Oxygen-containing functional groups in land-derived humic acids—II. Changes in the oxygen distribution of humic acids during early diagenesis as revealed by derivatization methods

Extensive functional group analyses were performed on humic acids representative of eight increasing depth levels from a core drilled in the Mahakam delta (East Kalimantan, Indonesia). Oxygen amounts decrease observed during early diagenesis was related chiefly to loss of hydroxyl (lignol?) groups. Comparison between upper and deeper levels shows the following variations: hydroxyl group abundances go from 19 to 6% of humic oxygen. Identified functional groups amounts represent 47 to 32% of weight of moisture- and ash-free humic acids. No evidence of decarboxylation of humic material was detected.     

Immunological studies on microbial mats from Solar Lake (Sinai)— A contribution to the organic geochemistry of sediments

Immunological and biochemical techniques were used to investigate organic matter in microbial mats from Solar Lake (Sinai, Egypt). Antibodies, elicited in rabbits against samples taken at different depths from a core of these mats, were used for the detection of immunological determinants preserved in these samples. Special attention was given to an antiserum directed against a top mat fraction (3–10 mm depth) and an antiserum against a fraction from a lower section of the core (380–390 mm depth). Both antisera, tested in a dot-blot immunobinding assay, were found to give positive reactions with organic matter from different depths of the sediment. An immunohistochemical experiment with the antisera points to antigenic determinants on Recent and subfossil sheaths of Microcoleus. In addition, extracts of sediment samples were submitted to electrophoresis in polyacrylamide gels in order to characterize the separated macromolecules by immunological means. The results showed a rapid decrease in the number of antigenic determinants from Recent to subfossil samples. However, even in the deepest layers of the sediment (690–700 mm depth) intact biopolymers were detected.     

Organic geochemistry of Recent equatorial deltaic sediments

The organic matter of recent deltaic sediments cored in the Mahakam delta, East Kalimantan, has been studied before and after physical fractionation into sands >50 μm, silts 5–50 μm and clays <5 μm. Both the lipid and non-lipid components have been investigated.Weight, carbon and nitrogen fractionation budgets were used to define three types of samples, depending on coarse particle contributions to the total amount of organic matter: a = a first type with more than 50% of the O.M. in the coarse particles, high C/N ratios and O.M. content, b = an intermediary type with medium C/N ratios and O.M. content, each fraction having quite the same O.M. content, c = a third type with less than 5% of the whole O.M. in the sands and the lowest C/N ratios and O.M. content.Concerning the global organic characteristics of the fractions, a systematic increase of C/N ratios occurs when going from clays to sands; the finer the fraction is, the more nitrogenous the compounds are. This enrichment in nitrogen is related to a persistent high rate of hydrolysable material either for argillaceous organic matter-poor sediments or for the clay fractions of all types of samples. Conversely, the type (a) coarse sediments, in particular the sandy components were resistant to acid hydrolysis with burial.Concerning the geochemical markers signatures of granulometric fractions, the distribution patterns of n-alkanes and n-fatty acids are characterized by the predominance of high molecular weight compounds >C₂₂. Carbon preference index (CPI) values are higher in the sands and silts, reflecting their enrichment in continentally-derived vegetation debris. For type (c), the fractionation revealed markers of microbial activity within the clay fractions. For all types of samples, we observed an increase with burial of the n-alkane and n-fatty acid concentrations, particularly in the clay fractions, suggesting possibly a better preservation and/or affinity of lipids with the finest fractions.     

Characterization of the particulate organic matter in the Loire Estuary (France) using ETS activity measurements

The major problems encountered in studying estuarine particulate organic matter (POM) are the characterization and quantitation of different kinds of materials (e.g. detrital and living matter, algal and bacterial matter…) each type contributing a specific role in the ecosystem. The study of the activity of the electron transport system (ETS) is proposed as a tool for resolving these problems. Results obtained in our laboratory with cultures of planktonic algae and bacteria provided us with numerical relationships between ETS activity and various organic components such as chlorophyll, carbon and protein. These relationships were: ETS activity/chlorophyll = 2.6, carbon/ETS activity = 17.3, protein/ETS activity = 9.6 in algae; carbon/ETS activity = 5.9, protein/ETS activity = 7.7 in bacteria (ETS activity expressed in /i₂h⁻¹ at 20°C; chlorophyll, carbon and protein in μg). Such data can be applied in field studies to characterize the living algal and bacterial matter and, by difference, the detrital organic matter. We report here a study of the Loire estuary as an example.     

Effect of monochloramine on isolated fulvic acid

Monochloramine is interesting both as a selective oxidant of fulvic acid and as a drinking water disinfectant. In this study, the controlled reaction of aquatic fulvic acid with monochloramine did not result in products detectable by ether extraction-gas chromatography-flame ionization detection techniques. Evidence of a reaction was shown by bleaching of the fulvic acid solution (decreased absorbance at 465 nm) and chlorine substitution. Chlorine-containing products were quantified by the total carbon adsorbable organic halide (TOX) parameter. Bleaching and organic chlorine formation were much less extensive than in the reaction of free chlorine with fulvic acid. Monochloramine was shown to produce an organic chlorine fraction more hydrophilic and with higher molecular size than that produced by chlorine and fulvic acid. Results suggest that monochloramine may be useful tool for the investigation of certain humic functionalities because it reacts rather selectively and to a small extent with aquatic fulvic acid.     

The kerogen type, depositional environment and maturity, of the Irati Shale, Upper Permian of Paraná Basin, Southern Brazil

Two samples from the upper and lower horizons of the Irati oil shale of the Paraná Basin, Brazil were sampled in a single borehole, and analysed using organic petrography and geochemistry. The results are interpreted in terms of the kerogen type, maturity and depositional environment of the two horizons.Organic petrography shows the oil-shales to be composed of a mineral groundmass, mainly clay minerals, carbonate and pyrite, associated, and sometimes impregnated, with fluorescing organic material and disseminated phytoclasts. Humic material is fairly rare and mostly present as very small particles. The liptinitic particles are mostly alginite (A and B), sporinite and more rarely resinite. Reflectance measurements (upper seam = 0.34% R₀; lower seam = 0.40% R₀) indicate an equivalent rank of lignite/sub-bituminous coal (ASTM), i.e. immature with respect to oil and gas generation. Different organic geochemical methods (Rock-Eval pyrolysis, solvent extraction, GC and GC-MS) demonstrate both samples to be immature, rich oil-shales (100–114 kg/ton) containing Type I kerogen, of a dominantly bacterially-degraded algal origin deposited in a lacustrine environment. The presence of Botryococcus suggests deposition under fresh/brackish water conditions.A tentative interpretation of the extract and vitrinite reflectance data suggests a maximum paleo-burial of between 1.3 and 2.8 km for the analysed section of the Irati Formation.     

Organic geochemical characterization of the New Albany Shale group in the Illinois Basin

Benzene extractable aliphatic hydrocarbons from the New Albany Shale in the Illinois Basin were characterized by gas chromatography and mass spectrometry, and the total organic matter of the shale was characterized by solid state carbon-13 cross polarization magic angle spinning nuclear magnetic resonance. Core samples from a northwest-trending cross-section of the Illinois Basin were studied. Gas chromatography (GC) and gas chromatography-mass spectrometric analysis (GC/MS) data indicate a regional variation of the aliphatic composition of the shale extracts. A positive, linear relationship between the two ratios, pristane/n-C₁₇ and phytane/n-C₁₈, is indicated. The NMR results indicated that organic matter deposited in northwestern Illinois shale is relatively high in aliphatic hydrocarbon content while, in contrast, organic matter found in southeastern Illinois shale is relatively low in aliphatic hydrocarbon content. Our findings suggest that the organic variation of the shale is mainly due to the differences in thermal maturity of the shale organic matter and the use of pristane/n-C₁₇ ratio as a thermal parameter in the study of oil may be extended to the study of the ancient sediments.     

Distribution of carbazole derivatives in petroleum

Carbazole, its alkyl derivatives and higher benzologs have been selectively isolated from six different crude oils. In all samples, benzocarbazoles are major constituents of a series which may extend up to dibenzocarbazole derivatives. The distribution includes unsubstituted parent compounds and shows a maximum content of methyl and dimethyl substituted species. Sixteen individual constituents have been identified by means of comparison with reference compounds using gas chromatography, mass spectrometry and high resolution spectrofluorimetry. So far, no generally acceptable explanation has been given for the origin of these compounds, which presumably are the most stable ones in their respective series of aromaticity. Thus, carbazole derivatives may result from a complex sequence of reactions during kerogen formation, not allowing the recognition of precursing molecules. The geochemical significance of this series of nitrogen compounds needs to be clarified, requiring further studies.     

Near UV absorption spectra and photolysis products of difunctional organic nitrates: Possible importance as NO x reservoirs

Difunctional organic nitrates are important products of the atmospheric reaction of NO₃ radicals with unsaturated hydrocarbons about which relatively little is known. In a continuation of the investigation of the atmospheric chemistry of such compounds, the UV absorption spectra of the following organic dinitrates and keto nitrates have been quantitively measured in the gas phase at 298±2 K and atmospheric pressure: 1,2-propandiol dinitrate, CH₃CH(ONO₂)CH₂(ONO₂); 1,2-butandiol dinitrate, CH₃CH₂CH(ONO₂)CH₂(ONO₂); 2,3-butandiol dinitrate, CH₃CH(ONO₂)CH(ONO₂)CH₃;cis 1,4-dinitrooxy-2-butene, CH₂(ONO₂)CH=CHCH₂(ONO₂); 3,4-dinitrooxy-1-butene, CH₂(ONO₂CH(ONO₂)CH=CH₂; -nitrooxy acetone, CH₃COCH₂(ONO₂); 1-nitrooxy-2-butanone, CH₃CH₂COCH₂(ONO₂); 3-nitrooxy-2-butanone, CH₃CH(ONO₂)COCH₃.Although the UV spectra of the nitrates are all very similar in shape those of the keto nitrates are red-shifted compared to the dinitrates and in the spectral range of atmospheric interest (>290 nm) their absorption cross-sections are approximately a factor of 5 higher. The cross-sections of the dinitrates are a factor of 2 higher than those reported in the literature for the corresponding alkyl mononitrates.The UV absorption cross-sections of the difunctional nitrates were used in combination with solar actinic flux data to estimate photolysis frequencies and consequently atmospheric lifetimes for these compounds. The results indicate that for the saturated difunctional nitrates studied in this work photolysis will generally be somewhat some important than reaction with OH radicals as an atmospheric removal process. However, for unsaturated nitrates loss due to reaction with OH will dominate over photolysis as an atmospheric sink.Preliminary FT-IR analyses of the photolysis products of -nitrooxy acetone, 3-nitrooxy-2-butanone and 2,3-butandiol dinitrate using both mercury and fluorescent lamps indicate that NO₂ is released in the primary step. The further reactions of the radicals thus produced result in the formation of CO, aldehydes and PAN. The possible significance of the results for difunctional organic nitrate as reservoirs for reactive odd nitrogen NO _y in the atmosphere, especially during the night, is briefly discussed.     

陕北高挥发分烟煤煤质特征与应用研究

通过煤质分析、煤岩分析与葛-金干馏试验等对比实验，研究了陕北横山、神府矿区等地侏罗纪不粘-弱粘煤及其配煤的煤炭特性、低温干馏特性以及单种煤与配煤低温干馏性能差异和变化规律。结果表明，陕北侏罗纪煤具有较高的焦油产率，配煤在降低煤中含硫量的同时，有利于低温干馏过程的进行和产品质量的提高；此外，在掌握原煤显微组成和低温干馏特性的情况下，可以预测配煤低温干馏产品的相关参数。