analysis programs were developed allowing basic, comparison and identification operations. Basic operations enabled the visualisation of two-dimensional plots and the determination of retention times, peak heights and volumes. The overlaying feature in the comparison program allowed easy comparison of 2D plots. An automated identification procedure based on mass spectra and retention parameters allowed the qualitative analysis of data obtained by GC×GC and time-of-flight mass spectrometry. In the methodological development, sample preparation (extraction and clean-up) and GC×GC methods were developed for the analysis of atmospheric aerosol and sediment samples. Dynamic sonication assisted extraction was well suited for atmospheric aerosols collected on a filter. A clean-up procedure utilising normal phase liquid chromatography with ultra violet detection worked well in the removal of aliphatic hydrocarbons from a sediment extract. GC×GC with flame ionisation detection or quadrupole mass spectrometry provided good reliability in the qualitative analysis of target analytes. However, GC×GC with time-of-flight mass spectrometry was needed in the analysis of unknowns. The automated identification procedure that was developed was efficient in the analysis of large data files, but manual search and analyst knowledge are invaluable as well. Quantitative analysis was examined in terms of calibration procedures and the effect of matrix compounds on GC×GC separation. In addition to calibration in GC×GC with summed peak areas or peak volumes, simplified area calibration based on normal GC signal can be used to quantify compounds in samples analysed by GC×GC so long as certain qualitative and quantitative prerequisites are met. In a study of the effect of matrix compounds on GC×GC separation, it was shown that quality of the separation of PAHs is not significantly disturbed by the amount of matrix and quantitativeness suffers only slightly in the presence of matrix and when the amount of target compounds is low. The benefits of GC×GC in the analysis of complex samples easily overcome some minor drawbacks of the technique. The developed instrumentation and methodologies performed well for environmental samples, but they could also be applied for other complex samples.

A New Rare-Gas Compound: HXeOXeH

Rare-gas chemistry is of growing interest, and the recent advances include the "insertion" of a Xe atom into OH and water in the rare-gas hydrides HXeO and HXeOH. The insertion of Xe atoms into the H-C bonds of hydrocarbons was also demonstrated for HXeCC, HXeCCH and HXeCCXeH, the last of which was the first rare-gas hydride containing two rare-gas atoms. We describe the preparation and characterization of a new rare-gas compound, HXeOXeH. HXeOXeH was prepared in solid xenon by photolysis of a suitable precursor, for example water, and subsequent mobilization of the photoproducts. The experimental identification was carried out by FTIR spectroscopy, isotopic substitution and by use of various precursors. The photolytical and thermal stability of the new rare-gas hydride was also studied. The experimental work was supported by extensive quantum chemical calculations provided by our co-workers. HXeOXeH forms in a cryogenic xenon matrix from neutral O and H atoms in a two-step diffusion-controlled process involving HXeO as an intermediate [reactions (1) and (2)]. This formation mechanism is unique in that a rare-gas hydride is formed from another rare-gas hydride. H + Xe + O → HXeO (1) HXeO + Xe + H → HXeOXeH (2) Similarly to other rare-gas hydrides, HXeOXeH has a strongly IR-active H-Xe stretching vibration, allowing its spectral detection at 1379.3 cm-1. HXeOXeH is a very high-energy metastable species, yet thermally more stable than many other rare-gas hydrides. The calculated bending barrier of 0.57 eV, is not enough to explain the observed stability, and HXeOXeH might be affected by additional stabilization from the solid xenon environment. Chemical bonding between xenon and environmentally abundant species like water is of particular importance due to the “missing-xenon” problem. The relatively high thermal stability of HXeOXeH compared to other oxygen containing rare-gas compounds is relevant in this respect. Our work also raises the possibility of polymeric (–Xe–O)n networks, similarly to the computationally studied (XeCC)n polymers.

Baseline and greenhouse-gas emissions in extensive livestock enterprises, with a case study of feeding lipid to beef cattle

For accurate calculation of reductions in greenhouse-gas (GHG) emissions, methodologies under the Australian Government's Carbon Farming Initiative (CFI) depend on a valid assessment of the baseline and project emissions. Life-cycle assessments (LCAs) clearly show that enteric methane emitted from the rumen of cattle and sheep is the major source of GHG emissions from livestock enterprises. Where a historic baseline for a CFI methodology for livestock is required, the use of simulated data for cow-calf enterprises at six sites in southern Australia demonstrated that a 5-year rolling emission average will provide an acceptable trade off in terms of accuracy and stability, but this is a much shorter time period than typically used for LCA. For many CFI livestock methodologies, comparative or pair-wise baselines are potentially more appropriate than historic baselines. A case study of lipid supplementation of beef cows over winter is presented. The case study of a control herd of 250 cows used a comparative baseline derived from simple data on livestock numbers and class of livestock to quantify the emission abatement. Compared with the control herd, lipid supplementation to cows over winter increased livestock productivity, total livestock production and enterprise GHG emissions from 990 t CO2-e to 1022 t CO2-e. Energy embodied in the supplement and extra diesel used in transporting the supplement diminished the enteric-methane abatement benefit of lipid supplementation. Reducing the cow herd to 238 cows maintained the level of livestock production of the control herd and reduced enterprise emissions to 938 t CO2-e, but was not cost effective under the assumptions of this case study.

Line tension of a two dimensional gas-liquid interface

In two dimensional (2D) gas-liquid systems, the reported simulation values of line tension are known to disagree with the existing theoretical estimates. We find that while the simulation erred in truncating the range of the interaction potential, and as a result grossly underestimated the actual value, the earlier theoretical calculation was also limited by several approximations. When both the simulation and the theory are improved, we find that the estimate of line tension is in better agreement with each other. The small value of surface tension suggests increased influence of noncircular clusters in 2D gas-liquid nucleation, as indeed observed in a recent simulation.

LPG Gas-Sensing System With SnO2 Thin-Film Transducer and 0.7-mu m CMOS Signal Conditioning ASIC

The design and implementation of a complete gas sensor system for liquified petroleum gas (LPG) gas sensing are presented. The system consists of a SnO2 transducer, a lowcost heater, an application specific integrated circuit (ASIC) with front-end interface circuitry, and a microcontroller interface for data logging. The ASIC includes a relaxation-oscillator-based heater driver circuit that is capable of controlling the sensor operating temperature from 100degC to 425degC. The sensor readout circuit in the ASIC, which is based on the resistance to time conversion technique, has been designed to measure the gas sensor response over three orders of resistance change during its interaction with gases.

Experimental investigation of catalytic and non-catalytic surface reactions on SiO2 thin films with shock heated oxygen gas

The present study is to investigate the interaction of strong shock heated oxygen on the surface of SiO2 thin film. The thermally excited oxygen undergoes a three-body recombination reaction on the surface of silicon dioxide film. The different oxidation states of silicon species on the surface of the shock-exposed SiO2 film are discussed based on X-ray Photoelectron Spectroscopy (XPS) results. The surface morphology of the shock wave induced damage at the cross section of SiO2 film and structure modification of these materials are analyzed using scanning electron microscopy and ion microscopy. Whether the surface reaction of oxygen on SiO2 film is catalytic or non-catalytic is discussed in this paper.

Experimental investigation of interaction of strong shock heated oxygen gas on the surface of ZrO2 - a novel method to understand re-combination heating

Interaction of shock heated test gas in the free piston driven shock tube with bulk and thin film of cubic zirconium dioxide (ZrO2) prepared by combustion method is investigated. The test samples before and after exposure to the shock wave are analyzed by X-ray diffraction (XRD), X-Ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscope (SEM). The study shows transformation of metastable cubic ZrO2 to stable monoclinic ZrO2 phase after interacting with shock heated oxygen gas due to the heterogeneous catalytic recombination surface reaction.

Does manure management affect the latent greenhouse gas emitting potential of livestock manures?

With livestock manures being increasingly sought as alternatives to costly synthetic fertilisers, it is imperative that we understand and manage their associated greenhouse gas (GHG) emissions. Here we provide the first dedicated assessment into how the GHG emitting potential of various manures responds to the different stages of the manure management continuum (e.g., from feed pen surface vs stockpiled). The research is important from the perspective of manure application to agricultural soils. Manures studied included: manure from beef feedpen surfaces and stockpiles; poultry broiler litter (8-week batch); fresh and composted egg layer litter; and fresh and composted piggery litter. Gases assessed were methane (CH4) and nitrous oxide (N2O), the two principal agricultural GHGs. We employed proven protocols to determine the manures’ ultimate CH4 producing potential. We also devised a novel incubation experiment to elucidate their N2O emitting potential; a measure for which no established methods exist. We found lower CH4 potentials in manures from later stages in their management sequence compared with earlier stages, but only by a factor of 0.65×. Moreover, for the beef manures this decrease was not significant (P < 0.05). Nitrous oxide emission potential was significantly positively (P < 0.05) correlated with C/N ratios yet showed no obvious relationship with manure management stage. Indeed, N2O emissions from the composted egg manure were considerably (13×) and significantly (P < 0.05) higher than that of the fresh egg manure. Our study demonstrates that manures from all stages of the manure management continuum potentially entail significant GHG risk when applied to arable landscapes. Efforts to harness manure resources need to account for this.

Application of sorbers to mitigate greenhouse gas emissions from land-applied pig litter

Nitrous oxide is the foremost greenhouse gas (GHG)generated by land-applied manures and chemical fertilisers (Australian Government 2013). This research project was part of the National Agricultural Manure Management Program and investigated the potential for sorbers (i.e. specific naturally-occurring minerals) to decrease GHG emissions from spent piggery litter (as well as other manures)applied to soils. The sorbers investigated in this research were vermiculite and bentonite. Both are clays with high cation exchange capacities, of approximately 100–150 cmol/kg Faure 1998). The hypothesis tested in this study was that the sorbers bind ammonium in soil solution thereby suppressing ammonia (NH3)volatilisation and in doing so, slowing the kinetics of nitrate formation and associated nitrous oxide (N2O) emissions. A series of laboratory, glasshouse and field experiments were conducted to assess the sorbers’ effectiveness. The laboratory experiments comprised 64 vessels containing manure and sorber/manure ratios ranging from 1 : 10 to 1 : 1 incorporated into a sandy Sodosol via mixing. The glasshouse trial involved 240 pots comprising manure/sorber incubations placed 5 cm below the soil surface, two soil types (sandy Sodosol and Ferrosol) and two different nitrogen (N) application rates (50 kg N/ha and 150 kg N/ha) with a model plant (kikuyu grass). The field trial consisted of 96, 2 m · 2 m plots on a Ferrosol site with digit grass used as a model plant. Manure/ sorber mixtures were applied in trenches (5 cm below surface) to these plots at increasing sorber levels at anNloading rate of 200 kg/ha. Gas produced in all experiments was plumbed into a purpose-built automated gas analysis (N2O, NH3, CH4, CO2) system. In the laboratory experiments, the sorbers showed strong capacity to decreaseNH3 emissions (up to 80% decrease). Ammonia emissions were close to the detection limit in all treatments in the glasshouse and field trial. In all experiments, considerable N2O decreases (>40%) were achieved by the sorbers. As an example, mean N2O emission decreases from the field trial phase of the project are shown in Fig. 1a. The decrease inGHGemissions brought about by the clays did not negatively impact agronomic performance. Both vermiculite and bentonite resulted in a significant increase in dry matter yields in the field trial (Fig. 1b). Continuing work will optimise the sorber technology for improved environmental and agronomic performance across a range of soils (Vertosol, Dermosol in addition to Ferrosol and Sodosols) and environmental parameters (moisture, temperature, porosity, pH).

Controlled release of ethylene gas from the ethylene-α-cyclodextrin inclusion complex powder with deliquescent salts

Deliquescent calcium chloride (CaCl2) and magnesium chloride (MgCl2) were investigated for their practical application to release ethylene gas from an ethylene-α-cyclodextrin inclusion complexes (CD IC) powder at relative humidities (RHs) between 11.2 and 93.6 % at 18 °C. The IC powder and deliquescent salts were mixed at a ratio of 1:5, respectively. CaCl2 and MgCl2 started to deliquesce at 32.7 % RH. The IC powder dissolved in the concentrated salt solutions to release ethylene gas. Increasing the RH accelerated the release rate. Maximum release of ethylene gas was achieved after 24 h at 75.5 and 93.6 % RH for both IC powder-deliquescent salts mixture. The deliquescent salts proved to be a simple option for releasing ethylene gas from the IC powder.

Gas-crystal photoreaction: the structures of 4,4'-dimethoxy(thiobenzophenone) (I), C15H14O2S, and 4,4'-bis(dimethylamino)thiobenzophenone (II), C17H20N2S

(I): M r = 258.34, triclinic, Pi, a = 9.810 (3), b=9.635(3), e=15.015(4)A, a=79.11(2), #= 102.38 (3), y = 107.76 (3) o, V= 1308.5 A 3, Z = 4, Din= 1.318 (3) (by flotation in KI solution), D x = 1.311 g cm -3, Cu Ka, 2 = 1.5418/~, g = 20-05 cm -1, F(000) = 544, T---- 293 K, R = 0.074 for 2663 reflections. (II): M r = 284.43, monoclinic, P2~/c, a= 17.029 (5), b=6.706 (5), c= 14.629 (4), t= 113.55 (2) ° , V=1531.4A 3, Z=4, Dm=1.230(5) (by flotation in KI solution), Dx= 1.234gem -3, Mo Ka, 2 = 0.7107 A, g = 1.63 cm-1; F(000) = 608, T= 293 K, R = 0.062 for 855 reflections. The orientation of the C=S chromophores in the crystal lattice and their reactivity in the crystalline state are discussed. The C--S bonds are much shorter than the normal bond length [1.605 (4) (I), 1.665 (8) A (II) cf. 1.71 A].

Establishing turf grass increases soil greenhouse gas emissions in peri-urban environments

Urbanization is becoming increasingly important in terms of climate change and ecosystem functionality worldwide. We are only beginning to understand how the processes of urbanization influence ecosystem dynamics and how peri-urban environments contribute to climate change. Brisbane in South East Queensland (SEQ) currently has the most extensive urban sprawl of all Australian cities. This leads to substantial land use changes in urban and peri-urban environments and the subsequent gaseous emissions from soils are to date neglected for IPCC climate change estimations. This research examines how land use change effects methane (CH4) and nitrous oxide (N2O) fluxes from peri-urban soils and consequently influences the Global Warming Potential (GWP) of rural ecosystems in agricultural use undergoing urbanization. Therefore, manual and fully automated static chamber measurements determined soil gas fluxes over a full year and an intensive sampling campaign of 80 days after land use change. Turf grass, as the major peri-urban land cover, increased the GWP by 415 kg CO2-e ha 1 over the first 80 days after conversion from a well-established pasture. This results principally from increased daily average N2O emissions of 0.5 g N2O ha-1 d-1 from the pasture to 18.3 g N2O ha-1 d-1 from the turf grass due to fertilizer application during conversion. Compared to the native dry sclerophyll eucalypt forest, turf grass establishment increases the GWP by another 30 kg CO2-e ha 1. The results presented in this study clearly indicate the substantial impact of urbanization on soil-atmosphere gas exchange in form of non-CO2 greenhouse gas emissions particularly after turf grass establishment.

Using Big Data to manage safety-related risk in the upstream oil and gas industry: A research agenda

Despite considerable effort and a broad range of new approaches to safety management over the years, the upstream oil & gas industry has been frustrated by the sector’s stubbornly high rate of injuries and fatalities. This short communication points out, however, that the industry may be in a position to make considerable progress by applying “Big Data” analytical tools to the large volumes of safety-related data that have been collected by these organizations. Toward making this case, we examine existing safety-related information management practices in the upstream oil & gas industry, and specifically note that data in this sector often tends to be highly customized, difficult to analyze using conventional quantitative tools, and frequently ignored. We then contend that the application of new Big Data kinds of analytical techniques could potentially reveal patterns and trends that have been hidden or unknown thus far, and argue that these tools could help the upstream oil & gas sector to improve its injury and fatality statistics. Finally, we offer a research agenda toward accelerating the rate at which Big Data and new analytical capabilities could play a material role in helping the industry to improve its health and safety performance.

Discontinuities in an arbitrarily moving gas in special relativity

Singular surface theory and ray theory are used to study the propagation of a weak discontinuity in an arbitrarily moving gas within the framework of special relativity. A differential equation is obtained describing the variation of the strength of the discontinuity along rays.