Characterisation of brown coal humic acids and modified humic acids using pyrolysis gcms and other techniques

It has been proposed that Victorian brown coal can be considered as a two-component structure — a lignocellulosic “host”, containing various amounts of weakly bound or entrapped “guest” material together with very small amounts of inorganic and/or mineral matter. The latter predominantly consists of wax esters and/or terpenoid material. In this paper we describe attempts to gain structural information regarding the more complex, “host” component of the coal. Our initial model compound has been humic acid that can be readily obtained from the coal by alkaline extraction. It has been found that “pure” humic acid, free from material associated with the “guest” components of the coal, can be obtained by a highly selective, low-yielding alkaline extraction. This humic acid has been studied by nmr spectroscopy and pyrolysis gas chromatography-mass spectroscopy (py-gc/ms). The products arising from py-gc/ms have been compared with those obtained from similar pyrolysis of whole coals. Alkylation of humic acids using alkyl halides in the presence of base has been successfully carried out and reactivity of the resulting materials compared with those of the parent coal and humic acid.     

Mapping and monitoring carbon stocks with satellite observations: a comparison of methods

Mapping and monitoring carbon stocks in forested regions of the world, particularly the tropics, has attracted a great deal of attention in recent years as deforestation and forest degradation account for up to 30% of anthropogenic carbon emissions, and are now included in climate change negotiations. We review the potential for satellites to measure carbon stocks, specifically aboveground biomass (AGB), and provide an overview of a range of approaches that have been developed and used to map AGB across a diverse set of conditions and geographic areas. We provide a summary of types of remote sensing measurements relevant to mapping AGB, and assess the relative merits and limitations of each. We then provide an overview of traditional techniques of mapping AGB based on ascribing field measurements to vegetation or land cover type classes, and describe the merits and limitations of those relative to recent data mining algorithms used in the context of an approach based on direct utilization of remote sensing measurements, whether optical or lidar reflectance, or radar backscatter. We conclude that while satellite remote sensing has often been discounted as inadequate for the task, attempts to map AGB without satellite imagery are insufficient. Moreover, the direct remote sensing approach provided more coherent maps of AGB relative to traditional approaches. We demonstrate this with a case study focused on continental Africa and discuss the work in the context of reducing uncertainty for carbon monitoring and markets.     

One-dimensional baroclinically unstable waves on the Gulf Stream potential vorticity gradient near Cape Hatteras

Application of linear baroclinic instability theory to the observed distributions of velocity, stratification, and potential vorticity in the Gulf Stream near 74° W is successful in predicting the time and length scales of the most rapidly growing disturbances. A continuously-stratified, one-dimensional model with realistic bottom slope predicts propagation speeds of 10–50 cm s⁻¹ associated with two regimes of rapid temporal growth centered at periods of 28 days and 5–7 days. This prediction is consistent with observations of the propagation and growth of Gulf Stream meanders derived from inverted echo sounder measurements in this region. The instability model also predicts that for realistic bottom slopes the baroclinic energy transfer should be weakly negative (eddy-to-mean) in deep water, but for low-frequency waves should change to significant positive (mean-to-eddy) transfer above depths of 1500 m, consistent with observations.     

Complete chemical analyses of metamorphic hornblendes: implications for normalizations,calculated H2O activities,and thermobarometry

Twenty-two hornblendes separated from amphibolites and granulites of the Grenville Orogen of Ontario have been quantitatively analyzed for major and minor elements by electron microprobe, for FeO/Fe₂O₃ by wet chemistry, and for H₂O by manometric measurement as H₂. Hornblende formulae were calculated on the basis of 24O+OH+Cl+F. Most samples are magnesio-hornblendes, ferroan pargasitic hornblendes and ferroan hastingsitic hornblendes, with weight fractions of Fe³⁺/(Fe²⁺+Fe³⁺) ranging from 0.15 to 0.50. An oxy-amphibole component of 0–25 mol%, with an average value of 17 mol%, is obtained for these complete analyses. When compared with structural formulae determined solely from microprobe data, normalization based on 13=Si+Ti+Al+Fe+Mn+Mg cations provides the best approximation to hornblende formulae calculated from the complete analyses. Less satisfactory agreement is obtained from a normalization scheme based on 15=Si+Ti+Al+Fe+Mn+Mg+Ca, while worst agreement is obtained from normalization to 23 oxygens assuming all Fe is Fe²⁺. No normalization scheme based on microprobe data alone consistently replicates the measured FeO, Fe₂O₃, and H₂O; accurate determination of these values requires complete chemical analysies. Ionic solution models previously have been proposed to evaluate the activity of Ca₂Mg₅Si₈ O₂₂(OH)₂(a _Trem) in hornblende for use in equilibria that constrain the activity of H₂O (a _{H 2}O) in igneous and metamorphic rocks. Application of ionic models to typical hornblendes produces low a _Trem (usually<0.01), consequetly yielding extremely low a _{H 2}O. If an oxy-amphibole component is present, the calculated a _Trem and H₂O is further reduced. An oxy-amphibole component of 25% reduces the calculated H₂O activity and that of any hydroxyl-amphibole component by 50% below that calculated with simplified assumptions regarding X _OH in the hydroxyl site (i.e., X _OH=1, or X _OH=1–X _Cl–X _f). Thus, methods of amphibole normalizations appear to have a substantial effect on calculated amphibole and H₂O activites. Before quantitative hornblende thermobarometry can be calibrated and applied, the amounts of FeO, Fe₂O₃ and H₂O must be measured in order to fully characterize hornblende solid solutions.Contribution No. 478 from the Mineralogical Laboratory, University of Michigan     

Structural relationships between a brown coal and its kerogen and humic acid fractions

A South Australian Tertiary brown coal is fractionated into humic acid and kerogen fractions. These related samples are then subjected to a number of different analytical techniques including infrared and¹³C-Nuclear Magnetic Resonance spectroscopies and pertrifluoroacetic acid oxidation. Structural conclusions are drawn from an integrated consideration of the data. Brown coal aliphatic structure is concentrated in the kerogen and the solvent soluble polar acid fractions. The humic acids are the most aromatic and contain a high degree of hydrogen bonding. Only very minor amounts of long polymethylene chain structures are observed in the humic acids, in complete contrast to the kerogen fraction. Different organic detrital origins are proposed for the coal fractions.     

Organic geochemical studies of a recent Inner Great Barrier Reef sediment—I. Assessment of input sources

The concentration of solvent-extractable (SE) and bound hydrocarbons, ketones, alcohols, sterols, monocarboxylic acids, hydroxyacids and α,ω-dicarboxylic acids of a surface sample (0–2.5 cm) from a recent carbonate tropical sediment taken at 60ft (18m) depth north-west of the Low Isles, North Queensland, are reported in detail. n-Alkanes are a minor constituent in the SE and bound hydrocarbon fractions with the major component being unresolved complex hydrocarbon material which is not an anthropogenic input. 6,10,14-Trimethylpentadecan-2-one derived from chlorophyll, as well as phytol, were identified as major components of the ketone and alcohol constituents. No chlorophyll pigments or pigmented degradation products were present, implying degradation before incorporation into the sediment. This conclusion is consistent with evidence for higher-plant input in which all sensitive lipids have been degraded before incorporation. SE and bound fractions have been studied in detail and show considerable differences probably arising from the importance of viable biomass in the SE fraction. Inputs to the sediment are determined as higher plants, algae, bacteria, fungi and meiofauna in descending order of importance.     

An evaluation of Rock-Eval pyrolysis for the study of Australian coals including their kerogen and humic acid fractions

Rock-Eval pyrolysis was performed on lithotype and depth profiles of Tertiary brown coals and a coalification profile of Permian bituminous coals. The humic acid and kerogen fractions from the coals are also investigated by this technique along with the effect of base extraction on the kerogen fraction. Structural variations between brown coal lithotypes are primarily reflected by changes in Oxygen Index Value. This result was supported by the results from the depth profile (same lithotype). A wide range of Hydrogen Indices (independent of depth) but similar Oxygen Indices were observed. The results from the Qualification profile show that the Oxygen Indices varied with rank, whereas Hydrogen Indices show a greater dependence on coal type. A plot of $\text{H}\text{C}$versus Hydrogen Index produced good correlations with the brown (0.77) and bituminous (0.90) samples lying on two separate lines intersecting at high H/C. This result (and higher correlation for bituminous samples) reflects the expected dependence of hydrogen index on oxygen content (present primarily as hydroxyl groups). A high correlation (0.95) between quantitative IR data (K 2920 cm mg^?1) and Hydrogen Indices supports previous conclusions regarding the dependence of Hydrogen Indices on the aliphatic structure of the samples.     

Mapping the Globalization of the Temporary Staffing Industry*

Very little is currently known about the globalization of the temporary staffing industry, a strategically significant sector given its role in promulgating wider labor market flexibility. This article starts to rectify this research lacuna in four ways: by conceptualizing the international expansion of temporary staffing and comparing it to other business service sectors, by identifying and mapping the top twenty transnational staffing agencies, by offering a typology of the leading transnational agencies based on their functional and geographic characteristics, and by charting a research agenda for future work on this sector.     

On increasing the structural damping of a steel chimney

Experimental results of a study which was commissioned to investigate the possible benefit of added structural damping in reducing the susceptibility of a steel chimney to wind-excited swaying vibrations are presented and discussed. The experimental and analytical techniques used are briefly described. The results indicated a significant increase in structural damping when pads of a special damping material were incorporated into the foundation structure of the chimney.