The nature of straight-chain aliphatic structures in green river kerogen

Previous studies of the Green River kerogen only provide apparently contradictory conclusions about the size of the straight-chain aliphatic structures as well as the manner in which these structures form part of the kerogen matrix.The present investigation is an attempt to resolve this contradiction. A mild stepwise oxidation procedure was followed so that extensive degradation of kerogen-derived intermediates could be prevented. Products isolated from each oxidation step were analyzed by conventional GLC techniques, GC-MS, and proton-NMR measurements in order to ascertain the significance of the straight-chain aliphatic structures present in the Green River kerogen.The following results were obtained: (a) Green River kerogen contains a substantial portion (ca 2–4 carbons out of every 10) of straight-chain aliphatic structures which are longer than C₄, (b) the kerogen matrix forms a three-dimensional network of non-straight-chain clusters interconnected by long polymethylene cross-links, (c) the ‘core’, in comparison with the ‘periphery’ of the kerogen matrix, contains a greater proportion of straight-chain and branched aliphatic structures which are attached to the kerogen matrix at one terminus, (d) some of the straight-chain structures may exist as physically entrapped components in the kerogen matrix.     

Polymer-stabilized emulsions and fine-particle recovery,I. The calcite-quartz system

The interaction between polymer-stabilized oil droplets and fine calcite particles has been studied at pH 10. Large calcite-droplet aggregates form and may be efficiently separated from fine quartz gangue. The influence of particle size, pulp density, oil-droplet size, oil volume, stirring speed and stirring time on separation efficiency have been investigated.     

Polymer-stabilized emulsions and fine-particle recovery,II. The chalcopyrite-quartz system

The interaction between fine, generally ?2 μm chalcopyrite and polymer-stabilized oil droplets has been studied as a function of pH and weight percent solids in the pH range from 5 to 12. Oil droplets stabilized by partially esterified polymethacrylic acid and cellulose xanthate have been used as collectors. Chalcopyrite may be efficiently separated from fine quartz gangue at pH 11, using cellulose xanthate stabilized emulsions. Good recovery and grade may be obtained at pH 11 up to pulp densities of at least 5.1 wt.%. At other pH values, selectivity is poor due to Cu¹¹ species from chalcopyrite activating the quartz surface.     

Carbonate equilibria in hydrothermal systems: First ionization of carbonic acid in NaCl media to 300°C

The ionization quotients of aqueous carbon dioxide (carbonic acid) have been precisely determined in NaCl media to 5 m and from 50° to 300°C using potentiometric apparatus previously developed at Oak Ridge National Laboratory. The pressure coefficient was also determined to 250°C in the same media. These results have been combined with selected information in the literature and modeled in two ways to arrive at the best fits and to derive the thermodynamic parameters for the ionization reaction, including the equilibrium constant, activity coefficient quotients, and pressure coefficients. The variation with temperature of the two fundamental quantities $\text{Δ}\text{V}\text{?}{}^{\mathrm{o}}$ and $\text{Δ}\text{C}\text{?}{}^{\mathrm{o}}{}_{\mathrm{p}}$ were examined along the saturation vapor pressure curve and at constant density. The results demonstrated again that for reactions with minimal electrostriction changes the magnitudes and variations of $\text{Δ}\text{C}\text{?}{}^{\mathrm{o}}{}_{\mathrm{p}}$ and $\text{Δ}\text{V}\text{?}{}^{\mathrm{o}}$ with temperature are small and, in addition, $\text{Δ}\text{C}\text{?}{}_{\mathrm{p}}$ and $\text{Δ}\text{V}\text{?}$ are approximately independent of salt concentration.The results have also been applied to an examination of the solubility of calcite as a function of pH (in a given NaCl medium) for the neutral to acidic region both for systems with fixed CO₂ pressure and systems where the calcium ion concentration equals the concentration of carbon. The pH of saturated solutions of calcite with P_CO2 of 12 bars increases from 5.1 to 5.5 between 100° and 300°C.     

[1H] and [13C]NMR studies on the importance of aromatic structures in fulvic and humic acids

To obtain information on the contribution of aromatic fragments to the chemical structure of humic substances, we carried out a study on the [¹H]NMR and [¹³C]NMR spectra of humic and fulvic acids and their oxidative degradation products extracted from an Andosol soil.[¹H]NMR spectra of all organic fractions present considerable adsorption between 7.4 and 8.8 ppm, due to the presence of aromatic protons.The percentages of aromatic protons in respect to the total amount of protons are as follows: FA 20%, HA 19%, degraded FA < 12%, degraded HA 14%. The values indicate that the contribution of aromatic structures to the humic substances is significant, also considering that they are highly substituted.The degraded fractions contain smaller amounts of aromatic protons, because degradation causes the opening of the aromatic rings. Thus results obtained from the degradation do not seem to be reliable for defining the importance of aromatic structures in humic substances.Also the [¹³C]NMR spectra show signals in the aromatic region which derive from unsubstituted carbon atoms, while signals originating from tertiary carbon atoms merge with the noise. We believe that, at present, [¹H]NMR spectroscopy is more suited for studying the role played by aromatic compounds in organic soil fractions.     

Infrared study of the adsorption on silica of a collector with an oxyethylene chain

Positive results obtained for the flotation of quartz at low pH by a molecule containing a polyoxyethylene chain ($\text{OPEG}\text{=}\text{Triton}\text{× 100}$) led us to examine the nature of the interactions between this collector and the quartz surface, using infrared spectroscopy and considering a porous silica as a model adsorbent.The infrared spectra obtained after adsorption of increasing amounts of OPEG show the disappearance of the free OH groups of silica surface and the development of a band due to bridged hydroxyls. This indicates the formation of hydrogen bonds between ether groups of the collector and silica surface hydroxyls.     

The stereoisomeric composition of phytanyl chains in lipids of Dead Sea sediments

Lipid extracts from five recent Dead Sea sediments were analyzed for isoprenoid compounds and the following were isolated: free and phospholipid-bound di-O-phytanylglycerol, free phytanol and free and esterifled phytanic acid. The phytanyl groups of the diether and the free phytanol were oxidized to the corresponding phytanic acid; the stereoisomeric composition of the derived phytanic acids as well as of the ester-bound phytanic acid was determined by open-tubular gas-liquid chromatography of the corresponding methyl esters on butanediolsuccinate polyester. Only the 3R,7R,11R-isomer of phytanic acid was detected in each of the phytanate samples, indicating that these phytanyl chains in the Dead Sea sediments are most likely derived from extremely halophilic bacteria rather than from phytol of chlorophyll origin. These findings also provide further evidence that the mixtures of RRR and SRR-phytanic acids previously isolated from organic-rich shales were most likely derived from the phytyl chain in chlorophyll.     

The solubility of medium molecular weight aromatic hydrocarbons and the effects of hydrocarbon co-solutes and salinity

The solubilities of several medium molecular weight aromatic hydrocarbons were determined at 25°C in aqueous binary, ternary, and quaternary systems. The binary systems consisted of distilled water plus one each of the following: naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, biphenyl, 2-ethylnaphthalene, 1,5-dimethylnaphthalene, 2,3-dimethylnaphthalene, 2,6-dimethylnaphthalene, acenaphthene and phenanthrene. The ternary systems consisted of distilled water plus one of the following hydrocarbon pairs: naphthalene/biphenyl, naphthalene/acenaphthene, naphthalene/phenanthrene, biphenyl/phenanthrene, biphenyl/2-methylnaphthalene, acenaphthene/phenanthrene and 2-methylnaph-thalene/phenanthrene. Quaternary systems consisted of distilled water and one of the following hydrocarbon mixtures: naphthalene/biphenyl/phenanthrene, 2-methylnaphthalene/biphenyl/phenanthrene and naphthalene/acenaphthene/phenanthrene. In binary systems at S%. = 0, solubilities ranged from 31.3 ppm for naphthalene to 1.07 ppm for phenanthrene. The alkyl naphthalenes exhibited solubilities which were a function of molar volume and substituent size and position. In ternary and quaternary systems, solubilities often deviated from values obtained in binary systems presumably due to solute-solute interactions and/or formation of solid solutions. Aromatic hydrocarbons are ‘salted out’ by increasing concentrations of inorganic salts. At S%. = 35, the solubility of naphthalene is 22.0 ppm and of phenanthrene, 0.71 ppm. The empirical salting parameters are identical in both binary and quaternary systems.     

Biogeochemistry of fatty acids in recent sediments from Narragansett Bay,Rhode Island

The fatty acid composition of sediments from Narragansett Bay show significant variation between certain areas of the Bay. Both the organic carbon and fatty acid concentrations decrease with increasing distance from the Providence River area—an area which received municipal sewage and industrial effluents. The ratio of the fatty acid concentration to organic carbon concentration is fairly constant for all stations sampled. The variations in the relative abundance of fatty acids may reflect either the influence of fatty acids discharged to the river area by sewage effluents or the synthesis of fatty acids by microbial populations which probably differ for the areas compared. Temporal variations in fatty acid composition and fatty acid concentration are minimal. Lipolytic activity has been demonstrated and probably acts on glycerides deposited to the sediments releasing free fatty acids shortly after deposition. A model for the diagenesis of fatty acids in Recent sediments is proposed based upon the above findings and upon earlier reports by the authors and by other investigators.     

Oxidation products of Mn(II) in lake waters

Oxygenation of Mn(II)-rich water samples taken from two English lakes (Esthwaite Water, Cumbria, and Rostherne Mere, Cheshire) during the summer months caused the precipitation of Mn-oxide, the process being catalysed by particulate matter. The Mnoxide formed resembles vernadite (δ-MnO₂) with regard to: (1) Mn oxidation state (> 3.6 in all but one case); and (2) its fine morphology (crumpled thin sheets) as determined by electron microscopy. The precipitates are, however, rather amorphous to X-rays, giving only very weak reflections which cannot be assigned unequivocally. Electron probe microanalysis shows the presence of a number of other elements in the Mn-containing phase. The most abundant is Ca (Ca/Mn weight ratio $\text{? 0.1}$), others are Mg, Si, P, S, Cl, K, Ba and Fe. The precipitates contain much organic matter (20–30 wt.%) but little appears to be associated directly with the Mn phase. Only small amounts (～ 1 wt.%) of humic substances are present. Some but not all of the specimens examined had the gross morphology of Metallogenium, a Mn-depositing bacterium.Naturally occurring Mn-oxides present in Esthwaite Water during the summer resemble, the products of oxygenation in their fine morphology and contents of other elements. Mn-oxides present during the winter are somewhat different morphologically. In one summer sample of particulate matter from Esthwaite Water no Mn-oxide could be found by electron microscopic examination, but Mn was found concentrated in bacteria. This observation, the rapid rates of oxidation and the high Mn oxidation states, suggest that bacteria might play a rôle in catalysing the oxidation of Mn(II).     

Sulfur speciation and associated trace metals (Fe,Cu) in the pore waters of Great Marsh,Delaware

The pore waters of sediments from a salt marsh along the Delaware estuary have been analyzed for sulfur species and associated trace metals. Since the sediment interface is usually in contact with the atmosphere, the sulfur species are dependent on the production of hydrogen sulfide by sulfate reduction and subsequent oxidation by diffusing oxygen. The most important species observed are hydrogen sulfide, polysulfide ions and thiosulfate. Secondary reactions of hydrogen sulfide and polysulfides with decomposing organic matter yield significant concentrations of both thiols and organic polysulfides. Upon isolation of the sediment from the atmosphere due to tidal inundation, bacterial sulfate reduction becomes the dominant process. This results in the reduction of the polysulfides in agreement with thermodynamic predictions, and suggests that the redox couple sulfide/polysulfide is a good redox indicator under such reducing environments.The concentrations of trace elements Cu and Fe in the pore waters are mainly controlled by sulfide formation. Calculations show that copper is strongly complexed probably with organo-sulfur ligands. Iron might be complexed as such sulfur species to a much lesser extent than copper.     

Selecting test conditions for high gradient magnetic separation

The use of a Davis tube coil adapted for high gradient magnetic separation (hgms) and mathematical modelling techniques as aids for selecting test conditions for hgms is described. A recovery model based on the loading number concept of Nesset and Finch is shown to give reliable predictions for a wide range in conditons. The ability to select operating conditions from the model and conduct exploratory runs on the Davis tube adaptation have resulted in making more effective use of limited access time on a commercial hgms.     

Gypsum-organic interactions in the marine environment: sorption of fatty acids and hydrocarbons

Free fatty acids make up the bulk (50–84% wt/wt) of lipid materials recovered from artificial gypsum precipitates and crystals collected from sea salt evaporation pans. Both the fatty acids and hydrocarbons associated with artificial gypsum tend to be of longer mean chain length than organic materials dissolved in the mother liquor. Increased specific adsorption of n-fatty acids at Ca²⁺ sites on gypsum surfaces is positively correlated with alkyl chain length. Neutral lipids were not significantly enriched in either type of gypsum precipitates. The fatty acids associated with gypsum from sea salt evaporation pans are branched fatty acids in contrast to the predominantly normal acids associated with artificial gypsum samples. Differences in the two adsorbed acid distributions are attributed to the unique lipids of hypersaline biota.     

Predominance of isoprenoids among the alkanes in the Irati oil shale,Permian of Brazil

An alkane distribution in which isoprenoid alkanes are present in excess of n-paraffins and pristane, phytane, and norpristane (in this order) are the major components, has been found in two different beds of the Irati oil shale, Brazilian Permian formation of São Mateus do Sul, Paranã.     

Closed system Fischer-Tropsch synthesis over meteoritic iron,iron ore and nickel-iron alloy

Meteoritic iron, iron ore and nickel-iron alloy (either alone or in some cases mixed with alumina, carbonaceous chondrite, potassium carbonate or sodium carbonate) were used to catalyze the reaction of deuterium and carbon monoxide in a closed reaction vessel. The mole ratio of deuterium to carbon monoxide ranged from 1/2:1 to 10:1, the reaction temperature from 195 to 370°C, and the reaction time from 6 to 480 hr. Analysis of the reaction products showed that normal alkanes and alkenes (C₁₁-C₂₅), their monomethyl substituted isomers and aromatic hydrocarbons (e.g. naphthalene, acenaphthene, fluorene, phenanthrene and the methyl derivatives of these hydrocarbons) were synthesized. In addition to the aforementioned hydrocarbons, one reaction product was shown to contain perdeutero normal fatty acids (10:0–16:0).     

Phylogeny of transfer RNA and origins of organelles

By using nucleotide sequences of transfer RNA's, the endosymbiotic model for the origin of chloroplasts and mitochondria is examined. The endosymbiotic origin of the chloroplasts is confirmed, but concerning the origin of the mitochondria no conclusion can be drawn. Phyletic relations of euglenoids to higher plants and to animals are also discussed. Finally, phylogeny of fungi is discussed in terms of tRNA sequences and it is proposed that the classical taxonomy of fungi should be reconsidered in terms of molecular taxonomy or molecular paleontology.     

Factors affecting the association of fatty acids with mineral particles in sea water

Certain factors influencing the incorporation, transport and release of fatty acids by clay minerals, calcite and marine sediments have been investigated.Salinity was found to be an important factor. The adsorption of heptadecanoic acid by bentonite clay at 4%. was nearly triple that at 0%.. However, from 4%. to 35%., only a minor adsorption increase occurred. This behavior is believed to be related to flocculation of the clay at the lower salinity range. The pH over the range of 6.0–8.5 has a small influence on fatty acid-clay association, depressing it somewhat as the basicity increases.When the temperature of the fatty acid solution was increased from 0°C to 50°C, a decrease in adsorption on to clay was found. This effect may be due to increased water solubility of the acid at higher temperatures, since solubility is very important in controlling the degree of fatty acid-mineral interaction. Furthermore, apparent solubilization of fatty acids by indigenous dissolved organic matter in sea water reduces adsorption on to clay minerals.Based upon the heat of adsorption of ?14.6 kcal/mole, fatty acids are physically bound to clay minerals by weak van der Waals forces and hydrogen bonds.Bentonite and kaolinite were found to be the most adsorptive minerals investigated, followed in order by illite, montmorillonite and calcite. Sediments from Narragansett Bay were found to lie between illite and montmorillonite in adsorptive capacity after indigenous sediment organic matter had been removed. Sediment organic matter reduced fatty acid uptake by a factor of 1.6.     

Maximum carbon isotope fractionation in photosynthesis by blue-green algae and a green alga

The maximum carbon isotope fractionation occurring in photosynthetic fixation of carbon dioxide in pure cultures of blue-green algae was ?23.9%. and for a green alga was ?22.6%., Maximum fractionations were obtained where cell densities were low and carbon dioxide concentrations were greater than 0.5%. Fractionation was reduced at higher temperatures using a thermophilic blue-green alga. For filamentous blue-green algae wherein clumping occurs and localized cell concentrations were high, fractionation was also lower. Fractionations reported in literature for Precambrian organic materials are comparable to the maximum fractionations reported here. This suggests that the early photosynthetic organisms developed under conditions of high carbon dioxide availability, i.e. slow growth rates and/or low population densities.