The micro-scale simulation of maturation: outline of a new technique and its potential applications

A micro-analytical technique has been developed for artifically maturing sedimentary organic matter and then quantifying the major components generated during this process in a single analytical step. Such a capability is well-suited for examining the compositional relationships between kerogens and petroleums, determining reaction kinetics and making precursor-product mass balances. According to this technique, simulations are made using sealed glass capillary tubes (heated here for three days at 300 °C, 330 °C and 350 °C). Pyrolysis products are then released directly into a combined thermovaporisation/pyrolysis-GC instrument and the major components of the entire C₁ yto C³⁵ range can be quantified in a single step using gas chromatography. Alkene yields are very low and pyrolysates are oil-like. This is exemplified by the fact that then–C₉–C₁₉ alkane distribution range of simulated whole petroleum chromatograms, from originally immatureGloeocapsamorpha-typz alginite A, resembles that seen in crude oils generated from this same kerogen type in nature. Sealed tube experiments usingBotryococcus type alginite A generated a »high wax« pyrolysate. The relative abundance ofn-alkanes in the C₂–C₃₂ range of many kerogen pyrolysates does not appear to change significantly despite an approximately fifteen-fold difference inn-alkane yield between the 300 °C and 350 °C experiments. Kerogens which are »paraffinic« oil-prone, and whose pyrolysates are very rich inn-alkanes might therefore generate petroleums in nature with a fixed wet gas (C₂-C₄) to oil (C₅+) ratio. Alginite B in a Greenland shale is much more thermally labile than eitherBotryococcus-type alginite A orGloeocapsamorpha-type alginite A. The mass balance capabilities of the technique have been tested using Alum Shale kerogen. Two gas chromatograms were obtained, one for the free compounds generated during simulation, and one for the high temperature pyrolysate of the kerogen residue, for each heating experiment. Precursor-product relationships were qualitatively assessed, and dead carbon formation was quantified in this exercise.

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Zusammenfassung Eine mikro-analytische Methode zur künstlichen Reifung sedimentärer organischer Substanz konnte entwickelt werden. Dabei werden die Hauptkomponenten, die während des Vorgangs freigesetzt werden, quantitativ erfaßt. Grundlagen dieser Methode sind Simulationen mit kapillaren Glasröhren, nach welchen die Pyrolyse-Produkte direkt in ein kombiniertes Thermovaporation/Pyrolyse-GC Instrument freigesetzt werden. Mit Hilfe der Gas-Chromatographie können in einem einzigen Schritt die Hauptkomponenten der gesamten C₁ bis C₃₅ Spannbreite quantitativ erfaßt werden. Kerogen-Typisierung und Abschätzung des Muttergesteinspotentials werden stark vereinfacht, wenn die Verhältnisse der Vorläufer-Produkte sorgfältig bestimmt und die chemisch-kinetischen Parameter für einzelne Komponenten, Komponentengruppen und/oder Siedepunktbereiche berechnet werden. Diese Anwendung stimmt mit Techniken im Makro-Bereich (z. B. Hydro-Pyrolyse) überein, aber die Vorteile der Annäherung im Mikro-Bereich liegen darin, daß geochemische Informationen schneller und bequemer gewonnen werden können und sehr kleine Probenmengen ausreichen. Ferner kann neben der Möglichkeit der singulären Anwendung die Annäherung im Mikro-Bereich dazu verwendet werden, Proben für detailierte und Labor-intensive Simulationen im Makro-Bereich effizient auszuwählen.

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Résumé Les auteurs présentent une technique micro-analytique qui comporte la maturation artificielle de la matière organique sédimentaire suivie du dosage des composants majeurs ainsi engendrés. Dans le cadre de ce procédé, on réalise des simulations dans des tubes capillaires en verre, après quoi les produits de la pyrolyse sont libérés directement dans un instrument combiné de thermovaporisation/hydrolyse-GC et les composants majeurs de la lignée complète C₁ à C₃₅ peuvent être dosés en une seule opération de Chromatographie en phase gazeuse. De cette manière, la caractérisation du kérogène et l'estimation du potentiel de la rochemère sont grandement facilitées dans la mesure où les relations des produits précurseurs sont soigneusement établies et où il est possible de calculer les paramètres chimico-cinétiques pour des composants isolés, pour des groupes de composants et/ou les domaines de température où se situent les points d'ébullition. Ces procedures sont en accord avec celles des techniques macroscopiques (p.ex l'hydro-pyrolyse), mais l'avantage de l'approche microanalytique réside dans le fait que les résultats géochimiques sont obtenus plus rapidement et plus aisément et qu'il est possible de traiter de très petits échantillons. Enfin, nonobstant ses avantages propres, l'approche micro-analytique peut être utilisée à la sélection d'échantillons destinés à des simulations détaillées et laborieuses à l'échelle macroscopique.

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Flotation als einfache Anreicherungsmethode für die Spurenanalyse in Wässern

Recently the method of flotation is used as a simple step within a number of procedures of chemical analysis for enrichment of waters or industrial lyes to be investigated by ions. By the example of tin analysis all the possible variants are compared with regard to their efficiency. The advantages result from the using conventional methods of chemical analysis in connection with coprecipitation of traces and their flotation at trace levels of ng/ml. The flotation is a fast method of enrichment, it is easily to handle and sufficiently exact. As a proof example the chemical analysis of Sn, Au and Ag is described.     

On the effect of emissions from aircraft engines on the state of the atmosphere

Emissions from aircraft engines include carbon dioxide, water vapour, nitrogen oxides, sulphur components and various other gases and particles. Such emissions from high-flying global civil subsonic air traffic may cause anthropogenic climate changes by an increase of ozone and cloudiness in the upper troposphere, and by an enhanced greenhouse effect. The absolute emissions by air traffic are small (a few percent of the total) compared to surface emissions. However, the greenhouse effect of emitted water and of nitrogen oxides at cruise altitude is potentially large compared to that of the same emissions near the earth’s surface because of relatively large residence times at flight altitudes, low background concentrations, low temperature, and large radiative efficiency. Model computations indicate that emission of nitrogen oxides has doubled the background concentration in the upper troposphere between 40○N and 60○N. Models also indicate that this causes an increase of ozone by about 5-20%. Regionally, the observed annual mean change in cloudiness is 0.4%. It is estimated that the resultant greenhouse effect of changes in ozone and thin cirrus cloud cover causes a climatic surface temperature change of 0.01-0.1 K. These temperature changes are small compared to the natural variability. Recent research indicates that the emissions at cruise altitude may increase the amount of stratospheric aerosols and polar stratospheric clouds and thereby have an impact on the atmospheric environment. Air traffic is increasing about 5-6% per year, fuel consumption by about 3%, hence the effects of the related emissions are expected to grow. This paper surveys the state of knowledge and describes several results from recent and ongoing research.     

On the dynamics of photochemical smog over the Swiss Middleland — Results of the first POLLUMET field experiment

Summary The Swiss Middleland is a 300×50 km large plain embedded between the Jura, whose highest elevations are between 1000 and 2000m MSL, and the Alps, whose highest peaks are about 400m MSL. Because this plain is the main residence area of Switzerland with a great variety of emission sources, it is also a location with high photosmog concentrations during the summer months.Within the framework of the Swiss POLLUMET (Air Pollution and Meteorology) programme, an initial summer smog field experiment was carried out during July 1990 with the participation of different research groups from Switzerland and Germany. The measurements showed that the ozone concentrations within the atmospheric boundary layer were remarkably variable. The highest concentrations in the upper mixed layer varied between 100 and 130 ppb. The background ozone concentration in the upper atmospheric boundary layer increased from day to day. However, a clear indication of long-range transport could not be found. Remarkable local and regional concentration differences are not only based on the complex structure of the large emission sources (highways, urban plumes). They are also the result of the interaction of convectively driven motion systems like slope and valley winds and mountain-plain circulation.With 14 Figures     

Studies on hydrothermal alteration by acid solutions dominated by SO4 2−: Formation of the alteration products of the Gleichenberg latitic rock (Styria,Austria)—Experimental evidence

Summary The latitic rock mined at the Gossendorf open pit in the Gleichenberg Volcanic Area of Styria, Austria, has in places been completely altered to various associations of the secondary minerals opal-C/-CT, alunite, kaolinite and montmorillonite. These associations occur in a zonal arrangement, in which the innermost part has been totally altered to opal and moreover has retained its original latitic structure. The results of experimental alteration tests on the latitic rock in open hydrological systems suggest that these secondary minerals and some of the associations observed in the field as well as their zonal distribution, may have been formed by an originally strongly acid solution rich in SO₄ ^2– which, undergoing progressive chemical variation by reaction with the rock, exhibits a chemical gradient. Some of the mineral associations, however, may not be explained by a single alteration process, but must be regarded as the result of multi-stage alteration in which alteration products from weak leaching are super-imposed on alteration products from intense leaching.

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Untersuchungen zur hydrothermalen Umwandlung unter dem Einfluß saurer SO₄ ^2–-Lösungen: Diskussion der Bildungsbedingungen der Umwandlungsprodukte der Latite von Gleichenberg, Steiermark, Österreich anhand experimenteller Umwandlungen.

Zusammenfassung Latitische Gesteine sind im Tagbau Gossendorf des Gleichenberger Vulkangebietes, Steiermark, Österreich, z. T. vollständig in verschieden zusammengesetzte Kombinationen der Mineralneubildungen Opal-C/-CT, Alunit, Kaohnit und Montmorillonit umgewandelt. Diese Kombinationen treten in einer zonaren Anordnung auf, wobei der zentrale Bereich vollständig in Opal umgewandelt ist und darüberhinaus noch das ehemalige Latitgefüge aufweist. Experimentelle Umwandlungsversuche mit dem latititschen Gestein im offenen System haben gezeigt, daß diese Neubildungen und einige der beobachteten Kombinationen sowie deren zonare Anordnung durch den Einfluß einer ursprünglich stark sauren SO₄ ^2–-Lösung entstehen können, die sich durch die Reaktion mit dem Gestein chemisch ständig ändert, d. h. einen chemischen Gradienten aufweist. Einige der auftretenden Kombinationen sind jedoch nicht durch ein Umwandlungsgeschehen zu erklären, sondern nur als Ergebnis einer mehraktigen Umwandlung, wodurch sich Umwandlungsprodukte einer starken Auslaugung und die einer schwachen Auslaugung überlagern können.

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With 9 Figures     

Kationenaustauschkapazität als Grundlage für die Schätzung der Schwermetallmigration im Boden

The adsorption/desorption ratio is an important quantity of the displacement of heavy metals in the soil. Adsorption isotherms as controlled quantities are suitable for the development of a transport model. With the aid of the T value the sorption coefficients and distribution quotients can be determined for different soils. By two examples of simulation the migrations of Cd and Pb were calculated with soil samples of warp clay/gley and loam/para-brown earth. It was found, inter alia, that with increasing time of input the concentration of dissolved and adsorbed heavy metals grows and that the added heavy-metal ions are absorbed in the uppermost layers already. For cases of continuous input the simulation model is recommended for the practice to estimate the migration of heavy metals in soils.     

IMPROVEMENT OF OBSERVATION ACCURACY OF THE LACOSTE-ROMBERG (MODEL D) GRAVITY METER BY SUPPLEMENTARY INSTALLATION OF ELECTRONIC FEEDBACK1

Recent years have seen an increasing need for high-precision gravity meters. A widely used and the most accurate one is the LaCoste-Romberg, model D (LCR-D) meter, equipped with electronic readout. According to the manual the reading accuracy is 5 μGal. A way of reducing most of the instrumental factors limiting the accuracy is the use of an electronic feedback system. We have fitted the LCR-D 34 with a Schnüll-Röder-Wenzel, model D (SRW-D) feedback. After installation the readout voltage was calibrated, the instrumental behaviour tested, and the accuracy of the system determined. By repeat readings in the laboratory without moving the meter, the standard deviation for a single reading is better than 4 μGal in normal mode and better than 1 μGal in feedback mode. The accuracy of gravity differences - this is usually observed in field practice - is the mean value of the repeat errors of several sets of differences observed in a short time to avoid any corrections. This accuracy is better than 9 μGal in normal mode and better than 5 μGal in feedback mode. With this, the accuracy of a single reading becomes more than 6 μGal and more than 3 μGal, respectively. As the described improvement of accuracy was found to be not as good as expected, additional improvements should centre on the use of electronic levels instead of the standard liquid ones.